Claudio Frausto-Reyes

Raman spectroscopy for the identification of pigments and color measurement in Dugès watercolors.

Spectroscopic and colorimetric analysis of a representative set of Dugès watercolor paintings was performed. These paintings were the result of scientific studies carried out by the zoologist Alfredo Dugès, who recorded the fauna of the Mexican Republic between 1853 and 1910. Micro-Raman spectroscopy, with an excitation wavelength of 830 nm, and colorimetric techniques were employed in order to understand if different colors with the same hue were reproduced using the same pigments. The color coordinates of the measured areas were obtained in the CIEL*a*b* color space. Raman analysis showed that, in some cases, to reproduce colors with the same hue the pigment employed was not the same. Pigments identified in the watercolors were vermilion, carbon-based black, lead white, gamboge and chrome yellow, Prussian and ultramarine blue. Some of these pigments have been used since ancient times, others as Prussian blue, chrome yellow and synthetic ultramarine blue arrived to the market at the beginning of the 18th and 19th centuries, respectively. Furthermore, regarding the white color, instead of left the paper unpainted, lead white was detected in the eye of a bird. The green color was obtained by mixing Prussian blue with chrome yellow. The results of this work show the suitability of using Raman spectroscopy for watercolor pigment analysis and colorimetric techniques to measure the color of small areas (246 microm x 246 microm) that was the case for the lead white pigment.

Use of Raman spectroscopy and chemometrics for the quantification of metal ions attached to Lactobacillus kefir

Aims:  To set‐up an experimental and analytical methodology to evaluate the feasibility of developing simple, accurate and quantitative models based on Raman spectroscopy and multivariate analysis for the quantification of metal ions adsorbed to the bacterial surface of Lactobacillus kefir.

Detection of the presence of antibodies against Toxoplasma gondii in human colostrum by Raman spectroscopy and principal component analysis

More than 60 million people in the United States and 23 million people in Mexico probably are infected with the Toxoplasma parasite, but very few have symptoms because the immune system usually keeps the parasite from causing illness. However, for people whose immune system is compromised, the consequences can be fatal. Toxoplasmosis is detected indirectly by different serological tests, where the sample requires a previous preparation. We analyze the feasibility to use Raman spectroscopy and principal component analysis (PCA) as an alternative method to detect the presence or absence of antibodies IgG (immunoglobulin G), IgM (immunoglobulin M), and IgA (immunoglobulin A), against Toxoplasma gondii, in a simple and fast way, in samples of human colostrum from a group of volunteers who were in contact with the parasite and others who were not in contact with the parasite.

Development of a method based on chemometric analysis of Raman spectra for the discrimination of heterofermentative lactobacilli.

In this work, a method based on Raman spectroscopy in combination with Principal Component Analysis (PCA) and Partial Least Square-Discriminant Analysis (PLS-DA) has been developed for the rapid differentiation of heterofermentative related lactobacilli. In a first approach, Lactobacillus kefir strains were discriminated from other species of heterofermentative lactobacilli: Lb. parakefir and Lb. brevis. After this first approach, PCA allowed for a clear differentiation between Lb. parakefir and Lb.brevis. For the first level of discrimination, PCA was performed on the whole spectra and also on delimited regions, defined taking into consideration the loading values. The best regions allowing a clear differentiation between Lb. kefir and non-Lb. kefir strains were found to be: the 1700-1500 cm(-1), 1500-1185 cm(-1) and 1800-400 (whole spectrum) cm(-1) Raman ranges. In order to develop a classification rule, PLS-DA was carried out on the mentioned regions. This method permitted the discrimination and classification of the strains under study in two groups: Lb. kefir and non-Lb. kefir. The model was further validated using lactobacilli strains from different culture collections or strains isolated from kefir grains previously identified using molecular methods. The second approach based on PCA was also performed on the whole spectra and on delimited regions, being the regions 1700-1500 cm(-1), 1500-1185 cm(-1) and 1185-1020 cm(-1), i.e., those allowing the clearest discrimination between Lb. parakefir and Lb. brevis. The results obtained in this work, allowed a clear discrimination within heterofermentative lactobacilli strains, proteins being the biological structures most determinant for this discrimination.

Raman spectroscopic analysis of iron chromium oxide microspheres generated by nanosecond pulsed laser irradiation on stainless steel

Iron chromium oxide microspheres were generated by pulsed laser irradiation on the surface of two commercial samples of stainless steel at room temperature. An Ytterbium pulsed fiber laser was used for this purpose. Raman spectroscopy was used for the characterization of the microspheres, whose size was found to be about 0.2-1.7 μm, as revealed by SEM analysis. The laser irradiation on the surface of the stainless steel modified the composition of the microspheres generated, affecting the concentration of the main elemental components when laser power was increased. Furthermore, the peak ratio of the main bands in the Raman spectra has been associated to the concentration percentage of the main components of the samples, as revealed by Energy-Dispersive X-ray Spectroscopy (EDS) analysis. These experiments showed that it is possible to generate iron chromium oxide microspheres on stainless steel by laser irradiation and that the concentration percentage of their main components is associated with the laser power applied.

Infrared nanosecond pulsed laser irradiation of stainless steel: micro iron-oxide zones generation.

Nanosecond-pulsed, infrared (1064 nm) laser irradiation was used to create periodic metal oxide coatings on the surface of two samples of commercial stainless steel at ambient conditions. A pattern of four different metal oxide zones was created using a galvanometer scanning head and a focused laser beam over each sample. This pattern is related to traverse direction of the laser beam scanning. Energy-dispersive X-ray spectroscopy (EDS) was used to find the elemental composition and Raman spectroscopy to characterize each oxide zone. Pulsed laser irradiation modified the composition of the stainless steel samples, affecting the concentration of the main components within each heat affected zone. The Raman spectra of the generated oxides have different intensity profiles, which suggest different oxide phases such as magnetite and maghemite. In addition, these oxides are not sensible to the laser power of the Raman system, as are the iron oxide powders reported in the literature. These experiments show that it is possible to generate periodic patterns of various iron oxide zones by laser irradiation, of stainless steel at ambient conditions, and that Raman spectroscopy is a useful punctual technique for the analysis and inspection of small oxide areas.

Spectroscopic study of honey from Apis mellifera from different regions in Mexico

The objective of this study was to analyze by Raman and UV-Vis-NIR Spectroscopic techniques, Mexican honey from Apis Mellífera, using representative samples with different botanic origins (unifloral and multifloral) and diverse climates. Using Raman spectroscopy together with principal components analysis, the results obtained represent the possibility to use them for determination of floral origin of honey, independently of the region of sampling. For this, the effect of heat up the honey was analyzed in relation that it was possible to greatly reduce the fluorescence background in Raman spectra, which allowed the visualization of fructose and glucose peaks. Using UV-Vis-NIR, spectroscopy, a characteristic spectrum profile of transmittance was obtained for each honey type. In addition, to have an objective characterization of color, a CIE Yxy and CIE L*a*b* colorimetric register was realized for each honey type. Applying the principal component analysis and their correlation with chromaticity coordinates allowed classifying the honey samples in one plot as: cutoff wavelength, maximum transmittance, tones and lightness. The results show that it is possible to obtain a spectroscopic record of honeys with specific characteristics by reducing the effects of fluorescence.

Raman Spectroscopy Study of Calcium Oxalate Extracted from Cacti Stems

To find markers that distinguish the different Cactaceae species, by using near infrared Raman spectroscopy and scanning electron microscopy, we studied the occurrence, in the stem, of solid deposits in five Cactaceae species (Coryphantha clavata, Ferocactus latispinus, Opuntia ficus-indica, O. robusta, and O. strepthacantha) collected from their natural habitats from a region of México. The deposits in the tissues usually occurred as spheroidal aggregates, druses, or prismatic crystals. From the Raman spectra, the crystals were identified either as calcium oxalate monohydrate (CaC2O4H2O) or calcium oxalate dihydrate (CaC2O4·2H2O) Opuntia species (subfamily Opuntioideae) showed the presence of CaC2O4·H2O, and the deposition of CaC2O4·2H2O was present in C. clavata and F. latispinus (subfamily Cactoideae, Cacteae tribe). As a punctual technique, Raman spectroscopy seems to be a useful tool to identify crystal composition. In addition to allowing the analysis of crystal morphology, this spectroscopic technique can be used to identify Cactaceae species and their chemotaxonomy.

Chemometric Techniques on the Analysis of Raman Spectra of Serum Blood Samples of Breast Cancer Patients

Raman spectroscopy and Multivariate methods were used to study serum blood samples of control and breast cancer patients. Blood samples were obtained from 11 patients and 12 controls from the central region of Mexico. Our results show that principal component analysis is able to discriminate serum sample of breast cancer patients from those of control group, also the loading vectors of PCA plotted as a function of Raman shift shown which bands permitted to make the maximum discrimination between both groups of samples.

Self-Cleaning Test of Doped Anatase-Coated Glass Plates

Doped anatase thin films on glass were deposited by ultra-spinning from titanium isopropoxide-based sol-gels. To test the self-cleaning properties of anatase-coated glass, crystalline fluoranthene, a polycyclic aromatic compound, was sprayed over the glass and then irradiated using a 365 nm UV source. This anthropogenic contaminant was removed until 98 wt.% at 140 h of irradiation time with the 2 wt.% zinc ferrite-doped anatase film. The fluoranthene proportion degraded on anatase-free glass was much lower than with anatase coating giving only 12% for an irradiation time of 140 h. In this form, the coated-glass transparency was recovered almost totally at this irradiation time for the doped anatase film mentioned, which did not occur with anatase-free glass, even after more than 400 h of UV irradiation. A correlation was found between the total weight losses of the solid compound and the intensity of the Raman vibration at 671 cm-1 during photocatalytic degradation. After 140 h of irradiation, while the presence of fluoranthene is not detected by Raman spectroscopy, glass plate presented ultra-thin zones of degradation products. Thus, the removal of these intermediate products deposited on glass was directly measured by means of weight difference. The self-cleaning properties of doped anatase coating on window glass could have a positive influence on outdoor and indoor air quality. In this work, degradation mechanisms and intermediate products were not discussed or identified.