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Progress in Chemistry 2008, No.0708 Previous issue Next issue

In this issue:

Invited Article
Polymer Controlled Biomimetic Mineralization
Cai Guobin|Guo Xiaohui|Yu Shuhong**
2008, 20 (0708): 1001-1014 |
Published: 24 August 2008
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Abstract
Recently, bio-inspired synthetic strategies for functional materials have gained lots of attentions due to their advantages. This review focuses on recent progresses in biomimetic mineralizations using molecular templates, morphology and structure control for inorganic and inorganic-organic hybrid materials using molecular templates, and the synergetic effects of molecular and solid matrix. We focus on template effects of simple organic additives such as hydrophilic polymer, polyelectrolyte, and surfactant, and their synergestic effects in growth of complex inorganic superstructures and new effects in a mixed solvent. The mechanisms used in biomimetic mineralization for control of new inorganic nanomaterials and inorganic-organic hybrid materials will be discussed. Recent progress indicates that it is possible to control morphologies of all inorganic crystals and hybrid structures via choosing a proper molecular template, a solid matrix, suitable reaction micro-environments, and appropriate self-assembly mechanisms. These materials with controllable length scale and complex form may have potential applications in various fields.
Review
Approximation Expressions for the Temperature Integral

Chen Haixiang**|Liu Naian**

2008, 20 (0708): 1015-1020 |
Published: 24 August 2008
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Abstract
The recent ten-year research progress in the approximation expressions for the temperature integral in the field of thermal analysis kinetics is reviewed. Some new approaches to approximate the temperature integral are introduced, and the relationship between various approximation expressions is presented. The accuracy in calculating kinetic parameters by different integral methods with different approximation expressions is commented, and the methods to avoid the problem of the temperature integral are summarized. The research tendency about the temperature integral is also suggested.
Heterogeneous Catalysts for Olefin Cross-Metathesis
Li Xin|Zhang Weiping**|Li Xiujie|Liu Shenglin
2008, 20 (0708): 1021-1031 |
Published: 24 August 2008
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Abstract
Olefin metathesis has been widely used in the fields of petrochemical industry and organic synthesis. It can be classified as ring-opening metathesis, ring-opening metathesis polymerization, ring-closing metathesis, cross-metathesis, etc. Recent developments in the heterogeneous catalysts for olefin cross-metathesis are summarized in this review. Much attention has been paid not only to the heterogeneous catalysts based on Re, Mo and W, but also to the effects that may influence the catalyst activity, such as the metal oxidation state, structure and dispersion of the active species, properties of the support and the addition of promoters, etc. The reaction mechanisms and possible deactivation routes are also discussed in detail.
Nickle-Based Catalysts for Ethylene Oligomerization to α-Olefin
Zhang Juntao1,2* Zhang Guoli3 Feng Xiao1
2008, 20 (0708): 1032-1036 |
Published: 24 August 2008
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Abstract
Progress of nickel-based catalysts for ethylene oligomerizatioin to α-olefin has been introduced. The influences of the varieties, steric structures and properties of ligands in homogeneous nickel-based catalysts, the structures, properties of carriers and valent state of nickel cation in heterogeneous nickel-based catalysts on the reaction of ethylene oligomerization are discussed. Moreover, the reaction mechanism of nickel-based catalysts has been clarified in detail. Finally, it was proposed that more attentions should be paid to the ligands with proper electronic effectiveness, steric structure and dielectric stability when synthesizing homogeneous nickel-based catalysts. On the other hand, the emphasis is focused on the new style carriers and the additive components for maintaining active center stability when developing heterogeneous nickel-based catalysts.
Redox Properties of Pure and Doped Ceria and Their Application in Catalysis

Yan Zhipeng|Chong Mingben|Cheng Dangguo**|Chen Fengqiu|Zhan Xiaoli

2008, 20 (0708): 1037-1043 |
Published: 24 August 2008
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Abstract
The redox properties of pure and doped ceria and their application in catalysis are summarized. CeO2 plays an important role in catalyzing many reactions, including redox reactions, synthesis gas production, organic synthesis, catalytic abatement of organic pollutants and so on. This arises from the ability of ceria to store and release oxygen depending upon the conditions. Several Ce3+ interacting with reactants and intermediate retentions at the same time can make some contribution as well. Furthermore, the catalytic performance of ceria can be improved by doping other oxides. The research tendencies for promoting development of the applications of pure and doped ceria in catalysis are proposed.
Preparation of Novel Microcapsules by Emulsion Droplet Template Method

Liu Hongxia|Wang Chaoyang**|Gao Quanxing|Tong Zhen

2008, 20 (0708): 1044-1049 |
Published: 24 August 2008
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Abstract
The present article focuses on a facile and versatile technique of emulsion droplet template method, developed for preparing novel capsules. Colloid particles adsorb on the surface of the emulsion droplets and self-assemble into an ordering spherical solid shell. Cross-linking and fixing the shell, the novel capsule “colloidosome”, which is composed of a close-packed shell of colloid particles, can be fabricated. The strategy outlined readily affords the facility of fabrication and precise control over the size, permeability, mechanical strength of the capsules. Consequently these capsules have potential applications in functional foods, drug delivery, biomedicine, especially cell transplant.
White Organic Light Emitting Diodes Based on Combination of Fluorescence and phosphorescence

Wang Lei|Lei Gangtie** Yi Xiaohua

2008, 20 (0708): 1050-1056 |
Published: 24 August 2008
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Abstract
White organic light-emitting diodes (WOLEDs) have been attracting considerable attention due to their potential applications in large-area flat panel displays and solid-state light sources. In recent years, many highly efficient WOLEDs with various structures have been fabricated by combination of fluorescence and phosphorescence because this method can combine the merit of fluorescent and phosphorescence devices. In this paper, recent progress of this kind of WOLEDs is reviewed with a view to the materials, device structure and light-emitting mechanism. Some issues to be addressed and orientations to be further studied are also put forward and discussed.
Imidazolium-Based Ionic Liquids
Wang Zhongni|Wang Jieying|Si Youhua|Zhou Wu
2008, 20 (0708): 1057-1063 |
Published: 24 August 2008
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Abstract
The unique physicochemical properties of imidazolium-based ionic liquids (IBILs) have attracted increasing interests due to their potential applications in various areas. In this paper, combining with our works, recent progress in some physicochemical properties of IBILs have been reviewed and discussed, including the gas-liquid and liquid-liquid equilibrium of IBILs, the surfactant behaviour of IBILs, the aggregations of traditional surfactant in IBILs, as well as the supramolecular self-assemblies formed in surfactant/IBILs/water(or oil) ternary systems. Suggestions for further studies have been proposed to investigate the self-assemblies formed in non-traditional surfactant/IBILs systems and to make clear that how the structures of IBILs influence the formation and properties of surfactant self-assemblies.
Controlled Preparation and Mechanism Study of One-dimensional Silicon Nanomaterials
Zhang Xiaodan1,2 Cao Yang1 He Junhui1**
2008, 20 (0708): 1064-1072 |
Published: 24 August 2008
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Abstract

One-dimensional silicon nanomaterials have unique optoelectronic properties compared with bulk silicon materials, and possess potential applications in optical and electronic fields. Their physicochemical properties can be tuned by tailoring their size, morphology and composition. Therefore, it is extremely important to explore and realize controlled preparation of one-dimensional silicon nanomaterials for their future applications. The recent progress in controlled preparation of one-dimensional silicon nanomaterials is reviewed. Several important preparation methods and their growth mechanisms are introduced, and the advanteges and disadvanteges of these different methods in controlled preparation of one-dimensional silicon nanomaterials are discussed. The research trends for their future are prospected.

Rare Earth Complexes with Nitroxide Radicals

Yang Xuhong|Yang Shutao|Wang Shuping**

2008, 20 (0708): 1073-1089 |
Published: 24 August 2008
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Abstract
Rare earth complexes with nitroxide radicals show novel optical and magnetic properties. It is one of the hotspots for molecule-based magnets and multi-functional molecular materials. The structural characteristics, magnetic and optical properties for this kind of complexes are reviewed in this paper, and the influencing factors are also discussed.
“Click” Chemistry in Fields of Materials Science
Zhang Tao1,2 Zheng Zhaohui1 Cheng Xu1 Ding Xiaobin1* Peng Yuxing1*
2008, 20 (0708): 1090-1101 |
Published: 24 August 2008
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Abstract
TIn recent years, click reactions have converged into a powerful tool set for materials scientists becauce of their high yields, high selectivity and exceptional tolerance towards a wide range of functional groups and reaction conditions. In this paper, the conception, characteristic, reactive mechanism and applications of click chemistry are reviewed. In particular, applications of click chemistry in the modification of polymers, surface and nanomaterials are reviewed. The problem of click chemistry and the trend in the future are analyzed.
Advances in the Synthesis of Thiocarbamates
Zhang Xiaopeng1,2 Jing Huanzhi1 Miao Jianghuan1 Lu Shiwei2**
2008, 20 (0708): 1102-1107 |
Published: 24 August 2008
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Abstract
Thiocarbamates, a type of compounds containing many functional groups and possessing bioactivity, have been widely applied in medicine, biology and agricultural chemicals. In this paper, the main methods to thiocarbamates such as hydrolysis or alcoholysis of thiocyanate, rearrangement reaction, phosgene derivatives method and carbonylation of nitro compounds or amines are summarized. Their advantages and disadvantages are also compared. It is pointed out that selenium-catalyzed carbonylation of nitro compounds or amines with thiols to thiocarbamates is a promising method which is characterized by benign environment, high atomic economy and “one-pot” approach.
Asymmetric Transformation of Carbonyl Compounds Using Plant Cells
Liu Xiang1,2** Zhang Baoli1 Xia Yongmei1 Fang Zhijie2 Xu Jianhe3
2008, 20 (0708): 1108-1114 |
Published: 24 August 2008
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Abstract
Recent progress in asymmetric transformation of carbonyl compounds using plant cells is reviewed in this paper. Using plant cells, not only carbonyl group of some ketones and α- keto esters or β-keto esters can be enantioselectively reduced, but also asymmetric hydroxycyanidation of carbonyl group of some aldehydes can be catalyzed. Furthermore, C＝C double bonds of some unsaturated carbonyl compounds can also be regioselectively transformed. Asymmetric transformation of substrate is influenced by regioselectivity and stereoselectivity of cells from different plant even different part of the same plant. The results of asymmetric transformation can also be affected by steric effect and electronic effect of substitute group of the substrate. Influence of steric effect on asymmetric transformation is more prominent.
The Surface Modification of Silica with GPTMS
Li Deliang1,2** Wang Jun3 Chang zhixian2 Zhang zhijun1
2008, 20 (0708): 1115-1121 |
Published: 24 August 2008
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Abstract
γ-glycidoxypropyltrimethoxysilane(GPTMS) is an important silane coupling agent, and nano-silicasts modified with GPTMS (GPTMS-SiO2) has being used widely. In this review, the recent progress of the surface modification of GPTMS-SiO2 is summarized. The typical methods to modifying GPTMS on nano-silica surface such as liquid phase process and sol-gel process, the modification, mechanism and the existing problems of modifications are discussed. The determination and characterization of GPTMS layers by Fourier transform infrared spectroscopy(FT-IR), X-ray photoelectron spectroscopy(XPS), nuclear magnetic resonance(NMR), elemental analysis and atomic force microscopy(AFM) are introduced. The structure and stability of the GPTMS layers and the controllability of the different modified methods are elucidated. Application of GPTMS-SiO2 in chromatography stationary phase, biochemical separation and analysis, optical material, industry of adhesive and coatings and mesoporous catalysis are described. The development trend of new synthesis method, evaluation system, determination of active group and application of GPTMS-SiO2 are prospected.
Surface-Initiated Living Radical Polymerization from Inorganic Nanomaterials
Sui Xiaofeng Yuan Jinying** Yuan Weizhong Zhou Mi
2008, 20 (0708): 1122-1127 |
Published: 24 August 2008
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Abstract

The inorganic-polymer hybrid nanomaterials have many excellent properties. So they are becoming increasingly important for various applications ranging from biomaterials to semiconductors in many fields and arouse much interest of scientists all over the world. This review highlights the development of surface-initiated living radical polymerizations from the inorganic materials including surface-initiated atom transfer radical polymerization(ATRP), surface-initiated addition-fragmentation chain transfer radical polymerization(RAFT), surface-initiated nitroxide-medicated polymerization(NMP) in thr preparation of inorganic-polymer hybrid nanomaterials. The emphasis is put upon the new developments of various approaches taken to prepare hybrid nanomaterials in the recent years. Also, new research trends are pointed out.

Reversible Addition Fragmentation Chain Transfer Polymerization Mediated by Xanthate
Jiang Bo1 Yi Lingmin1,2** Zhan Xiaoli1** Chen Bi1 Chen Fengqiu1
2008, 20 (0708): 1128-1135 |
Published: 24 August 2008
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Abstract
The RAFT radical polymerization of non-conjugated vinyl monomers and conjugated vinyl monomers mediated by xanthate are reviewed in this paper. Because the alkyloxy in xanthate (Z group) increases the electron density on central carbon atom of xanthate and stabilizes the fragmentation product, the RAFT radical polymerization of non-conjugated vinyl monomers mediated by xanthate could proceed in a living way. Introducing fluorin atom into Z group of xanthate improves fragmentation of intermedia by decreasing the stabilization of intermedia, instead of stabilizing the fragmentation product. Mediated by this kind of xanthate, conjugated vinyl monomers could be polymerized in a living radical way. Moreover, block copolymers comprised of non-conjugated vinyl monomer and conjugated vinyl monomer can be prepared by fluorinated xanthate.
Heparan sulfate: Structure, Function, modification and Synthesis
Sun Zicai|Wei Zheng**|Wei Kemei
2008, 20 (0708): 1136-1142 |
Published: 24 August 2008
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Abstract
Heparan sulfate is a typical kind of glycosaminoglycan(GAG), having complex structures and charged with many particular biological activities. This paper elucidated the structures of heparan sulfate as well as the structure-function relationships, reviews the chief work of structural modification, simulation as well as biosynthesis and chemical synthesis.
Ionic Liquids Functional Polymers
Zhu Lili|Chen Zhengguo**|Luo Chuan|Zhang Meng
2008, 20 (0708): 1143-1150 |
Published: 24 August 2008
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Abstract

Ionic liquid functional polymers (ILFPs) are organic polymers synthesized mainly by the polymerization of unsaturated ionic liquid monomers. These polymers combine the advantages of ionic liquids which have drawn great attention due to their special structures and properties. In this paper, we summerize the research on ILFPs developed in recent years. According to the kinds of ions linking with chains, we classify the existing ILFPs into three types, which are polycations, polyanions and zwitterions. Then, the synthesis methods of ILFPs and several structural factors which have effects on their Tg are introduced. Besides, we review the using of ILFPs as polymer electrolytes, surfactant, catalysts, enzyme carriers and gas adsorbents. On this basis, we point out the science questions such as less variety and characterization in the present research of ILFPs, and give the possible prospects in future.

Synthesis and Applications of 2-Methacryloyloxyethyl Phosphorylcholine Monomer and Its Polymers
Ma Jiani|Gong Ming|Zhang Shiping|Gong Yongkuan**
2008, 20 (0708): 1151-1157 |
Published: 24 August 2008
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Abstract
The research on 2-methacryloyloxyethyl phosphorylcholine(MPC) and its polymers by mimicking the structure of outer cell membrane has been a new hot topic. Numerous studies have demonstrated that the surface of materials modified with MPC polymers shows excellent hemocompatibility and tissue compatibility. In this article, the synthesis of MPC monomer and its polymers is reviewed. The applications of MPC polymers in biomedical fields, such as artificial organs, tissue engineering, blood purificaion, controlled drug delivery and gene therepy, are summerized briefly. Furthermore, the prospects of research and application of MPC polymers are also discussed.
Techniques for Staining Glycoprotein on Gel Electrophoresis or Electroblotting

Zhang Ying|Huang Linjuan|Wang Zhongfu**

2008, 20 (0708): 1158-1164 |
Published: 24 August 2008
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Abstract
Glycosylation is one of the most important protein post-translational modification methods, which is essential to life and function of proteins. Two-dimensional gel electrophoresis (2-DE) is one of the most commonly used methods developed for the separation of proteins, and identification of glycoproteins in gel is a key step for the separation and purification of glycoproteins. This review gives an overview of derivatization reagents for detecting of glycoprotein on gel electrophoresis or electroblotting, and the reaction mechanisms of most derivative reagents are also introduced.
Application of LIBS Technology to the rapid Measure of heavy Metal Contamination in Soils
Wang Jianwei1,3 Zhang Nazhen1,2 Hou Keyong1,2 Li Haiyang1**
2008, 20 (0708): 1165-1171 |
Published: 24 August 2008
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Abstract
Laser-induced breakdown spectroscopy（LIBS）has emerged in the past ten years as a technique for analysis and measure. The fundamental principle of LIBS for in situ qualitative analysis is introduced. Current development of the instrument and its applications in rapid detection of heavy metal contamination elements, such as As, Cd, Cr, Hg, Pb and Zn in soils are reviewed in detail. The critical problems such as how to achieve quantitative measurement and improve the detection limit of LIBS are discussed.
Immobilization of Enzymes on Mesoporous Materials

Lv Yongjun|Li Peijin|Guo Yanglong|Wang Yanqin|Lu Guanzhong**

2008, 20 (0708): 1172-1179 |
Published: 24 August 2008
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Abstract
The recent achievement of the immobilization of enzymes on mesoporous materials is reviewed and immobilizing methods on different supports, including physical absorption, chemical binding and encapsulation are summarized. The factors that influence the immobilization of enzymes on mesoporous materials are investigated in detail. The applications and prospects of the immobilization of enzymes on mesoporous materials are presented.
Photochemical Degradation of Polybrominated Diphenyl Ethers

Fang Lei|Huang Jun|Yu Gang**

2008, 20 (0708): 1180-1186 |
Published: 24 August 2008
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Abstract
Polybrominated diphenyl ethers (PBDEs) are considered as a group of global organic pollutants, and have recently received increasing concerns due to their persistence, toxicity and potential for bioaccumulation. Photochemical degradation is one of the important fates for PBDEs in natural environment. In this paper, recent developments about the photochemical degradation of PBDEs under artificial UV light or sunlight in different matrices are reviewed, such as organic solvents, water and solid. Not only the influences of light sources, reaction matrices, number of bromine substituents and substitution pattern on the photolysis rates and photoproducts of PBDEs are introduced, but also the quantitative structure-property relationships based on the photochemical degradation of PBDEs are referred. In addition, the research prospects about the photochemical behavior of PBDEs in the environment are proposed.
Treatment of Organic Pollutants in Water by Ultrasound
Li Mei1,2 Li Jitai1** Sun Hanwen1
2008, 20 (0708): 1187-1195 |
Published: 24 August 2008
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Abstract
In recent years, increasing attention has been focused on the application of ultrasound for the destruction of organic contaminations in water. Compared with conventional treatment methods, the ultrasonic treatment increases the degradation efficiency and reduces the time required for removing the organic contaminations. Ultrasonic technology has been proven to be effective for the degradation of the most refractory organic pollutants. The principle and the major influencing factors on degradation efficiency and methods (including ultrasound irradiation individually and ultrasonic waves in conjunction with other techniques such as bio-catalyst, chemical oxidation, and adsorption) of ultrasonic degradation are described in this paper. Progress in treatment of organic pollutants in water by using ultrasound technology is reviewed. Moreover, existing problems and future study directions are discussed.
Organic Polluted Soil and Groundwater Remediation by in situ Fenton Oxidation

Cui Yingjie|Yang Shiying**|Wang Ping|Jia Yonggang

2008, 20 (0708): 1196-1201 |
Published: 24 August 2008
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Abstract
This paper provides an up-to-date overview of the progress of in situ Fenton oxidation in remediation of soil and groundwater polluted by organic pollutants. As one of the advanced oxidation technologies, Fenton oxidation has been deeply researched in wastewater treatment. Recently, Fenton oxidation attracts more and more attentions in organic polluted soils and groundwater remediation. Fenton reagent has been constantly modified from traditional Fenton reagent in acid reaction to modified Fenton reagent in natural. The rate of degradation has being improved, and the technology is being applied in field scale. The mechanism for the Fenton’s degradation of the organic pollutants in soil and groundwater is discussed, and research trends are prospected.
Template Synthesis of Mesoporous Carbon Materials

Li Na|Wang Xianyou**|Yi Siyong|Dai Chunling

2008, 20 (0708): 1202-1207 |
Published: 24 August 2008
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Abstract
Template method provides a new technology for synthetizing controllable and directional various mesoporous carbon materials; it has currently become one of the most popular topics in the advanced materials preparation at home and abroad. Due to their uniform and ordered pores, narrow pore size distribution and high specific surface area, mesoporous carbon materials had been widely used in gas separation, catalyst support, adsorption, chromatographic analysis, supercapacitors and fuel cells, etc. Based on the recent research progress of the template synthesis technology of mesoporous carbon, we discuss the effect of different template preparation technology on the performance of mesoporous carbon, analyze mesoporous carbon’s formation mechanism and its application in biology, catalysis, electronic energy resource areas. It is pointed that preparing mesoporous carbon by template technology is a promising method, and in the future the mesoporous molecular sieve template method and soft template method should be emphasized for template synthesis of mesoporous carbon materials.
Ceramic Modification of the Porous Stainless-Steel Surface Toward the Supported Palladium Membranes for Hydrogen Separation

Yu Jian|Hu Xiaojuan|Huang Yan**

2008, 20 (0708): 1208-1215 |
Published: 24 August 2008
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Abstract
The composite palladium membrane comprises a porous substrate and a thin layer of palladium or Pd-alloy which is highly permeable for hydrogen. These membranes can be applied in production and recovery of hydrogen, and they can be also employed as membrane reactors which couple the reaction with separation together. In recent years, a great progress has been achieved in development of the palladium membranes based on porous stainless-steel substrates, which helps to ease the problems of membrane sealing and assembling, and therefore makes the membranes more feasible in industry. Since the porous stainless-steel in general is unsuitable to be employed directly as membrane substrate, its surface should be modified with a ceramic layer. This review introduces the stainless-steel material, surface ceramic coating and the membrane layer, wherein the ceramic modification of the stainless-steel surface, as a key process in membrane development, is particularly elucidated in detail.
Advance in Functional Materials of Reverse Osmosis Composite Membranes
Wu Liguang1,3* Zhou Yong2,3 Zhang Lin2 Chen Huanlin2 Gao Congjie2,3
2008, 20 (0708): 1216-1221 |
Published: 24 August 2008
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Abstract
The shortage of water resource has severely impacted on the development of social economy and the enhancement of the people living standard of our nation. Seawater desalination technology is one the important means to solve current water resource deficient problem. Reverse osmosis membrane process has won the bid in international calling for tenders of seawater desalination, because its low capital invest, low energy consumption, low cost price and shorter construction period in recent years. On basis of a brief introduction of the development history of reverse osmosis membranes, this paper reviews the research progress of the functional materials of reverse osmosis composite membranes, with authors’s work in preparation of the functional materials of reverse osmosis composite membranes referred. The possible topics of reverse osmosis membranes in the future investigation are discussed.
The Fabrication Technique of YSZ Electrolyte Film
Liang Mingde1,2 Yu Bo2** Wen Mingfen2 Chen Jing2 Xu Jingming2 Zhai Yuchun1
2008, 20 (0708): 1222-1232 |
Published: 24 August 2008
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Abstract
One of the key technologies for preparing solid oxide fuel cells and solid oxide electrolytic cells is to make the yttria-stabled zirconia(YSZ) electrolyte to be thinner film on the premise that the gas-tight density is guaranteed. The recent research advances on the preparation methods of the YSZ film are reviewed in this paper. These methods are classified into ceramic powder processes, chemical methods and physical methods. Each method is described with its special technical features and relative experimental examples of fuel cells made from these films are introduced. The advantages and drawbacks of these methods and their applications are summarized. Through the analysis and comparison, the future development prospects of fabricating YSZ electrolyte thin film are also proposed.
Mechanism of Energy Generation of Microbial Fuel Cells
Lu Na1,2 Zhou Shungui2 Ni Jinren1**
2008, 20 (0708): 1233-1240 |
Published: 24 August 2008
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Abstract
Microbial fuel cell(MFCs) are the emerging technology for producing electricity directly from biodegradable organic matter using bacteria as catalyst. One of the most promising applications for MFCs is to use them simultaneously treating organic wastes while accomplishing power generation. The main problems for MFC are low electron transfer and power density.The electron transfer from microbial cell to the fuel cell anode, as a process that links microbiology and electrochemistry, represents a key factor that defines the MFC power and energy output. In the paper, five key steps including fuel bio-oxidation, electron transfer to anode, electron transfer through the external circuit, proton diffusion and cathode reaction for electricity generation by MFC systems are identified and discussed in detail. Finally, the potential study directions in the future are prospected.