Loading...
中文
Announcement
More
Progress in Chemistry 2014, No.05 Previous issue Next issue

In this issue:

Review
DNA Origami Nanoreactors
Jia Sisi, Chao Jie, Fan Chunhai, Liu Huajie
2014, 26 (05): 695-705 | DOI: 10.7536/PC140130
Published: 15 May 2014
Abstract

It is a new idea to construct DNA nanoreactor with nanometer addressability using DNA origami technology. One of the most remarkable features of the DNA origami method is the precise addressability of the structures formed. By biologically and chemically modifying specific staple strands, it is possible to functionalize DNA origami nanostructures with small chemical molecules, biomacromolecules and artificial nanomaterials on well-defined positions with nanoscale precision. The shape diversity and good biological compatibility of DNA origami makes it a perfect nanomaterial for constructing nanoscale biomimetic confinement environment. In this review, we first introduce the general method and the latest progress for nano-addressable positioning of different materials and molecules on DNA origami nanostructures. Then utilizing DNA origami nanostructures as nano-addressable reactors with confined nanoscale spaces, we focus on the regulation of chemical and biochemical reactions in these nanoreactors. At the end, the future directions and potential applications of DNA origami nanoreactors are foreseen.

Contents
1 Introduction
2 Nano-addressable positioning on DNA origami nanostructures
2.1 Positioning of functional groups
2.2 Positioning of biomacromolecules
2.3 Positioning of synthetic nanomaterials
3 Regulation of single molecular chemical reactions
3.1 Cleavage reactions
3.2 Coupling reactions
3.3 Polymerization reactions
4 Regulation of single molecular bio-recognitions and biochemical reactions
4.1 Molecular recognitions
4.2 Enzymatic cascade reactions
5 Conclusion and outlook

Triply and Quadruply Hydrogen Bonded Systems:Design, Structure and Application
Yang Yong, Dou Dandan
2014, 26 (05): 706-726 | DOI: 10.7536/PC131051
Published: 15 May 2014
Abstract

Hydrogen bonding is a kind of noncovalent interaction that holds a very important position in the field of supramolecular chemistry. In the past few years, hydrogen bonding mediated supramolecular polymer has become a hot research topic in supramolecular chemistry. The construction of excellent hydrogen bonding building blocks lies the basis for the area. Among that, triply and quadruply hydrogen bonded systems are widely used for the construction of supramolecular assemblies. In this article, we summarize the progress and applications of triply and quadruply hydrogen bonded systems. We put our emphasis on the design principles of such systems and the factors affecting the stability of each system.

Contents
1 Introduction
2 Triply hydrogen bonded systems and their
applications
2.1 ADA·DAD triply hydrogen bonded systems
2.2 DDA·AAD triply hydrogen bonded systems
2.3 DDD·AAA triply hydrogen bonded systems
3 Quadruply hydrogen bonded systems and their applications
3.1 Quadruply hydrogen bonded systems of separated hydrogen bonding building blocks
3.2 Self-complementary quadruply hydrogen bonded system with DADA·ADAD hydrogen bonding sites
3.3 Self-complementary quadruply hydrogen bonded system with DDAA·AADD hydrogen bonding sites
3.4 Complementary quadruply hydrogen bonded system with DAAD·ADDA hydrogen bonding sites
3.5 Quadruply hydrogen bonded system with AAAA·DDDD hydrogen bonding sites
3.6 Quadruply hydrogen-bonded molecular duplexes free of secondary electrostatic interactions
3.7 Other quadruply hydrogen bonded systems
4 Conclusion and outlook

Electrocatalytic Oxidation of Ethanol
Rao Lu, Jiang Yanxia, Zhang Binwei, You Lexing, Li Zhanhong, Sun Shigang
2014, 26 (05): 727-736 | DOI: 10.7536/PC131015
Published: 15 May 2014
Abstract

As a typically renewable environmental fuel, ethanol has numerous advantages, including easy to storage and production, and high energy density. Therefore, it attracts an extensive attention. In this review we detailedly introduced the significant progress on ethanol electrocatalytic oxidation in recent years. The thermodynamics process, reaction mechanism of ethanol electrooxidation, and the advantages and disadvantages of different electrocatalysts are emphatically described. Furthermore, the factors affecting the reaction activity and selectivity of ethanol electrooxidation, such as support, size, structure, alloy and additive, are discussed. Also, the strategy to enhance activity and selectivity of ethanol electrooxidation is summarized. In the end, we prospect the future of possible research direction of ethanol electrooxidation.

Contents
1 Introduction
2 Thermodynamics process and reaction mechanism of ethanol electrooxidation
2.1 Thermodynamics process
2.2 Reaction mechanism
3 Different kinds of electrocatalysts
3.1 Binary electrocatalysts
3.2 Ternary electrocatalysts
4 Factors affecting ethanol electrooxidation
4.1 Support effect
4.2 Size effect
4.3 Structure effect
4.4 Alloy effect
4.5 Additive effect
5 The strategy to enhance activity and selectivity of ethanol electrooxidation
6 Conclusions and outlook

Immobilization of Metallocene Catalysts
Qi Meizhou, Fu Zhisheng, Fan Zhiqiang
2014, 26 (05): 737-748 | DOI: 10.7536/PC130941
Published: 15 May 2014
Abstract

Metallocene catalysts form a new generation of catalysts for olefin polymerization after Ziegler-Natta catalysts. Compared with multi-active site catalysts, this kind of single-site catalysts has higher polymerization activity and produces polyolefin with narrower molecular weight distribution and composition distribution. Immobilization of metallocene catalysts on solid supports is an important step toward its industrial application, as it can largely overcome the drawbacks of homogeneous catalysts in controlling nascent polymer morphology. The amount of alkylaluminoxane cocatalyst can also be reduced after immobilization. Thus, research on immobilization of metallocene catalysts is still active in recent years. This paper reviews the progress in immobilization of metallocene cataylsts in recent ten years with emphasis on the morphologies and modifications of supports, immobilization methods of metallocene catalysts, and applications of supported metallocene catalysts. The prospects and development trends on immobilization of metallocene catalysts are also discussed.

Contents
1 Introduction
2 Morphologies of supports
2.1 Spherical supports
2.2 Tubular supports
2.3 Rodlike supports
2.4 Sheet supports
2.5 Irregular supports
3 Modifications of supports
3.1 Treatment with alkylaluminoxanes
3.2 Treatment with aluminum alkyls
3.3 Treatment with oxides
3.4 Treatment with chlorides
3.5 Treatment with silane compounds
3.6 Treatment with other modifiers
4 Immobilization methods of metallocene catalysts
4.1 Immobilization of bi-components
4.2 Immobilization of single components
5 Applications of supported metallocene catalysts
5.1 Polyethylene composites
5.2 Polypropylene composites
6 Conclusion and outlook

Nano Metal Catalysts in Dehydrogenation of Ammonia Borane
Zhang Lei, Tu Qian, Chen Xuenian, Liu Pu
2014, 26 (05): 749-755 | DOI: 10.7536/PC131128
Published: 15 May 2014
Abstract

As the chemical hydrogen storage material, it must have a high hydrogen storage capacity. Ammonia borane (NH3BH3, AB), whose hydrogen content is as high as 19.6 wt%, is regarded as a potential hydrogen storage medium with the bright future. The capacity of AB hydrolysis dehydrogenation is up to 7.8 wt%. The capacity of AB pyrolysis dehydrogenation can release 19.6 wt% of hydrogen. Both the hydrolysis dehydrogenation and the pyrolysis dehydrogenation have shown its great potential in the chemical hydrogen storage. In the study of AB dehydrogenation, catalyst is the key technology and the important research direction. Among all the catalysts about AB dehydrogenation, nano metal catalysts have been investigated for their excellent performance. In this paper, the nano catalysts and their performance about the dehydrogenation of ammonia borane are reviewed.

Contents
1 Introduction
2 One-component nano metal catalysts
2.1 Nano rhodium catalysts
2.2 Nano palladium catalysts
2.3 Nano ruthenium catalysts
2.4 Nano nickel catalysts
2.5 Other nano metals catalysts
3 Two-components nano metal catalysts
3.1 The supported bimetal catalysts
3.2 The alloy bimetal catalysts
3.3 The core-shell bimetal catalysts
4 Three-components nano metal nanoparticles
5 Conclusions and outlook

Ordered Mesoporous Carbon Materials Synthesized by Organic-Organic Self-Assembly
Liu Lei, Yuan Zhongyong
2014, 26 (05): 756-771 | DOI: 10.7536/PC131125
Published: 15 May 2014
Abstract

Ordered mesoporous carbon materials have attracted great research interests due to their extremely large surface area, uniform pore size, high thermal stability and chemical inertness, which have been widely used in the areas including catalysis, adsorption, energy storage and conversion. The direct synthesis strategy from organic-organic self-assembly involving the combination of polymerizable precursors and block copolymer templates is expected to be more flexible in preparing mesoporous carbons, compared with the traditional nanocasting strategy of fussy and high-cost procedures using mesoporous silica materials as the hard template. In this critical review, we present the fundamentals and recent advances related to the researches of ordered mesoporous carbon materials from the direct synthesis strategy of block copolymer soft-templating, with a focus on their controllable preparation, modification and potential applications. Under the guidance of their formation mechanism, the preparation of ordered mesoporous carbons are detailedly discussed by synthetic pathways, including evaporation induced self-assembly method, dilute aqueous route, macroscopic phase separation and hydrothermal autoclaving process. The mesopore size and morphology control, and the hybrid carbon materials are also demonstrated. The potential applications of pure and modified mesoporous carbons in adsorption, catalysis and electrochemistry are detailed discussed. Furthermore, remarks on the challenges and perspectives of research directions are proposed for further development of ordered mesoporous carbons.

Contents
1 Introduction
2 Synthesis of ordered mesoporous carbon
2.1 Synthesis mechanism
2.2 Synthesis pathway
2.3 Mesostructure control
2.4 Pore size control
2.5 Morphology control
2.6 Hybrid carbon materials
3 Applications
3.1 Gas adsorption and storage
3.2 Dye and protein adsorption
3.3 Electrode materials for supercapacitors
3.4 Catalysis
4 Conclusion and outlook

Synthesis and Application of Three-Dimensionally Ordered Macroporous Carbon with Designed Pore Architecture
Qiu Shi, Zheng Jingwei, Yang Guitang, Zheng Jingtang, Wu Mingbo, Wu Wenting
2014, 26 (05): 772-783 | DOI: 10.7536/PC131104
Published: 15 May 2014
Abstract

Porous carbon materials have been widely studied due to their remarkable physicochemical properties, including the high specific surface area, extensively pore structure, good thermal stability, high corrosion resistance, easy handling and low cost of manufacture. In order to reap the full benets of designer porous carbons, it is necessary to develop controlled surface properties and structural ordering from fundamental and application point of view. Three-dimensionally ordered macroporous (3DOM) carbon materials, prepared by colloidal crystal templating (CCT) methods, using so-called hard templates, possess well-ordered periodicity and interconnected pore systems that are of interest for numerous applications, such as sorption and controlled release, catalysts and power sources. Recent breakthroughs have resulted in the development of CCT methods for the preparation of macro-mesoporous carbon by combining CCT with additional templating techniques. This review surveys literatures and highlights recent progress in the synthesis routes of 3DOM carbon by CCT methods, and the hierarchical pore structure by a dual-templating method. It discusses aspects of the main performance parameters, including the choice of colloidal particles, precursors, deposition techniques, and other necessary modications to enhance the functionality of 3DOM carbon materials, and puts emphasis on overviewing the applications in environmental purification and advanced energy conversion and storage.

Contents
1 Introduction
2 Morphological control and structural design of 3DOM carbon materials
2.1 Microstructure
2.2 Macroscopic feature
3 Designing and constructing of 3DOM carbon materials
3.1 Hard templating pathways by colloidal crystal
3.2 Dual-templating methods
4 Key factors in the preparation of 3DOM carbon materials
4.1 Types of colloidal crystal templates
4.2 Types of carbon precursors
5 Application
5.1 Environmental purification
5.2 Advanced energy conversion and storage
6 Conclusion and outlook

Deep Eutectic Solvents to Organic Synthesis
Wang Ailing, Zheng Xueliang, Zhao Zhuangzhi, Li Changping, Zheng Xuefang
2014, 26 (05): 784-795 | DOI: 10.7536/PC131124
Published: 15 May 2014
Abstract

Deep eutectic solvents(DES) is a new type of environmentally green solvents. Compared with conventional organic solvents, DES have more advantages, such as negligible vapor pressure, non-flammability, good chemical and thermal stability, non-toxicity, biodegradability, recyclability and low price among others. As a new type of solvent, DES has an extremely extensive application prospect. The latest research results of DES is reviewed in this paper. DES as a novel solvent and catalyst was applied in the traditional organic synthesis reaction, mainly including Helogenation reaction, Diels-Alder reaction, Knoevenagel reaction, Henry reaction, Perkin reaction, Paal-Knorr reaction, Biginelli reaction. At last, we hope that DES has a good application prospect in the field of organic synthesis.

Contents
1 Introduction
2 DES in the replacement reaction
2.1 Alkylation of nitrogen
2.2 Alkylation of the alcohol
2.3 Friedel-Crafts alkylation reaction
2.4 Halogenation
2.5 Esterification
3 DES in addition reactions
3.1 Diels-Alder reaction
3.2 Henry reaction
3.3 Cycloaddition
4 DES in condensation reaction
4.1 Knoevenagel condensation
4.2 Perkin reaction
5 DES in the cyclization
5.1 Fischer indole synthesis
5.2 Paal-Knorr reaction
5.3 Biginelli reaction
6 DES in the elimination reactions
7 DES in rearrangement reactions
8 DES in reducing reactions
9 Conclusions and outlook

Aerogel Materials Based on Cellulose
Ma Shurong, Mi Qinyong, Yu Jian, He Jiasong, Zhang Jun
2014, 26 (05): 796-809 | DOI: 10.7536/PC131032
Published: 15 May 2014
Abstract

Cellulose, as the most abundant biopolymer in nature, has attracted extensive interest from both academia and industry in recent years due to its specific properties such as biocompatibility, biodegradability, thermal and chemical stability. Nowadays, cellulose aerogel, which possesses extremely low density, large open pores, and a high specific surface area, has become one of topical polymer materials that are based on this sustainable resource. The combination of the advantages and characteristics of the renewable biopolymer and highly porous material has made cellulose aerogel as the new generation succeeding the inorganic and synthetic polymer-based aerogel. In this review, recent research progress in cellulose aerogel materials is summarized based on about 70 relevant papers. The preparation of cellulose aerogel materials is mainly focused on the dissolving solvents of cellulose, including hydrous and anhydrous systems, and aqueous dispersion media of cellulose nanofibers, which are separated from native lignocellulose biomass and bacterial cellulose. The recent development to enhance the mechanical properties of cellulose aerogel by improving the strength of solid network via addition of inorganic components, is described, along with that to introduce functionality (hydrophobicity, superoleophobicity, electrical and magnetic properties, etc.) in cellulose aerogel. Finally, a perspective on the cellulose aerogel materials and the research directions in the future is briefly discussed.

Contents
1 Introduction
2 Preparation of cellulose aerogels
2.1 Dissolution of cellulose by non-derivative solvents
2.2 Dispersion of cellulose nanofibers in water
3 Modification of cellulose aerogels
3.1 Enhancement of mechanical properties
3.2 Modification of hydrophobicity and oleophobicity
3.3 Electrical and magnetic functionalization
3.4 Loading of active compounds on aerogels
4 Perspective

Block Copolymer Nanotubular Aggregates Prepared via Direct Self-Assembly in Solution
Wang Lulu, Huang Haiying, He Tianbai
2014, 26 (05): 810-819 | DOI: 10.7536/PC131010
Published: 15 May 2014
Abstract

As a kind of novel material, nanotubes with special one-dimensional hollow structure have attracted more and more attention and investigation. Compared with widely studied carbon nanotubes or small amphiphilic molecular nanotubes, block copolymer nanotubes show advantages in dimension scales, functionalization of both inner and outer spaces and structure stability. Recent progress in preparation of nanotubular aggregates via direct self-assembly of block copolymer in selective solvent is reviewed in this paper. According to properties of blocks, block copolymers that can form nanotubes are divided into three categories, including coil-coil block copolymers, rod-coil block copolymers, and pseudo-block copolymers with specific structures. For each category, the preparation procedures, structure characterizations and formation conditions of the nanotubes are introduced. Moreover, mechanisms and regularities of such hollow one-dimensional structure formation are discussed as well. It is proposed that nanotube formation required highly ordered molecular packing and anisotropic intermolecular interactions; thus rod-coil block copolymers are more likely to form polymer nanotube than coil-coil blockcopolymers. Based on these studies, potential applications and possible trends for future research are briefly described finally.

Contents
1 Introduction
2 Preparation methods and structure characterizations of self-assembled nanotubes
2.1 Direct dissolution
2.2 Selective solvent addition
2.3 Film rehydration
2.4 Solution temperature control
2.5 Characterization of nanotubular structures
3 Classification of nanotube-forming block copolymers
3.1 Coil-coil block copolymers
3.2 Rod-coil block copolymers
3.3 Pseudo-block copolymers with specific structures
4 Conclusions and outlook

Graphene and Its Composites in Sample Preparation
Han Qiang, Wang Zonghua, Zhang Xiaoqiong, Ding Mingyu
2014, 26 (05): 820-833 | DOI: 10.7536/PC131145
Published: 15 May 2014
Abstract

Sample preparation procedure is crucial for the sensitivity, selectivity and accuracy of the quantitative analysis. The exploration and study of new technologies and methods in sample preparation have become important subject and direction in current analytical chemistry owing to its significance. Sorption-based extraction techniques are currently the most widely applied sample preparation techniques. The core component of the sorption-based extraction techniques is adsorbent material, which dominates the selectivity and sensitivity of the method. Therefore, the development of new adsorbent materials is a hot research topic in sample preparation. As a novel class of carbonaceous nanomaterials, graphene has attracted considerable interest in many subjects due to its excellent physical and chemical properties. Remarkably, the superior merits of graphene, for instance, large specific surface area, good thermal and chemical stability, entirely lead to its numerous applications in separation science. This article focuses on the application of graphene and its composites in many sample preparation technologies (including solid-phase extraction, solid-phase microextraction, magnetic solid-phase extraction and other technologies) in order to monitor the trace substances in different matrices (such as environmental, food, biological samples and so on). Finally the existing problem of graphene in sample preparation is summarized, and the possible challenges and future perspectives in this field are also described.

Contents
1 Introduction
2 Graphene and its composites in sample preparation
2.1 Graphene and its composites in solid-phase extraction
2.2 Graphene and its composites in solid-phase microextraction
2.3 Graphene and its composites in magnetic solid-phase extraction
2.4 Graphene and its composites in sample preparation technologies
3 Conclusions and outlook

Fabrication and Application of Photoelectrochemical Sensor
Sun Bing, Ai Shiyun
2014, 26 (05): 834-845 | DOI: 10.7536/PC131014
Published: 15 May 2014
Abstract

Photoelectrochemical sensor is a dynamically developed and promising analytical method, based on the photoelectrochemical process and chemical or biological probing recognition. Benefitting from the separation of the excitation source (light) and electrochemical detection signal (photocurrent), the photoelectrochemical sensor possesses many intrinsic advantages, such as higher sensitivity with low background signals, simpler and low-cost instruments, and inherent miniaturization. It has received an increasing attention and shows an extensive application potential in rapid and high-throughput biological and chemical assays. Under light irradiation, the photocurrent is recorded on the basis of the electron transfer among the photoelectrochemical materials in excited state, electrode surface, and electrolyte. Depending on the photocurrent change resulting from the interactions between various sensing elements and their target analytes, the quantitative photocurrent-analyte relationship is obtained. There are two key portions in the development of photoelectrochemical sensor: the fabrication of the photosensitive layer and the assembly of the molecular recognition layer at the transducer surface. The design and fabrication of photosensitizer, deriving from photoelectrochemically active species and the exploitation of exquisite sensing mechanisms are of extreme importance in the achievements of acceptable sensitivity. In this paper, the sensing principle of photoelectrochemical sensor, lasted applications, design and fabrication of photosensitizer and developments of sensing strategies are reviewed.

Contents
1 Photoelectrochemistry and photoelectrochemical process
2 Introduction to photoelectrochemical sensor
3 Photoelectrochemically active species for the design and fabrication of photoelectrochemical sensor
3.1 Organic photovoltaic molecule
3.2 Conducting polymer
3.3 Inorganic semiconductor and its composites
3.4 Other photovoltaic materials
4 Signal generating mechanism and sensing strategies
4.1 Direct charge transmission and redox reaction
4.2 Signal-off strategy derived from steric hindrance based on molecular recognition
4.3 Enzymatic inhibition and enzymatic catalysis
4.4 Local surface plasma resonance (LSPR) of noble metal nanoparticles and energy transfer in exciton-plasmon interaction (EPI)
4.5 Other probing strategies
5 Prospective of photoelectrochemical sensor

Influence Factors on the Performance of DNA Self-Assembled Monolayers on Gold
Li Zhiguo, Zhang Lingling
2014, 26 (05): 846-855 | DOI: 10.7536/PC131035
Published: 15 May 2014
Abstract

Thiol-modified DNA self-assembled monolayers (SAMs) on gold is the ideal heterogeneous system for studying DNA charge transfer through DNA duplex, designing DNA sensor with high sensitivity and identifying single base mismatch etc. The performance of DNA SAMs on gold is related to three aspects: gold surface conditions, DNA characteristics and surroundings. Gold surface conditions mainly include substrate configuration by different surface pretreatment, gold shapes, substrate potential and substrate temperature; DNA characteristics include the difference of double-stranded and single-stranded DNA, DNA base types, types for thiols modification and factors related to DNA electron transfer; Surroundings mainly include ionic strength or types of cations, ambient medium, temperature in solution and types of mixed thiols. These factors influence surface density and conformation of DNA SAMs on gold, which determine its charge transfer or hybridization performance. In order to controllably construct DNA SAMs with the optimal performance for satisfying different researches about DNA, it is very necessary to understand the effect of different factors on the performance of DNA SAMs on gold. In this article we review the research progress of influence factors on the performance of DNA SAMs on gold from three aspects including gold surface conditions, DNA characteristics and surroundings.

Contents
1 Introduction
2 Gold surface conditions
2.1 Surface pretreatment
2.2 Gold substrate shapes
2.3 Gold substrate potential
2.4 Gold substrate temperature
3 DNA characteristics
3.1 Double-stranded and single-stranded DNA
3.2 DNA base types
3.3 Types for thiols modification
3.4 Factors related to DNA electron transfer
4 Surroundings
4.1 Ionic strength and types of cations
4.2 Ambient medium
4.3 Temperature in solution
4.4 Types of mixed thiols
5 outlook

Electrochemical Detection of Protein Phosphorylation
Gao Feifei, Wang Yuebo
2014, 26 (05): 856-865 | DOI: 10.7536/PC131056
Published: 15 May 2014
Abstract

The phosphorylation of proteins is a reversible post-translational modification, which is almost involved in all the life activities in organisms. Protein phosphorylation plays a significant role in specific genes expressing, cell proliferation and differentiation, especially in the further transduction of various life activities. Based on the changes of electrochemical signal, protein phosphorylation can be detected conveniently by electrochemical methods because of its high sensitivity and selectivity. This review summarizes several electrochemical methods for the detection of phosphorylation based on the electrode materials, and the common materials or molecules using for electrode modification. At the end of this review, the advantages and disadvantages, as well as a prospect of effective electrochemical detection of phosphorylation are given.

Contents
1 Introduction
2 The electrochemical detection for protein phosphorylation based on modified electrode
3 Several methods about electrode modification
3.1 Monolayer modified electrode
3.2 Multi molecular layer modified electrode
4 Several common modified electrodes used for electrochemical detection of protein phosphorylation
4.1 Electrochemical biosensor based on screen printed electrodes
4.2 Substrate peptide modified gold electrode
4.3 Glassy carbon electrodes
4.4 Indium tin oxide electrodes
4.5 Other modified electrodes
5 Conclusion and outlook

Fluorescent Probes for Reactive Nitrogen Species
Jing Xiaotong, Yu Fabiao, Chen Lingxin
2014, 26 (05): 866-878 | DOI: 10.7536/PC131025
Published: 15 May 2014
Abstract

It is generally established that the intracellular reactive nitrogen species (RNS) which contain nitrogen atoms are one class of highly chemical active species. These species have attracted increasing attention and become an active research field based on their key roles in special functions during a series of physiological and pathological processes. In order to elucidate these roles of RNS, the design and development technology for selective and sensitive detection to RNS in vivo are crucial. Advanced with high sensitivity, good selectivity, noninvasive detection and real-time visualization in situ, fluorescent probes provide facilitative and effective chemical approaches in modern biochemistry analysis. Progress in the field of fluorescent probes for RNS promises to advance our knowledge of essential cellular signal transduction during the varieties of physiological and pathological processes, which is indicated in human health and disease. According to the current situation, we review the past four years'latest five types of RNS probes for nitric oxide (NO), peroxynitrite (ONOO-), nitroxyl (HNO), nitrite (NO2-) and nitrogen dioxide (NO2). In this article, the design strategies, fluorescent response mechanisms and biological applications of the probes are discussed. Finally, the prospect to design and applications of probes is given.

Contents
1 Introduction
2 Fluorescent probes for NO
2.1 NO-induced o-phenylenediamine cyclization reaction
2.2 NO-induced spirocyclic opening reaction
2.3 NO-induced diazotization
2.4 Reaction between transition metal and NO
2.5 NO-induced denitrogenation reaction
3 Fluorescent probes for ONOO-
3.1 ONOO- probe based on mimicked selenoenzyme
3.2 ONOO- probe based on oxidized-borate reaction
3.3 ONOO- probe based on oxidative coupling reaction
3.4 ONOO- probes based on like-Baeyer-Villiger reaction
3.5 ONOO- probes based on other chemical reaction
4 Fluorescent probes for HNO
4.1 Fluorescent probe based on the reaction between Cu(Ⅱ) and HNO
4.2 HNO probes based on other chemical reaction
5 Fluorescent probes for NO2-
6 Fluorescent probes for NO2
7 Conclusion and outlook

Structure and Function of Cholesteryl Ester Transfer Protein in Transferring Cholesteryl Ester
Lei Dongsheng, Tong Huimin, Zhang Lei, Zhang Xing, Zhang Shengli, Ren Gang
2014, 26 (05): 879-888 | DOI: 10.7536/PC131028
Published: 15 May 2014
Abstract

Cardiovascular diseases (CVDs) are the leading cause of death worldwide. Human cholesteryl esters (CEs) are naturally transferred from atheroprotective high-density lipoproteins (HDLs) to atherogenic low-density lipoproteins (LDLs) and very low-density lipoproteins (VLDLs) by cholesteryl ester transfer protein (CETP), resulting in a higher probability of CVDs. Finding out the mechanism of CETP in CE transport is an important basis for designing new CETP inhibitors for treating CVDs. This review is focused on the recent studies of CETP structure and interactions with lipoproteins. Transmission electron microscopy (TEM) studies showed that CETP not only can bind to HDL, LDL and VLDL into binary complexes, respectively, but also connects HDL and LDL or VLDL into a ternary complex via penetrating into the HDL core with its N-terminal domain and the LDL or VLDL surface with its C-terminal domain. Molecular dynamics simulations suggested that the penetrated distal ends are highly flexible under physiological conditions and when CETP contacts lipid droplets. This flexibility allows for large-scale conformational changes, and can even open pores in the distal ends. These pores and the original hydrophobic cavities within the CETP crystal structure are generally stable in physiological solution, and can even connect together into a continuous tunnel for CE transfer. Based on above results, scientists introduced and discussed the "tunnel" model for CETP-mediated lipid transfer in detail, and further suggested new interfaces of CETP for being targeted by a new generation CETP inhibitors to treat CVDs.

Contents
1 Introduction
2 Structure of CETP and lipoproteins by electron microscopy
2.1 Structure of the CETP·HDL complex by electron microscopy
2.2 3D reconstruction of CETP·HDL complex
2.3 Structure of the CETP·LDL and CETP·VLDL complexes by electron microscopy
2.4 Labeling of binding sites
2.5 Structure of the HDL·CETP·LDL and HDL·CETP·VLDL complexes by electron microscopy
2.6 Verification of CETP lipid transfer activity
3 CETP structural features by molecular dynamics simulations
3.1 Structural flexibility
3.2 Internal cavities and surface pores
3.3 Surface hydrophobicity
4 Tunnel mechanism for CETP-mediated lipid transfer
4.1 "Tunnel" model for CETP-mediated lipid transfer
4.2 CETP-lipoprotein binding
4.3 Formation of transfer tunnel
4.4 Neutral lipid transfer
5 Conclusions and outlook

Small Molecular Pharmacological Chaperone for Gaucher Disease
Li Jing, Xie Xiaoli, Wang Jiajia, Wang Xiaomin, Li Jing, Wang Peng
2014, 26 (05): 889-897 | DOI: 10.7536/PC131020
Published: 15 May 2014
Abstract

Gaucher disease (GD) is a human autosomal recessive disorder mainly due to mutations in the gene encoding for the lysosomal enzyme acid β-glucocerebrosidase (GCase). It is the most common lysosomal storage disorder. Endoplasmic reticulum associated degradation (ERAD) and limitation for translocation to lysosome are two main pathological factors for GD. So far, enzyme replcement therapy (ERT) and substrate reduction therapy (SRT) are approved medical treatments for type Ⅰ GD patients with non-neurological involvement. However, they are intrinsically associated with low stability in biological media as well as the impossibility to cross the blood brain barrier (BBB). GCase competitive inhibitors can bind mutant GCase in cytoplasm with low concentration substrates, induce it fold and translocate it to lysosome. In lysosome with high concentration substrates, competitive inhibitors dissociate from GCase and release it. Therefore, PCs (pharmacological chaperones) based on competitive inhibitors become the most promising drugs. According to the research on GCase PC in our group, the structure and the catalytic mechanism of GCase and related GCase PCs are introduced. Particularly, the structure and activity relationships of deoxynojirimycin, 1,5-dideoxy-1,5-imino-D-xylitol, isofagomine, aminoinositol and bicyclic iminosugar are discussed emphatically. In addition, other non-sugar derived PCs are briefly introduced. Finally, we analysize the future prospect of GCase PCs and propose the directions in development.

Contents
1 Introduction
2 Structure and catalytic mechanism of GCase
3 GCase pharmacological chaperones
3.1 Deoxynojirimycin
3.2 1,5-dideoxy-1,5-imino-D -xylitol
3.3 Isofagomine
3.4 Aminoinositol
3.5 Bicyclic iminosugar
3.6 Other non-sugar derived pharmacological chaperones
4 Conclusion and outlook

In Situ Chemical Oxidation of Organic Contaminated Soil and Groundwater Using Activated Persulfate Process
Long Anhua, Lei Yang, Zhang Hui
2014, 26 (05): 898-908 | DOI: 10.7536/PC130952
Published: 15 May 2014
Abstract

In-situ chemical oxidation (ISCO) is an effective technology for the remediation of organic contaminated soils and groundwater, as it has high contaminants removal rates and offers the possibility of fast treatment. As an in-situ remediation technology, ISCO can be also used for minimizing contaminants dispersion and lowering the overall treatment cost. Persulfate (PS) is an emerging and promising oxidant for in-situ soil and groundwater remediations due to its high redox potential (E0=2.01 V), long-term stability, high-water solubility, easy transport and wide operative pH range. It can be thermally or chemically activated by initiators to form sulfate radical (SO4·-), a strong oxidant (E0 =2.60 V) which has been successfully used for environmental applications in the remediation of aqueous and sediment systems. The activation methods include UV, heat, transition metals ions, alkaline condition and PS combined with other oxidants. Therefore, the application of activated persulfate (APS) oxidation has emerged as a novel ISCO. This paper provides an overview of mechanism and research progress of APS oxidation. It also reviews the engineering application of APS oxidation technology such as synergistic and hyphenated action for remediation of organic contaminated soils and groundwater, and points out the prospects of the research areas meriting further investigation and development trends.

Contents
1 Introduction
2 Mechanism and research progress of activation oxidation
2.1 Methods of activation and reaction mechanism
2.2 Heat activation
2.3 Transition metals activation
2.4 Alkaline activation
2.5 Combination of other oxidants
2.6 Research areas meriting further investigation and development trends
3 Engineering application of APS
3.1 Synergistic activation of PS
3.2 Integration of APS with other processes
4 Conclusion and perspective