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Progress in Chemistry 2014, No.0203 Previous issue Next issue

In this issue:

Review
Novel Non-TiO2 Semiconductor Photocatalysts
Jin Chao, Qin Yao, Yang Jinhu
2014, 26 (0203): 225-233 | DOI: 10.7536/PC130822
Published: 15 February 2014
Abstract

Photocatalysis, in which solar photons are used to drive redox reactions to produce clean energy resources or to decompose environmental pollutants, has attracted considerable attention as we are facing the increasing challenges of diminishing fossil fuels and severe environmental pollution. Significant efforts have been made to develop various photocatalysts which can fundamentally dictate the overall efficiency of the solar energy conversion system. As a typical class of semiconductor photocatalysts, TiO2 based composites have been widely investigated and well reviewed in literatures. Therefore, this review mainly gives a concise overview of several novel non-TiO2 photocatalysts with a focus on their structural architectures and components which affect the catalytic activity. The article here includes five sections. After the first introduction section, the general working principles of semiconductor photocatalysts are presented in the second section. The main factors such as the light harvesting ability, the charge separation efficiency, the structure of the catalyst and the photoelectrochemical stability influencing the overall efficiency of photocatalytic reactions are discussed in section 3. Novel photocatalysts include Ag3PO4 based composites, non-TiO2 metal oxides, sulfides, bismuth compounds and cobalt compounds are reviewed in section 4. Lastly, the fundamental challenges and perspectives of semiconductor photocatalysts are briefly brought up in section 5.

Contents
1 Introduction
2 Process and mechanism of photocatalysis
3 Factors affecting the photocatalytic efficiency
3.1 Light harvesting ability
3.2 Separation efficiency of photogenerated charges
3.3 Active specific surface area
3.4 Stability and recoverability
4 Novel photocatalysts without TiO2 involved
4.1 Ag3PO4 based photocatalysts
4.2 Metal oxides
4.3 Sulfides
4.4 Bismuth compounds
4.5 Cobalt compounds
5 Conclusion and outlook

Preparation and Catalytic Properties of Nano-Au Catalytic Materials Based on the Reduction of 4-Nitrophenol
Wang Zhenzhen, Zhai Shangru, Zhai Bin, Xiao Zuoyi, An Qingda
2014, 26 (0203): 234-247 | DOI: 10.7536/PC130810
Published: 15 February 2014
Abstract

Nitrophenols are one of the most common organic pollutants in industrial and agricultural wastewater. In recent years, due to the excellent catalytic properties of nano-Au catalytic materials, as highly efficient, fast and eco-friendly catalysts, nano-Au catalytic materials have been widely applied to the reduction of 4-nitrophenol. Correspondingly, synthesis of highly dispersed, size controllable, long-term and recycleable nano-Au catalytic materials is the main stream of this field. Based on the overall structure of the nano-Au catalytic materials, this review summarizes the latest progress on this direction, especially for the preparative methods, catalytic performance, stability, recyclability and reusability. Finally, the remaining problems and the future developing prospects are also proposed.

Contents
1 Introduction
2 Nano-Au catalyst and its catalytic performance
2.1 Polymer-based elastic nanocatalysts
2.2 Hollow spherical nanocatalysts
2.3 Core@shell structured nanocatalysts
2.4 Yolk@shell-like nanocatalysts
2.5 Other nanocatalysts
3 Conclusion and outlook

NO Decomposition and Selective Catalytic Reduction of NO over Cu-ZSM-5 Zeolite
Chen Yanping, Cheng Dang-guo, Chen Fengqiu, Zhan Xiaoli
2014, 26 (0203): 248-258 | DOI: 10.7536/PC130857
Published: 15 February 2014
Abstract

More attention to Cu-ZSM-5 zeolite has been paid due to its excellent catalytic activities in removal of NO, and the process it concerned is non-polluting. In this review, the reaction mechanism and catalyst improvement of NO decomposition, selective catalytic reduction of NO with ammonia (NH3-SCR-NO) and with hydrocarbons (CH-SCR-NO) over Cu-ZSM-5 zeolite are summarized. The possible developing orientations in the field of removal of NO over Cu-ZSM-5 zeolite are also prospected. Direct catalytic decomposition of NO to N2 and O2 has been recognized as the most attractive method for removal of NO, which involves redox process of Cu+ and formation of N2O. NH3-SCR-NO reaction is one of the most efficient and widely-used techniques. Firstly, NO is oxidized to NO2, and then NH4NO3 is formed from the reaction of NO2 and NH3. Finally, NH4NO3 reacts with NO generating N2. CH-SCR-NO reaction over Cu-ZSM-5 zeolite is an efficient way for the treatment of automobile-exhaust pollution. The formation of key intermediates such as isocyanate and cyanide species is a necessary process during CH-SCR-NO reaction. However, Cu-ZSM-5 zeolite suffers from poor hydrothermal stability and high sulfur dioxide (SO2) poisoning property which have suppressed its industrial applications. Introduction of a second metal and fabrication of monolithic catalyst can significantly improve the catalytic performance of Cu-ZSM-5 zeolite. The systematic understanding of reaction mechanism is beneficial to the improvement of Cu-ZSM-5 zeolite and also important for the design of novel,efficient,environmentally-friendly catalysts.

Contents
1 Introduction
2 NO decomposition over Cu-ZSM-5 zeolite
2.1 Reaction mechanism of NO decomposition
2.2 Improvement of Cu-ZSM-5 zeolite for NO decomposition
3 NH3-SCR-NO reaction over Cu-ZSM-5 zeolite
3.1 Reaction mechanism of NH3-SCR-NO reaction
3.2 Improvement of Cu-ZSM-5 zeolite for NH3-SCR-NO reaction
4 CH-SCR-NO reaction over Cu-ZSM-5 zeolite
4.1 Reaction mechanism of CH-SCR-NO reaction
4.2 Choice of reductants of hydrocarbon
4.3 Improvement of Cu-ZSM-5 zeolite for CH-SCR-NO reaction
5 Conclusion and prospects

Li-Rich Transition Metal Oxide xLi2MnO3·(1-x)LiMO2 (M=Ni, Co or Mn) for Lithium Ion Batteries
Bai Ying, Li Yu, Zhong Yunxia, Chen Shi, Wu Feng, Wu Chuan
2014, 26 (0203): 259-269 | DOI: 10.7536/PC130767
Published: 15 February 2014
Abstract

As a promising candidate of the cathode materials for the next generation of high energy density lithium-ion batteries, the Li-rich transition metal oxide xLi2MnO3 ·(1-x)LiMO2 (M=Ni, Co or Mn) is superior to the traditional cathode materials for its potential of achieving very high capacity of over 300mAh/g. Therefore, this type of materials is caught more and more attention in recent years. Here we give an overview of recent progress of xLi2MnO3 ·(1-x)LiMO2 in recent years. The research hotspots, the crystal structure characteristics and the mechanism of initial charge and discharge, the development of various synthesis methods, as well as the improvement of the electrochemical performances for xLi2MnO3 ·(1-x)LiMO2(M=Ni, Co or Mn) are commented. The future development trends of the xLi2MnO3 ·(1-x)LiMO2 (M=Ni, Co or Mn) is put forward.

Contents
1 Introduction
2 Research on initial charge-discharge mechanism of Li-rich composite cathode materials
2.1 Crystal structure of Li-rich composite cathode materials
2.2 Initial charge-discharge mechanism of Li-rich composite cathode materials
3 Synthesis methods for xLi2MnO3·(1-x)LiMO2
3.1 Co-precipitation method
3.2 Sol-gel method
3.3 Solid state method
3.4 Sucrose combustion method
3.5 Hydrothermal method
3.6 Low-temperature molten salt method
3.7 Other synthesis methods
4 Improvements on electrochemical properties of Li-rich composite cathode materials
4.1 Doping in the lattice
4.2 Surface coating
4.3 Doping other materials
4.4 Particle nanocrystallization and control of structures or morphologies of cathode materials
4.5 Proposing and exploration of new method
5 Conclusions and outlook

Synthesis and Applications of Graphene-Quantum Dot Composites
Niu Jingjing, Gao Hui, Tian Wanfa
2014, 26 (0203): 270-276 | DOI: 10.7536/PC130659
Published: 15 February 2014
Abstract

Due to its unique physical and chemical properties and promising widespread application value, graphene has been attracting intensive research interest. However, it has been limited the applications in the field of optoelectronics due to its special structure of zero bandgap. Semiconductor quantum dots (QDs) exhibit the fascinating optical properties associated with its special quantum size effect. They have been successfully applied in biological detection and optoelectronic applications. But the recombination and annihilation between the electrons and the holes greatly restrict the QDs application in optoelectronic conversion because it lowers the electron conductivity and mobility. The special electronic properties and structures of graphene make it an excellent conductive scaffolds, which would capture and transport electrons from the excited QDs and also effectively separate the electron-hole pair. Therefore, graphene-QDs composites would be an good candidate for combining the advantages of two materials. Graphene-QDs composites not only inherit the high speed electron transport property of the intrinsic graphene, but also possess the quantum size effect and edge effect origining from the special structure of QDs, suggesting the potential applications in the fields of nanodevices and optoelectronics. In this paper, we summerized the synthetic methods of graphene-QDs composites, including the phase-transfer methods, electrostatic compound strategies, hydrothermal and solvothermal methods, electrochemical template method and the microwave-assisted ways. The brief introduction of the applications has also been presented, which would provide the reference for the research and development of graphene-based nanocomposites.

Contents
1 Introduction
2 Synthesis of graphene-quantum dot composites
2.1 Phase-transfer methods
2.2 Electrostatic compound strategies
2.3 Solvothermal methods
2.4 Hydrothermal methods
2.5 Electrochemical template method
2.6 Microwave-assisted ways
3 Applications of graphene-quantum dot composites
3.1 The applications in optoelectronic devices of graphene-quantum dot composites
3.2 The applications in photocatalysis of graphene-quantum dot composites
3.3 The applications in biosensing of graphene-quantum dot composites
4 Conclusion and outlook

Synthesis and Applications in Catalysis of Porphyrinic Metal-Organic Frameworks
Zhuang Changfu, Liu Jianlu, Dai Wen, Wu Zhongping, Wang Ying, Gao Shuang*
2014, 26 (0203): 277-292 | DOI: 10.7536/PC130646
Published: 15 February 2014
Abstract

Heterogeneous catalysis is one of the promising applications for metal-organic frameworks (MOFs) materials because of their high porosity, large surface areas and their flexible tailoring. An attractive approach to design MOFs-based catalysts is to heterogenize them by employing known homogeneous molecular catalysts as struts. In view of the enormous utility as active sites in metallo-enzymes, metalloporphyrin is obvious candidates for incorporation into MOFs as catalytically functional struts. Many efficient strategies have been established for the rational design and synthesis of catalytically functional porphyrinic MOFs. This review is aimed to summarize recent progress on porphyrinic MOFs, including new synthesis strategies and applications in catalysis. The development trends of porphyrinic MOFs are also prospected.

Contents
1 Introduction
2 Synthesis strategies for porphyrinic MOFs
2.1 Utility of extendable porphyrinic ligands in generating secondary building units (SBUs)
2.2 Using specially designed spacers to stabilize secondary building units (SBUs)
2.3 Combination of mixed-ligands
2.4 Template-directed synthesis
3 Heterogeneous catalytic performances of porphyrinic MOFs
3.1 MOFs-based catalysts constructed by porphyrinic ligands
3.2 Catalytic reactions of MOFs-encapsulated porphyrinic catalysts
4 Conclusions and outlook

Nonlinear Optical Crystals LiBX2(B=Ga, In; X=S, Se, Te)
Sun Liang, Yang Chunhui, Ma Tianhui, Zhu Chongqiang
2014, 26 (0203): 293-302 | DOI: 10.7536/PC130806
Published: 15 February 2014
Abstract

LiBX2(B=Ga, In; X=S, Se,Te) crystal is one of the most promising frequency converters materials for IR due to extended transparency range, sufficiently large birefringence, high laser induced damage thresholds and small two-photon absorption coefficient. This article focuses on the optical properties, defect structures and applications of these crystals reported in the past few years. The promising applications on the phase-matched second harmonic generation (SHG), continuous-wave (cw) difference-frequency generation (DFG), optical parametric amplifier (OPA) and optical parametric oscillator (OPO) are summarized. The major native defects, defect concentration and optimal annealing temperature can be indicated by the transmission, absorption and photoluminescence (PL) spectra and irradiation with fast electrons. The relationship between color and composition and crystal defects is analyzed. Finally, the trends in the investigation on crystal growth, reduction of the residual losses and optimization of the antireflection (AR)-coating process are prospected.

Contents
1 Introduction
2 Structural characteristics
3 Polycrystalline synthesis and crystal growth
4 Optical properties and defect structures
4.1 LiInS2 crystal
4.2 LiInSe2 crystal
4.3 LiGaS2 crystal
4.4 LiGaTe2 and LiGaSe2 crystal
5 Crystal applications
6 Conclusions and Outlook

Fabrication of the Self-Assembly Systems Based on Protein Molecules
He Naipu, Lu Shengfang, Zhao Weigang, Du Xi, Huang Sikai, Wang Rongmin
2014, 26 (0203): 303-309 | DOI: 10.7536/PC130749
Published: 15 February 2014
Abstract

Proteins possess versatile function and unique structure, and show the distinguished self-assembly feature. Polypeptide chains with the determined amino acid sequence are formed through amide bond and considered as the primary building blocks of protein. The weak intermolecular interactions of polypeptide chains control the folding of the polypeptide chains and high-level structure of protein. In addition, proteins are a class of renewable resources and show biodegradable and biocompatible. Using the self-assembly feature of protein is the potential strategy for fabricate the controlled self-assembly system with biofunctional in the field of nanoscience, materials and biomedical and so on. Hence, the present review describes the self-assembly feature of protein from the chemical point of view. The self-assembly of heat-denatured protein, metal-induced self-assembly of protein, self-assembly of protein with polymer and self-assembly of protein hybrids are further explored. The goal of this review is to further learn and understand the self-assembly feature of protein, and provide ideas for designing and fabricating the controlled structural self-assembly systems with unique function.

Contents
1 Introduction
2 Self-assembly feature of protein structure
3 Self-assembly of denatured protein
4 Metal-induced self-assembly of protein
5 Self-assembly of polymer with protein
6 Self-assembly of protein-polymer hybrid
7 Conclusions and outlook

Organosilicon in Antimicrobial Agent
Zhao Jie, An Qiufeng, Li Xianqi, Wei Yuanbo
2014, 26 (0203): 310-319 | DOI: 10.7536/PC130828
Published: 15 February 2014
Abstract

Organosilicon, as one of the most popular softeners in the textile industry, not only can impart unique softness, smoothness, elasticity and silk-and cotton-like hands to treated fabrics, but also confer the fabrics with a perfect drape, anti-wrinkle, wettability and breathability. In recent years, with the widespread of highly pathogenic microorganism and viruses, people pay more and more attention to the antibacterial finishing of fabric. Moreover,the antibacterial finishing agent is also thought to be one of the most promising finishing agent. So a large number of organosilicon antimicrobial agents were prepared though chemical grafting or physical blending of the microbicides and organic silicon. Relevant researches have been becoming active and some important achievements have been made. The review systematically summarized the recent advances in the synthesis and antimicrobial effect of organosilicon quaternary ammonium salts, N-halamine compounds, organosilicon with antimicrobial inorganic materials and so on. What is more, the mechanism of organosilicon antimicrobial agents is briefly introduced in three aspects: targeting on microbial cell wall, cell membranes, restraining biosynthesis of protein and nucleic acid. Finally, based on the analysis of the present situation of antibacterial finishing agent, the ideal characteristics of antibacterial finishing agent come forward. Besides, the development and application prospect of antibacterial finishing agent are discussed.

Contents
1 Introduction
2 The classification of organosilicon antimicrobial agent(OSAA)
2.1 Organosilicon quaternary ammonium salts
2.2 Regenerable N-halamine compounds
2.3 Organosilicon with antimicrobial inorganic materials
2.4 Others
3 The Mechanism of OSAA
3.1 The OSAA target cell wall synthesis
3.2 The OSAA target cell membrane synthesis
3.3 The OSAA inhibit or interfere with microbial nucleic acid and protein synthesis
4 Prospect

Synthesis and Biological Activity of Steroids Bearing Aromatic Rings and Heterocycles
Cui Jianguo, Liu Liang, Gan Chunfang, Xiao Qi, Huang Yanmin
2014, 26 (0203): 320-333 | DOI: 10.7536/PC130652
Published: 15 February 2014
Abstract

Steroids bearing aromatic rings and heterocycles are types of compounds with significant physiological activities. Generally, they possess a good antibacterial, anti-inflammatory and anti-tumor activity. In this paper, the synthesis and biological activity of steroids bearing aromatic rings and heterocycles in recent year are reviewed according to the classification of their structures, such as steroidal heterocycles bonded A-ring, fused A-ring, bonded B-ring, bonded D-ring, etc. Their developing trends and applying prospects are also expected.

Contents
1 Steroids bearing aromatic rings and heterocycles bonded A-ring
2 Steroids bearing aromatic rings and heterocycles fused A-ring
3 Steroids bearing aromatic rings and heterocycles bonded B-ring
4 Steroids bearing aromatic rings and heterocycles bonded D-ring
4.1 Steroids bearing aromatic rings and heterocycles bonded 17-C
4.2 Steroids bearing aromatic rings and heterocycles bonded 16-C
5 Steroids bearing aromatic rings and heterocycles fused D-ring
6 Outlook

Direct and Oxidatively Dehydrogenative Coupling of Alcohols with Amines to Amides
Ma Wenchan, Zhou Qiao, Zhang Yuecheng, Zhao Jiquan
2014, 26 (0203): 334-344 | DOI: 10.7536/PC130740
Published: 15 February 2014
Abstract

Direct and oxidatively dehydrogenative coupling of alcohols with amines or ammonia to amides have the advantages of high atom economy and environmental friendliness, therefore,they have received much attention from scientists. They have been found that some ruthenium and rhodium complexes, supported gold and silver nanoparticles, manganese oxide based molecular sieves (OMS-2), and copper and iron-based catalytic systems have exhibited excellent performances on the amidation reactions. In this article, the progress of direct dehydrogenative coupling of alcohols with amines or ammonia to amides respectively catalyzed by ruthenium and rhodium complexes, supported gold and silver nanoparticles is introduced firstly. Then the oxidative amidation reactions of alcohols with amines or ammonia respectively catalyzed by supported gold nanoparticles, manganese oxide based molecular sieves (OMS-2), and copper and iron-based catalytic systems with different reagents, including molecular oxygen, tert-butyl peroxide (TBHP) and molecular iodine as oxidants are reviewed. The possible catalytic mechanisms of some catalysts or catalytic systems are discussed. Meanwhile, the scope of application, advantages and disadvantages of each catalyst or catalytic system are described. In addition, some transition metal-free reaction systems for the oxidative amidation of alcohols with amines are also summarized. Finally, the development directions in this field are predicted based on the results described above.

Contents
1 Introduction
2 Direct dehydrogenative coupling of alcohols with amines to amides
2.1 Ruthenium and rhodium complexes as homogeneous catalysts for the reaction
2.2 Supported gold and silver as heterogeneous catalysts for the reaction
3 Oxidative amidation of alcohols with amines
3.1 Oxidative amidation of alcohols with amines by molecular oxygen
3.2 Oxidative amidation of alcohols with amines by other oxidants
4 Conclusions

Reaction Mechanisms of Olefin Hydrosilylation Catalyzed by Several Transition Metal Complexes
Zhao Yan, Guo Caihong, Wu Haishun
2014, 26 (0203): 345-357 | DOI: 10.7536/PC130745
Published: 15 February 2014
Abstract

Silicon-based products such as oil, grease, rubbers, resin, etc. are widely used in the industrial, agricultural, medicinal, and other areas. The above-mentioned are not naturally substances, and organosilicon compounds as the effective component are manufactured artificially. The hydrosilylation of olefins is one of the most straightforward and atom-economical methods for the generation of versatile silicon-containing intermediates in silicon chemistry. Also the catalysts are very necessary. Transition metal complexes are confirmed to have high activity and selectivity. The Pt-based complexes, such as Karstedts and Speiers catalysts, are most widely used in the past. Over the past years, the transition-metal-based catalysts such as Pd, Rh, Ru, Zr, etc. have been reported to be efficient in the alkene hydrosilylation reaction. In this paper, we mainly introduce the advances in new reaction mechanisms of olefin hydrosilylation catalyzed by several transition metal complexes. In particular, we highlight the new mechanistic pathways from the experimental studies and quantum mechanics calculations. Not only a summary of previous works is given, but also some ideas and inspirations are provided for future research.

Contents
1 Introduction
2 Mechanisms of olefin hydrosilylation catalyzed by late transition metal complexes
2.1 Platinum complexes catalysts
2.2 Reaction mechanism catalyzed by platinum complexes
2.3 Ruthenium complexes catalysts and reaction mechanisms of olefin hydrosilylation
3 Mechanisms of olefin hydrosilylation catalyzed by middle transition metal complexes
3.1 Family of chromium (Cr、Mo、W) complexes catalysts and reaction mechanism
3.2 Family of manganese (Mn、Tc、Re) complexes catalysts and reaction mechanism
4 The mechanism of olefin hydrosilylation catalyzed by early transition metal (Zr、Ti、Hf) complexes
5 Conclusion and outlook

Computer Simulation of Self-Assembly of Block Copolymers in Selective Solvent
Sheng Yuping, Yan Nan, Zhu Yutian, An Jian
2014, 26 (0203): 358-365 | DOI: 10.7536/PC130704
Published: 15 February 2014
Abstract

Due to the difference in the property of each block, block copolymers can self-assemble into various nanoscale morphologies spontaneously, including sphere, rod, ring, lamella, vesicle and compound micelle etc. These micelles have potential applications in nanotechnology such as drug delivery, catalysts, electronic information and so on. Recently, the computer simulations are widely used to monitor the process of self-assembly, reveal the mechanism of self-assembly, and illuminate the influence of various control factors on micellar structures, which can provide mentality and theoretical support for the experimental research. This review mainly summarizes the latest progresses in computer simulation of self-assembly of block copolymers in selective solvent, and discussed various effects on the micellar morphologies and the process of self-assembly. Moreover, the future development in this filed is also discussed in this review.

Contents
1 Introduction
2 Self-assembly of AB diblock copolymers in selective solvents
3 Self-assembly of ABA triblock copolymers in selective solvents
3.1 Self-assembly of ABA triblock copolymers in A-selective solvents
3.2 Self-assembly of ABA triblock copolymers in B-selective solvents
4 Self-assembly of ABC triblock copolymers in selective solvents
4.1 Self-assembly of ABC triblock copolymers in A-and C-selective solvents
4.2 Self-assembly of ABC triblock copolymers in C-selective solvents
4.3 Self-assembly of ABC miktoarm star terpolymers in selective solvents
5 Self-assembly of mixtures of copolymers in selective solvents
6 Conclusion and outlook

Biological Application of Sulfobetaine Methacrylate Polymers
Xu Lina, Ma Peipei, Chen Qiang, Lin Sicong, Shen Jian
2014, 26 (0203): 366-374 | DOI: 10.7536/PC130839
Published: 15 February 2014
Abstract

Zwitterionic polymers have anion and cation groups simultaneously, which make them highly hydrated and render them unique biocompatibility. Because of their unique zwitterionic pendant-side chain structures, sulfobetaine methacrylate (SBMA) polymers present the excellent anti-biofouling properties, i.e. the resistance to protein adsorption, the inhibition of bacterial and blood coagulation, which make them increasingly applied in a wide range of biological and medical related fields recently. The hydration theory, one of the widely accepted antifouling mechanisms, is briefly introduced. In this article, recent progress in the properties, synthesis methods and surface construction methods is reviewed, the applications of SBMA polymers in the materials for artificial organs, tissue engineering, biological separation, bio-monitoring system and temperature-sensitive materials are summarized. In addition, SBMA polymers holding great potential for use in biomaterials and issues existed in these applications are also discussed.

Contents
1 Introduction
2 Mechanism investigation of biocompatibility
3 Preparation of SBMA polymers and methods of immobilization of SBMA polymers onto the materials
4 Application of SBMA polymers
4.1 Application of SBMA polymers in the materials for artificial organs
4.2 Application of SBMA polymers in the tissue engineering
4.3 Application of SBMA polymers in the biological separation
4.4 Application of SBMA polymers in the bio-monitoring system
4.5 PSBMA used for temperature-sensitive materials
4.6 Others
5 Conclusion and perspective

Recent Progress in Gene Delivery Based on Cyclodextrin
Xu Niwei, Liu Mengyan, Hong Shibin, Yan Wei, Fu Jifang, Deng Wei
2014, 26 (0203): 375-384 | DOI: 10.7536/PC130632
Published: 15 February 2014
Abstract

Safe and efficient delivery of nucleic acid constructs to target cells has great potential for the treatment of genetic diseases. Non-viral gene delivery has attracted considerable attention because of large-scale production, immunogenicity and safety concerns. Whereas, non-viral gene delivery still suffered from low transfection efficiency and lack of selectivity, which is the main target on this field. The gene delivery based on cyclodextrin (CD) can offer the possibility for construction of various multi-functional gene deliveries. As a FDA approved bio-material, CDs have been extensively used for gene delivery because of their ability to stabilize the nucleic acids in biological media and their ability to destabilize and permeate biological membranes and for obviating undesirable side effects. CD is not only a widely used host molecule capable of internalizing guest molecules in water, but also a core with abundant OH groups. Therefore, a variety of nonviral vectors have been explored based on CD's host-guest interaction and core structure. Recently, CD modified gene delivery has achieved to the clinic test with remarkable result, showing great potential application. In this review the newest development of the gene delivery based on cyclodextrin is summarized. The article provides detail information about the rotaxanes type, side-chain type, star-shape type and branched type deliveries of nucleic acid. Furthermore, the advantage of CD based gene delivery is emphasized herein, which has been applied in clinical test.

Contents
1 Introduction
2 Gene delivery based on cyclodextrin
2.1 Rotaxane type gene deliveries
2.2 Side-chain type gene deliveries
2.3 Star-shape type gene deliveries
2.4 Branched type gene deliveries
2.5 Other type gene deliveries
3 Conclusion and outlook

Strengthening of Hydrogels Based on Polysaccharide and Polypeptide
Song Lifeng, Zhao Jin, Yuan Xiaoyan
2014, 26 (0203): 385-393 | DOI: 10.7536/PC130812
Published: 15 February 2014
Abstract

Hydrogels based on polysaccharide and polypeptide have been utilized in a wide range of biomedical applications because of the rich resources, good biocompatibility and biodegradability. However, their wide applications are always restricted by the relatively poor mechanical strength. This review aims to give an overview of strengthening of hydrogels based on these materials, and highlights four kinds of ways: strengthening via blending; strengthening via special topological structure; strengthening via crystallization; and strengthening via imitating robust hydrogels based on synthetic materials, in terms of their enhanced mechanical properties and corresponding strengthening mechanisms. Finally, we describe the main current achievements in the study of strengthening of hydrogels based on polysaccharide and polypeptide, and also provide some suggestions for further work particularly with regard to some unanswered questions and possible avenues for further enhancement of gel mechanical properties.

Contents
1 Introduction
2 Strengthening via blending
2.1 Blending via hydrogen bond
2.2 Blending via electrostatic interaction
3 Designing special topological structures
3.1 Dendritic topology structure
3.2 Star topology structure
4 Strengthening via crystallization
5 Strengthening via imitating robust hydrogels based on synthetic materials
5.1 Nanocomposite hydrogels
5.2 Double-network hydrogels
6 Conclusion and outlook

Functional POSS-Containing Polymers and Their Applications
Zhang Kaiqiang, Li Bo, Zhao Yunhui, Li Hui, Yuan Xiaoyan
2014, 26 (0203): 394-402 | DOI: 10.7536/PC130759
Published: 15 February 2014
Abstract

Polyhedral oligomeric silsesquioxanes (POSS) are silsesquioxane molecules with a special cage-like nanoscaled organic/inorganic hybrid structure. Among them, octa-silsesquioxanes have been mostly investigated. Compared with other inorganic agents, the structure of a rigid, cubic inorganic silica core and eight corner organic groups endow POSS possesses unique physical properties and chemical reactivities. The corner substituents, identical or different, can be used to design and prepare POSS-containing hybrid polymers. Owing to the special structure, functional POSS-containing polymers can be prepared through physical mixing or chemical copolymerization. With the development of advanced polymer-synthesis methods including "click" chemistry, reversible addition-fragmentation chain transfer polymerization and atom transfer radical polymerization, well-defined POSS-containing hybrid polymers have been obtained, such as star-shaped, branch or block polymers, which has aroused extensive interests in recent years. Based on the nature of POSS, the main routes for synthesizing the functional POSS-containing polymers are briefly reviewed in this paper. Furthermore, applications of POSS-containing polymers are particularly introduced including constructing superhydrophobic films or surfaces for fabrics or anti-icing, developing amphiphilic polymers, and taking advantage of POSS as a building block for shape memory polymers. The challenges of POSS-containing polymers are also proposed based on the current progress. Finally, the research trends of the POSS-containing polymers are prospected.

Contents
1 Introduction
2 POSS-containing polymeric surfaces
2.1 Omniphobic POSS-containing polymers
2.2 POSS-containing coatings for anti-icing
3 Amphiphilic POSS-containing polymers
4 POSS-containing shape memory polymers
5 Conclusion

Functionalization and Applications of Nanocrystalline Cellulose
Wu Weibing, Zhang Lei
2014, 26 (0203): 403-414 | DOI: 10.7536/PC130657
Published: 15 February 2014
Abstract

Nanocrystalline cellulose (NCC) is a kind of rod-like nanomaterial obtained from inexpensive renewable biomass. The presence of hydroxyl groups on NCC surface allows it to be further functionalized through chemical modification or deposition of nanoparticles. An introduction of the assembly and deposition of metal element, non-metal element, metal oxide, non-metal oxide, and inorganic salt nanoparticles on NCC is presented in this review. NCC has important application value in many fields owing to the unique structure, exceptional strength and physicochemical properties, biocompatibility and low toxicity. NCC has been widely used as reinforcing agent because of its nanoscale dimensions and outstanding mechanical strength. As a nanoscale biotemplate suitable for the assembly of nanoparticles, NCC has been designed to be high-efficiency composite catalyst. With the characteristics of anisotropy, birefringence and liquid crystallinity, NCC has shown important applications as optical and electronic material. Since NCC is modifiable, biocompatible and biodegradable, this review espically focuses on the applications of NCC in the field of biomedicine, such as enzyme immobilization, antimicrobial and medical materials, biosensors, fluorescent probes and drug delivery. The practical considerations including stability, compatibility and cytotoxicity are also discussed. In the future, NCC still needs to overcome the problems of dispersity, intrinsic hydrophily and manufacturing difficulty to realize industrialization and commercialization.

Contents
1 Introduction
2 Functionalization of NCC
2.1 Covalent modification
2.2 Deposition of nanoparticles on NCC
3 Applications of NCC
3.1 Reinforced composites
3.2 Catalysis
3.3 Optical and electronic materials
3.4 Enzyme immobilization
3.5 Antimicrobial and medical materials
3.6 Biosensors
3.7 Fluorescent probes
3.8 Drug delivery
4 Outlook

Progress in Preparation and Applications of Cellulose Derivatives-Based Chiral Stationary Phase
Weng Xilun, Bao Zongbi, Luo Fei, Su Baogen, Yang Yiwen, Ren Qilong
2014, 26 (0203): 415-423 | DOI: 10.7536/PC130776
Published: 15 February 2014
Abstract

Preparation of optically pure isomers and determination of the enantiomeric excess of chiral racemates are becoming increasingly important. Nowadays, many top selling drugs around the world have been administrated as single enantiomer with its desired physiological effect. Direct enantioseparation using chiral stationary phases (CSPs) by high performance liquid chromatography (HPLC) has signicantly evolved during the past few decades and has been recognized as the most popular and reliable tool for both analysis and preparation purposes.This paper reviewed the recent progress and breakthroughs made on the preparation of CSPs based on cellulose derivatives as selector. The new approaches for preparing the coated-type, bonded-type and hybrid-type CSPs are specifically discussed and evaluated. Many attempts to clarify the chiral recognition mechanism of cellulose derivatives-based CSPs on liquid chromatography have been carried out by NMR spectroscopy, ATR-FTIR, X-ray analysis and DFT etc. Apart from HPLC, the polysaccharide-based CSPs have also been used for simulated moving bed (SMB) and supercritical fluid chromatography (SFC), which are well-established techniques and becoming potential alternative for production of single enantiomer drugs. The applications performed by SFC and SMB are also summarized, and the purities, productivities and solvent consumptions are specifically displayed.Moreover, future prospects on design of new chiral selectors and optimization of supporting medium of CSPs based on cellulose derivatives are presented.

Contents
1 Introduction
2 Classification and preparation methods
2.1 Coated-type CSPs
2.2 Bonded-type CSPs
2.3 Organic-inorganic hybrid CSPs
3 Chiral discrimination mechanism
4 Application
5 Outlook

Synthesis of Core-Shell Metal-Organic Frameworks
Song Xiaokai, Zhou Yajing, Li Liang
2014, 26 (0203): 424-435 | DOI: 10.7536/PC130832
Published: 15 February 2014
Abstract

Core-shell metal-organic frameworks (MOFs) composed of MOFs as core (or shell) and another material, such as MOFs, carbon, inorganic compounds and organic polymers, as shell (or core), are a typical class of multifunctional MOFs composites. Because of the combination of the properties of core and shell materials, core-shell MOFs have better performances, such as increasing framework stability, selective separation and gas sorption, than the core or shell materials. Therefore, core-shell MOFs have high potentials for industrial applications. In this paper, the research progress of core-shell MOFs in recent years is reviewed. Synthesis methods and applications of variously structural core-shell MOFs, such as MOF@MOF, MOF@carbon, metal oxide@MOF, and polymer@MOF are introduced. Besides, the future development of core-shell MOFs is prospected.

Contents
1 Introduction
2 Synthesis methods and applications of variously structural core-shell MOFs
2.1 MOF@MOF
2.2 Core-shell structures of MOFs with carbon
2.3 Core-shell structures of MOFs with inorganic compounds
2.4 Core-shell structures of MOFs with organic polymers
3 Conclusion and outlook

Photoinduced Toxic Mechanism of Metallic Nanoparticles toward Bacteria in Water
Li Yang, Niu Junfeng, Zhang Chi, Wang Zhengzao, Zheng Mengyuan, Shang Enxiang
2014, 26 (0203): 436-449 | DOI: 10.7536/PC130779
Published: 15 February 2014
Abstract

Nanoparticles (NPs) have been widely used in the fields of chemistry, optics, and biology because of their unique physicochemical properties. The mass production and extensive applications of commercially manufactured NPs inevitably leads to NPs release into the aqueous environment and poses a risk to the ecosystem and human health accidentally or intentionally during production, distribution, use or disposal. The progress on the types, sources, and the physicochemical properties of NPs is critically reviewed in this work. In addition, the factors (i.e., light source wavelength, particle size, natural organic matter, and medium components) that influence the photoinduced toxicity of metallic NPs toward bacteria in the aqueous environments are also summarized. Under light irradiation conditions, metallic NPs can release toxic ions, generate reactive oxygen species (ROS), and change the particle size in the aqueous environment. However, whether the toxicity of metallic NPs toward the bacteria is owing to the released ions, photogenerated ROS (superoxide anion, hydroxyl radical, and singlet oxygen), particle size change, or the combination of the three photochemical behaviors is still uncertain. Therefore the three photochemical behaviors of metallic NPs are critically reviewed to elucidate the possible mechanism of photoinduced toxicity toward the bacteria. Finally, the challenges and existing problems of environmental behavior of metallic NPs are listed and the direction for further research of photoinduced toxicity after metallic NPs entry into the aqueous environment are pointed out (such as quantitative structure-activity relationship of metallic NPs, the complex photoinduced toxic effect of metallic NPs and other pollutants).

Contents
1 Introduction
2 Influence factors for photoinduced toxicity of metallic nanoparticles to bacteria
2.1 Light source wavelength
2.2 Particle size
2.3 Natural organic matter
2.4 Medium component
2.5 Other factors
3 Photoinduced toxicity mechanisms of metallic nanoparticles to bacteria
3.1 Release of metal ions
3.2 Oxidative stress response
3.3 Size effect of metallic nanoparticles
4 Existing problems and perspectives

Preparation and Theranostic Applications of Polymer-Inorganic Hybrid Nanospheres
Lin Ying, Ding Yin, Jiang Xiqun
2014, 26 (0203): 450-457 | DOI: 10.7536/PC130705
Published: 15 February 2014
Abstract

Polymer-inorganic hybrid nanospheres have attracted increasing attention in recent years because of the synergic properties arising from both the polymeric nanospheres and inorganic nanomaterials. Especially, the nanospheres composed by the polymers that have desirable plasticity and biocompatibility, and the inorganic materials with unique optical, magnetic and electric properties are greatly useful in diagnosis and therapy disease. The combinations of functional polymers, inorganic nanomaterials and bioactive molecules can offer synergetic multifunctional nanomedical platforms, which make it possible to accomplish multimodal imaging and monitoring therapy. This article provides a review on the synthetic methodologies for building hybrid nanospheres, and their applications in targeted drug delivery, bio-imaging, cell separation, biosensing and hyperthermia. Perspective and challenges in nanomedical fields are discussed to provide the reference information for development of novel theranostic hybrid nanospheres.

Contents
1 Introduction
2 Preparation of polymer-inorganic hybrid nanospheres
2.1 Encapsulation method
2.2 In situ synthesis of inorganic nanoparticles
2.3 Surface-initiated polymerization coated method
2.4 Hole-doping method
2.5 Layer-by-layer method
2.6 Film rehydration method
3 Theranostic applications of polymer-inorganic hybrid nanospheres
3.1 Magnetic resonance imaging
3.2 CT imaging and surface enhanced raman imaging
3.3 Optical imaging in vivo
3.4 Triggered drug release and monitoring of therapy
3.5 Targeted drug delivery and hyperthermia treatment
3.6 Photothermal therapy
3.7 Cell separation
4 Conclusion and outlook

Studies on Formation of Aqueous Secondary Organic Aerosols
Qi Qian, Zhou Xuehua, Wang Wenxing
2014, 26 (0203): 458-466 | DOI: 10.7536/PC130827
Published: 15 February 2014
Abstract

Secondary organic aerosol (SOA) is the major species in the atmospheric particles and has an important impact on the atmospheric environment, climate and human health. In recent years, the formation of aqueous SOA has been becoming a research hotspot. This is due to its comparable contribution to SOA budget to that from the traditional reaction of gas phase, and the important roles in explaining the discrepancies between field observation and model results, field observation and chamber simulation results in the laboratory on size, distribution, concentration and aging degree of SOA, which cannt be understood by the traditional SOA formation through gas phase. In this article, we introduce current major ways to form aqueous SOA in laboratory studies, including non-radical reactions in the dark (related to hydration, acetal/hemiacetal, aldol condensation and catalytic reactions) and radical reactions under the light. Meanwhile, the prospects for the study direction of the formation of aqueous SOA are given.

Contents
1 Introduction
2 The major physical and chemical processes of the formation of aqueous SOA
3 Formation of aqueous SOA
3.1 Reactions under the dark
3.2 Photochemical reactions
4 Conclusions

Antibody-Drug Conjugates
Cao Gang, Huang Zuogang, Cheng Jiefei, Jiang Biao
2014, 26 (0203): 467-477 | DOI: 10.7536/PC130650
Published: 15 February 2014
Abstract

Over 35 monoclonal antibody drugs have been marketed since the approval of first monoclonal antibody drug in 1986, making the antibody drug development one of the most exciting fields. Antibody-drug conjugate (ADC), which combines a monoclonal antibody (mAb) with a cytotoxic (drug) molecule through a linker and thereby the name, is a new class of highly potent biopharmaceutical drugs designed as a targeted therapy. ADC takes advantage of the high binding specificity of mAbs and superior efficacy of cytotoxic molecules, while avoiding the dose-limiting toxicity of cytotoxic molecules. The first ADC, Mylotarg, was approved in 2000, which was late withdrawn by the manufacture due to the lack of appropriate stability of the linker. So far, there are two approved ADCs in the market for cancer therapy and over twenty ADCs in various stages of clinical trials. Creating a successful antibody drug conjugate requires careful selection of the drug, antibody and linker. Linker has a great influence on a conjugate's biological characteristics, such as stability in circulation and drug release at the target site. ADCs have been proven to be effective weapons against cancers and will certainly become useful therapeutics against other diseases.

Contents
1 Introduction
1.1 Approved ADC
1.2 ADC in clinical trials
2 Choose the right antibody
3 Choose the right cytotoxic small molecule
4 Choose the right linker
4.1 Chemical labile linker
4.2 Enzyme labile linker
4.3 Noncleavable linker
4.4 Other linkers
5 Conclusions and outlook

Pharmaceutical Coamorphous——A Newly Defined Single-Phase Amorphous Binary System
Guo Huihui, Miao Nana, Li Tengfei, Hao Jun, Gao Yuan, Zhang Jianjun
2014, 26 (0203): 478-486 | DOI: 10.7536/PC130755
Published: 15 February 2014
Abstract

Pharmaceutical coamorphous, a kind of single-phase amorphous binary system, is formed between an active pharmaceutical ingredient (API1) and another solid small molecular compound (API2 or excipient). As a newly defined solid form, pharmaceutical coamorphous has been one new approach for drug research and development, due to its great potential in the improvement of solubility, dissolution, stability or even bioavailability. Several methods can be used for the preparation of coamorphous drugs, including quench-cooling, solvent evaporation and milling/cryo-milling. In this paper, the definition, preparation, physicochemical characterization and formation mechanism of pharmaceutical coamorphous are addressed. The comparison between coamorphous and solid dispersion or cocrystals is also presented.

Contents
1 Introduction
2 Overview of pharmaceutical coamorphous
2.1 Definition and classification of coamorphous
2.2 Comparison between coamorphous and solid dispersion
2.3 Relationship and differences of coamorphous and cocrystal
3 Formation mechanisms
3.1 Type of interaction
3.2 Flory-Huggins theory
4 Preparation of pharmaceutical coamorphous
4.1 Preparation methods
4.2 Factors affecting the formation of pharmaceutical coamorphous
5 Properties of pharmaceutical coamorphous
5.1 Identification
5.2 Stability
5.3 Solubility and dissolution
6 Outlooks