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Progress in Chemistry 2019, No.11 Previous issue Next issue

In this issue:

The Total Synthesis of ent-Kaurane Diterpenoids
Wu Li, Junjie Wang, Dawei Ma
2019, 31 (11): 1460-1471 | DOI: 10.7536/PC190809
Published: 15 November 2019
Abstract

The ent-kaurane diterpenoids, widely distributed in terrestrial plants, represent an important group of tetracyclic diterpenes with diverse scaffolds and varied bioactivities. More and more studies have revealed that these compounds possess potent antitumor, antibacterial and anti-inflammatory activities. The tetracyclic ent-kaurane diterpenoids have attractive structural diversity owing to intramolecular cyclization, oxidative cleavage and rearrangements of their parent compounds. As a result, the total synthesis of ent-kaurane diterpenoids has received great attention from synthetic community during the past decades. This review describes the recent progress in this field, which includes total synthesis of C-20 non-oxygenated ent-kauranes such as(+)-lungshengenin D and pharicins A-C; total synthesis of C-20 oxygenated ent-kauranes such as maoecrystal P, eriocalyxin B, neolaxiflorin L and xerophilusin I; total synthesis of seco-ent-kauranes such as sculpomeatin N, trichorabdal A, maoecrystal Z, enmein, isodocarpin, sculponin R, londirabdiol, longirabdolactone and effusin; and total synthesis of nor or rearranged-ent-kauranes such as jungermannenones B and C, maoecrystal V, jungermatrobrunin A and kauradienone.

Glycosylated Iminosugars: Isolation, Synthesis and Biological Activities
Xin Yan, Yi-Xian Li, Yue-Mei Jia, Chu-Yi Yu
2019, 31 (11): 1472-1508 | DOI: 10.7536/PC190307
Published: 15 November 2019
Abstract

In this paper, the separation, synthesis and biological activities of glycosylated iminosugars are systematically summarized. The naturally occurring glycosylated iminosugar products can be classified into five types according to their iminosugar units. Most of them have important biological activities, especially glycosidase inhibitory activities. Potential pharmacological activities of these compounds promote the study of synthetic strategies. According to the construction methods of glycoside bonds, these strategies can be roughly divided into enzyme catalyzed transglycosylation and chemical synthesis, of which the main difference is reaction condition. Enzyme catalyzed transglycosylation features mild reaction conditions and possible avoidance of protection groups, but the reaction efficiency and selectivity still need further improvement. Many synthetic strategies for ordinary glycosides can be used in chemical synthesis of glycosylated iminosugars, and are applicable for almost all synthetic targets. However, burdensome protection-deprotection procedures pull down the efficiency of chemical synthesis. The development of synthetic strategies have promoted the design and synthesis of the natural products and their analogues, which greatly enriches the variety and biological activities of glycosylated iminosugars. Generally, biological activities of glycosylated iminosugars are influenced by both the glycosyl groups and the iminosugar units. As the cross-domain of traditional carbohydrate chemistry and iminosugar chemistry, the structural diversity of glycosylated iminosugars provides excellent parent skeletons for the development of highly active and selective lead compounds, which endows these compounds with potential applications in drug discovery.

Fluorescent Polymer Materials for Detection of Explosives
Xiaofu Wu, Hui Tong, Lixiang Wang
2019, 31 (11): 1509-1527 | DOI: 10.7536/PC190734
Published: 15 November 2019
Abstract

As fluorescent sensing materials, fluorescent polymers not only have many sensing units, high brightness and good light stability, but also facilitate the fabrication of fluorescent sensing films, which are easy to implement devices. Therefore, fluorescent polymers have been widely studied and applied in fluorescence detection of explosives. In recent years, a large number of fluorescent polymers with various functional units have been developed, and their structures have evolved from common linear structures to branched and porous network structures, which have effectively improved the sensitivity, selectivity and response rate of explosive detection. This review is aimed to summarize the research progress on fluorescent polymers used for detection of explosives, including linear polymers, branched polymers and porous polymers. The emphasis of this review is especially focused on the structure design strategies, functional characteristics and sensing performances of typical linear conjugated and non-conjugated polymers, dendrimers and hyperbranched polymers and amorphous and crystalline porous polymers. Finally, the future opportunities and challenges of fluorescent polymers in application of explosive detection are presented.

Photo-Controlled Supramolecular Assemblies Based on Azo Group
Yao-Hua Liu, Yu Liu
2019, 31 (11): 1528-1539 | DOI: 10.7536/PC190708
Published: 15 November 2019
Abstract

Azo compounds are a class of trans-cis(E/Z) photoisomerization compounds which have advantages of simple synthesis, high isomerization rate and efficiency, and resistance to photobleaching. Due to their outstanding photoisomeric properties and ability to form stable inclusion complexes with macrocyclic hosts, azo compounds have shown great potential application in many fields. In this review, we show the design principles, assembly mechanism, application and development of the photo-controlled supramolecular assemblies in topologically morphological regulation, drug delivery, smart materials and so on, which are constructed by host-guest interaction using azo modified cyclodextrin, bis-cyclodextrin bridged by azobenzene, crown ether derivatives, azo aromatic macrocyclic compounds as the hosts or azobenzene or azobenzene derivatives as guests. At the same time, we also discuss the opportunities and challenges of the development of such supramolecular assemblies, and hope to further promote the development of intelligent supramolecular assemblies.

Supramolecular Self-Assembly Applied for the Design of Drug Delivery Systems
Zi-Yue Xu, Yun-Chang Zhang, Jia-Le Lin, Hui Wang, Dan-Wei Zhang, Zhan-Ting Li
2019, 31 (11): 1540-1549 | DOI: 10.7536/PC190817
Published: 15 November 2019
Abstract

Supramolecular self-assembly provides a new strategy for the development of drug delivery systems from molecular components. With non-covalent interactions as driving forces, supramolecular drug delivery systems(SDDSs) can realize precise component control at the molecular level, increased predictability of the self-assembled structures, tunable control of morphologies and sizes, controlled release of delivered drugs. In this review, we first concisely introduce the background for the design of SDDSs and then describe important advances in SDDS development that involves the applications of cyclodextrin, calixarene, pillararene and cucurbituril based on host-guest interactions. Following these popular design principles, we further present the applications of water-soluble supramolecular organic frameworks as SDDSs. Finally, the challenges that need to be addressed for the practical translation of SDDSs are discussed.

Structure and Performance Modulation of Photo-Responsive Ionic Liquids
Zhiyong Li, Ying Feng, Huiyong Wang, Xiaoqing Yuan, Yuling Zhao, Jianji Wang
2019, 31 (11): 1550-1559 | DOI: 10.7536/PC190731
Published: 15 November 2019
Abstract

Light-responsive ionic liquids(ILs) are a class of functional materials that combine the characteristics of light stimuli responsive materials and ILs. Upon UV/vis light irradiation, the structure, property and performance of these “smart” ILs can be significantly changed, which are expected to have important applications in many practical processes. Light trigger is of great importance because of its superiority, such as stable optical signal, accurate stimulation spot, and ability to be rapidly switched in a clean and non-invasive manner. In this work, the photo-isomerization of ILs and light modulation of IL properties, aggregation behavior of ILs, phase transfer of ILs, and phase behavior of emulsions involving IL are critically reviewed based on the structure-property-performance relationship of photo-responsive ILs. Meanwhile, the main problems in this field have been analyzed, and the future development is discussed.

Clustering-Triggered Emission of Nonconventional Luminophores
Xiaohong Chen, Yunzhong Wang, Yongming Zhang, Wangzhang Yuan
2019, 31 (11): 1560-1575 | DOI: 10.7536/PC190812
Published: 15 November 2019
Abstract

Intrinsic emission from nonconventional luminophores without classic remarkable conjugation has aroused increasing attention due to its significant fundamental importance and promising applications. These nonconventional luminophores generally contain the heteroatoms(i.e. N, O, S, P), unsaturated units of C≡N, C=O, C=C, etc., and their grouped moieties(i.e. hydroxyl, amino, ester, anhydride, amide, uramido, oxime, sulfone). In recent years, despite great progress has been achieved, the emission mechanism still remains under debate. Previously, we proposed the clustering-triggered emission(CTE) mechanism, namely the clustering of nonconventional chromophores with π and n electrons and subsequent through space conjugation result in extended electron delocalization and conformation rigidification, to rationalize the emission. Herein, based on the CTE mechanism, we review such typical emission characteristics of nonconventional luminophores as concentration enhanced emission, aggregation-induced emission(AIE), excitation-dependent emission, and phosphorescence. It is also noted that CTE mechanism can be used to rationalize the photophysical behaviors of different types of nonconventional luminophores of natural products, synthetic compounds, and biomolecules. Furthermore, it is also helpful to guide the rational discovery or design of new nonconventional luminogens. In addition, we briefly summarize the progress of different kinds of nonconventional luminophores. Finally, the perspectives of this emerging area are also discussed.

Biomaterials for Regulating Cell Migration and Tissue Regeneration
Xingang Zuo, Haolan Zhang, Tong Zhou, Changyou Gao
2019, 31 (11): 1576-1590 | DOI: 10.7536/PC190432
Published: 15 November 2019
Abstract

Regenerative biomaterials provide the necessary substances to support the growth of cells and tissues, maintain the shape and mechanical properties of regenerated tissues, and promote the integration with surrounding tissues. The surfaces and interfaces of biomaterials interact directly with cells and tissues, and thus significantly influencing on many cellular behaviors such as adhesion, spreading, proliferation, migration and differentiation as well as the outcomes of tissue repair and regeneration. Moreover, most tissues and organs possess a 3 dimensional shape with specific microstructures. Therefore, the construction of regenerative biomaterials with a 3 D shape and control over their microstructures are key issues as well. In this review, the recent works on the factors affecting cellular uptake of colloidal particles and cell adhesion are introduced. The adhesion and directional migration of cells mediated by gradient biomaterials are summarized. The latest works on migration of cells into 3 D hydrogels are reviewed. The implantable biomaterials with 3D microstructures for skin and cartilage repair and regeneration are also introduced. Finally, the application and perspectives of biomaterials in tissue regenerative are discussed.

Stabilizing Structure and Performances of Lithium Rich Layer-Structured Oxide Cathode Materials
Zhaoxiang Wang, Jun Ma, Yurui Gao, Shuai Liu, Xin Feng, Liquan Chen
2019, 31 (11): 1591-1614 | DOI: 10.7536/PC190820
Published: 15 November 2019
Abstract

The lithium ion(Li-ion) batteries, known for their high energy density and high energy conversion efficiency, have been widely applied in portable electronics and electric transportation. With reversible capacities over 300 mAh·g-1, the Li-rich layer-structured oxides are important candidiates of the cathode materials for the Li-ion batteries with energy densities of 350 Wh·kg-1 or higher. However, the issues related to the structural degradation during long-term cycling and the high surface/interface sensitivity(dissolution of the transition metal ions and the side reactions with the electrolyes) have to be well addressed before these materials can be commercially applied. This review is to present some of our efforts in stabilizing the structure and electrochemical performances of these materials by way of elemental substitution in the bulk and on the surface and by designing new structures, on the basis of comprehensive understandings on their crystalline and electronic structures and the structural evolution. Meanwhile, for the purpose of providing the audience with some overview about the world-wide research progress on these oxide materials, some important achievements are introduced including homogeneous elemental substitution in the lattice, structurally integrated surface modification(such as multilayer modification and construction of concentration-gradient materials), surface coating and surface doping. We will share our thinking on the research directions of these materials before ending this review.

External Field Enhanced Environmental Responsive Solid Extraction Technology
Liangrong Yang, Huifang Xing, Hongnan Qu, Jiemiao Yu, Huizhou Liu
2019, 31 (11): 1615-1622 | DOI: 10.7536/PC190808
Published: 15 November 2019
Abstract

Efficient, precise and controllable separation of target compounds in low concentration and large volume complex solutions is a world frontier in the field of chemical separation science. Solid phase extraction technology currently faces two challenges in industrial separation of low-concentration complex systems. On the one hand, it is difficult to give consideration to both of the high selective precision capture and the mild green desorption. On the other hand, solid phase extraction technology lacks efficient separation process and equipment for large scaled continuous separation. This review summarizes the research progress of new environmental responsive solid phase extraction technology, magnetic field responsive solid phase extraction technology, electric field- and ultrasound field- assisted solid phase extraction technology in order to solve the problems of current solid phase extraction technology, and achieve the efficient and precise separation for low concentration complex systems. Finally, the research and development direction of solid phase extraction technology in this application field is prospected. In this review, the key scientific issues of external field enhanced environmental responsive solid phase extraction technology, including environmental responsive problems, controllable separation problems and process amplification problems, are further discussed. Besides, measures and suggestions are proposed for the development of related fields.