MOF-801 based solid phase microextraction fiber for the monitoring of indoor BTEX pollution.

Benzene, toluene, ethylbenzene and xylenes (BTEX) are some of the better-known indoor air pollutants, for which effective monitoring is important. The analysis of BTEX can be performed by different type of solid phase microextraction (SPME) fibers. This study presents a proposal for a low cost, convenient and environmentally friendly analytical method for the determination of BTEX in air samples using custom made SPME fibers. In this context, custom made metal organic frameworks (MOF-801) were coated on a stainless-steel wire for SPME fiber preparation. The analysis of BTEX was performed by introducing SPME fiber into an analyte-containing Tedlar bag in steady-state conditions. After the sampling step, the analytes were analyzed using gas chromatography mass spectrometry in selected ion monitoring mode. Parameters that affect the analysis results were optimized; these include desorption temperature and time, preconditioning time, extraction temperature and time, and sample volume. Under optimized conditions, analytical figure of merits of developed method were obtained, including limits of detection (LOD) (0.012 - 0.048 mg/m3), linear ranges (0.041-18 mg/m3), intraday and interday repeatability (2.08 - 4.04% and 3.94 - 6.35%), and fiber to fiber reproducibility (7.51 - 11.17%). The proposed method was successfully applied to real air samples with an acceptable recovery values between 84.5% and 110.9%. The developed method can be applied for the effective monitoring of BTEX.

Electrothermaly conditioned carbon fibre for the analysis of volatile pollutants.

This study deals with the development of an inexpensive and single-step sorbent manufacturing methodology for the analysis of air pollutants. Disposable carbon fibre sorbents were prepared in a few minutes using the electrothermal conditioning technique. The sorbent conditioning current and time were optimised to obtain the best extraction of benzene, toluene, ethylbenzene and xylenes (BTEX) from the air samples. After sorbent characterisation, analysis parameters affecting the BTEX extraction efficiency, such as sampling volume, humidity and sampling flow rate, were optimised for active BTEX sampling. Under optimum conditions, validation parameters such as the limit of detection (LOD), repeatability, reproducibility, and linear range were found to be 0.07-0.11 mg m - 3, 1.1%-1.8%, 5.6%-9.5% and 0.24-45 mg m - 3, respectively. Thereafter, the BTEX analysis was successfully conducted using the proposed method, with acceptable recovery values (96%-103%) in the real indoor environments.

Development of a solventless method for the pesticides analysis.

This paper represents the results of a case study investigating the development of a novel, simple, cost-effective, solventless and sensitive chromatographic method for the determination of volatile pesticides in aqueous samples by an electrothermally prepared pencil graphite (PG). In this study, PG were conditioned by passing a suitable direct current to activate PG by Joule effect. Conditioned PG was used for the extraction of Chlorpyrifos (CP), which is used as case study. The method was also found successful in the determination of CP in real water samples, providing acceptable recovery values (82-111%).

Concordance in molecular genetic analysis of tumour tissue, plasma, and exhaled breath condensate samples from lung cancer patients.

AIM: Lung adenocarcinoma is characterized by poor prognosis and short survival rates. Therefore, tools to identify the tumoural molecular structure and guide effective diagnosis and therapy decisions are essential. Surgical biopsies are highly invasive and not conducive for patient follow-up. To better understand disease prognosis, novel non-invasive analytic methods are needed. The aim of the present study is to identify the genetic mutations in formalin-fixed paraffin-embedded (FFPE) tissue, plasma, and exhaled breath condensate (EBC) samples by next-generation sequencing and evaluate their utility in the diagnosis and follow-up of patients with lung adenocarcinoma. METHOD: FFPE, plasma, and EBC samples were collected from 12 lung adenocarcinoma patients before treatment. DNA was extracted from the specimens using an Invitrogen PureLink Genomic DNA Kit according to the manufacturer's instructions. Amplicon-based sequencing was performed using Ion AmpliSeq Colon and Lung Cancer Research Panel v2. RESULTS: Genetic alterations were detected in all FFPE, plasma, and EBC specimens. The mutations in PIK3CA, MET, PTEN, SMAD4, and FGFR2 genes were highly correlated in six patients. Somatic and novel mutations detected in tissue and EBC samples were highly correlated in one additional patient. The EGFR p.L858R and KRAS p.G12C driver mutations were found in both the FFPE tissue specimens and the corresponding EBC samples of the lung adenocarcinoma patients. CONCLUSION: The driver mutations were detected in EBC samples from lung adenocarcinoma patients. The analysis of EBC samples represents a promising non-invasive method to detect mutations in lung cancer and guide diagnosis and follow-up.

A novel polythiophene - ionic liquid modified clay composite solid phase microextraction fiber: Preparation, characterization and application to pesticide analysis.

This report comprises the novel usage of polythiophene - ionic liquid modified clay surfaces for solid phase microextraction (SPME) fiber production to improve the analysis of pesticides in fruit juice samples. Montmorillonite (Mmt) clay intercalated with ionic liquids (IL) was co-deposited with polythiophene (PTh) polymer coated electrochemically on an SPME fiber. The surface of the fibers were characterized by using scanning electron microscopy (SEM). Operational parameters effecting the extraction efficiency namely; the sample volume and pH, adsorption temperature and time, desorption temperature and time, stirring rate and salt amount were optimized. In order to reveal the major effects, these eight factors were selected and Plackett-Burman Design was constructed. The significant parameters detected; adsorption and temperature along with the stirring rate, were further investigated by Box-Behnken design. Under optimized conditions, calibration graphs were plotted and detection limits were calculated in the range of 0.002-0.667ng mL(-1). Relative standard deviations were no higher than 18%. Overall results have indicated that this novel PTh-IL-Mmt SPME surface developed by the aid of electrochemical deposition could offer a selective and sensitive head space analysis for the selected pesticide residues.

Ionic liquid intercalated clay sorbents for micro solid phase extraction of steroid hormones from water samples with analysis by liquid chromatography-tandem mass spectrometry.

Clay material plays an important role in the transport and retention of many compounds in the soil, therefore, clay based sorbents are promising alternatives for selective sorption of organic pollutants. In the present work, different chain length ionic liquids (ILs) namely, 1-methyl-3-octyl-imidazolium bromide, 1-methyl-3-undecyl-imidazolium bromide and 1-methyl-3-octadecyl-imidazolium bromide were intercalated in the galleries of montmorillonite (MMT) clay. Then, this novel nanofiller surface was utilized in micro extraction of estrogenic hormones for the first time. A fast procedure where sonication-assisted emulsification microextraction combined with vortex assisted micro-solid phase extraction (µ-SPE) was developed for the LC-MS/MS analysis of estrone (E1), 17ß-estradiol (E2), estriol (E3) and ethynylestradiol (EE2). The parameters related to the µ-SPE procedure namely; pH, sorbent amount, extraction solvent type and volume, sonication and vortex time, sample volume and salt effect on the extraction efficiency were screened by applying Plackett-Burmann design. The selected parameters were then optimized by using Box-Behnken design. The method was validated for the determination of estrogenic hormone residues in river water samples. Linear calibration plots were obtained for all hormones whose regression coefficients were larger than 0.98. RSD values were found less than 10% for three levels of concentration. LOD levels were calculated as; 0.012, 0.062, 0.018 and 0.693 ng L(-1) for E1, E2, E3 and EE2, respectively. Recovery values were calculated in the range of 86.9-97.7%. Considering large sample volumes required for attaining low limits of these hormones, present method provides an ease for analyst as 10 mL of the sample is adequate for achieving the same sensitivity.

Application of solidified floating organic drop microextraction method for biomonitoring of chlorpyrifos and its oxon metabolite in urine samples.

A simple, efficient and green analytical procedure for monitoring sub ppb amounts of chlorpyrifos (CP) and chlorpyrifos-oxon (CPO) in urine samples was reported. The methodology is based on the solidified floating organic drop microextraction of the analytes with a free microdrop of 2-dodecanol. The parameters those can affect the microextraction efficiency, such as solvent type, extraction solvent volume, extraction time and temperature, salt effect, pH and stirring rate on extraction were optimized. The analytes were extracted from the urine samples by using 10µL of 2-dodecanol for 40min at 70°C and then, the extracts were injected to GC-MS column by applying 100kPa injection pressure. The regression coefficients relating to linearity were at least 0.99. The accuracy of the developed method was tested upon recovery studies for CP and CPO calculated as 100±7% and 110±9% (at 0.1ngmL(-1) level), respectively. LOD value for CP was found 4.8ngL(-1) and for CPO it was found 3.8ngL(-1). This method can easily be adopted by clinical laboratories for the contribution to policies aiming to reduce exposure of pesticides.

Preparation and characterization of sodium dodecyl sulfate doped polypyrrole solid phase micro extraction fiber and its application to endocrine disruptor pesticide analysis.

A robust in house solid-phase micro extraction (SPME) surface has been developed for the headspace (HS)-SPME determination of endocrine disruptor pesticides, namely, Chlorpyrifos, Penconazole, Procymidone, Bromopropylate and Lambda-Cyhalothrin in wine sample by using sodium dodecylsulfate doped polypyrrole SPME fiber. Pyrrole monomer was electrochemically polymerized on a stainless steel wire in laboratory conditions in virtue of diminishing the cost and enhancing the analyte retention on its surface to exert better selectivity and hence the developed polymerized surface could offer to analyst to exploit it as a fiber in headspace SPME analysis. The parameters, mainly, adsorption temperature and time, desorption temperature, stirring rate and salt amount were optimized to be as 70°C and 45min, 200°C, 600rpm and 10gL(-1), respectively. Limit of detection was estimated in the range of 0.073-1.659ngmL(-1) for the pesticides studied. The developed method was applied in to red wine sample with acceptable recovery values (92-107%) which were obtained for these selected pesticides.

Investigation of heavy metal content of Turkish tobacco leaves, cigarette butt, ash, and smoke.

A procedure for the determination of cadmium, copper, manganese, and zinc in Turkish tobaccos, which were of different origins, years, and grades, and in the butt, ash, and smoke, which were obtained by smoking the cigarettes that were prepared manually from the said tobaccos in a smoking apparatus, was devised as proposed. The collected samples were digested by wet ashing technique by using HNO3-HClO4 and were analyzed by flame atomic absorption spectrometry with satisfactory recoveries (94% to 98%). The regression coefficients were above 0.99, and the detection limits were in the range of 0.03-0.12 mg/L(-1). The performance and accuracy of the method was tested by analyzing "Certified Reference Material GBW 08501-Peach Leaves." The determined values were in agreement with the standard values for the heavy metals analyzed. Thus, it was concluded that the developed method could offer a wide range of application for establishing a relationship between the makeup and composition of tobacco plant, products, ash, smoke, and smoking.

Assessment of DFG-S19 method for the determination of common endocrine disruptor pesticides in wine samples with an estimation of the uncertainty of the analytical results.

A gas chromatographic method for the determination of endocrine disruptor pesticides (Chlorpyrifos, Penconazole, Procymidone, Iprodione, Bromopropylate and Lambda-Cyhalothrin) in wine samples is described. A general DFG-S19 method for residual pesticide determination in all kind of food stuff was investigated to simplify and adopt for wine samples in this work. Alternative sample preparation routes were elucidated and compared according to their recovery values. Four different separation techniques were tested and the method employing florosil column after a LLE procedure was applied for wine samples with satisfactory recovery ratios (72-97%). The pesticides were extracted from the sample by cyclohexane-ethyl acetate mixture (1:1 v/v) and cleaned up by florosil column. The regression coefficients were at least 0.99 and relative standard deviations were no higher than 16%. Detection limits were in the range of 0.6-2.9 ng/mL and the relative expanded measurement uncertainties were calculated in the 7-22% range.

Development of a gas chromatographic method for the determination of Chlorpyrifos and its metabolite Chlorpyrifos-oxon in wine matrix.

A reliable method has been developed for the determination of Chlorpyrifos (CP) and its metabolite Chlorpyrifos-oxon (CPO) in wine sample using pulsed splitless technique coupled with gas chromatography by using electron capture detector. In this study, a quick, easy and cheap sample preparation method (QuEChERS) based on liquid extraction with acetonitrile, followed by dispersive solid phase extraction using primary secondary amine was tested for the separation and quantification of CP and CPO in wine samples. The accuracy of the developed method was tested upon recovery studies and it was calculated as (92.3 ± 18.2)% for CP and (96.6 ± 16.1)% for CPO. LOD and LOQ values of CP were found as 0.04 and 0.15 ng/mL and 0.49 and 1.62 ng/mL for CPO respectively. By using the pulsed splitless injection mode, the sensitivity of the determination of CP and its metabolite CPO in wine samples was improved compared to splitless technique. CP content of analyzed wine sample was found as 2.05 ± 0.15 ng/mL with a RSD of 7.6% and CPO content was found as 4.99 ± 0.15 ng/mL with a RSD of 3.0% (n=3). The expanded measurement uncertainties were calculated as 17% and 6% for CP and CPO, respectively.