Thermal-oxidative degradation of high-amylose corn starch

Thermal oxidation degradation of high-amylose (80 %) cornstarch has been studied using thermogravimetry analyser coupled to Fourier transform infrared spectroscopy (TG-FTIR). The linear structure of amylose provides a modal material to understand how the starch microstructure affects on the decomposition mechanisms. Kinetics of the thermal oxidation has been studied using different methods. It is found that the thermal oxidation degradation is more complex than thermal degradation, thermal oxidation degradation kinetics of the starch can be interpreted in terms of multi-step degradation mechanism, the activation energies obtain from Flynn–Wall–Ozawa (F–W–O) method and modified Coats–Redfern method are in good agreement. TG-FTIR and FTIR results confirm that the thermal oxidation mechanism of starch is a process containing long chain scission and glowing combustion.     

Pyrone Diels–Alder Routes to Indolines and Hydroindolines: Syntheses of Gracilamine,Mesembrine, and Δ7‐Mesembrenone

Although the Diels–Alder reaction has long been utilized for the preparation of numerous heterocycles, opportunities to extend its power remain. Herein, we detail a simple, modular, and robust approach that combines various amines regioselectively with 4,6‐dichloropyrone to create substrates which, under appropriate conditions, can directly deliver varied indolines and hydroindolines through [4+2] cycloadditions with substitution patterns difficult to access otherwise. As an initial demonstration of the power of the strategy, several different natural products have been obtained either formally or by direct total synthesis, with efforts toward one of these—the complex amaryllidaceae alkaloid gracilamine—affording the shortest route to date in terms of linear step count.     

Synthesis and photovoltaic properties of conjugated side chains polymers with different electron‐withdrawing and donating end groups

A series of novel low band gap polymers containing conjugated side chains with 4,7‐dithien‐5‐yl‐2,1,3‐benzodiathiazole and different electron‐withdrawing end groups of aldehyde ( PT‐DTBTCHO ), 2‐ethylhexyl cyanoacetate ( PT‐DTBTCN ), 1,3‐diethyl‐2‐thiobarbituric acid ( PT‐DTBTDT ), and electron‐donating end group of 2‐methylthiophene ( PT‐DTBTMT ) have been designed and synthesized. All polymers exhibit good solubility in common organic solvents, film‐forming ability, and thermal stability. These conjugated polymers show the broad ultraviolet‐visible absorption and the narrow optical band gaps in the range of 1.65–1.90 eV. Through changing the end group of conjugated side chains, the photophysical properties and energy levels of the polymers were tuned effectively. Bulk heterojunction solar cells based on the blend of these polymers and (6,6)‐phenyl‐C₆₁‐butyric acid methyl ester (PC₆₁BM) reached the best power conversion efficiency (PCE) of 2.72%. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis,characterization, and electrochemistry of monophosphine‐containing diiron propane‐1,2‐dithiolate complexes related to the active site of [FeFe]‐hydrogenases

Five monophosphine‐substituted diiron propane‐1,2‐dithiolate complexes as the active site models of [FeFe]‐hydrogenases have been synthesized and characterized. Reactions of complex [Fe₂(CO)₆{μ‐SCH₂CH(CH₃)S}] ( 1 ) with a monophosphine ligand tris(4‐methylphenyl)phosphine, diphenyl‐2‐pyridylphosphine, tris(4‐chlorophenyl)phosphine, triphenylphosphine, or tris(4‐fluorophenyl)phosphine in the presence of the oxidative agent Me₃NO·2H₂O gave the monophosphine‐substituted diiron complexes [Fe₂(CO)₅(L){μ‐SCH₂CH(CH₃)S}] [L = P(4‐C₆H₄CH₃)₃, 2 ; Ph₂P(2‐C₅H₄N), 3 ; P(4‐C₆H₄Cl)₃, 4 ; PPh₃, 5 ; P(4‐C₆H₄F)₃, 6 ] in 81%–94% yields. Complexes 2 – 6 have been characterized by elemental analysis, spectroscopy, and X‐ray crystallography. In addition, electrochemical studies revealed that these complexes can catalyze the reduction of protons to H₂ in the presence of HOAc.     

Limit cycle bifurcations near a double homoclinic loop with a nilpotent saddle of order m

In this paper, we study the explicit expansion of the first order Melnikov function near a double homoclinic loop passing through a nilpotent saddle of order m in a near-Hamiltonian system. For any positive integer $m(m\ge 1)$, we derive the formulas of the coefficients in the expansion, which can be used to study the limit cycle bifurcations for near-Hamiltonian systems. In particular, for $m=2$, we use the coefficients to consider the limit cycle bifurcations of general near-Hamiltonian systems and give the existence conditions for 10, 11, 13, 15 and 16 (11, 13 and 16, respectively) limit cycles in the case that the homoclinic loop is of cuspidal type (smooth type, respectively) and their distributions. As an application, we consider a near-Hamiltonian system with a nilpotent saddle of order 2 and obtain the lower bounds of the maximal number of limit cycles.     

A highly selective dual-channel Hg2+ chemosensor based on an easy to prepare double naphthalene Schiff base

Science China Chemistry - A non-sulfur chemosensor based on an easy to prepare double naphthalene Schiff base is reported for the colorimetric and fluorometric dual-channel sensing of Hg2+ ions by...     

Synthesis of the Novel Chiral Catalysts by Click Chemistry and Their Application

Novel cinchonine ammonium salt derivatives have been prepared by 1,3‐dipolar cycloaddition. Their chiral catalytic efficacy was investigated in the asymmetric alkylation of N‐diphenylmethyleneglycine t‐butyl ester in the water phase. As the special structure of the catalyst, its asymmetric alkylation catalytic behavior both in organic solvents and in water is satisfactory, which is environmentally friendly.