Green HPLC Enantioseparation of Chemopreventive Chiral Isothiocyanates Homologs on an Immobilized Chiral Stationary Phase Based on Amylose tris-[(S)-α-Methylbenzylcarbamate].

Sulforaphane is a chiral phytochemical with chemopreventive properties. The presence of a stereogenic sulfur atom is responsible for the chirality of the natural isothiocyanate. The key role of sulfur chirality in biological activity is underscored by studies of the efficacy of individual enantiomers as chemoprotective agents. The predominant native (R) enantiomer is active, whereas the (S) antipode is inactive or has little or no biological activity. Here we provide an enantioselective high-performance liquid chromatography (HPLC) protocol for the direct and complete resolution of sulforaphane and its chiral natural homologs with different aliphatic chain lengths between the sulfinyl sulfur and isothiocyanate group, namely iberin, alyssin, and hesperin. The chromatographic separations were carried out on the immobilized-type CHIRALPAK IH-3 chiral stationary phase with amylose tris-[(S)-methylbenzylcarbamate] as a chiral selector. The effects of different mobile phases consisting of pure alcoholic solvents and hydroalcoholic mixtures on enantiomer retention and enantioselectivity were carefully investigated. Simple and environmentally friendly enantioselective conditions for the resolution of all chiral ITCs were found. In particular, pure ethanol and highly aqueous mobile phases gave excellent enantioseparations. The retention factors of the enantiomers were recorded as the water content in the aqueous-organic modifier (methanol, ethanol, or acetonitrile) mobile phases progressively varied. U-shaped retention maps were generated, indicating a dual and competitive hydrophilic interaction liquid chromatography (HILIC) and reversed-phase liquid chromatography retention mechanism on the CHIRALPAK IH-3 chiral stationary phase. Finally, experimental chiroptical studies performed in ethanol solution showed that the (R) enantiomers were eluted before the (S) counterpart under all eluent conditions investigated.

Microencapsulation by a Spray Drying Approach to Produce Innovative Probiotics-Based Products Extending the Shelf-Life in Non-Refrigerated Conditions.

Recently, there has been a growing interest in producing functional foods containing encapsulated probiotic bacteria due to their positive effects on human health. According to their perceived health benefits, probiotics have been incorporated into a range of dairy products, but the current major challenge is to market new, multicomponent probiotic foods and supplements. Nevertheless, only a few products containing encapsulated probiotic cells can be found as non-refrigerated products. In this work, spray drying technology was investigated in order to produce an innovative nutraceutical formulation based on lactic acid bacteria (LAB), and was able to ensure a good storage stability of probiotics (no less than 109 CFU/cps) in non-refrigerated conditions. Probiotic-loaded microparticles from spray drying experiments were produced under different conditions and compared by thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and the enumeration of the number of viable cells in order to identify the formulation exhibiting the most promising characteristics. Results from the dissolution test revealed that the optimized formulation provides a suitable amount of living cells after digestion of microparticles stored for 12 months at room temperature and confirmed that the microencapsulation process by spray drying ensures a good protection of probiotics for nutraceutical purposes.

On-Line Thermally Induced Evolved Gas Analysis: An Update-Part 1: EGA-MS.

Advances in on-line thermally induced evolved gas analysis (OLTI-EGA) have been systematically reported by our group to update their applications in several different fields and to provide useful starting references. The importance of an accurate interpretation of the thermally-induced reaction mechanism which involves the formation of gaseous species is necessary to obtain the characterization of the evolved products. In this review, applications of Evolved Gas Analysis (EGA) performed by on-line coupling heating devices to mass spectrometry (EGA-MS), are reported. Reported references clearly demonstrate that the characterization of the nature of volatile products released by a substance subjected to a controlled temperature program allows us to prove a supposed reaction or composition, either under isothermal or under heating conditions. Selected 2019, 2020, and 2021 references are collected and briefly described in this review.

On-Line Thermally Induced Evolved Gas Analysis: An Update-Part 2: EGA-FTIR.

The on-line thermally induced evolved gas analysis (OLTI-EGA) is widely applied in many different fields. Aimed to update the applications, our group has systematically collected and published examples of EGA characterizations. Following the recently published review on EGA-MS applications, this second part reviews the latest applications of Evolved Gas Analysis performed by on-line coupling heating devices to infrared spectrometers (EGA-FTIR). The selected 2019, 2020, 2021 and early 2022 references are collected and briefly described in this review; these are useful to help researchers to easily find applications that are sometimes difficult to locate.

Development of a novel test for the identification of hereditary erythrocyte membrane defects by TGA/Chemometrics.

Systematic screening for congenital erythrocyte disorders is not a common practice, due to a lack in the accuracy of the methods and to the costs of the analyses. As a consequence, the diagnosis is usually made when a severe complication occurs. This study introduces an innovative method to perform the screening of a hereditary disease characterized by erythrocyte membrane defects such as hereditary spherocytosis (HS) and hereditary elliptocytosis (HE). Blood samples from healthy donors and patients affected by HS and HE were processed by thermogravimetric analysis (TGA) and the resulting curves were analyzed by chemometrics in order to develop a model of prediction. A novel test was developed and validated by chemometrics and results were found to be in accordance with the genetic diagnosis, confirming the prediction ability of the optimized model that uses few microliters of whole non pretreated blood to perform the diagnosis of HS/HE in less than one hour.

The detection of cannabinoids in veterinary feeds by microNIR/chemometrics: a new analytical platform.

In this work, the capabilities of a novel miniaturized and portable microNIR spectrometer were investigated in order to propose a practical and intelligible test allowing the rapid and easy screening of cannabinoids in veterinary feeds. In order to develop a predictive model that could identify and simultaneously quantify the residual amounts of cannabinoids, specimens from popular veterinary feeds were considered and spiked with increasing amounts of cannabidiol (CBD), Δ9-tetrahydrocannabinol (THC), and cannabigerol (CBG). Partial least squares discriminant analysis (PLS-DA) and partial least squares regression (PLSr) were applied for the simultaneous detection and quantification of cannabinoids. The results demonstrated that the microNIR/chemometric platform could statistically identify the presence of CBD, THC and CBG in the simulated samples containing cannabinoids from 0.001 to 0.01%w/w, with the accuracy and sensitivity of the official reference methods actually proposed. The method was checked against false positive and true positive responses, and the results proved to be those required for confirmatory analyses, permitting to provide a fast and accurate method for monitoring cannabinoids in veterinary feeds.

Protein Extraction, Enrichment and MALDI MS and MS/MS Analysis from Bitter Orange Leaves (Citrus aurantium).

Citrus aurantium is a widespread tree in the Mediterranean area, and it is mainly used as rootstock for other citrus. In the present study, a vacuum infiltration centrifugation procedure, followed by solid phase extraction matrix-assisted laser desorption ionization tandem mass spectrometry (SPE MALDI MS/MS) analysis, was adopted to isolate proteins from leaves. The results of mass spectrometry (MS) profiling, combined with the top-down proteomics approach, allowed the identification of 78 proteins. The bioinformatic databases TargetP, SignalP, ChloroP, WallProtDB, and mGOASVM-Loc were used to predict the subcellular localization of the identified proteins. Among 78 identified proteins, 20 were targeted as secretory pathway proteins and 36 were predicted to be in cellular compartments including cytoplasm, nucleus, and cell membrane. The largest subcellular fraction was the secretory pathway, accounting for 25% of total proteins. Gene Ontology (GO) of Citrus sinensis was used to simplify the functional annotation of the proteins that were identified in the leaves. The Kyoto Encyclopedia of Genes and Genomes (KEGG) showed the enrichment of metabolic pathways including glutathione metabolism and biosynthesis of secondary metabolites, suggesting that the response to a range of environmental factors is the key processes in citrus leaves. Finally, the Lipase GDSL domain-containing protein GDSL esterase/lipase, which is involved in plant development and defense response, was for the first time identified and characterized in Citrus aurantium.

"2 n Analytical Platform" To Update Procedures in Thanatochemistry: Estimation of Post Mortem Interval in Vitreous Humor.

In this work, a novel multiway approach by spectroscopy and thermogravimetry associated with chemometrics is developed, providing a multiparametric characterization of vitreous humor as a function of the time since death. Estimation of the precise time since death was performed on hospital deaths occurred in casualty, by medico-legal and post mortem examination, with no metabolic disorders. Micro and macro elements in vitreous specimens were determined by ICP-OES and were found to be diagnostic in predicting the post mortem interval (PMI). The percentage of bulk and bound water provided by thermal analysis investigation was correlated to spectroscopic analysis, and chemometric tools were used to compare results and to develop a model of prediction of PMI. The study reveals a significant role of P, S, and Mg in addition to the potassium concentration in determining the death interval and permits increased accuracy with respect to conventional procedures and allows the investigation of PMI to be extended to 15 days.

"Lab-on-Click" Detection of Illicit Drugs in Oral Fluids by MicroNIR-Chemometrics.

A novel, entirely automated MicroNIR-chemometric platform was developed for the "lab-on-click" detection of illicit drugs in nonpretreated oral fluids, and a novel tool for the first-level test is proposed. Calibration of the method was achieved by collecting oral-fluid specimens from volunteers, and chemometric analysis was considered for the development of models for prediction for cocaine, amphetamine, and Δ9-tetrahydrocannabinol. In addition, a comprehensive model was optimized for the simultaneous prediction of positive-negative samples and the specific illicit drug used by abusers in a single "click". The detection ability of the method was checked for true-positive and false-positive outcomes, and results were validated by a GC-MS reference official method. The MicroNIR-chemometric platform provided the simultaneous prediction of the three most frequently abused addictive drugs with the sensitivity and accuracy of the confirmatory analyses, offering the advantages of rapidity and simplicity and demonstrating that it is a promising tool for supporting public-health surveillance.

Modeling Solid State Stability for Speciation: A Ten-Year Long Study.

Speciation studies are based on fundamental models that relate the properties of biomimetic coordination compounds to the stability of the complexes. In addition to the classic approach based on solution studies, solid state properties have been recently proposed as supporting tools to understand the bioavailability of the involved metal. A ten-year long systematic study of several different complexes of imidazole substituted ligands with transition metal ions led our group to the definition of a model based on experimental evidences. This model revealed to be a useful tool to predict the stability of such coordination complexes and is based on the induced behavior under thermal stress. Several different solid state complexes were characterized by Thermally Induced Evolved Gas Analysis by Mass Spectrometry (TI-EGA-MS). This hyphenated technique provides fundamental information to determine the solid state properties and to create a model that relates stability to coordination. In this research, the model resulting from our ten-year long systematic study of complexes of transition metal ions with imidazole substituted ligands is described. In view of a systematic addition of information, new complexes of Cu(II), Zn(II), or Cd(II) with 2-propyl-4,5-imidazoledicarboxylic acid were precipitated, characterized, and studied by means of Thermally Induced Evolved Gas Analysis performed by mass spectrometry (TI-EGA-MS). The hyphenated approach was applied to enrich the information related to thermally induced steps, to confirm the supposed decomposition mechanism, and to determine the thermal stability of the studied complexes. Results, again, allowed supporting the theory that only two main characteristic and common thermally induced decomposition behaviors join the imidazole substituted complexes studied by our group. These two behaviors could be considered as typical trends and the model allowed to predict coordination behavior and to provide speciation information.

"Click and Screen" Technology for the Detection of Explosives on Human Hands by a Portable MicroNIR-Chemometrics Platform.

Portable near-infrared spectroscopy (MicroNIR) coupled with chemometrics was investigated for the first time as a new tool for the on-site analysis of explosives on human hands. A novel, entirely on-site approach based on the use of a particular miniaturized NIR spectrometer was developed and validated in cooperation with the Scientific Investigation Department (Carabinieri RIS) of Rome. Spectra from 25 volunteers were acquired in the NIR region in reflectance mode, and a prediction model was optimized on the basis of chemometric tools. The results demonstrated the capability of the MicroNIR-Chemometrics approach to correctly identify explosives from hands and not be affected by the complexity and variability of the matrix. This study has shown that the MicroNIR-Chemometrics approach can be considered a useful, fast, nondestructive tool identifying the manipulation of explosives in real forensic cases.

Towards innovation in paper dating: a MicroNIR analytical platform and chemometrics.

Using a miniaturized near infrared spectrometer associated to chemometrics we developed a rapid and non destructive procedure to characterise paper and investigate its aging with the aim of solving dating problems. Two sets of paper were considered in this study (books and sheets) in order to ensure the results are not dependent of the storage conditions. The MicroNIR has the ability to distinguish paper according to the chemical composition of the surface as a function of the period of manufacturing. The optimized analytical platform is fast and simple, avoiding sample pre-treatment procedures. As a consequence, the approach may be considered as the optimal technology to carry out analysis of ancient paper or other similar materials for diagnostic or forensic purposes as it is entirely portable and non-destructive.

Evaluation of the Difference in the Content of Essential and Non-Essential Elements in Wild Boar and Swine Tissues Sampled in the Same Area of Northern Italy.

This study aimed to investigate the exposure of wild boars and swine from semi-extensive farms in the same area to essential and non-essential elements, measuring their concentration in liver and muscle. Furthermore, the study explored the influence of factors such as sex, age, and the sampling location on wild boars. Higher liver element concentrations were observed in both wild boars and swine. Geographical comparisons revealed minor differences. Young wild boars showed significantly higher Cu, Se, Cd, and Cr levels, while older subjects exhibited elevated Mn levels, reflecting age-related element absorption variations. No significant sex-based variations were noted. Comparing wild boars to swine, wild boars had more non-essential elements due to their foraging behavior and a larger home range. Conversely, swine exhibited a greater prevalence of essential elements, potentially resulting from dietary supplementation.

Insight into the photolytic degradation products of Rosuvastatin: Full chiral and structural elucidation and conversion kinetics by a combined chromatographic, spectroscopic and theoretical approach.

Rosuvastatin (RSV) is a well-established lipid-lowering drug. RSV is susceptible to degradation under various stress conditions and forms two cyclic derivatives by a radical-mediated photolytic mechanism. On a structural basis, these epimeric compounds (reported as FP-B in the European Pharmacopeia monograph Rosuvastatin tablets) retain the configuration of the stereogenic carbons of RSV (3R,5S) and have opposite absolute configurations at the third stereogenic center. Herein, we report the kinetics of formation and the complete structural characterization, including the assignment of the absolute configuration, of each epimer collected after HPLC separation on a chiral stationary phase. The stereochemistry of the epimers was determined by comparison of the experimental circular dichroism data with the corresponding theoretical values. Kinetic studies revealed that RSV degrades completely to FP-B within 3 h at room temperature. Furthermore, through a multi-disciplinary approach involving chromatography (HPLC and UHPLC), circular dichroism (CD), nuclear magnetic resonance (NMR) spectroscopy and mass spectrometry (MS), it was demonstrated that FP-B in turn degrades to the lactones under the mild acidic conditions of the chromatographic mobile phase. The ability of RSV to form multiple degradation products may affect the quantification of RSV-related substances and draw attention to potentially toxic RSV-like species in the environment.

Phytochemical Characterization of Malt Spent Grain by Tandem Mass Spectrometry also Coupled with Liquid Chromatography: Bioactive Compounds from Brewery By-Products.

BACKGROUND: Brewer's spent grain (BSG) is one of the main by-products of beer industry, little used because of its high moisture making it difficult to transport and store. Mainly used as animal feed and for energy production, the agro-industrial waste have recently attracted attention as source of bioactive compounds, with potential applications in many sectors as food, nutraceutical, pharmaceutical, cosmetic, food packaging. The present work focuses on BSG as potential source of valuable small-size bioactive compounds. METHODS: Laboratory-made BSG was obtained by using four base malts for mashing. After drying, BSG was eco-friendly extracted with water and the extracts analyzed by untargeted ElectroSpray Ionization (ESI)-Mass Spectrometry (MS)/Mass Spectrometry (MS) (ESI-MS/MS) infusion experiments and by targeted High Performance Liquid Chromatography-PhotoDiodeArray-ElectroSpray Ionization-Mass Spectrometry (HPLC-PDA-ESI-MS) in Selected Ion Recording (SIR) mode analysis, to investigate the metabolic profile, the phenolic profile, the individual phenolic content, and tryptophan content. Aqueous extracts of malts and wort samples were also analyzed for a comparison. Data were statistically analyzed by ANOVA test. An explorative analysis based on Principal Component Analysis (PCA) was also carried out on malts, wort and threshes, in order to study correlation among samples and between samples and variables. RESULTS: The untargeted ESI-MS/MS infusion experiments provided the mass spectral fingerprint of BSG, evidencing amino acids (γ-aminobutyric acid, proline, valine, threonine, leucine/isoleucine, lysine, histidine, phenylalanine and arginine) and organic and inorganic acids (pyruvic, lactic, phosphoric, valerianic, malonic, 2-furoic, malic, citric and gluconic acids), besides sugars. γ-Aminobutyric acid and lactic acid resulted predominant among the others. The targeted HPLC-PDA-ESI-MS in SIR mode analysis provided the phenolic profile of the polar fraction of BSG, evidenced tryptophan as the main residual metabolite in BSG (62.33-75.35 µg/g dry BSG), and catechin (1.13-4.24 µg/g dry BSG) as the representative phenolic antioxidant of not pre-treated BSG samples. The chemometric analysis of the individual compounds content in BSG, malt and wort evidenced similarities and differences among the samples. CONCLUSIONS: As main goal, the phytochemical characterization of BSG from base malts highlighted BSG as a potential source of small biomolecules, as tryptophan and catechin, besides γ-aminobutyric acid and lactic acid, opening to new perspectives of application for BSG. Strategies for their recovery are a future challenge. Moreover, ESI-MS/MS analysis was confirmed as a powerful tool for fast characterization of complex matrix. Last, results obtained by chemometric elaboration of data demonstrated the possibility to monitor a small number of molecules to ensure the quality of a final product.

Novel terephthalamide diol monomers synthesis from PET waste to Poly(Urethane acrylates).

Due to its excellent properties, poly(ethylene terephthalate) (PET) is one of the most produced and consumed polymers. Among plastics, it represents the main contributor to environmental pollution. Following the circular economy model, the chemical upcycling of PET reduces the amount of waste generated and transforms it into high-value products. The depolymerization of poly(ethylene terephthalate) into oligomers or monomers leads to forming a library of reactive molecules involved in different polymerization processes to obtain compounds with improved properties. Herein, several ß-hydroxy amines were synthesized and used for the chemical recycling of water bottle waste by an environmental benefit aminolysis process to get very useful new terephthalamide diol monomers. The recycled diol monomers were subsequently exploited to synthesize poly(urethane acrylates) (PUAs) UV-curable coatings, and their chemical, thermal and mechanical characterizations were performed. The results show the great potential of the developed synthesis protocols to obtain PUAs with final properties that can be modulated to meet the requirements of different applications.

Hemorheological profiles and chronic inflammation markers in transfusion-dependent and non-transfusion- dependent thalassemia.

The rheological properties of blood play an important role in regulating blood flow in micro and macro circulation. In thalassemia syndromes red blood cells exhibit altered hemodynamic properties that facilitate microcirculatory diseases: increased aggregation and reduced deformability, as well as a marked increase in adherence to the vascular endothelial cells. A personalized approach to treating thalassemia patients (transfusions, iron chelation, and splenectomy), has increased patients' life expectancy, however they generally present many complications and several studies have demonstrated the presence of high incidence of thromboembolic events. In this study the hemorheological profiles of thalassemia patients have been characterized to point out new indices of vascular impairment in thalassemia. Plasma viscosity, blood viscosities at low and high shear rates (η1 and η200, respectively), erythrocyte aggregation index (η1/η200), and the erythrocyte viscoelastic profile (elastic modulus G', and viscous modulus G") have been studied in transfusion-dependent and non-transfusion-dependent thalassemia patients. Moreover, the levels of inflammation biomarkers in thalassemia have been evaluated to investigate a relationship between the biomarkers, the disease severity and the rheological parameters. The biomarkers studied are the main components of the immune and endothelial systems or are related to vascular inflammation: cytokines (IL-2, IL-6, IL-10, IL-17A, TNF-alpha), chemokines (IL-8, MIP-1alpha), adipocytokines (leptin and adiponectin), growth factors (VEGF, angiopoietin-1), adhesion molecules (ICAM-1, VCAM-1, E-selectin, L-selectin), and a monocyte/macrophage activation marker (CD163). This study shows that transfusion-dependent thalassemia patients, both major and intermedia, have blood viscosities comparable to those of healthy subjects. Non-transfusion-dependent thalassemia intermedia patients show high blood viscosities at low shear rates (η1), corresponding to the flow conditions of the microcirculation, an increase in erythrocyte aggregation, and high values of the elastic G' and viscous G" modules that reflect a reduced erythrocyte deformability and an increase in blood viscosity. Levels of cytokines, chemokines and adhesion molecules are different in transfusion- and non-transfusion dependent patients and positive correlations between η1 or η1/η200 and the cytokines IL-6 and IL-10 have been observed. The evaluation of the hemorheological profiles in thalassemia can provide new indicators of vascular impairment and disease severity in thalassemia in order to prevent the onset of thromboembolic events.

Application of Innovative TGA/Chemometric Approach for Forensic Purposes: The Estimation of the Time since Death in Contaminated Specimens.

Chronothanatology has always been a challenge in forensic sciences. Therefore, the importance of a multidisciplinary approach for the characterization of matrices (organs, tissues, or fluids) that respond linearly to the postmortem interval (PMI) is emerging increasingly. The vitreous humor is particularly suitable for studies aimed at assessing time-related modifications because it is topographically isolated and well-protected. In this work, a novel approach based on thermogravimetry and chemometrics was used to estimate the time since death in the vitreous humor and to collect a databank of samples derived from postmortem examinations after medico-legal evaluation. In this study, contaminated and uncontaminated specimens with tissue fragments were included in order to develop a classification model to predict time of death based on partial least squares discriminant analysis (PLS-DA) that was as robust as possible. Results demonstrate the possibility to correctly predict the PMI even in contaminated samples, with an accuracy not lower than 70%. In addition, the correlation coefficient of the measured versus predicted outcomes was found to be 0.9978, confirming the ability of the model to extend its feasibility even to such situations involving contaminated vitreous humor.

Synthesis, Structural, Morphological and Thermal Characterization of Five Different Silica-Polyethylene Glycol-Chlorogenic Acid Hybrid Materials.

The present study investigated the structure, morphology, thermal behavior, and bacterial growth analysis of novel three-component hybrid materials synthesized by the sol-gel method. The inorganic silica matrix was weakly bonded to the network of two organic components: a well-known polymer such as polyethylene glycol (PEG, average molar mass of about 4000 g/mol), and an antioxidant constituted by chlorogenic acid (CGA). In particular, a first series was made by a 50 wt% PEG-based (CGA-free) silica hybrid along with two 50 wt% PEG-based hybrids containing 10 and 20 wt% of CGA (denoted as SP50, SP50C10 and SP50C20, respectively). A second series contained a fixed amount of CGA (20 wt%) in silica-based hybrids: one was the PEG-free material (SC20) and the other two contained 12 and 50 wt% of PEG, respectively (SP12C20 and SP50C20, respectively), being the latter already included in the first series. The X-ray diffraction (XRD) patterns and scanning electron microscope (SEM) images of freshly prepared materials confirmed that all the materials were amorphous and homogeneous regardless of the content of PEG or CGA. The thermogravimetric (TG) analysis revealed a higher water content was adsorbed into the two component hybrids (SP50 and SC20) because of the availability of a larger number of H-bonds to be formed with water with respect to those of silica/PEG/CGA (SPC), where silica matrix was involved in these bonds with both organic components. Conversely, the PEG-rich materials (SP50C10 and SP50C20, both with 50 wt% of the polymer) retained a lower content of water. Decomposition of PEG and CGA occurred in almost the same temperature interval regardless of the content of each organic component. The antibacterial properties of the SiO2/PEG/CGA hybrid materials were studied in pellets using either Escherichia coli and Enterococcus faecalis, respectively. Excellent antibacterial activity was found against both bacteria regardless of the amount of polymer in the hybrids.

Development of a "single-click" analytical platform for the detection of cannabinoids in hemp seed oil.

In this work, an innovative screening platform is developed and validated for the on site detection of cannabinoids in hemp seed oil, for food safety control of commercial products. The novelty of this completely automated tool consists of a miniaturized NIR spectrometer operating in a wireless mode that permits processing samples in a rapid and accurate way and to obtain in a single click the early detection of a residual amount of cannabinoids in oil, including cannabidiol (CBD), the psychoactive Δ9-tetrahydrocannabinol (THC) and the Δ9-tetrahydrocannabinolic acid (THCA). Simulated samples were realized to instruct the platform and prediction models were developed by chemometric analysis of the NIR spectra using partial least square regression algorithms. Once calibrated, the platform was used to predict samples acquired in the market and on websites. Validation of the system was achieved by comparing results with those obtained from GC-MS analyses and a good correlation was observed.