Enthalpies of formation of methoxybenzoic acids and their dependence on structure

The energy of combustion of 2,5-dimethoxybenzoic acid has been determined using a static bomb calorimeter. The vapor pressures of the compound have been measured over a 18 K temperature interval by the Knudsen effusion technique. Heat capacity measurements betweenT=270 K andT=338 K were carried out by DSC. From these experimental results the standard molar enthalpies of combustion, sublimation, and formation in the crystalline and gaseous state at the temperature 298.15 K have been derived. With this compound, the series of mono- and dimethoxy-benzoic acids have been completed. Their_f H _m ^o values were expressed by an additive relationship, taking into account the number of methoxy groups and the number of all 1,2 interactions: an accuracy of 3.3 kJ·mol^–1 was achieved. In an alternative approach the substituent effect of the methoxy groups was evaluated within the framework of isodesmic reactions. The effect of disubstitution was referred to mono derivatives and the excess energy—the so-called buttressing effect—was evaluated (2–24 kJ· mol^–1 for individual bis derivatives). These values were explained in terms of the conformation of the methoxy group around the C_ar-O bond.     

High throughput screening of O-glycosylation conditions

We report a novel methodology for rapid and quantitative screening of O-glycosylation reactions of application to the analysis of parallel reaction systems. Our system exploits perdeuterated benzyl (Bn-d₇) ether, and stereoselectivity and yield are evaluated by ¹H NMR and MALDI-TOF MS, respectively. This paper summarizes over 240 screenings of 1 → 3 linkage formation between glucose residues targeting the α-isomer in high yield.     

Construction of Spatiotemporal-Coupling Optimal Low-Dimensional Dynamical Systems for Compressible Navier-Stokes Equations; [可压缩 Navier-Stokes 方程的时空耦合优化低维动力系统建模方法]北大核心CSCD

For the low-dimensional dynamical system model to study dynamics properties of Navier-Stokes equations, it is very important that the attraction domain of the low-dimensional model is the same as that of Navier-Stokes equations. However, to date, there is no universal approach to ensure this purpose for general problems. Herein, it is found that any low-dimensional model based on spatial bases, such as proper orthogonal decomposition bases, optimal spatial bases, and other classical spatial bases, is not predictable, i.e., the error increases with the time evolution of the flow field. With the theoretical framework for building optimal dynamical systems and the new concept of spatiotemporal-coupling spectrum expansion, the low-dimensional model for compressible Navier-Stokes equations was constructed to approximate the numerical solution to large-eddy simulation equations, and the numerical results and novel time evolution of spatiotemporal-coupling bases were given. The entire field error is typically below 10−2%, and the average error at each grid point is below 10−8%. The spatiotemporal-coupling optimal low-dimensional dynamical systems can ensure that the attraction domain of the low-dimensional model is the same as that of Navier-Stokes equations. Therefore, characteristic dynamics properties of spatiotemporal-coupling optimal low-dimensional dynamical systems are the same as those of real flow. © 2022 Editorial Office of Applied Mathematics and Mechanics. All rights reserved.     

基于主被动合作博弈的医患关系研究

针对我国医患关系日趋紧张,医患矛盾逐渐凸显这一问题,在对中国近五年医患事件进行分析的基础上,分别从信任程度、信息不对称程度、诊疗代价等多个视角出发,利用演化博弈理论和复制动态方程,构建了医患双方合作策略选择演化博弈模型,探究了影响医患关系演化的相关因素。研究表明:从长期来看,医患关系博弈系统存在两种演化路径:主动合作和被动合作;增大医患双方的信任程度,减小医患双方的信息不对称程度,降低医患双方合作成本,增大以政府为主导的仲裁机构对医患双方的奖励和惩罚都将会促使医患双方由被动合作转向主动合作。     

A bi-virus competing model with time-varying susceptibility and repeated infection

This paper introduces a bi-virus model with time-varying susceptibility. The model describes the case that there coexist two viruses and the time-varying susceptibility due to repeated infections. For different parameters, we investigate the stability of various equilibriums. Under appropriate conditions the two viruses show competitive relationship, that is, one virus will eventually become a pandemic, and the other virus will eventually disappear. For this case, we further study the dynamical behavior of virus transmission. The model shows some new phenomena, that is, the outbreak of the virus will be delayed appropriately, giving people an illusion. Finally, we present a numerical example to illustrate the effectiveness of the theoretical results.     

Quantitative weight of evidence method for combining predictions of quantitative structure-activity relationship models

ABSTRACT

A method for combining statistical-based QSAR predictions of two or more binary classification models is presented. It was assumed that all models were independent. This facilitated the combination of positive and negative predictions using a quantitative weight of evidence (qWoE) procedure based on Bayesian statistics and the additivity of the logarithms of the likelihood ratios. Previous studies combined more than one prediction but used arbitrary strengths for positive and negative predictions. In our approach, the combined models were validated by determining the sensitivity and specificity values, which are performance metrics that are a point of departure for obtaining values that measure the weight of evidence of positive and negative predictions. The developed method was experimentally applied in the prediction of Ames mutagenicity. The method achieved a similar accuracy to that of the experimental Ames test for this endpoint when the overall prediction was determined using a combination of the individual predictions of more than one model. Calculating the qWoE value would reduce the requirement for expert knowledge and decrease the subjectivity of the prediction. This method could be applied to other endpoints such as developmental toxicity and skin sensitisation with binary classification models.     

Thermoanalytische Charakterisierung Strahlengehärteter Polymerfilme

Thermo-oxidative and thermo-mechanical stabilities of radiation-cured acrylates and epoxides were examined by TG, DMA and DSC.The polymeric trifunctional acrylates PETIA, TMPTA and THEIC displayed the highest temperatures of onset of degradation. The high crosslinking density of the films resulted in an almost temperature-independent complex E-modulus, as measured by DMA. With increasing degree of ethoxylation or propoxylation of the monomers, decreases in thermal stability and strength were found. For difunctional polymeric acrylates and epoxides, the glass transition temperature was measured.The average degree of curing of UV-cured epoxy films can be determined from the temperature of the maximum in the loss modulus (E_max.This revised version was published online in November 2005 with corrections to the Cover Date.     

A pseudoreceptor docking study of 4,5-α-epoxymorphinans with a range of dielectric constants

Summary Thirteen 4,5-epoxymorphinan agonists with established analgesic action were docked into an Asp-Lys-His-Phe pseudoreceptor complex under a range of distance-dependent dielectric conditions. The number of compounds with potential energies of the docked complexes that agreed in rank order with corresponding analgesic potencies was determined for each condition. Two dielectric conditions, n-decane (1.991) and ethanol (24.3), enabled the greatest number of compounds to relate to their pseudoreceptors with each having 9 and 8 successes respectively. Both of these conditions demonstrated unique influences on the types of structures that were successfully docked. For example, the morphine stereoisomer -isomorphine, the geometric isomer B/C trans-morphine, and the 8-position-substituted -isomorphine were successes in the n-decane condition, whereas the ethanol condition produced the substituted codeine derivatives dihydroco-deinone and dihydroxycodeinone. These findings emphasize the importance of dielectric influence when developing force-field modeled quantitative structure-activity relationships for a closely related homologous series.     

Comparison of quantitative methods for analysis of polyphasic pharmaceuticals

Adequate very sensitive quantification methods are needed for the development and are also now required for the monitoring of undesirable solid form(s) as routine tests. The pre-requisite for quantitation are selectivity, sensitivity and most important the purity of standards and their proper storage, what is a challenge for metastable forms. Several analytical techniques are available such as X-ray diffraction, spectroscopy, thermal analysis and microcalorimetry. The different steps of the validation of the analytical methods and problems to be solved are discussed. Examples illustrate the different techniques and compare their possible advantages and limits. The relative standard deviation of measurements should allow for checking the homogenization procedure of mixtures for calibration. The validation should be carried out following ICH guidelines for validation of analytical methods. Comparison of different techniques in adequate concentration range add confidence in the analytical results.