POROUS MEMBRANE TEMPLATED SYNTHESIS OF POLYMER PILLARED LAYER

The anodic porous alumina membranes with a definite pore diameter and aspect ratio were used as templates tosynthesize polymer pillared layer structures. The pillared polymer was produced in the template membrane pores, and thelayer on the template surfaces. Rigid cured epoxy resin, polystyrene and soft hydrogel were chosen to confirm themethodology. The pillars were in the form of either tubes or fibers, which were controlled by the alumina membrane pore surface wettability. The structural features were confirmed by scanning electron microscopy results.

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

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.

Synthesis and Theoretical Investigation of a New Hybrid Polymeric Iodoplumbate Based on Co-template:[(ipq)_2(pea)(Pb_3I_9)·DMF]_n

A new iodiplumbate polymer [（ipq）2（pea）（Pb3I9）-DMF]n 1 （ipq = N-（isopentyl）- quinolinium, pea = protonated ethylamine） was synthesized by self-assembly reaction of ipq·I, PbI2 with ethylamine and structurally characterized. 1 crystallizes in the triclinic system, space group P1 with α= 1.0731（4）, b = 1.2560（4）, c = 2.0785（7） nm, α = 96.378（5）, β= 91.132（2）, γ= 100.303（5）°, V= 2.7369（16） nm^3, Z= 2, Dc = 2.770 g/cm^3,μ = 14.307 mm^-1, F（000） = 2014, R = 0.0588 and wR = 0.1345. 1 features its hybrid structure concertedly templated by two kinds of organic cations, which exhibits interesting semiconductor property. In 1, the [Pb2I6]^2 n infinite chains shape the sketch of the title compound constructed from face-sharing of ideal and distorted PbI6 octahedra. Based on the crystal structure data, quantum chemistry calculation with DFT was used to reveal the electronic structure of 1.

Mesoporous polymers:soft-template self-assembly synthesis and applications

Mesoporous polymers combine the advantages of polymer materials(abundant polar functional groups,lightweight,flexibility,and processability)and mesoporous structures(high specific surface area,adjustable pore structure,and large pore volume);hence,they have great application potential in sensing,adsorption,catalysis,energy storage,biomedicine,etc.Currently,developing advanced synthetic strategies for mesoporous polymers and investigating their intrinsic applications have become hot research topics.Soft-template-based self-assembly is regarded as a promising approach for synthesizing mesoporous polymers.This work reviews recent progress in the synthetic strategy for producing various mesoporous polymers using soft-template selfassembly,focusing on the synthesis of conductive polymers,phenol-based polymers,and resin-based polymers and their potential applications.Finally,perspectives on future applications of mesoporous polymers,along with a few challenges that need to be resolved,are also discussed in this review.

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

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.

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

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.

Facile synthesis of metal-organic frameworks embedded in interconnected macroporous polymer as a dual acid-base bifunctional catalyst for efficient conversion of cellulose to 5-hydroxymethylfurfural

5-Hydroxymethylfurfural(5-HMF),as a key platform compound for the conversion of biomass to various biomass-derived chemicals and biofuels,has been attracted extensive attention.In this research,using Pickering high internal phase emulsions(Pickering HIPEs)as template and functional metal-organic frameworks(MOFs,UiO-66-SO;H and UiO-66-NH;)/Tween 85 as co-stabilizers to synthesis the dual acid-base bifunctional macroporous polymer catalyst by one-pot process,which has excellent catalytic activity in the cascade reaction of converting cellulose to 5-HMF.The effects of the emulsion parameters including the amount of surfactant(ranging from 0.5%to 2.0%(mass)),the internal phase volume fraction(ranging from 75%to 90%)and the acid/base Pickering particles mass ratio(ranging from 0:6 to 6:0)on the morphology and catalytic performance of solid catalyst were systematically researched.The results of catalytic experiments suggested that the connected large pore size of catalyst can effectively improve the cellulose conversion,and the synergistic effect of acid and base active sites can effectively improve the 5-HMF yield.The highest 5-HMF yield,about 40.5%,can be obtained by using polymer/MOFs composite as catalyst(Poly-P12,the pore size of(53.3±11.3)μm,the acid density of 1.99 mmol·g^(-1)and the base density of 1.13 mol·g^(-1))under the optimal reaction conditions(130℃,3 h).Herein,the polymer/MOFs composite with open-cell structure was prepared by the Pickering HIPEs templating method,which provided a favorable experimental basis and theoretical reference for achieving efficient production of high addedvalue product from abundant biomass.

Crystallographic Characterization of the Novel Inorganic-organic Hybrid Coordinated Polymer: [(C_(22)H_(50)N_2)(Ag_2I_4)]_n

A novel coordinated polymer [(C22H50N2)(Ag2I4)]n([C22H50N2]2+ = N,N?-1,2- ethylence-bis(N,N?-dimethyl octane ammonium) (EDO)) was synthesized by the reaction of AgI and EDO at room temperature with pH = 6.8, and structurally characterized by means of X-ray single- crystal diffraction. It crystallizes in triclinic, space group P1 with a = 9.6080(1), b = 12.7643(2), c = 7.2157(8) ? a = 100.835(8), ?= 91.030(3), ? = 91.297(9)o, (C21.50H48.50Ag2I4N2), Mr = 1058.46, V = 868.71(19) 3, Z = 1, Dc = 2.023g/cm3, F(000) = 497.5, ?MoKa) = 4.692 mm-1, the final R = 0.0623 and wR = 0.1949 for 2641 observed reflections with I > 2s(I). The title compound consists of cations ([C22H50N2]2+) and anion chain (Ag2I42-)∞ which are combined by static attracting forces in the crystal to form the so-called organic-inorganic hybrid material.

Synthesis and Crystal Structure of a Novel One- dimensional Coordination Polymer [(C_(14)H_(18)N_2)(Pb_2I_6)]_n

The organic-inorganic hybrid [(C14H18N2)(Pb2I6)]n ([C14H18N2]2+ = N,N?-1,4-buthy- lenedipyridinium (BDP)) with one-dimensional structure was self-assembling synthesized by the organic quaternary ammonium template. It crystallizes in monoclinic, space group P21/n with a = 8.2596(9), b = 15.1363(19), c = 11.1603(13) , b = 97.915(5)o, C14H18N2Pb2I6, Mr = 1390.10, V = 1382.0(3) 3, Z = 2, Dc = 3.341 g/cm3, m(MoKa) = 18.870 mm-1, F(000) = 1196, the final R = 0.0420 and wR = 0.0921 for 2156 observed reflections with I > 2s(I). The title compound consists of cations ([C14H18N2]2+ ) and anion chain ([Pb2I62]n) which are combined by static attractive forces in the crystal.

虚拟模板MIPs-SPE联用技术对茶叶粗提物中咖啡因的分离纯化研究

目的 采用儿茶素作为虚拟模板制备分子印迹聚合物(Molecular imprintingpolymers,MIPs)结合固相萃取(Solid phase extraction,SPE)技术对茶叶粗提物中的咖啡因进行分离纯化。方法 以儿茶素为虚拟模板,4-乙烯基吡啶为功能单体,乙二醇二甲基丙烯酸酯为交联剂,聚苯乙烯为大分子拥挤试剂,以原位聚合的方式制备虚拟模板分子印迹聚合物。测定该分子印迹聚合物的保留性能、形貌特征和孔径分布等性能,以该分子印迹聚合物作为固相萃取吸附剂,对茶叶粗提物中的咖啡因进行分离纯化。结果 所制备儿茶素分子印迹聚合物对咖啡因的最优印迹因子为4.57。对茶叶粗提物中的咖啡因进行分离纯化后,在咖啡因纯度高于95%的条件下,咖啡因的回收率可达85%以上。结论 以儿茶素为虚拟模板合成的分子印迹聚合物,可以用于茶叶粗提物中咖啡因的分离纯化。

用于去除饮用水中硝基酚的双模板磁性分子印迹聚合物的制备及性能

为高效去除4-硝基酚(4-NP)和2,4-二硝基酚(2,4-DNP),本实验采用4-NP和2,4-DNP作为模板分子,以衣通酸(IA)为功能单体,磁性纳米氧化铁(Fe3O4@SiO2)为载体,乙二醇二甲基丙烯酸酯(EGDMA)为交联剂,偶氮二异丁腈(AIBN)为引发剂,采用表面分子印迹技术制备了双模板磁性分子印迹聚合物(D-MIPs)。利用傅里叶变换红外光谱(FT-IR)和扫描电子显微镜(SEM)对D-MIPs的形貌进行表征。研究了D-MIPs的吸附性能、可再生性和适用性。结果表明,D-MIPs成功地包覆在Fe3O4@SiO2载体表面,聚合效果良好,且具有特异的识别位点和良好的印迹性能,其直径为90 nm,形状均匀。4-NP-MIPs、2,4-DNP-MIPs和D-MIPs对目标分子的理论吸附量分别为103.97,73.14和123.99 mg/g,存在许多不同吸附能的吸附位点。D-MIPs在30 min内达到最佳吸附平衡状态,其最佳拟合模型为Freundlich吸附模型和拟二阶动力学模型,表明其吸附是通过化学吸附过程进行的。实验结果表明,在不同水样中,MIPs具有高度的特异性识别和选择性吸附能力。经过8次再生循环后,D-MIPs的吸附能力仅下降7.51%,证实了MIPs具有优异的再生性能。

Synthesis of 3D ordered macroporous indium tin oxide using polymer colloidal crystal template

Three-dimensional (3D) ordered macroporous indium tin oxide (ITO) is pre- pared using a polymer colloidal crystal template that is formed by self-assembly of the monodisperse poly(methyl methacrylate) (PMMA) microspheres. The morphologies and BET surface area of the macroporous material is examined by scanning electron micro- scope, transmission electron microscopy and N2 adsorption/desorption. Results indicate that the macroporous material has highly ordered arrays of the uniform pores replicated from the PMMA colloidal crystal template when the polymer colloidal crystal template is removed by calcinations at 500℃. The pore diameter (about 450 nm) of macroporous ITO slightly shrank to the PMMA microspheres. The BET surface area and pore volume of the macroporous material are 389 m2·g-1 and 0.36 cm3·g-1, respectively. Moreover, the macroporous ITO, containing 5 mol% Sn and after annealing under vacuum, shows the minimum resistivity of ρ = 8.2×10-3 Ω· cm. The conductive mechanism of macroporous ITO is discussed, and it is believed that the oxygen vacancies are the major factor for excellent electrical properties.

Polymer-virus core-shell structures prepared via co-assembly and template synthesis methods

Bionanoparticles(BNPs),consisting of virus and virus-like assemblies,have attracted much attention in the biomedical field for their applications such as imaging and targeted drug delivery,owing to their well-defined structures and well-controlled chemistries.BNPs-based core-shell structures provide a unique system for the investigation of biological interactions such as protein-protein and protein-carbohydrate interactions.However,it is still a challenge to prepare the BNPs-based core-shell structures.Herein,we describe(i) co-assembly method and(ii) template synthesis method in the development of polymer-BNPs core-shell structures.These two methods can be divided into three different systems.In system A,different polymers including poly(2-vinylpyridine)(P2VP),poly(4-vinylpyridine)(P4VP) and poly(ε-caprolactone)-block-poly(2-vinylpyridine)(PCL-b-P2VP) can form a raspberry-like structure with BNPs.In system B,polystyrene(PS) spheres end capped with free amine and BNPs can form a core-shell structure.In System C,layer-by-layer(LBL) method is used to prepare positive charged PS particles,which can be used as a template to form the core-shell structures with BNPs.These two methods may open a new way for preparing novel protein-based functional materials for potential applications in the biomedical field.

Screening the Insecticidal Efficacy of Nano ZnO Synthesized via in-situ Polymerization of Crosslinked Polyacrylic Acid as a Template

Nano zinc oxide （ZnO） is a very useful and important material in many industrial and biological applications. In the present work, ZnO was synthesized by post thermal degradation of the precursor ＂zinc acetate di-hydrate＂ templated in crosslinked polyacrylic acid （PAA）. The crosslinked PAA template was prepared through an in-situ polymerization process adopted in presence of ammonium per sulphate, as an initiator, and N, Nt- methylene bis-acrylamide as the crosslinker. Variation of preparation parameters and their impact on the oxide stoichiometry, crystal structure, crystallite size and surface texture of the oxide were investigated. Energy dispersive X-ray technique （EDX）, X-ray diffraction （XRD） and scanning electron microscopy （SEM） were convincingly used to reveal the oxide structural features and characteristics. The performed bioassay tests indicated the efficacy of this method of preparation to produce nano ZnO with novel insecticidal activity against the greater wax moth, Galleria rnellonella.

Template Effect of Hydrophobically Associating Polymers on the Construction of Cuprous Oxide Micro Structure

To determine the template effect of hydrophobically associating copolymers（HACPs） on the morphology of nano/micro structures, six HACPs were synthesized and used as templates to biomimetically synthesize cuprous oxide（Cu2O）, an important semiconductor. This experiment showed a clear relationship between the associating state of the HACP molecules and the morphology of the Cu2O particles. Cu2O hollow spheres were preferentially prepared when the HACP molecules were in an intramolecular associating state. Furthermore, a Cu2O hexapod was easily obtained when the HACP molecules were in an intermolecular associating state. The morphologies of the Cu2O crystals prepared in the presence of the HACPs also confirmed this result.

Controlled growth of ZnO nanorods by polymer template and their photoluminescence properties

A large amount of one-dimensional ZnO nanorods with diameters in 15―50 nm aligned in radial cluster were successfully synthesized by polar polymer polyvinyl alcohol (PVA) as soft-template. The growth of ZnO nanorods was controlled by changing annealing temperature. The evolution of the morphology and microstructure was investigated by scanning electron microscope, transmission electron micro- scope and X-ray diffraction. It is shown that ZnO nanorods tend to be uniform and the crystallization is gradually improved with the temperature increasing from 400℃ to 700℃. The photoluminescence spectra of products show a strong ultra violet emission and relatively weak defect emissions. The sharp strong emission peak at 354 nm owing to the inter-band transition indicates the extraordinary photoluminescence property of ZnO nanorods.

CONTROLLED FABRICATION OF ONE-DIMENSIONAL POLYMER NANOSTRUCTURES via METALLOGEL TEMPLATE POLYMERIZATION

A facile method is reported to controllably fabricate one dimensional （1D） polymer nan,astructures via metallogel template polymerization. The metallogel was prepared through coordination interactions between silver ions and a ligand （L） bearing three pyridyl groups in tetrahydrofuran （THF）. The diameters of the metallogel nanofibers could be tuned by the gel concentration （GC）. Due to its high thermal stability and facility of removal, the metallogel was used as the template for radical polymerization of diacryolyl-2,6-diaminopyridine （DADAP） to form poly-diacryolyl-2,6-diaminopyridine （PDADAP） nanostructures. The gradually eroding of the templates by PDADAP provided us an effective way to fabricate various nanostructures of the polymer. We have demonstrated that different 1D nanostructures, including n^noribbons, nanotubes and nanowires, could be selectively fabricated by adjusting polymerization time, monomer concentration and GC. The rheological properties of the gel samples were tested by a rheometer. As prolonging the reaction time, more and more polymers were formed and the strength of the resulting polymer gels became higher and higher. The simple preparation process, easy controlled microstructures and adequate gel strength would make it a facile synthetic method for different 1D polymer nanosturctures.

Hierarchical Porous Polymer Beads Prepared by Polymerization-induced Phase Separation and Emulsion-template in a Microfluidic Device

Porous polymer beads（PPBs） containing hierarchical bimodal pore structure with gigapores and meso-macropores were prepared by polymerization-induced phase separation（PIPS） and emulsion-template technique in a glass capillary microfluidic device（GCMD）. Fabrication procedure involved the preparation of water-in-oil emulsion by emulsifying aqueous solution into the monomer solution that contains porogen. The emulsion was added into the GCMD to fabricate the（water-in-oil）-in-water double emulsion droplets. The flow rate of the carrier continuous phase strongly influenced the formation mechanism and size of droplets. Formation mechanism transformed from dripping to jetting and size of droplets decreased from 550 μm to 250 μm with the increase in flow rate of the carrier continuous phase. The prepared droplets were initiated for polymerization by on-line UV-irradiation to form PPBs. The meso-macropores in these beads were generated by PIPS because of the presence of porogen and gigapores obtained from the emulsion-template. The pore morphology and pore size distribution of the PPBs were investigated extensively by scanning electron microscopy and mercury intrusion porosimetry（MIP）. New pore morphology was formed at the edge of the beads different from traditional theory because of different osmolarities between the water phase of the emulsion and the carrier continuous phase. The morphology and proportion of bimodal pore structure can be tuned by changing the kind and amount of porogen.

吡啶盐/咪唑盐调控钴萘基二膦酸配位聚合物的结构和性质

通过引入质子化的1,3-二(4-吡啶基)丙烷(1,3-dppH_(2)^(2+))和双(咪唑-1-甲基)苯(1,4-bixH_(2)^(2+))作为阳离子模板,采用水热反应,得到3种基于1,4-萘二膦酸(1,4-ndpaH4)配体的钴萘二膦酸配位聚合物:(1,3-dppH_(2))2[Co_(4)(1,4-ndpa)(1,4-ndpaH)_(2)(1,4-ndpaH_(2))]·6H_(2)O(1)、(1,4-bixH_(2))_(0.5)[Co(1,4-ndpaH)](2)和(1,4-bixH_(2))_(0.5)[Co2(1,4-ndpaH)(1,4-ndpaH_(2))(H_(2)O)_(2)](3)。对配合物1~3分别进行了元素分析、红外光谱、单晶X射线衍射、粉末X射线衍射和热重分析表征。在配合物1和2中,四面体{CoO_(4)}和{PO_(3)C}通过共角形成一维无机链,无机链进一步被萘环交联成三维开放框架结构。阳离子模板1,3-dppH_(2)^(2+)和1,4-bixH_(2)^(2+)分别填充在配合物1和2晶体结构的骨架空隙内。有趣的是,配合物3的化学成分与2相似,只是增加了1个1,4-ndpaH_(2)^(2-)配体和2个配位水分子,但显示出不同于2的二维波形层状结构,其中{Co1O_(5)}三棱锥、{Co2O_(6)}八面体和{PO_(3)C}四面体通过共角形成一维链,再由萘环连接成层。相邻的层以AB堆积的方式构成超分子结构,层间填充阳离子模板1,4-bixH_(2)^(2+),以平衡电荷。磁性研究表明,在配合物1和2中,磁性中心之间存在反铁磁相互作用。