稀土(Ⅲ)-冠醚配位作用的热力学性质Ⅱ:臂式15-冠-5和臂式18-冠-6与稀土(Ⅲ)硝酸盐在无水乙腈溶液中配位的量热滴定

本文用量热滴定研究了N-苄基-单氮杂-15-冠-5与稀土(Ⅲ)硝酸盐(La,Ce,Pa,Nd,Sm,En,Gd,Tb,Dy,Ho,Er,Yb)和N-苄基-单氮杂-18-冠-6与稀土(Ⅲ)硝酸盐(La和Ce)在无水乙腈溶液中,298.15K时配位作用的热力学性质、化学计量法表明,所有稀土硝酸盐均与臂式冠醚形成1:1配合物.实验中,由联接的计算机直接算出了配合物 的稳定常数和配位反应的热焓,进而算出了配位自由能和配位熵.从热力学的观点,讨论了冠醚环的尺寸效应、空间构型等对配位稳定性的影响.     

稀土(Ⅲ)-冠醚配位作用的热力学性质Ⅱ:臂式15-冠-5和臂式18-冠-6与稀土(Ⅲ)硝酸盐在无水乙腈溶液中配位的量热滴定

本文用量热滴定研究了N-苄基-单氮杂-15-冠-5与稀土(Ⅲ)硝酸盐(La,Ce,Pa,Nd,Sm,En,Gd,Tb,Dy,Ho,Er,Yb)和N-苄基-单氮杂-18-冠-6与稀土(Ⅲ)硝酸盐(La和Ce)在无水乙腈溶液中,298.15K时配位作用的热力学性质、化学计量法表明,所有稀土硝酸盐均与臂式冠醚形成1:1配合物.实验中,由联接的计算机直接算出了配合物 的稳定常数和配位反应的热焓,进而算出了配位自由能和配位熵.从热力学的观点,讨论了冠醚环的尺寸效应、空间构型等对配位稳定性的影响.     

稀土(Ⅲ)-冠醚配位作用的热力学性质——Ⅱ.臂式15-冠-5和臂式18-冠-6与稀土(Ⅲ)硝酸盐在无水乙腈溶液中配位反应的量热滴定

本文用量热滴定研究了N-苄基-单氮杂-15-冠-5与稀土(Ⅲ)硝酸盐(La,Ce,Pa,Nd,Sm,En,Gd,Tb,Dy,Ho,Er,Yb)和N-苄基-单氮杂-18-冠-6与稀土(Ⅲ)硝酸盐(La和Co)在无水乙腈溶液中,298.15 K时配位作用的热力学性质、化学计量法表明,所有稀土硝酸盐均与臂式冠醚形成1∶1配合物.实验中,由联接的计算机直接算出了配合物的稳定常数和配位反应的热焓,进而算出了配位自由能和配位熵.从热力学的观点,讨论了冠醚环的尺寸效应、空间构型等对配位稳定性的影响.     

镧对油菜抗病性相关酶活性的影响

通过水培试验,研究了La对与油菜抗病性相关的过氧化物酶(POD)、过氧化氢酶(CAT)、超氧化物歧化酶(SOD)和多酚氧化酶(PPO)酶活性以及对膜脂过氧化产物丙二醛(MDA)含量的影响。结果表明:喷施0.3mg·kg-1的La3+油菜叶绿素含量显著增加,POD,CAT,SOD和PPO活性增高,MDA含量降低,但可溶性蛋白含量无显著变化。可见La具有诱导植株产生抗病性的作用。     

皂角苷对镧、铈、钇的淋洗效果及影响因素研究

以稀土污染土壤为研究目标,采用生物表面活性剂皂角苷淋洗土壤中La,Ce和Y,探讨皂角苷浓度、淋洗液pH值、土液比和淋洗时间对淋洗效果的影响。结果表明,皂角苷浓度为25 g·L~(-1),pH=5.5,土液比为1∶40,淋洗时间为6 h时,土壤中La,Ce和Y的淋洗率分别为58.05%,57.78%,64.43%。对比淋洗前后土壤中稀土的形态分布,弱酸可提取态与可还原态的淋洗效果最为明显;弱酸可提取态含量均降低了80%以上,La,Ce和Y的可还原态含量分别下降58.98%,57.76%,69.32%,可氧化态分别下降35.71%,47.57%,98.28%,Ce的残渣态降低了64.64%,而La和Y的残渣态分别上升了32.37%,322.23%。且淋洗后土壤中La,Ce和Y稳定性指数IR分别提高了50.58%,7.55%和104.26%,降低了土壤中稀土的生物可利用性。     

稀土对UV-B辐射伤害植物的影响Ⅰ. Ce(Ⅲ)对UV-B胁迫下油菜幼苗生长及光合作用影响

用水培法研究了Ce(Ⅲ)对紫外辐射(UV-B, 280～320 nm)胁迫下油菜幼苗生长与光合作用的影响. 实验表明, 在紫外辐射(T1/0.15 W·m-2和T2/0.35 W·m-2)胁迫下, 油菜幼苗生长受到严重抑制. 地上部茎(株)高、叶片数、叶面积、叶鲜(干)重、茎鲜(干)重等生长指标均低于对照植株13.2%～44.1%(T1), 21.4%～49.3%(T2); 地下部除根系活跃吸收面积降幅不明显外, 主根长、根体积、根鲜(干)重均低于对照14.1%～35.6%(T1), 20.3%～42.6%(T2). Ce处理油菜幼苗, 上述各项指标降幅均低于未用Ce处理植株(地上部, Ce+T1降低4.1%～23.6%, Ce+T2降低10.8%～28.4%; 地下部, Ce+T1降低5.2%～23.3%, Ce+T2降低 7.0%～27.8%). 表明Ce对紫外辐射伤害油菜幼苗有防护效应,且对低剂量UV-B伤害的防护效果更优. 光合参数测定显示, UV-B胁迫下植株Chl含量, Pn, En, Gs及WUE降低, Ci增高. Ce处理植物的5项参数降幅减小, 表明对光合作用的改善是Ce防护效应的生态生理学基础. 光合参数动态测定显示, Ce介导使油菜光致修复历程缩短(逼向CK的拐点前置), 或各时段变幅陡减.     

稀土对LaNi_(3.5)Co_(0.8)Mn_(O.4)Al_(0.3)合金电化学及储氢特性的影响

研究了以Ce,Nd和Pr部分替代LaNi(3．5)Co(0.8)Mn(0.4)Al(0.3)中的La后对合金电化学及储氢特性的影响。稀土含量的变化明显改变合金的电化学及储氢特性。Pr对合金的电化学性能影响小于Ce。Ce使合金的放电容量降低,并升高合金的氢分解压。随着Nd含量的增加,合金的放电容量降低。     

混合稀土和镧施加后苗期玉米体内稀土元素分布的剂量／效应关系研究

以潮土和玉米分别为供试土壤和作物进行盆栽实验.当混合稀土或La与土壤混合后,苗期玉米根系和地上部分中稀土元素含量存在明显的剂量-效应关系.施加混合稀土时,玉米根系和地上部分中轻稀土和Gd含量分别在10和50mg@kg-1风干土时出现显著性聚集效应;在La施用量为5和10mg@kg-1风干土时,玉米根系和地上部分中La含量分别出现显著性聚集效应.施加较大剂量混合稀土或La时,玉米根系和地上部分中Gd含量均出现显著性正异常;当混合稀土施用量为50mg@kg-1时,玉米根系和地上部分中均出现显著性Ce负异常现象;苗期玉米地上部分和根系LaCe和LaSm比值均随混合稀土或La施用量增大而呈增加趋势;在高剂量稀土(＞50mg@kg-1),尤其在La作用时,玉米根系吸收的La向地上部分运移明显受到抑制.     

La 或 Ce 增强 Y型分子筛结构稳定性的机制

 采用 X 射线粉末衍射、²⁹Si 固体核磁共振、X 射线光电子能谱和扫描电镜及能谱等方法研究了 La, Ce 增强 Y 分子筛结构稳定性的差异. 结果表明, La 和 Ce 的引入均可稳定 Y 分子筛的骨架结构, 但 La 离子比含量相当的 Ce 离子更容易进入分子筛内部和抑制骨架铝的脱除, 因而对分子筛结构的稳定作用更优. 结合量子力学密度泛函计算方法, 从理论上阐述了这种增强机制, 即La 或 Ce 的引入能显著增加分子筛骨架 Al 和相邻 O 原子的作用力, 有效稳定分子筛骨架 Al 位, 并且稀土离子与分子筛间存在较强的作用力; 与 Ce 相比, La 与分子筛的相互作用更大, Al–O 作用力更强, 因此, La 比 Ce 更有利于稳定分子筛的骨架结构.     

稀土金属氧化物对Pd/δ,θ-Al2O3催化蒽醌氢化制H2O2性能的影响

 采用湿浸法制备了用于蒽醌氢化制过氧化氢的系列氢化催化剂. 考察了不同稀土金属(La, Ce,Pr,Nd和Sm)氧化物对Pd/δ,θ-Al2O3催化剂性能的影响. 采用XRD,H2-O2滴定和N2物理吸附等技术对催化剂进行了表征. 结果表明,适量稀土金属氧化物的加入能抑制高温处理时Al2O3晶粒的增长,增大催化剂比表面积,提高金属Pd的分散度,从而提高催化剂的氢化活性. 稀土金属氧化物对Pd/δ,θ-Al2O3催化性能的影响顺序为La＞Nd＞Pr＞Sm＞Ce.     

谷胱甘肽和Ebselen对胰岛素硝化的抑制及其相互作用机理的研究

生物体内NO和超氧阴离子快速反应生成的过氧亚硝酸根离子(ONOO^-，peroxynitrite)是一种强细胞毒性物质，它诱导蛋白质酪氨酸残基硝化是其损伤生物系统的重要途径之一。为了探讨谷胱甘肽和ebselen对胰岛素硝化的抑制及其相互作用机理，采用UV-Vis、HPLC和ESI-MS等方法，研究了ONOO^-对胰岛素的硝化作用、小分子抗氧化剂谷胱甘肽(GSH)和ebselen对ONOO^-硝化胰岛素的影响以及它们之间的相互作用。结果表明单独的GSH和ebselen对ONOO^--引发的胰岛素硝化均有明显的抑制，而作为谷胱甘肽过氧化物酶(GPx)的底物GSH 与GPx的模型化合物ebselen之间存在相互拮抗作用，经过对其产物分析，确定其机理是GSH和ebselen能够直接反应生成一种加合物，从而抑制了GSH和ebselen各自的抗硝化能力。     

Studies on the Adsorption and Dissociation of Methane and Carbon Dioxide on Nickel

The adsorption and dissociation of methane and carbon dioxide for reforming on nickel catalysts were extensively investigated by TPSR, TPD, XPS and pulse reaction methods. These studies showed that the decomposition of methane results in the formation of at least three kinds of surface carbon species on supported nickel catalysts. Carbidic Cα, carbonaceous Cβ and carbidic clusters Cγ surface carbon species formed by the decomposition of methane demonstrated different surface mobility, thermal stability and reactivity. Carbidic Cα is a very active and important intermediate in carbon dioxide reforming with methane, and the carbidic clusters Cγ species might be the precursor of surface carbon deposition. The partially dehydrogenated Cβ species can react with H2 or CO2 to form CH4 or CO. On the other hand, it was proven that CO2 can be weakly adsorbed on supported nickel catalysts, and only one kind of CO2 adsorption state is formed. The interaction mechanism between the species dissociated from CH4 and CO2 during reforming was then hypothesized.     

Comparative study on sorption of individual and coupling cesium and selenium on mudrock

This study focused on sorption mechanism of Cs and Se in mudrock by batch techniques. Batch kinetics tests have been conducted with carriers 10^{− 4}M CsCl and SeO₂ by using individual and coupling radiotracers of ¹³⁷Cs and ⁷⁵Se. The distribution coefficients (K _d ) of Cs in synthetic groundwater (GW) and seawater (SW) showed that there is no interference between individual and coupling value (13 and 6 ml/g). Moreover, individual and coupling K _d ) (80 and 40 ml/g) of Se in GW and SW are in agreement with Cs. It is quite clear that the sorption mechanisms of Cs and Se on mudrock are independent and different by using radiotracer’s technique.     

Influence of platinum and hydrogen on n-butane isomerization on H-Mordenite

Hydrogen inhibits n-butane isomerization of H-MOR and improves catalyst stability and selectivity. Similarly, when Pt is present, hydrogen inhibits the reaction which is always controlled by the acid function.     

Effect of molecule-substrate interaction on thin-film structures and molecular orientation of pentacene on silver and gold

Evaporated pentacene thin films with thicknesses from several nm to 150 nm on gold and silver substrates have been studied by ultraviolet photoelectron spectroscopy (UPS), near-edge X-ray absorption fine structure (NEXAFS), scanning tunneling microscopy (STM), and atomic force microscopy (AFM). It was found that pentacene thin-film structures, particularly their molecular orientations, are strongly influenced by the metal substrates. UPS measurements revealed a distinct change in the valence band structures of pentacene on Au compared to those on Ag, which is attributed to the different packing between adjacent molecules. Using NEXAFS, we observed 74+/-5 degrees and 46+/-5 degrees molecular tilt angles on Ag and Au, respectively, for all measured thicknesses. We propose that pentacene molecules stand up on the surface and form the "thin-film phase" structure on Ag. On Au, pentacene films grow in domains with molecules either lying flat or standing up on the substrate. Such a mixture of two crystalline phases leads to an average tilt angle of 46 degrees for the whole film and the change in valence band structures. STM and distance-voltage (z-V) spectroscopy studies confirm the existence of two crystalline phases on Au with different conducting properties. z-V spectra on the low conducting phase clearly indicate its nature as "thin-film phase".     

压力和温度对水型相图平衡影响的探讨

重点从热力学原理的角度探讨压力和温度对水型相图平衡的影响,并通过计算解释了水型相图中固液平衡线上随压力升高,熔点下降的原因。     

Effect of Charge and Hydrophobicity on Adsorption of Modified Starches on Polyester

Polyester fabric (poly(ethylene terephthalate)) is a hydrophobic polymer. Its hydrophobic nature can be a disadvantage for certain applications like dyeing, finishing, detergency, etc. Physical or chemical modification of the polyester to make it more hydrophilic is therefore desirable for certain performance characteristics. Surface modification of polyester to make it hydrophilic can be achieved by adsorbing polymers on the polyester surface. Starch is a commonly available, hydrophilic polymer used in many textile applications that can be used to modify polyester. However, it needs to be chemically modified so that it can adsorb on the polyester fabric and physically modify the fabric characteristics. The polymers used in this study are two different modified starches—cationic and anionic starches and mixtures of the two. The adsorption kinetics on a polyester substrate was studied. The effect of charge and hydrophobicity on adsorption was investigated. Cationic starches were shown to readily adsorb on polyester and this was attributed to electrostatic interactions. Hydrophobic substituents on the cationic moiety resulted in increased adsorption. This was attributed to the weak hydrophobic interaction between the polymer chains which could result in a more coiled polymer conformation. It is hypothesized that more starch molecules are required for surface coverage of the polyester, resulting in an increase in adsorption. Anionic starch was adsorbed on the substrate but at a slower rate than the cationic starches. It is likely that there is a H bonding between acid groups on the starch and the ester groups of the polyester. However, the anionic starch is desorbed when the polyester is placed in an aqueous medium. When a blend of cationic starch and anionic starch was used, a low concentration of anionic starch was seen to increase adsorption, indicating that the polyelectrolyte complex itself may be adsorbing on the substrate. Further increases cause a decrease in adsorption as no sites may be available on the complex for adsorption. When hydrophobic substituents are present, addition of the anionic starch causes a decrease in adsorption at all concentrations. This was attributed to the “crosslinking” between the hydrophobically modified starch and the anionic polymer.     

Note on ordering and complexity of Platonic and Archimedean polyhedra based on solid angles

The missing values for the solid angles of the two snub semiregular polyhedra have been calculated, and integrated into the whole series of Platonic and Archimedean polyhedra. This is the only criterion which so far gives an unambiguous answer (without any degeneracy leading to posets) on how to order these polyhedra according to their increasing complexity.     

Studies on the Adsorption and Dissociation of Methane and Carbon Dioxide on Nickel Catalysts

The adsorption and dissociation of methane and carbon dioxide for reforming on nickel catalysts were extensively investigated by TPSR, TPD, XPS and pulse reaction methods. These studies showed that the decomposition of methane results in the formation of at least three kinds of surface carbon species on supported nickel catalysts. Carbidic Cα, carbonaceous Cβ and carbidic clusters C-γ surface carbon species formed by the decomposition of methane demonstrated different surface mobility, thermal stability and reactivity. Carbidic Cα is a very active and important intermediate in carbon dioxide reforming with methane, and the carbidic clusters Cγ species might be the precursor of surface carbon deposition. The partially dehydrogenated Cβ species can react with H2 or CO2 to form CH4 or CO. On the other hand, it was proven that CO2 can be weakly adsorbed on supported nickel catalysts, and only one kind of CO2 adsorption state is formed. The interaction mechanism between the species dissociated from CH4