Rapid shifted excitation Raman difference spectroscopy with a distributed feedback diode laser emitting at 785 nm

A distributed feedback (DFB) laser diode emitting at 785 nm was tested and applied as a light source for shifted excitation Raman difference spectroscopy (SERDS). Due to the physical properties of the laser diode, it was possible to shift the emission wavelength by 8 cm^-1 (0.5 nm) required for our SERDS measurements by simply changing the injection current. The internal grating ensured single mode operation at both wavelength with the frequency stability of ±0.06 cm^-1 (0.004 nm) required for high resolution Raman spectroscopic applications. The shifted spectra were used for calculating enhanced Raman spectra being obscured by a strong scattering background. A 16 dB (≈38 fold) improvement of the signal-to-background noise S̄/σ_B was demonstrated using blackboard chalk as a sample. The tunable DFB laser is a versatile excitation source for SERDS, which could be used in any dispersive Raman system to subtract fluorescence contributions and scattering background. PACS 82.80.Gk; 42.55.-f; 42.64.Fi     

Dual‐wavelength monolithic Y‐branch distributed Bragg reflection diode laser at 671 nm suitable for shifted excitation Raman difference spectroscopy

A dual‐wavelength monolithic Y‐branch distributed Bragg reflection (DBR) diode laser at 671 nm is presented. The device is realized with deeply etched surface DBR gratings by one‐step epitaxy. A maximum optical output power of 110 mW is obtained in cw‐operation for each laser cavity. The emission wavelengths of the device are 670.5 nm and 671.0 nm with a spectral width of 13 pm (0.3 cm⁻¹) and a mean spectral distance of 0.46 nm (10.2 cm⁻¹) over the whole operating range. Together with a free running power stability of ± 1.1% this most compact diode laser is ideally suited as an excitation light source for portable shifted excitation Raman difference spectroscopy (SERDS).     

785nm便携式光栅外腔可调谐半导体激光器的研制和输出特性

针对移频激发拉曼光谱测试系统的小型化需求,在Littrow结构中,采用商用的785nm大功率激光二极管作为增益器件,构建了一款便携式光栅外腔可调谐半导体激光器。该激光器通过采用一种新型的波长调谐方法,即以改变半导体增益器件相对于准直透镜的水平位置来实现波长的连续调谐,实现了尺寸为140mm×65mm×50mm的小型化结构设计。相比于传统的旋转衍射光栅改变光线在光栅上的入射角来实现波长调谐的方式,该方法有效地缩减了增益器件的平移距离,从而有利于便携式外腔激光器波长的快速宽带调谐。实验结果表明,该激光器具有较宽的波长调谐范围,在340~900mA注入电流下均可实现10nm以上的波长调谐,尤其在900mA大注入电流下,其波长调谐覆盖779.40~791.07nm,调谐范围可达11.67nm,且激射线宽小于0.2nm,单波长输出功率最高可达280mW,放大的自发辐射抑制比大于25dB,呈现出较优异的输出性能,满足移频激发拉曼光谱检测系统对光源的基本要求。此外,该激光器可采用一微型压电陶瓷驱动器来实现波长的电动调谐,实验获得了1.35nm的波长调谐范围,证实了所制785nm便携式光栅外腔可调谐半导体激光器适合作为便携式移频激发拉曼光谱检测系统的光源用于减除原始拉曼光谱中的荧光背景。     

Naturally grown Ag nanoparticles on quartz substrates as SERS substrate excited by a 488 nm diode laser system for SERDS

A silver nanoparticle ensemble was prepared under ultrahigh vacuum (UHV) conditions by Volmer–Weber growth on a quartz substrate for surface-enhanced Raman scattering (SERS) investigations of pyrene molecules. To tune the surface plasmon resonance frequency in the vicinity of the excitation wavelength of 488 nm of the diode laser, the morphology of the silver nanoparticles was optimized. The substrates were mounted in a flow-through cell as part of the optical Raman set-up. A microsystem diode laser generates two slightly different emission wavelengths (λ=487.61 nm and λ=487.91 nm) with a spectral width <10 pm and an optical power of 20 mW, i.e. SERS experiments are possible but also shifted excitation Raman difference spectroscopy (SERDS) can be carried out. For trace analysis of pyrene in water we demonstrate SERS/SERDS experiments which lead to a limit of detection of 2 nmol/l for pyrene. These results suggest that with silver nanoparticle ensembles excited at their plasmon resonance at 488 nm combined SERS/SERDS measurements can be effectively performed for in-situ trace analysis of pollutant chemicals in water.     

双波长LD模块的拉曼光谱测试系统

荧光干扰是拉曼光谱检测过程中常见的干扰因素之一,而移频激发法是一种有效的克服荧光干扰的检测手段。移频激发法利用两个波长相近的激光分别激发被测物质,并将获得的拉曼光谱进行差谱。由于两次激发的荧光背景相同,而拉曼特征峰会产生平移,因此可有效地消除荧光背景的干扰,进而利用一定的算法还原拉曼特征峰。移频激发法的关键在于两个激发光波长的稳定性,不稳定的波长差将严重影响对拉曼特征峰的还原效果。本文研制了一种拉曼光谱测试系统,该系统的双波长LD模块能够产生两个波长稳定的激发光(分别为784.7和785.8 nm),满足移频激发法的测试要求。影响激发光波长稳定性的因素主要是光功率和温度,本系统中对这两个因素均进行了实时的监控,以保证激发光波长的稳定。系统的硬件部分主要包括ARM主控板、双波长LD模块及其驱动电路、温度控制板、数字光开关、光谱检测光路和光纤探头(两个高功率的蝶形封装激光器);软件部分可自动获取被测物质的拉曼光谱图,并对其进行后续的处理。在稳定性测试实验中,对系统驱动电源电流和激光器温度的稳定性均进行了测试。测试结果显示,电流波动范围小于0.01 mA、温度变化范围小于0.004 ℃,能够有效地保证激发光波长的稳定性。最后,对某品牌花生油进行了拉曼光谱检测,并对检测结果进行了处理,获得了良好的效果。     

SERS signal response and SERS/SERDS spectra of fluoranthene in water on naturally grown Ag nanoparticle ensembles

We present experimental results of the time‐dependent Raman signal response of fluoranthene adsorbed on a naturally grown Ag nanoparticle ensemble, which serves as surface enhanced Raman scattering (SERS) substrate. In addition, SERS characteristics such as the concentration‐dependent calibration curves and the limit of detection (LOD) for fluoranthene in distilled water will be shown. The SERS substrate was prepared by Volmer–Weber growth under ultrahigh vacuum condition and exhibits a plasmon resonance wavelength at 491 nm. For the measurement of SERS signal response and SERS/shifted excitation Raman difference spectroscopy spectra of fluoranthene in water, experimental Raman setup containing a microsystem light source with two emission wavelengths (487.61 nm and 487.91 nm) was used. We experimentally demonstrate that the maximum SERS intensity is achieved 9 min after changing the analyte concentration from 0 nmol/l to 600 nmol/l. This response time is explained by a time‐dependent adsorption of the probe molecules onto the nanoparticles. The LOD for fluoranthene in water was evaluated applying shifted excitation Raman difference spectroscopy (SERDS) at different molecule concentrations. For SERDS, two emission wavelengths of a prototype microsystem light source have been used for Raman excitation. The experimental results reveal that the LOD for the probe molecules is very low. Experimentally, we have detected a fluoranthene concentration of only 4 nmol/l, which is very close to our estimated LOD of 2 nmol/l. Thus, the presented Raman setup, with a SERS substrate, whose plasmon resonance coincides with the excitation wavelength for SERS measurements, is well suited for in‐situ trace detection of pollutant chemicals in water. Copyright © 2013 John Wiley & Sons, Ltd.     

Instantaneous shifted‐excitation Raman difference spectroscopy (iSERDS)

Shifted‐excitation Raman difference spectroscopy (SERDS) is an experimental method to recover spontaneous Raman spectra despite the presence of strong fluorescence interference. The common scheme requires a tunable laser source and recording two spectra after each other. In this paper, an approach for instantaneous SERDS (iSERDS) is presented utilizing a broadband light source. The broadband radiation is spatially dispersed in the focal plane inside the object of investigation. The generated scattering signal is imaged onto the slit of an imaging spectrograph. The individual pixel lines on the detector represent Raman spectra with slightly shifted excitation wavelength and hence allow SERDS spectra to be derived. The proposed iSERDS technique is a suitable approach for obtaining Raman spectra from fluorescing samples provided they are homogenous on the length scale of the measurement volume. Copyright © 2014 John Wiley & Sons, Ltd.     

Effects of laser excitation wavelength and optical mode on Raman spectra of human fresh colon,pancreas, and prostate tissues

Early cancer detection is the central and most important factor for allowing successful treatment and resultant positive long‐term patient outcomes. Recently, optical techniques have been applied to this purpose, although each has inherent limitations. In particular, Raman spectroscopy applied in the pathological diagnosis of cancerous tissues has received increasing attention, with the merit of being highly sensitive to the biochemical alterations in tissue compositions and applicable in vivo. Nevertheless, its application has been impeded by the high background intensity, which masks the Raman signal of biological molecules. In this work, the influence of laser excitation wavelength (785 vs. 830 nm) and optical mode (single mode vs. multimode) on the background intensity of fresh human tissues was studied. Based on the results, laser with 830 nm excitation demonstrated better background reduction than that with 785 nm excitation for the same optical mode, but the Raman signal intensity was conversely reduced, and the signal‐to‐noise ratio (SNR) not improved. In contrast, by comparing single‐mode and multimode 785 nm excitations, it was shown that the single‐mode laser with its smaller beam waist and beam propagation factor had better background reduction ability and an improvement of the SNRs. It is speculated that this decrease in background intensity comes from the effect of the optical mode on the Mie scattering from the biological tissue. High‐quality spectra based on a careful selection of both laser excitation wavelength and optical mode will benefit Raman measurements in further research focusing on spectral interpretation and histopathological correlation ultimately aimed toward intraoperative applications. Copyright © 2014 John Wiley & Sons, Ltd.     

Comparison of near infrared laser excitation wavelengths and its influence on the interrogation of seized drugs‐of‐abuse by Raman spectroscopy

The laser excitation wavelength is an important parameter in obtaining Raman spectra from drugs‐of‐abuse. This article compares the effect of near infrared wavelengths, 785 nm, using both benchtop and portable instrumentation and benchtop 1064 nm on the Raman spectra of seized drugs‐of‐abuse, including cocaine hydrochloride, cocaine freebase (crack), methylenedioxymethamphetamine (‘ecstasy’), amphetamine, diamorphine (heroin) and cannabis. The significant benefit of using 1064 nm for the interrogation of this type of sample is highlighted. Copyright © 2009 John Wiley & Sons, Ltd.     

Surface‐enhanced Raman spectra of melamine and other chemicals using a 1550 nm (retina‐safe) laser

Many trace chemical analyses are being transitioned from the lab to the field, among which is surface‐enhanced Raman spectroscopy. Although initial portable Raman analyzers primarily employ 785 nm laser excitation, recent studies suggest longer wavelengths, with an appropriate surface‐enhanced Raman‐active substrate, may provide equal sensitivity. Furthermore, 1550 nm excitation may provide added safety for the user, in that permanent retina damage does not occur. Here, we show that a reasonable enhancement factor can be obtained for melamine using 1550 nm laser excitation that is nearly equivalent to those obtained using 785 and 1064 nm laser excitation. We also demonstrate that a number of other chemicals of interest can be measured by 1550 nm surface‐enhanced Raman scattering, albeit only modest sensitivity is achieved because of instrument limitations, not enhancement factors. Copyright © 2011 John Wiley & Sons, Ltd.     

噻菌灵农药的表面增强拉曼光谱分析

利用表面增强拉曼光谱技术(SERS)分析噻菌灵农药的拉曼特征峰。采用微波法制备银溶胶表面增强基底,利用激光显微共焦拉曼光谱仪分别采集514.5和785 nm激发波长下的噻菌灵农药拉曼光谱,解析不同激发波长下的拉曼特征峰并进行比较。结果表明：不同激发波长下噻菌灵的拉曼峰强度和拉曼频移差异较大,514.5 nm激发波长下的782和1 012 cm-1最强,是C—H变形振动较强特征峰,而785 nm激发波长下的1 284,1 450和1 592 cm-1最强,是环振动和CN伸缩振动较强特征峰。对比分析各个激发波长下噻菌灵的SERS谱图,找到了噻菌灵农药的5个较强特征拉曼峰：782,1 012,1 284,1 450和1 592 cm-1。这些特征峰可作为食品及农产品中噻菌灵农药残留定性定量判别的依据。     

Laser wavelength dependence of background fluorescence in Raman spectroscopic analysis of synovial fluid from symptomatic joints

Gout is a disease process where the nucleation and growth of crystals in the synovial fluid of joints elicit painful arthritis‐like symptoms. Raman spectroscopy is evolving as a potential diagnostic tool in identifying such crystals; however, attainment of sufficient Raman signal while overcoming the background fluorescence remains as a major challenge. The current study focused on assessing whether excitation in 532–700 nm range will provide greater signal intensity than the standard 785 nm while not being impeded by background fluorescence. We characterized the fluorescence spectra, absorption spectra and Raman spectra of synovial fluid from patients who presented ‘gout‐like symptoms’ (symptomatic) and controls (asymptomatic). A digestion and filtration method was developed to isolate crystals from synovial fluid while reducing the organic burden. Spectral profile and photobleaching dynamics during Raman spectroscopy were observed under an excitation wavelength range spanning 532 to 785 nm. Absorbance and fluorescence profiles indicated the digestion and filtration worked effectively to extract crystals from symptomatic synovial fluid without introducing additional fluorescence. Raman spectral analyses at 532 nm, 660 nm, 690 nm and 785 nm indicated that both asymptomatic and symptomatic samples had significant levels of fluorescence at excitation wavelengths below 700 nm, which either hindered the collection of Raman signal or necessitated prolonged durations of photobleaching. Raman‐based diagnostics were more feasible at the longest excitation wavelength of 785 nm without employing photobleaching. This study further demonstrated that a near‐infrared (NIR) OEM‐based lower‐cost Raman system at 785 nm excitation has sufficient sensitivity to identify crystals isolated from the synovial fluid. In conclusion, while lower excitation wavelengths provide greater signal, the fluorescence necessitates NIR wavelengths for Raman analysis of crystal species observed in synovial aspirates. Copyright © 2013 John Wiley & Sons, Ltd.     

Implementation of a novel low‐noise InGaAs detector enabling rapid near‐infrared multichannel Raman spectroscopy of pigmented biological samples

Pigmented tissues are inaccessible to Raman spectroscopy using visible laser light because of the high level of laser‐induced tissue fluorescence. The fluorescence contribution to the acquired Raman signal can be reduced by using an excitation wavelength in the near infrared range around 1000 nm. This will shift the Raman spectrum above 1100 nm, which is the principal upper detection limit for silicon‐based CCD detectors. For wavelengths above 1100 nm indium gallium arsenide detectors can be used. However, InGaAs detectors have not yet demonstrated satisfactory noise level characteristics for demanding Raman applications. We have tested and implemented for the first time a novel sensitive InGaAs imaging camera with extremely low readout noise for multichannel Raman spectroscopy in the short‐wave infrared (SWIR) region. The effective readout noise of two electrons is comparable to that of high quality CCDs and two orders of magnitude lower than that of other commercially available InGaAs detector arrays. With an in‐house built Raman system we demonstrate detection of shot‐noise limited high quality Raman spectra of pigmented samples in the high wavenumber region, whereas a more traditional excitation laser wavelength (671 nm) could not generate a useful Raman signal because of high fluorescence. Our Raman instrument makes it possible to substantially decrease fluorescence background and to obtain high quality Raman spectra from pigmented biological samples in integration times well below 20 s. Copyright © 2015 John Wiley & Sons, Ltd.     

Fast detection of sulphate minerals (gypsum,anglesite, baryte) by a portable Raman spectrometer

Well‐resolved Raman spectra of gypsum, anglesite and baryte were detected using a portable Raman instrument (Ahura First Defender XL) in the laboratory and outdoor under atmospheric conditions. Spectra were obtained using a 785‐nm excitation. The portable spectrometers display generally lower spectral resolution compared with the laboratory confocal instrument but permit the fast, unambiguous detection of minerals under field conditions. Portable Raman instruments can be advocated as excellent tools for field geological, environmental as well as exobiological applications. A miniaturized Raman instrument will be included in the Pasteur analytical package of the ESA ExoMars mission and interesting research applications can now be proposed for in situ field planetary studies. Additionally, portable Raman instruments represent an ideal tool for demonstrating possible applications of Raman spectroscopic techniques outdoor. In geosciences this approach represents a new field which could completely change classical field work. Copyright © 2009 John Wiley & Sons, Ltd.     

Increase of the stimulated Raman scattering threshold at droplets by spectral broadening of nanosecond laser pulses

We show that the threshold of stimulated Raman scattering (SRS) from single micro‐droplets increases with the bandwidth of the pulsed excitation laser radiation. SRS thresholds were experimentally investigated for two droplet sizes and two excitation bandwidths. For the narrowband excitation, a frequency doubled Nd:YAG laser with a central wavelength of 532 nm, a full width half maximum (FWHM) bandwidth of 0.05 nm and a repetition rate of 10 Hz was used. For the comparison with the broadband excitation, a dye resonator containing Rhodamine 6G being pumped by the Nd:YAG laser was utilized with a central wavelength of 566 nm and a FWHM bandwidth of 4 nm. Droplets of 89 and 116 µm diameters, respectively, were illuminated by a vertical light sheet. If the broadband excitation is applied instead of the narrowband excitation ‐ for both droplet sizes ‐ the pulsed excitation energies can be increased by a factor of approximately 5 before the SRS threshold is reached. The multiplication register of an emCCD detector was used to detect low signals. The gain factor of the detector was calibrated and adapted to different excitation energies and signal intensities. Copyright © 2012 John Wiley & Sons, Ltd.     

Quantitative analysis of sugar composition in honey using 532‐nm excitation Raman and Raman optical activity spectra

Raman spectroscopy based on the 1064‐nm laser excitation was suggested as a handy non‐invasive technique allowing to quickly determine sugar content in honey and similar food products. In the present study, the green 532‐nm laser radiation is explored instead as it provides higher‐quality spectra in a shorter time. The sample fluorescence was quenched by purification with activated carbon. For control mixture decomposition of Raman spectra to standard subspectra led to a typical error of the sugar content of 3%. Raman optical activity (ROA) spectra that could be measured at the shorter excitation wavelength as well provided a lower accuracy (~8%) than the Raman spectra because of instrumental sensitivity and noise limitations. The results show that Raman spectroscopy provides elegant and reliable means for fast analyses of sugar‐based food products. Copyright © 2016 John Wiley & Sons, Ltd.     

Multiexcitation Raman Spectroscopy in Identification of Chinese Jade

The high-fluorescence background of jade creates a great impact on the Raman spectra measurements that impedes their application in jade analysis and treatment, particularly with ancient jade. The five most important materials of Chinese ancient jade are amphibole, serpentine, turquoise, agate/chalcedony, and anorthite-zoisite (Dushan jade). This study comparatively analyzed the Raman spectra of different wavelengths' excitation light sources (514.5 nm, 632.8 nm, 785 nm) in identifying these Chinese jades, and this article discusses the most applicable ones to the analysis of different jade materials. The results show that although 632.8 nm He-Ne laser is appropriate for turquoise jades, generally speaking, Raman spectra produced by the 785 nm semiconductor laser and the 632.8 nm He-Ne laser are better for most kinds of jades than the spectra produced by the 514.5 nm argon ion laser, and both of them can be effectively used jointly in research by nondestructive phase analysis of Chinese ancient jade.     

胞嘧啶核苷在纳米银膜上的NIR-SERS光谱检测

采用一种高活性的纳米银膜作为表面增强拉曼散射(SERS)基底,以近红外激光(785 nm)作为激发光源,对胞嘧啶核苷(胞苷)水溶液(10-2～10-8 mol·L-1)进行了近红外表面增强拉曼散射(NIR-SERS)光谱检测。实验结果表明,当胞苷水溶液浓度等于或低于10-7 mol · L-1时,可在300～2 000 cm-1范围内获得信噪比较好的NIR-SERS光谱。将胞苷水溶液(10-2～10-5 mol · L-1)分别滴在10片不同的纳米银薄膜上进行检测,结果表明该纳米银膜体现出了较好的光谱重现性。通过对纳米银膜表面形貌进行表征发现聚乙烯醇(PVA)包覆的纳米银颗粒在铝片表面形成“草状”结构。并通过对吸附了胞苷分子的纳米银膜进行紫外-可见光反射光谱检测,发现在800 nm处出现等离子共振峰。因此采用785 nm的近红外激光作为激发光时,该体系能够体现出强烈的表面等离子共振(surface plasmon resonance, SPR)特性。同时采用DFT-B3LYP/6-311G对胞苷分子进行了拉曼光谱计算,计算所采用入射光波长为785 nm,通过计算结果与实验测得的胞苷固体的拉曼光谱对比发现在300～2 000 cm-1范围内两者匹配得较好,进而对其振动进行了归属。最后通过比较胞苷的拉曼光谱和NIR-SERS光谱对胞苷分子在纳米银膜上的可能吸附方式进行了分析。分析结果表明胞苷分子主要为其核糖部分吸附纳米银颗粒上,同时该分子的17NH₂基团可能靠近局域电磁场增强区域。     

Rapid outdoor non‐destructive detection of organic minerals using a portable Raman spectrometer

Raman spectral signatures have been obtained for a series of organic minerals using a compact portable Raman instrument equipped with 785‐nm laser excitation. Well‐resolved Raman spectra of crystalline salts of carboxylic acids, whewellite and mellite, as well as of the aromatic mineral idrialite were recorded. For comparative purposes, an amorphous fossil resin, baltic amber, was also investigated. The results obtained confirm that portable Raman instruments can be considered as excellent tools for field geological applications, including the detection of organic minerals in the frame of outcrops of sedimentary rocks or coal beds. Organic minerals can be added to the list of established biomarkers, including porphyrins, hydrocarbons and organic acids, which are important for the study with regard to future exobiological missions such as the ESA ExoMars mission to detect the presence of extinct or extant life on Mars. Copyright © 2009 John Wiley & Sons, Ltd.     

Influence of surface plasmon resonance wavelength on SERS activity of naturally grown silver nanoparticle ensemble

We present experimental results to quantify and optimize the surface‐enhanced Raman scattering (SERS) activity of naturally grown silver nanoparticles. Ag nanoparticle ensembles with mean equivalent radii ranging from 10.6 to 20.3 nm were prepared under ultrahigh vacuum conditions by Volmer–Weber growth on quartz plates. A tuning of the localized surface plasmon polariton resonance wavelength from 453 to 548 nm was performed by varying the morphology of the silver nanoparticles. The dependence of the SERS activity on the plasmon resonance wavelength was investigated with a Raman set‐up containing a microsystem light source with an emission line at 488 nm. Shifted excitation Raman difference spectroscopy was applied to remove the fluorescence‐based background from the SERS spectra of pyrene in water using two slightly different emission wavelengths (487.61 and 487.91 nm) of the microsystem light source. We demonstrate that the Raman activities for all SERS substrates are available in the nanomolar range in a water sample. However, the Raman activity crucially depends on the plasmon resonance wavelength of the nanoparticle ensembles. Although for an on‐resonance ensemble the limit of detection for pyrene in water is very low and was estimated to be 2 nmol/L, it increases rapidly to several tens of nanomol for slightly off‐resonance ensembles. Hence, the highest SERS activity was obtained with a nanoparticle ensemble exhibiting a plasmon resonance wavelength at 491 nm, which almost coincides with the excitation wavelengths. Copyright © 2012 John Wiley & Sons, Ltd.