三嵌段共聚物EO20PO70EO20相分离行为的耗散粒子动力学模拟

采用耗散粒子动力学(DPD)方法研究了嵌段共聚物EO₂₀PO₇₀EO₂₀(P123)在水、乙醇/水溶液及二氧化硅溶胶体系中的相分离行为. 不同质量分数的P123在水溶液中共形成4种相分离状态: 球状胶束(10%); 椭球胶束(20%)、棒状胶束(30%)和三维立方胶束(50%). 在模板剂质量分数为10%的乙醇/水溶液中, 模板剂胶束稳定性随着乙醇含量的增加而变差. 在二氧化硅溶胶体系中, 模板剂质量分数低于5%时无胶束形成; 模板剂质量分数增至10%时, P123发生相分离形成三维球状胶束; 随着模板剂质量分数的进一步增加, 模板剂分子夹含着水分子形成三维椭球状结构(20%)、三维立方结构(40%)和层状结构(60%). 模拟结果与实验结果一致, 说明DPD模拟可以从计算角度推测模板剂对介孔材料结构的影响.     

多壁纳米碳管/二氧化硅复合膜中的联吡啶钌电化学发光法测定氧氟沙星的研究与应用

基于氧氟沙星对联吡啶钌(Ru(bpy)_3~(2+))电化学发光的增敏作用,建立了一种以多壁纳米碳管(MWCNTs)/二氧化硅-联吡啶钌复合物修饰的玻碳电极电化学发光检测氧氟沙星的新方法.利用溶胶-凝胶(sol-gel)固定化稳定的优点和纳米碳管的电催化作用,提高了传感器的电流响应.在最佳实验条件下,氧氟沙星浓度在4.0×10~(-6) ～1.0×10~(-4) mol/L范围内与相对发光强度呈线性关系(r~2=0.994 8),检出限(S/N=3)为2.0×10~(-6) mol/L.连续平行测定2.4×10~(-5) mol/L的氧氟沙星溶液 5次,发光强度的RSD为1.8%.     

Comparison of the adsorption orientation for 2-mercaptobenzothiazole and 2-mercaptobenzoxazole by SERS spectroscopy

In this study, the adsorption orientation for 2-mercaptobenzothiazole (MBT) and 2-mercaptobenzoxazole (MBO) on to silver mirror and silver sol substrates have been studied by surface enhanced Raman scattering (SERS). The MBT and MBO were chemisorbed on both silver mirror and silver sol after deprotonation with a tilted orientation to the silver surfaces. The surface enhanced properties of MBT and MBO showed that the substrate of silver mirror was superior to the sliver sol. The SERS spectra of MBT and MBO revealed that both of the MBT and MBO were adsorbed on silver surfaces strongly by a common sulfur molecule and a sulfur atom from MBT and an oxygen atom from MBO. Therefore, the adsorption orientation of MBT and MBO was little tilted perpendicularly to the silver surfaces. The adsorption geometry did not undergo any significant changes in acidic and basic solutions. It showed that the adsorption orientation for MBT and MBO were stable in the both solutions.     

Dual‐Amplification of Antigen–Antibody Interactions via Backfilling Gold Nanoparticles on (3‐Mercaptopropyl) Trimethoxysilane Sol‐Gel Functionalized Interface

A new dual‐amplification strategy of electrochemical signaling from antigen–antibody interactions was proposed via backfilling gold nanoparticles on (3‐mercaptopropyl) trimethoxysilane sol‐gel (MPTS) functionalized interface. The MPTS was employed not only as a building block for the electrode surface modification but also as a matrix for ligand functionalization with first amplification. The second signal amplification strategy introduced in this study was based on the backfilling immobilization of nanogold particles to the immunosensor surface. Several coupling techniques, such as with nanogold but not MPTS or with MPTS but not nanogold, were investigated for the determination of carcinoembryonic antigen (CEA) as a model, and a very good result was obtained with nanogold and MPTS coupling immunosensor. With the noncompetitive format, the formation of the antigen–antibody complex by a simple one‐step immunoreaction between the immobilized anti‐CEA and CEA in sample solution introduced membrane potential change before and after the antigen–antibody interaction. Under optimal conditions, the proposed immunosensor exhibited a good electrochemical behavior to CEA in a dynamic concentration range of 4.4 to 85.7 ng/mL with a detection limit of 1.2 ng/mL (at 3 δ). Moreover, the precision, reproducibility and stability of the as‐prepared immunosensor were acceptable. Importantly, the proposed methodology would be valuable for diagnosis and monitoring of carcinoma and its metastasis.     

Acetic Anhydride as an Oxygen Donor in the Non-Hydrolytic Sol–Gel Synthesis of Mesoporous TiO2 with High Electrochemical Lithium Storage Performances

An original, halide-free non-hydrolytic sol–gel route to mesoporous anatase TiO₂ with hierarchical porosity and high specific surface area is reported. This route is based on the reaction at 200 °C of titanium(IV) isopropoxide with acetic anhydride, in the absence of a catalyst or solvent. NMR spectroscopic studies indicate that this method provides an efficient, truly non-hydrolytic and aprotic route to TiO₂. Formation of the oxide involves successive acetoxylation and condensation reactions, both with ester elimination. The resulting TiO₂ materials were nanocrystalline, even before calcination. Small (about 10 nm) anatase nanocrystals spontaneously aggregated to form mesoporous micron-sized particles with high specific surface area (240 m² g⁻¹ before calcination). Evaluation of the lithium storage performances shows a high reversible specific capacity, particularly for the non-calcined sample with the highest specific surface area favouring pseudo-capacitive storage: 253 mAh g⁻¹ at 0.1 C and 218 mAh g⁻¹ at 1 C (C=336 mA g⁻¹). This sample also shows good cyclability (92 % retention after 200 cycles at 336 mA g⁻¹) with a high coulombic efficiency (99.8 %). Synthesis in the presence of a solvent (toluene or squalane) offers the possibility to tune the morphology and texture of the TiO₂ nanomaterials.     

聚烯丙醇/SiO2有机无机杂化材料的研究

制备;溶胶-凝胶工艺;聚烯丙醇/SiO2有机无机杂化材料的研究     

Effect of Oxalic Acid on Stabilization and Property of Sb-Doped Tin Oxide Sol

Zeta potential studies show that the ATO nanoparticle surface is positively charged in pH range from 2 to 5 without oxalic acid. The addition of oxalic acid brings a charge reversal on the surface of ATO particle in a wide pH range. The interaction of oxalic acid with surface of ATO nanoparticle was studied by FTIR and indicates that the most probable mechanism is the formation of Sn-O-C bonds via the condensation reaction between the oxalic acid and surface hydroxyl groups. TEM, X-ray diffraction and UV-Vis-Near IR spectra were used to characterize the nanocrystalline ATO sol and thin gel film.     

超临界干燥法制备TiO2气凝胶

以钛酸四丁酯为原料,采用溶胶-凝胶过程及及超临界干燥法制备了TiO2气凝胶,并通过XRD,BET和TEM等方法对所得样品进行了表征.结果表明,该法制备的TiO2气凝胶具有很高的比表面积(488 m2/g),平均粒径为4.6nm,具有锐钛矿型晶体结构.经400℃煅烧2 h所得的纳米粉体,其锐钛矿型晶体结构更为明显,平均粒径6.7 nm,比表面积158 m2/g.     

TiO2薄膜光催化还原Hg2+的研究

采用溶胶法制备出TiO2、SO42-/TiO2、CdS/TiO2薄膜光催化剂,研究了TiO2薄膜光催化还原Hg2+的最佳实验条件以及SO42-/TiO2、CdS/TiO2薄膜与TiO2薄膜、TiO2粉体与薄膜之间的光催化活性差异.结果表明:当pH=5.34时,经30 min紫外光照射,Hg2+的还原率达到最大;Hg2+初始浓度越高,光致还原量越低;光源波长越短,Hg2+的还原率越高;当甲醇添加量达到15%(体积比)时,反应30 min后,Hg2+的还原率即达100%;CdS改性薄膜的光催化活性高于未改性薄膜;CdS/TiO2薄膜的光催化活性略高于粉体.     

不同nCu2+:nCit3-的Cu(Ⅱ)-Cit3--SiO2溶胶中电沉积制备CuxO-SiO2复合薄膜

以醋酸铜(Cu(Ac)2)和正硅酸乙酯(TEOS)为前驱体,柠檬酸钠(Na_3Cit)为配合剂,在室温下制备出物质的量之比n_(Cu~(2+))∶n_(Cit~(3-)) 为1∶1和1∶2的2种透明稳定的Cu(Ⅱ)-Cit~(3-)-SiO_2复合溶胶。以此为电解液,采用恒电位方法,在ITO阴极上直接制备出了Cu_xO-SiO_2复合薄膜。CV(循环伏安)和XRD(X射线衍射)结果表明,在低过电位和高过电位分别得到Cu2_O-SiO_2和Cu/Cu_2O-SiO_2薄膜。XRD和EDX(X射线散射能谱)结果表明,相同沉积条件下,n_(Cu~(2+))∶n_(Cit~(3-)) 为1∶1溶胶中得到的薄膜中Cu含量较1∶2溶胶中的高。薄膜在2种溶胶中的电化学形成机理不同,其原因在于溶胶中Cu(Ⅱ)存在的形式不同。CA(计时安培)和SEM(扫描电镜)结果一致表明,Cu和Cu_2O在2种溶胶中的成核机理与电位有关,随着过电位增大,成核机理从三维连续成核逐渐转向瞬时成核。