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101. Determination of some quinolones in tablets, human plasma and urine by differential-pulse polarography

Author: Corti, P., Corbini, G., Gratteri, P., and Furlanetto, S.
Published: 1994
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102. New Trends in the Quality Control of Enantiomeric Drugs: Quality by Design-Compliant Development of Chiral Capillary Electrophoresis Methods

Author: Serena Orlandini, Gabriel Hancu, Zoltán-István Szabó, Adriana Modroiu, Lajos-Attila Papp, Roberto Gotti, Sandra Furlanetto, Orlandini S., Hancu G., Szabo Z.-I., Modroiu A., Papp L.-A., Gotti R., and Furlanetto S.
Subjects: Quality Control, chiral separation, enantiomeric purity, experimental design, capillary electrophoresi, Organic Chemistry, Pharmaceutical Science, Electrophoresis, Capillary, Stereoisomerism, Analytical Quality by Design, Analytical Chemistry, Pharmaceutical Preparations, Chemistry (miscellaneous), ICH guideline, Drug Discovery, Molecular Medicine, Physical and Theoretical Chemistry, Drug Contamination
Abstract: Capillary electrophoresis (CE) is a potent method for analyzing chiral substances and is commonly used in the enantioseparation and chiral purity control of pharmaceuticals from different matrices. The adoption of Quality by Design (QbD) concepts in analytical method development, optimization and validation is a widespread trend observed in various analytical approaches including chiral CE. The application of Analytical QbD (AQbD) leads to the development of analytical methods based on sound science combined with risk management, and to a well understood process clarifying the influence of method parameters on the analytical output. The Design of Experiments (DoE) method employing chemometric tools is an essential part of QbD-based method development, allowing for the simultaneous evaluation of experimental parameters as well as their interaction. In 2022 the International Council for Harmonization (ICH) released two draft guidelines (ICH Q14 and ICH Q2(R2)) that are intended to encourage more robust analytical procedures. The ICH Q14 guideline intends to harmonize the scientific approaches for analytical procedures’ development, while the Q2(R2) document covers the validation principles for the use of analytical procedures including the recent applications that require multivariate statistical analyses. The aim of this review is to provide an overview of the new prospects for chiral CE method development applied for the enantiomeric purity control of pharmaceuticals using AQbD principles. The review also provides an overview of recent research (2012–2022) on the applicability of CE methods in chiral drug impurity profiling.
Published: 2022

103. Effects of model incompleteness on the drift-scan calibration of radio telescopes

Author: Phil Bull, David DeBoer, Adam P. Beardsley, Nipanjana Patra, Ziyaad Halday, Nima Razavi-Ghods, Nicholas S. Kern, Aaron R. Parsons, Piyanat Kittiwisit, Kingsley Gale-Sides, Robert Pascua, Max Tegmark, Judd D. Bowman, Adam Lanman, Samantha Pieterse, James Robnett, Peter Sims, Gianni Bernardi, Peter K. G. Williams, Miguel F. Morales, Chris Carilli, Saul A. Kohn, Zara Abdurashidova, Eloy de Lera Acedo, Zaki S. Ali, Steven R. Furlanetto, Abraham R. Neben, Eunice Matsetela, Randall Fritz, Bojan Nikolic, Aaron Ewall-Wice, Bryna J. Hazelton, Deepthi Gorthi, Richard F. Bradley, Matthew Kolopanis, Jon Ringuette, Brian Glendenning, Matt Dexter, Joshua S. Dillon, Carina Cheng, Paul La Plante, Austin Julius, S. H. Carey, Nithyanandan Thyagarajan, Haoxuan Zheng, David B. Lewis, Mario G. Santos, Daniel C. Jacobs, Joshua Kerrigan, Steven G. Murray, Cresshim Malgas, Jack Hickish, Adrian Liu, James E. Aguirre, Nicolas Fagnoni, Jacob Burba, Yanga Balfour, Lourence Malan, Craig Smith, Raul A. Monsalve, Bradley Greig, Jonathan C. Pober, Andrei Mesinger, Jasper Grobbelaar, Tashalee S. Billings, Zachary E. Martinot, Telalo Lekalake, Matthys Maree, B. K. Gehlot, David MacMahon, Yin-Zhe Ma, Mathakane Molewa, Paul Alexander, Kathryn Rosie, Tshegofalang Mosiane, Nivedita Mahesh, John Ely, Jacqueline N. Hewitt, Angelo Syce, Gehlot, B. K., Jacobs, D. C., Bowman, J. D., Mahesh, N., Murray, S. G., Kolopanis, M., Beardsley, A. P., Abdurashidova, Z., Aguirre, J. E., Alexander, P., Ali, Z. S., Balfour, Y., Bernardi, G., Billings, T. S., Bradley, R. F., Bull, P., Burba, J., Carey, S., Carilli, C. L., Cheng, C., Deboer, D. R., Dexter, M., De Lera Acedo, E., Dillon, J. S., Ely, J., Ewall-Wice, A., Fagnoni, N., Fritz, R., Furlanetto, S. R., Gale-Sides, K., Glendenning, B., Gorthi, D., Greig, B., Grobbelaar, J., Halday, Z., Hazelton, B. J., Hewitt, J. N., Hickish, J., Julius, A., Kern, N. S., Kerrigan, J., Kittiwisit, P., Kohn, S. A., Lanman, A., La Plante, P., Lekalake, T., Lewis, D., Liu, A., Ma, Y. -Z., Macmahon, D., Malan, L., Malgas, C., Maree, M., Martinot, Z. E., Matsetela, E., Mesinger, A., Molewa, M., Monsalve, R. A., Morales, M. F., Mosiane, T., Neben, A. R., Nikolic, B., Parsons, A. R., Pascua, R., Patra, N., Pieterse, S., Pober, J. C., Razavi-Ghods, N., Ringuette, J., Robnett, J., Rosie, K., Santos, M. G., Sims, P., Smith, C., Syce, A., Tegmark, M., Thyagarajan, N., Williams, P. K. G., Zheng, H., ITA, and USA
Subjects: Cosmology and Nongalactic Astrophysics (astro-ph.CO), 010504 meteorology & atmospheric sciences, media_common.quotation_subject, statistical [methods], FOS: Physical sciences, 01 natural sciences, Radio telescope, Settore FIS/05 - Astronomia e Astrofisica, 0103 physical sciences, Calibration, Instrumentation and Methods for Astrophysics (astro-ph.IM), 010303 astronomy & astrophysics, Reionization, 0105 earth and related environmental sciences, Remote sensing, media_common, Physics, COSMIC cancer database, Astrophysics::Instrumentation and Methods for Astrophysics, Astronomy and Astrophysics, interferometric [techniques], interferometer [instrumentation], Interferometry, Amplitude, 13. Climate action, Space and Planetary Science, Sky, data analysi [methods], dark ages, reionization, first star, Antenna (radio), Astrophysics - Instrumentation and Methods for Astrophysics, miscellaneou [instrumentation], Astrophysics - Cosmology and Nongalactic Astrophysics
Abstract: Precision calibration poses challenges to experiments probing the redshifted 21-cm signal of neutral hydrogen from the Cosmic Dawn and Epoch of Reionization (z~30-6). In both interferometric and global signal experiments, systematic calibration is the leading source of error. Though many aspects of calibration have been studied, the overlap between the two types of instruments has received less attention. We investigate the sky based calibration of total power measurements with a HERA dish and an EDGES style antenna to understand the role of auto-correlations in the calibration of an interferometer and the role of sky in calibrating a total power instrument. Using simulations we study various scenarios such as time variable gain, incomplete sky calibration model, and primary beam model. We find that temporal gain drifts, sky model incompleteness, and beam inaccuracies cause biases in the receiver gain amplitude and the receiver temperature estimates. In some cases, these biases mix spectral structure between beam and sky resulting in spectrally variable gain errors. Applying the calibration method to the HERA and EDGES data, we find good agreement with calibration via the more standard methods. Although instrumental gains are consistent with beam and sky errors similar in scale to those simulated, the receiver temperatures show significant deviations from expected values. While we show that it is possible to partially mitigate biases due to model inaccuracies by incorporating a time-dependent gain model in calibration, the resulting errors on calibration products are larger and more correlated. Completely addressing these biases will require more accurate sky and primary beam models., Comment: 16 pages, 13 figures, 1 table; accepted for publication in MNRAS main journal
Published: 2021

104. Foreground modelling via Gaussian process regression: an application to HERA data

Author: Max Tegmark, Aaron R. Parsons, Samavarti Gallardo, Angelo Syce, Jon Ringuette, Adam P. Beardsley, Gianni Bernardi, Richard F. Bradley, Matthew Kolopanis, Mario G. Santos, Adrian Liu, Kathryn Rosie, T. L. Grobler, Nicholas S. Kern, Brian Glendenning, Amy S. Igarashi, Siyanda Matika, Daniel C. Jacobs, Carina Cheng, Oleg Smirnov, Nithyanandan Thyagarajan, Haoxuan Zheng, Peter K. G. Williams, Matthys Maree, Roshan K. Benefo, Nathan Mathison, Lourence Malan, Austin Julius, Nima Razavi-Ghods, Cresshim Malgas, B. K. Gehlot, Nicolas Fagnoni, Bryna J. Hazelton, Andrei Mesinger, Chuneeta D. Nunhokee, Jasper Grobbelaar, David MacMahon, Deepthi Gorthi, Léon V. E. Koopmans, Joshua S. Dillon, Steve R. Furlanetto, Abraham R. Neben, Chris Carilli, Tashalee S. Billings, Zachary E. Martinot, Judd D. Bowman, Samantha Pieterse, Paul Alexander, Randall Fritz, James Robnett, Telalo Lekalake, Raddwine Sell, Saul A. Kohn, Eloy de Lera Acedo, Florent Mertens, Alec Josaitis, Bradley Greig, Nipanjana Patra, Craig Smith, Austin F. Fortino, David DeBoer, Miguel F. Morales, Zaki S. Ali, Bojan Nikolic, Aaron Ewall-Wice, Eunice Matsetela, MacCalvin Kariseb, Gcobisa Fadana, Paul M. Chichura, Jack Hickish, James E. Aguirre, Abhik Ghosh, Anita Loots, Ghosh, A., Mertens, F., Bernardi, G., Santos, M. G., Kern, N. S., Carilli, C. L., Grobler, T. L., Koopmans, L. V. E., Jacobs, D. C., Liu, A., Parsons, A. R., Morales, M. F., Aguirre, J. E., Dillon, J. S., Hazelton, B. J., Smirnov, O. M., Gehlot, B. K., Matika, S., Alexander, P., Ali, Z. S., Beardsley, A. P., Benefo, R. K., Billings, T. S., Bowman, J. D., Bradley, R. F., Cheng, C., Chichura, P. M., Deboer, D. R., Acedo, E. D. L., Ewall-Wice, A., Fadana, G., Fagnoni, N., Fortino, A. F., Fritz, R., Furlanetto, S. R., Gallardo, S., Glendenning, B., Gorthi, D., Greig, B., Grobbelaar, J., Hickish, J., Josaitis, A., Julius, A., Igarashi, A. S., Kariseb, M., Kohn, S. A., Kolopanis, M., Lekalake, T., Loots, A., Macmahon, D., Malan, L., Malgas, C., Maree, M., Martinot, Z. E., Mathison, N., Matsetela, E., Mesinger, A., Neben, A. R., Nikolic, B., Nunhokee, C. D., Patra, N., Pieterse, S., Razavi-Ghods, N., Ringuette, J., Robnett, J., Rosie, K., Sell, R., Smith, C., Syce, A., Tegmark, M., Thyagarajan, N., Williams, P. K. G., Zheng, H., Laboratoire d'Etude du Rayonnement et de la Matière en Astrophysique (LERMA (UMR_8112)), Sorbonne Université (SU)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université de Cergy Pontoise (UCP), Université Paris-Seine-Université Paris-Seine-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL), ITA, USA, ZAF, Astronomy, and Kapteyn Astronomical Institute
Subjects: Cosmology and Nongalactic Astrophysics (astro-ph.CO), interferometers [instrumentation], first stars, statistical [methods], FOS: Physical sciences, Astrophysics::Cosmology and Extragalactic Astrophysics, Astrophysics, Astronomy & Astrophysics, 01 natural sciences, Signal, Settore FIS/05 - Astronomia e Astrofisica, 0103 physical sciences, Coherence (signal processing), dark ages, reionization, first stars, dark ages, instrumentation: interferometers, 010306 general physics, 010303 astronomy & astrophysics, Reionization, Astrophysics::Galaxy Astrophysics, Physics, methods: statistical, COSMIC cancer database, Astrophysics::Instrumentation and Methods for Astrophysics, Spectral density, Astronomy and Astrophysics, White noise, observations [cosmology], Redshift, diffuse radiation, Periodic function, interferometer [instrumentation], Space and Planetary Science, cosmology: observations, astro-ph.CO, reionization, dark ages, reionization, first star, large-scale structure of Universe, [PHYS.ASTR]Physics [physics]/Astrophysics [astro-ph], Astronomical and Space Sciences, Astrophysics - Cosmology and Nongalactic Astrophysics, observation [cosmology]
Abstract: The key challenge in the observation of the redshifted 21-cm signal from cosmic reionization is its separation from the much brighter foreground emission. Such separation relies on the different spectral properties of the two components, although, in real life, the foreground intrinsic spectrum is often corrupted by the instrumental response, inducing systematic effects that can further jeopardize the measurement of the 21-cm signal. In this paper, we use Gaussian Process Regression to model both foreground emission and instrumental systematics in $\sim 2$ hours of data from the Hydrogen Epoch of Reionization Array. We find that a simple co-variance model with three components matches the data well, giving a residual power spectrum with white noise properties. These consist of an "intrinsic" and instrumentally corrupted component with a coherence-scale of 20 MHz and 2.4 MHz respectively (dominating the line of sight power spectrum over scales $k_{\parallel} \le 0.2$ h cMpc$^{-1}$) and a baseline dependent periodic signal with a period of $\sim 1$ MHz (dominating over $k_{\parallel} \sim 0.4 - 0.8$h cMpc$^{-1}$) which should be distinguishable from the 21-cm EoR signal whose typical coherence-scales is $\sim 0.8$ MHz., 15 pages, 15 figures, 1 table, Accepted to MNRAS
Published: 2020

105. HERA Phase I Limits on the Cosmic 21 cm Signal: Constraints on Astrophysics and Cosmology during the Epoch of Reionization

Author: The HERA Collaboration, Abdurashidova, Zara, Aguirre, James E., Alexander, Paul, Ali, Zaki, Balfour, Yanga, Barkana, Rennan, Beardsley, Adam, Bernardi, Gianni, Billings, Tashalee, Bowman, Judd, Bradley, Richard, Bull, Phillip, Burba, Jacob, Carey, Steven, Carilli, Christopher, Cheng, Carina, DeBoer, David, Dexter, Matthew, Acedo, Eloy de Lera, Dillon, Joshua, Ely, John, Ewall-Wice, Aaron, Fagnoni, Nicolas, Fialkov, Anastasia, Fritz, Randall, Furlanetto, Steven, Gale-Sides, Kingsley, Glendenning, Brian, Gorthi, Deepthi, Greig, Bradley, Grobbelaar, Jasper, Halday, Ziyaad, Hazelton, Bryna, Heimersheim, Stefan, Hewitt, Jacqueline, Hickish, Jack, Jacobs, Daniel, Julius, Austin, Kern, Nicholas, Kerrigan, Joshua, Kittiwisit, Piyanat, Kohn, Saul, Kolopanis, Matthew, Lanman, Adam, La Plante, Paul, Lekalake, Telalo, Lewis, David, Liu, Adrian, Ma, Yin-Zhe, MacMahon, David, Malan, Lourence, Malgas, Cresshim, Maree, Matthys, Martinot, Zachary, Matsetela, Eunice, Mesinger, Andrei, Mirocha, Jordan, Molewa, Mathakane, Morales, Miguel, Mosiane, Tshegofalang, Munoz, Julian, Murray, Steven, Neben, Abraham, Nikolic, Bojan, Nunhokee, Chuneeta Devi, Parsons, Aaron, Patra, Nipanjana, Pieterse, Samantha, Pober, Jonathan, Qin, Yuxiang, Razavi-Ghods, N., Reis, Itamar, Ringuette, Jon, Robnett, James, Rosie, Kathryn, Santos, Mario, Sikder, Sudipta, Sims, Peter, Smith, Craig, Syce, Angelo, Thyagarajan, Nithyanandan, Williams, Peter, Zheng, Haoxuan, Abdurashidova, Z., Aguirre, J. E., Alexander, P., Ali, Z. S., Balfour, Y., Barkana, R., Beardsley, A. P., Bernardi, G., Billings, T. S., Bowman, J. D., Bradley, R. F., Bull, P., Burba, J., Carey, S., Carilli, C. L., Cheng, C., Deboer, D. R., Dexter, M., De Lera Acedo, E., Dillon, J. S., Ely, J., Ewall-Wice, A., Fagnoni, N., Fialkov, A., Fritz, R., Furlanetto, S. R., Gale-Sides, K., Glendenning, B., Gorthi, D., Greig, B., Grobbelaar, J., Halday, Z., Hazelton, B. J., Heimersheim, S., Hewitt, J. N., Hickish, J., Jacobs, D. C., Julius, A., Kern, N. S., Kerrigan, J., Kittiwisit, P., Kohn, S. A., Kolopanis, M., Lanman, A., La Plante, P., Lekalake, T., Lewis, D., Liu, A., Ma, Y. -Z., Macmahon, D., Malan, L., Malgas, C., Maree, M., Martinot, Z. E., Matsetela, E., Mesinger, A., Mirocha, J., Molewa, M., Morales, M. F., Mosiane, T., Munoz, J. B., Murray, S. G., Neben, A. R., Nikolic, B., Nunhokee, C. D., Parsons, A. R., Patra, N., Pieterse, S., Pober, J. C., Qin, Y., Razavi-Ghods, N., Reis, I., Ringuette, J., Robnett, J., Rosie, K., Santos, M. G., Sikder, S., Sims, P., Smith, C., Syce, A., Thyagarajan, N., Williams, P. K. G., Zheng, H., USA, GBR, ZAF, Aguirre, JE [0000-0002-4810-666X], Barkana, R [0000-0002-1557-693X], Beardsley, AP [0000-0001-9428-8233], Bernardi, G [0000-0002-0916-7443], Bowman, JD [0000-0002-8475-2036], Bradley, RF [0000-0003-1172-8331], Bull, P [0000-0001-5668-3101], Carilli, CL [0000-0001-6647-3861], Deboer, DR [0000-0003-3197-2294], Dillon, JS [0000-0003-3336-9958], Ewall-Wice, A [0000-0002-0086-7363], Fialkov, A [0000-0002-1369-633X], Furlanetto, SR [0000-0002-0658-1243], Gorthi, D [0000-0002-0829-167X], Greig, B [0000-0002-4085-2094], Hazelton, BJ [0000-0001-7532-645X], Heimersheim, S [0000-0001-9631-4212], Hewitt, JN [0000-0002-4117-570X], Jacobs, DC [0000-0002-0917-2269], Kern, NS [0000-0002-8211-1892], Kerrigan, J [0000-0002-1876-272X], Kittiwisit, P [0000-0003-0953-313X], Kohn, SA [0000-0001-6744-5328], Kolopanis, M [0000-0002-2950-2974], La Plante, P [0000-0002-4693-0102], Liu, A [0000-0001-6876-0928], Ma, YZ [0000-0001-8108-0986], Mesinger, A [0000-0003-3374-1772], Mirocha, J [0000-0002-8802-5581], Morales, MF [0000-0001-7694-4030], Munoz, JB [0000-0002-8984-0465], Neben, AR [0000-0001-7776-7240], Nunhokee, CD [0000-0002-5445-6586], Patra, N [0000-0002-9457-1941], Pober, JC [0000-0002-3492-0433], Qin, Y [0000-0002-4314-1810], Reis, I [0000-0002-6203-7496], Santos, MG [0000-0003-3892-3073], Sims, P [0000-0002-2871-0413], Thyagarajan, N [0000-0003-1602-7868], and Apollo - University of Cambridge Repository
Subjects: High Energy Physics - Theory, Cosmology and Nongalactic Astrophysics (astro-ph.CO), 010308 nuclear & particles physics, astro-ph.GA, hep-th, Astrophysics::High Energy Astrophysical Phenomena, FOS: Physical sciences, Astronomy and Astrophysics, Astrophysics::Cosmology and Extragalactic Astrophysics, 01 natural sciences, Astrophysics - Astrophysics of Galaxies, High Energy Physics - Theory (hep-th), Settore FIS/05 - Astronomia e Astrofisica, Space and Planetary Science, Astrophysics of Galaxies (astro-ph.GA), 0103 physical sciences, astro-ph.CO, 010303 astronomy & astrophysics, Astrophysics::Galaxy Astrophysics, Astrophysics - Cosmology and Nongalactic Astrophysics
Abstract: Recently, the Hydrogen Epoch of Reionization Array (HERA) collaboration has produced the experiment's first upper limits on the power spectrum of 21-cm fluctuations at z~8 and 10. Here, we use several independent theoretical models to infer constraints on the intergalactic medium (IGM) and galaxies during the epoch of reionization (EoR) from these limits. We find that the IGM must have been heated above the adiabatic cooling threshold by z~8, independent of uncertainties about the IGM ionization state and the nature of the radio background. Combining HERA limits with galaxy and EoR observations constrains the spin temperature of the z~8 neutral IGM to 27 K < T_S < 630 K (2.3 K < T_S < 640 K) at 68% (95%) confidence. They therefore also place a lower bound on X-ray heating, a previously unconstrained aspects of early galaxies. For example, if the CMB dominates the z~8 radio background, the new HERA limits imply that the first galaxies produced X-rays more efficiently than local ones (with soft band X-ray luminosities per star formation rate constrained to L_X/SFR = { 10^40.2, 10^41.9 } erg/s/(M_sun/yr) at 68% confidence), consistent with expectations of X-ray binaries in low-metallicity environments. The z~10 limits require even earlier heating if dark-matter interactions (e.g., through millicharges) cool down the hydrogen gas. Using a model in which an extra radio background is produced by galaxies, we rule out (at 95% confidence) the combination of high radio and low X-ray luminosities of L_{r,ν}/SFR > 3.9 x 10^24 W/Hz/(M_sun/yr) and L_X/SFR, 40 pages, 19 figures, accepted to ApJ
Published: 2022

106. Automated Detection of Antenna Malfunctions in Large-N Interferometers: A Case Study with the Hydrogen Epoch of Reionization Array

Author: Dara Storer, Joshua S. Dillon, Daniel C. Jacobs, Miguel F. Morales, Bryna J. Hazelton, Aaron Ewall‐Wice, Zara Abdurashidova, James E. Aguirre, Paul Alexander, Zaki S. Ali, Yanga Balfour, Adam P. Beardsley, Gianni Bernardi, Tashalee S. Billings, Judd D. Bowman, Richard F. Bradley, Philip Bull, Jacob Burba, Steven Carey, Chris L. Carilli, Carina Cheng, David R. DeBoer, Eloy Lera Acedo, Matt Dexter, Scott Dynes, John Ely, Nicolas Fagnoni, Randall Fritz, Steven R. Furlanetto, Kingsley Gale‐Sides, Brian Glendenning, Deepthi Gorthi, Bradley Greig, Jasper Grobbelaar, Ziyaad Halday, Jacqueline N. Hewitt, Jack Hickish, Tian Huang, Alec Josaitis, Austin Julius, MacCalvin Kariseb, Nicholas S. Kern, Joshua Kerrigan, Piyanat Kittiwisit, Saul A. Kohn, Matthew Kolopanis, Adam Lanman, Paul La Plante, Adrian Liu, Anita Loots, David MacMahon, Lourence Malan, Cresshim Malgas, Zachary E. Martinot, Andrei Mesinger, Mathakane Molewa, Tshegofalang Mosiane, Steven G. Murray, Abraham R. Neben, Bojan Nikolic, Chuneeta Devi Nunhokee, Aaron R. Parsons, Robert Pascua, Nipanjana Patra, Samantha Pieterse, Jonathan C. Pober, Nima Razavi‐Ghods, Daniel Riley, James Robnett, Kathryn Rosie, Mario G. Santos, Peter Sims, Saurabh Singh, Craig Smith, Jianrong Tan, Nithyanandan Thyagarajan, Peter K. G. Williams, Haoxuan Zheng, Storer, D., Dillon, J. S., Jacobs, D. C., Morales, M. F., Hazelton, B. J., Ewall-Wice, A., Abdurashidova, Z., Aguirre, J. E., Alexander, P., Ali, Z. S., Balfour, Y., Beardsley, A. P., Bernardi, G., Billings, T. S., Bowman, J. D., Bradley, R. F., Bull, P., Burba, J., Carey, S., Carilli, C. L., Cheng, C., Deboer, D. R., de Lera Acedo, E., Dexter, M., Dynes, S., Ely, J., Fagnoni, N., Fritz, R., Furlanetto, S. R., Gale-Sides, K., Glendenning, B., Gorthi, D., Greig, B., Grobbelaar, J., Halday, Z., Hewitt, J. N., Hickish, J., Huang, T., Josaitis, A., Julius, A., Kariseb, M., Kern, N. S., Kerrigan, J., Kittiwisit, P., Kohn, S. A., Kolopanis, M., Lanman, A., La Plante, P., Liu, A., Loots, A., Macmahon, D., Malan, L., Malgas, C., Martinot, Z. E., Mesinger, A., Molewa, M., Mosiane, T., Murray, S. G., Neben, A. R., Nikolic, B., Nunhokee, C. D., Parsons, A. R., Pascua, R., Patra, N., Pieterse, S., Pober, J. C., Razavi-Ghods, N., Riley, D., Robnett, J., Rosie, K., Santos, M. G., Sims, P., Singh, S., Smith, C., Tan, J., Thyagarajan, N., Williams, P. K. G., and Zheng, H.
Subjects: Cosmology and Nongalactic Astrophysics (astro-ph.CO), 010308 nuclear & particles physics, FOS: Physical sciences, interferometry, Condensed Matter Physics, 01 natural sciences, Settore FIS/05 - Astronomia e Astrofisica, 0103 physical sciences, radio cosmology, reionization, General Earth and Planetary Sciences, flagging, Electrical and Electronic Engineering, Astrophysics - Instrumentation and Methods for Astrophysics, systematics, 010303 astronomy & astrophysics, Instrumentation and Methods for Astrophysics (astro-ph.IM), Astrophysics - Cosmology and Nongalactic Astrophysics
Abstract: We present a framework for identifying and flagging malfunctioning antennas in large radio interferometers. We outline two distinct categories of metrics designed to detect outliers along known failure modes of large arrays: cross-correlation metrics, based on all antenna pairs, and auto-correlation metrics, based solely on individual antennas. We define and motivate the statistical framework for all metrics used, and present tailored visualizations that aid us in clearly identifying new and existing systematics. We implement these techniques using data from 105 antennas in the Hydrogen Epoch of Reionization Array (HERA) as a case study. Finally, we provide a detailed algorithm for implementing these metrics as flagging tools on real data sets., Comment: 31 pages, 17 figures
Published: 2021

107. First Results from HERA Phase I: Upper Limits on the Epoch of Reionization 21 cm Power Spectrum

Author: The HERA Collaboration, Abdurashidova, Zara, Aguirre, James E., Alexander, Paul, Ali, Zaki S., Balfour, Yanga, Beardsley, Adam P., Bernardi, Gianni, Billings, Tashalee S., Bowman, Judd D., Bradley, Richard F., Bull, Philip, Burba, Jacob, Carey, Steve, Carilli, Chris L., Cheng, Carina, DeBoer, David R., Dexter, Matt, Acedo, Eloy de Lera, Dibblee-Barkman, Taylor, Dillon, Joshua S., Ely, John, Ewall-Wice, Aaron, Fagnoni, Nicolas, Fritz, Randall, Furlanetto, Steven R., Gale-Sides, Kingsley, Glendenning, Brian, Gorthi, Deepthi, Greig, Bradley, Grobbelaar, Jasper, Halday, Ziyaad, Hazelton, Bryna J., Hewitt, Jacqueline N., Hickish, Jack, Jacobs, Daniel C., Julius, Austin, Kern, Nicholas S., Kerrigan, Joshua, Kittiwisit, Piyanat, Kohn, Saul A., Kolopanis, Matthew, Lanman, Adam, La Plante, Paul, Lekalake, Telalo, Lewis, David, Liu, Adrian, MacMahon, David, Malan, Lourence, Malgas, Cresshim, Maree, Matthys, Martinot, Zachary E., Matsetela, Eunice, Mesinger, Andrei, Molewa, Mathakane, Morales, Miguel F., Mosiane, Tshegofalang, Murray, Steven G., Neben, Abraham R., Nikolic, Bojan, Nunhokee, Chuneeta D., Parsons, Aaron R., Patra, Nipanjana, Pascua, Robert, Pieterse, Samantha, Pober, Jonathan C., Razavi-Ghods, Nima, Ringuette, Jon, Robnett, James, Rosie, Kathryn, Sims, Peter, Singh, Saurabh, Smith, Craig, Syce, Angelo, Thyagarajan, Nithyanandan, Williams, Peter K. G., Zheng, Haoxuan, USA, GBR, ZAF, Abdurashidova, Z., Aguirre, J. E., Alexander, P., Ali, Z. S., Balfour, Y., Beardsley, A. P., Bernardi, G., Billings, T. S., Bowman, J. D., Bradley, R. F., Bull, P., Burba, J., Carey, S., Carilli, C. L., Cheng, C., Deboer, D. R., Dexter, M., De Lera Acedo, E., Dibblee-Barkman, T., Dillon, J. S., Ely, J., Ewall-Wice, A., Fagnoni, N., Fritz, R., Furlanetto, S. R., Gale-Sides, K., Glendenning, B., Gorthi, D., Greig, B., Grobbelaar, J., Halday, Z., Hazelton, B. J., Hewitt, J. N., Hickish, J., Jacobs, D. C., Julius, A., Kern, N. S., Kerrigan, J., Kittiwisit, P., Kohn, S. A., Kolopanis, M., Lanman, A., La Plante, P., Lekalake, T., Lewis, D., Liu, A., Macmahon, D., Malan, L., Malgas, C., Maree, M., Martinot, Z. E., Matsetela, E., Mesinger, A., Molewa, M., Morales, M. F., Mosiane, T., Murray, S. G., Neben, A. R., Nikolic, B., Nunhokee, C. D., Parsons, A. R., Patra, N., Pascua, R., Pieterse, S., Pober, J. C., Razavi-Ghods, N., Ringuette, J., Robnett, J., Rosie, K., Sims, P., Singh, S., Smith, C., Syce, A., Thyagarajan, N., Williams, P. K. G., Zheng, H., Aguirre, JE [0000-0002-4810-666X], Beardsley, AP [0000-0001-9428-8233], Bernardi, G [0000-0002-0916-7443], Bowman, JD [0000-0002-8475-2036], Bull, P [0000-0001-5668-3101], Carilli, CL [0000-0001-6647-3861], Deboer, DR [0000-0003-3197-2294], Dillon, JS [0000-0003-3336-9958], Ewall-Wice, A [0000-0002-0086-7363], Furlanetto, SR [0000-0002-0658-1243], Gorthi, D [0000-0002-0829-167X], Greig, B [0000-0002-4085-2094], Hazelton, BJ [0000-0001-7532-645X], Jacobs, DC [0000-0002-0917-2269], Kern, NS [0000-0002-8211-1892], Kerrigan, J [0000-0002-1876-272X], Kittiwisit, P [0000-0003-0953-313X], Kohn, SA [0000-0001-6744-5328], Kolopanis, M [0000-0002-2950-2974], Liu, A [0000-0001-6876-0928], Mesinger, A [0000-0003-3374-1772], Morales, MF [0000-0001-7694-4030], Murray, SG [0000-0003-3059-3823], Neben, AR [0000-0001-7776-7240], Nunhokee, CD [0000-0002-5445-6586], Patra, N [0000-0002-9457-1941], Pober, JC [0000-0002-3492-0433], Sims, P [0000-0002-2871-0413], Singh, S [0000-0001-7755-902X], Thyagarajan, N [0000-0003-1602-7868], Williams, PKG [0000-0003-3734-3587], and Apollo - University of Cambridge Repository
Subjects: Cosmology and Nongalactic Astrophysics (astro-ph.CO), Settore FIS/05 - Astronomia e Astrofisica, Space and Planetary Science, astro-ph.GA, Astrophysics of Galaxies (astro-ph.GA), astro-ph.CO, FOS: Physical sciences, Astronomy and Astrophysics, Astrophysics - Astrophysics of Galaxies, Astrophysics - Cosmology and Nongalactic Astrophysics
Abstract: We report upper-limits on the Epoch of Reionization (EoR) 21 cm power spectrum at redshifts 7.9 and 10.4 with 18 nights of data ($\sim36$ hours of integration) from Phase I of the Hydrogen Epoch of Reionization Array (HERA). The Phase I data show evidence for systematics that can be largely suppressed with systematic models down to a dynamic range of $\sim10^9$ with respect to the peak foreground power. This yields a 95% confidence upper limit on the 21 cm power spectrum of $\Delta^2_{21} \le (30.76)^2\ {\rm mK}^2$ at $k=0.192\ h\ {\rm Mpc}^{-1}$ at $z=7.9$, and also $\Delta^2_{21} \le (95.74)^2\ {\rm mK}^2$ at $k=0.256\ h\ {\rm Mpc}^{-1}$ at $z=10.4$. At $z=7.9$, these limits are the most sensitive to-date by over an order of magnitude. While we find evidence for residual systematics at low line-of-sight Fourier $k_\parallel$ modes, at high $k_\parallel$ modes we find our data to be largely consistent with thermal noise, an indicator that the system could benefit from deeper integrations. The observed systematics could be due to radio frequency interference, cable sub-reflections, or residual instrumental cross-coupling, and warrant further study. This analysis emphasizes algorithms that have minimal inherent signal loss, although we do perform a careful accounting in a companion paper of the small forms of loss or bias associated with the pipeline. Overall, these results are a promising first step in the development of a tuned, instrument-specific analysis pipeline for HERA, particularly as Phase II construction is completed en route to reaching the full sensitivity of the experiment., Comment: Accepted to ApJ. https://reionization.org/science/public-data-release-1/
Published: 2021

108. Methods of Error Estimation for Delay Power Spectra in $21\,\textrm{cm}$ Cosmology

Author: David MacMahon, Zara Abdurashidova, Bryna J. Hazelton, David DeBoer, Austin Julius, Jon Ringuette, Jacqueline N. Hewitt, Joshua Kerrigan, Adam Lanman, Jack Hickish, Richard F. Bradley, Matthew Kolopanis, Mathakane Molewa, Angelo Syce, Aaron Ewall-Wice, Jacob Burba, Kathryn Rosie, Daniel C. Jacobs, Judd D. Bowman, Samantha Pieterse, Tshegofalang Mosiane, Cresshim Malgas, Nicolas Fagnoni, James E. Aguirre, Yanga Balfour, Lourence Malan, Paul Alexander, Brian Glendenning, Carina Cheng, Deepthi Gorthi, Nithyanandan Thyagarajan, Joshua S. Dillon, Telalo Lekalake, Jonathan C. Pober, Steve R. Furlanetto, John Ely, Matt Dexter, Andrei Mesinger, Jasper Grobbelaar, Steven Carey, Haoxuan Zheng, Gianni Bernardi, Bradley Greig, Peter Sims, Chuneeta D. Nunhokee, Miguel F. Morales, Craig Smith, Chris Carilli, Matthys Maree, Eloy de Lera Acedo, Tashalee S. Billings, Zachary E. Martinot, Zaki S. Ali, Jianrong Tan, Eunice Matsetela, Adrian Liu, Philip Bull, Bojan Nikolic, Paul La Plante, Peter K. G. Williams, Nima Razavi-Ghods, James Robnett, Nicholas S. Kern, Abraham R. Neben, Randall Fritz, Aaron R. Parsons, Adam P. Beardsley, Saul A. Kohn, Saurabh Singh, Steven G. Murray, Piyanat Kittiwisit, Kingsley Gale-Sides, Nipanjana Patra, Ziyaad Halday, Tan, J., Liu, A., Kern, N. S., Abdurashidova, Z., Aguirre, J. E., Alexander, P., Ali, Z. S., Balfour, Y., Beardsley, A. P., Bernardi, G., Billings, T. S., Bowman, J. D., Bradley, R. F., Bull, P., Burba, J., Carey, S., Carilli, C. L., Cheng, C., Deboer, D. R., Dexter, M., De Lera Acedo, E., Dillon, J. S., Ely, J., Ewall-Wice, A., Fagnoni, N., Fritz, R., Furlanetto, S. R., Gale-Sides, K., Glendenning, B., Gorthi, D., Greig, B., Grobbelaar, J., Halday, Z., Hazelton, B. J., Hewitt, J. N., Hickish, J., Jacobs, D. C., Julius, A., Kerrigan, J., Kittiwisit, P., Kohn, S. A., Kolopanis, M., Lanman, A., La Plante, P., Lekalake, T., Macmahon, D., Malan, L., Malgas, C., Maree, M., Martinot, Z. E., Matsetela, E., Mesinger, A., Molewa, M., Morales, M. F., Mosiane, T., Murray, S. G., Neben, A. R., Nikolic, B., Nunhokee, C. D., Parsons, A. R., Patra, N., Pieterse, S., Pober, J. C., Razavi-Ghods, N., Ringuette, J., Robnett, J., Rosie, K., Sims, P., Singh, S., Smith, C., Syce, A., Thyagarajan, N., Williams, P. K. G., and Zheng, H.
Subjects: Physics, Noise power, Cosmology and Nongalactic Astrophysics (astro-ph.CO), Spectral density, FOS: Physical sciences, Astronomy and Astrophysics, Probability density function, 06 humanities and the arts, HERA, 0603 philosophy, ethics and religion, 01 natural sciences, Signal, Power (physics), Settore FIS/05 - Astronomia e Astrofisica, Space and Planetary Science, 060302 philosophy, 0103 physical sciences, Limit (mathematics), Astrophysics - Instrumentation and Methods for Astrophysics, 010303 astronomy & astrophysics, Reionization, Algorithm, Instrumentation and Methods for Astrophysics (astro-ph.IM), Astrophysics - Cosmology and Nongalactic Astrophysics
Abstract: Precise measurements of the 21 cm power spectrum are crucial for understanding the physical processes of hydrogen reionization. Currently, this probe is being pursued by low-frequency radio interferometer arrays. As these experiments come closer to making a first detection of the signal, error estimation will play an increasingly important role in setting robust measurements. Using the delay power spectrum approach, we have produced a critical examination of different ways that one can estimate error bars on the power spectrum. We do this through a synthesis of analytic work, simulations of toy models, and tests on small amounts of real data. We find that, although computed independently, the different error bar methodologies are in good agreement with each other in the noise-dominated regime of the power spectrum. For our preferred methodology, the predicted probability distribution function is consistent with the empirical noise power distributions from both simulated and real data. This diagnosis is mainly in support of the forthcoming HERA upper limit, and also is expected to be more generally applicable., Comment: 35 Pages, 9 Figures, 4 Tables. Replaced with accepted ApJ version; some clarifying text added in response to referee comments with no changes to results
Published: 2021
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109. A Real Time Processing System for Big Data in Astronomy: Applications to HERA

Author: Aaron Ewall-Wice, Daniel C. Jacobs, Craig Smith, Cresshim Malgas, Nicolas Fagnoni, Nipanjana Patra, James Robnett, Lourence Malan, Yanga Balfour, Joshua Kerrigan, Ziyaad Halday, Steve R. Furlanetto, M. Wilensky, Peter Sims, Paul Alexander, Judd D. Bowman, Samantha Pieterse, Nima Razavi-Ghods, Piyanat Kittiwisit, Angelo Syce, Richard F. Bradley, Matthew Kolopanis, Peter K. G. Williams, Jonathan C. Pober, Telalo Lekalake, Andrei Mesinger, Jasper Grobbelaar, Brian Glendenning, D. R. DeBoer, Kingsley Gale-Sides, John Ely, Gianni Bernardi, Tashalee S. Billings, Zachary E. Martinot, Mario G. Santos, Carina Cheng, Matthys Maree, Miguel F. Morales, Adrian Liu, Kathryn Rosie, Robert Pascua, Nithyanandan Thyagarajan, Zaki S. Ali, Nicholas S. Kern, Bryna J. Hazelton, Bojan Nikolic, Zara Abdurashidova, Jacqueline N. Hewitt, Chris Carilli, Austin Julius, P. La Plante, S. Murray, Mathakane Molewa, Bradley Greig, David B. Lewis, Tshegofalang Mosiane, Adam Lanman, Deepthi Gorthi, Joshua S. Dillon, Haoxuan Zheng, Eunice Matsetela, James E. Aguirre, Dave MacMahon, S. H. Carey, E. de Lera Acedo, Aaron R. Parsons, Matthew R. Dexter, Jon Ringuette, Abraham R. Neben, Randall Fritz, Jack Hickish, Jacob Burba, Adam P. Beardsley, Saul A. Kohn, Philip Bull, La Plante, P., Williams, P. K. G., Kolopanis, M., Dillon, J. S., Beardsley, A. P., Kern, N. S., Wilensky, M., Ali, Z. S., Abdurashidova, Z., Aguirre, J. E., Alexander, P., Balfour, Y., Bernardi, G., Billings, T. S., Bowman, J. D., Bradley, R. F., Bull, P., Burba, J., Carey, S., Carilli, C. L., Cheng, C., Deboer, D. R., Dexter, M., de Lera Acedo, E., Ely, J., Ewall-Wice, A., Fagnoni, N., Fritz, R., Furlanetto, S. R., Gale-Sides, K., Glendenning, B., Gorthi, D., Greig, B., Grobbelaar, J., Halday, Z., Hazelton, B. J., Hewitt, J. N., Hickish, J., Jacobs, D. C., Julius, A., Kerrigan, J., Kittiwisit, P., Kohn, S. A., Lanman, A., Lekalake, T., Lewis, D., Liu, A., Macmahon, D., Malan, L., Malgas, C., Maree, M., Martinot, Z. E., Matsetela, E., Mesinger, A., Molewa, M., Morales, M. F., Mosiane, T., Murray, S., Neben, A. R., Nikolic, B., Parsons, A. R., Pascua, R., Patra, N., Pieterse, S., Pober, J. C., Razavi-Ghods, N., Ringuette, J., Robnett, J., Rosie, K., Santos, M. G., Sims, P., Smith, C., Syce, A., Thyagarajan, N., Zheng, H., ITA, and USA
Subjects: Data analysis — Software, Astronomy — Software, Computer science, Real-time computing, Big data, FOS: Physical sciences, 0102 computer and information sciences, Development, Terabyte, Interference (wave propagation), 7. Clean energy, 01 natural sciences, Computer Science::Digital Libraries, Settore FIS/05 - Astronomia e Astrofisica, 0103 physical sciences, Methods, 010303 astronomy & astrophysics, Reionization, Instrumentation and Methods for Astrophysics (astro-ph.IM), business.industry, SIGNAL (programming language), Astrophysics::Instrumentation and Methods for Astrophysics, Astronomy and Astrophysics, HERA, Computer Science Applications, 010201 computation theory & mathematics, Space and Planetary Science, Computer data storage, Data analysis — Physical sciences and engineering, Astrophysics - Instrumentation and Methods for Astrophysics, business, Raw data
Abstract: As current- and next-generation astronomical instruments come online, they will generate an unprecedented deluge of data. Analyzing these data in real time presents unique conceptual and computational challenges, and their long-term storage and archiving is scientifically essential for generating reliable, reproducible results. We present here the real-time processing (RTP) system for the Hydrogen Epoch of Reionization Array (HERA), a radio interferometer endeavoring to provide the first detection of the highly redshifted 21 cm signal from Cosmic Dawn and the Epoch of Reionization by an interferometer. The RTP system consists of analysis routines run on raw data shortly after they are acquired, such as calibration and detection of radio-frequency interference (RFI) events. RTP works closely with the Librarian, the HERA data storage and transfer manager which automatically ingests data and transfers copies to other clusters for post-processing analysis. Both the RTP system and the Librarian are public and open source software, which allows for them to be modified for use in other scientific collaborations. When fully constructed, HERA is projected to generate over 50 terabytes (TB) of data each night, and the RTP system enables the successful scientific analysis of these data., Comment: 15 pages, 3 figures, published in Astronomy and Computing
Published: 2021
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110. Redundant-baseline calibration of the hydrogen epoch of reionization array

Author: Adrian Liu, Craig Smith, Paul Alexander, John Ely, Deepthi Gorthi, Nithyanandan Thyagarajan, Steven G. Murray, Joshua S. Dillon, Bryna J. Hazelton, Phil Bull, Nipanjana Patra, Jon Ringuette, Zara Abdurashidova, Ziyaad Halday, Aaron R. Parsons, Bradley Greig, Lourence Malan, Angelo Syce, Gianni Bernardi, Piyanat Kittiwisit, Austin Julius, Daniel C. Jacobs, Kingsley Gale-Sides, Jack Hickish, Yin-Zhe Ma, Jonathan C. Pober, Kathryn Rosie, Adam P. Beardsley, Robert Pascua, Peter K. G. Williams, Cresshim Malgas, S. H. Carey, Jacob Burba, Nicolas Fagnoni, David MacMahon, Andrei Mesinger, Jasper Grobbelaar, Yanga Balfour, Joshua Kerrigan, Max Tegmark, Richard F. Bradley, Matthew Kolopanis, David DeBoer, Abraham R. Neben, Mario G. Santos, Randall Fritz, Jacqueline N. Hewitt, Tashalee S. Billings, Zachary E. Martinot, Eunice Matsetela, Saul A. Kohn, David Lewis, Peter Sims, Mathakane Molewa, Naomi Orosz, Steven R. Furlanetto, Paul La Plante, Chuneeta D. Nunhokee, Matt Dexter, Tshegofalang Mosiane, Nicholas S. Kern, Judd D. Bowman, Samantha Pieterse, Max E. Lee, James E. Aguirre, Nima Razavi-Ghods, Miguel F. Morales, Zaki S. Ali, Bojan Nikolic, Aaron Ewall-Wice, Chris Carilli, Eloy de Lera Acedo, James Robnett, Brian Glendenning, Carina Cheng, Matthys Maree, Telalo Lekalake, Haoxuan Zheng, Adam Lanman, ITA, USA, ZAF, Dillon, J. S., Lee, M., Ali, Z. S., Parsons, A. R., Orosz, N., Nunhokee, C. D., La Plante, P., Beardsley, A. P., Kern, N. S., Abdurashidova, Z., Aguirre, J. E., Alexander, P., Balfour, Y., Bernardi, G., Billings, T. S., Bowman, J. D., Bradley, R. F., Bull, P., Burba, J., Carey, S., Carilli, C. L., Cheng, C., Deboer, D. R., Dexter, M., de Lera Acedo, E., Ely, J., Ewall-Wice, A., Fagnoni, N., Fritz, R., Furlanetto, S. R., Gale-Sides, K., Glendenning, B., Gorthi, D., Greig, B., Grobbelaar, J., Halday, Z., Hazelton, B. J., Hewitt, J. N., Hickish, J., Jacobs, D. C., Julius, A., Kerrigan, J., Kittiwisit, P., Kohn, S. A., Kolopanis, M., Lanman, A., Lekalake, T., Lewis, D., Liu, A., Ma, Y. -Z., Macmahon, D., Malan, L., Malgas, C., Maree, M., Martinot, Z. E., Matsetela, E., Mesinger, A., Molewa, M., Morales, M. F., Mosiane, T., Murray, S., Neben, A. R., Nikolic, B., Pascua, R., Patra, N., Pieterse, S., Pober, J. C., Razavi-Ghods, N., Ringuette, J., Robnett, J., Rosie, K., Santos, M. G., Sims, P., Smith, C., Syce, A., Tegmark, M., Thyagarajan, N., Williams, P. K. G., Zheng, H., Alexander, Paul [0000-0002-0292-9513], De Lera Acedo, Eloy [0000-0001-8530-6989], Nikolic, Bojan [0000-0001-7168-2705], Razavi-Ghods, Nima [0000-0003-2930-5396], and Apollo - University of Cambridge Repository
Subjects: Cosmology and Nongalactic Astrophysics (astro-ph.CO), Calibration (statistics), interferometers [instrumentation], first stars, Degrees of freedom (statistics), FOS: Physical sciences, Astronomy & Astrophysics, 01 natural sciences, Settore FIS/05 - Astronomia e Astrofisica, 0103 physical sciences, Astronomical interferometer, dark ages, reionization, first stars, dark ages, instrumentation: interferometers, 010303 astronomy & astrophysics, Reionization, Instrumentation and Methods for Astrophysics (astro-ph.IM), Physics, 010308 nuclear & particles physics, Noise (signal processing), Astrophysics::Instrumentation and Methods for Astrophysics, Astronomy and Astrophysics, HERA, Interferometry, Dark ages, reionization, first star, Space and Planetary Science, astro-ph.CO, reionization, Antenna (radio), Astrophysics - Instrumentation and Methods for Astrophysics, Algorithm, Astronomical and Space Sciences, Astrophysics - Cosmology and Nongalactic Astrophysics, astro-ph.IM
Abstract: In 21 cm cosmology, precision calibration is key to the separation of the neutral hydrogen signal from very bright but spectrally-smooth astrophysical foregrounds. The Hydrogen Epoch of Reionization Array (HERA), an interferometer specialized for 21 cm cosmology and now under construction in South Africa, was designed to be largely calibrated using the self-consistency of repeated measurements of the same interferometric modes. This technique, known as "redundant-baseline calibration" resolves most of the internal degrees of freedom in the calibration problem. It assumes, however, on antenna elements with identical primary beams placed precisely on a redundant grid. In this work, we review the detailed implementation of the algorithms enabling redundant-baseline calibration and report results with HERA data. We quantify the effects of real-world non-redundancy and how they compare to the idealized scenario in which redundant measurements differ only in their noise realizations. Finally, we study how non-redundancy can produce spurious temporal structure in our calibration solutions--both in data and in simulations--and present strategies for mitigating that structure., Comment: 24 Pages, 19 Figures. Updated to match the accepted MNRAS version
Published: 2020

111. Detection of cosmic structures using the bispectrum phase. II. First results from application to cosmic reionization using the Hydrogen Epoch of Reionization Array

Author: Kathryn Rosie, James E. Aguirre, Jonathan C. Pober, Andrei Mesinger, Jasper Grobbelaar, David MacMahon, Nipanjana Patra, Tashalee S. Billings, Zachary E. Martinot, Ziyaad Halday, Deepthi Gorthi, Joshua S. Dillon, S. H. Carey, Paul Alexander, Haoxuan Zheng, Eunice Matsetela, Piyanat Kittiwisit, Adam P. Beardsley, Saul A. Kohn, Jon Ringuette, Kingsley Gale-Sides, Joshua Kerrigan, John Ely, Siyanda Matika, Zara Abdurashidova, David DeBoer, Nithyanandan Thyagarajan, Aaron R. Parsons, Matt Dexter, Bryna J. Hazelton, Adrian Liu, Nicholas S. Kern, James Kent, Jack Hickish, Judd D. Bowman, Samantha Pieterse, James Robnett, Miguel F. Morales, Paul La Plante, Richard F. Bradley, Matthew Kolopanis, Austin Julius, Chris Carilli, Eloy de Lera Acedo, Peter K. G. Williams, Craig Smith, Jacob Burba, Zaki S. Ali, Brian Glendenning, Jacqueline N. Hewitt, Carina Cheng, Gianni Bernardi, David B. Lewis, Bojan Nikolic, Aaron Ewall-Wice, Abraham R. Neben, Randall Fritz, Steven R. Furlanetto, Mathakane Molewa, Tshegofalang Mosiane, Lourence Malan, Bradley Greig, Nima Razavi-Ghods, Adam Lanman, Peter Sims, Daniel C. Jacobs, Cresshim Malgas, Nicolas Fagnoni, Yanga Balfour, Angelo Syce, Telalo Lekalake, Matthys Maree, Thyagarajan, N., Carilli, C. L., Nikolic, B., Kent, J., Mesinger, A., Kern, N. S., Bernardi, G., Matika, S., Abdurashidova, Z., Aguirre, J. E., Alexander, P., Ali, Z. S., Balfour, Y., Beardsley, A. P., Billings, T. S., Bowman, J. D., Bradley, R. F., Burba, J., Carey, S., Cheng, C., Deboer, D. R., Dexter, M., Acedo, E. D. L., Dillon, J. S., Ely, J., Ewall-Wice, A., Fagnoni, N., Fritz, R., Furlanetto, S. R., Gale-Sides, K., Glendenning, B., Gorthi, D., Greig, B., Grobbelaar, J., Halday, Z., Hazelton, B. J., Hewitt, J. N., Hickish, J., Jacobs, D. C., Julius, A., Kerrigan, J., Kittiwisit, P., Kohn, S. A., Kolopanis, M., Lanman, A., La Plante, P., Lekalake, T., Lewis, D., Liu, A., Macmahon, D., Malan, L., Malgas, C., Maree, M., Martinot, Z. E., Matsetela, E., Molewa, M., Morales, M. F., Mosiane, T., Neben, A. R., Parsons, A. R., Patra, N., Pieterse, S., Pober, J. C., Razavi-Ghods, N., Ringuette, J., Robnett, J., Rosie, K., Sims, P., Smith, C., Syce, A., Williams, P. K. G., Zheng, H., Nikolic, Bojan [0000-0001-7168-2705], Kent, James [0000-0003-3331-2409], Alexander, Paul [0000-0002-0292-9513], Razavi-Ghods, Nima [0000-0003-2930-5396], Apollo - University of Cambridge Repository, ITA, USA, and ZAF
Subjects: Brightness, Cosmology and Nongalactic Astrophysics (astro-ph.CO), FOS: Physical sciences, Astrophysics, Astrophysics::Cosmology and Extragalactic Astrophysics, Atomic, 01 natural sciences, Cosmology, Radio telescope, Particle and Plasma Physics, Settore FIS/05 - Astronomia e Astrofisica, 0103 physical sciences, Nuclear, Astrophysics - Cosmology and Nongalactic Astrophysic, 010306 general physics, Instrumentation and Methods for Astrophysics (astro-ph.IM), Reionization, Physics, Quantum Physics, COSMIC cancer database, 010308 nuclear & particles physics, Astrophysics::Instrumentation and Methods for Astrophysics, Molecular, Nuclear & Particles Physics, Redshift, 5101 Astronomical Sciences, astro-ph.CO, Hydrogen line, Astrophysics - Instrumentation and Methods for Astrophysics, 51 Physical Sciences, Bispectrum, Astronomical and Space Sciences, astro-ph.IM, Astrophysics - Cosmology and Nongalactic Astrophysics
Abstract: Characterizing the epoch of reionization (EoR) at $z\gtrsim 6$ via the redshifted 21 cm line of neutral Hydrogen (HI) is critical to modern astrophysics and cosmology, and thus a key science goal of many current and planned low-frequency radio telescopes. The primary challenge to detecting this signal is the overwhelmingly bright foreground emission at these frequencies, placing stringent requirements on the knowledge of the instruments and inaccuracies in analyses. Results from these experiments have largely been limited not by thermal sensitivity but by systematics, particularly caused by the inability to calibrate the instrument to high accuracy. The interferometric bispectrum phase is immune to antenna-based calibration and errors therein, and presents an independent alternative to detect the EoR HI fluctuations while largely avoiding calibration systematics. Here, we provide a demonstration of this technique on a subset of data from the Hydrogen Epoch of Reionization Array (HERA) to place approximate constraints on the brightness temperature of the intergalactic medium (IGM). From this limited data, at $z=7.7$ we infer "$1\sigma$" upper limits on the IGM brightness temperature to be $\le 316$ "pseudo" mK at $\kappa_\parallel=0.33$ "pseudo" $h$ Mpc$^{-1}$ (data-limited) and $\le 1000$ "pseudo" mK at $\kappa_\parallel=0.875$ "pseudo" $h$ Mpc$^{-1}$ (noise-limited). The "pseudo" units denote only an approximate and not an exact correspondence to the actual distance scales and brightness temperatures. By propagating models in parallel to the data analysis, we confirm that the dynamic range required to separate the cosmic HI signal from the foregrounds is similar to that in standard approaches, and the power spectrum of the bispectrum phase is still data-limited (at $\gtrsim 10^6$ dynamic range) indicating scope for further improvement in sensitivity as the array build-out continues., Comment: 22 pages, 12 figures (including sub-figures). Published in PhRvD. Abstract may be slightly abridged compared to the actual manuscript due to length limitations on arXiv
Published: 2020

112. Mitigating Internal Instrument Coupling for 21 cm Cosmology. II. A Method Demonstration with the Hydrogen Epoch of Reionization Array

Author: Nipanjana Patra, Ziyaad Halday, Adrian Liu, Matt Dexter, Joshua Kerrigan, Judd D. Bowman, Samantha Pieterse, Chris Carilli, David DeBoer, Eloy de Lera Acedo, Peter K. G. Williams, Zara Abdurashidova, Haoxuan Zheng, Piyanat Kittiwisit, Nithyanandan Thyagarajan, Kathryn Rosie, Austin Julius, Adam P. Beardsley, Philip Bull, David MacMahon, Adam Lanman, Jack Hickish, Gianni Bernardi, James Robnett, Angelo Syce, Jacob Burba, Bryna J. Hazelton, Deepthi Gorthi, Joshua S. Dillon, Richard F. Bradley, Matthew Kolopanis, Brian Glendenning, Matthys Maree, Paul Alexander, Carina Cheng, Miguel F. Morales, Mathakane Molewa, Zaki S. Ali, Bradley Greig, Craig Smith, Aaron Ewall-Wice, Saul A. Kohn, Telalo Lekalake, Nima Razavi-Ghods, Tshegofalang Mosiane, Jon Ringuette, Steve R. Furlanetto, Lourence Malan, Jacqueline N. Hewitt, Aaron R. Parsons, Jonathan C. Pober, Andrei Mesinger, Jasper Grobbelaar, Nicholas S. Kern, Zachary E. Martinot, Paul La Plante, Steven G. Murray, Daniel C. Jacobs, Cresshim Malgas, Abraham R. Neben, Nicolas Fagnoni, Randall Fritz, Yanga Balfour, Eunice Matsetela, Peter Sims, James E. Aguirre, ITA, USA, ZAF, Kern, N. S., Parsons, A. R., Dillon, J. S., Lanman, A. E., Liu, A., Bull, P., Ewall-Wice, A., Abdurashidova, Z., Aguirre, J. E., Alexander, P., Ali, Z. S., Balfour, Y., Beardsley, A. P., Bernardi, G., Bowman, J. D., Bradley, R. F., Burba, J., Carilli, C. L., Chen, Cheng, Deboer, D. R., Dexter, M., De Lera Acedo, E., Fagnoni, N., Fritz, R., Furlanetto, S. R., Glendenning, B., Gorthi, D., Greig, B., Grobbelaar, J., Halday, Z., Hazelton, B. J., Hewitt, J. N., Hickish, J., Jacobs, D. C., Julius, A., Kerrigan, J., Kittiwisit, P., Kohn, S. A., Kolopanis, M., La Plante, P., Lekalake, T., Macmahon, D., Malan, L., Malgas, C., Maree, M., Martinot, Z. E., Matsetela, E., Mesinger, A., Molewa, M., Morales, M. F., Mosiane, T., Murray, S. G., Neben, A. R., Patra, N., Pieterse, S., Pober, J. C., Razavi-Ghods, N., Ringuette, J., Robnett, J., Rosie, K., Sims, P., Smith, C., Syce, A., Thyagarajan, N., Williams, P. K. G., and Zheng, H.
Subjects: Coupling, Physics, 010504 meteorology & atmospheric sciences, Dynamic range, Spectral density, Astronomy and Astrophysics, Astrophysics, HERA, Astrophysics::Cosmology and Extragalactic Astrophysics, 01 natural sciences, Signal, Noise floor, Cosmology, Settore FIS/05 - Astronomia e Astrofisica, Space and Planetary Science, 0103 physical sciences, 010303 astronomy & astrophysics, Reionization, 0105 earth and related environmental sciences
Abstract: We present a study of internal reflection and cross-coupling systematics in Phase I of the Hydrogen Epoch of Reionization Array (HERA). In a companion paper, we outlined the mathematical formalism for such systematics and presented algorithms for modeling and removing them from the data. In this work, we apply these techniques to data from HERA’s first observing season as a method demonstration. The data show evidence for systematics that, without removal, would hinder a detection of the 21 cm power spectrum for the targeted Epoch of Reionization (EoR) line-of-sight modes in the range 0.2 h -1 Mpc-1 < {k}\parallel < 0.5 h -1 Mpc-1. In particular, we find evidence for nonnegligible amounts of spectral structure in the raw autocorrelations that overlaps with the EoR window and is suggestive of complex instrumental effects. Through systematic modeling on a single night of data, we find we can recover these modes in the power spectrum down to the integrated noise floor, achieving a dynamic range in the EoR window of 106 in power (mK2 units) with respect to the bright galactic foreground signal. Future work with deeper integrations will help determine whether these systematics can continue to be mitigated down to EoR levels. For future observing seasons, HERA will have upgraded analog and digital hardware to better control these systematics in the field.
Published: 2020

113. Validation of the HERA Phase I Epoch of Reionization 21 cm Power Spectrum Software Pipeline

Author: Aguirre, James E., Murray, Steven G., Pascua, Robert, Martinot, Zachary E., Burba, Jacob, Dillon, Joshua S., Jacobs, Daniel C., Kern, Nicholas S., Kittiwisit, Piyanat, Kolopanis, Matthew, Lanman, Adam, Liu, Adrian, Whitler, Lily, Abdurashidova, Zara, Alexander, Paul, Ali, Zaki S., Balfour, Yanga, Beardsley, Adam P., BERNARDI, GIANNI, Billings, Tashalee S., Bowman, Judd D., Bradley, Richard F., BULL, PHILIP, Carey, Steve, Carilli, Chris L., Cheng, Carina, DeBoer, David R., Dexter, Matt, de Lera Acedo, Eloy, Ely, John, Ewall-Wice, Aaron, Fagnoni, Nicolas, Fritz, Randall, Furlanetto, Steven R., Gale-Sides, Kingsley, Glendenning, Brian, Gorthi, Deepthi, Greig, Bradley, Grobbelaar, Jasper, Halday, Ziyaad, Hazelton, Bryna J., Hewitt, Jacqueline N., Hickish, Jack, Julius, Austin, Kerrigan, Joshua, Kohn, Saul A., La Plante, Paul, Lekalake, Telalo, Lewis, David, MacMahon, David, Malan, Lourence, Malgas, Cresshim, Maree, Matthys, Matsetela, Eunice, Mesinger, Andrei, Molewa, Mathakane, Morales, Miguel F., Mosiane, Tshegofalang, Neben, Abraham R., Nikolic, Bojan, Parsons, Aaron R., Patra, Nipanjana, Pieterse, Samantha, Pober, Jonathan C., Razavi-Ghods, Nima, Ringuette, Jon, Robnett, James, Rosie, Kathryn, Santos, Mario G., Sims, Peter, Singh, Saurabh, Smith, Craig, Syce, Angelo, Thyagarajan, Nithyanandan, Williams, Peter K. G., Zheng, Haoxuan, HERA Collaboration, Aguirre, J. E., Murray, S. G., Pascua, R., Martinot, Z. E., Burba, J., Dillon, J. S., Jacobs, D. C., Kern, N. S., Kittiwisit, P., Kolopanis, M., Lanman, A., Liu, A., Whitler, L., Abdurashidova, Z., Alexander, P., Ali, Z. S., Balfour, Y., Beardsley, A. P., Bernardi, G., Billings, T. S., Bowman, J. D., Bradley, R. F., Bull, P., Carey, S., Carilli, C. L., Cheng, C., Deboer, D. R., Dexter, M., De Lera Acedo, E., Ely, J., Ewall-Wice, A., Fagnoni, N., Fritz, R., Furlanetto, S. R., Gale-Sides, K., Glendenning, B., Gorthi, D., Greig, B., Grobbelaar, J., Halday, Z., Hazelton, B. J., Hewitt, J. N., Hickish, J., Julius, A., Kerrigan, J., Kohn, S. A., La Plante, P., Lekalake, T., Lewis, D., Macmahon, D., Malan, L., Malgas, C., Maree, M., Matsetela, E., Mesinger, A., Molewa, M., Morales, M. F., Mosiane, T., Neben, A. R., Nikolic, B., Parsons, A. R., Patra, N., Pieterse, S., Pober, J. C., Razavi-Ghods, N., Ringuette, J., Robnett, J., Rosie, K., Santos, M. G., Sims, P., Singh, S., Smith, C., Syce, A., Thyagarajan, N., Williams, P. K. G., Zheng, H., USA, GBR, ZAF, Aguirre, JE [0000-0002-4810-666X], Murray, SG [0000-0003-3059-3823], Dillon, JS [0000-0003-3336-9958], Jacobs, DC [0000-0002-0917-2269], Kern, NS [0000-0002-8211-1892], Kittiwisit, P [0000-0003-0953-313X], Kolopanis, M [0000-0002-2950-2974], Lanman, A [0000-0003-2116-3573], Liu, A [0000-0001-6876-0928], Beardsley, AP [0000-0001-9428-8233], Bernardi, G [0000-0002-0916-7443], Bowman, JD [0000-0002-8475-2036], Bradley, RF [0000-0003-1172-8331], Bull, P [0000-0001-5668-3101], Carilli, CL [0000-0001-6647-3861], Deboer, DR [0000-0003-3197-2294], Ewall-Wice, A [0000-0002-0086-7363], Furlanetto, SR [0000-0002-0658-1243], Gorthi, D [0000-0002-0829-167X], Greig, B [0000-0002-4085-2094], Hazelton, BJ [0000-0001-7532-645X], Hewitt, JN [0000-0002-4117-570X], Kerrigan, J [0000-0002-1876-272X], Kohn, SA [0000-0001-6744-5328], Mesinger, A [0000-0003-3374-1772], Morales, MF [0000-0001-7694-4030], Neben, AR [0000-0001-7776-7240], Patra, N [0000-0002-9457-1941], Pober, JC [0000-0002-3492-0433], Santos, MG [0000-0003-3892-3073], Sims, P [0000-0002-2871-0413], Singh, S [0000-0001-7755-902X], and Apollo - University of Cambridge Repository
Subjects: Settore FIS/05 - Astronomia e Astrofisica, 010308 nuclear & particles physics, Space and Planetary Science, 0103 physical sciences, FOS: Physical sciences, Astronomy and Astrophysics, Astrophysics - Instrumentation and Methods for Astrophysics, Instrumentation and Methods for Astrophysics (astro-ph.IM), 010303 astronomy & astrophysics, 01 natural sciences, astro-ph.IM
Abstract: We describe the validation of the HERA Phase I software pipeline by a series of modular tests, building up to an end-to-end simulation. The philosophy of this approach is to validate the software and algorithms used in the Phase I upper limit analysis on wholly synthetic data satisfying the assumptions of that analysis, not addressing whether the actual data meet these assumptions. We discuss the organization of this validation approach, the specific modular tests performed, and the construction of the end-to-end simulations. We explicitly discuss the limitations in scope of the current simulation effort. With mock visibility data generated from a known analytic power spectrum and a wide range of realistic instrumental effects and foregrounds, we demonstrate that the current pipeline produces power spectrum estimates that are consistent with known analytic inputs to within thermal noise levels (at the 2 sigma level) for k > 0.2 h/Mpc for both bands and fields considered. Our input spectrum is intentionally amplified to enable a strong `detection' at k ~0.2 h/Mpc -- at the level of ~25 sigma -- with foregrounds dominating on larger scales, and thermal noise dominating at smaller scales. Our pipeline is able to detect this amplified input signal after suppressing foregrounds with a dynamic range (foreground to noise ratio) of > 10^7. Our validation test suite uncovered several sources of scale-independent signal loss throughout the pipeline, whose amplitude is well-characterized and accounted for in the final estimates. We conclude with a discussion of the steps required for the next round of data analysis., 32 pages, 20 figures. Submitted to the Astrophysical Journal
Published: 2022

114. Application of Experimental Design Methodologies in the Enantioseparation of Pharmaceuticals by Capillary Electrophoresis: A Review

Author: Adriana Modroiu, Serena Orlandini, Gabriel Hancu, Lajos Attila Papp, Sandra Furlanetto, Roberto Gotti, Hancu G., Orlandini S., Papp L.A., Modroiu A., Gotti R., and Furlanetto S.
Subjects: chiral separation, experimental design, quality by design, Computer science, capillary electrophoresis, Pharmaceutical Science, Review, 01 natural sciences, Quality by Design, Analytical Chemistry, QD241-441, Capillary electrophoresis, Drug Discovery, Humans, Physical and Theoretical Chemistry, Critical perspective, Chiral separation, Capillary electrophoresis, Experimental design, Screening, Optimization, Quality by design, 010405 organic chemistry, screening, Design of experiments, 010401 analytical chemistry, Organic Chemistry, Electrophoresis, Capillary, Stereoisomerism, Method development, 0104 chemical sciences, Capillary electrophoresi, Pharmaceutical Preparations, Chemistry (miscellaneous), Molecular Medicine, Biochemical engineering, optimization
Abstract: Chirality is one of the major issues in pharmaceutical research and industry. Capillary electrophoresis (CE) is an interesting alternative to the more frequently used chromatographic techniques in the enantioseparation of pharmaceuticals, and is used for the determination of enantiomeric ratio, enantiomeric purity, and in pharmacokinetic studies. Traditionally, optimization of CE methods is performed using a univariate one factor at a time (OFAT) approach; however, this strategy does not allow for the evaluation of interactions between experimental factors, which may result in ineffective method development and optimization. In the last two decades, Design of Experiments (DoE) has been frequently employed to better understand the multidimensional effects and interactions of the input factors on the output responses of analytical CE methods. DoE can be divided into two types: screening and optimization designs. Furthermore, using Quality by Design (QbD) methodology to develop CE-based enantioselective techniques is becoming increasingly popular. The review presents the current use of DoE methodologies in CE-based enantioresolution method development and provides an overview of DoE applications in the optimization and validation of CE enantioselective procedures in the last 25 years. Moreover, a critical perspective on how different DoE strategies can aid in the optimization of enantioseparation procedures is presented.
Published: 2021

115. Analytical quality by design in the development of a solvent-modified micellar electrokinetic chromatography method for the determination of sitagliptin and its related compounds

Author: Benedetta Pasquini, Sandra Furlanetto, Lapo Renai, Serena Orlandini, Roberto Gotti, Massimo Del Bubba, Mercedes Villar-Navarro, Michal Douša, Pasquini B., Gotti R., Villar-Navarro M., Dousa M., Renai L., Del Bubba M., Orlandini S., and Furlanetto S.
Subjects: Clinical Biochemistry, Analytical chemistry, Pharmaceutical Science, Electrolyte, 01 natural sciences, Micelle, Micellar electrokinetic chromatography, Analytical Chemistry, Matrix (chemical analysis), chemistry.chemical_compound, Capillary electrophoresis, Drug Discovery, Impuritie, Sitagliptin, Quality by Design, Response surface methodology, Micelles, Spectroscopy, Chromatography, Micellar Electrokinetic Capillary, 010405 organic chemistry, Experimental Design, Sitagliptin Phosphate, Method Operable Design Region, 010401 analytical chemistry, Reproducibility of Results, Sodium Dodecyl Sulfate, Capillary Electrophoresi, 0104 chemical sciences, Solvent, chemistry, Solvents, Methanol
Abstract: A solvent-modified micellar electrokinetic chromatography method was developed following the Quality by Design approach for the simultaneous determination of sitagliptin (SIT), an oral antihyperglycemic drug, and its main impurities derived from the synthesis process. The separation system was identified in the scouting phase and was made by sodium dodecyl sulphate (SDS) micelles with the addition of n-butanol and methanol. The knowledge space was investigated through an asymmetric screening matrix, taking into consideration eight critical method parameters (CMPs) involving the composition of the background electrolyte in terms of buffer concentration and pH, the concentration of surfactants and organic modifiers, and voltage. The critical method attributes (CMAs) were identified as analysis time and the distance between the tail of the electroosmotic flow system peak and the front edge of impurity I1 (sitagliptin triazole hydrochloride). A Box-Behnken Design was used in response surface methodology for calculating the quadratic models relating the CMPs to the CMAs. From the models it was possible to compute the method operable design region (MODR) through Monte-Carlo simulations. The MODR was identified in the probability maps as the multidimensional zone where the risk of failure to achieve the desired values for the CMAs was lower than 10 %. The experimental conditions corresponding to the working point, with the MODR interval, were the following: background electrolyte, 14 (10−18) mM borate buffer pH 9.20, 100 mM SDS, 13.6 (11.1–16.0) %v/v n-butanol, 6.7 (4.5–8.8) %v/v methanol; voltage and temperature were set to 28 kV and 22 °C, respectively. The developed CE method was validated in accordance with International Council for Harmonisation guidelines and was applied to the analysis of SIT tablets. The routine analysis for the quality control of the pharmaceutical product could be conducted in about 11 min.
Published: 2021

116. Optimizing sparse RFI prediction using deep learning

Author: Nithyanandan Thyagarajan, Adam Lanman, Kathryn Rosie, Angelo Syce, Gianni Bernardi, Deepthi Gorthi, Joshua S. Dillon, Peter Sims, Judd D. Bowman, Brian Glendenning, Carina Cheng, Samantha Pieterse, Craig Smith, Nicholas S. Kern, Eunice Matsetela, Joshua Kerrigan, Miguel F. Morales, Piyanat Kittiwisit, Mathakane Molewa, Zaki S. Ali, Paul Alexander, Tshegofalang Mosiane, Aaron Ewall-Wice, Daniel C. Jacobs, Jack Hickish, Haoxuan Zheng, David MacMahon, Telalo Lekalake, Matt Dexter, Cresshim Malgas, Nicolas Fagnoni, Jacob Burba, Yanga Balfour, Adam P. Beardsley, Bradley Greig, Abraham R. Neben, Steve R. Furlanetto, Matthys Maree, Julia Estrada, David DeBoer, Randall Fritz, James E. Aguirre, Nipanjana Patra, Peter K. G. Williams, Nima Razavi-Ghods, Ziyaad Halday, Richard F. Bradley, Matthew Kolopanis, Paul La Plante, Aaron R. Parsons, Lourence Malan, Adrian Liu, Zara Abdurashidova, Austin Julius, Eloy de Lera Acedo, Jon Ringuette, James Robnett, Jonathan C. Pober, Andrei Mesinger, Jasper Grobbelaar, Saul A. Kohn, Chris Carilli, Zachary E. Martinot, Bryna J. Hazelton, USA, Kerrigan, J., la Plante, P., Kohn, S., Pober, J. C., Aguirre, J., Abdurashidova, Z., Alexander, P., Ali, Z. S., Balfour, Y., Beardsley, A. P., Bernardi, G., Bowman, J. D., Bradley, R. F., Burba, J., Carilli, C. L., Cheng, C., Deboer, D. R., Dexter, M., de Lera Acedo, E., Dillon, J. S., Estrada, J., Ewall-Wice, A., Fagnoni, N., Fritz, R., Furlanetto, S. R., Glendenning, B., Greig, B., Grobbelaar, J., Gorthi, D., Halday, Z., Hazelton, B. J., Hickish, J., Jacobs, D. C., Julius, A., Kern, N. S., Kittiwisit, P., Kolopanis, M., Lanman, A., Lekalake, T., Liu, A., Macmahon, D., Malan, L., Malgas, C., Maree, M., Martinot, Z. E., Matsetela, E., Mesinger, A., Molewa, M., Morales, M. F., Mosiane, T., Neben, A. R., Parsons, A. R., Patra, N., Pieterse, S., Razavi-Ghods, N., Ringuette, J., Robnett, J., Rosie, K., Sims, P., Smith, C., Syce, A., Thyagarajan, N., Williams, P. K. G., and Zheng, H.
Subjects: Cosmology and Nongalactic Astrophysics (astro-ph.CO), FOS: Physical sciences, Context (language use), 02 engineering and technology, Astrophysics::Cosmology and Extragalactic Astrophysics, Astronomy & Astrophysics, 01 natural sciences, Radio telescope, Settore FIS/05 - Astronomia e Astrofisica, 020204 information systems, 0103 physical sciences, 0202 electrical engineering, electronic engineering, information engineering, data analysis [methods], 010303 astronomy & astrophysics, Reionization, Instrumentation and Methods for Astrophysics (astro-ph.IM), Discrete mathematics, Physics, business.industry, Deep learning, Astrophysics::Instrumentation and Methods for Astrophysics, Astronomy and Astrophysics, HERA, interferometric [techniques], Amplitude, Space and Planetary Science, data analysis – Techniques: interferometric [Methods], astro-ph.CO, Artificial intelligence, Radio interferometer, Astrophysics - Instrumentation and Methods for Astrophysics, business, Astronomical and Space Sciences, Astrophysics - Cosmology and Nongalactic Astrophysics, astro-ph.IM
Abstract: Radio Frequency Interference (RFI) is an ever-present limiting factor among radio telescopes even in the most remote observing locations. When looking to retain the maximum amount of sensitivity and reduce contamination for Epoch of Reionization studies, the identification and removal of RFI is especially important. In addition to improved RFI identification, we must also take into account computational efficiency of the RFI-Identification algorithm as radio interferometer arrays such as the Hydrogen Epoch of Reionization Array grow larger in number of receivers. To address this, we present a Deep Fully Convolutional Neural Network (DFCN) that is comprehensive in its use of interferometric data, where both amplitude and phase information are used jointly for identifying RFI. We train the network using simulated HERA visibilities containing mock RFI, yielding a known "ground truth" dataset for evaluating the accuracy of various RFI algorithms. Evaluation of the DFCN model is performed on observations from the 67 dish build-out, HERA-67, and achieves a data throughput of 1.6$\times 10^{5}$ HERA time-ordered 1024 channeled visibilities per hour per GPU. We determine that relative to an amplitude only network including visibility phase adds important adjacent time-frequency context which increases discrimination between RFI and Non-RFI. The inclusion of phase when predicting achieves a Recall of 0.81, Precision of 0.58, and $F_{2}$ score of 0.75 as applied to our HERA-67 observations., Comment: 11 pages, 7 figures
Published: 2019

117. Understanding the HERA Phase I receiver system with simulations and its impact on the detectability of the EoR delay power spectrum

Author: Richard F. Bradley, Matthew Kolopanis, Nithyanandan Thyagarajan, Adam Lanman, Lourence Malan, Saul A. Kohn, Alec Josaitis, Adrian Liu, Bryna J. Hazelton, Matt Dexter, Haoxuan Zheng, Piyanat Kittiwisit, Nicholas S. Kern, Kingsley Gale-Sides, Deepthi Gorthi, Joshua S. Dillon, Paul Alexander, Honggeun Kim, Craig Smith, Miguel F. Morales, Steve R. Furlanetto, Adam P. Beardsley, Mathakane Molewa, Zaki S. Ali, Bojan Nikolic, Aaron Ewall-Wice, Tshegofalang Mosiane, Phil Bull, Nipanjana Patra, Jacqueline N. Hewitt, Ziyaad Halday, Angelo Syce, Abraham R. Neben, Randall Fritz, Juan Mena Parra, Jack Hickish, Aaron R. Parsons, Joshua Kerrigan, Brian Glendenning, Carina Cheng, Paul La Plante, James Robnett, Jacob Burba, Chris Carilli, Eloy de Lera Acedo, Telalo Lekalake, Zara Abdurashidova, Kathryn Rosie, Gianni Bernardi, David MacMahon, Austin Julius, Daniel C. Jacobs, Nima Razavi-Ghods, Cresshim Malgas, Nicolas Fagnoni, Yanga Balfour, Matthys Maree, Peter Sims, Jonathan C. Pober, Andrei Mesinger, Jasper Grobbelaar, Tashalee S. Billings, Zachary E. Martinot, Bradley Greig, James E. Aguirre, Peter K. G. Williams, Eunice Matsetela, Judd D. Bowman, Samantha Pieterse, David DeBoer, ITA, USA, GBR, Fagnoni, N., De Lera Acedo, E., Deboer, D. R., Abdurashidova, Z., Aguirre, J. E., Alexander, P., Ali, Z. S., Balfour, Y., Beardsley, A. P., Bernardi, G., Billings, T. S., Bowman, J. D., Bradley, R. F., Bull, P., Burba, J., Carilli, C. L., Cheng, C., Dexter, M., Dillon, J. S., Ewall-Wice, A., Fritz, R., Furlanetto, S. R., Gale-Sides, K., Glendenning, B., Gorthi, D., Greig, B., Grobbelaar, J., Halday, Z., Hazelton, B. J., Hewitt, J. N., Hickish, J., Jacobs, D. C., Josaitis, A., Julius, A., Kern, N. S., Kerrigan, J., Kim, H., Kittiwisit, P., Kohn, S. A., Kolopanis, M., Lanman, A., Plante, P. L., Lekalake, T., Liu, A., Macmahon, D., Malan, L., Malgas, C., Maree, M., Martinot, Z. E., Matsetela, E., Mena Parra, J., Mesinger, A., Molewa, M., Morales, M. F., Mosiane, T., Neben, A. R., Nikolic, B., Parsons, A. R., Patra, N., Pieterse, S., Pober, J. C., Razavi-Ghods, N., Robnett, J., Rosie, K., Sims, P., Smith, C., Syce, A., Thyagarajan, N., Williams, P. K. G., and Zheng, H.
Subjects: interferometers [instrumentation], first stars, Phase (waves), FOS: Physical sciences, 02 engineering and technology, Astrophysics::Cosmology and Extragalactic Astrophysics, Astronomy & Astrophysics, 01 natural sciences, law.invention, Radio telescope, Telescope, Optics, Settore FIS/05 - Astronomia e Astrofisica, law, 0103 physical sciences, 0202 electrical engineering, electronic engineering, information engineering, dark ages, 010303 astronomy & astrophysics, Reionization, Instrumentation and Methods for Astrophysics (astro-ph.IM), Physics, business.industry, Astrophysics::Instrumentation and Methods for Astrophysics, Spectral density, 020206 networking & telecommunications, Astronomy and Astrophysics, numerical [methods], telescopes, HERA, interferometric [techniques], interferometer [instrumentation], Transmission (telecommunications), Space and Planetary Science, reionization, dark ages, reionization, first star, Antenna (radio), Astrophysics - Instrumentation and Methods for Astrophysics, business, Astronomical and Space Sciences, astro-ph.IM
Abstract: The detection of the Epoch of Reionization (EoR) delay power spectrum using a "foreground avoidance method" highly depends on the instrument chromaticity. The systematic effects induced by the radio-telescope spread the foreground signal in the delay domain, which contaminates the EoR window theoretically observable. Applied to the Hydrogen Epoch of Reionization Array (HERA), this paper combines detailed electromagnetic and electrical simulations in order to model the chromatic effects of the instrument, and quantify its frequency and time responses. In particular, the effects of the analogue receiver, transmission cables, and mutual coupling are included. These simulations are able to accurately predict the intensity of the reflections occurring in the 150-m cable which links the antenna to the back-end. They also show that electromagnetic waves can propagate from one dish to another one through large sections of the array due to mutual coupling. The simulated system time response is attenuated by a factor $10^{4}$ after a characteristic delay which depends on the size of the array and on the antenna position. Ultimately, the system response is attenuated by a factor $10^{5}$ after 1400 ns because of the reflections in the cable, which corresponds to characterizable ${k_\parallel}$-modes above 0.7 $h\;\rm{Mpc}^{-1}$ at 150 MHz. Thus, this new study shows that the detection of the EoR signal with HERA Phase I will be more challenging than expected. On the other hand, it improves our understanding of the telescope, which is essential to mitigate the instrument chromaticity., Comment: 13 pages, 17 figures - Submitted to MNRAS - 2nd revision
Published: 2019
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118. Measuring HERA's Primary Beam in Situ: Methodology and First Results

Author: Richard F. Bradley, Matthew Kolopanis, Jonathan C. Pober, Andrei Mesinger, Daniel C. Jacobs, Bradley Greig, Jasper Grobbelaar, Cresshim Malgas, Craig Smith, Nicolas Fagnoni, Peter Sims, Yanga Balfour, Joshua Kerrigan, Angelo Syce, Tashalee S. Billings, Zachary E. Martinot, Piyanat Kittiwisit, Aaron R. Parsons, Chuneeta D. Nunhokee, Chris Carilli, Kingsley Gale-Sides, Nicholas S. Kern, Eloy de Lera Acedo, Peter K. G. Williams, Paul Alexander, Eunice Matsetela, Saul A. Kohn, Adam Lanman, Paul La Plante, David DeBoer, Nima Razavi-Ghods, David MacMahon, Bryna J. Hazelton, Nipanjana Patra, Adam P. Beardsley, Jon Ringuette, Matt Dexter, Ziyaad Halday, Deepthi Gorthi, Adrian Liu, Brian Glendenning, Nithyanandan Thyagarajan, Abraham R. Neben, Joshua S. Dillon, Gianni Bernardi, Zara Abdurashidova, Carina Cheng, Lourence Malan, Judd D. Bowman, Randall Fritz, Samantha Pieterse, Jacob Burba, Miguel F. Morales, Austin Julius, Zaki S. Ali, Bojan Nikolic, Aaron Ewall-Wice, James Robnett, Jacqueline N. Hewitt, James E. Aguirre, Kathryn Rosie, Steve R. Furlanetto, Mathakane Molewa, Haoxuan Zheng, Tshegofalang Mosiane, Matthys Maree, Telalo Lekalake, ITA, USA, CAF, Nunhokee, C. D., Parsons, A. R., Kern, N. S., Nikolic, B., Pober, J. C., Bernardi, G., Carilli, C. L., Abdurashidova, Z., Aguirre, J. E., Alexander, P., Ali, Z. S., Balfour, Y., Beardsley, A. P., Billings, T. S., Bowman, J. D., Bradley, R. F., Burba, J., Cheng, C., Deboer, D. R., Dexter, M., Acedo, E. D. L., Dillon, J. S., Ewall-Wice, A., Fagnoni, N., Fritz, R., Furlanetto, S. R., Gale-Sides, K., Glendenning, B., Gorthi, D., Greig, B., Grobbelaar, J., Halday, Z., Hazelton, B. J., Hewitt, J. N., Jacobs, D. C., Julius, A., Kerrigan, J., Kittiwisit, P., Kohn, S. A., Kolopanis, M., Lanman, A., Plante, P. L., Lekalake, T., Liu, A., Macmahon, D., Malan, L., Malgas, C., Maree, M., Martinot, Z. E., Matsetela, E., Mesinger, A., Molewa, M., Morales, M. F., Mosiane, T., Neben, A. R., Patra, N., Pieterse, S., Razavi-Ghods, N., Ringuette, J., Robnett, J., Rosie, K., Sims, P., Smith, C., Syce, A., Thyagarajan, N., Williams, P. K. G., and Zheng, H.
Subjects: In situ, Physics, Cosmology and Nongalactic Astrophysics (astro-ph.CO), Astrophysics::Instrumentation and Methods for Astrophysics, FOS: Physical sciences, Astronomy and Astrophysics, Astrophysics::Cosmology and Extragalactic Astrophysics, HERA, 01 natural sciences, Cosmology, Nuclear physics, Settore FIS/05 - Astronomia e Astrofisica, Space and Planetary Science, Primary (astronomy), 0103 physical sciences, H I line emission, Radio astronomy, Astrophysics - Instrumentation and Methods for Astrophysics, 010306 general physics, Instrumentation and Methods for Astrophysics (astro-ph.IM), 010303 astronomy & astrophysics, Beam (structure), Astrophysics - Cosmology and Nongalactic Astrophysics
Abstract: The central challenge in 21~cm cosmology is isolating the cosmological signal from bright foregrounds. Many separation techniques rely on the accurate knowledge of the sky and the instrumental response, including the antenna primary beam. For drift-scan telescopes such as the Hydrogen Epoch of Reionization Array \citep[HERA, ][]{DeBoer2017} that do not move, primary beam characterization is particularly challenging because standard beam-calibration routines do not apply \citep{Cornwell2005} and current techniques require accurate source catalogs at the telescope resolution. We present an extension of the method from \citet{Pober2012} where they use beam symmetries to create a network of overlapping source tracks that break the degeneracy between source flux density and beam response and allow their simultaneous estimation. We fit the beam response of our instrument using early HERA observations and find that our results agree well with electromagnetic simulations down to a -20~dB level in power relative to peak gain for sources with high signal-to-noise ratio. In addition, we construct a source catalog with 90 sources down to a flux density of 1.4~Jy at 151~MHz., 22 pages, 22 figures, accepted for publication in ApJ
Published: 2020

119. The HERA-19 Commissioning Array: Direction-dependent Effects

Author: Judd D. Bowman, Samantha Pieterse, Daniel C. Jacobs, Gcobisa Fadana, Paul M. Chichura, C. H. Smith, Jacqueline N. Hewitt, Richard F. Bradley, Matthew Kolopanis, Joshua S. Dillon, Jon Ringuette, Cresshim Malgas, Jonathan C. Pober, Andrei Mesinger, Nicolas Fagnoni, Jasper Grobbelaar, Chris Carilli, Nima Razavi-Ghods, Tashalee S. Billings, Zachary E. Martinot, Eloy de Lera Acedo, David DeBoer, Chuneeta D. Nunhokee, Miguel F. Morales, Roshan K. Benefo, Haoxuan Zheng, Brian Glendenning, Austin Julius, Amy S. Igarashi, Gianni Bernardi, Carina Cheng, Zaki S. Ali, Nipanjana Patra, Bojan Nikolic, Aaron Ewall-Wice, Anita Loots, Angelo Syce, Peter Williams, Paul Alexander, Lourence Malan, Eunice Matsetela, Nithyanandan Thyagarajan, Steven R. Furlanetto, James E. Aguirre, Raddwine Sell, MacCalvin Kariseb, Telalo Lekalake, Max Tegmark, Matthys Maree, Bryna J. Hazelton, Bradley Greig, Adrian Liu, Jack Hickish, Nicholas S. Kern, Paul La Plante, Abraham R. Neben, Randall Fritz, Aaron R. Parsons, Samavarti Gallardo, Austin F. Fortino, Philip Bull, James Robnett, David MacMahon, Adam P. Beardsley, Saul A. Kohn, Kathryn Rosie, Nathan Mathison, ITA, USA, Kohn, SA [0000-0001-6744-5328], Aguirre, JE [0000-0002-4810-666X], La Plante, P [0000-0002-4693-0102], Nunhokee, CD [0000-0002-5445-6586], Kern, NS [0000-0002-8211-1892], Liu, A [0000-0001-6876-0928], Beardsley, AP [0000-0001-9428-8233], Bernardi, G [0000-0002-0916-7443], Bowman, JD [0000-0002-8475-2036], Carilli, CL [0000-0001-6647-3861], Dillon, JS [0000-0003-3336-9958], Ewall-Wice, A [0000-0002-0086-7363], Furlanetto, SR [0000-0002-0658-1243], Hazelton, BJ [0000-0001-7532-645X], Jacobs, DC [0000-0002-0917-2269], Kolopanis, M [0000-0002-2950-2974], Morales, MF [0000-0001-7694-4030], Neben, AR [0000-0001-7776-7240], Patra, N [0000-0002-9457-1941], Tegmark, M [0000-0001-7670-7190], Thyagarajan, N [0000-0003-1602-7868], Williams, PKG [0000-0003-3734-3587], Apollo - University of Cambridge Repository, Kohn, S. A., Aguirre, J. E., La Plante, P., Billings, T. S., Chichura, P. M., Fortino, A. F., Igarashi, A. S., Benefo, R. K., Gallardo, S., Martinot, Z. E., Nunhokee, C. D., Kern, N. S., Bull, P., Liu, A., Alexander, P., Ali, Z. S., Beardsley, A. P., Bernardi, G., Bowman, J. D., Bradley, R. F., Carilli, C. L., Cheng, C., Deboer, D. R., Acedo, E. D. L., Dillon, J. S., Ewall-Wice, A., Fadana, G., Fagnoni, N., Furlanetto, S. R., Glendenning, B., Greig, B., Grobbelaar, J., Hazelton, B. J., Hewitt, J. N., Hickish, J., Jacobs, D. C., Julius, A., Kariseb, M., Kolopanis, M., Lekalake, T., Loots, A., Macmahon, D., Malan, L., Malgas, C., Maree, M., Mathison, N., Matsetela, E., Mesinger, A., Morales, M. F., Neben, A. R., Nikolic, B., Parsons, A. R., Patra, N., Pieterse, S., Pober, J. C., Randall, F., Razavi-Ghods, N., Ringuette, J., Robnett, J., Rosie, K., Sell, R., Smith, C., Syce, A., Tegmark, M., Thyagarajan, N., Williams, P. K. G., and Zheng, H.
Subjects: 010504 meteorology & atmospheric sciences, interferometers [instrumentation], Atomic, Physical Chemistry, 7. Clean energy, 01 natural sciences, Spectral line, Particle and Plasma Physics, Astronomical interferometer, Stokes parameters, dark ages, instrumentation: interferometers, 010303 astronomy & astrophysics, Physics, Linear polarization, Astrophysics::Instrumentation and Methods for Astrophysics, HERA, Polarization (waves), observations [cosmology], interferometric [techniques], interferometer [instrumentation], Amplitude, techniques: interferometric, symbols, reionization, dark ages, reionization, first star, Astrophysics - Instrumentation and Methods for Astrophysics, Astronomical and Space Sciences, observation [cosmology], Physical Chemistry (incl. Structural), first stars, FOS: Physical sciences, Astrophysics::Cosmology and Extragalactic Astrophysics, Astronomy & Astrophysics, symbols.namesake, Settore FIS/05 - Astronomia e Astrofisica, 0103 physical sciences, Nuclear, dark ages, reionization, first stars, Reionization, Instrumentation and Methods for Astrophysics (astro-ph.IM), Astrophysics::Galaxy Astrophysics, 0105 earth and related environmental sciences, polarization, 010308 nuclear & particles physics, Molecular, Astronomy and Astrophysics, Computational physics, Space and Planetary Science, 13. Climate action, cosmology: observations, astro-ph.IM
Abstract: Foreground power dominates the measurements of interferometers that seek a statistical detection of highly-redshifted HI emission from the Epoch of Reionization (EoR). The chromaticity of the instrument creates a boundary in the Fourier transform of frequency (proportional to $k_\parallel$) between spectrally smooth emission, characteristic of the strong synchrotron foreground (the "wedge"), and the spectrally structured emission from HI in the EoR (the "EoR window"). Faraday rotation can inject spectral structure into otherwise smooth polarized foreground emission, which through instrument effects or miscalibration could possibly pollute the EoR window. Using data from the HERA 19-element commissioning array, we investigate the polarization response of this new instrument in the power spectrum domain. We perform a simple image-based calibration based on the unpolarized diffuse emission of the Global Sky Model, and show that it achieves qualitative redundancy between the nominally-redundant baselines of the array and reasonable amplitude accuracy. We construct power spectra of all fully polarized coherencies in all pseudo-Stokes parameters. We compare to simulations based on an unpolarized diffuse sky model and detailed electromagnetic simulations of the dish and feed, confirming that in Stokes I, the calibration does not add significant spectral structure beyond the expected level. Further, this calibration is stable over the 8 days of observations considered. Excess power is seen in the power spectra of the linear polarization Stokes parameters which is not easily attributable to leakage via the primary beam, and results from some combination of residual calibration errors and actual polarized emission. Stokes V is found to be highly discrepant from the expectation of zero power, strongly pointing to the need for more accurate polarized calibration., Comment: 21 pages, 12 figures, submitted to ApJ
Published: 2018
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120. Internet pseudoscience. Testing opioid containing formulations with tampering potential

Author: Stefano D'Errico, Fabio Vaiano, Jennifer P. Pascali, Paolo Fais, Sandra Furlanetto, Elisabetta Bertol, Diego Palumbo, Nicola Pigaiani, Pascali, Jp, Fais, P, Vaiano, F, Pigaiani, N, D'Errico, S, Furlanetto, S, Palumbo, D, Bertol, E, Pascali, Jennifer P, Fais, Paolo, Vaiano, Fabio, Pigaiani, Nicola, D'Errico, Stefano, Furlanetto, Sandra, Palumbo, Diego, and Bertol, Elisabetta
Subjects: Misuse, lc–ms/ms, misuse, opioids, paracetamol, pharmaceutical preparations, tampering, Chemistry, Pharmaceutical, Clinical Biochemistry, Pharmaceutical Science, Opioid, Cold water extraction, Dextromethorphan, Analytical Chemistry, Fentanyl, 03 medical and health sciences, 0302 clinical medicine, LC–MS/MS, Tandem Mass Spectrometry, Drug Discovery, medicine, Tampering, 030212 general & internal medicine, Opioids, Paracetamol, Pharmaceutical preparations, Spectroscopy, Tramadol, Acetaminophen, Analgesics, Chromatography, Liquid, Internet, Chemistry, Codeine, Dexketoprofen, Analgesics, Opioid, Chromatography, Liquid, Tablets, Pharmaceutical, 030211 gastroenterology & hepatology, Opioids, Tampering, Misuse, LC–MS/MS, Paracetamol, Pharmaceutical preparations, Oxycodone, Pharmaceutical preparation, medicine.drug
Abstract: Drug tampering practices, with the aim to increase availability of drug delivery and/or enhance drug effects, are accessible on Internet and are practiced by some portion of recreational drug users. Not rarely, recreational misuse may result in toxic and even fatal results. The aim of the present study was to assess the tampering risk of medicaments containing different formulations of an opioid in combination with paracetamol or dexketoprofen, following the procedures reported in dedicated forums on the web. Tablets and suppositories containing codeine, tramadol and oxycodone were extracted following the reported “Cold water extraction”; dextromethorphan was extracted from cough syrup following the procedure reported as “Acid/base extraction” and fentanyl was extracted from transdermal patches according the procedure reported in Internet. The tampered products and opportunely prepared calibrators in water were analysed by liquid chromatography coupled to tandem mass spectrometry (LC–MS/MS). The separation of the analytes was carried on Agilent ZORBAX Eclipse Plus C18 (RRHT 2.1 mm × 50 mm, 1.8 μm) by the gradient elution of 0.01% formic acid in water and 0.01% formic acid in methanol. Acquisition was by MRM mode considering at least two transitions for compound. Declared recoveries for these home-made extractions claimed to exceed 99% for the opioid and to complete remove paracetamol, often associated to liver toxicity and thus to obtain a “safer” preparation. In this study, the authors demonstrated that rarely the recoveries for the opioid reached 90% and that up to 60% of the paracetamol amount remained in solution. Thus, high risks for health remained both for the potential lethality of the opioid content, but also for the sub-lethal chronic use of these mixtures, which contained still uncontrolled, ignored, but often important amounts of paracetamol.
Published: 2018

121. Multivariate optimization of capillary electrophoresis methods: a critical review

Author: Roberto Gotti, Sandra Furlanetto, Serena Orlandini, Orlandini S., Gotti R., and Furlanetto S.
Subjects: Multivariate statistics, Management science, Chemistry, Clinical Biochemistry, Electrophoresis, Capillary, Pharmaceutical Science, Equipment Design, Multivariate optimization, Mass Spectrometry, Experimental design, Analytical Chemistry, Critical discussion, Capillary electrophoresis, Capillary Electrochromatography, Research Design, Drug Discovery, Humans, Spectroscopy, Electromigration method
Abstract: In this article a review on the recent applications of multivariate techniques for optimization of electromigration methods, is presented. Papers published in the period from August 2007 to February 2013, have been taken into consideration. Upon a brief description of each of the involved CE operative modes, the characteristics of the chemometric strategies (type of design, factors and responses) applied to face a number of analytical challenges, are presented. Finally, a critical discussion, giving some practical advices and pointing out the most common issues involved in multivariate set-up of CE methods, is provided.
Published: 2014

122. Detection of gamma-hydroxybutyrate in hair: Validation of GC–MS and LC–MS/MS methods and application to a real case

Author: Sandra Furlanetto, Paolo Procaccianti, Antonina Argo, Fabio Vaiano, Francesco Mari, Maria Grazia Di Milia, Elisabetta Bertol, Bertol, E, Argo, A, Procaccianti, P, Vaiano, F, Di Milia, MG, Furlanetto, S, and Mari, FM
Subjects: Adult, Male, Quality Control, Spectrometry, Mass, Electrospray Ionization, Substance-Related Disorders, Electrospray ionization, Clinical Biochemistry, Liquid-Liquid Extraction, Pharmaceutical Science, Acetates, Tandem mass spectrometry, Mass spectrometry, Gas Chromatography-Mass Spectrometry, Analytical Chemistry, Forensic Toxicology, Settore MED/43 - Medicina Legale, Liquid chromatography–mass spectrometry, Limit of Detection, Tandem Mass Spectrometry, Drug Discovery, Humans, Sodium Hydroxide, Spectroscopy, Detection limit, Chromatography, Chemistry, Illicit Drugs, Selected reaction monitoring, Hair, Segmental analysis GC–MS LC–MS/MS, Temperature, Reproducibility of Results, Gamma hydroxybutyrate, Reference Standards, Substance Abuse Detection, Gamma-hydroxybutyrate, GHB, Calibration, Linear Models, Crime, Gas chromatography–mass spectrometry, Sodium Oxybate, Chromatography, Liquid, Hair
Abstract: A gas chromatography-mass spectrometry (GC-MS) and a liquid chromatography tandem mass spectrometry (LC-MS/MS) method were validated for quantifying endogenous and exogenous hair concentrations of gamma-hydroxybutyrate (GHB). The GC-MS method is based on overnight extraction of 25 mg hair in NaOH at 56 °C, liquid/liquid extraction in ethylacetate and trimethylsylil derivatization; analysis is by electron ionization and single ion monitoring of three ions. The LC-MS/MS method entails a rapid digestion of 25 mg hair with NaOH at 75 °C for 40 min, liquid/liquid extraction in ethylacetate and reconstitution of the extract in the LC mobile phase; negative ion electrospray ionization and multiple reaction monitoring (MRM) analysis are employed for the LC-MS/MS detection. In both cases, GHB-d6 is used as an internal standard. The endogenous amount in "blank" hair are estimated by the standard addition method. Limits of detection are 0.4 and 0.5 ng/mg for GC-MS and LC-MS/MS respectively, while the limit of quantification (LOQ) is 0.6 ng/mg for both methods; the GC-MS method proved to be linear in the range 1-50 ng/mg whereas linearity was demonstrated from 0.6 to 50 ng/mg for the LC-MS/MS; imprecision and inaccuracy were always lower than 23% for quality controls samples. The two methods were applied to a real case of a man addicted to GHB; the drug concentration in segments from 17 cm hair strand well correlated with self-reported use of GHB in different periods of his life. Performances of the two methods were similar.
Published: 2012

123. The Inhomogeneous Ionizing Background Following Reionization

Author: Steven R. Furlanetto, Andrei Mesinger, Mesinger, ANDREI ALBERT, and Furlanetto, S.
Subjects: Physics, Cosmology and Nongalactic Astrophysics (astro-ph.CO), 010308 nuclear & particles physics, Dark matter, FOS: Physical sciences, Astronomy and Astrophysics, Astrophysics, Astrophysics::Cosmology and Extragalactic Astrophysics, Lyman-alpha forest, 01 natural sciences, Redshift, Galaxy, Stars, 13. Climate action, Space and Planetary Science, 0103 physical sciences, Galaxy formation and evolution, Halo, 010303 astronomy & astrophysics, Reionization, Astrophysics - Cosmology and Nongalactic Astrophysics
Abstract: We study the spatial fluctuations in the hydrogen ionizing background in the epoch following reionization (z ~ 5--6). The rapid decrease with redshift in the photon mean free path (m.f.p.), combined with the clustering of increasingly rare ionizing sources, can result in a very inhomogenous ionizing background during this epoch. We systematically investigate the probability density functions (PDFs) and power spectra of ionizing flux, by varying several parameters such as the m.f.p., minimum halo mass capable of hosting stars, and halo duty cycle. In order to be versatile, we make use of analytic, semi-numeric and numeric approaches. Our models show that the ionizing background indeed has sizable fluctuations during this epoch sourced by the clustering of sources, with the PDFs being a factor of few wide at half of the maximum likelihood. The distributions also show marked asymmetries, with a high-value tail set by clustering on small scales, and a shorter low-value tail which is set by the mean free path. The power spectrum of the ionizing background is much more sensitive to source properties than the PDF and can be well-understood analytically with a framework similar to the halo model (usually used to describe dark matter clustering). Nevertheless, we find that Lya forest spectra are extremely insensitive to the details of the UVB, despite marked differences in the PDFs and power spectra of our various ionizing backgrounds. Assuming a uniform ionizing background only underestimates the value of the mean ionization rate inferred from the Lya forest by a few percent. Instead, analysis of the Lya forest is dominated by the uncertainties in the density field. Thus, our results justify the common assumption of a uniform ionizing background in Lya forest analysis even during this epoch., 11 pages, 11 figures, submitted to the MNRAS
Published: 2009

124. The ionizing background at the end of reionization

Author: Steven R. Furlanetto, Andrei Mesinger, Furlanetto, S, and Mesinger, ANDREI ALBERT
Subjects: Physics, Photon, 010308 nuclear & particles physics, Attenuation length, Astronomy and Astrophysics, Quasar, Astrophysics::Cosmology and Extragalactic Astrophysics, Astrophysics, 01 natural sciences, Ionizing radiation, Amplitude, Space and Planetary Science, Ionization, 0103 physical sciences, Probability distribution, 010303 astronomy & astrophysics, Reionization
Abstract: One of the most sought-after signatures of reionization is a rapid increase in the ionizing background (usually measured through the Lyman-alpha optical depth toward distant quasars). Conventional wisdom associates this with the "overlap" phase when ionized bubbles merge, allowing each source to affect a much larger volume. We argue that this picture fails to describe the transition to the post-overlap Universe, where Lyman-limit systems absorb ionizing photons over moderate lengthscales (20-100 Mpc). Using an analytic model, we compute the probability distribution of the amplitude of the ionizing background throughout reionization, including both discrete ionized bubbles and Lyman-limit systems (parameterized by an attenuation length). We show that overlap does not by itself cause a rapid increase in the ionizing background or a rapid decrease in the mean Lyman-alpha transmission toward distant quasars. More detailed semi-numeric models support these conclusions. We argue that rapid changes should instead be interpreted as evolution in the attenuation length itself, which may or may not be directly related to overlap.
Published: 2009

125. Lyα damping wing constraints on inhomogeneous reionization

Author: Andrei Mesinger, Steven R. Furlanetto, Mesinger, ANDREI ALBERT, and Furlanetto, S.
Subjects: Physics, education.field_of_study, media_common.quotation_subject, Population, Astronomy and Astrophysics, Quasar, Astrophysics::Cosmology and Extragalactic Astrophysics, Astrophysics, Universe, Spectral line, Space and Planetary Science, Ionization, Halo, education, Absorption (electromagnetic radiation), Reionization, Astrophysics::Galaxy Astrophysics, media_common
Abstract: One well-known way to constrain the hydrogen neutral fraction, x_H, of the high-redshift intergalactic medium (IGM) is through the shape of the red damping wing of the Lya absorption line. We examine this method's effectiveness in light of recent models showing that the IGM neutral fraction is highly inhomogeneous on large scales during reionization. Using both analytic models and "semi-numeric" simulations, we show that the "picket-fence" absorption typical in reionization models introduces both scatter and a systematic bias to the measurement of x_H. In particular, we show that simple fits to the damping wing tend to overestimate the true neutral fraction in a partially ionized universe, with a fractional error of ~ 30% near the middle of reionization. This bias is generic to any inhomogeneous model. However, the bias is reduced and can even underestimate x_H if the observational sample only probes a subset of the entire halo population, such as quasars with large HII regions. We also find that the damping wing absorption profile is generally steeper than one would naively expect in a homogeneously ionized universe. The profile steepens and the sightline-to-sightline scatter increases as reionization progresses. Of course, the bias and scatter also depend on x_H and so can, at least in principle, be used to constrain it. Damping wing constraints must therefore be interpreted by comparison to theoretical models of inhomogeneous reionization.
Published: 2008

126. Efficient Simulations of Early Structure Formation and Reionization

Author: Andrei Mesinger, Steven R. Furlanetto, Mesinger, ANDREI ALBERT, and Furlanetto, S.
Subjects: Physics, Structure formation, Astrophysics (astro-ph), FOS: Physical sciences, Astronomy and Astrophysics, Astrophysics, Astrophysics::Cosmology and Extragalactic Astrophysics, Redshift, Computational physics, Orders of magnitude (time), Space and Planetary Science, Brightness temperature, Radiative transfer, Halo, Perturbation theory (quantum mechanics), Reionization
Abstract: We present a method to construct semi-numerical ``simulations'', which can efficiently generate realizations of halo distributions and ionization maps at high redshifts. Our procedure combines an excursion-set approach with first-order Lagrangian perturbation theory and operates directly on the linear density and velocity fields. As such, the achievable dynamic range with our algorithm surpasses the current practical limit of N-body codes by orders of magnitude. This is particularly significant in studies of reionization, where the dynamic range is the principal limiting factor. We test our halo-finding and HII bubble-finding algorithms independently against N-body simulations with radiative transfer and obtain excellent agreement. We compute the size distributions of ionized and neutral regions in our maps. We find even larger ionized bubbles than do purely analytic models at the same volume-weighted mean hydrogen neutral fraction. We also generate maps and power spectra of 21-cm brightness temperature fluctuations, which for the first time include corrections due to gas bulk velocities. We find that velocities widen the tails of the temperature distributions and increase small-scale power, though these effects quickly diminish as reionization progresses. We also include some preliminary results from a simulation run with the largest dynamic range to date: a 250 Mpc box that resolves halos with masses M >~ 2.2 x10^8 M_sun. We show that accurately modeling the late stages of reionization requires such large scales. The speed and dynamic range provided by our semi-numerical approach will be extremely useful in the modeling of early structure formation and reionization., 13 pages, 10 figures; ApJ submitted
Published: 2007

127. Analytical quality by design-based development of a capillary electrophoresis method for Omeprazole impurity profiling.

Author: Modroiu A, Marzullo L, Orlandini S, Gotti R, Hancu G, and Furlanetto S
Subjects: Reproducibility of Results, Solvents chemistry, Chromatography, Micellar Electrokinetic Capillary methods, Hydrogen-Ion Concentration, Micelles, 1-Butanol chemistry, Omeprazole analysis, Omeprazole chemistry, Drug Contamination prevention & control, Electrophoresis, Capillary methods, Proton Pump Inhibitors analysis, Sodium Dodecyl Sulfate chemistry
Abstract: Omeprazole (OME) is a proton pump inhibitor used to treat gastroesophageal reflux disease associated conditions. The current study presents an Analytical Quality by Design-based approach for the development of a CE method for OME impurity profiling. The scouting experiments suggested the selection of solvent modified Micellar ElectroKinetic Chromatography operative mode using a pseudostationary phase composed of sodium dodecyl sulfate (SDS) micelles and n-butanol as organic modifier in borate buffer. A symmetric three-level screening matrix 3 7 //16 was used to evaluate the effect of Critical Method Parameters, including Background Electrolyte composition and instrumental settings, on Critical Method Attributes (critical resolution values, OME peak width and analysis time). The analytical procedure was optimized using Response Surface Methodology through a Central Composite Orthogonal Design. Risk of failure maps made it possible to define the Method Operable Design Region, within which the following optimized conditions were selected: 72 mM borate buffer pH 10.0, 96 mM SDS, 1.45 %v/v n-butanol, capillary temperature 21 °C, applied voltage 25 kV. The method was validated according to ICH guidelines and robustness was evaluated using a Plackett-Burman design. The developed procedure enables the simultaneous determination of OME and seven related impurities, and has been successfully applied to the analysis of pharmaceutical formulations., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)
Published: 2024
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128. Special Issue dedicated to Prof. Jun Haginaka.

Author: Chankvetadze B, Ciesla L, Furlanetto S, Ganzera M, Jiang Z, Kang J, Markuszewski M, and Ozkan S
Published: 2024
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129. Optimization of hydrolysis conditions of amino acid analysis for UHPLC-UV antigens content determination: Bexsero vaccine a case study.

Author: Nompari L, Orlandini S, Pasquini B, Fontana L, Rovini M, Masi F, Gotti R, and Furlanetto S
Subjects: Amino Acids, Hydrolysis, Chromatography, High Pressure Liquid, Antigens, Bacterial, Meningococcal Vaccines
Abstract: In the present study the compositional analysis of the amino acids released by the acidic hydrolysis of the vaccine antigens was approached as an alternative to the dye-binding methods, for improvement of the quality control. In particular, the Analytical Quality by Design principles were undertaken in optimizing the hydrolysis conditions of the antigens to be applied prior to the quantitation by UHPLC-UV. Bexsero was used as a case study; it is a recombinant meningococcal B vaccine and one of its critical quality attributes is the content of the three core protein antigens, namely Neisseria Heparin Binding Antigen, factor H binding protein and Neisseria adhesin A, in the final formulation. Conventionally, the proteins quantitation is carried out by dye-binding assays. Analytical Target Profile was defined as the accurate determination of amounts of the Bexsero antigens. The Critical Method Parameters were chosen by means of the cause-effect matrix. A Face Centered Design was used to select the experiments to investigate the process and finally a Method Operable Design Region with a risk of failure of 5% was defined. The selected working point for routine use was: hydrolysis time, 17 hrs; temperature, 112 °C; 6 M HCl volume, 300 µl; antioxidant 90% phenol volume, 5 µl., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)
Published: 2024
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130. Innovative Reversed-Phase Chromatography Platform Approach for the Fast and Accurate Characterization of Membrane Vesicles' Protein Patterns.

Author: Nompari L, Coccone SS, Sardone GL, Corrado A, Berti S, Biagini M, Rovini M, Magagnoli C, Cianetti S, Orlandini S, Furlanetto S, and De Ricco R
Abstract: Outer membrane vesicles (OMVs) have been widely explored to develop vaccine candidates for bacterial pathogens due to their ability to combine adjuvant properties with immunogenic activity. OMV expresses a variety of proteins and carbohydrate antigens on their surfaces. For this reason, there is an analytical need to thoroughly characterize the species expressed at their surface: we here present a simple and accurate reversed-phase ultrahigh-performance liquid chromatography (RP-UPLC) method developed according to quality by design principles. This work provides an analytical alternative to the classical sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) characterization. The higher selectivity and sensitivity of the RP-UHPLC assay allow for the identification of additional protein species with respect to SDS-PAGE and facilitate its precise relative abundance quantification. According to validation results, the assay showed high accuracy, linearity, precision, repeatability, and a limit of quantification of 1% for less abundant proteins. This performance paves the way for improved production campaign consistency while also being analytically simple (no sample pretreatment required), making it suitable for routine quality control testing. In addition, the applicability of the assay to a wider range of vesicle classes (GMMA) was demonstrated., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)
Published: 2024
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131. Analysis of Volatile Hydrocarbons (Pentene Dimers and Terpenes) in Extra Virgin Olive Oil: Optimization by Response Surface Methodology and Validation of HS-SPME-GC-MS Method.

Author: Cecchi L, Orlandini S, Balli D, Zanoni B, Migliorini M, Giambanelli E, Catola S, Furlanetto S, and Mulinacci N
Subjects: Olive Oil analysis, Solid Phase Microextraction methods, Gas Chromatography-Mass Spectrometry methods, Alkenes analysis, Hydrocarbons, Terpenes analysis, Volatile Organic Compounds analysis
Abstract: A head space-solid phase microextraction-gas chromatography-mass spectrometery (HS-SPME-GC-MS) method for the simultaneous analysis of pentene dimers from lipoxygenase (LOX) pathway, monoterpenes, and sesquiterpenes in extra virgin olive oil (EVOO) was proposed. A Doehlert design was performed; the conditions of the HS-SPME preconcentration step (extraction temperature, extraction time, sample amount, and desorption time) were optimized by response surface methodology, allowing defining the method operable design region. A quantitative method was set up using the multiple internal standard normalization approach: four internal standards were used, and the most suitable one was selected for area normalization of each external standard. The quantitative method was successfully validated and applied to a series of monocultivar EVOOs. This is the first paper in which a quantitative method using commercial standards has been proposed for the analysis of an important class of molecules of EVOO such as pentene dimers. The optimized method is suitable for routine analysis aimed at characterizing high quality EVOOs.
Published: 2024
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132. Chiral high-performance liquid chromatography analysis of mono-, di-, and triacylglycerols with amylose- and cellulose-phenylcarbamate-based stationary phases.

Author: Ianni F, Carotti A, Protti M, Favilli A, Gerli S, Furlanetto S, Mercolini L, and Sardella R
Abstract: The ever-increasing technological advancement in the (ultra)high-performance liquid chromatography tandem (high-resolution) mass spectrometry platforms have largely contributed to steeply intensify the interest towards lipidomics research. However, mass spectrometers alone are unable to distinguish between enantiomers. This obstacle is especially evident in the case of glycerolipids analysis due the prochiral nature of glycerol. Until a couple of decades ago, the stereoselective analysis of triacylglycerols (TAGs) was performed on the end products generated either from their enzymatic or chemical hydrolysis, namely on mono- or diacyl-sn-glycerols (MAGs and DAGs, respectively). These were then mostly analyzed with Pirkle-type chiral stationary phases (CSPs) after dedicated multi-step derivatization procedures. One of the most significant drawbacks of these traditional methods for enantioselective TAGs analysis (actually of the produced MAGs and DAGs, often investigated as target species per se) was the difficulty to totally abolish the migration of fatty acyls between glycerol positions. This made difficult to control and keep unaltered the stereochemistry of the original molecules. Over the last two decades, it has been widely demonstrated that the enantioselective analysis of intact TAGs as well as of non-derivatized MAGs and DAGs can be efficiently obtained using polysaccharide-based CSPs incorporating either amylose- or cellulose-phenylcarbamate derivatives chiral selectors. In this paper, the enantioselective methods developed with these CSPs for the enantioselective direct LC analysis of MAGs, DAGs and TAGs embedding different types of fatty acid residues are comprehensively reviewed., Competing Interests: Declaration of Competing Interest The authors declare no conflict of interest., (Copyright © 2023 Elsevier B.V. All rights reserved.)
Published: 2023
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133. Analytical Quality by Design-Compliant Development of a Cyclodextrin-Modified Micellar ElectroKinetic Chromatography Method for the Determination of Trimecaine and Its Impurities.

Author: Marzullo L, Gotti R, Orlandini S, Slavíčková P, Jireš J, Zapadlo M, Douša M, Nekvapilová P, Řezanka P, and Furlanetto S
Subjects: Micelles, Trimecaine, Sodium Dodecyl Sulfate, Borates, Reproducibility of Results, Cyclodextrins chemistry, Chromatography, Micellar Electrokinetic Capillary methods
Abstract: In 2022, the International Council for Harmonisation released draft guidelines Q2(R2) and Q14, intending to specify the development and validation activities that should be carried out during the lifespan of an analytical technique addressed to assess the quality of medicinal products. In the present study, these recommendations were implemented in Capillary Electrophoresis method development for the quality control of a drug product containing trimecaine, by applying Analytical Quality by Design. According to the Analytical Target Profile, the procedure should be able to simultaneously quantify trimecaine and its four impurities, with specified analytical performances. The selected operative mode was Micellar ElectroKinetic Chromatography employing sodium dodecyl sulfate micelles supplemented with dimethyl-β-cyclodextrin, in a phosphate-borate buffer. The Knowledge Space was investigated through a screening matrix encompassing the composition of the background electrolyte and the instrumental settings. The Critical Method Attributes were identified as analysis time, efficiency, and critical resolution values. Response Surface Methodology and Monte Carlo Simulations allowed the definition of the Method Operable Design Region: 21-26 mM phosphate-borate buffer pH 9.50-9.77; 65.0 mM sodium dodecyl sulfate; 0.25-1.29% v / v n -butanol; 21-26 mM dimethyl-β-cyclodextrin; temperature, 22 °C; voltage, 23-29 kV. The method was validated and applied to ampoules drug products.
Published: 2023
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134. Millet Fermented by Different Combinations of Yeasts and Lactobacilli: Effects on Phenolic Composition, Starch, Mineral Content and Prebiotic Activity.

Author: Balli D, Cecchi L, Pieraccini G, Venturi M, Galli V, Reggio M, Di Gioia D, Furlanetto S, Orlandini S, Innocenti M, and Mulinacci N
Abstract: Millet is the sixth-highest yielding grain in the world and a staple crop for millions of people. Fermentation was applied in this study to improve the nutritional properties of pearl millet. Three microorganism combinations were tested: Saccharomyces boulardii (FPM1), Saccharomyces cerevisiae plus Campanilactobacillus paralimentarius (FPM2) and Hanseniaspora uvarum plus Fructilactobacillus sanfranciscensis (FPM3). All the fermentation processes led to an increase in minerals. An increase was observed for calcium: 254 ppm in FPM1, 282 ppm in FPM2 and 156 ppm in the unfermented sample. Iron increased in FPM2 and FPM3 (approx. 100 ppm) with respect the unfermented sample (71 ppm). FPM2 and FPM3 resulted in richer total phenols (up to 2.74 mg/g) compared to the unfermented sample (2.24 mg/g). Depending on the microorganisms, it was possible to obtain different oligopeptides with a mass cut off ≤10 kDalton that was not detected in the unfermented sample. FPM2 showed the highest resistant starch content (9.83 g/100 g) and a prebiotic activity on Bifidobacterium breve B632, showing a significant growth at 48 h and 72 h compared to glucose ( p < 0.05). Millet fermented with Saccharomyces cerevisiae plus Campanilactobacillus paralimentarius can be proposed as a new food with improved nutritional properties to increase the quality of the diet of people who already use millet as a staple food.
Published: 2023
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135. Effect of mobile phase pH on liquid chromatography retention of mepartricin related compounds and impurities as support to the structural investigation by liquid chromatography-mass spectrometry.

Author: Tengattini S, Rimaroli C, Galmozzi MR, Furlanetto S, Massolini G, and Temporini C
Subjects: Acetonitriles, Amines, Antifungal Agents, Chromatography, High Pressure Liquid methods, Chromatography, Liquid, Drug Contamination, Hydrogen-Ion Concentration, Mass Spectrometry, Polyenes, Mepartricin
Abstract: Mepartricin is a semisynthetic polyene macrolide with antifungal and anti-protozoal activities, and it is widely used for the treatment of benign prostatic hyperplasia. Mepartricin is produced by synthetic methyl esterification of the more toxic partricin, and its activity is due to a complex of related compounds. Among them, the main ones are mepartricin B and mepartricin A which are characterized by the presence of a primary and a secondary amine group, respectively. In this work a previously reported HPLC-UV method was properly modified to make it MS-compatible. The selected conditions entail the use of a C18 reverse phase column, and a mobile phase composed by ammonium formate and acetonitrile, with the addition of heptafluorobutyric acid as modifier. The developed method was applied to the characterization of a mepartricin reference standard and a mepartricin experimental batch. All the UV responding peaks, 30 for the standard and 21 for the experimental batch, were successfully detected by MS, allowing to define their m/z values and acquire their fragmentation spectra. For the structural elucidation of isobaric species and, in particular, the identification of toxic partricin-related impurities, the presence of differently ionisable chemical groups was considered, as partricins contain free caboxy-groups, while mepartricins represent their estherified counterparts. A deep study of the effect of mobile phase pH on the chromatographic retention of partricin and mepartricin related compounds was performed in the pH range 2.5-6.5. This study allowed to successfully cluster all the detected species and asses, in the considered batch, the absence of other partricin-related impurities in addition to partricin B and partricin A., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)
Published: 2022
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136. New Trends in the Quality Control of Enantiomeric Drugs: Quality by Design-Compliant Development of Chiral Capillary Electrophoresis Methods.

Author: Orlandini S, Hancu G, Szabó ZI, Modroiu A, Papp LA, Gotti R, and Furlanetto S
Subjects: Stereoisomerism, Quality Control, Pharmaceutical Preparations, Electrophoresis, Capillary methods, Drug Contamination
Abstract: Capillary electrophoresis (CE) is a potent method for analyzing chiral substances and is commonly used in the enantioseparation and chiral purity control of pharmaceuticals from different matrices. The adoption of Quality by Design (QbD) concepts in analytical method development, optimization and validation is a widespread trend observed in various analytical approaches including chiral CE. The application of Analytical QbD (AQbD) leads to the development of analytical methods based on sound science combined with risk management, and to a well understood process clarifying the influence of method parameters on the analytical output. The Design of Experiments (DoE) method employing chemometric tools is an essential part of QbD-based method development, allowing for the simultaneous evaluation of experimental parameters as well as their interaction. In 2022 the International Council for Harmonization (ICH) released two draft guidelines (ICH Q14 and ICH Q2(R2)) that are intended to encourage more robust analytical procedures. The ICH Q14 guideline intends to harmonize the scientific approaches for analytical procedures' development, while the Q2(R2) document covers the validation principles for the use of analytical procedures including the recent applications that require multivariate statistical analyses. The aim of this review is to provide an overview of the new prospects for chiral CE method development applied for the enantiomeric purity control of pharmaceuticals using AQbD principles. The review also provides an overview of recent research (2012-2022) on the applicability of CE methods in chiral drug impurity profiling.
Published: 2022
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137. Assessment of bioaccumulation of glyphosate and aminomethylphosphonic acid in marine mussels using capillary electrophoresis with light-emitting diode-induced fluorescence detection.

Author: Gotti R, Fiori J, Furlanetto S, Orlandini S, Candela M, and Franzellitti S
Subjects: Animals, Bioaccumulation, Borates analysis, Electrophoresis, Capillary, Glycine analogs & derivatives, Humans, Organophosphonates, Organophosphorus Compounds, Soil chemistry, alpha-Amino-3-hydroxy-5-methyl-4-isoxazolepropionic Acid analysis, Glyphosate, Bivalvia, Herbicides analysis, Water Pollutants, Chemical analysis
Abstract: Glyphosate or N-(phosphonomethyl)glycine, widely used as herbicide in agriculture to control weeds and to facilitate harvesting, has been included in Group 2A pollutants (probably carcinogenic to humans) by the International Agency for Research on Cancer (IARC). In intensive agricultural areas, runoff and soil leaching are likely to drive glyphosate to surface waters, where the compound is often detected together with its main microbial metabolite, aminomethylphosphonic acid (AMPA). In the present study a method based on capillary electrophoresis coupled with light-emitting diode-induced fluorescence detection has been developed and validated for the determination of the two compounds in whole soft mass of marine mussels (Mytilus galloprovincialis). The method is based on the acidic hydrolysis of lyophilized tissue using 6 M HCl (oven at 110 °C for 22 h) to release the target analytes; their subsequent derivatization using 4-fluoro-7-nitro-2,1,3-benzoxadiazole, was found to be suitable for the sensitive fluorescence detection. To achieve optimum separation of the analytes from the matrix and degradation reagent interferences, the background electrolyte constituted by borate buffer (pH 9.2, 30 mM) was supplemented with 10 mM heptakis(2,6-di-O-methyl)-β-cyclodextrin. The method was validated for linearity, precision, accuracy, robustness and sensitivity showing LOQ of 0.2 and 1.0 µg/g in fresh tissues, for AMPA and glyphosate, respectively; the recovery values ranged within 88.5 - 94.6% for glyphosate and 70.4 - 76.6% for AMPA. Experimental samples of Mediterranean mussels M. galloprovincialis treated with 100 µg/L or 500 µg/L of both glyphosate and AMPA, showed a dose dependent bioaccumulation of the compounds reaching maximum level of 77.0 µg/g and 11.3 µg/g of AMPA and glyphosate, respectively. The study demonstrates for the first time M. galloprovincialis as potential sentinel organisms for the environmental occurrence of these small amphoteric pollutants., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. The authors declare the following financial interests/personal relationships which may be considered as potential competing interests, (Copyright © 2022 Elsevier B.V. All rights reserved.)
Published: 2022
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138. Quality by Design in optimizing the extraction of (poly)phenolic compounds from Vaccinium myrtillus berries.

Author: Marzullo L, Ochkur O, Orlandini S, Renai L, Gotti R, Koshovyi O, Furlanetto S, and Del Bubba M
Subjects: Antioxidants analysis, Fruit chemistry, Methanol analysis, Phenols analysis, Plant Extracts chemistry, Polyphenols analysis, Solvents analysis, Tandem Mass Spectrometry, Vaccinium myrtillus chemistry
Abstract: Quality by Design was adopted for developing an effective extraction procedure of (poly)phenolic compounds from bilberry (Vaccinium myrtillus L.) fruits, using a pooled sample of berries from different regions of Ukraine. Mechanical solvent extraction, microwave-assisted extraction (MAE) and ultrasonic-assisted extraction (UAE) were investigated by screening matrices. Extraction time (Time, from 5 to 15 min), organic solvent type (OS type, methanol, ethanol and acetone), organic solvent percentage (OS%, from 50% to 90%), sample/extractant ratio (S/E ratio, from 0.025 to 0.1 g mL -1 ), and, only for MAE, extraction temperature (T, from 30 to 60°C), were selected as critical method parameters (CMPs). The spectrophotometric assays total soluble polyphenols (TSP), total monomeric anthocyanins (TMA), and radical scavenging activity (evaluated by the 2,2-diphenyl-1-picrylhydrazyl radical (DPPH), the 2,2'-azino-di-(3-ethylbenzthiazoline sulfonic acid), and the ferric reducing antioxidant power methods) were chosen as critical method attributes (CMAs). The screening procedure allowed for selecting UAE and methanol, while the other CMPs underwent further optimization through Response Surface Methodology. Target values for TSP, TMA and DPPH were selected and the method operable design region (MODR) was defined by means of Monte-Carlo simulations. The optimized conditions, with the corresponding MODR intervals in bracket, were the following: (i) Time, 17 min (15-23 min); OS%, 56% (44-59%); S/E ratio, 0.030 (0.022-0.034) g mL -1 . Under these experimental conditions, CMAs values of the pooled sample were the following (n = 3): TSP=4433±176 mg (+)-catechin eq/100 g dry weight (d.w.); TMA=3575±194 mg cyanidin-3-glucoside eq/100 g d.w.; DPPH=273±5 μg DPPH inhib./mg d.w. The optimized extraction method was tested for matrix effect (ME%) in the UHPLC-MS/MS analysis of 15 anthocyanins and 20 non-anthocyanins individual (poly)phenols commonly found in bilberries, as well as for luteolin, sinapic acid, and pelargonidin-3-glucoside, absent in this fruit and therefore added to the extracts as surrogate standards for evaluating apparent recovery (AR%). |ME%| was in any case ≤ 23% and AR% of the surrogate standards in the range 91-95%, confirming the very good performances of the optimized extraction method., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)
Published: 2022
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139. Analytical quality by design in the development of a solvent-modified micellar electrokinetic chromatography method for the determination of sitagliptin and its related compounds.

Author: Pasquini B, Gotti R, Villar-Navarro M, Douša M, Renai L, Del Bubba M, Orlandini S, and Furlanetto S
Subjects: Reproducibility of Results, Sitagliptin Phosphate, Sodium Dodecyl Sulfate, Solvents, Chromatography, Micellar Electrokinetic Capillary, Micelles
Abstract: A solvent-modified micellar electrokinetic chromatography method was developed following the Quality by Design approach for the simultaneous determination of sitagliptin (SIT), an oral antihyperglycemic drug, and its main impurities derived from the synthesis process. The separation system was identified in the scouting phase and was made by sodium dodecyl sulphate (SDS) micelles with the addition of n-butanol and methanol. The knowledge space was investigated through an asymmetric screening matrix, taking into consideration eight critical method parameters (CMPs) involving the composition of the background electrolyte in terms of buffer concentration and pH, the concentration of surfactants and organic modifiers, and voltage. The critical method attributes (CMAs) were identified as analysis time and the distance between the tail of the electroosmotic flow system peak and the front edge of impurity I 1 (sitagliptin triazole hydrochloride). A Box-Behnken Design was used in response surface methodology for calculating the quadratic models relating the CMPs to the CMAs. From the models it was possible to compute the method operable design region (MODR) through Monte-Carlo simulations. The MODR was identified in the probability maps as the multidimensional zone where the risk of failure to achieve the desired values for the CMAs was lower than 10 %. The experimental conditions corresponding to the working point, with the MODR interval, were the following: background electrolyte, 14 (10-18) mM borate buffer pH 9.20, 100 mM SDS, 13.6 (11.1-16.0) %v/v n-butanol, 6.7 (4.5-8.8) %v/v methanol; voltage and temperature were set to 28 kV and 22 °C, respectively. The developed CE method was validated in accordance with International Council for Harmonisation guidelines and was applied to the analysis of SIT tablets. The routine analysis for the quality control of the pharmaceutical product could be conducted in about 11 min., Competing Interests: Declaration of Competing Interest The authors report no declarations of interest., (Copyright © 2021 Elsevier B.V. All rights reserved.)
Published: 2021
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140. Application of Experimental Design Methodologies in the Enantioseparation of Pharmaceuticals by Capillary Electrophoresis: A Review.

Author: Hancu G, Orlandini S, Papp LA, Modroiu A, Gotti R, and Furlanetto S
Subjects: Humans, Stereoisomerism, Electrophoresis, Capillary methods, Pharmaceutical Preparations chemistry, Pharmaceutical Preparations isolation & purification
Abstract: Chirality is one of the major issues in pharmaceutical research and industry. Capillary electrophoresis (CE) is an interesting alternative to the more frequently used chromatographic techniques in the enantioseparation of pharmaceuticals, and is used for the determination of enantiomeric ratio, enantiomeric purity, and in pharmacokinetic studies. Traditionally, optimization of CE methods is performed using a univariate one factor at a time (OFAT) approach; however, this strategy does not allow for the evaluation of interactions between experimental factors, which may result in ineffective method development and optimization. In the last two decades, Design of Experiments (DoE) has been frequently employed to better understand the multidimensional effects and interactions of the input factors on the output responses of analytical CE methods. DoE can be divided into two types: screening and optimization designs. Furthermore, using Quality by Design (QbD) methodology to develop CE-based enantioselective techniques is becoming increasingly popular. The review presents the current use of DoE methodologies in CE-based enantioresolution method development and provides an overview of DoE applications in the optimization and validation of CE enantioselective procedures in the last 25 years. Moreover, a critical perspective on how different DoE strategies can aid in the optimization of enantioseparation procedures is presented.
Published: 2021
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141. Quality by design optimization of a liquid chromatographic-tandem mass spectrometric method for the simultaneous analysis of structurally heterogeneous pharmaceutical compounds and its application to the rapid screening in wastewater and surface water samples by large volume direct injection.

Author: Renai L, Scordo CVA, Ghadraoui AE, Santana-Viera S, Rodriguez JJS, Orlandini S, Furlanetto S, Fibbi D, Lambropoulou D, and Bubba MD
Subjects: Pharmaceutical Preparations chemistry, Reproducibility of Results, Solid Phase Extraction methods, Wastewater chemistry, Chromatography, Liquid methods, Pharmaceutical Preparations analysis, Tandem Mass Spectrometry methods, Water Pollutants, Chemical analysis
Abstract: This study focused on the Analytical Quality by Design (AQbD) optimization of the chromatographic separation and mass spectrometric detection of a wide group of structurally heterogeneous model pharmaceutical compounds (PhCs) and transformation products (TPs), chosen to cover the challenging issues of the co-presence of compounds characterized by (i) a wide range of physicochemical properties, (ii) the same mass transitions, and (iii) different ionisation modes. Italian consumption of PhCs were also considered as election criteria of target analytes. Octadecyl and pentafluorophenyl stationary phases, acetonitrile/methanol ratios and acidity of the eluents, column temperature, initial organic phase percentage, and elution gradient were investigated by AQbD, aiming at optimizing critical resolutions, sensitivities, and analysis time. Statistically significant models were obtained in most cases with fitting and cross-validation coefficients in the ranges of 0.681-0.998 and 0.514-0.967, respectively. After optimization, the analysis of target analytes was performed in a single chromatographic run, adopting a mixed acquisition mode based on scheduled acquisition windows comprising both single polarity and continuous polarity switching. For most investigated analytes the method provided detection limits in the sub-ng/L to low ng/L range, meeting for macrolides the sensitivity requested by the "Watch List" 2018/840/EU. The optimized method was applied to the direct injection analysis of PhCs and TPs in four wastewater treatment plant (WWTP) effluents and surface water (SW) samples collected in the receiving water bodies. Absolute values of matrix effect were found to be far higher than 20% for most target analytes in most samples. Seventeen PhCs and two TPs were quantified in at least one sample, at the wide concentration range of about 1-3200 ng/L. The most occurring PhCs in both WWTP effluents and SWs were levofloxacin (202-1239 and 100-830 ng/L), furosemide (865-3234 and 230-880 ng/L), ketoprofen (295-1104 and 270-490 ng/L), and ibuprofen (886-3232 and 690-1440 ng/L)., Competing Interests: Declaration of Competing Interest None, (Copyright © 2021. Published by Elsevier B.V.)
Published: 2021
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142. Development of novel cocrystal-based active food packaging by a Quality by Design approach.

Author: Bianchi F, Fornari F, Riboni N, Spadini C, Cabassi CS, Iannarelli M, Carraro C, Mazzeo PP, Bacchi A, Orlandini S, Furlanetto S, and Careri M
Subjects: Acrolein analogs & derivatives, Acrolein chemistry, Acrolein pharmacology, Anti-Infective Agents pharmacology, Crystallization, Cymenes chemistry, Cymenes pharmacology, Escherichia coli drug effects, Food Microbiology, Food Quality, Microbial Sensitivity Tests, Salmonella typhimurium drug effects, Staphylococcus aureus drug effects, Thymol chemistry, Thymol pharmacology, Anti-Infective Agents chemistry, Food Packaging methods, Oils, Volatile chemistry
Abstract: A way to reduce food waste is related to the increase of the shelf-life of food as a result of improving the package type. An innovative active food packaging material based on cocrystallization of microbiologically active compounds present in essential oils i.e. carvacrol, thymol and cinnamaldehyde was developed following the Quality by Design principles. The selected active components were used to produce antimicrobial plastic films with solidified active ingredients on their surface characterized by antimicrobial properties against four bacterial strains involved in fruit and vegetable spoilage. The developed packaging prototypes exhibited good antimicrobial activity in vitro providing inhibition percentage of 69 (±15)% by contact and inhibition diameters of 32 (±6) mm in the gas phase, along with a prolonged release of the active components. Finally, the prolonged shelf-life of grape samples up to 7 days at room temperature was demonstrated., (Copyright © 2021 Elsevier Ltd. All rights reserved.)
Published: 2021
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143. Preface.

Author: Barbas C, Chankvetadze B, Furlanetto S, Ganzera M, Haginaka J, Li S, Moaddel R, Ozkan S, and Veuthey JL
Subjects: Periodicals as Topic, Biomedical Technology, Chemistry, Pharmaceutical
Published: 2020
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144. Quality by Design as a risk-based strategy in pharmaceutical analysis: Development of a liquid chromatography-tandem mass spectrometry method for the determination of nintedanib and its impurities.

Author: Pasquini B, Orlandini S, Furlanetto S, Gotti R, Del Bubba M, Boscaro F, Bertaccini B, Douša M, and Pieraccini G
Subjects: Indoles chemistry, Monte Carlo Method, Probability, Quality Control, Reproducibility of Results, Risk, Solvents, Chromatography, Liquid methods, Indoles analysis, Tandem Mass Spectrometry methods
Abstract: Nintedanib (NIN) is a tyrosine kinase inhibitor recently approved for the treatment of idiopathic pulmonary fibrosis. As a new drug, no monograph is available so far in official compendia. A liquid chromatography-tandem mass spectrometry method is presented for the simultaneous determination of NIN and its seven potential impurities. The risk-based approach of Analytical Quality by Design was applied in method development. The critical method parameters (CMPs) were the type of organic solvent in the mobile phase, formic acid percentage, column flow rate, oven temperature, gradient slope of organic eluent. The critical method attributes (CMAs) were selected as analysis time and selectivity between the main compound NIN and the adjacent peaks. Design of Experiments methodology was effectively employed for establishing the relationship between the CMPs and the CMAs. In the scouting step, a Restek Ultra AQ C18 (100 × 2.1 mm, 2.7 µm) core-shell column was selected, and then the effects of different levels of the five CMPs on the CMAs were evaluated by means of a 3 5 //16 symmetric screening matrix. A Box-Behnken Design made it possible to obtain detailed maps of predicted CMAs throughout the investigated experimental domain, pointing out the presence of interaction and quadratic effects. The probability of meeting the specifications for the CMAs was calculated by Monte-Carlo simulations, performing a risk analysis and drawing risk of failure maps, which were used to visualize and define the method operable design region (MODR) with a probability π ≥ 90%. The final working conditions (enclosing the MODR interval) were as follows: methanol as organic solvent; formic acid percentage, 0.15% v/v; flow rate, 0.40 mL min -1 (0.37-0.43 mL min -1 ); oven temperature, 40 °C (38-40 °C); gradient slope of organic eluent, 14.00% eluent B min -1 (12.85-15.15% eluent B min -1 ). The resulting analysis time was about 10 min. Validation was carried out according to International Council for Harmonisation guidelines and the optimized method was applied to the analysis of NIN soft capsules for quality control purposes., (Copyright © 2019. Published by Elsevier B.V.)
Published: 2020
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145. Application of an HPLC-MS/MS method for Teicoplanin drug substance and related impurities, part 2: Identity assignment of related impurities.

Author: Tengattini S, Corana F, Bianchi D, Marrubini G, Colombo R, Furlanetto S, Terreni M, and Temporini C
Subjects: Anti-Bacterial Agents chemistry, Drug Contamination prevention & control, Teicoplanin chemistry, Anti-Bacterial Agents administration & dosage, Chromatography, High Pressure Liquid methods, Tandem Mass Spectrometry methods, Teicoplanin analysis
Abstract: A liquid chromatographic MS-compatible method was applied to the structural elucidation of Teicoplanin for identification CRS components. The method, previously developed by our group, involves the use of LiChrospher 100 RP-18 column with a mobile phase composed of ammonium formate 25 mM at pH 6.00 and acetonitrile (ACN). All the peaks with a 0.10% UV area, largely above the disregard limit of 0.15% as fixed by EMA, were considered and submitted to MS/MS fragmentation experiments. The study of MS/MS spectrum collected for Teicoplanin complex major component (namely A 2-2 ) allowed to elucidate the fragmentation pathway and enabled the successful identity assignment of all the 42 detected species. Elution order was also rationalized. An in house batch sample of Teicoplanin was analyzed and, while the 86% of the detected species were structurally identical to those in Teicoplanin for identification CRS, five new derivatives were revealed and structurally characterized. In both the Teicoplanin samples, all the considered species were found to have a Teicoplanin-like structure that allows their classification as closely related impurities, with a significant implication in their qualification threshold., (Copyright © 2019 Elsevier B.V. All rights reserved.)
Published: 2019
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146. Analytical quality by design: Development and control strategy for a LC method to evaluate the cannabinoids content in cannabis olive oil extracts.

Author: Deidda R, Avohou HT, Baronti R, Davolio PL, Pasquini B, Del Bubba M, Hubert C, Hubert P, Orlandini S, and Furlanetto S
Subjects: Bayes Theorem, Chromatography, High Pressure Liquid, Italy, Reproducibility of Results, Cannabidiol analysis, Cannabis chemistry, Dronabinol analysis, Medical Marijuana analysis, Olive Oil chemistry, Plant Extracts chemistry, Research Design standards
Abstract: Cannabidiol (CBD) and Δ 9 -tetrahydrocannabinol (Δ 9 -THC) are considered as the most interesting cannabinoids in Cannabis sativa L. for the clinical practice. Since 2013, the Italian law allows pharmacists to prepare and dispense cannabis extracts to patients under medical prescription, and requires the evaluation of CBD and Δ 9 -THC content in cannabis extracts before sale. Cannabis olive oil extracts are prepared from dried female cannabis inflorescences, but a standard protocol is still missing. In this study, a fast RP-HPLC/UV method has been developed to quantify CBD and Δ 9 -THC in cannabis olive oil extracts. The analytical quality by design strategy has been applied to the method development, setting critical resolution and total analysis time as critical method attributes (CMAs), and selecting column temperature, buffer pH and flow rate as critical method parameters. Information from Doehlert Design in response surface methodology combined to Monte-Carlo simulations led to draw the risk of failure maps and to identify the method operable design region. The method was validated according to the International Council for Harmonisation of Technical Requirements for Pharmaceuticals for Human Use (ICH) guidelines and then implemented in routine analysis. A control strategy based on system control charts was planned to monitor the developed method performances. Evaluation data were recorded over a period of one year of routine use, and both the CMAs showed values within the specifications in every analysis performed. Hence, a new risk evaluation for the future performances of the method was achieved by using a Bayesian approach based on the routine use data, computing the future distribution of the two CMAs. Finally, a study focusing on the monitoring of CBD and Δ 9 -THC concentrations in cannabis olive oil extracts was carried out. The developed method was applied to 459 extracts. The statistical analysis of the obtained results highlighted a wide variability in terms of concentrations among different samples from the same starting typology of cannabis, underlining the compelling need of a standardised procedure to harmonise the preparation of the extracts., (Copyright © 2019 Elsevier B.V. All rights reserved.)
Published: 2019
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147. Editorial for Sergio and Sandor.

Author: Barbas C, Chankvetadze B, Furlanetto S, Haginaka J, Li S, Moaddel R, and Veuthey JL
Subjects: Humans, Chemistry Techniques, Analytical, Periodicals as Topic, Technology, Pharmaceutical
Published: 2019
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148. Quality by design compliant strategy for the development of a liquid chromatography-tandem mass spectrometry method for the determination of selected polyphenols in Diospyros kaki.

Author: Ancillotti C, Orlandini S, Ciofi L, Pasquini B, Caprini C, Droandi C, Furlanetto S, and Del Bubba M
Subjects: Antioxidants analysis, Food Analysis instrumentation, Fruit chemistry, Chromatography, Liquid, Diospyros chemistry, Food Analysis methods, Polyphenols analysis, Tandem Mass Spectrometry
Abstract: Diospyros kaki fruits possess great beneficial properties for human health due to their strong antioxidant and antiradical activities related to the high level of bioactive compounds and particularly polyphenols. In this paper a rapid and efficient liquid chromatography-tandem mass spectrometry method for the determination of 38 polyphenolic compounds in Diospyros kaki flesh was developed. The optimization of the chromatographic method was performed applying a Quality by Design approach, which is unexplored in the field of food analysis. The Critical Method Attributes (CMAs) were the critical resolutions of some isobaric compounds and analysis time. The Critical Methods Parameters (CMPs) were related to the characteristics of both the mobile phase and the column: flow rate, temperature, starting organic phase concentration of the mobile phase, formic acid percentage in the eluents, type of organic solvent in the mobile phase and gradient of organic eluents. The effects of the CMPs on the CMAs were evaluated by experimental design, at first carrying out a screening phase by an asymmetric screening matrix and then applying Response Surface Methodology by a Doehlert Design. The quadratic polynomial models postulated to link the CMAs to CMPs were calculated and the Method Operable Design Region was identified with the aid of Monte Carlo simulations as the multidimensional combination of the CMPs that satisfied the requirements for the CMAs with a probability ≥90%. The developed method was applied to real samples obtained by the extraction of Diospyros kaki flesh from two different cultivars (Rojo Brillante and Kaki Tipo), making it possible to obtain extensive information on their polyphenolic profiles., (Copyright © 2018 Elsevier B.V. All rights reserved.)
Published: 2018
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149. Chiral capillary zone electrophoresis in enantioseparation and analysis of cinacalcet impurities: Use of Quality by Design principles in method development.

Author: Pasquini B, Orlandini S, Villar-Navarro M, Caprini C, Del Bubba M, Douša M, Giuffrida A, Gotti R, and Furlanetto S
Subjects: Drug Contamination, Hydrogen-Ion Concentration, Monte Carlo Method, Probability, Risk Assessment, Solvents, Stereoisomerism, beta-Cyclodextrins chemistry, gamma-Cyclodextrins chemistry, Cinacalcet chemistry, Cinacalcet isolation & purification, Electrophoresis, Capillary methods
Abstract: A capillary electrophoresis method for the simultaneous determination of the enantiomeric purity and of impurities of the chiral calcimimetic drug cinacalcet hydrochloride has been developed following Quality by Design principles. The scouting phase was aimed to select the separation operative mode and to identify a suitable chiral selector. Among the tested cyclodextrins, (2-carboxyethyl)-β-cyclodextrin and (2-hydroxypropyl)-γ-cyclodextrin (HPγCyD) showed good chiral resolving capabilities. The selected separation system was solvent-modified capillary zone electrophoresis with the addition of HPγCyD and methanol. Voltage, buffer pH, methanol concentration and HPγCyD concentration were investigated as critical method parameters by a multivariate strategy. Critical method attributes were represented by enantioresolution and analysis time. A Box-Behnken Design allowed the contour plots to be drawn and quadratic and interaction effects to be highlighted. The Method Operable Design Region (MODR) was identified by applying Monte-Carlo simulations and corresponded to the multidimensional zone where both the critical method attributes fulfilled the requirements with a desired probability π≥90%. The working conditions, with the MODR limits, corresponded to the following: capillary length, 48.5cm; temperature, 18°C; voltage, 26kV (26-27kV); background electrolyte, 150mM phosphate buffer pH 2.70 (2.60-2.80), 3.1mM (3.0-3.5mM) HPγCyD; 2.00% (0.00-8.40%) v/v methanol. Robustness testing was carried out by a Plackett-Burman matrix and finally a method control strategy was defined. The complete separation of the analytes was obtained in about 10min. The method was validated following the International Council for Harmonisation guidelines and was applied for the analysis of a real sample of cinacalcet hydrochloride tablets., (Copyright © 2018 Elsevier B.V. All rights reserved.)
Published: 2018
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150. Combining excitation-emission matrix fluorescence spectroscopy, parallel factor analysis, cyclodextrin-modified micellar electrokinetic chromatography and partial least squares class-modelling for green tea characterization.

Author: Casale M, Pasquini B, Hooshyari M, Orlandini S, Mustorgi E, Malegori C, Turrini F, Ortiz MC, Sarabia LA, and Furlanetto S
Subjects: Cyclodextrins metabolism, Factor Analysis, Statistical, Least-Squares Analysis, Spectrometry, Fluorescence methods, Tea metabolism, Chromatography, Micellar Electrokinetic Capillary methods, Cyclodextrins chemistry, Tea chemistry
Abstract: In this study, an alternative analytical approach for analyzing and characterizing green tea (GT) samples is proposed, based on the combination of excitation-emission matrix (EEM) fluorescence spectroscopy and multivariate chemometric techniques. The three-dimensional spectra of 63 GT samples were recorded using a Perkin-Elmer LS55 luminescence spectrometer; emission spectra were recorded between 295 and 800 nm at excitation wavelength ranging from 200 to 290 nm, with excitation and emission slits both set at 10 nm. The excitation and emission profiles of two factors were obtained using Parallel Factor Analysis (PARAFAC) as a 3-way decomposition method. In this way, for the first time, the spectra of two main fluorophores in green teas have been found. Moreover, a cyclodextrin-modified micellar electrokinetic chromatography method was employed to quantify the most represented catechins and methylxanthines in a subset of 24 GT samples in order to obtain complementary information on the geographical origin of tea. The discrimination ability between the two types of tea has been shown by a Partial Least Squares Class-Modelling performed on the electrokinetic chromatography data, being the sensitivity and specificity of the class model built for the Japanese GT samples 98.70% and 98.68%, respectively. This comprehensive work demonstrates the capability of the combination of EEM fluorescence spectroscopy and PARAFAC model for characterizing, differentiating and analyzing GT samples., (Copyright © 2018 Elsevier B.V. All rights reserved.)
Published: 2018
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