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The three possible 1-(n-pyridinyl)butane-1,3-diones (nPM) have been synthesized. Structures, tautomerism, and conformations are investigated by means of DFT calculations. 1H and 13C NMR spectra are assigned, and deuterium isotope effects on 13C chemical shifts have been measured. Analysis of the isotope effects leads to the equilibrium constants of the keto–enol tautomers. Some interesting differences are seen between the three compounds and the phenyl analogs. The isotope effects can also rank the hydrogen bonds of the compounds, with the one with nitrogen in the three positions of the pyridine ring as the weakest. Structures, conformers, energies, and NMR nuclear shieldings are calculated using DFT calculations at the B3LYP/6-311++G(d,p) level.

In this article, Hansen analyzes and discusses the construction of the fourth-century BC. Temple of Apollo at Delphi, taking into consideration the practical aspects of this difficult construction process. He includes the unique epigraphic building accounts that have been made accessible to non-philologists with Jean Bousque’s edition and French translation of the fragments published in 1989. Thereby Hansen offers a masterful revised calendar of the whole building process of the third largest temple on the Greek mainland.

The present overview concentrates on recent developments of tautomerism of β-diketones and β-thioxoketones, both in solution and in the solid state. In particular, the latter has been a matter of debate and unresolved problems. Measurements of 13C, 17O, and 2H chemical shifts have been used. Deuterium isotope effects on chemical shifts are proposed as a tool in the study of this problem. Photoconversion of β-diketones and β-thioxoketones are discussed in detail, and the incorporation of β-diketones into molecules with fluorescent properties is assessed. Finally, docking studies of β-diketones are scrutinized with an emphasis on correct tautomeric structures and knowledge about barriers to interconversion of tautomers.

Redaktørens dagbogsnoter fra en bibliotekstur i Baltikum.

Erfaringer med chatbot-teknologi. Det Kgl. Biblioteks centrale kontaktservice ”Spørg biblioteket” har det seneste år været suppleret med en virtuel assistent.

The photochemistry of a cyclic β-thioxoketone (2-methyl-1-(2-thioxycyclohexyl)propan-1-one (MTPO)) is investigated by NMR, UV, and IR experiments supported by DFT calculations. MTPO exists as a tautomeric mixture of an enol and a thiol form. Irradiation at low temperature led to a

We present numerical computation of back-reflected fields resulting from the interaction of 2D and 3D photonic jets with planar air-silicon interfaces. The photonic jets are generated by a plane wave-illuminated glass ball (3D) and cylinder (2D) in the presence of a silicon substrate. Our results are applicable in the use of photonic jets as highly focused probes in far-field optical microscopy.

PURPOSE This study aimed to assess long-term follow-up after chemoresection with mitomycin (MMC), a nonsurgical treatment modality for recurrent nonmuscle invasive bladder cancer (NMIBC). At the time of recurrence, chemoresection has previously been shown to reduce the number of patients requiring a procedure (transurethral resection of bladder tumors [TURBT] or office biopsy) by more than 50%. This study investigated the number of patients requiring a procedure during initial treatment and 2-year follow-up in patients treated with short-term, intensive chemoresection with MMC compared with patients undergoing standard surgical treatment of recurrent NMIBC. METHODS A randomized, controlled trial was conducted in two urological departments in Denmark from January 2018 to August 2021. In total, 120 patients with a history of Ta low- or high-grade NMIBC were included upon recurrence. The intervention group received intravesical MMC (40 mg/40 mL) three times a week for 2 weeks and TURBT or office biopsy only if the response was incomplete. The control group received TURBT or office biopsy and 6 weekly adjuvant instillations. The primary outcome was the number of patients undergoing a procedure within 2 years from inclusion, which was compared between groups using the chi-squared test. Recurrence-free survival was analyzed using the Kaplan-Meier method. RESULTS Significantly fewer patients were in need of a procedure in the intervention group than in the control group: 71% (95% CI, 57 to 81) and 100% (95% CI, 94 to 100), P < .001. The 12-month recurrence-free survival was 36% (95% CI, 24 to 50) and 43% (95% CI, 30 to 56) in the intervention and control groups, respectively ( P = .5). CONCLUSION Short-term intensive chemoresection is an effective treatment strategy for recurrent NMIBC that leads to a reduced number of required procedures without compromising long-term oncological safety.

The scattering characteristics of random rough surfaces illuminated with a 3D converging–diverging Gaussian beam are investigated by applying the conventional Harvey–Shack theory in conjunction with 2D plane-wave decomposition. The Gaussian beam is assumed to have an arbitrary angle of incidence and to be linearly s-polarized. Using data obtained from laser BRDF measurements on isotropic random rough surfaces with low surface roughness, we demonstrate that the Gaussian beam Harvey–Shack theory is in better accordance with the experimental data than the conventional Harvey–Shack theory. The two models become identical for a large beam waist radii but are significantly different for smaller ones.

Large biomolecules often have multiple intramolecular hydrogen bonds. In the cases where these interact, it requires special tools to disentangle the patterns. Such a tool could be deuterium isotope effects on chemical shifts. The use of theoretical calculations is an indispensable tool in such studies. The present paper illustrates how DFT calculations of chemical shifts and deuterium isotope effects on chemical shifts in combination with measurements of these effects can establish the complex intramolecular hydrogen bond patterns of rifampicin as an example) The structures were calculated using DFT theoretical calculations, performed with the Gaussian 16 software. The geometries were optimized using the B3LYP functional and the Pople basis set 6-31G(d) and the solvent (DMSO) was taken into account in the PCM approach. Besides the 6-31G(d) basis set, the 6-31 G(d,p) and the 6-3111G(d,p) basis sets were also tested. The nuclear shieldings were calculated using the GIAO approach. Deuteriation was simulated by shortening the X-H bond lengths by 0.01 Å.

We have demonstrated a hydrogen (H2) refueling solution capable of delivering precooled, compressed gaseous hydrogen for heavy duty vehicle (HDV) refueling applications by refueling transit buses over a three-month period under real-world conditions. The system uses a submerged pump to deliver pressurized liquid H2 from a cryogenic storage tank to a dispensing control loop that vaporizes the liquid and adjusts the pressure and temperature of the resulting gas to enable refueling at 35 MPa and temperatures as low as −40 °C, consistent with the SAE J2601 standard. Using our full-scale mobile refueler, we completed 118 individual bus filling events using 13 different vehicles, involving a total of 3,700 kg of H2 dispensed. We report filling statistics from the entire campaign, details on individual fills (including fill times, final state of charge, benefits of pre-cooled fills, and back-to-back filling capabilities), and discuss transit agency feedback on technology performance. In our final test, the system successfully completed an endurance test using a single dispenser involving 52 consecutive individual fills over an 11.5-h period, dispensing 1,322 kg of H2 with an average fill rate of 3.4 kg/min and peak rate of 7.1 kg/min, and reaching an average SOC of 97.6% across all fills.

A promising technique in optical super-resolution microscopy is the illumination of the sample by a highly localized beam, a photonic jet (also called photonic nanojet). We propose a method of computation of incident field amplitude and phase profiles that produce photonic jets at desired locations in the near field after interaction with a fixed micro-scale dielectric lens. We also describe a practical way of obtaining the incident field profiles using spatial light modulators. We expect our photonic jet design method to work for a wide range of lens shapes, and we demonstrate its application numerically using two-dimensional micro-lenses of circular and square cross-sections. We furthermore offer a theoretical analysis of the resolution of photonic jet design, predicting among other that a larger lens can produce a narrower photonic jet. Finally, we give both theoretical and numerical evidence that the waist width of the achieved designed jets is increasing linearly and slowly over a large interval of radial distances. With uniform plane wave illumination, the circular two-dimensional micro-lens produces a similar-sized jet at a fixed radial distance, while the square lens does not form a jet at all. We expect our steerable optical photonic jet probe to enable highly localized adaptive real-time measurements and drive advances in super-resolution optical microscopy and scatterometry, as well as fluorescence and Raman microscopy. Our relatively weak peak jet intensity allows application in biology and health sciences, which require high resolution imaging without damaging the sample bio-molecules.

The lateral and vertical resolution in conventional optical microscopy is restricted by fundamental diffraction limits. One direction towards super-resolution optical microscopy is the use of photonic nanojets (PNJs) for sample illumination. Here, the aim is to exploit the high spatial localization of PNJs to allow measurements of sub-classical particles and features in spite of their small size compared to the operating wavelength. The applications of super-resolution methods include fluorescence and Raman microscopy, catterometric measurements, and optical imaging. As a step towards PNJ scanning microscopy, we here apply our recently proposed method for fast and precise steering of PNJs over a large dynamical range in the near field. In a proof-of-concept computation, we use the steerable optical probe to extract information on structures beyond the classical lateral and vertical resolution limits.

O objetivo desta pesquisa foi verificar a viabilidade e identificar as peculiaridades de aplicação do Custeio Alvo em cursos de Pós-graduação. Inicialmente, foi efetuado um levantamento bibliográfico para verificar como o assunto é tratado pela literatura, buscando-se subsídios para explicar o processo de aplicação do Custeio Alvo em cursos de Pós-graduação, bem como demonstrar as diferenças e dificuldades desta utilização em relação ao seu emprego em indústrias. Paralelamente, foi elaborado um questionário aplicado aos alunos dos cursos de Pós-graduação do Centro Universitário do Leste de Minas Gerais Unileste-MG, matriculados na primeira quinzena março de 2002. O questionário em questão objetivou verificar a percepção dos alunos em relação ao grau de importância de cada serviço que lhes foi prestado e em relação as características de cada curso oferecido. Ao mesmo tempo, foi desenvolvido, pelo autor, um segundo questionário, aplicado às Instituições de Ensino Superior de Minas Gerais, com a finalidade de conhecer os preços dos serviços educacionais praticados pelo mercado de cursos de Pós-graduação nas mesmas áreas de conhecimento dos cursos oferecidos pelo Unileste-MG. Foram, também, realizadas entrevistas junto a direção do Unileste-MG, com o objetivo de verificar como é estabelecido o preço e como é definida a margem de lucro de um curso de Pós-graduação. Além disso, foi efetuada análise documental em planilhas de custos e nos registros do sistema contábil do Unileste-MG, visando conhecer os procedimentos, os métodos e os tratamentos dos dados adotados pela Instituição. A partir destas informações foi possível estabelecer um modelo de aplicação do Custeio Alvo em cursos de Pós-graduação, além de se constatar alguns aspectos específicos da aplicação em serviços de ensino não encontrados na literatura consultada. Por fim, foi utilizado o modelo gerencial proposto, no curso de Pós-graduação em Administração Financeira do Unileste-MG, constatando-se que é viável a aplicação do Custeio Alvo em cursos de Pós-graduação. This research intended to verify the application and feasibility of Target Costing in a project or a program of graduate courses. First of all, a bibliographic study was conducted in order to verify how this subject is treated by the literature, looking for subsidies to explain the application of the Target Costing process in graduate courses, as well as to demonstrate the differences and the difficulties of its application in relation to the process in manufacturing industries where it is mostly applied. At the same time, a questionnaire was elaborated and applied to the graduate students at Centro Universitario do Leste de Minas Gerais - Unileste-MG enrolled in the first half of March 2002. This questionnaire was intended to verify their perception of the level of importance of each service provided to them according to the specific characteristics of each graduate course offered. A second questionnaire was also elaborated by the author and applied to the directors of graduate schools located in the state of Minas Gerais to evaluate the market price of the educational services for graduate courses at the same area of the graduate courses offered by Unileste-MG. In addition, the Unileste-MG Board of Directors was also interviewed in order to identify the costing system used to establish the price and marginal profit of a graduate course. Furthermore, a documental analysis of cost tables and data of the Unileste-MG accounting system was performed in order to evaluate the data collected and to identify the procedures, methods and treatment of the data adopted by the institution. Through all this information, it was possible to establish a model of application of the Target Costing in graduate courses, obtaining specific aspects that werent found in the literature sources. Finally, the proposed model was applied, certifying that the application of the Target Costing for graduate courses is possible and feasible.

The possible effect of curcumin as a potential natural cancer treatment drug has been intensively discussed. In the present study the probabilities of a series of curcumin analogues to possess potential as antineoplastic, prostate cancer treatment and anticarcinogenic agents has been studied theoretically applying a selection of quantitative structure-activity relation and absorption, distribution, metabolism, and excretion (ADME) approaches. From spectroscopic studies it is evident that these compounds can be found in both enol and diketo forms, the former in general the more predominant in non-polar solvents, whereas in polar solvents, like water an increasing amount of the diketo form can be noted. Hence, the probabilities for both the enols and diketo forms to possess the above-mentioned effects were studied. In most cases the enol form shows the highest probabilities for being effective although the differences are not significant. Thus, it is suggested to look at the sum of effects of the keto and the enol forms in relation to the possible therapeutic effects of the compounds here studied.

We have developed a hydrogen (H2) refueling solution capable of delivering precooled, compressed gaseous hydrogen for heavy duty vehicle (HDV) refueling applications. The system uses a submerged pump to deliver pressurized liquid H2 from a cryogenic storage tank to a dispensing control loop that vaporizes the liquid and adjusts the pressure and temperature of the resulting gas to enable refueling at 35 MPa and temperatures as low as −40 °C. A full-scale mobile refueler was fabricated and tested over a 6-month campaign to validate its performance. We report results from tests involving a total of 9000 kg of liquid H2 pumped and 1350 filling cycles over a range of conditions. Notably, the system was able to repeatably complete multiple, back-to-back 30 kg filling cycles in under 6 min each, in full compliance with the SAE J2601-2 standard, demonstrating its potential for rapid-throughput HDV refueling applications.

The prediction of 13 C chemical shifts can be challenging with density functional theory (DFT). In this study 39 different functionals and three different basis sets were tested on three neutral alkylpyrroles and their corresponding protonated species. The calculated shielding constants were compared to experimental data and results from previous calculations at the MP2. We find that the meta-hybrid functional TPSSh with either the Pople style basis set 6-311++G(2d,p) or the polarization consistent basis set pcSseg-1 gives the best results for the 13 C chemical shifts, whereas for the 1 H chemical shifts it is the TPSSh functional with either the 6-311++G(2d,p) or pcSseg-2 basis set. Including an explicit solvent molecule hydrogen bonded to NH in the alkylpyrroles improves the results slightly for the 13 C chemical shifts. On the other hand, for 1 H chemical shifts the opposite is true. Compared to calculations at the MP2 level none of the DFT functionals can compete with MP2 for the 13 C chemical shifts but for the 1 H chemical shifts the investigated DFT functionals are shown to give better agreement with experiment than MP2 calculations.

A series of five intramolecularly hydrogen-bonded arylhydrazone (aryl = phenol, p-nitrophenol, anisole, quinoline) derived molecular switches have been synthesized and characterized by NMR and HRMS techniques. It was found that the compounds exist as different isomers in solution. An investigation of both conformational and/or configurational changes of the azo-hydrazone compounds was carried out by 1D 1 H- and 13 C- spectra, 2D NOESY, COSY, HSQC, and HMBC techniques. It was found that these stimuli-responsive molecular switches exist mainly in the E form by intramolecularly hydrogen bonded between NH and the pyridine nitrogen at equilibrium. Deprotonation of the neutral E form yields the E' deprotonated isomer. Prediction of 13 C-NMR chemical shifts was achieved by DFT quantum mechanical calculations. Anions have traditionally been difficult to calculate correctly, so calculations of the anion using different functionals, basis sets, and solvent effects are also included. Deuterium isotope effects on the 13 C-NMR chemical shifts were employed in the assignments and furthermore utilized as indicators of intramolecular hydrogen bonding. Studies in various organic solvents including CDCl3 , CD3 CN, and DMSO-d6 were also performed aiming to monitor dynamic changes over several days. The effect of the hydrogen bonded solvents leads to Z forms.

This review is giving a short introduction to the techniques used to investigate isotope effects on NMR chemical shifts. The review is discussing how isotope effects on chemical shifts can be used to elucidate the importance of either intra- or intermolecular hydrogen bonding in ionic liquids, of ammonium ions in a confined space, how isotope effects can help define dimers, trimers, etc., how isotope effects can lead to structural parameters such as distances and give information about ion pairing. Tautomerism is by advantage investigated by isotope effects on chemical shifts both in symmetric and asymmetric systems. The relationship between hydrogen bond energies and two-bond deuterium isotope effects on chemical shifts is described. Finally, theoretical calculations to obtain isotope effects on chemical shifts are looked into.

”Nu handler det om at få implementeret de konkrete ting, som vi har snakket om i strategien. Især kompetencebehovet er et af de punkter hvor kollegerne derude rigtig gerne vil bruge foreningen til. At styrke fagligheden på tværs og erfaringsudveksle.” - interview med Karin Englev, nyvalgt DFFU-formand.

Interview med informationsspecialister og undervisere, Annemette Møller Hansen og Susie Rimborg. Vi taler online-undervisning og hvordan corona-tiden også blev et strategisk tigerspring for dem selv - og for Københavns Universitetsbibliotek.

Introduction Buprenorphine is a partial μ-opioid receptor agonist that, unlike full μ-opioid receptor agonists, has been shown to have a ceiling effect on respiratory depression. Buprenorphine buccal film (BBF) is approved by the US Food and Drug Administration for use in patients with chronic pain severe enough to require daily, around-the-clock, long-term opioid treatment and for whom alternative treatment options are inadequate. This study was conducted to compare the effects of BBF and immediate-release oral oxycodone hydrochloride administration on respiratory drive, as measured by the ventilatory response to hypercapnia (VRH) after drug administration. Methods Subjects (N = 19) were men and women, ages 27–41 years, self-identifying as recreational opioid users who were not physically dependent on opioids as determined via a Naloxone Challenge Test. Respiratory drive was evaluated by measuring VRH through the assessment of the maximum decrease in minute ventilation (Emax) after administration of each treatment. The treatments utilized in this study included 300, 600, and 900 μg BBF; 30 and 60 mg orally administered oxycodone; and placebo (each separated by a 7-day washout period). Effects on respiratory drive were assessed using a double-blind, double-dummy, six-treatment, six-period, placebo-controlled, randomized crossover design. Statistical analyses were performed using a linear mixed-effects model. Results The least squares mean differences in minute volume Emax (L/min, versus placebo) were as follows: 300 μg BBF (+ 1.24, P = 0.529), 600 μg BBF (+ 0.23, P = 0.908), 900 μg BBF (+ 0.93, P = 0.637), 30 mg oxycodone (− 0.79, P = 0.687), and 60 mg oxycodone (− 5.23, P = 0.010). Conclusions BBF did not significantly reduce respiratory drive at any dose compared with placebo, including at the maximum available prescription dose of 900 μg. Administration of oxycodone resulted in a significant dose-dependent decrease in respiratory drive. These data suggest that BBF may be a safer treatment option than full μ-opioid receptor agonists for patients with chronic pain. Trial Registration ClinicalTrials.gov identifier, NCT03996694. Electronic supplementary material The online version of this article (10.1007/s12325-020-01481-0) contains supplementary material, which is available to authorized users.

From the ethyl acetate extract of the stems of Miliusa velutina, seven compounds (1-7) were isolated, including two new compounds such as mivelutina A acid (1), mivelutina B acid (2) and one known compound mivelutina B methyl ester (3). For this NMR data were not known previously. Their relative structures were elucidated based on NMR spectroscopic analysis. The absolute configuartions were determined based on DFT calculations of 13C chemical shifts. All of the seven compounds were screened for their in vitro cytotoxic activities against HepG2 cell line using the SRB assay. Epoxyconiferyl alcohol (7) showed the highest potential for the cytotoxicity of cancer cell lines HepG2 with the IC50 values of 95.94 μg/mL (527 μM).

1 J(15 N,H) coupling constants for enaminones and NH-forms of intramolecularly hydrogen-bonded Schiff bases as model compounds for sp2 -hybridized nitrogen atoms are evaluated using density functional theory (DFT) to find the optimal functionals and basis sets. Ammonia is used as a test molecule and its one-bond coupling constant is compared with experiment. A methylamine Schiff base of a truncated molecule of gossypol is used for checking the performance of selected B3LYP, O3LYP, PBE, BHandH, and APFD density functionals and standard, modified, and dedicated basis sets for coupling constants. Both in vacuum and in chloroform, modeled by the simple continuum model of solvent, the modified basis sets predict significantly better the 1 J(15 N,H) value in ammonia and in the methylamine Schiff base of a truncated molecule of gossypol than the standard basis sets. This procure is then used on a broad set of intramolecularly hydrogen-bonded molecules, and a good correlation between calculated and experimental one-bond NH coupling constants is obtained. The 1 J(15 N,H) couplings are slightly overestimated. The calculated data show for hydrogen-bonded NH interatomic distances that the calculated values depend on the NH bond lengths. The shorter the bond lengths, the larger the 1 J(15 N,H). A useful correlation between 1 J(15 N,H) and NH bond length is derived that enables realistic predictions of one-bond NH coupling constants. The calculations reproduce experimentally observed trends for the studied molecules.

Sidst i februar trådte Bertil Dorch tilbage som formand for DFFU efter næsten 5½ års virke. REVY satte ham stævne et sted ude i den gamle virkelighed.

The outset of realistic rendering is a desire to reproduce the appearance of the real world. Rendering techniques therefore operate at a scale corresponding to the size of objects that we observe with our naked eyes. At the same time, rendering techniques must be able to deal with objects of nearly arbitrary shapes and materials. These requirements lead to techniques that oftentimes leave the task of setting the optical properties of the materials to the user. Matching the appearance of real objects by manual adjustment of optical properties is however nearly impossible. We can render objects with a plausible appearance in this way but cannot compare the appearance of a manufactured item to that of its digital twin. This is especially true in the case of translucent objects, where we need more than a goniometric measurement of the optical properties. In this survey, we provide an overview of forward and inverse models for acquiring the optical properties of translucent materials. We map out the efforts in graphics research in this area and describe techniques available in related fields. Our objective is to provide a better understanding of the tools currently available for appearance specification when it comes to digital representations of real translucent objects.

”Som forskningsbibliotek skal vi i fremtiden være væsentligt bedre til at byde ind i denne type samarbejder og udvikle os i forhold til behovene for services fra vores moderinstitution.”

Non-invasive imaging is a key clinical tool for detection and treatment monitoring of infections. Existing clinical imaging techniques are frequently unable to distinguish infection from tumors or sterile inflammation. This challenge is well-illustrated by prosthetic joint infections that often complicate joint replacements. D-methyl-614.5 ± 100.2 MBq of D-D-D