Search results for: chemometric

Authors: Sanja O. Podunavac-Kuzmanović, Strahinja Z. Kovačević, Lidija R. Jevrić, Stela Jokić

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The subject of this paper is to correlate antibacterial behavior of benzimidazole derivatives with their molecular characteristics using chemometric QSAR (Quantitative Structure–Activity Relationships) approach. QSAR analysis has been carried out on the inhibitory activity of benzimidazole derivatives against Staphylococcus aureus. The data were processed by linear least squares (LLS) and artificial neural network (ANN) procedures. The LLS mathematical models have been developed as a calibration models for prediction of the inhibitory activity. The quality of the models was validated by leave one out (LOO) technique and by using external data set. High agreement between experimental and predicted inhibitory acivities indicated the good quality of the derived models. These results are part of the CMST COST Action No. CM1306 "Understanding Movement and Mechanism in Molecular Machines".

Keywords: Antibacterial, benzimidazoles, chemometric, QSAR.

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Authors: Marwa A. A. Ragab, Amira F. El-Yazbi, Amr El-Hawiet

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The analysis of heavy metals in honey samples is crucial. When found in honey, they denote environmental pollution. Some of these heavy metals as lead either present at low or high concentrations are considered to be toxic. Other heavy metals, for example, copper and zinc, if present at low concentrations, they considered safe even vital minerals. On the contrary, if they present at high concentrations, they are toxic. Their voltammetric determination in honey represents a challenge due to the presence of other electro-active components as vitamins, which may overlap with the peaks of the metal, hindering their accurate and precise determination. The simultaneous analysis of some vitamins: nicotinic acid (B3) and riboflavin (B2), and heavy metals: lead, cadmium, and zinc, in honey samples, was addressed. The analysis was done in 0.1 M Potassium Chloride (KCl) using a hanging mercury drop electrode (HMDE), followed by chemometric manipulation of the voltammetric data using the derivative method. Then the derivative data were convoluted using discrete Fourier functions. The proposed method allowed the simultaneous analysis of vitamins and metals though their varied responses and sensitivities. Although their peaks were overlapped, the proposed chemometric method allowed their accurate and precise analysis. After the chemometric treatment of the data, metals were successfully quantified at low levels in the presence of vitamins (1: 2000). The heavy metals limit of detection (LOD) values after the chemometric treatment of data decreased by more than 60% than those obtained from the direct voltammetric method. The method applicability was tested by analyzing the selected metals and vitamins in real honey samples obtained from different botanical origins.

Keywords: chemometrics, overlapped voltammetric peaks, derivative and convoluted derivative methods, metals and vitamins

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Authors: Sanja Podunavac-Kuzmanović, Denis Kučević, Strahinja Kovačević, Milica Karadžić, Lidija Jevrić

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The present study describes the application of chemometric methods in analysis of milk samples which were collected in a conventional dairy farm and an organic dairy farm in AP Vojvodina, Republic of Serbia. The chemometric analysis included the application of univariate regression modeling and Analysis of Variance (ANOVA) method. The ANOVA was used in order to determine the differences in fatty acids content in the milk samples from conventional and organic farm. The results of the ANOVA testing indicate that there is a highly statistically significant difference between the content of fatty acid (saturated fatty acid vs. unsaturated fatty acids) in different dairy farming. Besides, the linear univariate models have been obtained as a result of modeling the linear relationships between the milk fat content and saturated fatty acids content, and the linear relationships between the milk fat content and unsaturated fatty acids content. The models obtained on the basis of the milk samples which originate from the organic farming are statistically better than the models based on the milk samples from conventional farming.

Keywords: hemometrics, milk, organic farming, quality control

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Authors: Marwa A. A. Ragab, Hadir M. Maher, Eman I. El-Kimary

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Co-administration of methotrexate (MTX) and aspirin (ASP) can cause a pharmacokinetic interaction and a subsequent increase in blood MTX concentrations which may increase the risk of MTX toxicity. Therefore, it is important to develop a sensitive, selective, accurate and precise method for their simultaneous determination in urine. A new hybrid chemometric method has been applied to the emission response data of the two drugs. Spectrofluorimetric method for determination of MTX through measurement of its acid-degradation product, 4-amino-4-deoxy-10-methylpteroic acid (4-AMP), was developed. Moreover, the acid-catalyzed degradation reaction enables the spectrofluorimetric determination of ASP through the formation of its active metabolite salicylic acid (SA). The proposed chemometric method deals with convolution of emission data using 8-points sin xi polynomials (discrete Fourier functions) after the derivative treatment of these emission data. The first and second derivative curves (D1 & D2) were obtained first then convolution of these curves was done to obtain first and second derivative under Fourier functions curves (D1/FF) and (D2/FF). This new application was used for the resolution of the overlapped emission bands of the degradation products of both drugs to allow their simultaneous indirect determination in human urine. Not only this chemometric approach was applied to the emission data but also the obtained data were subjected to non-parametric linear regression analysis (Theil’s method). The proposed method was fully validated according to the ICH guidelines and it yielded linearity ranges as follows: 0.05-0.75 and 0.5-2.5 µg mL-1 for MTX and ASP respectively. It was found that the non-parametric method was superior over the parametric one in the simultaneous determination of MTX and ASP after the chemometric treatment of the emission spectra of their degradation products. The work combines the advantages of derivative and convolution using discrete Fourier function together with the reliability and efficacy of the non-parametric analysis of data. The achieved sensitivity along with the low values of LOD (0.01 and 0.06 µg mL-1) and LOQ (0.04 and 0.2 µg mL-1) for MTX and ASP respectively, by the second derivative under Fourier functions (D2/FF) were promising and guarantee its application for monitoring the two drugs in patients’ urine samples.

Keywords: chemometrics, emission curves, derivative, convolution, Fourier transform, human urine, non-parametric regression, Theil’s method

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Authors: Wendy Flory, Kazi Czarnecki, Matthijs Mercy, Mark Joswiak, Mary Beth Seasholtz

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Polyurethane Materials are present in a wide range of industrial segments such as Furniture, Building and Construction, Composites, Automotive, Electronics, and more. Dow is one of the leaders for the manufacture of the two main raw materials, Isocyanates and Polyols used to produce polyurethane products. Dow is also a key player for the manufacture of Polyurethane Systems/Formulations designed for targeted applications. In 1990, the first analytical chemometric models were developed and deployed for use in the Dow QC labs of the polyols business for the quantification of OH, water, cloud point, and viscosity. Over the years many models have been added; there are now over 140 models for quantification and hundreds for product identification, too many to be reasonable for support. There are 29 global models alone for the quantification of OH across > 70 products at many sites. An attempt was made to consolidate these into a single model. While the consolidated model proved good statistics across the entire range of OH, several products had a bias by ASTM E1655 with individual product validation. This project summary will show the strategy for global model updates for OH, to reduce the number of models for quantification from over 140 to 5 or less using chemometric methods. In order to gain an understanding of the best product groupings, we identify clusters by reducing spectra to a few dimensions via Principal Component Analysis (PCA) and Uniform Manifold Approximation and Projection (UMAP). Results from these cluster analyses and a separate validation set allowed dow to reduce the number of models for predicting OH from 29 to 3 without loss of accuracy.

Keywords: hydroxyl, global model, model maintenance, near infrared, polyol

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Authors: Robert Cazar, Nathaly Maza

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Energy drinks and sports drinks are quite popular among young adults and teenagers worldwide. Some concerns regarding their health effects – particularly those of the energy drinks - have been raised based on scientific findings. Differentiating between these two types of drinks by means of their chemical properties seems to be an instructive task. Chemometrics provides the most appropriate strategy to do so. In this study, a discrimination analysis of the energy and sports drinks has been carried out applying chemometric methods. A set of eleven samples of available commercial brands of drinks – seven energy drinks and four sports drinks – were collected. Each sample was characterized by eight chemical variables (carbohydrates, energy, sugar, sodium, pH, degrees Brix, density, and citric acid). The data set was standardized and examined by exploratory chemometric techniques such as clustering and principal component analysis. As a preliminary step, a variable selection was carried out by inspecting the variable correlation matrix. It was detected that some variables are redundant, so they can be safely removed, leaving only five variables that are sufficient for this analysis. They are sugar, sodium, pH, density, and citric acid. Then, a hierarchical clustering `employing the average – linkage criterion and using the Euclidian distance metrics was performed. It perfectly separates the two types of drinks since the resultant dendogram, cut at the 25% similarity level, assorts the samples in two well defined groups, one of them containing the energy drinks and the other one the sports drinks. Further assurance of the complete discrimination is provided by the principal component analysis. The projection of the data set on the first two principal components – which retain the 71% of the data information – permits to visualize the distribution of the samples in the two groups identified in the clustering stage. Since the first principal component is the discriminating one, the inspection of its loadings consents to characterize such groups. The energy drinks group possesses medium to high values of density, citric acid, and sugar. The sports drinks group, on the other hand, exhibits low values of those variables. In conclusion, the application of chemometric methods on a data set that features some chemical properties of a number of energy and sports drinks provides an accurate, dependable way to discriminate between these two types of beverages.

Keywords: chemometrics, clustering, energy drinks, principal component analysis, sports drinks

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Authors: Milica Ž. Karadžić, Lidija R. Jevrić, Sanja Podunavac-Kuzmanović, Strahinja Z. Kovačević, Anamarija I. Mandić, Katarina Penov-Gaši, Andrea R. Nikolić, Aleksandar M. Oklješa

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This study considered selection of the in silico molecular descriptors and the models for newly synthesized steroid derivatives description and their characterization using chemometric techniques. Multiple linear regression (MLR) models were established and gave the best molecular descriptors for quantitative structure-retention relationship (QSRR) modeling of the retention of the investigated molecules. MLR models were without multicollinearity among the selected molecular descriptors according to the variance inflation factor (VIF) values. Used molecular descriptors were ranked using generalized pair correlation method (GPCM). In this method, the significant difference between independent variables can be noticed regardless almost equal correlation between dependent variable. Generated MLR models were statistically and cross-validated and the best models were kept. Models were ranked using sum of ranking differences (SRD) method. According to this method, the most consistent QSRR model can be found and similarity or dissimilarity between the models could be noticed. In this study, SRD was performed using average values of experimentally observed data as a golden standard. Chemometric analysis was conducted in order to characterize newly synthesized steroid derivatives for further investigation regarding their potential biological activity and further synthesis. This article is based upon work from COST Action (CM1105), supported by COST (European Cooperation in Science and Technology).

Keywords: generalized pair correlation method, molecular descriptors, regression analysis, steroids, sum of ranking differences

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Authors: Strahinja Kovacevic, Milica Karadzic Banjac, Jasmina Vitas, Stefan Vukmanovic, Radomir Malbasa, Lidija Jevric, Sanja Podunavac-Kuzmanovic

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The present study deals with chemometric regression analysis of quality parameters and the radical scavenging ability of kombucha fermented kefir-like products obtained with winter savory (WS), peppermint (P), stinging nettle (SN) and wild thyme tea (WT) kombucha inoculums. Each analyzed sample was described by milk fat content (MF, %), total unsaturated fatty acids content (TUFA, %), monounsaturated fatty acids content (MUFA, %), polyunsaturated fatty acids content (PUFA, %), the ability of free radicals scavenging (RSA Dₚₚₕ, % and RSA.ₒₕ, %) and pH values measured after each hour from the start until the end of fermentation. The aim of the conducted regression analysis was to establish chemometric models which can predict the radical scavenging ability (RSA Dₚₚₕ, % and RSA.ₒₕ, %) of the samples by correlating it with the MF, TUFA, MUFA, PUFA and the pH value at the beginning, in the middle and at the end of fermentation process which lasted between 11 and 17 hours, until pH value of 4.5 was reached. The analysis was carried out applying univariate linear (ULR) and multiple linear regression (MLR) methods on the raw data and the data standardized by the min-max normalization method. The obtained models were characterized by very limited prediction power (poor cross-validation parameters) and weak statistical characteristics. Based on the conducted analysis it can be concluded that the resulting radical scavenging ability cannot be precisely predicted only on the basis of MF, TUFA, MUFA, PUFA content, and pH values, however, other quality parameters should be considered and included in the further modeling. This study is based upon work from project: Kombucha beverages production using alternative substrates from the territory of the Autonomous Province of Vojvodina, 142-451-2400/2019-03, supported by Provincial Secretariat for Higher Education and Scientific Research of AP Vojvodina.

Keywords: chemometrics, regression analysis, kombucha, quality control

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Authors: Mohamed Izzharif Abdul Halim, Niamh Nic Daeid

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Determining the source of pen inks used on a variety of documents is impartial for forensic document examiners. The examination of inks is often performed to differentiate between inks in order to evaluate the authenticity of a document. A ballpoint pen ink consists of synthetic dyes in (acidic and/or basic), pigments (organic and/or inorganic) and a range of additives. Inks of similar color may consist of different composition and are frequently the subjects of forensic examinations. This study emphasizes on blue ballpoint pen inks available in the market because it is reported that approximately 80% of questioned documents analysis involving ballpoint pen ink. Analytical techniques such as thin layer chromatography, high-performance liquid chromatography, UV-vis spectroscopy, luminescence spectroscopy and infrared spectroscopy have been used in the analysis of ink samples. In this study, application of Diamond Attenuated Total Reflectance (ATR) FTIR is straightforward but preferable in forensic science as it offers no sample preparation and minimal analysis time. The data obtained from these techniques were further analyzed using multivariate chemometric methods which enable extraction of more information based on the similarities and differences among samples in a dataset. It was indicated that some pens from the same manufactures can be similar in composition, however, discrete types can be significantly different.

Keywords: ATR FTIR, ballpoint, multivariate chemometric, PCA

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Authors: Strahinja Z. Kovačević, Lidija R. Jevrić, Sanja O. Podunavac Kuzmanović

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The relationship between antibacterial activity of eighteen different substituted benzimidazole derivatives and their molecular characteristics was studied using chemometric QSAR (Quantitative Structure–Activity Relationships) approach. QSAR analysis has been carried out on inhibitory activity towards Staphylococcus aureus, by using molecular descriptors, as well as minimal inhibitory activity (MIC). Molecular descriptors were calculated from the optimized structures. Principal component analysis (PCA) followed by hierarchical cluster analysis (HCA) and multiple linear regression (MLR) was performed in order to select molecular descriptors that best describe the antibacterial behavior of the compounds investigated, and to determine the similarities between molecules. The HCA grouped the molecules in separated clusters which have the similar inhibitory activity. PCA showed very similar classification of molecules as the HCA, and displayed which descriptors contribute to that classification. MLR equations, that represent MIC as a function of the in silico molecular descriptors were established. The statistical significance of the estimated models was confirmed by standard statistical measures and cross-validation parameters (SD = 0.0816, F = 46.27, R = 0.9791, R2CV = 0.8266, R2adj = 0.9379, PRESS = 0.1116). These parameters indicate the possibility of application of the established chemometric models in prediction of the antibacterial behaviour of studied derivatives and structurally very similar compounds.

Keywords: antibacterial, benzimidazole, molecular descriptors, QSAR

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Authors: Vanessa G. P. Severino, JOÃO Gabriel M. Junqueira, Michelle N. G. do Nascimento, Francisco W. B. Aquino, João B. Fernandes, Ana P. Terezan

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The scientific interest in analyzing VOCs represents a significant modern research field as a result of importance in most branches of the present life and industry. Therefore it is extremely important to investigate, identify and isolate volatile substances, since they can be used in different areas, such as food, medicine, cosmetics, perfumery, aromatherapy, pesticides, repellents and other household products through methods for extracting volatile constituents, such as solid phase microextraction (SPME), hydrodistillation (HD), solvent extraction (SE), Soxhlet extraction, supercritical fluid extraction (SFE), stream distillation (SD) and vacuum distillation (VD). The Chemometrics is an area of chemistry that uses statistical and mathematical tools for the planning and optimization of the experimental conditions, and to extract relevant chemical information multivariate chemical data. In this context, the focus of this work was the study of the chemical VOCs by SPME of the specie X. aromatica, in search of constituents that can be used in the industrial sector as well as in food, cosmetics and perfumery, since these areas industrial has a considerable role. In addition, by chemometric analysis, we sought to maximize the answers of this research, in order to search for the largest number of compounds. The investigation of flowers from X. aromatica in vitro and in alive mode proved consistent, but certain factors supposed influence the composition of metabolites, and the chemometric analysis strengthened the analysis. Thus, the study of the chemical composition of X. aromatica contributed to the VOCs knowledge of the species and a possible application.

Keywords: chemometrics, flowers, HS-SPME, Xylopia aromatica

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Authors: Dana Alina Magdas, Nicoleta Simona Vedeanu, Ioana Feher, Rares Stiufiuc

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Food and beverages authentication using rapid and non-expensive analytical tools represents nowadays an important challenge. In this regard, the potential of vibrational techniques in food authentication has gained an increased attention during the last years. For wines discrimination, Raman spectroscopy appears more feasible to be used as compared with IR (infrared) spectroscopy, because of the relatively weak water bending mode in the vibrational spectroscopy fingerprint range. Despite this, the use of Raman technique in wine discrimination is in an early stage. Taking this into consideration, the wine discrimination potential of surface-enhanced Raman scattering (SERS) technique is reported in the present work. The novelty of this study, compared with the previously reported studies, concerning the application of vibrational techniques in wine discrimination consists in the fact that the present work presents the wines differentiation based on the individual signals obtained from deconvoluted spectra. In order to achieve wines classification with respect to variety, geographical origin and vintage, the peaks intensities obtained after spectra deconvolution were compared using supervised chemometric methods like Linear Discriminant Analysis (LDA). For this purpose, a set of 20 white Romanian wines from different viticultural Romanian regions four varieties, was considered. Chemometric methods applied directly to row SERS experimental spectra proved their efficiency, but discrimination markers identification found to be very difficult due to the overlapped signals as well as for the band shifts. By using this approach, a better general view related to the differences that appear among the wines in terms of compositional differentiation could be reached.

Keywords: chemometry, SERS, variety, wines discrimination

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Authors: Sumira Jan, Javid Iqbal Mir, Desh Beer Singh, Anil Sharma, Shafia Zaffar Faktoo

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Background and Aims: Climatic and edaphic factors immensely influence crop quality and proper development. Regardless of economic potential, Himalayan Oregano has not subjected to phytonutrient and chemometric evaluation and its relationship with environmental conditions are scarce. The central objective of this research was to investigate microclimatic variation among wild and cultivated populations located in a microclimatic gradient in north-western Himalaya, Kashmir and analyse if such disparity was related with diverse climatic and edaphic conditions. Methods: Micrometeorological, Atomic absorption spectroscopy for micro elemental analysis was carried for soil. HPLC was carried out to estimate variation in phytonutrients and phytochemicals. Results: Geographic variation in phytonutrient was observed among cultivated and wild populations and among populations diverse within regions. Cultivated populations exhibited comparatively lesser phytonutrient value than wild populations. Moreover, our results observed higher vegetative growth of O. vulgare L. with higher pH (6-7), elevated organic carbon (2.42%), high nitrogen (97.41Kg/ha) and manganese (10-12ppm) and zinc contents (0.39-0.50) produce higher phytonutrients. HPLC data of phytonutrients like quercetin, betacarotene, ascorbic acid, arbutin and catechin revealed direct relationship with UV-B flux (r2=0.82), potassium (r2=0.97) displaying parallel relationship with phytonutrient value. Conclusions: Catechin was found as predominant phytonutrient among all populations with maximum accumulation of 163.8 ppm while as quercetin exhibited lesser value. Maximum arbutin (53.42ppm) and quercetin (2.87ppm) accumulated in plants thriving under intense and high UV-B flux. Minimum variation was demonstrated by beta carotene and ascorbic acid.

Keywords: phytonutrient, ascorbic acid, beta carotene, quercetin, catechin

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Authors: Mohamed Korany, Azza Gazy, Essam Khamis, Marwa Adel, Miranda Fawzy

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Background: Two new, simple and specific methods; First, a Zero-crossing first-derivative technique and second, a chemometric-assisted spectrophotometric artificial neural network (ANN) were developed and validated in accordance with ICH guidelines. Both methods were used for the simultaneous estimation of the two closely related antioxidant nutraceuticals ; Coenzyme Q10 (Q) ; also known as Ubidecarenone or Ubiquinone-10, and Vitamin E (E); alpha-tocopherol acetate, in their pharmaceutical binary mixture. Results: For first method: By applying the first derivative, both Q and E were alternatively determined; each at the zero-crossing of the other. The D1 amplitudes of Q and E, at 285 nm and 235 nm respectively, were recorded and correlated to their concentrations. The calibration curve is linear over the concentration range of 10-60 and 5.6-70 μg mL-1 for Q and E, respectively. For second method: ANN (as a multivariate calibration method) was developed and applied for the simultaneous determination of both analytes. A training set (or a concentration set) of 90 different synthetic mixtures containing Q and E, in wide concentration ranges between 0-100 µg/mL and 0-556 µg/mL respectively, were prepared in ethanol. The absorption spectra of the training sets were recorded in the spectral region of 230–300 nm. A Gradient Descend Back Propagation ANN chemometric calibration was computed by relating the concentration sets (x-block) to their corresponding absorption data (y-block). Another set of 45 synthetic mixtures of the two drugs, in defined range, was used to validate the proposed network. Neither chemical separation, preparation stage nor mathematical graphical treatment were required. Conclusions: The proposed methods were successfully applied for the assay of Q and E in laboratory prepared mixtures and combined pharmaceutical tablet with excellent recoveries. The ANN method was superior over the derivative technique as the former determined both drugs in the non-linear experimental conditions. It also offers rapidity, high accuracy, effort and money saving. Moreover, no need for an analyst for its application. Although the ANN technique needed a large training set, it is the method of choice in the routine analysis of Q and E tablet. No interference was observed from common pharmaceutical additives. The results of the two methods were compared together

Keywords: coenzyme Q10, vitamin E, chemometry, quantitative analysis, first derivative spectrophotometry, artificial neural network

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Authors: Sarwar Beg, Gajanand Sharma, O. P. Katare, Bhupinder Singh

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The current studies entail development of self-nano emulsifying drug delivery systems (SNEDDS) of rosuvastatin, employing rational QbD-based approach for enhancing its oral bioavailability. SNEDDS were prepared using the blend of lipidic and emulsifying excipients, i.e., Peceol, Tween 80, and Transcutol HP. The prepared formulations evaluated for in vitro drug release, ex vivo permeation, in situ perfusion studies and in vivo pharmacokinetic studies in rats, which demonstrated 3-4 fold improvement in biopharmaceutical performance of the developed formulations. Cytotoxicity studies using MTT assay and histopathological studies in intestinal cells revealed the lack of cytotoxicity and thereby safety and efficacy of the developed formulations.

Keywords: SNEDDS, bioavailability, solubility, Quality by Design (QbD)

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Authors: Lidija R. Jevrić, Sanja O. Podunavac-Kuzmanović, Strahinja Z. Kovačević

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This study considers the selection of the most suitable in silico molecular descriptors that could be used for s-triazine pesticides characterization. Suitable descriptors among topological, geometrical and physicochemical are used for quantitative structure-retention relationships (QSRR) model establishment. Established models were obtained using linear regression (LR) and multiple linear regression (MLR) analysis. In this paper, MLR models were established avoiding multicollinearity among the selected molecular descriptors. Statistical quality of established models was evaluated by standard and cross-validation statistical parameters. For detection of similarity or dissimilarity among investigated s-triazine pesticides and their classification, principal component analysis (PCA) and hierarchical cluster analysis (HCA) were used and gave similar grouping. This study is financially supported by COST action TD1305.

Keywords: chemometrics, classification analysis, molecular descriptors, pesticides, regression analysis

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Authors: A. Kudrev

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The duplex Poly(A)-Poly(U) denaturation in an aqueous solutions in mixtures with the tetracationic MeTMPyP4 (Me = 2H, Zn(II); TMPyP4 is 5,10,15,20-tetrakis(N-methylpyridinium-4-yl)porphyrin), was investigated by monitoring the changes in the UV-Vis absorbance spectrum with increasing temperatures from 20°С to 70°С (рН 7.0, I=0.15M). The absorbance data matrices were analyzed with a versatile chemometric procedure that provides the melting profile (distribution of species) and the pure spectrum for each chemical species present along the heating experiment. As revealed by the increase of Tm, the duplex structure was stabilized by these porphyrins. The values of stabilization temperature ΔTm in the presence of these porphyrins are relatively large, 1.2-8.4 °C, indicating that the porphyrins contribute differently in stabilizing the duplex Poly(A)-Poly(U) structure. Remarkable is the fact that the porphyrin TMPyP4 was less effective in the stabilization of the duplex structure than the metalloporphyrin Zn(X)TMPyP4 which suggests that metallization play an important role in porphyrin-RNA binding. Molecular Dynamics Simulations has been used to illustrate melting of the duplex dsRNA bound with a porphyrin molecule.

Keywords: melting, Poly(A)-Poly(U), TMPyP4, Zn(X)TMPyP4

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Authors: Kali Prasad Sarma, Nibedita Baul, Jinu Deka

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In the present study, pollution level of polycyclic aromatic hydrocarbon (PAH) in surface soil of historic Tezpur town located in the north bank of the River Brahmaputra were evaluated. In order to determine the seasonal distribution and concentration level of 16 USEPA priority PAHs surface soil samples were collected from 12 different sampling sites with various land use type. The total concentrations of 16 PAHs (∑16 PAHs) varied from 242.68µgkg-1to 7901.89µgkg-1. Concentration of total probable carcinogenic PAH ranged between 7.285µgkg-1 and 479.184 µgkg-1 in different seasons. However, the concentration of BaP, the most carcinogenic PAH, was found in the range of BDL to 50.01 µgkg-1. The composition profiles of PAHs in 3 different seasons were characterized by following two different types of ring: (1) 4-ring PAHs, contributed to highest percentage of total PAHs (43.75%) (2) while in pre- and post- monsoon season 3- ring compounds dominated the PAH profile, contributing 65.58% and 74.41% respectively. A high PAHs concentration with significant seasonality and high abundance of LMWPAHs was observed in Tezpur town. Soil PAHs toxicity was evaluated taking toxic equivalency factors (TEFs), which quantify the carcinogenic potential of other PAHs relative to BaP and estimate benzo[a]pyrene-equivalent concentration (BaPeq). The calculated BaPeq value signifies considerable risk to contact with soil PAHs. We applied cluster analysis and principal component analysis (PCA) with multivariate linear regression (MLR) to apportion sources of polycyclic aromatic hydrocarbons (PAHs) in surface soil of Tezpur town, based on the measured PAH concentrations. The results indicate that petrogenic and pyrogenic sources are the important sources of PAHs. A combination of chemometric and molecular indices were used to identify the sources of PAHs, which could be attributed to vehicle emissions, a mixed source input, natural gas combustion, wood or biomass burning and coal combustion. Source apportionment using absolute principle component scores–multiple linear regression showed that the main sources of PAHs are 22.3% mix sources comprising of diesel and biomass combustion and petroleum spill,13.55% from vehicle emission, 9.15% from diesel and natural gas burning, 38.05% from wood and biomass burning and 16.95% contribute coal combustion. Pyrogenic input was found to dominate source of PAHs origin with more contribution from vehicular exhaust. PAHs have often been found to co-emit with other environmental pollutants like heavy metals due to similar source of origin. A positive correlation was observed between PAH with Cr and Pb (r2 = 0.54 and 0.55 respectively) in monsoon season and PAH with Cd and Pb (r2 = 0.54 and 0.61 respectively) indicating their common source. Strong correlation was observed between PAH and OC during pre- and post- monsoon (r2=0.46 and r2=0.65 respectively) whereas during monsoon season no significant correlation was observed (r2=0.24).

Keywords: polycyclic aromatic hydrocarbon, Tezpur town, chemometric analysis, ecological risk assessment, pollution

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Authors: R. Velvarska, A. Vrablik, M. Fiedlerova, R. Cerny

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Near-infrared spectrometry (NIR) was tested as a rapid and alternative tool for determination of biodiesel oxidation stability. A PetroOxy method is standardly used for the determination, but this method is hazardous due to the possibility of explosion and ignition of flammable fuels. The second disadvantage is time consuming. The near-infrared spectrometry served for the development of the calibration model which was composed of 133 real samples (calibration standards). The reference values of these standards were obtained by PetroOxy method. Many chemometric diagnostics were used for the development of the final NIR model with the aim to have accurate prediction of the oxidation stability. The final NIR model was validated by 30 validation standards. The repeatability was determined as well with the acceptable residual standard deviation (8.59 %). The NIR spectrometry has proved to be an accurate alternative method for the determination of biodiesel oxidation stability with advantages as the time and cost saving, non-destructive character of analyzing and the possibility of online monitoring in safe mode.

Keywords: biodiesel, fatty acid methyl ester, NIR, oxidation stability

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Authors: Milica Karadzic, Lidija Jevric, Sanja Podunavac-Kuzmanovic, Strahinja Kovacevic, Aleksandra Tepic-Horecki, Zdravko Sumic

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In this paper, the influence of six different phytochemical content (phenols, carotenoids, chlorophyll a, chlorophyll b, chlorophyll a + b and vitamin C) on antioxidant potential of Murai and Levistro lettuce varieties was evaluated. Variable selection was made by generalized pair correlation method (GPCM) as a novel ranking method. This method is used for the discrimination between two variables that almost equal correlate to a dependent variable. Fisher’s conditional exact and McNemar’s test were carried out. Established multiple linear (MLR) models were statistically evaluated. As the best phytochemicals for the antioxidant potential prediction, chlorophyll a, chlorophyll a + b and total carotenoids content stand out. This was confirmed through both GPCM and MLR, predictive ability of obtained MLR can be used for antioxidant potential estimation for similar lettuce samples. This article is based upon work from the project of the Provincial Secretariat for Science and Technological Development of Vojvodina (No. 114-451-347/2015-02).

Keywords: antioxidant activity, generalized pair correlation method, lettuce, regression analysis

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Authors: Ke Lin, Steve Wu Qing Yang, Zhang Nan

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The medicine and drugs has in the past been manufactured to the final products and then used laboratory analysis to verify their quality. However the industry needs crucially a monitoring technique for the final batch to batch quality check. The introduction of process analytical technology (PAT) provides an incentive to obtain real-time information about drugs on the production line, with the following optical techniques being considered: near-infrared (NIR) spectroscopy, Raman spectroscopy and imaging, mid-infrared spectroscopy with the use of chemometric techniques to quantify the final product. However, presents problems in that the spectra obtained will consist of many combination and overtone bands of the fundamental vibrations observed, making analysis difficult. In this work, we describe a non-destructive system and method for capsule and liquid medicine identification, more particularly, using terahertz time-domain spectroscopy and/or designed terahertz portable system for identifying different types of medicine in the package of capsule or in liquid medicine bottles. The target medicine can be detected directly, non-destructively and non-invasively.

Keywords: terahertz, non-destructive, non-invasive, chemical identification

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Authors: Ahmed Metawea, Rodrigo Soto, Majeida Kharejesh, Gavin Walker, Ahmad B. Albadarin

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In this study, towards a green approach, we have investigated the effect of operating conditions of solvent assessed twin-screw extruder (TSE) for the production of 4, 4-bipyridine (1-dimensional coordinated polymer (1D)) based coordinated polymer using cobalt nitrate as a metal precursor with molar ratio 1:1. Different operating parameters such as solvent percentage, screw speed and feeding rate are considered. The resultant product is characterized using offline characterization methods, namely Powder X-ray diffraction (PXRD), Raman spectroscopy and scanning electron microscope (SEM) in order to investigate the product purity and surface morphology. A lower feeding rate increased the product’s quality as more resident time was provided for the reaction to take place. The most important influencing factor was the amount of liquid added. The addition of water helped in facilitating the reaction inside the TSE by increasing the surface area of the reaction for particles

Keywords: MOFS, multivariate analysis, process optimization, chemometric

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Authors: Meghana Shankara, Priyadarshini Natarajan

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Infrared (IR) spectroscopy has revolutionized the way we look at materials around us. Unraveling the pattern in the molecular spectra of materials to analyze the composition and properties of it has been one of the most interesting challenges in modern science. Applications of the IR spectrometry are numerous in the field’s pharmaceuticals, health, food and nutrition, oils, agriculture, construction, polymers, beverage, fabrics and much more limited only by the curiosity of the people. Near Infrared (NIR) spectrometry is applied robustly in analyzing the solids and liquid substances because of its non-destructive analysis method. In this paper, we have reviewed the application of NIR spectrometry in milk quality analysis and have presented the modes of measurement applied in NIRS measurement setup, Design of Experiment (DoE), classification/quantification algorithms used in the case of milk composition prediction like Fat%, Protein%, Lactose%, Solids Not Fat (SNF%) along with different approaches for adulterant identification. We have also discussed the important NIR ranges for the chosen milk parameters. The performance metrics used in the comparison of the various Chemometric approaches include Root Mean Square Error (RMSE), R^2, slope, offset, sensitivity, specificity and accuracy

Keywords: chemometrics, design of experiment, milk quality analysis, NIRS measurement modes

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Authors: E. Izsó, M. Bartalné-Berceli, Sz. Gergely, A. Salgó

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The aims of this investigation is to elaborate near-infrared methods for testing and recognition of chemical components and quality in “Pannon wheat” allied (i.e. true to variety or variety identified) milling fractions as well as to develop spectroscopic methods following the milling processes and evaluate the stability of the milling technology by different types of milling products and according to sampling times, respectively. This wheat categories produced under industrial conditions where samples were collected versus sampling time and maximum or minimum yields. The changes of the main chemical components (such as starch, protein, lipid) and physical properties of fractions (particle size) were analysed by dispersive spectrophotometers using visible (VIS) and near-infrared (NIR) regions of the electromagnetic radiation. Close correlation were obtained between the data of spectroscopic measurement techniques processed by various chemometric methods (e.g. principal component analysis (PCA), cluster analysis (CA) and operation condition of milling technology. Its obvious that NIR methods are able to detect the deviation of the yield parameters and differences of the sampling times by a wide variety of fractions, respectively. NIR technology can be used in the sensitive monitoring of milling technology.

Keywords: near infrared spectroscopy, wheat categories, milling process, monitoring

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Authors: Sanja O. Podunavac-Kuzmanović, Strahinja Z. Kovačević, Lidija R. Jevrić, Stela Jokić

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The complexes of transition metals with various organic ligands have been extensively studied as models of some important pharmaceutical molecules. It was found that biological properties of different substituted organic molecules are improved when they are complexed by different metals. Therefore, it is of great importance for the development of coordination chemistry to explore the assembly of functional organic ligands with metal ion and to investigate the relationship between the structure and property. In the present work, we have bioassayed the antibacterial potency of benzimidazoles and their metal salts (Cu or Zn) against yeast Sarcina lutea. In order to validate our in vitro study, we performed in silico studies using molecular docking software. The investigated compounds and their metal complexes (Cu, Zn) showed good to moderate inhibitory activity against Sarcina lutea. In silico docking studies of the synthesized compounds suggested that complexed benzimidazoles have a greater binding affinity and improved antibacterial activity in comparison with non-complexed ligands. These results are part of the CMST COST Action No. 1105 "Functional metal complexes that bind to biomolecules".

Keywords: organometallic complexes, benzimidazoles, chemometric design, Sarcina lutea

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Authors: Sanja Podunavac-Kuzmanović, Strahinja Kovačević, Lidija Jevrić, Evgenija Djurendić, Jovana Ajduković

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In the present study, the molecular modeling of a series of 24 17-picolyl and 17-picolinylidene androstane derivatives whit significant anticancer activity was carried out. Modelling of studied compounds was performed by CS ChemBioDraw Ultra v12.0 program for drawing 2D molecular structures and CS ChemBio3D Ultra v12.0 for 3D molecular modelling. The obtained 3D structures were subjected to energy minimization using molecular mechanics force field method (MM2). The cutoff for structure optimization was set at a gradient of 0.1 kcal/Åmol. Full geometry optimization was done by the Austin Model 1 (AM1) until the root mean square (RMS) gradient reached a value smaller than 0.0001 kcal/Åmol using Molecular Orbital Package (MOPAC) program. The obtained physicochemical, lipophilicity and topological descriptors were used for analysis of molecular similarities and dissimilarities applying suitable chemometric methods (principal component analysis and cluster analysis). These results are the part of the project No. 114-451-347/2015-02, financially supported by the Provincial Secretariat for Science and Technological Development of Vojvodina and CMST COST Action CM1306.

Keywords: androstane derivatives, anticancer activity, chemometrics, molecular descriptors

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Authors: Marijana M. Ačanski, Kristian A. Pastor, Djura N. Vujić

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The identification of lipid and soluble sugar components in flour samples of different cultivars belonging to common oat species (Avena sativa L.) was performed: spring oat, winter oat and hulless oat. Fatty acids were extracted from flour samples with n-hexane, and derivatized into volatile methyl esters, using TMSH (trimethylsulfonium hydroxide in methanol). Soluble sugars were then extracted from defatted and dried samples of oat flour with 96% ethanol, and further derivatized into corresponding TMS-oximes, using hydroxylamine hydrochloride solution and BSTFA (N,O-bis-(trimethylsilyl)-trifluoroacetamide). The hexane and ethanol extracts of each oat cultivar were analyzed using GC-MS system. Lipid and simple sugar compositions are very similar in all samples of investigated cultivars. Chemometric tool was applied to numeric values of automatically integrated surface areas of detected lipid and simple sugar components in their corresponding derivatized forms. Hierarchical cluster analysis shows a very high similarity between the investigated flour samples of oat cultivars, according to the fatty acid content (0.9955). Moderate similarity was observed according to the content of soluble sugars (0.50). These preliminary results support the idea of establishing methods for oat flour authentication, and provide the means for distinguishing oat flour samples, regardless of the variety, from flour samples made of other cereal species, just by lipid and simple sugar profile analysis.

Keywords: oat cultivars, lipid composition, soluble sugar composition, GC-MS, chemometrics, authentication

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Authors: Shima Behkami, Nor Shahirul Umirah Idris, Sharifuddin Md. Zain, Kah Hin Low, Mehrdad Gholami, Nima A. Behkami, Ahmad Firdaus Kamaruddin

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In this work, Inductively Coupled Plasma Mass Spectrometry (ICP-MS), Isotopic Ratio Mass Spectrometry (IRMS) and Ultrasound Milko Tester were used to study milk samples obtained from various geographical locations in Malaysia. ICP-MS was used to determine the concentration of trace elements in milk, water and soil samples obtained from seven dairy farms at different geographical locations in peninsular Malaysia. IRMS was used to analyze the milk samples for isotopic ratios of δ13C, 15N and 18O. Nutritional parameters in the milk samples were determined using an ultrasound milko tester. Data obtained from these measurements were evaluated by Principal Component Analysis (PCA) and Hierarchical Analysis (HA) as a preliminary step in determining geographical origin of these milk samples. It is observed that the isotopic ratios and a number of the nutritional parameters are responsible for the discrimination of the samples. It was also observed that it is possible to determine the geographical origin of these milk samples solely by the isotopic ratios of δ13C, 15N and 18O. The accuracy of the geographical discrimination is demonstrated when several milk samples from a milk factory taken from one of the regions under study were appropriately assigned to the correct PCA cluster.

Keywords: inductively coupled plasma mass spectroscopy ICP-MS, isotope ratio mass spectroscopy IRMS, ultrasound, principal component analysis, hierarchical analysis, geographical origin, milk

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Authors: Omar Dib, Rita Yaacoub, Luc Eveleigh, Nathalie Locquet, Hussein Dib, Ali Bassal, Christophe B. Y. Cordella

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The potential of front-face fluorescence coupled with chemometric techniques, namely parallel factor analysis (PARAFAC) and multiple linear regression (MLR) as a rapid analysis tool to characterize Lebanese virgin olive oils was investigated. Fluorescence fingerprints were acquired directly on 102 Lebanese virgin olive oil samples in the range of 280-540 nm in excitation and 280-700 nm in emission. A PARAFAC model with seven components was considered optimal with a residual of 99.64% and core consistency value of 78.65. The model revealed seven main fluorescence profiles in olive oil and was mainly associated with tocopherols, polyphenols, chlorophyllic compounds and oxidation/hydrolysis products. 23 MLR regression models based on PARAFAC scores were generated, the majority of which showed a good correlation coefficient (R > 0.7 for 12 predicted variables), thus satisfactory prediction performances. Acid values, peroxide values, and Delta K had the models with the highest predictions, with R values of 0.89, 0.84 and 0.81 respectively. Among fatty acids, linoleic and oleic acids were also highly predicted with R values of 0.8 and 0.76, respectively. Factors contributing to the model's construction were related to common fluorophores found in olive oil, mainly chlorophyll, polyphenols, and oxidation products. This study demonstrates the interest of front-face fluorescence as a promising tool for quality control of Lebanese virgin olive oils.

Keywords: front-face fluorescence, Lebanese virgin olive oils, multiple Linear regressions, PARAFAC analysis

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Authors: Milica Karadžić, Lidija Jevrić, Sanja Podunavac-Kuzmanović, Strahinja Kovačević, Anamarija Mandić, Aleksandar Oklješa, Andrea Nikolić, Marija Sakač, Katarina Penov Gaši

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Using chemometric approach, the relationships between the chromatographic lipophilicity and in silico molecular descriptors for twenty-nine selected steroid derivatives were studied. The chromatographic lipophilicity was predicted using artificial neural networks (ANNs) method. The most important in silico molecular descriptors were selected applying stepwise selection (SS) paired with partial least squares (PLS) method. Molecular descriptors with satisfactory variable importance in projection (VIP) values were selected for ANN modeling. The usefulness of generated models was confirmed by detailed statistical validation. High agreement between experimental and predicted values indicated that obtained models have good quality and high predictive ability. Global sensitivity analysis (GSA) confirmed the importance of each molecular descriptor used as an input variable. High-quality networks indicate a strong non-linear relationship between chromatographic lipophilicity and used in silico molecular descriptors. Applying selected molecular descriptors and generated ANNs the good prediction of chromatographic lipophilicity of the studied steroid derivatives can be obtained. This article is based upon work from COST Actions (CM1306 and CA15222), supported by COST (European Cooperation and Science and Technology).

Keywords: artificial neural networks, chemometrics, global sensitivity analysis, liquid chromatography, steroids

Procedia PDF Downloads 305