无定型氧化硅转变为α-方石英的振动光谱

红外和喇曼光谱是分子结构信息的重要来源,也是研究表面和催化问题的强有力手段,常用来表征活性中心及吸附物种的结构．为提高稳定性,催化剂一般都要经过焙烧处理,在焙烧过程中,载体结构可能会发生变化,有时还会形成一定的晶相．载体结构变化时,一般会伴随振动光谱的变化,因此在利用振动光谱研究催化体系时,弄清载体的振动光谱是十分必要的．二氧化硅是最常用的催化剂载体之一,但它具有比较多的结构形式,除无定型氧化硅中硅氧四面体可连接成不同的结构外,它还具有石英、鳞石英、方石英等多个晶相系列．对氧化硅的不同结构形式,…     

α-氨基酸在水-乙醇中羟基质子化热力学

α 氨基酸为重要的两性物质 ,其酸碱性质对于维持生物体内的酸碱平衡和蛋白质的生物活性起着十分重要的作用．α 氨基酸在纯水溶剂中的质子化反应热力学性质已进行了广泛的研究［１ -６］,但对球形蛋白来说 ,蛋白亚基间的作用是处在一个大量但不完全由水组成的非水环境中 ,因此 ,研究氨基酸在水 有机物混合溶剂中的质子化热力学性质具有重要意义．但这方面的工作 ,特别是用量热法直接研究溶剂对质子化焓变的影响开展得不多．本文选择乙醇和水组成的混合溶剂模拟蛋白质亚基所处的介质环境 ,利用精密微量流动热量计测定２９８．１５Ｋ时甘氨…     

α-氯丙酸乙酯对映体与β-环糊精的主客体相互作用

运用量子力学PM3方法模拟α-氯丙酸乙酯((R/S)-ECPA)与β-环糊(β-CD)的主客体相互作用, 探讨(R/S)-ECPA在β-CD上的手性识别机理. 结果表明, (R/S)-ECPA对映体与β-CD形成稳定结合物的结合方式完全不同, (R)-ECPA位于β-CD空腔宽口端, 形成缔合物; (S)-ECPA插入β-CD空腔内形成包结物. 而且, (S)-ECPA与β-CD的结合稳定能低于(R)-ECPA与β-CD的结合稳定能. 在(R/S)-ECPA与β-CD结合物中, (R/S)-ECPA中的手性碳接近葡萄糖单元的C2和C3. (R/S)-ECPA与β-CD之间的手性识别与葡萄糖单元的C2和C3所提供的手性环境和(R/S)-ECPA与β-CD结合的紧密程度密切相关.     

3-(2-吡啶基)-1,2,4-三唑衍生物的合成

1,2,4-三唑是五员含氮杂环化合物,其五员环上的三个N原子均可以同金属配位,因此它与金属离子的结合力很强,配位方式也很丰富,所构筑出来的配合物在生物、医药、磁性材料、手性催化剂、电致发光材料等方面都存在着诱人的应用前景,因而成为化学界和生物界的研究热点[1-4].     

氧化乐果的振动光谱及其表面增强拉曼散射研究

采用ATR-FTIR、FT-拉曼表征了氧化乐果在酸、碱、中性条件下的振动光谱,获得了氧化乐果分子较为全面的结构振动信息;以金/银核-壳粒子为基底,获得了不同浓度及其酸碱条件下氧化乐果的表面增强拉曼散射(SERS)光谱,考察了其分子在该基底表面的吸附状态及其酸碱影响,推测了氧化乐果的SERS机理;结果表明:νas(NH),νas(CH3),Amide Ⅰ,ν( POC ),ν( PO ),ν(C-S)为氧化乐果分子特征振动;中性条件下,氧化乐果浓度低于2.0×10-2 mol/L已无明显SERS,酸、碱条件下,在2.0×10-10 mol/L氧化乐果分子与基底的作用仍显著,尤其酸性的SERS更强;氧化乐果主要以磷酸酯结构与基底表面作用,探讨了酸碱条件下的不同水解历程对该作用的影响,为研究有机磷农药的形态变化提供了参考.     

α -羟基-α -氨甲酰基酰胺类化合物的合成新方法

N, N-二甲氨酰基三甲基硅烷与一系列α -羰基酰胺在无水无氧、105 ℃的条件下反应, 较高产率地合成了α -羟基-α -氨甲酰基酰胺类化合物或α -三甲基硅氧基-α -氨甲酰基酰胺衍生物。 其结构用元素分析、¹H NMR、¹³C NMR和IR等技术手段进行了表征。 通过研究反应机理和影响反应的因素发现, 在α -羰基上连的烃基的空间位阻是该加成反应的重要影响因素, 而电子效应则影响反应的速率。 提出了可能的反应机理。     

齐墩果酸的结构修饰和α-葡萄糖苷酶抑制活性

以天然五环三萜类化合物齐墩果酸为原料, 通过氧化、酯化、环合和曼尼希等反应, 对A环2, 3位和28位进行结构修饰, 设计合成了16个衍生物; 通过理化性质、质谱和核磁数据确定了化合物结构. 对合成的衍生物进行了体外α-葡萄糖苷酶抑制活性筛选, 结果表明, 受试化合物在200 μg/mL浓度下显示出不同程度的酶抑制活性. 初步构效关系分析表明, 28位游离羧基是活性必需基团, 3位羟基或相应的氢键供体取代基有利于提高活性.     

异烟酸在碱性溶液中金电极上的现场表面增强振动光谱研究

应用表面增强红外吸收光谱法、循环伏安法和微分电容法研究了0.1 mol•L^－1 KClO₄和0.1 mol•L^－1 KCl碱性化溶液(pH 10)中, 异烟酸(INA)在Au电极表面的吸附取向和结构. 结果表明: －0.5～0.2 V (vs. SCE)间INA阴离子(INA^－)通过其羧酸根上的两个氧原子垂直吸附在Au电极表面; 特性吸附Cl^－对上述吸附结构无实质影响. 进一步的表面增强拉曼光谱的测试表明即使在－0.8～－0.5 V, 极少量吸附的INA^－很可能仍维持上述基本构型.     

1-(2-氯-4-吡啶基)-3-苯基脲的合成

氯氨基吡啶;氯吡啶基苯基脲;1-(2-氯-4-吡啶基)-3-苯基脲的合成     

α-氨基酸在丁酸钠水溶液中的体积性质(308.15K)

盐溶液对蛋白质的结构和性质（例如蛋白质的溶解度、变性、解离为次级结构以及酶的活性’‘’等）有很大的影响．由于蛋白质是一个结构复杂的大分子,直接研究它与电解质的相互作用比较困难．因而,对蛋白质的模型化合物氨基酸和肽的研究具有重要的意义．关于氨基酸在氯化钙、碱金属卤化物（LICI,NaCI,KCI,CsCI,KBr,KI）、硫氨酸钾和氯化控水溶液中的体积性质已有文献报导’‘－”．丁酸钠是一种有机盐,丁酸根离子具有疏水的丙基和亲水的核基,因而它对氨基酸的作用与简单阴离子的作用可能会有所不同．另外,丁酸钠在水溶液中…     

pH值对2-(2-吡啶基)咪唑荧光光谱的影响研究

合成了2-(2-吡啶基)咪唑,并通过稳态荧光光谱研究了它在溶液中的光物理行为及溶液酸碱度的影响.发现2-(2-吡啶基)咪唑化合物存在分子内光诱导电子转移反应(PET),并且这一过程强烈地依赖于溶液的pH值,但是氮原子的质子化会影响PET过程.     

Temporal Response of SERS to the Potential for 4-Cyanopyridine Adsorbed on Ag Electrode

Time-resolved surface-enhanced Raman scattering (SERS) was applied to study the response of Raman bands from 4-cyanopyridine (PyCN) adsorbed on a Ag electrode to variation of the potential; the temporal resolution was 0.1 s. The response of the SERS signals of PyCN was instantaneous to the oxidation potential of Ag electrode. However, delay of the SERS signals was observed while AgCl was reducing. The decay and growth of the SERS bands look place within 1 s in the cases of desorption and adsorption of PyCN on the electrode. It took much longer for PyCN to alter from one adsorption geometry to another on the electrode.     

基于拉曼光谱的细菌检测研究进展

细菌是一种与人类生命活动息息相关的微生物,其快速、高灵敏检测对重大传染性疾病的防控至关重要.本文介绍了拉曼光谱用于细菌检测的基本原理,综述了3种拉曼光谱用于细菌检测的主要方式,包括细菌组成成分检测、细菌代谢物检测以及基于拉曼探针标记的检测模式,并对各种拉曼检测方法进行了分析比较.最后,展望了拉曼光谱在细菌检测领域的发展前景,并提出了5条建议.     

Reinterpretation of Dynamic Vibrational Spectroscopy to Determine the Molecular Structure and Dynamics of Ferrocene

Molecular distortion of dynamic molecules gives a clear signature in the vibrational spectra, which can be modeled to give estimates of the energy barrier and the sensitivity of the frequencies of the vibrational modes to the reaction coordinate. The reaction coordinate method (RCM) utilizes ab initio‐calculated spectra of the molecule in its ground and transition states together with their relative energies to predict the temperature dependence of the vibrational spectra. DFT‐calculated spectra of the eclipsed (D_5h) and staggered (D_5d) forms of ferrocene (Fc), and its deuterated analogue, within RCM explain the IR spectra of Fc in gas (350 K), solution (300 K), solid solution (7–300 K), and solid (7–300 K) states. In each case the D_5h rotamer is lowest in energy but with the barrier to interconversion between rotamers higher for solution‐phase samples (ca. 6 kJ mol^?1) than for the gas‐phase species (1–3 kJ mol^?1). The generality of the approach is demonstrated with application to tricarbonyl(η⁴‐norbornadiene)iron(0), Fe(NBD)(CO)₃. The temperature‐dependent coalescence of the ν(CO) bands of Fe(NBD)(CO)₃ is well explained by the RCM without recourse to NMR‐like rapid exchange. The RCM establishes a clear link between the calculated ground and transition states of dynamic molecules and the temperature‐dependence of their vibrational spectra.     

表面增强拉曼光谱研究吸附态的变化

测量了吡啶分子在电化学处理的银表面和亚甲基蓝分子在硝酸刻蚀银表面的表面增强拉曼光谱（ＳＥＲＳ）．对ＳＥＲＳ谱线的分析结果表明，吡啶分子在较低的表面吸附分子密度时倾向于平躺方式；而在较高的表面分子密度时，则倾向于向垂直吸附态转化．亚甲基蓝分子在较低浓度时主要是平躺吸附，随Ｃｌ－浓度的增加，亚甲基蓝从“平躺”吸附态转向“站立”吸附态．     

碘化银胶体上四苯基卟啉金属配合物的表面增强拉曼光谱研究

研究了四苯基卟啉金属配合物（MTPP,M=Ag,Mg,Cu,Pd）在AgI胶体上的表面增强拉曼光谱（SERS）。结果显示MgTPP与基底发生金属交换生成AgTPP,而在PdTPP和CuTPP上则未发现金属交换。除卟啉环的振动外,一些苯环振动带也被显著增强。在1400～1600cm-1范围,PdTPP和CuTPP的SERS与AgTPP有很大差别,可能反映了吸附分子在次甲基桥碳原子Cm附近立体构型的差异。     

Vibrational Spectroscopy in Supercritical Fluids: From Analysis and Hydrogen Bonding to Polymers and Synthesis

Supercritical fluids are beginning to be used widely in chemistry. Applications range from extraction and chromatography in analytical chemistry to solvents for reaction chemistry and preparation of new materials. Spectroscopic monitoring is important in much of supercritical chemistry, and vibrational spectroscopy is particularly useful in this context because the vibrational spectrum of a given molecule is usually quite sensitive to the environment of that molecule. Thus, vibrational spectra are excellent probes of conditions within the fluid. In this review, we describe a variety of techniques and cells for IR and Raman spectroscopy in supercritical fluids and illustrate the breadth of applications in supercritical fluids. The examples include: the use of supercritical Xe as a spectroscopically transparent solvent for chemistry and for supercritical fluid chromatography with FTIR detection of analytes; Raman spectroscopy as a monitor for gases dissolved in supercritical CO₂; the effect of solvent density on hydrogen bonding in supercritical fluids and the formation of reverse micelles; IR as a monitor for the supercritical impregnation/extraction of polymers and the reactions of organometallic compounds impreganated into polymers; reactions of organometallic compounds in supercritical fluids; and finally, the use of miniature flow reactors for laboratory-scale preparative chemistry. Overall, our aim is to provide a starting point from which individual readers can judge whether such measurements might usefully be applied to their own particular problems.     

Ternary Alkali Metal Transition Metal Acetylides

The first alkali metal transition metal acetylides of general composition A₂M⁰C₂ (A = Na ? Cs, M⁰ = Pd, Pt) were obtained by solid state reactions of alkali metal acetylides with palladium and platinum. They are characterized by chains, which are separated by alkali metal ions. Analogous chains also separated by alkali metal ions are the characteristic structural feature of acetylides of composition AM^IC₂, which are accessible by reacting AC₂H with M^II in liquid ammonia (A = Li ? Cs, M^I = Cu, Ag, Au). Despite their structural similarities they possess different properties, as acetylides of composition A₂M⁰C₂ are semiconductors with very small indirect band gaps and slightly extended C–C distances compared to a C–C triple bond, whereas acetylides of composition AM^IC₂ show a typical salt‐like behavior with C–C distances close to the expected value for a C–C triple bond of 120 pm. But with the help of simple chemical models these differences can be made plausible. Furthermore, it is shown that only by a combination of different methods (powder diffraction with X‐rays and neutrons, solid state NMR spectroscopy, Raman spectroscopy) it was possible to characterize this new class of compounds structurally and chemically.     

Vibrational Spectroscopy of Ion Irradiated Carbon Containing Macromolecules

A large variety of carbon rich macromolecules has been studied in our laboratory, before, during, and after ion irradiation (3-60 keV ions), by in situ IR and Raman spectroscopies. In this paper we present results obtained on: (a) Films of frozen H₂O:CH₄:N₂ mixtures that have been deposited at low temperature (12 K) on a silicon substrate, and irradiated with fast ions. Irradiation causes the formation of organic refractory residues whose spectra have been recorded and studied also after further irradiation at room temperature. (b) Pentacene (a Polyciclic Aromatic Hydrocarbon, PAH) whose Raman spectra have been studied also during ion irradiation at room temperature. (c) Thin samples of fullerene (C₆₀) films also irradiated at room temperature. Here we discuss some of the most relevant results and compare the spectra of the very different samples that after prolonged irradiation, evolve towards amorphous carbons that have common spectral characteristic. The results are discussed in terms of their astrophysical relevance. It is demonstrated that frozen hydrocarbons, PAHs and fullerenes are rapidly converted to amorphous carbon in space. Amorphous carbon has to be a widespread material in many astrophysical environments.