Effects of anharmonicity on nonadiabatic electron transfer: a model

The effect of anharmonicity in the intramolecular modes of a model system for exothermic intramolecular nonadiabatic electron transfer is probed by examining the dependence of the transition probability on the exoergicity. The Franck-Condon factor for the Morse potential is written in terms of the Gauss hypergeometric function both for a ground initial state and for the general case, and comparisons are made between the first-order perturbation theory results for transition probability for harmonic and Morse oscillators. These results are verified with quantum dynamical simulations using wave-packet propagations on a numerical grid. The transition-probability expression incorporating a high-frequency quantum mode and low-frequency medium mode is compared for Morse and harmonic oscillators in different temperature ranges and with various coarse-graining treatments of the delta function from the Fermi golden rule expression. We find that significant deviations from the harmonic approximation are expected for even moderately anharmonic quantum modes at large values of exoergicity. The addition of a second quantum mode of opposite displacement negates the anharmonic effect at small energy change, but in the inverted regime a significantly flatter dependence on exoergicity is predicted for anharmonic modes.     

A Sequential Debonding Fracture Model for Hydrogen-Bonded Hydrogels

Hydrogen bonds are known to play an important role in prescribing the mechanical performance of certain hydrogels such as polyether-based polyurethanes. The quantitative contribution of hydrogen bonds to the toughness of polymer networks, however, has not been elucidated to date. Here, a new physical model is developed to predict the threshold fracture energies of hydrogels physically crosslinked via hydrogen bonds. The model is based on consecutive and sequential dissociation of hydrogen-bonded crosslinks during crack propagation. It is proposed that the scission of hydrogen bonds during crack propagation allows polymer strands in the deformation zone to partially relax and release stored elastic energy. The summation of these partial chain relaxations leads to amplified threshold fracture energies which are 10–45 times larger than those predicted by the classical Lake–Thomas theory. Experiments were performed on a hydrophilic polyurethane hydrogel where urea additions were used to control the density of hydrogen bonds. The measured fracture energies were in good agreement with the calculated values. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 1287–1293     

Comparison of Electrochemical Oxidation of Flavonols and Calculated Proton Affinity and Electron Transfer Enthalpy in Water

Flavonols, a class of flavonoids, are present in flowers, fruits and vegetables. They are jointly responsible for antioxidant activity as free radical acceptors. The redox behaviour of myricetin, quercetin, isorhamnetin, fisetin, morin and kaempferol is investigated using cyclic and differential pulse voltammetry. Quantum chemical calculations of proton affinities and electron transfer enthalpies were performed to identify possible reactive sites and radical species to compare them with measured oxidation potentials of the flavonols. Regarding to their chemical structure, these flavonols showed an oxidation order: myricetin > quercetin > isorhamnetin > fisetin > morin > kaempferol.     

Changes in the Structural Dimensionality of Selenidostannates in Ionic Liquids: Formation,Structures, Stability,and Photoconductivity

In situ transformations of selenidostannate frameworks in ionic liquids (ILs) were initiated by treatment of the starting phase K₂[Sn₂Se₅] and the consecutive reaction products by means of temperature increase and/or amine addition. Along the reaction pathway, the framework dimensionalities of the five involved selenidostannate anions develop from 3D to 1D and back, both in top‐down and bottom‐up style. Addition of ethane‐1,2‐diamine (en) led to the reversion of the 2D→1D step from 2D‐{[Sn₂₄Se₅₆]^16?} to 1D‐{[Sn₆Se₁₄]^4?}. As rationalized by DFT investigations, the 2D anion is thermodynamically favored. Photoconductivity measurements reveal that all samples show Schottky contact behavior with absolute thresholds below 10 V. One of the samples exhibits conductive states within the energy range of visible photons.     

Efficient synthesis of a nucleoside-diphospho-exo-glycal displaying time-dependent inactivation of UDP-galactopyranose mutase

A short and efficient synthesis of UDP-exo-galactofuranosyl-glycal is presented. This molecule displayed an interesting time-dependent inactivation of UDP-galactopyranose mutase, an essential enzyme of the mycobacterial cell wall biosynthesis.     

Cover Picture

The cover picture shows how thrombosis occurs in the deep veins of the lower limbs. Stasis, which results from slow and turbulent blood flow, combined with hypercoagulation, caused, for example, by a surgical procedure, may result in thrombus formation. The synthetic sulfated pentasaccharide shown in part is a potent antithrombotic compound that exerts its effect by activation of the plasma protein antithrombin III. Conformationally locked monosaccharides have now been synthesized to demonstrate that L-iduronic acid, one part of the pentasaccharide, must adopt an unusual distorted conformation to activate antithrombin III. Such conformational effects might be relevant in explaining the unique biological properties of glycosaminoglycans that contain L-iduronic acid. In the background of the picture, a flight of vampire bats is attracted by the pentasaccharide. Vampire was the name given to South American blood-sucking bats (Latin name: desmodus rotundus) in 1761 by the French naturalist Georges Louis Leclerc Comte de Buffon (1707-1788). These bats are known to attack cattle and, very rarely, sleeping human beings. Although their saliva has been shown to contain an anticoagulant compound, they would also be happy to benefit from the pentasaccharide mentioned above, to suck the blood out of the vein more easily. More details about this compound which would be helpful to vampire bats are reported by Petitou, Sina? et al. on p. 1670 ff.     

A general mass spectrometry-based assay for the quantitation of protein-ligand binding interactions in solution

A new method that utilizes matrix-assisted laser desorption/ionization (MALDI) mass spectrometry and exploits the hydrogen/deuterium (H/D) exchange properties of proteins was developed for measuring the thermodynamic properties of protein-ligand complexes in solution. Dissociation constants (Kd values) determined by the method for five model protein-ligand complexes that included those with small molecules, nucleic acids, peptides, and other proteins were generally in good agreement with Kd values measured by conventional methods. Important experimental advantages of the described method over existing methods include: the ability to make measurements in a high-throughput and automated fashion, the ability to make measurements using only picomole quantitities of protein, and the ability to analyze either purified or unpurified protein-ligand complexes.     

Evaluating and selecting the supplier in detergent production industry using hierarchical fuzzy TOPSIS

Supply chain management has increasingly attracted attention as a systematic approach to integrate the supply chain in order to planning and controlling the materials and information from suppliers to customers. One of the most important issues in supply chain management is selection of the appropriate supplier which has significant effect on purchasing cost decrease and increase in the organization’s competition ability. Selection of the best supplier is naturally complex with no definite structure, and dependent on the type of suppliers’ activity. In the process of decision making about suppliers and many qualitative and quantitative performance indicators such as quality, price, flexibility, and due date should be considered. Then, the supplier selection problem is a multi-criteria decision making problem where numerous methods have been proposed to solve this problem so far. In the current paper, four suppliers of imported raw material “Tripolyphosphate (TPP)” (primary material to produce the detergent powder with a case study in Iran) are evaluated based on 25 effective criteria using the hierarchical fuzzy TOPSIS (HFTOPSIS) approach.