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Background: Bisphenols are major industrial chemicals that have raised public concern due to their endocrine disrupting properties and toxicity. Sample preparation is the most critical step for the determination of bisphenols, especially if the analyst has to deal with environmental samples which are complex matrices and the co-extraction and co-elution of other relevant compounds results in the enhancement or suppression of the analyte signal. The need for the precise determination of bisphenols has signaled the development of effective microextraction techniques according to the Green Analytical Chemistry (GAC) guidelines. Objective: The objective of this review is to gather and discuss all the recent advances in the development of microextraction techniques such as solid phase extraction (SPE), solid phase microextraction (SPME), magnetic solid phase microextraction (MSPE), liquid-phase microextraction (LPME), dispersive liquid-liquid microextraction (DLLME), stir bar sorptive extraction (SBSE), and matrix solid-phase dispersion (MSPD), that have been successfully applied in the extraction of bisphenols from environmental matrices. Conclusion: The analytical performance of the proposed techniques is critically discussed, highlighting the potential and the limitations of each method.

Background:: Nuts have been incorporated into guidelines for healthy eating since they contain considerable amounts of antioxidants and their effects are related to health benefits since they contribute to the prevention of nutritional deficiencies. The micronutrient characterization is based mainly on the determination of phenolics, which is the most abundant class of bioactive compounds in nuts. Terpenes constitute another class of bioactive compounds that are present in nuts and show high volatility. The analysis of phenolic compounds and terpenes is a very demanding task that requires optimization of the chromatographic conditions to improve the separation of the components. Moreover, nuts are rich in unsaturated fatty acids and they are therefore considered as cardioprotective. Gas chromatography is the predominant instrumental analytical technique for the determination of derivatized fatty acids and terpenes in food matrices, while high performance liquid chromatography is currently the most popular technique for the determination of phenolic compounds. Objective:: This review summarizes all the recent advances in the optimization of the chromatographic conditions for the determination of phenolic compounds, fatty acids and terpenes in nuts. Conclusion:: The state-of-the art in the technology available is critically discussed, exploring new analytical approaches to reduce the time of analysis and improve the performance of the chromatographic systems in terms of precision, reproducibility, limits of detection and quantification and overall quality of the results.

Monitoring the residual toxicant concentrations in foods is the key step for minimizing potential hazards. The huge interest about food contamination and exposure to endocrine disruptors such as bisphenol A has emerged the development of sensitive analytical methodologies to guarantee the safety and quality of foods. In this work, a green molecularly imprinted solid-phase extraction protocol coupled with high-performance liquid chromatography with UV detection was optimized following the principles of green analytical chemistry. An imprinted sol-gel silica-based hybrid inorganic-organic polymeric sorbent was used to monitor the leaching of bisphenol A from different packaging materials (glass vessels, cans, and polypropylene containers) in walnuts stored within a period of 6 months at 25 and 4°C. Extraction parameters including loading time (5-20 min), solvent type (acetonitrile, ethanol, methanol, acetone, acetonitrile:methanol, 50:50, v/v), and elution flow rate (0.2-1 mL/min) were optimized with one-factor-at-a-time method. The selected extraction optimum parameters incorporated elution with acetonitrile at 0.2 mL/min flow rate, for 10 min sample holding time. The imprinting factor was equal to 4.55 ± 0.26 (n = 3). The optimized method presented high recovery (94.3 ± 4.2%, n = 3), good linearity (>0.999), intra-assay repeatability (90.2-95.6%, n = 3), and interassay precision (86.7-93.1%, n = 3).

Benzoyl urea insecticides are a class of pesticides used in agriculture for the inhibition of chitin synthesis in pests. These compounds are persistent in environmental samples, and thus their monitoring is necessary to avoid detrimental effects to human health and the environment. Magnet integrated fabric phase sorptive extraction (MI-FPSE) is a recently introduced sample preparation technique that combines sample stirring and analyte extraction into one stand-alone device. However, the applicability and the potential benefits of this technique in environmental analysis remain unexplored. In the present study, MI-FPSE was employed for the first time for the extraction and preconcentration of benzoyl urea insecticides (i.e., diflubenzuron, triflumuron, hexaflumuron, lufenuron and chlorfluazuron) from environmental water samples prior to their determination by high performance liquid chromatography-diode array detection (HPLC-DAD). The main factors affecting the performance of the proposed methodology were thoroughly investigated and optimized and the MI-FPSE-HPLC-DAD method was validated. The proposed method enabled the handling of relatively high sample quantity resulting in high preconcentration factors (501 and 731) and good sensitivity. Under optimum conditions, the limits of detection and the limits of quantification for the benzoyl urea insecticides were 0.06 ng mL

Two novel microwave-assisted extraction (MAE) methods were developed for the isolation of phenols and tocopherols from pistachio nuts. The extracts were analyzed by reversed-phase high-pressure liquid chromatography coupled with a UV detector (RP-HPLC-UV). In total, eighteen pistachio samples, originating from Greece and Turkey, were analyzed and thirteen phenolic compounds, as well as α-tocopherol, (β + γ)-tocopherol, and δ-tocopherol, were identified. The analytical methods were validated and presented good linearity (r2 > 0.990) and a high recovery rate over the range of 82.4 to 95.3% for phenols, and 93.1 to 96.4% for tocopherols. Repeatablility was calculated over the range 1.8–5.8%RSD for intra-day experiments, and reproducibility over the range 3.2–9.4%RSD for inter-day experiments, respectively. Principal component analysis (PCA) was employed to analyze the differences between the concentrations of the bioactive compounds with respect to geographical origin, while agglomerative hierarchical clustering (AHC) was used to cluster the samples based on their similarity and according to the geographical origin.

Walnut byproducts have been shown to exert functional properties, but the literature on their bioactive content is still scarce. Among walnut byproducts, walnut septum is a dry ligneous diaphragm tissue that divides the two halves of the kernel, exhibiting nutritional and medicinal properties. These functional properties are owing to its flavonoid content, and in order to explore the flavonoid fraction, an ultrasound-assisted (UAE) protocol was combined with solid phase extraction (SPE) and coupled to high-performance liquid chromatography with diode array detection (HPLC-DAD) for the determination of flavonoids in Greek walnut septa membranes belonging to Chandler, Vina, and Franquette varieties. The proposed UAE-SPE-HPLC-DAD method was validated and the relative standard deviations (RSD%) of the within-day and between-day assays were lower than 6.2 and 8.5, respectively, showing good precision, and high accuracy ranging from 90.8 (apigenin) to 97.5% (catechin) for within-day assay, and from 88.5 (myricetin) to 96.2% (catechin) for between-day assay. Overall, seven flavonoids were determined (catechin, rutin, myricetin, luteolin, quercetin, apigenin, and kaempferol) suggesting that the walnut septum is a rich source of bioactive constituents. The quantification results were further processed using ANOVA analysis to examine if there are statistically significant differences between the concentration of each flavonoid and the variety of the walnut septum.

Reversed phase-high-pressure liquid chromatographic methodologies equipped with UV detector (RP-HPLC-UV) were developed for the determination of phenolic compounds and tocopherols in almonds. Nineteen samples of Texas almonds originating from USA and Greece were analyzed and 7 phenolic acids, 7 flavonoids, and tocopherols (−α, −β + γ) were determined. The analytical methodologies were validated and presented excellent linearity (r2 &gt, 0.99), high recoveries over the range between 83.1 (syringic acid) to 95.5% (ferulic acid) for within-day assay (n = 6), and between 90.2 (diosmin) to 103.4% (rosmarinic acid) for between-day assay (n = 3 × 3), for phenolic compounds, and between 95.1 and 100.4% for within-day assay (n = 6), and between 93.2–96.2% for between-day assay (n = 3 × 3) for tocopherols. The analytes were further quantified, and the results were analyzed by principal component analysis (PCA), and agglomerative hierarchical clustering (AHC) to investigate potential differences between the bioactive content of almonds and the geographical origin. A decision tree (DT) was developed for the prediction of the geographical origin of almonds proposing a characteristic marker with a concentration threshold, proving to be a promising and reliable tool for the guarantee of the authenticity of the almonds.

Background: Medicinal plants consist a rich source of natural pharmacologically active compounds. The aim of the current work, was the study and optimization of the extraction conditions of phenolic constituents from important medicinal and aromatic plants, id. Sideritis raeseri, Sideritis scardica and Origanum vulgare, implementing microwave assisted extraction technique. Methods: Optimization was based on various parameters affecting extraction procedure, such as the duration of microwave radiation, the ratio of plant material mass to the solvent, the type and the concentration of the solvent. Results: The results revealed that 10 min of microwave radiation provided the maximum extraction yield of the phenolic constituents. The ratio of the plant material mass and the solvent had minor effect to the extraction efficiency. Conclusion: The examined solvents provided an extraction yield of phenolic constituents following the order: EtOH

Background: Biopharmaceuticals are biological drugs consisting of a complex compound that can be produced by a living organism or derive from it. Biopharmaceuticals are very complicated compounds from structural point of view and for this reason, they cannot be fully characterized in terms of their structure with current analytical methods as it happens instead of low molecular weight chemicals drugs. Introduction: The regulatory guidelines require the characterization of the primary or higher sequence of these molecules and the characterization of any post-translational modifications. The use of biopharmaceuticals has really grown in the last few years: in 2016, the number of biopharmaceuticals approved by the Food and Drug Administration (FDA) and European Medicines Agency (EMA) for use in humans’ diseases was 1357. From 2013 to 2016, 73 of these compounds were approved for the treatment of cancer, inflammation, immune disorders, infections, anemia and cardiovascular diseases. Aim/Conclusion: The aim of the present review is to provide an overview of recent approaches for the characterization of biopharmaceutical products in HPLC that have been presented in the literature in the last years.

Background:The sample preparation is the most crucial step in the analytical method development. Taking this into account, it is easily understood why the domain of sample preparation prior to detection is rapidly developing. Following the modern trends towards the automation, miniaturization, simplification and minimization of organic solvents and sample volumes, green microextraction techniques witness rapid growth in the field of food quality and safety. In a globalized market, it is essential to face the consumers need and develop analytical methods that guarantee the quality of food products and beverages. The strive for the accurate determination of organic hazards in a famous and appreciated alcoholic beverage like wine has necessitated the development of microextraction techniques.Objective:The objective of this review is to summarize all the recent microextraction methodologies, including solid phase extraction (SPE), solid phase microextraction (SPME), liquid-phase microextraction (LPME), dispersive liquid-liquid microextraction (DLLME), stir bar sorptive extraction (SBSE), matrix solid-phase dispersion (MSPD), single-drop microextraction (SDME) and dispersive solid phase extraction (DSPE) that were developed for the determination of hazardous organic compounds (pesticides, mycotoxins, colorants, biogenic amines, off-flavors) in wine. The analytical performance of the techniques is evaluated and their advantages and limitations are discussed.Conclusion:An extensive investigation of these techniques remains vital through the development of novel strategies and the implication of new materials that could upgrade the selectivity for the extraction of target analytes.

Background:Silk fibroin is the main protein of silk, and it has recently been evaluated for drug delivery applications due to its excellent properties. Specifically, silk fibroin exhibits good biocompatibility, biodegradability and low immunogenicity. Fibroin nanoparticles have attracted attention due to their high binding ability to different drugs as well as their ability for controlled drug release. The improvement of the therapeutic efficiency of drug encapsulation is important and depends on the particle size, the chemical structure and the properties of the silk fibroin nanoparticles.Methods:There is a variety of methods for the preparation of fibroin nanoparticles such as (i) electrospraying and desolvation method, (ii) supercritical fluid technologies, (iii) capillary-microdot technique, (iv) salting out etc. Furthermore, various techniques have been used for the characterization of nanoparticles such as SEM (scanning electron microscopy), TEM (transmission electron microscopy), DLS (dynamic light scattering), Zeta-potential and FTIR (Fourier transform infrared spectroscopy). Different drugs (paclitaxel, curcumin, 5-fluorouracil etc) have been encapsulated in fibroin nanoparticles.Results:Each separated synthesis method has different advantages such as (i) high yield, (ii) avoid use of toxic solvents, (iii) low cost, (iv) controllable particle size, (v) no organic solvent residue, (vi) simplicity of operation, (vii) small particles size, (viii) homeliness of operation, (ix) restrainable particle size, (x) easy and safe to operate, (xi) no use of organic solvent. Moreover, some major drugs studied are Floxuridine, Fluorouracil, Curcumin, Doxorubicin, Metotrexate, Paclitaxel and Doxorubicin, Horseradish peroxidase. All the above combinations (preparation method-drug) are studied in detail.Conclusion:Various drugs have been encapsulated successfully in silk fibroin and all of them exhibit a significant release rate. Finally, the encapsulation efficiency and release rate depend on the molecular weight of the drugs and it can be adjusted by controlling the crystallinity and concentration of silk fibroin.

An innovative fabric phase sorptive extraction-high performance liquid chromatography-diode array detection (FPSE-HPLC-DAD) method is developed and validated herein for the simultaneous extraction and analysis of five common antidepressants (venlafaxine, paroxetine, fluoxetine, amitriptyline, clomipramine) in human urine samples. Separation was obtained using a reverse phase column LiChroCART-LiChrospher®100 RP-8e (5 μm, 250 × 4 mm) with diode array detection monitoring at 235 nm. Gradient elution was applied at a flow rate of 1.2 mL/min with a mobile phase that consisted of acetonitrile and ammonium acetate (0.05 M). Fabric Phase Sorptive Extraction was evaluated for the first time with regards to the extraction of the examined antidepressants from human urine and proved to be a rapid, simple, environmentally friendly, efficient, and selective sample preparation approach. Sol-gel graphene sorbent, coated on cellulose FPSE media, were the most efficient among other with different polarities. The absolute recovery values were 25.5% for venlafaxine, 33.9% for paroxetine, 67.0% for fluoxetine, 43.0% for amitriptyline and 29.0% for clomipramine, while relative recoveries were higher than 90%. The developed method provides satisfactory limit of detection 0.15 ng/μL.

In current paper, a new advanced modification of fabric phase sorptive extraction is introduced for the first time. This advantageous configuration that integrates the stirring and extraction mechanism into a single sample preparation device was originated by equally considering the beneficial role of the increase of extraction kinetics and more specifically of diffusion on the extraction efficiency of the equilibrium based microextraction techniques and the need for integrating and unite processes for better promotion and implementation of the principles of Green Analytical Chemistry. The resulted magnet integrated fabric phase sorptive extraction (MI-FPSE) device was the spearhead to develop a new analytical methodology for the determination of selected very common endocrine disrupting chemicals as model analytes in human urine by high-performance liquid chromatography-photodiode array analysis. More specifically, the sol-gel Carbowax 20 M coated on hydrophilic cellulose fabric substrate, MI-FPSE device was efficiently employed for the establishment of a new extraction protocol before the chromatographic determination. The sample preparation workflow was methodically optimized in terms of the elution solvent mixture, the volume of the sample, the extraction and the elution time, the stirring speed during the extraction, the ionic strength, and the pH of the sample matrix. The chromatographic separation was performed on a Spherisorb C18 column and a gradient elution program within 14 minutes. Mobile phase consisted of 0.05 ammonium acetate aqueous solution and acetonitrile. The method was validated towards linearity, sensitivity, selectivity, precision, accuracy, and stability. LOD and LOQ ranged between 1.05-1.80 and 3.5-6.0 ng/mL, while %RSD values were found lower than 9.0% in all cases. The method was efficiently applied to the bioanalysis of real samples. All the chosen EDCs were measured at high detection levels. The new MI-FPSE device has demonstrated its performance superiority as a magnet integrated stand-alone extraction device and could be considered as a significant improvement in the field of analytical/bioanalytical sample preparation.

The determination of triazine herbicides in water samples is of utmost importance, due to their persistence and excessive use. However, since the concentration of triazine pesticides in real samples is low, an extraction/preconcentration step is typically required. Capsule phase microextraction (CPME) is a recently introduced sample preparation technique in which highly efficient sol-gel sorbents are encapsulated in a tubular polymer membrane. This particular design integrates the filtration and stirring mechanism into one extraction device, enabling the application of CPME for in situ sampling. In this study, CPME coupled to high performance liquid chromatography-diode array detection (HPLC-DAD) was employed for the first time for the determination of six triazine herbicides (i.e., simazine, cyanazine, atrazine, prometryn, terbuthylazine and propazine) in water samples. Microextraction capsules containing a moderately hydrophobic sol‐gel Carbowax 20 M sorbent provided the highest extraction efficiency towards the examined pesticides. The main parameters affecting the adsorption and desorption steps of the CPME procedure were investigated and optimized. Under the selected conditions, limits of detection (signal/noise = 3.3) were 0.15 ng mL−1 for the target analytes. Moreover, the relative standard deviation for the within-day and between-days repeatability were less than 7.2% and 9.9%, respectively. The method was successfully applied to the analysis of mineral water, tap water, rainwater and lake water samples. The reported protocol could overcome the need for sample filtration prior to the sample preparation of the water samples, resulting in simplification of the overall sample handling, improved data quality with minimal loss of analytes and reduced sample preparation cost.

It is challenging to establish a correlation between the agronomical practices and the volatile profile of high-value agricultural products. In this study, the volatile metabolome of walnut oils from conventional and organic farming type was explored by HS-SPME-GC-MS. The SPME protocol was optimized after evaluating the effects of extraction time, extraction temperature, and sample mass. The optimum parameters involved the extraction of 0.500 g walnut oil at 40 °C within 60 min. Twenty Greek walnut oils produced with conventional and organic farming were analyzed and 41 volatile compounds were identified. The determined compounds were semi-quantified, and further processed with chemometrics. Agglomerative hierarchical clustering (AHC) and principal component analysis (PCA) were used. A robust classification model was developed using sparse partial least squares–discriminant analysis (sPLS-DA) for the discrimination of walnut oils into conventional and organic, establishing volatile markers that could be used to guarantee the type of farming.

Thiophenic compounds constitute a class of sulfur compounds derived by thiophene, containing at least one thiophenic ring. Their presence in fuels (crude oil, etc.) is important and can reach 3% m/m. The combustion of fuels leads to the formation of sulfur oxides a severe source of environmental pollution issues, such as acid rain with adverse effects both to humans and to the environment. To reduce such problems, the EU and other regulatory agencies worldwide set increasingly stringent regulations for sulfur content in fuels resulting in the necessity for intense desulphurization processes. However, most of these processes are inefficient in the total removal of sulfur compounds. Therefore, thiophenic compounds such as benzothiophenes and dibenzothiophenes are still present in heavier fractions of petroleum, therefore, their determination is of great importance. Until now, all HPLC methods applied in similar studies use gradient elution programs that may last more than 25 min with no validation results provided. To fill this gap, the aim of the present study was to develop and validate a simple and fast HPLC-UV method in order to be used as a useful monitoring tool in the evaluation studies of novel desulfurization technologies by means of simultaneous determination of dibenzothiophene (DBT) and 4,6-dimethyl-dibenzothiophene and dibenzothiophene sulfone in the desulfurization effluents.

Parabens have been widely employed as preservatives since the 1920s for extending the shelf life of foodstuffs, medicines, and daily care products. Given the fact that there are some legitimate concerns related to their potential multiple endocrine-disrupting properties, the development of novel bioanalytical methods for their biomonitoring is crucial. In this study, a fabric phase sorptive extraction reversed-phase liquid chromatography method coupled with UV detection (FPSE-HPLC-UV) was developed and validated for the quantitation of seven parabens in human plasma samples. Chromatographic separation of the seven parabens and p-hydroxybenzoic acid was achieved on a semi-micro Spherisorb ODS1 analytical column under isocratic elution using a mobile phase containing 0.1% (v/v) formic acid and 66% 49 mM ammonium formate aqueous solution in acetonitrile at flow rate 0.25 mL min−1 with a 24-min run time for each sample. The method was linear at a concentration range of 20 to 500 ng mL−1 for the seven parabens under study in human plasma samples. The efficiency of the method was proven with the analysis of 20 human plasma samples collected from women subjected to breast cancer surgery and to reconstructive and aesthetic breast surgery. The highest quantitation rates in human plasma samples from cancerous cases were found for methylparaben and isobutylparaben with average plasma concentrations at 77 and 112.5 ng mL−1. The high concentration levels detected agree with previous findings for some of the parabens and emphasize the need for further epidemiological research on the possible health effects of the use of these compounds.

A fast fabric phase sorptive extraction method is presented herein for the rapid isolation of selected beta-blocker drugs from human serum and urine. Among many high efficiency sol-gel sorbent coated FPSE membranes, sol-gel CW20 M coated FPSE membrane was identified as the best FPSE membrane for the target beta-blocker drugs possessing logP values ranging from 0.1 (highly polar) to 3.1 (moderately polar). Due to the engineered affinity towards the analytes via complementary intermolecular interactions and high mass transfer rate of the analytes from the bulk sample solution to the FPSE membrane, the extraction is accomplished in relatively short time (15 min) while its high permeability permits the direct extraction of biological samples without any other pretreatment. The advantages of the fabricated extraction membrane were exploited for the determination of six beta-blockers (namely atenolol, nadolol, metoprolol, oxprenolol, labetalol and propranolol) in biological matrices in combination with UHPLC-ESI-MS/MS. Important parameters including extraction time, sample volume, sorbent size, elution solvent, etc. affecting the performance of the extraction were systematically investigated. The linearity of the method was evaluated in the range of 50–5000 ng mL−1 by constructing weighted (1/X) matrix-matched calibration curves. The intra-day and inter-day trueness were ranged between – 17.2 to 13.3% and – 10.8 to 12.6%, respectively. The intra-day and inter-day precision were less than 11.5 and 14.5 %, respectively. The proposed analytical scheme was successfully applied to the determination of the target drugs in human serum and urine.

In this review, the ever-increasing use of deep eutectic solvents (DES) in microextraction techniques will be discussed, focusing on the reasons needed to replace conventional extraction techniques with greener approaches that follow the principles of green analytical chemistry. The properties of DES will be discussed, pinpointing their exceptional performance and analytical parameters, justifying their current extensive scientific interest. Finally, a variety of applications for commonly used microextraction techniques will be reported.

Capsule phase microextraction is introduced herein for the first time to determine four sulfonamide residues in milk samples (sulfanilamide, sulfadiazine, sulfamethizole, and sulfathiazole). The technique eloquently integrates filtration and stirring mechanism into the extraction device, as such no filtration of the sample is needed prior to introducing the extraction device into the sample, and when placed on a magnetic stirrer, the device spins itself in order to diffuse the sample, resulting in faster extraction equilibrium. Microextraction capsules consist of three main parts; a magnet, a cellulose fiber substrate coated with high performance sol-gel hybrid organic-inorganic sorbent, and a porous membrane. Various encapsulated sol-gel sorbents were tested in standard solutions prepared in deionized water and milk samples under different operational conditions. Analyte extraction time and elution time, type of sol-gel sorbent, elution solvent, as well as the ratio of the sorbent to the elution solvent were among the optimized conditions. The protocols that yielded the best absolute recovery rates were subsequently tested in various milk samples. Method validation was performed in terms of linearity, accuracy and precision, reusability and ruggedness using the Youden test. The examined sulfonamides were subsequently analysed by reversed phase high performance liquid chromatography with diode array detection.

An improved pretreatment approach of human breast tissue is demonstrated for subsequent analysis of seven parabens including methyl paraben (MPB), ethyl paraben (EPB), propyl paraben (PPB), butyl paraben (BPB), isopropyl paraben (iPPB), isobutyl paraben (iBPB), and benzyl paraben (BzPB). Specifically, a well-designed homogenization procedure, conjugated with an optimized fabric phase sorptive extraction (FPSE) protocol, resulted in a carefully outlined sample preparation process as part of a green, simple, sensitive, economical and fast HPLC-PDA analytical method in agreement with Green Analytical Chemistry (GAC) demands. Among all tested FPSE membranes, the highest extraction efficiency was achieved by employing sol-gel poly(tetrahydrofuran) (sol-gel PTHF) coating on 100% cotton cellulose fabric that represents a medium polarity microextraction device, which combined the advanced material characteristics of sol-gel sorbent and the rich surface chemistry of an inherent porous cellulose fabric substrate. The chromatographic separation was accomplished with a Spherisorb C18 column and an isocratic mobile phase consisted of ammonium acetate and acetonitrile at a flow rate of 1.4 mL/min. The total analysis time was 13.6 min. The analytical adequacy of the composite sample preparation and chromatographic separation method was strongly evidenced by its successful application in the bioanalysis of real cancerous and non-cancerous tissue samples originated from different sub regions of human breast including axila, the upper left and the right quadrant. In all samples, at least one paraben was detected, while 35% of the samples were tested positive for all seven target parabens. Moreover, concentration levels of parabens in cancerous tissues were unambiguously higher than in healthy tissues. The obtained results underlined bioaccumulation potential of parabens in human breast tissue as a consequence of constant low-dose exposure of humans, despite the statutory concentration limits. The developed methodology has demonstrated to be suitable and efficient for future epidemiological and toxicological studies.

A new sample preparation and chromatographic separation method for methyl paraben (MP), propyl paraben (PP) and butyl paraben (BP) in cosmetic and environmental samples has been developed, based on fabric phase sorptive extraction (FPSE) and high performance liquid chromatography-photodiode array (HPLC-PDA) detection. In the proposed method, MP, PP and BP molecules were efficiently retained on a sol–gel Carbowax-20M sorbent-coated FPSE membrane when the matrix pH was adjusted to 5. Subsequently, the extracted analytes were desorbed from the FPSE membrane with methanol prior to chromatographic separation and determinations. The samples were transferred to HPLC vials after filtration with a 0.45 μm porous PTFE filter. Experimental conditions were studied to optimize variables such as pH, adsorption time and desorption solvent. Using the optimal conditions, analytical parameters such as linearity ranges, detection limits, and pre-concentration factors for each of the selected parabens were calculated from experimental data. HPLC analyses of MP, PP and BP were carried out in isocratic elution mode using acetic acid (3%) : acetonitrile : methanol in the ratio 70 : 20 : 10. Limit of detection (LOD) values for MP, PP and BP were calculated as 2.85, 2.98 and 2.75 ng mL−1, respectively. Relative standard deviations (RSDs) were below 3.8% for determinations of model solutions including 100 ng mL−1 of each paraben. Finally, the developed method was applied to cosmetic and environmental samples and quantitative results were obtained in recovery experiments.

Graphene oxide (GO) is a chemical compound with a form similar to graphene that consists of one-atom-thick two-dimensional layers of sp2-bonded carbon. Graphene oxide exhibits high hydrophilicity and dispersibility. Thus, it is difficult to be separated from aqueous solutions. Therefore, functionalization with magnetic nanoparticles is performed in order to prepare a magnetic GO nanocomposite that combines the sufficient adsorption capacity of graphene oxide and the convenience of magnetic separation. Moreover, the magnetic material can be further functionalized with different groups to prevent aggregation and extends its potential application. Until today, a plethora of magnetic GO hybrid materials have been synthesized and successfully employed for the magnetic solid-phase extraction of organic compounds from environmental, agricultural, biological, and food samples. The developed GO nanocomposites exhibit satisfactory stability in aqueous solutions, as well as sufficient surface area. Thus, they are considered as an alternative to conventional sorbents by enriching the analytical toolbox for the analysis of trace organic compounds.

In present study the use of Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) was investigated for the detection and differentiation of mechanically deboned meat (MDM) content treated with high pressure techniques in meat products. A number of samples of meat products were prepared containing different proportions of MDM and elemental analysis was performed by a multi-element ICP-MS method after microwave assisted acid digestion of processed meat samples in closed vessels acid microwave digestion method. Element concentrations were plotted versus MDM content and obvious differences were observed for certain elements. Among all examined elements, barium presented a clear trend in correlation of its concentration with the MDM content. The results of this preliminary study indicate that it is possible to detect the proportion of % MDM content in processed meat products by its correlation to barium concentration.

A simple and sensitive analytical methodology is developed for rapid screening and quantification of selected estrogenic endocrine disrupting chemicals and bisphenol A from intact milk using fabric phase sorptive extraction in combination with high-performance liquid chromatography coupled to ultraviolet detection/tandem mass spectrometry. The new approach eliminates protein precipitation and defatting step from the sample preparation workflow. In addition, the error prone and time-consuming solvent evaporation and sample reconstitution step used as the sample post-treatment has been eliminated. Parameters with most significant impact on the extraction efficiency of fabric phase sorptive extraction including sorbent chemistry, sample volume, extraction time have been thoroughly studied and optimized. Separation of the selected estrogenic endocrine disrupting chemicals including α-estradiol, hexestrol, estrone, 17α-ethinyl estradiol, diethylstilboestrol, and bisphenol A were achieved using a Zorbax Extend-C18 high-performance liquid chromatography column (15 cm × 4.6 mm, 5 μm particle size). The limit of detection values obtained in fabric phase sorptive extraction with high-performance liquid chromatography with ultraviolet detection ranged from 25.0 to 50.0 ng/mL. The method repeatability values were 3.6-13.9 (relative standard deviation, %) and intermediate precision values were 4.6-12.7 (relative standard deviation, %). The fabric phase sorptive extraction method was also coupled to liquid chromatography with tandem mass spectrometry for identifying each endocrine disrupting chemical at 10 ng/mL.

A UPLC-QTOF-MS method for the simultaneous determination of 20 veterinary drug residues and metabolites (tetracyclines, quinolones, sulfonamides and diaminopyrimidines) in edible muscle plus skin tissue of European sea bass (Dicentrarchus Labrax) was developed. For the identification of analytes a positive electrospray ionization quadropole time-of flight mass spectrometer operating in MSE mode (UPLC-QTOF-MSE) was used. MSE mode provides high chromatographic resolution and accurate mass measurements in both MS and MS/MS modes simultaneously in a single run. Separation was achieved on a UPLC BEH C18 (50 mm × 2.1 mm, 1.7 μm) column in a gradient elution program of 10 min. Examined antibiotics were isolated easily after a simple solid-liquid extraction procedure with acidic acetonitrile (0.1% v/v formic acid) and Na2EDTA 0.1 M. Recovery rates from muscle plus skin tissue ranged from 93.8% to 107.5% for all targeted compounds. The detection limits and the limits of quantification ranged from 2.22 to 15.00 μg/kg, and from 6.67 to 45.46 μg/kg, respectively. The developed method was validated in terms of selectivity, matrix effect, linearity, accuracy, precision, stability and sensitivity, CCα and CCβ according to European Union Decision 2002/657/EC. The proposed method was applied for the analysis of contaminated fish samples after in feed administration of danofloxacin mesylate.

An HPLC method was applied to evaluate the inhibiting effect of phosphate buffer on the leaching pattern of resin composites and the significance of pH levels during the storage period in the solutions. Ten (10) disk-shaped specimens (2 mm × 12 mm diameter) from Evetric restorative resin composite were immersed by means of a silk string in each of the following solutions: Distilled water (solution A), phosphate buffer of pH = 4.5 (solution B) and phosphate buffer of pH = 6.8 (solution C). After storage for 7, 30 and 60 days’ period, the eluates were examined by means of High Performance Liquid Chromatography (HPLC) at each time interval. The storage of the resin composite specimens in the phosphate buffer solution demonstrated an inhibiting effect on the leaching pattern compared to the distilled water solution. The results of this study suggest that HPLC is a useful tool to investigate the effect of the pH value of phosphate buffer solution, which resembles saliva, on the leaching pattern of resi...

Α novel, green, and facile fabric phase sorptive extraction (FPSE) prior to high pressure liquid chromatography with diode array detection (HPLC-DAD) methodology was developed for the efficient extraction and quantitative determination of tocopherols (α-, sum of (β+γ), and δ-) in edible oils. Among several highly hydrophobic FPSE membranes, sol-gel polycaprolactone-polydimethylsiloxane-polycaprolactone (sol-gel PCAP-PDMS-PCAP) coated polyester FPSE membrane was found as the most efficient in extracting tocopherol homologues from edible oil samples. To maximize the extraction efficiency of FPSE membrane, major parameters of FPSE including the membrane size, sample loading time, the choice of the appropriate elution solvent and the elution solvent volume, desorption time, and the influence of stirring were systematically optimized. The developed FPSE-HPLC-DAD methodology was validated and presented adequately low limits of detection (LODs) and limits of quantification (LOQs) over the ranges 0.05-0.10 μg/g, and 0.17-0.33 μg/g, respectively. The RSD% of the within-day and between-day assays were lower than 1.3, and 11.8, respectively, demonstrating good method precision. The trueness of the method was assessed by means of relative percentage of recovery and ranged between 90.8 and 95.1% for within-day assay, and between 88.7-92.8% for between-day assay. The developed methodology was applied in the analysis of edible oils.

Undoubtedly, the exploration of new sample preparation techniques is in the forefront of research in bioanalysis. Capsule phase microextraction (CPME) is a recently introduced extraction technique based on the sol–gel sorbents which are incorporated into a porous tubular polymeric membrane. Herein, we exploited the advantageous features of CPME in biological matrices by utilizing sol–gel poly(tetrahydrofuran) (sol–gel PTHF) sorbent in CPME device for the extraction of ibuprofen (model compound) from urine samples. In CPME, both filtration and stirring mechanisms are merged into a unified extraction device allowing the direct extraction of the analytes from biological matrix without any pretreatment process. The main parameters (sample pH and volume, adsorption and elution time, volume of elution volume etc.) affecting the extraction efficiency of the CPME method were systematically investigated and optimized. The determination of ibuprofen was performed using UHPLC-PDA. The reported method was validated in terms of linearity, selectivity, accuracy, and precision, limit of detection and limit of quantification using the total error concept. Employing the accuracy profiles – as a graphical decision-making tool – the β-expectation tolerance intervals did not exceed the acceptance criteria of ± 15% meaning that 95% of future results will be included in the defined bias limits. The limit of detection (LOD) of the method was adequate, corresponding to 14 ng mL−1. The relative bias in the spiking levels was acceptable being in the range of −4.1 and +3.9% while the relative standard deviation (RSD) was lower than 4.6%. Moreover, the sol–gel sorbent integrated microextraction capsules were found to be reusable for at least 20 extraction cycles. The CPME protocol was successfully employed for the analysis of real urine samples obtained by a healthy volunteer. Finally, the developed CPME method was characterized by absence of matrix-effect and thus its application can be potentially expanded to other types of biological matrices.

A high-performance liquid chromatographic method was applied to evaluate the effect of bicarbonate (NaHCO3) and phosphate (NaH2PO4, Na2HPO4) buffers on monomer leachability of dental resin composites. Evetric was the restorative resin composite that was investigated in current study. Forty disk-shaped resin composite specimens (n = 40) were immersed by means of a silk string in the following solutions: Distilled water (A), phosphate buffer (B), bicarbonate buffer (C), artificial saliva (D). After seven (7) and fourteen (14) days, the eluates were analyzed by means of High Performance Liquid Chromatography (HPLC). Subsequently, new specimens were fabricated and immersed in fresh solutions in which methanol 12% (v/v) was added. After seven and fourteen days of storage, the leaching of monomers was examined by means of HPLC, which was proved to be an effective tool to buffers demonstrate the inhibiting effect of phosphate and bicarbonate ions on the leaching pattern of dental resin composites.

C-Phycocyanin is the major phycobiliprotein in Arthrospira platensis, also known as Spirulina, which is a cyanobacterium used as a dietary supplement because of its powerful effects on body and brain. C-phycocyanin is a blue-colored accessory photosynthetic pigment with multiple applications in food industry as natural dye or additive, and in pharmaceuticals. This study presents a simple protocol for the extraction and purification of food-grade C-phycocyanin from Arthrospira platensis. The cell lysis of cyanobacterium was performed by sonication combined with repeated freezing and thawing cycles. The purification of the crude extract of C-phycocyanin was carried out by ammonium sulfate precipitation followed by ion exchange chromatography resulting in 2.5 purity. The purity of phycocyanobilin chromophore has been tested by UV-visible spectrophotometry by monitoring the absorption after each stage of purification. A high-performance liquid chromatography method has been developed and validated for the determination of food-grade C-phycocyanin. Intra- and interday precision values less than 5.6% and recovery greater than 91.2% indicated high precision and accuracy of the method for analysis of C-phycocyanin. The method has been applied to commercial confectionery of blue color and to the purified protein obtained in the first stage of the study.

The study describes the functionalization of melamine sponges with graphene and its use as an adsorbent for the microextraction of sulfonamides from food and environmental samples. The graphene-functionalized melamine sponge (GMeS) was prepared by an easy, one-step procedure, which complies with the principles of green chemistry and is proved advantageous over previously described methods. The applicability of the GMeS in extraction procedures was studied and an analytical method for the determination of sulfonamides in milk, eggs and lake water was developed and validated according to SANCO/12571/2013 guideline. The developed method was highly accurate and reproducible, while the limits of quantification were found to be relatively low (0.31-0.91μgkg-1, 0.96-1.32μgkg-1 and 0.10-0.29μgL-1 in the case of milk, eggs and lake water respectively). Furthermore, matrix effects were absent in all cases, since the microextraction procedure serves also as a clean-up step. The low cost of synthesis, the environmentally friendly conditions, the efficiency and high extraction recoveries are some additional advantages of the proposed procedure. To the best of our knowledge, this is the first time that a GMeS is prepared in a straightforward way and used for analytical purposes.

Fabric-phase sorptive extraction has already been recognized as a simple and green alternative to the conventional sorbent-based sorptive microextraction techniques, using hybrid organic-inorganic sorbent coatings chemically bonded to a flexible fabric surface. Herein, we have investigated the synergistic combination of the advanced material properties offered by sol-gel graphene sorbent and the simplicity of Fabric phase sorptive extraction approach in selectively extracting bisphenol A and residual monomers including bisphenol A glycerolatedimethacrylate, urethane dimethacrylate, and triethylene glycol dimethacrylate derived dental restorative materials from cow and human breast milk samples. Different coatings were evaluated. Final method development employed sol-gel graphene coated media. The main experimental parameters influencing extraction of the compounds, such as sorbent chemistry used, sample loading conditions, elution solvent, sorption stirring time, elution time, impact of protein precipitation, amount of sample, and matrix effect, were investigated and optimized. Absolute recovery values from standard solutions were 50% for bisphenol A, 78% for T triethylene glycol dimethacrylate, 110% for urethane dimethacrylate, and 103% for bisphenol A glycerolatedimethacrylate, while respective absolute recovery values from milk were 30, 52, 104, and 42%. Method validation was performed according to European Decision 657/2002/EC in terms of selectivity, sensitivity, linearity, accuracy, and precision.

The concept of metal-organic frameworks (MOFs) was first introduced in 1990; nowadays they are among the most promising novel materials. MOFs belong to a new class of crystalline materials that consist of coordination bonds between metal clusters (e.g., metal-carboxylate clusters and metal-azolate clusters), metal atoms, or rod-shaped clusters and multidentate organic linkers that contain oxygen or nitrogen donors (like carboxylates, azoles, nitriles, etc.); thus, a three-dimensional structure is formed [...].

Back in 1894, Wilhelm Ostwald defined analytical chemistry as “the art of recognizing different substances and determining their constituents”, which “occupies a prominent position among the applications of science, since the questions it allows us to answer arise wherever chemical processes are used for scientific or technical purposes”. In 1993, the Working Party of Analytical Chemistry (WPAC), held in Edinburgh, UK, stated that analytical chemistry “is that scientific discipline that develops and applies methods, tools and strategies to obtain information on the composition and nature in space and time”. Nowadays, these definitions remain very modern and, above all, they are reflected in an uncountable number of application sectors, ranging from biology, geology, environmental sciences, agricultural chemistry, physics, engineering, medicine, and materials science, to social sciences and, of course, in chemistry itself. Often, this discipline is relegated into a corner and considered merely a support for other subjects; this, however, is without realizing that without it and, above all, without its principles, theories, and tools, nothing could make any applicative or rational sense.

In the present study, a novel, simple, and fast sample preparation technique is described for the determination of four sulfonamides (SAs), namely Sulfathiazole (STZ), sulfamethizole (SMT), sulfadiazine (SDZ), and sulfanilamide (SN) in cow milk prior to HPLC. This method takes advantage of a novel material that combines the extractive properties of graphene oxide (GO) and the known properties of common polyurethane sponge (PU) and that makes sample preparation easy, fast, cheap and efficient. The PU-GO sponge was prepared by an easy and fast procedure and was characterized with FTIR spectroscopy. After the preparation of the sorbent material, a specific extraction protocol was optimized and combined with HPLC-UV determination could be applied for the sensitive analysis of trace SAs in milk. The proposed method showed good linearity while the coefficients of determination (R2) were found to be high (0.991&ndash, 0.998). Accuracy observed was within the range 90.2&ndash, 112.1% and precision was less than 12.5%. Limit of quantification for all analytes in milk was 50 &mu, g kg&minus, 1. Furthermore, the PU-GO sponge as sorbent material offered a very clean extract, since no matrix effect was observed.

Tricyclic antidepressant drugs (TCAs) are a main category of antidepressants, which are until today widely used for the treatment of psychological disorders due to their low cost and their high efficiency. Therefore, there is a great demand for method development for the determination of TCAs in biofluids, especially for therapeutic drug monitoring. Gas chromatography (GC) was the first chromatographic technique implemented for this purpose. With the recent development in the field of sample preparation, many novel GC applications have been developed. Herein, we aim to report the recent application of GC for the determination of tricyclic antidepressants in biofluids. Emphasis is given to novel extraction techniques and novel materials used for sample preparation.

A novel fabric phase sorptive extraction protocol is developed for rapid exposure monitoring of six bisphenol analogues, including bisphenol A, bisphenol S, bisphenol F, bisphenol E, bisphenol B, bisphenol C, and diethylstilbestrol (DES) from human urine prior to high-performance liquid chromatography-photodiode array analysis. FPSE sample pretreatment protocol ensures the harmonization of the proposed method with the principles of Green Analytical Chemistry (GAC). Among eighteen evaluated FPSE membranes, sol-gel poly (ethylene glycol) (PEG) coated cellulose FPSE membrane resulted in the most efficient extraction. This polar FPSE membrane effectively exploits a number of advantageous features inherent to FPSE including sponge-like porous architecture of the sol-gel sorbent coating, favorable surface chemistry, flexibility and built-in permeability of cellulose fabric substrate, high primary contact surface area for rapid sorbent-analyte interaction, expanded pH, solvent and thermal stability as well as reusability of the FPSE membrane. Optimization was centered on the evaluation of critical parameters, namely the size of the FPSE membrane, the elution solvent mixture, the volume of the sample, the extraction time, the elution time, the kind of the external agitation mechanical stimulus, the ionic strength and the pH of the sample. The chromatographic separation was achieved on a Spherisorb C18 column and a gradient elution program with mobile phase consisted of 0.05 ammonium acetate solution and acetonitrile. The total analysis time was 17.4 min. The developed method was validated in terms of linearity, sensitivity, selectivity, precision, accuracy, stability, and ruggedness. The limits of detection and quantification varied from 0.26-0.62 ng/mL and 0.8-1.9 ng/mL, respectively. The relative recoveries were calculated between 90.6 and 108.8%, while the RSD values were10% in all cases. The effectiveness of the proposed method was confirmed by its successful implementation in the bioanalysis of real urine samples.

Sample preparation and extraction of the analytes are the cornerstones of any bioanalytical method, exerting profound influence on the entire procedure. Herein is presented an overview of sample pretreatment and extraction approaches of the esters of p-hydroxybenzoic acid also known as parabens, from human biological matrices prior to liquid chromatography analysis. Parabens are homologues chemicals compounds that are omnipresent as preservatives in products of daily use due to their efficient antimicrobial activity. However, parabens demonstrate estrogenic activity and thus are endocrine disrupting chemicals, involved in the deregulation of the hormone system and connected with the incidence of human breast cancer and other health malfunctions and disease processes. Consequently, the determination of parabens in human biological samples, which is a challenging task due to the matrix complexity, is a matter of great interest for epidemiological and toxicological purposes. Matrix complexity and interferences may be avoided by adopting an appropriate extraction protocol. Thus, this review focused on efficient previous reported sample pretreatment and extraction protocols coupled with liquid chromatography, which is the most prevalent analytical technique.

The great concern about food contamination and human exposure to bisphenol A (BPA) necessitated the development of a green and highly selective method for the efficient monitoring of BPA migration from the packaging materials to alcoholic and non-alcoholic beverages. Molecularly imprinted solid phase extraction (MISPE) coupled to high pressure liquid chromatography-diode array detection (HPLC-DAD) using an imprinted sol–gel silica-based hybrid inorganic–organic polymeric sorbent (sol–gel MIP) was applied in the determination of BPA in trace levels. The sorbent mass was optimized. The highest absolute recovery (RE = 84.1%) was obtained with the use of 50 mg of mass sorbent. The extraction protocol involved 0.5 mL sample loading, 15 min of holding time and elution with 2 mL ACN. The imprinting factor (IF) was equal to 3.63 ± 0.11 (n = 3). The developed MISPE-HPLC-DAD method was validated and demonstrated excellent linearity (0.997), high recovery (RE: 99.5% ± 5.7, n = 3), intra-assay repeatability over the range 92.4–98.1%, n = 3; and inter-assay precision over the range 81.2–102.3%, n = 3. Overall, 36 alcoholic and non-alcoholic beverages available in the Greek market were tested for BPA and the quantification results were below the regulation limit for all the samples over the range 0.011–0.041ng mL−1.

The development and approbation of new, automated UHPLC-DAD method for the quantification of 25-hydroxyvitamin D3/D2 (25OH-D3/D2) metabolites in plasma/serum for the evaluation of patient's vitamin D status are presented. The method was developed on the Ultimate 3000 UHPLC dual gradient system supplied with the on-line SPE-concentration column coupled through six port switching valve to analytical column. This configuration and materials selected enable large volume sample injection (500μL) and on-line sample preconcentration, clean up and subsequent selective metabolites transfer onto the analytical column. The new method abrogates main conventional time consuming and error source off-line steps of analysis and thus simplifies analysis. The large volume injection increases the sensitivity of instrumental analysis by about ten-fold on-line pre-concentration of metabolites. The instrument response is linear (R>0.99) in the investigated concentration range 10-100ngmL-1 which covers all the possible vitamin D status from serious deficiency (

A method for the determination of five sulfonamide drugs: sulfadiazine (SDZ), sulfamethazine (SMTH), sulfisoxazole (SIX), sulfadimethoxine (SDMX), sulfaquinoxaline (SQX) in shrimps was developed using a high-pressure liquid chromatography–diode array detection (HPLC–DAD) instrumentation. The drugs were extracted from the samples using a solid-liquid extraction, with a mixture of acetonitrile-methanol and aqueous solution of acetic acid. The separation was achieved with LiChroCART-LiChrospher® 100 RP-18 (5 μm, 250 × 4 mm), and the mobile phase consisted of (A) aqueous solution of acetic acid 0.1% (65%) and (B) mixture of ACN-MeOH 50:50 v/v (35%), delivered at a flow rate of 0.8 mL/min isocratically. A DAD detector was used for the detection of the sulfonamides at 265 nm. The method was validated according to the 657/2002/EC decision of the European Union. The recoveries for within-day repeatability were 90.2–109.0% and for between-day precision 88.6–108.4%. The limit of quantitation for all five suflonamides was 50 μg/kg, and the limit of detection was 15 μg/kg.

Highly selective and efficient chloramphenicol imprinted sol-gel silica based inorganic polymeric sorbent (sol-gel MIP) was synthesized via matrix imprinting approach for the extraction of chloramphenicol in milk. Chloramphenicol was used as the template molecule, 3-aminopropyltriethoxysilane (3-APTES) and triethoxyphenylsilane (TEPS) as the functional precursors, tetramethyl orthosilicate (TMOS) as the cross-linker, isopropanol as the solvent/porogen, and HCl as the sol-gel catalyst. Non-imprinted sol-gel polymer (sol-gel NIP) was synthesized under identical conditions in absence of template molecules for comparison purpose. Both synthesized materials were characterized by Scanning Electron Microscopy (SEM), Fourier Transform Infrared Spectroscopy (FT-IR) and nitrogen adsorption porosimetry, which unambiguously confirmed their significant structural and morphological differences. The synthesized MIP and NIP materials were evaluated as sorbents for molecularly imprinted solid phase extraction (MISPE) of chloramphenicol in milk. The effect of critical extraction parameters (flow rate, elution solvent, sample and eluent volume, selectivity coefficient, retention capacity) was studied in terms of retention and desorption of chloramphenicol. Competition and cross reactivity tests have proved that sol-gel MIP sorbent possesses significantly higher specific retention and enrichment capacity for chloramphenicol compared to its non-imprinted analogue. The maximum imprinting factor (IF) was found as 9.7, whereas the highest adsorption capacity of chloramphenicol by sol-gel MIP was 23 mg/g. The sol-gel MIP was found to be adequately selective towards chloramphenicol to provide the necessary minimum required performance limit (MRPL) of 0.3 μg/kg set forth by European Commission after analysis by LC-MS even without requiring time consuming solvent evaporation and sample reconstitution step, often considered as an integral part in solid phase extraction work-flow. Intra and inter-assay RSD values were less than 13% and accuracy expressed as relative recovery ranged from 85 to 106%.