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Progress in Chemistry 2016, No.11 Previous issue Next issue

In this issue:

Review and comments
Micro/Nano Structure Regulation of Donor/Acceptor Interface for High-Performance Organic Solar Cells
Xie Xiang, Lv Wenzhen, Chen Runfeng, Huang Wei
2016, 28 (11): 1591-1600 | DOI: 10.7536/PC160630
Published: 15 November 2016
Abstract
With apparent advantages of low cost, low weight, high flexibility, high efficiency, and high processability in large size device manufacture, organic solar cells (OSCs) have aroused a great deal of attention in current studies of organic electronics all over the world. Especially, the interface structure investigations of acceptor and donor materials in the active layer of OSCs are of particular attraction due to the great influence of micro/nano structures on the photovoltaic performance. The micro/nano structured donor/acceptor interface leads to the enlarged interface area, the reduced distance between acceptor and donor, and the enhanced sunlight absorption, which are favorable to increase the molecular excitation, promote the efficient charge separation and effective exciton dissociation, produce the continuous paths for efficient charge transport, and finally improve the power conversion efficiency (PCE) in OSC applications. In this review, we summarize the recent development of micro/nano interface structured organic solar cells made by various methods in controlling the structures of donor/acceptor interface through nanoimprint lithography, self-assembly technology, solvent evaporation and template methods. The basic principles of these fabrication techniques in producing various micro/nano interface structures, including nano-textured interface, nano-gratings, nanorods array, nanoparticle mediated layer, rough interface and some special patterns, are discussed in detail with particular attention on the effects of the resulted nanostructures on the photovoltaic performance. Further, the current difficulties and future research directions of the micro/nano-structured OSCs are also discussed to give an outlook of the prospect trends and application potentials in modulating photovoltaic devices for high PCEs.

Contents
1 Introduction
2 Effects of micro/nano structures on photovoltaic properties
3 Methods to construct micro/nano interface structures
3.1 Nanoimprint lithography
3.2 Self-assembly technology
3.3 Solvent evaporation
3.4 Template methods
4 Applications of micro/nano structures on solar cells
4.1 Nano-textured interface
4.2 Nano gratings structure
4.3 Nanorods arrays
4.4 Nanoparticles
4.5 Rough interface
4.6 Special patterns
5 Conclusions and perspectives

Research Advances of Boron Clusters, Borane and Metal-Doped Boron Compounds
Shen Yanfang, Xu Chang, Huang Min, Wang Haiyan, Cheng Longjiu
2016, 28 (11): 1601-1614 | DOI: 10.7536/PC160533
Published: 15 November 2016
Abstract
Boron atom has received much attention from scientists owing to its unique characters, such as short covalent radius, electron deficiency, large coordination number, sp2 hybridization of valence electrons and three-center bonds. Due to the research of the electronic structure, stability, aromaticity and bonding nature, boron clusters have become a sparkling rising star on the horizon of chemistry. Meanwhile, boron compounds have a vast applications in optics, energy and industrial gas storage because of their rich features. This paper systematicly reviewes the recent research progresses of pure-boron clusters, borane and metal-doped boron clusters. The pure-boron clusters and borane are generalized from neutral, anionic and cationic three types. The metal-doped boron clusters mainly include metal-doped all-boron clusters and borane, transition-metal sandwich-type complexes as well as metal-centered boron molecular wheels.

Contents
1 Introduction
2 Pure-boron clusters
2.1 Neutral boron clusters
2.2 Anionic boron clusters
2.3 Cationic boron clusters
3 Borane clusters
3.1 Anionic borane clusters
3.2 Neutral borane clusters
3.3 Cationic borane clusters
4 Metal-doped boron clusters
4.1 Metal-doped all-boron clusters
4.2 Metal-doped borane compounds
4.3 Transition-metal sandwich-type complexes
4.4 Metal-centered boron molecular wheels
5 Conclusion

Plasmon-Enhanced Upconversion Fluorescence and Its Application
Zhao Bing, Qi Ning, Zhang Keqin
2016, 28 (11): 1615-1625 | DOI: 10.7536/PC160547
Published: 15 November 2016
Abstract
Lanthanide-doped upconversion nanoparticles (UCNPs) are capable of emitting visible light under near-infrared light excitation through a two-photon or multi-photon mechanism. Compared to other fluorescent materials such as organic dyes and quantum dots, UCNPs own superior physicochemical features such as chemical stability, high photostability, long-lived luminescence, large anti-Stokes shifts, narrow emission bands and deep penetration, which show potential applications in bioimaging, sensors, lasers, photodynamic therapy, solar cells and so on. However, the quantum yield of UCNPs is relatively low due to the small absorption cross-section of activator in UCNPs, limiting their further application. Therefore, how to improve the luminescence intensity of UCNPs has become a hotspot. A variety of methods such as core-shell nanostructure, phase transition and plasmon-enhanced upconversion have been developed in order to improve the fluorescence intensity of UCNPs. Among these methods, plasmon-enhanced upconversion as an efficient strategy has attracted extensive interests. In this review, three kinds of mechanisms about plasmon-enhanced upconversion luminescence are introduced firstly. Then construction methods of metal-UCNPs systems including chemical methods and physical methods, application of plasmon-enhanced upconversion luminescence in solar cells, bioimaging, bioassay, photothermal therapy and photocatalysis are discussed in detail. Finally, the limitations and directions for future research of plasmon-enhanced upconversion luminescence are also proposed.

Contents
1 Introduction
2 Mechanisms
2.1 Plasmon-enhanced excitation
2.2 Plasmon-enhanced emission
2.3 Energy transfer
3 Methods
3.1 Chemical methods
3.2 Physical methods
4 Applications
4.1 Solar cells
4.2 Bioimaging
4.3 Bioassay
4.4 Photothermal therapy
4.5 Photocatalysis
5 Conclusion

Suzuki-Miyaura Carbonylative Reaction in the Synthesis of Biaryl Ketones
Zhu Zhuangli, Zhang Weiqiang, Gao Ziwei
2016, 28 (11): 1626-1633 | DOI: 10.7536/PC160503
Published: 15 November 2016
Abstract
Palladium-catalyzed carbonylative coupling reactions of aromatic halides and aryl boronic acids have been rapidly developed during recent years. Nowadays, a plethora of boronic acid compounds, palladium catalyst precursors and CO resources are available for the synthesis of diaryl ketones, which are important intermediates in the manufacture of dyes, pharmaceuticals and natural products. In this review, we summarize the development of these carbonylative reactions with aspects of palladium catalyst system, transmetallation, alternative CO resources and application. The progress on palladium catalyst system covers both homogeneous and heterogeneous reaction systems. A large variety of palladium catalyst precursors, phosphine ligands, HNC ligands in different solvents are discussed in detail, whilst palladium catalysts immobilized on active carbon, graphene, ligand functionalized silica gel, Fe3O4 are also included. Notably, the improvement in the transmetallation process is potentially valuable of achieving efficient carbonylative coupling reaction, in which the pivalic acid additive is found to accelerate the carbonylative coupling. In the classic carbonylative procedure, CO gas from high pressurized cylinders is required in palladium catalyzed Suzuki carbonylative reaction. Although few innovations using CO balloon is reported, the replace of odorless and toxic CO gas by carbon monoxide release molecules (CORM) are highly desirable and offered a safer and greener carbonylation process. To supply CO for palladium-catalyzed carbonylative coupling reaction, various organic CORMs releases CO via controllable degradation in two-chamber system. Transition metal carbonyl compounds as solid CORM directly provides CO under microwave radiation.

Contents
1 Introduction
2 Pd catalyzed Suzuki carbonylation
2.1 Homogeneous Suzuki carbonylation
2.2 Heterogeneous Suzuki carbonylation
3 Transmetalation of Suzuki carbonylation
4 New carbonyl source of Suzuki carbonylation
5 Examples
6 Prospect of Suzuki carbonylation

Well-Defined Polyolefin Graft Copolymers: Syntheses, Structures, and Properties
Zhang Yongjie, Li Huayi, Qu Minjie, Feng Na, Yang Wei, Zhang Chong
2016, 28 (11): 1634-1647 | DOI: 10.7536/PC160410
Published: 15 November 2016
Abstract
Serving as an essential strategy to further expand polyolefin (PO) applications into high performance PO-based materials, functionalization of PO, including preparation of PO segmented graft copolymers, has drawn extensive attention for decades from both academia and industry. PO graft copolymers, containing both PO segments (PP, PE, etc.) and functional polymer segments (PS, PMMA, PEG, etc.), could well retain the excellent properties of PO (crystallinity, processablity) while achieving high functional group concentration. Well defined PO graft copolymers, those with controllable structural parameters (mainly graft density and graft length), are often highly desirable since well-defined structure not only renders tunable chemical and physical properties but also helps to better understand the structure-property relationships, which are crucial to exploring the applications of PO graft copolymers. Three general methods are employed to synthesize well defined PO graft copolymers, namely "graft-through", "graft-from", and "graft-onto". Among them, the further two approaches generally involve mechanism transformation between coordination polymerization and other polymerizations (anionic, radical), where reactive polymer "intermediates" are required, either as macrointiator or macroRAFT agent, or macromonomer. The third approach, which is easier to understand, simply links side-groups functionalized PO and end-groups functionalized polymers together via efficient coupling reactions to form graft architectures. From three aspects, i.e., syntheses, structures and properties, this review outlines the advances in well-defined polyolefin graft copolymers, especially highlighting newly developed synthetic methods (visible light-induced grafting, e.g.) and emerging applications (solid polymer electrolyte, e.g.) of graft copolymers derived thereof.

Contents
1 Introduction
2 Graft-through method
2.1 Polyolefin as backbone
2.2 Polyolefin as graft chain
3 Graft-from method
3.1 Borane Approach
3.2 Tolyl Group
3.3 (hydrochlorinated) Vinylphenyl group
3.4 Hydroxyl
3.5 Inimer
3.6 Non-olefin-coordination-polymerization approach
4 Graft-onto method
5 Conclusion

Multi-Stimuli Induced Shape Memory Effect of Polymers Based on Poly(vinyl alcohol)
Du Haiyan, Lei Xia, Xu Yuyu, Liang Zhenhai, Wang Yonghong
2016, 28 (11): 1648-1657 | DOI: 10.7536/PC160333
Published: 15 November 2016
Abstract
Shape memory polymers (SMPs) are a class of environment stimulated intelligent materials that developed in recent years. Under extra stimulation, physical and chemical changes will take place within or between molecules, and the deformed material can recover to its original shape due to the change of molecular structure and morphology. Various common SMPs such as poly(ethylene), poly(urethane), poly(caprolactone) have been developed, however, the shape memory effect of poly(vinyl alcohol) (PVA) has not attracted the attention until the thermal induced shape memory behavior of PVA gel was reported. Because there are abundant hydroxyl groups with high chemical activity in PVA side chains, it is easy to modify PVA with other functional groups. Different stimuli induced molecular structures can be designed according to the environmental requirement. Up to now, different methods including freeze-thaw cycle, chemical or irradiation cross-linking, graft modification and blending have been used to prepared various multi-stimuli (e.g. temperature, solvent, light, electricity, microwave and ultrasound) induced shape memory poly(vinyl alcohol) (SM-PVA), PVA derivatives and composites. The present article summarizes the research development of different stimuli induced SM-PVA of recent years. The structures and properties of different materials, the recovery mechanism, and the problems are described. The future development and applications of PVA in this field are also prospected.

Contents
1 Introduction
2 Multi-stimuli induced shape memory polymers based on PVA
2.1 Temperature induced shape memory gel and polymer
2.2 Light induced shape fix of PVA derivative
2.3 Solvent induced shape memory PVA and composites
2.4 Electroactive shape memory PVA composites
2.5 Ultrasound-triggered shape memory PVA
2.6 Microwave induced shape memory PVA and composites
3 Conclusion

A Bridge Spanning Microscopic to Macroscopic Assembly: Application of the Technique of Polymerization of Concentrated Emulsion
Feng Yanyan, Jin Ming, Wan Decheng
2016, 28 (11): 1658-1663 | DOI: 10.7536/PC160701
Published: 15 November 2016
Abstract
Open-cellular materials can be obtained by polymerization of concentrated emulsion (high internal phase emulsion:HIPE) (polyHIPE), by which nano-objects can be assembled at macroscopic scale, resulting in ordered surface, and the material is producible in large scale. However, earlier polyHIPE technique just provides a porous framework because the small surfactants can just serve as stabilizers but cannot serve as a surface modifier. Postmodification of such polyHIPE usually appears to be tedious, arising from the inert matrix and the nature of a heterogeneous reaction. Recently, certain breakthrough in surface functionalization of polyHIPE occurs:(1) pickering stabilizing particles are tailored with surface chemistry; (2) amphiphilic block copolymers are used in place of the readily leachable small surfactant for direct preparation of surface-functionalized polyHIPE; (3) dendritic amphiphile based on hyperbranched polymers are used to one-pot prepare polyHIPE with active-groups dictated surface; (4)metal nanoparticle-dendritic amphiphile nanocomposites are used as stabilizer to prepare polyHIPE with metal nanoparticle-dictated surface. The polyHIPEs are of large size, ready separation and good recycling, high specific surface area, structured surface, thus are highly potential in supramolecular water treatment, low-leaching catalyst, etc.

Contents
1 Introduction
2 Direct surface functionalization of polyHIPE
3 Direct preparation of metal nanoparticle-decorated polyHIPE
4 Conclusion

Supramolecular Artificial Enzyme Based on Assembling Peptide Gel
Zhao Yanan, Wang Mengfan, Qi Wei, Su Rongxin, He Zhimin
2016, 28 (11): 1664-1671 | DOI: 10.7536/PC160221
Published: 15 November 2016
Abstract
Mimic enzyme, or artificail enzyme, is a kind of non-protein molecule which is synthesized by the organic chemical method. With the development of nanoscience and supramolecular technology, the establishment of supramolecular artificial enzyme with biocatalytic function has attracted increasingly attention in the field of scientific research and application development. Peptide-based gel is a new type of supramolecular assembly which is formed with polypeptides as the building block and driven by non-covalent forces. As a novel supramolecular material, the peptide-based gel exhibits unique advantages compared with other functional materials:the similar structural and biochemical properties to those of natural enzymes, easy to be modified and functionalized, and the good biocompatibility. These properties make peptide-based gel a ideal material to construct artificial enzyme. In this review, we summarize the characteristics of artificial enzyme based on the assembling peptide gel and introduce the recent research progress of it as the catalysts in hydrolysis, Aldol and redox reactions. The main factors which influence the catalytic activity, such as the assembly degree, structure, active-site microenvironment and pH, are also discussed. Some examples are provided to illustrate the protential application of peptide-based artificial enzyme. Finally, the problems and prospective tendency are presented.

Contents
1 Introduction
2 Reaction types catalyzed by peptide-based artificial enzyme
2.1 Hydrolysis reaction
2.2 Aldol reaction
2.3 Redox reaction
3 Influence factors on the activity of peptide-based artificial enzyme
3.1 Assembly degree
3.2 Microstructure
3.3 Supramolecular structrue
3.4 Active-site microenvironment
3.5 pH
4 Application of peptide-based artificial enzyme
5 Conclusion

Applications of Novel Biomass-Derived Platform Molecule γ-Valerolactone
Wei Junnan, Tang Xing, Sun Yong, Zeng Xianhai, Lin Lu
2016, 28 (11): 1672-1681 | DOI: 10.7536/PC160502
Published: 15 November 2016
Abstract
The transformation of renewable biomass resources into a variety of chemicals and fuels via biomass-derived platform molecules has recently attracted increasing attention from industrial and academic communities. Of numerous platform molecules, γ-valerolactone (GVL) is able to be employed as a sustainable starting material that can be used to produce carbon-based chemicals and energy, which thus is considered as one of the most promising biomass-derived platform molecules. This paper mainly introduces and summarizes research advances on the downstream applications of GVL which have been made in the last decade, including employing GVL as a green solvent and employing GVL as a starting material to produce carbon-based chemicals, polymers and liquid hydrocarbon fuels. The perspective of GVL is also suggested in this review.

Contents
1 Introduction
2 Employing GVL as a green solvent
3 Synthesis of carbon-based chemicals from GVL
4 Synthesis of polymeric materials from GVL
5 Synthesis of liquid hydrocarbon fuels from GVL
6 Conclusion

Bacterial Cellulose Based Electrode Material for Supercapacitors
Xia Wen, Li Zheng, Xu Yinli, Zhuang Xupin, Jia Shiru, Zhang Jianfei
2016, 28 (11): 1682-1688 | DOI: 10.7536/PC160517
Published: 15 November 2016
Abstract
Supercapacitors as a new-type energy storage devices have drawn much attention because they can provide higher power density than batteries and higher energy density than traditional dielectric capacitors. But at present their application are still exist the defect of low energy density. Carbon materials, metal oxides and conductive polymers are three more commonly utilized electrode materials for supercapacitors, and the different forms of carbon materials are the most widely research and application of capacitor electrode materials.Bacterial cellulose (BC) is a porous and biological polymer which secreted by some bacterias, and BC has special properties of high mechanical strength and modulus, high porosity, good size and thermal stability. Consequently, significant research interest has been directed into the research of the carbon electrode materials which use bacterial cellulose as a raw material. In this paper, we present a review of the research progress of the BC based electrode material for supercapacitor application in term of the types of materials, preparation methods and performances. Furthermore, the optimum configuration, synthesizing method and the developing trend for the bacterial cellulose composite are summarized.

Contents
1 Introduction
2 BC and BC based carbon nanofiber electrode material for supercapacitors
2.1 BC based flexible electrical double-layer capacitive supercapacitor
2.2 BC based pseudo-capacitive supercapacitor
3 Conclusion

Reaction Mechanism of Metastable Intermolecular Composite
Wang Yajun, Li Zexue, Yu Haiyang, Feng Changgen
2016, 28 (11): 1689-1704 | DOI: 10.7536/PC160519
Published: 15 November 2016
Abstract
Due to the superfast combustion velocity and energy releasing rate, high volume energy density, low diffusion distance and being environmental friendly, metastable intermolecular composites (MIC) show great and important potential in both military and civil systems, such as microenergetic device, rocket propellant, green pyrotechnics, etc. However, the reaction mechanism of metastable intermolecular composition is still poorly clear and understood. The ultra-fast transient nature, and the complexity of probing both the vapor-phase and condensed-state chemistries of MIC materials make the reaction mechanism being different from that of traditional energetic materials, which prevents its further development in application research. The present paper summarizes the overseas and domestic research status of reaction mechanism of MIC materials so far. "Metal-oxygen flip mechanism" and "pre-combustion sintering mechanism" are discussed in detail. According to research methods, experimental research, theoretical model research, and numerical simulation research are presented respectively. Modification of MIC materials is an important method for adjusting the performances of the materials, and is one of the developing trends. We discuss the reaction mechanism of the modified materials in the end of the paper. Based on the comprehensive analysis of the study status, the challenges and prospective tendencies of reaction mechanism of MIC are also given.

Contents
1 Introduction
2 Experimental research
2.1 Partical size
2.2 Loading density
2.3 Content of reactive Al
2.4 Al/oxide ratio
2.5 Microstructure
2.6 Preparation method
2.7 Properties of oxidizer
2.8 Role of oxygen[O]
2.9 Microscale charge
2.10 Ignition mechanism
2.11 Others
3 Numerical simulation research
3.1 Molecular dynamics simulation
3.2 Thermal diffusion simulation
3.3 Output pressure simulation
3.4 Rapid oxidation simulation
3.5 Fluid dynamics simulation
3.6 Detonation simulation
4 Theoretical model research
4.1 Diffusion oxidation mechanism
4.2 Ion diffusion mechanism
4.3 Polymorphic phase change oxidation mechanism
4.4 Melt-dispersion mechanism
4.5 Metal-oxygen flip mechanism
4.6 Convective combustion mechanism
4.7 Modified Cabrera-Mott model
4.8 Pre-ignition sintering mechanism
5 Reaction mechanism of modified MIC
6 Conclusion

Abstract
The deficiency or maladjustment of ascorbic acid, dopamine, and uric acid in human body may lead to symptoms of many diseases such as cancer, Alzheimer's disease and hyperuricemia. The three species usually coexist in body fluid and possess adjacent redox potentials, thus it is extremely important and challenging to accomplish the simultaneous detection of these species. In recent years, electrochemical sensors for simultaneous detection of ascorbic acid, dopamine, and uric acid, have made a great progress. Especially, carbon nanomaterials draw considerable attentions owing to their intrinsic properties such as low cost, excellent conductivity, chemical stability, large specific surface area etc. This review mainly focuses on designing non-enzymatic electrochemical sensors based on carbon nanomaterials for simultaneous detection of ascorbic acid, dopamine, and uric acid in recent years. Additionally, the perspective of future development of this type of electrochemical sensors is discussed.

Contents
1 Introduction
2 Carbon nanomaterials-based non-enzymatic electrochemical sensors for simultaneous detection of ascorbic acid, dopamine, and uric acid
2.1 One-dimensional carbon nanomaterials
2.2 Two-dimensional carbon nanomaterials
2.3 Zero-dimensional carbon nanomaterials
2.4 Three-dimensional carbon nanomaterials
3 Conclusion

Design and Discovery of Sialyltransferase Inhibitors
Guo Jian, He Yun, Ye Xin-Shan
2016, 28 (11): 1712-1720 | DOI: 10.7536/PC160442
Published: 15 November 2016
Abstract
Sialylation at the non-reducing end of glycoconjugates is involved in lots of important physiological and pathological processes. Especially cancer cells express high density of sialic acids known as hypersialylation that contributes to cancer cell progression and metastasis. Sialyltransferase is the glycosyltransferase in charge of sialylation of glycoconjugates. Effective sialyltransferase inhibitors could be not only of medicinal interests, especially in the therapy of cancer diseases, but also biological probes for studying fuctions of sialylation in glycobiology. Here we review recent progress of design and discovery of sialyltransferase inhibitors. The major content is about the design of different types of inhibitors and their structure-activity relationship. The current challenges and development trends are also proposed.

Contents
1 Introduction
2 Relationship between sialic acids and cancers
3 Design and discovery of sialyltransferase inhibitors
3.1 Donor-analog inhibitors
3.2 Acceptor-analog inhibitors
3.3 Bisubstrate-analog inhibitors
3.4 Transition-state-analog of the sialyl donor inhibitors
3.5 Other types of inhibitors
4 Conclusion