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Progress in Chemistry 2008, No.09 Previous issue Next issue

In this issue:

Review
Quantum Chemistry Computation on pKa Values of Organic Compounds in Solution
Liu Yuanhai1 Wang Yongjian2 Yu Ao1** Zhang Xinrui1 Li Jiuhong1
2008, 20 (09): 1241-1250 |
Published: 24 September 2008
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Abstract
Finding a theoretical calculation method to obtain the accurate solvation free energy and pKa value so as to verify or complement the experimental data has long been an important aspect for many theoretical chemists. In this review, an overview of quantum chemistry computation research achievements concerning solvation free energy and pKa value of organic compounds in aqueous or organic mediums with the PCM solvation model in the recent few years is presented. The accuracy and characteristics of different computational methods are also discussed.
Thermodynamic Properties of Carbon Dioxide Expanded Liquids and Applications in Chemical Reactions
Yin Jianzhong1** Ma Xiaorong1 Zhang Xianzhen1 Wang Aiqin2

2008, 20 (09): 1251-1262 |
Published: 24 September 2008
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Abstract
Carbon dioxide expanded liquids (CXLs) have been considered as environmentally benign solvents. They present unique features of high gas solubility, good mass transfer, low viscosity, mild operation conditions, as well as less employment of organic solvents. The present work reviews the recent studies on the volume expansibility, phase equilibrium thermodynamics, transfer properties, acidities, and conductivities of CXLs, and summarized the chemical reactions based on the CXLs, including hydrogenation, hydroformylation and oxidation etc. Finally, the existing problems associated with the CXLs are analyzed and the research directions in future are pointed out.
Nanotechnology in Heterogeneous Catalysis
Wang Yang|Yan Zhipeng|Chen Fengqiu** Zhan Xiaoli
2008, 20 (09): 1263-1269 |
Published: 24 September 2008
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Abstract
“Nanomania” has reached the area of heterogeneous catalysis, therefore, a new concept namely called nanocatalysis is generated. Firstly, the importance and essence of nanocatalysis is illuminated from such aspects as size, composition and morphology of nanoparticles. Subsequently, two preparation methods including microemulsion and sol-gel methods of nanocatalysts and their applications are reviewed. Advances in physical methods for characterizing the structure and composition of nanoparticles are contributing to a molecular-level understanding of their structure-performance relationships.
Aerobic Oxidation of Alcohols in Supercritical CO2
Zhang Tengyun 1,2** Fang Hongbo1 Zhong Li2
2008, 20 (09): 1270-1275 |
Published: 24 September 2008
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Abstract
Advances in cleaner oxidation of alcohols by molecular oxygen instead of stoichiometric oxidants in supercritical carbon dioxide were introduced according to the catalytic systems. The catalytic performances were analyzed for the catalytic systems including the palladium-based, the platinum-based, the ru-thenium-based, the gold-based and the polyoxometalate catalysts. The influence of the phase behavior in supercritical carbon dioxide on the aerobic oxidation of alcohols was also introduced. The study of the cleaner oxidation of alcohols in supercritical carbon dioxide is just a new field coming into research. It should be no-ticed that the high activity and selectivity of the catalysts is the key factor for the industrial application of the cleaner oxidation of alcohols in supercritical carbon dioxide.
Nanoelectrode Ensembles and Arrays
Cao Lixin1,2** Yan Peisheng2 Sun Kening1 D W Kirk3
2008, 20 (09): 1276-1282 |
Published: 24 September 2008
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Abstract
As an assembled nanostructure, nanoelectrode ensembles (NEEs) or arrays (NEAs) present many advantages such as enhanced mass transport, lower double layer charging current, short time constant, lower electrolyte voltage drop, higher ratio of signal to noise, as well as good maneuverability, with higher sensitivity and reliability in electroanalysis. Therefore, they have found broad applications in a variety fields including the stuty of electrochemical theory, biosensor, electrocatalysis and electrode materials in high energy chemical batteries. So far, researchers have tried various methods to made many NEEs(NEAs) with different materials and shapes, such as disk, cylindrical, conic, interdifitated and recessed well NEE(NEAs). The developed ingenious fabrication methods might be systematically classified as template synthesis, etching and self-assembly. Nee(NEAs) are characterized by electron microscopy and electrochemistry method. In this paper, the fabrication methods, characterization techniques and application of NEEs (NEAs) are reviewed according to some of our work and the reported literatures published so far. The main problems and trends in the development and study of NEEs (NEAs) are discussed and prospected.
Preparation of 3D Photonic Crystals
Ding Tao1 Liu Zhanfang2 Song Kai1*
2008, 20 (09): 1283-1293 |
Published: 24 September 2008
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Abstract
Three-dimensional photonic crystals, also known as band gap materials, have broad potential applications in the area of optical devices, biochemical sensors, information transmission and storage, etc. Since the concept of 3D photonic crystals was first proposed in 1987, scientists devoted themselves to the preparation of 3D photonic crystals with different materials and different topologies in various methods. In this article, various methods reported in recent years are reviewed and divided into three types, “top-down method”, “bottom-up method” and “template-assisted method”. Every method is given representative examples, and evaluated its excellence, shortcoming and applicable scope.
Synthesis of Chiral (salen) Co Complexes and Their Applications in Hydrolytic Kinetic Resolution
Jiang Chengjun1,2 Chen Zhirong1*
2008, 20 (09): 1294-1305 |
Published: 24 September 2008
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Abstract
Synthesis of the chiral (salen) Co complexes and their applications in racemic terminal epoxides are reviewed. The main aspects will be focused on designation of more suitable ligands, development of reusable highly enantioselective catalysts and simulation of the catalysts and catalytic systems.
Partial Oxidation of Methane to Synthesis Gas Using Lattice Oxygen
Li Kongzhai|Wang Hua**|Wei Yonggang|Ao Xianquan|Liu Chunming
2008, 20 (09): 1306-1314 |
Published: 24 September 2008
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Abstract
According to the redox mode, the partial oxidation of methane to synthesis gas using lattice oxygen of oxygen storage compound (OSC) instead of molecular oxygen could be implemented in the flow manner: the synthesis gas is directly produced through the gas-solid reaction between methane and OSC, and the reduced OSC is re-oxidized by air, H2O or CO2 to restore its initial state. Since the reaction occurred between methane and lattice oxygen in the absence of gas-phase oxygen, the non-selective oxidation could be inhibited and a high selectivity of product could be obtained. Also, this process can keep from the risk of explosion and does not need the pure oxygen supply. Obviously, this new technology is very useful for improving environment and enhancing economic benefit. In this paper, the process in partial oxidation of methane to synthesis gas using lattice oxygen is reviewed, the focus about the new technology is on the development of OSC and reaction systems. We also mention the process of co-production of metal and synthesis gas and the technology of molten salt storage for solar power, then, the future study direction and the applications of this new technology are discussed.
Biological Activities of the Complexes of Arsenic, Antimony and Bismuth
Zhang Zhipeng|Zhong Guoqing**|Jiang Qiying

2008, 20 (09): 1315-1323 |
Published: 24 September 2008
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Abstract
The complexes of arsenic, antimony and bismuth are used as antibacterial and antitumor drugs in the field of clinical medicine. It is significantly important to synthesize new arsenic, antimony and bismuth complexes and study on the inner relationship of their biological activities and structures. This paper briefly introduces the chemical properties of arsenic, antimony and bismuth, reviews the applications of their complexes in anti-cancer and antibacterial activities, and prospects the application potential in the future.
Antitumor Platinum(Ⅱ) Drugs
Zhu Xingyong1 Zhang Wenping2 You Qidong1* Zhang Cang2 Zuo Lijuan2
2008, 20 (09): 1324-1334 |
Published: 24 September 2008
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Abstract
Since cis-[PtⅡCl2(NH3)2] was used as an antitumor drug, the work to find novel antitumor agents among the platinum(Ⅱ) complexes has been developed extensively in the last decades. Cisplatin , carboplatin and oxaliplatin are so effective that they are widely used in clinical therapies. Nowadays, thousands of platinum complexes are designed and synthesized according to classical quantitative structure-activity relationship. In our paper, we reviewed the progress of antitumor platinum(Ⅱ) drug studies in recent five years. The antitumor mechanisms and activities of platinum(Ⅱ) complexes containing bioactive groups, sterically hindered platinum(Ⅱ) complexes, trans-platinum(Ⅱ) complexes, platinum(Ⅱ) complexes containing S or P atom and multiplatinum(Ⅱ) complexes are introduced and summaried.
Drug-likeness: Predication and Practice
Han Chunyan|Li Yan|Liu Gang**

2008, 20 (09): 1335-1344 |
Published: 24 September 2008
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Abstract
The studies of compounds becoming safe and orally bioavailable medicines have led to the concept of ‘drug-likeness’.It is of equal importance to the biological activity in the drug discovery process. Researchers currently try to address the drug-likeness of compounds in three aspects: (1)physical and chemical properties; (2) topological structures; (3)pharmacokinetic (ADME) properties. This review summarizes the research progress and discusses the development tendency in this area.
Hypocrellin-Based Photodynamic Sensitizers
Liu Yanyan Wang Xuesong** Zhang Baowen**

2008, 20 (09): 1345-1352 |
Published: 24 September 2008
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Abstract
As a new type of non-porphyrin photodynamic antitumor drugs, naturally occurring hypocrellins, including hypocrellin A (HA) and hypocrellin B (HB), present many advantages over hematoporphyrin derivative (HpD), such as single and definite chemical composition, ease in purification, low dark toxicity, dual sensitization mechanisms of Type I and Type II. In this paper, we review the development of hypocrellin-based photosensitizers in the field of photodynamic therapy (PDT) over the past five years, from chemical modification and physical encapsulation to interaction with biomolecules and photodynamic behaviors in vitro and in vivo of HA and HB. The future research directions for hypocrellin-based photosensitizers are also discussed.
Preparation and Mechanism of Electrochromic Viologens
Cao Liangcheng|Wang Yuechuan*

2008, 20 (09): 1353-1360 |
Published: 24 September 2008
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Abstract
Viologens(1,1′-disubstituted-4,4′-bipyridinium) and polymers containing viologen moieties exhibit electrochromic and photochromic effects with remarkable color changes. These promising materials will find applications in electrochromic smart windows, new display devices and etc. This review summerized the preparation, electrochromic mechanism and research progress of electrochromic viologens and polyviologens.
Bulk Heterojunction Solar Cell Based on Fullerene and Thiophene
Jiang Hongji, Deng Xianyu|Huang Wei**

2008, 20 (09): 1361-1374 |
Published: 24 September 2008
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Abstract
Organic and polymer photovoltaic cells are becoming an extremely active area of research to meet the urgent need for clean and renewable energy management due to their potential applications as flexible, low cost and solution processable energy sources. The photophysics of such photoactive devices is based on the photo-induced charge transfer from donor-type semiconducting conjugated polymers to acceptor-type conjugated polymers or acceptor molecules such as Buckminsterfullerene, C60. At present, so-called bulk heterojunction structures based on blends of a polymeric donor of polythiophene and the soluble fullerene derivative [6,6]-phenyl C61 butyric acid methyl ester (PCBM) as an acceptor component represent the material system with the highest power conversion efficiency reported to date (approximately 7%), and the regioregular head-to-tail poly(3-hexylthiophene) (P3HT) is still the most promising polymeric donor material for such photovoltaic cells, as its efficient interchain π-stacking of the conjugated backbones allows for the optimum transport of positive charge carriers (holes) until now. The present review summarizes and analyzes the progresses made about the bulk heterojunction solar cell based on fullerene and thiophene at home and abroad in the past few years. Some issues to be addressed and hotspots to be further investigated are also put forward to and discussed.
High Sensitive Optical Biosensors Based on Conjugated Polymers
Liu Xingfen1,2 Wang Lihua3 Song Shiping3** Fan Chunhai1,2,3 Huang Wei1,2**

2008, 20 (09): 1375-1384 |
Published: 24 September 2008
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Abstract
Conjugated polymers (CPs) with large, delocalized molecular structures exhibit unique optical characteristics, which can be used as excellent sensing elements. Recently, the use of water-soluble CPs as either chemical or biological sensor elements has received intense research interest. The sensing mechanism can be variable when different conjugated polymers are used. For example, million-fold signal amplification can be achieved when electron/energy that moves along a conjugated chain is transferred to an appropriate acceptor ultrafastly, so the sensitivity of the biosensor can be improved remarkably. Some CP’s optical characteristics can be changed when the conformations of the conjugated backbone or the profile substitutes are changed. With this, the colorimentric and fluorometric biosensor were designed by changing the conformation of the probes mediated by the combination of the specific targets.
Application of Quantum Dots(QDs) as Fluoresent Probes in Quantitative Analysis
Liang Jiaran1 Zhong Wenying1** Yu Junsheng2
2008, 20 (09): 1385-1390 |
Published: 24 September 2008
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Abstract
Quantum Dots (QDs) are a kind of semicoductor nanopaticles which radius is near or smaller than the exciton Bohr radius. They have tremendous potential in the field of Biology and Medicine because of their unique and tuned optical properties（broad excitation spectrum, narrow emission spectrum, precise tunability of their emission peak and negligible bleaching, etc）as new fluoresent probes. Recently, because of their superiority in sensitivity, a new method and technology was introduced to analysis, great progress has been made in the quantitative analysis. Here the application of QDs in the assay of metal ions, some drugs and other compounds, as well as the current research progress are reviewed according to the advanced works of worldwide.
Purification of Carbon Nanotubes Using Chromatography Methods
Cai Ying1 Yan Zhihong2 Zi Min1 Ding Hui1 Yuan Liming1**

2008, 20 (09): 1391-1395 |
Published: 24 September 2008
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Abstract
Although there are many initial separation methods for carbon nanotubes, chemical and physical-chemical ways, high pure carbon nanotubes can’t be obtained yet. However, most forms of carbon nanotubes are insoluble in sovent, which need to be stabilized dispersions. Chromatography is attractive as a method of separation power. Now, the chromatographic purification of nanotube methods are mainly size exclusion chromatography and capillary electrophoresis. The isolation of carbon nanotubes using chromatographic methods results in not only purification but also separation of nanotubes with different lengths and diameters. In this review, the methods for this purpose are introduced in detail.
Fluorescent Probes for Sensing Nitric Oxide
Zhang Dengqing*|Zhao Shengyin|Liu Haixiong
2008, 20 (09): 1396-1405 |
Published: 24 September 2008
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Abstract

Nitric oxide (NO), a reactive free radical, regulates a variety of biological processes. Therefore its accurate detection and quantification are critical to understanding health and disease. In this review, two types of fluoresent probes for NO are mainly desccibed, namely, metal-based sensors, which utilizing NO binding to the metal center, such as Co(Ⅱ), Fe(Ⅱ), Ru(Ⅱ), Rh(Ⅱ) and Cu(Ⅱ) complexes as turn-on fluoresent NO sensors; Organic molecule-based sensors, which are mainly diamine fluoresent indicators for NO, such as DAN, DAFs, DARs, BODIPY and DACs.

Delivery and Control Techniques for Microfluids

Li Qingling1** Chen Lingxin2

2008, 20 (09): 1406-1415 |
Published: 24 September 2008
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Abstract
The microfluid delivery and control operation unit is very important among all the necessary functional units used in microfluidic system. The effect of the surface tension is serious in microsystem conditions, and the conventional liquid delivery methods based on volumetric flow show lower efficiency or are impossible in view of engineering meaning. In this paper, several important liquid delivery techniques for microfluid, including mechanical displacement micropumps techniques, non-mechanical micropumps techniques based on electric, optic and magnetic, etc, are reviewed concisely. The high efficiency mixing techniques for controlling the liquids in microsystems are also summarized. The prospect of the liquid delivery and control for the microfluidic system is proposed.
Ethanol Perm-selective Membranes by Pervaporation
Zhan Xia|Li Jiding** Huang Junqi| Chen Cuixian
2008, 20 (09): 1416-1426 |
Published: 24 September 2008
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Abstract
The production of renewable ethanol biofuel from fermentation process as well as the investigation of energy-saving separation technics was advanced by the energy crisis in 1970s. As a rising membrane separation technology, pervaporation(PV) is especially attractive in the separation of azeotropic mixtures such as ethanol/water mixtures due to high separation efficiency, low energy consumption, integration of per-vaporation with fermentor and synergy of performing pervaporation and other separation methods etc. A brief introduction of investigation background of ethanol perm-selective membrane by pervaporation was given in this paper. Theories used for the selection of ethanol perm-selective membrane materials were summarized and analyzed. And the structure characteristics, modification methods and PV performance of ethanol perm-selective membrane materials (such as silicon-containing polymers, fluorine-containing polymers, or-ganic/inorganic composite membrane materials and other polymers etc.) with separation priorities were pre-sented in detail. The relationship between the structure characteristics of PV membrane materials and their separation performance was discussed thoroughly. The pervaporation performance of various ethanol perm-selective membranes was summarized and compared. Problems existed in PV membrane for etha-nol/water separation was proposed based on discussion above. And the foresight of development and investi-gation of ethanol perm-selective PV membrane was also brought forward.
Direct Borohydride Fuel Cell
Wei Jianliang|Wang Xianyou*|Yi Siyong|Dai Chunling|Li Na
2008, 20 (09): 1427-1432 |
Published: 24 September 2008
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Abstract
Direct borohydride fuel cell (DBFC) is a kind of novel fuel cell. It has a high theoretical specific energy, discharge products are water-soluble and environmentally benign. The fuel is easily storable and transportable. For these reasons, DBFC gets more and more attention recently, along with its potential as a future technology for mobile and portable power supplies. Based on the principle of DBFC, the recent progress of anode electrocatalyst and cathode electrocatalyst are reviewed, and the influence of electrolyte and temperature on the performance of DBFC are introduced in this paper. Finally, the key factor of developing DBFC is analyzed and discussed.
A Novel Advanced Oxidation Technology: Activated Persulfate
Yang Shiying** Chen Youyuan|Xu Huizhen|Wang Ping|Liu Yuhong|Zhang Wei|Wang Maodong
2008, 20 (09): 1433-1438 |
Published: 24 September 2008
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Abstract

The thermal, photochemical or metal ions activated decomposition of persulfate anions (S2O82-) produces a powerful oxidant known as the sulfate free radical (·SO4-), which can potentially destroy organic compounds. Activated persulfate oxidation chemistry is an emerging advanced oxidation technology (AOT) for organic pollutants degradation. This paper, for the first time, provides an up-to-date overview of application of the novel technology in not only soil and groundwater remediation, but also wastewater treatment. S2O82- is a relatively new form of in situ chemical oxidation (ISCO) oxidant that has mainly been investigated at bench-scale. However, the technology has developed rapidly due to the considerable research and applied use of this oxidant at an increasing number of field sites. As for wastewater treatment, S2O82- was mostly used as an electron-trapping agent to suppress hole-electron recombination in the TiO2 photocatalytic system, and only a very few reports have discussed organic pollutants direct-degradation by activated persulfate oxidation. The prospects of activated persulfate oxidation technology are also discussed.

A New Approach of Bio-Refinery Based on Pulp and Paper Platform
Hu Zhanbo1,2* Chai Xinsheng3 Wang Jingquan2 Kong Hainan1
2008, 20 (09): 1439-1446 |
Published: 24 September 2008
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Abstract
In this paper, it provided a comprehensive review, particularly on addressing the problems and limitations in the existing processes and technologies in wood and non-wood fiber material based bio-refinery process and pulp and paper industry; and proposed a new approach that integrating bio-refinery into pulp and paper industry. This new approach can effectively utilized the bio-mass materials through pre-extracting its hemicelluloses that could be converted into bio-energy or other chemicals; chemical/mechanical or solvent pulping to produce paper fibers etc. This new concept also provides a new solution for the future development of pulp and paper industry in a cost effec-tive and less environmental impact way.