Sulfameter Research Articles

An autocatalytic hybridization circuit-based FRET aptasensor for detection of low-abundant sulfameter in human serum

Exposure to antibiotics is considered a potential risk factor for human health. Yet, the extensive and cost-effective detection of low-abundant antibiotics in complex matrices remains a significant challenge. Herein, an aptamer and an autocatalytic hybridization circuit (AHC) were used to fabricate a fluorescence resonance energy transfer (FRET) platform to detect sulfameter (SME) in human serum. The AHC system comprised two mutually motivated hybridization chain reactions (HCR) modules, ultimately producing long-branched DNA copolymeric nanowires. This mutually reciprocal activation of two HCR modules enables continuous signal amplification, providing the AHC system with wide linear range and high sensitivity for the SME detection. Compared to the HCR-based aptasensor, the AHC-based aptasensor exhibited a wider linear range and improved sensitivity (3.3 times greater). Under optimal conditions, the fluorescent AHC-based aptasensor demonstrated a linear range (R2 was 0.996) from 0.5 to 2000 nM, with a low detection limit of 0.301 nM (S/N = 3). The fluorescent aptasensor was also validated by SME-spiked human serum samples, showing average recoveries ranging from 96.40 % to 109.30 %, with a relative standard deviation below 10.45 %. Furthermore, when tested on six human serum samples, the aptasensor results were consistent with those obtained from the commercial ELISA method. These findings demonstrate that the proposed aptasensor provides a promising approach for the practical monitoring of low-abundant SME in human serum.

Isolation of aptamers with excellent cross-reactivity and specificity to sulfonamides towards a ratiometric fluorescent aptasensor for the detection of nine sulfonamides in seafood

Sulfonamides (SAs) is a class of antibiotics that extensively used for treating infectious diseases in livestock industries and aquaculture. Thus, it is urgent need to obtain the bio-receptor, which has excellent cross-reactivity and specificity to SAs, for developing high-throughput methods for the determination of multiple SAs even all commonly-used SAs, to realize the quick screening/detection of total SAs in animal-derived foods. We herein isolated several SAs-specific cross-reactive aptamers by using a library-immobilized SELEX with multi-SAs parallel selection strategy. Two of the isolated aptamers (Sul-01 and Sul-04) can specifically recognize and bind seven SAs respectively with higher binding affinity and no interference of non-sulfonamide antibiotics, and thus can be applied as bio-receptors for developing high-throughput aptasensors for the quick screening/detection of multiple SAs. By using the mixture of Sul-01 and Sul-04 as bio-receptor, a ratiometric fluorescent aptasensor was created for the quick detection of nine SAs including sulfamethoxydiazine (SMD), sulfapyridine (SPD), sulfaquinoxaline (SQ), sulfathiazole (ST), sulfamonomethoxine (SMM), sulfamerazine (SMR), sulfaguanidine (SG), sulfamethazine (SMZ) and sulfadiazine (SD) with a detection limit (LOD) of 0.10–0.50 μM, or total of above nine SAs with a LOD of 0.20 μM. The fluorescent aptasensor was successfully applied to detect each or total of SMD, SPD, SQ, ST, SMM, SMR, SG, SMZ and SD in fish samples with a recovery of 83 %–92 % and a relative standard deviation (RSD, n = 5) < 5 %. This study not only provided several promising bio-receptors for the development of diverse high-throughput aptasensors to achieve the quick screening of multiple SAs residues, but also provided a simple, stable and sensitive method for the quick screening of SMD, SPD, SQ, ST, SMM, SMR, SG, SMZ and SD in seafood.

A Paper-Based Multicolor Colorimetric Aptasensor for the Visual Determination of Multiple Sulfonamides Based on Aptamer-Functionalized Magnetic Beads and NADH–Ascorbic Acid-Mediated Gold Nanobipyramids

It is crucial that simple and high-throughput methods for determining multiple, or groups of, sulfonamides (SAs) be developed since they are widely used in animal husbandry and aquaculture. We developed a paper-based multicolor colorimetric aptasensor to detect 3 SAs: sulfaquinoxaline (SQ), sulfamethoxypyridazine (SMP) and sulfamethoxydiazine (SMD). Using a broad-specificity aptamer as a bioreceptor, we reduced the growth of nicotinamide adenine dinucleotide I (NADH)–ascorbic acid (AA)-mediated gold nanobipyramids (AuNBPs) to generate a multicolor signal. We also used a paper-based analytical device (PAD) system to deposit AuNBPs for a sensitive color signal read out. The aptasensor can detect more color changes corresponding to the concentrations of SQ, SMP and SMD and has higher sensitivity, better specificity and stability. It can also be used to determine SQ, SMP and SDM individually, or collectively, or any two together with a visual detection limit of 0.3–1.0 µM, a spectrometry quantification limit (LOQ) of 0.3–0.5 µM and a spectrometry detection limits (LOD) of 0.09–0.15 µM. The aptasensor was successfully used to determine SQ, SMP and SDM in fish muscle with a recovery of 89–94% and a RSD n = 5) &lt; 8%, making it a promising method for the rapid screening of total SQ, SMP and SDM residue in seafood.

A multicolor immunosensor for the visual detection of six sulfonamides based on manganese dioxide nanosheet-mediated etching of gold nanobipyramids.

In reality, various sulfonamides (SAs) were alternately used in animal husbandry to avoid generating drug resistance. Thus, it is crucial to develop simple and high-throughput methods for detecting multiple or groups of SAs to realize rapid screening of total SAs residues in foods. We herein developed a sensitive and efficient MnO2 nanosheets-mediated etching of gold nanobipyramids (AuNBPs), which can generate more vivid color changes, and further fabricated a high-throughput multicolor immunosensor for the visual screening/semi-quantitative detection of 6 different SAs including sulfamethazine (SMZ), sulfamethoxydiazine (SMD), sulfisomidine (SIM), sulfamerazine (SMR), sulfamonomethoxine (SMM) and sulfaquinoxaline (SQ) by using AuNBPs as signal and broad-specificity anti-SAs antibody as a bio-receptor. The immunosensor displays more vivid color changes, and has a lower visual detection limit and excellent specificity. It can be applied to detect as little as 1.0ng/mL of SMZ, SMD, SMR and 2.0ng/mL of SIM, SMM, SQ by bare eye observation, and 0.2ng/mL of above 6 SAs by UV-visible spectrophotometry. The visual detection limit of the immunosensor is much lower than the maximum residue limit of total SAs (100μg/kg) in edible tissues. The immunosensor was successfully applied to detect SMZ, SMD, SIM, SMR, SMM and SQ in milk with a recovery of 84%-106% and a RSD (n=5)<8%. The success of this study provided a promising assay for the on-site rapid screening of SMZ, SMD, SIM, SMR, SMM and SQ in food by bare eye observation. Importantly, the immunosensor may be expended as a general method for the visual screening/semi-quantitative detection of the group of other antibiotics by using the corresponding broad-specificity antibody as a bio-receptor.

Selected ssDNA aptamers-graphene oxide based fluorescent biosensor to detect sulfameter in milk.

The abuse of sulfameter (SME) in animal husbandry can cause drug resistance and toxic or allergic reactions in humans. Therefore, it is very important to establish a simple, inexpensive and efficient method for detecting SME in food. In this work, we propose a single fluorescent aptamer/graphene oxide (GO)-based biosensor to detect SME residues in milk. Aptamers that specifically bind to SME were screened by capture-SELEX using an ssDNA library immobilized on magnetic beads. The 68 active candidate aptamers were chemically synthesized for specificity and affinity characterization. Among the aptamers, the aptamer sulf-1 revealed the highest affinity (Kd =77±15 nM) to SME and was selected to construct a GO-based fluorescent biosensor for real milk sample detection. Under optimal conditions, the single fluorescent aptasensor had a wide linear range (R2 was 0.997) from 7 to 336 ng/mL and low detection limit of 3.35 ng/mL that was calculated with a 3 SD/slope. The single fluorescent method was also validated by SME-fortified milk samples, showing average recoveries ranging from 99.01% to 104.60% with a relative standard deviation below 3.88%. These results demonstrate that this novel aptamer sensor provides an opportunity for sensitive, convenient and accurate detection of SME residues in milk.

Identification and characterization of Fe3O4/peroxodisulfate advanced oxidation products from sulfameter

Sulfonamides (SAs) are one of the most widely used antibiotics and their residuals in the environment could cause some negative environmental issues. Advanced oxidation such as Fenton-like reaction has been widely applied in the treatment of SAs polluted water. Degradation rates of 95%-99.7% were achieved in this work for the tested 8 SAs, including sulfisomidine, sulfameter (SME), phthalylsulfathiazole, sulfamethoxypyridazine, sulfamonomethoxine, sulfisoxazole, sulfachloropyridazine, and sulfadimethoxine, in the Fe3O4/peroxodisulfate (PDS) oxidation system after the optimization of PDS concentration and pH. Meanwhile, it was found that a lot of unknown oxidation products were formed, which brought up the uncertainty of health risks to the environment, and the identification of these unknown products was critical. Therefore, SME was selected as the model compound, from which the oxidation products were never elucidated, to identify these intermediates/products. With liquid chromatography-high resolution tandem mass spectrometry (LC-HRMS/MS), 10 new products were identified, in which 2-amino-5-methoxypyrimidine (AMP) was confirmed by its standard. The investigation of the oxidation process of SME indicated that most of the products were not stable and the degradation pathways were very complicated as multiple reactions, such as oxidation of the amino group, SO2 extrusion, and potential cross-reaction occurred simultaneously. Though most of the products were not verified due to the lack of standards, our results could be helpful in the evaluation of the treatment performance of SAs containing wastewater.

Occurrence and Risk Assessment of Antibiotics in Manure, Soil, Wastewater, Groundwater from Livestock and Poultry Farms in Xuzhou, China.

Antibiotics in manure, soil, wastewater, and groundwater samples from the livestock and poultry farms in Xuzhou City were investigated in the present study. The concentrations of antibiotics in all matrices varied greatly among farms. Total concentrations of fluoroquinolones and macrolides were much higher than those of sulfonamides in manures and soil samples. Total concentrations of antibiotics in wastewater of livestock farms were higher than those of poultry farm. Josamycin (JM) and tilmicosin (TIL) accounted for more than 74% of the nine macrolides in all groundwater samples. Sulfamethizole (SMT), fleroxacin (FLE), cinoxacin (CIN) and JM were the main antibiotics detected in manure and soil samples, while sulfamethoxypyridazine (SMP), sulfameter (SME), SMT, FLE, JM and TIL accounted for a large proportion of antibiotics in surface and groundwater. The risk assessment of target antibiotics revealed that JM in wastewater showed relatively high RQs for aquatic organisms.

Density functional theory study of direct and indirect photodegradation mechanisms of sulfameter

Sulfonamide antibiotics (SAs) have been observed to undergo direct and indirect photodegradation in natural water environments. In this study, the density functional theory (DFT) method was employed for the study of direct and indirect photodegradation mechanisms of sulfameter (SME) with excited triplet states of dissolved organic matter ((3)DOM(*)) and metal ions. SME was adopted as a representative of SAs, and SO2 extrusion product was obtained with different energy paths in the triplet-sensitized photodegradation of the neutral (SME(0)) and the anionic (SME(-)) form of SME. The selected divalent metal ions (Ca(2+), Mg(2+), and Zn(2+)) promoted the triplet-sensitized photodegradation of SME(0) but showed an inhibitory effect in triplet-sensitized photodegradation of SME(-). The triplet-sensitized indirect photodegradation mechanism of SME was investigated with the three DOM analogues, i.e., 2-acetonaphthone (2-AN), fluorenone (FN), and thioxanthone (TN). Results indicated that the selected DOM analogues are highly responsible for the photodegradation via attacking on amine moiety of SME. According to the natural bond orbital (NBO) analysis, the triplet-sensitized photodegradation mechanism of SME(0) with 2-AN, FN, and TN was H-transfer, and the SME(-) was proton plus electron transfer with these DOM analogues.

Monitoring and determination of sulfonamide antibiotics (sulfamethoxydiazine, sulfamethazine, sulfamethoxazole and sulfadiazine) in imported Pangasius catfish products in Thailand using liquid chromatography coupled with tandem mass spectrometry

This research aimed to monitor the concentrations of sulfamethoxydiazine (SMD), sulfamethazine (SMT), sulfamethoxazole (SMX) and sulfadiazine (SDZ) in imported Pangasius catfish products in Thailand. The residues of the four sulfonamides (SAs) were analyzed by extraction process and liquid chromatography coupled with tandem mass spectrometry. The highest concentrations found were 10.97ng/g for SMD, 6.23ng/g for SMT, 11.13ng/g for SDZ and 245.91ng/g for SMX, which was higher than the European Union (EU) standard (100ng/g). Moreover, all samples contaminated with SMX also contained SMT, indicating that more than one antibiotic was used for production in the country of origin. Because Thai standards for antibiotics in food have not been completely set, all contaminated discovered would not be considered to be an illegal food, in which antibiotic residues may affect human health in the long term. Therefore, antibiotic residues in Pangasius catfish products should be continually regulated and monitored.

Hirshfeld surface analysis of sulfameter (polymorph III), sulfameter dioxane monosolvate and sulfameter tetrahydrofuran monosolvate, all at 296 K.

The ability of the antibacterial agent sulfameter (SMT) to form solvates is investigated. The X-ray crystal structures of sulfameter solvates have been determined to be conformational polymorphs. Both 1,4-dioxane and tetrahydrofuran form solvates with sulfameter in a 1:1 molar ratio. 4-Amino-N-(5-methoxypyrimidin-2-yl)benzenesulfonamide (polymorph III), C11H12N4O3S, (1), has two molecules of sulfameter in the asymmetric unit cell. 4-Amino-N-(5-methoxypyrimidin-2-yl)benzenesulfonamide 1,4-dioxane monosolvate, C11H12N4O3S·C4H8O2, (2), and 4-amino-N-(5-methoxypyrimidin-2-yl)benzenesulfonamide tetrahydrofuran monosolvate, C11H12N4O3S·C4H8O, (3), crystallize in the imide form. Hirshfeld surface analyses and fingerprint analyses were performed to study the nature of the interactions and their quantitative contributions towards the crystal packing. Finally, Hirshfeld surfaces, fingerprint plots and structural overlays were employed for a comparison of the two independent molecules in the asymmetric unit of (1), and also for a comparison of (2) and (3) in the monoclinic crystal system. A three-dimensional hydrogen-bonding network exists in all three structures, involving one of the sulfone O atoms and the aniline N atom. All three structures are stabilized by strong intermolecular N-H···N interactions. The tetrahydrofuran solvent molecule also takes part in forming significant intermolecular C-H···O interactions in the crystal structure of (3), contributing to the stability of the crystal packing.

Chemiluminescence enzyme immunoassay for the determination of sulfamethoxydiazine

Sulfamethoxydiazine (SMD), which is often used for animal disease treatment, is harmful to human health. No SMD residue should be detected in food in some countries, such as USA and Japan. Therefore, it is significant to develop a high-throughput, high-sensitivity and accurate method for the determination of the content of SMD in food. In this paper, chemiluminescence enzyme immunoassay (CLEIA) was developed for quantification of SMD. For this method, the limit of detection was 3.2 pg/ml, the linear range was from 10 to 2000 pg/ml, the within-day and inter-day precision were below 13% and below 18%, respectively, and the recovery was from 85% to 105%. Milk and egg were selected as samples to be examined with this method, and the result indicated that this CLEIA method was suitable for screening and quality control of food.

Effect of antibiotics on methane arising from anaerobic digestion of pig manure

Laboratory scale digesters were used to study effects of tetracycline (TC) and sulfamethoxydiazine (SMD) on CH4 production from anaerobic digestion of pig manure at 25°C. Tetracycline and SMD were added to digesters at concentrations of 0, 25 and 50mg/L. Results show a delay in initial production of CH4 and lower daily CH4 production peaks with addition of antibiotics compared to control. Cumulative CH4 volumes for all treatments within 20d were lower (P<0.05) than the control indicating that TC and SMD in manure reduced CH4 production. The extent of inhibition on CH4 production depended on the dosage of antibiotics added. Concentrations of TC and SMD in digesters declined rapidly with more than half of the antibiotics disappearing after 12h of digestion, with only trace antibiotics remaining after 2–3d. Rapid disappearance of antibiotics could be due their adsorption onto solid materials or degradation by microorganisms. Antibiotics appear to inhibit bacterial activity resulting in a delay and overall decline in CH4 production.This article is part of the special issue entitled: Greenhouse Gases in Animal Agriculture – Finding a Balance between Food and Emissions, Guest Edited by T.A. McAllister, Section Guest Editors; K.A. Beauchemin, X. Hao, S. McGinn and Editor for Animal Feed Science and Technology, P.H. Robinson.

Determination of sulfonamides in soil samples based on alumina-coated magnetite nanoparticles as adsorbents

In this study, alumina-coated magnetite nanoparticles (Fe 3O 4/Al 2O 3 NPs) were synthesized, and they were applied to the analysis of sulfonamides (SAs) including sulfadiazine (SDZ), sulfamerazine (SMR), sulfamethoxazole (SMX), sulfamonomethoxine (SMM), sulfamethoxydiazine (SMD), sulfadimethoxine (SDM) and sulfaquinoxaline (SQX) in different soil samples based on magnetic solid-phase extraction (MSPE). The extraction and concentration process was carried out in a single step by mixing the extraction solvent, magnetic adsorbents and soil sample under ultrasonic action. Then, the adsorbents were isolated from the complicated matrix easily with an external magnetic field. The SAs desorbed from the adsorbents were determined by liquid chromatography–tandem mass spectrometry. Compared with traditional methods, the MSPE method simplified the operation procedure and reduced the analysis time. Under the optimum conditions, the recoveries of SDZ, SMR, SMX, SMM, SMD and SDM by analyzing the five spiked soil samples were between 71% and 93% except for SQX (42–60%). This may be due to the stronger hydrophobic property of SQX. Detection limits of SAs were between 0.37 and 6.74 ng g −1. It was also found that the “aging” effect of SAs contaminated soil could cause the recoveries to decrease.

Analysis of sulfonamides in environmental water samples based on magnetic mixed hemimicelles solid-phase extraction coupled with HPLC–UV detection

The magnetic mixed hemimicelles solid-phase extraction (MMHSPE), based on the adsorption of cation surfactant octadecyltrimethylammonium bromide (OTMABr) onto magnetite nanoparticles (Fe 3O 4 NPs) to form mixed hemimicelles, was proposed for the preconcentration of several sulfonamides (SAs) compounds including sulfamethoxazole (SMX), sulfamethoxydiazine (SMD), sulfadimethoxine (SDM) and sulfaquinoxaline (SQX) from environmental water samples. This method avoided the time-consuming column-passing process of loading large volume samples in traditional SPE through the rapid isolation of OTMABr-coated Fe 3O 4 NPs with an adscititious magnet. Mixed hemimicelles formed on the surface of Fe 3O 4 NPs by OTMABr showed great adsorptive tendency towards analytes. The OTMABr-coated Fe 3O 4 NPs adsorbents were easy to be prepared, low cost and environmentally friendly. A comprehensive study on the adsorption conditions such as the amount of the surfactant, the solution pH, the desorption condition and the maximum extraction sample volume were optimized. A concentration factor of 1000 was achieved by the extraction of 500 mL of environmental water samples using MMHSPE. Detection limits obtained for SMX, SMD, SDM and SQX were 0.026, 0.024, 0.033 and 0.030 μg L −1, respectively. Good recoveries (70–102%) with low relative standard deviations (1–6%) were achieved in analyzing spiked water samples. Low concentration of SQX was found in hospital primary and final sewage effluent sample.