乙二胺四乙酸辅助水热法合成NaYF_4纳米晶

用络合剂乙二胺四乙酸(EDTA)辅助水热法合成了NaYF4纳米球和微米棱柱,通过控制反应条件得到了立方相和六方相纳米晶体;采用X射线粉末衍射仪(XRD)、扫描电子显微镜(SEM)及荧光光谱仪(PL)分析了产物的结构、形貌及发光性能.结果表明,络合剂EDTA和氟化物的物质的量对NaYF4的形貌和粒度有很大影响,且产物的荧光性能呈现出尺寸依赖性.     

Synthesis, photophysical and electrochemical properties and theoretical studies on three novel indolo[3,2-b]carbazole derivatives containing benzothiazole units

Three novel indolo[3,2-b]carbazoles derivatives were successfully synthesized by condensation reaction and structurally characterized by elemental analysis, mass spectrometry and proton nuclear magnetic resonance spectroscopy methods, which belong to donor-π-acceptor systems comprising an indolo[3,2-b]carbazole group as an electron donor and two benzothiazole rings as electron acceptors. The thermal, electrochemical and photophysical properties of the compounds were characterized by thermogravimetric analysis combined with electrochemistry, UV-vis absorption spectroscopy and fluorescence spectroscopy. On the other hand, the geometries, molecular orbitals, charge-injection and transport properties were determined by quantum chemical calculations. The results show that the compounds synthesized exhibit good thermal stability and high fluorescence quantum yields, indicating the potential application as optoelectronic materials.     

肌红蛋白在氧化镍纳米粒子中的固定及新型生物传感器的制备

研究了在氧化镍纳米粒子改性石墨电极(GE)上肌红蛋白(Mb)的直接电化学行为, 并制备了新型H2O2 传感器.在0.1 mol/L 磷酸盐缓冲溶液(PBS, pH 7.0)中, 肌红蛋白有稳定而明确的氧化还原峰,电子转移速率常数为6.48/s;式量电位为-0.34 V(vs·SCE), 表面覆盖量8.06×10-10 mol/cm2.二甲亚砜(DMSO)的存在对加速肌红蛋白分子与电极之间的电子传递起了重要作用.光谱分析表明: 固定在Mb/NiO/DMSO膜中肌红蛋白能保持其生物活性,对H2O2有电催化活性,电催化响应与H2O2浓度呈线性关系,线性范围为0.8～24 μmol/L;检出限为0.039 μmol/L. 对H2O2的表观米氏常数为0.21 mmol/L, 灵敏度为417 mA cm2 L/mol, 呈现出高亲和性.     

对位取代苯甲酸与2,2'-联吡啶配体构筑的两种二价铅配合物的合成、晶体结构及性质

水热条件下,合成了2个含对位取代苯甲酸和2,2'-联吡啶配体的二价铅配合物[Pb(4-HOBA)2(2,2'-bipy)]·H2O(4-HOBAH=4-hydroxybenzoic acid,2,2'-bipy=2,2'-bipyridine)(1)及[Pb(4-MBA)2(2,2'-bipy)](4-MBAH=4-methylbenzoic acid)(2),并通过X-射线单晶结构分析、元素分析、红外光谱、紫外光谱、荧光光谱以及热重分析等手段对配合物进行了表征与研究.X-射线单晶结构测定表明,2种晶体的不对称单元中,六配位的二价铅离子分刖与来自1个2.2'-联吡啶的2个N原子和2个对位取代苯甲酸的4个O原子螫合.配合物1属单斜晶系,P21/c空间群,a=1.09483(4)nm,b=1.751 94(6)nm,c=1.20479(4)nm,β=100.334(2)°,V=2.27339(14)nm3,Z=4,final R1=0.0254,wR2=0.0674.广泛存在的分子间氢键和弱π…π堆积作用将配合物1组装成稳定的三维超分子结构.配合物2属三斜晶系,P-1空间群,a=0.955 10(11)nm,b=1.00805(12)am,c=1.324 83(15)nm,a=109.865(1)°,β=97.322(1)°,γ=90.643(1)°,V=1.1878(2)nm3,Z=2,final R1=0.0284,wR2=0.0508.配合物2经由一对Pb…O(0.3185(2)nm)弱相互作用被组装成二聚体结构.弱的Ph…O相互作用及与配合物1中类似的π…π堆积作用共同构筑了配合物2的三维结构.在配合物1和2中,铅的6s孤电子均显示了立体化学活性,使配位键分布于半球型区域.同时,两种配合物固体均具有光致发光特性,并在蓝光区有较强发射.     

Simultaneous determination of cadmium(II), lead(II) and copper(II) by using a screen-printed electrode modified with mercury nano-droplets

We are presenting a strategy for the fabrication of disposable screen-printed electrodes modified with mercury nano-droplets and capable of sensing heavy metal ions. They were prepared by coating electrodes with a mixture of multi-walled carbon nanotubes and chitosan, this followed by adsorption of mercury. The resulting sensor was characterized by cyclic voltammetry and impedance spectroscopy. Also the effects caused by adsorption of mercury were investigated. It is shown that square wave anodic stripping voltammetry enables simultaneous determination of cadmium(II), lead(II) and copper(II), for which detection limits of 12, 23 and 20 nM, respectively, are found. Relative standard deviations for ten determinations at 0.6 µM concentrations of these ions are in the range of 3.0 to 5.7%. The applicability was tested by analyzing river water and showed recoveries between 94.1 and 104.6%, thus demonstrating its utility for in-field monitoring of these heavy metal ions.     

Chromatographic fingerprint study on Evodia rutaecarpa (Juss.) Benth by HPLC/DAD/ESI‐MSn technique

The LC–ESI‐MSⁿ method was developed for the analysis and characterization of alkaloids in the extract of E. rutaecarpa (called Wuzhuyu in Chinese). Thirty‐six batches of Wuzhuyu from different locations of China were investigated and the common fingerprinting profile was established with a professional analytical software recommended by the State Food and Drug Administration. Fifteen chemical components of the common peaks were identified by multi‐stage MS. The effects on the chromatographic profile resulting from different collecting locations, harvesting times or storage times were studied. Hierarchical clustering analysis and principal components analysis were also performed to classify and differentiate the 36 batches of the samples. As a result, those which had same chemical properties were sorted into one cluster, which was very useful in evaluating and controlling the quality of Wuzhuyu.     

Time and poling history dependent energy storage and discharge behaviors in poly(vinylidene fluoride-<Emphasis Type="Italic">co</Emphasis>-hexafluoropropylene) random copolymers

 We studied cycle time (0.01–10 s with triangular input waves) and poling history (continuous versus fresh poling) dependent electric energy storage and discharge behaviors in poly(vinylidene fluoride-co-hexafluoropropylene) [P(VDF-HFP)] films using the electric displacement ― the electric field (D-E) hysteresis loop measurements. Since the permanent dipoles in PVDF are orientational in nature, it is generally considered that both charging and discharging processes should be time and poling history dependent. Intriguingly, our experimental results showed that the charging process depended heavily on the cycle time and the prior poling history, and thus the D-E hysteresis loops had different shapes accordingly. However, the discharged energy density did not change no matter how the D-E loop shape varied due to different measurements. This experimental result could be explained in terms of reversible and irreversible polarizations. The reversible polarization could be charged and discharged fairly quickly (< 5 ms for each process), while the irreversible polarization depended heavily on the poling time and the prior poling history. This study suggests that it is only meaningful to compare the discharged energy density for PVDF and its copolymer films when different cycle times and poling histories are used.     

CoPy/C催化剂应用碱性介质氧还原催化的电化学性能

利用碳黑（Vulcan XC-72R）中加入硫酸钴和吡啶（Py）作为催化剂前驱体,经溶剂分散热处理构建了一类新型的高效氧还原CoPy/C复合催化剂.并运用循环伏安法（CV）和旋转圆盘电极（RDE）技术研究了不同Co含量的CoPy/C催化剂在碱性介质中对氧还原的电催化活性.结果表明:Co的存在对氧的催化剂活性位的形成有重要影响,800℃下所制备的10%Co30%Py/C（质量分数）复合催化剂表现出最佳的氧还原催化活性.以其制备的气体扩散电极在3.0 mol·L^-1KOH电解质溶液（O₂气氛）中0.014 V（相对于标准氧电极（RHE））即可产生明显的氧还原电流.同40%Py/C相比,10%Co30%Py/C催化氧还原的起峰电位正移了71 mV,同时表现出明显的极限扩散电流.在-0.16 V时电流密度达到最大值,电流密度为1.0 mA·cm^-2,半波电位在-0.07 V.透射电镜分析表明所制备的碳黑载吡啶钴（10%Co30%Py/C）催化剂平均粒径为20 nm.     

HO3+ 杂Ge-In-Sb-S玻璃陶瓷光谱特性

采用熔融淬冷法和热处理工艺制备了系列掺Ho3+的透明G eS2-In2S3-Sb2S3硫系玻璃陶瓷.测试了Ho3掺杂的基质玻璃和玻璃陶瓷样品的密度、显微硬度、红外光谱以及在900 nm激光泵浦下的近红外及中红外荧光光谱.结果表明:热处理后样品析出的晶相为In2S3和Sb2S3颗粒的混合体,晶粒尺寸限制在～100 nm以...     

The use of ethylene glycol solution as the running buffer for highly efficient microchip-based electrophoresis in unmodified cyclic olefin copolymer microchips

An ethylene glycol solution was used as the electrophoretic running buffer in unmodified cyclic olefin copolymer (COC) microchips to minimize the interactions between the analytes and the hydrophobic walls of the plastic microchannels, enhance the resolution of the analytes and eliminate the uncontrollable dispersion caused by uneven liquid levels and non-uniform surfaces of the separation channels. Five amino acids that were labeled with fluorescein isothiocyanate (FITC) were used as model analytes to examine the separation efficiency. The effects of ethylene glycol concentration, pH and sodium tetraborate concentration were systematically investigated. The five FITC-labeled amino acids were effectively resolved using a COC microchip with an effective length of 2.5 cm under optimum conditions, which included using a running buffer of 20 mmol/L sodium tetraborate in ethylene glycol:water (80:20, v/v), pH 6.7. A theoretical plate number of 4.8 × 10(5)/m was obtained for aspartic acid. The system exhibited good repeatability, and the relative standard deviations (n=5) of the peak areas and migration times were no more than 3.4% and 0.7%, respectively. Furthermore, the system was successfully applied to elucidate these five amino acids in human saliva.