氧化锆/聚亚甲基蓝修饰电极检测CaMV35S启动子基因

制备了基于氧化锆(ZrO_2)/聚亚甲基蓝(PMB)修饰电极的无标记DNA传感器,用于转基因植物CaMV35S启动子基因的检测。探针DNA(ssDNA)通过ZrO_2和DNA的磷酸基的相互作用修饰到电极表面,以PMB氧化峰的示差脉冲伏安响应为检测信号,传感器和完全互补的DNA片段杂交后,PMB的氧化峰电流明显降低,当和完全不匹配的DNA片段杂交时,峰电流无明显变化。对于完全互补的DNA片段,在2.0×10~(-12)~2.0×10~(-8) mol/L浓度范围内峰电流的变化值和浓度的对数成良好的线性关系,检测限为4.1×10~(-13) mol/L(S/N=3)。所制备的传感器具有良好的稳定性、再生性和重现性,用于样品检测,结果令人满意。     

表面修饰ZrO2纳米微粒的结构表征及摩擦学行为研究

采用XPS,FTIR,DSC,TGA等多种现代分析手段表征了理解旨酸修饰ZrO2纳米微粒的结构,在四球磨摩擦员试验机上,首次评价了表面ZrO2纳米微粒用作润滑油添加剂的摩擦学性能,结果表明ZrO2纳米微粒具有良好的抗磨减摩性。     

普鲁士蓝/氧化锆复合材料的电化学行为及对H2O2的电催化

通过一步电沉积技术制备了普鲁士蓝/氧化锆修饰玻碳电极。采用电化学阻抗技术表征修饰电极。采用循环伏安法研究了pH值和扫描速率对该修饰电极的电化学行为的影响。结果表明:普鲁士蓝的峰电流与其扫描速率的一次方在一定范围内呈良好的线性关系。此外,该修饰电极在含有KCl(1.0mol/L)的磷酸盐缓冲溶液(0.1mol/L,pH=7.0)中,对H2O2具有明显的电催化作用,在无酶检测H2O2领域具有潜在的应用价值。     

纳米稀土-介质薄膜光电发射光谱和能带结构

用真空蒸发沉积的方法制备了纳米稀土(La、Nd、Sm)粒子 BaO介质薄膜.研究表明薄膜的光电发射光谱响应阈值受纳米稀土粒子形状和大小的影响,球形纳米稀土(Sm)粒子 BaO介质薄膜的光谱响应阈值波长为720 nm,条状纳米稀土(La和Nd)粒子 BaO介质薄膜阈值波长分别为650 nm和660 nm.研究得到纳米稀土粒子 介质薄膜等效界面位垒高度在1.7～2.0 eV之间.由于纳米稀土粒子与BaO介质各自逸出功不同,当构成薄膜后使得纳米粒子周围的空间电荷分布发生变化,纳米粒子周围的能带发生弯曲.     

The synthesis of Lewis acid ZrO2 nanoparticles and their applications in phospholipid adsorption from Jatropha oil used for biofuel

ZrO(2) nanoparticles were successfully fabricated via a facile hydrothermal process. The diameter and surface area of the as-prepared ZrO(2) nanoparticles were approximately 5-10 nm and 102 m(2)/g, respectively. For the first time, Zr atoms with partial positive charges in a Lewis acid ZrO(2) nanoparticle adsorbent were used for the adsorption of negatively charged phospholipids from Jatropha oil. The capacity for phospholipid adsorption using the ZrO(2) nanoparticles was better than that of commercial ZrO(2) powder due to the larger surface area of the ZrO(2) nanoparticles. Phospholipid removal makes Jatropha oil a potential oil for biofuel applications.     

Interaction of Au with thin ZrO2 films: influence of ZrO2 morphology on the adsorption and thermal stability of Au nanoparticles

The model catalysts of ZrO(2)-supported Au nanoparticles have been prepared by deposition of Au atoms onto the surfaces of thin ZrO(2) films with different morphologies. The adsorption and thermal stability of Au nanoparticles on thin ZrO(2) films have been investigated using synchrotron radiation photoemission spectroscopy (SRPES) and X-ray photoelectron spectroscopy (XPS). The thin ZrO(2) films were prepared by two different methods, giving rise to different morphologies. The first method utilized wet chemical impregnation to synthesize the thin ZrO(2) film through the procedure of first spin-coating a zirconium ethoxide (Zr(OC(2)H(5))(4)) precursor onto a SiO(2)/Si(100) substrate at room temperature followed by calcination at 773 K for 12 h. Scanning electron microscopy (SEM) investigations indicate that highly porous "sponge-like nanostructures" were obtained in this case. The second method was epitaxial growth of a ZrO(2)(111) film through vacuum evaporation of Zr metal onto Pt(111) in 1 × 10(-6) Torr of oxygen at 550 K followed by annealing at 1000 K. The structural analysis with low energy electron diffraction (LEED) of this film exhibits good long-range ordering. It has been found that Au forms smaller particles on the porous ZrO(2) film as compared to those on the ordered ZrO(2)(111) film at a given coverage. Thermal annealing experiments demonstrate that Au particles are more thermally stable on the porous ZrO(2) surface than on the ZrO(2)(111) surface, although on both surfaces, Au particles experience significant sintering at elevated temperatures. In addition, by annealing the surfaces to 1100 K, Au particles desorb completely from ZrO(2)(111) but not from porous ZrO(2). The enhanced thermal stability for Au on porous ZrO(2) can be attributed to the stronger interaction of the adsorbed Au with the defects and the hindered migration or coalescence resulting from the porous structures.     

Particle-particle interactions and chain dynamics of fluorocarbon and hydrocarbon functionalized ZrO2 nanoparticles

The chain conformation and dynamics of hydrocarbon and perfluorocarbon fatty acids adsorbed on 4 nm ZrO2 particles were characterized by solid-state 13C chemical shift and 19F NMR relaxation measurements, respectively, and compared to those from previous studies on lower surface area fumed metal oxide powders. The interdigitation of chains between neighboring particles, which increases with chain length, can be detected from the splitting of the 13C NMR and 19F NMR signals of the CH3 and CF3 groups, respectively. Similar to the case of alkanethiol self-assembled monolayers (SAMs) on gold nanoparticles, this interdigitation allows for efficient chain packing despite the high surface curvature. The hydrocarbon chains on the ZrO2 nanoparticles are more ordered, and the reversible chain length dependent order-disorder transition temperatures are elevated relative to those of the same fatty acids adsorbed on fumed ZrO2 powder. Likewise, the 19F spin lattice relaxation times of the fluorocarbon chains approach those of the bulk acids with increasing chain length and interdigitation, indicating densely packed chains.     

Au/ZrO2催化剂中ZrO2的尺寸效应:1,3-丁二烯加氢反应

在不同温度(673～1073K)下,于流动N2气中焙烧ZrO(OH)2醇(乙醇)凝胶,制备了不同尺寸的ZrO2-AN纳米晶(6～30nm).采用沉积-沉淀方法制备了相应的质量分数为0.7%的Au/ZrO2-AN催化剂.用XRD,XRF,TEM/HRTEM,EDS,N2吸附和1,3-丁二烯加氢反应对ZrO2-AN和Au/ZrO2-AN催化剂进行了表征.结果表明,在所有的Au/ZrO2-AN样品中,Au粒子的平均尺寸为4～5nm,ZrO2-AN的颗粒大小没有因为负载Au粒子而发生改变.1,3-丁二烯在Au/ZrO2-AN催化剂催化下能以100%的选择性进行加氢反应生成单烯烃.随着Au/ZrO2-AN催化剂中ZrO2-AN纳米晶尺寸的增加或“载体”焙烧温度的升高,1,3-丁二烯的转化率明显降低;1-丁烯的选择性先增加后减小,2-丁烯中反/顺异构体的摩尔比在0.5～1.0的范围内逐渐增大,TEM/HRTEM表征结果清楚地表明,Au/ZrO2-AN催化剂中Au粒子与ZrO2-AN颗粒接触界面/周边随ZrO2-AN颗粒尺寸的减小而明显增加,这很可能是含有更小尺寸ZrO2-AN纳米粒子的Au/ZrO2-AN催化剂具有更高的催化活性的重要原因.     

Synthesis and Optical Properties of Mn2+-Doped ZnS Nanoparticles in Solutions and Coatings

Mn2+-doped ZnS nanoparticles with different Mn-doping concentrations stabilized by hydroxypropyl cellulose (HPC) have been synthesized in ethanolic solutions and coatings. Their optical and structural properties have been characterized by means of UV-vis spectroscopy, luminescence spectroscopy, high resolution transmission electron microscopy (HRTEM) and small angle X-ray scattering (SAXS). Solutions and coatings exhibit a strong luminescence at 590 nm when excited with UV light showing that Mn2+ is incorporated into the ZnS nanoparticles. The highest luminescence intensity is obtained with an Mn2+ concentration of 2 mol%. HRTEM and SAXS investigations show that the particles are crystalline and are 3 ± 0.5 nm in size. Irradiation of the coatings with UV light leads to a photochemical oxidation of the particles, as shown by the decreasing absorption of the coating with irradiation time and a blue shift of the absorption maximum. Furthermore, the luminescence intensity first strongly increases and then decreases completely with UV-irradiation time. Both phenomena can be explained by the photochemical oxidation of the particles.     

复合镀层中ZrO2微粒对基质Ni晶体结构的影响

采用复合电沉积方法制备了Ｎｉ－ＺｒＯ２复合镀层，探讨了ＺｒＯ２微粒引起的基质金属Ｎｉ的晶体择优取向及点阵常数的变化，及其对析氢电催化活性的影响。结果表明，ＺｒＯ２微粒的存在改变了Ｎｉ的电沉积层结构，使基质金属Ｎｉ产生新的沿（２２０）晶面的择优取向。这一新的择优取向不利于析氢反应。择优取向的改变说明复合电沉积过程中，Ｎｉ与ＺｒＯ２微粒是以一定的界面匹配进入复合镀层的，基质金属Ｎｉ点阵参数的改变也证明     

Precursor and Solvent Effects in the Nonhydrolytic Synthesis of Complex Oxide Nanoparticles for Bioimaging Applications by the Ether Elimination (Bradley) Reaction

Investigation of the solvent and alkoxide precursor effect on the nonhydrolytic sol–gel synthesis of oxide nanoparticles by means of an ether elimination (Bradley) reaction indicates that the best crystallinity of the resulting oxide particles is achieved on application of aprotic ketone solvents, such as acetophenone, and of smallest possible alkoxide groups. The size of the produced primary particles is always about 5 nm caused by intrinsic mechanisms of their formation. The produced particles, possessing the composition of natural highly insoluble minerals, are biocompatible. Optical characteristics of the perovskite complex oxide nanoparticles can easily be controlled through doping with rare earth cations; for example, by Eu³⁺. They can be targeted through surface modification by anchoring the directing biomolecules through a phosphate or phosphonate moiety. Testing of the distribution of Eu‐doped BaTiO₃ particles, modified with ethylphosphonic acid, demonstrates their facile uptake by the plants with active fluid transport, resulting finally in their enhanced concentration within the cell membranes.     

Synthesis and Luminescent Properties of Terbium(III) and Europium(III) Fluoride Nanoparticles Modified with Aromatic Carboxylic Acids

Europium(III) and terbium(III) fluoride nanoparticles modified with citric, anthranilic, benzoic, salicylic, and acetylsalicylic acids have been obtained by means of sorption from solution and modification in statu nascendi. The shape and size of the particles have been determined by scanning electron microscopy. The luminescence of the samples was studied and it has been established that terbium fluoride nanoparticles modified with acetylsalicylic acid exhibits the highest luminescence intensity.     

表面修饰ZrO_2纳米微粒的合成及结构表征(英文)

在溶液中化学合成了硬脂酸修饰ZrO2 纳米微粒 ,采用XRD、TEM和EA表征了ZrO2 纳米微粒的结构 ,结果表明成功合成了表面包覆硬脂酸分子的ZrO2 纳米微粒。     

MoO3/ZrO2纳米固体强酸催化剂的制备及其在异丁烷-丁烯烷基化反应中的应用

利用AOT/异辛烷反胶束体系制备了MoO3/ZrO2纳米粒子.TEM结果表明,反胶束法制得粒子的粒径均匀,95%以上处于38～60nm之间.将此纳米粒子负载于γ-Al2O3上,呈现高度分散状态.NH3-TPD和烷基化反应的测定结果表明,其酸量和反应活性明显高于浸渍法和溶胶-凝胶法制备的样品,烷基化产物中C8的含量在79%左右.     

Remarkable nanosize effect of zirconia in Au/ZrO2 catalyst for CO oxidation

Nanosize effect of ZrO2 in Au/ZrO2 catalyst was studied by deposition-precipitation of Au nanoparticles in similar sizes (4-5 nm) on ZrO2 nanoparticles of varying sizes. The catalysts were characterized with XRD, TEM, XPS, and nitrogen adsorption to understand the effect of ZrO2 particle size on the catalytic nanostructures. Nanocomposite Au/ZrO2 catalysts consisting of comparably sized Au-metal (4-5 nm) and ZrO2 (5-15 nm) nanoparticles are found advantageous over those containing similarly sized Au-metal but larger ZrO2 (40-200 nm) particles for CO oxidation. This finding may have important implications on the designed preparation of advanced nanostructured catalysts and other chemical materials.     

空心球形In2O3/ZrO2-TiO2纳米复合材料多模式光催化

本文以聚苯乙烯(PS)胶球为模板,通过一步水浴法结合煅烧后处理制备了不同比例的In_2O_3/ZrO_2-TiO_2空心球状复合材料(简写为In_2O_3/ZrO_2-TiO_2-H)。通过X-射线衍射、扫描电镜、X-射线光电子能谱、紫外-可见漫反射吸收光谱和氮气吸附-脱附等测试手段对该系列复合材料的结构、组成和形貌进行了表征。结果表明,In_2O_3/ZrO_2-TiO_2复合材料经PS模板处理后呈现空心球状结构,球壁由纳米粒子堆积而成。将In_2O_3与ZrO_2-TiO_2复合后其光吸收性能呈现了一定的红移现象,且In_2O_3/ZrO_2-TiO_2-H(1∶4)的比表面积较大(66.92m~2·g~(-1))。同时,为了考察该复合材料的光催化性能,在多模式光催化条件下对甲基橙的降解情况进行了研究。结果表明,In_2O_3/ZrO_2-TiO_2-H(1∶4)表现出较好的光催化性能,其光催化活性高于P25、ZrO_2、In_2O_3/ZrO_2-TiO_2及其他体积比的In_2O_3/ZrO_2-TiO_2-H。     

Gas transport in TiO2 nanoparticle-filled poly(1-trimethylsilyl-1-propyne)

Titanium dioxide (TiO₂) nanoparticles were dispersed via solution processing in poly(1-trimethylsilyl-1-propyne) (PTMSP) to form nanocomposite films. Nanoparticle dispersion was investigated using atomic force microscopy and transmission electron microscopy. At low-particle loadings, nanoparticles were dispersed individually and in nanoscale aggregates. At high-particle loadings, some nanoparticles formed micron-sized aggregates. The gas transport and density exhibited a strong dependence on nanoparticle loading. At low-TiO₂ loadings, the composite density was similar to or slightly higher than that predicted by a two-phase additive model. However, at particle loadings exceeding approximately 7 nominal vol.%, the density was markedly lower than predicted, suggesting that the particles induced the creation of void space within the nanocomposite. For example, when the TiO₂ nominal volume fraction was 0.35, the polymer/particle composite density was 40% lower than expected based on a two-phase additive model for density. At low-nanoparticle loading, light gas permeability was lower than that of the unfilled polymer. At higher nanoparticle loadings, light gas permeability (i.e., CO₂, N₂, and CH₄) increased to more than four times higher than in unfilled PTMSP. At most, selectivity changed only slightly with particle loading.     

Preparation and stability of strongly luminescent CdSe/Cd(OH)<Subscript>2</Subscript>/SiO<Subscript>2</Subscript> nanocomposite particles in aqueous solution

Cadmium hydroxide-deposited cadmium selenide nanoparticles were prepared by the addition of cadmium sulfate solution to cadmium selenide nanoparticles in a weak alkaline solution at room temperature. The photoluminescence measurements displayed that the luminescence intensity was greatly increased by the addition of cadmium ions due to the formation of cadmium hydroxide on the surfaces of the cadmium selenide nanoparticles. Then, CdSe/Cd(OH)₂/SiO₂ nanocomposite particles were synthesized using 3-mercatopropyl trimethoxysilane by Stöber method. After the formation of CdSe/Cd(OH)₂/SiO₂ nanocomposite particles, the emission ability was mostly stabilized. Additionally, the stabilization of the composite particles against dilution with the physiological saline was checked. The results showed that the photoluminescence stability was promoted after the deposition of silica on the surfaces of the CdSe/Cd(OH)₂ nanoparticles. Comparison of the stability of CdSe/SiO₂ nanoparticles with that of CdSe/Cd(OH)₂/SiO₂ ones showed that Cd(OH)₂ shell could enhance the photoluminescence effectively.     

Electron injection into the surface states of ZrO2 nanoparticles from photoexcited quinizarin and its derivatives: effect of surface modification

The effect of surface modification on interfacial electron transfer (IET) dynamics into the surface states of ZrO(2) nanoparticles sensitized by quinizarin (Qz) and its derivatives has been carried out using time-resolved emission spectroscopy. The surface of ZrO(2) nanoparticles has been modified by sodium dodecyl benzyl sulfonate . We have observed that Qz's can form a strong charge-transfer (CT) complex with both unmodified and surface-modified (SM) ZrO(2) nanoparticles. We have confirmed electron injection into the surface states of ZrO(2) nanoparticles from the photoexcited Qz molecule in our earlier work (J. Phys. Chem. B 2004, 108, 4775; Langmuir 2004, 20, 7342). In the present investigation, we have observed electron injection from photoexcited Qz derivatives into the surface states of both unmodified and SM ZrO(2) nanoparticles and also detected CT emission. Monitoring CT emission, we have determined back electron transfer (BET) dynamics of the dye-nanoparticle systems. We have found that the BET rate for the QZs/ZrO(2) systems decreases as the relative driving force increases following Marcus inverted region kinetic behavior for an IET process. BET dynamics was found to be faster on SM ZrO(2) nanoparticles as compared to that of the unmodified (bare) one. Our time-resolved emission data indicates that upon surface modification the majority of the deeper trap states of ZrO(2) nanoparticles can be removed with the formation of some new shallower trap states in the band gap region.     

Composites comprising CdS nanoparticles and poly(ethylene oxide): optical properties and influence of the nanofiller content on the thermal behaviour of the host matrix

Tri-n-octylphosphine oxide-capped CdS nanoparticles were synthesized with the cadmium(II) complex of thiocarbohydrazide as a precursor. Nanocomposites were prepared by mixing a toluene solution of poly(ethylene oxide) (PEO) and the obtained CdS nanoparticles. The ultraviolet-visible spectroscopy measurements showed a blue shift of the onset of optical absorption, compared to bulk CdS, which confirmed the presence of nanostructured CdS. A transmission electron microscopy micrograph of the nanocomposite depicted that the nanoparticles are well dispersed in the PEO matrix. Differential scanning calorimetry analysis revealed hindered crystallization of PEO in the presence of CdS nanoparticles. It was also found that increasing the nanoparticle content led to the shift of the onset of decomposition of the matrix towards higher temperature.