Characterization of formate complexes formed as corrosion products on copper by raman spectroscopy

Different copper formate complexes formed on the surface of metallic copper have been studied by Raman spectroscopy. Their Raman spectra have been correlated with the dehydrated copper formate, the copper formate dihydrate and the copper formate tetrahydrate. Experiments with deuterated formic acid reveal the influence of water molecules coordinated to the copper ion on the position of Raman bands of the formate ion.     

Analytical characterization of corrosion products of copper and its alloys on stained stone surfaces

Monuments, where stone and metals or metallic alloys are used together, are very frequently met in all historical periods and in all countries. In the case of bronze and other copper alloys, their corrosion products can be dissolved by the action of acid rain and thus reach the porous building materials in contact with (or near to) the metallic structures. Once absorbed by the stone, they precipitate on the external stone surface and inside its porous space. As the majority of these products are coloured, their precipitates may produce stains, which are perceived as unpleasant alterations of the original ‘values’ of the stone monuments. The removal of stains is therefore required on the occasion of conservation treatments. The paper reports on the characterisation of copper corrosion products found on two, very different, monuments in Rome: ‘Fontana delle Tartarughe’ (by T. Landini, last quarter of the 16th century) and ‘Statua dello Studente’ (by A. Cataldi, 1920). To identify the speciation of copper compounds in their carbonate matrices, different techniques [X‐ray diffraction, X‐ray fluorescence, SEM/energy‐dispersive X‐ray spectroscopy (EDS), micro‐Raman and XPS] had to be employed. To further confirm the identification of the chemical species, SEM/EDS data were also processed by principal component analysis. Copyright © 2013 John Wiley & Sons, Ltd.     

Raman spectroscopic studies of the interaction of oxalic acid and sodium oxalate used as corrosion inhibitors with copper

The Raman spectra of the liquid-solid interface recorded in situ show the formation of a salt complex of the inhibitor molecules and the copper ions. This suggests that this chemisorbed surface species produces the protective layer.     

Application of FT-Raman spectroscopy to the study of the benzotriazole inhibition of acid copper corrosion

The initial stages of the corrosion protection of copper surfaces by benzotriazole in sulfuric acid solution are investigated using FT-Raman SERS and X-ray photoelectron spectroscopy. Spectra are measured in the presence of ppm levels of inhibitor on a copper surface in situ. The dependence of the adsorbate spectra on the electrode potential, solution pH, oxidation/reduction cycles and time is observed. Good spectra are obtained from copper electrodes prepared using in situ oxidation/reduction cycling in low pH sulfate solutions free from chloride at negative potentials.     

气质联用技术在药食同源植物分析中的研究进展

药食同源植物是指既可食用又能作为药材防病治病的植物,此类植物不良反应小、药用作用强且价格低廉,因此在临床上应用广泛.对于该类药物含有的活性成分进行深入研究能够更好地明确与发挥其药用价值和营养价值. 20世纪以来,气相色谱质谱联用技术的飞速发展推动了药食同源植物的活性成分的发现与研究,在药食同源植物的质量分析与成分开发中得到广泛应用并成为其主流分析技术之一.本文从近年来气质联用技术发展以及其在药食同源植物中的应用两个方面,对该技术在药食同源类植物的活性成分分析中的应用进行了综述.     

A Raman spectroscopy study of the properties and chemical state of the surface of CdTe and CdHgTe

The Raman spectra of CdTe and Cd_0.2Hg_0.8Te single crystals held in air for a long time were analyzed. It was found that the properties of the surface of CdTe changed under the action of probing laser radiation.     

Two different types of hollow-cathode discharges used for high resolution laser spectroscopy on copper

Two different techniques, Doppler-free saturation spectroscopy on a hollow-cathode discharge and fluorescence spectroscopy on a collimated atomic beam produced from a hollow-cathode discharge, have been used for high-resolution laser-spectroscopy measurements on the 3d ¹⁰ 4p and 5p states in neutral Copper. The relative merits of the two techniques are discussed.     

Optimization of the solution composition for laser-induced chemical liquid phase deposition of copper

Optimal compositions of autocatalytic solutions for laser-induced deposition of copper were established. The copper salt concentration range in which the process gives the best results was determined. It is shown that optical microscopy, as a means of controlling the topology of the deposited structures, has limited applicability. The results obtained by this method should be verified by alternative techniques, e.g., electron microscopy or measurements of the electrical conductivity of deposited structures.     

Fourier transform Raman spectroscopy: Its value in the study of polymers

The advantages of FT Raman spectroscopy, using a near-infrared excitation source, are discussed. The details of the instrumentation are described and the many applications of FT Raman spectroscopy in polymer science are surveyed.     

Characterization of an effective cleaning procedure for aluminum alloys: surface enhanced Raman spectroscopy and zeta potential analysis

We have developed a cleaning procedure for aluminum alloys for effective minimization of surface-adsorbed sub-micrometer particles and nonvolatile residue. The procedure consists of a phosphoric acid etch followed by an alkaline detergent wash. To better understand the mechanism whereby this procedure reduces surface contaminants, we characterized the aluminum surface as a function of cleaning step using surface enhanced Raman spectroscopy (SERS). SERS indicates that phosphoric acid etching re-establishes a surface oxide of different characteristics, including deposition of phosphate and increased hydration, while the subsequent alkaline detergent wash appears to remove the phosphate and modify the new surface oxide, possibly leading to a more compact surface oxide. We also studied the zeta potential of <5 microm pure aluminum and aluminum alloy 6061-T6 particles to determine how surface electrostatics may be affected during the cleaning process. The particles show a decrease in the magnitude of their zeta potential in the presence of detergent, and this effect is most pronounced for particles that have been etched with phosphoric acid.     

A study on the formation mechanism of graphite fluorides by Raman spectroscopy

Raman spectra were measured of highly fluorinated graphite samples prepared at room temperature, 380 and 515 °C. C_xF prepared at room temperature showed a novel downshifted band at 1555–1542 cm⁻¹ along with G band at 1593–1583 cm⁻¹. Similar behavior is also observed for samples prepared at 380 and 515 °C at early stages of fluorination, after which the Raman shifts completely disappeared. Raman spectra as well as X-ray diffraction (XRD) analysis suggest that graphite fluorides, (CF)_n and (C₂F)_n are formed via fluorine-intercalated phase with planar graphene layers.     

The chemical composition of mixed wastes: Analysis of the photolysis products of organic ligands

A survey of the literature regarding the composition of mixed wastes originating from the clean ups of spills of radioactive solutions shows that (1) the mixtures obtained in studies of the X-ray and -ray radiolysis, and of the UV-photolysis of organics in aqueous solutions have very similar composition provided the photolysis is carried out with UV beams with wavelengths below 242 nm; (2) the composition of the organic fraction of mixed wastes containing initially EDTA, NTA, and/or citric acid is complex. The mass recoveries are between 20 and 60%; and (3) the UV-photolysis of complexing agents gives much more complex mixtures at high pH than at low pH, because carbonyl compounds are formed, and these compounds undergo complex series of reactions in strongly alkaline solutions. The mixed wastes considered have a high pH due to the necessity of complexing strongly the heavy metals involved in spills. These results are confirmed by an investigation of the properties of the products of the UV-irradiation of EDTA, citric acid and some of their binary mixtures. The products of the esterification by BF₃/BuOH are only partly soluble in methylene chloride. Much better yields are obtained by using BF₃/BuOH as the reagent.¹³C NMR illustrates the composition of the mixture, without requiring a separation and is useful to follow the fate of compounds during their methylene chloride extraction after esterification.     

Use of in situ and confocal Raman spectroscopy to study the nature and distribution of carotenoids in brown patinas from a deteriorated wall painting in Marcus Lucretius House (Pompeii)

Colonisation of wall paintings by microorganisms and other organisms is a well-known problematic phenomenon. Besides taxonomic identification of the biodeteriogen, it is essential to evaluate the consequences of the colonisation, e.g., unsightly coloured patinas. This work proposes new methodology for characterisation of the nature of the main carotenoids and their distribution in brown stains or patinas of a deteriorated wall painting on the north wall of the atrium of Marcus Lucretius House (Pompeii, Italy). Characterisation of the brown patinas and surrounding areas (plaster and polychromy) from the wall painting started with in situ screening using, mainly, a portable Raman instrument with a handheld FTIR (DRIFTS sampling interface) in order to select the sampling areas suitable for further analysis in the laboratory. Two wall painting fragments were then analysed in the laboratory in two steps. First, microscopic observations (SEM and phase-contrast microscopy) were used to determine whether biodeteriogens were present in the samples. In a second step, confocal Raman microscopy (785 and 514 nm excitation lasers) was used to characterise the main biogenic compounds of the brown stains. Because of the resonance Raman effect (514 nm excitation laser), it was possible to obtain reliable Raman features to assign not only the nature of the main biogenic pigments (carotenoids) present in the stains, but also their spatial conformation. Moreover, Raman confocal applications, for example, Raman imaging and depth profiling were also used in a first attempt to determine the distribution of biosynthesised carotenoids in the stains, and to determine the thickness of the brown patinas.     

Experimental and quantum chemical study on the vibrational spectroscopy of N-methylphenothiazines: part 1

In this work the authors deal with the vibrational spectroscopy of three derivatives of phenothiazine: the 10-methyl-10H-phenothiazine, the 10 methyl-10H-phenothiazine-3-carbaldehyde and the 10-methyl-10H-phenothiazine-3-yl-methanol. The authors investigated the vibrational spectroscopic behaviour of the phenothiazine skeleton and dealt with the aldehyde and the alcohol substituent effect on the vibrational spectroscopic and structural properties of these skeleton. The infrared and Raman spectra of the compounds have been recorded in condensed state. The Gaussian 98 program package was applied with the ab initio HF method since in this case beside the infrared also the Raman spectoroscopic properties appear in the output file. On the basis of the calculated force constants and geometric parameters, normal coordinate analysis was applied for the interpretation of the experimental vibrational spectra. Problems arose with the choice of the internal coordinates of the molecules. Full interpretations of the vibrational fundamentals of the compounds are presented. The relative mean deviations between the measured and calculated frequencies were below 1%.     

Diffusing wave spectroscopy used to study the influence of shear on aggregation

In this study, diffusing wave spectroscopy (DWS) is used to investigate the effect of shear on a food-related aggregating emulsion. The principle of the method is validated using a nonaggregating, nearly monodisperse latex suspension. In general, with increasing shear rate the diffusive motion of the scatterers becomes negligible compared to the convective motion. This causes a decrease in the decay time of the autocorrelation curves and a change in the form of the autocorrelation curves from nearly exponential to Gaussian. This is reflected in the exponent of the mean square displacement that changes from 1 to 2. The effect of shear on the acidification of a sodium caseinate-stabilized emulsion was studied by DWS and by rheometry. The emulsion droplets in the food-related emulsion were uniformly dispersed at neutral pH. Upon acidification down to a pH of 5.2 +/- 0.05, the emulsion showed Newtonian behavior with constant viscosity over the whole pH range. At pH 5.17 +/- 0.05, independent of the applied shear rate during acidification, the viscosity suddenly increased. From this point on, the emulsion showed shear-thinning behavior. The photon-transport mean free path ( l*) was not influenced by the applied shear rate and did not change down to pH 5.2 +/- 0.05. Close to this pH, l* increased, and the decay of the autocorrelation curves shifted to longer correlation times when shear rates smaller than 1 s (-1) were applied. At lower pH (5.05 +/- 0.05), l* started to fluctuate, and the autocorrelation curves no longer decayed to zero, indicating that at these shear rates the system behaved nonergodicly. Assuming that the convective motion and the Brownian motion are independent of each other, the mean square displacement as a result of Brownian motion was determined. From this, the sol-gel point and the radius of the aggregates at this point as a function of the shear rate was determined. The results indicated that the radius of the aggregates at the sol-gel transition decreased with increasing shear rate and suggested that shear will result in a more open structure of the network formed by the aggregates.     

Surface enhanced Raman spectroscopy (SERS) for the discrimination of Arthrobacter strains based on variations in cell surface composition

Surface enhanced Raman spectroscopy (SERS) is a rapid and highly sensitive spectroscopic technique that has the potential to measure chemical changes in bacterial cell surface in response to environmental changes. The objective of this study was to determine whether SERS had sufficient resolution to differentiate closely related bacteria within a genus grown on solid and liquid medium, and a single Arthrobacter strain grown in multiple chromate concentrations. Fourteen closely related Arthrobacter strains, based on their 16S rRNA gene sequences, were used in this study. After performing principal component analysis in conjunction with Linear Discriminant Analysis, we used a novel, adapted cross-validation method, which more faithfully models the classification of spectra. All fourteen strains could be classified with up to 97% accuracy. The hierarchical trees comparing SERS spectra from the liquid and solid media datasets were different. Additionally, hierarchical trees created from the Raman data were different from those obtained using 16S rRNA gene sequences (a phylogenetic measure). A single bacterial strain grown on solid media culture with three different chromate levels also showed significant spectral distinction at discrete points identified by the new Elastic Net regularized regression method demonstrating the ability of SERS to detect environmentally induced changes in cell surface composition. This study demonstrates that SERS is effective in distinguishing between a large number of very closely related Arthrobacter strains and could be a valuable tool for rapid monitoring and characterization of phenotypic variations in a single population in response to environmental conditions.     

Fourier transform infrared spectroscopy and the analytical study of works of art for purposes of diagnosis and conservation

This paper is a study of the analytical capacity of Fourier transform infrared spectroscopy (FT-IR) for any type of samples from works of art. The analytical information obtained with this technique on organic and inorganic compounds is extremely useful in the preliminary studies necessary for diagnosis and to decide on the conservation process. This paper reports the analysis and study with FT-IR on samples extracted from the microlayers in several works of art from different periods (16th to 18th century) comprising wall paintings and canvas. The most outstanding of these being the frescoes by A. Palomino from two ceilings in the Santos Juanes church. The analytical procedures for the different components of the works studied such as

1. (a) varnish applied to wood panels and canvas paintings,

2. (b) binding media and pigments used by the artists,

3. (c) inerts, mortars, stuccos and grounds have been optimized. The FT-IR technique offers a quick analysis of microsamples (less than 0.5 mg) and is able to characterise the different molecular groups which provide information on the nature of the different materials of organic and inorganic origin used by the artist and thus permits the diagnosis of pathologies requiring conservation treatment.

Surface enhanced Raman spectroscopy study of the potential dependence of thymine on silver electrodes

The potential-induced changes in thymine coordination on polycrystalline silver electrodes are studied by surface enhanced Raman spectroscopy (SERS) for potentials positive to the potential of zero charge up to the end of the double layer range. Two distinct sets of spectra could be obtained in the range of potentials studied. Both states correspond to chemisorbed phases of thymine on silver, where a distinct heteroatom is deemed responsible for the bond with the surface. At less positive potentials, one of the ring oxygen atoms is responsible for the chemical bond and the molecule assumes a tilted position. At more positive potentials, one of the ring nitrogen atoms, possibly deprotonated, establishes a new bond with the surface, aligning the molecule's axis closer to the surface normal.This paper is dedicated to Prof. Wolf Vielstich on the occasion of his 80th birthday for his outstanding contributions to electrochemistry