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Progress in Chemistry 2016, No.9 Previous issue Next issue

In this issue:

Review and comments
Capsid-Inspired Multi-Component Self-Assembly of Nanocontainers: Structure, Functionalization, and Applications
Zhang Guanglu, Zhang Ting, Zhou Lipeng, Sun Qingfu
2016, 28 (9): 1289-1298 | DOI: 10.7536/PC160418
Published: 15 September 2016
Abstract
Inspired by the spontaneous self-assembly of hollow virus capsids and protein cages found in nature, a family of hollow spherical structure with general formula MnL2n can be obtained via the coordination-directed multi-component self-assembly of bent bis(pyridine) ligands and square-planar Pd2+ ions. Endo and exo-hedral functionalization of the nanocontainer complexes have been realized by introduction of functional groups into the organic ligands. Due to the nanoconcentrator effect, endo-functionalised spherical complex could be used not only for the template-synthesis of mono-dispersed polymers or nanoparticles, but also for the catalytic transformations of small substrates. Meanwhile, exo-functionalized complexes can selectively recognize a variety of substrates, such as oligonucleotides and DNA. The design principles, synthesis, characterization and functional applications of such nano-container molecules are summarized in this paper.

Contents
1 Introduction
2 Design and synthesis of the nano-containers
3 Functionalization and applications
3.1 Functional cavity
3.2 Functional surface
4 Conclusion and outlook

Lithium-Ion Battery Electrolyte Containing Fluorinated Solvent and Additive
Ma Guoqiang, Wang Li, Zhang Janjun, Chen Huichuang, He Xiangming, Ding Yuansheng
2016, 28 (9): 1299-1312 | DOI: 10.7536/PC151212
Published: 15 September 2016
Abstract
With the development of large mobile equipments (such as electric vehicles), energy storage power stations and the other portable charging devices, lithium-ion battery is gradually occupying the dominant position of the chemical power market. Electrolyte is one of the most important components of lithium-ion battery, having a significant impact on many properties of lithium-ion battery, such as the output voltage, energy density, power density, longevity, temperature range, safety performance and so on. In general, owing to the very high electronegativity and low polarizability of fluorine, fluorinated organic solvent shows very different physical properties compared to the common organic solvent. Specifically, fluorinated solvent has a low melting point, high flash point, high oxidation decomposition voltage, and good wettability with the electrode material. Therefore, fluorinated solvent has a potential application in the research and development for high voltage electrolyte, high security electrolyte, wide temperature window liquid electrolyte, and the other special functional electrolyte. Here, the recent research and applications on fluorinated solvents and additives in lithium-ion battery electrolyte are reviewed. The mechanisms for the enhancement performance of lithium-ion battery electrolyte with the use of fluorinated solvents and additives are also analyzed and discussed in detail. Simultaneously, the fabrication methods of fluorinated solvents such as fluorinated ethylene carbonate (FEC) are summarized. Finally, the research prospects and problems for fluorinated solvents and additives in lithium-ion battery electrolyte are also discussed in detail.

Contents
1 Introduction
2 High-voltage electrolyte
2.1 The solvent of high-voltage electrolyte
2.2 The additive of high-voltage electrolyte
3 High security electrolyte
3.1 The nonflammable electrolyte containing flrorinated solvent
3.2 Fluorinated flame retardant additives
4 High and low temperature electrolyte
4.1 High temperature electrolyte
4.2 Low temperature electrolyte
5 The other functional electrolytes
5.1 Fluorinated solvent and additive with special function
5.2 The application of fluorinated solvent and additive in new type battery

Application of Ionic Liquids to the Carbonylation Reactions
Song Heyuan, Kang Meirong, Jin Ronghua, Jin Fuxiang, Chen Jing
2016, 28 (9): 1313-1327 | DOI: 10.7536/PC160213
Published: 15 September 2016
Abstract
Ionic liquids have been widely applied as an alternative reaction medium as well as environmentally benign catalysts of chemical transformations due to their favorable properties of excellent solubility, strong complexing activity, good thermal and chemical stability over a wide temperature range, modifiable, low corrosion and environment-friendly. Ionic liquids also possess the advantageous characteristics of both homogenous and heterogeneous catalyst system, such as uniform catalytic active centers, easy separation and recyclability. In this review, the latest achievements in the carbonylation reactions and catalytic reaction mechanism in ionic liquids are summarized,mainly including the carbonylation of alkene, alcohol, arene, amines/amino alcohols, halogeno-arenes, and formaldehyde with CO, CO2, and dimethyl carbonate as carbonyl source. As for the type of task-specific ionic liquids, the review focuses on acidic ionic liquids, basic ionic liquids, organometallic ionic liquids, supported ionic liquids and so on. The previous progress show that there are several merits for the application of ionic liquids in the carbonylation reactions, which not only improved the catalytic activity and selectivity of reaction, but also simplified the work-up, and facilitated the separation and reuse of traditional catalyst. Furthermore, the prospective to the development and application of ionic liquids in the carbonylation reactions is also discussed.

Contents
1 Introduction
2 Application of ionic liquids in the carbonylation reactions
2.1 Carbonylation of alkenes
2.2 Carbonylation of alcohol compounds
2.3 Carbonylation of arenes
2.4 Carbonylation of N-containing compounds
2.5 Carbonylation of halogeno-arenes
2.6 Carbonylation of formaldehyde
3 Conclusion

The Structural Designs and Property Analysis of Polyamide Based Structures as Peptide Secondary Structure Mimics
Wang Zhipeng, Tian Changlin, Zheng Jishen
2016, 28 (9): 1328-1340 | DOI: 10.7536/PC160343
Published: 15 September 2016
Abstract
The peptides and proteins lay the foundation of diverse functions including structural supporting, enzymatic catalysis, protein-protein interactions etc. Specifically, secondary structures are essential elements for any possible higher structures, as rather localized motifs with limited amino acid residues involved. Nowadays, different non-natural oligomers have been developed for the peptide structural and functional mimicking, such as α-helix and turns. Protein secondary structure mimics are a group of organic compounds with theoretical importance, which can be further applied to protein-protein inhibitor study as well as drug design. This manuscript starts with the property analysis of typical protein secondary structures, followed by the introduction of current peptide secondary structure mimics. These foldamers are divided into three main groups, and the design principles as well as the structural diversity of oligo/poly-amide based peptide secondary structure mimics are emphasized. Additionally, the draft provides several visualizable nomenclature, including χ-peptides, ζ/ξ-peptides, and ζ-ξ-peptides.

Contents
1 Introduction
2 Analysis on the peptide secondary structures
2.1 α-helix
2.2 β-strain/sheet
2.3 Turns
3 Oligo/poly-amide based peptide secondary structure mimics
3.1 β-peptide & its analogs
3.2 γ-peptide & its analogs
3.3 χ-peptides
3.4 ζ/ξ-peptides
3.5 ζ-ξ-peptides
3.6 Peptoids
3.7 Other unnatural oligo/poly-amides
4 Helix mimics based on the stick structures
5 Turn mimics based on the introduction of non-natural structures
6 Conclusion

Biosensors in POCT Application
Deng Wangping, Wang Lihua, Song Shiping, Zuo Xiaolei
2016, 28 (9): 1341-1350 | DOI: 10.7536/PC160422
Published: 15 September 2016
Abstract
Point-of-care testing (POCT) is a test that performed at or near the site of patient care whenever the medical care is needed, POCT has become an indicator of in vitro diagnosis (IVD) because of its simple, rapid, low cost, portable and without being limited by the place. Biosensors possesses characteristics such as rapid, sensitive, high efficiency, portable and easy to automation and miniaturization, so they have great potential in the development of point-of-care testing technology. In recent years, with the development of the biosensor, internet technology and the rise of new and integrated technology, POCT device has obtained substantial progress. In this review, we first briefly introduced the classification of the biosensors and described the state of the art of biosensors that could be performed in POCT, and then reviewed the representative research progress of biosensors in POCT application.According to the emerging technologies, they are classified into microfluidics based biosensors for POCT,paper based biosensors for POCT, nanomaterials based biosensors for POCT, cell phone based biosensors for POCT and the integrated device for POCT. However, the successful commercialization and widespread implementation of such viable technologies remained subject to several challenges and pending issues. Finally, we discussed the current problems, the future development trend and prospects of biosensors for POCT application.

Contents
1 Introduction
2 Current situation of the biosensor in POCT application
3 Microfluidics based biosensors for POCT
3.1 Optical method based detection
3.2 Electrochemical method based detection
4 Paper-based biosensors for POCT
5 Nanomaterials based biosensors for POCT
6 Cell-phone based platforms for POCT
7 Integrated devices for POCT
8 Conclusion

Electrochemiluminescence Analysis Based on Molecular Imprinting Technique
Yang Yukun, Wang Xiaomin, Fang Guozhen, Yun Yaguang, Guo Ting, Wang Shuo
2016, 28 (9): 1351-1362 | DOI: 10.7536/PC160326
Published: 15 September 2016
Abstract
Electrochemiluminescence (ECL) analysis based on molecular imprinting technique, as a new analysis method, has made great progress in recent years. Molecular imprinted ECL analysis owns the advantages of both ECL analysis and molecular imprinting technology, namely high sensitivity, high selectivity, good controllability, easy miniaturization and simple operation, suggesting a wide range of applications in the fields of life sciences, food safety and environmental monitoring. In this review, the common ECL systems and basic ECL principles are introduced in detail, and the research advances of molecular imprinted ECL analysis are reviewed. The ECL mechanism mainly includes annihilation type ECL mechanism and co-reactant type ECL mechanism, examples based on ECL mechanism are introduced. Construction procedure, principles and performance of different types of molecular imprinted ECL analysis, including sensitivity, selectivity, detection range and stability of the established methods, are remarked extensively. The development of molecular imprinted polymers (MIPs)-based ECL analysis could be divided into three types:MIPs-ECL sensor based on solid-state light-emitting electrode, MIPs-ECL sensor based on non-solid-state light-emitting electrode and MIPs based-solid phase extraction coupled with ECL analysis. Among the three types mentioned above, the fabrication of solid-state light-emitting electrode to establish molecular imprinted ECL sensor is the most promising direction, in which the organic combination of ECL light-emitting materials and molecular imprinted material is achieved. In addition, the outlook of future development directions and trends of molecular imprinted ECL analysis are discussed.

Contents
1 Introduction
2 Common ECL system and ECL mechanism
2.1 Annihilation type ECL mechanism
2.2 Co-reactant type ECL mechanism
3 Research advances of MIPs-based ECL analysis
3.1 MIPs-ECL sensor based on solid-state light-emitting electrode
3.2 MIPs-ECL sensor based on non-solid-state Light-emitting electrode
3.3 MIPs based-solid phase extraction coupled with ECL
4 Conclusion

Abstract
How to cure serious diseases which do harm to the health of human being such as tumor and virus infection by "precision medicine" is always a difficult problem and a research hotspot in the medical field. With the launch of "precision medicine" project, contemporary drug design has reached the new era, namely, "precise" targeted drug molecular design should be one of the key pillars of precision medicine. The structure-based rational drug design and the targeted drug delivery system are important aspects of the contemporary "precision drug design". Precise noncovalent interactions between ligands and proteins lay the theoretical foundations for structure-based rational drug design. The development of new synthetic methodologies provides a powerful tool for drug precise synthesis, focusing both on the identification of intrinsically novel reactions, as well as the discovery of improved methods for carrying out existing transformations. Chemical biology has a significant role to play in the discovery and validation of new therapeutic targets. Over the past few years, many sensitive and accurate probes based on small organic molecules have demonstrated considerable promise in "precision drug design" as they provide a chemoproteomic means to confirm and quantify target engagement and selectivity of small molecule drug candidates. In the viewpoint of medicinal chemistry, this review highlights recent advances made in contemporary molecular targeted drug design in the context of "precision medicine".

Contents
1 Introduction
2 Structure-based "precision drug design"
2.1 Target-specific drug design
2.2 Isoform-selective drug design
2.3 Drug design strategies to overcome drug resistance
3 Kinetic target-guided dynamic combina-toril chemistry
4 Precise noncovalent interactions between ligands and proteins
5 The development of new synthetic methodologies:late stage functionalization of drug-like molecules
6 Targeted drug precise delivery systems
6.1 Biomarker-based drug precise delivery systems
6.2 Microenvironment-based drug precise delivery systems
6.3 Drug precise delivery systems based on organ-specific enzymes
6.4 Organelle-targeted drug precise delivery systems:mitochondria
6.5 Photodynamic therapy
7 Probes:chemical biology tools for "precision drug design"
7.1 Peptides-based probes
7.2 H2O2 probes
7.3 H2S probes
7.4 Thiol-mediated cleavable fluorescent probles
7.5 Fluoride probes
7.6 Cysteamine two-photon fluorescence probes
7.7 Photo-triggered probes
7.8 MAO-B-specific probes
7.9 Biotin-based probes and diagnostic reagents
8 Conclusions and outlook

Light-Controlled Nanocarriers for Drug Release
Gong Zhaocui, Yin Chao, Zhao Hui, Lu Xiaomei, Fan Quli, Huang Wei
2016, 28 (9): 1387-1396 | DOI: 10.7536/PC160211
Published: 15 September 2016
Abstract
The study of light-responsive nanocarriers is becoming one of the hottest topics in biomedical field due to their precise control of drug release for cancer therapy in spatiotemporal level. This contribution systematically reviewed three mechanisms for controlled drug release of photosensitive nanocarriers, including (1) photoisomerization caused morphological transformation of nanocarriers, (2) photoreaction caused degradation of nanocarriers, and (3) photothermal caused disruption of nanocarriers. This review briefly introduced the three mechanisms and their corresponding photosensitive materials. In addition, the recent research developments and problems remained of photosensitive materials for drug delivery and controlled release were pointed out. This review also provided useful references for photosensitive nanocarriers in biological applications and the research prospects were further proposed.

Contents
1 Introduction
2 Light-responsive nanocarriers for drug release
2.1 Photoisomerization-induced morphological trans-formation
2.2 Photoreaction-induced degradation
2.3 Photothermal-induced disruption
3 Conclusion

Enhancement of Intra-Tumor Penetration and Distribution of Nano-Drug Carriers
Han Donglin, Qi Hongzhao, Zhao Jin, Long Lixia, Ren Yu, Yuan Xubo
2016, 28 (9): 1397-1405 | DOI: 10.7536/PC160423
Published: 15 September 2016
Abstract
The tumor therapeutics effect of chemotherapeutant, proteins and genes could be improved when they are loaded in nano-drug carriers. But in some cases the therapeutics effects are modest due to the poor penetration and distribution of nano-carriers in the heterogeneous tumor tissue. During the recent years, increasing efforts have been dedicated to improve the intra-tumor penetration by controlling the size, surface zeta potential, targeting agents, and shape of nano-drug carriers. This paper reviews the progress in enhancement of intra-tumor penetration and distribution of nano-drug carriers through the modification of their components, structures and physicochemical properties. The challenges of nano-drug carriers in tumor treatment are raised and the possible solutions are proposed.

Contents
1 Introduction
2 Inorganic nano-drug carriers
2.1 Meso-porous silicon nano-drug carriers
2.2 Gold nano-drug carriers
3 Organic nano-drug carriers
3.1 Micelles
3.2 Dendrimers
3.3 Liposomes
3.4 Polymer nanocapsule
4 Conclusion

Application of Amide Bioisosteres in the Optimization of Lead Compounds
Mei Yicheng, Yang Baowei
2016, 28 (9): 1406-1416 | DOI: 10.7536/PC160414
Published: 15 September 2016
Abstract
Bioisosteres are a class of compounds or groups,these compounds with similar molecular shapes or volume, similar electronic distribution, and similar physical properties. Bioisosteres play a role in the same related biochemical system as agonist or antagonist, which possessed in related biological activities. The amide structure can be an important part of drugs and a constituent of a pharmacophore. However, the presence of this moiety can also be responsible for some significant drawbacks about drug molecular, including metabolic instability, toxicity, as well as limited passive diffusion across biological membranes. To avoid some of these shortcomings while retaining the desired attributes of the amide moiety, bioisosteric replacement of the amide moiety in lead compounds is an effective method. Through the amide bioisosteric replacements, other aims would be goal such as increasing the target potency and selectivity, developing new structures to expand or break through the patents and decreasing the difficulty of the synthesis of the compounds. This review focuses on the application of the replacement between amide and amide bioisosteres in the optimization of lead compounds in recent five years. We wish our review would offer a new thinking in the design and optimization of the compounds in the research and development of the new drugs.

Contents
1 Introduction
2 Amide bioisosteric replacement in lead compounds optimization
2.1 Increasing the target potency and selectivity
2.2 Improving the drug-likeness of the lead compounds
2.3 Developing new structures to expand or break through the patents
2.4 Decreasing the difficulty of the synthesis of the compounds
3 Conclusion

Flotation Mechanism of Soluble Salts with High Ionic Strength
Li Enze, Du Zhiping, Wang Bo, Cheng Huaigang, Cheng Fangqin
2016, 28 (9): 1417-1425 | DOI: 10.7536/PC160413
Published: 15 September 2016
Abstract
Froth flotation, based on chemical phenomena occurring at the interfaces including solid/water and air/water, becomes an efficient means of separating heterogeneous mixtures of finely subdivided solids with bubbles floating and is widely used within the primary mineral and chemical industries. In the process of froth flotation, collectors are always used to adjust the hydrophobicity of mineral surface through selective adsorption. Nowadays, most of soluble salts, especially potash, are produced through froth flotation. Although the flotation systems of soluble salts are complicated in the actual production, they are mainly comprised of salt crystal, collector, bubbles and saturated salt solution with high ionic strength. Actually, the soluble salt flotation is the results of the interaction among these four components. Thus, lots of researches about flotation mechanism of soluble salts focus on these interactions. This paper summarizes the recent progress in the flotation mechanism of soluble salts with high ionic strength. The solution chemistry of soluble salts, colloidal properties of collector in saturated salt solution, adsorption behaviors of collectors on surface of salt crystal, interfacial properties of salt crystal/saturated salt solution and the role of bubbles in the froth flotation are reviewed emphatically. Finally, the trend for future research on flotation mechanism of soluble salts is also prospected.

Contents
1 Introduction
2 Solution chemistry of soluble salts
2.1 Structure of hydrated ions
2.2 Viscosity
3 Properties of collector in solution with high ionic strength
3.1 Krafft point
3.2 Surface activity and aggregation behaviors
4 Selective adsorption of collector
5 Interfacial properties of mineral crystal/saturated salt solution in high ionic strength environment
5.1 Surface charge of crystal surface
5.2 Wetting characteristics of crystal surface
6 The role of bubbles in flotation system with high ionic strength
7 Conclusion

Application of Glycerol in Microbial Biosynthesis and Biocatalysis
Sun Jia, Wang Pu, Zhang Pengpeng, Huang Jin
2016, 28 (9): 1426-1434 | DOI: 10.7536/PC160224
Published: 15 September 2016
Abstract
Renewable biodiesel is a widely accepted energy for its alternative use of petroleum diesel. Glycerol is an inevitable byproduct of biodiesel production. With the vigorous development of biodiesel industry, there is an obvious oversupply of glycerol. This over-generated green resource urgently needs further exploration for the sustainable new applications, which is critical to the development of biodiesel industry and is in accordance with the demands of green chemistry. In recent years, glycerol has become one of the most important raw material for the production of high value-added chemicals. Moreover, based on its special physicochemical properties, as well as degradability and good biocompatibility, glycerol plays an increasingly important role in biocatalysis and can be used as a new green solvent. This paper mainly reviews the progress on glycerol for industrial biotechnology application in microbial fermentation, biosynthesis and green solvent. Some practical application problems involved in glycerol biotransformation, such as feedstock quality and microbial utilization efficiency, are also discussed in detail. The future application development of glycerol in biocatalysis is also prospected.

Contents
1 Introduction
2 Glycerol uptake and intracellular metabolism
3 Glycerol for microbial growth
4 Glycerol-based raw material for biotransformation
4.1 Glycerol to value-added chemicals
4.2 Solution to the inhibition of high glycerol concentration
4.3 Strategy for biotransformation efficiency
4.4 Bioconversion of crude glycerol
5 Application of glycerol in biocatalysis
5.1 Biocompatibility of glycerol
5.2 Application in asymmetric bioreduction
5.3 Glycerol as green solvent
5.4 Glycerol to deep eutectic solvents (DESs)
6 Conclusion

Research and Prospect of Lithium-Sulfur Battery System
Deng Nanping, Ma Xiaomin, Ruan Yanli, Wang Xiaoqing, Kang Weimin, Cheng Bowen
2016, 28 (9): 1435-1454 | DOI: 10.7536/PC160203
Published: 15 September 2016
Abstract
The lithium-sulfur batteries are rather latest and high-performance storage batteries due to their rather high theoretical specific capacity(1675 mAh ·g-1) and energy density(2600 Wh ·kg-1). This study provides the entire and latest fundamental studies in lithium-sulfur batteries. The cathodes, binders, separators, electrolytes, anodes, some novel cell configurations and structure design of battery are introduced in details. For improving the conductivity of cathode material and suppressing the "shuttle effect", elemental sulfur can be combined with other materials as the cathodes of batteries through various ways. These can enhance the batteries performances. In terms of binders and electrolyte, some appropriate and functional binders and electrolyte are chosen which are compatible with electrode material. At the same time, in terms of separators, researchers mainly pay attention to the type choice or the separators composition and modified treatment. With regard to anodes, several methods have been considered for improving the batteries stability and safety based on metallic lithium such as coating thin dense protective layers or pre-lithiation treatment. Some novel cell configurations such as the application of interlayer, new collectors and new type structures of lithium-sulfur batteries are also vital aspects to greatly improve cell performances. At last, the future research directions associated with lithium-sulfur batteries have also been indicated.

Contents
1 Introduction
2 The principle and characterization of lithium-sulfur batteries
3 Cathode materials of lithium-sulfur batteries
3.1 Sulfur/carbon composites
3.2 Sulfur/conductive polymer composites
3.3 Sulfur/metal and its oxide composites
3.4 Sulfur/multiple sulfur-based compound
4 Binder of lithium-sulfur batteries
5 Electrolytes of lithium-sulfur batteries
5.1 Liquid electrolytes
5.2 Solid state electrolytes
5.3 Gel polymer electrolytes
5.4 Ionic liquid electrolytes
6 Separators of lithium-sulfur batteries
7 Anodes of lithium-sulfur batteries
8 Electrode structure design and modification of lithium-sulfur batteries
8.1 Interlayers and new type of collectors
8.2 New type structures of lithium-sulfur batteries
9 Summary and future directions