酞菁键合硅胶的制备及分离取代酞菁异构体

制备和表征了一种新的酞菁键合硅胶，三-β-(辛巯基)-β-(磺酰胺基)-酞菁铜键合硅胶。研究了该键合酞菁硅胶作为HPLC固定相的基本色谱性能。实验结果表明，该固定相可以分离四-α-(2，2，4-三甲基-3-戊氧基)酞菁(铜、镍)的4种异构体，也可以观察到四-α-(2，2，4-三甲基-3-戊氧基)无金属酞菁的4种异构体，而商业C₁₈(VERTEX Eurospher)却只能观察到两组峰，表明这种酞菁键合硅胶固定相在分析、分离一些取代酞菁异构体方面比商业C₁₈具有更好的分离效果。     

分散固相萃取结合气相色谱-高分辨质谱快速筛查酱油中多种氯丙醇

建立了酱油中1，3-二氯-2-丙醇、2，3-二氯-1-丙醇、3-氯-1，2-丙二醇和2-氯-1，3-丙二醇的分散固相萃取-气相色谱-高分辨质谱快速筛查检测方法。样品采用乙酸乙酯提取，提取液浓缩后经N-丙基乙二胺净化，气相色谱-高分辨质谱测定，内标法定量。结果表明，该方法对于酱油中4种氯丙醇的定量限为0.5~10 μg/kg。在3个浓度水平下的加标回收率为78%~103%；相对标准偏差均不大于8.8%。该方法快速、简便、准确、灵敏，可作为酱油中4种氯丙醇的有效检测方法。     

Generalization of in-situ polymerization method for preparing core-shell polymeric nanospheres and hollow spheres

According to the new method of preparing core-shell nanospheres developed by our group, by using two monomers, 2-hydroxypropyl methacrylate(HPMA) and vinyl acetate(VAc), two kinds of core-shell nanospheres with poly(ɛ-caprolactone) (PCL) as the core and crosslinked poly(2-hydroxypropyl methacrylate) (PHPMA) or poly(vinyl acetate) (PVAc) as the shell were successfully prepared under similar conditions. After degrading the PCL cores of the two kinds of nanospheres by lipase, the corresponding crosslinked poly(methyl acrylic acid) hollow spheres and crosslinked poly(vinyl alcohol) hollow spheres were obtained. Results indicate that the new method we proposed for preparing core-shell polymeric nanospheres via in-situ polymerization can be generalized to a certain extent, and it is suitable for many systems provided the monomer used is soluble in water, while its corresponding polymer is insoluble in water. Translated from Chemical Journal of Chinese University, 2006, 27(9): 1762–1766 [译自: 高等学校化学学报]     

包覆Y(OH)3的球形Ni(OH)2的电化学性能

利用软嵌式粉末电极技术研究了Y(OH)3包覆对球形Ni(OH)2电化学性能的影响. 循环伏安结果表明, 在球形Ni(OH)2的氧化过程中存在Ni(Ⅲ)和Ni(Ⅳ)的两步氧化反应, 产生的Ni(Ⅳ)不稳定, 能分解产生NiOOH和氧气, 所以可将Ni(Ⅲ)→Ni(Ⅳ)看作副反应. Y(OH)3包覆层对Ni(OH)2氧化过程后期的副反应, 特别是Ni(Ⅲ)→Ni(Ⅳ)具有较好的抑制作用. 由包覆后的Ni(OH)2制成的模拟电池表现出很好的高温性能, 在1C充放电条件下, 当Y的摩尔分数为1.61%时, 在60 ℃时所对应的容量保持率可达到25 ℃的92.7％; 当Y的摩尔分数仅为0.55 %时, 在60 ℃时所对应的质量比容量也可达到241.3 mA·h/g.     

方酸染料在远红光区／近红外区对纳米晶二氧化钛电极的高效敏化作用

Four para-dialkylaminophenyl （PDAAP1-PDAAP4） bearing carboxyl groups were studied for application to the dye-sensitized solar cells （DSC）. It was found the short spacer CH2 between carboxyl and dialkylaminophenyl chromophore in PDAAP3 and PDAAP4 led to highly efficient monochromatic incident photon-to-current conversion efficiencies （IPCE）, however the long alkyl group C4H9 attached on aniline moieties in PDAAP2 and PDAAP4 favored improvement of open-circuit photovoltage. Thus, the solar cell sensitized by PDAAP4, having both short carboxyl groups CH2COOH and long alkyl groups C4H9, exhibited the IPCE maximum of 73% at 670 nm and overall energy conversion efficiency η of 3.06%, representing the highest IPCE and η values so far in dialkylaminophenyl-based organic dye-sensitized semiconductor solar cells. Taking advantage of the highly efficient sensitizing ability of PDAAP4 in far-red region, the data of IPCE above 630 nm of the solar cells were improved greatly by cosensitization with both N3 and PDAAP4. The influences of the TiO2 film thickness and the concentration of 4-tert-butylpyridine （TBP） in electrolyte were also investigated.     

超高交联吸附树脂对芳香有机物的吸附机理

通过3种吸附树脂AmberliteXAD-4、AM-1和JX101对芳香化合物苯胺、苯酚和苯甲酸在不同温度下的吸附特征,利用前线轨道理论进行了合理解释。结果表明,吸附剂表面进行适当的修饰,可以改变吸附剂的LUMO或HOMO,使吸附质分子与吸附剂表面的功能基产生化学作用,从而产生额外的化学吸附量,为优化设计吸附剂提供了理论指导。     

化学镀法制备银壳聚苯乙烯微球

采用一种新的化学镀法合成银壳包覆聚苯乙烯微球, 通过三乙醇胺和银离子络合来减小反应的氧化还原电位差, 降低银在改性聚苯乙烯微球表面的沉积速率. 采用TEM、XRD、UV 等测试手段对样品进行了分析和表征, 并考察了不同反应条件对实验结果的影响.实验表明, 该方法可在改性聚苯乙烯微球上包覆均匀的银层.     

Analysis of Zoledronic Acid and Its Related Substances by Ion-Pair RP-LC

A simple high-performance liquid chromatographic method – ion-pair reversed- phase high performance liquid chromatography (RPIC) has been developed and employed for the analysis of zoledronic acid and its related substances in bulk material and commercial dosage forms. The mobile phase was a mixture of methanol (20%) and 5 mmol L^–1 phosphate buffer (80%) containing 6 mmol L^–1 tetrabutylammonium bromide, adjusted to pH 7.0 with sodium hydroxide. C₈ column was used as the stationary phase. The chromatographic conditions were optimized. The active ingredient – zoledronic acid was successfully separated from its related substances, including remained imidazol-1-yiacetic acid in the synthesis of zoledronic acid and other possible impurities of oxidation and decomposition. The excipients did not interfere with the determination of zoledronic acid in commercial dosage formulations. The method was rapid, simple, accurate and reproducible. It was not only successfully employed for the assay of zoledronic acid in bulk material and pharmaceutical dosage forms but also for the determination of its related substances.     

Anodic stripping voltammetry of sulphide at a nickel film: towards the development of a reagentless sensor

The determination of sulphide at an electrochemically generated nickel oxide layer at glassy carbon and screen-printed electrodes in acidic media has been examined and appraised. The NiO layer was found to produce a stripping-like signal to sulphide and gave a linear peak current response from 20 to 90 μM. The response was further enhanced by repetitive cycling allowing accumulation of nickel sulphide at the electrode surface such that lower micromolar levels of sulphide (i.e. 5 μM) can be determined. The response at the NiO layer to sulphide is shown to be reproducible over a period of 24 h, thereby offering the development of a disposable amperometric sensor for sulphide.     

球状蛋白质分子中氨基酸紧密接触对性质的研究

采用CSU软件 (Contactsofstructuralunits) ,对 61种球状蛋白质分子中氨基酸紧密接触对 (Residue residuecontact)进行了研究 .重点研究了不同氨基酸在形成远程紧密接触对 (Long rangecontact)和近程紧密接触对 (Short rangecontact)时的不同能力 .发现氨基酸Leu,Val,Ile,Met,Phe,Tyr,Cys,Trp(疏性氨基酸 ,H)比较容易形成远程紧密接触对 ,氨基酸Glu,Gln ,Asp ,Asn,Lys,Ser,Arg,Pro(亲水氨基酸 ,P)比较难形成远程紧密接触对 ,而氨基酸Ala,Gly,Thr,His(中性氨基酸 ,N)在形成远程紧密接触对时能力一般 .它们平均每个氨基酸可形成 6 0 3 ,3 64和 4 43个远程紧密接触对 .同时它们在形成近程紧密接触对时能力非常接近 ,平均每个氨基酸可形成的近程紧密接触对数目在 2 3 4～ 2 85变化 ,差别非常小 .亲水氨基酸 (P) ,中性氨基酸 (N)和疏水性氨基酸 (H)在蛋白质分子结构稳定性上起着不同的作用