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Nano Research 2021年第7期14卷 2321-2329页

作者： Na Gao Rubo Zhang Bingkun Chen Jinfeng Zhang Xiaoling Zhang Andrey L.Rogach School of Chemistry and Chemical Engineering Beijing Institute of TechnologyBeijing 100081China School of Optics and Photonics Beijing Institute of TechnologyBeijing 100081China School of Life Science Beijing Institute of TechnologyBeijing 100081China Department of Materials Science and Engineering and Centre for Functional Photonics(CFP)City University of Hong KongHong Kong SARChina

Heavy-metal-free silver based I-III-VI semiconductor nanocrystals(NCs),including ternary silver indium sulfide(AgInS_(2))and derivative quaternary silver indium zinc sulfide(i.e.,AgInZn_(2)S_(4))NCs,possess advantages of low toxicity,and size-tunable band gaps approaching near-infrared spectral range,which make them candidates for use in optoelectronic and biological devices.Herein,we report syntheses of AgInS_(2) based NCs starting from In_(2)S_(3) template,which have been performed both in organic and aqueous phase through cation exchange.As a result,ternary silver indium sulfide and quaternary silver indium zinc sulfide NCs are obtained in both organic and aqueous media,and confirmed to be orthorhombic AgInS_(2) NCs and hexagonal AgInZn_(2)S_(4) NCs,respectively.Furthermore,the aqueous AgInZn_(2)S_(4) NCs with red emission and low cytotoxicity are explored for the cancer cell imaging.

关键词： template synthesis silver indium sulfide based nanocrystals cation exchange organic and aqueous media

template synthesis of imine-based covalent organic framework core-shell structure and hollow sphere:a case of COFTTA-DHTA

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Science China Chemistry 2017年第8期60卷 1098-1102页

作者： Sun,Bing Wang,Dong Wan,Lijun Chinese Acad Sci Inst ChemKey Lab Mol Nanostruct&NanotechnolBeijing 100190Peoples R China Univ Chinese Acad Sci Beijing 100049Peoples R China

Controllably synthesizing well-dispersed covalent organic frameworks(COFs) with uniform both morphology and size is still a challenge. Herein, we report the template-directed synthesis of COFTTA-DHTA-based core-shell hybrids under solvothermal conditions by using amino-functionalized SiO_2 microspheres as templates coupled with stepwise addition of initial monomer molecules. The modified amino groups on the surfaces of SiO_2 templates play an important role in the formation of well-defined NH_2-f-SiO_2@COFTTA-DHTA core-shell hybrids. COFTTA-DHTA hollow spheres can be obtained by etching SiO_2 cores of NH_2-f-SiO_2@COFTTA-DHTA. Both the NH_2-f-SiO_2@COFTTA-DHTA and COFTTA-DHTA hollow spheres possess the well-defined morphology, high crystallinity and porosity, excellent dispersion property and high chemical stability. The template synthesis method demonstrated in this work provides a general method for the shape-controlled synthesis of COF-based materials, which is important for the further applications in the fields such as energy storage, drug delivery and catalysis.

关键词： covalent organic framework template synthesis organic porous material core-shell structure hollow sphere

Functional nanoemulsions: Controllable low-energy nanoemulsification and advanced biomedical application

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Chinese Chemical Letters 2024年第2期35卷 57-69页

作者： Maojie Zhang Qiang Cao Yuming Yuan Xiaohan Guo Dawei Pan Rui Xie Xiaojie Ju Zhuang Liu Wei Wang Liangyin Chu College of Engineering Sichuan Normal UniversityChengdu 610101China School of Chemical Engineering Sichuan UniversityChengdu 610065China State Key Laboratory of Polymer Materials Engineering Sichuan UniversityChengdu 610065China

Nanoemulsions are widely used as advanced pharmaceutical delivery systems in biomedical field, due to their high encapsulation efficiency and good therapy efficacy.Nanoemulsification techniques that produce nanoemulsions with controllable sizes and compositions are promising for creating advanced nanoemulsion systems for pharmaceutical delivery.This review summarizes recent advances on low-energy emulsification techniques for producing nanoemulsions, and the use of these nanoemulsions as advanced pharmaceutical delivery systems and as templates to create drug-loaded functional particles for biomedical application.First, nanoemulsification techniques that utilize elaborate interfacial physics/chemistry and micro-/nano-fluidics, featured with relatively-low energy input, to produce nanoemulsions with controllable sizes and compositions, are introduced.Uses of these nanoemulsions to create nanoemulsionincorporated milli-particles, drug-loaded nanoparticles and nanoparticle-incorporated microparticles with sizes ranging from several millimeters to sub-10 nm are emphasized.Flexible and efficient use of the nanoemulsions, functional nanoparticles and milli-/micro-particles integrated with nanoemulsions or nanoparticles for advanced pharmaceutical delivery in biomedical field are highlighted, with focus on how the interplay between their sizes and compositions achieve desired pharmaceutical-delivery performances.Finally, perspectives on further advances on the controllable production of nanoemulsions are provided.

关键词： Nanoemulsions Interfaces Drug delivery template synthesis Nanoparticles

synthesis and Structure of Ag(I)- Containing Coordination Polymers Based on Quaternary Ammonium template Reagent

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Chinese Journal of Structural Chemistry 2005年第5期24卷 509-512,489页

作者：柯子厚陈之荣李浩宏黄长沧肖光参赵斌 College of Chemistry and Chemical Engineering Fuzhou University Fujian 350002 China Central Laboratory Fuzhou University Fujian 350002 China

A novel coordination polymer [(C8H20N)(Ag2I3)]n ([C8H20N]+ = tetraethyl ammo- nium (TEA)) was synthesized by the reaction of AgI and C8H20NI at room temperature with pH = 6.5, and structurally characterized by means of X-ray single-crystal diffraction. It crystallizes in orthorhombic, space group Pna21 with a = 7.3323(9), b = 18.250(2), c =12.5294(15) ?, C6.33H16.16NAg2I3, Mr = 702.76, V = 1676.6(4) ?3, Z = 4, Dc = 2.784 g/cm3, F(000) = 1256.6, μ(MoKα) = 7.828 mm-1, the final R = 0.0529 and wR = 0.1586 for 1189 observed reflections with I > 2σ(I). X-ray analysis shows that the [Ag2I3]n- chain is built up by AgI4 tetrahedron and in combination with quaternary ammonium cations ([C8H20N]+) by static attractive forces to form the so-called organic-inorganic hybrid material.

关键词： coordination polymers template synthesis iodide quaternary ammonium

Phase-mediated controllable intramolecular and intermolecular photocycloadditions assisted by supramolecular templates

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Science China Chemistry 2022年第6期65卷 1129-1133页

作者： Yi-Shou Wang Li-Ying Sun Yao-Yu Wang Ying-Feng Han Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education Xi’an Key Laboratory of Functional Supramolecular Structure and MaterialsCollege of Chemistry and Materials ScienceNorthwest UniversityXi’an710127China

Understanding and controlling supramolecular template effect assembly via a photochemical reaction in different solid and solution phases is one of the main topics in photochemistry. Here, an interesting case of phase-mediated controllable intramolecular/intermolecular photochemical [2+2] cycloadditions assisted by supramolecular templates was demonstrated. Direct irradiation of the complexes in solution yields intramolecular photoproducts exclusively, whereas exposure of the solid powder sample under the same conditions yields intermolecular dinuclear species quantitatively. The nature of the phase and supramolecular interaction affects the geometrical arrangements of the metallacycles, leading to different cycloaddition products under photoirradiation. The crystal structures of different products were investigated by single-crystal X-ray diffraction, nuclear magnetic resonance(NMR) spectrometry, and electrospray ionization mass spectrometry(ESI-MS).

关键词： N-heterocyclic carbene photochemical cycloaddition template synthesis topochemistry stacking interactions

Supramolecular template-Assisted Catalytic[2+2]Photocycloaddition in Homogeneous Solution

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CCS Chemistry 2023年第3期5卷 633-640页

作者： Fang Wang Sha Bai Qing-Wen Zhu Zi-Hang Wei Ying-Feng Han Key Laboratory of Synthetic and Natural Functional Molecule of the Ministry of Education Xi’an Key Laboratory of Functional Supramolecular Structure and MaterialsCollege of Chemistry and Materials ScienceNorthwest UniversityXi’an 710127

Supramolecular interactions can help recognize and organize substrates around an enzyme’s active sites and subsequently assemble a new molecule in a certain way.Inspired by nature’s control of reactions,in this work we designed a template catalyst equipped with ditopic Au(I)–N-heterocyclic carbene(NHC)functional sites that direct olefin substrates into reactive geometries via collaboration of coordination-driven interactions.Notably,this catalyst enables the realization of catalytic[2+2]photocycloadditions with as low as 2 mol%catalyst loading in homogeneous solution and the delivery of a series of cyclobutane derivatives with excellent conversions and stereoselectivities.The success of gram-scale reactions further demonstrates the feasibility of this strategy,which lays a solid foundation for the large-scale preparation of cyclobutane derivatives in the future.

关键词： N-heterocyclic carbene supramolecular catalysis template synthesis photocycloaddition self-assembly

Nanohollow Carbon for Rechargeable Batteries:Ongoing Progresses and Challenges

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Nano-Micro Letters 2020年第12期12卷 362-391页

作者： Jiangmin Jiang Guangdi Nie Ping Nie Zhiwei Li Zhenghui Pan Zongkui Kou Hui Dou Xiaogang Zhang John Wang Jiangsu Key Laboratory of Electrochemical Energy Storage Technology College of Material Science and EngineeringNanjing University of Aeronautics and AstronauticsNanjing 210016People’s Republic of China Department of Materials Science and Engineering National University of SingaporeSingapore 117574Singapore Industrial Research Institute of Nonwovens and Technical Textiles College of Textiles and ClothingQingdao UniversityQingdao 266071People’s Republic of China Key Laboratory of Preparation and Application of Environmental Friendly Materials College of ChemistryJilin Normal UniversitySiping 136000People’s Republic of China

Among the various morphologies of carbon-based materials,hollow carbon nanostructures are of particular interest for energy storage.They have been widely investigated as electrode materials in different types of rechargeable batteries,owing to their high surface areas in association with the high surface-to-volume ratios,controllable pores and pore size distribution,high electrical conductivity,and excellent chemical and mechanical stability,which are beneficial for providing active sites,accelerating electrons/ions transfer,interacting with electrolytes,and giving rise to high specific capacity,rate capability,cycling ability,and overall electrochemical performance.In this overview,we look into the ongoing progresses that are being made with the nanohollow carbon materials,including nanospheres,nanopolyhedrons,and nanofibers,in relation to their applications in the main types of rechargeable batteries.The design and synthesis strategies for them and their electrochemical performance in rechargeable batteries,including lithium-ion batteries,sodium-ion batteries,potassium-ion batteries,and lithium–sulfur batteries are comprehensively reviewed and discussed,together with the challenges being faced and perspectives for them.

关键词： Hollow carbon nanospheres Nanopolyhedrons and nanofibers template synthesis Rechargeable batteries Electrochemical performance

synthesis,Characterization and DFT Calculation of a New Silver(I) Iodid templated by Conjugated Cation:(ipq)_4Ag_4I_8

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Chinese Journal of Structural Chemistry 2006年第9期25卷 1148-1153页

作者： XIAO Guang-Can Center of Analysis and Measurement Fuzhou University Fuzhou Fujian 350002 China

A silver iodide, （ipq）4Ag418 1, has been synthesized in the presence of ipq （ipq = N-（isopentyl）-quinolinium） acting as a structure-directing reagent （SDA）. Compound 1 crystallizes in the triclinic system, space group PT, with a = 9.850（2）, b = 11.564（2）, c = 16.111（3） ,A ,α = 104.64（3）, β = 105.73（3）, γ = 94.37（3）o, V= 1688.3（7） A^3, Z = 2, D,= 2.205 g/cm^3, F（000） = 1042, C28H33Ag2l4N2, Mr= 1120.90, μ（MoKa） = 4.836 mm^-1, the final R = 0.0363 and wR = 0.0761 for 5465 observed reflections with 1 〉 2σ（I）. 1 consists of uncoordinated structure-directing molecule and inorganic moiety tuned by organic SDA. Tetrameric Ag4I8^4- anion in 1 is composed of edgesharing AgI4 tetrahedra and AgI3 planar triangles. Electrostatic interaction between organic counter cations and inorgan!c moieties is present and contributes to the crystal packing. 1 was further characterized with IR, UV-Vis, elemental analysis and cyclic voltammetry. Based on the crystal structure data, quantum chemical calculation with DFr method was used to reveal the electronic structure and optical property of 1.

关键词： coordination polymers template synthesis iodide quaternary ammonium

4.8 nm Concave {M_(72)}(M=Co,Ni,Fe) metal-organic polyhedra capped by 18 calixarenes

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Science China Chemistry 2021年第3期64卷 426-431页

作者： Haitao Han Liang Kan Ping Li Guoshuai Zhang Kaiyue Li Wuping Liao Yunling Liu Wei Chen Chunhua T.Hu State Key Laboratory of Rare Earth Resource Utilization Changchun Institute of Applied ChemistryChinese Academy of SciencesChangchun 130022China State Key Laboratory of Inorganic synthesis and Preparative Chemistry College of ChemistryJilin UniversityChangchun 130012China State Key Laboratory of Electroanalytical Chemistry Changchun Institute of Applied ChemistryChinese Academy of SciencesChangchun 130022China Department of Chemistry New York University100 Washington Square EastRoom 1001New YorkNY 10003USA University of Chinese Academy of Sciences Beijing 100049China

Three 4.8 nm isostructural{M_(72)}(M=Co^(Ⅱ) for CIAC-128,Ni^(Ⅱ) for CIAC-129,Fe^(Ⅱ) for CIAC-130) metal-organic polyhedra(MOPs) are constructed by eighteen M_(4)-p-tert-butylthiacalix[4]arene (M_(4)-TC4A) units bridged via sixteen four-connected 5,5′-(1H-1,2,4-triazole-3,5-diyl) diisophthalic acid (H_(4)TADIPA) linkers.These MOPs are featured with a rarely reported concave coordination cage,which can be simplified as a squeezed double-decker hexagonal prism pressed from the top and bottom hexagonal faces.Furthermore,CIAC-128,CIAC-129 and CIAC-130 are the highest nuclearity discrete clusters of Co,Ni and Fe reported so far.CIAC-128 has higher separation selectivity of C_(3)H_(8) than CH_(4) under ambient conditions,and also exhibits separation selectivity for C_(2)H_(6)/CH_(4),C_(2)H_(2)/CH_(4),and C_(2)H_(4)/CH_(4).In addition,CIAC-128 can provide the cavity for the confined synthesis of noble metal nanoclusters such as Pd nanoclusters and the resulting Pd@CIAC-128 hybrids show higher electrocatalytic activity than commercial Pt/C towards hydrogen evolution reaction (HER).

关键词： cluster compounds thiacalixarene gas separation template synthesis nanoparticles

synthesis and Structure of A Novel Quasi-Two Dimensional Organic-inorganic Hybrid Coordination Polymer:{[Cu(en)_2][Ag_2I_4]}_n

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Chinese Journal of Structural Chemistry 2006年第2期25卷 149-152页

作者： SUN Ling-Guo LI Hao-Hong CHEN Zhi-Rong HUANG Chang-Cang ZHAO Bin LI Jun-Qian College of Chemistry and Chemical Engineering Fuzhou University Fuzhou Fujian 350002 China

A novel coordination polymer {[Cu（en）2][Ag2I4]}, （en = ethylenediamine） was synthesized by the reaction of NaAgI2 and Cu（en）2（NO3）2·2H2O at room temperature with pH = 6.0, and the structure was characterized by X-ray single-crystal diffraction. It crystallizes in monoclinic, space group C2/m, with a=10.646（2）, b = 13.304（3）, c = 6.8445（14） ,A°, β = 118.95（3）°, C4H16N4CuAg2I4, Mr = 907.10, V= 848.3（4） A°^3, Z= 2, Dc = 3.551 g/cm^3, F（000） = 806, μ（MoKa） = 10.787 mm^-1, the final R1 = 0.0256 and wR2 = 0.0654 for 900 observed reflections with I 〉 2σ（I）. According to structural analysis, the title compound consists of template cation [Cu（en）2]^2＋ and inorganic chain [Ag2I4]n^2-. The polymeric negative chain [Ag2I4]n^2- is built up from pairs of AgI4 tetrahedron by sharing one edge. Through N-H…I hydrogen-bonding interactions, the whole structure represents a quasi-two dimensional arrangement. Electrostatic attraction exists between organic cations and inorganic chains, leading to a so-called organic-inorganic hybrid structure.

关键词： coordination polymer single-crystal diffraction template synthesis iodide