P14原子簇的理论研究

以Ｐ_２、Ｐ_４（Ｔｄ）、Ｐ_８（Ｃ_（２ｖ））及Ｐ_（１０）（Ｃ_（２ｖ））为结构单元设计了Ｐ_２＋Ｐ_４（Ｔ_ｄ）＋Ｐ_８（Ｃ_（２ｖ））→Ｐ_（１４）（Ｃ_ｓ）（Ａ）、Ｐｓ（Ｃ_（２ｖ）＋３Ｐ_２→Ｐ_（１４）（Ｃ_（２ｖ））（Ｉ）（Ｂ）、Ｐ_（１０）（Ｃ_（２ｖ）＋２Ｐ_２→Ｐ１４（Ｃ_（２ｖ））（Ⅱ）（Ｃ），利用从头算Ｇａｕｓｓｉａｎ－９４程序，选择６－３１Ｇ基组，对４种结构单元及Ｐ_（１４）原子簇的３种几何构型Ｃｓ、Ｃ_（２ｖ）（Ⅰ）、Ｃ_（２ｖ）（Ⅱ）进行全优化。相对能量的计算结果表明，Ｐ_（１４）（Ｃ_ｓ）与Ｐ_（１４）（Ｃ_（２ｖ））（Ⅰ）构型稳定。进一步设计（７／２）Ｐ_４（Ｔ_ｄ）→Ｐ_（１４）（Ｄ）及７Ｐ_２→Ｐ_（１４）（Ｅ），其相对能量表明，Ｐ_（１４）（Ｃ_ｓ）构型是稳定的．磷与磷连结单键键长范围为０．２２０～０．２２８ｎｍ，双键键长范围为０．２００～０．２０２ｎｍ，与实验结果大体相当。     

负载型贵金属催化剂的制备化学－载体等电点对Pd／A1_2O_3催化剂结构与催化性能的影响

本文通过化学修饰的方法改变了γ－Ａｌ_２Ｏ_３载体等电点（ＩＥＰＳ），并用具有不同等电点的Ａｌ_２Ｏ_３作载体，以（ＮＨ_４）_２ＰｄＣｌ４为活性组分前身制备了一系列Ｐｄ／Ａｌ_２Ｏ_３催化剂，在固定床微反色谱装置上考察了其对ＣＯ氧化的催化活性，用Ｈｉ—Ｏ_２滴定、紫外漫反射光谱（ＤＲＳ）、透射电子显微镜（ＴＥＭ）中的能量色散谱（ＥＤＸＳ）等方法对上述催化剂进行了表征，结果表明：Ａｌ_２Ｏ_３的等电点（ＩＥＰＳ）对所得催化剂中金属分散度和浓度分布都有明显影响，ＩＥＰＳ越高。活性组分越靠近外表面，在相同担载量下，其分散度也越高。这主要是由于载体ＩＥＰＳ的改变，导致了（ＮＨ_４）_２ＰｄＣｌ_４在γ－Ａｌ_２Ｏ_３上吸附机理的变化，并使所得催化剂对ＣＯ氧化的催化活性发生了规律性的变化。     

THE REACTION OF（μ_3－CPh）Co_3（CO）_9 WITH TRANSITION METAL CARBONYL ANION M（CO）_3（RCOCp）AND CHARACTERIZATION OF CLUSTERS（μ_3－CPh）CO_2M（CO）_8（RCOCPp）（M＝Mo，W；R＝H，CH_3．C_2H_5O）

ＴＨＥＲＥＡＣＴＩＯＮＯＦ（μ_３－ＣＰｈ）Ｃｏ_３（ＣＯ）_９ＷＩＴＨ　ＴＲＡＮＳＩＴＩＯＮＭＥＴＡＬＣＡＲＢＯＮＹＬＡＮＩＯＮＭ（ＣＯ）_３（ＲＣＯＣｐ）ＡＮＤＣＨＡＲＡＣＴＥＲＩＺＡＴＩＯＮＯＦＣＬＵＳＴＥＲＳ（μ_３－ＣＰｈ）ＣＯ_２Ｍ（ＣＯ）_８（ＲＣＯＣＰｐ）（Ｍ＝Ｍｏ，Ｗ；Ｒ＝Ｈ，ＣＨ_３．Ｃ_２Ｈ_５Ｏ）Ａｕｔｈｏｒｔｏｗｈｏｍｃｏｒｍｓｐｏｎｄｅｎｃｅｓｈｏｕｌｄａｄｄｒｅｓｓｅｄ．ＥｘｐｅｒｉｍｅｎｔａｌｓｅｃｔｉｏｎＧｅｎｅｒａｌｐｒｏｃｅｄｕｒｅａｎｄｍａｔｅｒｉａｌＡｌｌｏｐｅｒａｔｉｏｎｗａｓｃａｒｒｉｅｄｏｕｔｕｎｄｅｒｈｉｇｈｌｙｐｕｒｅｎｉｔｒｏｇｅｎａｔｍｏｓｐｈｅｒｅｕｓｉｎｇｓｈａｄａｒｄＳｃｈｌｅｎｌｃａｎｄｖａｃｕｕｍｔｅｃｈｎｉｑｕｅｓ．Ｈｅ－ｃａｎｅ，ｂｅｎｚｅｎｅａｎｄｔｅｔｒａｈｙｄｒｏｆｕｒａｎｗｅｒｅｐｒｅｄｒｉｅｄｏｖｅｒｓｏｄｉｕｍｗｉｒｅａｎｄｄｉｓｔｉｌｌｅｄｆｒｏｍｓｏｄｉｕｍ－ｂｅｎｚｏｐｈｅｎｏｎｅｕｎｄｅｒｎｉｔｒｏｇｅｎ．ＮａＭ（ＣＯ）３（ＲＣＯＣＰ）ａｎｄＰｈＣＣｏ３（ＣＯ），ｗｅｒｅｐｒｅｐａｒｅｄａｃｃｏｒｄｉｎｇｔｏｌｉｔｅｒａｔＵｒｅ     

ErCl_3－CaCl_2－LiCl三元体系相图的研究

利用ＤＴＡ研究了ＥｒＣｌ_３ＣａＣｌ_２ＬｉＣｌ三元体系相图。发现该相图有对应于ＥｒＣｌ_３、ＣａＣｌ_２、ＬｉＣｌ和Ｌｉ_３ＥｒＣｌ_６的４个液相面，５条二次结晶线，一个三元低共熔点Ｅ（５８．５％ＥｒＣｌ_３，２３．７％ＣａＣｌ_２，１７．８％ＬｉＣｌ，３９７℃），一个三元转熔点Ｐ（５２．５％ＥｒＣｌ_３，２７．２％ＣａＣｌ_２，２０．３％ＬｉＣｌ，４２８℃）。相应的４相平衡反应为：Ｌ＝ＥｒＣｌ_３＋Ｌｉ_３ＥｒＣｌ_６＋ＣａＣｌ_２；Ｌ＋ＬｉＣｌ＝Ｌｉ_３ＥｒＣｌ_６＋ＣａＣｌ_２．     

含TBP的PS－EC复合膜微胶囊的制备及对Cr_2O_7~（2－）传输的研究

将聚苯乙烯（ＰＳ）和乙基纤维素（ＥＣ）溶于ＣＨ_２Ｃｌ_２中，利用水中干燥法制备ＰＳ－ＥＣ复合膜微胶囊。当复合膜的微孔中含有磷酸三丁酯（ＴＢＰ）时，微胶囊膜对Ｃｒ_２Ｏ_７~（２－）具有传输功能。芯材采用高浓度ＮａＯＨ时，可使Ｃｒ_２Ｏ_７~（２－）逆浓差传输。研究了ＰＳ和ＥＣ的比例、微胶囊粒径、ＮａＯＨ浓度及ＴＢＰ含量对传输的影响．在适当条件下，１０ｍｉｎ内Ｃｒ_２Ｏ_７~（２－）的浓度由１×１０~（－４）ｍｏｌ／Ｌ降至１×１０~（－７）ｍｏｌ／Ｌ以下。     

Syntheses， Structuresand Reactivity of Incomplete Cubane－like Compound［｛W_3S_4｝｛S_2P（OEt）_2｝_4（H_2O）］and Its Derivates

Ｓｙｎｔｈｅｓｅｓ,ＳｔｒｕｃｔｕｒｅｓａｎｄＲｅａｃｔｉｖｉｔｙｏｆＩｎｃｏｍｐｌｅｔｅＣｕｂａｎｅ－ｌｉｋｅＣｏｍｐｏｕｎｄ［｛Ｗ_３Ｓ_４｝｛Ｓ_２Ｐ（ＯＥｔ）_２｝_４（Ｈ_２Ｏ）］ａｎｄＩｔｓＤｅｒｉｖａｔｅｓ￥ＷｕＸｉｎ－Ｔａｏ;ＷａｎｇＱｕａ...     

PREPARATION AND PROPERTIES OF THE NEW ORGANIC CONDUCTOR (BEDT-TTF)_3Cu_2Cl_4

ＰＲＥＰＡＲＡＴＩＯＮＡＮＤＰＲＯＰＥＲＴＩＥＳＯＦＴＨＥＮＥＷＯＲＧＡＮＩＣＣＯＮＤＵＣＴＯＲ（ＢＥＤＴ－ＴＴＦ）_３Ｃｕ_２Ｃｌ_４ＰｅｉＪｉＷＵ；ＸｕｅＹｏｎｇＹＡＮＧａｎｄＤａｏＢｅｎＺＨＵ（ＩｎｓｔｉｔｕｔｅｏｆＣｈｅｍｉｓｔｒｙ，Ａｃａｄｅ?..     

PREPARATION AND CHARACTERIZATION OF K_(13)[Nd(Gew_9Mo_2O_(39)_2]·23H_2O

ＰＲＥＰＡＲＡＴＩＯＮＡＮＤＣＨＡＲＡＣＴＥＲＩＺＡＴＩＯＮＯＦＫ_（１３）［Ｎｄ（Ｇｅｗ_９Ｍｏ_２Ｏ_（３９）_２］·２３Ｈ_２ＯＱｉｎｇＹｉｎＷＵ；ＳｈｅｎｇＸｉａｎＸＵａｎｄＹｕＬｉｎＳＯＮＧ（ＤｅｐａｒｔｍｅｎｔｏｆＣｈｅｍｉｓｔｒｙ，Ｌｉａｏｎ...     

卟啉配位剂meso－四（对－羧基苯基）卟啉（H_2TCPP）极谱行为的研究

采用直流极谱和循环伏安等多种手段研究了卟啉配位剂（Ｈ_２ＴＣＰＰ）在汞电极上的极谱性质。在碱性介质中，Ｈ_２ＴＣＰＰ的电极反应具有以下三个特性：（１）第一步为受扩散控制的２ｅ并有２Ｈ~＋参与的可逆还原过程，第二和第三步为不可逆各为２ｅ的还原反应；（２）Ｈ_２ＴＣＰＰ在汞电极上存在强吸附性；（３）第一步电极反应产物可发生随后的化学反应，即前两步还原经由ＥＣＥ机理进行。     

Synthesis,Characterization and Catalytic Activity of Polyoxometalates Derived from α-P_2W_(15)O_56~(12

Ｓｙｎｔｈｅｓｉｓ,ＣｈａｒａｃｔｅｒｉｚａｔｉｏｎａｎｄＣａｔａｌｙｔｉｃＡｃｔｉｖｉｔｙｏｆＰｏｌｙｏｘｏｍｅｔａｌａｔｅｓＤｅｒｉｖｅｄｆｒｏｍα－Ｐ_２Ｗ_（１５）Ｏ_５６~（１２－）ＬｉｇａｎｄＭＥＮＧＬｕ,ａｎｄＬＩＵＪｉｎｇ－ｆｕ（Ｄｅｐａ...     

Atomic Absorption Determination of Metals in Soils Using Ultrasonic Sample Preparation

It was shown that ultrasonic treatment accelerates sample preparation of soil extracts from chernozem into different solvents by a factor of 6 to 60. These extracts are used for the atomic absorption determination of soluble species of Cd, Co, Cr, Cu, Ni, Pb, and Zn. The optimum ultrasound parameters (frequency, intensity, and treatment time) were found for preparing soil extracts containing analytes in concentrations required in agrochemical procedures. Different extractants used to extract soluble heavy metals from soils of a standard chernozem type in agrochemical procedures using ultrasonic treatment were classified in accordance with the element nature.     

Comparison of different extraction methods for the determination of polycyclic aromatic hydrocarbons in soil

Two different extraction methods for the determination of polycyclic aromatic hydrocarbons in soil are compared: the extraction in combination with ultrasonic treatment, and the Soxhlet extraction method according to DIN-draft 38414 Part 21. Different types of real soil were extracted and analysed by HPLC with diode-array detector and fluorescence detection. The results show that the efficiency of the ultrasonic method is comparable to the Soxhlet method.     

超声波提取-气相色谱法测定油田区土壤中21种酚类化合物

采用超声波提取—气相色谱法测定油田区土壤中21种酚类化合物,主要研究了提取时间及净化条件等对测定结果的影响.对比了加压流体萃取与超声波提取方式对回收率的影响,结果表明:超声波提取法回收率优于加压流体萃取法,其中2,4-二硝基酚和4-硝基酚两种化合物比加压流体萃取法回收率提高了30%.以10.0 g土壤样品计,酚类化合物的检出限为0.01～0.05 mg/kg,样品加标回收率为81.5%～110%,精密度为2.6%～11%.经有证标准物质验证,相对误差为2.6%～14%.试验结果表明,超声波提取法适合于油田区土壤中21种酚类化合物的测定.     

超声水浴-王水浸提-全自动测汞仪测定重度污染土壤中的总汞

为准确测定重度污染土壤中的总汞含量,本文建立了以超声水浴辅助王水浸提,使用全自动测汞仪测定的方法。 通过单因素实验考察了王水用量、超声时间和超声温度对土壤中总汞测定的影响,得到最佳前处理方法,最后应用建立的方法对重度污染土壤进行方法验证。确定了0.5 g土壤样品中加入5 mL的王水溶液,放入超声波清洗器中70℃水浴下超声提取70 min,使用超纯水定容至50mL的前处理方法,直接进样测定的实验方法。对该实验进行验证,结果表明,该方法汞低标准曲线汞含量在0～20ng范围内线性良好,相关系数R=0.9995;汞高标准曲线汞含量在20～150 ng范围内线性良好,相关系数R=0.9993;方法检出限为0.0055 mg/kg,方法定量下限为0.022 mg/kg;通过对土壤样品及土壤加标样品的测定,回收率为90.40～116.80%,表明该方法的准确度较高,RSD为1.89～3.34%（n=6）,表明该方法的精确度较高。超声水浴-王水浸提-全自动测汞仪法用于测定重度污染土壤中的总汞,前处理简单,自动化程度较高,可快速,高效的用于重度污染土壤总汞测定工作。     

碱蒸馏/超声波衍生化-气相色谱-质谱法测定土壤中的偏二甲肼

建立了碱蒸馏/超声波衍生化预处理的气相色谱-质谱法测定土壤中偏二甲肼的分析方法。通过碱蒸馏预处理方法,以水杨醛为衍生化试剂,采用超声波加速衍生化反应,在选择离子检测( SIM)模式下进行定量分析,衍生化产物的特征离子为m/z 164。考察了碱蒸馏、超声波衍生化条件的影响,并对衍生化条件进行优化,方法的线性范围在0.4~30 mg/L之间,方法检出限为0.0078 mg/kg。以此方法测定已知浓度的土壤样品,目标化合物的含量在10~100 mg/kg之间,回收率在76％~108％之间,相对标准偏差在12％~19％之间。与分光光度法、索氏提取/超声波衍生化-气相色谱-质谱法相比较,本方法检出限显著优于二者。     

超声-索氏萃取-重量法测定土壤中总石油烃含量

采用正交实验设计,分别对超声萃取法(UE)和超声-索氏萃取法(USE)测定土壤中总石油烃(TPH)的影响因素进行分析,获得优化条件。采用以上两种方法及传统的索氏萃取法(SE)对新鲜石油污染土、微生物修复土和老化植物修复土进行提取。结果表明:超声萃取法的优化条件为选用15mL三氯甲烷,萃取4次;超声-索氏萃取法的优化条件为60W超声萃取10min,萃取剂用量125mL,萃取6h;超声-索氏萃取法平均回收率最高,为102.98%,且数据稳定可靠;其次是超声萃取法,为99.69%;而传统的索氏萃取法最低,为97.31%。研究证明超声-索氏分析法在缩短测定时间的同时提高了回收率,可作为不同土壤中总石油烃(TPH)含量测定的新方法。     

超高效液相色谱法检测土壤中硝基呋喃类药物残留

建立超高效液相色谱法检测土壤中硝基呋喃类药物残留。通过单因素和正交设计试验,考察了超声时间、提取温度、提取次数对硝基呋喃类药物残留回收率的影响。最优提取条件为超声时间10 min、提取温度45℃、提取次数为4次。硝基呋喃类药物的质量浓度在1~4μg/mL范围内与色谱峰面积成良好的线性关系,线性相关系数均大于0.9999。加标回收率为74.34%~102.52%,测定结果的相对标准偏差为0.91%~4.49%(n=6)。该方法简单、快速,测定结果准确可靠,可用于土壤中硝基呋喃类药物残留量的测定。     

Microwave and ultrasonic extraction of chlorophenoxy acids from soil and their determination by fluorescence polarization immunoassay

Procedures were developed for the ultrasonic and microwave extraction of pesticides, 2,4-dichlorophenoxyacetic (2,4-D) and 2,4,5-trichlophenoxyacetic (2,4,5-T) acids from soils for the subsequent determination by fluorescence polarization immunoassay (FPIA). The effect of the matrix composition of soils on the FPIA results was studied, and the optimum extractants and extraction conditions were selected. It was found that 40% ethanol is optimum for both extraction and FPIA determination, because it does not cause antibody denaturation. The recovery of pesticides in soil was 80–132% for 2,4-D and 101–138% for 2,4,5-T. Microwave extraction is more efficient than ultrasonic extraction for the determination of 2,4-D and 2,4,5-T in soil. The detection limit in soil and the analytical range are 2 and 4–200 μg/g, respectively, for 2,4-D and 20 and 80–5000 μg/g, respectively, for 2,4,5-T. Results of the determination of 2,4-D in soil by FPIA are in good agreement with the results of the determination by high-performance liquid chromatography. The procedures can be used for the rapid determination of chlorophenoxy acids in soils.     

超声波萃取-SPE净化-双柱双检测器测定土壤和沉积物中的20种有机氯

建立了超声波萃取-SPE硅胶小柱净化-双柱双检测器气相色谱法测定土壤和沉积物中20种有机氯农药的方法。样品中添加高纯铜粉除硫,二氯甲烷超声萃取9 min,使用SPE硅胶小柱,9 mL丙酮:正己烷(1:9)洗脱净化。采用单进样口,双色谱柱双μ-ECD同时分离测定。土壤和沉积物样品中的方法检出限为0.001 mg/kg,平均回收率为73.17%～112.5%,相对标准偏差为0.33%～16%。     

Simultaneous determination of pharmaceuticals, endocrine disrupting compounds and hormone in soils by gas chromatography-mass spectrometry

Analytical methods have been developed for simultaneous determination of six different pharmaceuticals and personal care products (PPCPs) (clofibric acid, ibuprofen, naproxen, ketoprofen, diclofenac, and triclosan), three endocrine disrupting compounds (EDCs) (4-tert-octylphenol, 4-n-nonylphenol, and bisphenol A (BPA)) and one estrogenic compound (estrone) in soil matrix. The soils were extracted by different solvents with the help of an ultrasonic treatment at 42 kHz, followed by a solid phase extraction (SPE) as a cleanup procedure. The purified extracts were derivatized with N-methyl-N-(tert-butyldimethylsilyl) trifluoroacetamide (MTBSTFA) and then analyzed by GC-MSD (SIM mode). The method was evaluated by testing the following variables: initial spiking levels, extraction solvents, solvent volumes, and soil types (sandy and clay soils). For 5 g of soil, four successive extraction steps with the mixture of acetone-ethyl acetate provided satisfactory recoveries. In the sandy soil, the recoveries of all the compounds were from 63.8 to 110.7% for the spiking level of 100 ng/g dry soil, and from 52.2 to 108.2% for 5 ng/g dry soil, respectively. Result was similar for the clay soil. The precision across all recoveries was high, suggesting that this method has a good reproducibility. The method was successfully employed to soil samples collected from a golf course irrigated with reclaimed wastewater in southern California, and resulted in the detection of clofibric acid, ibuprofen, naproxen, triclosan, bisphenol A, and estrone at ng per gram dry weight concentration levels. The method is robust and simple, and provides straightforward analyses of these current-emerging trace organic pollutants in solid matrices.