微波场对固态氧离子导体上的甲烷氧化偶联的影响

研究了微波场下甲烷在具有δ－Ｂｉ２Ｏ３结构的固态氧离子导体上氧化偶联反应行为。与常规加热条件下的反应结果相比较，微波辐射下的反应有上特点：（１）在达到相同甲烷转化率时，微波辐照下所需床层温度要远低于常规加热条件下所需床层温度；（２）微波辐照下，甲烷氧化偶联产物中Ｃ２烃的选择性普遍较高，在低温区尤为突出。微波场下甲烷偶联产物乙烷、乙烯的再氧化得到一定程度的抑制，致使微波场下的甲烷氧化偶联反应通常有较     

微波技术在固相配位化学反应中的应用研究(Ⅰ)──CO(Ⅱ)、Ni(Ⅱ)、Cu(Ⅱ)配合物在微波条件下的固相合成

在微波辐射条件下研究了过渡金属[Co（Ⅱ），Ni（Ⅱ），Cu（Ⅱ）的醋酸盐与氨基酸、席夫碱、β-二酮、8-羟基隆琳等有机配体之间的固相配位化学反应，发现微波辐射条件下的固相化学反应与传统加热条件下的固相化学反应相比速度提高了数十倍甚至数百倍，并在此条件下合成出了相应的配合物．     

微波技术在固相配位化学反应中的应用研究（I）

在微波辐射条件下研究了过渡金属「Ｃｏ（Ⅱ），Ｃｕ（Ⅱ）」的醋酸盐与氨基酸、席夫碱、β－二酮、８－羟基喹啉等有机配体之间的固相配位化学反应，发现微波辐射条件下的固相化学反应与传统加热条件下的固相化学反应相比速度提高了数十倍甚至数百倍，并在此条件下合成出了相应的配合物。     

微波常压法制备三聚氰酸

研究了在常压条件下尿素与助溶剂通过微波辐射制备三聚氰酸的反应条件，结果表明，采用594W微波辐射3min，转化率达83．5％。     

PEG在微波诱导下对高岭石插层及剥片的研究

利用微波能量，快速制备了高岭石/DMSO插层复合物，并以其为前驱体，在熔融状态，微波诱导聚乙二醇(PEG)置换出高岭石层间的DMSO，微波继续协同PEG作用，可以实现其对高岭石的剥片。同时提出了微波作用机理和微波条件下插层物对高岭石的剥片机理。采用X-射线衍射、FTIR光谱、TG-DTA、TEM等技术对插层复合物进行了表征。     

铜酞菁的微波辐照法合成

在微波辐照条件下，对铜酞菁的合成进行了研究。考察了辐照时间、尿素和氯化亚铜的用量、催化剂的种类及用量对铜酞菁产率的影响。发现在高功率微波辐照条件下，采用间歇辐照方式，以苯酐质量3％的钼酸铵为催化剂，mol苯酐：mol尿素：mol氯化亚铜＝1：5：0.20-0.23，累计辐照630s，产率最高。若以氧化钼为催化剂，产率随其用量的增加而增加，并逐步趋向平稳，但催化效果不如钼酸铵。在相同原料配比条件下，微波法的产率比用常规的加热方法（200℃）高、反应时间短。两种方法所得产物的晶型经X－射线粉末衍射分析均是β型为主，经浓硫酸精制转变为α型。     

微波合成SrTiO3的工艺、结构与性能研究

应用微波会成这一材料合成新方法制备SrTiO3，研究了不同工艺条件下微波合成产物的结构，确定出制备纯净SrTiIO。的合成条件．对微波合成的工艺及其影响因素进行详细的探索，从合成产物的显微结构、粒度分布、比表面积、烧结性能等方面比较了微波合成与常规固相合成的差别，结果表明微波合成与各种常规方法相比有合成时间短、合成工艺简单、合成产物性能好等特点，是一种有发展潜力的材料合成技术．     

无溶剂条件下微波辐射合成2-氨基噻唑衍生物

在无溶剂条件下, 用微波辐射法以碘、酮和硫脲为原料合成了9个2-氨基噻唑衍生物. 利用正交法优化了微波促进此类环化反应的最佳条件, 提出了微波条件下碘催化环化合成2-氨基噻唑衍生物可能的反应机理.     

食品接触用纸中铅、砷迁移分析

为研究食品接触用纸中铅、砷迁移规律,选择4批次食品接触用纸,通过测定其在不同介质(人造自来水、50%乙醇和4%乙酸三种模拟物)、不同加热方式[常温（22℃）、加热（70℃）、模拟微波（98℃）、实际微波加热]等条件下铅、砷迁移量来考察其迁移规律。结果表明,50%乙醇模拟物中,4个样品铅、砷迁移均未检出。4个样品在自来水和4%乙酸模拟物中,模拟微波15min条件下的铅、砷迁移量高于或接近常温10d条件,铅、砷迁移受温度影响较大,2#和4#两个样品实际微波条件下铅迁移量高于模拟微波条件迁移量的2倍,实际微波加热条件比模拟微波加热更严苛。     

微波辐射固体酸催化合成马来酸双酯

首次在微波辐射下，用活性炭固载对甲苯磺酸催化合成了马来酸双酯．当微波辐射功率为150W．正辛醇：酸酐＝3：1，催化剂用量为2．5g时，反应20min后，马来酸酐转化率达89．8％，产物的选择性为99．5％．同时，也发现随着醇的炭数增多，反应温度和反应速率增加；在微波辐射条件下，酯化反应速率、产物选择性都高于常规加热方式下的反应结果．     

芳烃酰基化后还原制备芳香醇的工艺进展

芳烃制备高附加值精细化学品芳香醇(9-芴甲醇),一直以来存在产物选择性低以及合成成本高等问题。基于此,本文主要综述了芳烃酰基化后还原合成芳香醇的工艺,包括第一步采用Friedel-Crafts酰基化反应、Vilsmeier-Haack反应、Reimer-Tiemann反应、Duff反应等过程将芳烃酰基化合成芳香醛/酮;第二步通过金属氢化物还原、催化加氢还原、活泼金属还原、Cannizarro反应、Meerwein-Ponndorf-Verley还原反应等过程将芳香醛/酮还原合成芳香醇。在总结和归纳各种工艺过程优缺点的基础上,提出了合理的芳香醇制备工艺,为9-芴甲醇产业化制备技术的开发提供帮助。     

C−N Coupling Reactions on Graphene with Aromatic Macromolecules and the Spatial Conformation of Grafted Macromolecules

The fabrication of advanced graphene-based nanocomposites with high-performance polymers requires covalent modification of graphene with aromatic macromolecules. Herein, C−N coupling reactions between fluorinated graphene (FG) and aromatic polyamides containing the benzimidazole moiety are successfully achieved. The optimized conditions are presented based on the nucleophilic behavior of the C−N coupling reaction on graphene. Different from the C−N coupling reaction between two small aromatic molecules, the conformation of grafted aromatic polyamide after reaction changes from torsional to paralleled alignment on graphene with the molecular length increment. Non-covalent interactions between graphene and aromatic polyamides result in this conformational change owing to the extended π systems of graphene and aromatic polyamides, and the synergistic effect of covalent and non-covalent interactions is put forward. As a consequence, graphene dispersibility is greatly enhanced in the solution of aromatic polyamide.     

Silver‐Catalyzed Arylation of (Hetero)arenes by Oxidative Decarboxylation of Aromatic Carboxylic Acids

A long‐standing challenge in Minisci reactions is achieving the arylation of heteroarenes by oxidative decarboxylation of aromatic carboxylic acids. To address this challenge, the silver‐catalyzed intermolecular Minisci reaction of aromatic carboxylic acids was developed. With an inexpensive silver salt as a catalyst, this new reaction enables a variety of aromatic carboxylic acids to undergo decarboxylative coupling with electron‐deficient arenes or heteroarenes regardless of the position of the substituents on the aromatic carboxylic acid, thus eliminating the need for ortho‐substituted aromatic carboxylic acids, which were a limitation of previously reported methods.     

芳香烃双加氧酶的结构与功能研究

芳香烃双加氧酶是细菌来源的参与生物降解芳香烃类化合物的主要酶类,它们能将空气中的氧分子活化,并使芳香烃类化合物在邻位碳上双氧化.这是一类具有重要生物功能和潜在应用前景的酶.本文从生物学与化学相结合的角度,介绍了以邻苯二酚双加氧酶、萘双加氧酶、联苯双加氧酶及栎精双加氧酶为代表的一系列能够催化氧化芳香烃类化合物的双加氧酶,重点讨论了它们的结构与功能,综述了这一领域的研究进展。     

Orbital views of the electron transport through heterocyclic aromatic hydrocarbons

Electron-transport properties of heterocyclic aromatic hydrocarbons are investigated with theoretical methods. The present study is based on a previously derived concept for orbital control of electron transport through aromatic hydrocarbons. The orbital control concept provided crucial basic understanding for the best conductance channels in the aromatic hydrocarbons and was successfully applied in the design of molecular devices. That concept was proven to hold true for small aromatic molecules, large polycyclic aromatic hydrocarbons with different edge structures, and in weak and strong coupling with the electrodes junctions. The polycyclic aromatic hydrocarbons and nanographenes used in the molecular electronics are often immobilized with different types of defects, which require the application of the orbital control concept on heterocyclic aromatic hydrocarbons. In this work, the effect of the heteroatoms in aromatic hydrocarbons on their electron-transport properties and the applicability of the orbital control concept on heterocyclic aromatic hydrocarbons are studied. Effective routes for electron transport are predicted in weak coupling junctions by analyzing the phase and amplitude of the frontier orbitals. The qualitative predictions are made with the nonequilibrium Green??s function method combined with the Hückel approximation. Quantitative, first principle calculations are performed with the nonequilibrium Green??s function method combined with density functional theory. The obtained results are in good agreement with the expectations on the basis of the orbital control concept, which proves its applicability in heterocyclic aromatic hydrocarbons.     

Selective Activation of Aromatic Aldehydes Promoted by Dispersion Interactions: Steric and Electronic Factors of a π-Pocket within Cage-Shaped Borates for Molecular Recognition

Selective bond formations are one of the most important reactions in organic synthesis. In the Lewis acid mediated electrophile reactions of carbonyls, the selective formation of a carbonyl–acid complex plays a critical role in determining selectivity, which is based on the difference in the coordinative interaction between the carbonyl and Lewis acid center. Although this strategy has attained progress in selective bond formations, the discrimination between similarly sized aromatic and aliphatic carbonyls that have no functional anchors to strongly interact with the metal center still remains a challenging issue. Herein, this work focuses on molecular recognition driven by dispersion interactions within some aromatic moieties. A Lewis acid catalyst with a π-space cavity, which is referred to as a π-pocket, as the recognition site for aromatic carbonyls is designed. Cage-shaped borates 1 B with various π-pockets demonstrated significant chemoselectivity for aromatic aldehydes 3 b – f over that of aliphatic 3 a in competitive hetero-Diels–Alder reactions. The effectiveness of our catalysts was also evidenced by intramolecular recognition of the aromatic carbonyl within a dicarbonyl substrate. Mechanistic and theoretical studies demonstrated that the selective activation of aromatic substrates was driven by the preorganization step with a larger dispersion interaction, rather than the rate-determining step of the C−C bond formation, and this was likely to contribute to the preferred activation of aromatic substrates over that of aliphatic ones.     

Aromatic hydroxyl group plays a critical role in antibacterial activity of the curcumin analogues

The aim of this study was to investigate the role of the aromatic substituents of the curcumin scaffold on the antibacterial activity of the resulting curcumin analogues. Six curcumin analogues with different aromatic substituents were prepared and their antibacterial activities were evaluated against two Gram-positive and four Gram-negative bacteria. The structure-activity relationship study demonstrated that antibacterial activity of the curcumin analogues was critically dependent upon the aromatic hydroxyl group. Thus, hydroxycurcumin with an additional aromatic hydroxyl group on the curcumin scaffold showed antibacterial activity against all six pathogens tested and it remained effective even against ampicillin-resistant Enterobacter cloacae. Along with the previously reported antioxidative effect, the broad-spectrum antibacterial activity of the hydroxycurcumin warrants further investigation of its biological activity as well as extensive structure-activity relationship study of the curcumin analogues with various aromatic substituents.     

Transition‐Metal‐Mediated Cleavage of C−C Bonds in Aromatic Rings

Metal‐mediated cleavage of aromatic C?C bonds has a range of potential synthetic applications: from direct coal liquefaction to synthesis of natural products. However, in contrast to the activation of aromatic C?H bonds, which has already been widely studied and exploited in diverse set of functionalization reactions, cleavage of aromatic C?C bonds remains Terra incognita. This Minireview summarizes the recent progress in this field and outlines key challenges to be overcome to develop synthetic methods based on this fundamental organometallic transformation.     

Quantitative determination of intermolecular interactions with fluorinated aromatic rings

The chemical double mutant cycle approach has been used to investigate substituent effects on intermolecular interactions between aromatic rings and pentafluorophenyl pi-systems. The complexes have been characterised using 1H and 19F NMR titrations, X-ray crystal structures of model compounds and molecular mechanics calculations. In the molecular zipper system used for these experiments, H-bonds and the geometries of the interacting surfaces favour the approach of the edge of the aromatic ring with the face of the pentafluorophenyl pi-system. The interactions are generally repulsive and this repulsion increases with more electron-withdrawing substituents up to a limit of +2.2 kJ mol(-1), when the complex distorts to minimise the unfavourable interaction. Strongly electron-donating groups cause a change in the geometry of the aromatic interaction and attractive stacking interactions are found (-1.6 kJ mol(-1) for NMe2). These results are generally consistent with an electrostatic model: the polarisation of the pentafluorophenyl ring leads to a partial positive charge located at the centre and this leads to repulsive interactions with the positive charges on the protons on the edge of the aromatic ring; when the aromatic ring has a high pi-electron density there is a large electrostatic driving force in favour of the stacked geometry which places this pi-electron density over the centre of the positive charge on the pentafluorophenyl group.     

Characterization of cyclodextrin modified infrared chemical sensors. Part II. Selective and quantitative determination of aromatic acids

In this paper, the selectivity and sensitivity of cyclodextrin (CD) modified infrared (IR) chemical sensor in detection of aromatic acids in aqueous solutions were reported. To eliminate the interference from water, the technique of attenuated total reflection was employed. By surface treated with CD molecules on the internal reflection elements, the sensors were selective in sensing of aromatic acids compared to aromatic compounds with other functional groups. To facilitate the use of this method for the quantitative analyses of aromatic acids in aqueous solutions, analytical functions were also developed in this work and a linear relationship between analytical responses and concentrations of analytes can be obtained. To optimize the analytical conditions, the factors that influence the IR spectroscopic signals were examined. These factors included response time, CD loadings of the sensors, pH effect on response, regeneration efficiency and stability of sensors. Under the optimal conditions, the detection limits for aromatic acids at a detection time of 2 min can be <100 μg/L. Meanwhile, the dynamic linear range for detection was only ca. two orders of magnitude if direct IR signals were used. Using the analytical function developed in this work, the linearity can be extended up to a concentration of 100 mg/L.