过渡金属离子(Fe~(3+),Co~(2+),Ni~(2+))和UO_2~(2+)与不同取代基偕胺肟络合机理的理论研究

偕胺肟基对铀酰离子具有很强的络合能力及较高的选择性,目前已成为海水提铀吸附材料研究的热点.本文运用阿姆斯特丹密度泛函(Amsterdam density functional,简称ADF)方法研究了UO_2~(2+)、Fe~(3+)、Ni~(2+)、Co~(2+)与不同取代基(—OH,—NH_2,—H,—F,—CF_3)偕胺肟的络合反应.密度泛函理论(density functional theory,简称DFT)对这些配位化合物的几何结构进行优化和相关热力学参数的计算与收集.从键能强弱方面分析,不同取代基偕胺肟螯合的基本趋势都是Fe~(3+)最稳定的,而UO_2~(2+)螯合是最不稳定的.从热力学角度分析,表明偕胺肟最容易与UO_2~(2+)和Co~(2+)进行螯合,而取代基为—CF_3的偕胺肟最难与UO_2~(2+)和Co~(2+)进行螯合.在液相环境中不同取代基偕胺肟与UO_2~(2+)和Co~(2+)离子螯合的稳定顺序均为—NH_2—OH—H—F—CF_3.在η2构型中,偕胺肟比其他取代基偕胺肟更稳定,其中UO2+2与氨基偕胺肟螯合过程中的ΔG(吉布斯自由能变)最低为-646.65 k J/mol.     

无机物的络合萃取研究Ⅷ磷酸三丁酯萃取硝酸铀酰的研究

本文对磷酸三丁酯(TBP)萃取UO_2(NO_3)_2的热力学平衡进行了研究。根据电解质的静电互吸理论和盐效应理论,提出了一种有盐析剂存在时计算水相中被萃取物质活度系数的方法。同时提出了在UO_2~(2 )—NO_3~-水溶液体系中铀酰离子可以通过硝酸根而聚合生成UO_2[(NO_3)_2UO_2]_(m=1)~(2 )多核络合物,并通过萃取平衡研究,测得了UO_2~(2 )—NO_3~-单核络合物的络合常数和多核络合物的聚合常数以及萃取反应的平衡常数等。运用这些结果能够较好的解释和计算分配曲线。     

弱碱性阴离子交换树脂对酸性含铀浸出液中铀的吸附机理

研究弱碱性阴离子交换树脂D301处理酸性含铀浸出液的吸附机理,分析D301载铀饱和树脂淋洗异常的原因,优化D301载铀树脂的淋洗参数。研究结果表明:某酸法地浸浸出液中含不同比例的UO_2~(2+),UO_2SO_4,UO_2(SO_4)_2~(2-)和UO_2(SO_4)_3~(4-)等配合物,D301树脂对UO_2(SO_4)_2~(2-)和UO_2(SO_4)_3~(4-)的吸附是离子交换机理,对UO_2~(2+)和UO_2SO_4吸附是表面络合机理,铀酰络合物与树脂以2种不同的化学键结合是导致淋洗曲线出现2个峰的原因;提高淋洗剂酸质量浓度为30 g/L或提高淋洗剂NaCl质量浓度为90 g/L都可以优化淋洗曲线,其中提高淋洗剂NaCl质量浓度更具实际意义。     

微波辅助合成色控型CMC-Tb/Eu纳米复合物的荧光性质

微波辅助下通过共同沉淀法制备了一系列可色控的CMC-Tb/Eu复合物,并通过SEM-EDS、TEM、XPS、UV-Vis,荧光光谱和荧光寿命检测等方法考察了复合物的形貌、结构、荧光性能以及能量转移特征.结果表明:CMC-Tb/Eu复合物的表面与CMC的相比裂痕多,有小粒子集聚于CMC表面,颗粒为实心结构,平均直径为75~98 nm;纳米复合物中金属离子都与CMC分子链上的—OH、—COO~-以及—COC—中O原子发生配位键合和离子;CMC为主要的光能量吸收体,在其与稀土离子的能量传递过程中,传递给Tb~(3+)的效率要远大于传递给Eu~(3+);在激发光为350 nm下,CMCTb/Eu发射光谱中存在~5D_4→~7F_5(544 nm)和~5D_4→~7F_6(489 nm)Tb~(3+)跃迁峰;589 nm和616 nm附近的两个发射峰是由Tb~(3+)的~5D_4→~7F_3和~5D_4→~7F_4跃迁以及Eu~(3+)的~5D_0→~7F_1和~5D_0→~7F_2跃迁叠加所致;实现了荧光光色可控.Tb~(3+)的~5D_4→~7F_5跃迁峰强度变化以及纳米复合物的荧光寿命变化证明了纳米复合物存在Tb(Ⅲ)Eu(Ⅲ)能量转移.     

双功能抑制剂SK10对Cu~(2+)存在下Aβ聚集的抑制和解聚作用

由于β-淀粉样蛋白(amyloidβ-protein,Aβ)的聚集是阿尔茨海默症(Alzheimer’s disease,AD)发病机制中的关键过程,而金属离子Cu~(2+)存在下的Aβ的聚集速率加快,且Cu~(2+)本身会促进活性氧(ROS)的产生,增加神经毒性,因此开发既能螯合Cu~(2+)又能抑制Aβ聚集的双功能抑制剂非常重要.本文将金属螯合三肽(SSH)和Aβ聚集七肽抑制剂相组合,设计合成了新的双功能Aβ聚集十肽抑制剂SSHLVFFARK-通过硫代黄素T(ThT)荧光实验、聚集动力学实验、原子力显微镜检测(AFM)、等温滴定量热和MTT细胞毒性测定等研究了SK10对Cu~(2+)存在下Aβ聚集的抑制和解聚作用以及细胞毒性的抑制作用.实验结果表明:SK10不仅可以抑制Cu~(2+)存在下的Aβ40聚集(ThT荧光强度降低了60%),随着SK10浓度的提高使Aβ40纤维逐渐减少,还能降低Cu~(2+)存在下Aβ40聚集产生的细胞毒性,使细胞活性恢复至90%以上;同样,SK10对Cu~(2+)存在下的Aβ42聚集也有抑制作用.由于SK10对Cu~(2+)具有较强的特异性亲和力,能够螯合复合物中的Cu~(2+),因此能抑制由Cu~(2+)催化产生的活性氧(ROS)对细胞的毒性.进一步研究表明SK10还可解聚形成的聚集体,使已形成的聚集体消失,缓解其产生的细胞毒性,使细胞活性提高到90%.以上研究结果不但体现了SK10的药用潜力,也为今后设计和开发金属螯合Aβ聚集双功能抑制剂提供了思路.     

重金属对气孔保卫细胞功能和活性的影响

为深入了解重金属的毒性作用,我们选用蚕豆气孔保卫细胞系统检测了Al ~(3+)、Cr~(6+)、Cu~(2+)、Hg~(2+)及电镀废水对气孔开度和细胞活性的影响,发现0.05mg/L的Al ~(3+)、Cr~(6+)、Cu~(2+)、Hg~(2+)作用于蚕豆表皮,可降低叶面气孔开度;抗坏血酸或LaCl_3能阻止金属离子诱发的气孔关闭,说明活性氧和钙离子参与了金属离子诱导的气孔关闭;当金属离子浓度提高至0.5~5mg/L时,气孔保卫细胞活性降低,随着浓度增大,金属离子对细胞的毒性增高。用电镀废水处理同样导致气孔开度减小,细胞活性降低。上述结果表明,环境金属离子含量达到一定值后会对植物细胞的功能产生影响,浓度提高时细胞活性受损,即使单一离子含量达到国家颁布的废水排放标准,也可能直接影响气孔开度,进而干扰植物生理,而高浓度金属离子引发的植物细胞活性丧失,对植物的危害将更为严重。     

508树脂吸铀机理研究[Ⅰ]

本文应用红外光谱与紫外光谱实验手段报导了508树脂吸附铀酰离子反应机理研究成果。研究成果初步得到以下三个结论: (1) 由701预聚浆与5NAP生成508树脂的反应是生成醚键的化学反应,反应产物是R—O—R′。(其中R—OH是指(?)—NH_2,代号为5NAP化合物,而R′是指具有树脂母体,代号为701树脂)。 (2) 紫外光谱方法证实,5NAP不吸铀。而508树脂却是一个优良铀吸附剂。 (3) 508树脂吸铀机理,是508树脂醚键与—NH_2基和UO_2~(2+)进行螯合。以上结论,在国内外尚未见正式文献报导。     

花生壳生物炭对水中重金属Cr6+、Cu2+的吸附研究

生物碳因其来源广泛、低廉及良好的表面理化性能,作为吸附材料在处理水中有机及重金属污染方面具有较大的潜力。研究利用花生壳制得生物炭,用于处理含~(6+)和Cu~(2+)的模拟废水。探讨了接触时间、p H值、生物炭投加量及温度等对吸附效果的影响。结果表明,生物碳吸附~(6+)和Cu~(2+)时间在120 min达到平衡。在酸性条件下(p H=2~5),生物炭投加量为4g/L,温度为30℃时生物炭对~(6+)的吸附效果较好;在偏碱性条件下(p H≥5),生物炭投加量为10 g/L,温度为40℃时生物炭对Cu~(2+)有较好的吸附效果。通过Langmuir和Frenudlich吸附等温方程拟合,表明生物炭对~(6+)和Cu~(2+)的吸附过程更符合Frendlich模型,吸附过程可以用假二级动力学模型描述,说明吸附主要是表面化学吸附。     

氯盐侵蚀作用对水泥固化铅污染土化学稳定性的影响

含侵蚀性盐离子(SO_4~(2-)、Cl-等)的地下水环境可能会改变水泥固化污染土中重金属离子的溶出特性.通过毒性浸出试验模拟研究了遭受NaCl溶液侵蚀的水泥固化铅污染土的化学稳定性.试验结果表明,遭受NaCl溶液侵蚀后,随着NaCl浓度的增加,浸出液pH值略有减小,浸出液中Pb~(2+)质量浓度亦有所降低.短期浸泡,浸出液pH值最低,Pb~(2+)质量浓度最大;随后,pH值随浸泡时间增加而增大,Pb~(2+)质量浓度随浸泡时间增加而减小.当Pb~(2+)含量≤5 000 mg/kg时,浸出液中Pb~(2+)质量浓度均小于5 mg/L,满足环境要求;而Pb~(2+)含量为10 000 mg/kg的固化土体,滤出的Pb~(2+)质量浓度均超过5 mg/L,不能满足环境要求.     

N,N'-二(N'-(氨基乙基)-2,3-二羟基苯甲酰胺)丙二酰胺的合成及其对铀酰离子的螯合性能

通过苄基保护酚羟基、Boc单保护乙二胺等反应合成一种新型四齿螯合剂N,N'-二(N'-(氨基乙基)-2,3-二羟基苯甲酰胺)丙二酰胺;采用傅里叶变换红外光谱(FT-IR)、核磁共振氢谱(1H NMR)和核磁共振碳谱(13C NMR)对产物结构进行表征;测定了配体的质子化常数及其与铀酰离子配合物的稳定常数,并计算了p UO2值(=-log[UO_2]_(游离))。结果表明,N,N'-二(N'-(氨基乙基)-2,3-二羟基苯甲酰胺)丙二酰胺是一种潜在的铀酰离子促排剂,其与铀酰离子配合物的稳定常数达到35.68,pUO_2值达到20.85。     

Preparation and characterization of some surface negatively charged residue mutants of cytochrome b5

Site-directed mutagenesis was used to obtain seven variants of tryptic fragment of bovine liver cytochrome b_m5 (cyt b₅), in which the negatively charged residues around the heme exposed edge of cyt b₅ were replaced by hydrophobic amino acid alanine. Double-site mutants, triple-site mutants and even quadruple-site mutants were obtained. DNA sequencing and molecular weight measurements of the mutant proteins both confirmed that these site-directed mutagenesises were successfully performed. Spectroelectrochemistry of these mutant proteins revealed that the apparent redox potentials of these mutant proteins caused a positive shift of 2–10 mV. The global structure of these mutant proteins did not show much difference from that of the wild type cyt b₅, providing a solid base for the further study on the roles of the proteins’ surface charges.     

混合配体构筑的钌-铀酰异金属配位聚合物的合成和晶体结构及荧光性能

利用钌金属络合物离子和芳香有机二羧酸配体与铀酰离子在水热条件下反应，合成了一例新的异金属有机配位聚合物，也即[Ru(bipy)₃][(UO₂)₂(BDC)₃]·2H₂O，利用单晶X-射线衍射方法、粉末X-射线衍射方法、红外光谱对该配位聚合物结构进行了基本表征。该配合物是由金属配合物阳离子客体[Ru(bipy)₃]²⁺ 、二维蜂窝状平面结构的聚阴离子主体框架[(UO₂)₂(BDC)₃]_n^2-之间通过分子内和分子间C-H···O氢键的相互作用形成准三维超分子结构。此外，固体紫外-可见漫反射光谱测试表明此配合物具有半导体性质，是潜在的光电材料。固体荧光测量表明配合物表现出强烈的发光性能。     

CO2和O2共注入下方解石溶解对黄铁矿氧化固铀的影响

我国大型可地浸砂岩型铀矿床普遍存在黄铁矿和方解石与铀矿物密切共生现象。中性地浸采铀过程中O₂和CO₂的共注入会诱导黄铁矿氧化和方解石溶解,目前针对二者共存体系中方解石溶解对黄铁矿氧化固铀的影响尚不明确。本文通过静态批实验和数值模拟的方法对比研究了CO₂和O₂条件下方解石溶解对黄铁矿氧化固铀的影响。结果表明：无CO₂分压下中性Tris缓冲体系中黄铁矿氧化对U(VI)的吸附率高达90%,有CO₂分压下碳酸铀酰体系中铀的固定率明显降低,约有32%的铀被吸附。在方解石和黄铁矿共存体系中,单独通O₂条件下铀的吸附率为27%,CO₂和O₂共通时黄铁矿氧化对铀的吸附率仅为2%,结合数值模拟结果表明O₂+黄铁矿+方解石体系和CO₂+O₂+黄铁矿+方解石体系中Ca₂(UO₂)(CO₃     

Roles of Phe58 residue in stabilizing structure of cytochrome b<Subscript>5</Subscript>

To understand effect of π-stacking interactions between the side chain of aromatic amino acids and the porphyrin ring on structures and properties in cytochrome b₅ (cyt b₅), the Phe58 residue was mutated to tyrosine and tryptophan, respectively by site-directed mutagenesis. The denaturation of cyt b₅ F58W and F58Y toward guanidine hydrochloride was examined by UV-visible and fluorescence spectroscopy. The kinetics of heme transfer reactions between apo-myoglobin and the mutants were studied. The results indicated that the mutation of F58 residue for Y58 or W58 reduced the interaction between of peptide and the heme group, resulting in decrease of the T _m and C _m values of the proteins, increase of the heme transfer reaction rate, and shifts of the redox potential.     

Identifying neutral allele Sb at pollen-sterility loci in cultivated rice with Oryza rufipogon origin

Pollen sterility is commonly found in the intra-specific hybrids of indica and japonica rice, which is one of the main constrains for the utilization of heterosis between indica and japonica. Six loci controlling the pollen sterility of F1 between indica and japonica have been identified from previous studies. Neutral alleles at each locus are potential to overcome the F1 pollen sterility associated with the locus. Therefore, exploitation and utilization of neutral alleles are of significant importance. The present research was based on fine mapping of the F1 pollen-sterility gene Sb and the abundant genetic diversity of Oryza rufipogon Griff. indigenous to Gaozhou, Guangdong Province （referred to as Gaozhou wild rice）. Crosses were made using Taichung65 （with the genotype of Sb^jSb^j and referred to as El） and its near-isogenic line of F1 pollen sterility gene Sb（with the genotype of Sb^iSb^i, E2） as female parents, and 12 different accessions of Gaozhou wild rice as male parents. F1 pollen fertility was examined to identify the materials having the neutral alleles at the F1 pollen-sterility locus. Segregation of 4 molecular markers tightly linked with the Sb locus was analyzed in the F2 populations derived from the FlS carrying the neutral gene. The pollen fertility related to the 3 genotypes of the molecular markers was also checked by statistical test to determine whether it was consistent with the hypothesis. The results showed that the pollen fertility of two F1s from one accession of Gaozhou wild rice （GZW099） with E1 and E2 was （89.2±21.07）% and （85.65±1.05）%, respectively. Both of them were fertile and showed no significant difference by t-test. Segregation of the 3 genotypes of the 4 molecular markers followed the expected Mendelian ratio （1：2：1） in the F2 populations. There was no significant difference for the averaged pollen fertility of the plants related to the 3 genotypes, suggesting that no interaction exists between the alleles at the Sb locus in GZW099 and Taichung65 or E2. Evidentially, GZW099 carried the neutral gene （named Sb″Sb″） at the Sb locus, which provides valuable theoretical basis and resources for further studying and overcoming the sterility of indica-japonica hybrids.     

基于掺铕钨酸盐荧光强度比的非接触温度传感

为了突破传统测温技术应用的局限性,利用NaY （WO₄）₂：Eu³⁺玻璃陶瓷（glass ceramics,GC）实现了具有非接触、实时响应、自校准等优势的双模荧光强度比（luminescence intensity ratio,LIR）测温。采用高温熔融淬灭法制备出含NaY （WO₄）₂：Eu³⁺纳米晶的透明GC样品,并进行系列光谱测量和热敏性能分析。结果表明,样品中Eu³⁺的激发态能级⁵D₁和⁵D₀和基态能级⁷F₂和⁷F₀为两对独立的热耦合能级,可分别基于这两对热耦合能级实现性能优异的双模LIR温度传感。该双模LIR测温技术数据可靠、测温范围广、灵敏度高,再结合GC材料优势,是可用于光纤温度传感器的核心技术材料。     

The new sideway of CNTF signal transduction pathway

The action of ciliary neurotrophic factor (CNTF) on intercellular free Ca²⁺ concentrations [Ca²⁺]_i induced by glutamate (Glu) in primary cultured hippocampal neurons were detected with Fura2/AM, a Ca²⁺-sensitive fluorophore, and the morphological influence of G-protein on it was objected. Glu could induce rapid increase of [Ca²⁺]_i in hippocampal neurons. CNTF had no significant action on [Ca²⁺]_i in resting hippocampal neurons. However, after incubation of CNTF for 5 min, the increase of [Ca²⁺]_i in hippocampal neurons rapidly induced by Glu was inhibited. Pretussis toxin (PTX)-sensitive G protein could block the action. These results indicate that a new non-genomic rapid sideway might exist in the upper stream of CNTF signal transduction pathway, which was related to Ca²⁺ signal transduction. Keywords:     

Pu(H2O)53+和Pu(H2O)54+ 团簇的相对论密度泛函研究

用TPSSTPSS密度泛函方法, Pu离子和H₂O分子分别采用相对论有效原子实势(RECP)和6-31g基组, 研究了Pu(H₂O)₅³⁺和Pu(H₂O)₅⁴⁺ 团簇溶剂化和非溶剂化效应中的几何结构及紫外可见吸收光谱. 计算结果表明: 水溶剂环境对Pu(H₂O)₅³⁺及Pu(H₂O)₅⁴⁺ 团簇的几何结构影响都比较明显. NBO电荷分析表明水分子与钚离子之间没有直接的电荷转移. 所研究团簇的未配对电子都占据5f轨道. 在气相及水溶剂环境下, 所研究团簇的紫外可见吸收光谱存在较大差距. 主要的吸收峰大都源于f电子之间的跃迁.     

GeLi62+团簇的结构及储氢性能研究

利用密度泛函B3LYP理论在6-311+G(d,p)基组水平上研究四价锗负离子经过6个一价锂正离子修饰后的结构和电子特征,并计算了H2分子在其表面的吸附行为,进而研究其储氢性能。结果表明,由6个Li离子修饰锗离子形成GeLi_6~(2+)团簇结构具有较高的动力学稳定性。GeLi_6~(2+)团簇表面最多能够有效吸附18个氢分子,其质量密度为24.10wt%。H2分子与GeLi_6~(2+)团簇的相互作用能量范围为2.14～4.004k Cal.mol-1。储氢性能研究表明GeLi_6~(2+)团簇在储氢领域有望具有良好的应用前景。     

Theoretical study of partial oxidation of ethylene by vanadium trioxide cluster cation

Density functional theory （DFT） study of reaction between vanadium trioxide cluster cation （VO3^＋） and ethylene （C2H4） to yield VO2^＋ ＋ CH3CHO （acetaldehyde） and VO2CH2^＋ ＋ HCHO （formaldehyde） is carried out. Structures of all reactants, products, intermediates, and transition state in the reaction have been optimized and characterized. The results show unexpected barriers in the reaction due to the existence of a η^2-O2 moiety in the ground state structure of VO3^＋. The initial reaction steps combining ethylene adsorption, C=C activation and O-O cleavage are proposed as rate limiting processes. Comparison of reactions of VO3^＋ ＋ C2H4 with VO3 ＋ C2H4 and VO2^＋ ＋ C2H4 in the previous studies is made in detail. The results of this work may shed light on the understanding of C=C bond cleavage in related heterogeneous catalysis.