小尺寸金石墨纳米颗粒的合成与表征

在表面增强拉曼光谱(SERS)的研究领域中,基于局域表面等离子体共振效应的等离子体SERS基底的制备成为过去几十年的研究热点。然而,通常开发的等离子体金属基底具有较差的稳定性和重现性。对于SERS而言,石墨烯类材料具有拉曼化学增强效应,除此之外,还具有分子富集、强的稳定性与荧光猝灭能力等优点,因此基于石墨金属复合纳米材料的SERS基底受到了研究人员的重视。我们利用化学气相沉积(CVD)法制备了小尺寸的金石墨核壳纳米颗粒(Au@G),其粒径约为17 nm。我们通过在Au NP上包覆介孔二氧化硅来控制Au@G的尺寸,同时还研究了包覆二氧化硅过程中,正硅酸乙酯(TEOS)的浓度对于石墨壳层形成的影响。结果表明当TEOS在一定浓度范围内,其浓度的降低有利于得到石墨化程度高的Au@G。进一步利用Au@G对结晶紫分子进行拉曼检测,也表明了Au@G具有较好的拉曼增强效果。这种小尺寸的Au@G在分子检测与细胞成像分析领域中具有广泛的应用潜力。     

Synthesis of Monodisperse Hollow Carbon Nanocapsules by Using Protective Silica Shells

Monodisperse hollow carbon nanocapsules (<200 nm) with mesoporous shells were synthesized by coating their outer shells with silica to prevent aggregation during their high‐temperature annealing. Monodispersed silica nanoparticles were used as starting materials and octadecyltrimethoxysilane (C18TMS) was used as a carbon source to create core–shell nanostructures. These core–shell nanoparticles were coated with silica on their outer shell to form a second shell layer. This outer silica shell prevented aggregation during calcination. The samples were characterized by TEM, SEM, dynamic light scattering (DLS), UV/Vis spectroscopy, and by using the Brunauer–Emmett–Teller (BET) method. The as‐synthesized hollow carbon nanoparticles exhibited a high surface area (1123 m² g^?1) and formed stable dispersions in water after the pegylation process. The drug‐loading and drug‐release properties of these hollow carbon nanocapsules were also investigated.     

聚合物中空微球的合成策略（英文）

在过去的20年中,聚合物中空微球由于其独特的结构和优异的性质受到了广泛的关注.它们表现出低密度、高比表面积和高负载力的特性,在催化、药物递送及能量存储等领域中展现出巨大的应用前景.本文综合评述了聚合物中空微球的合成策略,主要包括模板法、乳液聚合法、自组装与及微流控等,并详细阐述和讨论了这些合成策略的原理、典型过程以及优缺点.同时,还指出了现有合成策略面临的挑战以及聚合物中空微球存在的不足,并对聚合物中空微球的制备和应用前景进行了展望.     

Synthesis and Characterization of Microcapsules with Chlorpyrifos Cores and Polyurea Walls

Microcapsules with chlorpyrifos cores and polyurea walls were synthesized with 2,4-tolylene diisocyanate as an oil-soluble monomer and ethylenediamine as a water-soluble monomer via an interracial polycondensation reaction. The products were characterized by means of Fourier transform infrared spectrometry, ^13C NMR spectrometry and ^31p NMR spectrometry. The morphology, the particle size and the particle size distribution, and the thermal properties were also evaluated. The prepared microcapsules exhibit clear and smooth surfaces and have a mean diameter of 28. 13 μm. These microcapsules also have a good thermal stability for long-term use, and have potential applications in minimizing the toxicity of chlorpyrifos through controlled release.     

孔壁部分有序化的介孔二氧化硅材料的合成与表征

采用一种“改进的二次晶化”的方法处理介孔二氧化硅SBA-15. 用X射线衍射(XRD)、 透射电镜(TEM)、 电子衍射(ED)、 红外光谱(FTIR)以及固体核磁共振(NMR)等多种技术对样品进行了表征.　结果表明， 在所得样品的孔壁中, 原子的排列方式与普通介孔二氧化硅材料的孔壁不同， 显示一定程度的有序性. 同时, 高度有序的介孔结构得到很好的保持, 且样品的水热稳定性大幅度提高.     

带有酰胺侧基的中空手性高分子微球的合成及其分离性能

合成了带有手性基团的多孔高分子微球, 并将其作为高效液相色谱手性固定相用于分离制备盐酸贝那普利的一个重要中间体(R)-α-羟基苯丁酸乙酯.     

Synthesis,Structure,and Characterization of a Novel Coordination Polymer with Polythreading Feature

A novel coordination polymer 1 with formula of Zn₂(BDC)₂(TPPA) was built from 1,4-dicarboxybenzene (H₂BDC),tris(4-(pyridin-3-yl)phenyl)amine (TPPA),and Zn(Ⅱ) ion.It was characterized by single-crystal and powder X-ray diffraction,Fourier-transform infrared spectra (FT-IR),thermal gravimetric analysis (TGA),and UV-vis.1 crystallizes in triclinic space group P1 with a=14.589,b=14.606,c=16.108?,α=115.635~o,β=90.328~°,γ=114.662~o,V=2738.6A³,Z=2,M_r=935.52 g/mol,D_c=1.134 g/cm~3,F(000)=956,GOOF=1.062,the final R=0.0685 and w R=0.1817 for 7701 observed reflections with (I>2σ(I)),and R=0.0717 and w R=0.1843 for all data.In 1,Zn(Ⅱ) is coordinated with H₂BDC to form a 2D square grid,and TPPA ligands were arranged above and beneath the 2D layer.Two neighbor layers are interpenetrated each other byπ-πinteractions to generate a polythreading framework structure.Moreover,the photoluminescence of 1 was also studied.     

环形侧链聚合物刷的合成与表征

通过grafting-onto方法合成高侧链接枝密度的环形侧链聚合物刷并进行结构表征.先通过开环易位聚合(ROMP)制备带有炔基侧基的线形聚降冰片烯衍生物主链(l-PND),通过原子转移自由基聚合(ATRP)和铜催化的叠氮-炔环加成(Cu AAC)反应制备带有一个叠氮基的环形聚丙烯酸叔丁酯侧链(c-Pt BA),再利用Cu AAC反应将环形侧链高密度地接入主链,得到环形侧链聚合物刷.通过核磁氢谱(1H-NMR)、凝胶渗透色谱(GPC)和红外光谱(IR)对聚合物主/侧链及聚合物刷的结构和组成进行了表征.该聚合物刷主链聚合度为400,高接枝密度的环形侧链使主链构象伸展.聚合物刷在原子力显微镜(AFM)下呈单分子蠕虫形貌(柱状形貌),分子长度为200 nm,直径为30 nm.     

Synthesis and Characterization of New Polymer Nanocontainers

New type of reactive, water-soluble and filled polymer nanocontainers that can be covalently attached to surfaces were synthesized. The encapsulation of a dye inside the nanocontainers allows their rapid detection. The model systems are based on crosslinked polystyrene (PS) and polymethylmethacrylate (PMMA). The synthesis of nanocontainers by two-step emulsion polymerization and characterization by NMR, IR, Dynamic Light Scattering, TEM and Confocal Laser Scanning Microscopy (CLSM) is presented.     

网状纳米结构希夫碱卟啉聚合物的合成和表征

网状纳米结构希夫碱卟啉聚合物的合成和表征     

单分散空心SiO2纳米微球的合成与表征

聚乙烯吡咯烷酮(PVP)功能化的聚苯乙烯(PS)粒子在SiO2包覆的同时被乙醇/氨水介质溶解, 得到了单分散空心SiO2纳米微球. 该空心SiO2纳米微球的尺寸和形态可以通过PVP, NH4OH和正硅酸乙酯(TEOS)的用量来调节. PVP用量增加导致PS粒子变小, 从而得到较小的空心SiO2纳米微球; NH4OH用量增加, 空心SiO2纳米微球表面变得粗糙; TEOS用量增加, 空心SiO2纳米微球的壳层厚度增加. 包覆(溶解)温度是控制空心SiO2纳米微球形成的最有效手段. 在70 ℃的包覆(溶解)温度下可以获得全部空心的SiO2纳米微球.     

N掺杂空心TiO2微球的合成与表征

采用无皂乳液聚合合成的聚苯乙烯(PS)微球为模板、氨水/三乙醇胺为催化体系, 通过溶胶-凝胶方法合成了PS/TiO₂(核/壳)复合微球, 然后通过煅烧制备了N掺杂、锐钛型空心TiO₂微球. 在反应体系中三乙醇胺扮演双重角色, 既是TiO₂生成及包覆过程的抑制剂又是空心TiO₂微球的N掺杂剂. 改变氨水、三乙醇胺和钛酸正丁酯用量可控制TiO₂壳的形态和尺寸. 氨水用量增加, PS/TiO₂复合微球的壳表面变得粗糙|三乙醇胺用量增加, 壳表面变得光滑|钛酸正丁酯用量提高导致壳层变厚. 改变三乙醇胺用量可调节空心TiO₂微球中的N掺杂量|N掺杂空心TiO₂微球具有可见光响应和光催化作用.     

Synthesis, Characterization and Crystal Structure of a Noncentrosymmetric Coordination Polymer with 3-Aminopyridine

Hydrothermal reaction of 3-aminopyridine, NaSCN and cadmium cation led to the formation of complex [Cd（3-ampy）（NCS）2]n 1 （3-aminopyridine = 3-ampy）, and its crystal structure was determined by X-ray diffraction analysis. The crystal data for compound 1： C7H6N4S2Cd, orthorhombic Fdd2, Mr = 322.68, Z = 16, a = 26.884（4）, b = 27.445（3）, c = 5.8671（7）A, V = 4329.0（10） A3 Dc= 1.974 g/cm^3, μ= 2.368 mm^-1, F（000） = 2496, R = 0.0203 and wR = 0.0491 for 2347 observed reflections with Ⅰ 〉 2σ（Ⅰ）, and absolute structure parameter is 0.00（3）. X-ray diffraction reveals that the compound consists of interesting two-dimensional wave sheet structure. The photoluminescence spectrum and interesting second-order nonlinear optical （NLO） property for compound 1 have also been studied.     

Silver Hollow Microspheres: Large-scale Synthesis, Characterization and Electromagnetic Shielding Property

A facile and large-scale synthesis method to fabricate silver hollow microspheres with controllable morphologies and shell thickness is described using low-cost glass microspheres as templates. The method mainly involves two steps of the preparation of silver-coated glass microsphere core-shell particles by a controllable liquid reduced reaction of Ag[(NH3)2]+ solution, which only produces silver nanoparticles anchored on the surface of the thiolated glass microsphere templates, and the removal of glass microspheres by wet chemical etching with HF solution. The products are well characterized by field emitted scanning electron microscopy (SEM), transmitted electron microscopy (TEM), X-ray photoelectron spectra (XPS), X-ray diffraction (XRD) and energy dispersive X-ray (EDX) etc. The as-prepared core-shell particles and hollow particles have even and compact silver shells. The electromagnetic shielding coatings based on the silver hollow microspheres are demonstrated to have high conductivity, excellent shielding effectiveness and long durability, suggesting that the silver hollow microspheres obtained here are a novel light-weight electromagnetic shielding filler and will have extensive applications in the electromagnetic compatibility fields.     

含三苯胺单元的共轭聚合物的合成、表征及应用

采用 Wittig 方法制得了未封端及封端的线性聚三苯胺-对苯乙烯撑型聚合物(分别简称为:TPA-DOPPV1,TPA-DOPPV2),并对共轭聚合物进行了表征和性能测试.封端后的聚合物溶液和固体膜在紫外光照射下均发出较强的绿光.对这类聚合物在硝基化合物检测方面的应用进行了初步研究,结果表明:封端后的共轭聚合物在邻硝基甲苯(o-NT)荧光检测上的性能明显提高,当o-NT 浓度为 21.5×10-3 mol/L 时,荧光猝灭效果达到了 96%;在2,4-二硝基甲苯(DNT)、对硝基甲苯(P-NT)和对苯醌(p-BQ)蒸汽中放置 10 s 时,其薄膜的荧光猝灭效率分别达到 30%、15.6%和 3.1%.TPA-DOPPV2 的合成操作较为简便,具有一定的检测灵敏性,是一种潜在的硝基类爆炸物荧光检测材料.     

锆酸钡/聚合物复合中空纳米球的水热合成

采用聚合物辅助水热合成方法, 在强碱条件下加入PAA和PVA的混合液,实现了聚合物/锆酸钡复合中空纳米球的软化学一步合成, 而且球壳为有机-无机复合材料, 有望用于吸附分离、催化剂载体、轻质陶瓷和涂料等方面.     

Polymer Micro‐ and Nanocapsules as Biological Carriers with Multifunctional Properties

The design and development of multifunctional polymer capsules with controlled chemical composition and physical properties has been the focus of academic and industrial research in recent years. Especially in the biomedical field, the formulation of novel polymer‐based encapsulation systems for the early‐stage disease diagnostic and effective delivery of bioactive agents represent one of the most rapidly advancing areas of science. The stimuli‐responsive release of cargo molecules from the carrier gains remarkable attention for in vitro and in vivo delivery of contrast agents, genes, and pharmaceutics. In this Review, the current status and the challenges of different polymer‐based micro‐ and nanocapsule formulations are considered, emphasizing on their potential biological application as carriers for specific drug targeting and controlled release upon applying of external stimulus.