Substituent effects on thermal and photo‐alignment behavior of poly(ethylene imine)s carrying azobenzene side groups

A new class of liquid‐crystalline poly(ethylene imine)s (PEIs) having four differently substituted (? CN,? C₄H₉,? OCH₃ and? NO₂) azobenzene side‐chain groups attached through alkyl spacer groups were successfully synthesized using a solution polycondensation reaction. The synthesized polymers were characterized using differential scanning calorimetry, polarized optical microscopy and X‐ray diffraction. The photochemical, thermo‐optical and photo‐orientational behavior of the polymers were investigated in detail. Spin‐coated films of PEIs with azobenzene groups having? C₄H₉,? OCH₃ and? NO₂ substituents showed out‐of‐plane molecular orientation on annealing. Except for the PEI with an azobenzene group having ? NO₂ substituent, all polymers exhibited good photoresponsive properties upon irradiation with UV and visible light. Films of PEIs with azobenzene side groups having? CN,? C₄H₉ and? OCH₃ substituents showed reversible alignment behavior from random state to out‐of‐plane and from out‐of‐plane to random state on annealing and on irradiation with UV and non‐polarized visible light. The reversibility of the molecular orientation of PEIs from random state to out‐of‐plane and from out‐of‐plane to random state greatly depended on the substituent attached to the azobenzene side‐chain group. Copyright © 2010 Society of Chemical Industry     

Spray-dried high-amylose sodium carboxymethyl starch: impact of α-amylase on drug-release profile

Spray-dried high-amylose sodium carboxymethyl starch (SD HASCA) is a promising pharmaceutical excipient for sustained-release (SR) matrix tablets produced by direct compression. The presence of α-amylase in the gastrointestinal tract and the variations of the gastric residence time of non-disintegrating dosage forms may affect the presystemic metabolism of this excipient and, consequently, the drug-release profile from formulations produced with SD HASCA. In this study, the influence of α-amylase and the residence time in acidic conditions on the drug-release profile was evaluated for a once-daily acetaminophen formulation (Acetaminophen SR) and a once-daily tramadol hydrochloride formulation (Tramadol SR). Both formulations were based on SD HASCA. α-Amylase concentrations ranging from 0?IU/L to 20000?IU/L did not significantly affect the drug-release profiles of acetaminophen and tramadol hydrochloride from SD HASCA tablets (f_2?>_?50) for all but only one of the studied conditions (f_2?=_?47). Moreover, the drug-release properties from both SD HASCA formulations were not significantly different when the residence time in acidic medium was 1?h or 3?h. An increase in α-amylase concentration led to an increase in the importance of polymer erosion as the main mechanism of drug-release instead of drug diffusion, for both formulations and both residence times, even if release profiles remained comparable. As such, it is expected that α-amylase concentration and residence time in the stomach will not clinically affect the performance of both SD HASCA SR formulations, even if the mechanism of release itself may be affected.     

Encapsulation of nano Disperse Red 60 via modified miniemulsion polymerization. I. Preparation and characterization

Nanocolorant, nano Disperse Red 60, was successfully prepared via modified miniemulsion polymerization process. Transmission electron microscopy was employed to determine the droplet and particle sizes. The effects of the speed and the time of homogenization, the surfactant nature and its amount, the presence of dye, the initiator nature, and the presence of a crosslinker on the morphology and particle size of nanocolorant were studied. UV–vis absorption spectra of nanocolorant with respect to the commercial corresponding dye showed a hypsochromic shift confirming the decrease in particle size. Fourier transform infrared spectra proved the chemical composition of nanocolorant particles assisting the incorporation of the dye within the polystyrene particles. The monomer conversion, surface tension, and apparent sedimentation stability also were measured. The relative electrical conductivity of the suspension was used for determining the polymerization mechanism. The kinetic polymerization was investigated using a pseudofirst-order and it is found that the rate constant of polymerization equals 0.01358 min⁻¹. Zeta potential measurements were employed for miniemulsion which showed that it has good stability at all range of pH. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

添加剂对高模量沥青及其混合料性能的影响

为了给沥青路面推荐较优高模量沥青混合料添加材料,采用车辙试验、冻融劈裂试验和小梁弯曲试验,以试件的最大变形、冻融劈裂强度比(TSR)和疲劳寿命为评价指标,对比研究了苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)和聚乙烯(PE)两种添加材料,在不同添加剂量条件下对比沥青混合料的性能作用效果。根据研究结果在夏季高温地区,建议采用添加剂量为4.0%的聚合物SBS;在夏季多雨地区或者交通量繁重路段,建议聚合物SBS和聚乙烯PE混合使用,并且掺量为3%。     

A versatile strategy towards semi-interpenetrating polymer network for proton exchange membranes

A universal method to prepare proton exchange membrane (PEM) with semi-interpenetrating polymer network (semi-IPN) via a versatile crosslinker 1,3-benzenedisulfonyl azide (1,3-BDSA) is proposed. Sulfonyl azide groups can react with any polymer with carbon-hydrogen bonds via hydrogen abstraction. Polyvinylidene fluoride (PVDF) and perfluorosulfonic acid (PFSA) polymer are selected as two precursors for semi-IPN. When 1,3-BDSA is heated to a sufficiently high temperature it can form the nitrene and connect with PVDF via hydrogen abstraction reaction, recombination, or CH-bond insertion. The crosslinking structure of PVDF is formed, and semi-IPN is constructed in the presence of PFSA at the same time. The mechanical properties, degree of crosslinking, water uptake, and proton conductivity of semi-IPN membranes are investigated. Compared with pure PFSA membrane, the mechanical properties and the dimensional stability of the semi-IPN membranes are improved significantly. The tensile strength of the composite membrane (27.2 MPa) is much higher than that of PFSA membrane (10.1 MPa). The maximum power density of the composite membrane can reach 382 mW cm⁻² at 940 mA cm⁻². Sulfonyl azide based crosslinkers can be used to prepare semi-IPN or IPN PEMs from any paired polymers with carbon–hydrogen bonds.     

Porphyrin-grafted cellulose fabric: New photobactericidal material obtained by “Click-Chemistry” reaction

A new antibacterial material has been elaborated by grafting mesoarylporphyrin on cotton fabric by the means of cellulose azidation followed by “Click-Chemistry” reaction with acetylenic porphyrin. Azidation and functionalization have been checked by ATR-FTIR spectroscopy. Under irradiation with visible light, this material displayed an antibacterial activity against representative strains of Escherichia coli and Staphylococcus aureus. This new photobactericidal textile has potential for industrial, medical, and household applications.     

Effects of nematic coupling on the phase behaviour of nematogen mixtures

The phase behaviour of binary nematogen mixtures of side‐chain liquid crystal crosslinked polymers and low molecular weight liquid crystals is investigated with particular emphasis on the effects of nematic coupling. The cross nematic quadrupole parameter ν₁₂ is assumed to be proportional to the geometric average of ν₁₁ and ν₂₂ characteristic of single nematogens. In the weak coupling limit, the proportionality constant is lower than 1, and the phase diagram exhibits a reduced miscibility of the nematogens. In the case of strong coupling, the proportionality constant exceeds 1 resulting in higher miscibility. This is characterized by a nematic order that extends to temperatures above the upper nematic–isotropic transition temperature. A wide region of miscibility emerges showing a single nematic phase. Nematogens having similar nematic–isotropic transition temperatures exhibit different phase properties from systems with widely separated transition temperatures. Effects of the polymer volume fraction at crosslinking, rubber elasticity parameters of the network, and the Flory–Huggins interaction parameter on the equilibrium phase diagram of these systems are discussed. © 2001 Society of Chemical Industry     

New, low-cost, high-power poly(o-anisidine-co-metanilic acid)/activated carbon electrode for electrochemical supercapacitors

A poly(o-anisidine-co-metanilic acid)/activated carbon composite is evaluated as an active material for electrochemical supercapacitors. Poly(o-anisidine-co-metanilic acid) (PASM) is potentiodynamically deposited on an activated carbon (AC)-coated stainless-steel substrate, in a supporting electrolyte of 1.0 M H₂SO₄ containing dissolved o-anisidine and metanilic acid, at a sweep rate of 50 mV s⁻¹. Scanning electron micrographs show a uniformly deposited, thick PASM film on the activated carbon. Electrochemical techniques, such as impedance analysis, cyclic voltammetry and galvanostatic experiments, are carried out to investigate the suitability of the PASM/AC electrode for supercapacitor applications. A maximum specific capacitance of 576 F g⁻¹ is obtained for PASM/AC at a 5 mA cm⁻² current density.     

现浇有网聚苯乙烯板外墙外保温抗裂施工技术

外墙保温面层裂缝是保温建筑的质量通病，防裂性能是墙体保温体系要解决的关键技术之一。介绍一种既经济，又能有效解决有网聚苯乙烯板抹灰找平层开裂，减轻面层荷载，提高保温体系安全性及解决“热桥”等问题的施工技术。