萘醌及其衍生物的太赫兹时域光谱研究

用太赫兹(THz)时域光谱技术研究了室温条件下的萘醌及其衍生物1,2-萘醌、1,2-萘醌-4-磺酸钠、甲萘醌、白花丹素、胡桃醌的光谱特征,得到了各自的吸收谱和折射率。结果表明,萘醌及其衍生物在此波段有不同的吸收特征,利用太赫兹时域光谱能够鉴别分子结构存在微小差别的化合物。在对样品的吸收谱进行比较的基础上,讨论了分子结构和分子间晶格振动与THz光谱特征吸收的关系。     

固态多环芳烃化合物的THz时域光谱研究

利用太赫兹时域光谱技术室温下对芳烃化合物萘、联苯、葸、α-萘酚和β-萘酚在3-73cm^-1(0．1．2．2THz)频谱范围内进行了光谱测量。结果表明，多环芳烃化合物在此波段有不同的吸收特征。不能形成氢键的萘、联苯和蒽在67cm^-1(2．0THz)附近均有一吸收峰，这可能是由于分子之间的振动即晶格振动所引起的；而能够形成氢键的口一萘酚和卢．萘酚，其吸收峰可归结于分子间氢键的相互作用所引起的集体振动模式。1Hz时域光谱不仅能够鉴别分子结构存在微小差别的化合物而且还能鉴别同分异构体。     

乐果分子的太赫兹时域光谱研究

研究了有机磷农药乐果在0.2~2.5 THz波段的光谱特性。应用密度泛函理论的Becke-3-Lee-Yang-Parr(B3LYP)方法计算了乐果分子在THz波段的振动吸收谱,同时利用THz时域光谱系统(THz-TDS)测得了乐果在此波段的吸收谱和折射率谱。根据理论计算结果,借助于Gaussian View软件对乐果的THz吸收谱进行了指认,并给出了与光谱特征吸收对应的分子振动构象。研究表明:乐果分子在THz波段存在吸收峰,理论计算与实验结果符合较好,且乐果分子在THz波段的吸收是由分子内和分子间振动共同引起。本研究证明了将THz-TDS技术用于乐果分子探测和识别的可行性,为THz时域光谱技术在其它农药分子识别和残留检测中的应用提供了有益的借鉴。     

β-丙氨酸的THz时域光谱研究

运用THz时域光谱测试技术(THz-TDS)与理论模拟相结合的方法, 研究了β-丙氨酸在THz波段的光谱特性. 在室温氮气环境中, 得到了样品在0.2～2.4 THz波段的吸收谱和折射率谱, 表明其特征吸收峰位于2.11 THz处, 平均折射率为1.96. 同时利用Gaussian 03软件的半经验理论计算了该分子在0.1～10.0 THz的振动吸收谱, 其在0.2～2.4 THz波段的吸收峰与实验相互对应, 且峰位符合较好. 研究了分子低频的振动模式, 并给出了分子的构象参数.     

含硫氨基酸的太赫兹光谱

利用太赫兹时域光谱(THz-TDS)技术研究室温条件下多晶含硫氨基酸L-蛋氨酸(Met)和L-半胱氨酸(Cys)的光谱特性, 得到相应的吸收谱和折射率谱, 表明含硫氨基酸在THz波段具有区别于其它氨基酸的显著特征. 在实验测量的有效光谱范围0.2～2.8 THz内, L-蛋氨酸的THz吸收峰分别位于1.06, 1.88和2.70 THz; L-半胱氨酸的吸收峰分别位于1.40, 1.70, 2.33和2.61 THz, 两种氨基酸的平均折射率均为1.44. 利用GAUSSIAN 03软件包中的Hartree-Fock理论计算了蛋氨酸双分子的低频振动谱, 表明了与蛋氨酸各吸收峰对应的分子微观振动模式, 并对实验光谱进行了解析讨论.     

两个含双膦配体和[2,3-f]吡嗪并[1,10]菲咯啉的Cu髣配合物的合成、结构及光谱学性质（英文）

合成了2个新的铜髣配合物,[Cu(dppBz)(dpq)]ClO_4(1)和[Cu(dppe)(dpq)]ClO4(2)(dppBz=1,2-双(二苯基膦)苯,dppe=1,2-双(二苯基膦)乙烷,dpq=[2,3-f]吡嗪并[1,10]菲咯啉),通过X射线单晶衍射分析、元素分析、红外光谱、紫外吸收光谱、荧光光谱、核磁共振光谱和太赫兹时域光谱对其进行了分析和表征。1的中心Cu髣离子通过二亚胺配体和双膦配体共同螯合形成变形四面体结构,2的结构与1类似。配合物2的发光光谱表明它的发光具有金属-配体电荷转移(MLCT)特性。对配合物1和2在0.2～2.8 THz范围内进行了太赫兹时域光谱分析,结果表明0.40～0.90 THz的吸收与中心Cu髣离子的配位有关。     

两种联苯酚类化合物的太赫兹时域光谱研究

利用太赫兹时域光谱技术获得了295 K时2,2′-二羟基联苯(2,2′-biphenol, 2BP)和4,4′-二羟基联苯(4,4′-biphenol, 4BP)在0.1~1.6 THz波段的光谱. 实验结果显示, 两种同分异构体在太赫兹频率范围内的吸收谱有显著的差异. 结合量子化学计算, 2BP中的两个羟基间能够形成分子内氢键, 在1.45 THz的运动模式初步判断为包含氢键在内的两个苯环的低频摆动.     

太赫兹光谱和密度泛函理论(DFT)分析呋喃妥因和尿素共晶体

利用太赫兹时域光谱(Terahertz time-domain spectroscopy, THz-TDS)技术对呋喃妥因、尿素及其研磨和溶剂共晶体进行表征分析, 实验结果显示了呋喃妥因和尿素的研磨和溶剂共晶体位于0.85、1.23、1.60 THz的吸收峰明显区别于原料物质. 该结果表明太赫兹光谱技术可以有效鉴别呋喃妥因、尿素及其共晶体. 运用密度泛函理论(Density functional theory, DFT)对呋喃妥因和尿素共晶体的2种可能结构进行了结构优化和光谱模拟, 模拟结果显示其中的结构A在0.49、0.81、1.25、1.61 THz处具有吸收峰, 与实验结果较吻合. 推断共晶体氢键的形成位置为尿素中的氨基H6和呋喃妥因上的酰胺基O30, 该处形成第一处氢键, 而呋喃妥因的酰胺基H31和尿素上的羰基O1形成第二处氢键. 同时结合理论模拟结果对呋喃妥因和尿素共晶体分子振动模式进行归属.     

20种α-氨基酸的太赫兹光谱及其分子结构的相关性

应用太赫兹时域光谱(THz-TDS)技术, 在室温下对构成蛋白质的20种基本氨基酸的多晶粉末压片样品进行了光谱测试分析. 结果表明, 所有氨基酸对THz波反应非常灵敏, 在0.2-3.0 THz的有效频谱范围内, 表现出各自特征吸收峰, 故而利用THz光谱可以有效地区别不同种类的氨基酸. 我们以新数据验证和补充了前人的研究结果, 建立了以氨基酸分子结构及其THz光谱特征为基础的分类方案, 讨论并揭示了氨基酸分子的结构差异与其THz吸收光谱之间的相关性. 认知这些相关性将有助于鉴定氨基酸分子, 促进THz光谱学的理论研究以及在生物医学领域的推广应用.     

百菌清晶体太赫兹光谱理论模拟分析

本研究从实验和理论分析两方面探讨了杀菌剂百菌清固体在0.4～3.0 THz的光谱特性。利用太赫兹时域光谱技术(THz-TDS)获得了在这一频谱范围内百菌清固体分子的折射率谱和吸收谱。为了更好地对实验吸收谱进行解析,克服单分子模拟缺陷,从晶体分子结构方面分析在0.4～3.0 THz波段百菌清分子结构变化和振动吸收谱,对百菌清THz实验吸收谱进行了指认,并分析了百菌清固体分子特征吸收峰产生机理。研究表明,晶体结构理论模拟弥补了单分子模拟的缺陷,完成了对11处所有实验特征吸收峰的验证。实验谱主要由分子之间Cl—C—C,N—C—C键相互作用和晶胞内分子的集体振动产生。     

Electrohydrodynamic ionization mass spectrometry of sulfonates

Electrohydrodynamic ionization mass spectrometry has been applied to the analysis of 2-naphthol-3,6-disulfonic acid, disodium salt and 4,5-dihydroxy-2,7-naphthalenedisulfonic acid, disodium salt. The negative ion mass spectra indicate ions characteristic of the sample and no fragment ions are observed. Degrees of dissociation of the sulfonates and the ion-solvent interactions are reflected in the negative ion spectra.     

A pulse radiolysis study on electron affinity of piperonal

Many processes in organisms are involved in elec-tron transfer reaction, and radioactive effect, preven-tion and sensitization of radioactive injury are in-volved in it too. There exists a quantitative relation-ship between one-electron reduction potentia…     

Silver(I) coordination polymer based on anthraquinone-2,6-disulfonate: synthesis,crystal structure,and luminescent properties

Self-assembly of anthraquinone-2,6-disulfonic acid disodium salt (Na₂a-2,6-dad) and AgNO₃ under hydrothermal conditions resulted in an unprecedented coordination complex, which was characterized by single-crystal X-ray analyses, elemental analyses, IR spectra, TG analyses, and fluorescence investigations. Complex 1 is a 3-D coordination polymer, where a-2,6-dad and Ag–Ag bonds play vital roles. Two sulfonate groups of a-2,6-dad are μ ₄- and μ ₅-bridges. The unique packing environments of the Ag ions and Ag–Ag bonds lead to 1-D chains consisting of eight- and four-membered rings for Ag1 and Ag1, Ag2 and Ag2 connection, respectively.     

Synthesis and characterization of new azo-linked Schiff bases and their cobalt(II), copper(II) and nickel(II) complexes

Azo compounds were prepared by the reaction between benzenediazonium chloride and 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid monosodium salt under alkaline conditions. Two new azo-linked Schiff base ligands, 4-(3-methoxysalicylidene)-5-hydroxy-6-(2-hydroxyphenylazo)-2,7-naphthalene disulfonic acid disodium salt (H₂L) and 4-(3-methoxysalicylidene)-5-hydroxy-6-(2-hydroxy-4-cholorophenylazo)-2,7-naphthalenedisulfonic acid disodium salt (H₂L¹), have been synthesized. Also, the new Cu^II, Ni^II and Co^II complexes of the azo-linked Schiff base ligands were prepared and characterized by infrared spectra, UV–Vis, ¹H- and ¹³C-n.m.r., attached proton test (APT) and distortionless enhancement by polarization transfer (DEPT) and atomic absorption spectroscopy, mass spectrocopy, elemental analyses, thermogravimetric analysis, conductivity and magnetic measurements. It was determined that the synthesized ligands were comprised of six-membered rings due to intramolecular hydrogen bonding. The results suggested that condensation of the azo-derivative compounds and o-vanillin in a 1:1 molar ratio produces mononuclear Schiff base ligands with an ONO donor set. Preliminary histological studies were made. Magnetic moment studies showed that all complexes have a tetrahedral configuration.     

桥环二茂钛族金属衍生物的研究: (苯二亚甲基)-双(η^5-环戊二烯基)钛、锆衍生物的合成和光谱

本文报导了(苯基二亚甲基)双环戊二烯配体合成了新型的桥环(邻、间、对苯基二亚甲基)双(η^5-环戊二烯基)二氯化钛、锆衍生物并用这种配体高产率地合成了双钛化合物。     

Laser photolysis of interaction of poly-guanylic acid (5'''') with anthraquinone-2-sulfonate

The electron transfer reaction between triplet anthraquinone-2-sulfonate and poly-guanylic acid (5') in CH3CN-H2O (97 : 3) has been investigated by 248 nm (KrF) laser flash photolysis. The transient absorption spectra and kinetics obtained from the interaction of triplet anthraquinone-2-sulfonate and poly[G] demonstrate that the primary ionic radical pair, radical cation of poly[G] and radical anion of anthraquinone-2-sulfonate have been detected simultaneously. The free energy changes in the process of the electron transfer were also calculated.     

桥环二茂钛、锆、铁金属衍生物的研究

本文用β,β'-双环戊二烯基乙醚二钠与TiCl4, ZrCl4, (C5H5)TiCl3和FeCl2在四氢呋喃中反应合成了新型氧桥环戊二烯基钛、锆和铁衍生物。在企图合成硫桥环戊二烯基化合物时, 得到的却是四亚甲基桥联双环戊二烯基金属衍生物。(苯二亚甲基)双环戊二烯基二钠与FeCl2反应合成了对、间(苯二亚甲基)二茂铁。讨论了新化合物的X射线光电子能谱和Mossbauer谱。     

Thermal behavior of iminodiacetic acid and its disodium salt

The thermal properties of iminodiacetic acid (IDA) and its disodium salt were investigated by DTA, TG and static heating. The gaseous evolved products were analysed by chromatography in order to follow the thermal process. The heating of the samples was stopped at characteristic decomposition steps and the residual substances were investigated by IR spectroscopy. The obtained data suggest the processes of decomposition for these compounds.     

Laser photolysis of interaction of poly-guanylic acid (5′) with anthraquinone-2-sulfonate

The electron transfer reaction between triplet anthraquinone-2-sulfonate and poly- guanylic acid (5′) in CH3CN-H2O (97:3) has been investigated by 248 nm (KrF) laser flash photolysis. The transient absorption spectra and kinetics obtained from the interaction of triplet anthraquinone-2-sulfonate and poly[G] demonstrate that the primary ionic radical pair, radical cation of poly[G] and radical anion of anthraquinone-2-sulfonate have been detected simultaneously. The free energy changes in the process of the electron transfer were also calculated.