铝酸钠溶液的紫外吸收峰

分别用量子化学MNDO和DV-X_α方法计算了二聚铝酸离子[Al_2O(OH)_6]~(2-)和Al(OH)_4~-。结果表明前者旋转势垒很低, 只有10.08 kJ·mol~(-1), 最稳定平衡构型为C_s。用X_α过渡态理论计算获得这两个离子紫外吸收峰的理论值分别为266.6 nm和234.4 nm, 与实验值270.0 nm和230.0 nm相当接近。因此可以认为, 紫外吸收峰270.0 nm和230.0 nm分别为[Al_2O(OH)_6]~(2-)和Al(OH)_4~-离子的最高占有轨道电子向最低空轨道跃迁时产生的吸收峰。计算结果支持铝酸钠溶液中存在二聚铝酸离子的观点。     

新的聚合物支载硼氢负离子还原剂系统研究 3: 聚合物支载还原剂III

硼氢化钠的低分子还原系统研究很多,但其聚合物支载还原剂相对来说就很少,而且仅以强碱型阴离子交换树脂来制备的聚合物试剂。为了寻找用途更广泛的、新的聚合物支载还原剂,我们进行了硼氢负离子的聚合物还原系统的研究;发现能用弱酸型阳离子交换树脂制备出新的聚合物支载还原剂。前文报道了用NaBH_4的水溶液和阴离子交换树脂     

Tribromoisocyanuric Acid (TBCA) and Oxone®‐MX Systems as Oxidizing Agents: Oxidative Coupling of Thiols to Their Corresponding Disulfides under Mild and Heterogeneous Conditions

Tribromoisocyanuric acid (TBCA) and Oxone^®‐MX systems were used as effective oxidizing agents for the oxidation of thiols to their corresponding disulfides under mild conditions at room temperature with good to excellent yields.     

Comparison of standard capillary and chip separations of sodium dodecylsulfate-protein complexes

Conditions for converting a set of five standard proteins to electrochemically active sodium dodecylsulfate (SDS) complexes were worked out with the aim of using such complexes for conductivity detection with a a chip electrophoresis system. The results obtained were compared with standard capillary electrophoresis (37 cm (effective length 30 cm)×75 μm I.D. capillary, 10 kV, negative polarity at the inlet). The chip separations were run at 500 V per chip (100 V/cm) as compared to the standard capillary arrangement, which was run at 266.6 V/cm. For the capillary set-up the protein complexes were prepared in aqueous solution (Milli-Q water) made 10 mM with respect to SDS. If the SDS concentration was increased to 50 mM, the separation in the capillary was incomplete. On the other hand with the chip system both approaches yielded acceptable results. The chip separations were slightly (but not distinctly) shorter and offered better separations than the standard set-up. The concentration of the surfactant used for the preparation the complexes results in alternations of the elution sequence, which is preserved if the chip separation is used instead of the capillary set-up. Apparently the full capacity of protein–SDS binding is not exploited for the preparation of the adducts.     

Voltammetric Behavior of Arsenic(III) in the Presence of Sodium Diethyl Dithiocarbamate and Its Determination in Water and Highly Saline Samples by Adsorptive Stripping Voltammetry

This paper describes the voltammetric behavior of As(III) at the hanging mercury drop electrode (HMDE) in the presence of sodium diethyl dithiocarbamate (SDDC) and a new voltammetric method for the determination of As(III) at trace levels. The method is based on the adsorptive deposition of a As(III) complex with SDDC at ?0.45 V (vs. Ag/AgCl) on the HMDE in acidic medium of 0.01 mol L^?1 HCl (pH 2.0) and its cathodic stripping during the potential scan (100 mV s^?1). The linear range for the determination of As(III) in the presence of SDDC (4 μmol L^?1) in water samples was between 1 and 10 μg L^?1 for a deposition time of 300 s (r=0.994) and between 10 and 100 μg L^?1 for a deposition time of 60 s (r=0.999). For the determination of As(III) in dialysis concentrate samples, the linear range was between 5 and 25 μg L^?1 for a deposition time of 180 s (r=0.992) and between 10 and 100 μg L^?1 for a deposition time of 60 s (r=0.996). Detection limits of 0.3 and 2.2 μg L^?1 in water and dialysis concentrate samples were calculated for the method using a deposition time of 300 and 180 s, respectively. Recovery values between 93.0 and 110.0% for As(III) added to deionized, mineral, seawater (synthetic and real) and dialysis concentrate samples prove the satisfactory accuracy and applicability of the procedure.     

B2O3/TiO2-ZrO2催化环己酮肟气相Beckmann重排反应研究 Ⅰ.B2O3含量的影响

 制备了不同B2O3含量（0～20％）的B2O3／TiO2－ZrO2固体酸催\r\n化剂，用XRD，FT－IR，N2吸附及NH3－TPD等方法测定了其结构、比表\r\n面积、孔分布和表面酸性．结果表明，当B2O3含量较低（≤5％）时，\r\n催化剂呈无定形态，样品中的B2O3主要以BO4结构存在．当B2O3含量较\r\n高（≥8％）时，催化剂中的TiO2－ZrO2以ZrTiO4晶相存在，分散于Ti\r\nO2－ZrO2表面的B2O3主要以玻璃体形式和BO3结构存在．随着B2O3含量\r\n的增加，催化剂的比表面积减小，孔径增大．300℃下的环己酮肟气相\r\nBeck－mann重排反应结果表明，随着B2O3含量的增加，己内酰胺的选择\r\n性逐渐增大，而己内酰胺的收率在B2O3含量为12％时达到最大值．讨论\r\n了B2O3／TiO2－ZrO2的催化性能与其表面酸性及孔径大小的关系．     

硼原子的键合形式对硼酸盐晶体非线性光学行为的影响

在几种具有典型复杂结构的硼酸盐晶体中 ,从硼原子的键合形式出发讨论了不同键合情况下的B—O键对硼酸盐晶体的非线性光学行为的具体影响。结果表明 ,晶体中B—O键的键合形式是制约硼酸盐晶体非线性光学行为的重要因素。     

碳酸氢铵制纯碱的研究

本文对“中间盐”复分解制碱法进行了研究。“中间盐”的加入不能使两个三盐共饱和点在干盐图上发生明显的移动,但能使三盐介稳平衡点的介稳期延长,从而使得用碳酸氢铵和食盐通过复分解制碱成为可能。     

NaCl(或KCl)-CH3OH-H2O体系的摩尔电导

CHaOH－HzO体系具有非常特殊的性质，同时在工业生产及临床治疗方面有着十分广泛的应用，文献中有大量地从不同角度就这类体系进行研究的报道．然而，就N3CI及KCI－CH30H－H20体系的电导研究而言，文献中仅有关干KCI－CH30H－H20（间隔20％CH30H）的部分研究工作．作为全面、系