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Progress in Chemistry 2008, No.011 Previous issue Next issue

In this issue:

Review
Abstract
Recent researches on mechanism of hydrocarbon selective oxidations with hydrogen peroxide catalyzed by metalloporphyrins including iron porphyrins and manganese porphyrins are reviewed in this paper. The strategies to promote heterolytic cleavage of hydrogen peroxide to facilitate the formation of active high valent metal-oxo species were discussed in details.
Application of Ionic Liquids in Organic Synthesis Promoted by Microwave Irradiation
YING An-Guo Chen Xinzhi Chen
2008, 20 (11): 1642-1650 |
Published: 24 November 2008
Abstract
Application of ionic liquids in organic synthesis promoted by microwave irradiation as a new green methodology has been attracting great interests. Microwave-assisted organic transformations ,using ionic liquids as reaction medium or catalysis, have great advantages in accelerating reaction rate, obtaining products with high recovery yield and good selectivity, ease of work-up, as well as recycling usage of lionic liquids after simply regeneration. The paper reviews the progress of ionic liquids as microwave medium or catalyst in the fields of organic synthesis, mainly including cyclization reation, nucleophilic subsitution reaction, metathesis reaction, acylation reation, rearragement reaction, polymerization reaction, coupling reaction, oxidation and reduction reaction as well as selective debromination reaction etc.
Progress in Silicon-containing Metal Compounds
Wang Deng-Xu Wenyan Sun
2008, 20 (11): 1651-1658 |
Published: 24 November 2008
Abstract

Recently, more and more chemists are concerned about silicon-containing metal compounds because of its estensive applications in catalystic industry and other fields. Five species of silicon-containing metal compounds including metal complexes formed by silicon atom or heterosilicon chain as bridge in ligands, metallosiloxanes, silylmetal complexes, metal unsaturated silicon compounds, silicon-containing multimetallic compounds are introduced in this review. Finally, the future of these compounds is prospected.

Preparation of Patterned TiO2 Thin Films
Liang Shan Miao Chen
2008, 20 (11): 1659-1665 |
Published: 24 November 2008
Abstract
This article provides an overview of various patterning methodologies of TiO2 films, and it is organized into three major sections: Generation of patterns, replication of a mask, and replication of a master. Generation of patterns is usually accomplished by serial techniques, including the writhing process with a stylus, an electron beam or a laser beam, the self-assembly process and the photoelectromchemistry process. The patterned features on a mask are mainly used to direct a flux of radiation or physical matter from a source onto a substrate. This method can be carried out with photoresists, self assembled monolayers, and photosensitive gel films of TiO2. A master serves as the original for replication based on replica molding, transfer molding, molding in capillaries, microcontact printing and light stamping. The advantages and disadvantages of different methods are described. Some opinions on further studies on the preparation of patterned TiO2 films are also presented.
The Development of Azametallacrowns
Chen Yu-Ting Xu Hui Xu Dou Jian-Min Dou Li Da-Cheng Li
2008, 20 (11): 1666-1674 |
Published: 24 November 2008
Abstract

Azametallacrowns(azaMCs) with the M–N–N repeating units can be assembled by the trianionic pentadentate N-acylhydrazide ligands with different metal ions and their ring sizes have been enlarged from aza18-MC-6 to aza60-MC-20. Azametallacrowns not only exhibit uniquely physical and biologic properties, but also can be used as second building units (SBUs) to construct a series of azametallacrown supramolecular polymers. This review summarized structural characters, categories and properties of azametallacrowns.

Proline-Catalyzed Asymmetric Reactions
2008, 20 (11): 1675-1686 |
Published: 24 November 2008
Abstract
Proline has been gradually recognized as a simple , commercial and cheap chiral catalyst for many asymmetric reactions. The paper reviews recent advances in the development of direct proline-catalyzed asymmetric reactions including Aldol reaction, Mannich reaction, Michael reation, Diels-Alder reaction, direct α-amination reaction, α-oxo amination reaction, Baylis-Hillman reaction, reduction reaction and oxidation reaction. It also puts forward the future application of proline.
Biocatalytic Asymmetric Synthesis of beta-Hydroxy Acid derivatives
Ma Da-You
2008, 20 (11): 1687-1693 |
Published: 24 November 2008
Abstract
Chiral β-hydroxy acids are key intermidiates in chemical industry and organic synthesis. Biocatalytic asymmetric synthesis renders an enviromental benign, simple, efficient and high steroseletive method for production of chiral β-hydroxy acid derivatives. This mini-review systematically summarizes the progress of biocatalytic asymmetric synthesis of β-hydroxy acid and its derivatives with emphasis on biocatalyst as lipase, nitrile metabolism enzymes and reductase. The developing trends of biocatalytic asymmetric synthesis of β-hydroxy acids is also discussed.
The Application of Cyclodextrins in Greeen Organic Synthesis
Ai-You Hao Zhang Hua-Cheng Jian Shen
2008, 20 (11): 1694-1698 |
Published: 24 November 2008
Abstract
Cyclodextrins, widely applied in green organic synthesis, could transfer hydrophobic molecules into water by the supramolecular interaction. As an important kind of host molecules, they could also influence the microenviroment of hydrophobic molecules by the host-guest interaction and change traditional reaction conditions to obtain good yield without byproduct. The recent developments of appliacation of cycodextrins in green organic reactions such as oxidation reaction, addition reaction, ring opening reaction, deprotection reaction, coupling reaction, substitution reaction, et al were reviewed. The catalytic mechanisms were also discussed in this manuscript.
Chemical Synthesis of Rebeccamycin and Its Analogues
2008, 20 (11): 1699-1707 |
Published: 24 November 2008
Abstract
Rebeccamycin, as a new natural antibiotics, is of great interest to researchers for its potential antitumor activity. However, it cannot be directly utilized as a drug for some disadvantages by itself. To search for better lead compounds, the structure of rebeccamycin was modified or altered, and large numbers of its analogues have been obtained, via biosynthesis and chemical synthesis. Herein, we will present a review of recent progress in chemical synthesis of rebeccamycin and its analogues.
Fluoride sensors based on organoboron compounds
Shu-Juan Liu Qiang Zhao Wen-Juan Xu
2008, 20 (11): 1708-1715 |
Published: 24 November 2008
Abstract
Organoboron compounds can be used as fluoride sensor with high sensitivity and selectivity as Lewis acid because they have a unique LUMO in which the π-conjugation is divergently extended through the vacant p-orbital of the boron atom. The complexation of the boron π-electron systems with fluoride ion would interrupt the π-conjugation extended through the boron atom, causing the change of photophysical properties. The present review summarizes the development of triarylboranes, boronic acids and boronic esters used as fluoride ion sensors.
Dendrimers Based on Calixarene
Jian-hua bu Jian-hang Mai Huan-feng Jiang
2008, 20 (11): 1716-1725 |
Published: 24 November 2008
Abstract
Calixarenes and dendrimers are two types of the most important host molecules in supramolecular chemistry. The link between calixarene and dendrimer has long been regarded as one of the most ambitious targets in this field. Calixarenes-based dendrimers have some promising advantages and novel properties due to their unique structures consisting of both calixarene and dendrimer. They can be potentially applied to many fascinating areas such as smart materials, molecule devices and nano materials. In this paper, the research works on calixarene-based dendrimers are reviewed according to the category of calixarene and its position in dendirmers. Moreover, the progress in dendrimers base on calixarene has been prospected and more chemical examples of calixarenes-based dendrimers await discovery and creation.
Recent Developments of the Initiation System of Atom Transfer Radical Polymerizatio
2008, 20 (11): 1726-1732 |
Published: 24 November 2008
Abstract
Novel methods of fine tuning initiation, activation, and deactivation processes for atom transfer radical polymerization (ATRP) are reviewed, including reverse ATRP, simultaneous reverse and normal initiation (SR&NI) ATRP, activators generated by electron transfer (AGET) ATRP, activators regenerated by electron transfer (ARGET) ATRP and initiators for continuous activator regeneration (ICAR) ATRP, which gradually overcome the limitations of normal ATRP methods, especially the latter two methods whereby only small amount of high-oxidation-state transition metal complex is needed to mediate polymerization and therefore greatly simplify the commercial procedures. In addition, two novel catalyst systems, hybrid and bimetallic catalyst systems developed on the basis of immobilized catalyst, are thoroughly introduced, which show high catalytic activity and control capability to polymerization and can be removed mostly by simple filtration or precipitation.
Development of Research on Ladderlike Polysiloxane Liquid Crystalline
2008, 20 (11): 1733-1739 |
Published: 24 November 2008
Abstract
Abstract The ladderlike polysiloxane liquid crystalline was a novel functional material with many excellent and special properties, such as stability, transparency and film forming characteristic. In this paper, the main advances in the research of the ladderlike polysiloxane liquid crystalline in recent years were reviewed. The structural characteristics were particularly introduced. Then according to the different ways of mesogenic units connecting to the ladderlike main-chain, the ladderlike polysiloxane liquid crystalline was classified into fishbonelike and conoelike. The synthesis of ladderlike polysiloxanes with different side-groups was summarized. These kinds of ladderlike polysiloxane contained ladderlike polyphenylsiloxane, ladderlike polymethylsiloxane, ladderlike polyhydrosiloxane, ladderlike polyvinylsiloxane, and so on. Then the synthesis of ladderlike polysiloxane liquid crystalline with different mesogenic units was introduced. At last, the difficulties of research on ladderlike polysiloxane were mentioned, and its development prospect was looked forward.
Recent Progress in the Design, Synthesis and Application of the Main-chain-end Functional Polyolefin
jianzhuang chen Kun CUI Shu Yuan Zhang MA Zhi
2008, 20 (11): 1740-1750 |
Published: 24 November 2008
Abstract
Design and synthesis of main-chain-end functional polyolefins has become one hot topic of current polyolefin functionalization research. Firstly, the research on polyolefin functionalization is briefly introduced. Then, the recent progress in the main-chain-end functional polyolefin is reviewed with emphasis on its design, synthesis and application. The prospect of such functional polyolefin is also foreseen.
Special issues
Recent Progress of Solar Cells Based on Perylene Bisimide Derivatives
2008, 20 (11): 1751-1760 |
Published: 24 November 2008
Abstract
The solar energy is abundant and clean and is one of the best ways to solve the energy crisis. Recently, perylene bisimide derivatives have been extensively studied as one of the most functional materials, providing prospects for applications in organic solar cells, because of their cheap price, good thermal and photochemical stability, high electron affinity and high absorption and fluorescence quantum yield. Also, the derivatives are easy to functionalize at imide or “bay” positions. The present review summarizes the progress of solar cells based on perylene bisimide derivatives: Firstly, the P-N heterojunction solar cells based on n-type perylene bisimide derivatives and p-type materials; secondly, covalent linkage of n-type perylene bisimide derivatives and p-type monomer to form intermolecular Donor-Acceptor structure; thirdly, the application in the dye-sensitized solar cells. Finally, our work on the solar cells based on perylene bisimide derivatives is also introduced. And some issues and hotspots to be further investigated are also put forward to and discussed.
Review
Studies of Oxidation of Low Density Lipoprotein with Flourescence and Circular Dichroism Spectroscopy
孙霞 SUN Xia
2008, 20 (11): 1761-1767 |
Published: 24 November 2008
Abstract

Oxidized low density lipoprotein(oxLDL) is thought to be a key pro-atherogenic event. The function of oxLDL is highly related to the secondary structure , i . e. the conformation of only constitutive protein—apoliprotein B-100(apoB-100). Both florescence and circular dichroism (CD) spectroscopy are the powerful tools for the investigation of the protein conformations , so they are widely used in the study of apoB-100 as well . In this review , the research of the structures on oxLDL by both fluorescence and CD spectroscopy are summarized and the future studies are prospected.

Application of Synchrotron FTIR Techniques in Biomedical Fields
Jiaping Yan
2008, 20 (11): 1768-1778 |
Published: 24 November 2008
Abstract
Synchrotron infrared light source, characterized with broadband, high brightness and resolution is widely used in biomedical fields. With the progress in imaging technique of FTIR microscopy, the scientists could detect biochemical changes in vivo with synchrotron FTIR in subcellular scale and preserved the cells in life feature. By analysis the protein, nucleic acid and phospholipid components in animal and botanic tissues and cells qualitatively and quantitatively, the pathological changes of bone, the neurodegeneration, the progress of cancer cells and the nutrition in plants could be well understood. Furthermore, the controlled release of drugs and other biochemical processes could also be monitored by synchrotron FTIR. It is worth noting that the intermolecular vibrations of biomolecular assemblies lie in the long wavelength, the so-called far infrared region, where synchrotron FTIR could provide higher signal-to-noise ratio spectra compared with conventional FTIR with global light source.
Progress in Small Molecule Microarrays
Liu Shaobin Qinglin Zhang Wu Zuze
2008, 20 (11): 1779-1787 |
Published: 24 November 2008
Abstract
Small molecules that regulate biological processes serve as valuable tools in studies of the functions of biomolecules, especially proteins, as well as in the development of drugs. An important component of efforts that target the discovery of bioactive molecules is high-throughput screening (HTS). Newly emerging platform of high-throughput screening technology are small molecule microarrays. These arrays contain thousands of drug-like small molecules from parallel combinatorial synthesis and nature products. They enable the identification of new, and the screening of existing, lead molecules. They have already been successfully applied in important areas ranging from protein profiling to the discovery of therapeutic leads. Recent interesting developments towards improved immobilization strategies (such as in situ synthesis, non-in situ synthesis et al) and test methods (fluorescence immunodetection, surface plasmon resonance imaging technology) together with applications in academia and industry was described herein. The microarrays prepared by chemical lithography are introduced, too. As a rapidly maturing technology, SMMs will play an important role on the development of Chinese traditional drugs.
Progress in KARI and its Inhibitors
刘幸海 XingHai Liu
2008, 20 (11): 1788-1797 |
Published: 24 November 2008
Abstract

Ketol-acid reductoisomerase (KARI; EC 1.1.1.86) is an attractive targets for argochemical discovery because it catalyzes the second important step in the biosynthesis of the branched chain amino acid which exist in higher plants and certain fungi only and not in animals. Thus it is an ideal target from which to design non-toxic KARI-inhibitors as potential novel herbicides and antibiotics. The X-ray crystallography of the KARI enzyme, inhibitors and their inhibit mechanism, and theoretical research are reviewed.

Progress of the Applications of Carbon Nanotubes in Drug and Gene Delivery
Hua He
2008, 20 (11): 1798-1803 |
Published: 24 November 2008
Abstract
At present, many domestic and foreign research teams are committed to develop new and efficient drug and gene transfer systems for improving the pharmacological effects of many classes of therapeutic molecules and reduce their toxicity. Within the family of nanomaterials, carbon nanotubes (CNTs) is increasingly attracting attention. Two key advantages of functionalized carbon nanotubes ( f-CNTs) are their strong ability to translocate through plasma membranes and low toxicity, allowing their application in drug and gene transfer system. CNTs can form stable covalent bonds formations or supramolecular assemblies based on noncovalent interactions with active molecules such as peptide, protein, nucleic acid and drug. And then deliver them into specific cells, tissues and organs to express special biological functions. For this research hot spot, we reviewed the recent domestic and international research developments on the application of carbon nanotubes in drug and gene transfer systems, and discussed its toxicity, hope for providing some references for the researchers in this field.
The Research of Functional Polymeric Gene Vector
Hua Yuan Jie Ren
2008, 20 (11): 1804-1809 |
Published: 24 November 2008
Abstract
Developing of safe、efficient gene delivery systems is one of the most critical points for gene therapy. Polymeric non-viral gene carriers having good properties, such safety、easy to design、inexpensive, have been utilized to deliver therapeutic genes in vivo. However, traditional polymers as gene vector only have a few function can not meet gene therapy requirement, so it is necessary to decorate traditional polymer gene vectors, getting ideal gene vectors with multi-function. This review focuses on the development and means of the modification of polymeric gene vector making them have multi-function—the ability to maintain stability outside of cell、the ability of cell entrance、the ability of endosome escape and the ability of nuclear membrane traversing, at last, we highlight the main challenges that remain and the future direction of polymeric vectors research.
Progress in the Study of Polymer Materials for Optical Disk Substrate
曹艳霞 Cao Yan-Xia Guang -Ji Li Wei Qiang
2008, 20 (11): 1810-1815 |
Published: 24 November 2008
Abstract
The optical disc is a kind of optical recording medium to record/reproduce information in non-touching manners, which mainly consists of substrate layer, recording layer and protection layer. The raw material used to manufacture optical disc is optical plastics, which determines the performance and cost of optical disc. The study on polymer materials for optical disc substrate and the tendency of development were reviewed in this paper. The current polymer materials for optical disc substrate usually include polycarbonate (PC), poly (methyl methacrylate) (PMMA), epoxy resins and noncrystalline cyclo-olefin copolymer developed in recent years. Developing new polymer materials for the optical disc substrate that possess low birefringence, low hygroscopicity, low shrinkage, and improved density and longevity of storage is an important research area of polymeric substrates for optical disc.
Twenty-year Overview of the Recording Materials for Three-generation Recordable Optical Discs
Bin Yuejing
2008, 20 (11): 1816-1826 |
Published: 24 November 2008
Abstract
With the development for nearly 20 years, the recordable optical disc products have achieved tremendous success in global market. The corresponding research for recording materials has been greatly promoted. The requirements for the recording materials include excellent thin-film optical characteristic, high recording sensitivity, favorable photo-thermal stability, and good film spin-coating performance. The organic compounds like cyanine, macrocyclic azotic compound, azo-metal complex, metal chelate, benzoheterocycle dye, have been applied to recordable optical discs as the recording materials. The properties pertinent to the recording materials will be adjusted appropriately according to the different working wavelengths of the three-generation recordable optical discs, infrared light CD-R, red light DVD±R and blue light BD-R/HD DVD-R. Through analyzing the growing route of dyes for CD-R and DVD±R, the macrocyclic azotic metal complex is indicated to be an important direction of development as the recording material for high density blue light recordable optical disc. To start up the R&D of recording materials is of great significance to our national optical memory industry. Research on dyes for CD-R can meet the pressing need for upgrading domestic recordable optical disc industry, and research on dyes for blue-ray disc could make China to be in the leading position of the new generation recordable optical disc format.
Progress on First Principle Calculations of Cathode in Li-Ion Batteries
gepin yin pengjian zuo
2008, 20 (11): 1827-1833 |
Published: 24 November 2008
Abstract
The breakthrough of electrode materials dominates the developments of Li-ion batteries. It is the key technology for lithium ion batteries to resolve the problems for the present electrode materials and predict the novel ones, which can be realized by the first principle calculations. This paper introduces the principle and applications of first principle calculations in the cathode materials for Li-ion batteries, including average lithium intercalation voltage, intercalation/extraction mechanism, structure stabilization and the prediction of novel cathode. Moreover, the significances and the limitations of first principle calculations are also discussed for the design of electrode materials in Li-ion batteries.
Advances in the Adsorptive Desulfurization Technologies for Ultra-clean Oil Production
ZHANG Jing-Cheng
2008, 20 (11): 1834-1845 |
Published: 24 November 2008
Abstract
Compared with the conventional hydrodesulfurization technologies, the advantages of adsorptive desulfurization for ultra-clean oil production are attractive, such as lower investment and operating cost, much milder conditions, higher desulfurization efficiency and so on. Consequently, the investigation is becoming popular recently. The advances in this field are introduced briefly in this paper, as well as the designing principle. In addition, the opinions with respect to the future application trend of ultra-clean oil are proposed. The main problems of current works are lower sulfur capacity, selectivity and poor performance of regeneration. It has been indicated that the design and optimization of adsorption technologies, as well as the research on adsorption mechanism would be the most prospective areas.