Nicolae Tarcea

Raman study on B2O3–CaO glasses

Abstract Glasses are of special interest nowadays mainly because of the large applications that they span. Raman spectroscopy is an experimental technique appropriate for providing information about the structure of local arrangements of the atoms in glasses. The influence of CaO content on the structure of borate glasses was investigated by Raman spectroscopy. At low calcium oxide content the structure of calcium borate glass consists mainly of boroxol groups and a smaller number of pentaborate groups. In the vitreous network there are few diborate groups, chain type metaborate groups and pyroborate groups. At high calcium oxide content, pentaborate, orthoborate and metaborate groups appear. The increase of calcium oxide content yields an increase in number of non-bridging oxygen ions. Therefore, we conclude that calcium ions act as network modifiers in borate glasses.

Three-dimensional molecular mapping of a multiple emulsion by means of CARS microscopy.

Multiple emulsions consisting of water droplets dispersed in an oil phase containing emulsifier which is emulsified in an outer water phase (W/O/W) are of great interest in pharmacology for developing new drugs, in the nutrition sciences for designing functional food, and in biology as model systems for cell organelles such as liposomes. In the food industry multiple emulsions with high sugar content in the aqueous phase can be used for the production of sweets, because the high sugar content prevents deterioration. However, for these emulsions the refractive indexes of oil and aqueous phase are very similar. This seriously impedes the analysis of these emulsions, e.g., for process monitoring, because microscopic techniques based on transmission or reflection do not provide sufficient contrast. We have characterized the inner dispersed phase of concentrated W/O/W emulsions with the same refractive index of the three phases by micro Raman spectroscopy and investigated the composition and molecular distribution in water-oil-water emulsions by means of three-dimensional laser scanning CARS (coherent anti-Stokes Raman scattering) microscopy. CARS microscopy has been used to study water droplets dispersed in oil droplets at different Raman resonances to visualize different molecular species. Water droplets with a diameter of about 700 nm could clearly be visualized. The advantages of CARS microscopy for studying this particular system are emphasized by comparing this microscopic technique with conventional confocal reflection and transmission microscopies.

Deeper Understanding of Biological Tissue: Quantitative Correlation of MALDI-TOF and Raman Imaging

In order to achieve a comprehensive description of biological tissue, spectral information about proteins, lipids, nucleic acids, and other biochemical components need to be obtained concurrently. Different analytical techniques may be combined to record complementary information of the same sample. Established techniques, which can be utilized to elucidate the biochemistry of tissue samples are, for instance, MALDI-TOF-MS and Raman microscopic imaging. With this contribution, we combine these two techniques for the first time. The combination of both techniques allows the utilization and interpretation of complementary information (i.e., the information about the protein composition derived from the Raman spectra with data of the lipids analyzed by the MALDI-TOF measurements). Furthermore, we demonstrate how spectral information from MALDI-TOF experiments can be utilized to interpret Raman spectra.

Checking and Improving Calibration of Raman Spectra using Chemometric Approaches

Abstract A wavenumber and intensity calibration procedure of Raman spectra by using chemometric techniques is presented. This approach allows the fine tuning of calibration parameters and routines with the final goal to eliminate setup dependent differences within experimentally recorded Raman spectra. This seems to be necessary since more and more Raman databases are needed for different analytical tasks, like identification of minerals or bacteria. Minimizing the impact of the applied experimental Raman setup on the reference (database stored) Raman spectra allows the databases to be enlarged very easily by feeding the database with Raman spectra recorded with different setups. Furthermore the chemometric analysis performance increases due to the larger number and better quality of reference spectra.

Raman imaging with a fiber-coupled multichannel spectrograph.

Until now, spatially resolved Raman Spectroscopy has required to scan a sample under investigation in a time-consuming step-by-step procedure. Here, we present a technique that allows the capture of an entire Raman image with only one single exposure. The Raman scattering arising from the sample was collected with a fiber-coupled high-performance astronomy spectrograph. The probe head consisting of an array of 20 × 20 multimode fibers was linked to the camera port of a microscope. To demonstrate the high potential of this new concept, Raman images of reference samples were recorded. Entire chemical maps were received without the need for a scanning procedure.

The effect of antimonate, arsenate, and phosphate on the transformation of ferrihydrite to goethite, hematite, feroxyhyte, and tripuhyite

Iron oxides, typical constituents of many soils, represent a natural immobilization mechanism for toxic elements. Most iron oxides are formed during the transformation of poorly crystalline ferrihydrite to more crystalline iron phases. The present study examined the impact of well known contaminants, such as P(V), As(V), and Sb(V), on the ferrihydrite transformation and investigated the transformation products with a set of bulk and nano-resolution methods. Irrespective of the pH, P(V) and As(V) favor the formation of hematite (α-Fe2O3) over goethite (α-FeOOH) and retard these transformations at high concentrations. Sb(V), on the other hand, favors the formation of goethite, feroxyhyte (d’-FeOOH), and tripuhyite (FeSbO4) depending on pH and Sb(V) concentration. The elemental composition of the transformation products analyzed by inductively coupled plasma optical emission spectroscopy show high loadings of Sb(V) with molar Sb:Fe ratios of 0.12, whereas the molar P:Fe and As:Fe ratios do not exceed 0.03 and 0.06, respectively. The structural similarity of feroxyhyte and hematite was resolved by detailed electron diffraction studies, and feroxyhyte was positively identified in a number of the samples examined. These results indicate that, compared to P(V) and As(V), Sb(V) can be incorporated into the structure of certain iron oxides through Fe(III)-Sb(V) substitution, coupled with other substitutions. However, the outcome of the ferrihydrite transformation (hematite, goethite, feroxyhyte, or tripuhyite) depends on the Sb(V) concentration, pH, and temperature.

Raman investigations of Upper Cretaceous phosphorite and black shale from Safaga District, Red Sea, Egypt.

The mineral composition of the Upper Cretaceous Duwi phosphorite deposits and underlying Quseir Variegated Shale from Safaga district, Red Sea Range, Egypt, was investigated by dispersive and Fourier transformed Raman spectroscopy. The only phosphorous containing mineral detected in the phosphorite deposits was carbonate fluorapatite. Often carbonate fluorapatite appears associated with calcium sulfate and seldom with calcium carbonate in the investigated samples. Iron is present in the form of goethite and pyrite in the phosphorite layer, while pyrite, marcasite and hematite were identified in the Quseir Shale samples. Also, a high amount of disordered carbon was detected in the black shale layers. The Raman results confirm the hypothesis that the formation of the phosphorites took place in a marine environment. During the formation of black shale, the redox conditions changed, with the pH reaching values of 4 or even lower. Diagenetic and weathering transformations had taken place in the phosphorite deposits, calcium sulfate and goethite being products of these types of processes.

Temperature-Dependent Raman Study of the Smectic to Nematic Phase Transition and Vibrational Analysis Using Density Functional Theory of the Liquid Crystalline System 4-Decyloxy Benzoic Acid:

Room-temperature Raman spectra of the thermotropic liquid crystalline system, 4-decyloxy benzoic acid (4DBA) have been recorded and the experimentally observed bands are assigned by density functional theory (DFT) for the first time. The C–O and C–C stretching and C–H in-plane bending modes of the phenyl ring and C=O stretching modes of the -COOH group are the marker bands for the smectic (S) → nematic (N) and nematic (N) → isotropic (I) transitions for this system. The temperature-dependent Raman spectra for these bands in the heating cycle clearly characterize the S→N and the N→I transition over a range <1 °C, which is much better than the earlier range of 23 °C for S→N and 26 °C for the N→I transition. The ∼773, ∼807, ∼881, and ∼1146 cm−1 bands disappear, whereas a band at ∼830 cm−1 appears at the S→N transition. The relative intensity of the ∼1257 and ∼1280 cm−1 bands distinguishes the three phases, namely smectic, nematic, and isotropic, in 4DBA. The variation of line width and peak wavenumber of the ∼1128 and ∼1168 cm−1 bands also clearly shows the two transitions. The molecular reorientation at the transition and the effect of local fields present in the liquid crystalline mesophases are also briefly discussed on the basis of changes in intensity, linewidth and peak wavenumber with temperature.

The effect of surface texture on the mineralogical analysis of chondritic meteorites using Raman spectroscopy

Abstract Raman imaging on different types of meteorite surfaces was performed. Three different surface textures on a chondritic meteorite from the Dhofar 005 strewnfield and a fourth surface with a very rough texture on a goethite mineral have been investigated. The Raman measurements were made with and without autofocus. The influence of the surface texture on the quality of the Raman spectra was analyzed. The percentage of the informative Raman spectra obtained from every sampled area were sufficient to assert the local mineral composition. For obtaining a spatial distribution of minerals (in the micrometer range), an autofocus device needed to be employed. It was found that approximately 85% of all Raman spectra taken at λ ext =633 nm show sufficient information to establish a clear assignment to a certain mineral. In the case of the rough goethite surface, measured without an autofocus device approx. 60% of the recorded spectra could be assigned.

Elemental analysis-aided Raman spectroscopic studies on Chinese cloisonné wares and painted enamels from the Imperial Palace

Two kinds of enamels, including Chinese cloisonné wares from Fuwang chamber and gourd-shaped painted enamels decorations from the Forbidden City, in the Imperial Palace of China, are investigated by micro-Raman spectroscopy in combination with laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and energy-dispersive X-ray fluorescence (EDXRF) in order to examine and analyze the composition of the glaze layer in each case. In this study the excitation is employed with either a NIR laser (785 nm) or a red laser (632.8 nm) in order to effectively eliminate the interference of background fluorescence and resonance effect. We have identified that the major matrix ingredients of the cloisonné wares are lead-based potash-lime silicate glasses while lead-potash silicate glass matrix is the main constituent for the painted enamels. Eight different colored areas of glaze layer also have been discussed in detail due to the distinct colors including turquoise, deep blue, yellow, white, red, pink, deep green and pale green. Their identification based on Raman data will be useful with regard to rapid and on site analysis and the restoration of the enamel decorations.