Time‐dependent Density Functional Theory Study on the Hydrogen‐bonded Dimers Formed by Gauche‐1PA and Trans‐1PA

Three hydrogen bonding complexes of the gauche‐1PA dimer (GG), trans‐1PA dimer (TT) and mixed dimer (GT) have been calculated for the geometry conformations and excited‐state energies. The electron distribution at the site of C‐O of H‐donor moiety in HOMO transfers to the direction of O‐H of H‐acceptor moiety in LUMO. The hydrogen bond between two 1PAs is the bridge of the intermolecular charge transfer. By the Zhao and Han's excited‐state hydrogen bonding dynamics rule, the first excited‐state hydrogen bonding change has been discussed without optimizing the excited‐state geometry conformations. According to the distinct difference between GT and GG (TT), we concluded that two gauche‐1PA monomers of one dimer are transformed at the same time to two trans‐1PA monomers.     

Thermal properties and flame retardancy of novel epoxy based on phosphorus‐modified Schiff‐base

Through addition reaction of Schiff‐base terephthalylidene‐bis‐(p‐aminophenol) ( DP‐1 ) and diethyl phosphite (DEP), a novel phosphorus‐modified epoxy, 4,4'‐diglycidyl‐(terephthalylidene‐bis‐(p‐aminophenol))diphosphonate ether ( EP‐2 ), was obtained. An modification reaction between EP‐2 and DP‐1 resulted in an epoxy compound, EP‐3 , possessing both phosphonate groups and C?N imine groups. The structure of EP‐2 was characterized by Fourier transform infrared (FTIR), elemental analysis (EA), ¹H, ¹³C, and ³¹P NMR analyses. The thermal properties of phosphorus‐modified epoxies cured with 4,4'‐diaminodiphenylmethane (MDA) and 4,4'‐diaminodiphenyl ether (DDE) were studied by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The activation energies of dynamic thermal degradation (E_d) were calculated using Kissinger and Ozawa's methods. The thermal degradation mechanism was characterized using thermogravimetric analysis/infrared spectrometry (TG‐IR). In addition, the flame retardancy of phosphorus‐modified epoxy thermosets was evaluated using limiting oxygen index (LOI) and UL‐94 vertical test methods. Via an ingenious design, phosphonate groups were successfully introduced into the backbone of the epoxies; the flame retardancy of phosphorus‐modified epoxy thermosets was distinctly improved. Due to incorporation of C?N imine group, the phosphorus‐modified epoxy thermosets exhibited high thermal stabilities; the values of glass‐transition temperatures (T_gs) were about 201–210°C, the values of E_d were about 220–490 kJ/mol and char yields at 700°C were 49–53% in nitrogen and 45–50% in air. These results showed an improvement in the thermal properties of phosphorus‐modified epoxy by the incorporation of C?N imine groups. Copyright © 2010 John Wiley & Sons, Ltd.     

TiO2 mesocrystals: Synthesis, formation mechanisms and applications

Mesocrystals, which are assemblies of crystallographically oriented nanocrystals, have received increasing attention due to their unique properties such as high crystallinity, high porosity, oriented subunit alignment, and similarity to highly sophisticated biominerals. However, the controlled synthesis of TiO 2 mesocrystals has not been realized until recently, probably because of the difficulty in accurately controlling the reaction processes that produce TiO 2 crystals. In this review, recent advances in the synthesis and applications of TiO 2 mesocrystals are summarized with particular attention paid to the mechanisms of their formation. Three typical pathways for the preparation of TiO 2 mesocrystals are discussed, namely topotactic transformation, direct synthesis in solution, and growth on supports. The potential applications of TiO 2 mesocrystals in lithium ion batteries, photocatalysis, enzyme immobilization, and antireflection materials are also described.     

基于巯基点击反应与RAFT聚合的功能性聚合物合成

可逆加成-裂解链转移聚合(RAFT)由于单体适用面广、聚合条件温和、不受聚合方法的限制等特性, 已经成为活性合成聚合物的有效手段之一。点击化学(click chemistry)由于具有良好的选择性、模块性以及官能团耐受性等特点迅速成为许多研究领域,如药物、聚合物、功能材料等合成的有力工具,同时涌现出了多种基于巯基的点击反应。本文综述了近年来基于巯基的点击反应, 如巯基-烯、巯基-炔、巯基-异氰酸酯、巯基-环氧化物以及巯基-卤代烃等新型点击反应与RAFT聚合相结合在功能性聚合物的制备和修饰中的应用, 相信这两种手段的结合将在其中发挥积极的作用。     

1,2,3,4-四氢喹啉衍生物合成进展

1,2,3,4-四氢喹啉类化合物是一类重要的含氮杂环化合物,具有众多的生物活性和广泛的用途,因此,四氢喹啉合成新方法的研究受到人们的关注。本文分别从通过氢化还原策略、关环转化反应策略以及通过多分子缩合反应策略等几个方面综述1,2,3,4-四氢喹啉衍生物合成的进展。     

Radiation-induced crosslinking of polyacrylonitrile fibers and the subsequent regulative effect on the preoxidation process

To investigate the radiation effect on polyacrylonitrile (PAN) fibers as well as on the preoxidation process, PAN fibers were irradiated by γ-rays at room temperature at 50–500 kGy in vacuum and then were thermally oxidized in air. Gel fraction determination indicated that γ irradiation led to the predominant crosslinking of PAN fibers, with G values (the number of event per 100 eV absorbed) of G(X)=0.28 and G(S)=0.16 for chain crosslinking and scission, respectively. It was found that irradiation caused a slight change in the crystal structure and tensile strength at low dose. Radiation led to a reduction of the onset temperature of cyclization reaction and moderated the exothermic behavior. The density of the PAN fibers after thermal oxidation was used to evaluate the preoxidation extent. It was proven that radiation could significantly accelerate the preoxidation process and consequently shortened the preoxidation time. Radiation crosslinking may have potential application in the production of PAN-based carbon fibers.     

Calorimetric Studies on Enthalpy Relaxation in Maltitol Glass Transition Based on Phenomenological Models

To investigate the enthalpy relaxation behavior of maltitol glass system, differential scanning calorimetry (DSC) was used to obtain the specific heat capacity[C_p(T)] near the glass transition temperature(T_g) at different coo- ling rates ranged between 1 and 20 K/min. Three phenomenological models of enthalpy relaxation, Tool-Narayanaswamy-Moynihan(TNM) model, Adam-Gibbs-Vogel(AGV) model and Gómez Ribelles(GR) model, were used to simulate the experimental data. The models’ parameters were obtained via a curve-fitting method. The results indicate that TNM and AGV models gave the almost identical prediction powers and can reproduce the curves of experimental C_p(T) very well. However, the prediction power of GR model evolved from configurational entropyapproach is not so good as those of TNM and AGV models. In particular, the metastable limit state parameter(δ) introduced by Gómez Ribelles has insignificant effect on the enthalpy relaxation of the small molecular hydrogen-bonding glass system.     

A new two‐dimensional cadmium coordination polymer with 1H‐imidazole‐4‐carboxylate and oxalate

The title compound, poly[aqua(μ₂‐1H‐imidazole‐4‐carboxylato‐κ³N³,O:O′)hemi(μ₂‐oxalato‐κ⁴O¹,O²:O^1′,O^2′)cadmium(II)], [Cd(C₄H₃N₂O₂)(C₂O₄)_0.5(H₂O)]_n, exhibits a two‐dimensional network. The Cd^II cation is coordinated to one N atom and two carboxylate O atoms from two 1H‐imidazole‐4‐carboxylate (Himc) ligands, two carboxylate O atoms from the bridging oxalate anion and one ligated water molecule; these six donor atoms form a distorted octahedral configuration. The oxalate anion lies on a centre of inversion. The Himc ligands connect the Cd^II cations to form –Cd–Himc–Cd–Himc–Cd– zigzag chains, with a Cd...Cd separation of 5.8206 (6) Å along the b direction, which are further linked by tetradentate oxalate anions to generate a two‐dimensional herringbone architecture in the ab plane. These layers are extended to form a three‐dimensional supramolecular framework via O—H...O and N—H...O hydrogen bonds and π–π stacking interactions. The solid‐state photoluminscent behaviour of the title compound has been investigated at room temperature.