双(8-乙氧羰甲氧基-2-亚甲喹啉基)缩连氮的合成及其选择传感性能

以水合肼和2-甲酰基-8-乙氧羰甲氧基喹啉为原料合成了希夫碱双(8-乙氧羰甲氧基-2-亚甲喹啉基)缩连氮(BEQA),经1HNMR、元素分析等进行了结构表征,在乙醇-水混合溶剂中采用UV-Vis光谱法研究了H+、Ca2+、Mg2+、Sr2+、Mn2+、Co2+、Ni2+、Cu2+、Zn2+、Cd2+及Hg2+对BEQA光谱的影响,结果表明,BEQA分子的UV-Vis光谱仅对体系中的H+、Cu2+和Cd2+有特殊的选择传感性,在体系中的pH值或Cu2+、Cd2+浓度增大时,BEQA在380 nm处的吸收峰强度会逐渐减小,并伴随有不同程度的蓝移;Job′s法测定Cu2+和Cd2+与BEQA形成配合物的化学计量比为1∶4。     

非原位拉曼光谱区分富锂层状氧化物的集成结构:一种预测Li2MnO3活化程度的有效方法

采用5种方法,即溶胶-凝胶法、高温固相法、共沉淀法、水热法和溶剂热法合成了富锂材料Li_1.2Mn_0.6Ni_0.2O₂。拉曼光谱研究发现共沉淀法制备的样品是固溶体结构,而其他4个样品是以不同尺度共生形成的复合物结构。电化学性能测试结果表明这5个富锂材料性能存在明显差异,尤其是在首次充电过程中5个样品位于4.5 V以上由Li₂MnO₃组分活化所贡献的容量明显不同,共沉淀法制备的具有固溶体结构的样品中由Li₂MnO₃组分活化贡献的容量最多。因此我们建立起电化学性能与两相集成方式的联系,不同的集成方式使得Li₂MnO₃组分活化所贡献的容量不同,进而影响了最终的电化学性能。     

Synthesis and characterization of a tetranuclear copper(Ⅱ) complex with a chiral Schiff base ligand

The title complex l-[Cu^Ⅱ₄（Hvap）₂（vap）₂（MeOH）₂]（CIO₄）₂ 1 has been synthesized and characterized by EA. IR,TGA,solid-state CD spectra and X-ray single-crystal analyses（l-H₂vap’.a Schiff base ligand derived from the condensation of o-vanillin and l-2-amino-3-phenyl-l-propanol）.Complex 1 crystallizes in monoclinic system,chiral space group P2₁ with a =10.4257（18）.b = 21.695（4）,c = 15.721（3）A,β= 94.443（3）.V= 3545.1（11） ³,Z=2,Cu₄C₇₀H₇₈N₄O₂₂Cl₂.Mr= 1652.42,D_c= 1.548 g/cm³, F（000）= 1704 andμ（MoKα） = 1.338 mm^-1.The final R = 0.0682 and wR = 0.1420 for 6170 observed reflections with I > 2σ（I） and R = 0.1775 and wR = 0.1830 for all data.The structure of complex 1 contains a boat-shaped(Cu₄O₄} motif.The solid-state CD spectra confirm the chiral nature of complex 1.     

两个手性氧钒配合物[VO(Naph-Leu)(OMe)(CH3OH)] 和[VO(Naph-Phe)(OMe)(CH3OH)] 的合成、晶体结构和光谱表征

合成了2个新的手性L-亮氨酸萘酚醛和L-苯丙氨酸萘酚醛希夫碱氧钒配合物, [VO(Naph-Leu)(OMe)(CH₃OH)] (1)和[VO(Naph-Phe)(OMe)(CH₃OH)] (2)。X-射线单晶衍射分析表明, 1晶体属于正交晶系, P2₁2₁2空间群, 晶胞参数为:a=0.946 80(8) nm, b=3.246 3(3) nm, c=0.662 37(5) nm, V=2.035 9(3) nm³, Z=4, F(000)=864, R₁=0.046 3, wR₂=0.112 7, S=1.076。2晶体属于单斜晶系, P2₁空间群, 晶胞参数为:a=1.113 41(11) nm, b=0.724 09(6) nm, c=1.342 99(12) nm, V=1.047 95(16) nm³, Z=2, F(000)=464, R₁=0.035 8, wR₂=0.088 8, S=1.024。测定了它们的红外光谱、紫外光谱和圆二色光谱, 讨论了紫外吸收光谱和圆二色光谱性质。     

铽(Ⅲ)与PvdA作用的光谱研究

Pyoverdine A(PvdA)是荧光假单胞菌分泌的一种水溶性较高的黄绿色荧光铁载体。在50mmol·L^-1Tris-HCl,pH8.0条件下,使用紫外-可见吸收差光谱、荧光光谱研究了铽(Ⅲ)与荧光铁载体PvdA的结合。结果表明铽(Ⅲ)可与PvdA结合形成1：1的配合物,条件结合常数为(4.44±0.82)×10¹⁴mol^-1·L。在生理条件下,PvdA可竞争伴清蛋白N-,C-端结合的铽(Ⅲ)形成Tb-PvdA配合物;Tb-PvdA与荧光假单胞菌细胞表面受体FpvA结合形成Tb-PvdA-FpvA复合物。     

LiYF4晶体中Ho3+离子真空紫外吸收光谱的理论解析

运用配位场理论方法获得了Ho3+离子低自旋4f95d组态的谱项和J-光谱多重态,根据电偶极跃迁选律合理地解析了LiYF4晶体中Ho3+离子在真空紫外区(120～160 nm)的吸收光谱,4个主要的吸收峰分别被归属为从基态(5I8)到Ho3+离子的低自旋4f95d组态的自旋允许跃迁。     

Magnetic separation of heavy metal ions and evaluation based on surface‐enhanced Raman spectroscopy: Copper(II) ions as a case study

A new approach was developed for the magnetic separation of copper(II) ions with easy operation and high efficiency. p‐Mercaptobenzoic acid served as the modified tag of Fe₂O₃@Au nanoparticles both for the chelation ligand and Raman reporter. Through the chelation between the copper(II) ions and carboxyl groups on the gold shell, the Fe₂O₃@Au nanoparticles aggregated to form networks that were enriched and separated from the solution by a magnet. A significant decrease in the concentration of copper(II) ions in the supernatant solution was observed. An extremely sensitive method based on surface‐enhanced Raman spectroscopy was employed to detect free copper(II) ions that remained after the magnetic separation, and thus to evaluate the separation efficiency. The results indicated the intensities of the surface‐enhanced Raman spectroscopy bands from p‐mercaptobenzoic acid were dependent on the concentration of copper(II) ions, and the concentration was decreased by several orders of magnitude after the magnetic separation. The present protocol effectively decreased the total amount of heavy metal ions in the solution. This approach opens a potential application in the magnetic separation and highly sensitive detection of heavy metal ions.     

从分子碎片到活性位：分子筛催化材料的原位、共振紫外拉曼光谱研究

在过去的近十年中,各种新型原位表征技术和反应器设计被应用于多相催化过程和催化材料的合成研究中,并获得了许多新认识．特别是最近几年,利用原位、共振拉曼光谱技术对分子筛合成关键物种检测、杂原子分子筛催化活性位的研究取得了一系列进展．这些技术的应用使得从分子水平认识复杂的多孔材料成为可能：从合成初期碎片基元检测、碎片相互连接的关键化学键到预组装类微孔结构;从高度隔离过渡金属中心到配位化学键断裂生成活性中间物种,再到完成催化反应循环．这为设计特定功能和结构的催化材料及高选择性的活性中心奠定了坚实的基础．     

Facile Fabrication of Multi‐targeted and Stable Biochemical SERS Sensors

The direct transfer of single‐crystalline Au nanowires (NWs) onto Au substrates was achieved by a simple attachment and detachment process. In the presence of a lubricant, Au NWs grown vertically on a sapphire substrate were efficiently moved to an Au substrate through van der Waals interactions. We demonstrate that the transferred Au NWs on the Au substrate can act as sensitive, reproducible, and long‐term‐stable surface‐enhanced Raman scattering (SERS) sensors by detecting human α‐thrombin as well as Pb²⁺ and Hg²⁺ ions. These three biochemically and/or environmentally important analytes were successfully detected with high sensitivity and selectivity by Au NW‐SERS sensors bound by a thrombin‐binding aptamer. Furthermore, the as‐prepared sensors remained in working order after being stored under ambient conditions at room temperature for 80 days. Because Au NWs can be routinely transferred onto Au substrates and because the resultant Au NW‐SERS sensors are highly stable and provide with high sensitivity and reproducibility of detection, these sensors hold potential for practical use in biochemical sensing.