CdS和CdSe新型纳米结构的高效溶剂热合成

采用快速高效的溶剂热法合成了海星形CdS纳米结构和一维CdSe纳米结构。用XRD、SEM和UV-Vis等表征手段对产物进行了表征，结果表明产物为单一的CdS和CdSe纳米结构，且CdS纳米结构具有良好的分散性，其形成极大地受到pH值影响，而CdSe先形成层状的二维结构、再形成一维纳米结构。     

不同溶剂对甲氨蝶呤/类水滑石复合物性质的影响

采用共沉淀法将甲氨蝶呤(MTX)插层组装到类水滑石(LDHs)层间,分别考察了不同溶剂(如:水、乙醇/水、聚乙二醇-400/水、聚乙二醇-4000/水)对合成的甲氨蝶呤/类水滑石(MTX/LDHs)纳米复合物性质的影响.利用透射电镜(TEM)和原子力显微镜(AFM)观察产物形貌,利用X-射线衍射(XRD)、傅里叶变换红外(FTIR)、热重/差式扫描量热(TG-DSC)和紫外光谱(UV-Vis)等表征手段,对纳米复合物的结构及热力学性质进行了系统的研究.在pH=7.4的磷酸盐缓冲溶液中测定不同时间点药物累积释放量,考察了不同溶剂中合成的MTX/LDHs纳米复合物的药物控释性能.结果表明,短链聚乙二醇的加入保证了纳米粒子的稳定生长,能有效控制产物形貌,合成出的产物呈规则的圆片状,单分散性好,药物缓释性能平稳,释放过程属于药物扩散控制过程.当聚乙二醇分子链过长时,由于其自身容易发生缠绕,反而不利于纳米粒子的生长.     

HAP自组装球的简易合成及其光催化增效作用

选择生物协同模板,通过简单的控制组装工艺,制备出结构均一有序的羟基磷灰石(HAP)纳米组装球.该纳米组装球整体尺寸约5-6 μm,球体中心部分尺寸约为2.5-3 μm.通过X射线粉末衍射(XRD)、透射电子显微镜(TEM)、扫描电子显微镜(SEM)、傅里叶变换红外(FT-IR)光谱、比表面积(BET)测试等手段对产物形貌、结构和比表面积进行了表征.产物作为催化剂载体,对氧化锌催化降解罗丹明B (RhB)的催化效率提高了125%,催化剂回收率提高了23.1%,有效降低了催化剂的用量,在有机物降解领域具有潜在的应用价值.同时还对产物的控制生成过程和催化增效机理做了初步探讨.     

配体链包覆纳米粒子的表面相分离及自组装的模拟研究

通过耗散粒子动力学方法,模拟了二元配体链包覆的纳米粒子表面的相分离行为,并与现有的模拟和实验体系进行对比.研究结果印证了相分离驱动力是配体链错位所导致的构象熵的结论.进一步以相分离得到的Janus和三嵌段Janus结构纳米粒子作为构筑单元,研究了其在选择性溶剂中的自组装行为.结果表明,Janus粒子易自组装成为双层囊泡结构,而三嵌段Janus粒子则更易形成单层囊泡结构.对于从配体链包覆的纳米粒子出发,设计具有特殊功能的囊泡提供了理论支持.     

新型共价交联纳米胶囊的构筑、调控与功能

利用共价自组装的方法，将刚性组装基元与柔性链在一定条件下进行横向交联，可以方便地制备出单层高分子纳米胶囊.相比于传统的非共价超分子囊泡，这种新型的共价纳米胶囊具有结构稳定、尺度可控且分散性优异等诸多优点.因此，如何利用化学合成的手段来制备新型的纳米胶囊，并进一步实现对其结构调控和性能的探究具有十分重要的意义.针对这些问题，分别发展了功能化的柱[5]芳烃、四苯乙烯、卟啉、三嗪、苯硼酸酐等不同类型构筑基元，并使之与两端具有活性位点的柔性烷基链在适当的溶剂中进行聚合反应，最终获得了一系列的共价纳米胶囊.通过对其结构的修饰和调控，发现这些功能化的高分子纳米胶囊在光捕获、人工酶、抗菌材料以及药物载体等领域具有诸多潜在应用价值.未来，新型共价高分子纳米胶囊的开发、功能化以及应用有望得到进一步的拓展.     

不同铁盐氧化掺杂导电聚苯胺纳米结构的合成及性能研究

在没有外加掺杂剂的条件下,以FeCl3,Fe(NO3)3,Fe2(SO4)3,FePO4等多种铁盐为氧化剂,在水溶液中采用"无模板"的方法制备了具有较高电导率的聚苯胺纳米结构.铁盐是一种强酸弱碱盐,在水溶液中发生水解释放出质子,质子可以作为掺杂剂进入聚苯胺主链,因此,在苯胺的聚合过程中,铁盐同时起到氧化剂和掺杂剂的双重功能,进一步简化了导电聚苯胺纳米结构的合成条件,降低了反应成本.FTIR,UV-Vis,XRD等结构表征证实所得的纳米结构的聚苯胺均为掺杂态.试验发现,铁盐较低的氧化/还原电位使产物具有较小的直径和较高的电导率和结晶性.不同的对阴离子对聚苯胺产物的形貌有一定的影响,但对产物的结构和性能影响不大.铁盐与苯胺单体的比例对聚苯胺的形貌和电导率均有较大的影响.     

基于G-四链体结构多态性的核酸纳米技术

G-四链体是由富G核酸形成的独特四链螺旋结构,区别于遵循A-T、G-C碱基互补配对原则形成的传统Watson-Crick双链结构.基于G-四链体的特异分子识别特性,能够引导纳米粒子的有序组装、赋予纳米器件以刺激一响应功能,使得核酸纳米技术领域的内容更丰富多样.本文介绍了G-四链体的结构多态性,从纳米材料组装和纳米器件设...     

物理混合法制备分级混晶TiO2微纳米材料及其光催化性能

通过物理混合法可控合成了分级混晶TiO₂微纳米材料, 采用扫描电子显微镜(SEM)、 透射电子显微镜(TEM)、 X射线衍射仪(XRD)、 X射线光电子能谱仪(XPS)和固体紫外-可见分光光度计(UV-Vis)等对该微纳米材料进行了表征, 并评价了不同混晶比材料的光催化性能. 结果表明, 所得材料是由均匀负载金红石纳米颗粒的锐钛矿纳米片组装的三维分级结构. 其具有很高的光催化活性, 分级结构和混晶异相结的同时引入是提高材料光催化活性的关键.     

SBA-15模板法合成硫化锌纳米束及其光电性能

以乙基黄酸锌(ZnR2)作为单分子前驱体, SBA-15作为模板, 合成高度有序的ZnS纳米束, 并通过透射电子显微镜(TEM)、热重-差热分析(TG-DTA)、X射线衍射(XRD)、N2吸附-脱附、紫外-可见(UV-Vis)光谱、荧光光谱和扫描电子显微镜(SEM)等一系列手段对其形貌、结构及性能进行表征. 结果表明, 此阵列具有高度有序的六方介孔结构, 同时具有类似于母模板的纤维状形貌. 采用一种简单的交流电场辅助的方法把纳米束组装到电极上, 然后通过半导体表征仪器进行测试, 表征结果发现单束ZnS纳米束呈现出非线性的整流行为, 在紫外光照射下, 其电流-电压(I-V)曲线发生了很大的变化, 说明利用它们组装的纳米器件具有良好的光开关效应,并对整流及光响应机理进行了解释.     

气-液界面Au纳米粒子网状结构薄膜的制备及SERS性能研究

本研究通过自组装法在气-液界面得到Au纳米粒子网状结构,并通过进一步生长得到连续的Au纳米粒子网状结构薄膜.该方法无需加入任何诱导剂,在室温条件下即可得到稳定性良好的纳米金薄膜.通过改变HAuCl_4和AgNO_3相对用量、陈化时间等条件对网状结构薄膜的形成机理进行了研究.结果发现,AgNO_3用量对Au纳米粒子薄膜的形成至关重要,通过调控AgNO_3用量可以促进纳米金粒子间的融合并形成纳米链、进一步演化为纳米链网状结构.在初步形成的Au纳米粒子网状结构表面通过抗坏血酸还原进一步生长纳米金粒子,有利于形成较大面积、较好稳定性的纳米Au粒子网状结构薄膜.以对氨基苯硫酚(4-ATP)作为探针分子,研究表明,与未发生组装的金纳米粒子相比,自组装形成的Au纳米粒子网状结构薄膜对4-ATP具有较强的表面增强拉曼效应.     

A facile one-pot method to fabricate gold nanoparticle chains with dextran

A biocompatible water-soluble dextran has been used for controllable one-dimensional assembly of gold nanoparticles via a one-pot method.Long gold nanoparticle chains with good dispersion in water could be easily obtained after adding dextran into the mixture of HAuCl 4 and sodium citrate.The measurements of scanning electron microscopy(SEM) and dynamic light scattering(DLS) confirmed the formation of gold nanoparticle chains.The morphology and dispersion properties of gold nanoparticle chains could be tuned by adjustment of the reagent ratio,stirring speed,and reaction time.     

Bottom-up assembly of colloidal gold and silver nanostructures for designable plasmonic structures and metamaterials

We report on bottom-up assembly routes for fabricating plasmonic structures and metamaterials composed of colloidal gold and silver nanostructures, such as nanoparticles ("metatoms") and shape-controlled nanocrystals. Owing to their well-controlled sizes/shapes, facile surface functionalization, and excellent plasmonic properties in the visible and near-infrared regions, these nanoparticles and nanocrystals are excellent building blocks of plasmonic structures and metamaterials for optical applications. Recently, we have utilized two kinds of bottom-up techniques (i.e., multiple-probe-based nanomanipulation and layer-by-layer self-assembly) to fabricate strongly coupled plasmonic dimers, one-dimensional (1D) chains, and large-scale two-dimensional/three-dimensional (2D/3D) nanoparticle supercrystals. These coupled nanoparticle/nanocrystal assemblies exhibit unique and tunable plasmonic properties, depending on the material composition, size/shape, intergap distance, the number of composing nanoparticles/nanocrystals (1D chains), and the nanoparticle layer number in the case of 3D nanoparticle supercrystals. By studying these coupled nanoparticle/nanocrystal assemblies, the fundamental plasmonic metamaterial effects could be investigated in detail under well-prepared and previously unexplored experimental settings.     

Inversion of Optical Activity in the Synthesis of Mercury Sulfide Nanoparticles: Role of Ligand Coordination

Optical activity in inorganic colloidal materials was controlled through interactions of chiral molecules with the nanoparticle (NP) surface. An inversion of optical activity in the synthesis of mercury sulfide (HgS) NPs was demonstrated with an intrinsically chiral crystalline system in the presence of an identical chiral capping ligand. A continuous decrease in the positive first Cotton effect and an eventual reversal of CD profile were observed upon heating the aqueous solution of HgS NPs capped with N‐acetyl‐l ‐cysteine (Ac‐l ‐Cys) at 80 °C. Ac‐l ‐Cys afforded two bidentate coordination configurations with an almost mirror image of each other using the thiolate and either of carboxylate or acetyl–carbonyl groups on the HgS core. Experiment and calculation suggest that a shift in the distribution of the NP formation with energy in response to the combinations of ligand coordination structure and chiral crystalline surface is responsible for the inversion of optical activity.     

多嵌段共聚物/纳米粒子杂化多级结构的光学性能

结合耗散粒子动力学模拟和时域有限差分方法,研究了A(BC)_n多嵌段共聚物和纳米粒子共混体系的自组装行为及其光学性能,分析了纳米粒子体积分数和嵌段间相互作用强度对自组装形貌及其光学性能的影响。结果表明,A(BC)_n多嵌段共聚物/纳米粒子共混体系可形成有机/无机杂化的多级结构,改变纳米粒子的体积分数和嵌段间相互作用强度可以调控纳米粒子的分布及其相应的多级结构。不同尺度的结构对不同频率光的反射作用有明显区别,而纳米粒子的加入显著增大了反射峰的强度和宽度。改变纳米粒子的分布可调控反射峰的强度和宽度。     

碳纤维上电沉积Pd-Ag合金纳米粒子链及其氢传感性能

在碳纤维上采用三脉冲电沉积的方法制备出钯银合金纳米粒子链.把表面覆盖有Pd-Ag合金纳米粒子链的碳纤维组装成氢气传感器.采用扫描电子显微镜(SEM)和X射线能谱(EDX)表征了合金纳米粒子链的形貌和成分,应用CHI660B电化学工作站测试其氢传感性能.结果表明,在钯、银离子摩尔比为15∶1的电解液中,在-1.0--1.5 V下,成核5-40 ms;在-0.25--0.35 V,生长200-300 s的条件下,即可获得银的质量分数为16.0%-25.0%的钯银合金纳米粒子链阵列.在室温下,传感器对在0.30%-5.00%(φ,体积分数,下同)范围内的氢气有响应,最快响应时间约为300 s,灵敏度最高可达31.0%;氢在0.30%-1.20%的范围内响应电流与氢气浓度成线性关系,超过4.00%时响应电流不再随浓度的增加而变化;在低于3.50%的浓度下氢传感器的重现性良好.     

Biomolecule-nanoparticle hybrids as functional units for nanobiotechnology

Biomolecule-metal or semiconductor nanoparticle (NP) hybrid systems combine the recognition and catalytic properties of biomolecules with the unique electronic and optical properties of NPs. This enables the application of the hybrid systems in developing new electronic and optical biosensors, to synthesize nanowires and nanocircuits, and to fabricate new devices. Metal NPs are employed as nano-connectors that activate redox enzymes, and they act as electrical or optical labels for biorecognition events. Similarly, semiconductor NPs act as optical probes for biorecognition processes. Double-stranded DNA or protein chains that are modified with metallic nanoclusters act as templates for the synthesis of metallic nanowires. The nanowires are used as building blocks to assemble nano-devices such as a transistor or a nanotransporter.     

Interplay between fluorescence and morphology in composite MEH-PPV/PCBM nanoparticles studied at the single particle level

We report the study of the photoluminescence properties of composite conjugated polymer (MEH-PPV)/fullerene (PCBM) nanoparticles as a function of PCBM doping level. The emission properties of individual nanoparticles were studied by Single Particle Spectroscopy (SPS), and distinct changes in vibronic structure with nanoparticle composition were observed. These changes are found to be due to the presence of domains in the nanoparticles with two distinct types of optical signatures, one with molecular and one with aggregate character, for which the abundance and morphology is found to change with PCBM doping levels. Interestingly, highly delocalized structures with a large extent of exciton migration are formed at low PCBM doping levels, while at high PCBM doping levels the exciton collapses into highly localized structures. Furthermore, at very high doping levels phase separation within the MEH-PPV/PCBM nanoparticles is found, even though the reported nanoparticles are only a few tens of nanometers in diameter.     

Probing dynamic generation of hot-spots in self-assembled chains of gold nanorods by surface-enhanced Raman scattering

Further progress in the applications of self-assembled nanostructures critically depends on developing a fundamental understanding of the relation between the properties of nanoparticle ensembles and their time-dependent structural characteristics. Following dynamic generation of hot-spots in the self-assembled chains of gold nanorods, we established a direct correlation between ensemble-averaged surface-enhanced Raman scattering and extinction properties of the chains. Experimental results were supported with comprehensive finite-difference time-domain simulations. The established relationship between the structure of nanorod ensembles and their optical properties provides the basis for creating dynamic, solution-based, plasmonic platforms that can be utilized in applications ranging from sensing to nanoelectronics.     

Frequency dependence of gold nanoparticle superassembly by dielectrophoresis

Dielectrophoresis is an effective method for capturing nanoparticles and assembling them into nanostructures. The frequency of the dielectrophoretic alternating current (ac) electric field greatly influences the morphology of resultant nanoparticle assemblies. In this study, frequency regimes associated with specific gold nanoparticle assembly morphologies were identified. Gold nanoparticles suspended in water were captured by microelectrodes at different electric field frequencies onto thin silicon nitride membranes. The resultant assemblies were examined by transmission electron microscopy. For this system, the major frequency-dependent influence on morphology appears to arise not from the Clausius-Mossotti factor of the dielectrophoretic force itself, but instead from ac electroosmotic fluid flow and the influence of the electrical double layer at the electrode-solution interface. Frequency regimes of technological interest include those forming one-dimensional nanoparticle chains, microwires, combinations of microwires and nanoparticle chains suitable for nanogap electrode formation, and dense three-dimensional assemblies with very high surface area.     

Structural control of peptide-coated gold nanoparticle assemblies by the conformational transition of surface peptides

Gold nanoparticles having peptide chains on the surfaces have been prepared yb ring-opening polymerization of gamma-methyl L-glutamate N-carboxyanhydride with fixed amino groups on the nanoparticle surface as an initiator. The number of peptide chains on the surface was adjusted to ca. 2 molecules per gold nanoparticle by controlling the number of fixed amino groups on the surface. The peptide chains on the surface were partially saponified to obtain poly(gamma-methyl L-glutamate-co-L-glutamic acid) with 28 mol% of glutamic acid residues. The number-average molecular weight of the peptide was 73,000. We described structural control of the peptide-coated gold nanoparticle assembly by conformational transition of the surface peptides. In deionized water, the peptide chains on the nanoparticle took a random coil conformation, and the individual nanoparticles existed in dispersed globular species. On the other hand, the peptide chains on the nanoparticle took an alpha-helical conformation in trifluoroethanol. Under this condition, the alpha-helical peptide chains on distinct gold nanoparticles connected the nanoparticles to form a fibril assembly owing to the dipole-dipole interaction between the surface peptide chains. The morphology of the peptide-coated gold nanoparticle assembly could be controlled by the conformational transition of surface peptides, which was attended by solution composition changes.