Anti-inflammatory Drugs In Water Samples Research Articles

Preparation of Hypercrosslinked Polymer-Based Sponge and its Application for the Removal of Non-Steroidal Anti-Inflammatory Drugs in Water Samples

Preparation of Hypercrosslinked Polymer-Based Sponge and its Application for the Removal of Non-Steroidal Anti-Inflammatory Drugs in Water Samples

Mixed Matrix Membrane Tip Extraction Coupled with UPLC–MS/MS for the Monitoring of Nonsteroidal Anti-Inflammatory Drugs in Water Samples

An ultra-performance liquid chromatography–tandem mass spectrometry (UPLC–MS/MS) method, in combination with a mixed matrix membrane microextraction method for the quantification of nonsteroidal anti-inflammatory drugs (NSAIDs) in environmental water samples, is reported. The extraction device was prepared by casting well-dispersed polymeric bonded octadecyl (C18) particles in a cellulose triacetate matrix solution onto commercially available 200 μL micropipette tips. The membrane formed contains 25% of the adsorbent loading amount and was firmly attached to the inner wall of the membrane tip. The dynamic extraction was performed by withdrawing and dispensing the sample solution through the tip device for effective analyte adsorption, followed by the analyte desorption process into 40 μL of methanol and acetonitrile (1:1) prior to UPLC–MS/MS analysis. NSAIDs—namely diclofenac, ibuprofen, indoprofen, naproxen and sulindac—were chosen as targeted analytes. Several extraction parameters were comprehensively optimized, including sample pH value, ionic strength, dynamic extraction cycle, desorption solvent and desorption time. The optimized conditions demonstrated a linear range from 0.25 to 500 ng L−1, with correlation coefficients (r2) from 0.9988 to 0.9992 and detection limits ranging from 0.08 to 0.40 ng L−1. The recoveries of the spiked water samples were between 92% and 99% and exhibited excellent precision relative to standard deviations (RSDs ≤ 4.9%), and enrichment factors (EFs) were at 201–249 for the developed approach.

PEG modified column MIL-101(Cr)/PVA cryogel as a sorbent in stir bar solid phase extraction for determination of non-steroidal anti-inflammatory drugs in water samples

In this study, poly(ethylene glycol) (PEG) acted as the porogen to increase the adsorption capacity of the composite MOFs/PVA cryogel. The characterization results demonstrated that the BET surface area of PEG modified MIL-101(Cr)/PVA cryogel obviously increased. The factors influencing the extraction efficiency, such as the ratio of PVA/PEG, the amount of MIL-101(Cr), pH adjustment, effect of salt, extraction and elution time and elution solvent, were studied. MIL-101(Cr)/PVA/PEG cryogel was used as a SB-SPE sorbent for the extraction of five non-steroidal anti-inflammatory drugs (NSAIDs) in environmental water samples. A satisfactory result of methodology validation was obtained. Under the optimum condition, good sensitivity levels were achieved with the limit of detection between 0.011 and 0.035 μg/L, and the analytical method showed good linearity in the range of 0.10–10 μg/L for ketoprofen, naproxen, diclofenac and carprofen and 0.05–5 μg/L for mefenamic acid (r2 ≥ 0.9912). The relative recoveries of the target analytes were in the range from 77.41% to 102.3% with relative standard deviation (RSD) from 1.67% to 9.52%. The MIL-101(Cr)/PVA/PEG composite cryogel has an environmentally friendly fabrication process and higher adsorption capacity comparing with the previously fabricated MIL-101(Cr)/PVA cryogel.

Fabrication of calixarene-grafted bio-polymeric magnetic composites for magnetic solid phase extraction of non-steroidal anti-inflammatory drugs in water samples.

Calixarene framework functionalized bio-polymeric magnetic composites (MSp-TDI-calix) were synthesized and utilized as magnetic solid-phase extraction (MSPE) sorbent for the extraction of non-steroidal anti-inflammatory drugs (NSAIDs), namely indoprofen (INP), ketoprofen (KTP), ibuprofen (IBP) and fenoprofen (FNP), from environmental water samples. MSp-TDI-calix was characterized by FT-IR, XRD, FESEM, EDX, VSM and BET analysis, and the results were compared with Sp-TDI and Sp-TDI-calix. To maximize the extraction performance of MSp-TDI-calix decisive MSPE affective parameters such as sorbent amount, extraction time, sample volume, type of organic eluent, volume of organic eluent, desorption time and pH were comprehensively optimized prior to HPLC-DAD determination. The analytical validity of the proposed MSPE method was evaluated under optimized conditions and the following figures of merit were acquired: linearity with good determination coefficient (R2 ≥ 0.991) over the concentration range of 0.5–500 µg/L, limits of detection (LODs) ranged from 0.06–0.26 µg/L and limits of quantitation (LOQ) between 0.20–0.89 µg/L. Excellent reproducibility and repeatability under harsh environment with inter-day and intra-day relative standard deviations were obtained in the range of 2.5–3.2% and 2.4–3.9% respectively. The proposed method was successfully applied for analysis of NSAIDs in tap water, drinking water and river water with recovery efficiency ranging from 88.1–115.8% with %RSD of 1.6–4.6%.

Fabrication and characterization of metal organic frameworks/ polyvinyl alcohol cryogel and their application in extraction of non-steroidal anti-inflammatory drugs in water samples

A series of novel MOFs/PVA composite cryogel (MIL-101(Cr)/PVA, MIL-100(Fe)/PVA, ZIF-8(Zn)/PVA, MOF-199(Cu)/PVA and MIL-53(Al)/PVA) were fabricated by using a facile and green freeze-thaw approach for the first time. MIL-101(Cr)/PVA cryogel was selected as a VA-SPE sorbent for extraction of four NSAIDs in environmental water samples. The procedures of condition investigation (synthesis and extraction optimization) and characterization were also performed. And a satisfactory result of methodology validation was obtained by making use of HPLC-MS/MS. Under the optimum conditions, good sensitivity levels were achieved with the limits of detection between 0.007 and 0.037 μg L−1, a linearity of 0.10–10 μg L−1 for phenylbutazone, indomethacin, nimesulide and 0.020–2.0 μg L−1 for benorilate (r2 ≥ 0.9934). The relative recoveries of the target analytes were in the range from 78.44% to 105.7% with relative standard deviation (RSD) from 1.33% to 9.85%. In the extraction process, MIL-101(Cr)/PVA cryogel as a whole sheet outperformed the pristine dispersive MIL-101(Cr) in separation from solvent, and the application of cryogel also simplified the operation procedure. Additionally, the combination of PVA with MOFs might strengthen the interaction ability between the sorbent and analytes. This novel pretreatment method had a variety of merits, such as easy operation, high enrichment efficiency and low matrix effect. It looks forward to further optimization or functionalization and application of these MOFs/PVA cryogel in various disciplines.

Magnetic sporopollenin-cyanopropyltriethoxysilane-dispersive micro-solid phase extraction coupled with high performance liquid chromatography for the determination of selected non-steroidal anti-inflammatory drugs in water samples

A facile dispersive-micro-solid phase extraction (D-μ-SPE) method coupled with HPLC for the analysis of selected non-steroidal anti-inflammatory drugs (NSAIDs) in water samples was developed using a newly prepared magnetic sporopollenin-cyanopropyltriethoxysilane (MS-CNPrTEOS) sorbent. Sporopollenin homogenous microparticles of Lycopodium clavatum spores possessed accessible functional groups that facilitated surface modification. Simple modification was performed by functionalization with 3-cyanopropyltriethoxysilane (CNPrTEOS) and magnetite was introduced onto the biopolymer to simplify the extraction process. MS-CNPrTEOS was identified by infrared spectrometrywhile the morphology and the magnetic property were confirmed by scanning electron microscopy (SEM) and vibrating sample magnetometer (VSM), respectively. To maximize the extraction performance of ketoprofen, ibuprofen, diclofenac and mefenamic acid using the proposed MS-CNPrTEOS, important D-μ-SPE parameters were comprehensively optimized. The optimum extraction conditions were sorbent amount, 40 mg; extraction time, 5 min; desorption time; 5 min; sample volume, 15 mL; sample pH 2.0; and salt addition, 2.5% (w/v). The feasibility of the developed method was evaluated using spiked tap water, lake water, river water and waste water samples. Results showed that ketoprofen and ibuprofen were linear in the range of 1.0–1000 μg L−1 whilst diclofenac and mefenamic acid were linear in the range 0.8–500 μg L−1. The results also showed good detection limits for the studied NSAIDs in the range of 0.21–0.51 μg L−1 and good recoveries for spiked water samples in the range of 85.1–106.4%. The MS-CNPrTEOS proved a promising dispersive sorbent and applicable to facile and rapid assay of NSAIDs in water samples.

Membrane protected C18 coated stir bar sorptive extraction combined with high performance liquid chromatography-ultraviolet detection for the determination of non-steroidal anti-inflammatory drugs in water samples

By wrapping a porous membrane around the coated stir bar, a novel membrane protected stir bar sorptive extraction (MPSBSE) was proposed to filter out the high molecular weight interferences (such as humic acid), resulting in the analysis of real environmental water samples without filtration or centrifugation. Hydrophilic and hydrophobic membranes were compared and hydrophobic polytetrafluoroethylene (PTFE) membrane impregnated with methanol was employed to protect the C18 coated stir bar. The impregnated methanol improves the transfer of target analytes from sample solution to the pores and lumen of the membrane, and then to the coated stir bar inside. By combining C18-MPSBSE with HPLC-UV, a method was proposed for the direct determination of two common non-steroidal anti-inflammatory drugs, Ketoprofen (KEP) and Naproxen (NAP) in complex water samples. Under the optimized conditions, the limit of detections of KEP and NAP are 7.89, 9.52μgL−1 in the waste water and 7.69, 6.90μgL−1 in the pure water, respectively, with the enrichment factors of 32.0–49.1-fold. Besides, the lifetime of the prepared C18 stir bar protected by PTFE membrane (50 times) is longer than that of C18 stir bar without membrane protection (20 times), indicating that the friction damage of SBSE coating during extraction was effectively avoided. The developed method was successfully applied to the analysis of KEP and NAP in domestic sewage and campus lake water samples.

New Sol–Gel Hybrid Material in Solid Phase Extraction Combined with Liquid Chromatography for the Determination of Non-steroidal Anti-inflammatory Drugs in Water Samples

A new sol–gel hybrid methyltrimethoxysilane–mercaptopropyltrimethoxysilane (MTMOS–MPTMS) was synthesized, characterized and applied as sorbent for solid phase extraction (SPE) of selected non-steroidal anti-inflammatory drugs (NSAIDs) as target analytes. Analysis was performed using high performance liquid chromatography with UV detection at 234 nm. Under the optimum extraction conditions (100 mg sorbent, 20 mL sample loading volume and 7 mL acetonitrile as desorption eluent), the method using the sol–gel organic–inorganic hybrid MTMOS–MPTMS as SPE sorbent showed good linearity in the range of 1–550 μg L−1, good repeatability (RSD 1.4–6.0 %, n = 3), low limits of detection at S/N = 3 (0.10–0.29 μg L−1) and limit of quantification (0.33–0.89 μg L−1, S/N = 10). The developed MTMOS–MPTMS SPE method was successfully applied to real sample analysis of the selected NSAIDs from several water samples. In-house MTMOS–MPTMS sol–gel hybrid material was able to extract the selected NSAIDs (diclofenac sodium, ketoprofen, mefenamic acid) in water samples comparable to commercial cyano sorbent. Excellent relative recoveries (RR) and RSDs of the NSAIDs were obtained from the various water samples (RR: 85.8–104.2 %, RSDs 1.2–6.0 %, n = 3) using the MTMOS–MPTMS SPE sorbent. The sol–gel hybrid MTMOS–MPTMS SPE sorbent demonstrates promising potential as an alternative inexpensive extraction sorbent for NSAIDs from water samples and with higher selectivity.

Determination of non-steroidal anti-inflammatory drugs in water samples by solid-phase microextraction based sol–gel technique using poly(ethylene glycol) grafted multi-walled carbon nanotubes coated fiber

In this study, poly(ethylene glycol) (PEG) grafted multi-walled carbon nanotubes (PEG-g-MWCNTs) were synthesized by the covalent functionalization of MWCNTs with hydroxyl-terminated PEG chains. PEG-g-MWCNTs was used as a novel stationary phase to prepare the sol–gel solid-phase microextraction (SPME) fiber in combination with gas chromatography–flame ionization detector (GC–FID) for the determination of ibuprofen, naproxen and diclofenac in real water samples.Some parameters which influencing the extraction efficiency were such as desorption temperature and time, extraction temperature and time, pH, salt effect and stirring speed that were investigated and optimized. Under the optimal conditions, the method detection limits (S/N=3) were in the range of 0.007–0.03ngmL−1 and the limits of quantification (S/N=10) between 0.05 and 0.07ngmL−1. The relative standard deviations (RSDs) for one fiber (repeatability) (n=5) were obtained from 5.9 up to 8.1% and between fibers or batch to batch (n=3) (reproducibility) in the range of 7.2–9.1%. The developed method was successfully applied to real water samples while the relative recovery percentages obtained for the spiked water samples at 0.2ngmL−1 were from 84 to 107%.

Determination of widely used non-steroidal anti-inflammatory drugs in water samples by in situ derivatization, continuous hollow fiber liquid-phase microextraction and gas chromatography-flame ionization detector

The aim of this study was to develop an analytical procedure which allows the quantification of pharmaceuticals in water at the ng L −1 level. Hence, it is reported research on the application of a rapid, inexpensive and simple continuous hollow fiber liquid-phase micro extraction (CHF-LPME) for the pre-concentration and determination of non-steroidal anti-inflammatory drugs (NSAIDs), such as ibuprofen (IBP), naproxen (NAP), and ketoprofen (KEP), in wastewater. In this method, a 2.50 cm end sealed piece of a polypropylene hollow fiber was immersed into the organic solvent, octanol, for 30 s. After solvent impregnation with the pores of the fiber, the excess amounts of solvent were removed from inside the fiber, and 4.0 μL of octanol, as the acceptor phase, was injected into the fiber carefully. The fiber was settled using a microsyringe into a 10.0 mL glass test tube, and 20.00 mL of the aqueous solution (the donor phase), was circulated by a pump around it. After analyte extraction for an optimized period of time (20 min), 2 μL of the organic solvent was withdrawn into the microsyringe and injected into the GC-FID for further analysis. Finally, based on the optimized analytical conditions, the method was linear in the range of 2.5–500 ng L −1. The limits of detection were 1–2 ng L −1. Repeatability of this method on an intra-day scale was 3.4–10.2% (RSD%). NSAIDs have been detected in several municipal wastewater samples, and the concentration range was 9.0–19.0 ng L −1.

Counter-flow electrokinetic supercharging for the determination of non-steroidal anti-inflammatory drugs in water samples

Electrokinetic supercharging (EKS) has been used in the last few years as a powerful tool for separation and on-line preconcentration of different types of analytes. We have developed a valuable modification for EKS system, namely counter-flow EKS (CF-EKS) and applied it for the separation and on-line preconcentration of seven non-steroidal anti-inflammatory drugs (NSAIDs) in water samples. In CF-EKS, a hydrodynamic counter-flow is applied during electrokinetic injection of the analytes within the EKS system. This counter-flow minimises the introduction of the sample matrix into the capillary, allowing longer injections to be performed. Careful choice of the optimum counter-flow as well as the optimum injection voltage allowed the sensitivity to be enhanced by 11,800-fold, giving limits of detection (LODs) of 10.7–47.0 ng/L for the selected NSAIDs. The developed method was validated and then applied for the determination of the studied NSAIDs in drinking water as well as wastewater samples from Hobart city.

Electrokinetic supercharging for on-line preconcentration of seven non-steroidal anti-inflammatory drugs in water samples

The development of new sensitive methods for the analysis of non-steroidal anti-inflammatory drugs (NSAIDs) in water samples is of great importance. In this work, seven NSAIDs were separated within 9 min using 15 mM sodium tetraborate (pH 9.2) containing 0.1% (w/v) hexadimethrine bromide (HDMB) and 10% (v/v) methanol. Field-amplified sample injection (FASI) was examined and found to improve the detection limits by 200-fold providing detection limits of 0.6–2.0 μg/L, but these are insufficient for the determination of NSAIDs as environmental pollutants in water samples. To improve the sensitivity further, electrokinetic supercharging (EKS) was examined. The optimum EKS method involved hydrodynamic injection leading electrolyte (100 mM NaCl, 30 s, 50 mbar), electrokinetic injection of the sample (200 s, −10 kV) and finally injection of the terminating electrolyte (100 mM 2-(cyclohexylamino) ethanesulphonic acid, CHES, 40 s, 50 mbar). With this method, the sensitivity was improved by 2400-fold giving detection limits of 50–180 ng/L. The developed method was validated and then applied to the analysis of wastewater samples from a local sewage treatment plant. The detection limits were found to increase by approximately 10-fold, however, this is still lower than levels previously found in wastewater samples from European and Mediterranean cities. The proposed method has the advantage of simplicity and achieving sensitivity through high-preconcentration power without the use of off-line chromatographic sample cleanup.

Determination of anti-inflammatory drugs in water samples, by in situ derivatization, solid phase microextraction and gas chromatography–mass spectrometry

A new analytical method for the determination of non-steroidal acidic anti-inflammatory drugs in water samples is described. These compounds are used as anti-inflammatory, antipyretic and analgesic drugs in human health care and in veterinary applications. Analytical procedure involves in situ derivatization of analytes to their methyl esters with dimethyl sulphate, headspace sampling using solid-phase microextraction (SPME), and gas chromatography–mass spectrometry (GC–MS). The effects of pH, ionic strength, extraction time, SPME fibre, extraction temperature as well as derivatization conditions were studied. Methyl esters were extracted with a fused-silica fibre coated with 100 μm polydimethylsiloxane. Response was linearly dependent on concentration in the range 0.1–10.0 ng mL −1. Detection limits were achieved at the level of 0.3–2.9 ng L −1. Derivatization-SPME/GC–MS analysis yielded good precision (R.S.D. between 7.9 and 17.2%). The method was validated by analysis of spiked matrix samples.

Analysis of Nonsteroidal Anti-inflammatory Drugs in Water Samples Using Microemulsion Electrokinetic Capillary Chromatography Under pH-Suppressed Electroosmotic Flow with an On-Column Preconcentration Technique

Microemulsion electrokinetic capillary chromatography (MEEKC) in a suppressed electroosmotic flow (EOF) strategy was investigated for analysing a group of nonsteroidal anti-inflammatory drugs (NSAIDs) in water samples. The EOF was effectively suppressed with an acidic buffer as the aqueous phase. Four water immiscible solvents, oils (n-heptane, n-octane, ethyl acetate and di-n-butyl tartrate) and three organic solvents (methanol, 2-propanol and acetonitrile) were tested to optimise the pseudostationary phase and to obtain efficient separations. The optimum microemulsion background electrolyte (BGE) solution consisted of 0.8% (w/w) n-heptane, 6.6 (w/w) butan-1-ol, 15.0% (w/w) acetonitrile, 3.3% (w/w) sodium dodecyl sulfate (SDS), and 74.3% (w/w) of 25 mM sodium phosphate at pH 2.5. Stacking with reverse migrating pseudostationary phase (SRMP) was applied to enhance the concentration sensitivity of the NSAIDs. When this preconcentration technique was used, the sample stacking and the separation processes took place successively with the same voltage without an intermediate polarity switching step. Detection limits (LODs) in the order of 5–15 µg L−1 for the NSAIDs were obtained using SRMP for standard solutions. The developed method was validated for the analysis of NSAIDs in tap water samples by combining an off-line solid-phase extraction (SPE) step and the on-column preconcentration technique SRMP. The LODs were in the 100–230 ng L−1 range.

Determination of nonsteroidal antiinflammatory drugs in water samples using liquid chromatography coupled with diode‐array detector and mass spectrometry

An analytical method for the determination of trace levels of six different nonsteroidal antiinflammatory drugs (NSAIDs) in water samples has been developed and validated. Environmentally relevant pharmaceuticals were chosen according to human consumption in Poland. Final analysis of the target compounds was performed by RP LC-diode-array detection-MS, whereas sample preparation included an SPE step. For this SPE step, a number of packing materials, such as LiChrolut RP-18, calixarene, Strata-X, BAKERBOND Narc-2, BAKERBOND Polar Plus, BAKERBOND styrene divinylbenzene-1, and Discovery DSC-18, were used, and their respective advantages and disadvantages in this study were discussed. The RP-18 phase was found to be the most retentive for all analytes. The detection limits for compounds in surface waters were varied from 0.005 for diflunisal to 0.095 microg/L for ibuprofen. The average recoveries of NSAIDs from the surface water samples ranged from 80 up to 103%. RSD value is relatively low (from 4% for fenoprofen up to 8% for ibuprofen). The performance of the method was tested with several environmental water samples.

Application of strategic sample composition to the screening of anti-inflammatory drugs in water samples using solid-phase microextraction

The usefulness of the strategically designed sample composition (SSC) methodology for the screening of four anti-inflammatory drugs (ibuprofen, naproxen, tolfenamic acid and diclofenac) in water samples is demonstrated. Assuming that in screening campaigns only a limited number of the samples are contaminated with the analytes, the proposed approach allows the reliable identification of the contaminated specimens and the approximate estimation of their concentrations, with a 50% reduction in the total number of processed samples. To achieve this, a limited number of composite samples are built from the individual specimens. Automatic preparation of composite samples avoids human mistakes during this time-consuming and tedious operation, increasing the reliability of the predictions. In this work, a low-cost automatic device able to mix the individual specimens in the proportions indicated in the composition matrix is used. Moreover, the efficiency of evolutionary algorithms to predict the concentrations of the anti-inflammatory drugs in ultrapure and river water samples, artificially polluted in the laboratory and their robustness against large errors during the analysis of the composite samples, are evaluated.

Solid-phase microextraction with on-fiber derivatization for the analysis of anti-inflammatory drugs in water samples

A sensitive and solvent-free procedure for the determination of non-steroidal acidic anti-inflammatory drugs in water samples was optimized using solid-phase microextraction (SPME) followed by on-fiber silylation of the acidic compounds and gas chromatography–mass spectrometry (GC–MS) determination. Microextraction was carried out directly over the filtered water samples using a polyacrylate fiber. Derivatization was performed placing the SPME fiber, loaded with the extracted analytes, in the headspace of a vial containing 50 μl of N-methyl- N-( tert-butyldimethylsilyl)-trifluoroacetamide (MTBSTFA). Derivatives were desorbed for 3 min in the GC injector. Influence of several parameters in the efficiency of microextraction (volume of sample, time, pH, type of fiber coating, etc.) and derivatization steps (time, temperature and volume of MTBSTFA) was systematically investigated. In the optimal conditions an excellent linearity over three orders of magnitude and quantification limits at the ng/l level (from 12 to 40 ng/l) were achieved. The proposed method was applied to the determination of acidic compounds in sewage water and results compared to those obtained using solid-phase extraction (SPE) followed by the derivatization of the compounds in the organic extract of the solid-phase extraction cartridge.