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.     

Time resolved Raman spectroscopy for depth analysis of multi‐layered mineral samples

Time resolved Raman spectroscopy (TRRS) can provide subsurface information from multi‐layered samples of transparent and translucent evaporative and silicate minerals up to several centimetres thick. Depth information was obtained using 3‐ps pulsed laser excitation at 720 nm and a gated intensified charge‐coupled device detector with stepwise increasing delay times. Blocks of different minerals were used as first, second or third layers, and Raman spectra from deeper layers could be detected through 10 mm of translucent calcite and up to 40 mm of transparent halite crystals. Measurements by conventional confocal Raman, as well as spatially offset Raman spectroscopy were also successful in distinguishing different mineral layers. This study establishes the great potential for the use of Raman spectroscopy in future planetary exploration, where TRRS could be used as a non‐invasive tool for profiling the (sub‐)surface at millimetre‐depth resolution. Copyright © 2013 John Wiley & Sons, Ltd.     

Microanalysis of clay‐based pigments in painted artworks by the means of Raman spectroscopy

FT Raman spectroscopy and micro‐Raman spectroscopy with lasers of three different wavelengths (1064 nm, 785 nm and 532 nm) were used for analysis of reference samples of natural clay pigments including white clay minerals (kaolinite, illite, montmorillonite), green earths (glauconite and celadonite) and red earths (natural mixtures of white clay minerals with hematite). In addition, eight micro‐samples obtained from historical paintings containing clay pigments in ground and colour layers have been examined. Powder X‐ray diffraction and micro‐diffraction were used as supplementary methods. It was found that laser operating at 1064 nm provided the best quality Raman spectra for distinguishing different white clay minerals, but the spectra of green and red earths were affected by strong fluorescence caused by the presence of iron. Green earth minerals could be easily distinguished by 532 or 785 nm excitation lasers, even in small concentrations in the paint layers. On the other hand, when anatase (TiO₂) or iron oxides (such as hematite) were present as admixtures (both are quite common, particularly in red earths), the collection of characteristic spectra of clay minerals which form the main component of the layer was hindered or even prevented. Another complicating factor was the fluorescence produced by organic binders when analysing the micro‐samples of artworks. In those cases, it is always necessary to use powder X‐ray micro‐diffraction to avoid misleading interpretations of the pigment's composition. Copyright © 2013 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.     

The effect of spectral resolution on the Raman spectra of polyaromatic hydrocarbons and beta‐carotene mixtures

The spectroscopic basis for extraterrestrial life‐detection through the molecular signatures of relevant biomaterials is dependent upon several instrumental facilities which could effect the diagnostic interpretation of key Raman bands from relevant substances occurring together in the geological record. To this effect, the Raman spectra of several polyaromatic hydrocarbons have been investigated under different conditions of spectral resolution using FT‐Raman‐spectroscopy operating at 1064 nm laser excitation wavelength. The observed Raman spectra are considerably altered under different conditions of spectral resolution; in particular, the discrimination between several polyaromatic hydrocarbons and beta‐carotene no longer becomes possible as the spectral resolution decreases. These results are relevant for the evaluation of miniaturised Raman spectrometers for space flight missions and incorporation into instrumentation for landers and rovers being proposed for future missions to Mars. Copyright © 2010 John Wiley & Sons, Ltd.     

两种激发波长下蔬菜水果的拉曼光谱对比研究

本文通过改变不同的激光光源波长,测试分析了一系列蔬菜水果表面的拉曼谱。比较514.5nm和1064nm波长下的拉曼谱,发现514.5nm激发下许多蔬菜水果的拉曼谱均出现胡萝卜素的共振拉曼光谱,同时有很强的光荧光。更换成1064nm的近红外激光波长后,基本消除了光荧光和共振效应的影响,可用来测量蔬菜水果的有效成分,而514.5nm激发下只出现胡萝卜素的光谱,为区分蔬菜水果表面的外来物质,如农药,提供了很大的方便。     

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.     

Detection of biologically active diterpenoic acids by Raman Spectroscopy

Three poorly detectable, biologically active diterpenoic acids, kaurenoic, abietic, and gibberellic acid, were studied by using different modes of Raman spectroscopy. Because of their structural similarities, in the absence of strongly polarizable groups, conventional Raman spectroscopy is not suitable for their unambiguous identification, especially not in solution. We attempted to increase the sensitivity by applying UV‐resonance Raman spectroscopy and surface‐enhanced Raman spectroscopy (SERS) techniques. The UV‐Raman spectra of the three compounds in ethanol/water 50:50 showed only very few enhanced Raman lines. SERS spectra with 514‐nm excitation with Ag colloids were also relatively weak. The best SERS spectra were obtained with 785‐nm excitation on a novel nanostructured substrate, ‘black silicon’ coated with a 400‐nm gold layer. The spectra showed clear differences, and these ‘fingerprints’ would be suitable for the unambiguous identification of these diterpenoic acids. Copyright © 2009 John Wiley & Sons, Ltd.     

Characterization of carbon nanotube filters and other carbonaceous materials by Raman spectroscopy—II: study on dispersion and disorder parameters

Recently, we have reported on the characterization of various carbonaceous materials including multiwalled carbon nanotube (MWCNT) filters, which have specific molecular filtering capabilities and good mechanical strength and can be produced in bulk as highly aligned arrays of bundles of CNTs. We have extended our studies using Fourier transform‐Raman spectroscopy with 1064 nm excitation wavelength and a rotating sample holder in the region 1000–2800 cm⁻¹, in addition to 532 and 785 nm, which were used for Raman excitation in our previous study. Raman spectra were analyzed for band positions and line shape with special emphasis on the D‐, G‐ and G′‐ bands. For the single‐walled species, Carbotrap and graphite spectra were also recorded with 488 nm excitation. A dispersion study has been made from the Raman data available with the different excitation wavelengths. Slight band shifts and band broadening could be observed under the two sample conditions, one with the stationary sample and the other with sample rotation. The spectral changes are related to the excessive heating caused in a stationary sample by laser irradiation. Based on our findings in this study combined with our earlier study, we can state that only a careful line shape analysis and study of intensity pattern of the D‐ and G‐Raman bands under well‐defined measurement conditions lends itself as a good measure of degree of alignment in the MWCNT bundles. Copyright © 2010 John Wiley & Sons, Ltd.     

Identification of reddish pigments in octocorals by Raman spectroscopy

The nature of the pigments in octocorals has been investigated by Raman spectroscopy, where laser excitation at 632.8 and 1064 nm were used to characterize the colored components present in the skeleton of the exotic pink‐yellow soft coral Chromonephthea braziliensis, the reddish purple sea fan Leptogorgia punicea and the endemic deep violet red Leptogorgia violacea from the southeastern coast of Brazil. The observed positions of two major Raman bands at ca 1500 cm⁻¹ [ν(CC)] and 1130 [ν(C C)] for all specimens strongly suggest the presence of a mixtureof conjugated polyenes belonging to a class of compounds named parrodienes. The hemiketal steroidal feeding deterrent, 23‐keto‐cladiellin‐A, isolated from C. braziliensis was identified in the crude extracts by the Raman analysis using 1064 nm excitation. The observation of the most important vibrational bands of this compound can be useful in future investigations to monitor its presence in crude extracts of C. braziliensis and or other species. Copyright © 2010 John Wiley & Sons, Ltd.     

Temperature dependence of the raman spectra of carbon nanotubes with 1064 nm excitation

In this report, the near infrared 1064 nm line of an Nd:YAG laser, which has strong thermal effect, was used as the excitation. A temperature dependence of the Raman spectra of carbon nanotubes was observed at different temperatures by varying the incident laser power. The results show that the relative Raman intensities to the tangential stretching mode (G mode) of the higher-order Raman modes within 2500–3500 cm⁻¹ increase with increasing excitation laser power at the sample and the changes in the relative Raman intensities are linear in the excitation laser power. This has not been reported elsewhere. Thorough analysis shows that this is a temperature dependence of double-phonon Raman scattering and maybe provide important information for the studying of CNTs and double-phonon Raman scattering.     

Observation of resonance electronic and non‐resonance‐enhanced vibrational natural Raman optical activity

Natural resonance electronic Raman optical activity (ROA) is observed for the first time. Coincidently, the first example of vibrational ROA enhanced by low‐lying electronic transition is reported. These new phenomena were measured using the rare‐earth complex Eu(tfc)₃ (+)‐tris[3‐trifluoroacetyl‐D ‐camphorato]europium(III), where electronic resonance occurs between the 532‐nm laser excitation and the ⁷F₁ → ⁵D₁ transition of the Eu³⁺ metal center. Electronic Raman spectra involve the Raman transitions terminating on the low‐lying electronic states of Eu(tfc)₃. The observed vibrational ROA spectra are enhanced relative to typical ROA spectra by the proximity of vibrational states of Eu(tfc)₃ to its low‐lying electronic states with significant magnetic‐dipole character, whereas the parent vibrational Raman spectra do not appear to be resonance‐enhanced since the 532‐nm vibrational Raman spectrum has similar relative intensities to the corresponding Raman spectrum measured with 1064‐nm laser excitation. Copyright © 2010 John Wiley & Sons, Ltd.     

Plasmon‐enhanced Raman scattering of coaxial hybrid nanowires made with light‐emitting polymer and gold

We report on the plasmon‐enhanced Raman scattering of coaxial hybrid nanowires (NWs) made with light emitting poly(3‐methylthiophene) (P3MT) and gold (Au) core or coating. Absorption spectra of coaxial hybrid NWs showed the absorption peaks because of localized surface plasmon (SP) excitation at ~ 567 and ~ 610 nm, in addition to the π–π* transition peaks of P3MT. Raman spectra of a single strand of coaxial hybrid NW and plain P3MT NW was obtained by using three different wavelengths of laser excitation of 514, 633, and 785 nm. We found that Raman intensities of hybrid coaxial NWs were enhanced by 4 to 15 times over those of plain P3MT NWs with the Raman excitation wavelengths close to the observed SP energies of coaxial NWs. We attributed the observed enhancement of the Raman signal to the resonance of the incident laser with the matching SP energies, rather than the possible doping level change, in hybrid coaxial NWs. Copyright © 2012 John Wiley & Sons, Ltd.     

Forensic and security applications of a long‐wavelength dispersive Raman system

A novel dispersive system operating at 1064‐nm excitation and coupled with transfer electron InGaAs photocathode and electron bombardment CCD technology has been evaluated for the analysis of drugs of abuse and explosives. By employing near‐IR excitation at 1064‐nm excitation wavelength has resulted in a significant damping of the fluorescence emission compared to 785‐nm wavelength excitation. Spectra of street samples of drugs of abuse and plastic explosives, which usually fluoresce with 785‐nm excitation, are readily obtained in situ within seconds through plastic packaging and glass containers using highly innovative detector architecture based upon a transfer electron (TE) photocathode and electron bombarded gain (EB) technology that allowed the detection of NIR radiation at 1064 nm without fluorescence interference. This dispersive near‐IR Raman system has the potential to be an integral part in the armoury of the forensic analyst as a non‐destructive tool for the in‐situ analysis of drugs of abuse and explosives. Copyright © 2015 John Wiley & Sons, Ltd.     

Study of Raman spectrum of uranium using a surface‐enhanced Raman scattering technique

Raman spectroscopic investigation on weak scatterers such as metals is a challenging scientific problem. Technologically important actinide metals such as uranium and plutonium have not been investigated using Raman spectroscopy possibly due to poor signal intensities. We report the first Raman spectrum of uranium metal using a surface‐enhanced Raman scattering‐like geometry where a thin gold overlayer is deposited on uranium. Raman spectra are detected from the pits and scratches on the sample and not from the smooth polished surface. The 514.5‐ and 785‐nm laser excitations resulted in the Raman spectra of uranium metal whereas 325‐nm excitation did not give rise to such spectra. Temperature dependence of the B_3g mode at 126 cm⁻¹ is also investigated. Copyright © 2011 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.     

Raman spectroscopy of proteins: a review

In this work, 26 proteins of different structure, function and properties are investigated by Raman spectroscopy with 488, 532 and 1064 nm laser lines. The excitation lines were chosen in NIR and Vis range as the most common and to show the difference due to normal and resonance effect, sometimes accompanied by the fluorescence. The selected proteins were divided, according to the Structural Classification of Proteins, into four classes according to their secondary structure, i.e. α‐helical (α), β‐sheet (β), mixed structures (α/β, α + β, s) and others. For all compounds, FT‐Raman and two Vis spectra are presented along with the detailed band assignment. To the best of our knowledge, this is the first review showing the potential of Raman spectroscopy for the measurement and analysis of such a large collection of individual proteins. This work can serve as a comprehensive vibrational spectra library, based on our and previous Raman measurements. Copyright © 2013 John Wiley & Sons, Ltd.     

不同激发波长下单壁碳纳米管与多壁碳纳米管的拉曼光谱比较

对不同激发波长下单壁和多壁碳纳米管的激光拉曼光谱进行了比较。发现单壁碳纳米管D峰强度和G峰强度的比值(ID/IG)几乎不随激发光子能量的改变而变化,多壁碳纳米管ID/IG值随着激发光子能量的增加以斜率0 3/eV减小。并对此现象进行了初步的分析。此外,还发现在1064nm激发波长下,单壁和多壁碳纳米管2500-3500cm-1之间拉曼峰的相对强度随着入射激光功率的增加而增加。     

Surface‐enhanced Raman micro‐spectroscopy of DNA/RNA bases adsorbed on pyroxene rocks as a test of in situ search for life traces on Mars

SERS spectroscopy with 785‐nm laser excitation minimizing fluorescence emission is exploited for remote analysis of life traces in an extraterrestrial environment. Adenine and guanine, nucleobases present in both DNA and RNA strands, and microRNA containing adenine and guanine have been used as testing ligands for identifying traces of nucleic acids in Martian rocks and sediments. SERS spectra of these nucleobase samples adsorbed on pyroxene substrates have been investigated with micro‐Raman apparatus in the absence of sample manipulation and inducing the signal enhancement by deposition of silver colloidal nanoparticles over the pyroxene/nucleobase substrates. An order‐of‐magnitude estimate of the sample amount responsible for the SERS spectra is given. Copyright © 2009 John Wiley & Sons, Ltd.