On-line FT-Raman and dispersive Raman spectra database of artists’ materials (e-VISART database)

Raman spectroscopy has been widely applied in the analysis of different types of artwork. This technique is sensitive, reliable, non-destructive and can be used in situ. However, there are few references in the literature regarding specific Raman spectra libraries for the field of artwork analysis. In this paper, the development of two on-line databases with Fourier transform Raman (FT-Raman; 1064 nm) and dispersive Raman (785 nm) spectra of materials used in fine art is presented; both are implemented in the e-vibrational spectroscopic databases of artists materials database (e-VISART). The database provides not only spectra, but also information about each pigment. It must be highlighted that for each pigment or material several spectra are available from different dealers. Some of the FT-Raman spectra available in the e-VISART database have not been published until now. Some examples in which the e-VISART database has been successfully used are presented.     

Synthesis and Characterization of Polymeric Materials from Vegetable Oils

Although the petrochemical polymers have revolutionized the technological development, the intensive use of these materials have contributed to the global pollution. In this context, researches involving ecofriendliness materials are growing up, as well as, a current interest in developing materials from inexpensive and renewable resources, such as vegetable oils. In this work, is described the synthesis of polymeric materials by thermal polymerization from linseed oil (Linum usitatissimum L.) and passion fruit oil (Passiflora edulis) and their characterization by gas chromatographic (GC), Fourier transform infrared (FTIR) spectroscopy, solubility in organic solvents, thermogravimetry (TG), differential scanning calorimetry (DSC) and Raman spectroscopy. The TG curve shows that those polymeric materials present two stages of decomposition. DSC plots of the vegetable oils showed some endothermic and exothermic transitions which are not present in the DSC curves corresponding to oil-based polymers. The Raman spectra of the polymers indicate declining of absorbance in the region of CC stretching (∼1600 cm⁻¹). This absorption was used to estimate the degree of polymerization (79% and 67.5% for linseed and passion fruit oils, respectively).     

Raman spectroscopic study of amorphous and crystalline hydrocarbons from soils, peats and lignite

FT-Raman spectra were obtained from the natural hydrocarbon mixtures ozokerite and hatchettite as well as from the terpenoid minerals fichtelite (norabietane) and hartite (alpha-phyllocladane). Some of these hydrocarbons occur in soil and peat environments of Holocene age. However, hartite occurs in lignite, in fossilised Glyptostrobus (Taxodiaceae) trees and in pelosiderites of the Bílina Miocene series (about 20 Ma); it represents the accumulated and crystallised product of diagenetic transformation of precursor biogenic terpenoids. Raman spectra of earth waxes investigated confirm their dominantly aliphatic character and oxidative degradation (related to weathering and/or subaerial alteration in museum cabinets). Vibrational assignments are proposed and differences in Raman spectra of fichtelite and hartite discussed. Some of the individual features can be used for discrimination (e.g., hartite bands at 1480, 1310, 1287, 1041, 729 and 693 cm(-1) and fichtelite bands at 1302, 836, 717 and 533 cm(-1)).     

Comparison of UV and visible Raman spectroscopy of bulk metal molybdate and metal vanadate catalysts

The visible (532 and 442 nm) and UV (325 nm) Raman spectra of bulk mixed metal oxides (metal molybdates and metal vanadates) were compared on the same spectrometer, for the first time, to allow examination of how varying the excitation energy from visible to UV affects the resulting Raman spectra. The quality of the Raman spectra was found to be a strong function of the absorption properties of the bulk mixed oxide. For bulk mixed metal oxides that absorb weakly in the visible and UV regions, both the visible and UV Raman spectra were of high quality and exhibit identical vibrational bands, but with slightly different relative intensities. For bulk mixed metal oxides that absorb strongly in the UV and visible regions and/or strongly in the UV and weakly in the visible regions, the visible Raman spectra are much richer in structural information and of higher resolution than the corresponding UV Raman spectra. This is a consequence of the strong UV absorption that significantly reduces the sampling volume and number of scatterers giving rise to the Raman signal. The shallower escape depth of UV Raman, however, was not sufficient to detect vibrations from the surface metal oxide species that are present on the outermost surface layer of these crystalline mixed metal oxide phases as previously suggested. It was also demonstrated that there is no sample damage by the more energetic UV excitation when very low laser powers and fast detectors are employed, thus avoiding the need of complicated fluidized bed sample arrangements sometimes used for UV Raman investigations. The current comparative Raman investigation carefully documents, for the first time, the advantages and disadvantages of applying different excitation energies in collecting Raman spectra of bulk mixed metal oxide materials.     

Raman microspectroscopic studies of amber resins with insect inclusions

Raman microscope spectra of specimens of Baltic and Mexican amber resins containing insect inclusions have been analysed using near-infrared excitation to assess the potential for discrimination between the keratotic remains of the insects and the terpenoid matrix. For the Mexican amber specimen the insect spectra exhibit evidence of significant protein degradation compared with the insect remains in the Baltic amber specimen. In both cases the Raman spectra of the insect remains are still distinguishable from the amber resins. Despite its better preservation, however, no spectra could be obtained from the inside of the larger insect preserved in the Baltic amber in agreement with the observation that most insect inclusions in amber are hollow. It is noted that the Mexican amber insect is located adjacent to a large gas bubble in the amber matrix, to which the observed degradation of the insect and its poor state of preservation are attributed. It is concluded that Raman spectra of insect inclusions can provide useful information about the chemical composition of the remains and that confocal microscopy is particularly advantageous in this respect.     

The influence of intracellular storage material on bacterial identification by means of Raman spectroscopy

Previous studies dealing with bacterial identification by means of Raman spectroscopy have demonstrated that micro-Raman is a suitable technique for single-cell microbial identification. Raman spectra yield fingerprint-like information about all chemical components within one cell, and combined with multivariate methods, differentiation down to species or even strain level is possible. Many microorganisms may accumulate high amounts of polyhydroxyalkanoates (PHA) as carbon and energy storage materials within the cell and the Raman bands of PHA might impede the identification and differentiation of cells. To date, the identification by means of Raman spectroscopy have never been tested on bacteria which had accumulated PHA. Therefore, the aim of this study is to investigate the effect of intracellular polymer accumulation on the bacterial identification rate. Combining fluorescence imaging and Raman spectroscopy, we identified polyhydroxybutyrate (PHB) as a storage polymer accumulating in the investigated cells. The amount of energy storage material present within the cells was dependent on the physiological status of the microorganisms and strongly influenced the identification results. Bacteria in the stationary phase formed granules of crystalline PHB, which obstructed the Raman spectroscopic identification of bacterial species. The Raman spectra of bacteria in the exponential phase were dominated by signals from the storage material. However, the bands from proteins, lipids, and nucleic acids were not completely obscured by signals from PHB. Cells growing under either oxic or anoxic conditions could also be differentiated, suggesting that changes in Raman spectra can be interpreted as an indicator of different metabolic pathways. Although the presence of PHB induced severe changes in the Raman spectra, our results suggest that Raman spectroscopy can be successfully used for identification as long as the bacteria are not in the stationary phase.     

On optical depth profiling using confocal Raman spectroscopy

Until 2006 the performance of confocal Raman spectroscopy depth profiling was typically described and modeled through the application of geometrical optics, including refraction at the surface, to explain the degree of resolution and the precise form of the depth profile obtained from transparent and semicrystalline materials. Consequently a range of techniques, physical and analytical, was suggested to avoid the errors thus encountered in order to improve the practice of Raman spectroscopy, if not the understanding of the underlying mechanisms. These approaches were completely unsuccessful in accounting for the precise form of the depth profile, the fact that spectra obtained from laminated samples always contain characteristic peaks from all materials present both well above and below the focal point and that spectra can be obtained when focused some 40 μm above the sample surface. This paper provides further evidence that the physical processes underlying Raman spectroscopy are better modeled and explained through the concept of an extended illuminated volume contributing to the final Raman spectrum and modeled through a photon scattering approach rather than a point focus ray optics approach. The power of this numerical model lies in its ability to incorporate, simultaneously, the effects of degree of refraction at the surface (whether using a dry or oil objective lens), the degree of attenuation due to scatter by the bulk of the material, the Raman scattering efficiency of the material, and surface roughness effects. Through this we are now able to explain why even removing surface aberration and refraction effects through the use of oil immersion objective lenses cannot reliably ensure that the material sampled is only that at or close to the point of focus of the laser. Furthermore we show that the precise form of the depth profile is affected by the degree of flatness of the surface of the sample. Perhaps surprisingly, we show that the degree of flatness of the material surface is, in fact, more important than obtaining a precise refractive index match between the immersion oil and the material when seeking a high-quality depth profile or Raman spectrum from within a transparent or semicrystalline material, contrary to accepted norms that samples for interrogation by Raman spectroscopy require little preparation.     

Raman line mapping as a fast method for analyzing pharmaceutical bead formulations

This paper describes the use of principal component analysis (PCA) to de-noise Raman spectra and considerably shorten data acquisition time in Raman mapping experiments. A solid dosage pharmaceutical material (bead) is mapped by a Raman line-mapping system. The mapping acquisition time was varied from 30 s (usually employed in practice) to only 3 s. Apparently excessive noise in the maps measured for 3 s is removed by PCA and the maps of all three components of the bead are then binarized and compared. It is found that spatial difference is negligible despite the remarkably different acquisition times employed. The spectra acquired for 3 s and reconstructed via PCA are found to largely overlap with the spectra acquired for 30 s. The signal to noise ratio of the Raman mapping spectra does not obey the expected root t dependence, thereby preventing straightforward estimation of the shortest usable acquisition time (which is to a lesser extent also a function of the binarization threshold). The results reveal that Raman microscopy can be considered a fast method for mapping some materials, in contrast to the established opinion that it is an inherently slow technique.     

A compact collinear AOTF Raman spectrometer

A compact, lightweight, completely packaged, uncooled, fully-automated collinear acousto-optic tunable-filter (AOTF) based spectrometer has been used to measure Raman spectra of three organic energetic materials (NQ, HMX, and TNT) using argon-ion laser excitation. Even though the resolution of the AOTF spectrometer is modest (7.4 cm(-1)) and it was not specifically designed for measuring Raman spectra, it has performed impressively. Such an instrument is specially useful for remote sensing and field measurements. In this paper, we will describe this instrument, present the measured Raman spectra and their comparison with the corresponding FT-IR spectra.     

Headspace solid-phase microextraction combined with mass spectrometry as a powerful analytical tool for profiling the terpenoid metabolomic pattern of hop-essential oil derived from Saaz variety

Hop (Humulus lupulus L., Cannabaceae family) is prized for its essential oil contents, used in beer production and, more recently, in biological and pharmacological applications. In this work, a method involving headspace solid-phase microextraction and gas chromatography-mass spectrometry was developed and optimized to establish the terpenoid (monoterpenes and sesquiterpenes) metabolomic pattern of hop-essential oil derived from Saaz variety as a mean to explore this matrix as a powerful biological source for newer, more selective, biodegradable and naturally produced antimicrobial and antioxidant compounds. Different parameters affecting terpenoid metabolites extraction by headspace solid-phase microextraction were considered and optimized: type of fiber coatings, extraction temperature, extraction time, ionic strength, and sample agitation. In the optimized method, analytes were extracted for 30 min at 40°C in the sample headspace with a 50/30 μm divinylbenzene/carboxen/polydimethylsiloxane coating fiber. The methodology allowed the identification of a total of 27 terpenoid metabolites, representing 92.5% of the total Saaz hop-essential oil volatile terpenoid composition. The headspace composition was dominated by monoterpenes (56.1%, 13 compounds), sesquiterpenes (34.9%, 10), oxygenated monoterpenes (1.41%, 3), and hemiterpenes (0.04%, 1) some of which can probably contribute to the hop of Saaz variety aroma. Mass spectrometry analysis revealed that the main metabolites are the monoterpene β-myrcene (53.0 ± 1.1% of the total volatile fraction), and the cyclic sesquiterpenes, α-humulene (16.6 ± 0.8%), and β-caryophyllene (14.7 ± 0.4%), which together represent about 80% of the total volatile fraction from the hop-essential oil. These findings suggest that this matrix can be explored as a powerful biosource of terpenoid metabolites.     

Stand-off Raman spectroscopy: a powerful technique for qualitative and quantitative analysis of inorganic and organic compounds including explosives

A pulsed stand-off Raman system has been built and optimised for the qualitative and quantitative analysis of inorganic and organic samples including explosives. The system consists of a frequency doubled Q-switched Nd:YAG laser (532 nm, 10 Hz, 4.4 ns pulse length), aligned coaxially with a 6″ Schmidt–Cassegrain telescope for the collection of Raman scattered light. The telescope was coupled via a fibre optic bundle to an Acton standard series SP-2750 spectrograph with a PI-MAX 1024RB intensified CCD camera equipped with a 500-ps gating option for detection. Gating proved to be essential for achieving high signal-to-noise ratios in the recorded stand-off Raman spectra. In some cases, gating also allowed suppression of disturbing fluorescence signals. For the first time, quantitative analysis of stand-off Raman spectra was performed using both univariate and multivariate methods of data analysis. To correct for possible variation in instrumental parameters, the nitrogen band of ambient air was used as an internal standard. For the univariate method, stand-off Raman spectra obtained at a distance of 9 m on sodium chloride pellets containing varying amounts of ammonium nitrate (0–100%) were used. For the multivariate quantification of ternary xylene mixtures (0–100%), stand-off spectra at a distance of 5 m were used. The univariate calibration of ammonium nitrate yielded R ² values of 0.992, and the multivariate quantitative analysis yielded root mean square errors of prediction of 2.26%, 1.97% and 1.07% for o-, m- and p-xylene, respectively. Stand-off Raman spectra obtained at a distance of 10 m yielded a detection limit of 174 μg for NaClO₃. Furthermore, to assess the applicability of stand-off Raman spectroscopy for explosives detection in “real-world” scenarios, their detection on different background materials (nylon, polyethylene and part of a car body) and in the presence of interferents (motor oil, fuel oil and soap) at a distance of 20 m was also investigated.     

Raman and 29Si MAS NMR spectroscopy of framework materials containing three-membered rings

Raman and ²⁹Si MAS NMR spectroscopies are evaluated for the identification of three-membered rings (3MR) in framework oxide materials. Raman and ²⁹Si MAS NMR spectra from the 3MR-containing materials euclase, phenakite, clinohedrite, willemite, lovdarite, VPI-7, ZSM-18 and dipotassium zinc tetrasilicate are presented. The Raman spectra from these materials do not exhibit common bands representing vibrational modes assignable to individual 3MR. The dense beryllosilicate and zincosilicate minerals exhibit ²⁹Si MAS NMR resonances indicative of silicon positioned in 3MR while the molecular sieves lovdarite and VPI-7 give ²⁹Si MAS NMR resonances that can be assigned to silicons located at the center of “spiro-5” units that are constructed from two 3MR. Silicon atoms located in isolated 3MR in the molecular sieves ZSM-18 and dipotassium zinc tetrasilicate do not exhibit ²⁹Si MAS NMR resonances that can be distinguished from those assigned to silicons residing in 4MR and larger.The ²⁹Si MAS NMR spectra from the new materials VPI-8, VPI-9 and VPI-10 do not exhibit ²⁹Si MAS NMR resonances indicative of “spiro-5” units. The presence of isolated 3MR in these materials cannot be ruled out from the ²⁹Si MAS NMR spectroscopic results.     

Raman spectroscopy of different types of Mexican copal resins

Dispersive Raman spectra of six copal resins, that were purchased in local markets in Mexico, are presented. The spectra were interpreted and compared with each other. For all these spectra, the relative intensity of the Raman band at approximately 1645 cm(-1), attributed to the exomethylene nu(C=C) stretching vibration, was rather low, especially as fresh samples are involved. In one resin, viz. Incienso, CaCO3 was detected. Probably this inorganic pigment was added as a whitener. In the spectrum of Lágrima a starch fraction was present. Raman spectra of a sample from an Aztec figurine were recorded. It was shown that its composition was inhomogeneous at the micrometer level. Here, too, CaCO3 was observed. It was not possible to identify the resin applied in the antique figurine due to material degradation by age and environmental exposure.     

Examination of cellulose textile fibres in historical objects by micro-Raman spectroscopy

The investigation and characterisation of historical objects can be an exacting piece of work because of the small quantity of material that can be investigated and the degradation of the material and its value, which sometimes demands only non-destructive methods. In this study, as one such method, Raman spectroscopy was used to investigate the cellulose fibres of painting canvases and linings. Historical samples of fabrics were taken from different paintings and their linings from different locations in Slovenia. Raman spectra were recorded on the fibres of these historical samples. Additionally, a database of the Raman spectra of modern cellulose fibres was created and compared with the literature data. Differences in the Raman spectra of different cellulose fibres were observed, and on this basis fibres of different types were discriminated. The recorded Raman spectra of historical samples were compared with the database spectra of modern cellulose fibres. Strong luminescence effects because of the changes caused by ageing, degradation products and surface contamination caused difficulties in interpreting the Raman spectra of historical fibres. The luminescence effects were partly overcome by prolonged exposition times and previous "signal quenching" with the laser. The Raman spectra of historical cotton showed no luminescence effects, and only slight differences to the reference spectra of modern cotton fibres appeared, whereas the Raman spectra of historical flax fibres were overwhelmed with luminescence and showed changes in spectra through degradation. The research showed that by using Raman spectroscopy the identification and differentiation of different cellulose fibres and materials that accompany cellulose in the fibres are possible and that degraded and aged material can be differentiated.     

Spectral analysis of pharmaceutical formulations prepared according to ancient recipes in comparison with old museum remains

A study of the composition of the remains of ancient ointments from museums was undertaken to enable understanding of the preparation techniques. Comparison of ancient recipes from different historical periods and spectroscopic characteristics of inorganic and/or organic remains recovered in museum vessels enabled preparation of ancient pharmaceutical–cosmetic formulations. Farmacopea Augustana by Occo was one the most important books studied for the 14 formulations prepared in the laboratory. Three formulations are discussed in detail and raw materials and new preparations were proposed for ozone ageing. The most important micro Raman results are discussed. The spectra of the raw materials lipids, beeswax, and resins are discussed; beeswax and pig suet (axŭngia) Raman spectra were found to be similar, but different from those of the aged oils. SERS was applied to ancient ointments and galbanum and the Raman spectra are reported and discussed for the first time.     

The displacement efficiency and rheology of welan gum for enhanced heavy oil recovery

The displacement efficiency of welan gum on enhanced heavy oil recovery has been investigated by comparing that of xanthan gum which is commonly used for polymer flooding, and it is found that the displacement efficiency of biopolymer welan gum is higher (>7.0 % at the normal permeability) than that of xanthan gum. In‐depth rheological investigations show that both storage modulus and loss modulus of welan gum solution are higher than those of xanthan gum solutions at the same concentration, temperature and salinity. The higher displacement efficiency for enhanced heavy oil recovery by welan gum is mainly caused by its stronger ability to form aggregates. Although the molecular weight of welan gum is lower than that of xanthan gum, the aggregates of welan gum molecules help to improve the sweep efficiency. It is proposed that welan gum improves oil recovery by drawing and dragging on the residual oils which is derived from the interlinked network structures formed by the adjacent double helices in the arrangement of the zipper model. The intermolecular structures formed by zipper model are stable in high temperature and high salinity condition. Copyright © 2014 John Wiley & Sons, Ltd.     

Raman spectroscopy of natural accumulated paraffins from rocks: evenkite, ozokerite and hatchetine

Raman spectra were obtained from the natural crystalline (evenkite) and amorphous (ozokerite and hatchetin) hydrocarbons, originating from volcanic and sedimentary rocks from several sites (Merník, Evenki, Zastávka). Raman spectra of all materials investigated confirm their exclusively aliphatic character. Vibrational assignments are proposed and compared with pure synthetic compounds and the differences in Raman spectra obtained from materials from different sites are discussed. Monoclinic evenkite corresponds to n-tetratracosane (C(24)H(50)). Noncrystalline waxy ozokerite and hatchetine contain several degradation products in addition to higher paraffins.     

Pigment identification in artwork using graphite furnace atomic absorption spectrometry

The use of a sampling technique is described for the identification of metals from inorganic pigments in paint. The sampling technique involves gently contacting a cotton swab with the painted surface to physically remove a minute quantity (∼1-2 μg) of pigment. The amount of material removed from the painted surface is invisible to the unaided eye and does not cause any visible effect to the painted surface. The cotton swab was then placed in a 1.5 ml polystyrene beaker containing HNO₃ to extract pigment metals prior to analysis using graphite furnace atomic absorption spectrometry (GFAAS). GFAAS is well suited for identifying pigment metals since it requires small samples and many pigments consist of main group elements (e.g. Al) as well as transition metals (e.g. Zn, Fe and Cd). Using Cd (cadmium red) as the test element, the reproducibility of sampling a paint surface with the cotton swab was approximately 13% in either a water or oil medium. To test the feasibility of cotton sampling for pigment identification, samples were obtained from paintings (watercolour and oil) of a local collection. Raman spectra provided complementary information to the GFAAS, which together are essential for positive identification of some pigments. For example, GFAAS indicated the presence of Cu, but the Raman spectra positively identified the modern copper pigment phthalocyanine green (Cu(C₃₂Cl₁₆N₈). Both Raman spectroscopy and GFAAS were useful for identifying ZnO as a white pigment.     

Evaluation of a spectral searching algorithm for the comparison of Raman band positions

Raman spectroscopic identification of unknown materials involves often the comparison of the spectrum of the unknown spectrum with previously recorded reference spectra or data from literature. However, when spectra with many Raman bands or spectra of mixtures are involved, searching can be quite complex. Different chemometrical approaches have been proposed, but these have some drawbacks. Therefore, in this paper a novel approach is proposed, which is based on a multivariate comparison of Raman band positions. Different similarity measures can be used and are evaluated with spectra of test samples that were recorded on different spectrometers, using different laser wavelengths. Moreover, this study evaluates the performances of this algorithm for identifying different compounds in mixtures, by using an iterative approach.     

STRUCTURAL AND FUNCTIONAL INTEGRITY OF THE PHOTOSYSTEM II REACTION CENTER ON SILVER ELECTRODES: FLUORESCENCE AND REDOX PROBES

Two simple and sensitive methods have been developed to assess the structural and functional integrity of isolated photosystem II reaction centers deposited on a roughened Ag electrode. Surface-enhanced resonance Raman scattering (SERRS) spectra useful for ascertaining structural information can be obtained from biological materials with this technique. The first method presented is based on observing differences in the fluorescence emission properties of reaction centers; these depend on the activity of the material. The second is based on the observation of changes in Raman bands that are sensitive to the redox state of cytochrome b₅₅₉ present in the reaction center complex. It is concluded that the conditions used here to obtain SERRS spectra do not affect the structural or functional integrity of the isolated photosystem II reaction center complex. In principle these approaches also could be used with other chromoproteins.