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.

Combined spatial frequency spectroscopy analysis with visible resonance Raman for optical biopsy of human brain metastases of lung cancers

The purpose of this study is to examine optical spatial frequency spectroscopy analysis(SFSA)combined with visible resonance Raman(VRR)spectroscopic method,for thefirst time,to discriminate human brain metastases of lung cancers adenocarcinoma(ADC)and squamous cell carcinoma(SCC)from normal tissues.A total of 31 label-free micrographic images of three type of brain tissues were obtained using a confocal micro-Raman spectroscopic system.VRR spectra of the corresponding samples were synchronously collected using excitation wavelength of 532 nm from the same sites of the tissues.Using SFSA method,the difference in the randomness of spatial frequency structures in the micrograph images was analyzed using Gaussian functionfitting.The standard deviations,calculated from the spatial frequencies of the micrograph images were then analyzed using support vector machine(SVM)classifier.The key VRR biomolecularfingerprints of carotenoids,tryptophan,amide II,lipids and proteins(methylene/methyl groups)were also analyzed using SVM classifier.All three types of brain tissues were identified with high accuracy in the two approaches with high correlation.The results show that SFSA–VRR can potentially be a dual-modal method to provide new criteria for identifying the three types of human brain tissues,which are on-site,real-time and label-free and may improve the accuracy of brain biopsy.

Investigation of the Short-Time Photodissociation Dynamics of Furfural in S2 State by Resonance Raman and Quantum Chemistry Calculations

Raman(resonance Raman,FT-Raman),IR and UV-visible spectroscopy and quantum chemistry calculations were used to investigate the photodissociation dynamics of furfural in S2 state.The resonance Raman(RR)spectra indicate that the photorelaxation dynamics for the S0→S2 excited state is predominantly along nine motions:C=O stretchν5(1667 cm-1),ring C=C antisymmetric stretchν6(1570 cm-1),ring C=C symmetric stretchν7(1472 cm-1),C2-O6-C5 symmetric stretch/C1-H8 rock in planeν8(1389 cm-1),C3-C4 stretch/C1-H8 rock in planeν9(1370 cm-1),C5-O6 stretch in planeν12(1154 cm-1),ring breathν13(1077 cm-1),C3-C4 stretchν14(1020 cm-1),C3-C2-O6 symmetric stretchν16(928 cm-1).Stable structures of S0,S1,S2,T1 and T2 states with Cs point group were optimized at CASSCF method in Franck-Condon region there are S2/S1 conical intersection was found by state average method and RR spectra.

Robust and high-sensitivity thermal probing at the nanoscale based on resonance Raman ratio (R3)

Raman spectroscopy-based temperature sensing usually tracks the change of Raman wavenumber,linewidth and intensity,and has found very broad applications in characterizing the energy and charge transport in nanomaterials over the last decade.The temperature coefficients of these Raman properties are highly material-dependent,and are subjected to local optical scattering influence.As a result,Raman-based temperature sensing usually suffers quite large uncertainties and has low sensitivity.Here,a novel method based on dual resonance Raman phenomenon is developed to precisely measure the absolute temperature rise of nanomaterial(nm WS_(2) film in this work)from 170 to 470 K.A 532 nm laser(2.33 eV photon energy)is used to conduct the Raman experiment.Its photon energy is very close to the excitonic transition energy of WS_(2) at temperatures close to room temperature.A parameter,termed resonance Raman ratio(R3)Ω=I_(A1g)/IE_(2g) is introduced to combine the temperature effects on resonance Raman scattering for the A_(1g) and E_(2g) modes.Ω has a change of more than two orders of magnitude from 177 to 477 K,and such change is independent of film thickness and local optical scattering.It is shown that when Ω is varied by 1%,the temperature probing sensitivity is 0.42 K and 1.16 K at low and high temperatures,respectively.Based on Ω,the in-plane thermal conductivity(k)of a∼25 nm-thick suspended WS_(2) film is measured using our energy transport state-resolved Raman(ET-Raman).k is found decreasing from 50.0 to 20.0 Wm^(−1) K^(−1) when temperature increases from 170 to 470 K.This agrees with previous experimental and theoretical results and the measurement data using our FET-Raman.The R3 technique provides a very robust and high-sensitivity method for temperature probing of nanomaterials and will have broad applications in nanoscale thermal transport characterization,non-destructive evaluation,and manufacturing monitoring.

Selective conformer detection of short-lived base pair tautomers: A computational study of the unusual guanine-cytosine pairs using ultrafast resonance Raman spectroscopy

Base pair mismatch has been regarded as the main source of DNA point mutations, where minor shortlived tautomers were usually involved. However, the detection and characterization of these unnatural species pose challenges to existing techniques. Here, by using systematic structural and ultrafast resonance Raman(RR) spectral analysis for the four possible conformers of guanine-cytosine base pairs, the prominent marker Raman bands were identified. We found that the hydrogen bonding vibrational region from 2300 cm^(-1) to 3700 cm^(-1) is ideal for the identification of these short live species. The marker bands provide direct evidence for the existence of the tautomer species, thus offering an effective strategy to detect the short-lived minor species. Ultrafast resonance Raman spectroscopy would be a powerful tool to provide direct evidence of critical dynamical details of complex systems involving protonation or tautomerization.

Structural insights of catalytic intermediates in dialumene based CO_(2) capture: Evidences from theoretical resonance Raman spectra

CO_(2) capture is considered as one of the most ideal strategies for solving the environmental issues and against global warming.Recently,experimental evidence has suggested that aluminum double bond(dialumene) species can capture CO_(2) and further convert it into value-added products.However,the catalytic application of these species is still in its infancy.Both the dynamics mechanism of CO_(2) fixation and the detailed structures of catalytic intermediates are not well understood.In this work,we investigate the structure dependent resonance Raman(RR) signals for different reaction intermediates.Ab-initio simulations of spontaneous resonance Raman(spRR) and time-domain stimulated resonance Raman(stRR) give spectral signatures correlated to the existence of different intermediates during the CO_(2)-dialumene binding process.The unique Raman vibronic feature s contain rich structural information with high temporal resolution,enabling to monitor the transient catalytic intermediates under reaction conditions.Our work shows that RR can be used to monitor intermediates during the dialumene based CO_(2) capture reaction.The spectral features not only provide insight into the structural information of intermediate species,but also allow a deeper understanding of the dynamical details of this kind of catalytic process.

A pilot study for distinguishing basal cell carcinoma from normal human skin tissues using visible resonance Raman spectroscopy

Aim: The aim of the study is to test visible resonance Raman (VRR) spectroscopy for rapid skin cancer diagnosis,and evaluate its effectiveness as a new optical biopsy method to distinguish basal cell carcinoma (BCC) from normal skin tissues.Methods: The VRR spectroscopic technique was undertaken using 532 nm excitation. Normal and BCC human skin tissue samples were measured in seconds. The molecular fingerprints of various native biomolecules as biomarkers were analyzed. A principal component analysis - support vector machine (PCA-SVM) statistical analysis method based on the molecular fingerprints was developed for differentiating BCC from normal skin tissues.Results: VRR provides a rapid method and enhanced Raman signals from biomolecules with resonant and nearresonant absorption bands as compared with using a near-infrared excitation light source. The VRR technique revealed chemical composition changes of native biomarkers such as tryptophan, carotenoids, lipids and proteins.The VRR spectra from BCC samples showed a strong enhancement in proteins including collagen type I combined with amide I and amino acids, and a decrease in carotenoids and lipids. The PCA-SVM statistical analysis based on the molecular fingerprints of the biomarkers yielded a 93.0% diagnostic sensitivity, 100% specificity, and 94.5%accuracy compared with histopathology reports.Conclusion: VRR can enhance molecular vibrational modes of various native biomarkers to allow for very fast display of Raman modes in seconds. It may be used as a label-free molecular pathology method for diagnosis of skin cancer and other diseases and be used for combined treatment with Mohs surgery for BCC.

The stimulated Raman scattering competition between solute and solvent in Rhodamine B solution

The competition between the stimulated resonance Raman scattering （SRRS） of Rhodamine B （RhB） and the stimulated Raman scattering （SRS） of ethanol （C2H50H） is observed at the RhB in C2H5OH solution. For different concentrations of the solution, the peak wavelengths of the SRRS, the amplified spontaneous emission （ASE）, the fluorescence and the absorption of RhB are different. The SRRS of RhB and the SRS of C2H50H are simultaneously generated when the concentration of the solution is 10-5 mol/L and the energy of the excitation laser is 20.4 mJ. Otherwise, only either the SRRS of RhB or the SRS of C2H5OH is generated. The SRRS can be amplified by the ASE gain when the SRRS is near the peak of the ASE, and the peak wavelength of the SRRS coincides with the wavelength of the maximal intensity ASE.

Influence of tip geometry on the spatial resolution of tip enhanced Raman mapping

In 2013,a breakthrough experiment pushed the Raman mapping of molecules via the tip-enhanced Raman scattering（TERS） technique to a sub-nanometer spatial resolution,going into the single-molecule level.This surprising result was well explained by accounting for the critical role of elastic molecule Rayleigh scattering within a plasmonic nanogap in enhancing both the localization and the intensity level of the Raman scattering signal.In this paper,we theoretically explore the influence of various geometric factors of the TERS system on the spatial resolution of Raman mapping,such as the tip curvature radius,tip conical angle,tip–substrate distance,and tip–molecule vertical distance.This investigation can help to find out the most critical geometric factor influencing the spatial resolution of TERS and march along in the right direction for further improving the performance of the TERS system.

Study of second-order nonlinear hyperpolarisability of all-trans-β-carotene in solutions by linear spectroscopic technique

This paper demonstrates the second-order nonlinear hyperpolarisability γ of all-trans-β-carotene in different solvents by linear spectroscopic technique that is based on resonance Raman scattering and UV-VIS （Ultraviolet-visible） absorption spectroscopy. Owing to the two-level model well describing the link that exists between the resonance Raman scattering and stimulated Raman scattering, the stimulated Raman polarisability αR can be calculated through the two-photon resonance system. The value of γ of all-trans-β-carotene in carbon bisulfide solution is 6.435×10^-33 esu （1 esu of resistance = 8.98755×10^11Ω） that is close to the true value, because the solution of all-trans-β-carotene in carbon bisulfide satisfies the rigid resonance Raman scattering condition. This method is expected to be worthy of applications to measure the second-order nonlinear hyperpolaxisability of a conjugate organic molecule.

Enhancing sensitivity of SERRS nanoprobes by modifying heptamethine cyanine-based reporter molecules

Surface enhanced resonance Raman scattering(SERRS)is a physical phenomenon that occurs when the energy of incident light is dose to that of electronic excitation of reporter molecules(RMs)attached on substrates.SERRS has showed great promise in healthcare applications such as tumor diagnosis,image guided tumor surgery and real-time evaluation of therapeutic response due to its ultra-sensitivity,manipulating convenience and easy acessibility.As the most widely used organic near-infrared(NIR)fuorophore,heptamethine cyanines possess the electronic ex-citation energy that is close to the plasmon absorption energy of the gold nano scafolds,which results in the extraordinary enhancement of the SERRS signal.However,the effect of hepta-methine cyanine structure and the gold nanoparticle morphology to the SERRS intensity are barely investigated.This work developed a series of SERRS nanoprobes in which two hepta-methine cyanine derivatives(IR783 and IR780)were used as the RM and three gold nanoparticles(nanorod,nanosphere and nanostar)were used as the substrates.Interestingly,even though IR780 and IR783 possess very similar chemical structure,SERRS signal produced by IR780 was determined as 14 times higher than that of IR783 when the RM concentration was6.5 × 10^(-6) M.In contrast,less than 4.0 fold SERRS signal intensity increase was measured by changing the substrate morphologies.Above experimental results indicate that finely tuning the chemical structure of the heptamethine cyanine could be a feasible way to develop robust SERRS probes to visualize tumor or guide tumor resection with high sensitivity and target to background ratio.

Isolation,Purification and Spectral Characteristics of Soluble Guanylate Cyclase from Bovine Lung

We isolated and purified high purity and high activity soluble Guanylate cyclase(sGC) from bovine lung. The electronic absorption and resonance Raman spectra of the ferrous and ferric forms of sGC were recorded. In the ferrous state of sGC, the electronic absorption spectra showed a sharp peak at 431 nm and a single broad peak in the α/β region at 559 nm. The resonance Raman spectra of sGC(ferrous) showed a stronger band at 1357 cm -1 and a single peak at 1473 cm -1 . For the ferric form of sGC, the Soret band was at 390 nm and resonance Raman peak was at 1375 cm -1 . These spectra show that the heme iron of the ferrous and ferric sGC are all 5 coordination and high spin.

Surface-enhanced Raman scattering on dielectric microspheres with whispering gallery mode resonance

Conventionally, metallic nanostructures are used for surface-enhanced Raman spectroscopy(SERS), but recently there has been increasing interest in the enhancement of Raman scattering from dielectric substrates due to their improved stability and biocompatibility compared with metallic substrates. Here, we report the observation of enhanced Raman scattering from rhodamine 6 G molecules coated on silica microspheres. We excite the whispering gallery modes(WGMs) supported in the microspheres with a tapered fiber coupler for efficient WGM excitation, and the Raman enhancement can be attributed to the WGM mechanism. Strong resonance enhancement in pump laser intensity and modified Raman emission from the Purcell effect in the microsphere resonator are observed from the experiment and compared with theoretical results. A total Raman enhancement factor of 1.4 × 10~4 is observed, with contribution mostly from the enhancement in pump laser intensity. Our results show that, with an efficient pumping scheme, dielectric microspheres are a viable alternative to metallic SERS substrates.

A dual-functional membrane for bisphenol A enrichment and resonance amplification by surface-enhanced Raman scattering

Bisphenol A （BPA） was one of the environmental hormones that would cause endocrine and metabolic disorders in human or wildlife. This paper proposed a method to detect the trace amounts of BPA in water samples by fully utilizing the enrichment and resonance amplification functions of a new dual-functional membrane. In this work, gold nanoparticles （AuNPs） modified by 3-amino-5-mercapto-1,2,4-triazole （AMT） were embedded in nylon66 membrane to produce a dual-functional membrane which could carry out sample enrichment by capturing BPA molecules from water and achieve resonance amplification by connecting BPA to the surfaces of AuNPs. By designing an automatic sampler for large-volume enrichment, the SERS enhancement factor （EF） of the method was further improved to 1.2 × 105. The present method had been successfully applied to detect BPA in drinking water and environmental water by SERS with the detection limit of 0.012 μg/L. It had the potential for on-site detecting of BPA in various water samples.

Breakdown of Raman selection rules by Frohlich interaction in few-layer WS_(2)

The polarization selection rule of Raman scattering is crucial in symmetry analysis of elementary excitations in semiconductors and correlated electron systems.Here we reported the observation of breakdown of Raman selection rules in few-layer WS_(2) by using resonant Raman spectroscopy.When the excitation energy is close to the dark A exciton state,we observed some infrared active modes and backscattering forbidden modes.Importantly,we found that all observed phonon modes follow the same paralleled-polarization behavior.According to the electron-phonon coupling near the band edge in WS_(2),we proposed a theoretical model based on the intraband Frohlich interaction.In this case,the polarization response of the scattering signal is no longer determined by the original Raman tensor of scattered phonons.Instead,it is determined by a new isotropic Raman tensor that generated from this intraband Frohlich interaction between dark A exciton and phonons.We found that this theoretical model is in excellent agreement with the observed results.The breakdown of Raman selection rules can violate the conventional limitations of the optical response and provide an effective method to control the polarization of Raman scattering signals in two-dimensional materials.

New selection rule of resonant Raman scattering in MoS_(2) monolayer under circular polarization

The first-order resonant Raman spectra of monolayer MoS_(2)are calculated under the circularly polarized photoexcitation.The anomalously nonzero Raman intensity of the in-plane E mode under the Z(σ+σ+)Zor Z(σ−σ−)Zgeometry,which goes against the conventional selection rule,appears under some circum-stances when optical absorption occurs at some special reciprocal points between the zone-center Γ and the zone-edge-center M points.At that moment,the valley selectivity to the circular polarization is lifted.The analysis shows that the anomalous Raman intensity of the E mode for the same circularly polarized incident and scattered light is consistent with the pseudo-angular-momentum conservation law.The cal-culated E Raman tensor of monolayer MoS_(2)is found to vary with laser energy.The two diagonal terms of the Raman tensor change their signs from mutually opposite to the same when the relative intensity of the in-plane E mode to the out-of-plane A'_(1)mode increases,indicating the increasingly important role played by the Frölich-type electron-phonon interaction over the deformation potential.Our study may shed new light on the understanding of the novel electron-photon process and assist in the design of new type of optoelectronic devices.

Resonant Raman scattering in GaN single crystals and GaN-based heterostructures: feasibility for laser cooling

The recent progress on Raman scattering in GaN single crystals and GaN/A1N heterostructures is re- viewed. Anti-Stokes Raman scattering is used to determine electron-phonon scattering time and decay time constant for longitudinal-opticat phonons. In a typical high electron mobility transistor based on GaN/A1N heterostructures, strong resonances are reached for the first-order and second-order Raman scattering processes. Therefore, both Stokes and anti-Stokes Raman intensities are dramatically enhanced. The feasibility for laser cooling of a nitride structure is studied. A further optimization will enable us to reach the threshold for laser cooling. Raman scattering have potential applications in up-conversion lasers and laser cooling of nitride ultrafast electronic and optoelectronic devices.

Accurate assignment of double resonant Raman bands in Janus MoSSe monolayer from first-principles calculations

Janus transition metal dichalcogenides(TMDs)structures,as a new type of two-dimensional layered materials,have drawn increasing research efforts mostly by the Raman characterization technique since their successful synthesis.First-and second-order resonant Raman spectra(RRS)have been reported by experiments.But,unlike much interest paid to the first-order RRS,there has been so far no much discussion dedicated to the second-order double resonant Raman(DRR)bands and band assignments of Janus TMDs,which nevertheless is indispensable but hampered by the difficulty of calculations.In this work,we calculate the DRR spectra of Janus Mo SSe monolayer within the first-principles framework and succeed in achieving accurate assignments of the DRR bands.The assignments are in agreement with our group theoretical analysis.Moreover,taking advantage of its strain-sensitive feature,we calculate the DRR spectra under biaxial strain,and further verify the rationality of our assignments by analyzing strain-induced shift of the DRR bands.Our present study supplies an efficient strategy for quantitative understanding on the electron-phonon coupling in the Janus structures.

Photodamage to Pigment in the Photosystem Ⅱ Reaction Center D1/D2/Cytochrome b559 Complex

Strong light （800μmol photons/m^2 per s）-induced bleaching of the pigment in the isolated photosystem Ⅱ reaction center （PSII RC） under aerobic conditions （in the absence of electron donors or acceptors） was studied using high-pressure liquid chromatography （HPLC）, absorption spectra, 77K fluorescence spectra and resonance Raman spectra. Changes in pigment composition of the PSII RC as determined by HPLC after light treatment were as follows： with Increasing illumination time chlorophyll （Chl） a and β-carotene （β-car） content decreased. However, decreases in pheophytin （Pheo） could not be observed because of the mixture of the Pheo formed by degraded chlorophyll possibly. On the basis of absorption spectra, it was determined that, with a short time of illuminatlon, the initial bleaching occurred maximally at 680 nm but that with Increasing Illumination time there was a blue shift to 678 nm. It was suggested that P680 was destroyed Initially, followed by the accessory chlorophyll. The activity of P680 was almost lost after 10 mln light treatment. Moreover, the bleaching of Pheo and β-car was observed at the beginning of illumination. After Illumination, the fluorescence emission Intensity changed and the fluorescence maximum blue shifted, showing that energy transfer was disturbed. Resonance Raman spectra of the PSII RC excited at 488.0 and 514.5 nm showed four main bands, peaking at 1 527 cm^-1 （υ101）, 1 159 cm^-1 （υ2）, 1 006 cm^-1 （υ3）, 966 cm^-1 （υ4） for 488.0 nm excitation and 1 525 cm^-1 （υ1）, 1 159 cm^-1 （υ2）, 1 007 cm^-1 （υ3）, 968 cm^-1 （υ4） for 514.5 nm excitation. It was confirmed that two spectroscopically different β-car molecules exist In the PSII RC. After light treatment for 20 mln, band positions and bandwidths were unchanged. This indicates that carotenoid configuration Is not the parameter that regulates photoprotectlon in the PSII RC.