Ru基化合物催化制氢的研究进展

氢的存储是车载燃料电池发展的关键环节。甲醇在室温下呈液态并且储氢量达12.6wt%,然而分解甲醇制氢需要较高的温度(超过200℃)和压强(25~50bar)。最近研究者报道了利用单核钌(Ru)基化合物作催化剂,在常温常压条件下可以将甲醇分解成CO_2和H_2;利用双核Ru基化合物作催化剂,可以将多聚甲醛或甲醛与水的混合溶液有选择性地脱氢生成H_2和CO_2,但是关于Ru基化合物微观层次的催化机制还需要进一步研究。本文综述了不同配体构型和不同种类配体对催化剂活性的影响及其脱氢路径,以及催化剂的催化活性和溶液的pH值之间的关系,阐明如何改进现有单核Ru基钳型化合物和双核Ru基化合物催化剂的性能,设计催化活性更优良的新型催化剂。     

白黄链霉菌TD-1菌株挥发性有机物对灰霉孢菌的抑制作用

为探讨白黄链霉菌TD-1菌株挥发性有机物(VOCs)对灰霉孢菌的抑制作用,采用双皿对扣法测定VOCs对灰霉孢菌的抑菌率,通过扫描电镜观察VOCs对灰霉孢菌菌丝体的影响,利用GC/MS技术对VOCs组分进行分析。结果表明,作用5d后,6.0g TD-1菌株麦麸培养物产生的VOCs对灰霉孢菌的抑菌率为66.67%,灰霉孢菌的产孢量(3.9×10⁶个/cm²)较空白组(5.9×10⁷个/cm²)显著降低(p<0.01),且菌丝形态异常、表面粗糙,菌体细胞膜通透性增强。TD-1菌株VOCs由63种组分组成,其中2-甲基异冰片(13.52%)和1,4-二甲基金刚烷(14.08%)的相对含量较高。白黄链霉菌TD-1菌株产生的VOCs对灰霉孢菌良好的抑制作用为将其开发成生物熏蒸剂提供了理论依据。     

基于Petri网的VOCs跨区域流动动态风险评估方法

为了评价污染天气下由于VOCs(volatile organic compounds)跨区域流动产生的区域间的相互影响作用的大小，找出对受污染区域影响较大的路径，结合Petri网模型提出了VOCs跨区域流动动态风险评估方法。利用HYSPLIT模型确定多个潜在污染源与受污染区域的VOCs迁移路径，运用Petri网去描述各个迁移路径之间的关系；将动态风险大小的计算融入到函数Petri网的运行中，定量评估潜在污染源到受污染区域的各条路径的风险程度；案例分析得出污染天气下周边区域对于西安的动态风险评估结果以及各污染路径的潜在风险指数。研究表明，在重污染天气下各个污染源城市对西安的影响程度大小由高到低依次为宝鸡>汉中>西宁>兰州。该方法为评估VOCs跨区域流动过程中潜在污染源的风险程度提供了依据。     

Characteristic investigation of trilayered Cu/Al8011/Al1060 composite: Interface morphology,microstructure, and in-situ tensile deformation

In this work, Cu/Al8011/Al1060 trilayered composite with an ultrathin copper layer was fabricated successfully by the hybrid process of cast-rolling and hot-roll-bonding. The effects of heat treatment were investigated on the microstructure and mechanical behavior of the composite. The results showed that annealing temperatures above 300 ​°C led to the formation of new intermetallic compounds that joined their initial counterparts. Also, the interface growth was fast above 340 ​°C. It was found that the annealing temperature of 320 ​°C led to the optimal tensile properties of the composite. Through rolling, hard-brittle IMCs imposed intense plastic strains on the surrounding regions, resulting in further grain refinement of both metals in the vicinity of the interface. Although the kernel average misorientation of the trilayered composite was almost identical with the Cu/Al8011 bimetal, its amount was considerably decreased after heat treatment, as the distorted structure changed into a nearly strain-free one using the restoration phenomenon. The SEM-based in-situ tensile test showed that crack initiation occurred within the IMCs and propagated into the Cu strip, leading to its early fracture. However, the strength-displacement curve during in-situ tensile deformation did not decrease significantly due to the ultrathin copper layer.     

Effects of metals and organic compounds on survival and bioaccumulation in two species of marine gammaridean amphipod,together with a summary of toxicological research on this group

The toxicity and bioaccumulation of arsenic, cadmium, copper, lead, mercury, zinc, DDT, PCB and the water-soluble fraction of diesel fuel to the gammaridean amphipods Corophium insidiosum and Elasmopus bampo were measured. At 96 h exposure C. insidiosum was more sensitive to arsenic, zinc, DDT, PCB and the water-soluble fraction of diesel fuel than E. bampo, whereas E. bampo was more sensitive to cadmium, chromium and copper than C. insidiosum. Over a 20-day period C. insidiosum accumulated greater amounts of chromium, copper, lead and zinc than E. bampo, whereas E. bampo accumulated more cadmium, DDT and PCB than C. insidiosum. The toxicity and bioaccumulation of toxicants to other species of marine gammaridean amphipods are tabulated.     

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.     

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）.     

萘及其1-卤素取代化合物的荧光光谱的量子化学研究

萘及其化合物一般具有较大的共轭体系,是一类良好的电致发光材料.对萘及其卤代化合物的荧光光谱进行了理论研究.在B3LYP/6-31G水平下优化了4种化合物的几何构型.在振动分析中,均未出现虚频率.基于此,在B3LYP/6-31G的水平下计算了该类化合物的荧光光谱,所有计算结果与实验值基本吻合.