Chiral bis(amino amides) as chiral solvating agents for enantiomeric excess determination of α-hydroxy and arylpropionic acids

A family of bis(amino amides) derived from natural amino acids has been synthesized and tested for the NMR enantiodiscrimination, as chiral solvating agents, for enantiomeric excess determination of some carboxylic acids. Those bis(amino amide) receptors contain different structural modifications and the splitting of the signals of the acids, after addition of the corresponding CSAs, depends on those structural variables. The influence of aminoacid side chain and the nature of the aliphatic spacer are important parameters to obtain good chiral discriminations. The results obtained clearly show the chiral recognition abilities of these bis(amino amide) ligands and suggest their advantageous use as chiral solvating agents for carboxylic acids. The binding between bis(amino amides) and carboxylic acids has been studied by ESI-MS, NMR, DSC, and molecular modeling. The data suggest that enantiodiscrimination involves the formation of an ionic pair after proton transfer from the carboxylic substrate to the bis(amino amides).     

Optimization of high-speed railway pantographs for improving pantograph-catenary contact

A crucial system for the operation of high-speed trains is the pantograph catenary interface as it is the sole responsible to deliver electrical power to the train. Being the catenary a stationary system with a long lifespan it is also less likely to be redesigned and upgraded than the pantographs that fit the train vehicles. This letter proposes an optimization procedure for the improvement of the contact quality between the pantograph and the catenary solely based on the redesign of the pantograph head suspension characteristics. A pantograph model is defined and validated against experimental dynamic characteristics of existing pantographs. An optimization strategy based on the use of a global optimization method, to find the vicinity of the optimal solution, followed by the use of a deterministic optimization algorithm, to fine tune the optimal solution, is applied here. The spring stiffness, damping characteristics and bow mass are the design variables used for the pantograph optimization. The objective of the optimal problem is the minimization of the standard deviation of the contact force history, which is the most important quantity to define the contact quality. The pantograph head suspension characteristics are allowed to vary within technological realistic limits. It is found that current high-speed railway pantographs have a limited potential for mechanical improvements, not exceeding 10%–15% on the decrease of the standard deviation of the contact force.     

Categorically perfect rings

An essential monoreflection is constructed on the category Sp of semiprirne commutative rings with identity, which is not a ring-of-quotients functor     

A detailed view of the Gaussian–Lorentzian sum and product functions and their comparison with the Voigt function

The Gaussian–Lorentzian sum (GLS) and product (GLP) functions remain important in X-ray photoelectron spectroscopy (XPS) peak fitting. Here, we present a detailed view of these functions, comparing them with each other and with the Voigt function (the “LA(m)” function). First, we show the GLS, GLP, and LA(m) functions as a function of their mixing parameters, m, which reveals differences between them. We then illustrate the use of these functions to fit a series of spectra acquired at different pass energies (resolutions). Next, we show the underlying Gaussian and Lorentzian components of a series of GLS and GLP functions as a function of m, which confirms that the GLS is a simple linear combination of Gaussian and Lorentzian functions. However, one of the two functions used to make the GLP can be very wide, that is, at its extremes, one of these functions has infinite width. We then discuss a plot of the areas of the GLS, GLP, and LA(m) functions as a function of m, which reveals the expected, linear increase in area of the GLS, but nonlinear changes in the areas of the other two functions. Finally, to better understand them, we fit these functions to each other. These results indicate that the GLS and GLP better match the LA(m) function at lower and higher values of the mixing parameter, respectively.     

Controlling Electronic Events Through Rational Structural Design in Subphthalocyanine–Corrole Dyads: Synthesis,Characterization, and Photophysical Properties

Porphyrinoids are considered perfect candidates for their incorporation into electron donor–acceptor (D–A) arrays due to their remarkable optoelectronic properties and low reorganization energies. For the first time, a series of subphthalocyanine (SubPc) and corrole (Cor) were covalently connected through a short-range linkage. SubPc axial substitution strategies were employed, which allowed the synthesis of the target molecules in decent yields. In this context, a qualitative synthetic approach was performed to reverse the expected direction of the different electronic events. Consequently, in-depth absorption, fluorescence, and electrochemical assays enabled the study of electronic and photophysical properties. Charge separation was observed in cases of electron-donating Cors, whereas a quantitative energy transfer from the Cor to the SubPc was detected in the case of electron accepting Cors.     

Insights on the cellulose pretreatment at room temperature by choline-chloride-based deep eutectic solvents: an atomistic study

Cellulose - The pretreatment or disruption of a cellulose I $$\beta $$ crystallite by four deep eutectic solvents (DES): choline-chloride ethylene glycol, choline-chloride oxalic acid,...     

CMMSE: analysis and comparison of some numerical methods to solve a nonlinear fractional Gross–Pitaevskii system

Journal of Mathematical Chemistry - In this work, we introduce and theoretically analyze various computational techniques to approximate the solutions of solve a fractional extension of a double...     

Urinary volatomic profile of traditional tobacco smokers and electronic cigarettes users as a strategy to unveil potential health issues

Many harmful and potentially harmful constituents are present in tobacco products. Cigarette smoke is known to cause different forms of cancer and trigger the development of chronic diseases. In the last decade, electronic cigarettes have emerged as a healthier alternative associated to less harmful effects in comparison to traditional tobacco. However, the lack of standardization of electronic cigarettes products makes it difficult to establish and compare the real effects on health of products from different manufacturers. To better understand the impact of smoking and vaping, the volatomic composition of urine samples from traditional tobacco smokers and electronic cigarette users was established and compared with nonsmokers (control group), using headspace solid-phase microextraction combined with gas chromatography–mass spectrometry. A total of 45 urinary volatile organic metabolites belonging to different chemical families were identified in the urine of the studied groups. Benzene derivatives, terpenes, and aromatics were the chemical families that contributed the most to the urinary profile of smokers. The vapers urinary volatomic pattern was also dominated by terpenes and aromatics, in addition to alcohols. The orthogonal partial least squares-discriminant analysis of the data obtained indicated that the urinary profile of vapers is more closely related to the control group, reinforcing the hypothesis of the lowest harmfulness of electronic cigarettes. Further studies recruiting a higher number of subjects are therefore necessary to consolidate the data obtained.     

Dynamic effects in inefficiency: Evidence from the Colombian banking sector

Firms face a continuous process of technological and environmental changes that requires them to make managerial decisions in a dynamic context. However, costs and constraints prevent firms from making instant adjustments towards optimal conditions and may cause inefficiency to persist in time. We propose a dynamic inefficiency specification that captures differences in the adjustment costs among firms and non-persistent effects of inefficiency heterogeneity. The model is fitted to a ten year sample of Colombian banks. The new specification improves model fit and have effects on efficiency estimations. Overall, Colombian banks present high inefficiency persistence but important differences between institutions are found. In particular, merged banks present low adjustment costs that allow them to recover rapidly efficiency losses derived from merging processes.