Mechanistic insights into the structure‐dependent selectivity of catalytic furfural conversion on platinum catalysts

The effects of surface structures on the selectivity of catalytic furfural conversion over platinum (Pt) catalysts in the presence of hydrogen have been studied using first principles density functional theory (DFT) calculations and microkinetic modeling. Three Pt model surface structures, that is, flat Pt(111), stepped Pt(211), and Pt₅₅ cluster are chosen to represent the terrace, step, and corner sites of Pt nanoparticle. DFT results show that the dominant reaction route (hydrogenation or decarbonylation) in furfural conversion depends strongly on the structures (or reactive sites). Using the size‐dependent site distribution rule, our microkinetic modeling results indicate the decarbonylation route prevails over smaller Pt particles less than 1.4 nm while the hydrogenation is the dominant reaction route over larger Pt catalyst particles at T = 473 K and = 93 kPa. This is in good agreement with the reported experimental observations. © 2015 American Institute of Chemical Engineers AIChE J, 61: 3812–3824, 2015     

Residue Asn277 Affects the Stability and Substrate Specificity of the SMG1 Lipase from Malassezia globosa

Thermostability and substrate specificity are important characteristics of enzymes for industrial application, which can be improved by protein engineering. SMG1 lipase from Malassezia globosa is a mono- and diacylglycerol lipase (MDL) that shows activity toward mono- and diacylglycerols, but no activity toward triacylglycerols. SMG1 lipase is considered a potential biocatalyst applied in oil/fat modification and its crystal structure revealed that an interesting residue-Asn277 may contribute to stabilize loop 273–278 and the 3₁₀4 helix which are important to enzyme characterization. In this study, to explore its role in affecting the stability and catalytic activity, mutagenesis of N277 with Asp (D), Val (V), Leu (L) and Phe (F) was conducted. Circular dichroism (CD) spectral analysis and half-life measurement showed that the N277D mutant has better thermostability. The melting temperature and half-life of the N277D mutant were 56.6 °C and 187 min, respectively, while that was 54.6 °C and 121 min for SMG1 wild type (WT). Biochemical characterization of SMG1 mutants were carried out to test whether catalytic properties were affected by mutagenesis. N277D had similar enzymatic properties as SMG1 WT, but N277F showed a different substrate selectivity profile as compared to other SMG1 mutants. Analysis of the SMG1 3D model suggested that N277D formed a salt bridge via its negative charged carboxyl group with a positively charged guanidino group of R227, which might contribute to confer N277D higher temperature stability. These findings not only provide some clues to understand the molecular basis of the lipase structure/function relationship but also lay the framework for engineering suitable MDL lipases for industrial applications.     

A Series of New Ligustrazine-Triterpenes Derivatives as Anti-Tumor Agents: Design,Synthesis, and Biological Evaluation

A series of novel ligustrazine-triterpenes derivatives was designed, synthesized and screened for their cytotoxicity against five cancer cell lines (Bel-7402, HepG2, HT-29, Hela, and MCF-7) and Madin-Darby canine kidney (MDCK). Current study suggested that most of the ligustrazine-triterpenes conjunctions showed better cytotoxicity than the starting materials. In particular, compound 4a exhibited better cytotoxic activity (IC₅₀ < 5.23 μM) against Bel-7402, HT-29, MCF-7, Hela, and HepG2 than the standard anticancer drug cisplatin (DDP). The cytotoxicity selectivity detection revealed that 4a exhibited low cytotoxicity (IC₅₀ > 20 μM) towards MDCK cells. A combination of fluorescence staining observation and flow cytometric analysis indicated that 4a could induce HepG2 cell apoptosis. Further studies suggested that 4a-induced apoptosis is mediated through depolarization of the mitochondrial membrane potential and increase of intracellular free Ca²⁺ concentration. In addition, the structure-activity relationships of these derivatives were briefly discussed.     

SNIPPET ON DRYING

ABSTRACT

When regarding the atmospheric contact drying of granular beds wetted with a liquid mixture, both the drying rate and the selectivity of the process, i.e. the change of moisture composition, are of interest. The batch drying of a free flowing ceramic substance, wetted with a 2-propanol-water mixture, is investigated in a rotary dryer with heated wall and air flow.

The theoretical analysis is based on physical models for heat and mass transfer, moisture migration and particle transport, which are presented in examples.

The experimental and theoretical results show that higher selectivities can be achieved by reducing the particle size because of the lower liquid-phase mass-transfer resistance. An increase of the rotational speed leads to a higher drying rate with slightly decreased selectivity if the particles are sufficiently small, since contact heat transfer is enhanced.     

Blocking the Peroxisome Proliferator‐Activated Receptor (PPAR): An Overview

Peroxisome proliferator‐activated receptors (PPARs) have been studied extensively over the last few decades and have been assessed as molecular targets for the development of drugs against metabolic disorders. A rapid increase in understanding of the physiology and pharmacology of these receptors has occurred, together with the identification of novel chemical structures that are able to activate the various PPAR subtypes. More recent evidence suggests that moderate activation of these receptors could be favorable in pathological situations due to a decrease in the side effects brought about by PPAR agonists. PPAR partial agonists and antagonists are interesting tools that are currently used to better elucidate the biological processes modulated by this family of nuclear receptors. Herein we present an overview of the various molecular structures that are able to block each of the PPAR subtypes, with a focus on promising therapeutic applications.     

LIQUID PHASE CO-OXIDATION OF THIOPHENOL AND STYRENE BY OXYGEN AND t-BUTYL HYDROPEROXIDE

ABSTRACT

Instability problems in both shale and petroleum derived middle distillate jet fuels have been correlated with the presence of peroxidic species. Although a good body of knowledge exists concerning the formation of peroxides in the liquid phase, relatively little is known about the reaction/ decomposition pathways available when other functional groups are present, since sulfur is the most abundant heteroatam present in jet fuels, the reaction of t-butyl hydroperoxide (tBKP) and/or oxygen with thiophenol in the presence of the active olefin, styrene, was examined in deaerated benzene at 120°C. The complex product mixture was analyzed by combined capillary column GC/MS. Major products included acetone, t-butanol and isdbutylene from the tBHP. Thiophenol and styrene combined to form addition products. Phenyl disulfide was observed from the thiophenol. The results indicated that although the product slate was complex, it was possible to explain the product mix in terms of a few competing reactions.     

A Study on the Selectivity of Methanol Aromatization

Abstract

The present study describes the performance of the HZSM-5 zeolite catalyst modified by Cu, Zn, Ga, La, P, Ag, and other ions for the conversion of methanol to aromatics in a fixed-bed reactor, and the influences of the system pressure and temperature on methanol aromatization are in discussion. The results show that the optimum single ion for the modification of catalyst was Zn or Cu. The optimum combined ions were Zn and Ga. The yield of aromatics could reach up to 66.6% on the catalyst modified with Ga2% and Zn10%.     

Removal of arsenic from aqueous solutions by an adsorption process with titania–silica binary oxide nanoparticle loaded polyacrylonitrile polymer

A new and simple method was developed to produce gelatin nanoparticles of ～ 30–40 nm for use as carriers for drug release applications. The nanoparticles were uniform in size and well dispersed. An anticancer drug, 5‐fluorouracil, was encapsulated with an efficiency as high as 85%. The nanoparticles showed sustained release of 5‐fluorouracil, and release rates varied with amount of crosslinking in the nanoparticles. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Effect of the diffusion phenomena in the catalyst grain on the selectivity of a system of parallel-consecutive reactions involved in the process of n-heptane dehydrocyclization

Analytical relations were derived for analyzing the selectivity of consecutive-parallel reactions occurring under conditions of the reforming process. With these relations it is also possible to determine how the shape of the catalyst grain, as well as the kinetic and diffusion phenomena that govern the process, affects the efficiency of the desired final products.