Novel Potentiometric Membrane Sensor for the Determination of Trace Amounts of Chromium(III) Ions

A plasticized Cr3+ ion sensor by incorporating 2,3,8,9-tetraphenyl-1,4,7,10-tetraazacyclododeca-1,3,7,9-tetraene (TTCT) ionophore exhibits a good potentiometric response for Cr3+ over a wide concentration range (1.0×10-6-1.0×10-1 M) with a slope of 19.5 mV per decade. The sensor response is stable for at least three months. Good selectivity for Cr3+ in comparison with alkali, alkaline earth, transition and heavy metal ions, and minimal interference are caused by Li+, Na+, K+, Co2+, Hg2+, Ca2+, Pb2+ and Zn2+ ions, which are known to interfere with other chromium membrane sensors. The TTCT-based electrode shows a fast response time (15 s), and can be used in aqueous solutions of pH 3 - 5.5. The proposed sensor was used for the potentiometric titration of Cr3+ with EDTA and for a direct potentiometric determination of Cr3+ content in environmental samples.

Mercury(II) ion sensing with PVC-matrix based membrane sensors

Thiosemicarbazone derivatives have been used as ion carriers for the preparation of PVC-matrix based mercury(II)-selective membrane sensors. The electrodes give near-Nernstian responses in the linear concentration range of 1.0×10-1-5.0×10-6 M with detection limits of the order of 10-6 M. The stable potentiometric signals are obtained within a short time period of 20-25s. The effect of different plasticizers has been studied and dioctylsebacate (DOS) found to give a better response in comparison to other plasticizers. Selectivity coefficient values (log KPotHg,M) have been evaluated using fixed interference method. Better selectivity for mercury(II) ions is observed over many of the monovalent (Na+, K+ and NH4+) and divalent ions (Mg2+, Ca2+, Zn2+, Pb2+, Ni2+, Co2+, etc.). The sensors have also been used as indicator electrodes in potentiometric titration of mercury(II) ions with EDTA and its determination in synthetic water samples.

科尔沁沙地小叶锦鸡儿群落保育土壤作用的研究

以流动沙丘和不同恢复年限的人工和天然小叶锦鸡儿群落为研究对象,从植被重建前后土壤理化性质变化方面分析了小叶锦鸡儿群落保育土壤的作用。结果表明,6 a生、11 a生和22 a生人工小叶锦鸡儿群落对土壤理化性质均有明显的改善作用,且总体上土壤改良效果与恢复年限成正相关。建立人工植被后,土壤中微沙(0.05~0.1 mm)和黏粒(<0.05 mm)的含量增加,表层(0—10 cm)土壤容重减小,孔隙度和饱和含水率增大,土壤持水能力提高;土壤有机碳、全氮、碱解氮、全磷、有效磷和有效钾含量均有不同程度增加,尤以表层增加幅度最大,并且灌丛对养分有明显的富集效应。

毛细管电泳电化学法对苯丙胺的检测

建立了毛细管电泳电化学法检测尿样中苯丙胺的方法。以直径33μm的碳纤维电极为工作电极,在最佳检测条件即检测电位1.30 V,15 kV下电动进样3 s,选择电泳分离高压为15 kV,电泳缓冲液为pH10.0的20 mmol/L的磷酸盐,实验发现,在1.0×10-8~1.0×10-5mol/L范围内,响应电流与苯丙胺浓度呈良好的线性关系,线性相关系数为0.998 4,检出限达3.3×10-9mol/L。对于浓度为1.0×10-5mol/L的苯丙胺,峰电流及迁移时间的RSD分别为2.4%和2.5%(n=7)。对于尿样中2.0×10-5mol/L的苯丙胺,回收率为75%。

有序介孔材料SBA-15吸附Ru(bpy)_3~(2+)修饰电极的电化学发光研究

制备了具有高比表面积且二维六方高度有序的介孔分子筛SBA-15,并采用TEM和氮气吸附实验对其结构性质进行了表征.利用静电作用将三联吡啶钌[Ru(bpy)32+]固定到表面带负电荷的SBA-15上,并将吸附有Ru(bpy)32+的SBA-15修饰到玻碳电极表面,研究了该固定化的Ru(bpy)32+的电化学发光行为.结果表明,随着三丙胺(TPA)的加入,氧化电流增加而还原电流减小,表明TPA对三价吡啶钌有催化作用,同时TPA的加入显著增强了发光强度.随着扫描速率的增加,发光强度逐渐降低.SBA-15较大的孔径和开放交联的孔结构体系促进了电极表面膜内的物质扩散和电子运动扩散.该修饰电极在5.0×10-5~1.0×10-2mol/LTPA浓度范围内,发光强度与浓度具有良好的线性关系,线性方程为y=71.7+41.2x,检出限为9.5×10-6mol/L.该电极在连续扫描下具有较好的稳定性.

Naphthyl and thionaphthyl end-capped oligothiophenes as organic semiconductors: Effect of chain length and end-capping groups

Two series of oligothiophenes (OThs), NaTn and TNTn (n = 2-6 represents the number of thiophene rings), end-capped with naphthyl and thionaphthyl units have been synthesized by means of Stille coupling. Their thermal properties, optical properties, single crystal structures, and organic field-effect transistor performance have been characterized. All oligomers display great thermal stability and crystallinity. ne crystallographic structures of NaT2, NaT3, TNT2, and TNT3 have been determined. The crystals of NaT2 and NaT3 are monoclinic with space group P2(1)/C, while those of TNT2 and TNT3 are triclinic and orthorhombic with space groups P-1(-) and P2(1)2(1)2(1), respectively. All oligomers adopt the well-known herringbone packing-mode in crystals with packing parameters dependent on the structure of the end-capping units and the number of thiophene rings. The shorter intermolecular distance in NaT3 compared to NaT2 indicates that the intermolecular interaction principally increases with increasing molecular length. X-ray diffraction and atomic force microscopy (AFM) characterization indicate that the NaTn oligomers can form films with better morphology and high molecular order than TNTn oligomers with the same number of thiophene rings. The NaTn oligomers exhibit mobilities that are much higher than those for TNTn oligomers (0.028-0.39 cm(2) V-1 s(-1) versus 0.010-0.055 cm(2) V-1 s(-1), respectively).

Preparation and properties of abzyme with thyroxine deiodinase

The abzyme (Se-6E8) with a higher thyroxine deiodinase activity was prepared by modifying the serine residues of monoclonal antibody (6E8)with phenylmethanesulfonyl fluoride and sodium hydrogen selenide, and the 6E8 against O-methyl-T-4, which is a kind of thyroxine derivatives and was taken as a hapten for the first time. Two bands were found corresponding to the 5.5 kD heavy chain and the 2.7 kD light chain respectively by SDS-PAGE. The characteristics of dissociation constants, pH, and temperature were also studied. The results show that the activity of Se-6E8 is 2 010 U/mumol protein, and the proper temperature and pH of the catalytic reactions is 57 degreesC and 8.2 respectively.

压力对尼龙1010凝聚态结构的影响

研究了尼龙(PA)1010在250℃、不同压力下退火30 min后凝聚态结构的变化。结果表明,在压力小于1.0 GPa和大于1.2 GPa的范围内,PA1010室温结晶的三斜晶系的晶体结构没有变化,但是(100)晶面的衍射强度随压力的增加而减弱,而(110/010)晶面的衍射强度增加;当压力在1.0～1.2 GPa时,PA1010的X射线衍射图谱没有明显的衍射峰,DSC和溶解实验证实,PA1010在该压力范围内发生了交联,并进一步讨论了PA1010在高压下发生交联的机理。

A novel epitaxy of isotactic polypropylene (alpha phase) on PTFE and organic substrates

Isotactic polypropylene in its a modification (alpha iPP) crystallises epitaxially on polytetrafluoroethylene (PTFE) and several hemiacids or salts of substituted benzoic acids via a novel contact plane, namely (110): so far, the only known contact plane involved in alpha iPP homo- and hetero-epitaxies was (010). In spite of its complicated architecture (alternation of antichiral helices with different azimuthal settings), the (110)(alpha iPP) contact plane displays well defined, if not prominent, rows of methyl side chains parallel to the crystallographic (112) direction (at 57 degrees to the c-axis) and approximate to 5.5 Angstrom apart. The matching contact planes of the substrates display linear gratings made of rows of e.g. chlorine atoms or PTFE chains with similar approximate to 5.5 Angstrom inter-row or interchain distances. Various morphologies are observed in iPP thin films crystallised at different cooling rates in the presence of PTFE; they can be analysed in terms of a succession and interplay of successive epitaxies: initial alpha iPP/PTFE heteroepitaxy, followed by alpha iPP/alpha iPP and gamma iPP/alpha iPP homoepitaxies. (C) 1999 Published by Elsevier Science Ltd. All rights reserved.

Homoepitaxial crystallization in films of a thermotropic liquid crystalline chloro-poly(aryl ether ketone)

The homoepitaxial crystallization in the films of a thermotropic liquid crystalline chloro-ply(aryl ether ketone) is studied by transmission electron microscopy (TEM) and electron diffraction (ED). The homoepitaxy takes place in the temperature range 330-320 degreesC, in which a highly-ordered smectic crystalline phase of the copolymer with a single-crystal-like banded structure is formed during the cooling process from the isotropic melt. The homoepitaxial crystallizations with angles of 32 degrees and 122 degrees between the two b axes are the major populations observed, and possess epitaxial contact planes of (100)(I)-(210)(II) and (010)(I)-(210)(II); respectively.

Lamellar single crystals of nylon-10,10 crown from a dimethylformamide solution

A new solvent, dimethylformamide (DMF), and the traditional solvent, 1,4-butanediol, were used to prepare single crystals of nylon-10,10 from a dilute solution. The lamellae grown from DMF inhabited a more perfect structure and regular shape than those crystals crystallized from traditional solvents such as 1,4-butanediol and glycerin. These thin and perfect lamellar crystals demonstrated patterns of variation in spacing different from those of melt-crystallized spherulites on heating. Specifically, the two main spacings slightly separated rather than continuously approaching each other when the temperature was greater than 180 degreesC. This is a novel phenomenon observed in nylons. Nevertheless, the usual pattern of change in spacing was observed during the cooling process. These lamellar crystals showed more compact spacing of the (002) and (010/100) planes than spherulites at room temperature. (C) 2001 John Wiley & Sons, Inc.

抗坏血酸自加速的圆二色谱电化学研究

以现场长光程薄层圆二色光谱电化学方法研究了抗坏血酸在玻碳电极上的电极反应过程.通过双对数法和非线性回归的方法处理了薄层圆二色光谱电化学实验数据,结果表明抗坏血酸在pH7.0的缓冲溶液中玻碳电极上为2个电子转移的不可逆电化学氧化,氧化产物在电极上发生了强吸附,吸附层对抗坏血酸的电化学氧化反应有自加速作用,并获得了抗坏血酸在探电极和在吸附电极上的式电位分别为E~(?)=0.09V,E~(?)=0.26V;电子转移数和电子转移系数分别为an=0.41,a_(?)n=0.07;标准复相电子转移速率常数分别为k~0=8.0×10~(-5)cm s~(-1),k~0_a=1.9×10~(-4)cm s~(-1);吸附系数为β=102.6±0.2.

谷物中噻吩甲氯残留量的气相色谱-质谱测定

应用气相色谱－ 质谱法确证及测定谷物( 糙米、玉米) 中噻吩甲氯的残留含量，试样采用水—丙酮提取，提取液经与石油醚液—液分配后， 再以硅酸镁载体(Florisil)柱净化，气相色谱—质量选择检测器选择离子监测方式(GC-MSD-SIM)进行测定和阳性确证。噻吩甲氯选择监测离子的种类为m/z287、288、323，其丰度比约为46:100:11。采用外标法定量，方法检出限为0.010 ×10-6。

用在线流动注射法研究膜基萃取过程中的铵离子传质规律

采用氨气敏电极结合流动注射分析法，对中空纤维膜器中氨化二(2,4,4-三甲基戊基)膦酸(HBTMPP)-庚烷体系萃 取镱、铒过程的铵离子进行在线分析．结果表明，当NaOH浓度为0.02mol/L，响应保留时间为90ｓ时，铵离子 标准曲线在20×10-5～1.0×10-1mol/L铵离子浓度范围内，具有良好的线性关系．样品溶液的用量由普通电极 法的30mL降至0.5mL；样品测定频率可达15次/h．当HBTMPP被氨化后，在高PH范围内，氢离子的传质仍优先 于铵离子，PH值下降很快；然后是H+、NH4+的混合交换 ，料液相形成缓冲体系，PH值基本不变．同级萃取反萃 中，也有基本相同的传质规律

增强辣根过氧化物酶催化鲁米诺化学发光反应的新型增强剂四苯硼钠

报道了新型增强剂四苯硼钠对过氧化物酶催化鲁米诺－过氧化氢发光反应的增强作用，建立了流动注射化学发光测定或辣过氧化物酶(HRP)的新体系。用该体系测定HRP线性范围为1.0×10－12×1.2×10－13mol/L；检测限为0.6×10－13mol/L。对0.6×10－13mmol/L的HRP进行11次平行测定，相对标准偏差为1.5%。