Determination Of Sulfonamides Research Articles

A new ionic liquid surface-imprinted polymer for selective solid-phase-extraction and determination of sulfonamides in environmental samples.

Toward improving the selective adsorption performance of molecularly imprinted polymers in strong polar solvents, in this work, a new ionic liquid functional monomer, 1-butyl-3-vinylimidazolium bromide, was used to synthesize sulfamethoxazole imprinted polymer in methanol. The resulting molecularly imprinted polymer was characterized by Fourier transform infrared spectra and scanning electron microscopy, and the rebinding mechanism of the molecularly imprinted polymer for sulfonamides was studied. A static equilibrium experiment revealed that the as-obtained molecularly imprinted polymer had higher molecular recognition for sulfonamides (e.g., sulfamethoxazole, sulfamonomethoxine, and sulfadiazine) in methanol; however, its adsorption of interferent (e.g., diphenylamine, metronidazole, 2,4-dichlorophenol, and m-dihydroxybenzene) was quite low. 1 H NMR spectroscopy indicated that the excellent recognition performance of the imprinted polymer was based primarily on hydrogen bond, electrostatic and π-π interactions. Furthermore, the molecularly imprinted polymer can be employed as a solid phase extraction sorbent to effectively extract sulfamethoxazole from a mixed solution. Combined with high-performance liquid chromatography analysis, a valid molecularly imprinted polymer-solid phase extraction protocol was established for extraction and detection of trace sulfamethoxazole in spiked soil and sediment samples, and with a recovery that ranged from 93-107%, and a relative standard deviation of lower than 9.7%.

Rapid Determination of Sulfonamides in Chicken Muscle and Milk Using Efficient Graphene Oxide-Based Monolith On-Line Solid-Phase Extraction Coupled with Liquid Chromatography–Tandem Mass Spectrometry

A graphene oxide-incorporated monolithic column was fabricated and developed as an on-line solid-phase extraction sorbent coupled with LC-MS/MS for the automatic and fast determination of 16 sulfonamides in chicken muscle and milk samples. The proposed hybrid sorbent was easily produced from graphene oxide and a single crosslinker of ethylene glycol dimethacrylate. It gave favorable properties including uniformer structure, larger specific surface area, and enhanced column efficiency compared to the neat polymer monolith. Loading and eluting solutions affecting the on-line SPE were studied in detail. Under the optimized conditions, the on-line solid phase extraction coupled with LC-MS/MS method was achieved in 23 min. The developed method exhibited good linearity in the range of 1–100 μg/kg for sulfonamides in milk samples, and 2–200 μg/kg in chicken muscle samples, with r ranging from 0.993 to 0.999. The detection limits (S/N = 3) were 0.3 μg/kg in milk and 0.6 μg/kg in chicken muscle. The spiked recoveries were in the range of 70.3–98.5% and 79.0–108.0%, with a precision of 5.19–9.37% and 4.04–8.57%, respectively. Furthermore, the graphene oxide-incorporated monolithic sorbent allowed more than 450 extraction cycles without any loss in the extraction efficiency. The developed method was successfully applied for the determination of 16 sulfonamides in milk and chicken muscle samples.

A Zr(IV)-based porphyrinic metal-organic framework as a solid-phase sorbent for extraction of sulfonamides prior to their quantitation by LC-MS.

A porphyrinic metal-organic framework (PCN-224) was fabricated and used as an adsorbent for solid-phase extraction of ultratrace levels of polar sulfonamide antibiotics from food and drinking waters. The PCN-224 was characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, and powder X-ray diffraction analyses. Parameters affecting the extraction efficiency were optimized. The sulfonamides were quantified by liquid chromatography-tandem mass spectrometry. Figures of merit include (a) low limits of detection (0.07-0.47ng·L-1), (b) wide linear ranges (0.5-2000ng·L-1), and (c) good repeatabilities (2.8%-6.7%) and reproducibilities (1.7%-5.1%). The method was successfully applied to the determination of sulfonamides in food and drinking water samples. Graphical abstract A Zr(IV)-based porphyrinic metal-organic framework (PCN-224) was synthesized from a Zr6 cluster and the H2TCPP ligand. It was used for solid-phase extraction of sulfonamides from food and drinking water samples coupled with liquid chromatography-tandem mass spectrometry (LC-MS/MS) for determination.

Analysis of pollution levels of 7 antibiotics in the Wenyu river water of Beiyun River water system in Beijing after the pollution control: a preliminary study

An analytical method was developed for the determination of sulfonamides and quinolones and tetracyclines antibiotics in black-odor river by SPE-HPLC-DAD/FLD. Water sample was purified and concentrated by HLB cartridge, sediment sample was purified in tandem. In the analysis of water sample from the Wenyu river in Beijing contents by this method, antibiotic concentration of water was between 0.02∼17.4μg/L. The results showed that antibiotic concentration in black and odorous water higher than those of surface water. The pollution by wastewater discharge and sediment release were the main ways that 7 target antibiotics entered the Wenyu River.

Open-tubular capillary electrochromatographic determination of ten sulfonamides in tap water and milk by a metal-organic framework-coated capillary column.

In this study, a metal-organic framework (MOF), [Mn(cam)(bpy)], was synthesized and characterized by thermogravimetric analysis, scanning electron microscopy, and Fourier transform infrared spectrometry. An open-tubular capillary column was fabricated from [Mn(cam)(bpy)] via the amide coupling method. Ten types of sulfonamides were separated through the fabricated capillary column, which showed a good limits of detection (<0.07μg/mL) and linear ranges (1-100 or 5-100μg/mL) with a high correlation coefficients (R2 > 0.9987). The intra-day, inter-day and column-to-column relative standard deviations (RSDs) in the migration times ranged from 0.44 to 4.87%, and the peak area RSDs ranged from 0.80 to 7.28%. The developed capillary electrochromatography method can be successfully utilized for the determination of sulfonamides in tap water and milk samples.

Determination of sulfonamides in milk by ID-LC-MS/MS

Determination of sulfonamides in milk by ID-LC-MS/MS

Food Sample Preparation for the Determination of Sulfonamides by High-Performance Liquid Chromatography: State-of-the-Art

Antibiotics are a common practice in veterinary medicine, mainly for therapeutic purposes. Sectors of application include livestock farming, aquacultures, and bee-keeping, where bacterial infections are frequent and can be economically damaging. However, antibiotics are usually administered in sub-therapeutic doses as prophylactic and growth promoting agents. Due to their excessive use, antibiotic residues can be present in foods of animal origin, which include meat, fish, milk, eggs, and honey, posing health risks to consumers. For this reason, authorities have set maximum residue limits (MRLs) of certain antibiotics in food matrices, while analytical methods for their determination have been developed. This work focuses on antibiotic extraction and determination, part of which was presented at the “1st Conference in Chemistry for Graduate, Postgraduate Students and PhD Candidates at the Aristotle University of Thessaloniki”. Taking a step further, this paper is a review of the most recent sample preparation protocols applied for the extraction of sulfonamide antibiotics from food samples and their determination with high-performance liquid chromatography (HPLC), covering a five-year period.

Determination of Sulfonamide Residues in Honey and Milk by HPLC Coupled with Novel Graphene Oxide/Polypyrrole Foam Material-Pipette Tip Solid Phase Extraction

A rapid, sensitive, and economical pipette tip solid phase extraction (PT-SPE) based on graphene oxide/polypyrrole (GO/PPy) coupled with high performance liquid chromatography (HPLC) was developed for the extraction and determination of sulfonamides (SAs) in honey and milk samples. The PT-SPE procedure involved only 3.0 mg of adsorbent, 3 min adsorptive extraction time, and less than 1.0 mL of solvent consumption (sample, washing, or eluent). Under the optimal conditions, good linearities (0.01–10.00 μg mL−1) were obtained with correlation coefficients (r) > 0.9996. The limits of detection (S/N = 3) were in the range of 1.04–1.50 ng mL−1. Meanwhile, the proposed method was successfully applied for the analysis of SAs in honey and milk with average recoveries within 62.3–109.0% and relative standard deviations less than 11.2%. The results demonstrated that the developed PT-SPE-HPLC method was suitable for the analysis of SAs in complex matrix due to its high sensitivity and accuracy.

Determination of sulfonamides in milk by capillary electrophoresis with PEG@MoS2 as a dispersive solid-phase extraction sorbent.

A synthetic polyethylene glycol-molybdenum disulfide (PEG@MoS2) composite was prepared using a simple method, and the application of this material in dispersive solid-phase extraction (DSPE) was investigated for the enrichment of eight sulfonamides (SAs) in milk samples. The composite was characterized by energy dispersive spectroscopy, scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy and Brunauer–Emmett–Teller measurements. The results showed that the MoS2 synthesized in the presence of PEG has the advantage of a larger surface area and that the adsorption effect of this MoS2 was enhanced. After extraction, the eight SAs were separated by capillary zone electrophoresis with a good linear relationship (R2 > 0.9902) in the range of 0.3–30 µg ml−1 and good precision (between 0.32% and 9.83%). Additionally, good recoveries (between 60.52% and 110.91%) were obtained for the SAs in the milk samples. The developed PEG@MoS2-based DSPE method could be applied for the enrichment of SAs in real milk samples.

Evaluation of ionic liquids supported on silica as a sorbent for fully automated online solid-phase extraction with LC-MS determination of sulfonamides in bovine milk samples.

Sulfonamides are antibiotics widely used in the treatment of diseases in dairy cattle. However, their indiscriminate use for disease control may lead to their presence in tissues and milk and their determination requires a sample preparation step as part of an analytical approach. Among the several sample preparation techniques available, those based upon the use of sorptive materials have been widely employed. Recently, the application of ionic liquids immobilized on silica surfaces or polymeric materials has been evaluated for such an application. This manuscript addresses the evaluation of silica-based ionic liquid obtained by a sol-gel synthesis process by basic catalysis as sorbent for online solid-phase extraction with liquid chromatography and electrospray ionization time-of-flight mass spectrometry for sulfonamides determination. Infrared vibrational spectroscopy confirmed the presence of the ionic liquid on the silica surface, suggesting that the ionic liquid was anchored on to the silica surface. Other sorbents varying the ionic liquid alkyl chain were also synthesized and evaluated by off-line solid-phase extraction in the sulfonamide extraction. As the length of the alkyl chain increased, the amount of extracted sulfonamides decreased, possibly due to a decrease in the electrostatic interaction caused by the reduction in the polarity, as well as the presence of a hexafluorophosphate anion that increases the hydrophobic character of the material. The use of 1-butyl-3-methylimidazolium hexafluorophosphate as a selective ionic liquid sorbent enabled the isolation and sulfonamide preconcentration in bovine milk by online solid-phase extraction with liquid chromatography and electrospray ionization time-of-flight mass spectrometry. The limit of quantification for the method developed was 5-7, 5 μg/mL, with extraction recoveries ranging between 74 and 93% and intra- and interassay between 1.5-12.5 and 2.3-13.1, respectively.

Simultaneous determination of sulfonamides and fluoroquinolones from environmental water based on magnetic double-template molecularly imprinting technique.

In this work, a fast and selective method based on magnetic extraction is presented for the simultaneous extraction of sulfonamides (SAs) and fluoroquinolones (FQs), followed by liquid chromatography-tandem mass spectrometry detection. In this method, magnetic surface double-template molecularly imprinted polymers (MSdt-MIPs) with superparamagnetic property and high selectivity toward both SAs and FQs were synthesized and directly applied to the simultaneous extraction of SAs and FQs from environmental water as magnetic adsorbents. The extraction and enrichment procedures could be accomplished in one single step by stirring the mixture of MSdt-MIPs and water sample, and the MSdt-MIPs with adsorbed analytes were easily separated from the water sample by a magnet afterwards. The adsorption mechanism of MSdt-MIPs was investigated by employing the adsorption thermodynamic and kinetic studies, and the selectivity of the MSdt-MIPs toward target analytes was evaluated through the selectivity test. For validation of the proposed method, the matrix effect was evaluated and compared to that of the traditional SPE method. Excellent linearity (R> 0.9990) for both SAs and FQs were obtained in the concentration range of 20-2000ngL-1, and the limits of detection are in the range of 3.0-4.7ngL-1 for SAs while 4.1-6.1ngL-1 for FQs. Finally, the proposed method was successfully applied to the simultaneous determination of SAs and FQs in several environmental water samples.

Smartphone-based colorimetric determination of sulfadiazine and sulfasalazine in pharmaceutical and veterinary formulations

ABSTRACTA novel, simple, accurate, and low-cost colorimetric device based on an Android smartphone was developed for sulfonamide determination. A software program was developed to be used for analyzing the samples. Various parameters for digital colorimetric detection were investigated and optimized, such as the volume of the sample drop, the type of sample holder, the distance from the mobile phone camera to the sample holder, and the effect of ambient light. From the optimized conditions, a calibration curve was created by the intensity of blue channel for sulfonamides for the concentration range of 0.5–2.5 µg mL−1 with good linearity and a regression coefficient (R2) of 0.996. The results obtained by the smartphone method were compared with a spectrophotometric procedure at the 95% confidence level (n = 3). Both methods correlated well with a regression coefficient (R2) of 0.997. The limit of detection of both methods was equal to 0.11 µg mL−1. The developed smartphone system was successfully used for the determination of sulfonamides in pharmaceutical and veterinary formulations with recoveries of 102 and 98.7%, respectively. The developed method provides good accuracy (relative error <5%) and precision (relative standard deviation <7%) and offers simple, convenient, rapid, and inexpensive determination of sulfonamides.

Fast Determination of Residual Sulfonamides in Milk by In-Tube Solid-Phase Microextraction Coupled with Capillary Electrophoresis-Laser Induced Fluorescence

Abstract A fast, feasible, eco-friendly method for determination of sulfonamides using in-tube solid-phase microextraction (IT-SPME) coupled with capillary electrophoresis-laser induced fluorescence was developed. The graphene-embedded porous polymer monolithic column prepared via in-situ UV polymerization was proposed as the IT-SPME column. The method was applied to determine residual sulfonamides in a real milk sample, and an amount of 3.7 ng mL−1 sulfamethazine was detected, which was much lower than the maximum residue limit.

Screening of sulfonamides in waters based on miniaturized solid phase extraction and microplate spectrophotometric detection

A simple and cost-effective screening method for determination of sulfonamides in water is proposed.

Розробка та оцінка придатності методу з визначення антибіотиків у молоці за допомогою рідинної хроматографії високого тиску - тандемної мас-спектрометрії (UPLC-MS-MS)

&lt;p&gt;On the basis of the conducted research, validation of the method for the determination of sulfonamides and antibiotics in milk by screening method was developed and conducted by LC / MS / MS. It has been confirmed that a method determination by ultra-high-performance liquid chromatography–tandem mass spectrometry (UPLC / MS / MS) is more sensitive and selective. Validation of the method was carried out in accordance with the Decision of the European Commission 2002/657 / EC of 12 August 2002, which ensures the implementation of Council Directive 96/23 / EC concerning the effectiveness of analytical methods and the interpretation of results, and in accordance with the recommendations of the reference laboratories of the European Union CRLs of 20/1/2010 on the assessment of the suitability of screening methods for the determination of veterinary drugs. It is proved that the adapted method for the determination of sulfonamides and antibiotics is sensitive and according to parameters meets the European requirements. This method is fast enough, practical and universal, since it allows simultaneous examination of about 70 antibacterial drugs at the same time in milk.&lt;/p&gt;&lt;p&gt;It has been established that the method of determining the residual amount of sulfonamides and antibiotics by the UPLC / MS / MS is suitable for the investigation of milk on the content of the following drugs: sulfaguanidine, sulfacetamide, sulfapiridine, sulfadiazine, sulfamethoxazole, sulfathiazole, sulfamethazine, sulfamethizole, sulfabenzamide, sulfaquinoxaline, sulfadoxine, sulfadimetoxin, sulfanilamide, trimethoprim, sulfamonomethoxine, sulfamethoxypyridazine, sulfachlorpyridazine, sulfamoxol, dapsone, amoxicillin, ampicillin, penicillin G, penicillin V, oxacillin, cloxacillin, nafcillin, dicloxacillin, cefalonium, cefazolin, cefoperazon, cefquinome, cefapirin, ceftiofur, cefalexin, norfloxacin, enrofloxacin, ciprofloxacin, marbofloxacin, difloxacin, danofloxacin, sarafloxacin, flumekvin, oxolinic acid, nalidixic acid, oxytetracycline, chlortetracycline, tetracycline, doxycycline, epi-oxytetracycline, epi-tetracycline, epi-chlortetracycline, streptomycin, dihydrostreptomycin, gentamicin, kanamycin, apramycin, paromomycin, lincomycin, spectinomycin, tilmycosin, erythromycin, josamycin, spiramycin, tylosin, tiamulin, colistin, gamitromycin, tulatromycin. In assessing the suitability of the method, the MS / MS detection parameters are set and the validation characteristics are determined.&lt;/p&gt;

Graphene-functionalized melamine sponges for microextraction of sulfonamides from food and environmental samples

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

Trends in Microextraction-Based Methods for the Determination of Sulfonamides in Milk

Sulfonamides (SAs) represent a significant category of pharmaceutical compounds due to their effective antimicrobial characteristics. SAs were the first antibiotics to be used in clinical medicine to treat a majority of diseases, since the 1900s. In the dairy farming industry, sulfa drugs are administered to prevent infection, in several countries. This increases the possibility that residual drugs could pass through milk consumption even at low levels. These traces of SAs will be detected and quantified in milk. Therefore, microextraction techniques must be developed to quantify antibiotic residues, taking into consideration the terms of Green Analytical Chemistry as well.

Development of an analysis method for determination of sulfonamides and their five acetylated metabolites in baby foods by ultra-high performance liquid chromatography coupled to high-resolution mass spectrometry (Orbitrap-MS)

A high sensitive and reliable multiresidue method was developed and validated for determination of twelve sulfonamides and five acetylated metabolites in baby foods by using UHPLC-Orbitrap-MS. The sample preparation included two extraction methods as QuEChERS and ASE. The original QuEChERS method was performed, whereas ASE method was optimized to achieve the best recovery for all analytes. UHPLC-Orbitrap-MS parameters were optimized to obtain good retention and separation in LC and high sensitivity and selectivity in MS. The performance of the method was evaluated according to the European Commision Decision 2002/657/EC. Matrix matched calibration curves showed good r2 (≥0.999) and LOQ was ranged from 0.10 to 0.55μg/kg. ASE was significantly more effective for extraction of the analytes (recovery ranged from 75.5 to 96.6% with RSD≤10.1%) than QuEChERS (recovery ranged from 60.9 to 85.9% with RSD≤19.1%). This method was applied to the analysis of 47 different baby foods and no positive samples were found.

Determination of Antibiotic Residues in Honey by High-Performance Liquid Chromatography with Electronspray Ionization Tandem Mass Spectrometry

The aim of the present study was to develop a rapid and simple method for the detection and quantification of antibiotic and antibacterial residues in honey using liquid chromatography with electronspray ionization tandem mass spectrometry. Two different extraction methods were used. The first method uses water and 1% formic acid in acetonitrile for the determination of sulfonamides while the second uses phosphate buffer, 10% trichloroacetic acid, and acetonitrile as the extracting solvent for the determination of tetracyclines, amphenicols, fluoroquinolones, penicillin g, trimethoprim, and tiamulin. The multi-residue method was validated in a thyme honey matrix. Thirty-six different antibiotics and residues from four different families (sulfonamides, tetracyclines, amphenicols, fluoroquinolones) and some individual antibiotics (penicillin g, trimethoprim, and tiamulin) were tested in 20 honey samples originating from Cyprus and Greece. The decision limits (CCα) were from 0.1 to 9.2 μg kg−1; the detection capabilities (CCβ) were from 0.3 to 27.6 μg kg−1 while recoveries were from to be between 65.0 and 116.1%. The method was successfully applied to commercial samples from different types of honey from Greece and Cyprus. Among them, oxolonic acid, sulfathiazole, and sulfadimethoxine were found in three honey samples. Finally, proficiency testing was applied to the proposed method while analysis of certified samples showed good method performance characteristics.

Towards the determination of sulfonamides in meat samples: A magnetic and mesoporous metal-organic framework as an efficient sorbent for magnetic solid phase extraction combined with high-performance liquid chromatography

A magnetic, mesoporous core/shell structured Fe3O4@JUC-48 nanocomposite was synthesized and employed as a magnetic solid phase extraction (MSPE) sorbent for the determination of trace sulfonamides (SAs) in meat samples. The synthesized nanocomposite was characterized by X-ray diffraction, Fourier transform infrared spectra, transmission electron microscopy, scanning electron microscopy, Brunner–Emmet–Teller, and vibrating sample magnetometry; the Fe3O4@JUC-48 nanocomposite exhibited a distinctive morphology, large surface area, high magnetism, open adsorption sites, and high chemical stability. By combining the optimized MSPE conditions with high performance liquid chromatography diode array detection, an accurate and sensitive method for the determination of 5 SAs, including sulfadiazine (SDZ), sulfathiazole (STZ), sulfamerazine (SMR), sulfamethazine (SMZ), and sulfamethoxypyridazine (SMP), was developed. The method exhibited good linearity in the range of 3.97–1000ng/g with R ranging from 0.9991 to 0.9994, high sensitivity with LODs ranging from 1.73 to 5.23ng/g, adequate recoveries between 76.1 and 102.6% with low relative standard deviations ranging from 2.1 to 6.4%, and high precision with RSD<4.5%. The Fe3O4@JUC-48 magnetic nanocomposite is a promising sorbent for the rapid and efficient extraction of SAs from complex biological samples such as chicken, pork, and shrimp.