ZIF-Induced d-Band Modification in a Bimetallic Nanocatalyst: Achieving Over 44 % Efficiency in the Ambient Nitrogen Reduction Reaction

The electrochemical nitrogen reduction reaction (NRR) offers a sustainable solution towards ammonia production but suffers poor reaction performance owing to preferential catalyst–H formation and the consequential hydrogen evolution reaction (HER). Now, the Pt/Au electrocatalyst d-band structure is electronically modified using zeolitic imidazole framework (ZIF) to achieve a Faradaic efficiency (FE) of >44 % with high ammonia yield rate of >161 μg mg_cat⁻¹ h⁻¹ under ambient conditions. The strategy lowers electrocatalyst d-band position to weaken H adsorption and concurrently creates electron-deficient sites to kinetically drive NRR by promoting catalyst–N₂ interaction. The ZIF coating on the electrocatalyst doubles as a hydrophobic layer to suppress HER, further improving FE by >44-fold compared to without ZIF (ca. 1 %). The Pt/Au-N_ZIF interaction is key to enable strong N₂ adsorption over H atom.     

Synthesis and characterization of interpenetrating polymer networks with nonlinear optical properties

We report the synthesis and characterization of interpenetrating polymer networks (IPNs) exhibiting nonlinear optical (NLO) properties. The network consists of aliphatic polycarbonate urethane (PCU) and poly(methyl methacrylate-co-N,N-disubstituted urea), with a nonlinear optical (NLO) chromophore incorporated into N,N-disubstituted urea. The full IPNs have only one T_g, as determined by differential scanning calorimetry (DSC), together with scanning electron microscopy (SEM) observations, suggest a single phase morphology. The thin films of IPNs are transparent and the unpoled samples produced second harmonic generation (SHG) signals at room temperature. This result indicates that the NLO chromophore is oriented noncentrosymmetrically during the IPN formation process and is tightly held between the permanent entanglements of the two component networks of the IPN. © 1996 John Wiley & Sons, Inc.     

Inhibition of LPS-induced no production in RAW264.7 cell lines: synthesis and molecular modeling of α-ketophosphonates of febuxostat

In an effort to develop novel anti-inflammatory agents, we synthesized phosphorylated derivatives of febuxostat using various phosphates/phosphonites by Michaelis-Arbuzov reaction. Their inhibitory activity on nitric oxide (NO) production, reactive oxygen species (ROS) production and cytotoxicity were evaluated using lipopolysaccharide (LPS) activated macrophages RAW264.7 assay, flow-cytometry analysis and MTT method respectively. Some of these compounds showed potent inhibition of NO and ROS production without obvious cytotoxicity. Furthermore, docking simulations were performed to positional compounds 3g, 3h, 3i and 3j into the COX-2 active site to determine the probable binding model. Physicochemical parameters revealed that most of the compounds possessed drug-like properties.     

The credit risk+ model with general sector correlations

We consider an enhancement of the credit risk⁺ model to incorporate correlations between sectors. We model the sector default rates as linear combinations of a common set of independent variables that represent macro-economic variables or risk factors. We also derive the formula for exact VaR contributions at the obligor level.     

Continuum model for polymorphism of bacterial flagella

Bacterial flagellar filaments can abruptly change shape in response to mechanical load or changes in solution pH or ionic strength. These polymorphic transformations are an instance of a ubiquitous phenomenon, the spread of conformational change in large macromolecular assemblies. We propose a new theory for polymorphism, whose essential elements are two molecular switches and an elastic mismatch strain between the inner and outer cores of the filament. We calculate the phase diagram for helical and straight states, and the response of a helical filament to an external moment.     

Non-isothermal thermoanalytical studies on the salt roasting of chalcopyrite using KCl

In an earlier study [1], the isothermal kinetics of salt roasting of chalcopyrite under an oxidizing atmosphere using KCl was studied in the temperature range 523–773 K. The salt roasting reaction was found to be chemically controlled at temperatures below 600 K both under static air and oxygen atmosphere. At higher temperatures, the process was not thermally activated because of a change in the chemistry of the process. In the present study, the salt roasting of chalcopyrite using KCl under oxygen and static air atmosphere was studied by non-isothermal thermoanalytical studies up to 723 K. The effect of salt content, heating rate and particle size on the salt roasting behavior was studied using TG/DTA techniques at a programmed linear heating rate. The TG and DTA studies reveal two distinct chemical processes, one operative up to 620 K and the other from 620 to 723 K. The integral method of Coats and Redfern was used for the treatment of non-isothermal kinetic data. The non-isothermal analysis confirmed the chemical control mechanism at temperatures below 620 K. However, the activation energy for the process derived from non-isothermal thermogravimetric analysis is almost twice as that deduced from isothermal measurements. In the temperature range 620–723 K, the kinetic data still obeys the interfacial reaction control model although the activation energy in this temperature range is very low.     

A comparison of analytic and knowledge-based approaches to closed-shop scheduling

This paper compares three different approaches to scheduling in a closed-shop environment, making the case for a knowledge-based approach. A manufacturing example from the food industry is used as a vehicle for the presentation. The first approach attempts to find an optimal solution using a mixed integer linear programming formulation, but the size of the problem renders this approach impractical. The second approach uses a spreadsheet program to obtain feasible solutions, but imbedded assumptions in the heuristics used allow it to be used only for simple demand patterns. The third approach employs expert systems technology. It includes several heuristics and takes all constraints into consideration. The solution obtained may not be optimal, but computational tests suggest that it is far superior to both spreadsheet and manual approaches.     

Glass physics: from fundamentals to applications

The European Physical Journal E -     

Specificity analysis-based identification of new methylation targets of the SET7/9 protein lysine methyltransferase

We applied peptide array methylation to determine an optimized target sequence for the SET7/9 (KMT7) protein lysine methyltransferase. Based on this, we identified 91 new peptide substrates from human proteins, many of them better than known substrates. We confirmed methylation of corresponding protein domains in?vitro and in?vivo with a high success rate for strongly methylated peptides and showed methylation of nine nonhistone proteins (AKA6, CENPC1, MeCP2, MINT, PPARBP, ZDH8, Cullin1, IRF1, and [weakly] TTK) and of H2A and H2B, which more than doubles the number of known SET7/9 targets. SET7/9 is inhibited by phosphorylation of histone and nonhistone substrate proteins. One lysine in the MINT protein is dimethylated in?vitro and in?vivo demonstrating that the product pattern created by SET7/9 depends on the amino acid sequence context of the target site.