稀土铕与2—[（取代苯胺基）羰基]苯甲酸配合物的研究

报道了配合物Ｅｕ（ＸｎＰ）３．３Ｈ２Ｏ「其中Ｘ＝Ｈ，２－Ｃｌ，３－ＯＨ，４－Ｂｒ，３－ＮＯ２，２－ＯＣＨ３，２－ＣＨ３，２，４－二氯；Ｐ＝２－（ＣＯＯ）Ｃ６Ｈ４ＣＯＮＨＣ６Ｈ５－＾－，ｎ＝１，２」的制备，并用元素分析，红外光谱，电子反射光谱，热重分析进行了表征。     

辐照异相成核结晶PA1010体系的ESR研究：结晶表面积对俘陷自由基…

本文通过ＷＡＸＤ，ＤＳＣ方法讨论成核剂对ＰＡ１０１０的聚集态结构的影响。用ＥＳＲ研究辐照不同态结构ＰＡ１０１０体系的俘陷自由基行为。结果表明：俘陷自由基－ＣＨ２ＣＯＮＨＣＨＣＨ２－主要存在于结晶表面，结晶的表面积越大，俘陷自由基－ＣＨ２ＣＯＮＨＣＨＣ２－的含量越高，在一定条件下，如升温，常温放置一段时间，转化为俘陷自由基－ＣＨ２Ｃ＝０的量也越大；俘陷自由基－ＣＨ２Ｃ＝０主要存在于非晶区。     

钴(Ⅲ)—邻菲绕啉混配型配合物的合成及结构研究

在不同条件下合成了［Ｃｏ（ｐｈｅｎ）ｍＸｐ］Ｙ１·ｎＨ２Ｏ型配合物，（ｍ＝１，２；ｐ＝１，２；１＝１－３；ｎ＝０－４；ｐｈｅｎ＝邻菲绕啉；Ｘ＝Ｃｌ－，Ｈ２Ｏ，酒石酸（ｔａｒｔ），甘氨酸（ｇｌｙ），α－皮可林酸（ｐｉｃ）．ＤＬ－两氨酸（ａｌａ），Ｌ－亮氨酸（ｌｅｕ），Ｌ－脯氨酸（ｐｒｏ）；Ｙ＝Ｃｌ－，］并进行了元素分析，热重分析，电子光谱，红外光谱和磁化率测定，计算它们的１０Ｄｑ和Ｂ值．Ｘ－ｒａｙ单晶衍射实验证明：［Ｃｏ（Ｐｈｅｎ）２（Ｈ２Ｏ）２］（ＮＯ３）３·２Ｈ２Ｏ，［Ｃｏ（Ｐｈｅｎ）２（ｇｌｙ）］Ｃｌ２·４Ｈ２Ｏ均为顺式结构．［Ｃｏ（Ｐｈｅｎ）（ａｌａ）２］Ｃｌ·３Ｈ２Ｏ，［Ｃｏ（Ｐｈｅｎ）（ｐｒｏ）２］ＣｌＯ４·４／３Ｈ２Ｏ均为ｔｒａｎｓ（Ｎ）结构．在［Ｃｏ（ｐｈｅｎ）２Ｘ２］（ｎ＋）型配合物中，Ｘ反位的键长均长于顺位键长，其反位效应的顺序为：Ｃｌ－＞羧基，ＮＨ２＞Ｈ２Ｏ。     

辐照异相成核结晶PA1010体系的ESR研究——结晶表面积对俘陷自由基的影响

本文通过ＷＡＸＤ，ＤＳＣ方法讨论成核剂（Ｎｄ２Ｏ３）对ＰＡ１０１０的聚集态结构的影响。用ＥＳＲ研究辐照不同聚集态结构ＰＡ１０１０体系的俘陷自由基行为。结果表明：俘陷自由基—ＣＨ２ＣＯＮＨＣＨＣＨ２—主要存在于结晶表面，结晶的表面积越大，俘陷自由基—ＣＨ２ＣＯＮＨＣＨＣＨ２—的含量越高，在一定条件下，如升温，常温放置一段时间，转化为俘陷自由基—ＣＨ２Ｃ＝Ｏ的量也越大；俘陷自由基－ＣＨ２Ｃ＝Ｏ主要存在于非晶区。     

[Cu_2(Gly-GlyO)_2(4,4′-bpy)(OH)_2]·10H_2O配合物的合成、晶体结构和分子结构研究

合成了以４，４′－ｂｐｙ为中继基、Ｇｌｙ－ＧｌｙＯ为螯环的新型双核铜配合物．经Ｘ射线单晶结构分析确定该配位化合物晶体的化学式为［（Ｈ２ＮＣＨ２ＣＯＮＨＣＨ２ＣＯＯ）Ｃｕ（ＯＨ）（Ｃ１０Ｈ８Ｎ２）Ｃｕ（ＯＨ）－（Ｈ２ＮＣＨ２ＣＯＮＨＣＨ２ＣＯＯ）］·１０Ｈ２Ｏ．晶体属三斜晶系，Ｐ１空间群，晶胞参数ａ＝０．７１２４（２）ｎｍ，ｂ＝１．１４０５（１０）ｎｍ，ｃ＝１．１４３４（１０）ｎｍ，α＝６７．５５°，β＝７９．０２°，γ＝７７．９７°，Ｖ＝０．８３４（３）ｎｍ３，Ｚ＝１．最终一致性因子Ｒ为０．０７２７．     

[Cu2（Gly—GlyO）2（4,4‘—bpy）（OH）2].9H2O配合物的合成,晶…

将Ｇｌｙ－ＧｌｙＯ，４，４＇－联吡啶与Ｃｕ（ＮＯ３）２．Ｈ２Ｏ在二次水溶液中反应，合成出以４，４＇－ｂｐｙ为中继基，Ｃｌｙ－ＧｌｙＯ为螯环的新型双核铜配合物，经Ｘ射线单晶结构分析确定该配合物晶体的化学结构式为［（Ｈ２ＮＣＨ２ＣＯＮＨＣＨ２ＣＯＯ）Ｃｕ（ＯＨ）（Ｃ１０Ｈ８Ｎ２）Ｃｕ（ＯＨ）（Ｈ２ＮＣＨ２ＣＯＮＨＣＨ２ＣＯＯ）］．９Ｈ２Ｏ。晶体属Ｐ１空间群，晶胞参数α＝１．１４１２ｎｍ，ｂ＝１．２２９     

稀土铕与2－［（取代苯胺基）羰基］苯甲酸配合物的研究

报道了配合物Ｅｕ（ＸｎＰ）３·３Ｈ２Ｏ［其中Ｘ＝Ｈ，２－Ｃｌ，３－ＯＨ，４－Ｂｒ，３－ＮＯ２，２－ＯＣＨ３，２－ＣＨ３，２，４－二氯；Ｐ＝２－（ＣＯＯ）Ｃ６Ｈ４ＣＯＮＨＣ６Ｈ５－ｎ－，ｎ＝１，２］的制备，并用元素分析，红外光谱，电子反射光谱，热重分析进行了表征。结果表明配位是通过羧酸基上氧原子和酰胺羰基氧原子进行的，含３分子水。通过电子反射光谱，对Ｎｅｐｈｅｌａｕｘｅｔｉｃ比率（Ｂ），平均共价参数（δ）和平均成键参数（ｂ１／２）进行了计算，对配合物的共价成键情况进行了讨论。     

［Cu_2（Gly－GlyO）_2（4，4＇－bpy）（OH）_2］·9H_2O

将Ｇｌｙ－ＧｌｙＯ、４，４＇－联吡啶与Ｃｕ（ＮＯ_３）_２·Ｈ_２Ｏ在二次水溶液中反应，合成出以４，４＇－ｂｐｙ为中继基、Ｃｌｙ－ＧｌｙＯ为螯环的新型双核铜配合物，经Ｘ射线单晶结构分析确定该配合物晶体的化学结构式为［（Ｈ_２ＮＣＨ_２ＣＯＮＨＣＨ_２ＣＯＯ）Ｃｕ（ＯＨ）（Ｃ_（１０）Ｈ_８Ｎ_２）Ｃｕ（ＯＮ）（Ｈ_２ＮＣＨ_２ＣＯＮＨＣＨ_２ＣＯＯ）］·９Ｈ_２Ｏ．晶体属Ｐ　空间群，晶胞参数ａ＝１．１４１２ｎｍ，ｂ＝１．２２９８ｎｍ，ｃ＝１．４２６９ｎｍ，α＝１１３．８２°，β＝１０１．９１°，γ＝１０３．６４°，Ｚ＝２．最终一致性因子Ｒ值为０．０６８，Ｒ_ｗ值为０．０５７，标准偏差σ＝０．１９５１。     

NHCH=CHR自由基结构和稳定性ab initio研究

用ＵＨＦ／４－３１Ｇ基组，全构型优化，研究了ＮＨＣＨ＝ＣＨＲ（Ｒ＝Ｈ，ＢＨ２，ＣＮ，Ｆ，ＯＨ，ＮＨ２）６个氮自由基的构型和稳定化能△Ｅ，以ＮＨＣＨ＝ＣＨ２自由基为参考，它们的△Ｅ分别为０．００，－３４．９２，－８．３５，－０．９３，３３．０５，５０．８５ｋＪ．ｍｏｌ＾－１，说明供电子基团ＯＨ和ＮＨ２对氮自由基起稳定化作用，吸电子基团ＣＮ和ＢＨ２起去稳定化作用，而Ｆ对氮自由基的稳定性影响不大。     

[NH4（15—C—5）2][C2（SCN）5配合物的晶体和分子结构

用凝胶法合成了标题化合物［ＮＨ４（１５－Ｃ－５）２］［Ｃｄ２（ＳＣＮ）５］（１５－Ｃ－５＝Ｃ１０Ｈ２０Ｏ５）的晶体，并对其进行了红外光谱，元素分析等各项物理性质的测试，并经Ｘ射线单晶结构分析得到了配合物的全部晶体学数据：Ｍｔ＝９７３．７８，正交晶系，空间群Ｐｎｍａ，晶胞参数α＝１０．５０７（１）Ａ，ｂ＝１６．５８４（２）Ａ，ｃ＝２３．４９４（２）Ａ，Ｖ＝４０９３．８（３）Ａ＾３，Ｚ＝４，Ｄｃ＝２．     

XPS研究等离子体处理的聚苯乙烯表面结构

采用不同功率(10、20、60、100、150W)、时间(0.5、1、3、6、15和30分),在Ar、N_2、O_2、H_2和空气中,对聚苯乙烯(PS)片基进行了等离子体处理。 通过XPS技术、谱图的拟合、差谱分析和Ar~+小功率剖面处理,研究了PS表面组成与结构变化,指出处理的聚苯乙烯表面有C—O、C—NH_2、C=O、COOH和基团嵌入,因而改变了材料特性。     

XPS研究等离子体处理的聚苯乙烯表面结构

采用不同功率、时间在不同气氛下对聚苯乙烯(PS)基片进行了等离子体处理。通过 X-射线光电子能谱技术、谱图的拟合、差谱分析和 Ar~+刻蚀的剖面处理,研究了 PS 表面组成与结构变化,指出处理的 PS 表面可能接入 C-O、C-NH、C=O、COOH 和 O-?-O 基团,因而改变了材料特性。     

Adsorption of glucose oxidase onto plasma-polymerized film characterized by atomic force microscopy, quartz crystal microbalance, and electrochemical measurement

Adsorption of glucose oxidase (GOD) onto plasma-polymerized thin films (PPF) with nanoscale thickness was characterized by atomic force microscopy (AFM), quartz crystal microbalance (QCM), and electrochemical measurements. The PPF surface is very flat (less than 1-nm roughness), and its properties (charge and wettability) can be easily changed while retaining the backbone structure. We focused on three types of surfaces: (1) the pristine surface of hexamethyldisiloxane (HMDS) PPF (hydrophobic and neutral surface), (2) an HMDS PPF surface with nitrogen-plasma treatment (hydrophilic and positive-charged surface), and (3) an HMDS PPF surface treated with oxygen plasma (hydrophilic and negative-charged surface). The AFM image showed that the GOD molecules were densely adsorbed onto surface 2 and that individual GOD molecules could be observed. The longer axis of GOD ellipsoid molecules were aligned parallel to the surface, called the "lying position", because of electrostatic association. On surface 1, clusters of GOD molecules did not completely cover the original PPF surface (surface coverage was ca. 60%). The 10-nm-size step height between the GOD clusters and the PPF surface suggests that the longer axes of individual GOD molecules were aligned perpendicular to the surface, called the "standing position". On surface 3, only a few of the GOD molecules were adsorbed because of electrostatic repulsion. These results indicate that the plasma polymerization process can facilitate enhancement or reduction of protein adsorption. The AFM images show a corresponding tendency with the QCM profiles. The QCM data indicate that the adsorption behavior obeys the Langmuir isotherm equation. The amperometric biosensor characteristics of the GOD-adsorbed PPF on a platinum electrode showed an increment in the current because of enzymatic reaction with glucose addition, indicating that enzyme activity was mostly retained in spite of irreversible adsorption.     

Density functional theory study of the oxidation of ammonia on the IrO2(110) surface

In this study, we employed density functional theory (DFT) to investigate the oxidation of ammonia (NH(3)) on the IrO(2)(110) surface. We characterized the possible reaction pathways for the dehydrogenation of NH(x) species (x = 1-3) and for the formation of the oxidation products N(2), N(2)O, NO, NO(2), and H(2)O. The presence of oxygen atoms on coordinatively unsaturated sites (O(cus)) of the oxygen-rich IrO(2)(110) surface promotes the oxidation of NH(3) on the surface. In contrast, NH(3) molecules prefer undergoing desorption over oxidation on the stoichiometric IrO(2)(110) surface. Moreover, the O(cus) atoms are also the major oxidants leading to the formation of oxidation products; none of the oxidations mediated by the bridge oxygen atoms were favorable reactions. The energy barrier for formation of H(2)O as a gaseous oxidation product on the IrO(2)(110) surface is high (from 1.83 to 2.29 eV), potentially leading to the formation of nitrogen-atom-containing products at high temperature. In addition, the selectivity toward the nitrogen-atom-containing products is dominated by the coverage of O(cus) atoms on the surface; for example, a higher coverage of O(cus) atoms results in greater production of nitrogen oxides (NO, NO(2)).     

等离子体改性的聚偏氟乙烯表面结构的XPS研究

采用5种气氛等离子体处理聚偏氟乙烯(PVF_2)基片,用XPS研究了PVF_2表面结构的变化。结果表明,处理后的PVF_2基片表面嵌入了C—O,C—NH_2,—CHF和COOH基团,因而改变了表面性质。     

Recombination reactions of oxygen atoms on an anodized aluminum plasma reactor wall, studied by a spinning wall method

We have studied the recombination of O atoms on an anodized Al surface in an oxygen plasma, using a new "spinning wall" technique. With this method, a cylindrical section of the wall of the plasma reactor is rotated and the surface is periodically exposed to an oxygen plasma and then to a differentially pumped mass spectrometer (MS). By varying the substrate rotation frequency (r), we vary the reaction time (t(r)), that is, the time between exposure of the surface to O atoms in the plasma and MS detection of desorbing O(2) (t(r) = 1/2r). As t(r) is increased from 0.7 to 40 ms, the O(2) desorption signal decreases by a factor of 2 for an O-atom flux of 1 x 10(16) cm(-2) s(-1) and by a factor of 6 when the O flux is 1 x 10(17) cm(-2) s(-1). The O(2) signal decay is highly nonexponential, slowing at longer times and reaching zero signal as r --> 0. A model of O-atom recombination is compared with these time-dependent results. The model assumes adsorption occurs at surface sites with a range of binding energies. O can detach from these sites, become mobile, and diffuse along the surface. This leads to desorption of O, reattachment at free adsorption sites, and recombination to form O(2) that promptly desorbs. With several adjustable parameters, the model reproduces the observed shapes of the O(2) desorption decay curves and the lack of detectable desorption of O and predicts a high O-atom recombination coefficient on anodized aluminum.     

Absolute rate coefficients for the reactions of O2- + N(4S(3/2)) and O2- + O(3P) at 298 K in a selected-ion flow tube instrument

The absolute rate coefficients at 298 K for the reactions of O(2) (-) + N((4)S(3/2)) and O(2) (-) + O((3)P) have been determined in a selected-ion flow tube instrument. O atoms are generated by the quantitative titration of N atoms with NO, where the N atoms are produced by microwave discharge on N(2). The experimental procedure allows for the determination of rate constants for the reaction of the reactant ion with N((4)S(3/2)) and O((3)P). The rate coefficient for O(2) (-) + N is found to be 2.3x10(-10)+/-40% cm(3) molecule(-1) s(-1), a factor of 2 slower than previously determined. In addition, it was found that the reaction proceeds by two different reaction channels to give (1) NO(2)+e(-) and (2) O(-)+NO. The second channel was not reported in the previous study and accounts for ca. 35% of the reaction. An overall rate coefficient of 3.9 x 10(-10) cm(3) molecule(-1) s(-1) was determined for O(2) (-) + O, which is slightly faster than previously reported. Branching ratios for this reaction were determined to be <55%O(3) + e(-) and >45%O(-) + O(2).     

Effect of Some Oxidation Treatments on the Textural Characteristics and Surface Chemical Nature of an Activated Carbon

The changes produced in an activated carbon by treatment in aqueous solutions of (NH(4))(2)S(2)O(8) and H(2)O(2) are compared with the modifications produced by oxygen plasma. These changes are monitored by measuring the textural characteristics (surface areas, porosity, pore size distributions) and surface chemical groups. The former are studied by N(2) and CO(2) adsorption, mercury porosimetry and hydrocarbon adsorption at zero surface coverage. The chemical surface groups are determined by chemical titrations and FTIR Spectroscopy. The results show large differences between the changes produced by treatment in aqueous solutions and those produced by oxygen plasma. Whereas both treatments in aqueous solution modify the textural characteristics, oxygen plasma maintains the surface area and pore network. However, plasma treatment introduces larger amounts of oxygen chemical groups than treatment in aqueous solution. Copyright 2000 Academic Press.     

Kinetics of sulfur oxide, sulfur fluoride, and sulfur oxyfluoride anions with atomic species at 298 and 500 K

The rate constants and product-ion branching ratios for the reactions of sulfur dioxide (SO2-), sulfur fluoride (SFn-), and sulfur oxyfluoride anions (SOxFy-) with H, H2, N, N2, NO, and O have been measured in a selected-ion flow tube (SIFT). H atoms were generated through a microwave discharge on a H2/He mixture, whereas O atoms were created via N atoms titrated with NO, where the N had been created by a microwave discharge on N2. None of the ions reacted with H2, N2 or NO; thus, the rate constants are <1 x 10(-12) cm3 s-1. SOxFy- ions react with H by only fluorine-atom abstraction to form HF at 298 and 500 K. Successive F-atom removal does not occur at either temperature, and the rate constants show no temperature dependence over this limited range. SO2- and F- undergo associative detachment with H to form a neutral molecule and an electron. Theoretical calculations of the structures and energetics of HSO2- isomers were performed and showed that structural differences between the ionic and neutral HSO2 species can account for at least part of the reactivity limitations in the SO2- + H reaction. All of the SOxFy- ions react with O; however, only SO2- reacts with both N and O. SOxFy- reactions with N (SO2- excluded) have a rate constant limit of <1 x 10(-11) cm3 s-1. The rate constants for the SOxFy- reactions with H and O are < or =25% of the collision rate constant, as seen previously in the reactions of these ions with O3, consistent with a kinetic bottleneck limiting the reactivity. The only exceptions are the reactions of SO2- with N and O, which are much more efficient. Three pathways were observed with O atoms: F-atom exchange in the reactant ion, F- exchange in the reactant ion, and charge transfer to the O atom. No associative detachment was observed in the N- and O-atom reactions.     

Absolute rate coefficients and branching percentages for the reactions of POxCly- + N (4S(3/2)) and POxCly- + O (3P) at 298 K in a selected-ion flow tube instrument

The absolute rate coefficients and product ion branching percentages at 298 K for the reactions of several POxCly- species with atomic nitrogen (N (4S(3/2))) and atomic oxygen (O (3P)) have been determined in a selected-ion flow tube (SIFT) instrument. POxCly- ions are generated by electron impact on POCl3 in a high-pressure source. O atoms are generated by quantitative titration of N atoms with NO, where N atoms are produced by microwave discharge on N2. The experimental procedure allows for the determination of rate coefficients for the reaction of the reactant ion with N (4S(3/2)) and O (3P) as well as with N2 and NO. None of the ions react with N2 or NO, giving an upper limit to the rate coefficient of <5 x 10(-12) cm3 molecules(-1) s(-1). POCl3- and POCl2- do not react with N atoms, giving an upper limit to the rate coefficient of <1 x 10(-11) cm3 molecules(-1) s(-1). The major product ion for POCl3- and POCl2- reacting with O involves loss of Cl from the reactant ion, accounting for >85% of the products. PO2- is a minor product (相似文献