Asymmetric catalytic anhydride openings via carbon-based nucleophiles

The asymmetric desymmetrization of cyclic anhydrides via the addition of carbon-based nucleophiles has been the focus of considerable levels of interest because it leads to optically active products. Over the past 20 years, a variety of different catalytic asymmetric alkylation reactions have been developed for the desymmetrization of cyclic anhydrides using different metal reagents as nucleophiles and using chiral ligands. The purpose of this review is to provide an overview of significant developments in this field. ~ 2013 Fen-Er Chen. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.     

具有优异甲醇催化氧化性能的Pt/MoO3-WO3/CNTs催化剂

以聚二烯丙基二甲基胺盐酸盐(PDDA)为连接剂,采用原位自组装方式将MoO3和WO3负载到碳纳米管(CNTs)上,然后通过乙二醇还原法负载Pt纳米颗粒,得到Pt纳米颗粒均匀分布的Pt/MoO3-WO3/CNTs催化剂.当氧化物总量控制在10 wt%,MoO3与WO3摩尔比为1:0.5时,Pt/MoO3-WO3/CNTs催化剂催化甲醇氧化活性最高,甲醇氧化峰电流If高达835 A/gPt.WO3和MoO3的加入提高了催化剂的甲醇氧化活性、抗CO中毒能力和稳定性,使得Pt/MoO3-WO3/CNTs催化剂表现出优异的甲醇电催化氧化性能.     

纤维素直接催化转化制乙二醇及其他化学品:从基础研究发现到潜在工业应用(英)

纤维素直接催化转化制乙二醇是一条极具吸引力的生物质转化途径,有助于减轻化石能源资源的消耗。综述了从该反应途径的发现到获得高效、高稳定性催化剂的快速发展过程。基于对钨基催化剂的大量研究结果,本文讨论了反应机制,明确了反应路径、催化剂状态、钨物种及加氢催化活性中心各自在串联反应中的作用。围绕该反应过程的工业化应用需要,讨论了有关原生木质纤维素生物质催化转化以及高效反应过程的发展策略。在此基础上,将纤维素催化转化制乙二醇过程与生物质发酵制丙酮-丁醇-乙醇的生物炼制路线进行整合,构建出一个理想的反应过程潜在应用范例。最后,对纤维素催化转化制乙二醇反应过程进行了总结和前景展望.     

Self-assembly behavior of copolymers with super segregated structure containing fluorinated segments

Copolymers with super segregated structure of hydrophilic methoxy poly（ethylene glycol） （mPEG） and fluorophilic poly（1H,1H,2H,2H-perfluorodecyl acrylate） （PFA） were prepared. And just because of this super segregated structure which was resulted from the extremely strong incompatibility between the two blocks, several interesting self- assembly behaviors of the copolymers were displayed and studied under different conditions. Transmission electron microscope （TEM） showed that with the increase of PFA in the polymerization system, the incompatibility in this super segregated structure became stronger, and the self-assembly behavior changed from ball-like or rod-like to vesicles, and finally collapsed to sheet-like. The self-assembly behavior changed likewise when the initial concentration increased. And the interesting formation of these barrel-like and spindle-like vesicles was finally studied with different cooling speeds. It＇s finally found that with this super segregation structure, these new self-assembly morphology might be formed due to the extremely strong incompatibility between mPEG and PFA segments.     

Synthesis of Star-like Polybutadienes by a Combination of Living Anionic Polymerization and “Click” Coupling Method

Three-arm and four-arm star-like polybutadienes(PBds) were synthesized via the combination of living anionic polymerization and the click coupling method. Kinetic study showed that the click reaction between the azido group terminated PBd-t-N3 and the alkyne-containing multifunctional linking reagent was fast and highly efficient. All coupling reactions were fully accomplished within 40 min at 50 °C in toluene in the presence of the reducing agent Cu(0), proven by 1H-NMR, FTIR and GPC measurements. For the coupling reactions between the PBd-t-N3 polymer and dialkyne-containing compound, the final conversion of the coupled PBd-PBd polymer was ca. 97.0%. When a PBd-t-N3 polymer was reacted with trialkyne-containing or tetraalkyne-containing compound, the conversion of three-arm or four-arm PBd was around 95.5% or 87.0%, respectively. Several factors influencing the coupling efficiency were studied, including the molecular weight of the initial PBd-t-N3, arm numbers and the molar ratio of the azido group to the alkynyl group. The results indicated that the conversion of the target products would be promoted when the molecular weight of the PBd-t-N3 was low and the molar ratio of the azido to alkynyl groups was close to 1.     

A new embedded 5(3) pair of modified Runge–Kutta–Nyström methods for the numerical solution of the Schrödinger equation

A new embedded 5(3) pair of modified Runge–Kutta–Nyström methods for the numerical solution of the Schrödinger equation is developed in this paper. The asymptotic expressions of the principal local truncation errors for large energies are obtained. We apply the new fifth-order method to the resonance problem, and apply the new embedded 5(3) pair to elastic scattering phase-shift problem. The numerical results show good numerical performance of the new embedded pair and the fifth-order method.     

Solubility and solution rheology of acrylamide-sulfobetaine copolymers

The copolymer of acrylamide and 3-[N-(2-methacryloxylethyl)-N,N-dimethylammonio]-propane sulfonate (PAM-MDMPS) was prepared via free radical copolymerization. Solubility of the copolymers was studied by turbidimetric titration method under different conditions. It was found for the first time that the critical salt concentration to dissolve the copolymer showed a plateau over one order of magnitude up to the critical overlap concentration. Rheological behavior and chain conformation of the copolymers in 1 M NaCl solution were also studied. The concentration regions according to scaling theory were found the same as neutral polymers in good solvent. The specific viscosities could be normalized by the overlap parameter. According to the Huggins relation, the copolymers adopted a more compact conformation in 1 M NaCl with increasing MDMPS content due to the hydrophobic association of the betaine unit in the macromolecular backbone, which was stabilized by the strongly hydrated dipolar pendant chains.     

Naturally Occurring Alkaline Amino Acids Function as Efficient Catalysts on Knoevenagel Condensation at Physiological pH: A Mechanistic Elucidation

To maintain biological functions, thousands of different reactions take place in human body at physiological pH (7.0) and mild conditions, which is associated with health and disease. Therefore, to examine the catalytic function of the intrinsically occurring molecules, such as amino acids at neutral pH, is of fundamental interests. Natural basic α-amino acid of l-lysine, l-arginine, and l-histidine neutralized to physiological pH as salts were investigated for their ability to catalyze Knoevenagel condensation of benzaldehyde and ethyl cyanoacetate. Compared with their free base forms, although neutralized alkaline amino acid salts reduced the catalytic activity markedly, they were still capable to perform an efficient catalysis at physiological pH as porcine pancreatic lipase (PPL), one of the best enzymes that catalyze Knoevenagel condensation. In agreement with the fact that the three basic amino acids were well neutralized, stronger basic amino acid Arg and Lys showed more obvious variation in NH bend peak from the FTIR spectroscopy study. Study of ethanol/water system and quantitative kinetic analysis suggested that the microenvironment in the vicinity of amino acid salts and protonability/deprotonability of the amine moiety may determine their catalytic activity and mechanism. The kinetic study of best approximation suggested that the random binding might be the most probable catalytic mechanism for the neutralized alkaline amino acid salt-catalyzed Knoevenagel condensation.     

Micellization of anionic gemini surfactants and their interaction with polyacrylamide

A series of anionic gemini surfactants have been synthesized. The surface properties and micellization process of as-prepared sulfonate gemini surfactants (SGS) and carboxylate gemini surfactant (CGS) have been studied by surface tension measurement and isothermal titration microcalorimetry. Meanwhile, the interaction of these five surfactants with polyacrylamide (PAM) was investigated using surface tension, steady-state fluorescence measurement, and isothermal titration microcalorimetry. The results show that the critical micelle concentrations (CMCs) of above-mentioned surfactants are more than 1 order of magnitude lower than those of corresponding single chain surfactants. Moreover, the enthalpy of micelle formation (ΔH _mic) for the investigated gemini surfactants is negative. In the surfactant–PAM systems, the thermodynamic parameters of binding have also been determined. The conclusion may be drawn that the binding strength of SGS onto PAM is stronger than that of CGS, resulting from more compact structure of SGS aggregates. With increasing surfactant hydrophobicity, the values of ΔH _agg become more exothermic and a ΔS _agg decrease was observed. Therefore, the interaction between SGS and PAM is enthalpy-driven.     

Synthesis and self-assembly behavior of thermoresponsive poly(oligo(ethylene glycol) methyl ether methacrylate)-POSS with tunable lower critical solution temperature

This article reports on the synthesis of a novel amphiphilic polyhedral oligomeric silsesquioxane (POSS) end-capped poly(2-(2-methoxyethoxy)ethyl methacrylate)-co-oligo(ethylene glycol) methacrylate) (POSS-P(MEO₂MA-co-OEGMA)). These thermoresponsive organic–inorganic hybrid polymers exhibit critical phase transition temperature in water, which can be finely tuned by changing the feed ratio of OEGMA and MEO₂MA. The lower critical solution temperature (LCST) of POSS-P(MEO₂MA-co-OEGMA) increases from 31 to 59 °C with the increasing of OEGMA content. Dynamic light scattering (DLS) and transmission electron microscopy (TEM) studies show that these polymers can self-assemble into spherical micelles with the thermosensitive block into the corona and the POSS forming the core, and larger aggregates are formed when the temperature values are above their LCSTs. These thermoresponsive polymers POSS-P(MEO₂MA-co-OEGMA) with self-assembly behavior and tunable tempetature-responsive property have the potential applications in material science and biotechnology.