366 results on '"Herman, L."'
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2. The Characterization of Linear Polyethylene SRM's 1482, 1483, and 1484. II. Number-Average Molecular Weights by Membrane Osmometry
- Author
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Peter H Verdier and Herman L. Wagner
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Linear low-density polyethylene ,Systematic error ,chemistry.chemical_compound ,Chromatography ,Membrane ,Molecular mass ,Osmometer ,Chemistry ,General Engineering ,Molar mass distribution ,Polyethylene ,Characterization (materials science) ,Physics and Chemistry - Abstract
Linear polyethylene Standard Reference Materials SRM 1482, 1483, and 1484 are certified for number-average molecular weight M(n). In this paper the experimental procedures employed for the determination of M(n) for these materials by membrane osmometry are described, and the techniques used to analyze the data and to estimate limits of systematic error are discussed.
- Published
- 2021
3. The Characterization of Linear Polyethylene SRM's 1482, 1483, and 1484. IV. Limiting Viscosity Numbers by Capillary Viscometry
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Peter H Verdier and Herman L. Wagner
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Linear low-density polyethylene ,Viscosity ,chemistry.chemical_compound ,Chemistry ,Capillary action ,General Engineering ,Analytical chemistry ,Viscometer ,Molar mass distribution ,Limiting ,Polyethylene ,Characterization (materials science) ,Physics and Chemistry - Abstract
Linear polyethylene Standard Reference Materials SRM 1482, 1483, and 1484 are certified for limiting viscosity number in 1,2,4-trichlorobenzene and 1-chloronaphthalene at 130 °C. In this paper the experimental procedures employed for the determination of limiting viscosity numbers for these materials by capillary viscometry are described, and the techniques used to analyze the data and to estimate limits of systematic error are discussed.
- Published
- 2021
4. Optimum Power in a Multi-Span DWDM System Limited by Non-Linear Effects
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Herman L. Offerhaus, Victor Golikov, Manuel May-Alarcon, J. R. Ek-Ek, R. Sanchez-Lara, Jose Alfredo Alvarez-Chavez, and Optical Sciences
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Optical amplifier ,Amplified spontaneous emission ,Materials science ,business.industry ,Amplifier ,chemistry.chemical_element ,Physics::Optics ,02 engineering and technology ,021001 nanoscience & nanotechnology ,01 natural sciences ,Noise (electronics) ,Non-linear effects ,010309 optics ,Erbium ,chemistry ,Wavelength-division multiplexing ,0103 physical sciences ,Dispersion (optics) ,Optoelectronics ,0210 nano-technology ,business - Abstract
Limitations imposed by Four-Wave Mixing (FWM), Amplified Spontaneous Emission (ASE), dispersion and Stimulated Raman Scattering (SRS) on a multi-spam DWDM system are theoretically studied. In this work, expression for the linear dispersion parameter D has been defined as a function of number of channels in order to separate FWM and SRS effects and calculates both maximum fibre length and optimum power. Additionally, our simulation results consider the effect of ASE noise from Erbium Doped Fibre Amplifiers (EDFAs). This theoretical analysis yields a set of design criteria from optimized multi-span DWDM systems.
- Published
- 2018
5. Chandra/LETGS Studies of the Collisional Plasma in 4U 1626-67
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Paul B. Hemphill, Norbert S. Schulz, Herman L. Marshall, and Deepto Chakrabarty
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Physics ,High Energy Astrophysical Phenomena (astro-ph.HE) ,Plasma parameters ,Astrophysics::High Energy Astrophysical Phenomena ,chemistry.chemical_element ,White dwarf ,FOS: Physical sciences ,Astronomy and Astrophysics ,Radius ,Astrophysics ,Neon ,Neutron star ,chemistry ,Space and Planetary Science ,Emission spectrum ,Low Mass ,Astrophysics - High Energy Astrophysical Phenomena ,Astrophysics::Galaxy Astrophysics ,Line (formation) - Abstract
We present an analysis of \chandra/LETGS observations of the ultracompact X-ray binary (UCXB) 4U 1626$-$67, continuing our project to analyze the existing Chandra gratings data of this interesting source. The extremely low mass, hydrogen-depleted donor star provides a unique opportunity to study the properties and structure of the metal-rich accreted plasma. There are strong, double-peaked emission features of OVII-VIII and Ne IX-X, but no other identified emission lines are detected. Our spectral fit simultaneously models the emission line profiles and the plasma parameters, using a two-temperature collisionally-ionized plasma. Based on our line profile fitting, we constrain the inclination of the system to 25--60$^{\circ}$ and the inner disk radius to $\sim$1500 gravitational radii, in turn constraining the donor mass to $\lesssim$0.026 M_sun, while our plasma modeling confirms previous reports of high neon abundance in the source, establishing a Ne/O ratio in the system of $0.47 \pm 0.04$, while simultaneously estimating a very low Fe/O ratio of $0.0042 \pm 0.0008$ and limiting the Mg/O ratio to less than 1% by number. We discuss these results in light of previous work., Comment: accepted by the Astrophysical Main Journal, 16 pages, 13 figures
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- 2021
- Full Text
- View/download PDF
6. Visualizing resonances in the complex plane with vibrational phase contrast coherent anti-stokes Raman scattering
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Jurna, Martin, Garbacik, Erik T., Korterik, Jeroen P., Herek, Jennifer L., Otto, Cees, and Offerhaus, Herman L.
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Resonance -- Research ,Vibration -- Research ,Raman effect -- Research ,Chemistry - Abstract
In coherent anti-Stokes Raman scattering (CARS), the emitted signal carries both amplitude and phase information of the molecules in the focal volume. Most CARS experiments ignore the phase component, but its detection allows for two advantages over intensity-only CARS. First, the pure resonant response can be determined, and the nonresonant background rejected, by extracting the imaginary component of the complex response, enhancing the sensitivity of CARS measurements. Second, selectivity is increased via determination of the phase and amplitude, allowing separation of individual molecular components of a sample even when their vibrational bands overlap. Here, using vibrational phase contrast CARS (VPC-CARS), we demonstrate enhanced sensitivity in quantitative measurements of ethanol/methanol mixtures and increased selectivity in a heterogeneous mixture of plastics and water. This powerful technique opens a wide range of possibilities for studies of complicated systems where overlapping resonances limit standard methodologies. 10.1021/ac101453s
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- 2010
7. Chemical imaging of oral solid dosage forms and changes upon dissolution using coherent anti-Stokes Raman scattering microscopy
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Windbergs, Maike, Jurna, Martin, Offerhaus, Herman L., Herek, Jennifer L., Kleinebudde, Peter, and Strachan, Clare J.
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Imaging systems -- Methods ,Oral medication -- Properties ,Oral medication -- Models ,Dissolution (Chemistry) -- Research ,Raman effect -- Research ,Raman spectroscopy -- Methods ,Raman spectroscopy -- Usage ,Pharmaceutical research -- Methods ,Solid state physics -- Research ,Drugs -- Product/Service Evaluations ,Drugs -- Methods ,Chemistry - Abstract
Dissolution testing is a crucial part of pharmaceutical dosage form investigations and is generally performed by analyzing the concentration of the released drug in a defined volume of flowing dissolution medium. As solid-state properties of the components affect dissolution behavior to a large and sometimes even unpredictable extent there is a strong need for monitoring and especially visualizing solid-state properties during dissolution testing. In this study coherent anti-Stokes Raman scattering (CARS) microscopy was used to visualize the solid-state properties of lipid-based oral dosage forms containing the model drug theophylline anhydrate during dissolution in real time. The drug release from the dosage form matrix was monitored with a spatial resolution of about 1.5 [micro]m. In addition, as theophylline anhydrate tends to form the less soluble monohydrate during dissolution, CARS microscopy allowed the solid-state transformation of the drug to be spatially visualized. The results obtained by CARS microscopy revealed that the method used to combine lipid and active ingredient into a sustained release dosage form can influence the physicochemical behavior of the drug during dissolution. In this case, formation of theophylline monohydrate on the surface was visualized during dissolution with tablets compressed from powdered mixtures but not with solid lipid extrudates.
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- 2009
8. A First Step towards Determining the Ionic Content in Water with an Integrated Optofluidic Chip Based on Near-Infrared Absorption Spectroscopy
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Elmar C. Fuchs, Herman L. Offerhaus, Gerwin W. Steen, Adam D. Wexler, and Optical Sciences
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optofluidic chip ,Fabrication ,Materials science ,business.industry ,Overtone ,010401 analytical chemistry ,Near-infrared spectroscopy ,Ionic bonding ,interferometry ,01 natural sciences ,0104 chemical sciences ,Ion ,010309 optics ,near IR spectroscopy ,chemistry.chemical_compound ,Interferometry ,Silicon nitride ,chemistry ,0103 physical sciences ,Optoelectronics ,business ,Spectroscopy - Abstract
In this work, we present a feasibility study of integrated optofluidic chips to measure the ionic content in water using differential absorption spectroscopy. The second overtone of the OH-stretch vibration of water is used as indicator for both the type and concentration of the dissolved ions. The optofluidic chips are based on silicon nitride (TripleX) containing Mach&ndash, Zehnder interferometers (MZI) with two 5 cm sensing paths for the sample and reference arms, respectively. Simulations show that, theoretically, the determination of both the type and concentration of a mixture of four electrolytes is possible with the techniques presented. However, the performance of the chips deviated from the expected results due to the insufficient reproducibility and precision in the fabrication process. Therefore, at this early stage, the chips presented here could only determine the ion concentration, but not differentiate between the different ion types. Still, this work represents the first steps towards the realization of an online and real-time sensor of ionic content in water.
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- 2020
- Full Text
- View/download PDF
9. Thermal effects on tapered holmium-doped fiber amplifiers
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Daniel Enrique Ceballos-herrera, Rafael Sanchez-lara, Jose L. Vazquez-avila, Jose Alfredo Alvarez-Chavez, Herman L. Offerhaus, and Optical Sciences
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Optical amplifier ,Materials science ,business.industry ,Optical engineering ,General Engineering ,chemistry.chemical_element ,Physics::Optics ,Signal ,Atomic and Molecular Physics, and Optics ,chemistry ,Fiber laser ,Optoelectronics ,Fiber ,business ,Holmium ,Absorption (electromagnetic radiation) ,Sensitivity (electronics) - Abstract
The temperature response of a tapered holmium-doped fiber amplifier and its impact in the performance of fiber lasers and temperature fiber sensors has numerically been analyzed. Different pump schemes and different longitudinal shapes of the tapered-doped fiber were investigated, and it was found that a parabolic shape of the tapered fiber amplifier in a co-propagating pump scheme shows the highest sensitivity to temperature changes. In particular, the temperature sensitivity of the amplified signal was 2.5 × 10 − 4 ° C for 1 W of pump power and 1 m of doped fiber length. In addition, this sensitivity can be increased up to 10 times for fiber lengths shorter than 1 m and pump powers lower than 300 mW. Our results can be used to describe the temperature response of tapered fiber amplifiers in the mid-infrared spectral region and contribute with new information for the development of fiber lasers and fiber temperature sensors.
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- 2020
10. Label-Free Prostate Cancer Detection by Characterization of Extracellular Vesicles Using Raman Spectroscopy
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Wooje Lee, Afroditi Nanou, Linda Gerritdina Rikkert, Leon W.M.M. Terstappen, Frank A. W. Coumans, Cees Otto, Herman L. Offerhaus, Optical Sciences, Medical Cell Biophysics, ACS - Atherosclerosis & ischemic syndromes, ACS - Microcirculation, CCA - Imaging and biomarkers, and Biomedical Engineering and Physics
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Blood Platelets ,Male ,0301 basic medicine ,Erythrocytes ,Prostate cancer cell ,UT-Hybrid-D ,02 engineering and technology ,Spectrum Analysis, Raman ,Extracellular vesicles ,Article ,Analytical Chemistry ,Extracellular Vesicles ,03 medical and health sciences ,Prostate cancer ,symbols.namesake ,LNCaP ,medicine ,Humans ,Label free ,chemistry.chemical_classification ,Biomolecule ,Prostatic Neoplasms ,021001 nanoscience & nanotechnology ,medicine.disease ,Biomarker (cell) ,030104 developmental biology ,chemistry ,symbols ,Biophysics ,0210 nano-technology ,Raman spectroscopy - Abstract
Mammalian cells release extracellular vesicles (EVs) into their microenvironment that travel the entire body along the stream of bodily fluids. EVs contain a wide range of biomolecules. The transported cargo varies depending on the EV origin. Knowledge of the origin and chemical composition of EVs can potentially be used as a biomarker to detect, stage, and monitor diseases. In this paper, we demonstrate the potential of EVs as a prostate cancer biomarker. A Raman optical tweezer was employed to obtain Raman signatures from four types of EV samples, which were red blood cell- and platelet-derived EVs of healthy donors and the prostate cancer cell lines- (PC3 and LNCaP) derived EVs. EVs’ Raman spectra could be clearly separated/classified into distinct groups using principal component analysis (PCA) which permits the discrimination of the investigated EV subtypes. These findings may provide new methodology to detect and monitor early stage cancer.
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- 2018
11. Optical properties of highly-crystalline tin-doped indium oxide films in their near-zero permittivity spectral region
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Herman L. Offerhaus, Israel De Leon, Hosein Ghobadi, Yury Smirnov, Monica Morales-Masis, Jose Alfredo Alvarez-Chavez, Optical Sciences, MESA+ Institute, and Inorganic Materials Science
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chemistry.chemical_compound ,UT-Gold-D ,Materials science ,chemistry ,business.industry ,Doping ,Oxide ,Optoelectronics ,chemistry.chemical_element ,business ,Indium ,Electronic, Optical and Magnetic Materials - Abstract
Transparent conducting oxides (TCOs) have recently attracted much attention in the fields of optics and photonics because of their outstanding linear and nonlinear optical response in the near-zero permittivity spectral region. The optical response of these materials can be further enhanced by optimizing the material properties through fabrication. In particular, two important TCO parameters affecting the strength of the optical interactions are the optical mobility and effective mass of free electrons. In this work, we fabricate epitaxial, highly-textured, and polycrystalline tin-doped indium oxide (ITO) films to experimentally study the effect of the crystal quality on the optical mobility and effective electron mass, and on the optical properties of the material in the near-zero permittivity spectral region. Compared to polycrystalline ITO, we report an increase in the optical mobility from 38 to 67 cm2/Vs and a reduction in the effective mass from 0.3 m0 to 0.24 m0 in oxygen-deficient epitaxially grown ITO films. The improved material parameters reduces the imaginary part of the permittivity (from 0.56 to 0.42) and results in a steeper material dispersion for the high-crystal-quality ITO films. Based on these results, an analysis of the figure of merit for nonlinear refraction reveals that epi- and tex-ITO films can achieve a stronger nonlinear response than poly-ITO samples. Our results show that controlling the free-electron optical mobility and effective mass through crystal quality along with tuning the free-electron density allows for tailoring simultaneously the near-zero-permittivity wavelength and the optical losses at that wavelength, which is of utmost importance for the ENZ photonics applications.
- Published
- 2021
12. Improvement of the output characteristics of magnetrons using the transparent cathode
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Bosman, Herman L., Fuks, Mikhail I., Prasad, Sarita, and Schamiloglu, Edl
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Magnetrons -- Research ,Electric waves -- Research ,Electromagnetic radiation -- Research ,Electromagnetic waves -- Research ,Computer-generated environments -- Analysis ,Computer simulation -- Analysis ,Business ,Chemistry ,Electronics ,Electronics and electrical industries - Abstract
The output characteristics of magnetrons can be significantly improved by using a cathode that is transparent to the synchronous electromagnetic fields thereby providing improved conditions for fast conversion of the electrons' potential energy into electromagnetic energy. The transparent cathode consists of separate longitudinal metal strips, arranged to forma cylindrical surface, that act as individual electron emitters. Favorable prebunching of electrons to excite the desired operating mode is provided by a suitable choice of the number and azimuthal position of the cathode strips. The strong azimuthal wave field in the cathode region rapidly captures the prebunched electrons into rotating spokes forming the anode current. This process provides faster start-of-oscillations than priming using a solid cathode. The strong wave field in the electron sheath over the cathode, for any sheath thickness, gives the possibility of improving the efficiency by concomitantly increasing the applied voltage and magnetic field. Computer simulations of the A6 magnetron driven both by a solid and transparent cathode demonstrate the advantages of this approach. Index Terms--Buneman-Hartree threshold, cathode and magnetic priming, electron spokes, magnetron, synchronous interaction.
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- 2006
13. Rapid kinematic bunching and parametric instability in a crossed-field gap with a periodic magnetic field
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Neculaes, V. Bogdan, Pengvanich, P., Hidaka, Y., Lau, Y.Y., Gilgenbach, Ronald M., White, William M., Jones, Michael C., Bosman, Herman L., and Luginsland, John W.
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Microwaves -- Research ,Magnetrons -- Research ,Plasma physics -- Research ,Business ,Chemistry ,Electronics ,Electronics and electrical industries - Abstract
Single particle orbit considerations show that the cycloidal orbits of electrons in a gap with crossed electric and magnetic fields lead to rapid spoke formation if the external magnetic field has a periodic variation. This spoke formation is primarily a result of kinematic bunching, which is independent of the radio frequency electric field and of the space charge field. A parametric instability in the orbits, which brings a fraction of the electrons from the cathode to the anode region, is discovered. These results are examined in light of the recent rapid startup, low noise magnetron experiments and simulations that employed periodic, azimuthal perturbations in the axial magnetic field. Index Terms--Low-noise, magnetron, microwave, parametric instability, vacuum electronics.
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- 2005
14. Magnetic priming effects on noise, startup, and mode competition in magnetrons
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Neculaes, V. Bogdan, Jones, Michael C., Gilgenbach, Ronald M., Lau, Y.Y., Luginsland, John W., Hoff, Brad W., White, William, M., Jordan, N.M., Pengvanich, P., Hidaka, Y., and Bosman, Herman L.
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Magnetism -- Research ,Microwaves -- Research ,Business ,Chemistry ,Electronics ,Electronics and electrical industries - Abstract
Azimuthally varying axial magnetic fields have been utilized to perform 'magnetic priming' of magnetrons for rapid startup, low noise, and mode control. An overview of the latest magnetic priming experimental and simulation results are presented in this paper. Magnetic priming experiments in dc-operating microwave oven magnetrons show sideband elimination, even with the cathode heater turned off. Simulations using three three-dimensional (3-D) improved concurrent electromagnetic particle-in-cell (ICEPIC) codes with two different computational algorithms recover the oven magnetron experimental results obtained with magnetic priming including fast mode growth, rapid spoke formation, and the tendency toward lower noise operation. A new, axially symmetric, azimuthally varying magnetic field geometry for oven magnetrons is explored and preliminary results are reported. Simulations using two-dimensional (2-D) MAGIC code for the University of Michigan/Titan relativistic magnetron show that the oscillation startup time can be dramatically decreased (almost by a factor of 3) and mode competition can be suppressed with magnetic priming. Index Terms--High-power microwaves, magnetron, microwave noise, mode competition.
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- 2005
15. Power absorption by thin films on microwave windows
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Bosman, Herman L., Lau, Yue Ying, and Gilgenbach, Ronald M.
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Microwaves -- Research ,Thin films -- Research ,Dielectric films -- Research ,Business ,Chemistry ,Electronics ,Electronics and electrical industries - Abstract
A recent theory for power absorption by continuous thin surface films on microwave windows is compared with experimental data, focusing on diamond gyrotron windows. Two measurement techniques, the dc method by Jory and the radio-frequency (RF) method by Heidinger et al., are used to estimate the fraction of the average power absorbed by the thin films, assuming that these films are spread uniformly over the window surface. Both measurements indicate that, on the average, about a fraction of 1% of the incident power is absorbed by the thin films, even though the local absorption coefficient may reach 50%. Discontinuous surface films, where the surface contaminants have a patchy or island structure, are modeled with an equivalent transmission line circuit. The discontinuous film model is also applied to alumina windows with TiN coatings, and the results are compared with the continuous film model. Index Terms--Contaminant, microwave window, thin film.
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- 2004
16. Tethering Cells via Enzymatic Oxidative Crosslinking Enables Mechanotransduction in Non‐Cell‐Adhesive Materials (Adv. Mater. 42/2021)
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Alexandra M. Smink, Niels G A Willemen, Marcel Karperien, Tom Kamperman, Bart J. de Haan, Wooje Lee, Herman L. Offerhaus, Su Ryon Shin, João F. Crispim, Martin Peter Neubauer, Jeroen Leijten, Sieger Henke, Pieter J. Dijkstra, and Paul de Vos
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chemistry.chemical_classification ,Materials science ,Tethering ,Mechanical Engineering ,Cell ,Inflammation ,Oxidative phosphorylation ,Cell biology ,Adhesive materials ,medicine.anatomical_structure ,Enzyme ,chemistry ,Single-cell analysis ,Mechanics of Materials ,medicine ,General Materials Science ,Mechanotransduction ,medicine.symptom - Published
- 2021
17. Molecular basis for enantioselectivity of lipase from Chromobacterium viscosum toward the diesters of 2,3-dihydro-3-(4'-hydroxyphenyl)-1,1,3-trimethyl-1H-inden-5-ol
- Author
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Gascoyne, David G., Finkbeiner, Herman L., Chan, Kwok P., Gordon, Janet L., Stewart, Kevin R., and Kazlauskas, Romas J.
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Chemistry, Organic -- Research ,Lipase -- Physiological aspects ,Bacteria -- Physiological aspects ,Esters -- Physiological aspects ,Hydrolysis -- Analysis ,Catalysts -- Physiological aspects ,Biological sciences ,Chemistry - Abstract
Research has been conducted on the lipase from Chromobacterium viscosum, a highly regio- and enantioselective catalyst for the diester hydrolysis. The identification of the remote ester group controlling the enantioselectivity has been performed via the combination of the nonsymmetrical diesters and computer modeling.
- Published
- 2001
18. Relationship between mutant Cu/Zn superoxide dismutase 1 maturation and inclusion formation in cell models
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Sabrina Gill, Julian P. Whitelegge, David R. Borchelt, Susan Fromholt, Herman L. Lelie, Jacob I. Ayers, Joan Selverstone Valentine, Hilda Brown, and Benjamin McMahon
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0301 basic medicine ,Protein Folding ,amyotrophic lateral sclerosis ,oxidation ,Mutant ,SOD1 ,CHO Cells ,Neurodegenerative ,Protein aggregation ,medicine.disease_cause ,Biochemistry ,Inclusion bodies ,Protein Aggregates ,03 medical and health sciences ,Cellular and Molecular Neuroscience ,Cricetulus ,Superoxide Dismutase-1 ,superoxide dismutase 1 ,Rare Diseases ,0302 clinical medicine ,Live cell imaging ,Cricetinae ,medicine ,Animals ,Humans ,2.1 Biological and endogenous factors ,Aetiology ,Inclusion Bodies ,Mutation ,Neurology & Neurosurgery ,Chemistry ,aggregation ,Neurosciences ,nutritional and metabolic diseases ,live imaging ,Brain Disorders ,Cell biology ,HEK293 Cells ,030104 developmental biology ,Protein folding ,Biochemistry and Cell Biology ,ALS ,030217 neurology & neurosurgery ,Intracellular - Abstract
A common property of Cu/Zn superoxide dismutase 1 (SOD1), harboring mutations associated with amyotrophic lateral sclerosis, is a high propensity to misfold and form abnormal aggregates. The aggregation of mutant SOD1 has been demonstrated invitro, with purified proteins, in mouse models, in human tissues, and in cultured cell models. In vitro translation studies have determined that SOD1 with amyotrophic lateral sclerosis mutations is slower to mature, and thus perhaps vulnerable to off-pathway folding that could generate aggregates. The aggregation of mutant SOD1 in living cells can be monitored by tagging the protein with fluorescent fluorophores. In this study, we have taken advantage of the Dendra2 fluorophore technology in which excitation can be used to switch the output color from green to red, thereby clearly creating a time stamp that distinguishes pre-existing and newly made proteins. In cells that transiently over-express the Ala 4 to Val variant of SOD1-Dendra2, we observed that newly made mutant SOD1 was rapidly captured by pathologic intracellular inclusions. In cell models of mutant SOD1 aggregation over-expressing untagged A4V-SOD1, we observed that immature forms of the protein, lacking a Cu co-factor and a normal intramolecular disulfide, persist for extended periods. Our findings fit with a model in which immature forms of mutant A4V-SOD1, including newly made protein, are prone to misfolding and aggregation.
- Published
- 2016
19. Novel macrocycles incorporating cyclic urea units
- Author
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Dave, Paritosh R., Doyle, Gerald, Axenrod, Theodore, Yazdekhasti, Hamid, and Ammon, Herman L.
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Cyclic compounds -- Research ,Biological sciences ,Chemistry - Abstract
A series of 16 and 18-membered macrocycles containing cyclic urea units can be synthesized by reacting 2-imidazolidone with 1,3- and 1,4-bis(bromomethyl)benzenes and 5-tert-butyltetrahydro-1,3,5-triazin-2(1H)-one. NMR and computational analysis of the structure of these macrocycles reveals conformational equilibria mediated by species containing syn and anti sequence of the urea carbonyl groups. Annulus rotation by carbonyl causes interconversion of these macrocycles.
- Published
- 1995
20. Novel and efficient azomethine ylide forming photoreactions of N-(silylmethyl)phthalimides and related acid and alcohol derivatives
- Author
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Ung Chan Yoon, Dong Uk Kim, Chan Woo Lee, Young Sun Choi, Yean-Jang Lee, Ammon, Herman L., and Mariano, Patrick S.
- Subjects
Azo compounds -- Research ,Photochemistry -- Analysis ,Chemistry - Abstract
Generation of azomethine ylide intermediates involves a novel photoreactions of N-(silylmethyl)phthalimides and related 2-phenylethanol and alpha-phthaloylacetic acids. Nonselective silyl migration is observed in the excited state of the 4-carbomethoxyphthalimide. Few suggested mechanism account for the nature, stereochemical and regiochemical course of the formation of azomethine ylide by photoreactions.
- Published
- 1995
21. Structural characterization of Pseudomonas 7A glutaminase-asparaginase
- Author
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Lubkowski, Jacek, Wlodawer, Alexander, Ammon, Herman L., Copeland, Terry D., and Swain, Amy L.
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Pseudomonas -- Research ,Enzymes -- Structure-activity relationship ,Biological sciences ,Chemistry - Abstract
The 2 angstroms crystallographic structure and amino acid sequence of Pseudomonas 7A glutaminase-asparaginase (PGA) are similar to those of other tetrameric bacterial amidohydrolases. The active site loop is present in one monomer of PGA in an open position. This open position is different for other amidohydrolases and is in a disordered state. The active site loop presence is indicated by the low occupancy of products of enzymatic interactions.
- Published
- 1994
22. Structure and function of the xenobiotic substrate binding site a glutathione S-transferase as revealed by x-ray crystallographic analysis of product complexes with the diastereomers of 9-(S-glutahionyl)-10-hydroxy-9, 10-dihydrophenanthrene
- Author
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Xinhua Ji, Johnson, William W., Sesay, Muctarr A., Dickert, Laura, Prasad, Satya M., Ammon, Herman L., Armstrong, Richard N., and Gilliland, Gary L.
- Subjects
Glutathione transferase -- Research ,Xenobiotics -- Observations ,Biological sciences ,Chemistry - Abstract
A study of glutathione (GSH) transferase 3-3-isoenzyme interaction with GSH-phenanthrene 9,10-oxide reveals the presence of xenobiotic substrate binding site residues in the variable sequence region of the enzyme. The Y115 located in the domain II is electrophilic and, hence, capable of better catalytic efficiency with alpha,beta-unsaturated ketones and epoxides. The variable regions enhance catalytic variety of the proteins.
- Published
- 1994
23. Evolocumab and clinical outcomes in patients with cardiovascular disease
- Author
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Sabatine, Marc S., Giugliano, Robert P., Keech, Anthony C., Honarpour, Narimon, Wiviott, Stephen D., Murphy, Sabina A., Kuder, Julia F., Wang, Huei, Liu, Thomas, Wasserman, Scott M., Sever, Peter S., Pedersen, Fish MP, Terje R., Abrahamsen, Te, Im, K, Kanevsky, E, Bonaca, Mp, Lira Pineda, A, Hanlon, K, Knusel, B, Somaratne, R, Kurtz, C, Scott, R, Accini Mendoza JL, Amerena, J, Badariene, J, Burgess, L, Ceska, R, Charng, Mj, Choi, D, Cobos, Jl, Dan, Ga, De Ferrari GM, Deedwania, Pc, Chopra, Vk, Erglis, A, Ezhov, Mv, Ferreira, J, Filipová, S, Gaciong, Za, Pasierski, T, Georgiev, Bg, Gonzalez-Galvez, G, Gouni-Berthold, I, Schäufele, T, Hirayama, A, Huber, K, Rammer, M, Kjaerulf Jensen, H, Wermuth, S, Jiang, L, Jukema, Jw, Kraydashenko, O, Leiter, La, Lewis, Bs, López-Miranda, J, Lorenzatti, Aj, Mach, F, Mcadam, B, Nilsson, L, Olsson, Å, Rallidis, L, Rogelio, Gg, Kerr Saraiva JF, Scheen, A, Schiele, F, Scott, Rs, Connolly, D, Siu, Cw, Tay, L, Thorgeirsson, G, Tikkanen, Mj, Tokgozoglu, Sl, Toth, K, Viigimaa, M, Wan Ahmad WA, Hennekens, Ch, Andreotti, F, Baigent, C, Brown, Wv, Davis, Br, Newcomer, Jw, Wood, Sk, Larosa, J, Ansell, B, Olsson, A, Lowe, C, Zahn, L, Awtry, E, Berger, C, Croce, K, Desai, A, Gelfand, E, Ho, C, Leeman, D, Link, M, Norden, A, Pande, A, Rost, N, Ruberg, F, Silverman, S, Singhal, A, Vita, J, Mackinnon, I, Vogel, Dr, Leon de la Fuente, R, Perna, E, Amuchastegui, M, Pacora, F, Hershson, A, Blumberg, E, Glenny, Ja, Colombo, H, Cuadrado, Ja, Nicolosi, L, Rojas, Cg, Ulla, Mr, Hasbani, Eg, Cuneo, C, Lopez Santi RG, Sanabria, Hd, Hrabar, A, Lozada, A, Begg, A, Lehman, S, Wittert, G, Juergens, C, Kostner, K, Beltrame, J, Simpson, R, Sinhal, A, Adams, M, Kritharides, L, Roberts Thomson, P, Cross, D, Thompson, P, Van Gaal, W, Cox, N, Farshid, A, Hammett, C, Garrahy, P, Prasan, A, Horrigan, M, Ebenbichler, C, Hanusch, U, Prager, R, Schernthaner, G, Luger, A, Siostrzonek, P, Toplak, H, Bergler-Klein, J, Paulweber, B, Sinzinger, H, Buysschaert, I, Thoeng, J, 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Tahirkheli, N, Delgado, E, Derian, W, Greenwald, J, Harris, M, Jackson, R, Marhefka, G, Mcelveen, W, Mooss, A, Morris, P, Murray, J, Pearlstein, P, Raisinghani, A, Rezkalla, S, Sakhrani, L, Schreibman, D, Shaoulian, E, Steinsapir, J, Yataco, A, De La Cruz, A, Fredrick, M, Goldenberg, E, Lee, D, Mccullum, K, Mclellan, B, Stephens, L, Wilson, S, Alfieri, A, Mandviwala, M, Orourke, D, Samal, A, Schmedtje, J, Waxman, F, Carhart, R, Clements, B, Dyke, C, Ghali, J, Gruberg, L, Hack, T, Jehle, A, Pogue, B, Schooley, C, and Shifrin, G
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Male ,STATIN THERAPY ,2700 General Medicine ,Disease ,Cardiovascular ,PLACEBO-CONTROLLED TRIAL ,Gastroenterology ,0302 clinical medicine ,Anticholesteremic Agent ,Medicine ,Myocardial infarction ,11 Medical and Health Sciences ,ddc:616 ,Incidence ,Antibodies, Monoclonal ,General Medicine ,Cholesterol ,Cardiovascular Diseases ,Monoclonal ,Drug Therapy, Combination ,Proprotein Convertase 9 ,Antibody ,Aged ,Anticholesteremic Agents ,Atherosclerosis ,Cholesterol, LDL ,Double-Blind Method ,Female ,Follow-Up Studies ,Humans ,Hydroxymethylglutaryl-CoA Reductase Inhibitors ,Hypercholesterolemia ,Least-Squares Analysis ,Middle Aged ,Medicine (all) ,REDUCING LIPIDS ,Human ,medicine.medical_specialty ,Evinacumab ,Clinical Trials and Supportive Activities ,PCSK9 INHIBITION ,Follow-Up Studie ,LDL ,03 medical and health sciences ,Drug Therapy ,Clinical Research ,LDL-C ,Least-Squares Analysi ,Science & Technology ,Unstable angina ,PCSK9 ,medicine.disease ,chemistry ,Clinical Biochemistry ,030204 cardiovascular system & hematology ,Bococizumab ,FOURIER Steering Committee and Investigators ,Medical and Health Sciences ,chemistry.chemical_compound ,Antibodies monoclonal ,Cardiovascular Disease ,030212 general & internal medicine ,Stroke ,Humanized ,RISK ,biology ,PCSK9 Inhibitors ,10051 Rheumatology Clinic and Institute of Physical Medicine ,Heart Disease ,Atherosclerosi ,6.1 Pharmaceuticals ,Combination ,Cardiology ,Life Sciences & Biomedicine ,Antibodies, Monoclonal, Humanized ,EZETIMIBE ,610 Medicine & health ,Antibodies ,Medicine, General & Internal ,General & Internal Medicine ,Internal medicine ,CORONARY-HEART-DISEASE ,In patient ,Heart Disease - Coronary Heart Disease ,Alirocumab ,Ldl cholesterol ,business.industry ,Evaluation of treatments and therapeutic interventions ,Evolocumab ,Good Health and Well Being ,Settore MED/11 - MALATTIE DELL'APPARATO CARDIOVASCOLARE ,biology.protein ,MODERATE ,Hydroxymethylglutaryl-CoA Reductase Inhibitor ,business - Abstract
Background Evolocumab is a monoclonal antibody that inhibits proprotein convertase subtilisin–kexin type 9 (PCSK9) and lowers low-density lipoprotein (LDL) cholesterol levels by approximately 60%. Whether it prevents cardiovascular events is uncertain. Methods We conducted a randomized, double-blind, placebo-controlled trial involving 27,564 patients with atherosclerotic cardiovascular disease and LDL cholesterol levels of 70 mg per deciliter (1.8 mmol per liter) or higher who were receiving statin therapy. Patients were randomly assigned to receive evolocumab (either 140 mg every 2 weeks or 420 mg monthly) or matching placebo as subcutaneous injections. The primary efficacy end point was the composite of cardiovascular death, myocardial infarction, stroke, hospitalization for unstable angina, or coronary revascularization. The key secondary efficacy end point was the composite of cardiovascular death, myocardial infarction, or stroke. The median duration of follow-up was 2.2 years. Results At 48 weeks, the least-squares mean percentage reduction in LDL cholesterol levels with evolocumab, as compared with placebo, was 59%, from a median baseline value of 92 mg per deciliter (2.4 mmol per liter) to 30 mg per deciliter (0.78 mmol per liter) (P
- Published
- 2017
24. Stereochemical probe for the mechanism of P-C bond cleavage catalyzed by theBacillus cereus phosphonoacetaldehyde hydrolase
- Author
-
Lee Sheng-Lian, Hepburn, Timothy W., Swartz, William H., Ammon, Herman L., Mariano, Patrick S., and Dunaway-Mariano, Debra
- Subjects
Organic compounds -- Synthesis ,Phosphonates -- Research ,Acetaldehyde -- Research ,Schiff bases -- Research ,Hydrolysis -- Research ,Enzymes -- Research ,Chemistry - Abstract
The synthesis of chiral (17O,18O)(thiophosphono)acetaldehyde provides a stereochemical probe to study the mechanism of the P-C bond cleavage in the enzymatic conversion of phosphonoacetaldehyde into phosphate and acetaldehyde. The probe compound is obtained from diastereomeric thiophosphonamides. The study reveals that conversion, which occurs with retention of configuration about the phosphorus atom, involves formation of a protonated Schiff base followed by nucleophilic attack by the enzyme to break the P-C bond and, finally, by hydrolysis of the acetaldehyde enamine and the phosphonoenzyme group.
- Published
- 1992
25. Syntheses and ion selectivity of conformational isomers derived from calix(4)arene
- Author
-
Shinkai, Seiji, Fujimoto, Kiyoshi, Otsuka, Toshio, and Ammon, Herman L.
- Subjects
Organic compounds -- Synthesis ,Conformational analysis -- Research ,Calixarenes -- Research ,Biological sciences ,Chemistry - Abstract
The synthesis of the cone, partial cone and 1,3-alternate conformers of 5,11,17,23-tetra-tert-butyl-25, 27-bis(ethoxycarbonyl)methoxy-26,28-bis(2- pyridylmethoxy)calix(4)arene leads to a study of the arene's metal selectivity. The two-phase solvent extraction study shows a preference for the cone conformer when the carbonate salt bears template metal cations. Salts with nontemplate metal cations lead to the formation of partial cones and 1,3-alternate conformers. Thus, metal selectivity of ionophoric calix(n)arenes may be controlled not only by ring size but also by conformation.
- Published
- 1992
26. Advances in nonlinear optical spectroscopies: a historical perspective of developments and applications presented at ECONOS
- Author
-
Johannes Kiefer, Herman L. Offerhaus, Peter Radi, Julian Moger, Aleksei M. Zheltikov, Andreas Volkmer, and Arnulf Materny
- Subjects
Chemistry ,010401 analytical chemistry ,Perspective (graphical) ,Nanotechnology ,02 engineering and technology ,021001 nanoscience & nanotechnology ,01 natural sciences ,0104 chemical sciences ,Nonlinear optical ,General Materials Science ,0210 nano-technology ,Spectroscopy ,Photonic-crystal fiber - Abstract
This article reviews the contributions to the special issues of the annual European Conference on Nonlinear Optical Spectroscopy (ECONOS) since its establishment in 2002. The review does not only highlight the developments of the scientific areas related to nonlinear optical spectroscopy in Europe but also shows how different sub-fields evolved globally because ECONOS evolved as an international meeting attracting participants from all over the world. Four main topical categories are identified: (1) theoretical and instrumental developments, (2) applications to gas-phase and combustion systems, (3) applications to condensed phase matter, and (4) development and applications of micro-spectroscopy methods. Copyright © 2015 John Wiley & Sons, Ltd.
- Published
- 2015
27. Skin penetration behavior of lipid-core nanocapsules for simultaneous delivery of resveratrol and curcumin
- Author
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Karine Coradini, Herman L. Offerhaus, Rossana B. Friedrich, Birthe Kann, Ruy Carlos Ruver Beck, Maike Windbergs, and Optical Sciences
- Subjects
Antioxidant ,Curcumin ,Cell Survival ,medicine.medical_treatment ,Polyesters ,Skin Absorption ,Pharmaceutical Science ,Human skin ,Pharmacology ,Resveratrol ,In Vitro Techniques ,Nanocapsules ,chemistry.chemical_compound ,Cellular uptake ,Stilbenes ,Stratum corneum ,medicine ,Organic chemistry ,Humans ,Cells, Cultured ,Hexoses ,Drug Carriers ,Grape Seed Extract ,integumentary system ,Lipid-core nanocapsules ,Chemistry ,Polyphenols ,food and beverages ,Fibroblasts ,Co-encapsulation ,Skin penetration ,Drug Liberation ,medicine.anatomical_structure ,Polyphenol ,2023 OA procedure ,Drug carrier ,Oils - Abstract
Polyphenols, which are secondary plant metabolites, gain increasing research interest due to their therapeutic potential. Among them, resveratrol and curcumin are two agents showing antioxidant, anti-inflammatory, antimicrobial as well as anticarcinogenic effects. In addition to their individual therapeutic effect, increased activity was reported upon co-delivery of the two compounds. However, due to the poor water solubility of resveratrol and curcumin, their clinical application is currently limited. In this context, lipid-core nanocapsules (LNC) composed of an oily core surrounded by a polymeric shell were introduced as drug carrier systems with the potential to overcome this obstacle. Furthermore, the encapsulation of polyphenols into LNC can increase their photostability. As the attributes of the polyphenols make them excellent candidates for skin treatment, the aim of this study was to investigate the effect of co-delivery of resveratrol and curcumin by LNC upon topical application on excised human skin. In contrast to the formulation with one polyphenol, resveratrol penetrated into deeper skin layers when the co-formulation was applied. Based on vibrational spectroscopy analysis, these effects are most likely due to interactions of curcumin and the stratum corneum, facilitating the skin absorption of the co-administered resveratrol. Furthermore, the interaction of LNC with primary human skin cells was analyzed encountering a cellular uptake within 24 h potentially leading to intracellular effects of the polyphenols. Thus, the simultaneous delivery of resveratrol and curcumin by LNC provides an intelligent way for immediate and sustained polyphenol delivery for skin disease treatment.
- Published
- 2015
28. Are DTTO and iso -DTTO Worthwhile Targets for Synthesis?
- Author
-
Karl O. Christe, David A. Dixon, Monica Vasiliu, Ross I. Wagner, Ralf Haiges, Jerry A. Boatz, and the late Herman L. Ammon
- Subjects
Crystal ,Explosive material ,Chemistry ,Computational chemistry ,General Chemical Engineering ,Detonation velocity ,Atom ,Detonation ,Thermodynamics ,General Chemistry ,Quantum ,Standard enthalpy of formation - Abstract
Theoretical calculations were carried out for the isomeric di-1,2,3,4-tetrazine tetraoxides (DTTO and iso-DTTO). The most important explosion performance parameters, the detonation pressure and detonation velocity, are dominated by the densities and not by the heats of formation of these compounds. Since DTTO and iso-DTTO are unknown, reliable predictions of their crystal densities are crucial for an evaluation of the potential of these materials as explosives. In this study, the crystal densities were predicted using both Ammon’s Atom/Functional Group and Atom Code Volume Additivity Parameters and Quantum Mechanical molecular Volume methods, resulting in similar densities and explosion parameters. Although the likely uncertainties in our predicted density values are difficult to assess due to a lack of experimental data for closely related known compounds, our results demonstrate that Shechter’s originally proposed densities and performance parameters were grossly overestimated. Furthermore, it is shown that, based on our predicted density value ranges, DTTO and iso-DTTO could match or substantially outperform the best state of the art explosives, such as CL-20. Therefore, the synthesis of DTTO and iso-DTTO should be further pursued.
- Published
- 2015
29. Yeast copper–zinc superoxide dismutase can be activated in the absence of its copper chaperone
- Author
-
Yuewei Sheng, Lindsay Kane Barnese, Edith Butler Gralla, Armando Durazo, Herman L. Lelie, Kevin Sea, and Joan Selverstone Valentine
- Subjects
animal diseases ,Saccharomyces cerevisiae ,SOD1 ,chemistry.chemical_element ,Biochemistry ,Article ,Inorganic Chemistry ,Superoxide dismutase ,chemistry.chemical_compound ,Superoxide Dismutase-1 ,Hydrogen peroxide ,biology ,Superoxide Dismutase ,Superoxide ,fungi ,nutritional and metabolic diseases ,biology.organism_classification ,Copper ,Yeast ,nervous system diseases ,Enzyme Activation ,Zinc ,nervous system ,chemistry ,Chaperone (protein) ,biology.protein ,Oxidation-Reduction - Abstract
Copper-zinc superoxide dismutase (Sod1) is an abundant intracellular enzyme that catalyzes the disproportionation of superoxide to give hydrogen peroxide and dioxygen. In most organisms, Sod1 acquires copper by a combination of two pathways, one dependent on the copper chaperone for Sod1 (CCS), and the other independent of CCS. Examples have been reported of two exceptions: Saccharomyces cerevisiae, in which Sod1 appeared to be fully dependent on CCS, and Caenorhabditis elegans, in which Sod1 was completely independent of CCS. Here, however, using overexpressed Sod1, we show there is also a significant amount of CCS-independent activation of S. cerevisiae Sod1, even in low-copper medium. In addition, we show CCS-independent oxidation of the disulfide bond in S. cerevisiae Sod1. There appears to be a continuum between CCS-dependent and CCS-independent activation of Sod1, with yeast falling near but not at the CCS-dependent end.
- Published
- 2013
30. Intracellular Delivery of Poorly Soluble Polyphenols: Elucidating the Interplay of Self-Assembling Nanocarriers and Human Chondrocytes
- Author
-
Lucas Almeida Rigo, Maike Windbergs, Christian Spengler, Herman L. Offerhaus, Birthe Kann, Ruy Carlos Ruver Beck, Karine Coradini, Martin L. Bennink, Karin Jacobs, Nanobiophysics, and Optical Sciences
- Subjects
0301 basic medicine ,Curcumin ,Nonlinear Optical Microscopy ,Carrier system ,Cell ,Polysorbates ,Resveratrol ,Microscopy, Atomic Force ,Nanocapsules ,Analytical Chemistry ,Cell membrane ,03 medical and health sciences ,chemistry.chemical_compound ,Chondrocytes ,Stilbenes ,medicine ,Humans ,Vitis ,Particle Size ,Inflammation ,Drug Carriers ,Grape Seed Extract ,Anti-Inflammatory Agents, Non-Steroidal ,Polyphenols ,Cell biology ,030104 developmental biology ,medicine.anatomical_structure ,Biochemistry ,chemistry ,2023 OA procedure ,Nanocarriers ,Intracellular - Abstract
Increased molecular understanding of multifactorial diseases paves the way for novel therapeutic approaches requiring sophisticated carriers for intracellular delivery of actives. We designed and characterized self-assembling lipid-core nanocapsules for coencapsulation of two poorly soluble natural polyphenols curcumin and resveratrol. The polyphenols were identified as high-potential therapeutic candidates intervening in the intracellular inflammation cascade of chondrocytes during the progress of osteoarthritis. To elucidate the interplay between chondrocytes and nanocapsules and their therapeutic effect, we pursued a complementary analytical approach combining label-free visualization with biological assays. Primary human chondrocytes did not show any adverse effects upon nanocapsule application and coherent anti-Stokes Raman scattering images visualized their intracellular uptake. Further, by systematically blocking different uptake mechanisms, an energy independent uptake into the cells could be identified. Additionally, we tested the therapeutic effect of the polyphenol-loaded carriers on inflamed chondrocytes. Treatment with nanocapsules resulted in a major reduction of nitric oxide levels, a well-known apoptosis trigger during the course of osteoarthritis. For a more profound examination of this protective effect on joint cells, we pursued studies with atomic force microscopy investigations. Significant changes in the cell cytoskeleton as well as prominent dents in the cell membrane upon induced apoptosis were revealed. Interestingly, these effects could not be detected for chondrocytes which were pretreated with the nanocapsules. Overall, besides presenting a sophisticated carrier system for joint application, these results highlight the necessity of establishing combinatorial analytical approaches to elucidate cellular uptake, the interplay of codelivered drugs and their therapeutic effect on the subcellular level.
- Published
- 2016
31. Phase aspects of (broadband) stimulated Raman scattering
- Author
-
E.T. Garbacik, Jennifer Lynn Herek, A.L. Fussell, A.C.W. van Rhijn, Herman L. Offerhaus, Faculty of Science and Technology, and Optical Sciences
- Subjects
Materials science ,business.industry ,nonlinear optics ,Phase (waves) ,Nonlinear optics ,Analytical Chemistry ,Chemistry ,symbols.namesake ,Narrowband ,Optics ,Coherent control ,Broadband ,Microscopy ,microscopy ,symbols ,coherent control ,Coherent anti-Stokes Raman spectroscopy ,business ,QD1-999 ,Raman scattering - Abstract
The phase of the molecular response can be exploited to improve selectivity without sacrificing speed in both narrowband and broadband coherent anti-Stokes Raman scattering (CARS) microscopy, both of which will be considered in this review of the work that was performed in our group.
- Published
- 2012
32. A theoretical investigation of super-resolution CARS imaging via coherent and incoherent saturation of transitions
- Author
-
Klaus J. Boller, Willem P. Beeker, Herman L. Offerhaus, Christopher James Lee, Jennifer Lynn Herek, Carsten Fallnich, Carsten Cleff, and Petra Groß
- Subjects
Density matrix ,Rabi cycle ,business.industry ,Chemistry ,Laser ,law.invention ,symbols.namesake ,Optics ,law ,symbols ,General Materials Science ,Coherent anti-Stokes Raman spectroscopy ,Spectral resolution ,Atomic physics ,business ,Raman spectroscopy ,Ground state ,Spectroscopy ,Raman scattering - Abstract
We review two approaches to achieving sub-diffraction-limited resolution coherent anti-Stokes Raman scattering (CARS) microscopy (Beeker et al., Opt. Express, 2009, 17, 22632 and Beeker et al., J. Herek, Phys. Rev. A, 2010, 81, 012507). We performed a numerical investigation, based on the density matrix model, of the CARS emission process and identified two modified CARS experiments that lead to sub-diffraction-limited resolution images. At the heart of both processes is the spatial manipulation of the coherence between the ground state and the vibrational state being probed by the CARS process via a control state and a control laser that is resonant with the ground state to control state transition. We find two possible regimes of operation: in the first regime, the control and vibrational states are coupled via incoherent processes so that the populations of the two states reach equilibrium very quickly compared to the relevant coherence times. Under these conditions, pre-populating the control state provides a saturable suppression of the coherence between the ground state and the vibrational state, suppressing CARS emission. By using a donut mode to pre-populate the control state, CARS is suppressed everywhere but the central node, allowing sub-diffraction-limited resolution imaging. In the second regime, the control state has a rather long coherence lifetime, and the resonant laser drives Rabi oscillations that periodically deplete the ground state. As a result, the CARS emission process is amplitude-modulated, which appear as sidebands on the CARS spectrum. By a process of spectral resolution and trilateration, sub-diffraction-limited resolution images can be obtained.
- Published
- 2011
33. On the Mechanism of Selective Chlorination of Ethers with Sulfuryl Chloride in the Dark
- Author
-
Laurent De Buyck and Herman L. De Pooter
- Subjects
chemistry.chemical_classification ,Chemistry ,Hydride ,Inorganic chemistry ,chemistry.chemical_element ,Ether ,General Chemistry ,Sulfuryl chloride ,Medicinal chemistry ,Catalysis ,chemistry.chemical_compound ,Nucleophile ,Chlorine ,Reactivity (chemistry) ,Alkyl - Abstract
Alkyl 4-chlorobutyl ethers reacted in the dark with an excess of sulfuryl chloride at 70–85°C (bath) to afford α,β,β-trichlorinated ethers. The reactions were accelerated 3− to 6-fold by N,N-dimethyl-octylammonium salts (0,12 to 1 mmol/mol ether). This catalyst promoted decomposition of sulfuryl chloride to chlorine and sulfur dioxide and thereby caused serious loss of sulfuryl chloride. The proportions of chlorination at α or α' position were identical in the catalyzed or uncatalyzed version and depended on inductive effects, correlating well with Taft's linear free energy relationship log k/kref = ρ* σ* for R = H, Me, Et, Pr in RCH2O(CH2)4Cl with ρ* = −2.6±0.1. The overall reactivity of ethers appears to vary like the nucleophilicity of the ether oxygen. It is concluded that hydride abstraction occurs indirectly, probably involving a chloroxonium ion pair.
- Published
- 2010
34. Visualizing Resonances in the Complex Plane with Vibrational Phase Contrast Coherent Anti-Stokes Raman Scattering
- Author
-
Herman L. Offerhaus, Jennifer Lynn Herek, Jeroen P. Korterik, Martin Jurna, Cees Otto, E.T. Garbacik, Optical Sciences, Medical Cell Biophysics, and Faculty of Science and Technology
- Subjects
Ethanol ,Chemistry ,business.industry ,Methanol ,Water ,IR-72649 ,Spectrum Analysis, Raman ,Vibration ,Signal ,Molecular physics ,Analytical Chemistry ,symbols.namesake ,Optics ,Amplitude ,Phase (matter) ,Computer Graphics ,symbols ,METIS-267949 ,Coherent anti-Stokes Raman spectroscopy ,business ,Complex plane ,Fabry–Pérot interferometer ,Raman scattering - Abstract
In coherent anti-Stokes Raman scattering (CARS), the emitted signal carries both amplitude and phase information of the molecules in the focal volume. Most CARS experiments ignore the phase component, but its detection allows for two advantages over intensity-only CARS. First, the pure resonant response can be determined, and the nonresonant background rejected, by extracting the imaginary component of the complex response, enhancing the sensitivity of CARS measurements. Second, selectivity is increased via determination of the phase and amplitude, allowing separation of individual molecular components of a sample even when their vibrational bands overlap. Here, using vibrational phase contrast CARS (VPC-CARS), we demonstrate enhanced sensitivity in quantitative measurements of ethanol/methanol mixtures and increased selectivity in a heterogeneous mixture of plastics and water. This powerful technique opens a wide range of possibilities for studies of complicated systems where overlapping resonances limit standard methodologies.
- Published
- 2010
35. Heterodyne interferometric polarization coherent anti-Stokes Raman scattering (HIP-CARS) spectroscopy
- Author
-
Cornelis Otto, E.T. Garbacik, Herman L. Offerhaus, K. Orsel, Jeroen P. Korterik, Jennifer Lynn Herek, and Martin Jurna
- Subjects
Chemistry ,business.industry ,Polarization (waves) ,symbols.namesake ,Interferometry ,Optics ,Picosecond ,Optical parametric oscillator ,symbols ,General Materials Science ,Coherent anti-Stokes Raman spectroscopy ,Spectroscopy ,business ,Raman spectroscopy ,Raman scattering - Abstract
We demonstrate a new technique that combines polarization sensitivity of the coherent anti-Stokes Raman scattering (CARS) response with heterodyne amplification for background-free detection of CARS signals. In this heterodyne interferometric polarization CARS (HIP-CARS), the major drawbacks of polarization and heterodyne CARS are rectified. Using a home-built picosecond optical parametric oscillator, we are able to address vibrational stretches between 600 and 1650 cm−1 and record continuous high-resolution Raman equivalent HIP-CARS spectra. Copyright © 2010 John Wiley & Sons, Ltd.
- Published
- 2010
36. Pairing Heterocyclic Cations with closo-Icosahedral Borane and Carborane Anions. I. Benchtop Aqueous Synthesis of Binary Triazolium and Imidazolium Salts with Limited Water Solubility
- Author
-
Herman L. Ammon, John L. Belletire, Scott A. Shackelford, Steven H. Strauss, Brett A. Wight, Leslie M. Hudgens, Amanda K. Wheaton, Jerry A. Boatz, and Stefan Schneider
- Subjects
chemistry.chemical_classification ,Aqueous solution ,Organic Chemistry ,Salt (chemistry) ,Borane ,Biochemistry ,Solvent ,chemistry.chemical_compound ,chemistry ,Polymer chemistry ,Anhydrous ,Carborane ,Organic chemistry ,Pyridinium ,Physical and Theoretical Chemistry ,Solubility - Abstract
Ten new salts that pair triazolium and imidazolium cations with closo-icosahedral anions [B(12)H(12)](2-) and [CB(11)H(12)](-) were synthesized in water solvent using an open-air, benchtop method. These unreported [Heterocyclium](2)[B(12)H(12)] and [Heterocyclium][CB(11)H(12)] salts extend reports of [Imidazolium][CB(11)H(12)] and [Pyridinium][CB(11)H(12)] salts that were synthesized in anhydrous organic solvents under an inert atmosphere with glovebox or Schlenk techniques. Spectroscopic data, melting points, and densities are reported for each salt. Single-crystal X-ray structures are provided for the five new [B(12)H(12)](2-) salts.
- Published
- 2009
37. Influence of Nonoptimal Ripener Applications and Postharvest Residue Retention on Sugarcane Second Ratoon Yields
- Author
-
Herman L. Waguespack, Windell Jackson, Edward P. Richard, Richard M. Johnson, and Ryan P. Viator
- Subjects
Sucrose ,biology ,food and beverages ,biology.organism_classification ,Saccharum ,chemistry.chemical_compound ,chemistry ,Saccharum officinarum ,Agronomy ,Glyphosate ,Postharvest ,Poaceae ,Cultivar ,Cane ,Agronomy and Crop Science ,Mathematics - Abstract
Retention of sugarcane (interspecifi c hybrids of Saccharum spp.) postharvest residue and certain glyphosate ripener application regimes may independently reduce yields of the subsequent ratoon crop in wet climates. Th e objective of this experiment was to determine the eff ects of ripener application and ripener treatment to harvest intervals (THI) on yields of the treated fi rst ratoon, and the combined eff ects of these treatments and postharvest residue retention on the subsequent second ratoon. Whole plots consisted of either a nontreated control or 0.21 kg a.e. ha –1 glyphosate applied to the fi rst ratoon of cultivar LCP 85–384. Splitplots consisted of THI of 40, 50, and 60 d for all plots. Split-split plot treatments consisted of partial removal of postharvest residue or complete retention for second ratoon. Averaged across all THIs for the fi rst ratoon, glyphosate increased sucrose yield by 300 kg ha –1 compared with the control. Th e 60 d THI reduced second ratoon cane and sucrose yields by 5.4 Mg ha –1 and 900 kg ha –1 , respectively, compared with the means of the 40 and 50 THI and sucrose yields by 300 kg ha –1 compared with the control. Full residue retention reduced second ratoon cane and sucrose yield by 2.3 Mg ha –1 and 300 kg ha –1 , respectively, compared with partial removal. Residue retention and glyphosate application were not negatively synergistic. Producers should remove postharvest residue from the row top and harvest ripener-treated cane at a THI of 40 to 50 d to maximize sucrose yields in the fi rst ratoon while also preventing yield losses in the subsequent second ratoon.
- Published
- 2008
38. Design, Synthesis and Biological Testing of Cyclohexenone Derivatives of Combretastatin-A4
- Author
-
Khyati Baxi, Brent Younglove, Herman L. Holt, Lawrence Nolan, John Dickson, Lori Forrest, Moses Lee, Toni Brown, Jennifer Ruprich, Regan M. LeBlanc, Andrew Prout, Hilary Mackay, Susan L. Mooberry, and Patrice Hills
- Subjects
biology ,Chemistry ,Stereochemistry ,Combretastatin a4 ,Pharmaceutical Science ,Biological Testing ,chemistry.chemical_compound ,Tubulin ,Design synthesis ,Cyclohexenone ,Drug Discovery ,biology.protein ,Molecular Medicine ,Cytotoxicity - Published
- 2007
39. The application of vinylogous iminium salt derivatives to an efficient synthesis of the pyrrole containing alkaloids Rigidin and Rigidin E
- Author
-
Anastasia Kharlamova, Jonathan E. Hempel, John T. Gupton, Keith Krumpe, Raymond N. Dominey, James A. Sikorski, Bradley K. Norwood, Barrett A. Little, Anthony Diebes, Shahnaz Ghassemi, Rene P.F. Kanters, Edith J. Banner, Charles R. Hickenboth, Matthew B. Coppock, Herman L. Holt, Bruce S. Burnham, Austin B. Scharf, Karen X. Du, Kartik M. Keertikar, Itta Bluhn-Chertudi, and Melissa D. Sartin
- Subjects
chemistry.chemical_classification ,Organic Chemistry ,Salt (chemistry) ,Halogenation ,Iminium ,Biochemistry ,Acylation ,Hydrolysis ,chemistry.chemical_compound ,chemistry ,Drug Discovery ,Organic chemistry ,Curtius rearrangement ,Pyrrole - Abstract
Studies directed on the synthesis of the pyrrole containing marine natural products Rigidin and Rigidin E via vinylogous iminium salts are described. The successful strategy relies on the formation of a 2,4-disubstituted pyrrole from a vinamidinium salt followed by acylation at the 5-position of pyrrole. Halogenation and aminocarbonylation at the 3-position of pyrrole followed by hydrolysis of the ester group at C-2 and subsequent Curtius rearrangement generates the pyrrolopyrimidine skeleton. A final deprotection step completes the synthesis of Rigidin and Rigidin E.
- Published
- 2006
40. Effects of media composition on submerged culture spores of the entomopathogenic fungus,Metarhizium anisopliaevar.acridumPart 2: Effects of media osmolality on cell wall characteristics, carbohydrate concentrations, drying stability, and pathogenicity
- Author
-
Herman L. Warren, Jarrod E. Leland, Donald E. Mullins, and Larry J. Vaughan
- Subjects
fungi ,Metarhizium anisopliae ,Polyethylene glycol ,Biology ,biology.organism_classification ,Trehalose ,Spore ,Conidium ,Cell wall ,chemistry.chemical_compound ,chemistry ,Insect Science ,Entomopathogenic fungus ,PEG ratio ,Botany ,Food science ,Agronomy and Crop Science - Abstract
This study evaluates osmolality of a submerged conidia-producing medium in relation to the following spore characteristics: yield, morphology (dimensions and cell wall structure), chemical properties of cell wall surfaces (charge, hydrophobicity, and lectin binding), cytoplasmic polyols and trehalose, and performance (drying stability and pathogenicity). Spore production was increased by the addition of up to 150 g l−1 polyethylene glycol 200 (PEG). Spores from high osmolality medium (HOM spores) containing 100 g l−1 PEG had thin cell walls and dimensions more similar to blastospores than submerged conidia or aerial conidia. However, a faint electron-dense layer separating primary and secondary HOM spores’ cell walls was discernable by transmission electron microscopy as found in aerial and submerged conidia but not found in blastospores. HOM spores also appeared to have an outer rodlet layer, unlike blastospores, although it was thinner than those observed in submerged conidia. HOM spores’ surfa...
- Published
- 2005
41. The effect of delayed harvest on moisture content, insect damage, moulds and aflatoxin contamination of maize in Mayuge district of Uganda
- Author
-
Samuel Kyamanywa, William Kyamuhangire, Herman L. Warren, and Archileo N. Kaaya
- Subjects
Aflatoxin ,Nutrition and Dietetics ,biology ,Moho ,food and beverages ,Contamination ,biology.organism_classification ,respiratory tract diseases ,Crop ,chemistry.chemical_compound ,Agronomy ,chemistry ,immune system diseases ,Postharvest ,Poaceae ,Mycotoxin ,Agronomy and Crop Science ,Water content ,Food Science ,Biotechnology - Abstract
Field drying is a traditional practice carried out by farmers in Uganda and it is one of those practices reported to affect the postharvest quality of maize. A study was therefore conducted to establish the effects of delayed harvest on moisture content, insect damage, moulds and aflatoxin contamination of maize in Mayuge district. Sixteen farmers were selected from Bayitambogwe sub-county, eight from each of the villages of Bugodi and Musita. Maize was sampled from each farmer's field in 2003B and 2004A seasons at harvest stages of physiological maturity and after delayed harvest for 1, 2, 3 and 4 weeks. Each sample was analysed for mould incidence, moisture content, insect damage and aflatoxin contamination. In each season, mould incidence, insect damage and aflatoxin levels significantly (P < 0.05) increased with delayed time of harvest. Moisture content reduced with delayed harvest time but the maize did not dry to the required safe storage moisture content of ⩽15%. Seasonal effects were only significant for moisture content: the 2003B crop had consistently lower moisture content than 2004A crop. These results indicate that, for improved harvest quality of maize, farmers should harvest no later than 3 weeks after maize has attained physiological maturity. Copyright © 2005 Society of Chemical Industry
- Published
- 2005
42. SYNTHESIS AND CYTOTOXIC PROPERTIES OF NITRO- AND AMINOCHALCONES
- Author
-
Toni Brown, Moses Lee, Michelle Stewart, Regan M. LeBlanc, Herman L. Holt, John Dickson, and Hari N. Pati
- Subjects
Chemistry ,Stereochemistry ,Organic Chemistry ,Nitro ,Cytotoxic T cell ,MTT assay ,General Pharmacology, Toxicology and Pharmaceutics ,Ring (chemistry) ,Continuous exposure ,Cytotoxicity ,IC50 ,B16 melanoma - Abstract
Twenty-two nitro- and aminochalcones were synthesized and characterized. Their cytotoxic properties were determined by a 3-day continuous exposure MTT assay with murine melanoma B16 cells. The aminochalcones were generally more cytotoxic than their nitro precursors. Aminochalcone 18, which has an IC50 value of 0.24 μM, was the most potent compound. The results demonstrated that the number and position of methoxy groups in ring A enhanced cytotoxicity of the chalcones. The location of the amino group on ring B also affected cytotoxicity.
- Published
- 2005
43. Coherent anti-Stokes Raman Scattering (CARS) Microscopy Visualizes Pharmaceutical Tablets During Dissolution
- Author
-
Herman L. Offerhaus, A.L. Fussell, Jennifer Lynn Herek, Peter Kleinebudde, Clare J. Strachan, Faculty of Science and Technology, and Optical Sciences
- Subjects
in situ analysis ,Chemistry, Pharmaceutical ,General Chemical Engineering ,dissolution ,Spectrum Analysis, Raman ,General Biochemistry, Genetics and Molecular Biology ,symbols.namesake ,chemistry.chemical_compound ,Ethyl cellulose ,Microscopy ,medicine ,Dissolution testing ,Theophylline ,Solubility ,Dissolution ,Coherent anti-Stokes Raman scattering ,Issue 89 ,tablet ,General Immunology and Microbiology ,Physics ,pharmaceutics ,General Neuroscience ,theophylline ,chemistry ,symbols ,Pharmaceutics ,Spectrophotometry, Ultraviolet ,Raman scattering ,Tablets ,Nuclear chemistry ,medicine.drug - Abstract
Traditional pharmaceutical dissolution tests determine the amount of drug dissolved over time by measuring drug content in the dissolution medium. This method provides little direct information about what is happening on the surface of the dissolving tablet. As the tablet surface composition and structure can change during dissolution, it is essential to monitor it during dissolution testing. In this work coherent anti-Stokes Raman scattering microscopy is used to image the surface of tablets during dissolution while UV absorption spectroscopy is simultaneously providing inline analysis of dissolved drug concentration for tablets containing a 50% mixture of theophylline anhydrate and ethyl cellulose. The measurements showed that in situ CARS microscopy is capable of imaging selectively theophylline in the presence of ethyl cellulose. Additionally, the theophylline anhydrate converted to theophylline monohydrate during dissolution, with needle-shaped crystals growing on the tablet surface during dissolution. The conversion of theophylline anhydrate to monohydrate, combined with reduced exposure of the drug to the flowing dissolution medium resulted in decreased dissolution rates. Our results show that in situ CARS microscopy combined with inline UV absorption spectroscopy is capable of monitoring pharmaceutical tablet dissolution and correlating surface changes with changes in dissolution rate.
- Published
- 2014
44. Coherent anti-Stokes Raman scattering microscopy driving the future of loaded mesoporous silica imaging
- Author
-
Hélder A. Santos, Clare J. Strachan, Pei Ting Mah, Jarno Salonen, Sanna-Mari Niemi, A.L. Fussell, Herman L. Offerhaus, Faculty of Science and Technology, and Optical Sciences
- Subjects
Materials science ,Silicon dioxide ,Biomedical Engineering ,Nanotechnology ,Spectrum Analysis, Raman ,Biochemistry ,Griseofulvin ,Biomaterials ,symbols.namesake ,chemistry.chemical_compound ,Imaging, Three-Dimensional ,Microscopy ,Microparticle ,Molecular Biology ,ta114 ,Biomaterial ,General Medicine ,Mesoporous silica ,Silicon Dioxide ,Amorphous solid ,chemistry ,Pharmaceutical Preparations ,2023 OA procedure ,Thermogravimetry ,symbols ,Microscopy, Electron, Scanning ,Particle size ,Itraconazole ,Porosity ,Raman scattering ,Biotechnology - Abstract
This study reports the use of variants of coherent anti-Stokes Raman scattering (CARS) microscopy as a novel method for improved physicochemical characterization of drug-loaded silica particles. Ordered mesoporous silica is a biomaterial that can be loaded to carry a number of biochemicals, including poorly water-soluble drugs, by allowing the incorporation of drug into nanometer-sized pores. In this work, the loading of two poorly water-soluble model drugs, itraconazole and griseofulvin, in MCM-41 silica microparticles is characterized qualitatively, using the novel approach of CARS microscopy, which has advantages over other analytical approaches used to date and is non-destructive, rapid, label free, confocal and has chemical and physical specificity. The study investigated the effect of two solvent-based loading methods, namely immersion and rotary evaporation, and microparticle size on the three-dimensional (3-D) distribution of the two loaded drugs. Additionally, hyperspectral CARS microscopy was used to confirm the amorphous nature of the loaded drugs. Z-stacked CARS microscopy suggested that the drug, but not the loading method or particle size range, affected 3-D drug distribution. Hyperspectral CARS confirmed that the drug loaded in the MCM-41 silica microparticles was in an amorphous form. The results show that CARS microscopy and hyperspectral CARS microscopy can be used to provide further insights into the structural nature of loaded mesoporous silica microparticles as biomaterials.
- Published
- 2014
45. Nonlinear Optics Approaches Towards Subdiffraction Resolution in CARS Imaging
- Author
-
Boller, Klaus-Jochen, Beeker, Willem P., Cleff, Carsten, Kruse, Kai, Lee, Chris J., Gross, Petra, Offerhaus, Herman L., Fallnich, Carsten, Herek, Jennifer Lynn, Fornasiero, Eugenio F., Rizzoli, Silvio O., Faculty of Science and Technology, Laser Physics & Nonlinear Optics, Optical Sciences, and MESA+ Institute
- Subjects
education.field_of_study ,Stimulated Raman ,Coherent anti-Stokes Raman (CARS) ,Rabi cycle ,Molecular energy level ,Chemistry ,business.industry ,Population ,Nonlinear optics ,Nonlinear polarizability ,Laser ,law.invention ,Optics ,law ,Subdiffraction imaging ,Stimulated emission ,Atomic physics ,Ground state ,education ,business ,Multiphoton numerical modeling ,Coherence (physics) - Abstract
In theoretical investigations, we review several nonlinear optical approaches towards subdiffraction-limited resolution in label-free imaging via coherent anti-Stokes Raman scattering (CARS). Using a density matrix model and numerical integration, we investigate various level schemes and combinations of the light fields that induce CARS along with additional control laser fields. As the key to techniques that gain far-field resolution below the diffraction limit, we identify the inhibition of the buildup of vibrational molecular coherence via saturation or depletion of population (Beeker et al. Opt Express 17:22632–22638, 2009) or the generation of Stark broadening and spatially dependent Rabi sideband generation (Beeker et al. Phys Rev A 81(1), 2010). Depending on the coherence and population decay rates offered by a particular molecular energy level scheme, we identify various different regimes. In the first case, where an additional state (called the control state) and a vibrational state are able to rapidly exchange population via incoherent processes, a prepopulation of the upper vibrational state inhibits the buildup of vibrational coherence. With increasing control laser intensity, this suppresses CARS emission via an incoherent, saturation type of nonlinear process. Using an intense, donut-shaped control laser beam, similar to stimulated emission depletion (STED) microscopy, this can suppress CARS emission from all sample locations except within a subdiffraction-sized range around the central node. Scanning the control beams across the sample provides subdiffraction-limited resolution imaging. An alternative, which does not require a rapid exchange of population with the control state, applies a control beam that only partially depletes the vibrational ground state. Thereby, a CARS point spread function containing a subdiffraction-limited component is generated. Subdiffraction images can then be retrieved through deconvolution. Further approaches are based on the coherent, nonlinear, resonant response of the sample. In this case, CARS signal depletion by Stark splitting of the weakly populated upper vibrational state or the observation of spatially dependent Rabi oscillation may increase the resolution beyond the diffraction limit.
- Published
- 2014
46. [Untitled]
- Author
-
Herman L. Ammon
- Subjects
Crystal ,chemistry.chemical_compound ,Volume (thermodynamics) ,Chemistry ,Additive function ,Functional group ,Atom ,Analytical chemistry ,Molecule ,Crystal structure ,Physical and Theoretical Chemistry ,Condensed Matter Physics ,Energetic material - Abstract
The solid-state density of an energetic material is one of the most important parameters related to performance. With crystal structure data from the Cambridge Structural Database, four new additivity data bases have been determined to provide atom and functional group volumes or densities for the calculation of solid-state densities of organic compounds with the elements C, H, N, O, F, P, S, Cl, and Br. Volumes and densities for 96 atoms/groups were determined from approximately 26,000 crystal structure data. Sets of linear volumes (from observed unit cell volume per molecule data) and nonlinear volumes and linear densities (from observed crystal densities) were determined. The concept of an atom code was also introduced to allow the atoms and their connections to define the types of atoms present in a molecule. This approach lead to 1601 atom codes. With more than 2000 crystal structure data that were not used in the initial parameterizations, average percentage differences between the observed volumes/densities and calculated values ranged from 1.8–2.3%.
- Published
- 2001
47. A test of crystal structure prediction of small organic molecules
- Author
-
Wijnand T. M. Mooij, Sarah L. Price, Frank J. J. Leusen, Jos P. M. Lommerse, D. W. M. Hofmann, Herman L. Ammon, Angelo Gavezzotti, W.D.S. Motherwell, Martin U. Schmidt, D.E. Williams, Jack D. Dunitz, B.P. van Eijck, B. Schweizer, and P. Verwer
- Subjects
Lattice energy ,N alkanes ,Computer program ,Chemistry ,Mineralogy ,Crystallographic data ,General Medicine ,Algorithm ,General Biochemistry, Genetics and Molecular Biology ,Force field (chemistry) ,Crystal structure prediction ,Organic molecules - Abstract
A collaborative workshop was held in May 1999 at the Cambridge Crystallographic Data Centre to test how well currently available methods of crystal structure prediction perform when given only the atomic connectivity for an organic compound. A blind test was conducted on a selection of four compounds and a wide range of methodologies representing the principal computer programs currently available were used. There were 11 participants who were allowed to propose at most three structures for each compound. No program gave consistently reliable results. However, seven proposed structures were close to an experimental one and were classified as `correct'. One compound occurred in two polymorphs, but only one form was predicted correctly among the calculated structures. The basic problem with lattice energy based methods of crystal structure prediction is that many structures are found within a few kJ mol−1 of the global minimum. The fine detail of the force-field methodology and parametrization influences the energy ranking within each method. Nevertheless, present methods may be useful in providing a set of structures as possible polymorphs for a given molecular structure.
- Published
- 2000
48. Hexagonally Poled Lithium Niobate: A Two-Dimensional Nonlinear Photonic Crystal
- Author
-
D.C. Hanna, Graeme W. Ross, Herman L. Offerhaus, Neil G. R. Broderick, and David J. Richardson
- Subjects
Fabrication ,Materials science ,business.industry ,Lithium niobate ,Physics::Optics ,General Physics and Astronomy ,Reciprocal lattice ,chemistry.chemical_compound ,Optics ,chemistry ,Picosecond ,Nonlinear photonic crystal ,Harmonic ,High harmonic generation ,business ,Refractive index - Abstract
We report on the fabrication of what we believe is the first example of a two-dimensional (2D) nonlinear photonic crystal [Berger, Phys. Rev. Lett. 81, 4136 (1998)], where the refractive index is constant but where the 2nd order nonlinear susceptibility is spatially periodic. Such crystals allow for efficient quasi-phase-matched 2nd harmonic generation using multiple reciprocal lattice vectors. External 2nd harmonic conversion efficiencies >60% were measured with picosecond pulses. The fabrication technique is extremely versatile and should allow for the fabrication of a broad range of 2D crystals including quasicrystals.
- Published
- 2000
49. The ring expansion of a dimethyl-substituted vinylcyclobutene derivative by metal complexes that can undergo an inner-sphere electron transfer
- Author
-
Herman L Holt, Allan R. Pinhas, and Tom Russo
- Subjects
Chemistry ,Organic Chemistry ,Inner sphere electron transfer ,Ring (chemistry) ,Photochemistry ,Biochemistry ,Inorganic Chemistry ,Metal ,chemistry.chemical_compound ,Crystallography ,visual_art ,Materials Chemistry ,visual_art.visual_art_medium ,Rearrangement reaction ,Physical and Theoretical Chemistry ,Derivative (chemistry) - Abstract
The ring expansion of a dimethyl-substituted vinylcyclobutene derivative to the corresponding dimethyl-substituted cyclohexadiene or aromatic compound was studied. It was found that metal complexes of Ni(I), Ti(III), Sm(II), and Fe(II), which can undergo an inner-sphere electron-transfer reaction, allow the rearrangement to occur at room temperature. Other oxidation states of these metals and complexes that can only undergo an outer-sphere electron-transfer process do not promote this ring expansion reaction.
- Published
- 2000
50. A New Atom/Functional Group Volume Additivity Data Base for the Calculation of the Crystal Densities of C, H, N, O and F-Containing Compounds
- Author
-
Sara Mitchell and Herman L. Ammon
- Subjects
Base (group theory) ,Crystal ,chemistry.chemical_compound ,Crystallography ,Volume (thermodynamics) ,chemistry ,General Chemical Engineering ,Additive function ,Functional group ,Atom (order theory) ,General Chemistry - Published
- 1998
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