Sono-assisted photocatalytic degradation of ciprofloxacin in aquatic media using g-C3N4/MOF-based nanocomposite under visible light irradiation.

This research study is centered on the sono-assisted photocatalytic degradation of a well-known antibiotic (ciprofloxacin; CIP) in aquatic media using a g-C3N4/NH2-UiO-66 (Zr) catalyst under visible light irradiation. Initially, the catalyst was prepared by a simple method, and its physiochemical features were thoroughly analyzed by XRD, FT-IR, FE-SEM, EDX, EDS-Dot-Mapping, and UV-Vis analytical techniques. After that, the impact of several influential factors affecting the performance of the applied sono-assisted photocatalytic process such as the initial concentration of CIP, solution pH, catalyst dosage, light intensity, and ultrasound power was fully assessed, and the optimal conditions were established. After 75 min of the sono-assisted photocatalytic treatment, the complete degradation of CIP (10 mg/L) was accomplished under the condition as follows: g-C3N4/NH2-UiO-66 (Zr), 0.6 g/L; pH, 5.0, and ultrasound power, light intensity 75 mw/cm2, 200 W/m2. Meanwhile, the photocatalytic degradation of CIP followed the pseudo-first-order kinetic model. In addition, the scavenger experiments demonstrated that OH˚ and O2°- radicals played a key role in the sono-assisted photocatalytic degradation process. It is also acknowledged that the applied catalyst was reused for five consecutive runs with a minor loss observed in its degradation efficiency. In a further experiment, a significant synergistic effect with regard to the degradation of CIP was observed once all three major parameters (visible light, ultrasound waves, and catalyst) were used in combination compared to each used alone. To sum up, it is thought that the integration of g-C3N4/MOF-based catalyst, ultrasound waves, and visible light irradiation could be potentially applied as a promising strategy for the degradation of various pharmaceuticals on account of high degradation performance, simple operation, excellent reusability, and eco-friendly approach.

A new MOF-based modified adsorbent for the efficient removal of Hg(ii) ions from aqueous media: isotherms and kinetics.

Herein, a new MOF-based modified adsorbent for the efficient removal of Hg(ii) ions from water media was successfully prepared. Initially, a MOF nanocomposite was synthesized and applied as an efficient adsorbent for the removal of the target heavy metal ion. Following the synthesis, the MOF-based modified adsorbent was identified and characterized by SEM, XRD and FT-IR analytical instruments. The impact of several key variables such as pH of aqueous solution, adsorbent dosage, contact time, and initial concentration of the analyte of interest on the adsorption efficiency was also investigated in detail. Under the optimal conditions established (pH, 3; dose of adsorbent, 0.4 g L-1; contact time, 40 min and the analyte's concentration of 1 mg L-1) the removal efficiency of 96.3% for Hg(ii) was obtained. The results of the studies on the isotherm and kinetics of adsorption revealed that the adsorption process of Hg(ii) matched with the Langmuir isotherm (R2 > 0.990) and the pseudo 2nd-order kinetic models (R2 > 0.998). Additionally, reuse of the applied adsorbent for five consecutive tests exhibited a small percentage of drop (about 8%) in the removal efficiency of the target ion. Finally, the results indicated that the MOF-based modified compound could be potentially applied as a highly efficacious adsorbent for the discharge of Hg(ii) from aquatic media.

Efficient removal of oxytetracycline antibiotic from aqueous media using UV/g-C3N4/Fe3O4 photocatalytic process.

Residual pharmaceuticals in the environment are a class of emerging pollutants that endanger human health. Tetracycline's family, including oxytetracycline (OTC), are known as one of the most produced and consumed antibiotics worldwide. The g-C3N4/Fe3O4 nanocomposite with high level of catalytic efficiency features suitable performance in water/wastewater treatment. Therefore, in the present study, this nanocomposite was applied to remove the oxytetracycline from the aqueous environment. In this research study, g-C3N4/Fe3O4 nanocomposite (serving as catalyst) was initially synthesized by a simple hydrothermal method. The effect of key operating parameters such as initial solution pH, dose of catalyst, contact time and initial concentration of OTC in aqueous solutions was investigated under UV irradiation. In addition, COD and TOC tests, the kinetics and the effect of radical scavengers on the applied photocatalytic process were all evaluated. The maximum removal efficiency of OTC (99.8 %) was achieved under the following conditions: neutral solution pH 7; catalyst dose, 0.7 g/L; and an initial OTC concentration of 5 mg/L. The data showed that the kinetics of the reaction followed the first-order model with R2 of 0.9755. The respective COD and TOC efficiency values for the applied photocatalytic process were determined to be 87 and 59 %, respectively. In addition, the lowest removal efficiency of OTC was observed in the presence of tert-butanol radical scavengers, and OH radicals played a main role. The UV/g-C3N4/Fe3O4 photocatalytic process proved to be highly efficient for the removal of OTC antibiotic and could be potentially applied for the removal of other pollutants from aqueous solutions.

Utilization of the copper recovered from waste printed circuit boards as a metal precursor for the synthesis of TiO2/magnetic-MOF(Cu) nanocomposite: Application in photocatalytic degradation of pesticides in aquatic solutions.

In this study, a number of leaching solutions (H2SO4, CuSO4 and NaCl) and an electrochemical method were used together for the separation of Cu from waste printed circuit boards. Secondly, the magnetic-MOF(Cu) was synthesized using the Cu recovered from waste printed circuit boards. Thereafter, TiO2/mag-MOF(Cu) composite was prepared and its photocatalytic activity was assessed in the photo degradation of two prominent organophosphorus pesticides, namely malathion (MTN) and diazinon (DZN). The catalytic structure of the MOF-based composite was fully characterized by various analyses such as XRD, SEM, EDAX, FT-IR, VSM and UV-vis. The obtained analyses confirmed the successful synthesis of TiO2/mag-MOF(Cu) composite. The synthesized composite exhibited highly efficient in the degradation of both pollutants under the following conditions: pH 7, contaminant concentration 1 mg/L, the catalyst dosage of 0.4 g/L, visible light intensity 75 mW/cm2 and reaction time of 45 min. First order kinetic model was best suited with the experimental results (R2: 0.97-0.99 for different MTN and DZN concentrations). Trapping studies revealed that superoxide radicals (O2•-) played an important role during the degradation process. Furthermore, the catalyst demonstrated a superb recovery as well as high stability over five cyclic runs of reuse. In addition, the total organic carbon (TOC) analysis showed over 83% and 85% mineralization for MTN and DZN, respectively. The combined system of TiO2/mag-MOF(Cu)/Vis also exhibited a great level of efficiency and feasibility in the treatment of tap water and treated wastewater samples. It is concluded that TiO2/mag-MOF(Cu) could be used as an excellent catalyst for the photodegradation of MTN and DZN in aqueous solution.

Application of a modified MWCNT-based d-µSPE procedure for determination of bisphenols in soft drinks.

Herein, a facile dispersive micro-solid phase extraction (d-µSPE) procedure using carboxylated multi-walled carbon nanotubes modified with silver nanoparticles (Ag/MWCNTs-COOH) was successfully developed for the adsorption and subsequent determination of low levels of two well-known contaminants, namely bisphenol A and S (BPA and BPS) in water and soft drink samples. The detection and measurement of the above-mentioned compounds were performed by HPLC-UV instrument. The applied d-µSPE procedure has several advantages such as rapidity, high degree of sensitivity, precision and efficiency. A combination of polar/non-polar interactions seems to play a key role in the adsorption process. Under the optimized conditions, the calibration curves were linear over the concentration range of 1-500 µg/L for the both targets. The practical limit of quantifications (LOQ) for the both analytes were determined to be 1.0 µg/L. The average relative recoveries obtained from the fortified samples varied between 92 and 110% with the relative standard deviations (RSD%) of 2.9-9.5%.

Efficient photocatalytic degradation of metronidazole from aqueous solutions using Co/g-C3N4/Fe3O4 nanocomposite under visible light irradiation.

Herein, the efficient degradation of a highly consumed antibiotic known as metronidazole (MNZ) in aqueous solutions using Co/g-C3N4/Fe3O4 nanocomposite under visible light irradiation was accomplished. Initially, the photocatalyst (Co/g-C3N4/Fe3O4) was synthesized by a simple hydrothermal method and then characterized by several analytical techniques, namely EDS, SEM, XRD, UV-vis DRS, and FTIR. The efficiency of the synthesized photocatalyst with regard to the degradation of the studied antibiotic (MNZ) under visible light irradiation was fully evaluated. The influential operational parameters affecting the efficiency of the degradation process such as pH (2-10), nanocomposite dosage (0.2-1 g/L), MNZ concentration (5-20 mg/L), and irradiation time (0-80 min) were optimized. The results revealed that the maximum degradation efficiency for MNZ was obtained under the following conditions: irradiation time of 60 min, pH = 8, MNZ concentration of 5 mg/L, and photocatalyst dosage of 0.7 g/L. In addition, the degradation of MNZ followed the pseudo-first-order kinetic model. The best rate constant (k) value was determined to be 0.0102 min-1 with the correlation coefficient (R2) of 0.992. According to the results of the quenching tests, it was found out that hydroxyl radicals (OH°) were the main species responsible for the MNZ degradation. Furthermore, the applied photocatalyst (Co/g-C3N4/Fe3O4) exhibited a high level of recovery and stability after five cycles of reuse. Co/g-C3N4/Fe3O4/Vis system exhibited an excellent performance in the treatment of wastewater and real water samples. Finally, it was concluded that the synthesized nanocomposite could be potentially used as a promising and suitable photocatalyst in the degradation of other antibiotics.

Synthesis and application of g-C3N4/Fe3O4/Ag nanocomposite for the efficient photocatalytic inactivation of Escherichia coli and Bacillus subtilis bacteria in aqueous solutions.

Contamination of water with bacteria is one of the main causes of waterborne diseases. The photocatalytic method on the basis of bacterial inactivation seems to be a suitable disinfectant due to the lack of by-products formation. Herein, g-C3N4/Fe3O4/Ag nanocomposite combined with UV-light irradiation was applied for the inactivation two well-known bacteria namely, E. coli and B. subtilis. The nanocomposite was prepared by a hydrothermal method, and subsequently it was characterized by XRD, FT-IR, SEM, EDX and PL analyses. The optimum conditions established for the inactivation of both bacteria were as follows: nanocomposite dosage 3 g/L and bacterial density of 103 CFU/mL. In the meantime, the efficient inactivation of E. coli and B. subtilis took 30 and 150 min, respectively. The results also revealed that inactivation rate dropped with an increase in the bacterial density. It is also pointed out that OH˚ was found out to be the main radical species involved in the inactivation process. Finally, the kinetic results indicated that the inactivation of E. coli and B. subtilis followed the Weibull model. It is concluded that C3N4/Fe3O4/Ag nanocomposite along with UV-light irradiation is highly effective in inactivating E. coli and B. subtilis bacteria in the aqueous solutions.

A global systematic review, meta-analysis and health risk assessment on the quantity of Malathion, Diazinon and Chlorpyrifos in Vegetables.

It is widely believed that an increasing trend in the production and consumption of vegetables has led to a dramatic rise in the use of pesticides potentially threatening the health of consumers around the world. This systematic study along with meta-analysis has mainly centered on the evaluation of the quantity of three well-known pesticides namely, Malathion (MLT), Diazinon (DZN) and Chlorpyrifos (CPF) in vegetables. In this regard, a comprehensive literature search has been performed over the last decade (January 1, 2011 to June 21, 2020) within the scientific databases including PubMed, Web of Science, and Scopus. Of 1239 articles identified through the database screening, 22 plus 37 data report were retained and included in the meta-analysis phase. Additionally, the probabilistic human health risks for the consumers due to the intake of CPF, DZN and MLT from eating vegetables were estimated by the Monte Carlo Simulated (MCS) method. According to the findings, the maximum quantities of MLT, DZN and CPF in the vegetables were observed in Pakistan (222 µg/kg, 95%CI = 214.94-229.08), Thailand (245.00, 95% CI = 235.2-254.8) and South Korea (440 µg/kg, 95% CI = 437.19-442.81), while the lowest concentration levels were reported in China (1.7 µg/kg, 95% CI = 1.56-1.84), Poland (0.57, 95% CI = 0.46-0.68) and Poland (5.78 µg/kg, 95% CI = 4.40-7.12), respectively. The results of the Egger's and the Begg's tests revealed that no bias with regard to the potential publication was observed. Finally, non-carcinogenic risk assessment results demonstrated that the exposure to the studied pesticides thorough vegetables consumption could not threaten the health of consumers.

Littered cigarette butt as a well-known hazardous waste: A comprehensive systematic review.

Most of cigarettes used in the world have filters. Following smoking, the cigarette butts (CBs) are often littered as wastes in the environment. CBs generally contain several toxic substances that are trapped in the cigarette filter. Filters are made of non-biodegradable materials and remain in the environment for a long time. Within this study, it is attempted to systematically review the articles on CBs and find out the answers to the problems associated with the factors including quantity, distribution, origin and toxicity of CBs in the environment. It is estimated that approximately 5.5 trillion cigarettes are being produced annually in the world and the CB wastes would reach 1.2 million tons and increase by 50% until 2025. CBs contain thousands of dangerous chemicals such as arsenic, benzene, hydrogen cyanide, PAHs, pyridine, heavy metals and so forth. It is also believed that eachCB can pollute 1000 liters of water. Given the inadequacy of mechanical equipment as well as the cost of collecting these wastes, there should be a special focus on these items as follows: producing cigarettes with degradable filters, reducing the rate of smoking in the world, reducing the toxic and chemical substances in the process of plant growth, processing and production of cigarettes, training people to discard CBs properly, putting legal and financial pressures on cigarettes production, and the last but not least, providing effective solutions for collecting CBs.

Dispersive solid-phase extraction of selected nitrophenols from environmental water samples using a zirconium-based amino-tagged metal-organic framework nanosorbent.

This study has centered on the establishment of an efficient, simple and reliable dispersive solid-phase extraction method followed by an accurate trace determination of selected nitrophenols as a class of compounds with high toxicity and low degradability. To achieve the above goal, a zirconium-based amino-tagged metal-organic framework nanosorbent was synthesized, characterized and eventually employed for the extraction of two nitrophenols from various environmental water samples. Once the extraction of analytes had occurred, they were desorbed from the metal-organic framework sorbent using an appropriate mixed solvent followed by high-performance liquid chromatography with ultraviolet detection. Under the optimal extraction conditions, the calibration curves for the analytes were linear over the concentration range of 1-200 µg/L. The accuracy of the method was tested by the relative recovery experiments on the fortified real samples with the results falling within the range of 91 to 106%, while the corresponding precisions varied in the span of 4.6-9.0%. Based on a signal-to-noise ratio of 3, the method detection limits were determined to be 0.5 µg/L for both analytes.

Application of a surfactant-assisted dispersive liquid-liquid microextraction method along with central composite design for micro-volume based spectrophotometric determination of low level of Cr(VI) ions in aquatic samples.

A fast, simple, low cost surfactant-assisted dispersive liquid-liquid microextraction method along with central composite design for the determination of low level of Cr(VI) ions in several aquatic samples has been developed. Initially, Cr(VI) ions present in the aqueous sample were readily reacted with 1,5­diphenylcarbazide (DPC) in acidic medium through complexation. Sodium dodecyl sulfate (SDS), as an anionic surfactant, was then employed as an ion-pair agent to convert the cationic complex into the neutral one. Following on, the whole aqueous phase underwent a dispersive liquid-liquid microextraction (DLLME) leading to the transfer of the neutral complex into the fine droplet of organic extraction phase. A micro-volume spectrophotometer was used to determine Cr(VI) concentrations. Under the optimized conditions predicted by the statistical design, the limit of quantification (LOQ) obtained was reported to be 5.0 µg/L, and the calibration curve was linear over the concentration range of 5-100 µg/L. Finally, the method was successfully implemented for the determination of low levels of Cr(VI) ions in various real aquatic samples and the accuracies fell within the range of 83-102%, while the precision varied in the span of 1.7-5.2%.

Application of dispersive solid phase extraction based on a surfactant-coated titanium-based nanomagnetic sorbent for preconcentration of bisphenol A in water samples.

Herein, a new extraction method employing a surfactant-coated titanium-based nanomagnetic sorbent for the effective extraction of bisphenol A (BPA) from various water samples was developed. Initially, the titanium-based nanomagnetic particles (Fe3O4/SiO2/TiO2 NPs) were successfully synthesized and subsequently characterized by Transmission Electron Microscopy and Fourier-transform infrared spectrometry. Two cationic surfactants were then incorporated into the particles to form a new sorbent for enhancing the extraction of BPA through micelle formation. Once the analyte was extracted, it was desorbed from the sorbent and quantified by high performance liquid chromatography with ultra violet detection (HPLC-UV). Various factors affecting the extraction and desorption of the analyte were investigated in detail and the optimum conditions established. Under these established conditions, the calibration curve was linear over the concentration range of 1-500ng/mL. The limit of detection was determined to be 0.5ng/mL based on a signal-to-noise ratio (S/N)=3. To test the extraction efficiency, the method was applied to various real water samples that were spiked. The average recoveries obtained from the spiked samples ranged between 92-105% with relative standard deviations of 3.2-7.8%. Finally, the approach was determined to be effective for BPA environmental analysis.

Contaminants of emerging concern: a review of new approach in AOP technologies.

The presence of contaminants of emerging concern (CECs) such as pharmaceuticals and personal care products (PPCPs), endocrine-disrupting compounds (EDCs), flame retardants (FRs), pesticides, and artificial sweeteners (ASWs) in the aquatic environments remains a major challenge to the environment and human health. In this review, the classification and occurrence of emerging contaminants in aquatic environments were discussed in detail. It is well documented that CECs are susceptible to poor removal during the conventional wastewater treatment plants, which introduce them back to the environment ranging from nanogram per liter (e.g., carbamazepine) up to milligram per liter (e.g., acesulfame) concentration level. Meanwhile, a deep insight into the application of advanced oxidation processes (AOPs) on mitigation of the CECs from aquatic environment was presented. In this regard, the utilization of various treatment technologies based on AOPs including ozonation, Fenton processes, sonochemical, and TiO2 heterogeneous photocatalysis was reviewed. Additionally, some innovations (e.g., visible light heterogeneous photocatalysis, electro-Fenton) concerning the AOPs and the combined utilization of AOPs (e.g., sono-Fenton) were documented.

Application of a dispersive solid-phase extraction method using an amino-based silica-coated nanomagnetic sorbent for the trace quantification of chlorophenoxyacetic acids in water samples.

Herein, an amino-based silica-coated nanomagnetic sorbent was applied for the effective extraction of two chlorophenoxyacetic acids (2-methyl-4-chlorophenoxyacetic acid and 2,4-dichlorophenoxyacetic acid) from various water samples. The sorbent was successfully synthesized and subsequently characterized by scanning electron microscopy, X-ray diffraction, and Fourier-transform infrared spectroscopy. The analytes were extracted by the sorbent mainly through ionic interactions. Once the extraction of analytes was completed, they were desorbed from the sorbent and detected by high-performance liquid chromatography with ultraviolet detection. A number of factors affecting the extraction and desorption of the analytes were investigated in detail and the optimum conditions were established. Under the optimum conditions, the calibration curves were linear over the concentration range of 1-250, and based on a signal-to-noise ratio of 3, the method detection limits were determined to be 0.5 µg/L for both analytes. Additionally, a preconcentration factor of 314 was achieved for the analytes. The average relative recoveries obtained from the fortified water samples varied in the range of 91-108% with relative standard deviations of 2.9-8.3%. Finally, the method was determined to be robust and effective for environmental water analysis.

Application of modified hollow fiber liquid phase microextraction in conjunction with chromatography-electron capture detection for quantification of acrylamide in waste water samples at ultra-trace levels.

Herein, a simple and sensitive method was successfully developed for the extraction and quantification of acrylamide in water samples. Initially, acrylamide was derivatized through a bromination process. Subsequently, a modified hollow-fiber liquid-phase microextraction was applied for the extraction of the brominated acrylamide from a 10-ml portion of an aqueous sample. Briefly, in this method, the derivatized acrylamide (2,3-dibromopropionamide) was extracted from the aqueous sample into a thin layer of an organic solvent sustained in pores of a porous hollow fiber. Then, it was back-extracted using a small volume of organic acceptor solution (acetonitril, 25µl) located inside the lumen of the hollow fiber followed by gas chromatography-electron capture detection (GC-ECD). The optimal conditions were examined for the extraction of the analyte such as: the organic solvent: dihexyl ether+10% tri-n-octyl phosphine oxide; stirring rate: 750rpm; no salt addition and 30min extraction time. These optimal extraction conditions allowed excellent enrichment factor values for the method. Enrichment factor, detection limit (S/N=3) and dynamic linear range of 60, 2ngL-1 and 50-1000ngL-1 to be determined for the analyte. The relative standard deviations (RSD%) representing precision of the method were in the range of 2.2-5.8 based on the average of three measurements. Accuracy of the method was tested by the relative recovery experiments on spiked samples, with results ranging from 93 to 108%. Finally, the method proved to be simple, rapid, and cost-effective for routine screen of acrylamide-contaminated highly-complicated untreated waste water samples.

An ab initio study on the concerted interaction between chalcogen and pnicogen bonds.

We analyzed cooperation between chalcogen-bonding and pnicogen-bonding interactions in XHS···NCH2P···NCY (X = F, Cl; Y = H, OH, NH2, CN and NC) complexes at the MP2/6-311++G** level. These effects were studied in terms of geometric and energetic properties, harmonic frequencies, and nuclear magnetic resonance (NMR). A cooperativity factor was adopted to measure the cooperativity between the two types of interaction in triads based on S-X and P-CN stretching frequencies. The size of the cooperative effect in each complex depends on the strength of S···N and P···N interactions. It is largest for FHSN⋯CH2P⋯NCNH2 and smallest for ClHS⋯NCH2P⋯NCCN and ClHS⋯NCH2P⋯NCNC complexes. The total spin-spin coupling constants across the chalcogen and pnicogen bonds in the ternary complexes are always larger than those in the binary systems. This trend can be also interpreted as a cooperative effect between chalcogen and pnicogen bond interactions. The enhancing mechanism was analyzed in terms of electron redistribution effects in XHS···NCH2P···NCY complexes.

Simultaneous derivatization and extraction of nitrophenols in soil and rain samples using modified hollow-fiber liquid-phase microextraction followed by gas chromatography-mass spectrometry.

A simple and sensitive method based on a modified hollow-fiber liquid-phase microextraction followed by gas chromatography-mass spectrometry has been successfully developed for the extraction and simultaneous derivatization of some nitrophenols (NPs) in soil and rain samples. Microwave-assisted solvent extraction was used for the extraction of NPs from the soil, while the rain sample was directly applied to the previously mentioned method. Briefly, in this method, the analytes were extracted from aqueous samples into a thin layer of organic solvent (dodecane + 10% tri-n-octylphosphine oxide) sustained in the pores of a porous hollow fiber. Then, they were back-extracted using a small volume of organic acceptor solution (25 µl; 10 mg/L N-methyl-N-(trimethylsilyl)trifluoroacetamide, as derivatization reagent, in acetonitrile) that was located inside the lumen of the hollow fiber. Under the optimized extraction conditions, enrichment factors of 255 to 280 and limits of detection of 0.1 to 0.2 µg/L (S/N = 3) with dynamic linear ranges of 1-100 µg/L were obtained for the analytes. The accuracy of the approach was tested by the relative recovery experiments on spiked samples, with results ranging from 93 to 113%. The method was shown to be rapid, cost-effective, and potentially interesting for screening purposes.

Comparison between a high-resolution single-stage Orbitrap and a triple quadrupole mass spectrometer for quantitative analyses of drugs.

The capabilities of a high-resolution (HR), accurate mass spectrometer (Exactive-MS) operating in full scan MS mode was investigated for the quantitative LC/MS analysis of drugs in patients' plasma samples. A mass resolution of 50,000 (FWHM) at m/z 200 and a mass extracted window of 5 ppm around the theoretical m/z of each analyte were used to construct chromatograms for quantitation. The quantitative performance of the Exactive-MS was compared with that of a triple quadrupole mass spectrometer (TQ-MS), TSQ Quantum Discovery or Quantum Ultra, operating in the conventional selected reaction monitoring (SRM) mode. The study consisted of 17 therapeutic drugs including 8 antifungal agents (anidulafungin, caspofungin, fluconazole, itraconazole, hydroxyitraconazole posaconazole, voriconazole and voriconazole-N-oxide), 4 immunosuppressants (ciclosporine, everolimus, sirolimus and tacrolimus) and 5 protein kinase inhibitors (dasatinib, imatinib, nilotinib, sorafenib and sunitinib). The quantitative results obtained with HR-MS acquisition show comparable detection specificity, assay precision, accuracy, linearity and sensitivity to SRM acquisition. Importantly, HR-MS offers several benefits over TQ-MS technology: absence of SRM optimization, time saving when changing the analysis from one MS to another, more complete information of what is in the samples and easier troubleshooting. Our work demonstrates that U/HPLC coupled to Exactive HR-MS delivers comparable results to TQ-MS in routine quantitative drug analyses. Considering the advantages of HR-MS, these results suggest that, in the near future, there should be a shift in how routine quantitative analyses of small molecules, particularly for therapeutic drugs, are performed.

Generic approach for the sensitive absolute quantification of large undigested peptides in plasma using a particular liquid chromatography-mass spectrometry setup.

A generic LC-MS approach for the absolute quantification of undigested peptides in plasma at mid-picomolar levels is described. Nine human peptides namely, brain natriuretic peptide (BNP), substance P (SubP), parathyroid hormone 1-34 (PTH), C-peptide, orexines A and B (Orex-A and -B), oxytocin (Oxy), gonadoliberin-1 (gonadothropin releasing-hormone or luteinizing hormone-releasing hormone, LHRH) and α-melanotropin (α-MSH) were targeted. Plasma samples were extracted via a 2-step procedure: protein precipitation using 1vol of acetonitrile followed by ultrafiltration of supernatants on membranes with a MW cut-off of 30 kDa. By applying a specific LC-MS setup, large volumes of filtrates (e.g., 2×750 µL) were injected and the peptides were trapped on a 1mm i.d.×10 mm length C8 column using a 10× on-line dilution. Then, the peptides were back-flushed and a second on-line dilution (2×) was applied during the transfer step. The refocalized peptides were resolved on a 0.3mm i.d. C18 analytical column. Extraction recovery, matrix effect and limits of detection were evaluated. Our comprehensive protocol demonstrates a simple and efficient sample preparation procedure followed by the analysis of peptides with limits of detection in the mid-picomolar range. This generic approach can be applied for the determination of most therapeutic peptides and possibly for endogenous peptides with latest state-of-the-art instruments.

Tandem use of solid-phase extraction and dispersive liquid-liquid microextraction for the determination of mononitrotoluenes in aquatic environment.

Solid-phase extraction (SPE) in tandem with dispersive liquid-liquid microextraction (DLLME) has been developed for the determination of mononitrotoluenes (MNTs) in several aquatic samples using gas chromatography-flame ionization (GC-FID) detection system. In the hyphenated SPE-DLLME, initially MNTs were extracted from a large volume of aqueous samples (100 mL) into a 500-mg octadecyl silane (C(18)) sorbent. After the elution of analytes from the sorbent with acetonitrile, the obtained solution was put under the DLLME procedure, so that the extra preconcentration factors could be achieved. The parameters influencing the extraction efficiency such as breakthrough volume, type and volume of the elution solvent (disperser solvent) and extracting solvent, as well as the salt addition, were studied and optimized. The calibration curves were linear in the range of 0.5-500 µg/L and the limit of detection for all analytes was found to be 0.2 µg/L. The relative standard deviations (for 0.75 µg/L of MNTs) without internal standard varied from 2.0 to 6.4% (n=5). The relative recoveries of the well, river and sea water samples, spiked at the concentration level of 0.75 µg/L of the analytes, were in the range of 85-118%.