K.S. Choudhari

Analytical predictive capabilities of Laser Induced Breakdown Spectroscopy (LIBS) with Principal Component Analysis (PCA) for plastic classification

A Laser Induced Breakdown Spectroscopy (LIBS) technique has been applied for the identification of four widely used plastics, polyethylene terephthalate (PET), high-density polyethylene (PE), polypropylene (PP) and polystyrene (PS), whose recycling is required from commercial and biosafety points of view. The 3rd harmonic (355 nm) nanosecond pulse from an Nd:YAG laser is used to create plasma on the sample surface and identification of the type of the plastic is derived from the plasma emission. Principal Component Analysis (PCA) of the LIBS spectra is employed for the classification of plastics. Distinct methods have been used, apart from principal components of PCA, to further confirm our results. Statistical parameters, viz., Mahalanobis distance (M-distance) and spectral residuals were used for decisive match/no match test which provided successful classification of plastics. Receiver Operating Characteristic (ROC) and Youdens index analyses were carried out to obtain the diagnostic threshold for classification of all four classes of plastics. Sensitivity, specificity, predictive values and discriminative accuracy of the classification tests based on the optimum threshold were calculated. This proves the analytical predictive capabilities of the LIBS technique for plastic identification and classification. The technique of LIBS, in future, can be routinely used in field applications such as plastic waste sorting and recycling.

Quantification and morphology studies of nanoporous alumina membranes: a new algorithm for digital image processing.

A new mathematical algorithm is reported for the accurate and efficient analysis of pore properties of nanoporous anodic alumina (NAA) membranes using scanning electron microscope (SEM) images. NAA membranes of the desired pore size were fabricated using a two-step anodic oxidation process. Surface morphology of the NAA membranes with different pore properties was studied using SEM images along with computerized image processing and analysis. The main objective was to analyze the SEM images of NAA membranes quantitatively, systematically, and quickly. The method uses a regularized shock filter for contrast enhancement, mathematical morphological operators, and a segmentation process for efficient determination of pore properties. The algorithm is executed using MATLAB, which generates a statistical report on the morphology of NAA membrane surfaces and performs accurate quantification of the parameters such as average pore-size distribution, porous area fraction, and average interpore distances. A good comparison between the pore property measurements was obtained using our algorithm and ImageJ software. This algorithm, with little manual intervention, is useful for optimizing the experimental process parameters during the fabrication of such nanostructures. Further, the algorithm is capable of analyzing SEM images of similar or asymmetrically porous nanostructures where sample and background have distinguishable contrast.

Evaluation of high-performance liquid chromatography laser-induced fluorescence for serum protein profiling for early diagnosis of oral cancer

The present work deals with the evaluation of a high-performance liquid chromatography laser-induced fluorescence (HPLC-LIF) technique developed in our laboratory for early detection of oral cancer from protein profiles of body fluids. The results show that protein profiles of serum samples from a given class of samples, say, normal, premalignant, or malignant, are statistically very close to each other, while profiles of members of any class are significantly different from other classes. The performance of the technique is evaluated by the use of sensitivity and specificity pairs, receiver operating characteristic (ROC) analysis, and Youdens Index. The technique uses protein profile differences in serum samples, registered by the HPLC-LIF technique. The study is carried out using serum samples from volunteers diagnosed as normal or premalignant clinically, and as malignant by histopathology. The specificities and sensitivities of the HPLC-LIF method at an ideal threshold (M-distance = 2) for normal, malignant, and premalignant classes are 100, 69.5, and 61.5%, and 86.5, 87.5, and 87.5% respectively.

Microwave solution route to ceramic ZnAl2O4 nanoparticles in 10 minutes: inversion and photophysical changes with thermal history

Microwave-assisted synthesis of ZnAl2O4 nanoparticles in minutes using metalorganic precursors is reported. Phase-pure ZnAl2O4 with an average crystallite size of ∼5 nm is formed in the solution medium at 185 °C. Annealing in air at temperatures between 500 and 1200 °C increases the crystallite size to ∼32 nm. The as-prepared particles are largely shapeless, whereas polyhedral crystallites with well-defined grain boundaries can be seen in the HR-TEM image of the annealed samples. Diffuse reflectance spectroscopy provides insight into the structural development of the oxide spinel. Rapid synthesis leads to significant crystallographic inversion (∼33%), as observed by X-ray photoelectron spectroscopy. Photoluminescence spectroscopy shows that the different emission bands are due both to anti-site defects in the form of zinc interstitials caused by cationic inversion and to oxygen and zinc vacancies. Optical measurements suggest that inhomogeneity in cationic distribution, probably caused by the rapidity of synthesis, is prevalent even after annealing at temperatures up to 1200 °C, and plays a significant role in controlling the emission properties of the spinel. The microwave-assisted technique using metalorganic precursors is an easy path to the rapid synthesis of doped ZnAl2O4 phosphors.

A hybrid LIBS–Raman system combined with chemometrics: an efficient tool for plastic identification and sorting

AbstractClassification of plastics is of great importance in the recycling industry as the littering of plastic wastes increases day by day as a result of its extensive use. In this paper, we demonstrate the efficacy of a combined laser-induced breakdown spectroscopy (LIBS)–Raman system for the rapid identification and classification of post-consumer plastics. The atomic information and molecular information of polyethylene terephthalate, polyethylene, polypropylene, and polystyrene were studied using plasma emission spectra and scattered signal obtained in the LIBS and Raman technique, respectively. The collected spectral features of the samples were analyzed using statistical tools (principal component analysis, Mahalanobis distance) to categorize the plastics. The analyses of the data clearly show that elemental information and molecular information obtained from these techniques are efficient for classification of plastics. In addition, the molecular information collected via Raman spectroscopy exhibits clearly distinct features for the transparent plastics (100% discrimination), whereas the LIBS technique shows better spectral feature differences for the colored samples. The study shows that the information obtained from these complementary techniques allows the complete classification of the plastic samples, irrespective of the color or additives. This work further throws some light on the fact that the potential limitations of any of these techniques for sample identification can be overcome by the complementarity of these two techniques. Graphical Abstractᅟ

Diffusion-controlled growth of CuAl2O4 Nanoparticles: Effect of Sintering and Photodegradation of Methyl Orange

ABSTRACT Facile synthesis of CuAl2O4 and sintering effects on the phase composition are reported. Annealing at 500 °C showed only CuO phase and the spinel phase started evolving at 700 °C with the concurrent decrease in the CuO phase. Diffusion-mediated growth of spinel phase was also observed at higher temperatures forming CuAl2O4 at 1000 °C. The material was stoichiometric and the average particle size was 55 nm, as evidenced by EDS and FE-SEM studies, respectively. The zeta potential of +30 mV and lower (0.346) value of the poly dispersive index (PDI), confirmed the high dispersability of CuAl2O4 in water. The favourable band gap (2.2 eV) makes it suitable as visible light photocatalyst. Owing to its positive surface charge and conducive pH, material could adsorb anionic methyl orange dye. A total of 74% of the dye could be recovered by a simple methanolic extraction. The visible light photocatalysis of the same dye leads to 67% decolouration and the addition of H2O2 accelerated the photodegradation to completion. The catalyst displayed excellent reusability and stability even after five successive runs.

Quantification of Mn in glass matrices using laser induced breakdown spectroscopy (LIBS) combined with chemometric approaches

A Q-switched solid state Nd:YAG laser operating at a third harmonic (355 nm) wavelength and an echelle spectrograph coupled with an ICCD system were used to study the plasma on a glass target. The present work is mainly focused on the investigation of multivariate calibration methods like principal component regression (PCR) and partial least squares regression (PLSR) for the analysis of Mn in complex matrices like glass. The glass studied has Mn as an analyte of interest whose doping concentration in the matrix varies from 0.77% to 11.61%. The performance of univariate and multivariate methods has been presented in this paper through their figures of merit. Improved prediction accuracy, limit of detection (LOD) and regression coefficients (R2) have been reported when the data were analyzed using PCR and PLSR. The calibration curves of six emission lines of Mn have been analyzed using a univariate method that resulted in R2 values varying from 0.85 to 0.98. This method resulted in a correlation uncertainty of 10% and a LOD of 0.20 wt%. R2 values of 0.98 to 0.99 have been obtained for the multivariate calibration curves of Mn analyzed in three selected regions of the LIBS spectrum. The optimum LOD and root mean square error of prediction (RMSEP) using PCR and PLSR were found to be 0.02 wt% and 0.54 wt%, respectively. The significant improvement in the analytical performances of multivariate calibration methods for the investigation of LIBS data is evident from the aforementioned results. Finally, the results of PCR and PLSR were confirmed by PCA classification.

Highly Sensitive High Performance Liquid Chromatography-Laser Induced Fluorescence for Proteomics Applications

This paper describes the sensitivity study and performance evaluation of high-performance liquid chromatography-laser-induced fluorescence detection (HPLC-LIF) system assembled in our laboratory for proteomics applications. The limits of Detection (LOD) of several serum proteins have been estimated with this instrument and are found to be much lower compared to other commonly used proteomics techniques like SELDI, MALDI, 2-D-SDS-PAGE, and so forth. Techniques for improving the LOD still further with similar setup are briefly discussed. Using the system, protein profiles of serum in normal, malignant, and premalignant conditions were recorded for different malignancy situations.

Adsorptive CuO/CuAl2O4 nanoparticles for the separation of aqueous methyl orange

A simple method for the separation of aqueous methyl orange, an azo dye, is reported, where CuO/CuAl2O4 nanoparticles synthesisedby co-precipitation methodwere used as the adsorbent. The presence of cubic CuAl2O4 (CAO) and monoclinic CuO phase of this composite material was confirmed by X-Ray diffraction and its specific surface area wasdetermined by BET nitrogen adsorption method.To study the nature of surface charge, theisoelectric point of the material was determined using the pH drift methodfollowing which the rate of decolouration was studied forpH 5and pH 7. Theexperiments in the absence oflight show that adsorption of the dye is prevalent even up to 6h leading to 86% decolouration.A methanolic extraction was effectivefor quantitative separation ofadsorbed dye fromCuO/CuAl2O4 nanoparticles regenerating them for reuse. The presence of methyl orange in the extracted solution and on the nanoparticles at various stages was verified byUV-Visible and FT-IR spectroscopic methods.The extent of adsorption was quantified and found tobe as high as 86%. The catalyst aftercomplete extraction ofmethyl orange (MO),could be reused for the decolouration. Stability of the nanoparticles after reuse was verified by the closematch of XRD patterns ofthe pure and reused CAOwhich show no significant changes in itscrystal structure. The separation method shown here can be extended for the removal of other azo dyesfrom textile effluents.