表面增强拉曼光谱研究硫脲衍生物与ClO_4~-的共吸附行为

表面增强拉曼光谱研究硫脲衍生物与ＣｌＯ－４的共吸附行为顾仁敖１姚建林１袁亚仙１钟起玲２田中群３（１苏州大学化学系苏州２１５００６）（２江西师范化学系南昌３３００２７）（３厦门大学固体表面物理化学国家重点实验室，化学系厦门３６１００５）Ｓｕｒｆａｃｅ...     

硅刻蚀的现场拉曼光谱研究

硅刻蚀的现场拉曼光谱研究刘峰名任斌汤儆田中群（厦门大学固体表面物理化学国家重点实验室，化学系，物理化学研究所厦门３６１００５）ＩｎＳｉｔｕＲａｍａｎＳｐｅｃｔｒｏｓｃｏｐｙｉｃＳｔｕｄｙｏｆＳｉｌｉｃｏｎＥｔｃｈｉｎｇｉｎＨＦＳｏｌｕｔｉｏｎｓＦ．...     

付立叶变换拉曼光谱研究液晶分子结构

付立叶变换拉曼光谱研究液晶分子结构姜世梅吴英徐蔚青李伯符（吉林大学国家教委超分子结构与谱学开放实验室长春１３００２３）田颜清赵英英汤心颐（吉林大学化学系长春１３００２３）ＦＴ┐ＲａｍａｎＳｐｅｃｔｒｏｓｃｏｐｉｃＳｔｕｄｉｅｓｏｎｔｈｅＭｏｌｅｃｕｌ...     

镍电极上表面拉曼光谱研究的新进展

镍电极上表面拉曼光谱研究的新进展黄群健黄开启田中群（厦门大学化学系固体表面物理化学国家重点实验室物理化学研究所厦门３６１００５）ＡＮｅｗＰｒｏｇｒｅｓｓｏｆＳｕｒｆａｃｅＲａｍａｎＳｐｅｃｔｒｏｓｃｏｐｉｃＳｔｕｄｉｅｓｏｎＮｉｃｋｅｌＥｌｅｃｔｒ...     

硫脲在硝酸介质中的拉曼光谱研究

硫脲在硝酸介质中的拉曼光谱研究钟起玲粟晓琼刘峰名＊田中群＊（江西师范大学化学系南昌３３００２７）（＊厦门大学固体表面物理化学国家重点实验室厦门３６１００５）ＲａｍａｎＳｐｅｃｔｒｏｓｃｏｐｉｃＳｔｕｄｉｅｓｏｆＴｈｉｏｕｒｅａｉｎＮｉｔｒｉｃＡｃｉ...     

GaN外延层的拉曼散射研究

ＧａＮ外延层的拉曼散射研究１李国华１韩和相１汪兆平２段树琨３王晓亮（１半导体超晶格国家重点实验室２集成光电子学国家重点联合实验室３半导体材料科学实验室中国科学院半导体研究所北京１０００８３）ＲａｍａｎＳｃａｔｅｒｉｎｇｏｆＧａＮＥｐｉｌａｙｅｒ１Ｌ...     

有机小分子在粗糙铂电极上表面拉曼光谱的初步研究

有机小分子在粗糙铂电极上表面拉曼光谱的初步研究李筱琴任斌佘春兴田中群（厦门大学固体表面物理化学国家重点实验室化学系物理化学研究所３６１００５）ＴｈｅＳｕｒｆａｃｅＲａｍａｎＳｐｅｃｔｒｏｓｃｏｐｉｃＳｔｕｄｙｏｆＳｍａｌＯｒｇａｎｉｎｃＭｏｌｅｃｕ...     

拉曼光谱测定散射介质的温度

本文发展了测量散射体温度的拉曼光谱方法,选用Ｓｒ（ＮＯ３）２粉晶做散射介质,观察到７３８ｃｍ＾－１,１０５７ｃｍ＾－１两个拉曼散射带,记录它们的Ｓｔｏｋｅｓ、Ａｎｔｉ－Ｓｔｏｋｅｓ分量的光谱强度,得到硝酸锶粉晶散射体的温度。实验结果显示,这种非接触光谱测温法具有重要的实用价值。     

第15届国际拉曼光谱会议的简介和体会

第１５届国际拉曼光谱会议的简介和体会田中群（厦门大学化学系固体表面物理化学国家重点实验室厦门３６１００５）一、会议概况：第１５届国际拉曼光谱会议（ＴｈｅＩｎｔｅｒｎａｔｉｏｎａｌＣｏｎｆｅｒｅｎｃｅｏｎＲａｍａｎＳｐｅｃｔｒｏｓｃｏｐｙ，ＴｈｅＸＶ...     

氢键诱导液晶的拉曼光谱研究

氢键诱导液晶的拉曼光谱研究徐蔚青赵冰姜世梅吴英陶艳春（吉林大学超分子结构与谱学开放实验室长春１３００２３）田颜青（吉林大学化学系长春１３００２３）ＲａｍａｎＳｐｅｃｔｒａｏｆＡＩｎｔｅｒｍｏｌｅｃｕｌａｒＨｙｄｒｏｇｅｎＢｏｎｄｉｎｇＬｉｑｕｉｄＣｒ...     

几种哌嗪类抗肿瘤化合物的拉曼光谱

几种哌嗪类抗肿瘤化合物的拉曼光谱刘社文１梁二军１李祥杰２（１郑州大学河南省激光应用技术重点实验室，２郑州大学化学化工学院，郑州４５００５２）ＲａｍａｎＳｐｅｃｔｒａｏｆＳｅｖｅｒａｌＡｎｔｉｔｕｍｏｒＰｉｐｅｒａｚｉｎｅｓＣｏｍｐｏｕｎｄｓＬｉｕＳｈ...     

SER(R)S of porphyrins on Ag nanoparticles immobilized by silane: a unique way to obtain free‐base porphyrin spectra

We measured the surface‐enhanced resonance Raman scattering (SER(R)S) spectra of 5,10,15,20‐tetrakis (1‐methyl‐4‐pyridyl)porphyrin (TMPyP) by using solid SERS‐active substrates: Ag nanoparticles immobilized by aminosilane on glass plates. We report the surprising result that by using such substrates it is possible to obtain SER(R)S spectra of porphyrins in the unperturbed free‐base form, although by using silver nanoparticles directly in solution, the porphyrin molecules are completely metalated. We suggest that silane used for nanoparticle immobilization modifies the surface properties and, therefore, makes porphyrin metalation impossible. Copyright © 2007 John Wiley & Sons, Ltd.     

Survival of molecular information under surfaced‐enhanced resonance Raman (SERRS) conditions

In the present paper, we discuss the molecular information that can be derived from surface‐enhanced resonance Raman Scattering (SERRS) experiments performed with different excitation wavenumbers, which are close to resonance with an excited electronic state of the molecule [surface‐enhanced Raman dispersion spectroscopy (SERADIS)]. We specifically consider the situation, where a molecule is physisorbed to a site characterized by a local electric field with a direction independent of the direction of the external, exciting field. The molecular information available in this experimental situation is compared with the information available in a corresponding Raman dispersion spectroscopy (RADIS) experiment performed on a free molecule or a molecule physisorbed to a site, where the local field is isotropic. The consequences for resonance Raman scattering (RRS) and RADIS, when the molecule is adsorbed in the highly anisotropic hot spot (HS), are discussed; here it is shown that only the molecular information originating from the symmetric part of the scattering tensor can survive in SERRS and in SERADIS. Besides, it is shown that the depolarization ratio can no longer be used to discriminate between totally and non‐totally symmetric modes in the polarized surface‐enhanced Raman scattering (SERS) spectra. These results have implications for the resonance Raman spectra, but even more important for the application of the resonance Raman effect in the investigation of excited vibronic molecular states, in general, and in the investigation of electronic states in larger bio‐molecules, such as the various metallo‐porphyrins. Copyright © 2009 John Wiley & Sons, Ltd.     

Raman and surface‐enhanced Raman spectra of flavone and several hydroxy derivatives

The Raman and surface‐enhanced Raman spectra (SERS) of flavone and three of its hydroxy derivatives, 3‐hydroxyflavone (3‐HF) and 5‐hydroxyflavone (5‐HF) and quercetin (3,5,7,3′,4′ pentahydroxyflavone) have been obtained. The normal Raman (NR) spectra were taken in the powder form. The SERS spectra were obtained both on Ag colloids and Ag electrode substrates. Assignments of the spectrally observed normal modes were aided by density functional theory (DFT) calculations using the B3LYP functional and the 6‐31 + G* basis, a split valence polarized basis set with diffuse functions. Excellent fits were obtained for the observed spectra with little or no scaling. The most intense lines of the NR spectra are those in the CO stretching region (near 1600 cm⁻¹). These lines are often weakened by proximity to the surface, while other lines at lower wavenumbers, due to in‐plane ring stretches, tend to be strongly enhanced. The SERS spectrum of flavone is weak both on the colloid and on the electrode, indicating weak attachment to the surface. In contrast, the SERS spectra of the hydroxy derivatives of flavone are intense, indicating the assistance of OH groups in attachment to the surface. The spectra of the various species are compared, and a case study of application to detection of a textile dye (Persian berries), which contains quercetin, is presented. Copyright © 2007 John Wiley & Sons, Ltd.     

The Utilization of Low Frequency Raman Spectra of Gases for the Study of Molecules with Large Amplitude Vibration

The utilization of the Raman spectra of the low frequency bending mode for three quasi-linear molecules: disiloxane,(SiH3)2O;methylisocyanate,CH3NCO;and dimethylisocyanate,(CH3)2SiHNCO for observing the low frequency anharmonic bending vibration is demonstrated which is superior to the corresponding far infrared spectra.From the observed frequencies from the Raman spectra the potential function governing the heavy atom motion to linearity has been obtained from which the barrier has been determined.These experimental values are compared to the ab initio predicted values.Also low frequency Raman spectra of the ring puckering vibration of chlorocyclobutane,c-C4H7Cl,bromocyclobutane,c-C4H7Br,and aminocyclobutane,c-C4H7NH2,have been utilized to obtain the potential function governing the ring inversion for these molecules.The determined barriers to planarity are compared to those obtained from MP2(full) ab initio and density functional theory B3LYP calculations by utilizing a variety of basis sets.For all of these studies it is shown that the Raman spectra are superior to the infrared spectra for determining the frequencies of the excited state transitions.     

Drop‐coating deposition Raman spectroscopy of porphyrins

We report an improvement of the Raman detection sensitivity of porphyrins by factor of 10⁵ using drop‐coating deposition Raman spectroscopy (DCDR). We were able to obtain Raman spectra from ~20 nM initial (deposited) concentrations of cationic and anionic porphyrin. This detection limit is comparable with or even better than that of surface‐enhanced Raman scattering spectroscopy using Ag nanoparticles. Moreover, DCDR spectrum of protoporphyrin IX, which is known as a marker in clinical diagnostics of cancer, was also obtained from 10 nM deposited concentration. To our knowledge, it is the first demonstration of the resonance DCDR spectroscopy. Copyright © 2015 John Wiley & Sons, Ltd.     

PS微球阵列的制备与表面增强拉曼散射研究

为了研究不同直径PS微球(表面溅射Ag膜)基底的表面增强拉曼散射(SERS)效应,制造了一个新的表面增强拉曼散射(SERS)基底。通过在n型(100)单晶硅片上采用旋涂的方法,得到不同直径的呈六角形有序排列的单层PS微球阵列,然后在PS微球阵列表面磁控溅射一层约30 nm的Ag膜。利用拉曼光谱仪以罗丹明R6G为探针进行了SERS光谱测定,分析比较了不同直径PS微球阵列的表面增强拉曼散射效应,结果表明,溅射有Ag膜的PS微球基底在不同直径下均有不同程度的SERS效应。随着微球直径的增加,PS微球阵列的起伏程度不断加强(粗糙度不断增加),SERS信号逐渐增强,当球直径达到600 nm时,峰的增强信号达到最大,进而获得了一个最优化的SERS基底。同时发现在基底上获得了高信噪比的R6G的SERS光谱, 与苯环相关的一系列CC双键伸缩振动特征谱以及与苯环相关的面内、面外变形振动特征谱均获得了明显增强。这种单一的大区域的拉曼散射基底,呈现出高低相间起伏分布的微观形貌,不同PS微球之间的空隙和深度有很明显的不同,能够显著改善表面Ag膜颗粒的大小和分布,进而提高了PS微球基底的SERS活性。该基底所具有的特殊阵列结构使其在利用SERS探究化学和生物等领域的单分子结构有很大的应用潜力。     

α-甘氨酸晶体中NH_3~+扭曲振动的变温拉曼光谱研究

1999年,Chilcott研究了α-甘氨酸单晶电阻抗随温度的变化,发现晶体在304 K开始导电。为了了解其导电机理,本文研究90 K到340 K的拉曼光谱,发现在α-甘氨酸单晶中NH3+扭曲振动模式分裂,表现为N-H(6)…O(1)(491 cm-1)和N-H(7)…O(2)(483 cm-1)模式,以及CO2-摇摆模式(503cm-1),在304 K均有不连续性变化,并与变温中子衍射晶体结构层内的氢键N-H(6)…O(1)键角和N-H(7)…O(2)长度出现转折点一致。由于α-甘氨酸晶胞中NH3+和CO2-基团构成的电偶极子在变温下重新定向,出现两性离子电荷重心变化致使晶体极化,引起晶体在304 K左右发生了铁电相变。     

The role of surface oxidation on luminescence degradation of porous silicon

This study reports a comparative analysis on time dependent degradation of photoluminescence (PL) spectra of porous silicon (PS) during dark-aging (DA) and photo-aging (PA). Fourier Transform Infrared (FTIR) spectroscopy studies have been performed to get an insight on possible chemical changes in the PS surface. It has been found that SiH_x bonds decrease progressively while SiO_x bonds increase. FTIR and PL measurements revealed presence of blue shifts in the PL spectra during the aging stages (PA and DA). While the PL intensity of dark aged PS shows a decrease during the first 3 weeks and an increase afterwards, the PL intensity decreases continuously for photo-aged PS. The change in the PL spectra has been investigated by overlapping of two different PL bands which are reflective of oxidation of PS surface and size of Si naonocrystallites. A possible bond configuration model about the oxidation of PS surface has also been proposed. The results are interpreted in terms of quantum size effects in PS and the influence of the surface composition.     

含硫双Schiff碱型配体的合成与表征

用桥联水杨醛OHC-C6H4O-R-OC6H4-CHO[R=-(CH2)2-，-(CH2)3-，-CH2CH2OCH2CH2-，-(CH2CH2O)2CH2CH2-]与肼基二硫代甲酸酯(H2NNH-CSSCH3)反应，合成了四个含硫双Sehiff碱，并进行了元素分析和IR,1HNMR、MS的表征，确定了其结构。