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Progress in Chemistry 2007, No.05 Previous issue Next issue

In this issue:

Invited Article
Fluorescent Labeling Reagents and Molecular Probes used in Separation and Detection of Bioactive Substances
Hong Wang|Huashan Zhang**
2007, 19 (05): 633-642 |
Published: 24 May 2007
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Abstract
Integrated with the authors' work，the recent development and application of the fluorescent labeling reagents and molecular probes for the determination of amino acids, peptides, proteins, biological amines, thiol compounds and NO etc, are reviewed. Besides OPA, NDA, DNS, FMOC, FITC, NBD-F, AQC, Cy5, some recent fluorescent label reagents and molecular probes are also discussed with respect to their application in the separation and fluorescent detection of HPLC or CE. They are N-hydrxylsuccinimidyl ester fluorescent labeling reagent, 6-oxo- N-hydroxysuccinimidyl acetic acid ester)-9-(2'-methyloxocabonyl) fluorescein, 8-phenyl-(4'-oxy-acetic acid N-hydroxysuccinimidyl ester)-4, 4-difluoro-1, 3, 5, 7-tetramethyl-4-bora-3a, 4a-diaza-S-indacene (TMPAB-OSu) etc , fluorescent probe 3-iodoacemidobenzanthranone and near-infrared fluorescent probe MCY5, DSTCY、DCDSTCY and DCTCY.
Review
Direct Oxidation of Propane to Acrylic Acid over MoVTe(Sb)Nbo Mixed Metal Oxide Catalysts
Yang Xiujuan,Feng Ruming,Li Li,Ji Weijie**|Chen Yi
2007, 19 (05): 643-650 |
Published: 24 May 2007
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Abstract
The direct oxidation of propane to acrylic acid has become a hot spot in catalytic oxidation of light alkanes in recent years. The MoVTe(Sb)NbO mixed metal oxide catalysts are the most important catalysts for this reaction. This article intends to review recent progresses in preparation methodologies and in understanding vital crystalline structures which are closely related to catalytic performance. The latest knowledge on the functions of the constituent main elements in the catalysts is summarized in terms of the reaction pathway of propane oxidation. It is recognized that modification of particle size and morphology, phase composition and structure, surface acidity and redox property of catalyst are critical to achieve superb catalyst performance and stability.
Studies and Applications of Catalytic Hydrogenolysis of Glycerol
Feng Jian,Yuan Maolin,Chen Hua*,Li Xianjun
2007, 19 (05): 651-658 |
Published: 24 May 2007
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Abstract
Because of the rapid development of biodiesel production by transesterification of vegetable oils and animal fats, large quantities of glycerol are formed as a reaction by-product. Seeking new utilization for the superfluous glycerol will improve the economy of the whole biodiesel production process. The studies of catalytic hydrogenolysis of glycerol have greatly increased in recent years, while no corresponding research has been reported in China. In this paper, the recent advances in catalytic hydrogenolysis of glycerol(1,2-propanediol,1,3-propanediol and ethylene glycol) are reviewed. The background of the studies of hydrogenolysis of glycerol is introduced. Then, emphases are focused on the reaction mechanisms (including the dehydration-hydrogenation mechanism,dehydrogenation-hydrogenation mechanism and chelation mechanism) and the application of catalytic hydrogenolysis of glycerol to glycols.The developing prospect of this research is also forecasted.
The Application of Mesoporous Molecular Sieves
Song Yan,Li Yonghong*
2007, 19 (05): 659-664 |
Published: 24 May 2007
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Abstract
This paper reviews the recent developments in the application of mesoporous molecular sieve in the fields of catalysis, biology fixation, adsorption, separation, preparation of nanomaterials and environmental protection, especially the desulfurization of gasoline prospects.
Properties and Distribution of the Surface Hydroxyl Groups of TiO2
Lin Huaxiang,Wang Xuxu** |Fu Xianzhi
2007, 19 (05): 665-670 |
Published: 24 May 2007
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Abstract
Having surface hydroxyl groups are one of the most important characteristics of TiO2 surface, and this has great effect on the photocatalysis and adsorption properties of TiO2. Study of surface hydroxyl groups of TiO2 is of importance in the investigation of surface properties and catalysis properties of TiO2. This review briefly summarized the investigations of surface hydroxyl groups in recent years, including the states and kinds of the hydroxyl groups of the different crystal phases of TiO2, the effect of absorbed H2O on the hydroxyl groups, and the photo electrochemical and photocatalytic behaviors of the hydroxyl groups. Finally, some problems In the study of surface hydroxyl groups is analyzed.
Toxicity of Ionic Liquids
Ke Ming*,Zhou Aiguo,Song Zhaozheng,Jiang Qingzhe
2007, 19 (05): 671-679 |
Published: 24 May 2007
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Abstract
Ionic liquids are gaining increasing interest due to their physical and chemical characteristics.Tthey are also considered sustainable "Green Product". But the potential toxicity of ionic liquids has been neglected, and few toxicological data of ionic liquids are available until now. This review presents the recent reports on the toxicity of ionic liquids from the following aspects: toxicity testing methods, acute and chronic toxicity on organisms, toxicity influenced by the substructures of ionic liquids, the application of the structure-activity relationship theory in the research of the toxicity of ionic liquids. The future research of the toxicity of ionic liquids is also approached.
Visible Light-Driven Semiconductor Photocatalysts for the Decomposition of Water
Tian Mengkui1,2,3|Shangguan Wenfeng2**|Wang Shijie1,Ouyang Ziyuan1
2007, 19 (05): 680-688 |
Published: 24 May 2007
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Abstract
The urgent work for photocatalytically splitting water into H2 and O2 is to develop photocatalysts capable of responding to visible light occupying nearly half amount of solar spectrum. Many ways to make photocatalysts active under visible light have been extensively studied and practiced. In this article, band engineering such as doping with cations and anions for TiO2, solid solution with narrow and wide precursor photocatalysts and Z -scheme system are reviewed.The implementation and characterization of different ways and their mechanisms for visualization based on electronic band structure is discussed.
Functional Gold Clusters and Their Applications in Biomedicine
Yang Xiaochao1|Qian Junzhen1|Wan Qiaoling1 ,Mo Zhihong1,2*
2007, 19 (05): 689-694 |
Published: 24 May 2007
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Abstract
Mixed monolayer protected gold clusters (Au-MMPCs) can be prepared by modifying the monolayer protected gold clusters（Au-MPCs） with various bioactive thiol or disulfide ligands. The interaction of these Au-MMPCs with biomaterials, such as protein, nucleic acid, and cell membrane, made them useful in cell transfection, drug delivery and enzyme activity regulation. In this paper, the factors that affect the synthesis of gold clusters in Brust-Schiffrin reaction are introduced. The strategies and mechanisms of preparation of mixed monolayer protected gold clusters (Au-MMPCs) based on the Brust-Schiffrin reaction are summarized, in which the ligand exchange reaction are described in detail. The applications of Au-MMPCs in biomedicine are reviewed.
A New Type of Lithium Salt Used as Electrolyte Salt of Lithium Ion Battery–Lithium Bis(oxalate)borate
Li Shiyou1,2*|Ma Peihua1,Teng Xiangguo1,2 |Li Faqiang1 |Ren Qidu1,2
2007, 19 (05): 695-699 |
Published: 24 May 2007
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Abstract
The basic characteristics and preparation of lithium bis(oxalate)borate (LiBOB) as a new lithium salt for lithium-ion batteries are summarized. The studies on application of this new salt in lithium-ion batteries, such as the conductance of LiBOB-based electrolytes, the stability of LiBOB-based electrolytes to the anode or cathode material, the performance of LiBOB mixed with other lithium are reviewed.
Microwave Irradiation and Selectivities in Organic Reactions
Xu Jiaxi**
2007, 19 (05): 700-712 |
Published: 24 May 2007
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Abstract
The different selectivities, including chemoselectivity, regioselectivity, syn/trans selectivity, disatereoselectivity, and enantioselectivity, of organic reactions under the microwave-assisted and conventional heating conditions are reviewed. The effect of microwave on these selectivities is discussed. According to a survey of literature, although some differences on the selectivities between the microwave-assisted and classical heating conditions are observed in some reactions, most of the reactions are not conducted under the strict same conditions except for heating mode, such as in different solvents, even under solvent-free conditions, under the catalysis of different catalysts or additives, at different temperatures. Some examples are conducted under the same reaction systems, but at different temperatures. For most of examples , the effects of the microwave irradiation on the selectivities are possibly caused by the actually different temperature and could be explained by the thermal effect. I am prone to consider that no specific athermal effect exists generally in the microwave-assisted organic reactions. The microwave-assisted technology can tune selectivities via changing reaction temperature for some organic reactions. I hope this review will provide some useful information to understand the microwave effect on the organic reactions and the origin of the microwave-induced organic reaction enhancement chemical techniques.
σ- Receptor Ligands as Imaging Agents
Zhang Qiuyan,Fan Caiyun,Jia Hongmei**
2007, 19 (05): 713-721 |
Published: 24 May 2007
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Abstract
Sigma (σ) receptors have been proposed to be involved in cellular functions, biological processes and diseased. Sigma-1 receptors have recently been a novel target of drug development related to CNS disorders such as schizophrenia, depression, Alzheimer, and Parkinson diseases, while sigma-2 receptors are regarded as a biomarker of tumor proliferation.Sigma-1 receptor imaging agents can provide a powerful diagnostic tool to fight with neuropsychiatric diseases of human beings, while sigma-2 receptors imaging agents are the sensitive molecular probes for the early diagnosis of malignant tumor. This review provides the overview of recent advance of sigma receptors imaging agents. The emphases are focused on design methods of different sigma receptor imaging agents based on their possible applications. The trend for development of σ receptor imaging agents has also been discussed.
Progress in Biscalixarene Research
Zheng Qin,Gong Shuling**,Zhang Chunlei,Wang Wei|Chen Yuanyin
2007, 19 (05): 722-734 |
Published: 24 May 2007
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Abstract
Biscalixarene is an important member of calixarene family, composed of two calixarene moieties linked at their upper (head) or lower (tail) rim through various spacers with more complicated structures and colorful properties as compared to calixarene. It can be divided into three basic types commonly known as head-to-head, tail-to-tail, and head -to- tail bridged biscalixarenen. Biiscalixarene contains two same or different recognition sites and can complex two same or different guests. Moreover, it has some high-level properties such as stronger inclusion ability, allosteric effects, oscallation between the two metal-binding sites and so on due to cooperative effect. Here, a survey of biscalixarene chemistry and recent research progress are reviewed according to the type of calixarene subunits. Thesyntheses of the biscalix[4] arene with various linked types are emphatically described, and some special biscalixarenes are described in detail as well. The prospect of biscalixarene chemistry is also discussed.
Direct Phenol Synthesis by Catalytic Oxidation of Benzene with Molecular Oxygen
Yin Shuangfeng**,Wu Shuisheng,Dai Weili|Li Wensheng,Huang Mengguang| Zhou Xiaoping**
2007, 19 (05): 735-744 |
Published: 24 May 2007
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Abstract
Phenol is an important synthesis intermediate in chemical industry. Currently, phenol is produced from the isopropylbenzene oxidation process, which consumes propylene and forms acetone as by-product. Phenol synthesis from the direct catalytic oxidation of benzene by molecular oxygen is attractive from the standpoint of its potential economical benefit, social benefit as well as environmental benefit. However, the research works in this area are still regarded as one of the most difficult challenges for both catalysis and organic synthesis. This mini-review systematically summarizes the progress of direct phenol synthesis by catalytic oxidation of benzene using molecular oxygen as oxidant, with emphasis on the explored catalysts such as Pd, Cu, V compounds. We also outline the factors affecting phenol synthesis and the possible reaction mechanisms on different catalysts. In addition, some suggestions are given for future investigations on direct phenol synthesis by catalytic oxidation of benzene with molecular oxygen.
Synthesis of Chiral Sulfoxides
Zeng Qingle**
2007, 19 (05): 745-750 |
Published: 24 May 2007
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Abstract
Chiral sulfoxides and their derivatives are extensively used as important chiral intermediates and auxiliaries, chiral ligands and catalysts, and chiral drugs. Chiral sulfoxides may be obtained by biological and chemical methods. The chemical methods include chiral auxiliary's induction, chiral oxidant's oxidation, chiral resolution, and enantioselective catalysisi. The applications and research advance of various synthetic methods of chiral sulfoxides, introduction of titanium-, vanadium-catalyzed enantioselective sulfoxidation, as well as author's recent research work about vanadium-catalyzed sulfoxidation are reviewed in this paper.
Synthesis of 3-Substituted Indole Derivatives
Li Jitai**,Dai Hongguang,Lin Zhiping
2007, 19 (05): 751-761 |
Published: 24 May 2007
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Abstract
The research of indoles has been one of the most active areas of heterocyclic chemistry. In particular, 3-substitued indole derivatives have been received much attention as building blocks for the synthesis of many natural products and other biologically active compounds. Recently, there are a lot of reports on the synthesis of 3-substitued indoles from indole. In this article, The one-pot synthesis of 3-substitued indole derivatives from indoles, such as bis (indolyl) methane, β-indolylketone, β-indolylalcohol, β-indolylnitro-compound, α-indolylmethylamine is reviewed according to the kinds of catalysts.
Cyclic Peptide Histone Deacetylases Inhibitors
Li Xiaohui1**|Li Jianxun1|Li Shirong1,Xiu Zhilong1,Nishino Norikazu2
2007, 19 (05): 762-768 |
Published: 24 May 2007
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Abstract
Histones acetyltransferases (HAT) and histone deacetylases (HDACs) as the corresponding enzymes regulate the change of histones in two antagonist forms, acetylated or deacetylated. In recent years, inhibition of HDACs has emerged as a potential strategy in human cancer therapy, since these enzymes play a fundamental role in regulating gene expression and chromatin assembly. The histone deacetylases inhibitors (HDACIs) are potent inducers of growth arrest, differentiation and apoptosis of tumor cells, and have entered clinical trials for both solid and liquid tumors. However, the molecular basis for their anticancer selectivity remains largely unknown. An improved understanding of the structure and action mechanism of HDAC inhibitors will likely accelerate the clinical development and broaden the future scope and utility ofHDAC inhibitors will likely accelerate the clinical development and broaden the future scope and utility of HDAC inhibitors for cancer treatment. In this review, we summarize recent advances of the HDACs inhibitors of cyclic peptide in structure, mechanism of action, clinical development.
Hydrogen Bonding Recognition in Supramolecular Polymers
Wang Yu,Tang Liming**
2007, 19 (05): 769-778 |
Published: 24 May 2007
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Abstract
The application of hydrogen bonding recognition in designing and controlling over supramolecular polymers has attracted great attention recently due to the influence of hydrogen bonds on the thermodynamic properties, microscopic self-assembling, crystallizing and liquid crystallizing behaviors of such polymers. In this paper, the types and characters of hydrogen bonding systems and the influences of molecular structures and intermolecular hydrogen bonds on the stability of hydrogen bonding systems are described systematically. The recent application of hydrogen bonding recognition systems, including carboxylic acids and pyridine based system, nucleobase derived system and quadrupolar hydrogen bonding system, in supramolecular polymers are introduced. The synthetic methods, structures, properties and functions of hydrogen bonded supramolecular polymers are mainly addressed.
High Performance Polybenzoxazines
Men Weiwei,Lu Zaijun*
2007, 19 (05): 779-786 |
Published: 24 May 2007
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Abstract
As a new type of phenolic resin, polybenzoxazines have attracted considerable attention in preparing high performance resins because of their fascinating characteristics such as no release of volatiles during cure, good thermal stability, and flame retardant. The research progress in preparing high performance polybenzoxazines is reviewed in this paper. The modification approached including incorporation of naphthalene, biphenyl, and benzophenone groups to benzoxazines, introduction of another polymerizable functional group into benzoxazine structure, and formation of copolymers, polymer alloys, composites and polymer-clay nanocomposites are reviewed. Moreover, the analyses of domestic and overseas research, developing tendency and industrial application of this kind of high performance polybenzoxazines are discussed.
Preparation and Properties of Nanocomposites of Polyaniline and Metal Nanoparticles
Li Xingui,Sun Jin,Huang Meirong*
2007, 19 (05): 787-795 |
Published: 24 May 2007
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Abstract
Polyaniline/metal nanoparticle composites，a kind of novel materials developed in recent years, have been systematically reviewed from the history, preparation and multi-functionalities based on our recent research and the latest literature. The technique of introducing metal nanoparticle into polyaniline matrix could be summarized in three categories：in-situ compound, direct blending and layer-by-layer self-assembly. The resulted hybrids from organic polyaniline and inorganic metals not only retain the original respective intrinsic performance, but also exhibit coadjutant effect that is beneficial for improving the properties of polyaniline matrix in composites. The maximal conductivity of the composite is ca.100 times higher than that of the matrix, and the maximal peak current of oxidation is ca.10 times higher than that of the matrix. Traces of platinum microparticles dispersed in polyaniline film could result in a stable corrosion potential of stainless steel within the passive range. The unique properties of polyaniline/metal nanoparticle composites including outstanding intrinsically electrical conductivity, excellent reactive catalysis and powerful anticorrosion properties make them lie in few high performance composites. They have shown attractive potential in applications.
Asymmetric Epoxidation of Electron-Deficient Olefins Catalyzed by Coordination Compound Derived From Chiral Binaphthol and Its Derivatives
Gao Yongjun,Ma Jingjun,Wu Qiuhua,Zang Xiaohuan,Wang Chun**
2007, 19 (05): 796-804 |
Published: 24 May 2007
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Abstract
The asymmetric epoxidation of electron-deficient olefins,especiallyα,β－unsaturated carbonyl compounds, is one of the most challenging fields in modern organic synthesis in recent years. The catalysts modified by chiral 1,1'-bi-2-naphthol and its derivatives are excellent chiral C2-symmetric inducers which can catalyze the asymmetric epoxidation reaction of electron-deficient olefins with high catalytic activity and excellent enantioselectivity. The substrates involves α,β－unsaturated ketones, α,β－unsaturated carboxylic acid amides, α,β－unsaturated esters and so on. The applications of small molecular catalysts generated from optically active 1,1'-bi-2-naphthol and its derivatives,polymer-supported catalysts and self-supported catalysts in the asymmetric epoxidation reaction of α,β－unsaturated carbonyl compounds are reviewed in this paper. In addition, the catalytic activity and enantioselectivity influenced by the catalysts derived from chiral binaphthol derivatives, cooridinative metal atoms, additives, oxidants, solvents and reaction temperature are also discussed.
Molecular Recognition in Aqueous Media with Molecular Imprinting Technique
Wang Xuejun, Xu Zhenliang*|Yang Zuoguo,Bing Naici
2007, 19 (05): 805-812 |
Published: 24 May 2007
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Abstract
Among the variety of biomimetic recognition systems based on supramolecular approaches, molecularly imprinted polymers (MIPs) have proven their potential as synthetic receptors receiving more and more attention. Conventional molecular imprinting technology allows the synthesis in organic solvents of molecularly imprinted polymers selective toward relatively low molecular weight compounds. However, synthesis in aqueous media of chemically and mechanically stable MIPs that can recognize biomolecules still is a great challenge. From small molecules to biomacromolecules, from organic phase to aqueous media, the application field expands with the development of molecular imprinting technique. The recent progress in preparation and recognition of molecularly imprinted polymers in aqueous phase are overviewed and discussed. The design strategy and preparation methods of aqueous MIPs are investigated. The emphasis is put on the applications of aqueous recognition in the fields of solid phase extraction, chromatographic stationary phases, drug delivery and controlled release, separation of active ingredients from herbs and recognition of biomolecules. The methods to improve the selectivities of MIPs in aqueous recognition are presented, and the challenges, as well as the suggestions to the development of molecular imprinting technique are outlined.
Left-Handed Materials and Negative Refraction
Hu Jinglei,Wang Rong,Zhou Dongshan|Xue Gi**
2007, 19 (05): 813-819 |
Published: 24 May 2007
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Abstract
This paper focused on left-handed materials(LHM) both from theoretical point and from experimental aspects. The methods to realize left-handed medium are reviewed, including combination of split ring resonators (SRRs) with thin metal wires, and those beyond SRRs. We concentrated on superlens effect, the most promosing effect of LHM, and photonic crystals, which bear some analogy to LHM but distinguished from LHM. A brief introduction to domestic research of negative refracting materials is given, and two possible routes to negative refracting via functional polymeric materials are suggeted.
Progress of Biochemical Reaction Technologies on Microfluidic Chips
Xu Yi1,2**,Lv Junjiang1,Fan Wei1,Wen Zhiyu2
2007, 19 (05): 820-832 |
Published: 24 May 2007
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Abstract
Different kinds of biochemical reaction approaches for the goal of detection and kinetics studies on microfluidic chips are reviewed, including enzymatic assay, immunoassay, enzyme-linked immunosorbent assay (ELISA), polymerase chain reaction (PCR) and nitric oxide release reaction. According to the very characteristics of certain derivative reaction, immobilization of proteins on channel wall for inhomogeneous reactions, channel network design for homogeneous reactions and as well the advantages of performing biochemical reaction on microfluidic chips are investigated in details