基于AFM纳米氧化技术的金纳米粒子定点组装

二维纳米粒子矩阵列在纳米电子器件^[1,2]、表面增强喇曼活性基底^[3,4]、刻蚀掩模^[5]等领域具有广泛的应用前景。在这些纳米粒子阵列为内部,纳米粒子的排布是随机、无序的。这一缺点已经妨碍了纳米粒子阵列在上述领域中的进一步应用。基于此,人们开始关注纳米粒子的可控组装。传统的光刻技术^[6]、微接触印刷技术^[7]以及生物分子模板技术^[8]都被用来实现纳米粒子在固体表面上的可控组装,本实验室在纳米粒子的合成及可控组装方面也进行了研究^[7,9,11]。本文力图精确控制单个纳米粒子在基底表面上的组装位置。利用AFM纳米氧化技术。在硅表面构建了纳米级的化学图形化表面,通过不同的化学官能团,如甲基、氨基对金纳米粒子亲和性质的差异,实现了纳米粒子在固体表面的定点组装。     

毛细管电泳在纳米粒子分离和性质表征中的应用进展

毛细管电泳方法被成功用于分离性质不同的纳米粒子,并且可对纳米粒子的表面zeta电势、等电点及表面电荷等表面性质进行表征.本文综述了毛细管电泳法在纳米粒子的分离分析以及其表面性质研究中的应用进展.     

荧光碳纳米粒子与纸张的相互作用及分析特性研究

在研究荧光碳纳米粒子与纸质材料相互作用的基础上,考察了荧光碳纳米粒子从纸质材料表面的洗脱去除方法以及残留荧光碳纳米粒子对纸质材料的性能如抗老化能力、机械强度等的影响,提出了一种可基于荧光碳纳米粒子原位、无损传感纸张表面pH的新方法,并测定了纸质文物表面的pH。     

金纳米粒子的表面修饰及生物应用进展

近年来纳米材料被广泛应用于生物医学、航空航天和精细化工等领域。构成纳米材料的纳米粒子具有小尺寸效应、表面效应和宏观量子隧道效应等性质。其中金纳米粒子由于其独特的荧光特性、良好的生物相容性和表面等离子共振等性质,被广大科研人员进行深入研究。例如,在生物医学领域,科研人员构建了一系列新型的金纳米比色传感器、光学探针及各类载药体系等。然而,目前金纳米粒子仍存在水分散性差、肾清除效率低和量子发射产率低等问题,限制了其广泛应用。因此,研究人员对金纳米粒子表面进行多样化修饰,从而能有效克服上述缺点。本文就目前主流配体表面修饰金纳米粒子的研究进展进行了详细总结,着重介绍了功能化金纳米粒子在生物成像、生物检测、生物治疗三方面的应用,最后对金纳米粒子的临床治疗机制的探索以及商业化的应用进行了展望,希望能为相关领域的研究者们提供新思路。     

用于纳米粒子合成的微乳液

微乳液作为纳米反应器的最大优点是可以实现纳米粒子尺寸控制。体系中水的含量、表面活性剂、助表面活性剂等都是控制粒子尺寸的可调因素,研究这些因素对所合成的纳米粒子尺寸以及产量的影响对于实际应用有重要的意义。本文评述了近年来相关的研究进展,对微乳液法在合成纳米粒子中的应用前景作了展望。     

大面积多元化表面等离激元金纳米粒子结构的制备

具有显著表面等离激元共振效应的贵金属纳米粒子因其独特的光电学性质在许多领域表现出了潜在的应用价值. 结合纳米压印技术与自组装技术发展了一种高效的多元化纳米粒子结构的制备方法, 并制备了一种由不同尺寸金纳米粒子构成的周期性表面等离激元纳米粒子结构. 实验结果证明此种方法在大批量制备和结构多元化的控制方面具有独特的优势. 利用不同的表面等离激元纳米粒子结构对不同荧光分子增强效果的差异, 设计了2种具有明显明暗差异的荧光条码, 展示了多重的荧光增强响应.     

Fe3O4纳米粒子的制备及耐盐性能研究

通过共沉淀法制备了Fe3O4纳米粒子,并采用十二烷基磺酸钠(SDS)对纳米粒子进行了表面修饰。FT IR显示SDS修饰到纳米粒子表面,XRD表明纳米粒子为立方晶相,从TEM照片中可看出纳米粒子粒径在10nm左右。纳米粒子耐盐性实验表明,在NaCl、MgCl2、Al2(SO4)3等盐溶液中,超声作用都有利于提高Fe3O4纳米粒子的分散稳定性能,但在不同盐溶液中,纳米粒子的优化超声时间不同。对于NaCl和Al2(SO4)3溶液,纳米粒子稳定分散的最佳超声时间是1h,而对于MgCl2溶液,纳米粒子稳定分散的最佳超声时间是2h。     

纳米粒子的界面自组装

近年来,随着纳米技术的发展及Pickering乳液在食品、化妆品、医药等领域中的应用,纳米粒子的界面自组装现象引起了人们的广泛关注。界面能的降低是纳米粒子液液界面自组装的主要驱动力。通过改变纳米粒子的尺寸和表面配体的化学性质,可控制纳米粒子的界面自组装行为。本文综述了不同类型纳米粒子实现界面自组装的研究工作,包括均质纳米粒子、Janus纳米粒子、棒状纳米粒子以及生物纳米粒子。最后,对纳米粒子的界面组装这一领域的可能发展做了展望。     

用硫脲分子表面修饰的CdS纳米粒子的合成和表征

报道了用硫脲分子进行表面化学修饰的CdS纳米粒子的合成方法,并引入了AOT(磺基琥珀酸双-2-乙基己基酯钠盐)作为平衡反离子,进一步对CdS表面作了修饰,增加了CdS纳米粒子在有机溶剂中的稳定性和可分散性。我们还探讨了温度、浓度、pH等因素对合成的影响,并通过TEM、XRD、FT-IR等手段对产物结构进行了表征。所得微粒粒径为5 nm左右,呈球形,硫脲分子与CdS纳米粒子富Cd²⁺表面通过形成Cd-S配位键而修饰在粒子表面。这种表面修饰的CdS纳米粒子将在非线性光学及自组装方面具有优     

二氧化硅纳米粒子表面修饰及其表征

采用溶胶-凝胶法合成粒径在50—150nm范围内的二氧化硅（SiO2）纳米粒子。用甲基丙烯酸-3-（三甲氧基硅基）丙酯（MPS）对SiO2纳米粒子表面进行修饰,使其表面接枝能参与自由基聚合反应的碳碳双键基团。用元素分析、FTIR、^13C CP／MASNMR和^29Si CP／MASNMR等手段对修饰过的SiO2纳米粒子进行表征,以确证MPS接枝在SiO2纳米粒子上。分析修饰过的SiO2纳米粒子的^29Si CP／MASNMR和FTIR谱图,还可初步推断MPS接枝在SiO2纳米粒子表面的机理：MPS首先发生水解缩合反应形成低聚物,然后通过氢键作用吸附到SiO2纳米粒子表面,最后MPS低聚物中未缩合的硅羟基与SiO2纳米粒子表面的硅羟基发生缩合反应。     

Ultrathin gradient films using thiol‐ene polymerizations

The application of surface‐attached, thiol‐ene polymer films for controlling material properties in a gradient fashion across a surface was investigated. Thiol‐ene films were attached to the surface by first depositing a thiol‐terminated self‐assembled monolayer and performing a thiol‐ene photopolymerization reaction on the surface. Property gradients were created either by creating and modifying a gradient in the surface thiol density in the SAM or by changing the polymerization conditions or both. Film thickness was modified across the substrate by changing either the density of the anchoring thiol functional groups or by changing the reaction conditions such as exposure time. Thicker films (1–11 nm) were obtained by polymerizing acrylate polymer brushes from the surface with varying exposure time (0–60 s). The two factors, that is, the surface thiol density and the exposure time, were combined in orthogonal directions to obtain thiol‐ene films with a two‐dimensional thickness gradient with the maximum thickness being 4 nm. Finally, a thiol‐acrylate Michael type addition reaction was used to modify the surface thiol density gradient with the cell‐adhesive ligand, Arg‐Gly‐Asp‐Ser (RGDS), which subsequently yielded a gradient in osteoblast density on the surface. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 7027–7039, 2006     

Organized surface functional groups: cooperative catalysis via thiol/sulfonic acid pairing

The synthesis and characterization of heterogeneous catalysts containing surfaces functionalized with discrete pairs of sulfonic acid and thiol groups are reported. A catalyst having acid and thiol groups separated by three carbon atoms is ca. 3 times more active than a material containing randomly distributed acid and thiol groups in the condensation of acetone and phenol to bisphenol A and 14 times more active in the condensation of cyclohexanone and phenol to bisphenol Z. Increasing the acid/thiol distance in the paired materials decreases both the activity and selectivity. This work clearly reveals the importance of nanoscale organization of two disparate functional groups on the surface of heterogeneous catalysts.     

Sulfur modification of polyethylene surfaces. II. Modification of polyethylene surfaces with fuming sulfuric acid

Previous work has shown that atomic sulfur irreversibility modifies polyethylene, presumably through an insertion reaction into carbon—hydrogen bonds with formation of surface thiol groups. The thiol groups were then oxidized to sulfonic acid surface groups, which were further reacted chemically as shown by wettability measurements. In this work the thiol group was bypassed and the surface sulfonic acid groups were obtained by exposing the polyethylene surface directly to fuming sulfuric acid. The sulfonic acid groups were reacted further. Critical surface tension values identical with those in the previous work with atomic sulfur were obtained, thus substantiating the previous work.     

Surface modification and particles size distribution control in nano-CdS/polystyrene composite film

Preparation of nano-CdS particles with surface thiol modification by microemulsion method and their influences on the particle size distribution in highly filled polystyrene-based composites were studied. The modified nano-CdS was characterized by X-ray photoelectron spectroscopy (XPS), light absorption and emission measurements to reveal the morphologies of the surface modifier, which are consistent with the surface molecules packing calculation. The morphologies of the surface modifier exerted a great influence not only on the optical performance of the particles themselves, but also on the size distribution of the particle in polystyrene matrix. A monolayer coverage with tightly packed thiol molecules was believed to be most effective in promoting a uniform particle size distribution and eliminating the surface defects that cause radiationless recombination. Control of the particles size distribution in polystyrene can be attained by adjusting surface coverage status of the thiol molecules based on the strong interaction between the surface modifier and the matrix.     

High surface density immobilization of oligonucleotide on silicon

Oligonucleotide (11-mer) molecules are immobilized on silicon in high surface population using either a permanent thioether bond or a chemo-selectively reversible disulfide bond to the surface thiol functionality. Substrate hydroxy groups are first silanized with an 11 carbon trichlorosilane containing a terminal, protected thiol moiety. Oligonucleotide modified with a tether possessing a terminal thiol group is further derivatized with a water-soluble, halobenzylic bifunctional reagent, which allows the complete conjugate to be attached to the surface through a permanent thioether bond. Alternatively, the oligonucleotide-tether complex can be combined with a pyridyldisulfide compound, which, in turn, facilitates the formation of a reversible disulfide bond with surface thiol. The amount of immobilized oligonucleotide was determined by radiochemical labeling with 32P. Additional verification of surface amounts was obtained from X-ray photoelectron spectroscopic analysis of substrates. The results of the immobilization protocols are compared with the oligonucleotide surface population achieved through the conventional silanizing agent, mercaptopropyltrimethoxysilane. Finally, a preliminary confirmation of duplex formation of a TTU-attached 25-mer with its complementary strand is outlined.     

Organo-soluble porphyrin mixed monolayer-protected gold nanorods with intercalated fullerenes

Organo-soluble porphyrin mixed monolayer-protected gold nanorods were synthesized and characterized. The resulting gold nanorods encapsulated by both porphyrin thiol and alkyl thiol on their entire surface with strong covalent Au-S linkages were very stable in organic solvents without aggregation or decomposition and exhibited unique optical properties different from their corresponding spherical ones. Alkyl thiol acts as a stabilizer not only to fill up the potential space on gold nanorod surface between bulky porphyrin molecules but also to provide space for further insertion of C(60) molecules forming a stable C(60)-porphyrin-gold nanorod hybrid nanostructure.     

Preparation of Nanoelectrode Ensembles by Assembly of Nano—Silver Colloid on Gold Surface

A novel method for preparing silver nanoelectrode ensembles(SNEEs) and gold nanoelectrode ensembles (GNEEs) has been developed. Silver colloid particles were first absorbed to the gold electrode surface to form a monolayer silver colloid. N-hexadecyl nercaptan was then assembled on the electrode to form a thoil monolayer on which hydrophilic ions cannot be transfered. The SNEEs was prepared by removing thiol from silver colloid surface through applying and AC voltage with increasing frequency at 0.20V(vs.SCE). Finally,GNEEs was obtained by immersing a SNEEs into 6 mol/L HNO3 to remove the silver colloid particles. By comparison with other methods such as template method ect., this method enjoys some advantages of lower resistance, same diameter,easy preparation,controllable size and density.     

Effect of surface chemical composition on the work function of silicon substrates modified by binary self-assembled monolayers

It has been shown that the application of self-assembled monolayers (SAMs) to semiconductors or metals may enhance the efficiency of optoelectronic devices by changing the surface properties and tuning the work functions at their interfaces. In this work, binary SAMs with various ratios of 3-aminopropyltrimethoxysilane (APTMS) and 3-mercaptopropyltrimethoxysilane (MPTMS) were used to modify the surface of Si to fine-tune the work function of Si to an arbitrary energy level. As an electron-donor, amine SAM (from APTMS) produced outward dipole moments, which led to a lower work function. Conversely, electron-accepting thiol SAM (from MPTMS) increased the work function. It was found that the work function of Si changed linearly with the chemical composition and increased with the concentration of thiol SAMs. Because dipoles of opposite directions cancelled each other out, homogeneously mixing them leads to a net dipole moment (hence the additional surface potential) between the extremes defined by each dipole and changes linearly with the chemical composition. As a result, the work function changed linearly with the chemical composition. Furthermore, the amine SAM possessed a stronger dipole than the thiol SAM. Therefore, the SAMs modified with APTMS showed a greater work function shift than did the SAMs modified with MPTMS.     

Photocaged pendent thiol polymer brush surfaces for postpolymerization modifications via thiol‐click chemistry

In this work, a postpolymerization surface modification approach is reported that provides pendent thiol functionality along the polymer brush backbone using the photolabile protection chemistry of both o‐nitrobenzyl and p‐methoxyphenacyl thioethers. Poly(2‐hydroxyethyl methacrylate) (pHEMA) brushes were synthesized via surface‐initiated atom transfer radical polymerization, after which the pHEMA hydroxyl groups were esterified with 3‐(2‐nitrobenzylthio)propanoic acid or 3‐(2‐(4‐methoxyphenyl)‐2‐oxoethylthio)propanoic acid to provide the photolabile protected pendent thiols. Addressing the protecting groups with light not only affords spatial control of reactive thiol functionality but enables a plethora of thiol‐mediated transformations with isocyanates and maleimides providing a modular route to create functional polymer surfaces. This concept was extended to block copolymer brush architectures enabling the modification of the chemical functionality of both the inner and outer blocks of the block copolymer surface. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013