Trace determination of parabens in cosmetics and personal care products using fabric-phase sorptive extraction and high-performance liquid chromatography with UV detection.

A simple, fast, and sensitive analytical protocol using fabric-phase sorptive extraction followed by high performance liquid chromatography with ultraviolet detection has been developed and validated for the extraction of five parabens including methylparaben, ethylparaben, propylparaben, butylparaben, and benzylparaben. In the present work, sol-gel polyethylene glycol coated fabric-phase sorptive extraction membrane is used for the preconcentration of parabens (polar) from complex matrices. The use of fabric-phase sorptive extraction membrane provides a high surface area which offers high sorbent loading, shortened equilibrium time, and overall decrease in the sample preparation time. Various factors affecting the performance of fabric-phase sorptive extraction, including extraction time, eluting solvent, elution time, and pH of the sample matrix, were optimized. Separation was performed using a mobile phase consisting of water:acetonitrile (63:37; v/v) at an isocratic elution mode at a flow rate of 0.9 mL/min with wavelength at 254 nm. The calibration curves of the target analytes were prepared with good correlation coefficient values (r2  > 0.9955). The limit of detection values range from 0.252 to 0.580 ng/mL. Finally, the method was successfully applied to various cosmetics and personal care product samples such as rose water, deodorant, hair serum, and cream with extraction recoveries ranged between 88 and 122% with relative standard deviation <5%.

Anthropometric and Skin Fold Thickness Measurements of Newborns of Gestational Glucose Intolerant Mothers: Does it Indicate Disproportionate Fetal Growth?

AIM OF THE STUDY: Studies have shown that gestational diabetes mellitus (GDM) causes disproportionate growth and increased adiposity in their newborns; however, the effect of gestational glucose intolerance (GGI), i.e., 2 h plasma glucose (PG) between 120 and 139 mg/dl in pregnancy on their newborns growth and adiposity is not well established. The objective of the present study is to evaluate the effect of GGI in pregnancy on anthropometry and adiposity of their newborns at birth in urban South Indian population. MATERIALS AND METHODS: An observational study was conducted on 119 urban South Indian pregnant women and their newborns. PG levels 2 h after ingestion of 75 g glucose load were determined between 24 and 28 weeks of gestation, and depending on their PG levels, these women were categorized into three different groups, (a) normal glucose tolerance (NGT)-2 h PG < 120 mg/dl, (b) GGI-2 h PG between 120 and 139 mg/dl and (c) GDM-2 h PG > or = 140 mg/dl. GDM mothers were treated with insulin and MNT advised. GGI mothers were advised MNT. These women were followed up till delivery. After delivery, their newborn's anthropometry like weight, length, head circumference (HC), chest circumference (CC), mid-arm circumference, abdominal circumference, bisacromial diameter and subscapular and triceps skin fold thicknesses (SFT) was measured within 72 h of birth. Effect of GGI in pregnancy on newborn's anthropometry and SFT was analyzed and studied in comparison with newborns of other two categories. Further, the newborns were stratified into four groups according to their birth weight and newborns of GGI category were compared with newborns of other two categories of same weight. RESULTS: The triceps and subscapular skin fold thicknesses which are direct measurements of adiposity were significantly higher in newborns of GGI mothers compared to newborns of GDM and NGT mothers. GGI category newborns showed increased adiposity even when they were compared with newborns of GDM and NGT category of same weight. Also measurements which are likely to increase due to increased adiposity like bisacromial diameter, abdominal circumference, mid-arm circumference were significantly higher in GGI category newborns. On the other hand, measurements which indicate skeletal growth like length, HC, CC were similar in all three category newborns. This confirmed disproportionate growth and increased adiposity in newborns of GGI mothers. It should be noted here that the GDM mothers were on MNT and treated with insulin, the dose of insulin was adjusted so as to mimick Fasting PG and Post Prandial PG levels of NGT mothers. CONCLUSION: Gestational glucose intolerance during pregnancy does cause disproportionate growth (increased fat body mass but not skeletal mass) and increased adiposity in their newborns. This emphasizes the need for strict glycemic control (2 h of PG level after 75 grams glucose load to < 120 mg/dl and PPPG levels to < 120 mg/dl) during pregnancy. Larger multicentered studies are recommended to confirm this association.

Fabric phase sorptive extraction/GC-MS method for rapid determination of broad polarity spectrum multi-class emerging pollutants in various aqueous samples.

A rapid extraction and cleanup method using selective fabric phase sorptive extraction combined with gas chromatography and mass spectrometry has been developed and validated for the determination of broad polarity spectrum emerging pollutants, ethyl paraben, butyl paraben, diethyl phthalate, dibutyl phthalate, lidocaine, prilocaine, triclosan, and bisphenol A in various aqueous samples. Some important parameters of fabric phase sorptive extraction such as extraction time, matrix pH, stirring speed, type and volume of desorption solvent were investigated and optimized. Calibration curves were obtained in the concentration range 0.05-500 ng/mL. Under the optimum conditions, the limits of detection were in the range 0.009 -0.021 ng/mL. This method was validated by analyzing the compounds in spiked aqueous samples at different levels with recoveries of 93 to 99% and relative standard deviations of <6%. The developed method was applied for the determination of the emerging contaminants in tap water, municipal water, ground water, sewage water, and sludge water samples. The results demonstrate that fabric phase sorptive extraction has great potential in the preconcentration of trace analytes in complex matrix.

Rapid Monitoring of Organochlorine Pesticide Residues in Various Fruit Juices and Water Samples Using Fabric Phase Sorptive Extraction and Gas Chromatography-Mass Spectrometry.

Fabric phase sorptive extraction, an innovative integration of solid phase extraction and solid phase microextraction principles, has been combined with gas chromatography-mass spectrometry for the rapid extraction and determination of nineteen organochlorine pesticides in various fruit juices and water samples. FPSE consolidates the advanced features of sol-gel derived extraction sorbents with the rich surface chemistry of cellulose fabric substrate, which could extract the target analytes directly from the complex sample matrices, substantially simplifying the sample preparation operation. Important FPSE parameters, including sorbent chemistry, extraction time, stirring speed, type and volume of back-extraction solvent, and back-extraction time have been optimized. Calibration curves were obtained in a concentration range of 0.1⁻500 ng/mL. Under optimum conditions, limits of detection were obtained in a range of 0.007⁻0.032 ng/mL with satisfactory precision (RSD < 6%). The relative recoveries obtained by spiking organochlorine pesticides in water and selected juice samples were in the range of 91.56⁻99.83%. The sorbent sol-gel poly(ethylene glycol)-poly(propylene glycol)-poly(ethylene glycol) was applied for the extraction and preconcentration of organochlorine pesticides in aqueous and fruit juice samples prior to analysis with gas chromatography-mass spectrometry. The results demonstrated that the present method is simple, rapid, and precise for the determination of organochlorine pesticides in aqueous samples.

Application of fabric phase sorptive extraction with gas chromatography and mass spectrometry for the determination of organophosphorus pesticides in selected vegetable samples.

In the present work, a high-efficiency and solvent minimized microextraction technique, fabric phase sorptive extraction followed by gas chromatography and mass spectrometry analysis is proposed for the rapid determination of four organophosphorus pesticides (terbufos, malathion, chlorpyrifos, and triazofos) in vegetable samples including beans, tomato, brinjal, and cabbage. Fabric phase sorptive extraction combines the beneficial features of sol-gel derived microextraction sorbents with the rich surface chemistry of cellulose fabric substrate, which collectively form a highly efficient microextraction system. Fabric phase sorptive extraction membrane, when immersed directly into the sample matrix, may extract target analytes even when high percentage of matrix interferents are present. The technique also greatly simplifies sample preparation workflow. Most important fabric phase sorptive extraction parameters were investigated and optimized. The developed method displayed good linearity over the concentration range 0.5-500 ng/g. Under optimum experimental conditions, the limits of detection were found in the range of 0.033 to 0.136 ng/g. The relative standard deviations for the extraction of organophosphorus pesticides were < 5%. Subsequently, the new method was applied to beans, tomato, brinjal, and cabbage samples. The results from the real sample analysis indicate that the method is green, rapid, and economically feasible for the determination of organophosphorus pesticides in vegetable samples.

Direct Rapid Determination of Trace Aluminum in Various Water Samples with Quercetin by Reverse Phase High-Performance Liquid Chromatography Based on Fabric Phase Sorptive Extraction Technique.

The determination of trace levels of aluminum by high-performance liquid chromatography (HPLC) with UV detection using quercetin, a natural bioactive flavonol, as a metal complexation agent is presented in the current article. The developed method has been successfully applied to the direct determination of aluminum in water samples collected from various sources. A preconcentration technique is indispensable due to the presence of aluminum in environmental water at trace levels. Fabric phase sorptive extraction (FPSE), a relatively new but promising sample preparation technique, was applied to preconcentrate quercetin-Al(III) complex from water samples. Efficient extraction of the quercetin-Al(III) complex from aqueous samples has been accomplished by applying FPSE using a cellulose fabric substrate coated with sol-gel C18 hybrid nanocomposite sorbent. Baseline separation of Al-quercetin complex has been achieved on a reverse phase C18 column with the use of acetonitrile: 3% acetic acid (30:70; v/v) as the mobile phase at a flow rate of 1.0 mL/min. The new FPSE-HPLC-UV method can be used for the routine screening of Al ions in various water samples with high sensitivity, precision and reliability.

Development of a microextraction by packed sorbent with gas chromatography-mass spectrometry method for quantification of nitroexplosives in aqueous and fluidic biological samples.

A new method for quantification of 12 nitroaromatic compounds including 2,4,6-trinitrotoluene, its metabolites and 2,4,6-trinitrophenyl-N-methylnitramine with microextraction by packed sorbent followed by gas chromatography and mass spectrometric detection in environmental and biological samples is developed. The microextraction device employs 4 mg of C18 silica sorbent inserted into a microvolume syringe for sample preparation. Several parameters capable of influencing the microextraction procedure, namely, number of extraction cycles, washing solvent, volume of washing solvent, elution solvent, volume of eluting solvent and pH of matrix, were optimized. The developed method produced satisfactory results with excellent values of coefficient of determination (R2  > 0.9804) within the established calibration range. The extraction yields were satisfactory for all analytes (> 89.32%) for aqueous samples and (> 87.45%) for fluidic biological samples. The limits of detection values lie in the range 14-828 pg/mL.

A Review on Recent Applications of High-Performance Liquid Chromatography in Metal Determination and Speciation Analysis.

High-performance liquid chromatography (HPLC) has several advantages over the conventional methods due to their operational simplicity. It is a vital tool to determine metal ions having same mass but different electronic configuration, to separate complex mixtures and to resolve ions that may be indistinguishable by mass spectrometry alone. Metal ions play vital role in many biological processes and involved in setting up of many diseases. Therefore, the development of simple methods for the detection and quantification of metals in real samples might serve as diagnostic tools for various diseases. This review article focuses on the recent main feature of this technique, i.e. speciation of metal ions and their applications to series of problem of metal ion chemistry in different environmental matrixes. Speciation of metals is of increasing interest and has a great importance because of bioavailability, environmental mobility, toxicity and potential risk of metals. With the capability of partitioning the complex species of different metal ions, HPLC is an efficient technique for this task. This review summarizes recent advances in the development of HPLC to the fundamental understanding of metal ion chemistry in the environment and discusses all the issues that still need a lot of consideration. It has been classified into different sections depending on the role of HPLC in separation used and metal speciation; furthermore, the underlying sample preconcentration techniques and detection systems involved for the determination of metal ions and their applications were discussed.

A Review for the Analysis of Antidepressant, Antiepileptic and Quinolone Type Drugs in Pharmaceuticals and Environmental Samples.

The analysis of drugs in various biological fluids is an important criterion for the determination of the physiological performance of a drug. After sampling of the biological fluid, the next step in the analytical process is sample preparation. Sample preparation is essential for isolation of desired components from complex biological matrices and greatly influences their reliable and accurate determination. The complexity of biological fluids adds to the challenge of direct determination of the drug by chromatographic analysis, therefore demanding a sample preparation step that is often time consuming, tedious and frequently overlooked. However, direct online injection methods offer the advantage of reducing sample preparation steps and enabling effective pre-concentration and clean-up of biological fluids. These procedures can be automated and therefore reduce the requirements for handling potentially infectious biomaterial, improve reproducibility, and minimize sample manipulations and potential contamination. This review is focused on the discovery and development of high-performance liquid chromatography (HPLC) and gas chromatography (GC) with different detectors. The drugs covered in this review are antiepileptics, antidepressant (AD), and quinolones. The application of these methods for determination of these drugs in biological, environmental and pharmaceutical samples has also been discussed.

Simple and rapid determination of phthalates using microextraction by packed sorbent and gas chromatography with mass spectrometry quantification in cold drink and cosmetic samples.

A simple and rapid method using microextraction by packed sorbent coupled with gas chromatography and mass spectrometry has been developed for the analysis of five phthalates, namely, diethyl phthalate, benzyl-n-butyl phthalate, dicyclohexyl phthalate, di-n-butyl phthalate, and di-n-propyl phthalate, in cold drink and cosmetic samples. The various parameters that influence the microextraction by packed sorbent performance such as extraction cycle (extract-discard), type and amount of solvent, washing solvent, and pH have been studied. The optimal conditions of microextraction using C18 as the packed sorbent were 15 extraction cycles with water as washing solvent and 3 × 10 µL of ethyl acetate as the eluting solvent. Chromatographic separation was also optimized for injection temperature, flow rate, ion source, interface temperature, column temperature gradient and mass spectrometry was evaluated using the scan and selected ion monitoring data acquisition mode. Satisfactory results were obtained in terms of linearity with R(2) >0.9992 within the established concentration range. The limit of detection was 0.003-0.015 ng/mL, and the limit of quantification was 0.009-0.049 ng/mL. The recoveries were in the range of 92.35-98.90% for cold drink, 88.23-169.20% for perfume, and 88.90-184.40% for cream. Analysis by microextraction by packed sorbent promises to be a rapid method for the determination of these phthalates in cold drink and cosmetic samples, reducing the amount of sample, solvent, time and cost.

Development of a rapid and sensitive method for the determination of aluminum by reverse-phase high-performance liquid chromatography using a fluorescence detector.

This study represents a new analytical high-performance liquid chromatography-fluorescence detector method for the determination of Al(III) as Al(III) complex with 8-hydroxyquinoline-5-sulfonic acid in a tap water sample and a coke sample. A micellar liquid chromatographic method is proposed for the determination of aluminum metal in the presence of cetyltrimethylammonium bromide, a cationic surfactant (0.05 M) used for the solubilization of the aluminum complex. The influence of pH and ligand concentration on the formation of the complex was studied by adding a small amount of 0.1 M sodium hydroxide. The metal chelate was detected at λEx 410 nm and λEm 510 nm. This method eliminates the need for addition of reagent or organic modifier to the mobile phase. The complex was analyzed using an Ascentis Express C18 column and a mobile phase consisting of acetonitrile, methanol and water (55 : 30 : 15). Under the optimized conditions, the linear range was 1-200 µg L(-1) and the limit of detection was 0.05 µg L(-1). The method showed a good detector response over the range of interest and was successfully applied for the determination of trace Al(III) in canned coke and water samples containing excess of Mg(II), Ca(II) and other matrices.

Determination of endosulfan isomers and their metabolites in tap water and commercial samples using microextraction by packed sorbent and GC-MS.

A simple, rapid, accurate and sensitive method using microextraction by packed sorbent (MEPS) followed by GC-MS has been pursued for the determination of organochlorine insecticide endosulfan isomers (α and ß) and their metabolites (ether, lactone and sulfate). MEPS is a miniaturised version of SPE employing C18 packing material. It is very efficient technique as it employs as low as 10 µL of sample volume. The distinct feature of MEPS is the magnitude of the elution volume that could be directly injected to GC system. Various parameters such as extraction cycles, washing solvent, elution solvent, elution volume and pH, which influenced the MEPS performance, were tested and optimised. The calibration curves were obtained in the concentration range 1-500 ng/mL. The results showed a close correlation coefficient (R(2) > 0.991) for all analytes in the calibration range studied. The LOD and LOQ obtained for GC-MS under selected ion monitoring acquisition are between 0.0038-0.01 and 0.0125-0.033 ng/mL, respectively. The developed method is applicable for the quantification of these compounds in tap water and commercial samples. This method has been shown to be selective as no interferences from endogenous substances were detected by analysis. This method not only decreases sample preparation time but is cheaper, eco-friendly and easier to perform compared to traditional techniques.

Microextraction by packed sorbent-high-pressure liquid chromatographic-ultra violet analysis of endocrine disruptor pesticides in various matrices.

Microextraction by a packed sorbent (MEPS) is the miniaturized version of solid-phase extraction whereby sample volumes as small as 10 µL can be used. A syringe (100-250 µL) is used in MEPS technique, which generally contains 4 mg of solid packing material inserted as a plug. The sample preparation occurs on the surface of this bed which can be modified to provide varied sampling conditions. In the present work, MEPS has been employed as a sample preparation technique for the analysis of endocrine disruptor (ED) and suspected ED pesticides in biological and environmental samples. The pesticides aldicarb, dimethoate, propazine and terbutryn have been successfully separated by high performance liquid chromatography-ultra violet (HPLC-UV) system with acetonitrile/water as the mobile phase in the ratio 60/40. Several factors affecting the performance of MEPS technique such as the number of extraction cycles, type of washing and elution solvent were optimized. This method has been applied to the analysis of these pesticides in urine, soil and tap water samples with good recoveries in the range of 81.4-97.8%. The detection limit ranged between 0.05 and 0.6 ng mL for the analyzed pesticides.

A novel microextraction by packed sorbent-gas chromatography procedure for the simultaneous analysis of antiepileptic drugs in human plasma and urine.

A simple, accurate, and sensitive microextraction by packed sorbent-gas chromatography-mass spectrometry method has been developed for the simultaneous quantification of four antiepileptic drugs; oxcarbazepine, carbamazepine, phenytoin, and alprazolam in human plasma and urine as a tool for drug monitoring. Caffeine was used as internal standards for the electron ionization mode. An original pretreatment procedure on biological samples, based on microextraction in packed syringe using C(18) as packing material gave high extraction yields (69.92-99.38%), satisfactory precision (RSD < 4.7%) and good selectivity. Linearity was found in the 0.1-500 ng/mL range for these drugs with limits of detection (LODs) between 0.0018 and 0.0036 ng/mL. Therefore, the method has been found to be suitable for the therapeutic drug monitoring of patients treated with oxcarbazepine, carbamazepine, phenytoin, and alprazolam. After validation, the method was successfully applied to some plasma samples from patients undergoing therapy with one or more of these drugs. A comparison of the detection limit with similar methods indicates high sensitivity of the present method over the earlier reported methods. The present method is applied for the analysis of these drugs in the real urine and plasma samples of the epileptic patients.

Liquid chromatographic determination of quinolones in water and human urine samples after microextraction by packed sorbent.

A method for the simultaneous determination of quinolones in water and urine samples by microextraction in a sorbent-packed syringe (MEPS) with LC is described. MEPS is a new miniaturized SPE technique that can be used with chromatographic instruments without any modifications. In MEPS, approximately 1 mg of the solid packing material is inserted into a syringe (100-250 microL) as a plug. Sample preparation takes place on the packed bed. The new method is promising, easy to use, economical, and rapid. The determination of quinolones in groundwater and urine was performed using MEPS as a sample preparation method with LC-UV determination. Four quinolone antibiotics--enrofloxacin, enoxacin, danofloxacin, and nalidixic acid--in groundwater and urine samples were used as analytes. The extraction recovery was found to be between 64.9 and 98.9%. The results showed high correlation coefficients (R2 > 0.992) for all of the analytes within the calibration range. The LOQ was between 0.091 and 0.315 ng/mL.

Novel micro-extraction by packed sorbent procedure for the liquid chromatographic analysis of antiepileptic drugs in human plasma and urine.

A method for the simultaneous determination of the antiepileptic drugs, phenobarbital (PHB), phenytoin (PTN), carbamazepine (CBZ), primidone (PRM) and oxcarbazepine (OXC) in human plasma and urine samples by using micro-extraction in a packed syringe as the sample preparation method connected with LC/UV (MEPS/LC/UV) is described. Micro-extraction in a packed syringe (MEPS) is a new miniaturized, solid-phase extraction technique that can be connected online to gas or liquid chromatography without any modifications. In MEPS approximately 1 mg of the solid packing material is inserted into a syringe (100-250 µL) as a plug. Sample preparation takes place on the packed bed. The bed can be coated to provide selective and suitable sampling conditions. The new method is very promising, easy to use, fully automated, inexpensive and quick. The standard curves were obtained within the concentration range 1-500 ng/mL in both plasma and urine samples. The results showed high correlation coefficients (R(2) >0.988) for all of the analytes within the calibration range. The extraction recovery was found to be between 88.56 and 99.38%. The limit of quantification was found to be between 0.132 and 1.956 ng/mL. The precision (RSD) values of quality control samples (QC) had a maximum deviation of 4.9%. A comparison of the detection limits with similar methods indicates high sensitivity of the present method. The method is applied for the analysis of these drugs in real urine and plasma samples of epileptic patients.