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Progress in Chemistry 2014, No.08 Previous issue Next issue

In this issue:

Review
Applications of Regulation of Protein Adsorption Using PNIPAAm Modified Surfaces
Yu Qian, Chen Hong
2014, 26 (08): 1275-1284 | DOI: 10.7536/PC140350
Published: 15 August 2014
Abstract

Control over the adsorption of proteins on surfaces according to the specific requirements of different fields is of crucial importance for various applications including implanted devices, biosensors, tissue engineering, and separation sciences. Surfaces modified by poly (N-isopropylacrylamide) (PNIPAAm) are capable of reversibly altering their properties in response to the change of environmental temperature, providing possibility to regulate protein adsorption on surfaces. In recent decades, considerable attentions have been paid to investigating protein adsorption on PNIPAAm modified surfaces under different temperatures using various characterization methods, and trying to understand the mechanism and influence factors in molecular level. In this paper, the recent progress on studies of protein adsorption on PNIPAAm modified surfaces are reviewed. It is found that when the thickness of PNIPAAm layer is within a certain range, PNIPAAm modified surfaces exhibit thermo-responsivity of protein adsorption, which can be used in applications of protein purification and separation as well as biosensors. On the other hand, when the thickness of PNIPAAm layer is beyond a critical thickness, PNIPAAm modified surfaces show good resistance to plasma proteins, making them beneficial for applications as hemocompatible surfaces. In the end, the directions of future development on regulation of protein adsorption using PNIPAAm modified surfaces are proposed.

Contents
1 Introduction
2 PNIPAAm modified surfaces
2.1 Preparation of PNIPAAm modified surfaces
2.2 Conformational changes of PNIPAAm grafted on surfaces
3 Studies on protein adsorption on PNIPAAm modified surfaces
3.1 Methods of characterization of protein adsorption
3.2 Mechanisms and influence factors of protein adsorption
4 Applications of PNIPAAm modified surfaces on regulation of protein adsorption
4.1 Purification and separation of protein
4.2 Biosensors
4.3 Hemocompatible surfaces
5 Conclusion and outlook

Hofmeister Ion Series and Its Mechanism of Action on Affecting the Behavior of Macromolecular Solutes in Aqueous Solution
Li Xiaopei, Huang Kun, Lin Jieyuan, Xu Yizhuang, Liu Huizhou
2014, 26 (08): 1285-1291 | DOI: 10.7536/PC140436
Published: 15 August 2014
Abstract

Hofmeister ion series is ubiquitous and turns up frequently in many chemical and biological processes. The explanations for its mechanism of action on target macromolecules in aqueous solutions fall into two categories. The first one states that ions affect the behavior of macromolecular solutes in the aqueous solution by interacting with water, while the other one claims that direct interactions between ions and macromolecules are the key point for comprehending the Hofmeister ion series. In this paper, research works on the two mechanisms of action are elaborately reviewed. In fact, actual solution systems are inevitably complicated by rather delicate balance of all the interactions (e.g., water-water, water-ion, water-solute, ion-solute, cation-anion) and the above mentioned two viewpoints explain the Hofmeister ion series just from one side. More work is still needed to dig into the secret behind the Hofmeister ion series.

Contents
1 Introduction
2 Indirect mechanism of action
3 Direct mechanism of action
4 Conclusion and outlook

Organic Cocrystal Optoelectronic Materials and Devices
Zhu Weigang, Zhen Yonggang, Dong Huanli, Fu Hongbing, Hu Wenping
2014, 26 (08): 1292-1306 | DOI: 10.7536/PC140339
Published: 15 August 2014
Abstract

Compared with one-component organic single crystals, organic cocrystals with unique packing structures and aggregate states show a variety of novel optoelectronic properties through multi-component synergistic and collective effects, paving the way to the development of high-performance or multifunctional optoelectronic devices, particularly in electrical conductors, ferroelectricity, ambipolar charge transporting, photoconductivity and luminescence. Moreover, the charge transfer pathway between donor (D) and acceptor (A) in organic cocrystal is also fundamentally interesting. Therefore, studies on organic cocrystals have gained much attentions in recent years. In this paper, firstly, we have classified organic cocrystals into three categories by the driving forces: charge transfer (CT), π-π interaction and halogen/hydrogen bond; secondly, we have introduced common organic donor materials, using 7,7,8,8-tetracyanoquinodimethane (TCNQ), 1,2,4,5-tetracyanobenzene (TCNB) and fullerene (C60) as the typical acceptors; Thirdly, we have listed eight popular methods used to prepare these organic cocrystals and discussed the relationship between molecule packing and performance of organic cocrystal; Finally, we have covered the applications of these novel cocrystals in organic optoelectronics. We believe that the study on the organic cocrystals is an effective way to achieve organic multi-functional single crystal materials and devices and to promote the development of organic solid state optoelectronics.

Contents
1 Introduction
2 Classification of organic cocrystals
2.1 Charge transfer complex crystals
2.2 Crystals formed by π-π interactions
2.3 Crystals formed by halogen and hydrogen bonds
2.4 Other crystals
3 Common donor/acceptor materials
3.1 TCNQ and its derivatives as acceptor
3.2 TCNB as acceptor
3.3 C60 as acceptor
4 Methods for preparation of crystals
4.1 Solution methods
4.2 Vapor phase method
4.3 Mechanochemical preparation
5 Relationship between molecular packing and function
6 Applications of organic cocrystals
6.1 Unipolar field effect transistors
6.2 Ambipolar field effect transistors
6.3 Photoresponse devices
6.4 Luminescent materials
6.5 Ambipolar field-effect and solid emitting crystals
6.6 Ferroelectric crystals
7 Conclusion and outlook

Metal Catalysts and Reaction Mechanisms in Propylene Epoxidation in Gas-Phase by Molecular Oxygen
Pang Yijun, Chen Xiaohui, Xu Chengzhi, Lei Yangjun, Wei Kemei
2014, 26 (08): 1307-1316 | DOI: 10.7536/PC140208
Published: 15 August 2014
Abstract

Propylene oxide (PO) is an important intermediate chemical and is widely used in chemical, pharmaceutical, food, light industry and other industries. In industry, PO is produced via multiple reaction steps in the liquid phase, using hazardous chlorine or costly organic hydroperoxides as oxidants. Considering the inherent defects of the traditional processes——the chlorohydrin and hydroperoxide process, a new production technology that propylene oxide production via hydrogen peroxide (HPPO) has been developed, but many problems such as the catalyst mass transfer limitation, the catalyst deactivation and regeneration, and the need of a dedicated hydrogen peroxide production plant are encountered. So, a more attractive method for PO production with molecular oxygen by gas-phase is discussed in this paper. The most important new developments for the production of propylene oxide discussed in this paper are concentrated on the supported gold, silver, copper, vanadium, molten salt catalysts and other catalysts that used molecular oxygen as the oxygen source. At the same time, the mechanism involved in the propylene epoxidation such as the Ti active sites mechanism in Au/Ti catalysts, the OMMP (OMMP refers to a ring made up of one oxygen atom, two metal atoms and a propylene unit) intermediate mechanism in silver and copper catalysts and the radical mechanism in silver and other metal oxide catalysts are also mentioned in this paper.

Contents
1 Introduction
2 Research progress in propylene epoxidation reaction
2.1 Ag catalysts
2.2 Au catalysts
2.3 Cu catalysts
2.4 Bi and Mo catalysts
2.5 Multi-metal catalysts
2.6 Molten salts catalysts
2.7 Others
3 Conclusion and outlook

Advances of Host-Guest Supramolecular Vesicles and Their Properties in Drug Delivery
Ma Mingfang, Xing Pengyao, Li Shangyang, Chu Xiaoxiao, Wang Bo, Hao Aiyou
2014, 26 (08): 1317-1328 | DOI: 10.7536/PC140341
Published: 15 August 2014
Abstract

The host-guest supramolecular vesicles are attracting more and more attention with the emergence of new host molecules. Cyclodextrin, calixarene, cucurbituril and pillararene can all form supramolecular amphiphiles with specific guest molecules based on host guest recognition, the obtained supramolecular amphiphiles can further self-assembled into the host-guest supramolecular vesicles under mild condition. The host-guest supramolecular vesicles is a sensitively responsive vesicular system, which possesses the advantages of simple preparation, good biocompatibility and controllable self-assembly. This vesicular system has good responsiveness to external stimuli, which can realize drug molecules controllable delivery and release, making it a unique drug delivery system. According to the development of the host molecules recently, the advances of cyclodextrin, calixarene, cucurbituril and pillararene host-guest supramolecular vesicles are introduced firstly. Then the drug delivery ways of this supramolecular vesicles system are summarized, drug molecules can not only be loaded in the cavities and membranes of the host-guest supramolecular vesicles, but also can be loaded in the cavities of the host molecules. Meanwhile, the stimuli (such as pH, ions, redox potential, enzyme, temperature and competitive guests) responsiveness of this drug loaded host-guest supramolecular vesicles is summed up. Finally, the prospects are pointed out based on the current development of this system.

Contents
1 Introduction
2 Different host-guest supramolecular vesicles
2.1 Host-guest supramolecular vesicles of cyclodextrin
2.2 Host-guest supramolecular vesicles of calixarene
2.3 Host-guest supramolecular vesicles of cucurbituril
2.4 Host-guest supramolecular vesicles of pillararene
3 Drug delivery ways of the host-guest supramolecular vesicles
3.1 Drugs loaded in the cavities of the host-guest supramolecular vesicles
3.2 Drugs loaded in the membranes of the host-guest supramolecular vesicles
4 Different stimuli responsiveness of the drug loaded host-guest supramolecular vesicles
4.1 pH response
4.2 Ion response
4.3 Redox response
4.4 Enzyme response
4.5 Temperature response
4.6 Competitive guests response
5 Summary and prospects

Advances in Mechanically Enhanced Silica Aerogel Monoliths as Thermal Insulating Materials
Shao Zaidong, Zhang Ying, Cheng Xuan
2014, 26 (08): 1329-1338 | DOI: 10.7536/PC140231
Published: 15 August 2014
Abstract

As a three-dimensional nanoporous material with low density and high porosity, silica aerogel exhibits a low thermal conductivity at room temperature and becomes an ideal nanoporous super thermal insulating material. However, the poor mechanic property and fragment occurred during ambient pressure drying have greatly limited the practical applications of silica aerogel. The apparent enhancements in integrity, strength and flexibility are achieved with the new-type of silica aerogels prepared by compositing or crosslinking, which makes it possible to be applied alone in the form of monolith as thermal insulating materials. In this paper, the porous structures, basic properties and thermal insulation principles of silica aerogels are briefly introduced. The research progress of newly developed fiber reinforced composite silica aerogels, polymer crosslinked silica aerogels, and the other combined silica aerogels as monolithic thermal insulation materials are focused. Finally, the key problems in the field of silica aerogels are summarized and the future research trends are highlighted.

Contents
1 Introduction
2 Basic properties of silica aerogels
3 Principles of thermal insulation of silica aerogel
4 Silica aerogels as thermal insulating materials
5 New-type silica aerogels as thermal insulating materials
5.1 Fiber reinforced composite silica aerogels
5.2 Polymer crosslinked silica aerogels
5.3 Combined silica aerogels
6 Conclusion and outlook

Gemini Surfactants: Role and Significance of Its Spacer in Self-Assembly
Zhao Jianxi
2014, 26 (08): 1339-1351 | DOI: 10.7536/PC140229
Published: 15 August 2014
Abstract

The special and unique role of the spacer of Gemini surfactant in self-assembly is reviewed, which is considered to benefit mainly from both the spacer length and the rigid/flexible features. These two effects lead to the synergism of two alkyl tails of a Gemini molecule, the change in the charge density of its headgroups, the variation of its molecule geometry by which rich structures and morphologies of aggregates yield, etc. More detailed, the flexible spacer influences the above functions of the Gemini mainly depending on its length. Too long flexible spacer can bend toward the alkyl tails so as to meet the chemical environment around the molecule, by which the molecule self-assembly is influenced. The effect of the short rigid spacer is almost identical with that of the flexible spacer having a similar length. However, the long rigid spacer yields quite different effects from the flexible spacer owing to the two alkyl tails are inhibited to be close, which leads to the column-like molecular shape and the identical probability for the cis/trans configuration of the two alkyl tails around the spacer. These make the Geminis with long rigid spacer form network-like aggregates at low concentrations, which can be transformed into threadlike micelles or vesicles with low surface curvature with increasing the Gemini concentration or adding a few additives. Under suitable conditions, a few molecules in the aggregates can be hastened to yield trans-form, resulting in the cohesion between the aggregates through the hydrophobic interactions between the extended alkyl tails. The chemical modification for the spacer is also discussed, which is expected to promote molecular self-assembly, or give some new functions to the aggregates. The cases listed here well indicate the specialty and uniqueness of the Gemini-structure of molecule and impress us for the complicated self-assembly behavior and diversified aggregates of Gemini surfactants.

Contents
1 Introduction
2 Basic understanding for the role of spacer
2.1 Hydrophobic synergism between alkyl tails and inhibition for headgroup separation
2.2 Strong salt-effect
2.3 Adjustment for molecular geometry
3 Adaptive behavior of flexible spacer
4 Gemini surfactants with short rigid spacer
5 Gemini surfactants with long rigid spacer
5.1 Aging effect of interfacial adsorption
5.2 Column-like molecular geometry
5.3 Network-like aggregates in dilute solution
6 Cis/trans configuration of two alkyl tails brought by spacer
7 Functioning about spacer
7.1 Hydroxyl modification
7.2 Light-sensitive group modification
7.3 Part fluocarbon modification
8 Other consideration about spacer role
9 Summary

Syntheses and Applications of Hybrid Mesoporous Silica Membranes
Bian Shujuan, Wu Hongqing, Jiang Xuheng, Long Yafeng, Chen Yong
2014, 26 (08): 1352-1360 | DOI: 10.7536/PC140212
Published: 15 August 2014
Abstract

Hybrid mesoporous silica membranes, in short HMSMs, are a kind of novel membrane materials with unique structure of pores-in-pores synthesized by sol-gel, evaporation-induced self-assembly, aspiration-induced infiltration, counter diffusion self-assembly, vapor-phase synthesis and microwave-assisted synthesis methods. Such hybrid mesoporous silica membranes are composed of mesoporous silica materials inside the confined channels of porous membranes including organic porous membranes and inorganic porous membranes employed as the hard templates. In addition, various surfactants are used as the structure directing agents (SDA). Due to the different structure of HMSMs with pores-in-pores from those conventional mesoporous silica membranes and their attractively potential applications in the membrane-based adsorption, filtration and catalysis etc., those hybrid mesoporous silica membranes have attracted great attention during the past decade. This review focuses on the recent developments of this kind of novel hybrid membranes including the synthesis methods and the applications in the membrane-based nanofiltration, templated-syntheses of nanomaterials, enzyme immobilization, artificial biomembrane, sensor, reactor and drug delivery etc. Additionally, some problems found in the syntheses and the applications of such hybrid mesoporous silica membranes are analyzed and concluded in this review. Moreover, the development prospect of this kind of hybrid mesoporous silica membranes is discussed.

Contents
1 Introduction
2 Syntheses of hybrid mesoporous silica membrane
2.1 Sol-gel method
2.2 Evaporation-induced self-assembly method
2.3 Aspiration-induced infiltration method
2.4 Counter diffusion self-assembly method
2.5 Vapor-phase synthesis method
2.6 Microwave-assisted synthesis method
3 Applications of hybrid mesoporous silica membranes
3.1 Membrane-based nanofiltration
3.2 Templated-syntheses of nanomaterials
3.3 Enzyme immobilization, artificial biomembrane, sensor and drug delivery
3.4 Catalysis and membrane reactor
4 Conclusion and outlook

Non-Covalent Separation of Optically Active Single-Walled Carbon Nanotubes
Li Yuda, Wang Xunchang, Lv Renliang, Wang Feng
2014, 26 (08): 1361-1368 | DOI: 10.7536/PC140225
Published: 15 August 2014
Abstract

Single-walled carbon nanotubes (SWNTs) have been attracting extensive interest because of their novel and unique chemical and physical properties. However, the present technologies for SWNTs synthesis always produce samples with both enantiomers in equal amounts. Since the optically active properties of SWNTs are closely correlated to their helical structures, structural control of SWNTs is very important for their potential applications in photonics and photoelectronics. A wide variety of methods have been devised so far for the non-covalent separation of SWNTs according to their left-and right-handed structure. In this paper, they are classified into the following five sections according to the separation methods: ion exchange chromatography, nanotweezers selective extraction, density-gradient ultracentrifugation (DGU), conjugated polymers wrapping and small molecules adsorption. We reviewed the recent advances in this research field, including the separation mechanisms. The relationship between these methods and the results of the optical and (n,m) enhancements of the extracted SWNTs is analyzed, and it may be useful for designing the novel host molecules to obtain single structure SWNTs in view of practical applications. At last, the existing problems and the direction of development of the regarding studies are pointed out.

Contents
1 Introduction
2 Helical structures of SWNTs
3 Non-covalent methods to separate chiral SWNTs
3.1 Ion exchange chromatography
3.2 Nanotweezers selective extraction
3.3 Density-gradient ultracentrifugation
3.4 Conjugated polymers wrapping
3.5 Small molecules adsorption
4 Conclusion and outlook

Functionalization of Polyolefin Based on Polyhomologation of Ylide
Rong Lei, Ning Yingnan, Gao Jinping, Mao Guoliang, Ma Zhi
2014, 26 (08): 1369-1377 | DOI: 10.7536/PC140336
Published: 15 August 2014
Abstract

In recent years, the discovery of new synthetic methodology and the application of combined strategy based on living polymerizations have become a hot topic of current researches in the functionalization of polyolefin field. Firstly, the research on mechanism, monomers and current research status of the polyhomologation of ylide which is a new synthetic methodology of constructing skeleton of molecular chain, are briefly introduced. In addition, new research progress of the design and synthesis of functionalized polyolefin copolymer by combining polyhomologation of ylide with living anionic polymerization, atom transfer radical polymerization, reversible addition-fragmentation chain transfer polymerization and ring opening polymerization, are reviewed in detail respectively. Finally, research foreground and practical application of the design and synthesis of functionalized polyolefin copolymer based on polyhomologation of ylide are also prospected.

Contents
1 Introduction
2 Polyhomologation of ylide
2.1 Mechanism of the polyhomologation of ylide
2.2 Monomers of the polyhomologation of ylide
2.3 Current research status of the polyhomologation of ylide
3 Combining with other methodologies to functionalize polyolefin
3.1 Combining with living anionic polymerization
3.2 Combining with atom transfer radical polymerization
3.3 Combining with reversible addition-fragmentation chain transfer polymerization
3.4 Combining with ring opening polymerization
4 Conclusion and outlook

Microbial and Chemical Production of Chondroitin Sulfate
Shi Yugang, Dang Yali, Liu Yuhua, Bai Xue
2014, 26 (08): 1378-1394 | DOI: 10.7536/PC140312
Published: 15 August 2014
Abstract

Chondroitin sulfates (ChS) are a complex polysaccharide having important structural and protective functions and play important roles in many biological processes. It has been widely applied in a variety of fields, such as medicine, biotechnology, pharmacy, food, cosmetics and textiles. This mini-review focuses on the recent advances in microbial and chemical synthesis of such molecules. The productive strains, fermentation conditions, convergent strategies, use of new starting materials, and syntheses of all the ChS variant oligosaccharides are discussed. In addition, suggestions for further studies in syntheses of ChS are proposed based on current research.

Contents
1 Introduction
2 Biotechnological production of ChS and ChS-like products
2.1 Enzymatic synthesis of ChS and ChS-like products
2.2 Microbial production of ChS and ChS-like products
3 Chemical synthesis of ChS and ChS-like products
4 Conclusion and outlook

Anti-Cancer Drug Delivery System
Li Yan, Huang Wei, Huang Ping, Zhu Xinyuan, Yan Deyue
2014, 26 (08): 1395-1408 | DOI: 10.7536/PC140308
Published: 15 August 2014
Abstract

Currently, most of the reported small molecular anti-cancer drugs have some inherent drawbacks, such as poor water solubility, high drug dosage, short drug half-life in vivo and so on. After taken by oral administration or intravenous injection, these anti-cancer drugs can permeate into cells only by the approach of free diffusion. In general, they can not only kill cancer cells but also normal ones due to lacking of selectivity, and even cause secondary injury to patients. As a result, the clinical applications of these anti-cancer drugs are limited to a large extent. The anti-cancer drug delivery systems (such as micelles, nanogels and nanoparticles, etc.) constructed from the suitable carrier materials may not only prolong the circulation in blood compartments and reduce side effects to normal tissues, but also enhance the water solubility as well as improve the bioavailability of the small molecular anti-cancer drugs. Thus, more and more attentions are paid to them by researchers and pharmacy companies. Up to now, anti-cancer drug delivery systems have advanced over 60 years, and the evolution can be divided into three stages approximately. In this review, three different development stages and the recent progress of anti-cancer drug delivery systems are summarized. Besides, the future development of anti-cancer drug delivery systems is also prospected.

Contents
1 Introduction
2 Anti-cancer drug delivery system
2.1 The first generation of drug delivery system
2.2 The second generation of drug delivery system
2.3 The third generation of drug delivery system
3 Outlook

Research Advances of Polypseudorotaxanes
Sun Shu, Shi Jianbing, Dong Yuping, Hu Xiaoyu, Wang Leyong
2014, 26 (08): 1409-1426 | DOI: 10.7536/PC140331
Published: 15 August 2014
Abstract

Polypseudorotaxanes have attracted great interest in the past twenty years, due to their potential applications in the fabrication of stimuli-responsive materials, self-healing materials, molecular machines and fluorescent sensors. Depending on the location of the pseudorotaxane unit, polypseudorotaxanes can be mainly divided into three types: main-chain polypseudorotaxanes, side-chain polypseudorotaxanes, and others (such as branched and crosslinked polypseudorotaxanes). In this review, the recent advances of these three types of polypseudorotaxanes constructed by supramolecular macrocycles, such as crown ether, cyclodextrin, calixarene, cucurbituril, and pillararene are reviewed, and their future developments are also briefly prospected.

Contents
1 Introduction
2 Crown ether based polypseudorotaxanes
2.1 Crown ether based main-chain polypseudorotaxanes
2.2 Crown ether based side-chain polypseudorotaxanes
2.3 Crown ether based crosslinked polypseudorotaxanes
3 Cyclodextrin-based polypseudorotaxanes
3.1 Cyclodextrin-based main-chain polypseudorotaxanes
3.2 Cyclodextrin-based side-chain polypseudorotaxanes
3.3 Other types of cyclodextrin-based polypseudorotaxanes
4 Calixarene-based polypseudorotaxanes
5 Cucurbituril-based polypseudorotaxanes
5.1 Cucurbituril-based main-chain polypseudorotaxanes
5.2 Cucurbituril-based side-chain polypseudorotaxanes
6 Pillararene-based polypseudorotaxanes
6.1 Pillararene-based main-chain polypseudorotaxanes
6.2 Pillararene-based side-chain polypseudorotaxanes
6.3 Pillararene-based crosslinked polypseudorotaxanes
7 Conclusion and outlook

Research of Ultrasound-Mediated Gene Delivery
Du Jianwei, Mou Yun, Wang Youxiang
2014, 26 (08): 1427-1433 | DOI: 10.7536/PC140328
Published: 15 August 2014
Abstract

Ultrasound wave can reach the deep tissues without any harm to human body. Ultrasound contrast agent (microbubble), which can highly enhance the ultrasound backscatter intensity, is widely employed in ultrasonography. Through the cavitation effects of microbubbles, the energy of ultrasound wave will be easily accumulated at the targeted tissue and finally released with the collapse of the bubbles, which will further promote the internalization of gene/drug into the cells, leading to the high transfection efficiency. Due to its non-invasiveness and safety, recent ultrasound-mediated gene therapy shows great potential via the combination of the clinic-realizable ultrasound microbubble technology and gene vectors. The ultrasound-mediated gene therapy, can not only be used in disease diagnosis, but also promote the spatio-temporal controlled release of drug/gene by sonicating at the targeted tissue. Furthermore, microbubble-induced sonoporation can be used as the driving force to transfer gene vectors into cells by improving the permeability of different biofilm. These will together provide approach to visualization of gene delivery and efficient controlled gene expression. In this paper, the recent progress is reviewed in details from the following aspects: development of microbubbles, the mechanism and influence factors, and construction of ultrasound-mediated gene delivery system. Challenges and prospects of ultrasound-mediated gene delivery system are also discussed.

Contents
1 Introduction
2 Development of microbubbles
3 Mechanism and influence factors of ultrasound- mediated gene delivery
4 Construction of ultrasound-mediated gene delivery system
4.1 Co-administration system
4.2 Gene-loaded microbubbles
4.3 Gene vector-microbubble conjugation system
5 Challenges and prospects

Sources, Analytical Methods and Environmental Characteristics of Polybrominated Biphenyls
Liu Guorui, Li Li, Sun Sufang, Jiang Xiaoxu, Wang Mei, Zheng Minghui
2014, 26 (08): 1434-1444 | DOI: 10.7536/PC140335
Published: 15 August 2014
Abstract

Polybrominated biphenyls (PBBs) had been widely produced and used as commercial chemicals including additive brominated flame retardants (BFRs) from 1970 to 2000. PBBs are highly toxic, lipophilic and bioaccumulative organic compounds. Owing to their persistence and semi-volatility, PBBs could transport long distance and thus pose potential risk to global environment and human health. Commercial hexabrominated biphenyls (technical Hexa-BBs) have been listed in the Annex A covered under Stockholm Convention on Persistent Organic Pollutants in 2009 for banning the manufacture and use of technical Hexa-BBs. Thus, the sources, analytical methods and environmental occurrence of PBBs have recently attracted increasing attentions. This paper summarizes the basic physico-chemical properties and toxicity of PBBs. The amounts of technical PBBs produced as commercial chemicals including BFRs in history are also summarized. The release of PBBs during dismantling of E-waste as one of important sources is also discussed. We also suggest that further study should be carried out to investigate if there is unintentional formation and emission of PBBs during industrial thermal processes. The research progress on analytical methods, quality assurance and quality control (QA/QC) used for identification and quantification of PBBs are also reviewed and discussed. The occurrence and profiles of PBBs in various matrices from contamination sites of Michigan accident, E-waste dismantling area, and polar area are also reviewed and discussed.

Contents
1 Introduction
2 Basic physico-chemical properties and toxicity of PBBs
2.1 Basic physico-chemical properties of PBBs
2.2 Toxicity of PBBs
3 Major sources of PBBs
3.1 Manufacture, use and release of PBBs
3.2 Unintentional emissions of PBBs from industrial sources
4 Analytical methods of PBBs
4.1 Sample extraction and purification of PBBs
4.2 Instrumental analytical technique
4.3 Quality assurance and quality control
5 Occurrence of PBBs in various matrices
5.1 Contamination levels of PBBs in samples from PBBs contamination accident area
5.2 Contamination levels of PBBs in samples from E-waste dismantling area
5.3 Contamination levels of PBBs in polar area and other regions
6 Conclusion and outlook