基于光强传输方程相位成像的宽场相干反斯托克斯拉曼散射显微背景抑制

相干反斯托克斯拉曼散射(CARS)显微能够对样品的特殊化学组分进行选择性成像,无需荧光标记,在生物医学领域被广泛应用.然而,传统的CARS图像往往存在非共振背景信号.本文将基于光强传输方程的单光束相位成像技术用于CARS显微成像,来抑制CARS的非共振背景信号.该方法通过记录样品在三个相邻平面上的CARS图像,然后利用光强传输方程获取CARS光场的相位分布,最后利用共振CARS信号和非共振背景信号在相位上的差异,实现了对背景噪声的抑制.该方法无需参考光,通过三次测量可完成CARS的背景噪声抑制,具有良好的应用前景.     

Interferometric polarization coherent anti-Stokes Raman scattering (IP-CARS) microscopy

We report a novel interferometry-based polarization coherent anti-Stokes Raman scattering (IP-CARS) implementation for effectively suppressing the nonresonant background while significantly amplifying the resonant signal for vibrational imaging. By modulating the phase difference between the two interference CARS signals generated from the same sample and measuring the peak-to-peak intensity of the periodically modulated interference CARS signal, the IP-CARS technique yields a sixfold improvement in the signal-to-background ratio compared with conventional CARS while providing an approximately 20-fold amplification of the resonant CARS signal compared with conventional polarization CARS. We demonstrate this method by imaging 4.69 microm polystyrene beads and unstained human epithelial cells immersed in water.     

Calculation of the signal time-profile in transient CARS experiments

The expressions for the resonant and non-resonant contributions to the CARS signal in a time-resolved CARS experiment are derived on the basis of a diagrammatic perturbative expansion of the polarization. The laser fields are assumed to be off-resonance with respect to any electronic level of the system. The probe pulse is supposed to be derived from one of the two pump pulses (₁). Under this assumption the effect of the noise content of ₁ laser pulses on the signal time-profile (coherence artefact) is correctly reproduced by modelling the noise as a stationary stochastic process. The choice of appropriate polarization geometries is shown to allow for direct measurement of the individual contributions to the CARS signal; the experiments performed on a KClO₄ single crystal fully confirm the results of the calculation based on our theoretical treatment.     

Validation experiments for spatially resolved one-dimensional emission spectroscopy temperature measurements by dual-pump CARS in a sooting flame

In this work, an emission spectroscopic (ES) technique for the determination of soot temperatures in an axisymmetric flame is validated against coherent anti-Stokes Raman spectroscopy (CARS) as preparation for a zero gravity measurement campaign. In order to reduce valuable measurement times during the parabolic flights, a setup for spatially resolved one-dimensional measurements along a line has been built up using an imaging spectrometer and a CCD-camera for data acquisition.In order to assess the performance of the ES technique, accurate coherent anti-Stokes Raman scattering (CARS) measurements have been performed at the same conditions. Hereby, great care has to be taken to minimize the known interferences in sooting flames. The non-resonant signal contribution was suppressed by a polarization technique and the signal wavelength was shifted to an interference free region. These modifications are discussed in detail. The temperatures obtained by both methods are in good agreement in most regions of the flame. It turned out that the described approach for ES is an appropriate and robust alternative for measuring temperatures in sooting axisymmetric flames, if more accurate techniques cannot be applied, e.g., during investigations in zero-g parabolic flight experiments.     

Is rotational CARS an alternative to vibrational CARS for thermometry?

Recent developments in rotational CARS thermometry and critical issues when comparing vibrational and rotational CARS thermometry are described. In particular, the development of dual broadband rotational CARS and the noise characteristics of this approach are emphasized. The difficulty with unambiguous temperature determination in vibrational CARS with unknown parameters, in particular the nonresonant background susceptibility, and the lower sensitivity of rotational CARS thermometry at flame temperatures are also discussed.     

Compact fibre-based coherent anti-Stokes Raman scattering spectroscopy and interferometric coherent anti-Stokes Raman scattering from a single femtosecond fibre-laser oscillator

We demonstrate a new approach to CARS spectroscopy by efficiently synthesizing synchronized narrow-bandwidth (less than 10 cm⁻¹) pump and Stokes pulses (frequency difference continuously tunable upto ≈3000 cm⁻¹) based on spectral compression together with second harmonic generation (in periodically-poled nonlinear crystals) of femtosecond pulses emitted by a single compact Er-fibre oscillator. For a far better signal to non-resonant background contrast, interferometric CARS (I-CARS) is demonstrated and CARS signal enhancement upto three orders of magnitude is achieved by constructive interference with an auxiliary local oscillator at anti-Stokes field, also synthesized by spectral compression of pulses emitted from the same fibre oscillator.     

CARS thermometry in high temperature gradients

CARS is an effective non-intrusive technique for measuring gas temperature in combustion environments. In regions of high temperature gradient, however, the CARS signal is complicated by contributions from gas at different temperature. This paper examines theoretically the uncertainty associated with CARS thermometry in steep temperature gradients. In addition, the work compares the temperature predicted from CARS with the adiabatic mixed temperature of the gas resident in the measurement volume. This comparison helps indicate the maximum sample volume size allowed for accurate temperature measurements.     

宽带相干反斯托克斯光谱显微成像技术的实验研究

由于该成像系统采用的超连续谱光源,可以满足所观测样品本源分子在0～4 000 cm-1内的所有拉曼振动活性模式同时共振增强,在探测光的作用下,同时产生宽带相干反斯托克斯拉曼散射信号。然后,根据不同的化学键进行光谱图像重构,可以获得反映不同化学键在样品中的分布的图像。对110 nm的纯的聚苯乙烯珠所形成的具有一定厚度的薄膜,通过改变探测激光与超连续谱脉冲之间的时间重合度,测量形成的相干反斯托克斯拉曼散射信号的时间分布迹线图,通过其中的1 000 cm-1的化学键强度信号进行指数衰减曲线拟合,得出具体的退相时间,与文献中已报道的三色CARS的退相时间相比,判断是否属于三色CARS。为了检验系统在实际生物学成像中存在的问题,我们开展了活体小鼠组织生物学应用成像实验,对记录的数据在2 940 cm-1的CARS信号进行图像重构,获得CH化学键在组织中的分布,然后,对重构图像直接使用小波变换的去噪方式进行图像去噪,去噪后的图像具有比较清晰的轮廓,结果表明,对于对比度比较强的CARS共振信号,直接使用小波变换的去噪方式就可以获得比较好的图像效果。但是,对于信噪比比较差的共振信号,使用这种处理方法是不合适的,需要使用别的方法,先获取好的信号对比度,再根据感兴趣的化学键进行图像重构,然后,再经过小波变换对图像去噪,图像不仅会变得清晰平滑,而且,具有较好的视觉感官效果。     

Coherent anti-stokes raman scattering spectral interferometry: determination of the real and imaginary components of nonlinear susceptibility chi(3) for vibrational microscopy

We demonstrate coherent anti-Stokes Raman scattering (CARS) heterodyne spectral interferometry for retrieval of the real and imaginary components of the third-order nonlinear susceptibility (chi(3)) of molecular vibrations. Extraction of the imaginary component of chi(3) allows a straightforward reconstruction of the vibrationally resonant signal that is completely free of the electronic nonresonant background and resembles the spontaneous Raman spectrum. Heterodyne detection offers potential for signal amplification and enhanced sensitivity for CARS microscopy.     

Diagrammatic representation of the third-order polarization in transient CARS

Summary A diagrammatic perturbative approach is adopted to derive the expression for the third-order polarization,P ⁽³⁾ which originates the anti-Stokes emission in a time-resolved CARS experiment. The various contributions toP ⁽³⁾ are calculated assuming that laser fields are off-resonance with respect to any electronic level of material system. The resonant part of the polarization consists of two terms, in which the roles of the pump and probe pulses at frequency ω₁ are exchanged. The global expression allows the direct calculation of the signal time profile in a transient CARS experiment once a model is assumed for the laser pulse shape.     

Heterodyne interferometric polarization coherent anti‐Stokes Raman scattering (HIP‐CARS) spectroscopy

We demonstrate a new technique that combines polarization sensitivity of the coherent anti‐Stokes Raman scattering (CARS) response with heterodyne amplification for background‐free detection of CARS signals. In this heterodyne interferometric polarization CARS (HIP‐CARS), the major drawbacks of polarization and heterodyne CARS are rectified. Using a home‐built picosecond optical parametric oscillator, we are able to address vibrational stretches between 600 and 1650 cm⁻¹ and record continuous high‐resolution Raman equivalent HIP‐CARS spectra. Copyright © 2010 John Wiley & Sons, Ltd.     

The application of CARS for temperature measurements in high pressure combustion systems

The determination of accurate temperatures from CARS N₂ Q-branch spectra in premixed flames is discussed for pressures up to 40 bar. The influence of collisional line narrowing in the CARS spectra is modelled by a MEG fitting law. It takes into account collisions of N₂ with CO₂ and H₂O. The analysis of the CARS data showed that the non-resonant background has an increasing influence on temperature with increasing pressure. Little influence on the quality of the fit between theory and experiment was found. Since there is a danger of residual systematic temperature deviations, which cannot be identified from the quality of the fit, spontaneous rotational Raman scattering is employed as an independent measuring technique.     

Coherent raman spectroscopy

A review of the salient features of five coherent Raman techniques is given, including typical spectra produced by each technique. The resonant and nonresonant signal contributions in the monochromatic plane wave limit are calculated for: (1) Coherent AntiStokes Raman Spectroscopy(CARS); (2) a polarization technique referred to as ASTERISK; (3) Raman-induced Kerr-effect Spectroscopy(RIKES); (4) Optically Heterodyned RIKES (OHD-RIKES); (5) Stimulated Raman Spectroscopy (SRS). The relevant noise contribution to each of these techniques is developed within the framework of a comparative signal-to-noise analysis, and realistic detection limits are discussed. The OHD-RIKES technique is selected as the most viable of the coherent Raman techniques which satisfies the following criteria: (A) suppression of nonresonant background signals and enhanced signal-to-noise ratio; (b) simplicity of operation and interpretation of results. This is the first known application of optical heterodyne detection and optimization to coherent Raman spectroscopy, and the principles developed are generally applicable to all forms of third-order nonlinear spectroscopu.     

Ultrabroadband single-pulse CARS of liquids using a spatially dispersive Stokes beam

A double-channel spectrometer, which enables to acquire ultrabroadband single-pulse spectra of liquids by Coherent Anti-Stokes Raman Spectroscopy (CARS), is described. The method used to fulfill the phase-matching condition is based on the fact that the CARS efficiency in dispersive media is the largest when the interactive waves cross each other under frequency-determined angles. The dependence of the spatial separation between the pump and Stokes beam, in front of the crossing CARS lens, due to their frequency difference is analysed. It is shown that the different spectral components of an ultrabroadband Stokes source have phase-matched the CARS process when they are laterally shifted by a conjugated prism pair and focused into the sample. The method is tested in the spectral region 2800–3800 cm^–1 of a non-resonant medium (CCl₄) using an ultrabroadband dye laser (1000 cm^–1 FWHM). The influence of the Stokes beam spatial dispersion on the width of CARS generation is demonstrated. By this method, 1060 cm^–1 wide single-pulse spectra of the OH stretching vibration of liquid water are obtained for the first time. The ratio between the resonant and non-resonant part of the third-order susceptibility in water and methanol is determined.     

用CARS技术确定拉曼退偏比的一种数据处理新方法

Yuika等人利用偏振CARS技术可以准确地确定分子的拉曼退偏比.其方法是，首先对不同检偏角_d所对应CARS谱峰的频率分布进行数学模拟，然后由所得系数随检偏角φ_d的变化求得使CARS信号中共振项消失的偏振角φ^０_d，最后由消失条件ρ＝-1/(tanθtanφ⁰_d)求出退偏比ρ，θ为产生CARS光的Pump光与Stokes光偏振方向的夹角.本文提出的数据处理方法，即交点法.同Yuika等人处理数据的方法相比，交点法毋需关于谱峰频率分布的知识，做法也更为简便.     

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.     

Polarization effects of picosecond CARS in liquids

Coherent Raman scattering of delayed probing pulses after ultrafast excitation is investigated under generalized polarization conditions. Three factors are shown to contribute to the scattering signal:

1. scattering off the isotropic part of the resonant material excitation via the isotropic component of the Raman polarizability
2. scattering via the anisotropic part of the Raman polarizability from a second, oriented component of the resonant material excitation
3. four-wave mixing via the non-resonant part χ_NR of the third-order susceptibility. We demonstrate theoretically and experimentally that different polarization conditions lead to drastic changes of the signal transients in liquids. For the ring breathing mode of C₆H₅Br the ratio of non-resonant to resonant contributions is measured to be χ_NR/χ_res=0.037±0.015.

     

激光诱导热光栅光谱测温技术研究

报道了激光诱导热光栅光谱测温技术的研究. 通过两束相干交叉的脉冲抽运光, 在NO₂/N₂混合气中诱导出热光栅, 一束满足布拉格散射条件的连续探测光在交叉区域激励出相干的热光栅信号, 经过空间和光谱滤波的信号光由光电倍增管探测, 并由数字示波器显示和存储. 该信号携带了丰富的流场信息, 通过频域分析, 对气体的温度进行了测量, 热光栅光谱技术测量的温度与热电偶温度符合得很好. 同时还利用热光栅光谱技术进行了气体声速的直接测量, 在一定的温度范围内, 测量结果与理论曲线基本一致, 显示了该技术具有较高的测量精度与多参数同时测量的能力. 对影响信号波形的因素进行了分析, 结果表明, 热光栅光谱测温技术在高压强环境下应用具有独特的优势, 是一种应用前景广阔的激光燃烧诊断技术.     

Spin-polarizing properties of heterostructures with magnetic nano elements

The problem of electron resonant and non-resonant scatterings on two magnetized barriers is studied in the one-dimension. The transfer-matrix is built up to exactly calculate the coefficient of the electron transmittance through the system of two magnetic barriers with non-collinear magnetizations. The polarization of the transmitted electron wave for resonance and non-resonance transmittances is calculated. The transmittance coefficient and spin polarization can be drastically enhanced and controlled by the angle between the barrier magnetizations.     

Chirped-pulse adiabatic control in coherent anti-Stokes Raman scattering for imaging of biological structure and dynamics

Two novel control methods based on adiabatic passage are proposed to be implemented in coherent anti-Stokes Raman scattering (CARS) microscopy for noninvasive imaging of biological structure and dynamics. The first method provides optimal pulse-area control of the resonant vibrational transitions by using a pair of equally linear-chirped pulses. The second method, named the 'roof' method, utilizes the chirp sign variation at the central time and gives robust adiabatic excitation of the resonant vibrational mode. Both methods are robust with respect to suppression of the off-resonant transitions. The methods allow one to achieve chemical sensitivity with high resolution and can be used to obtain CARS spectra of biological molecules with efficiently suppressed background.