Surface-enhanced resonance Raman scattering spectroscopy of single R6G molecules

Surface-enhanced resonance Raman scattering (SERRS) of Rhodamine 6G (R6G) adsorbed on colloidal silver clusters has been studied. Based on the great enhancement of the Raman signal and the quench of the fluorescence, the SERRS spectra of R6G were recorded for the samples of dye colloidal solution with different concentrations. Spectral inhomogeneity behaviours from single molecules in the dried sample films were observed with complementary evidences, such as spectral polarization, spectral diffusion, intensity fluctuation of vibrational lines and even ``breathing' of the molecules. Sequential spectra observed from a liquid sample with an average of 0.3 dye molecules in the probed volume exhibited the expected Poisson distribution for actually measuring 0, 1 or 2 molecules. Difference between the SERRS spectra of R6G excited by linearly and circularly polarized light were experimentally measured.     

钠分子的共振喇曼散射

本文用80mW6238.2(?)的He-Ne激光激发钠蒸气,用一种新颖的棱镜反射光路,从后向首次观察到了56O0～8200(?)钠分子的共振喇曼谱.     

Double resonance Raman effects in InN nanowires

We study the excitation wavelength dependence of the Raman spectra of InN nanowires. The $ E_1 ({\rm LO})$ phonon mode, which is detected in backscattering configuration because of light entering through lateral faces, exhibits an upward fre‐ quency shift that can be explained by Martin's double resonance. The $ E_1 ({\rm LO})$ /$ E_2^h $ intensity ratio increases with the excitation wavelength more rapidly than the $A_1 ({\rm LO})/E_2^h $ ratio measured in InN thin films. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Aluminium nanohole arrays enhanced resonance Raman scattering spectra in the near ultraviolet region

Aluminium nanohole arrays with fixed diameter were fabricated by focused ion beam and the periodicities were turned.Aluminium nanohole arrays enhanced resonance Raman scattering spectra in the near ultraviolet region were studied experimentally and theoretically,which revealed that the SERRS enhancement factor was as high as 6 orders.     

Pressure-tuned resonance Raman scattering and photoluminescence studies on MBE grown bulk GaAs at theE 0 gap

Hydrostatic pressure has been used to tune in resonance Raman scattering (RRS) in bulk GaAs. Using a diamond anvil cell, both the photoluminescence peak (PL) and the 2 LO and LO-phonon Raman scattered intensities have been monitored, to establish RRS conditions. When theE ₀ gap of GaAs matchesħω _S orħω _L, the 2 LO and LO-phonon intensity, respectively, exhibit resonance Raman scattering maxima, at pressures determined byħω _L. With 647.1 nm radiation (ħω _L = 1.916 eV), a sharp and narrow resonance peak at 3.75 GPa is observed for the 2 LO-phonon. At this pressure the 2 LO-phonon goes through its maximum intensity, and falls right on top of the PL peak, revealing thatħω _S(2 LO) =E ₀. This is the condition for “outgoing” resonance. Experiments with other excitation energies (ħω _L) show, that the 2 LO resonance peak-pressure moves to higher pressure with increasingħω _L, and the shift follows precisely theE ₀ gap. Thus, the 2 LO RRS is an excellent probe to follow theE ₀ gap, far beyond the Γ-X cross-over point. A brief discussion of the theoretical expression for resonance Raman cross section is given, and from this the possibility of a double resonance condition for the observed 2 LO resonance is suggested. The LO-phonon resonance occurs at a pressure whenħω _L ≈E ₀, but the pressure-induced transparency of the GaAs masks the true resonance profile.     

Residual benzamide contamination in synthetic oligonucleotides observed using UV resonance Raman spectroscopy

Spectroscopic methods based on Raman scattering have for many years employed synthetic oligonucleotides in a broad range of applications, either as probes or as model analytes for biophysical investigations. Benzamide is commonly used as a protecting group in the phosphoramidite synthesis of oligonucleotides and, while standard desalting used after synthesis yields sufficiently pure reagents for most assay reactions or other routine uses of the oligomer, it does not completely remove benzamide. We show that the 1609 cm⁻¹ band of residual benzamide contamination can interfere with certain nucleic acid bands, particularly when using excitation wavelengths near 244 nm where the benzamide band is strongly enhanced. For example, the 1609 cm⁻¹ band of benzamide could obscure (or be mistaken as) a weak vibration attributed to an  NH₂ scissoring. The extent of benzamide contamination in desalted preparations varies considerably among different commercial sources, and hence caution is advised when making direct comparisons of ultraviolet Raman data of oligonucleotides from different sources. Copyright © 2010 John Wiley & Sons, Ltd.     

Double resonance Raman scattering of second-order Raman modes from an individual graphite whisker

Resonant Raman scattering of second-order Raman modes from an individual graphite whisker synthesized by a high-temperature heat-treatment method at a special pressure was discussed here. The dependence of phonon frequencies on the incoming laser light and the frequency difference between Stokes and anti-Stokes scattering show their origin from double resonance Raman scattering. Our results show that all the experimental results of second-order Raman modes in graphite whiskers, such as the excitation-energy dependence on the mode frequency, the frequency shift between a second-order Raman mode and its fundamentals, and the frequency discrepancy between Stokes and anti-Stokes components of a second-order Raman mode can be well understood by double resonance Raman scattering.     

Single-site surface-enhanced Raman scattering beyond spectroscopy

Recent progress in the observation of surface-enhanced Raman scattering (SERS) is reviewed to examine the possibility of finding a novel route for the effective photoexcitation of materials. The importance of well-controlled SERS experiments on a single molecule at a single site is discussed based on the difference in the information obtained from ensemble SERS measurements using multiple active sites with an uncontrolled number of molecules. A single-molecule SERS observation performed at a mechanically controllable breaking junction with a simultaneous conductivity measurement provides clear evidence of the drastic changes both in the intensity and in the Raman mode selectivity of the electromagnetic field generated by localized surface plasmon resonance. Careful control of the field at a few-nanometer-wide gap of a metal nanodimer results in the modification of the selection rule of electronic excitation of an isolated single-walled carbon nanotube. The examples shown in this review suggest that a single-site SERS observation could be used as a novel tool to find, develop, and implement applications of plasmon-induced photoexcitation of materials.     

分子间费米共振增强二元溶液体系的受激拉曼散射研究

研究了液芯光纤内不同体积比的甲苯和间二甲苯二元混合溶液的受激拉曼散射.实验结果表明:在不同的体积比之下二元溶液的环呼吸振动模式1002 cm^-1,甲基的CH伸缩振动模式2920 cm^-1 以及芳香环CH对称伸缩振动模式3058 cm^-1的拉曼带同时产生受激拉曼辐射,并且2920 cm^-1 和 3058 cm^-1 拉曼带的一阶受激拉曼散射阈值要低于1002 cm^-1拉曼带的二阶 关键词： 分子间费米共振 二元溶液 受激拉曼散射 拉曼散射截面     

Raman scattering in annealed isotopic ( Ge) ( Ge) superlattices

Raman scattering by optical phonons is used to study the interface intermixing in isotopic ( Ge) ( Ge) thin superlattices, with and equal to 8, 12, 16 and 24 atomic monolayers, for annealling at C and various times. The experimental results compares very well with theoretical calculations within the planar force constant model and the bond polarizability approach. The diffusion is simulated by a combination of the virtual crystal approximation and the solution of the Fick’s diffusion equation for the superlattice geometry.     

Chemical aerosol detection and identification using Raman scattering

Early warning of the presence of chemical agent aerosols is an important component in the defense against such agents. A Raman spectrometer has been constructed for the purpose of detecting and identifying chemical aerosols. We report the detection and identification of a low‐concentration chemical aerosol in atmospheric air using 532‐nm continuous wave laser Raman scattering. We have demonstrated the Raman scattering detection and identification of an aerosol of isovanillin of mass concentration of 1.8 ng/cm³ with a signal‐to‐noise ratio of about 19 in 30 s for the 1116‐cm⁻¹ mode with a Raman cross section of 3.3 × 10⁻²⁸ cm² using 8‐W double‐pass laser power. Copyright © 2014 John Wiley & Sons, Ltd.     

Weak vibronic coupling in resonance Raman scattering: a unifying approach

Summary A unifying approach to the theory of Raman intensities including nonadiabatic coupling and vibronic coupling is presented and explicit equations of the resonant scattering tensor are obtained for weak vibronic coupling. Previous results reported in the literature are derived as special cases of the present treatment.

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Riassunto Si presenta un trattamento teorico delle intensità Raman comprendente sia l'accoppiamento non adiabatico che quello vibronico e si riportano le equazioni esplicite per il tensore di scattering risonante nel caso di accoppiamento vibronico debole. Vari risultati presentati in letteratura sono derivati come casi speciali di questo approccio unificante.

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Резюме Предлагается унифицировать подход к теоретическому описанию рамановских интенсивностей, включая неадиабатическую связь и колебательную связь. В случае слабой колебательной связи получаются точные уравнения для тензора резонансного рассеяния. Различные результаты опубликованные в литературе, получаются как частные случаи предложенного унифицированного подхода.

     

Near-infrared Raman spectroscopy using hollow-core photonic bandgap fibers

We report a NIR Raman spectroscopy system incorporating hollow-core photonic bandgap fibers (HC-PBFs) in both the excitation and collection paths. Raman excitation was achieved at NIR laser wavelength of 785 nm. We demonstrate that using HC-PBFs, Raman spectroscopy can be performed without the use of an additional longpass filter on the collection side. A narrow bandpass filter on the excitation side is also not required. These results provide a framework where HC-PBF based Raman probes can be developed and used in space restricted biomedical and sensing applications.     

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.     

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.     

Selective excitation of molecular mode in a mixture by femtosecond resonance-enhanced coherent anti-Stokes Raman scattering spectroscopy

Femtosecond time-resolved coherent anti-Stokes Raman scattering (CARS) spectroscopy is used to investigate gaseous molecular dynamics. Due to the spectrally broad laser pulses, usually poorly resolved spectra result from this broad spectroscopy. However, it can be demonstrated that by the electronic resonance enhancement optimization control a selective excitation of specific vibrational mode is possible. Using an electronically resonance-enhanced effect, iodine molecule specific CARS spectroscopy can be obtained from a mixture of iodine-air at room temperature and a pressure of 1 atm (corresponding to a saturation iodine vapour as low as about 35 Pa). The dynamics on either the electronically excited state or the ground state of iodine molecules obtained is consistent with previous studies (vacuum, heated and pure iodine) in the femtosecond time resolved CARS spectroscopy, showing that an effective method of suppressing the non-resonant CARS background and other interferences is demonstrated.     

Inhibition and Promotion of the Oxidation Processes of Water-Soluble Cationic Co(II)-Porphyrin Under Its Interaction with Nucleic Acids

Using the methods of absorption spectroscopy and resonance Raman scattering, we have made a comparative study of water-soluble cationic Co(II)- and Co(III)-5,10,15,20-tetrakis(4-N-methyl-pyridiniumyl)porphyrins(Co^II(TMpy-P4) and Co^III(TMpy-P4) with DNA and synthetic single- and double-stranded polynucleotides. It has been found that Co^II(TMpy-P4), which in aqueous solutions containing no nucleic acids is readily oxidized to Co^III(TMpy-P4) by the molecular oxygen dissolved there, markedly changes its oxidation ability when bound to nucleic acid. Under interaction with guanine-containing polynucleotides, the rate of change in the oxidation state of cobalt from Co(II) to Co(III) increases as compared to such for the solution of porphyrin in a buffer. But in complexes with DNA and adenine- and thymine-containing polynucleotides, CoII(TMpy-P4), on the contrary, becomes stable. The observed effects of inhibition/promotion of Co^II(TMpy-P4) oxidation when it is bound to nucleic acids are assumed to be due to the weakening/strengthening of the electron-donor properties of the extraligand on cobalt, which leads to a change in cobalt affinity to molecular oxygen. The role of immobilized water molecules in the change in the properties of cobalt extraligands has been considered. On the basis of the analysis of the spectral data obtained, modes for incorporating Co^II(TMpy-P4) into DNA and model polynucleotides are proposed. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 4, pp. 538–545, July–August 2005.     

改变溶液折射率方法研究Fermi共振

Fermi共振现象在光谱分析中的谱线认证、归属有重要应用,然而,它蕴含的丰富物理规律、内容及研究方法亟待开发和研究.本文提出了一种改变溶液折射率研究Fermi共振的方法,该方法以Onsager电介质极化理论为依据,利用分子在溶液中的Raman散射强度(散射系数)随溶液折射率的变化来研究Fermi共振规律.该方法不仅能给出Fermi共振各参数间及与溶液折射率之间的关系,而且发现了Fermi共振双峰的非对称移动、倍频的基频也受Fermi共振调谐等现象.为全面认识Fermi共振规律提供了一种研究方法.     

Propagating surface plasmon polaritons for remote excitation surface-enhanced Raman scattering spectroscopy

To illustrate the attractive potentials of remote-excitation surface enhanced Raman scattering (RE-SERS), we review the fundamental concepts and typical applications of propagating surface plasmon polaritons (PSPPs). Based on the RE-SERS technic, the adsorbed molecules are protected from being directly illuminated, while the merits of SERS still remained. However, the critical limitations of applying RE-SERS hinder its rapid development. Hence, drawing an overview about the PSPPs would be beneficial for further promoting the significance of RE-SERS in biological application and investigating the mechanism of surface catalytic reactions.