In-Line Monitoring of Particle Size during Emulsion Polymerization under Different Operational Conditions using NIR Spectroscopy

In the present work, the sensitivity of NIR spectroscopy toward the evolution of particle size was studied during emulsion homopolymerization of styrene (Sty) and emulsion copolymerization of vinyl acetate-butyl acrylate conducted in a semibatch stirred tank and a tubular pulsed sieve plate reactor, respectively. All NIR spectra were collected online with a transflectance probe immersed into the reaction medium. The spectral range used for the NIR monitoring was from 9 500 to 13 000 cm(-1), where the absorbance of the chemical components present is minimal and the changes in the NIR spectrum can be ascribed to the effects of light scattering by the polymer particles. Off-line measurements of the average diameter of the polymer particles by DLS were used as reference values for the development of the multi-variate NIR calibration models based on partial least squares. Results indicated that, in the spectral range studied, it is possible to monitor the evolution of the average size of the polymer particles during emulsion polymerization reactions. The inclusion of an additional spectral range, from 5 701 to 6 447 cm(-1), containing information on absorbances (""chemical information"") in the calibration models was also evaluated.

The application of chemometrics on Infrared and Raman spectra as a tool for the forensic analysis of paints

The aim of this work is to evaluate the capabilities and limitations of chemometric methods and other mathematical treatments applied on spectroscopic data and more specifically on paint samples. The uniqueness of the spectroscopic data comes from the fact that they are multivariate - a few thousands variables - and highly correlated. Statistical methods are used to study and discriminate samples. A collection of 34 red paint samples was measured by Infrared and Raman spectroscopy. Data pretreatment and variable selection demonstrated that the use of Standard Normal Variate (SNV), together with removal of the noisy variables by a selection of the wavelengths from 650 to 1830 cm−1 and 2730-3600 cm−1, provided the optimal results for infrared analysis. Principal component analysis (PCA) and hierarchical clusters analysis (HCA) were then used as exploratory techniques to provide evidence of structure in the data, cluster, or detect outliers. With the FTIR spectra, the Principal Components (PCs) correspond to binder types and the presence/absence of calcium carbonate. 83% of the total variance is explained by the four first PCs. As for the Raman spectra, we observe six different clusters corresponding to the different pigment compositions when plotting the first two PCs, which account for 37% and 20% respectively of the total variance. In conclusion, the use of chemometrics for the forensic analysis of paints provides a valuable tool for objective decision-making, a reduction of the possible classification errors, and a better efficiency, having robust results with time saving data treatments.

Profiling of counterfeit medicines by vibrational spectroscopy

Counterfeit pharmaceutical products have become a widespread problem in the last decade. Various analytical techniques have been applied to discriminate between genuine and counterfeit products. Among these, Near-infrared (NIR) and Raman spectroscopy provided promising results.The present study offers a methodology allowing to provide more valuable information fororganisations engaged in the fight against counterfeiting of medicines.A database was established by analyzing counterfeits of a particular pharmaceutical product using Near-infrared (NIR) and Raman spectroscopy. Unsupervised chemometric techniques (i.e. principal component analysis - PCA and hierarchical cluster analysis - HCA) were implemented to identify the classes within the datasets. Gas Chromatography coupled to Mass Spectrometry (GC-MS) and Fourier Transform Infrared Spectroscopy (FT-IR) were used to determine the number of different chemical profiles within the counterfeits. A comparison with the classes established by NIR and Raman spectroscopy allowed to evaluate the discriminating power provided by these techniques. Supervised classifiers (i.e. k-Nearest Neighbors, Partial Least Squares Discriminant Analysis, Probabilistic Neural Networks and Counterpropagation Artificial Neural Networks) were applied on the acquired NIR and Raman spectra and the results were compared to the ones provided by the unsupervised classifiers.The retained strategy for routine applications, founded on the classes identified by NIR and Raman spectroscopy, uses a classification algorithm based on distance measures and Receiver Operating Characteristics (ROC) curves. The model is able to compare the spectrum of a new counterfeit with that of previously analyzed products and to determine if a new specimen belongs to one of the existing classes, consequently allowing to establish a link with other counterfeits of the database.

Montage et caractérisation d’un système de spectroscopie Raman accordable en longueur d’onde utilisant des réseaux de Bragg comme filtre : application aux nanotubes de carbone

La spectroscopie Raman est un outil non destructif fort utile lors de la caractérisation de matériau. Cette technique consiste essentiellement à faire l’analyse de la diffusion inélastique de lumière par un matériau. Les performances d’un système de spectroscopie Raman proviennent en majeure partie de deux filtres ; l’un pour purifier la raie incidente (habituellement un laser) et l’autre pour atténuer la raie élastique du faisceau de signal. En spectroscopie Raman résonante (SRR), l’énergie (la longueur d’onde) d’excitation est accordée de façon à être voisine d’une transition électronique permise dans le matériau à l’étude. La section efficace d’un processus Raman peut alors être augmentée d’un facteur allant jusqu’à 106. La technologie actuelle est limitée au niveau des filtres accordables en longueur d’onde. La SRR est donc une technique complexe et pour l’instant fastidieuse à mettre en œuvre. Ce mémoire présente la conception et la construction d’un système de spectroscopie Raman accordable en longueur d’onde basé sur des filtres à réseaux de Bragg en volume. Ce système vise une utilisation dans le proche infrarouge afin d’étudier les résonances de nanotubes de carbone. Les étapes menant à la mise en fonction du système sont décrites. Elles couvrent les aspects de conceptualisation, de fabrication, de caractérisation ainsi que de l’optimisation du système. Ce projet fut réalisé en étroite collaboration avec une petite entreprise d’ici, Photon etc. De cette coopération sont nés les filtres accordables permettant avec facilité de changer la longueur d’onde d’excitation. Ces filtres ont été combinés à un laser titane : saphir accordable de 700 à 1100 nm, à un microscope «maison» ainsi qu’à un système de détection utilisant une caméra CCD et un spectromètre à réseau. Sont d’abord présentés les aspects théoriques entourant la SRR. Par la suite, les nanotubes de carbone (NTC) sont décrits et utilisés pour montrer la pertinence d’une telle technique. Ensuite, le principe de fonctionnement des filtres est décrit pour être suivi de l’article où sont parus les principaux résultats de ce travail. On y trouvera entre autres la caractérisation optique des filtres. Les limites de basses fréquences du système sont démontrées en effectuant des mesures sur un échantillon de soufre dont la raie à 27 cm-1 est clairement résolue. La simplicité d’accordabilité est quant à elle démontrée par l’utilisation d’un échantillon de NTC en poudre. En variant la longueur d’onde (l’énergie d’excitation), différentes chiralités sont observées et par le fait même, différentes raies sont présentes dans les spectres. Finalement, des précisions sur l’alignement, l’optimisation et l’opération du système sont décrites. La faible acceptance angulaire est l’inconvénient majeur de l’utilisation de ce type de filtre. Elle se répercute en problème d’atténuation ce qui est critique plus particulièrement pour le filtre coupe-bande. Des améliorations possibles face à cette limitation sont étudiées.

Tunable diode Laser Absorption Spectroscopy ,Nir Overtone and Life Studies of Some Organic Compound

The present work is mainly concentrated on setting up a NIR tunable diode laser absorption (TDLA) spectrometer for high-resolution molecular spectroscopic studies. For successfully recording the high-resolution tunable diode laser spectrum, various experimental considerations are to be taken into account like the setup should be free from mechanical vibrations, sample should be kept at a low pressure, laser should be in a single mode operation etc. The present experimental set up considers all these factors. It is to be mentioned here that the setting up of a high resolution NIR TDLA spectrometer is a novel experiment requiring much effort and patience. The analysis of near infrared (NIR) vibrational overtone spectra of some substituted benzene compounds using local mode model forms another part of the present work. An attempt is made to record the pulsed laser induced fluorescence/Raman spectra of some organic compounds. A Q-switched Nd:YAG laser is used as the excitation source. A TRIAX monochromator and CCD detector is used for the spectral recording. The observed fluorescence emission for carbon disulphide is centered at 680 nm; this is assigned as due to the n, p* transition. Aniline also shows a broad fluorescence emission centered at 725 nm, which is due to the p,p* transition. The pulsed laser Raman spectra of some organic compounds are also recorded using the same experimental setup. The calibration of the set up is done using the laser Raman spectra of carbon tetrachloride and carbon disulphide. The observed laser Raman spectra for aniline, o-chloroaniline and m-chlorotoluene show peaks characteristics of the aromatic ring in common and the characteristics peaks due to the substitutuent groups. Some new peaks corresponding to low-lying vibrations of these molecules are also assigned

Evaluating mid-infrared spectroscopy as a new technique for predicting sensory texture attributes of processed cheese

The objective of this study was to investigate the potential application of mid-infrared spectroscopy for determination of selected sensory attributes in a range of experimentally manufactured processed cheese samples. This study also evaluates mid-infrared spectroscopy against other recently proposed techniques for predicting sensory texture attributes. Processed cheeses (n = 32) of varying compositions were manufactured on a pilot scale. After 2 and 4 wk of storage at 4 degrees C, mid-infrared spectra ( 640 to 4,000 cm(-1)) were recorded and samples were scored on a scale of 0 to 100 for 9 attributes using descriptive sensory analysis. Models were developed by partial least squares regression using raw and pretreated spectra. The mouth-coating and mass-forming models were improved by using a reduced spectral range ( 930 to 1,767 cm(-1)). The remaining attributes were most successfully modeled using a combined range ( 930 to 1,767 cm(-1) and 2,839 to 4,000 cm(-1)). The root mean square errors of cross-validation for the models were 7.4(firmness; range 65.3), 4.6 ( rubbery; range 41.7), 7.1 ( creamy; range 60.9), 5.1(chewy; range 43.3), 5.2(mouth-coating; range 37.4), 5.3 (fragmentable; range 51.0), 7.4 ( melting; range 69.3), and 3.1 (mass-forming; range 23.6). These models had a good practical utility. Model accuracy ranged from approximate quantitative predictions to excellent predictions ( range error ratio = 9.6). In general, the models compared favorably with previously reported instrumental texture models and near-infrared models, although the creamy, chewy, and melting models were slightly weaker than the previously reported near-infrared models. We concluded that mid-infrared spectroscopy could be successfully used for the nondestructive and objective assessment of processed cheese sensory quality..

Studies on the resonance Raman spectra of polyaniline obtained with near-IR excitation

The effects of near-IR (NIR) laser power over the Raman spectra of poly(aniline) emeraldine salt (PANIES) and base (PANI-EB) were investigated. The reasons for the existence of several bands from 1324 to 1500 cm-1 in the Raman spectra of poly(aniline) obtained at NIR region were also studied. The bands from 1324 to 1375 cm-` were associated to vC-N of polarons with different conjugation lengths and the bands from 1450 to 1500 cm-1 in Raman spectra of PANI emeraldine and pernigraniline base forms were correlated to vC=N modes associated with quinoid units having different conjugation lengths. The increase of laser power at 1064.0 run causes the deprotonation of PANI-ES and the formation of cross-linking segments having phenazine and/or oxazine rings. For PANI-EB only a small spectral change is observed when the laser power is increased, owing to the low absorption of this form in the NIR region. Copyright (c) 2007 John Wiley & Sons, Ltd.

Monoclinic-tetragonal phase transition in Pb(Zr1-xTix)O-3 studied by infrared spectroscopy

The discovery of a new monoclinic phase in the PbZr1-xTixO3 (PZT) system in the vicinity of the morphotropic phase boundary (MPB), previously considered as a region where the rhombohedral and tetragonal phases of PZT coexist, was recently reported. Investigations of this new phase were reported using different techniques such as high-resolution synchrotron x-ray powder diffraction and Raman spectroscopy. The main objective has been to define a new phase diagram of PZT. In this context, infrared spectroscopic studies were performed in the vicinity of the MPB and studies were initially centred on a PZT sample with x = 0.49 mol% Ti content. Results suggested that the monoclinic --> tetragonal phase transition occurs at 237 K, confirming the use of IR as a useful technique to investigate this phase transition.

Structural study of thin films prepared from tungstate glass matrix by Raman and X-ray absorption spectroscopy

Thin films were prepared using glass precursors obtained in the ternary system NaPO(3)-BaF(2)-WO(3) and the binary system NaPO(3)-WO(3) with high concentrations of WO(3) (above 40% molar). Vitreous samples have been used as a target to prepare thin films. Such films were deposited using the electron beam evaporation method onto soda-lime glass substrates. Several structural characterizations were performed by Raman spectroscopy and X-ray Absorption Near Edge Spectroscopy (XANES) at the tungsten L(I) and L(III) absorption edges. XANES investigations showed that tungsten atoms are only sixfold coordinated (octahedral WO(6)) and that these films are free of tungstate tetrahedral units (WO(4)). In addition, Raman spectroscopy allowed identifying a break in the linear phosphate chains as the amount of WO(3) increases and the formation of P-O-W bonds in the films network indicating the intermediary behavior of WO(6) octahedra in the film network. Based on XANES data, we suggested a new attribution of several Raman absorption bands which allowed identifying the presence of W-O and W=O terminal bonds and a progressive apparition of W-O-W bridging bonds for the most WO(3) concentrated samples (above 40% molar) attributed to the formation of WO(6) clusters. (C) 2008 Elsevier B.V. All rights reserved.

Raman and infrared investigations of glass and glass-ceramics with composition 2Na2O·1CaO·3SiO2

Precursor glass and glass-ceramics with molar composition 2Na2O·1CaO·3SiO2 are studied by infrared, conventional, and microprobe Raman techniques. The Gaussian deconvoluted Raman spectrum of the glass presents bands at 625 and 660 cm-1, attributed to bending vibrations of Si-O-Si bonds, and at 860, 920, 975, and 1030 cm-1, attributed to symmetric stretching vibrations of SiO4 tetrahedra with 4, 3, 2, and 1 nonbridging oxygens, respectively. The Raman microprobe spectrum of a highly crystallized sample presents two narrow and intense bands at about 590 and 980 cm-1, associated with vibrations of SiO4 tetrahedra with two nonbridging oxygens, in agreement with the predicted chain-like structure of crystalline metasilicates. Scanning electron microscopy shows that the crystals distributed in partially crystallized samples have a spherical shape, built up by radially oriented needle-like single crystals. The Raman microprobe spectra of these spherulites show that they still contain residual amorphous material. A comparison of Raman and infrared spectra of amorphous and highly crystallized samples is presented.

Trasmission and Reflection (ATR)Far-Infrared Spectroscopy Applied in the Analysis of Cultural Heritage Materials

FIR spectroscopy is an alternative way of collecting spectra of many inorganic pigments and corrosion products found on art objects, which is not normally observed in the MIR region. Most FIR spectra are traditionally collected in transmission mode but as a real novelty it is now also possible to record FIR spectra in ATR (Attenuated Total Reflectance) mode. In FIR transmission we employ polyethylene (PE) for preparation of pellets by embedding the sample in PE. Unfortunately, the preparation requires heating of the PE in order to produces at transparent pellet. This will affect compounds with low melting points, especially those with structurally incorporated water. Another option in FIR transmission is the use of thin films. We test the use of polyethylene thin film (PETF), both commercial and laboratory-made PETF. ATR collection of samples is possible in both the MIR and FIR region on solid, powdery or liquid samples. Changing from the MIR to the FIR region is easy as it simply requires the change of detector and beamsplitter (which can be performed within a few minutes). No preparation of the sample is necessary, which is a huge advantage over the PE transmission method. The most obvious difference, when comparing transmission with ATR, is the distortion of band shape (which appears asymmetrical in the lower wavenumber region) and intensity differences. However, the biggest difference can be the shift of strong absorbing bands moving to lower wavenumbers in ATR mode. The sometimes huge band shift necessitates the collection of standard library spectra in both FIR transmission and ATR modes, provided these two methods of collecting are to be employed for analyses of unknown samples. Standard samples of 150 pigment and corrosion compounds are thus collected in both FIR transmission and ATR mode in order to build up a digital library of spectra for comparison with unknown samples. XRD, XRF and Raman spectroscopy assists us in confirming the purity or impurity of our standard samples. 24 didactic test tables, with known pigment and binder painted on the surface of a limestone tablet, are used for testing the established library and different ways of collecting in ATR and transmission mode. In ATR, micro samples are scratched from the surface and examined in both the MIR and FIR region. Additionally, direct surface contact of the didactic tablets with the ATR crystal are tested together with water enhanced surface contact. In FIR transmission we compare the powder from our test tablet on the laboratory PETF and embedded in PE. We also compare the PE pellets collected using a 4x beam condenser, focusing the IR beam area from 8 mm to 2 mm. A few samples collected from a mural painting in a Nepalese temple, corrosion products collected from archaeological Chinese bronze objects and samples from a mural paintings in an Italian abbey, are examined by ATR or transmission spectroscopy.

Internal characteristics, chemical compounds and spectroscopy of sapphire as single crystals

In this study more than 450 natural sapphire samples (most of basaltic type) collected from 19 different areas were examined. They are from Dak Nong, Dak Lak, Quy Chau, two unknown sources from the north (Vietnam); Bo Ploi, Khao Ploi Waen (Thailand); Ban Huay Sai (Laos); Australia; Shandong (China); Andapa, Antsirabe, Nosibe (Madagascar); Ballapana (Sri Lanka); Brazil; Russia; Colombia; Tansania and Malawi. rnThe samples were studied on internal characteristics, chemical compositions, Raman-, luminescence-, Fourier transform infrared (FTIR)-, and ultraviolet-visible-near infrared (UV-Vis-NIR)- spectroscopy. The internal features of these sapphire samples were observed and identified by gemological microscope, con focal micro Raman and FTIR spectroscopy. The major and minor elements of the samples were determined by electron probe microanalysis (EPMA) and the trace elements by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). rnThe structural spectra of sapphire were investigated by con focal Raman spectroscopy. The FTIR spectroscopy was used to study the vibration modes of OH-groups and also to determine hydrous mineral inclusions in sapphire. The UV-Vis-NIR absorption spectroscopy was used to analyze the cause of sapphire color. rnNatural sapphires contain many types of mineral inclusions. Typically, they are iron-containing inclusions like goethite, ilmenite, hematite, magnetite or silicate minerals commonly feldspar, and often observed in sapphires from Asia countries, like Dak Nong, Dak Lak in the south of Vietnam, Ban Huay Sai (Laos), Khao Ploi Waen and Bo Ploi (Thailand) or Shandong (China). Meanwhile, CO2-diaspore inclusions are normally found in sapphires from Tansania, Colombia, or the north of Vietnam like Quy Chau. rnIron is the most dominant element in sapphire, up to 1.95 wt.% Fe2O3 measured by EPMA and it affects spectral characteristics of sapphire.rnThe Raman spectra of sapphire contain seven peaks (2A1g + 5Eg). Two peaks at about 418.3 cm-1 and 577.7 cm-1 are influenced by high iron content. These two peaks shift towards smaller wavenumbers corresponding to increasing iron content. This shift is showed by two equations y(418.3)=418.29-0.53x andy(577.7)=577.96-0.75x, in which y is peak position (cm-1) and x is Fe2O3 content (wt.%). By exploiting two these equations one can estimate the Fe2O3 contents of sapphire or corundum by identifying the respective Raman peak positions. Determining the Fe2O3 content in sapphire can help to distinguish sapphires from different origins, e.g. magmatic and metamorphic sapphire. rnThe luminescence of sapphire is characterized by two R-lines: R1 at about 694 nm and R2 at about 692 nm. This characteristic is also influenced by high iron content. The peak positions of two R-lines shift towards to smaller wavelengths corresponding to increasing of iron content. This correlation is showed by two equations y(R_2 )=692.86-0.049x and y(R_1 )=694.29-0.047x, in which y is peak position (nm) of respective R-lines and x is Fe2O3 content (wt.%). Two these equations can be applied to estimate the Fe2O3 content of sapphire and help to separate sapphires from different origins. The luminescence is also applied for determination of the remnant pressure or stress around inclusions in Cr3+-containing corundum by calibrating a 0-pressure position in experimental techniques.rnThe infrared spectra show the presence of vibrations originating from OH-groups and hydrous mineral inclusions in the range of 2500-4000 cm-1. Iron has also an effect upon the main and strongest peak at about 3310 cm-1. The 3310 cm-1 peak is shifted to higher wavenumber when iron content increases. This relationship is expressed by the equation y(3310)=0.92x+3309.17, in which y is peak position of the 3310 cm-1 and x is Fe2O3 content (wt.%). Similar to the obtained results in Raman and luminescence spectra, this expression can be used to estimate the Fe2O3 content and separate sapphires from different origins. rnThe UV-Vis-NIR absorption spectra point out the strong and sharp peaks at about 377, 387, and 450 nm related to dispersed Fe3+, a broad band around 557 and 600 nm related to intervalence charge transfer (IVCT) Fe2+/Ti4+, and a broader band around 863 nm related to IVCT of Fe2+/Fe3+. rnGenerally, sapphires from different localities were completely investigated on internal features, chemical compounds, and solid spectral characteristics. The results in each part contribute for identifying the iron content and separate sapphires from different localities order origins. rn

Identification and relative quantification of tyrosine nitration in a model peptide using two-dimensional infrared spectroscopy

Nitration of tyrosine in proteins and peptides is a post-translational modification that occurs under conditions of oxidative stress. It is implicated in a variety of medical conditions, including neurodegenerative and cardiovascular diseases. However, monitoring tyrosine nitration and understanding its role in modifying biological function remains a major challenge. In this work, we investigate the use of electron-vibration-vibration (EVV) two-dimensional infrared (2DIR) spectroscopy for the study of tyrosine nitration in model peptides. We demonstrate the ability of EVV 2DIR spectroscopy to differentiate between the neutral and deprotonated states of 3-nitrotyrosine, and we characterize their spectral signatures using information obtained from quantum chemistry calculations and simulated EVV 2DIR spectra. To test the sensitivity of the technique, we use mixed-peptide samples containing various levels of tyrosine nitration, and we use mass spectrometry to independently verify the level of nitration. We conclude that EVV 2DIR spectroscopy is able to provide detailed spectroscopic information on peptide side-chain modifications and to detect nitration levels down to 1%. We further propose that lower nitration levels could be detected by introducing a resonant Raman probe step to increase the detection sensitivity of EVV 2DIR spectroscopy. (Graph Presented).

QUANTIFICATION OF CALCIUM IN SPARKLING WINES BY INFRARED SPECTROSCOPY

Markets are increasingly competitive and the companies feel the urge to improve their manufacturing processes. Blending that with a larger control of quality and safety it was created a need to develop new methods of analysis each time more accurate, faster and with lower costs. Alentejo is a region with a wide variety of soils, most of them are rich in calcium and potassium. In the production of sparkling wine many wineries use encapsulated yeast in alginate beads, instead of the traditional method, champenoise. The first method is faster, allowing a more versatile production, reducing the risk of contamination and features organoleptic characteristics similar to the traditional method (yeast free). However, encapsulated yeast spheres should be only used if the base wine matches a number of features, among them calcium content. In this study the calcium content in the wine was determined by atomic absorption spectroscopy (AAS) and by near-infrared spectroscopy. The AAS is a high sensitivity method clearly produces a reliable result, however it is very time consuming and produces great quantities of environmental waste, therefore the possibility of using near-infrared spectroscopy as a method was studied to be a fast, simple and clean alternative to the AAS. It was obtained a calibration model with a variation coefficient higher than 0.80 which indicates that the near-infrared spectroscopy as an adequately alternative the ASS.

Advanced Spectroscopy for the Study of Colourants in Cultural Heritage

Colourants are substances used to change the colour of something, and are classified in three typology of colorants: a) pigments, b) dyes, and c) lakes and hybrid pigments. Their identification is very important when studying cultural heritage; it gives information about the artistic technique, can help in dating, and offers insights on the condition of the object. Besides, the study of the degradation phenomena constitutes a framework for the preventive conservation strategies, provides evidence of the object's original appearance, and contributes to the authentication of works of art. However, the complexity of these systems makes it impossible to achieve a complete understanding using a single technique, making necessary a multi-analytical approach. This work focuses on the set-up and application of advanced spectroscopic methods for the study of colourants in cultural heritage. The first chapter presents the identification of modern synthetic organic pigments using Metal Underlayer-ATR (MU-ATR), and the characterization of synthetic dyes extracted from wool fibres using a combination of Thin Layer Chromatography (TLC) coupled to MU-ATR using AgI@Au plates. The second chapter presents the study of the effect of metallic Ag in the photo-oxidation process of orpiment, and the influence of the different factors, such as light and relative humidity. We used a combination of vibrational and synchrotron radiation-based X-ray microspectroscopy techniques: µ-ATR-FT-IR, µ-Raman, SR-µ-XRF, µ-XANES at S K-, Ag L3- and As K-edges and SR-µ-XRD. The third chapter presents the study of metal carboxylates in paintings, specifically on the formation of Zn and Pb carboxylates in three different binders: stand linseed oil, whole egg, and beeswax. We used micro-ATR-FT-IR, macro FT-IR in total reflection (rMA-FT-IR), portable Near-Infrared spectroscopy (NIR), macro X-ray Powder Diffraction (MA-XRPD), XRPD, and Gas Chromatography Mass-Spectrometry (GC-MS). For the data processing, we explored the data from rMA-FT-IR and NIR with the Principal Component Analysis (PCA).