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Progress in Chemistry 2009, No.05 Previous issue Next issue

In this issue:

Special issues
Abstract

The controversy about the safety issue concerning the agricultural application of lanthanides(Ln) has not yet been completely resolved. In recent years, the scientific basis of the safety in relation to their uses as diagnostic agents and potential drugs has become the research focus. This review proposed several related critical problems in view of the cellular inorganic chemistry and discussed them from the following aspects. First, the role of the solid-phase formation and deposition in biological systems, as in the study of the biological effects of Ln, as well as elucidation of their performance on the clinical pathology, the formation, transformation, distribution and modulation of insoluble compounds have always been involved. Second, issues on the absorption, excretion and accumulation of Ln, especially on whether Ln cross the blood-tissue barriers, it is one of the foci of debate over their toxicity. Third, in the light of the similarity/dissimilarity principle, the common and specific characteristics of biological effects induced by Ln elements have been discussed. Fourth, the signaling pathways involved in the Ln-promoted cell proliferation and apoptosis, as well as the arising problems have been discussed. Based on the above discussions, the key issues faced by the cellular and biological studies on the metal ions or metal-based compounds have been proposed.

Contents
1 Safety issues of lanthanides-based compounds as diagnostic and therapeutic agents
1.1 Gd-based compounds may cause nephrogenic systemic fibrosis(NSF)
1.2 Cerium levels has been related to endomyocardial fibrosis (EMF)
1.3 Debate on the safety of lanthanum carbonate(Fosrenol®
1.4 About anticancer drug Gd-Motexafin
2 Formation and deposition of solid phases of lanthanide compounds in biological systems
2.1 Precipitation is an inevitable problem in studies on biological effects of lanthanides
2.2 Chemical species of metal compounds under biological conditions
2.3 Chemical essence of transmetallation
3 Absorption, transport and accumulation of lanthanide compounds
3.1 Absorption, transport and accumulation of lanthanide compounds under pathological conditions
3.2 Whether Ln can cross blood-tissue barriers under pathological conditions?
4 How to explain the differential biological effects among lanthanides?
4.1 Similarity/dissimilarity principle for lanthanides induced biological effects
4.2 Diversity among lanthanides
5 Mechanism underlying lanthanides-promoted proliferation and apoptosis, as well as the arising problems
5.1 Is lanthanides' action a hormetic effect?
5.2 Whether lanthanides-induced apoptosis effect can be used for cancer treatment?
5.3 Possible signal transduction pathways involved in lanthanides-induced cell proliferation and apoptosis
5.4 May lanthanides-promoted proliferation trigger carcinogenic or mutagenic effects?
6 Concluding remarks

The Molecular Biology of Selenoproteins and Their Effects on Diseases
Liu Qiong Jiang Liang Tian Jing Ni Jiazuan
2009, 21 (05): 819-830 |
Published: 24 May 2009
Abstract

Selenoproteins are the major forms of selenium in vivo to exert the biological function. Since selenocysteine, the active center of selenoproteins, is encoded by a traditional stop codon TGA, it is difficult to predict selenoproteins from the genomes or to express them via genetic engineering. Although there are many reports on the antioxidative property of selenium and its effects on cancer, neurodegenerative diseases and virus, the results are inconsistent. This review summarizes recent progresses in selenoprotein prediction and expression, and in the pertinence and mechanism of selenium and selenoproteins on those diseases. It aims at increasing the accuracy of selenoprotein-prediction through bioinformatics and overexpression of selenoproteins via genetic engineering, analyzing the relation of selenoproteins with diseases development, and exploring the potentiality of selenoproteins as preventive agents or the target for cancer treatment and drug-screening.

Contents
1 Introduction
2 Prediction of selenoproteins via bioinformatics
3 Biosynthesis and regulation of selenoproteins
3.1 Comparison between prokaryotic and eukaryotic selenoprotein biosynthesis
3.2 cis-Acting elements and trans-acting factors of selenoprotein biosynthesis
3.3 Selenoprotein expression via prokaryotic and eukaryotic systems
4 Relation between selenoproteins and diseases
4.1 Selenoproteins and cancer prevention
4.2 selenoproteins and brain diseases
4.3 Selenium and virus
5 Perspectives

Vascular Selenoproteins and Atherosclerosis
Huang Kaixun Liu Hongmei Xu Huibi
2009, 21 (05): 831-835 |
Published: 24 May 2009
Abstract

Atherosclerosis, a chronic inflammatory disease of the arterial wall, exerts serious influence to human health. Along with the rising living standard and aging of the population, the morbidity of atherosclerosis increases year by year. This review discusses the relationship between vascular selenoprotein and atherosclerosis in corporation with authors′ work. Recent progresses show that the occurrence and development of atherosclerosis are closely related to oxidative damage of blood vessels, and selenium, as an essential trace element for humans, exerts its biological effect through selenoproteins and plays an important role in the inhibition of vascular oxidative damage and the prevention of atherosclerosis induced by oxysterols. The mechanism may be related to (i) effect on antioxidant capacity of arterial wall, (ii) regulation of oxysterols-induced abnormal ratio of prostacyclin and thromboxane, (iii) inhibiting effect on oxysterols-induced apoptosis of vascular smooth muscle cells.

Contents
1 Oxysterol and atherosclerosis
2 Selenium in vascular wall
3 Inhibition of selenium on atherosclerosis
4 Mmechanism of selenium inhibiting atherosclerosis
4.1 Effect of selenium on antioxidant capacity of arterial wall
4.2 Regulation of selenium on oxysterols-induced abnormality of prostacyclin and thromboxane
4.3 Inhibiting effect of selenium on oxysterols-induced apoptosis of vascular smooth muscle cells
5 Prospects

New Trends for Ruthenium Complexes with Anticancer Activity
Chen Yu Du Kejie Chao Hui Ji Liangnian
2009, 21 (05): 836-844 |
Published: 24 May 2009
Abstract

The study of ruthenium complexes as antitumor drugs has received intense interest and become an important research field of medicinal ionrganic chemistry. This review highlights some recent progresses in the antitumor activity of ruthenium complexes, including the design and screening of ruthenium complexes as cytotoxic drugs, and the inhibition of telomerase, topoisomerase and protein kinase with ruthenium complexes.

Contents
1 The antitumor activity of ruthenium complexes
1.1 KP1019-type complexes
1.2 NAMI-type complexes
1.3 Ruthenium(II)-arene complexes
1.4 Ruthenium polypyridyl complexes
2 Telomerase Inhibition
3 Topoisomerase Inhibition
4 Protein Kinase Inhibition
5 Prospect

New Strategies and Trends for the Design of Metal-Based Anticancer Drugs
Wang Xiaoyong Guo Zijian
2009, 21 (05): 845-855 |
Published: 24 May 2009
Abstract

Metal-based anticancer agents have many unique properties that are superior to those of other drugs. As a representative of platinum anticancer drugs, cisplatin plays a crucial role in the treatment of various cancers in clinical chemotherapy. However, the actual efficacy and applicability of this sort of drugs have been greatly limited by their severe toxic side-effects. In order to mend the defects of current platinum drugs, it is necessary to develop novel metal-based anticancer agents with different mechanism of action. In this review, some new strategies for the design of metal-based anticancer drugs are discussed. These include (1) altering the interaction mode of platinum drugs with DNA, (2) enhancing the tumor-targeting property of platinum drugs, (3) developing non-platinum metal-based anticancer drugs, and (4) exploring new potential biological targets other than DNA. All these respects reflect the major trends in this field, which provide some valuable information for researchers pursuing new metal-based anticancer agents.

Contents
1 Introduction
2 Alteration of the reaction mode with DNA
3 Improvement in the targeting property of drugs
4 Development of non-platinum metal-based anticancer drugs
5 Exploration of non-classical targets
6 Conclusion

Application of Arsenic, Antimony and Bismuth in Medicine
Yang Nan Sun Hongzhe
2009, 21 (05): 856-865 |
Published: 24 May 2009
Abstract

With deep understanding of the biological functions of the main group elements: arsenic, antimony and bismuth, more interests have been shifted from the biological toxicity of these elements to their potential application in chemotherapies. This paper reviews the medical history of arsenic, antimony and bismuth, and summarizes the applications of their compounds in human health as anti-cancer, anti-leukemia, anti-microbial and anti-parasite agents. The uses of modern bio-technology for the identification of targets or binding proteins of these elements are briefly mentioned.

Contents
1 Medicinal applications of arsenic compounds
2 Medicinal applications of antimony compounds
3 Medicinal applications of bismuth compounds
4 Conclusion

Interactions of Rare Earth-Amino Acid Complexes with Nucleic Acids
Geng Jie Yu Haijia Zhang Haiyuan Xu Haixia Qu Xiaogang
2009, 21 (05): 866-872 |
Published: 24 May 2009
Abstract

A number of metal-based anticancer drugs are designed to target nucleic acids. Therefore, the elucidation of their interactions with nucleic acids is important for rational design of new anticancer agents with high selectivity and low toxicity, which has been received much attention in this field. Lanthanide complexes have the potential to be therapeutic agents due to their unique magnetic, optical, electronic, and coordinate characteristics. However, lanthanide ions are easy to hydrolysis under physiological pH, which makes it difficult to study rare earth complexes nucleic acids selectivity. Recent studies have shown that natural amino acids can form stable complexes with rare earth ions under near physiological condition and the complexes have high solubility. This review summarizes the current progress in rare earth-amino acid complexes binding to nucleic acids and their selectivity.

Contents
1 Introduction
2 Structural diversity of rare earth-amino acid complexes
3 Molecular recognition of DNA by rare earth-amino acid complexes
3.1 Molecular recognition between rare earth-amino acid complexes and single-stranded DNA
3.2 Molecular recognition between rare earth-amino acid complexes and duplex DNA
3.3 Molecular recognition between rare earth-amino acid complexes and quadruplex DNA
4 Prospects

Achievement in SOD Mimics with Antioxidant and Anti-Inflammation Functions
Hu Ping Wu Gengwei Xia qing Mao Zongwan
2009, 21 (05): 873-879 |
Published: 24 May 2009
Abstract

As effective radical scavengers in vivo, superoxide dismutases (SODs) have the antioxidant, anti-inflammation and anti-aging functions, and have been applied in clinical treatments as drugs. Therefore, there is still an increasing interest in design and development of artificial SODs for potential application. In this article, a brief introduction about the research achievement of SOD mimics and their biomedical activities during past decades is shown. Our attention focuses on the relation between the structure and biological function of Cu,Zn-SOD mimics as well as the bio-activity and application of Mn-SOD mimics in medicine.

Contents
1 Introduction
2 Mn-SOD mimics
2.1 Mn-porphyrin complexes
2.2 Metaphore complexes
2.3 Other Mn-SOD mimics
3 Cu,Zn-SOD mimics
4 Summary

Monodisperse Mangetic Nanoparticles Carriers for Targeting Drug
Zhang Jilin Hong Guangyan Ni Jiazuan
2009, 21 (05): 880-889 |
Published: 24 May 2009
Abstract

The progress of preparation method and surface modification of monodisperse magnetic iron oxide nanoparticles, as well as their application in the magnetic targeted drug are reviewed. The synthetic methods such as thermal decomposition of organometallic precursors, solvothermal, and LSS(liquid-solid-solution) methods are comparatively effective means to prepare monodisperse magnetic nanoparticles of high quality. The magnetic drug-targeting carriers with good water-solubility, biology compatibility, and active functional groups are fabricated by surface modification technique. They would attain site-specific accumulation, effective drug-loading, controllable drug-releasing, biodegradablity to fulfill the requirment of targeted drug for cancer. Development of the multifunctional drug-targeting carrier with fluorescent detectabilty, active recognition-targeting, effective drug-loading, smart controlled drug release, no side-effect, and biology compatibility will be a tendency in the future.

Contents
1 Introduction
2 Preparation of monodisperse magnetic nanoparticles
2.1 Formation mechanisms of monodisperse nanoparticles
2.2 Preparation methods
3 Surface modification of magnetic nanoparticles
3.1 Monodispersion and stability
3.2 Water-solubility and biocompatibility
3.3 Biological active groups
4 Magnetic drug-targeting carriers
4.1 Magnetic field guiding acting force
4.2 Composition of magnetic drug-targeting carriers
4.3 Magnetic drug microsphere and magnetic liposome carriers
4.4 Monodisperse magnetic nanoparticle carriers
5 Prospect

Mechanisms Underlying Diversified Biological Effects of Vanadium Compounds
Yang Xiaogai Wang Qin Liu Jingcheng Wang Kui
2009, 21 (05): 890-895 |
Published: 24 May 2009
Abstract

In this review, the authors present a brief overview of research progress on mechanisms underlying the diversified biological effects of vanadium compounds. This review focuses on the signaling pathways mediating the insulin-mimetic and anticancer effects of vanadium compounds, as well as the correlationship between them. Besides, based on their intervention on phosphate transfer reactions and roles in modulating cellular redox reactions, the possibility of a universal mechanism is discussed. Finally, both the tendency and the challenge in the vanadium research are indicated.

Contents
1 Introduction
2 Antidiabetic effects and underlying mechanisms of vanadium compounds
2.1 Diabetes and insulin signaling pathway
2.2 Activation of insulin signaling pathway and action mechanisms of vanadium compounds
3 Anticancer effects and underlying mechanisms of vanadium compounds
4 Whether or not a unifying mechanism underlying diversified biological effects of vanadium compounds exists
5 Perspective

Research Progress in Anti-Diabetic Effects of Vanadium Compounds
Wei Dan Ding Wenjun Zhou Ju Peng Duan Li Ming
2009, 21 (05): 896-902 |
Published: 24 May 2009
Abstract

It is well known that diabetes mellitus (DM) is a chronic disease caused by inherited and/or acquired deficiency in production of insulin by the pancreas, or by the ineffectiveness of the insulin produced. Numerous studies have shown that vanadium and its compounds improve glucose homeostasis and insulin resistance in Type I and Type II diabetes mellitus. Vanadium and its compounds appear to have a profound impact on insulin action through the insulin signaling cascade, but the underlying mechanism is not fully understood. This review summarizes recent work to identify the effects of pharmaceutical treatment of vanadium compounds on insulin signaling and glucose uptake, in an attempt to characterize the molecular mechanism accounting for biological actions and insulin-mimesis of vanadium compounds in DM.

Contents
1 Introduction
2 Chemical properties of vanadium and anti-diabetic actions of vanadium compounds
2.1 Chemical properties of vanadium
2.2 Anti-diabetic actions of vanadium compounds
3 Mechanism of anti-diabetic effects of vanadium compounds
3.1 Coordination chemistry of vanadium compounds
3.2 Vanadium compounds and PTP1B
3.3 Vanadium compounds and glucose transport
3.4 Vanadium compounds and metabolism of glycogen and lipid
3.5 Molecular mechanism of insulin-mimetic action of vanadium compounds
4 Issues and perspective

Metal-Based Therapeutic Strategies of Neurodegenerative Diseases
Zhang Shibing Wang Ying Liu Changlin
2009, 21 (05): 903-910 |
Published: 24 May 2009
Abstract

The role of metal ions in both the pathology of neurodegenerative diseases and their treatments are summarized. The metal ion-mediated protein aggregation and oxidative stress in such as Alzheimer’s and Parkinson’s are discussed by integrating our preliminary data. The progress obtained to date shows that the metal chelation might be a preferred strategy in treatments of neurodegenerative diseases. Thus, a number of metal-chelating agents have been introduced into clinical trials. The alkylation of metal binding sites in the disease-linked proteins can significantly inhibit the formation of protein aggregates and reactive oxygen species, suggesting that this strategy may be a potential method to treat the diseases.

Contents
1 Introduction
2 Brain metal ions and maintenance of their homeostasis
3 Metal ion-induced protein aggregation and oxidative stress
4 Protein aggregation and oxidative stress in Alzheimer's disease
5 Oxidative stress and α-synuclein aggregation in Parkinson's disease
6 Other neurodegenerative diseases
7 Therapeutic strategies
8 Conclusions

Human Hepatic Cytochrome P450 2C Metalloenzymes and Drug Metabolism
Jiang Hualin Tan Xiangshi
2009, 21 (05): 911-918 |
Published: 24 May 2009
Abstract

Because of their close relationship to metabolism of clinically prescribed drugs, human hepatic cytochrome P450 2C subfamily have been paid wide attention. Research progress of four human hepatic cytochrome P450 2Cs are reviewed in this paper. Three of them, CYP2C9, CYP2C8, CYP2C19, are especially focused on. The function of some of their amino acid residues, distribution in various ethnic groups and difference in metabolizing drugs of their polymorphisms, and their relationship with drug specificity and some diseases susceptibility are reviewed. A pharmacophore model of CYP2C8 substrate is introduced, and main characteristics of CYP2C9, CYP2C8, CYP2C19, CYP2C18 are summarized.

Contents
1 Introduction
2 CYP2C9
3 CYP2C8
4 CYP2C19
5 Epilogue

Viewing Safety of Rare-Earths-Based Drugs from Effect of Rare Earth on Bone Metabolism
Zhang Jinchao Wang Peng Sun Jing Liu Cuilian Chen Hua Huang Jian
2009, 21 (05): 919-928 |
Published: 24 May 2009
Abstract

Some essential trace elements were reported to be involved in the normal bone metabolism. Nowadays rare earth elements are widely used in many fields and more and more rare earth elements enter the environment and food chains They are enriched in bone and difficult to be excreted. Because the similarity between rare earth ions (Ln3+) and Ca2+, they will intervene and regulate bone formation and remodeling. On one hand, rare earth are presumed to be drug candidates for bone disease; on the other hand, they have negative effects on bone metabolism. So the safety of rare-earth-based drugs deserves an answer. We review the effect of rare earth ions on bone metabolism as the following three aspects:(1)effect of rare earth ions on differentiation and function expression of osteoblasts and osteoclasts; (2)effect of rare earth ions on the osteogenic and adipogenic differentiation of bone marrow stromal cells; (3)effect of rare earth ions on bone mineral phase of animals. In addition, the scarcities and future developing perspectives in this field are also discussed.

Contents
1 Introduction
2 Effect of rare earth ions on differentiation and function expression of osteoblasts and osteoclasts
2.1 Effect of rare earth ions on differentiation and function expression of osteoblasts
2.2 Effect of rare earth ions on differentiation and function expression of osteoclasts
2.3 Effect of rare earth ions on bone resorption function of osteoclasts regulated by osteoblasts
3 Effect of rare earth ions on osteogenic and adipogenic differentiation of bone marrow stromal cells
4 Effect of rare earth ions on bone mineral phase of animals
5 Conclusion

Preliminary Studies on the Antitumor Metal-Based Drugs Basing on TCM Active Ingredients
Chen Zhenfeng Peng Yan Tan Mingxiong Liu Yancheng Wang Hengshan Liang Hong
2009, 21 (05): 929-933 |
Published: 24 May 2009
Abstract

The preliminary studies on the antitumor metal-based drugs basing on TCM active ingredients are reviewed. The studies on the synthesis, structure, antitumour activity and interaction with DNA of metal complexes with TCM active ingredients, alkaloids, flavonoids, quinones and cantharidin, coumarins, plumbagin as well as camphoic acid. The future development of metal-based antitumour drugs basing on TCM active ingredients is prospected.

Contents
1 Alkaloid-metal complexes with antitumour activity
2 Flavonoid-metal complexes with antitumour activity
3 Quinone-metal complexes with antitumour activity
4 Other active components metal complexes with antitumour activity
5 Concluding remarks

Advance in Nanorealgar Studies
Ye Xiaochuan Yang Xiangliang Xu Huibi
2009, 21 (05): 934-939 |
Published: 24 May 2009
Abstract

Mineral drug realgar has been extensively used in traditional Chinese medicine for a long time. Its therapeutic effects have attracted increasing attentions in recent years. However, the poor bioavailability owing to its poor water-solubility and potential toxicity hamper it from clinical applications. These problems may be improved when realgar is processed using nanotechnology. The pharmacokinetics of arsenic between nanorealgar and fraditionally prepared realgar is notably varied. Based on the studies of our group and other researchers, some aspects of nanorealgar are summarized in the paper, including preparation methods and characterization, pharmacokinetic behavior, mechanism of antitumour activity, active species and Chinese medicinal formulae of nanorealgar. Moreover, the further research trends of nanorealgar are also discussed.

Contents
1 Preparation methods and characterization of nanorealgar
2 Pharmacokinetic of nanorealgar
3 Action mechanism of antitumour of nanorealgar
4 Active species of nanorealgar
5 Chinese medicinal formulae of nanorealgar
6 Prospect
6.1 Hormesis effect of nanorealgar
6.2 Pharmacokinetics of nanorealgar and its formulae

Review
Measurement Methods for Charge Carrier Mobility in Organic Semiconductors
Chen Zhenyu Ye Tengling Ma dongge
2009, 21 (05): 940-947 |
Published: 24 May 2009
Abstract

The models of charge carrier mobility in organic semiconductors are briefly described. The measurement principles of various experiment techniques for charge carrier mobility in organic semiconductors are especially illustrated. Which include the constant wave current-voltage (CW I-V), time of flight (TOF) , transient electroluminescence, dark injection space charge limited current (DI SCLC), field-effect transistor (FET), flash-photolysis time-resolved microwave conductivity technique (FR TRMC), voltage-modulated millimeter-wave spectroscopy (VMS), photoinduced transient Stark spectroscopy, impedance(admittance) spectroscopy. The advantages, disadvantages and recent progress, the critical technical issues and the different applying fields are reviewed.

Contents
1 Introduction
2 The models of charge carriers’ mobility in the organic semiconductor
3 Measurement methods of charge carrier mobility in organic semiconductors
3.1 Constant wave current-voltage (CW I-V)
3.2 Time of flight (TOF)
3.3 Transient electroluminescence
3.4 Dark injection space charge limited current (DI SCLC)
3.5 Field effect transistor (FET)
3.6 Flash-photolysis time-resolved microwave conductivity technique (FR TRMC)
3.7 Voltage-modulated millimeter-wave spectroscopy (VMS)
3.8 Photoinduced transient Stark spectroscopy
3.9 Impedance(admittance) spectroscopy
4 Conclusion

Colloidal Crystal Templating Method to Synthesize Three-Dimensional Ordered Macroporous Complex Oxides
Zhang Guizhen Zhao Zhen Chen Shengli Dong Peng
2009, 21 (05): 948-956 |
Published: 24 May 2009
Abstract

Colloidal crystal templating method can effectively prepare three-dimensional ordered macroporous (3DOM) complex oxide materials. This method commonly involves three steps. Firstly, colloidal crystals are formed by packing uniform spheres into three-dimensional ordered arrays. Secondly, the interstitial space is filled by a liquid precursor converted into a solid skeleton. Finally, the spheres are removed, creating a solid skeleton in the location of the former interstitial spaces and interconnected voids where the spheres were originally located. Ordering of spheres, filling of interstices in colloidal crystals with precursor and removal of the template are all key factors for the synthesis of the 3DOM complex oxides. In this paper, a brief review concerning the effects of the above controlling factors on the synthesis of 3DOM complex oxides is provided. The characterization of macropores and potential application of such complex oxides, including catalysts and porous electrodes are briefly discussed.

Contents
1 Introduction
2 Synthesis of 3DOM complex oxides
2.1 Formation of the colloidal crystal template
2.2 Filling of precursors
2.3 Removal of the colloidal crystal template
3 Characterization of structure of pores in the 3DOM complex oxides
4 Applications of 3DOM complex oxides
5 Conclusions

Molecular Logic Function Materials
Fu Xiaofei Sun Wei Fang Chenjie Guo Rui Yan Chunhua
2009, 21 (05): 957-963 |
Published: 24 May 2009
Abstract

The mimicry of some elementary functions of neurons and electronic computers at the molecular scale has been attracting more and more interest, which has strongly pushed chemists to explore digital logic function and circuits at the molecular level for the purpose of molecular computing and biocomputer. As molecular switches convert input stimulations into output signals, the principles of binary Boolean logic can be applied to the signal transduction operated by molecules under appropriate conditions. Implementation of the most common Boolean functions (PASS, YES, NOT, AND, NAND, OR, NOR, XOR, XNOR, and INH) with chemical systems is possible now. Holding these basic logic functions in hands, the chemists are devoting to novel computational architectures of complicated functions, as well information security in the molecular platform, to create a molecular analogue for every electronic product. A molecular 2:1 multiplexer comprises two photochromic moieties, dihydropyrene and dihydroindolizine units, linked to a central porphyrin to perform as a combinational circuit to connect any one of several possible inputs to an output. Molecular sequential logic requires the control of the kinetic behavior of the chemical system. A molecular keypad lock and crossword puzzles and logic memory are capable based on a molecular species in solution whose fluorescence is switched on only in response to a correct sequence of input signals, which are reminiscent of electronic keypad locks, a common security device that can control the opening of a door or a safe. An approach to the assembly of the biomolecular keypad lock using the enzyme-based networking system is also realized. Further, a molecular computing platform in defending against information risk is constructed, where chemical-encoded user identity information can be transmitted from sequential logic unit to combinational logic circuit, and hence resulting in the user-specific digital functionalities.

Contents
1 Molecular 2:1 digital multiplexer
2 Sequential logic and logic memory
3 Biomolecular keypad lock
4 Molecular security computing platform
5 Prospect

NOx Storage-Reduction Catalysts Used for Lean-Burn NOx Removal
Guo Lihong Liu Yong Meng Ming
2009, 21 (05): 964-970 |
Published: 24 May 2009
Abstract

The NOx storage and reduction (NSR) technology will be the most promising way to reduce the NOx emission from lean-burn engines. Since the concept of NOx storage and reduction was firstly proposed by Toyota Co. in 1996, the NSR catalysts have attracted much attention in environmental catalysis area. The main advances in different formulated NSR catalysts (PBA-type、hydrotalcite-type、perovskite-type) in the last decade are systematically reviewed in this paper. The emphases are put on the commonly recognized NOx storage and reduction pathway and the NSR catalysts deactivation mechanism, including the negative effect of H2O and CO2, the thermal aging and SO2 poisoning. At last, the developing tendency for NSR technology is proposed.

Contents
1 PBA –type NSR catalysts
1.1 Precious metals
1.2 Storage components
1.3 Supports
2 Other materials and structures for NSR catalysts
3 Mechanisms of NOx storage-reduction reaction
4 Deactivation of NSR catalysts
5 Problems and Outlook

Synthesis of Spherical Monodisperse Gold Nanoparticles
Yan Ya Li Jinru Yang Yun
2009, 21 (05): 971-981 |
Published: 24 May 2009
Abstract

In this paper, the preparation methods of spherical monodisperse gold nanoparticles are reviewed. The potential applications of spherical monodisperse gold nanoparticles are analyzed. The main methods, such as seeding growth, refluxing ripening, size-selective precipitation and electrophoresis, are introduced respectively. Meanwhile, their corresponding strongpoints and weaknesses are also reviewed. In the last section, the challenges about preparing spherical monodisperse gold nanoparticles are figured out and the coming research fields are prospected.

Contents
1 Introduction
2 Preparation of spherical monodisperse gold nanoparticles
2.1 Preparation of hydrophobic spherical monodisperse gold nanoparticles
2.2 Preparation of hydrophilic spherical monodisperse gold nanoparticles
3 Prospect

Solid High-Proton Conductors Based on Heteropoly Acids
Liu Zhen Wu Qingyin Song Xiaoli Ma Sai
2009, 21 (05): 982-989 |
Published: 24 May 2009
Abstract

Heteropoly acids (HPAs) solid high-proton conductors have received increasing attention over the last few years owing to their applications in fuel cells, sensors and electrochemical chromogenic devices etc. The present paper summarizes and reviews the current development in the area of the conductivities of HPAs, HPAs-inorganic matrix composite materials, HPAs-organic hybrid materials and HPAs-multiple composite materials. The conductivities of these materials are listed in the corresponding tables. Some laws of proton conductivity are summarized. By loading various weight percentages of HPAs onto different solid matrixs, the stability and mechanical ductility of solid proton conducting materials can be increased. The composite materials combine the high thermal and structural stability of matrixs with outstanding conductivity of HPAs, which place them among one of the most promising solid proton conductors. The higher the humidity is and the more the doping amount of HPAs is, the higher the conductivities of the composite materials are. The applications of HPAs in proton exchange membrane fuel cell are described in detail. The future development and research trends of HPAs solid high-proton conductors are prospected.

Contents
1 Introduction
2 Proton conductivity of heteropoly acids(HPAs)
3 Proton conductivity of HPAs-inorganic matrix composite materials
4 Proton conductivity of HPAs-organic hybrid materials
5 Proton conductivity of HPAs-multiple composite materials
6 The applications of HPAs in proton exchange membrane fuel cells(PEMFC)
7 Summary and forecast

Asymmetric Hydrogenation of Unfunctionalized Alkenes Catalyzed by Ir-N,P-Ligands Catalysts
Chen Chuanjie Wei Zuojun Li Yan Ren Qilong
2009, 21 (05): 990-996 |
Published: 24 May 2009
Abstract

The asymmetric hydrogenation of unfunctionalized alkenes which the carbon-carbon double bonds are connected only to totally aliphatic groups is always a challenge in the field of alkene hydrogenation. It is reported that such reaction can be catalyzed by Ir-N, P-ligand catalysts with excellent catalytic activity and high enantioselectivity, which deserves much attention over the world. In the present review, the progress on asymmetric hydrogenation of unfunctionalized alkenes catalyzed by Ir-N,P-ligand catalysts are described, including the background of the hydrogenation history, the catalytic mechanisms (IrIII-IrV cycle mechanism and IrI-IrIII cycle mechanism), the composition of the catalysts (the precursors of Ir catalysts, the chiral ligands and the anions) and the comparison of their reactivity while catalyzing olefins with di-, tri- and tetra- substituted alkyl groups. The prospective of the asymmetric hydrogenation of unfunctionalized alkenes by Ir-N,P-ligand is also pvesented.

Contents
1 Catalytic mechanisms of Ir-N, P-ligand catalysts
2 Structure of Ir-N,P-ligand catalysts
2.1 The precursors of Ir catalysts
2.2 The chiral ligands of Ir catalysts
2.3 The anions of Ir catalysts
3 Comparison of hydrogenation activity of Ir-N,P-ligand catalysts
4 Conclusion and prospective

Application of Malononitrile in Multicomponent Reactions
Wang Qifang Song Xiaokai Yan Chaoguo
2009, 21 (05): 997-1007 |
Published: 24 May 2009
Abstract

Malononitrile is a particularly versatile compound, since the strongly electron-withdrawing cyano groups activate the methylene group, the polar multiple bond is suitable for nucleophilic addition and is also a good leaving group for substitution. The methylene group and one or both cyano groups can take part in condensation reactions to give a variety of addition products and heterocyclic compounds. This unique reactivity makes malononitrile an important candidate for multicomponent reactions. There have been a lot of multicomponent reactions with malononitrile for preparing carbocyclic and heterocyclic compounds. We reviews potential applications of malononitrile in multicomponent reactions, especially the recent representative examples for preparing heterocyclic compounds. The perspective for future development in this field is also briefly discussed.

Contents
1 Knoevenagel condensations
1.1 Reactions of aldehyde with malononitrile
1.2 Reactions of ketones with malononitrile
1.3 Synthesis of cyclopropanes
2 Michael additions
3 Elimination reactions

Organic-Inorganic Nanocomposite Hydrogels
Xu Shimei Zhang Shufen Yang Jinzong
2009, 21 (05): 1008-1014 |
Published: 24 May 2009
Abstract

This review addresses the recent developments on the field of organic- inorganic nanocomposite hydrogels. Organic-inorganic nanocomposite hydrogels are classified into three types based on different kinds of inorganic components, as well as their different complex forms with organic components: intercalated layered-silicate nanocomposite hydrogels, clay-crosslinked nanocomposite hydrogels and hybrid silica-based nanocomposite hydrogels. The developments on three types of nanocomposite hydrogels are reviewed comprehensively. Especially their preparation methods are introduced in detail. It is followed by an overview of proposed strengthen mechanisms of inorganic components for the nanocomposite hydrogels. The difference in the strengthen mechanism among three nanocomposite hydrogels are explained in more detail.

Contents
1 Introduction
2 Preparation of organic-inorganic nanocomposite hydrogels
2.1 Intercalated layered-silicate nanocomposite hydrogels
2.2 Clay-crosslinked nanocomposite hydrogels
2.3 Hybrid silica-based nanocomposite hydrogels
3 Strengthen mechanisms for organic-inorganic nanocomposite hydrogels
4 Conclusions

Polyaniline/Gold Nanoparticle Composites
Shu Jianhua Qiu Wei Zheng Shaoqin
2009, 21 (05): 1015-1022 |
Published: 24 May 2009
Abstract

Polyaniline/gold nanoparticle composites not only retain the original especial performance of polyaniline and gold nanoparticle respectively, but also exhibit coadjutant effect that is beneficial for improving the properties of polyaniline matrix in composites. The polyaniline/gold nanoparticle composites have been intensively studied in recent years due to their unique properties including outstanding intrinsically electrical conductivity, excellent reactive catalysis and especial behavior of charge transfer. In this paper, the recent developments of polyaniline/gold nanoparticle composites are reviewed, and the preparation methods and mechanisms are summarized. The applications of the composites are briefly introduced in aspects of biomedicine, sensors and microelectronic devices. Finally, the prospect of the future research is proposed.

Contents
1 Introduction
2 Preparation methods of polyaniline/gold nanoparticle composites
2.1 Chemical preparation methods
2.2 Electrochemical preparation methods
2.3 Physical compounding preparation methods
3 Applications for polyaniline/gold nanoparticle composites
3.1 Biological research
3.2 Sensor
3.3 Microelectronic devices
4 Conclusions

Application of FTIR Spectroscopy in Polymereric Systems under Supercritical CO2 Processing
Shi Jingya Wu Peiyi
2009, 21 (05): 1023-1033 |
Published: 24 May 2009
Abstract

Supercritical carbon dioxide (scCO2) is recognized as an outstanding solvent in polymer processing and scientific investigation, arising from its remarkable intrinsic traits such as high diffusivity and excellent solubility. Once applied into polymer processing, the interactions between CO2 and polymers may assist the sorption and diffusion of CO2 in polymer chains, which may perturb the chemical environment of the molecular structure with the penetrating of CO2 molecules, and can be probed by Fourier transform infrared (FTIR) spectroscopy. Besides, scCO2 may improve the mechanical properties of the material, ascribing to the CO2 sorption, the CO2-induced plasticization and the swelling of polymers. FTIR spectroscopy is also proved to be an effective tool in investigating on the structure information, especially of proteins or semicrystalline polymers. In this review, some researches in this field are discussed, in order to illuminate the handling of FTIR in studying the interaction between scCO2 and polymers and revealing the rearrangements of polymer chain at molecular level. Then the promising application of this method in scCO2 induced polymeric materials systems is clarified and prospected.

Contents
1 Introduction
2 Study of the interaction between CO2 and polymers by FTIR
2.1 On the Lewis acid-base interaction
2.2 On the hydrogen bonding in scCO2
3 Study of the polymer processing in scCO2 by FTIR
3.1 On the sorption of CO2 in polymers by ATR-IR
3.2 On the scCO2 induced crystallization of semicrystall polymers
3.3 On the conformational change of proteins in scCO2
4 Conclusion

Research and Application of Microfluidics in Protein Crystallization
Li Junjun Chen Qiang Li Gang Zhao Jianlong Zhu Ziqiang
2009, 21 (05): 1034-1039 |
Published: 24 May 2009
Abstract

With the significant development of the MEMS (micro electromechanical system) technology during these years, microfluidics is currently one of the most rapidly growing frontier fields, which provides a new and powerful platform for chemical and biological assays. The advantages of the microfuidic chip that include high-through, low-consumption and low-cost make it an attractive technique for both initial screening and subsequent optimization of protein crystallization conditions. This review presents the mechanisms and principles of microfluidic technologies applied to the crystallization of biological macromolecules. A comparison of the devices that are available commercially or described in the literature summarizes the current state-of-the-art in microfluidics-based protein crystallization.

Contents
1 Introduction
2 The advantage of microfluidics for protein crystallization application
3 Typical microfluidics in protein crystallization
3.1 Free interface diffusion-based microfluidic crystallization
3.2 Microbatch-based microfluidic crystallization
3.3 Vapor diffusion-hased microfluidic crystallization
3.4 Microdialysis-based microfluidic crystallization
4 Conclusion

Applications of NMR Techniques in the Research of Room Temperature Ionic Liquids
Zhai Cuiping Liu Xuejun Wang Jianji
2009, 21 (05): 1040-1051 |
Published: 24 May 2009
Abstract

As new green solvents and functional materials, room temperature ionic liquids (ILs) have attracted great attention. The present paper reviews the applications of NMR techniques in the research of structure, properties, and interactions of cations with anions of ILs, interactions between ILs and the other compounds, the dynamic characteristics of ILs and their mixtures, the aggregation behavior of ILs in solutions, and the determination of thermodynamic parameters of ILs.

Contents
1 Determination of the structure, purity and properties of ionic liquids
2 Study on the interactions of cations with anions of ionic liquids
3 Study on the interactions of ionic liquids with the other compounds
4 Study on the dynamic characteristics of ionic liquids and their mixtures
4.1 Measurements of the spin-lattice relaxation time and the molecular rotation correlation time of ionic liquids
4.2 Measurements of the self-diffusion coefficients of ionic liquids
5 Study on the aggregation behavior of ionic liquids in solutions
6 Determination of the thermodynamics parameters of ionic liquids

Development of Electrochemical DNA Biosensors
Huang Qiang Liu Hongying Fang Bin
2009, 21 (05): 1052-1059 |
Published: 24 May 2009
Abstract

Owing to the advantages of its high sensitivity, rapid response, easy handling, and low cost, the electrochemical DNA biosensor has received much attention in the field of genic sequence detection and has gradually become an important field in the study of molecular biology and biological research. Electroactive molecules and nano materials have been applied into the electrochemical DNA biosensors because of their special properties. Here, the principle and classification of the electrochemical DNA biosensors are introduced, and the applications of electroactive molecules and nano materials in electrochemical DNA biosensors in recent years are reviewed. A prospect for the future development in this field is also briefly given.

Contents
1 Principle of electrochemical DNA biosensors
2 The applications of electroactive molecules in electrochemical DNA biosensors
2.1 Non-labeling hybridization indicator as recognition element
2.2 Labeling hybridization indicator as recognition element
3 The applications of nano materials in electrochemical DNA biosensors
3.1 Use of metal nanoparticles
3.2 Use of semiconductor- and oxide- nanoparticles
3.3 Use of magnetic microspheres
3.4 Use of other nano materials
4 Outlook

Applications and Techniques of Microwave Spectroscopy
Tang Shouyuan Xia Zhining Fu Yujie Gou Qian
2009, 21 (05): 1060-1069 |
Published: 24 May 2009
Abstract

Microwave spectroscopy is suitable for studying chemically and physically very interesting molecular systems, including weakly bound complexes, radicals, ions, and other transient species. Information on molecular structure, internal motions and intermolecular interactions are easily obtained. Advances and techniques of microwave spectrometer are outlined in this article. The instruments developed, including microwave absorption spectrometer, pulsed nozzle Fourier transform microwave spectrometer and chirped pulse Fourier transform microwave spectrometer, etc. are described. Complimentary techniques in supersonic expansions, external applied fields with Stark modulation, fast scan, chirped pulse and double resonance are reviewed. Pulsed nozzles with heating system, fast-mixing, electric discharge and laser ablation are discussed. Meanwhile, the applications and developments of microwave spectrometers in the field of analytical chemistry are also reviewed. Finally, future trends of microwave spectrometers are prospected.

Contents
1 Introduction
2 Principle and structure of microwave spectrometer
3 Techniques in microwave spectrometer
3.1 Microwave absorption spectrometer
3.2 Fourier transform microwave spectrometer
3.3 Double resonator techniques
3.4 Chirped pulse Fourier transform microwave spectrometer (CP-FTMW)
3.5 Microwave spectrometer for chemical analysis
4 Conclusions

Enzymatic Conversion of Lignocellulose into Sugars
Zhang Mingjia Su Rongxin Qi Wei He Zhimin
2009, 21 (05): 1070-1074 |
Published: 24 May 2009
Abstract

The key issue for the industrialization of cellulosic ethanol is the conversion of lignocellulosic feedstocks into fermentable sugars. Enzymatic hydrolysis of lignocellulose has caught much attention because of its modest reaction conditions, fewer by-products and environmental benignity. A lot of chemical and biochemical technologies are developed to enhance the efficiency of lignocellulose hydrolysis or to reduce the cost of cellulase. In this paper, the effects of pretreatment methods, highly efficient enzyme mixtures, recycling of enzyme, integrated technologies and high solid substrate concentration on the efficiency of lignocellulose conversion are reviewed in details. The progress and prospects on enzymatic hydrolysis of lignocellulosic materials are also presented.

Contents
1 Introduction
2 Pretreatment of lignocellulose
3 Design of highly efficient cellulase mixtures
4 Adsorption, desorption and recycling of cellulase
5 Integrated technologies
5.1 Enzymatic membrane bioreactor
5.2 Simultaneous saccharification and fermentation
6 Enzymatic hydrolysis at high-solid concentrations
7 Conclusion