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 femtoseeond time resolved CARS spectroscopy, showing that an effective method of suppressing the non-resonant CARS background and other interferences is demonstrated.

Optimal quantum measurement of finite-dimensional systems and coherent anti-Stokes Raman spectroscopy

Quantum measurement is a fundamental problem in quantum control theory and experiments.It can obtain unknown information of quantum systems,and can also change state of the systems inevitably.Both the outcome and back action could be used to control quantum systems.This paper presents recent research progress about optimal control of state transformation in finite-dimensional quantum systems by back action of non-selective quantum measurement,and optimal control of signal and background of CARS (coherent anti-Stokes Raman spectroscopy) by phase shaping technique.In measurement sequence control of finite-dimensional quantum systems,the necessary condition for critical points of the underlying state transformation objective is found to be a highly symmetric form as a chain of equalities,and analytical and numerical solutions in several cases are explored.In the CARS control,it is found that the maximal resonant signal and minimal background at a specific frequency can be achieved by shaping the probe pulse only while keeping pump and Stokes pulses in transform limited forms (TLFs).An arctan-type phase function is obtained for the probe pulse to simultaneously enhance the resonant signal and suppress the background.For broadband background elimination,we find that the optimal phase shaping scheme of probe pulse is quasi-time-delay while keeping the pump and Stokes pulses in TLFs.These conclusions could help design control strategies of quantum devices.

Simultaneous measurements of global vibrational spectra and dephasing times of molecular vibrational modes by broadband time-resolved coherent anti-Stokes Raman scattering spectrography

In broadband coherent anti-Stokes Raman scattering （CARS） spectroscopy with supercontinuum （SC）, the simultaneously detectable spectral coverage is limited by the spectral continuity and the simultaneity of various spectral components of SC in an enough bandwidth. By numerical simulations, the optimal experimental conditions for improving the SC are obtained. The broadband time-resolved CARS spectrography based on the SC with required temporal and spectral distributions is realised. The global molecular vibrational spectrum with well suppressed nonresonant background noise can be obtained in a single measurement. At the same time, the measurements of dephasing times of various molecular vibrational modes can be conveniently achieved from intensities of a sequence of time-resolved CARS signals. It will be more helpful to provide a complete picture of molecular vibrations, and to exhibit a potential to understand not only both the solvent dynamics and the solute-solvent interactions, but also the mechanisms of chemical reactions in the fields of biology, chemistry and material science.

Selective excitation and suppression of coherent anti-Stokes Raman scattering by shaping femtosecond pulses

Femtosecond coherent anti-Stokes Raman scattering （CARS） suffers from poor selectivity between neighbouring Raman levels due to the large bandwidth of the femtosecond pulses. This paper provides a new method to realize the selective excitation and suppression of femtosecond CARS by manipulating both the probe and pump （or Stokes） spectra. These theoretical results indicate that the CARS signals between neighbouring Raman levels are differentiated from their indistinguishable femtosecond CARS spectra by tailoring the probe spectrum, and then their selective excitation and suppression can be realized by supplementally manipulating the pump （or Stokes） spectrum with the π spectral phase step.

Coherent coupling between vibrational modes of C-H bonds at different positions studied by femtosecond time-resolved coherent anti-Stokes Raman scattering

We performed femtosecond time-resolved coherent anti-Stokes Raman scattering （fs-CARS） measurements on liquid toluene and PVK film. For both samples, we selectively excited the CH stretching vibrational modes and observed the expected quantum beat signals. The frequency of the well-defined beats is in good agreement with the energy difference between the two simultaneously excited modes, which demonstrates that a coherent coupling between the vibrational modes of the C H chemical bonds exists at the different positions of the molecules. The dephasing times of the excited modes are obtained simultaneously.

High-resolution imaging of graphene by tip-enhanced coherent anti-Stokes Raman scattering

Coherent anti-Stokes Raman scattering(CARS)is able to enhance molecular signals by vibrational coherence compared to weak Raman signal.The surface or tip enhancement are successful technologies,which make it possible for Raman to detect single molecule with nanometer resolution.However,due to technical diffculties,tip-enhanced CARS(TECARS)is not as successful as expected.For single molecular detection,high sensitivity and resolution are two main challenges.Here,we reported the first single atom layer TECARS imaging on Graphene with the highest resolution about 20 nm,which has ever been reported.The highest EF_(TECARS/CARS) is about 10^(4),the similar order of magnitude with SECARS(EF of tip is usually smaller than that of substrates).Such resolution and sensitivity is promising for medical,biology and chemical applications in the future.

Supercontinuum fiber laser-based coherent anti-Stokes Raman scattering microscopy for label-free chemical imaging

Coherent anti-Stokes Raman scattering(CA RS)microscopy can resolve the chemical compo-nents and distribution of living biological systems in a label-firee manner and is favored in several disciplines.Current CA RS microscopes typically use bulky,high-performance solid-state lasers,which are expensive and sensitive to environmental changes.With their relatively low cost and environmental sensitivity,supercontinum fiber(SF)lasers with a small footprint have found increasing use in biomedical applications.Upon these features,in this paper,we homebuilt a low-cost CARS microscope based on a SF laser module(scCA RS microscope).This SF laser module is specially customized by adding a time synchronized seed source channel to the SF laser to form a dual-channel output laser.The performance of the scCARS microscope is evaluated with dimethyl sulfoxide,whose results confirm a spatial resolution of better than 500nm and a detection sensitivity of millimolar concentrations.The dual-color imaging capability is further demonstrated by imaging different species of mixed microspheres.We finally explore the potential of our scCARS microscope by mapping lipid droplets in different cancer cells and corneal stromal lenses.

COHERENT ANTI-STOKES RAMAN SCATTERING MICROSCOPY TO MONITOR DRUG DISSOLUTION IN DIFFERENT ORAL PHARMACEUTICAL TABLETS

Coherent anti-Stokes Raman scattering(CARS)microscopy is used to visualize the release of a model drug(theophylline)from a lipid(tripalmitin)based tablet during dissolution.The effects of transformation and dissolution of the drug are imaged in real time.This study reveals that the manufacturing process causes significant differences in the release process:tablets prepared from powder show formation of theophylline monohydrate on the surface which prevents a controlled drug release,whereas solid lipid extrudates did not show formation of monohydrate.This visualization technique can aid future tablet design.

Wide-Field Vibrational Phase Contrast Imaging Based on Coherent Anti-Stokes Raman Scattering Holography

We propose and implement a wide-field vibrational phase contrast detection to obtain imaging of imaginary components of third-order nonlinear susceptibility in a coherent anti-Stokes Raman scattering （CARS） microscope with full suppression of the non-resonant background. This technique is based on the unique ability of recovering the phase of the generated CARS signal based on holographic recording. By capturing the phase distributions of the generated CARS field from the sample and from the environment under resonant illumination, we demonstrate the retrieval of imaginary components in the CARS microscope and achieve background free coherent Raman imaging.

Theoretical and experimental investigations of coherent phonon dynamics in sapphire crystal using femto-second time-resolved coherent anti-Stokes Raman scattering

We report on the theoretical and the experimental investigations of the coherent phonon dynamics in sapphire crystal using the femtosecond time-resolved coherent anti-Stokes Raman scattering （fs-CARS） technique. The temporal chirped white-light continuum （WLC） is used for the Stokes pulse, therefore we can perform the selective excitation of the phonon modes without using a complicated laser system. The expected quantum beat phenomenon is clearly observed. The theoretical formulas consist very well with the experimental results. The dephasing times of the excited phonon modes, the wavenumber difference, and the phase shift between the simultaneously excited modes are obtained and discussed. This work opens up a way to study directly high-frequency coherent phonon dynamics in bulk crystals on a femtosecond time scale and is especially helpful for understanding the nature of coherent phonons.

Analysis of detection limit to time-resolved coherent anti-Stokes Raman scattering nanoscopy

In the implementation of CARS nanoscopy, signal strength decreases with focal volume size decreasing. A crucial problem that remains to be solved is whether the reduced signal generated in the suppressed focal volume can be detected. Here reported is a theoretical analysis of detection limit （DL） to time-resolved CARS （T-CARS） nanoscopy based on our proposed additional probe-beam-induced phonon depletion （APIPD） method for the low concentration samples. In order to acquire a detailed shot-noise limited signal-to-noise （SNR） and the involved parameters to evaluate DL, the T-CARS process is described with full quantum theory to estimate the extreme power density levels of the pump and Stokes beams determined by saturation behavior of coherent phonons, which are both actually on the order of ~ 109 W/cm2. When the pump and Stokes intensities reach such values and the total intensity of the excitation beams arrives at a maximum tolerable by most biological samples in a certain suppressed focal volume （40-nm suppressed focal scale in APIPD method）, the DL correspondingly varies with exposure time, for example, DL values are 103 and 102 when exposure times are 20 ms and 200 ms respectively.

Selective Excitation of Two-pulse Femtosecond Coherent Anti-Stokes Raman Scattering in a Mixture

In this paper, we experimentally study the selective excitation of two-pulse femtosecond coherent anti-Stokes Raman scattering (CARS) in a mixture of dibromomethane (CH2Br2) and chloroform (CHCl3) by adaptive pulse shaping based on genetic algorithm. Second harmonic generation frequency-resolved optical gating (SHG-FROG) traces indicate that the spectral amplitude and phase of the optimal pulse are both modulated. Finally, we discuss the physical mechanism for the selective excitation of femtosecond CARS based on the retrieved information from SHG-FROG traces.

Integrated System for Combined Optical Coherence Tomography-Raman Spectroscopy of Neocaridina denticulate sinensis

Optical coherence tomography(OCT)and Raman spectroscopy(RS)can be complementary biological tissue optical analysis methods.To study the internal structure and tissue compositions of biological samples,an OCT-RS system was built to carry out OCT section imaging and RS analysis in common.Neocaridina denticulate sinensis were collected regularly for morphological observation by OCT imaging and biochemical investigation based on the Raman spectra.The internal structure of the N.denticulate sinensis was imaged by OCT,and the morphology of the tissues and the position in the body were distinguished according to the gray scale changes.The imaging depth along the vertical direction of Z-axis in N.denticulate sinensis is about 1.60 mm.RS detection was selectively performed based on the OCT images.The main Raman peaks of the rostrum,the cephalothorax,the abdominal segment,and the telson section are at 1006,1156,1447,1491 and 1515 cm-1,which are identified as proteins and amino acids.The presence of 1497 cm-1 at the cephalothorax is different from other parts,probably due to the presence of organs such as ovary,whose compositions are different from those of other tissues.The combination of optical coherence tomography and Raman spectroscopy can provide information about morphological and biochemical features of tissues,and has potential applications in biomedical detection and imaging.

Anti-Stokes/Stokes temperature calibration and its application in laser-heating diamond anvil cells

Anti-Stokes/Stokes Raman peak intensity ratio was used to infer sample temperatures,but the influence factors of system correction factors were not clear.Non-contact in-situ anti-Stokes/Stokes temperature calibration was carried out for up to 1500 K based on six different samples under two excitation light sources(±50 K within 1000 K,±100 K above1000 K),and the system correction factorγwas systematically investigated.The results show that the correction factorγof anti-Stokes/Stokes thermometry is affected by the wavelength of the excitation light source,Raman mode peak position,temperature measurement region and other factors.The anti-Stokes/Stokes thermometry was applied to the laser-heating diamond anvil cell(LHDAC)experiment to investigate the anharmonic effect of h BN under high temperature and high pressure.It is concluded that the strong anharmonic effect caused by phonon scattering at low pressure gradually changes into the predominance of localized molecular lattice thermal expansion at high pressure.

Diagnosis of knee osteoarthritis by OCT and surface-enhanced Raman spectroscopy

In this paper,optical coherence tomography(OCT)and surface-enhanced Raman spectroscopy(SERS)were used to characterize normal knee joint(NKJ)tissue and knee osteoarthritis(KOA)tissue ex vivo.OCT images show that there is a clear hierarchical structure in NKJ tissue,including surface layer,transitional layer,radiation layer and cartilage matrix calcification layer tissue structure,while the hierarchical structure of KOA tissue is not clear and unevenly distributed,and the pathological tissues at different stages also show significant di®erences.SERS shows that NKJ tissue and mild osteoarthritic knee cartilage(MiKOA)tissue have strong characteristic Raman peaks at 964,1073(1086),1271,1305,1442,1660 and 1763 cm^(-1).Compared with the Raman spectrum of NKJ tissue,the Raman characteristic peaks of MiKOA tissue have some shifts,moving from 1073 cm^(-1)to 1086 cm^(-1)and from 1542 cm^(-1)to 1442 cm^(-1).There is a characteristic Raman peak of 1271 cm^(-1)in MiKOA tissue,but not in NKJ tissue.Compared with NKJ tissue,severely degenerated cartilage(SdKOA)tissues show some new SERS peaks at 1008,1245,1285,1311 and 1321 cm^(-1),which are not seen in SERS spectra of NKJ tissue.Principal component analysis(PCA)was used to analyze the Raman spectra of 1245–1345 cm^(-1)region.The results show that PCA can distinguish NKJ,MiKOA and SdKOA tissues and the accuracy is about 90%.These results indicate that OCT can clearly distinguish NKJ,MiKOA,moderate osteoarthritic knee cartilage(MoKOA)and SdKOA tissue,while SERS can provide further judgment basis.The results also prove that the contents of protein and polysaccharide in knee tissue are changed during the pathological process of knee tissue,which is the cause of pain caused by poor friction in knee joint during movement.

High enhancement factor of Au nano triangular prism structure for surface enhanced coherent anti-Stokes Raman scattering

Coherent anti-Stokes Raman scattering spectroscopy（CARS） is a well-known detecting tool in biosensing and nonlinear spectroscopy. It can provide a non-invasive alternative without the need for exogenous labels,while the enhancement factor for surface plasmon resonances（SPR） are extensively used to increase the local field close to the oscillators and which can obtain high enhancement. In this work, we investigate the enhancement factor of our structure for surface-enhanced coherent anti-Stokes Raman scattering. The absorption spectrum of the structure has been studied, a wide range of absorption has been realized. The enhancement can be as high as 10^（16） over standard CARS. Our design is very useful for improving the enhancement factor of surface-enhanced coherent anti-Stokes Raman scattering.

飞秒相干反斯托克斯拉曼散射光谱测温研究进展

当今世界大约90%的能量供应都是由燃烧生成的。在燃烧场中,火焰的温度影响着场中各种组分链式反应的途径和浓度,获取燃烧场温度信息可以为提高燃料燃烧效率,改进燃烧装置的设计提供重要的支撑依据。随着我国在航空、航天和航海这类高端制造业领域的不断发展,各种大型燃气轮机和超声速发动机的研发进入加速期,此类燃烧装置产生的火焰具有高温、高压、湍流超声速和持续时间短等特点。传统的接触式测温法难以对这类湍流燃烧场进行温度测量,近年以激光光谱法为代表的非接触式测温技术逐渐走向成熟,并获得了广泛地应用。与超短脉冲相结合的飞秒相干反斯托克斯拉曼散射光谱测温技术凭借可提供高时间分辨率(每秒可提供上千个测温数据)、高测温精度和高测温灵敏度等优势而被应用到各种高温、湍流等复杂燃烧场景温度诊断中。文章概述了飞秒相干反斯托克斯拉曼散射测温技术的基本原理,综述了该技术在稳态火焰、加热气体、模拟燃气轮机等燃烧环境中测温工作的研究进展,简要介绍了飞秒时间分辨相干反斯托克斯拉曼光谱的研究和应用,着重介绍了可以实现毫秒量级时间分辨率的飞秒啁啾探测脉冲相干反斯托克斯拉曼散射测温技术和混合飞秒/皮秒相干反斯托克斯拉曼散射测温技术的基本原理和应用进展。指出了三种测温技术的优缺点,并提出飞秒相干反斯托克斯拉曼散射测温技术目前需要关注并解决的技术问题,主要为在高温高压湍流燃烧等极端条件下实现高精度CARS光谱高保真反演出温度信息,以及高温高压湍流燃烧场极端条件下如何获得高信噪比CARS信号的问题。展望了今后的发展趋势:通过高时间分辨的测量,获得湍流火焰中温度的瞬时演化规律,并建立各种复杂火焰的温度演化信息数据库,为研究各种发动机机理提供支撑。

Computational coherent Raman scattering imaging:breaking physical barriers by fusion of advanced instrumentation and data science

Coherent Raman scattering(CRS)microscopy is a chemical imaging modality that provides contrast based on intrinsic biomolecular vibrations.To date,endeavors on instrumentation have advanced CRS into a powerful analytical tool for studies of cell functions and in situ clinical diagnosis.Nevertheless,the small cross-section of Raman scattering sets up a physical boundary for the design space of a CRS system,which trades off speed,signal fidelity and spectral bandwidth.The synergistic combination of instrumentation and computational approaches offers a way to break the trade-off.In this review,we first introduce coherent Raman scattering and recent instrumentation developments,then discuss current computational CRS imaging methods,including compressive micro-spectroscopy,computational volumetric imaging,as well as machine learning algorithms that improve system performance and decipher chemical information.We foresee a constant permeation of computational concepts and algorithms to push the capability boundary of CRS microscopy.

Coherent-interface-induced strain in large lattice-mismatched materials:A new approach for modeling Raman shift

Strain engineering as one of the most powerful techniques for tuning optical and electronic properties of III-nitrides requires reliable methods for strain investigation.In this work,we reveal,that the linear model based on the experimental data limited to within a small range of biaxial strains(<0.2%),which is widely used for the non-destructive Raman study of strain with nanometer-scale spatial resolution is not valid for the binary wurtzite-structure group-III nitrides GaN and AlN.Importantly,we found that the discrepancy between the experimental values of strain and those calculated via Raman spectroscopy increases as the strain in both GaN and AlN increases.Herein,a new model has been developed to describe the strain-induced Raman frequency shift in GaN and AlN for a wide range of biaxial strains(up to 2.5%).Finally,we proposed a new approach to correlate the Raman frequency shift and strain,which is based on the lattice coherency in the epitaxial layers of superlattice structures and can be used for a wide range of materials.

Simultons in Nonstationary CARS by Polaritons: Energy and Velocity

This paper is the continuation of our previous research in which we studied such aspects of CARS spectroscopy in dipole-active crystals by polaritons as the regimes of coherent simultaneous propagation of three waves (anti-Stokes, Stokes, and the pump field) to increase the efficiency of CARS as a spectroscopic method. In our previous research, we have shown the possibility of the existence of simultons at all frequencies of interacting waves. All interacting waves were supposed to be linearly polarised and plane, the medium was assumed to be nonmagnetic, and the medium was transparent at frequencies of anti-Stokes, Stokes, and the pump field (laser). The purpose of the present paper is to consider the energy carried by electromagnetic waves and its relationship with the gain factor and velocity of the simultons.