热处理条件对IrO2-pH电极性能的影响

在700℃炉冷、870℃空冷和炉冷三种热处理条件下,制备了氧化铱pH微电极,并对比了微电极的线性范围及响应时间.结果表明:热处理条件对Ir氧化物膜的均匀性有很大影响,进而影响其开路电位的稳定性及响应速度.700℃炉冷和870℃空冷制得的电极氧化膜表面粗糙,孔隙率不均匀并伴随有裂纹;而870℃炉冷条件下制得的电极具有表面氧化膜均匀、响应时间短以及线性好等优点.铱氧化物的形成机理是Ir丝被空气中的O2氧化,而高温Li2CO3起到一种溶剂的作用.铱氧化物电极的H+响应是由于电极表面水合氧化铱与溶液中H+发生化学反应,反应为Ir4+与Ir3+之间的转变.     

Serum levels of perfluorinated compounds in the general population in Shenzhen, China

Perfluorinated compounds (PFCs) have been detected in many environmental matrices, biota, and nonoccupationally exposed populations in China recently. However, little is known about the distribution and levels of various PFCs in the general population living in areas where there is PFC exposure. In the present study, the levels and prevalence of ten target PFCs were determined in 227 serum samples from a population of nonoccupationally exposed individuals in Shenzhen, China. Results indicated that human exposure to PFCs was prevalent in Shenzhen. Perfluorooctanoate (PFOA) was the dominant PFC contaminant in the serum samples, with a median concentration of 6.72 ng/mL, followed by perfluorooctane sulfonate (PFOS) with a median concentration of 2.07 ng/mL. Other PFCs were detected at much lower concentrations, with median concentrations ranging from 0.02 to 0.87 ng/mL. Statistically, no significant (P>0.05) gender differences were observed for any of the PFCs. Significant (P<0.01) positive correlations were found between age and serum concentrations of the target PFCs, except for perfluorobutane sulfonate (R = 0.16, P = 0.01), perfluorohexanoic acid (R = 0.08, P = 0.22), and perfluoroheptanoic acid (R = 0.11, P = 0.10). Based on the one-compartment pharmacokinetic model, the total daily intakes of PFOA and PFOS for the general population in Shenzhen were calculated as 0.63 and 0.20 ng/kg body weight/day, respectively.     

A gas chromatography/mass spectrometry method for the simultaneous analysis of 50 phenols in wastewater using deconvolution technology

Phenolic compounds exist widely in the influents and effluents of sewage treatment plants (STPs) and most are un-regulated. In this study, a gas chromatography-mass spectrometry (GC-MS) method for the simultaneous analysis of 50 phenolic compounds in wastewater was developed. Deconvolution technology was used to identify contaminants that are covered by co-extracted materials. A mass spectral library containing all 50 silylated phenolic compounds was first established and used for deconvolution. Twelve typical phenolic compounds were selected to optimize the sample preparation procedures. Solid-phase extraction using a C18 cartridge coupled with an HLB cartridge was used for pre-concentration and dichloromethane was used for elution. The solutes were derivatized and analyzed by GC-MS. The blank and matrix spike recoveries ranged from 57.46% to 136.4% and 47.87% to 114.8%, respectively. Method detection limits ranged from 3.64 to 97.64 ng L⁻¹. The relative standard deviations of all the recovery experiments were lower than 13.6%. The instrument limits of quantification ranged from 0.7 to 87.7 pg. The method has been applied to analyze the influents and effluents of 5 Chinese STPs. Except for regulated phenolic compounds (phenol and 2,4,6-trichlorophenol), three un-regulated phenolic compounds, including 2-chlorophenol, 2,5-dichlorophenol and 2,4-dichloro-3-ethyl-6-nitrophenol were identified in the effluent wastewater. The detected concentrations of un-regulated phenolic compounds could possibly cause environmental effects, indicating that immediate attention is required to prevent complications.     

典型多环芳烃电化学可逆增溶作用研究

提出采用具有电化学开关特性的季铵盐实现对典型多环芳烃(PAHs)的可逆增溶,研究了十一烷基二茂铁三甲基溴化铵(FTMA)的电化学可逆特性及其对菲、芘、苊的增溶作用.结果表明:FTMA具有良好的电化学可逆特性,通过电化学氧化及还原作用,其在氧化态与还原态之间的转化效率可达到90%以上,临界胶束浓度(CMC)及表面张力在2种状态时也发生了极大变化;FTMA对菲、芘、苊具有显著的增溶作用,且增溶作用大小顺序为芘>菲>苊;经电化学氧化之后FTMA失去表面活性及增溶能力,FTMA对3种PAHs的摩尔增溶比均降低了85%以上,但经电化学还原之后其增溶能力仍可恢复.     

氯代芳烃及其衍生物定量结构-色谱保留值的相关性研究

根据分子中原子的特性和连接性,将分子中原子i的特征值定义为iQδ.由iQδ建构了修正的拓扑定位指数mQt,mQt具有很强的结构选择性,且计算简单.用逐步回归法分别建立氯代芳烃及其衍生物在不同色谱柱上(SE-30/160℃、SE-30/100℃、CW 20M/100℃、DB-5、SE-54、OV-101)的色谱保留值与mQt的QSRR相关模型,各样本总体所建模型的相关系数均在0.97(R≥0.99(54.55%),0.95≤R<0.99(45.45%))以上.结果表明:该模型能较好解释氯代芳烃及其衍生物的色谱保留值的递变规律,而且模型的相关系数高、预测能力强、可靠性和稳健性好.     

贮藏温度对蓝莓活性成分及抗氧化活性的影响

研究不同贮藏温度下,蓝莓果实的活性成分及抗氧化活性的变化,确定蓝莓鲜果适宜的贮藏温度,并为研究蓝莓果实中主要的抗氧化成分提供参考.在贮藏温度为20~25,10~15,0~5℃下,于不同贮藏期取样测定蓝莓果实中花青素、总酚和总黄酮的质量分数;测定蓝莓对DPPH自由基（DPPH.）和羟自由基（OH.）的清除率,并分析3种活性成分与蓝莓抗氧化活性的相关性.结果表明,在不同的贮藏温度下,蓝莓果实中花青素、总酚和总黄酮的质量分数及抗氧化活性均呈现先上升后下降的趋势,在贮藏初期,较高的贮藏温度能明显促进蓝莓果实活性成分含量和抗氧化活性的增加,但在贮藏后期,较高的温度加速了蓝莓果实活性成分含量和抗氧化活性的下降速度,并缩短了蓝莓贮藏期;低温（0~5℃）能使蓝莓果实的活性成分含量和抗氧化活性始终维持在一个相对较高的水平,且能显著增加果实的贮藏期,是蓝莓较适宜的贮藏温度;蓝莓果实中花青素、总酚和总黄酮质量分数与其清除自由基的能力之间均呈显著正相关（P〈0.05）.     

取代芳烃与6种生物毒性的定量构效关系

根据成键原子的结构特征,提出了计算取代芳烃原子点价δi的新方法,并由δi建构了取代芳烃的分子连接性指数mXn,用mXn与取代芳烃对斜生栅列藻急性毒性,诱发浮萍萎黄病毒性、绿藻毒性、大型蚤毒性、斑马鱼毒性和金鱼毒性等6项生物活性相关联,获得令人满意的线性回归方程,相应的相关系数r依次为0.975 8、0.984 6、0....     

新型偶氮香豆素化合物的合成及光谱特性

为对比6-偶氮香豆素和7-偶氮香豆素的光物理特性,设计、合成并测定了一系列偶氮香豆素化合物的最大紫外吸收波长和最大荧光发射波长的数据,并求得了S tock位移值。     

桉树叶中黄酮类化合物的提取工艺研究

讨论了影响黄酮类化合物提取率的主要因素,并确定了较好的提取工艺,结果表明:以φ=65%的乙醇、粒度为30目的桉树叶粉按m料∶V乙醇=1∶12的比例,浸泡24 h,然后在70℃下提取2 h,可得到质量含量为3.41%的总黄酮.     

分子间相互作用对芳杂环聚合物PBO光谱性能影响的理论研究

采用量子化学计算方法AM1-ZINDO/CI对芳杂环聚合物PBO的光物理性能进行研究。结果表明:PBO分子链共轭平面结构间的面面相互作用,影响到前沿分子轨道的电子跃迁方式,从而导致聚集态电子光谱相对于理论单分子链存在红移现象。由含3个单元的PBO聚集态分子模型模拟计算显示,PBO分子链共轭平面结构间的面面相互作用使得电子光谱最大吸收峰由383.06 nm红移至407.19 nm。结合同系线性规律,推导出PBO聚合物聚集态的电子光谱最大吸收峰为425.33 nm,从本征结构上解释了PBO聚集态电子光谱的光谱性质。