基于空间位移拉曼光谱的皮肤含水量无创检测

基于空间位移拉曼光谱原理,搭建了一套可以实现微小空间位移的装置,确定了最优的空间位移距离为300μm,用于穿透皮肤表层,减少皮肤表面水份、油脂等污染物的干扰,最终采集到皮肤内层的水份拉曼信号。该装置采用拉曼波数在3 390 cm^-1(水拉曼峰)和2 935 cm^-1(蛋白峰)处的强度之比确定组织中的水-蛋白比例,采用便携式光谱仪使设备便于移动,探头和光谱仪以光纤相连使探头可灵活操作,设计满足临床使用要求。实验中检测了7个人、每人10个共70个不同位置的皮肤光谱,将光谱进行去背景算法处理,然后得到精确的拉曼峰强度。以电学法皮肤水份测试仪测试结果作为对比,以组内相关系数作为一致性分析指标,由单个测量组内相关系数为0.889可以看出,基于空间位移拉曼光谱法的人体活体皮肤含水量检测具有较高可行性。     

拉曼光谱检测淮山——大学物理光谱应用性实验拓展

以拉曼光谱检测淮山研究为例,引导大学生初步参与科研实验.初步学习用半导体激光、全息光栅和近红外增强CCD探测器等光电器件,构建近红外拉曼光谱探测系统,测试获得淮山拉曼光谱,以及淮山拉曼一阶导数谱,标记淮山特征峰.     

手持/便携式激光拉曼测试装置中探头的设计与实验研究

从手持/便携式角度出发,采用双光纤光路设计了激光拉曼测试装置中的探头,并确定关键器件性能、型号及尺寸.利用Zemax软件进行光学模拟仿真,得到入射光路的工作焦距为13.5mm,像方数值孔径为0.23;收集光路的像面焦距为13.46mm,数值孔径为0.235.用SolidWorks软件进行机械设计,TracePro软件进行探头整体光路模拟,通过计算机数字控制机加工和3D打印两种方式制作得到整体尺寸为50mm×33.5mm×17mm的探头.用设计的拉曼探头对酒精样品进行了测试,测得酒精拉曼光谱与商用产品测得的结果基本一致,且在200～300cm~(-1)波数范围内有更好的信号表现.对K粉及冰毒进行了拉曼光谱测试,实测数据与理论数据基本一致.实验结果表明拉曼探头的设计达到了预期效果,并具有良好的性能.     

多波长消荧光拉曼光谱仪的研制及应用研究

拉曼光谱技术作为探究分子、晶体及其结构特征的有力手段,具有快速、无损、样品用量小、无需前处理且适应性强等优点,已被广泛应用于食品安全、石油化工等领域。但在拉曼光谱应用中,常常受到荧光背景干扰,导致拉曼信号降低,严重的情况下拉曼信号甚至会淹没在荧光背景中。为解决拉曼技术在实际应用中荧光背景干扰的问题,从仪器角度出发,采用二色镜对多波长拉曼光谱进行光路耦合设计,研制了近红外拉曼光谱与移频差分拉曼复合一体的多波长消荧光拉曼光谱检测系统,其中近红外拉曼光谱采用1 064 nm激光光源设计,移频差分拉曼光谱选取784.5和785.5 nm两组激光光源进行时分复用,在移频差分拉曼光谱检测的同时,亦可获得两组单波长拉曼光谱数据。通过对比同步测试和分时逐次测试的强度及峰位稳定性,验证了多波长消荧光拉曼光谱仪的同步测试性能;选取了多种荧光背景强弱不同的样品,进行了单波长拉曼、近红外拉曼及移频差分拉曼光谱的对比分析。针对丙酮、乙腈等荧光背景较弱的样品,可采用单波长拉曼光谱对样品进行定量及定性分析;针对食用油、红色塑胶微粒等荧光背景与拉曼信号强度相当的样品,可采用近红外拉曼光谱对样品进行定量及定性分析;针对红酒、棕色塑胶微粒等荧光背景较强的样品,需结合近红外拉曼光谱和差分拉曼光谱对样品进行定性分析。研究表明：通过多波长消荧光拉曼光谱检测系统的研制,在常规单波长拉曼光谱技术的基础上,将两种抑制荧光干扰技术有机结合,有效扩充了应用领域及样品检测范围。     

基于啁啾光纤光栅的粮仓测温网络研究

为了解决传统光纤光栅测温系统中单根光纤上带光纤光栅探头数量少、回波光强弱以及复用能力差的问题,设计研究了基于啁啾光纤光栅的测温系统。通过啁啾调制技术提高了回波光的带宽,从而增强了信号的可处理性并大大提高了带探测点位的数量。推导了啁啾调制的光栅周期表达式,给出了调制方法及波长范围。实验采用LPT-102型宽带光源与F-P光纤解调仪等,调制带宽为1 535.0～1 555.0 nm,并结合WR-201型温度传感器作标定。对20～60 ℃范围内每1 ℃改变进行测试,实验结果显示,传统光纤光栅探头与啁啾光纤光栅探头的测试温度误差相近,都符合设计要求。相比而言,啁啾FBG的测试数据对应的波长偏移具有较为明显的单调线性的特征,即数据稳定性更高,同时,采用啁啾FBG的系统带光纤光栅探头数量明显优于传统光纤光栅测温系统。由此可知,本系统在不增加光纤个数及不降低温度测试精度的基础上,实现了大幅提高带探测点位数量的设计要求。     

FBG滤波的级联LPFG温度和折射率传感装置

利用长周期光纤光栅具有较高的温度、折射率灵敏度,以及光纤布喇格光栅具有较高反射效率的特点,设计了一种基于光纤布啦格光栅滤波的级联长周期光纤光栅温度和折射率传感装置.利用光纤布喇格光栅的高反射率,将级联长周期光纤光栅干涉波峰的局部功率反射到功率计中,实现了温度和折射率的测量.基于信号叠加原理,对光纤布喇格光栅滤波的级联长周期光纤光栅温度和折射率传感方法的可行性进行了分析.将实际测得的功率计示数与温度以及折射率的变化进行二项式拟合,其确定系数分别为0.9990和0.9959,表明该传感方法可用于温度和折射率的精确测量.最后对该装置的稳定性做了一系列的测试,验证了该传感系统具有较高的稳定性.     

绝对测温转动拉曼激光雷达分光系统设计及性能

为实现转动拉曼激光雷达的绝对测量温度技术,设计并测试了多通道转动拉曼分光系统.提出了一阶闪耀光栅与光纤Bragg光栅组成的两级并行多通道拉曼分光系统,优化了其核心级联器件(微米级光纤阵列)的参数及光路结构;仿真分析了一级分光系统的分光光路,转动拉曼谱线最大离心伸缩量约为0.0031 nm,离心伸缩比为0.69%;实验测试表明一级分光系统各转动拉曼通道的通道系数均在0.75以上,提取到拉曼光谱的实测中心波长与理论值的最大偏差约为0.0398 nm,偏离度为8.86%,可提供对弹性散射信号27 dB以上的有效抑制,结合已有光纤Bragg光栅二级分光实现高达62 dB弹性散射的抑制效果,可以实现对单条偶转动量子数转动拉曼谱线的精细光谱提取.     

鼻咽癌组织拉曼光谱研究进展

鼻咽癌是东南亚地区及中国南方地区高发的恶性肿瘤,具有独特的地理、种族分布特点,并且存在恶性程度高、预后差、早期诊断困难等问题。拉曼光谱技术是基于非弹性光散射基本原理的一种快速且无损的检测方法,能够在分子振动水平上提供生化成分等信息。综述基于拉曼光谱技术的鼻咽癌组织研究最新进展。主要介绍了国内外小组采用拉曼光谱及表面增强拉曼光谱(SERS)进行鼻咽癌组织检测研究的概况,其中重点介绍该研究小组近期在鼻咽癌组织的高波数拉曼光谱、鼻咽癌组织涂片的拉曼光谱,以及研发的人活体鼻咽癌组织内镜检测装置及其临床实验情况。最后,对鼻咽癌组织拉曼光谱研究的发展前景进行了展望。     

基于空芯光纤增强拉曼光谱气体探测方法研究

拉曼光谱技术具有多组分同时探测、分析周期短和非接触等特点,被应用于多个领域,但是由于较低的探测灵敏度,限制了拉曼光谱技术的发展。针对提高拉曼光谱技术对气体探测灵敏度问题,本文设计并搭建了一套基于空芯光纤气体拉曼光谱增强系统,开展了空芯光纤拉曼光谱系统和后向散射拉曼光谱实验系统对比实验研究。实验结果表明,空芯光纤对信号、背景和噪声都具有放大效果,以空气中氮气和氧气为探测物质,与后向拉曼光谱信号相比,在相同探测时间情况下,信号强度增强60倍以上,信噪比增强约6倍;在相同探测强度情况下,探测时间仅为后向散射的1/60,噪声为后向散射拉曼系统的1/2。     

陶瓷封装对光纤光栅体温测量探头效果的影响

利用陶瓷封装技术,设计并制作了多只光纤光栅温度传感头,测试了探头的测试灵敏度、稳定性、重复性、响应速度等多个参数受封装加工形式的影响。实验采用恒温水浴装置,在36℃~45℃的温度范围内使用了中心波长位于1 540 nm和1 550 nm附近的多只布拉格光纤光栅进行了对比测量。实验结果表明:陶瓷封装布拉格光纤光栅的波长/温度响应度为9.815 pm/℃,测量标准偏差为0.08 ℃。     

Rapid near-infrared Raman spectroscopy system for real-time in vivo skin measurements

A rapid dispersive-type near-infrared (NIR) Raman spectroscopy system and a Raman probe were developed to facilitate real-time, noninvasive, in vivo human skin measurements. Spectrograph image aberration was corrected by a parabolic-line fiber array, permitting complete CCD vertical binning, thereby yielding a 3.3-16-fold improvement in signal-to-noise ratio. Good quality in vivo cutaneous NIR Raman spectra free of interference from fiber fluorescence and silica Raman scattering can be acquired in less than 1 s, which greatly facilitates practical noninvasive tissue characterization and clinical diagnosis.     

Raman spectroscopy of Chinese human skin in vivo

A novel and compact near-infrared (NIR) Raman system is developed using 785-nm diode laser, volumephase technology (VPT) holographic system, and NIR intensified charge-coupled device (CCD). Signal-tonoise ratio (SNR) and resolution are improved compared with ordinary acquisition method by a specially designed optical fiber detector and the spectrograph image aberration correction with a parabolic-line fiber array. In 1-5 s, Raman spectra of different parts of Chinese human skin are acquired. Autofluorescence is subtracted from the raw spectrum by polynomial fitting and skin Raman spectrum is then smoothed for further analysis.     

基于二向色及透射准直的小型近红外拉曼光谱仪

搭建了可用于生物医学检测的小型近红外拉曼光谱仪。通过理论计算,几何光路设计,完成了系统组装。有别于传统反射式准直结构：(1)本光谱仪色散系统采用透射式准直的方法,将散射光投射到光栅上进行色散;(2)经二向色镜分光,采用物镜对入射光会聚和散射光收集,设计了与色散系统入射狭缝相匹配(共焦面)的外光路系统,进而有效收集拉曼信号和去除杂散光;(3)实现了高分辨率(3 cm-1)、高重复性和高灵敏度光谱检测,检测范围500~2 200 cm-1(785 nm激发);(4)小型化设计,整个系统尺寸约240 mm×200 mm×130 mm,自由度高。将此自开发小型拉曼光谱仪应用于葡萄糖和膝关节软骨的拉曼光谱测试,获得了与大型商业拉曼光谱仪相媲美的结果,验证了该光谱仪具有高分辨率,高重复性和高灵敏度的优越性能,可灵活地应用于生物医学等多领域的研究。     

山药近红外拉曼光谱分析

采用785 nm半导体激光光源,全息光栅和近红外增强CCD探测器等光电器件,构建了一套近红外拉曼光谱探测系统,测试获得了山药的拉曼光谱及拉曼一阶导数谱。山药拉曼光谱谱中出现了477, 863, 936 cm-1等较强的特征峰,主要归属为蛋白质、氨基酸、淀粉、多糖等物质,与已知山药生化成分基本相符。在山药拉曼一阶导数谱中,467,484,870,943 cm-1处出现明显特征峰。对比山药拉曼光谱,在600～800 cm-1,1 000～1 400 cm-1区域内,山药拉曼一阶导数谱变化较为明显,可以更为清晰地表现山药拉曼光谱,能作为山药拉曼光谱分析的补充方法。     

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.     

Raman spectroscopy at different excitation wavelengths (1064, 785 and 532 nm) as a tool for diagnosis of colon cancer

Raman spectroscopy is structure sensitive non‐destructive method that allows observing the status of biological tissues with minimal impact. This method has a great potential in the diagnosis of various types of degenerative diseases including cancer damages. Near‐infrared Fourier transform (NIR‐FT)‐Raman (λ_ex ~1064 nm), NIR‐visible (Vis)‐Raman (λ_ex ~785 nm) and Vis‐Raman (λ_ex ~532 nm) spectra of normal and colorectal carcinoma colon tissue samples were recorded in macroscopic mode at 10–20 randomly chosen independent sites. In the cases of NIR‐Vis‐ and Vis‐Raman spectra, enhanced resonance effects were observed for tissue chromophores absorbing in the visible area. Evident spectral differences were noticed for Raman spectra of normal colon tissue samples in comparison with abnormal samples. The average Raman spectra of colon tissue samples were analysed by principal component analysis (PCA) to discriminate normal and abnormal tissues. PCA of combined dataset containing Raman intensities of chosen NIR‐FT, NIR‐Vis or Vis‐Raman bands led to discrimination of normal and abnormal colon tissue samples. Therefore, combination of these three Raman methods can be helpful for recognizing cancer lesions in colon for diagnostic purposes. Copyright © 2014 John Wiley & Sons, Ltd.     

Near‐infrared Raman spectroscopy for gastric precancer diagnosis

Raman spectroscopy is a molecular vibrational spectroscopic technique that is capable of optically probing the biomolecular changes associated with neoplastic transformation. The purpose of this study was to apply near‐infrared (NIR) Raman spectroscopy for differentiating dysplasia from normal gastric mucosa tissue. A total of 65 gastric mucosa tissues (44 normal and 21 dysplasia) were obtained from 35 patients who underwent endoscopy investigation or gastrectomy operation for this study. A rapid NIR Raman system was utilized for tissue Raman spectroscopic measurements at 785‐nm laser excitation. High‐quality Raman spectra in the range of 800–1800 cm⁻¹ can be acquired from gastric mucosa tissue within 5 s. Raman spectra showed significant differences between normal and dysplastic tissue, particularly in the spectral ranges of 850–1150, 1200–1500 and 1600–1750 cm⁻¹, which contained signals related to proteins, nucleic acids and lipids. The diagnostic decision algorithm based on the combination of Raman peak intensity ratios of I₈₇₅/I₁₄₅₀ and I₁₂₀₈/I₁₆₅₅ and the logistic regression analysis yielded a diagnostic sensitivity of 90.5% and specificity of 90.9% for identification of gastric dysplasia tissue. This work demonstrates that NIR Raman spectroscopy in conjunction with intensity ratio algorithms has the potential for the noninvasive diagnosis and detection of precancer in the stomach at the molecular level. Copyright © 2009 John Wiley & Sons, Ltd.     

基于偏最小二乘法的三种光谱定量测定LDPE/PP共混物组分含量的比较研究

分别利用中红外(mid-infrared, MIR)、近红外(near-infrared, NIR)和拉曼光谱(Raman)采集了31种不同比例的低密度聚乙烯/聚丙烯(LDPE/PP)共混物样本的光谱,利用偏最小二乘法(partial least-square, PLS)建立了光谱数据与LDPE含量的模型,研究了不同光谱范围和预处理方法对模型准确性的影响,并比较了三种光谱定量测量的准确性。结果表明,对于光谱差异小、存在噪音或基线干扰的谱图,预处理方法和光谱范围对模型的准确性均有较大的影响;经过三种预处理以及选择合适的光谱范围建立的模型决定系数(R2)分别从未处理前的0.887 6,0.849 3和0.875 7提升到0.990 6,0.997 3和0.997 2,校正均方根误差(root mean square error of calibration, RMSEC)则分别从10.15,11.75和10.67降低到2.941,1.561和1.598;三种光谱在经过预处理之后均能够较好地定量测量LDPE的含量,NIR和Raman模型准确性更高,由于两者的测量速度快,因此尤其适合于进行快速、准确的定量测量。     

The influence of cation additives on the NIR luminescence intensity of Er³⁺-doped borate glasses

Er3+-doped 25BaO-(25-x)SiO2-xAl2O3-25B2O3 transparent glasses are prepared with x = 0,12.5 and 25 by a solid-state reaction.The Er-related NIR luminescence intensity,which corresponds to the transition of 4I15/2-4I13/2,is obviously altered with different silicon/aluminum ratios.The Judd-Ofelt parameters of the Er3+ ions are adopted to explain the intensity change in the NIR fluorescence,and the Raman scattering intensity versus the amount of Al and/or Si components are discussed.The spectra of the three samples are quite similar in the peak positions,but different in intensity.The maximal phonon density of state for the samples is calculated from the Raman spectra and is correlated to the NIR luminescence efficiency.     

氯离子对结晶紫-银胶-HOPG体系近红外表面增强拉曼散射增强作用的研究

利用银胶纳米颗粒与高取向性热解石墨(HOPG)制备表面增强基底,采用近红外激光(1064nm)激发,研究了氯离子对结晶紫(CV)分子近红外表面增强拉曼散射(Near-Infrared SurfaceEnhanced Raman Scattering,NIR-SERS)的影响.结果表明,氯离子对"化学增强"和"物理增强"都有作用.同时利用扫描电镜(SEM)图像间接证明了这一结论.