盐和有机物对氨基酸热力学性质的影响-NaCl氨基酸-葡萄糖-水体系

在278.15-318.15范围内，本文测定了以下四个无液接电池的电动势：Pt,H_2(g, 1 atm)|HCl(m)、X Mass% Glucose-H_2O|Ag-AgCl (A) Pt,H_2 (g, 1 atm)|G(m_1), HGCl (m_2), X Mass% Glucose-H_2O|Ag-AgCl (B) Pt,H_2 (g, 1 atm) |HCl (m), NaCl (M-m), X Mass% Glucose-H_2O|Ag-AgCl (C) Pt,H_2 (g, 1 atm)|G(m_1), HGCl (m_2), NaCl (M-m), X Mass% Glucose-H_2O|Ag-AgCl (D) 其中G为中性甘氨酸，NH_3CH_2COO~-, HGClm为甘氨酸的盐酸盐，为相应电解质的质量摩尔浓度，X为葡萄糖在葡萄糖-水混合溶剂中的质量百分数，M为恒定的离子强度且M = 1.0mol/kg。并且测定了Glucose-H_2O的密度和介电常数。利用传统的D-H公式外推法和基于Pitzer理论的多项式逼近法分别确定了电池的标准电动势E°_3、E°_3，以及甘氨酸的一级热力学解离1.0mol/kg）-葡萄糖-水-HCl的HCl无限稀释溶液为参考态，并将两种方法得到的结果作了比较。甘氨酸的一级热力学解离常数符合Harned-Robinson方程：pK = A_1/T + A_2 + A+3 T 本文讨论了盐和有机物对pK_1的影响，并根据前人及我们的工作，指出在极性质子溶剂中和在极性非质子溶剂中的pK_1对1/D作图，分别得到直线和曲线。同时讨论了混合溶剂中甘氨酸的一级解离过程的各个热力学量ΔG°，ΔH°，ΔS°，ΔCp°，并讨论HCl的迁移性质和有机物葡萄糖、盐对它们的影响。最后将不同混合溶剂中甘氨酸解离过程的迁移能，迁移熵等作了比较。

CeCl_3在NaCl溶液中对LC_4铝合金的缓蚀作用

本工作研究了CeCl_3在NaCl溶液中对LC_4铝合金（Al-Zn5.0/7.0-Mg1.3/2.8-Cu1.4/2.0-Cr0.10/0.25)的缓蚀作用。LC_4铝合金在NaCl溶液中腐蚀严重，腐蚀过程中有氢气析出，许多产物沉积在溶液底部，去膜后，光学显微显示，试样表面有很深的腐蚀坑。铝合金表面有很多缺陷，无氧化膜覆盖的铝成为活性中心，在NaCl溶液中做为阳极，铝合金中活性较低的杂质组分（如金属间化合物），突出氧化膜，在NaCl溶液中做为阴极，铝合金表面活性中心交替发生点蚀，腐蚀加重。LC_4铝合金在NaCl溶液中腐蚀的阴极去极化过程是氧的去极化。活性中心铝自溶解析氢，Cl~-在活性中心吸附，促进铝阳极溶解，氧去极化的慢步聚有扩散、吸附、电化学反应，控制步骤是扩散和吸附。LC_4铝合金在CeCl_3+NaCl溶液中腐蚀速度很底，腐蚀过程中极少有氢气极出，去膜后，光学显微显示，试样表面仍很均一，没有点蚀的迹象，Ce(+3)在阴极相表面吸附、沉积，阻碍氧的吸附，抑制阴极氧还原，降低腐蚀速度，铝腐蚀产生的H_2O_2可将Ce(+3)氧化到Ce(+4)，生成CeO_2：2Ce(OH)_3 + H_2O_2 = 2CeO_2 + 4H_2O在阴极相表面，H_2O_2将Ce(+3)氧化到Ce(+4)，消耗H_2O_2，消除H_2O_2对铝腐蚀的加速作用，进一步减慢活性中心铝阳极溶解的速度。LC_4铝合金在LaCl_3+NaCl溶液中的腐蚀速度下降，但局部腐蚀仍较严重，对析氢并无明显影响。La(+3)在阴极相表面吸附、沉积后，阻碍氧的吸附，抑制阴极氧还原，降低腐蚀速度，La(+3)不影响铝腐蚀产生的H_2O_2还原为OH~-的过程，H_2O_2对铝腐蚀的加速作用继续存在，不影响点蚀的孕育、发展，点蚀孔内铝自溶解析氢过程也不会受到影响。

Binding of metal ions with protein studied by a combined technique of microdialysis with liquid chromatography

A method has been developed for the determination of interactions of metal ions and protein by using microdialysis sampling technique combined with pre-column derivation and reversed-phase ion-pair liquid chromatographic (HPLC analysis. Cu(II), Zn(II) and human serum albumin (HSA) were chosen as model metal ions and protein, respectively. The mixed solutions of metal ions and HSA with different molar ratios buffered with 0.1 M Tris-HCl containing 0.1 M NaCl at pH 7.43 were sampled with a mirodialysis probe by keeping perfusion rate at 1 mul/min and the temperature at 37 degreesC. The free concentrations of metal ions in microdialysates were assayed by precolumn derivatization with meso-tetra(4-sulfophenyl)-porphyrin (TPPS4) followed ion-pair HPLC analysis. The recovery (R) of microdialysis sampling was measured in vitro under similar conditions as 65.74% for Cu(II), 70.45% for Zn(II) with R.S.D. below 3.2%. The primary binding constants and number of binding site estimated by the Scatchard plot analysis are 5.04 x 10(6) M-1 and 0.85 for Cu(II), and 9.87 x 10(6) M-1 and 1.10 for Zn(II), respectively. The competition of Cu(II) and Zn(II) at the second binding site on HSA was investigated, and it was observed that there is a second site on HSA to bind Cu(II) and Zn(II), the affinity of Cu(II) is stronger than that of Zn(II) to this second site of HSA. (C) 2001 Elsevier Science B.V. All rights reserved.

accurate and self-consistent ocean color algorithm:simultaneous retrieval of aerosol optical properties and chlorphyll concentrations

A new algorithm has been developed for simultaneous retrieval of aerosol optical properties and chlorophyll concentrations in case I waters. This algorithm is based on an improved complete model for the inherent optical properties and accurate simulations of the radiative transfer process in the coupled atmosphere-ocean system. It has been tested against synthetic radiances generated for the Sea-Viewing Wide Field-of-View Sensor (SeaWiFS) channels and has been shown to be robust and accurate. A unique feature of this algorithm is that it uses the measured radiances in both near-IR and visible channels to find that combination of chlorophyll concentration and aerosol optical properties that minimizes the error across the spectrum. Thus the error in the retrieved quantities can be quantified.