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Progress in Chemistry 2011, No.11 Previous issue Next issue
Mini Accounts
Abstract

This article briefly describes professor Wang Yu's academic origin, the major scientific activities and achievements in his whole life, his academic idea which displayed in these scientific activities and achievements, and the inheritance and development of his academic idea in Shanghai Institute of Organic Chemistry, CAS.

Invited Article
Functional Inorganic-Cellulose Hybrid Nanocomposites
Xu Yan
2011, 23 (11): 2183-2199 |
Published: 24 November 2011
Abstract

This paper provides an overview of the recent progress made in the area of functional inorganic-cellulose hybrid nanocomposites. The new advances reviewed are the use of nanocrystalline cellulose (NCC) as matrix materials to enhance the functionality of inorganic materials, as a biotemplating agent to generate nanocomposites with a hierarchical structure for improved functionality and the use of inorganic nanoparticles to generate functional inorganic-cellulose hybrid nanocomposites. An introduction into the methods used to assemble inorganic-cellulose hybrid nanocomposites is given with special attention to electrospinning method, templated mineralization via the structural feature, H-bonds network and the biosynthesis route of cellulose, sol-gel method, solution-casting method and layer-by-layer method. The types of NCC covered include those extracted from higher plants, tunicates and bacteria cellulose (BC). An introduction into NCC covering general aspects of their preparation, crystal structures and morphology, arrangement and orientation under different conditions, chemical modification and solvents is made. Lignocellulose and sea cucumber dermis are fiber nanocomposites with a hierarchical structure. Their exceptional mechanical properties and intelligence are believed to be due to a functional adaptation of the structure at all levels of hierarchy. Selected bio-inspired cellulose nanocomposites are discussed to manifest how the hierarchical and helical feature of NCC can be used in smart materials design. A comprehensive coverage of the literature is given and the author's view on where the field is likely to advance in the future is highlighted.

Contents
1 Introduction
2 Advances in inorganic-NCC hybrid nanocomposites
2.1 HAP-BC nanocomposites
2.2 Semiconductors-NCC nanocomposites
2.3 TiO2-NCC nanocomposites
2.4 Clay-NCC nanocomposites
2.5 Cellulose aerogel-based nanocomposites
3 Assembly of inorganic-NCC hybrid nancomposites
3.1 Electrospinning method
3.2 Templated mineralization
3.3 Sol-gel method
3.4 Solution casting method
3.5 Layer-by-layer method
4 NCC
4.1 Preparation
4.2 Properties
4.3 Arrangement and orientation
4.4 Chemical modification
4.5 Solvents
5 Innovation inspired by nature
5.1 Hierarchical and helical structure of cellulose
5.2 Chemoresponsive sea cucumber dermis
6 Conclusion and Outlook

Advances on Synthesis and Applications of Iptycenes and Their Derivatives
Cao Jing, Jiang Yi, Chen Chuan-Feng
2011, 23 (11): 2200-2214 |
Published: 24 November 2011
Abstract

Iptycenes and their derivatives are a class of structurally unique compounds consisting of more than three arene units fused together through a bicyclooctatriene framework. Iptycene is also extended triptycene, and it can be named after the number of arene planes separated by a bridgehead system. Pentiptycenes with five arene units are the most common members of iptycenes, and pentiptycene quinones are the most studied iptycene derivatives. Since they possess a rigid, aromatic, and three dimensional scaffold, iptycenes and their derivatives have been found more and more specific applications in supramolecular chemistry, material chemistry, molecular machines, etc. In this review, the synthesis of iptycenes, iptycene quinones and their derivatives is first highlighted, and then the recent progress in the applications of iptycene derivatives in conjugated polymeric materials, organic porous and low dielectric constant materials, chemical sensors, monolayer assemblied structures, molecular machinery, and supramolecular chemistry based on novel synthetic hosts are introduced.

Contents
1 Introduction
2 Synthesis of iptycenes and their derivatives
2.1 Synthesis of iptycenes
2.2 Synthesis of iptycene quinones
2.3 Derivatization of iptycene quinones
3 Applications of iptycenes and their derivatives
3.1 Conjugated polymeric materials
3.2 Organic porous and low dielectric constant materials
3.3 Chemical sensors
3.4 Monolayer assemblied structures
3.5 Molecular machinery
3.6 Supramolecular chemistry based on novel synthetic hosts
4 Conclusions and outlook

Review
Electrochemical Investigation of the Bandgap Structures and Electronic Properties of Semiconductor Nanocrystals
Li Yunchao, Wen Jing, Liu Jinjin, Jiang Feng, Li Yongfang
2011, 23 (11): 2215-2224 |
Published: 24 November 2011
Abstract

The widespread application of semiconductor nanocrystals (SNCs) in optoelectronic devices urgently demands an exact knowledge regarding their band structures and electronic properties. Cyclic voltammetry (CV) technique has been proven to be a simple and effective approach to acquire above key information. In this paper, we firstly elaborate the mechanism, method and limitation of employing CV technique to examine SNCs. Then, we systemically review recent progress in electrochemical characterization of SNCs from following three aspects: the factors that influence the band structures and electronic properties of SNCs, the charge transport properties of SNCs, and electrochemical redox reaction mechanism of SNCs. Finally, we point out the technical and theoretical challenges existing in current research, and predict the promising solutions to such issues.

Contents
1 Introduction
2 The methods of employing CV technique to characterize SNCs
2.1 Solution based measuring method
2.2 Coating-film based measuring method
2.3 LB film-liked measuring method
2.4 Electrochemical gating based measuring method
3 Electrochemical probing of the effect of size, composition, morphology, and defects in SNCs
4 Electrochemical screening of electronic interaction between SNCs and their environment
5 Electrochemical interrogations of the charge transport properties and redox reaction mechanism of SNCs
6 Conclusion and outlook

Preparation Methods of Ruthenium Catalysts for Ammonia Synthesis
Zhang Liuming, Lin Jianxin, Ni Jun, Lin Bingyu, Wang Rong, Wei Kemei
2011, 23 (11): 2225-2232 |
Published: 24 November 2011
Abstract

The ruthenium catalysts for ammonia synthesis have higher activity than the iron catalyst, especially under the condition of low temperature and pressure. Different preparation methods and preparation conditions will influence the ruthenium catalyst activity with different support materials. This paper describes the preparation methods of Ru catalysts for ammonia synthesis from three aspects, including the pretreatment of supports, the loading of Ru and the addition of promoters. Different methods such as melting method, sublimation method, ion exchange, ultrasound method, precipitation, sol-gel method, impregnate method, microwave-assisted method are reviewed and the shortages of some methods are discussed. The development trends of the preparation of Ru catalyst are also proposed.

Contents
1 Introduction
2 Pretreatment of supports
2.1 Heat treatment
2.2 Oxidation treatment
2.3 Other treatment methods
3 Preparation methods of ruthenium catalysts and promoters
3.1 Melting method
3.2 Sublimation method
3.3 Ion exchange method
3.4 Sol-gel method
3.5 Microwave-assisted synthesis
3.6 Ultrasound-assisted synthesis
3.7 Precipitation method
3.8 Impregnation method
4 Conclusions and outlook

Catalytically Active Absorber in Solar Reforming of Methane
Sang Lixia, Sun Biao, Li Yanxia, Wu Yuting, Ma Chongfang
2011, 23 (11): 2233-2239 |
Published: 24 November 2011
Abstract

Solar reforming of methane has attracted a great attention because this reaction can realize energy storage of high-temperature heat from concentrated solar radiation and optimal utilization of resources of natural gas. Catalytically active absorber has a key role on absorption of solar energy and reforming of methane and becomes focus of solar reforming of methane research. The article introduces that the composition of catalytically active absorber and three types of catalytically active absorbers in terms of their matrix (porous alumina and SiC ceramics, metal foam, ceramic tubular array (nicknamed “porcupine”)) combining the developments of reactor/receiver. Applied in directly irradiated solar reactor/receiver (volumetric reactor/receiver), the capability of catalytically active absorbers is mostly depended on the concentrated solar energy flux, matrix element, catalyst support (or washcoat) and active catalyst. According to the domestic and overseas researches, the future research directions and emphasis are analyzed and discussed. The future research should not only exploit the actual application system but also resolve the problem of uniform coating and combining between catalyst support and matrix for the high temperature reaction system. Photocatalytic enhancement of the reaction should also be taken into consideration, which will help to develop the cheap and efficient catalyst system.

Contents
1 Introduction
2 Catalytically active absorber of solar reforming of methane
2.1 Composition of catalytically active absorber
2.2 Porous alumina and SiC ceramic absorber
2.3 Metal foam absorber
2.4 “Porcupine” absorber
3 Analysis and prospects

Application of Metal Oxides in Electrocatalysts for Low Temperature Fuel Cells
Zhang Na, Zhang Sheng, Zhu Tong, Yin Geping
2011, 23 (11): 2240-2246 |
Published: 24 November 2011
Abstract

Low-temperature fuel cells can be as an ideal portable power, due to the high specific power and specific energy, low-temperature operation and environmentally friendly. It is considered to be a promising fuel cell. But owing to the high cost and low electrochemical stability of the traditional Pt/C catalyst, the commercialization of PEMFCs is hindered. Metal oxides, however, with high stability in the fuel cells work conditions, is beneficial to improve catalytic performance of catalysts due to strong interaction between metals and metal oxides, which might alert absorption properties of oxygen or fuel on the catalyst surface. In this paper, metal oxides as co-catalysts are employed to enhance the electrocatalytic activity and stability for fuel cell electrocatalysts. The latest research progress of niobium oxides, manganese oxides, titanium oxides, tungsten oxides and tin oxides in fuel cells is highlighted. Finally, the urgent existing main problems in this area are discussed and the future research trends are prospected.

Contents
1 Introduction
2 Research status of metal oxides in low-temperature fuel cells
2.1 Manganese oxides
2.2 Titanium oxides
2.3 Tin oxides
2.4 Tungsten oxides
2.5 Niobium oxides
2.6 Other metal oxides
3 Summary and prospects

Enzyme-Catalyzed Regioselective Synthesis of Carbohydrate Fatty Acid Esters in Ionic Liquids
Shi Yugang, Cai Yan, Li Jianrong, Chu Yenho
2011, 23 (11): 2247-2257 |
Published: 24 November 2011
Abstract

Carbohydrate fatty acid esters (CFAE) are nonionic biosurfactants, which can be synthesized from the enzyme-catalyzed esterification/transesterification of carbohydrates. These esters are increasingly used as valuable commodity chemicals in food, pharmaceutical and cosmetic industries. In addition, some CFAE also show antitumor and/or antibiotic activities. CFAE could be prepared enzymatically under mild conditions with a high regioselectivity. Synthesis of CFAE in non-aqueous solvents is difficult due to the low solubility of carbohydrates. The multi-hydroxyl groups of carbohydrates and the immiscibility with the acyl group donor are the major obstacles in the CFAE synthesis process. Although traditional water-miscible organic solvents also enhance solubility, they often inactivate enzymes. However, ionic liquids do not even when they have similar polarities. The use of ionic liquids has offered many advantages to the biocatalysis field, including improved enzyme's activity and stability, and better substrate dissolution makes the initial acylation faster and makes the regioselective acylation of sugars higher. Ionic liquids may be greener than organic solvents because the reaction system can be reused/recycled. Here, the main factors (enzymes, the solubility of substrates in ILs, property of substrates) affecting the enzymatic reaction are introduced. The latest progress of research on enzymatic synthesis of CFAE in ionic liquids is reviewed. In addition, the existing problems in the field of enzymatic synthesis of CFAE as well as its future perspectives are pointed out.

Contents
1 Introduction
2 Enzymes for the synthesis of CFAE
2.1 Enzymes from different sources
2.2 The pretreatment of enzymes
3 Ionic liquids and carbohydrates
3.1 Ionic liquids
3.2 Ionic liquids that dissolve carbohydrates
4 Property of substrates
5 Enzymatic synthesis of CFAE in ionic liquids
5.1 Monosaccharides
5.2 Disaccharides
5.3 Polysaccharides
5.4 Other related compounds
6 Conclusion and future outlook

Gas Separation Based on Ionic Liquids
Zhao Xu, Xing Huabin, Li Rulong, Yang Qiwei, Su Baogen, Ren Qilong
2011, 23 (11): 2258-2268 |
Published: 24 November 2011
Abstract

In recent years, ionic liquids have attracted considerable interests in the field of gas separation, due to their selective dissolution of certain gases, nearly non-volatility and tunable property and structure. In this article, the solubilities of CO2, SO2, H2, O2, CO, N2, Ar, Xe and short-chain alkanes, alkenes, alkynes in ionic liquids are summarized. The mechanism and the qualitative relationship between gas solubility and the structure of ionic liquid are introduced. Functionalized ionic liquids containing basic groups such as amino and guanidine have high performance to capture CO2 and SO2. The solubilities of alkenes in ionic liquids can be improved by adding unsaturated groups in ionic liquids via π-π interaction, and the solubility of alkynes in ionic liquids increases with increasing hydrogen-bond basicity of ionic liquids. The progress involving molecular simulation of ionic liquid/gas binary system, correlation models of gas solubility, and gas separation based on immobilized ionic liquids are introduced and summarized. Finally, the existing problems and development directions in the future of gas separation using ionic liquids are discussed.

Contents
1 Introduction
2 Solubilities of gases in ionic liquids
2.1 Acidic gases
2.2 Organic gases
2.3 Other gases
3 Molecular simulation study of ionic liquid/gas mixture
4 Correlation models of gas solubility in ionic liquids
5 Gas separation based on immobilized ionic liquids
6 Conclusions and outlook

Capture of CO2 by Ionic Liquids
Zhou Lingyun, Fan Jing, Wang Jianji
2011, 23 (11): 2269-2275 |
Published: 24 November 2011
Abstract

Since CO2 is one of the most important greenhouse gases, the research and development in the carbon capture have long been the focus of many academic and industrial studies. Ionic liquids have a number of unique properties, such as no-volatility, non-flammation, recyclability, high thermal stability, strong solubility capacity, and the tunability of molecular structures and physicochemical properties. Thus they have promising application in absorption and separation of CO2. In this paper, the recent progress in the CO2 capture by using regular ionic liquids, task-specific ionic liquids, supported ionic-liquids membranes, polymerized ionic liquids and the mixtures of ionic liquids with some molecular solvents have been reviewed. The effects of cationic structure, anionic property, alkyl chain length, functionalization of both the cations and the anions, characteristics of the supported membranes, the polymerized degree of ionic liquids, temperature and pressure of the systems on the selective capture of CO2 are discussed in detail. The possible mechanisms for the capture and selective separation of CO2 are also demonstrated. Furthermore, the advantages and disadvantages have been analyzed for the above mentioned ionic liquids systems in the capture of CO2. The future development in this area is prospected, and several important issues are suggested for the further work.

Contents
1 Introduction
2 CO2 capture by ionic liquids
2.1 Regular ionic liquids
2.2 Task-specific ionic liquids
2.3 Supported ionic liquid membranes
2.4 Polymerized ionic liquids
2.5 Mixtures of ionic liquids with molecular solvents
3 Conclusions and outlook

Ⅰ-Ⅲ-Ⅵ Semiconductor Nanocrystals
Chen Bingkun, Zhong Haizheng, Zou Bingsuo
2011, 23 (11): 2276-2286 |
Published: 24 November 2011
Abstract

Semiconductor nanocrystals have received considerable attention due to their size-tunable spectroscopic properties and their applications in solar cells, light-emitting diodes, photodetector, biolabeling and nonlinear optical devices. Among various materials, nanocrystals of Ⅰ-Ⅲ-Ⅵ compounds (CuInS2, AgInS2,CuInSe2 and CuInxGa1-xSe2, etc.) have been treated as not only alternative low toxic luminescent materials for bio-imaging, and light-emitting diodes, but also suitable ink materials for solution process solar cells due to their unique properties such as tunable bandgaps, high absorption coefficient, large Stokes shifts. Recently, synthesis of Ⅰ-Ⅲ-Ⅵ nanocrystals has been extensively studied, resulting in various methods including precursor decomposition, hot injection and solvothermal methods. The developments of synthetic chemistry also provide high quality materials with controlled size, shape and compositions. This opens up the possibility to investigate their optical properties and explore their functional applications. The physical properties, especially their photoluminescence and electrochemical properties have been investigated to elucidate their size-dependent quantum confinement. Several specific characteristics were observed and demonstrated, providing important information for their applications. Recent works also reported several initial results of functionalization and devices applications, which are promising for future study. In this review, we provide an in-depth discussion of current progress and problems of colloidal Ⅰ-Ⅲ-Ⅵ semiconductor nanocrystals with an emphasis on the developing Ⅰ-Ⅲ-Ⅵ nanocrystals such as materials preparations, spectroscopic study and application explorations.

Contents
1 Introduction
2 Synthetic chemistry
2.1 Synthetic methods
2.2 Phase control
2.3 Composition control
2.4 Core/shell nanocrystals
3 Quantum-confinement effects and optical properties
3.1 Size-dependent quantum confinement effects
3.2 Optical properties
4 Applications
4.1 Biolabeling and biosensing
4.2 Opt-electronic devices
5 Summary and perspective

Multifunctional Magnetic Nanoparticles: Synthesis, Modification and Biomedical Applications
Du Kai, Zhu Yanhong, Xu Huibi, Yang Xiangliang
2011, 23 (11): 2287-2298 |
Published: 24 November 2011
Abstract

Due to their unique characteristics including superparamagnetic or fluorescent properties and small size comparable to biomolecules, multifunctional magnetic nanoparticles (MFMNPs) have emerged as novel bioimaging, diagnostic and therapeutic agents in biomedical field. The combinations of various nanostructured materials with different propeties and magnetic nanoparticles (MNPs) can offer synergetic multifunctional nanomedical platforms, which make it possible to accomplish multimodal imaging and simultaneous diagnosis and therapy. This review summarizes the synthesis of MNPs and fabrication of MFMNPs, especially focuses on the three types of MFMNPs——core/shell MFMNPs, dumbbell MFMNPs and multicomponent hybrid nanoparticles. Furthermore, to perform real-time monitoring and drug treatment with high accuracy in vivo, stabilizing modification and target modification of MFMNPs are needed to enhance the stability of MFMNPs in physiological environment and localize MFMNPs in the special area in vivo. This paper reviews the general strategies for surface modification of MFMNPs and biomedical applications of these MFMNPs for multimodal imaging, target-specific drug delivery, gene transfection and so on. The development of MFMNPs fusing multiple fluorescent dyes, drugs, and MNPs into a single nanoprobe should provide superior fluorescent, enhanced magnetic resonance imaging (MRI) contrast, and targeted delivery capabilities. Finally, problems to be solved in the current research are also pointed out.

Contents
1 Introduction
2 Chemical synthesis of MNPs
2.1 Iron oxide MNPs
2.2 MFe2O4 MNPs(M=Mn, Co, Ni)
2.3 Alloy MNPs
3 Chemical synthesis of MFMNPs
3.1 Core/shell MFMNPs
3.2 Dumbbell MFMNPs
3.3 Multicomponent hybrid nanoparticles
4 Surface modification of MNPs
4.1 Stabilizing modification
4.2 Target modification
5 Biomedical applications of MFMNPs
5.1 In-vivo behaviour and safty
5.2 Molecular imaging
5.3 Drug delivery
5.4 Gene transfection
5.5 Other applications
6 Conclusions and Outlook

Inorganic Nickel-Based Nanocomposites
Lin Lijuan, Zhou Wei, Guo Lin
2011, 23 (11): 2299-2307 |
Published: 24 November 2011
Abstract

Nanocomposites have become hot issues in the field of nanomaterials due to their unique physical and chemical properties. As an important transitional metal nanomaterial, nickel material has been widely used in magnetics, electrochemistry, catalytic chemistry and other fields. The composites of nickel and other metals or oxides with improved inherent properties would show novel properties by the synergy of composition and nanostructure. Therefore, it is of scientific significance to study the nickel-based nanocomposites. Because of the differences of the combining positions and methods for different components in various nanostructures, the progress of nickel-based nanocomposites is reviewed according to three main structures, which are core-shell structure, supported structure, and multisegment nanowires. Based on the introduction to the various synthetic methods and structures, we summarize the advantages and disadvantages of these methods and composite structures, as well as probable applications. It will be helpful for preparing other similar nanocomposites.

Contents
1 Introduction
2 Core-shell structure nanocomposites
2.1 Core-shell nanostructure
2.2 Coaxial nanocables
3 Supported nickel-nanocomposites
3.1 Nickel-carbon nanocomposites
3.2 Nickel-semiconductor nanocomposites
4 Multisegment nanowires
5 Conclusions

Hierarchical Nanostructures and Their Solution-Phase Synthesis
Liu Guodong, Chen Dairong
2011, 23 (11): 2308-2317 |
Published: 24 November 2011
Abstract

The hierarchical nanostructures built from nanounits, such as nanoparticles, nanorods/wires/belts, and nanoplates/disks/sheets, which exhibit unique physical and chemical properties different from those of nanounits, have been widely investigated. To find and investigate the novel nanoarchitectures or hierarchical nanostructures for some functional compounds is still an interesting task not only in answering basic research questions but also in technological applications. This article reviews the recent progress of hierarchical nanomaterials research. In this article mesoporous material, hollow structures, aerogel and other typical hierarchical nanostructures are mainly introduced. A lot of useful solution-phase synthesis routes are classified according to the category, including hydro/solvothermal routes, template methods, solid spheres as precursors, structure-directed reagent assistant methods and irradiation of microwave reaction. The latest developments of hierarchical nanostructures prepared by above methods and their synthesis routes, mechanism are described in detail. And a brief outlook of potential applications of these new materials is also given.

Contents
1 Introduction
2 Typical hierarchical nanostructures
2.1 Mesoporous materials
2.2 Hollow structures
2.3 Aerogel
2.4 Other typical hierarchical nanostructures
3 Synthesis methods of hierarchical nanostructures
3.1 Hydro/solvothermal routes
3.2 Template methods
3.3 Solid spheres as precursors
3.4 Structure-directed reagent assistant methods
3.5 Irradiation of microwave reaction
4 Structure feather of hierarchical nanostructures and potential applications
5 Conclusion and outlook

Biotransformation of Limonene by Microorganisms
Li Houjin, Lan Wenjian
2011, 23 (11): 2318-2325 |
Published: 24 November 2011
Abstract

Limonene, a cheap and widely distributed monoterpene in nature, has important applications in daily chemical and pharmaceutical industries. In recent decades, the research and development of new products using limonene as the starting material continued to draw much attention. A number of literatures were concerned with the biotransformation of limonene which led to many oxygenated derivatives. These biotransformation products would be more valuable in the fields of cosmetics, food ingredients, drug, and chemical synthesis. This review provides a comprehensive summary of the microbial strains of limonene, their biotransformation products, and the main biotransformation pathways. The influence factors of biotransformation productivity are analyzed in detail. Some regio- and stereoselective biotransformation products are difficult to obtain through a routine chemical process. Hopefully, by optimizing the bioprocesses, the industrial production of these important compounds will become possible in the near future. In addition, the enzymes involved in the metabolic pathways of limonene, especially the monooxygenases and hydroxylases, also show an attractive prospect for their potential application in organic synthesis and industry.

Contents
1 Introduction
2 Microorganisms used in limonene biotransformation and their biotransformation products
3 Main microbial biotransformation pathways for limonene
4 Influence factors of productivity
4.1 Substrate toxicity
4.2 Low solubility
4.3 Strong volatility
4.4 Inhibiting effect of products
4.5 Culture condition
4.6 Simultaneous presence of multiple biotransfor-mation pathways
5 Conclusion and outlook

Application of Mesoporous Silica Nanoreservoir in Smart Drug Controlled Release Systems
Luo Zhong, Cai Kaiyong, Zhang Beilu, Duan Lin, Liu Aiping, Gong Duan
2011, 23 (11): 2326-2338 |
Published: 24 November 2011
Abstract

To develop novel cell microenvironment stimuli responsive smart controlled-release delivery systems is one of the current common interests of material science, pharmacology and clinical medicine. It's purpose includes to look for proper drug carriers, to enhance the safety and availability of drugs, and to reduce the side effect of drugs' toxicity. The article reviewed the research development of functional mesoporous silica nanoparticles (MSNs) composites for applications in the field of biomedicine. MSNs composites could be modified via specific chemical reactions, biological methods and physical approaches, to achieve not only targeting based on cell-specific recognition, but also site pointed, timed and quantitatively controlled drug release to malignant cells via a “biological explosion” approach. It presents wide potential applications in the fields of controlled drug release, targeted cancer therapy and targeted gene delivery. Meanwhile, this article systematically analyzed and summarized various methods for the fabrication of different smart mesoporous silica nanoreservoir and their mechanisms for smart controlled drug release,including inorganic nanoparticles sealed MSNs smart controlled release system, organic molecules sealed MSNs smart controlled release system,self-responsive novel molecular switch based on MSNs controlled release system, which affords references and ideas for designing novel stimuli responsive nanoreservoir system based on MSNs.

Contents
1 Introduction
2 The interactions between MSNs and cells
2.1 Biocompatibility assay of MSNs
2.2 The mechanism of the interactions between MSNs and cells
3 The application types of MSNs as drug nanoreservoirs in smart controlled release
3.1 The concept of MSNs nanoreservoirs
3.2 Inorganic nanoparticles sealed MSNs controlled release system
3.3 Specific responsive organic molecules sealed MSNs controlled release system
3.4 Self-responsive novel molecular switch based on MSNs nanoreservoirs
3.5 Other types of MSNs controlled release system
4 Model drugs used in MSNs controlled release system
5 Conclusion and outlook

The Role of Aliphatic Chains in Pyrrole-Imidazole Polyamides and Their Conjugates Binding to DNA
Jiang Shikun, Wang Pu, Wu Yanling, Zhang Wen
2011, 23 (11): 2339-2352 |
Published: 24 November 2011
Abstract

The pyrrole-imidazole (Py-Im) polyamides represent the only available class of synthetic small molecules which can be designed to recognize virtually any predetermined B-DNA sequence in minor groove and permeate into nucleus to regulate gene expression in vitro & in vivo due to affinities and specificities, and equal or exceed natural eukaryotic transcriptional regulatory proteins. They are mainly composed of N-methylpyrrole (Py), N-methylimidazole (Im), N-methyl-3-hydroxypyrrole (Hp) amino acids and aliphatic chain compounds including aliphatic amino acids. In these moieties, an aliphatic chain as a part of constructing polyamides and their conjugates plays a very important role in extending and specifically recognizing predetermined DNA sequences, linking functioned bioactive molecules to polyamides, and gene regulation. Understanding the role of aliphatic chains in polyamides and their conjugates may help us to better design suitable polyamides to be applied in DNA recognition,which can speed up research of polyamides as a gene-targeted clinical drug. In this paper, we review the application of aliphatic chains of polyamides and their conjugates in polyamides binding to B-DNA minor groove and analyze existing problems.

Contents
1 Introduction
2 The effect of γ-aminobutyric acid and its structural variants on interaction of polyamides with DNA
2.1 Role of γ-aminobutyric acid in DNA recognition by polyamides
2.2 The effect of structural modification with γ-aminobutyric acid on DNA recognition affinity and specificity by polyamides
2.3 The effect of cyclic polyamides linked by γ-aminobutyric acid on DNA recognition
3 The effect of β-alanine and its structural variants on interaction of polyamides with DNA
3.1 Role of β-alanine in DNA recognition by polyamides
3.2 The influence of β-alanine structural modification on DNA recognition by polyamides
4 Role of aliphatic chains in unusual structural polyamides
5 Role of the linkers of polyamides in biological application
5.1 Role of the linkers in polyamide-fluorophore conjugates
5.2 Role of the linkers in polyamide-alkylating agent conjugates
5.3 Role of the linkers of polyamides in gene regulation
6 Conclusion and outlook

 

Intelligent Cell Detachment Materials Based on Poly(N-Isopropylacrylamide)
Liu Dan, Wang Tao, Liu Xinxing, Wang Chaoyang, Tong Zhen
2011, 23 (11): 2353-2359 |
Published: 24 November 2011
Abstract

Poly(N-isopropylacrylamide) (PNIPAm) exhibits temperature-response due to the hydrophilic-hydrophobic transition in aqueous solutions and hydrogels at the lower critical solution temperature (LCST). This characteristic has been used for cell proliferation at the hydrophobic PNIPAm surface and spontaneous detachment of the cell sheet upon the hydrophilic transition at LCST. In this review, several methods were introduced to prepare temperature-responsive substrates for the cell culture, proliferation and detachment, including electron beam irradiation grafting, plasma treatment grafting, living radical polymerization on surface, and hydrogels. The two-step mechanism of spontaneous cell detachment from the PNIPAm modified substrates was briefly discussed considering the hydrophilic-hydrophobic transition and the cells' shape change induced by the cell metabolism. The limitation of this mechanism to other sorts of cells was pointed out. Some approaches to accelerate the spontaneous detachment of cells from PNIPAm modified substrates for rapid cell harvest were described, such as copolymerization of PNIPAm to increase hydrophilicity below the LCST, PNIPAm grafted porous membrane for fast water diffusion, poly(ethylene glycol)-co-PNIPAm grafted porous membrane for increasing hydrophilicity, and poly(vinylidene difluoride) membrane assistant cell transfer. Cell sheets harvested from the temperature-responsive PNIPAm substrates by lowering the temperature without enzymatic treatment retained their intact structure with the cell-cell junctions and deposited extracellular matrices (ECM), which promised applications in tissue repair.

Contents
1 Introduction
2 Preparation of temperature-responsive cell culture substrates
2.1 Electron beam irradiation grafting
2.2 Plasma treatment grafting
2.3 Living radical polymerization on surface
2.4 Hydrogels
3 Mechanism of cell detachment
4 Methods for accelerating cell detachment
4.1 Copolymerization of PNIPAm
4.2 PNIPAm grafted porous membrane
4.3 PEG-co-PNIPAm grafted porous membrane
4.4 PVDF membrane assistant cell transfer
5 Conclusions and perspectives

Preparation and Potential Application of Polymeric Micelles via RAFT Polymerization
Yang Zhenglong, Zhou Dan, Chen Qiuyun
2011, 23 (11): 2360-2367 |
Published: 24 November 2011
Abstract

The rapid progress of polymeric micelles, which due to their attractive advantages such as excellent tissue permeability, compatibilization effect, structural diversity and thermal stability, has raised interest in recent years. In this review, the research progress of amphiphilic block copolymer micelles with special structure and special properties is discussed. The formation mechanism and advantage of polymeric micelles via RAFT polymerization method are introduced. Different thermo- and pH-responsive micelles can be prepared quickly and easily in aqueous solution via RAFT polymerization method. However, dilution effect of polymer micelles greatly affect its practical application when the concentration of the polymer micelle below its critical micelle concentration. To improve the stability of polymer micelles, several methods to prepare polymeric cross-linked micelles are summarized. Finally, the current challenges for the polymeric micelles potential applications in controlled drug release, targeting, biological imaging, catalyst immobilization and other areas are highlighted.

Contents
1 Introduction
2 The RAFT polymerization mechanism
3 Methods to prepare polymeric cross-linked micelles
4 Potential applications of polymeric micelles
4.1 Polymeric micelles for controlled drug release
4.2 Polymeric micelles for drug targeting
4.3 Polymeric micelles for biological imaging
4.4 Polymeric micelles for catalyst immobilization and other area
5 Summary and outlook

Smart Polymers Based on Belousov-Zhabotinsky Reaction
Zhou Hongwei, Liang Enxiang, Zheng Zhaohui, Ding Xiaobin, Peng Yuxing
2011, 23 (11): 2368-2376 |
Published: 24 November 2011
Abstract

Self-oscillating polymer is a new kind of smart polymers, Its chemical and physical properties exhibit autonomous, reversible and periodic changes in a relatively closed system without any external “on-off” stimuli. Belousov-Zhabotinsky reaction (BZ reaction), which is similar to the tricarboxylic acid cycle in biological systems, is coupled with self-oscillating polymer prepared via copolymerization of N-isopropylacrylamide and double bond modified Ru(bpy)3(catalyst of BZ reaction). In the presence of BZ reaction solution, the polymer undergoes spontaneous cyclic soluble-insoluble or swelling-deswelling (in the case of gel) changes induced by the redox oscillation of Ru(bpy)3. Based on the unique self-oscillating properties, self-oscillating polymers may have potential applications in the fields of automatic actuators, impulsators, micro-machines and controlled drug-release. Meanwhile, it may be a appropriate choose for simulation of autonomous phenomena and study of mechanisms of nonequilibrium phenomena in biosystems. In this paper, recent progress in self-oscillating polymer is systematically reviewed, including the conception, mechanisms, design methods and potential applications, focusing on the design of self-oscillating polymers and gels with different chemical or physical structures. Self-oscillating polymers with basic structure of poly(Ru(bpy)3-co-NIPAAm) and others containing different modifying groups,such as AMPS, MAPTAC, VP, NAS, and AA are summarized. Self-oscillating gels with phase-separation structure and microgel with ordered structure are also introduced. Performances of self-oscillating polymers and gels with different chemical or physical structures are discussed and listed. Finally, preliminary work on design of self-driven autonomous transportation surface, self-walking motion and autonomous rotational motion actuator based on self-oscillating gels are introduced. The problems of self-oscillating polymer researches and the trend in the future are analyzed.

Contents
1 Introduction
2 Mechanisms of self-oscillating polymers
2.1 Self-oscillating phenomena and BZ reaction
2.2 Mechanisms of self-oscillating polymers
3 Design methods for self-oscillating polymers
3.1 Design of chemical structures for self-oscillating polymers
3.2 Design of physical structures for self-oscillating gels
4 Potential applications of self-oscillating polymers and gels
5 Prospects

The Application of Heated Electrodes in Electrochemical Sensors
Chen Yiting, Huang Lu, Lin Qi
2011, 23 (11): 2377-2388 |
Published: 24 November 2011
Abstract

The heated electrode technology which directly or indirectly heats the electrodes by applying an electric current could regulate the temperature of the electrodes by controlling the time and strength of the applied electric current. Its obvious advantage is that the electrode temperature could be elevated rapidly while keeping the solution temperature almost unchanged. Since the temperature has effects on the electrochemical reaction rate, diffusion and convection, this kind of electrodes could reduce the background noise, improve the detection sensitivity and reproducibility. Owing to their simple heating equipment, higher detection sensitivity and lower pollution, the heated electrodes have aroused great attention in electrochemical (EC) analysis. This article briefly introduces the recent developments in heated electrodes, including their working principles, electrode design, types, measurements and controls of electrode temperature, as well as the application of heated electrodes in the electrochemical, electrochemiluminescence (ECL), flow-injection amperometric detection systems, and capillary electrophoresis (CE) and CE-chip with EC/ECL detectors. Finally, the development trends and prospects of the heated electrode technology are discussed.

Contents
1 Introduction
2 Change method of electrode temperature
3 Heated electrodes
3.1 Heating by alternating current with high frequency
3.2 Heating by direct current
3.3 Heating and sensitizing
3.4 Measurement of heated electrode temperature
3.5 Types of heated electrodes
4 Application of heated electrodes
4.1 Electrochemical analysis system based on heated electrodes
4.2 Electrochemiluminescence analysis system based on heated electrodes
4.3 Amperometric monitoring system with flow injection based on heated electrodes
4.4 Capillary electrophoresis and chip with electrochemical detector based on heated electrodes
5 Conclusions and outlook

Development and Application of Effect-Directed Analysis in Environmental Research
Qu Guangbo, Shi Jianbo, Jiang Guibin
2011, 23 (11): 2389-2398 |
Published: 24 November 2011
Abstract

Environmental samples are often contaminated with complex mixtures of different chemicals and pose a thread to human health. It might thus be difficult to decide which chemicals are the key causative toxic pollutants in environmental sample. Risk assessment based on concentration of target chemicals monitored by chemical analysis may not correctly reflect the hazards in the environment due to the negligence of unknown active chemicals and combined effects. Using biological assay on complex mixtures extracted from environmental samples is able to evaluate the total toxicity, but can not provide further information of the specific chemicals inducing the observed toxicity. In order to solve these problems, effect-directed analysis/identification (or bioassay-directed analysis/identification)(EDA/EDI), a comprehensive approach integrating sample extraction, fractionation, biological assay and chemical identification, has been developed and successfully applied to determine the contaminants responsible for the measured toxicity in environmental samples. In the last three decades, EDA has been used to identify numerous key causative genetic toxicants, endocrine disruptors and aquatic toxicants in contaminated sites or living environment. In addition, numerous novel pollutants were found using EDA. In this paper, the methodology including the sample extraction, fraction strategies, important biological endpoints and chemical identification methods are reviewed. The new chemicals discovered with EDA from the environment, the limitations and perspectives of EDA development are also discussed.

Contents
1 Introduction
2 Methods
2.1 Environmental sample extract
2.2 Fractionation
2.3 Biological assay
2.4 Key toxicant identification
2.5 Key toxicant confirmation
3 Limitations of EDA
3.1 Novel biological endpoints application
3.2 Simultaneous multi-endpoint analysis
3.3 Bioavailability
4 Prospects
4.1 Combined effects
4.2 Novel chemical analysis method for EDA
4.3 High throughput system development
4.4 Standardization of EDA or risk assessment