表面修饰In纳米微粒的声化学法制备及结构表征

Surface modified indium nanoparticles were prepared by a simple and rapid process from bulk indium via ultrasound dispersion. The morphology and structure of synthesized nanoparticles were characterized by TEM, XRD, XPS and FTIR. The results show that the morphology of indium nanoparticles is spherical and the structure of indium nanoparticles is the tetragonal phase. The surface of indium nanoparticles was coated by 2 ethyl hexanoic acid, which could almost hold back oxidation of the indium nanoparticles. In addition, the tribological property of indium nanoparticles as additives in oil was evaluated on a four-ball tester and the results show that indium nanoparticles exhibit good performance in wear.     

Integrities and Skin Permeation-Enhancing Characteristics of Behenic Acid Nanoparticles

Fatty acid nanoparticles containing hinokitiol (HKL) were prepared by a melt-emulsification method. Behenic acid (BA) was used as a lipid for the matrix material of the nanoparticle. The size distribution was quite mono-dispersive and the mean diameter was around 200 nm. On a differential scanning calorimeter, no endothermic peak of HKL was observed when it was encapsulated in the nanoparticles. This indicates that HKL in the lipid matrix of the nanoparticles is not in a crystalline state, but rather in a dissolved state. The nanoparticles were stable over the range of pH 2–10 in terms of size. The absolute values of the zeta potentials in the pH range were high enough to prevent a particle-to-particle aggregation. Compared with stearic acid (SA) nanoparticles, which were completely disintegrated in sodium lauryl sulfate (SLS) solution of 4%, the BA nanoparticles were robust and remained intact even in SLS solutions of 14%. Therefore, BA nanoparticles would be applicable to cleansing products containing detergents for personal care. When encapsulated either in SA nanoparticles or in BA nanoparticles, the in vitro flux of HKL through hairless mouse skin was 10–15 times higher than dissolved in propylene glycol. BA nanoparticles, however, enhanced the transdermal delivery of HKL less than SA nanoparticles did.     

The role of PEG on the stability in digestive fluids and in vivo fate of PEG-PLA nanoparticles following oral administration

The aim of the present work was to evaluate if the presence of a polyethylenglycol (PEG) coating around PLA nanoparticles would affect their interaction with biological surfaces, following oral administration to rats. For this purpose, a model antigen, ¹²⁵I-radiolabeled tetanus toxoid, was encapsulated in PLA and PLA-PEG nanoparticles by a modified water-in-oil-in-water solvent evaporation technique. Firstly, the stability of the nanoparticles in simulated gastrointestinal fluids was evaluated. Results showed an interaction between the nanoparticles and the enzymes of the digestive fluids, this interaction being considerably reduced by the PEG coating around the particles. On the other hand, the PLA forming the nanoparticles was found to be only slightly degraded (9% converted to lactate for PLA nanoparticles and 3% for PLA-PEG nanoparticles) and that the encapsulated tetanus toxoid remained mostly associated to the nanoparticles upon incubation in the digestive fluids for up to 4 h. Finally, the in vivo experiments showed that, after oral administration to rats, the levels of encapsulated radioactive antigen in the blood stream and lymphatics were higher for PLA-PEG nanoparticles than for PLA nanoparticles. In conclusion, the PLA-PEG nanoparticles have a promising future as protein delivery systems for oral administration.     

Study on facile designing,swelling properties and structural relationship of gelatin nanoparticles

In the present work glutaraldehyde crosslinked gelatin (Type-A and Type-B) nanoparticles were fabricated following a microemulsion crosslinking technique. The structural, morphological, and stability features of nanoparticles were investigated using the techniques like FTIR, TEM, XRD, DLS, and surface charge measurements. The spectral peaks appeared in the FTIR spectra of gelatin nanoparticles confirmed the crosslinking of gelatin molecules with glutaraldehyde. The SEM analysis of the nanoparticles suggested that the size of gelatin nanoparticles was nearly 300 nm whereas the TEM analysis revealed their size around 200?nm. The size of nanoparticles was found to increase with increasing amounts of gelatin while it showed a decrease when the concentration of crosslinker was increased. An increase in percent crystallinity was observed when gelatin was crosslinked with glutaraldehyde. The water uptake capacity of the gelatin nanoparticles was evaluated under varying experimental conditions like, pH, temperature, presence of simulated physiological fluids and varying composition of the gelatin nanoparticles. To study the cytotoxic behavior of gelatin nanoparticles in vitro cytotoxicity analysis were performed. The gelatin nanoparticles demonstrated good stability and biocompatibility which suggested that these particles can be used as drug carrier in fabricating a swelling controlled drug delivery system.     

Heat-Induced Formation of Monodisperse Gold Nanoparticles in Different Conditions

We investigate the preparation of nearly monodisperse gold nanoparticles by heat treatment in different conditions. The effects of various solvents, heating temperature, and heating time length on the monodispersity of gold nanoparticles were studied systematically and a general route to generate gold nanoparticles with uniform size was determined. The first step was to prepare gold nanoparticles with less than 3 nm and the following operation was to heat the gold nanoparticles in the present of thiolated solvents where monodispersed gold nanoparticles could be obtained easily. Our approach has enriched synthesis of monodisperse gold nanoparticles, and may provide some valuable experimental data about how the heating process affects the size evolution of gold nanoparticles.     

Dual mode bioreactions on polymer nanoparticles covered with phosphorylcholine group

We investigated the preparation of polymer nanoparticles covered with phosphorylcholine (PC) groups and the immobilization of proteins in order to observe dual mode bioreactions on the nanoparticles. For the surface modification on the nanoparticles, a water-soluble amphiphilic phospholipid polymer with PC groups as a hydrophilic moiety was synthesized. In this polymer, an active ester group, which can immobilize proteins, was introduced. Using the phospholipid polymer as a solubilizer, poly(L-lactic acid) nanoparticles were prepared from its methylene chloride solution in an aqueous medium by the solvent evaporation method. The diameter of the nanoparticles was ca. 200 nm and the surface was covered with the PC groups and active ester groups. Proteins could immobilize on the nanoparticles under mild conditions by the reaction between the active ester group and amino group in the proteins. Both an antibody and enzyme were immobilized on the nanoparticles and bioreactions such as the antigen/antibody reaction and enzymatic reaction were observed. When an antigen was added to the suspension of the nanoparticles, aggregation of the nanoparticles occurred and then they precipitated. Also, the enzymatic reaction proceeded well when the enzyme substrate was added to the suspension. Based on these results, we provided polymer nanoparticles functionalized with both the antibody and enzyme, and the dual mode bioreactions could occur. We concluded that the novel polymer nanoparticles could be used for nano-/micro-scaled diagnostic and medical treatment systems.     

High capacity binding of antibodies by poly(hydroxyethyl methacrylate) nanoparticles

Poly(hydroxyethyl methacrylate) (PHEMA) nanoparticles with an average size of 150 nm in diameter and with a poly-dispersity index of 1.171 were produced by a surfactant free emulsion polymerization. Specific surface area of the PHEMA nanoparticles was found to be 1779 m(2)/g. Reactive imidazole containing 3-(2-imidazoline-1-yl)propyl(triethoxysilane) (IMEO) was used as a pseudo-specific ligand. IMEO was attached covalently onto the nanoparticles. PHEMA-IMEO nanoparticles were used for the affinity binding of immunoglobulin-G (IgG) from human plasma. To evaluate the degree of IMEO loading, the PHEMA nanoparticles were subjected to Si analysis by using flame atomizer atomic absorption spectrometer and it was estimated as 64.5 mg/g of polymer. The nanoparticles were characterized by transmission electron microscopy (TEM) and Fourier transform infrared spectroscopy (FTIR). IgG binding onto the PHEMA nanoparticles was found to be 5.2 mg/g. Much higher binding values (up to 843 mg/g) were obtained for the PHEMA-IMEO nanoparticles. IgG could be repeatedly bound and eluted on PHEMA-IMEO nanoparticles without noticeable loss in the IgG binding capacity.     

纳米银对表面吸附镝配合物的荧光增强效应研究

研究了不同粒径的纳米银对镝配合物(乙二胺四乙酸配合物)的光谱学性质影响。当配合物溶液的pH值范围为4.0～6.0时,加入纳米银,可观察到大量的纳米银聚集体形成,而在吸收光谱的长波处出现一个新的吸收峰,随着纳米银浓度的增加,该吸收峰逐渐红移,同时,镝配合物的荧光强度增强。实验结果表明,纳米银粒子对镝配合物的荧光增强效应及荧光增强因子与纳米银粒子的浓度和粒径密切相关。随着纳米银浓度的增加,配合物的荧光强度先增强而后又逐渐降低。小粒径的纳米银对镝配合物的荧光增强因子较小。本文从纳米银粒子的聚集效应、局部电磁场增强效应及光吸收效应等方面探讨了纳米银对表面吸附镝配合物的+荧光增强效应机理。     

Size effect in thiol and amine binding to small Pt nanoparticles

A study was carried out to compare the binding affinities of 1-dodecanethiol and dodecylamine for small Pt nanoparticles. The results showed that the affinity of thiol for Pt nanoparticles increases with increasing particle size whereas the affinity of amine for Pt nanoparticles decreases. The divergence in binding affinities has resulted in differences in catalytic activities of thiol- and amine-protected Pt nanoparticles in the room temperature electro-oxidation of methanol (a fuel cell reaction). It was therefore possible for the larger Pt nanoparticles to be catalytically more active than the smaller Pt nanoparticles up to a certain critical size, before the surface area effects of nanoparticles become noticeable.     

Improvement in the luminescence properties and processability of LaF3/Ln and LaPO4/Ln nanoparticles by surface modification

The surface of lanthanide(III)-doped LaPO4 nanoparticles was modified by reaction with an alcohol, leading to a covalent bond between the ligand and the particle surface. The surface of lanthanide(III)-doped LaF3 nanoparticles was modified to alter the solubility of the nanoparticles and study the influence of surface effects on the luminescence of lanthanide ions doped in the nanoparticles. The coordinated organic ligands can be modified by a quantitative exchange reaction in solution or by using functionalized ligands during the synthesis. Variation of the ratio of ligand to core reagents had a significant influence on the size of the nanoparticles. Smaller nanoparticles were formed with a higher ligand ratio. The optical properties of these nanoparticles show a strong dependence on nanoparticle size, indicating the influence of quenching probably by CH and OH groups at or near the surface of the nanoparticle cores. The luminescence lifetime of LaF3/Eu nanoparticles varied from 6.5 to 7.4 ms for nanoparticles with an average size of 7.1 to 8.4 nm. A significant reduction of the quenching from the surface of the nanoparticles was obtained by the synthesis of core-shell nanoparticles, in which a shell of LaF3 was grown epitaxially around the doped core nanoparticles. This leads to an increase in the luminescence lifetime of the Eu3+ ion and the observation of emissions from the 5D2 energy level, in addition to emissions from the 5D1 and 5D0 levels. The quantum yield of LaF3/Ce,Tb nanoparticles could be increased from 24 to 54% by the growth of a LaF3 shell around the nanoparticles.     

醇热解法合成超顺磁性氧化铁纳米粒子及其性能

以甲氧基聚乙二醇同时作为溶剂、还原剂及修饰剂,在高温下分解乙酰丙酮铁,制备了纳米Fe3O4粒子,采用透射电子显微镜和X射线衍射分析表征材料的形貌和相组成,傅里叶变换红外光谱仪表征材料的表面修饰物,超导量子干涉仪测试合成的纳米粒子的磁性能,纳米粒度与zeta电势分析仪测试磁性纳米粒子在水中的zeta电势。 结果表明,纳米Fe3O4粒子的大小为（10.1±1.6） nm,粒度均一,单分散性好,在300 K下具有超顺磁性,饱和磁化强度为45 A·m2/kg。 红外结果表明,-COO-共价结合在粒子表面。 zeta电势为-25 mV。 其在水中的稳定性与以三甘醇为反应介质、高温分解法制备的纳米Fe3O4粒子作比较,表现出长时间（60 d以上）的良好分散性。 静电作用及空间位阻效应是其高稳定分散性的原因。     

Formation and oxidation mechanisms of Pd-Zn nanoparticles on a ZnO supported Pd catalyst studied by in situ time-resolved QXAFS and DXAFS

Formation and oxidation processes of PdZn nanoparticles on ZnO were successfully observed by means of in situ time-resolved X-ray absorption fine structure spectroscopy (XAFS), and the analysis of data on near-edge (XANES) and extended (EXAFS) structures revealed detailed changes in Pd during both processes. PdZn nanoparticles were formed on ZnO through a two-step scheme under a hydrogen atmosphere. The first process was the formation of metallic Pd nanoparticles, which was quickly finished within 1 s. The second process was the formation of PdZn nanoparticles, which took several tens of minutes. Oxidation of the PdZn nanoparticles also consisted of two processes. Zn atoms were oxidized prior to Pd atoms and the metallic Pd nanoparticles surrounded by ZnO were formed afterwards. Oxidation of the metallic Pd nanoparticles was scarce and very slow. According to the results of kinetic analyses, the metallic Pd surrounded by ZnO was a stable species under the oxidative atmosphere.     

Enhanced transdermal delivery of indomethacin-loaded PLGA nanoparticles by iontophoresis

Nanoparticles effectively deliver therapeutic agent by penetrating into the skin. Indomethacin (IM) and coumarin-6 were loaded in PLGA nanoparticles with an average diameter of 100 nm. IM and coumarin-6 were chosen as a model drug and as a fluorescent marker, respectively. The surfaces of the nanoparticles were negatively charged. Permeability of IM-loaded PLGA nanoparticles through rat skin was studied. Higher amount of IM was delivered through skin when IM was loaded in nanoparticles than IM was free molecules. Also, iontophoresis was applied to enhance the permeability of nanoparticles. When iontophoresis with 3 V/cm was applied, permeability of IM was much higher than that obtained by simple diffusion of nanoparticles through skin. The combination of charged nanoparticle system with iontophoresis is useful for effective transdermal delivery of therapeutic agents.     

Entrapment of organic fluorophores in calcium phosphate nanoparticles with slow release

Two organic fluorophores, fluorescein (F) and rhodamine B (Rd), were entrapped in calcium phosphate nanoparticles. The as-obtained nanoparticles can be used for biological release applications. For this aim, calcium phosphate nanoparticles were synthesized using the precipitation method. Structural analysis of these nanoparticles was performed using XRD, FTIR, and Raman spectroscopy, confirming that the synthesized nanoparticles were hydroxyapatite. TEM and SEM analyses demonstrated that these nanoparticles had a size of 20 nm and a well-defined morphology. F and Rd (about 0.5 wt.%) were entrapped in these nanoparticles and their release, as a function of time, was studied via UV-Vis spectroscopy. The obtained results showed that the release of both fluorophores was progressive over time. The trapping efficiencies of the fluorophores were 67.15% and 90.76% for F and Rd, respectively.     

壳层厚度可调控的Ag@Pd@Pt纳米粒子的合成和甲酸电催化研究

在本课题组研究55 nm Au@Pd@Pt对甲酸电催化效果基础上,我们采用Ag取代Au制备55 nm Ag@Pd@Pt纳米粒子以降低催化剂的成本,并对甲酸的电催化行为进行研究. 研究表明：少量Pt的存在可大幅度提高催化剂的活性,当Pt的覆盖度为0.5 单原子层（ML）时,起始氧化电位最为靠前,氧化峰电流最大,这与Au@Pd@Pt纳米粒子对甲酸电催化行为类似. 与Au@Pd@Pt纳米粒子相比,其最佳起始氧化电位偏正0.05 V,但电催化活性并没有明显的降低. 通过改变催化剂比表面积研究甲酸的电催化行为,发现将9 nm Ag纳米粒子作为内核的9 nm Ag@Pd@Pt负载在活性炭中,在保持催化活性不变的情况下,碳载的催化剂价格可比55 nm Au@Pd@Pt纳米粒子降低220倍左右.     

Fluorescent Property of Gold Nanoparticles with Different Surface Structures

"?Fluorescence spectra of naked gold nanoparticles, triphenylphosphine stabled gold nanoparticles, and 3-mercaptopropionic acid substituted gold nanoparticles were studied. It was found that fluorescence intensities of gold nanoparticles were highly sensitive to surface molecules. The fluorescence quenching effect of these gold nanoparticles on CdSe nanoparticles was also investigated. This quenching effect was related to the overlap degree between the absorption spectra of gold nanoparticles and the emission spectrum of CdSe nanoparticles, and was surface-dependent as well. "     

硫化镉钠米微粒在聚合物网络中的组装

硫化镉钠米微粒在聚合物网络中的组装黄金满，杨毅，杨柏，刘式墉，沈家骢（吉林大学分子光谱与分子结构重点实验室、集成光电子国家重点实验室，长春，１３００２３）关键词组装，纳米微粒，离子交换，透射电子显微镜，电子衍射由于纳米半导体微粒的物理和化学性质介于分...     

混合表面活性剂体系聚苯乙烯/Fe3O4复合纳米粒子的制备

在TritonX-100/十二烷基苯磺酸钠混合表面活性剂体系中，制得核-壳型结构的聚苯乙烯/Fe₃O₄复合纳米粒子。通过X-射线衍射、傅立叶红外光谱测定表明，复合纳米粒子结构组成以Fe₃O₄为核_，聚苯乙烯为壳，证明聚苯乙烯在Fe₃O₄纳米粒子上的包覆是成功的。电子显微镜观察结果表明：Fe₃O₄纳米粒子的粒径约10 nm，聚苯乙烯/Fe₃O₄复合纳米粒子的粒径为25-35 nm。     

脉冲电沉积Pd-Ni合金纳米颗粒及其甲酸电催化氧化

采用方波脉冲方法,在钯镍合金电解液中成功地电化学沉积出镍原子含量分别为12.0%、16.4%和22.6%的钯镍合金纳米颗粒. 钯镍合金纳米颗粒为球状,粒径50 ~ 80 nm. 随钯镍合金生长电位负移,合金的镍含量提高,其纳米颗粒大小基本相似但纳米颗粒数目增多,交联度提高和真实活性面积增大. 钯镍合金纳米颗粒镍含量提高,在硫酸溶液中其氢弱吸附峰电流增大. 钯镍合金纳米颗粒电极的甲酸电催化氧化活性较好,随合金纳米颗粒的镍含量提高和交联度增加,合金纳米颗粒电极的甲酸电催化氧化稳定性更高.     

Structure,surface analysis and bioactivity of Mn doped zinc oxide nanoparticles

Undoped zinc oxide nanoparticles and Mn (5 atomic % & 10 atomic %) doped zinc oxide nanoparticles were prepared by soft chemical method. Antibacterial, antioxidant and anticancer activities in breast cancer cell line MDAMB231 of prepared nanoparticles were investigated. The nanoparticles were characterized using XRD, SEM, EDAX, UV–Vis, FT-IR, and room temperature PL Analysis. Antimicrobial activity was tested against both gram positive and gram negative human pathogens. The antioxidant potential of prepared nanoparticles was estimated using Phosphomolybdate and DPPH assay. The MTT assay was used for cytotoxicity evaluation of prepared nanoparticles against breast cancer cell line MDAMB231. XRD patterns confirmed the nanoparticles were crystallized hexagonal wurtzite structure with an average size of 38.95 ?nm. The absorption wavelength was observed at 361 ?nm in UV–Vis spectrum of Mn (10 atomic %) doped ZnO nanoparticles. The Mn (5 atomic %) doped ZnO nanoparticles exhibited significant antibacterial activity against the gram negative bacteria Escherichia coli, Klebsiella pneumonia at all concentrations. Undoped zinc oxide nanoparticles and Mn doped zinc oxide nanoparticles were effective against the breast cancer cell line MDAMB231.