Preparation of Nano‐Structured Polyaniline Composite Film via “Carbon Nanotubes Seeding” Approach and its Gas‐Response Studies

Summary: Polyaniline composite film with nano‐structure was prepared through a chemical oxidation method by adding carbon nanotubes (CNTs) as nano‐fiber seeds. Spin‐coating or casting method was employed on the interdigital electrodes of carbon and the composite film was formed with an in‐situ polymerization approach. The gas‐response to trimethylamine was also examined at room temperature. It was found that the difference was not only in the morphology, but also in the value of gas‐sensitivity. Comparing with films without the CNTs, the value of gas‐sensitivity decreased dramatically, while the baseline current of the sensor increased remarkably. This method can be an effective way to adjust the gas‐sensitivity of sensors made from polyaniline composite film by adding a small amount of carbon nanotube. XRD data showed that the degree of orientation of polyaniline was increased greatly with the addition of CNTs.

Morphology and reproducibility (inset) of polyaniline composite film containing carbon nanotubes.     

Mechanical and Thermal Properties of Flexible Poly(propylene) Composites

Summary: The melting temperature difference between poly(propylene) (PP) fibre and random poly(propylene‐co‐ethylene) (PPE) was exploited to establish processing conditions for all‐PP composite. Under these conditions, the matrix must be liquid to ensure good wetting and impregnation of fibres, though temperatures must be low enough to avoid melting of fibres. The high chemical compatibility of the two components allowed creation of strong physico‐chemical interactions, favouring strong interfacial adhesion. Static and dynamic mechanical properties and morphology of all‐PP composites were investigated according to method of preparation and compared with the behaviour of hot compacted composites, prepared under different moulding conditions. The composites were compacted with varying pressure and time, and mechanical and thermal properties of the resulting sheets were measured. With increased moulding time, more fibres melted or their original properties deteriorated. Fast cooling or quenching caused imperfect morphology. Moulding pressure played an important role. Morphology of the optimum hot compacted composite was investigated using scanning electron microscopy before and after tensile testing. Tensile fracture surfaces showed a melted phase epitaxially crystallised onto the remaining orientated phase. Compacted composites showed fibre shapes under a thin layer of PPE with all of the gaps between fibres filled by melted PPE matrix.

SEM of compacted all‐PP composite without quenching.     

Calixarene Derivatives as Novel Nanopore Generators for Templates of Nanoporous Thin Films

Summary: We report herein calixarene derivatives, which could adapt to various fields of application, as novel pore generators for making nanoporous materials. The pore structure of nanoporous materials exhibits disordered pores with small mesopore diameter (2–3 nm), which is similar to the micelle‐like assembled structure of the calixarene compounds. The electro‐optical properties such as dielectric constants and refractive indexes of these porous thin films can easily be manipulated. The calixarene‐templated nanoporous films could find a variety of potential applications, such as low‐dielectric constant (k) materials and high‐surface area materials for catalysis and biotechnology.

PM3‐optimized structures of CA[4] and CA[6].     

The One‐Pot Wittig Reaction: A Facile Synthesis of α,β‐Unsaturated Esters and Nitriles by Using Nanocrystalline Magnesium Oxide

Nanocrystalline magnesium oxide was found to be an effective heterogeneous, solid base catalyst for the one‐pot Wittig reaction to afford α,β‐unsaturated esters and nitriles in excellent yields with high E‐stereoselectivity in the presence of triphenylphosphine under mild conditions.     

Expedient Immobilization of TEMPO by Copper‐Catalyzed Azide‐Alkyne [3+2]‐Cycloaddition onto Polystyrene Resin

TEMPO was readily grafted by copper(I)‐catalyzed azide‐alkyne cycloaddition onto polystyrene. Starting with commercially available Merrifield resin (4.3 mmol/ g) almost quantitative loading of TEMPO onto the polymer was achieved (≥ 4 mmol/ g). The so obtained PS‐CLICK‐TEMPO allowed the oxidation of alcohols to aldehydes with bleach or molecular oxygen as the terminal oxidant with high yields and selectivity in multiple cycles without loss of activity.     

Organocatalytic and Stereoselective [3 + 2] Cycloadditions of Azomethine Imines with α,β‐Unsaturated Aldehydes

Bipyrazolidin‐3‐one derivatives are biologically significant compounds and their importance has increased in the past decades. In this paper, the first stereoselective [3 + 2] dipolar cycloadditions of azomethine imines with α,β‐unsaturated aldehydes catalyzed by readily available α,α‐diarylprolinol salts are reported, providing a facile route to the synthesis of various chiral bipyrazolidin‐3‐one derivatives under mild conditions. The organocatalyst 1 g with strongly electron‐withdrawing groups exhibited the best stereoselectivity (exo:endo up to 98:2, for exo product up to 97 % ee), in the combination with trifluoroacetic acid.     

Enzymatic Conversion of Unnatural Amino Acids by Yeast D‐Amino Acid Oxidase

Unnatural amino acids, particularly synthetic α‐amino acids, are becoming crucial tools for modern drug discovery research. In particular, this application requires enantiomerically pure isomers. In this work we report on the resolution of racemic mixtures of the amino acids d,l ‐naphthylalanine and d,l ‐naphthylglycine by using a natural enzyme, D ‐amino acid oxidase from the yeast Rhodotorula gracilis. A significant improvement of the bioconversion is obtained using a single‐point mutant enzyme designed by a rational approach. With this D ‐amino acid oxidase variant the complete resolution of all the unnatural amino acids tested was obtained: in this case, the bioconversion requires a shorter time and a lower amount of biocatalyst compared to the wild‐type enzyme. The simultaneous production of the corresponding α‐keto acid, a possible precursor of the amino acid in the L ‐form, improves the significance of the procedure.     

氧化还原功能纤维的研究 Ⅷ．含正丙胺基吸附剂与Au~（3＋）的氧化还原反应机理

通过元素分析、红外光谱分析、光电子能谱分析以及扫描电子显微镜分析等手段，证实含正丙胺基吸附剂与Ａｕ３＋的氧化还原反应过程中，氮原子邻近的羟基碳或Ｃ－Ｈ键被氧化，而氮原子并未参与氧化还原反应；吸附态Ａｕ（３＋）最终部分被还原成单质金；在非水介质中吸附在吸附剂上的金聚集成颗粒状。     

直接凝固注模成型Si_3N_4及SiC陶瓷──基本原理及工艺过程

直接凝固注模成型（ｄｉｒｅｃｔｃｏａｇｕｌａｔｉｏｎｃａｓｔｉｎｇ，ＤＣＣ）是一种崭新的（准）净尺寸陶瓷成型方法。本文报道了采用此法成型Ｓｉ_３Ｎ_４及ＳｉＣ陶瓷的基本原理和工艺过程。ＤＣＣ成型工艺过程为把高固相含量低粘度的陶瓷浆料浇注到无孔模具中，事先加入到浆料中的生物酶及化学物质通过改变浆料的ｐＨ或电解质浓度来改变浆料的胶体化学行为，从而使浆料原位凝固，得到有足够脱模强度的陶瓷坯体。ＤＣＣ成型的特点为坯体密度高（理论密度的５５％～７０％），坯体均匀，不用或只需少量的有机添加剂（少于１％），可成型大尺寸、复杂形状、高可靠性的陶瓷部件。     

树脂热解炭制备碳化硅晶须

用自制的配合醛树脂热解和炭源，用ＳＩＯ２超细汾作原，根据碳热还原原理，利用常规加热和微波加热两种方式，分别制备了直径在纳米级的ＳｉＣ晶须，Ｘ射线衍射、透射电检测结果表明：制备工艺和条件对ＳｉＣ晶须的性质有较大的影响。