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Progress in Chemistry 2015, No.1 Previous issue Next issue

In this issue:

Review
Electrochemical Analysis of Tumor Marker Proteins
Cao Ya, Zhu Xiaoli, Zhao Jing, Li Hao, Li Genxi
2015, 27 (1): 1-10 | DOI: 10.7536/PC140737
Published: 15 January 2015
Abstract

With the development of monoclonal antibody and immunological detection technology, the detection of tumor marker proteins becomes the most important method for early screening and diagnosis of cancer. On the other hand, with the development of molecular recognition and surface assembly techniques, electrochemical analysis displays some unique advantages in biological analysis, such as simple operation, easy-to-miniaturize nature, low cost, sensitivity, and so on. Especially in recent years, various antibodies, aptamers and peptides that can specifically bind with tumor marker proteins have been screened out. Various nanomaterials and nanotechnologies have been explored in the application to electrochemical analysis. Many novel techniques for molecule labeling, surface self-assembly, and signal amplification have been proposed. So, electrochemical analysis obtains unprecedented opportunities in the quantitative detection of tumor marker proteins, and more and more achievements are reported. In this review, by commenting on some typical work conducted in the lab of the authors, we summarize the recent research progress on the electrochemical analysis of tumor marker proteins and make an outlook on the trends of the related research fields in the future.

Contents
1 Introduction
2 Electrochemical immunoassay based on antibody
3 Electrochemical analysis based on aptamer
4 Electrochemical analysis based on polypeptide
5 Electrochemical analysis based on other recognition elements
6 Conclusion and outlook

Glucose-Responsive Synthetic Closed-Loop Insulin Delivery Systems
Zhang Yuqi, Yu Jicheng, Shen Qundong, Gu Zhen
2015, 27 (1): 11-26 | DOI: 10.7536/PC140942
Published: 15 January 2015
Abstract

Diabetes mellitus has become a major social health problem affecting all of the world. The key to efficiently treating type Ⅰ and advanced type Ⅱ diabetes is to inject insulin with a precise dose according to the blood glucose levels (BGLs). Thus, smart insulin delivery systems responding to glucose concentration of the surroundings have attracted extensive interest these years. This review mainly focuses on chemically controlled closed-loop insulin delivery able to mimic pancreas activity. One of the greatest advantages of these systems is to regulate insulin dosage and delivery by BGLs on an automated and continuous basis. So called this feedback-controlled insulin delivery system ‘artificial pancreas’. Strategies to achieve this ‘artificial pancreas’ are through glucose-responsive insulin delivery systems, typically based on the glucose-sensing elements of glucose oxidase (GOx), glucose binding protein (GBP), or phenylboronic acid (PBA). Main mechanisms and most recent studies are discussed in this review.

Contents
1 Introduction
2 Glucose oxidase based system
2.1 Swelling/shrinking mechanisms
2.2 Disassembling/degradation mechanisms
3 Glucose binding proteins based system
4 Phenylboronic acid moieties based system
4.1 Swelling/shrinking mechanisms
4.2 Glucose replacement mechanisms
4.3 Disassembling/degradation mechanisms
4.4 Other mechanisms
5 Conclusion and outlook

Synthesis of Ionic Phosphines and Corresponding Ionic Transition Metal Complexes and Their Applications in Homogeneous Catalysis
Wang Xue, Tan Chen, Li Yongqi, Zhang Heng, Liu Ye
2015, 27 (1): 27-37 | DOI: 10.7536/PC140813
Published: 15 January 2015
Abstract

Compared to the traditional neutral phosphine-ligated transition metal complexes (PTMCs), the ionic phosphine-ligated ones as the ionic salts are composed with the ion-pairs with unusual electronic effect and varied structural configurations. In these ionic PTMCs, not only the coordinating interaction but also the strong electron-withdrawing effect of the positive-charge and the electrostatic interaction between cations and anion are involved which correspond to the unique catalytic performance. In recent decade, the study on the ionic PTMCs has been concerned as a hot topic in coordination chemistry and homogeneous catalysis. In addition, when the ionic PTMCs are used as the catalysts in combination with the room temperature ionic liquids (RTILs, as the solvents) for catalytic reactions, the advantages such as the available recovery and recyclability of the catalysts, and the avoided catalyst leaching are evidently observed, which endows theses ionic transition metal complexes great potential applications in green chemistry. In this review, the syntheses of the ionic phosphines and the corresponding ionic PTMC (M=Rh, Pd, Ru, Pt, Au, Ni, Cu) and their applications for homogeneous catalysis, which have been developed in the past ten years, are summarized.

Contents
1 Introduction
2 Syntheses of imidazolium-phosphorous neighbored ionic phosphines
3 Syntheses of ionic transition metal complexes and their applications in homogeneous catalysis
3.1 Ionic Rh-complexes
3.2 Ionic Pd-complexes
3.3 Ionic Ru-complexes
3.4 Ionic Pt-complexes
3.5 Ionic Au-complexes
3.6 Ionic Ni-complexes
3.7 Ionic Cu-complexes
4 Conclusion and outlook

Graphitic Carbon Nitride Compound Photocatalyst
Qi Yuehong, Liu Li, Liang Yinghua, Hu Jinshan, Cui Wenquan
2015, 27 (1): 38-46 | DOI: 10.7536/PC140823
Published: 15 January 2015
Abstract

Utilizing photocatalysis technology to convert solar energy into chemical energy or direct degradation and mineralization of organic pollutants is a long-term solution to solve the problem of energy shortage and environmental pollution. Polymer type graphite carbon nitride (g-C3N4) possesses a similar structure with graphene and has been attracted widespread attention as a novel photocatalyst for the light catalytic conversion of solar energy due to its excellent chemical stability and unique electronic band structure. Moreover, the g-C3N4 can be used as a low-cost, stable and metal-free visible-light-driven photocatalyst in the degradation of pollutants, water splitting for hydrogen and oxygen evolution and organic synthesis, as the precursors of g-C3N4 are inexpensive and the synthesis is comparatively simple. Many efforts are still needed to overcome the limitation of fast recombination for pure g-C3N4 in practical application. In this review, recent research progress for g-C3N4 has been reviewed, including metal/non-mental doping, semiconductor coupling, depositing with metals. In addition, the catalytic mechanism for the g-C3N4-based composite is also reviewed.

Contents
1 Introduction
2 g-C3N4-metal composites photocatalyst
3 g-C3N4-oxide composites photocatalyst
4 g-C3N4-sulfide composites photocatalyst
5 g-C3N4-bismuth compounds composites photocatalyst
6 g-C3N4-carbon composites photocatalyst
7 Other g-C3N4 composites photocatalyst
8 Conclusion

Polyolefin Covalently Grafted Nanomaterials and Polyolefin Nanocomposites Derived Thereof
Zhang Yongjie, Li Huayi, Dong Jin-Yong, Hu Youliang
2015, 27 (1): 47-58 | DOI: 10.7536/PC140908
Published: 15 January 2015
Abstract

Over the past few decades, much effort has been devoted to the generation of polyolefin nanocomposites, which offers substantial improvements to polyolefin properties with minimal nanofiller mass (0.1 wt%~5 wt%). Nanomaterials covalently grafted with polyolefin show great potential in developing high performance polyolefin nanocomposites. Grafted polyolefin chains generally provide high compatibility and good interfacial interactions between nanomaterials and polyolefin matrix, and thus promote homogeneous dispersion of nanomaterials into polyolefin matrix and enhance mechanical, thermal (and other) properties of polyolefin nanocomposites. Three strategies employed to covalently graft polyolefin to nanomaterials include: graft-onto, graft-from and graft-through. The high availability and reactivity of functionalized polyolefin, together with the difficulties encountered in the latter two approaches, renders “grafting-onto” approach as the mainstream of surface grafting polyolefin to nanomaterials. Both chain end functionalized polyolefin and side group functionalized polyolefin (mainly maleic-anhydride-grafted polyolefin and its derivatives) have been extensively applied in surface grafting polyolefin to nanomaterials via “grafting-onto” approach while reports on “graft-from” and “graft-through” approaches are limited. Here we review recent progress on polyolefin covalently grafted nanomaterials (silica, zero dimensional; carbon nanotube, one dimensional; graphene (oxide), two dimensional) with a focus on the properties of polyolefin nanocomposites derived thereof.

Contents
1 Introduction
2 Graft-onto approach
2.1 Chain end functionalized polyolefin
2.2 Side group functionalized polyolefin
3 Graft-from approach
4 Graft-through approach
5 Conclusion and outlook

Synthesis, Structure and Properties of Chiral Polyimides
Kang Chuanqing, Yan Jijun, Gao Lianxun
2015, 27 (1): 59-69 | DOI: 10.7536/PC140933
Published: 15 January 2015
Abstract

As an important research field of chiral polymers, chiral polyimides have attracted much attention from polymer community for their potential applications in molecular recognition, enantioselective separation, and asymmetric catalysis. This paper reviews the advance on chiral polyimides in past 20 years. Optically active polyimides are divided into three types according to the position and type of the chiral groups, which are the chirality on side chain, the central chirality on main chain, and the axial chirality on main chain. Each type of chiral polyimides is summarized in details with representative structure, synthesis, properties, the formation of secondary structure, and applications related to the chiro-optical activity of the polymers. Chiral polyimides prepared by post-derivation on the side chains of the achiral backbones supplied chiral alignment surfaces to induce the alignment of liquid crystals in forms with enantiomeric excess or with specific directions. Chiral polyimides with chiral groups in main chains are prepared from chiral dianhydrides or chiral diamines that are usually derived from amino acids, trans-1,2-cyclohexanediamine, spirocyclic compounds, and binaphthyl derivatives. Studies have shown that both central chiral monomers and axial chiral monomers induced the formation of secondary structure by the chiral polyimides. Optical rotation and circular dichroism (CD) are still the few tools for the investigations to the chiral secondary structure of chiral polyimides. At the end of the review, we present the challenges and the future directions of the developments on chiral polyimides. Despite quick developments in recent years, preparations, structures, and applications of chiral polyimides, as well as scrutiny on the chiral secondary structure with rationale models and methodologies, are worthy of paying much attention.

Contents
1 Introduction
2 Polyimides with chiral groups in side chains
3 Polyimides with central chirality in main chain
3.1 Chiral polyimides from amino acids
3.2 Chiral polyimides from trans-1, 2-cyclohexanediamine
3.3 Chiral polyimides from chiral dianhydride
4 Polyimides with axial chirality in main chain
4.1 Chiral polyimides from binaphthyl compounds
4.2 Chiral polyimides from spirobifluorene
5 Conclusion and outlook

Application of the Heterogeneous Cyclodextrins in Aqueous Phase Organic Synthesis
Shen Haimin, Wu Hongke, Shi Hongxin, Ji Hongbing, Yu Wubin
2015, 27 (1): 70-78 | DOI: 10.7536/PC140818
Published: 15 January 2015
Abstract

The applications of the heterogeneous cyclodextrins in aqueous phase organic synthesis are reviewed in detail, including the applications in oxidation, reduction, substitution reaction, addition reaction and photocatalytic reaction. At the same time, the strategies to construct heterogeneous cyclodextrins in the catalysis or promotion of the aqueous phase organic synthesis are stated comprehensively, two strategies being the formation of water-insoluble cross-linking polymer and the grafting cyclodextrins to water-insoluble supporter. It is pointed out that the application of the heterogeneous cyclodextrins in aqueous phase organic synthesis is limited in the simple phase-transfer catalysis and there is fewer relevant literature, just in its infancy stage. The construction of artificial enzyme based on the heterogeneous cyclodextrins would be the development trend and inevitable affiliation in the construction of artificial enzyme based on cyclodextrins, possessing the advantage of the heterogeneous catalyst, meanwhile retaining the excellent function of the cyclodextrin unit in the construction of supramolecular artificial enzyme.

Contents
1 Introduction
2 Oxidation Reaction
3 Reduction Reaction
4 Substitution Reaction
5 Addition Reaction
6 Photocatalytic Reaction
7 Conclusion and outlook

Cyclodextrin-Based Smart Stimuli-Responsive Drug Carriers
Liao Rongqiang, Liu Manshuo, Liao Xiali, Yang Bo
2015, 27 (1): 79-90 | DOI: 10.7536/PC140829
Published: 15 January 2015
Abstract

Smart stimuli-responsive drug carriers (STRDCs) are a hot topic in current chemical and pharmaceutical research, owing to their merits of controlled release of drugs relying on unique stimuli-responsive mechanisms. Well-designed STRDCs could efficiently improve drug bioavailability and reduce side effects in vivo, thus they are of great potential in future clinical treatments. Cyclodextrin (CD)-based drug carriers, which have the ability to control drug delivery in temporal, spatial and dosage in a more precise fashion, have made tremendous progress in recent years. STRDCs could be constructed based on CDs ascribing to their virtues of readily availability, low toxicity, self-assembly and functional flexibility. More and more materials of good biocompatibility are employed to fabricate STRDCs in combination with CDs to furnish unique characteristics of self-assembly, molecular recognition and dynamical reversibility. These STRDCs could administrate drug controlled release upon the regulation of their physico-chemical properties in response to external stimuli, which usually fall into two categories: endogenous (pH, redox agents, enzyme concentration, etc.) and exogenous (temperature, light, magnetic force, ultrasound, voltage stimulation, etc.) ones. In this review, the recent advances on the cyclodextrin-based STRDCs are summarized, which are classified referring to the variations of stimulating factor. The features, mechanism of action and potent applications of STRDCs are discussed. In addition, some personal perspectives on this field are also presented.

Contents
1 Introduction
2 Endogenous stimuli-responsive drug delivery
2.1 pH sensitive systems
2.2 Redox sensitive systems
2.3 Enzyme sensitive systems
3 Exogenous stimuli-responsive drug delivery
3.1 Thermo sensitive systems
3.2 Light sensitive systems
3.3 Magnetically responsive systems
3.4 Ultrasound responsive systems
3.5 Electro responsive systems
4 Conclusion

Surface-Enhanced Raman Scattering Tags Used in Cell Recognition, Imaging, Diagnosis and Treatment
Song Chunyuan, Chen Wenqiang, Yang Yanjun, Yang Boyue, Su Shao, Wang Lianhui
2015, 27 (1): 91-102 | DOI: 10.7536/PC140738
Published: 15 January 2015
Abstract

Surface-enhanced Raman scattering (SERS) refers to an abnormal surface optical phenomenon that Raman spectra of the analyte adsorbed on metal nanostructures can be significantly enhanced under laser irradiation. In recent years, SERS has been widely used in the substance detection and biological sensing, which has achieved significant development and shown great potential applications in the biomedical field. In this paper, the preparation principle and the latest development of SERS tags used in cell detection are introduced, and their recent applications in cell recognition, imaging, diagnosis and treatment are reviewed, as well as the detection strategies and issues related to SERS tag-based cell detection are discussed.

Contents
1 Introduction
2 SERS tags
2.1 Noble metal nanoparticles
2.2 Raman reporter molecules
2.3 Surface coating for protection
2.4 Biofunction with biomolecules
3 Application of SERS tags in cell
3.1 Cell recognition
3.2 Cell imaging
3.3 Cell pH sensing
3.4 Cancer diagnosis and treatment
4 Conclusions and outlooks

The Recent Development in Reverse Gene Transfection
Zhang Pengfei, Hu Xiufeng, Cheng Lu, Wang Wei, Liu Wenguang
2015, 27 (1): 103-112 | DOI: 10.7536/PC140930
Published: 15 January 2015
Abstract

With the in-depth study of gene therapy, the gene transfection techniques have achieved rapid development. Since it was proposed in 1997, reverse transfection concept has also aroused considerable attention. Reverse gene transfection is also known as surface-mediated transfection or matrix-mediated transfection, or solid-phase transfection. In a typical procedure of reverse transfection, DNA (or RNA) is firstly anchored to the substrate; cells are transplanted on the substrate surface in the next step; the adsorbed DNA (or RNA) is internalized into post-attached cells to realize the gene transfection. Compared with conventional gene transfection, the reverse method is imparted with several advantages including more stable complexation of vector/DNA (or RNA), more effective contact between the transfection reagent and cells, which is favourable for achieving higher transfection efficiency and lower cytotoxicity, and well-maintained transfection performance in the presence of serum. The recent research progress of reverse gene transfection and its applications are focused on in this review.

Contents
1 Introduction 2 Approaches to reverse gene transfection
2.1 Nucleic acid (and vector) directly anchored to the substrate surface
2.2 Electrostatic adsorption
2.3 Layer-by-layer
2.4 Hydrogen bond
2.5 Specific interaction
2.6 Covalent bond
3 Applications of reverse gene transfection
3.1 Tissue engineering
3.2 Gene screening
3.3 Primary cells
3.4 Non-adherent cells
4 Conclusion and perspective

Researches on Mixing of Granular Materials with Discrete Element Method
Qi Huabiao, Zhou Guangzheng, Yu Fuhai, Ge Wei, Li Jinghai
2015, 27 (1): 113-124 | DOI: 10.7536/PC140502
Published: 15 January 2015
Abstract

The mixing of granular materials is an important unit operation in many industries. Due to the complex behaviors of granular flows, general laws and fundamental mechanisms of granular flows in industrial mixers are not completely understood yet. As a detailed numerical approach, the discrete element method (DEM) describes the forces and motions of granular materials at the particle scale, and thus has notable advantages over experimental approaches in the research of mixing mechanisms. With the rapid developments of its models and the computational technologies, this method becomes more and more popular in the simulations of various mixing processes. The effects of particle properties, mixer types, and operating parameters on mixing rate and mixing mechanisms could be investigated comprehensively through DEM, which would be quite valuable for the design and optimization of mixers as well as their optimal operations. Moreover, the high computational cost of industrial-scale simulations could be greatly alleviated by the fast developments of computer hardware, such as the advent of graphics processing unit (GPU). This review summarizes the recent progresses of DEM simulations on mixing, with emphasis on the treatments for non-cohesive particles in different kinds of mixers (rotary and fixed), cohesive particles (fine and wet), non-spherical particles (direct description of shape and multi-sphere method), and large-scale implementations. Finally, future development of the DEM method in mixing simulations is prospected.

Contents
1 Introduction
2 Non-cohesive particles
3 Cohesive particles
3.1 Fine particles
3.2 Wet particles
4 Non-spherical particles
4.1 Direct description of shape
4.2 Multi-sphere method
5 Large-scale implementations
6 Conclusions and outlook

Materials for Boron Adsorption
Zhang Xi, Ren Qilong, Yang Yiwen, Xing Huabin, Su Baogen, Bao Zongbi
2015, 27 (1): 125-134 | DOI: 10.7536/PC140819
Published: 15 January 2015
Abstract

Boric acid, as an important boron compound, has been widely used in industrial production and cutting-edge technology. Massive wastewater containing boron were discharged during the industrial process. Adsorption technique is an efficient method for removal or recovery of boron from aqueous solutions as it has advantages of high boron recovery, renewable adsorbents and easy operation. The key to the adsorption process is the the selection of adsorbents with high adsorption capacity, acceptable mechanical strength and regeneration capability. In this review, we mainly review different kinds of boron-selective adsorbents reported in recent years and their adsorption performances. Boron adsorbents are catalogued by their functional groups. Among the reported adsorbents, the most widely used N-methyl-D-glucamine (NMDG) functionalized adsorbents are extensively demonstrated, and the adsorbents with structure of diols binding phenolic moiety are discussed. Moreover, other organic-inorganic hybrid adsorbents are introduced. This review may be helpful to the design of novel high-performance adsorbents for boron recovery or removal from aqueous solutions such as from salt lake brine and desalinize seawater.

Contents
1 Introduction
2 NMDG functionalized adsorbents
2.1 NMDG functionalized organic resins
2.2 NMDG functionalized organic-inorganic hybrid materials
3 Other active diols functionalized adsorbents
3.1 Polymeric adsorbents
3.2 Phenolic adsorbents
4 Inorganic adsorbents
4.1 Magnesium hydroxide
4.2 Hydroxide of aluminum, iron, calcium
5 Natural adsorbents
6 Conclusion and outlook