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Progress in Chemistry 2011, No.01 Previous issue Next issue
Mini Accounts
Hydrogen bonded arylamide foldamers: From conformational control to functional evolution
Li Zhan ting
2011, 23 (01): 1-12 |
Published: 20 January 2011
Abstract

Hydrogen bonded aryl amide and hydrazide foldamers may adopt folded or helical, zigzag, straight or other extended conformations, depending on the positions of the amides and hydrogen bonding acceptors on the aromatic rings. Because of the relatively high strength of hydrogen bonding and the intrinsic planarity of the arylamide units, this family of amide oligomers usually possesses highly predictable conformations. The frameworks themselves can be conveniently constructed via simple amide coupling reactions, while discrete functional groups can be introduced to the frameworks or appended side chains at required positions. Thus, in the past few years, we have focused on their applications in designing new molecular tweezers, for generating welldefined and functional supramolecular systems, including organogels, vesicles and liquid crystals, and for directing the formation of complicated macrocyclic systems. More recently, we have found that hydrogen bonding-driven folded segments can also be incorporated into polymers to reversibly tune their mechanical property through the breaking and recovering of the intramolecular hydrogen bonds. This Mini Account summarizes our recent efforts along this line.

Invited Article
Abstract

Professor Yang Shixian devoted his whole lifetime to the advancement of China education and chemistry discipline. During 62 years, he fostered numerous high-quality specialists in the field of science and education. He was the president of Nankai University for 28 years, during which he founded the first research institute in Chinese universities, the Research Institute of elemento-organic chemistry. He was the first one to establish the research field of elemento-organic chemistry and pesticide chemistry in China and was acknowledged as the founder and explorer in these disciplines. He advocated to utilize the knowledge of organic chemistry to explore scientifically and systematically the research in pesticide chemistry. He organized a research team to accomplish 20 projects, published more than a hundred papers. He made important contribution in the innovation of new agrochemical bio-active candidates. He emphasized to learn international experience, to incorporate into our national situation, to serve our economy, and to contribute to the world pesticide science. His extraordinary devotion during his entire career to rear young qualified specialists to sustain our science and education in China has been highly appraised.

Progress in Polyoxometalates Catalysis
Chen Fawang, Hu Changwen
2011, 23 (01): 19-41 |
Published: 20 January 2011
Abstract

Polyoxometalates as industrial catalysts have been proven to have broad applications and prospects due to the advantages of their controllable composition and structures, strong acid and redox properties, low toxicity and corrosivity. Polyoxometalates catalysis is a hotspot in the field of polyoxometalates chemistry. The research situation and new progress in polyoxometalates catalysis in the last five years are reviewed, including acid catalysis, oxidation catalysis, bifunctional catalysis, other reactions containing hydrogenation and carbonate synthesis from carbon dioxide, and industrialization of polyoxometalate catalysis. In addition, the future development based on polyoxometalates catalysis is prospected.

The Functional Inorganic Composites
Wei Xiao, Wang Kaixue, Chen Jiesheng
2011, 23 (01): 42-52 |
Published: 20 January 2011
Abstract

Composite systems may be obtained through chemical-physical incorporation of various components, and if the components are inorganic or largely inorganic, the composites are designated inorganic composite systems. The properties and functions of inorganic composites can be tuned through controlling the composition, the structure and the morphology of the composites. The inorganic composite systems usually include the host-guest composites, coordination polymers and a variety of nanocomposites and so on. The functionalization of these inorganic composites is very important for develop and application of the new materials and energies. This article briefly reviews the recent advancement in design and preparation of inorganic composites such as the functional host-guest composites, functional nanocomposites as well as functional coordination polymers with the luminescent, magnetic and catalytic properties. And the relevant recent results achieved by our own research group have been summarized. The practical application of functional inorganic composites and its impact on the advancement of science and technology are also discussed.

Synthetic Chemistry of Fullerenes
Deng Shunliu, Xie Suyuan
2011, 23 (01): 53-64 |
Published: 20 January 2011
Abstract

Fullerenes are a class of cage-like molecules made of hexagons and exactly twelve pentagons. Since the discovery of fullerene in the middle of 1980’s, the chemistry of fullerenes has become a flourishing field as a result of their unique structures and remarkable properties. In the past twenty-five years, significant progress has been achieved in both fundamental and practical fields. Efforts have been made to improve synthetic efficiency and to synthesize new species of fullerene cage. Herein we review the methods for fullerene synthesis and the novel cage geometries (more than 60 fullerene structures) that have been retrieved and characterized to date. Advances in the production, separation and characterization of various fullerenes are presented, including hollow fullerenes, endohedral fullerenes, exohedral derivatives of fullerenes and azafullerenes.

Review
Research and Application of Particle Emulsifiers
Yi Chenglin, Yang Yiqun, Jiang Jinqiang, Liu Xiaoya, Jiang Ming
2011, 23 (01): 65-79 |
Published: 20 January 2011
Abstract

In recent years, great attention have been paid to particle emulsifiers due to their potential application prospects in food, oil recovery, cosmetics, pharmaceutical, catalyst and the preparation of functional nano-materials. The recent research progress in particle emulsifiers is reviewed in this paper. The types of particle emulsifiers are summarized, including inorganic nanoparticles, surface modified or hybrid inorganic particles, organic nanoparticles and special particle emulsifier, Janus particles; the thermodynamic mechanism and kinetic behaviors of the particle emulsifiers stabled at the oil-water interface are elucidated; the contact angle of the particle emulsifiers at the phase interface and the particle size are key parameters that effect the adsorption stability of particles at the interface, while the arrangement pattern of particle emulsifiers in the oil-water interface is affected mainly by the interaction between particles. The recent application of the particle emulsifiers is also highlighted, including (1) preparation of Pickering emulsions, and functional modification of particle emulsifiers to make emulsions sensitive to pH, salt concentration, temperature, UV light, magnetic field; (2) preparation of Janus particles, colloidosomes, the particles or membranes with multi-level structures, and materials with porous structures using particle emulsifier as block and Pickering emulsion as template; (3) application of Janus particles in catalysis.

Micellization and Phase Behavior of Biosurfactant Bile Salts
Wu Tonghao, Wang Zhongni
2011, 23 (01): 80-89 |
Published: 20 January 2011
Abstract

Biosurfactant bile salts have attracted wide attention in many fields due to their important physiological function and unique structural characteristics different from the conventional surfactants. In this paper, recent progress in research of bile salts have been reviewed, including the micellar structure, surface adsorption behavior and self-assembly behavior of bile salts in aqueous solution. The development of molecular interactions and the aggregations formed in the systems of bile salts/conventional surfactants, bile salts/double-tailed surfactants and bile salts/natural lipid surfactants, as well as bile salts-induced structural transition in self-assemblies have also summarized.

Mo-Based Zeolite Catalysts and Oxygen-Free Methane Aromatization
Xu Yuebing, Lu Jiangyin, Wang Jide, Zhang Zhanguo
2011, 23 (01): 90-106 |
Published: 20 January 2011
Abstract

Among the investigated catalysts, the Mo-based zeolite catalysts showed the highest catalytic activity. These catalysts were systematically discussed on MoO<em>x structure and its location in zeolite, the active Mo species and its carburization in the induction period. The issues on intermediates, the bi-functional reaction mechanism and catalyst deactivation with coke were also discussed. The effect of preparation method, calcination temperature and time, Mo loading, ratio of SiO2 to Al2O3 and the catalyst pretreatment in reaction on the catalytic performance of Mo-based catalyst were demonstrated. Then the ways to improve the catalyst activity and reaction stability were comprehensively introduced, pointing out that the catalyst was always deactivated due to coke and needed regeneration. At last according to our research results the discussion and analysis in the view of engineering technology for methane dehydroaromatization were given, and some problems needed to be solved were put forward.

AFM Study of Calcite Growth and Dissolution on the (104) Face
Wu Congmeng, Wang Xiaoqiang, Zhao Kang, Cao Meiwen, Xu Hai, Lü Jianren
2011, 23 (01): 107-124 |
Published: 20 January 2011
Abstract

Living organisms have evolved ability to produce biominerals or composites with exquisite structures and unique functionalities. Such a process is usually termed as biomineralization. Due to its high relevance to the fabrication of advanced materials, biomineralization has attracted tremendous interest in the past years. A comprehensive understanding of the biomineralization process and the underlying mechanism enables the biomimetic synthesis of functional materials with finely mediated structures. AFM is a powerful tool for in situ following the formation of biominerals at the micrometer and nanometer scale, particularly observing the crystal nucleation and growth. This paper reviews the recent advances in the AFM studies of calcite, focusing on the effects of organic additives on the growth and dissolution of the calcite (104) face. These organic additives include ethanol, carboxylic acids, amino acids, peptides, proteins and saccharides. Several proposed mechanistic interactions between organic additives and the (104) face are discussed. The documented investigations have indicated that step edge free energy, free energy barriers, and the number of active sites on surface can be tuned via site-specific interactions between organic additives and the crystal surface, thereby leading to the alteration of the step kinetics and the modification of the crystal morphology eventually. In the end, directions for future research in this regard are also discussed.

Environmental Responsive Smart Low Molecule Organogel Materials
Zhou Yifeng
2011, 23 (01): 125-135 |
Published: 20 January 2011
Abstract

Low molecule organogel(LMOG)is a new type of self-assembled materials gradually developed in recent years, with the further research, functional LMOGs, especially smart response system for the environment attracted great interests of the researchers. In this review, four types of smart response systems are mainly described, namely, photo response LMOG systems, which containing azobenzene, diarylethylene and other photochromic groups; electrochemical response LMOG systems, which containing tetrathiafulvalene (TTF) and other electrochemical response groups; ions (molecules) response LMOG systems, which responds through the charge transfer between the LMOGs and the guest ions (molecules) or the structure deformation; ultrasound response LMOG systems, with the external ultrasound force, molecular structure to facilitate the formation of intermolecular hydrogen bonds form, and thus to form a stable gel.

Development of Devices and Materials for Small Molecular Organic Light-emitting Diodes and Hurdles for Applications
Mi Baoxiu, Wang Haishan, Gao Zhiqiang, Wang Xupeng, Chen Runfeng, Huang Wei
2011, 23 (01): 136-152 |
Published: 20 January 2011
Abstract

Organic light-emitting diodes (OLEDs) are electrical driven devices which contain organic materials as emitting media. OLEDs have attracted attention widely in modern science and technology, due to their good features of high brightness, quick response, large viewing angle, simple manufacture process, and flexibility, etc. Currently, OLEDs have stridden forward to commercialization in its application field, such as flat panel display (FPD) and solid state lighting (SSL). Although small-size FPD products based on OLED have been in the markets, and prototype products in large dimensions also have come to true, there still exist challenges and hurdles. In this paper, we review the progress in OLED research of devices and materials, as well as OLED applications. Firstly, devices with different structures, such as host emitter based- and dopant emitter based devices, single-, double-, triple- and multilayer devices, as well as white OLED device are discussed, focusing on their working principles, corresponding device features and mechanism differences among them. Secondly, after introducing the strategies for OLED material research, different types of materials including hole transport materials, electron transport materials, various color emitters, and surface modification materials, are summarized, with their performance in OLED presented. Finally, the current challenges for applications are highlighted, and the focus of future research and development are proposed.

Near-Infrared Lanthanide Luminescence for Functional Materials
Liu Zheng, Sun Lining, Shi Liyi, Zhang Dengsong
2011, 23 (01): 153-164 |
Published: 20 January 2011
Abstract

Near-infrared (NIR) luminescent lanthanide materials are attractive due to their unique optical and chemical features, such as characteristic sharp luminescence, good photostability and low toxicity. Recently, startling interests for NIR luminescent lanthanide materials have been attracted for their highlighted value in the applications of fiber-optic communications, laser systems, bio-sensing and bio-imaging analysis, etc. NIR luminescent lanthanide materials have been developed as a new class of luminescent optical labels that have become promising alternatives to organic fluorophores and quantum dots for applications in biological assays and medical imaging. These lanthanide luminescent probes offer low autofluorescence background, large Stokes shifts, high resistance to photobleaching, high penetration depth and temporal resolution; such techniques also show potential for improving the selectivity and sensitivity of detecting methods. Different kinds of luminescent materials fabricated by lanthanides (upconversion nanocrystals, mesoporous materials, micelles, lanthanide metal-organic framework, ionic liquids and ionogels) exhibit various NIR luminescent properties, which are attributed to the distinct mechanisms of sensitisation. However, the sensitisation of NIR luminescence remains a real challenge. By summarizing the latest developments in the field of NIR lanthanide luminescent materials in this review, we show distinct design ideas on the NIR lanthanide luminescence, describe various NIR luminescent lanthanide functional materials, and evaluate the features and advantages of near-infrared luminescent materials for the developing trends in the future.

Regioselective Nucleophilic Ring Opening Reactions of Unsymmetric Oxiranes
Zhou Chan, Xu Jiaxi
2011, 23 (01): 165-180 |
Published: 20 January 2011
Abstract

Nucleophilic ring opening reactions of unsymmetric oxiranes and their regioselectivity with widely used nucleophiles are reviewed. Strong nucleophiles attack the less substituted carbon atom of unsymmetric oxiranes, whatever alkyl, alkenyl, and aryloxiranes, controlled by the steric hindrance only. They can undergo an SN2' ring-opening reaction with alkenyloxiranes via the attack on the β-carbon atom of their alkenyl group. Other nucleophiles generally attack the less substituted carbon atom for alkyloxiranes, controlled by the steric hindrance, but attack the arylmethyl and allyl carbon atom for aryl and alkenyloxiranes, controlled by the electronic effect. In the presence of proton acids or strong Lewis acids, although monoalkyloxiranes are attacked on their less substituted carbon atom with nucleophiles (steric hindrance control), aryl, alkenyl, and geminal dialkyloxiranes are attacked on their more substituted carbon atom with weak nucleophiles (electronic effect control). The regioselectivity of intramolecular nucleophilic ring opening reaction of oxiranes is controlled by the ring size of products. The favorable order is five-membered ring > six-membered ring > seven-membered ring. Thus, the regioselectivity is controlled by a balance between the steric hindrance and electronic effect of oxiranes and nucleophiles.

Novel Functional Molecules Containing Triterpenoid Units
Hu Jun, Ju Yong
2011, 23 (01): 181-191 |
Published: 20 January 2011
Abstract

Triterpenoids, which mainly comes from natural medicinal plants, is used for the treatment of anti-inflammation, anti-virus, anti-tumor, anti-bacteria and anti-fungal activities. Due to the characteristic stereostructure, hydrophobic property, biological activity and biocompatibility, to design and synthesize new functional molecules with triterpenoid chiral skeleton is significant in the potential drug delivery, molecular recognition and medicinal materials, etc. In this review, the recent development of the functional molecules containing triterpenoid units are briefly summarized in the bioactivities, recognition and self-assembly.

Synthesis,Self-Assembly,and Applications of Polyferrocenylsilane Diblock Copolymers
Fan Lihui, Zhou Yongfeng, Yan Deyue, Yang Jintian, Ji Bing
2011, 23 (01): 192-201 |
Published: 20 January 2011
Abstract

Ferrocene molecules possess special optical,electrical and magnetic properties due to the unique aromatic structure and transition metal Fe,and have been one of the focuses of scientific research and technology application in recent years.Polyferrocenylsilanes (PFS) are a novel class of transition metal-containing macromolecules with the backbone that consists of ferrocene and organosilane units.The PFS diblock copolymers are attracting intense current attentions recently because of their controllable molecular weight and varied self-assembly morphologies.This paper provides an overview of the works including the synthesis,self-assembly and potential applications of PFS-based diblock copolymers.For example,this article has introduced the living anionic ring-opening polymerization (ROP) and the two-steps anionic ROP as well as the polymerization mechanisms for the synthesis of all kind of PFS-based diblock copolymers.On the other hand,the self-assembly of this kind of diblock copolymers in selective solvents has also been summarized,it is found the polymers will self-assemble into well defined supramolecular micellar aggregates because of phase separation,such as cylinders,tubes,spheres,tapes and brushes.Especially,the formations of the micelles can also be named as a “living self-assembly” progress like the living polymerization.Some of the micelles can change to other morphology if some stimulations occurred,and also can be spatially selective functionalized to obtain specific properties.At last,some specific applications of PFS diblock copolymers and the assemblies in the area including drug delivery,nano-materials,and specific catalysts are illustrated and the future prospects for PFS diblock copolymers science are discussed in this paper.

Biomacromolecule-based Nanoparticle Drug Carriers
Chen Mengjie, Yao Jinrong, Shao Zhengzhong, Chen Xin
2011, 23 (01): 202-212 |
Published: 20 January 2011
Abstract

Biomacromolecules have attracted more and more attentions on drug carriers (especially in the application of nanoparticle drug carriers) in recent years because of their renewability,nontoxicity,biocompatibility,biodegradability and mucoadhesive ability.The common methods for the preparation of biomacromolecule-based nanopaticles,including emulsion method,self-assembly method and ionic-gelation method are introduced in this review in the first part.Among these methods,the self-assembly method and the ionic-gelation method are more promising because the emulsion method may affect the biocompatibility of the biomacromolecules to a certain extent.Since proteins contain both hydrophilic and hydrophobic segments and polysacchairde can be modified with the hydrophobic molecules,the self-assembly method is those amphiphilic biomacromolecules,for instance proteins and polysaccharide derivatives that contain both hydrophilic and hydrophobic segments,to form nanoparticles by self-assembly via electrostatic interaction,hydrophobic interaction and van der Waals' force.The ionic-gelation method is those polyelectrolytes,for instance proteins and polysaccharide that can be charged under certain condition,to form nanoparticles via the electrostatic interaction with the oppositely charged materials.It can be further divided into several concrete methods,such as ionic crosslinking,polyelectrolyte complex formation,layer-by-layer assembly and template polymerization.In the second part of this review,the progress in the application of these biomacromolecule-based nanoparticles as protein drug,anti-tumor drug,and gene drug carriers is summarized.The results show that these biomacromolecule-based nanoparticle drug carries have great potential in the drug controlled released system.

Sheddable Nanoparticles for Biomedical Application
Ren Tianbin, Feng Yue, Dong Haiqing, Li Lan, Li Yongyong
2011, 23 (01): 213-220 |
Published: 20 January 2011
Abstract

The development of new intelligent drug carrier is one of the most critical challenges in cancer treatment.Nano-vehicles such as liposomes,polymeric micelles and lipoplexes are extensively investigated for this purpose.For successful drug delivery,one prerequisite is the long circulating time in vivo.Nanoparticles which used hydrophilic polymers as the “stealth” coating materials can prolong the circulating time via preventing the vehicles from the clearance by blood proteins and being uptaken by macrophages.However,hydrophilic coatings of nanoparticles may hamper the drug release and interaction with target cell after localizing at the pathological site,limiting the therapeutic effect.Presently,this dilemma could be circumvented by the development of the sheddable nanoparticles.Sheddable nanoparticles,which are capable of shedding their “outer layers” when needed,may facilitate the drug release as well as the interaction with the target cell.Herein,we present an overview of the recent work on sheddable nanoparticles with different “shedding” mechanisms,including pH-sensitivity,redox sensitivity and enzyme digestion,with an emphasis on their designs and biomedical applications.In addition,recent advances and perspectives of the sheddable nanoparticles are included.

Microfluidic Chip Based Microarray Analysis
Qu Xiangmeng, Lin Rongsheng, Chen Hong
2011, 23 (01): 221-230 |
Published: 20 January 2011
Abstract

Microarray chip has been widely used in many fields because of its high throughput,miniaturization and automation.But there are still some disadvantages,such as highly priced instruments,long analysis time,low sensitivity and lacking of parallel analysis ability.Microfluidic device has large specific surface area and short diffusion distance because of its micrometer scale size,which can provide faster hybridization,higher detection efficiency,better analysis performance,and lots of parallel channels can be fabricated for multiple sample analysis.In present,the combination of microfluidic chip and microarray chip has been widely reported,specific hybridization method has been developed and the advantages have been demonstrated experimentally and theoretically.This review presents the research advances of microfluidic chip based microarray analysis,mainly including the specific hybridization procedures,improvement measures and mathematical modeling of hybridization.The progress in other steps has also been introduced.In addition,the disadvantages and advantages by combining microfluidic and microarray technologies are discussed.

Preparation,Application and Functionalization of Hydroxyapatite Microspheres
Ni Songbo, Li Yanbao, Wang Xiumei
2011, 23 (01): 231-245 |
Published: 20 January 2011
Abstract

Hydroxyapatite (HA) is a main mineral in vertebrate bone.During the latest years,HA has attracted attention from researchers in the areas of biology,medicine and materials,due to its special surface characteristics,physical and chemical properties,and excellent biocompatibility,bioactivity and osteoconductivity.In this review,the different methods used to prepare HA microspheres,including spray,template,microemulsion,emulsion technique and other methods are described in detail.The advantage and disadvantage of these methods are summarized.The pore sizes and surface areas of microspheres prepared in different ways are also listed.Subsequently,since HA microspheres possess high mobility,specific surface area and strength,low aggregation ability,injectability and light mass,they have been applied as carriers,scaffolds in tissue engineering,environmental protection,fillers and chromatography.Finally,three strategies are proposed to functionalize HA microspheres,which are surface treatment/modification,doping and dispersing HA in other matrix,respectively.HA microspheres have significantly potential to be applied as carriers,protein separation and cell scaffold in the future.

Advances in Pollution of Cyanobacterial Blooms-Producing Microcystins and their Ecotoxicological Effects on Aquatic Organisms
Jiang Jinlin, Song Rui, Ren Jinghua, Wang Xiaorong, Yang Liuyan
2011, 23 (01): 246-253 |
Published: 20 January 2011
Abstract

The frequent occurs of cyanobacterial blooms induced by eutrophication can bring about water pollution caused by various derivate pollutants,lead to great ecological disasters in severe cases and consequently threaten human health.Microcystins (MC) have become common potential hazardous pollutant in aquatic environments for their great toxicity,widespread distribution and structural stability.These toxin,producing mainly by Microcystis ,are family of monocyclic heptapeptides with many different isomerides.On the basis of the recent development of pollution status of microcystins and their ecotoxicological studies on aquatic organisms,we introduce the physicochemical properties and the fate of microcystins,their pollution in natural waters,reservoir water and potable water in China and their accumulation in some aquatic products, summarize the molecular toxicity mechanisms and their ecotoxicological effects on common aquatic plants and fishes which are the important components of aquatic ecosystem.Finally, the main research trend in this area are discussed.

Naturally Occurring Organobromine Compounds in Marine with Environmental Concern
Yin Yongguang, Liu Jingfu, Jiang Guibin
2011, 23 (01): 254-260 |
Published: 20 January 2011
Abstract

In recent years,the issue of brominated organic pollutants in environment is becoming a great concern.It was found that some of the organobromine compounds from marine environment are naturally occurring rather than anthropogenic.These naturally occurring organobromine compounds are widely present in various marine media including marine organism,sediment,seawater and atmosphere.Biomagnification of some naturally occurring organobromine compounds in marine mammals was demonstrated recently.In addition,many naturally occurring organobromine compounds have been suggested to exhibit biological activity or toxicity.Therefore,it is very important to study in-depth the environmental distribution and impact of naturally occurring organobromine compounds.This review summarizes the diversity,environmental behavior,and toxicity of naturally occurring organobromine compounds.Additionally,the possible sources of naturally occurring organobromine compounds are remarked and future prospects in this field are discussed.