含咔唑与偶氮分散红共聚物的表面增强共振拉曼光谱研究

借助于表面增强共振拉曼光谱散射(SERRS)技术,研究了一种新型的偶氮聚合物材料侧链含咔唑与偶氮分散红共聚物(CAP)在化学沉积法制备的银膜表面的拉曼峰增强和吸附行为。实验结果显示,CAP在银表面的状态为: 聚合物通过咔唑单体中咔唑基团和偶氮单体中硝基与银膜衬底发生物理吸附,而聚合物的主链与衬底相距较远没有相互作用。可以推测,聚合物在衬底表面的这种状态将对偶氮光存储器件的稳定性和工作效率产生不良影响。     

Electronic and Resonance Raman Spectra of a Multibridged Iron Porphyrin

Abstract

Reported are the electronic and resonance Raman (rR) spectra of a multibridged iron porphyrin derived from meso-tetra(4-pyridil)porphynate iron(II) by complexing the pyridine residues with [Ru^II(edta)]^2- ions. The polymetallated system exhibits the characteristic Soret band at 428 nm (log ε = 5.2) and a shoulder around 465 nm (4.6). The rR enhancement of the porphyrin vibrational modes is similar to those previously reported for typical porphyrins; however, an additional feature appears around 465 nm, associated with the selective enhancement of some pyridine vibrational modes. Based on the rR excitation profiles the absorption band at 465 nm was assigned to a Ru^II-to-pyridine dπ→Pπ? charge-transfer transition.     

共振拉曼效应和电子-声子耦合对线性多烯分子共振拉曼光谱的影响

线性多烯分子具有高强度且信息丰富的共振拉曼光谱,在生物学、光电材料和医学等方面都有一定应用.而含有共轭双键的短链β胡萝卜素分子是多烯分子中极具有代表性的分子.在激发光作用下π电子与CC键振动相互作用影响着吸收光谱和拉曼光谱,而共振拉曼效应和电子-声子耦合影响着共振拉曼光谱的强度、频率和线型.测量了β胡罗卜素分子在二氯乙...     

Distinguishing co‐existing unimolecular and bimolecular structural forms using joint analysis of Raman and UV absorption data

Standard Raman measurements of solutions require relatively high concentration of dissolved species, which supports formation of intermolecular complexes. In case of simultaneous presence of unimolecular and bimolecular structural forms, it is often difficult or even impossible to discriminate between them by using only the Raman data. We present a possible and effective way how to combine temperature dependencies of Raman scattering and UV absorption in a joint thermodynamic analysis. This approach is based on a joint fit of the results of multivariate analysis (singular value decomposition) of individual Raman and UV absorption spectral sets to a thermodynamic model. Our case study on RNA oligonucleotides, which can form imperfect intermolecular duplexes or intramolecular hairpin structures, demonstrates that this approach allows to determine thermodynamic parameters of co‐existing unimolecular and bimolecular structural forms and to isolate their Raman spectra. Copyright © 2014 John Wiley & Sons, Ltd.     

液芯光纤共振拉曼光谱法检测水中生物分子研究

拉曼光谱是研究水中生物分子重要的有效方法之一,然而由于拉曼散射截面小,特别是水分子的电子激发态能级高,因此水中生物分子的拉曼光谱测量甚为困难。将液芯光纤技术和共振拉曼技术结合起来,可大幅度提高拉曼光谱强度。实验中用可以获得最大的共振拉曼光谱强度的514.5 nm Ar+离子激光激发,分别用石英和Teflon液芯光纤对水中β-胡萝卜素生物分子进行了痕量检测研究。结果表明应用石英液芯光纤和Teflon液芯光纤可分别检测浓度为10-7～10-9mol·L-1和10-9～10-10mol·L-1的β-胡萝卜素。     

Detection of Heme-Distortions in Ferri- and Ferrocyto-Chrome C by Resonance Raman Scattering

Abstract

We have measured the depolarization ratio and polarized intensities of the oxidation marker A_1g-Raman line at 1363 cm^?1 and 1375 cm^?1 in ferri- and ferrocytochrome c respectively. From these data we derive symmetry classified distortions of the heme group from its ideal D_4h-symmetry. In ferrocytochrome c these distortions are independent of the pH-value of the solution, indicating that the heme environment is stable with respect to pH. In ferricytochrome c we observe pH-dependent changes of the distortions, indicating the well known conformational change with pK = 9.05, where the methionine 80 ligand is replaced by lysine-79. The data indicate that in this conformation due to opening of the heme crevice the heme group has a higher effective symmetry.     

Re_3N的变温拉曼散射与高压同步辐射研究

本工作通过高压固相复分解反应(HPSSM)合成块体Re_3N。利用X射线粉末衍射(XRD)、扫描电子显微镜(SEM)和能量色散X射线分析(EDS)对高压样品进行结构表征与元素成分确定,结果表明利用HPSSM法合成的Re_3N具有较高的晶体质量。在77K到873K温度范围内利用拉曼散射研究Re_3N的晶格振动特性。基于三(四)声子耦合模型,研究Re_3N拉曼声子模频率的红移和拉曼峰的宽化现象,结果表明高温条件下Re_3N拉曼散射效应中三声子耦合过程占主导。高压同步辐射研究表明Re_3N具有很高的体弹模量(B0=417GPa),是一种潜在的超硬材料。     

Deep UV resonance Raman spectroscopic study on electron‐phonon coupling in hexagonal III‐nitride wide bandgap semiconductors

Electron–phonon coupling (EPC) is an important issue in semiconductor physics because of its significant influence on the optical and electrical properties of semiconductors. In this work, the EPC in wide bandgap semiconductors including hexagonal BN and AlN was studied by deep UV resonance Raman spectroscopy. Up to fourth‐order LO phonons are observed in the resonance Raman spectrum of hexagonal AlN. By contrast, only the prominent emission band near the band‐edge and the Raman band attributed to E_2g mode are detected for hexagonal BN with deep UV resonance excitation. The different behavior in resonant Raman scattering between the III‐nitrides reflects their large difference in EPC. The mechanism for EPC in hexagonal BN is the short‐range deformation interaction, while that in hexagonal AlN is mainly associated with the weak long‐range Fröhlich interaction. Copyright © 2016 John Wiley & Sons, Ltd.     

飞秒受激拉曼光谱线形:基于泵浦及探测脉冲光的共振条件研究

Resonance enhancement has been increasingly employed in the emergent femtosecond stimulated Raman spectroscopy (FSRS) to selectively monitor molecular structure and dynamics with improved spectral and temporal resolutions and signal-to-noise ratios. Such joint efforts by the technique-and application-oriented scientists and engineers have laid the foundation for exploiting the tunable FSRS methodology to investigate a great variety of photosensitive systems and elucidate the underlying functional mechanisms on molecular time scales. During spectral analysis, peak line shapes remain a major concern with an intricate dependence on resonance conditions. Here, we present a comprehensive study of line shapes by tuning the Raman pump wavelength from red to blue side of the ground-state absorption band of the fluorescent dye rhodamine 6G in solution. Distinct line shape patterns in Stokes and anti-Stokes FSRS as well as from the low to high-frequency modes highlight the competition between multiple third-order and higher-order nonlinear pathways, governed by different resonance conditions achieved by Raman pump and probe pulses. In particular, the resonance condition of probe wavelength is revealed to play an important role in generating circular line shape changes through oppositely phased dispersion via hot luminescence (HL) pathways. Meanwhile, on-resonance conditions of the Raman pump could promote excited-state vibrational modes which are broadened and red-shifted from the coincident ground-state vibrational modes, posing challenges for spectral analysis. Certain strategies in tuning the Raman pump and probe to characteristic regions across an electronic transition band are discussed to improve the FSRS usability and versatility as a powerful structural dynamics toolset to advance chemical, physical, materials, and biological sciences.     

阿特拉津与RNA作用的共振光散射光谱及其应用

研究了阿特拉津与yRNA作用的共振光散射光谱 (RLS)和电子吸收光谱特征。建立了利用小分子农药阿特拉津作为探针测定痕量RNA的方法。在pH 1 5 0的酸度条件下 ,阿特拉津 yRNA系统在 32 0nm处有一增强的共振光散射光谱峰 ,且增强的共振散射光强度与 yRNA的浓度呈线性关系。在实验确定的优化条件下 ,RLS强度与 yRNA浓度的线性范围为 0 6～ 5 0 μg·mL-1,线性方程为I =2 5 88+14 0 0c(yR NA ,μg·mL-1) ,相关系数r =0 9975。方法的检出限为 2 0 7ng·mL-1(3δ)。该方法成功地用于人工混合样品和小盐芥中RNA含量的测定。对阿特拉津与RNA作用机制的研究表明 ,阿特拉津与RNA之间存在静电引力和嵌入式两种作用模式     

对硝基苯甲酸在水溶液和银胶中的紫外拉曼光谱(英文)

本文给出了紫外激发下的PNBA水溶液的拉曼光谱图,并对图中峰位做了相应的归属认证。本文还报道了PNBA在银胶中的表面非增强拉曼散射现象,并分析了导致该现象可能的原因     

紫金山金铜矿明矾石的拉曼光谱特征

紫金山金铜矿是我国大陆首例高硫化型浅成低温热液型矿床。矿床上金下铜,金矿主要赋存在潜水面以上,与强硅化有关;铜矿主要赋存于潜水面之下,与明矾石化有关。明矾石有四种产出状态,分别为蚀变岩型、与铜硫化物共生型、后期脉状、粉末状。不同产出状态的明矾石具有不同的拉曼光谱特征和荧光散射背景。明矾石流体包裹体激光拉曼谱图显示：(1)从蚀变岩型、与铜硫矿化物共生型到后期脉状明矾石均具有明矾石特征性的谱带,只是受荧光散射影响逐渐减弱;粉末状明矾石具有与前三者不同的谱带特性,各谱带强度均较弱,荧光散射较强烈。(2)100～700 cm-1区间谱带可作为明矾石分子结构中阳离子类质同象置换的“指纹谱带”。蚀变岩型明矾石,161和234 cm-1峰变化明显,具有较广泛的Na对K的类质同象置换;与铜硫化物共生的明矾石,381和484 cm-1峰变化明显,指示Cu和Ga等阳离子对Al离子的类质同象置换;后期脉状明矾石,161, 234,484,508 cm-1峰值均比较稳定,Na对K和Si对Al的类质同象置换较少;潜水面附近的粉末状明矾石因荧光散射强烈,各个谱带强度均较弱。(3)明矾石的激光拉曼光谱和红外光谱配合使用,可为明矾石矿物研究提供完整的分子振动光谱特征,为明矾石的成因提供结构信息。在岩相学、矿相学、矿床地质、矿床地球化学、区域地质特征研究的基础上,通过明矾石的激光拉曼光谱(结合荧光散射背景)可进一步为紫金山金铜矿这个典型的高硫化型浅成低温热液矿床的形成机制提供演化进程信息。     

Visible,near‐infrared,and ultraviolet laser‐excited Raman spectroscopy of the monocytes/macrophages (U937) cells

Raman spectra of the monocytes were recorded with laser excitation at 532, 785, 830, and 244 nm. The measurements of the Raman spectra of monocytes excited with visible, near‐infrared (NIR), and ultraviolet (UV) lasers lad to the following conclusions. (1) The Raman peak pattern of the monocytes can be easily distinguished from those of HeLa and yeast cells; (2) Positions of the Raman peaks of the dried cell are in coincidence with those of the monocytes in a culture cell media. However, the relative intensities of the peaks are changed: the peak centered around 1045 cm⁻¹ is strongly intensified. (3) Raman spectra of the dead monocytes are similar to those of living cells with only one exception: the Raman peak centered around 1004 cm⁻¹ associated with breathing mode of phenylalanine is strongly intensified. The Raman spectra of monocytes excited with 244‐nm UV laser were measured on cells in a cell culture medium. A peak centered at 1485 cm⁻¹ dominates the UV Raman spectra of monocytes. The ratio I₁₅₇₄/I₁₆₁₃ for monocytes is found to be around 0.71. This number reflects the ratio between proteins and DNA content inside a cell and it is found to be twice as high as that of E. coli and 5 times as high as that of gram‐positive bacteria. Copyright © 2009 John Wiley & Sons, Ltd.     

钢大气腐蚀锈层的红外、拉曼光谱研究

运用红外光谱、拉曼光谱分析的方法,对碳钢A₃和低合金钢10CrMoAl经青岛大气腐蚀的锈层样品,进行了比较测试,综合分析得出锈层中主要组成物相为α-Fe₂O₃,γ-FeOOH, α-FeOOH, δ-FeOOH,Fe₃O₄,以及各组成物相相对含量随腐蚀时间的变化情况。     

Electronic and Resonance Raman Spectra of the Hexanuclear Cluster [Ru30(02CCH3)6 {(pyrazine)Ru(NH3)5}3 6+

Abstract

The trinuclear [Ru³0(00CCH³)⁶, (pyrazine)³] cluster reacts with pentaammineruthenium(II) ions, yielding a hexanuclear pyrazine bridged complex. The hexanuclear cluster exhibits a broad absorption band around 1000 nm and a strong band at 533 nm, ascribed to metal-metal and metal-pyrazine charge transfer transitions, respectively. Excitation at the visible band leads to the enhancement of the totally symmetric vibrational modes of pyrazine at 1605, 1230, 1085 and 700 cm?¹, and of a vibrational peak at 335 cm?¹, ascribed to the Ru(peripheral)-N(pyrazine) stretching mode. The spectroscopic data are consistent with a weak coupling between the central and peripheral ruthenium ions.     

硅波导受激喇曼散射放大信号光的数值模拟

提出了用连续泵浦光在硅波导中的受激喇曼散射对信号光进行放大的方法.建立了信号光和泵浦光在硅波导中传输的耦合方程,得到了计算信号光增益的理论模型.利用数值模拟结果,对泵浦功率沿波导的分布,信号光在不同波导长度以及输入功率情况下的增益等进行了分析和讨论.结果表明,适当增加波导长度和泵浦光功率可以得到较高喇曼增益的结论.     

共振光散射法研究甲萘威与DNA的作用及其应用

通过共振光散射光谱(RLS)和电子吸收光谱的特征,探求了甲萘威与ctDNA的结合方式,实验表明在pH 1.97的条件下,甲萘威与ctDNA既有表面聚集又有嵌入式结合的双重作用,结合形式与二者之间的浓度比有关。在此条件下,甲萘威与ctDNA作用的RLS强度与ctDNA的浓度呈线性关系,据此建立了一种简单快速测定ctDNA的新方法。ctDNA的浓度在0.02～3 μg·mL-1的范围内与RLS强度呈良好的线性关系,线性方程为I= 200.77c(μg·mL-1)+118.91,相关系数r=0.998 9。该方法已成功地用于人工混合样品的测定。     

Investigation of Photoinduced Processes in Water-Soluble Cationic Ni-Porphyrin by the Resonance Raman Scattering Method

By the resonance Raman scattering spectroscopy (RRS) method, photoinduced processes involving cationic Ni-5,10,15,20-tetrakis(4-N-methylapyridiniumyl)porphyrin (Ni(TMpy-P4)) in a phosphate water buffer have been investigated. Excitation into different regions of the Soret band at wavelengths of 397, 423, 441.6, and 457.9 nm permitted separate investigation of the behavior of the 4- and 6-coordinated forms of Ni(TMpy-P4). It has been found that Ni(TMpy-P4) is characterized by two photoinduced processes: the deactivation of initially 4-coordinated Ni(TMpy-P4) is followed by the addition to it, as axial ligands, of two water molecules from the environment to form a nonequilibrium 6-coordinated form Ni(TMpy-P4)(H₂O)₂ in the ground state, whereas in the process of deactivation of the excited 6-coordinated complex there occurs a dissociation of the axial water ligands to form a nonequilibrium 4-coordinated complex Ni(TMpy-P4) in the ground state. Some of the 4-coordinated molecules of Ni(TMpy-P4) are deactivated through the excited B _1g ^*-state without undergoing extracoordination. Quantitative analysis of the RRS spectra using the global fitting method has shown that in the course of deactivation 33% of photoexcited 6-coordinated molecules of Ni(TMpy-P4)(H₂O)₂ retain their axial ligands, relaxing through the dark long-lived intermediate state of the 6-coordinated form.     

表面增强拉曼光谱和电化学方法研究中性条件下咪唑对镍电极的缓蚀作用

利用表面增强拉曼光谱技术(SERS)研究了咪唑在镍电极表面的吸附机理和吸附方式,并分别比较了镍电极在加入咪唑前后溶液中的循环伏安曲线和极化曲线,计算了其缓蚀效率。结果表明,在镍电极表面,咪唑起到了较好的缓蚀效果;在研究电位区间内所得的SERS谱图中,面内振动峰占据了主导地位,咪唑是以垂直略带倾斜的方式吸附在镍电极表面的;而N—H面内弯曲振动峰(1 173 cm-1)的出现和pH值接近中性的研究体系证明了咪唑是以中性咪唑分子的形式存在;低波数区N—Ni伸缩振动峰(214 cm-1)的出现进一步验证了咪唑通过N原子与镍电极表面略带倾斜的吸附方式。     

紫外拉曼光谱研究钇掺杂的氧化锆体系表面相变

本文用紫外拉曼 ,近可见拉曼光谱和XRD检测了不同焙烧温度下Y2 O3-ZrO2 的相变过程。紫外拉曼光谱对样品表面相变极其灵敏 ,而近可见拉曼光谱和XRD提供的主要是体相和表面的混合信息。在紫外拉曼谱图中 ,只观察到单斜相的谱峰 ,没有明显的四方晶相的信号 ,这表明样品的表面主要是单斜晶相。然而 ,XRD和近可见拉曼光谱的结果显示Y2 O3-ZrO2 体相是四方晶相。焙烧温度超过 40 0°时 ,紫外拉曼 ,近可见拉曼和XRD晶之间明显不同的结果表明Y2 O3-ZrO2 在表面区四方相很易转变为单斜相 ,体相中的四方相由于钇的添加而稳定存在。根据紫外拉曼和XRD结果 ,当升高温度时 ,在样品的表面形成一单斜相层 ,体相钇稳定的四方相 ,且由于Y2 O3的存在抑制了单斜相进一步向体相发展。