Heterometallic Eu/Zn-MOF-based ratiometric sensing platform: Highly sensitive fluorescence / second-order scattering identification of tetracycline analogs and its molecular informatization applications.

The traditional preparation method of ratiometric probes faces challenges such as cumbersome preparation and low sensitivity. Thus, there is an urgent need to provide a simple method of preparing a highly sensitive ratiometric probe. Here, Eu3+-doped zinc-based organic framework (Eu/Zn-MOF) was prepared through hydrothermal method for the detection of tetracycline analogs (TCs). Under the same excitation conditions, the probe can simultaneously display valuable fluorescence and second-order scattering signals. The developed probe enabled specific identification and fast detection (1 min) of TCs, including tetracycline, oxytetracycline, doxycycline, and chlortetracycline. The linear detection ranges of tetracycline, oxytetracycline, doxycycline and chlortetracycline were respectively 100 nM - 200 µM, 100 nM - 200 µM, 98 nM - 195 µM, and 97 nM - 291 µM, and the corresponding detection limits were respectively 15.79 nM, 20.83 nM, 15.31 nM, and 28.30 nM. The developed sensor was successfully applied to detect TCs in real samples, and the recovery rate was from 92.54 % to 109.69 % and the relative standard deviation was from 0.04 % to 2.97 %. Moreover, the heterometallic Eu/Zn-MOF was designed as a ratiometric neuron for Boolean logic computing and information encryption based on the specific identification of TCs. As a proof of concept, molecular steganography was successfully employed to encode, store, and conceal information by transforming the specific identification patterns of Eu/Zn-MOF into binary strings. This study is anticipated to advance the application of metal-organic frameworks in logic detection and information security, and bridging the gap between molecular sensors and the realm of information.

Construction of colorimetric sensor arrays using steel slag-based composites for highly sensitive detection of tetracycline antibiotics.

Sensor array methods have received much attention in recent years. In this study, a colorimetric sensor array consisting of three kinds of steel slag-based composites (including porphyrin-functionalized non-magnetic steel slag (NMSS-Por), alkali-excited steel slag (A-SS), and platinum modified steel slag (ALANH-Pt)) was developed for the detection and recognition of tetracycline antibiotics (TCs) such as tetracycline (TC), oxytetracycline (OTC) and doxycycline (DOX). Linear discriminant analysis (LDA) and hierarchical cluster analysis (HCA) showed that the colorimetric sensor array has excellent recognition ability for TCs. The detection limits of this sensor array for TC, OTC, and DOX were 0.059 µM, 0.111 µM and 0.118 µM, respectively, which provided higher sensitivity compared to the colorimetric sensors composed of a single steel slag-based composite material. At the same time, the array sensor has anti-interference ability, and this study provides a new application route for steel slag.

Enhancing solid-phase extraction of tetracyclines with a hybrid biochar sorbent: A comparative study of chlorella and bamboo biochars.

Biochar, a sustainable sorbent derived from pyrolyzed biomass, has garnered attention for its efficacy in solid-phase extraction (SPE) of antibiotics, with a particular focus on tetracyclines (TCs). Despite its recognized potential, the intricate separation mechanisms operative in biochar-based SPE systems have not been fully deciphered. This investigation contrasts chlorella biochar against commercial bamboo biochar, harnessing an array of analytical methodologies-microstructure characterization, adsorption thermodynamics, competitive adsorption kinetics, H+ back titration, and selectivity adsorption studies-complemented by a Box-Behnken design for the optimization of chlorella/bamboo-SPE and subsequent application in the analysis of animal-derived foodstuffs. The study unveils that a hybrid sorbent, integrating nitrogen-doped microporous chlorella biochar with mesoporous bamboo biochar in a 95/5 mass ratio, markedly diminishes irreversible adsorption while enhancing selectivity, surpassing the performance of single biochar SPE systems. The elucidated separation mechanisms implicate a partition model, propelled by oxygen-rich functional groups on chlorella biochar and the rapid adsorption kinetics of bamboo biochar, all orchestrated by electrostatic interactions within the mixed biochar framework. Moreover, the synergy of mixed biochar-SPE with high-performance liquid chromatography (HPLC) demonstrates exceptional proficiency in detecting TCs in animal viscera, evidenced by recovery rates spanning 80.80 % to 106.98 % and RSDs ranging from 0.24 % to 14.69 %. In essence, this research not only sheds light on the multifaceted factors influencing SPE efficiency but also propels the use of biochar towards new horizons in environmental monitoring and food safety assurance.

Tetracycline and fluoroquinolone antibiotics contamination in agricultural soils fertilized long-term with chicken litter: Trends and ravages.

We investigated the potential accumulation of tetracyclines (TCs) such as chlortetracycline (CTC), oxytetracycline (OTC) and doxycycline (DC), and fluoroquinolones (FQs) like enrofloxacin (ENR) and ciprofloxacin (CIP) in chicken litter and agricultural soils fertilized over short-term to long-term (<1-30 yrs) with chicken litter in a poultry hub for the first time from Tamil Nadu, India. CTC, OTC, DC, CIP, and ENR were detected in 46-92 % of the selected chicken litter samples, with mean levels ranging from 2.90 to 23.30 µg kg-1. Higher concentrations of TCs and FQs were observed in freshly collected chicken litter from poultry sheds than in those stockpiled in cultivated lands. CTC was the prevalent antibiotic in chicken litter. The overall occurrence, as well as the ecological risks of TCs and FQs, changed over a 30-yr period. The accumulation of veterinary antibiotics (VAs) (in µg kg-1) in short-term (>1 yr) to medium-term (1-3 yrs) chicken litter-fertilized soils reached a maximum of 11.60 for CTC, 6.50 for OTC, 0.80 for DC, 3.70 for CIP, and 3.60 for ENR, but decreased in long-term (10-30 yrs) fertilized soils. Ecological risk assessment revealed a Risk Quotient (RQ) of ≤0.10 for CTC, OTC, and DC in all soils, while an average risk (RQ >0.10-<1.0) was evident with CIP and ENR in short-term and medium-term fertilized soils. Antibiotic resistance genes (ARGs), including tetA, tetB, qnrA, qnrB and qnrS were detected in most of the chicken litter samples and litter-fertilized soils. Thus, it is critical to develop and adopt effective mitigation strategies before applying chicken litter in farmlands to decrease VAs and ARGs, reducing their associated risks to public health and ecosystems in India considering 'One Health' approach. Future investigations on the occurrence of other VAs and ARGs in soils fertilized with poultry litter at regional scale are required for effective risk mitigation of the widely used VAs.

Distribution pattern analysis of multiple antibiotics in the soil-rice system using a QuEChERS extraction method.

Antibiotics are commonly released into paddy fields as mixtures via human activities. However, the simultaneous extraction and detection of these chemicals from multiple media are technically challenging due to their different physicochemical properties, resulting in unclear patterns of their transport in the soil-rice system. In this study, a "quick, easy, cheap, effective, rugged, and safe" (QuEChERS) method was developed for the simultaneous analysis of 4 tetracyclines (TCs) and 4 fluoroquinolones (FQs) in the soil and rice tissues from a local poultry farm, and thereby the distribution patterns of the target antibiotics in the soil-rice system and their risk levels to the soil were analyzed. After parameter optimization, the calibration range used for the target antibiotics was 0.1-50 µg/L and each calibration curve was linear with a coefficient of determination (R2 > 0.995); The QuEChERS method achieved satisfactory recovery rates (70.3-124.6%) along with sensitive detection limits (0.005-0.21 ng/g) for TCs and FQs in the soil, root, stem, leaf, and grain. Among the 8 antibiotics, enrofloxacin (ENX), ciprofloxacin (CIP), oxytetracycline (OTC), and doxycycline (DOX) were detected around a poultry farm. The four antibiotics in the collected paddy soils around the poultry farm ranged from 7.1 ng/g to 395.5 ng/g. Notably, ENX and DOX had higher ecological risks (risk quotient values >1) than CIP and OTC in soil. ENX, CIP, and DOX were highly enriched in rice roots with concentrations up to 471.9, 857.3, and 547.4 ng/g, respectively, which were also detected in rice aboveground tissues. The findings may provide both technical and practical guidance for the understanding of antibiotic environmental behavior and risks.

Development, synthesis, and application of magnetic layered double hydroxides (Fe3O4@SiO-LDH/DS-) as an efficient adsorbent for the removal of tetracyclines from milk samples.

This work presents the development, synthesis, and application of a layered double hydroxide (LDH) coupled to magnetic particles for the removal of antibiotics as tetracyclines (TC´s): tetracycline (TC), chlortetracycline (CT), oxytetracycline (OT), and doxycycline (DT) from milk samples. The LDH synthesis conditions, reaction time (30-90 min), molar ratios Mg2+/Al3+ (7:1-1:7), interlayer anion (NO3-, Cl-, CO32-, and dodecyl sulphate (DS-)) were evaluated. Under synthesis conditions (reaction time of 30 min, Mg2+/Al3+ molar ratio of 7:1, and DS- as interlayer anion), the LDH was coupled in a magnetic solid phase microextraction (MSPµE) methodology. At the optimal extraction conditions (pH 6, 5 min of contact time, 10 mg of adsorbent), a removal percentage of 99.0 % was obtained for each tetracycline. FTIR, TGA, SEM, and adsorption isotherms were employed to characterize the optimal adsorbent. Each experiment was corroborated by large-volume sample stacking capillary electrophoresis (LVSS-CE). The adsorbent was applied directly to positive milk samples (previously tested) for TC´s removal.

Rapid Determination of Tetracyclines in Drinking and Environmental Waters Using Fully Automatic Solid-Phase Extraction with Ultra-Performance Liquid Chromatography-Tandem Mass Spectrometry.

The abuse and irrational use of tetracyclines (TCs) in human medicine and animal husbandry has become a serious concern, affecting the ecological environment and human health. The aim of this study was to develop a sensitive and selective method using fully automatic solid-phase extraction coupled with ultra-performance liquid chromatography-tandem mass spectrometry for the determination of twelve TCs in water. Four isotope-labeled internal standards for TCs were used to correct matrix effects. Several parameters affecting extraction efficiency were systematically optimized, and the optimum experimental conditions found were 1.0 L water sample with 0.5 g/L Na2EDTA (pH 3.0) extracted and enriched by CNW HLB cartridge and eluted by 4 mL of acetone:methanol (v/v, 1:1). The enrichment factors were up to 798-1059 but only requiring about 60 min per six samples. Under the optimized conditions, the linearity of the method ranged from 0.2 to 100 µg/L for 12 TCs, the detection limits were as low as 0.01-0.15 ng/L, and the recoveries were in the range of 70%-118%, with relative standard deviations less than 15%. The developed method can be successfully utilized for the determination of 12 TCs in pure water, tap water, river water, and mariculture seawater. In summary, three and six TCs were detected in river water and mariculture seawater, respectively, with total concentrations of 0.074-0.520 ng/L (mean 0.248 ng/L) and 0.792-58.369 ng/L (12.629 ng/L), respectively. Tetracycline (TC) and oxytetracycline (OTC) were the dominant TCs in river water, while doxytetracycline (DXC) and OTC were dominant in mariculture seawater.

Magnetic solid-phase extraction of tetracyclines from milk using metal-organic framework MIL-101(Cr)-NH2 functionalised hydrophilic magnetic nanoparticles.

Novel metal-organic framework MIL-101(Cr)-NH2 functionalised hydrophilic polydopamine-modified Fe3O4 magnetic nanoparticles (Fe3O4@PDA@MIL-101(Cr)-NH2) were synthesised and used as magnetic solid-phase extraction (MSPE) adsorbents for extracting tetracyclines (TCs) from milk samples. The integrated Fe3O4@PDA@MIL-101(Cr)-NH2 exhibited convenient magnetic separation and exceptional multi-target binding capabilities. Furthermore, the PDA coating significantly enhanced the hydrophilicity and extraction efficiency of the material, thereby facilitating the extraction of trace TCs. Various factors affecting MSPE, such as adsorbent dosage, extraction time, pH value, and desorption conditions, were optimised. The developed MSPE method coupled with high-performance liquid chromatography demonstrated good linearity (R2 ≥ 0.9989), acceptable accuracy (82.2%-106.1%), good repeatability (intra-day precision of 0.8%-4.7% and inter-day precision of 1.1%-4.5%), low limits of detection (2.18-6.25 µg L-1), and low limits of quantification (6.54-18.75 µg L-1) in TCs detection. The approach was successfully used for the quantification of trace TCs in real milk samples.

A novel fluorescence platform for specific detection of tetracycline antibiotics based on [MQDA-Eu3+] system.

Tetracycline antibiotics (TCs) are extensively used in clinical medicine, animal husbandry, and aquaculture because of their cost-effectiveness and high antibacterial efficacy. However, the presence of TCs residues in the environment poses risks to humans. In this study, an inner filter effect (IFE) fluorescent probe, 2,2'-(ethane-1,2-diylbis((2-((2-methylquinolin-8-yl)amino)-2-oxoethyl)azanediyl))diacetic acid (MQDA), was developed for the rapid detection of Eu3+ within 30 s. And its complex [MQDA-Eu3+] was successfully used for the detection of TCs. Upon coordination of a carboxyl of MQDA with Eu3+ to form a [MQDA-Eu3+] complex, the carboxyl served as an antenna ligand for the effective detection of Eu3+ to intensify the emission intensity of MQDA via "antenna effect", the process was the energy absorbed by TCs via UV excitation was effectively transferred to Eu3+. Fluorescence quenching of the [MQDA-Eu3+] complex was caused by the IFE in multicolor fluorescence systems. The limits of detection of [MQDA-Eu3+] for oxytetracycline, chlorotetracycline hydrochloride, and tetracycline were 0.80, 0.93, and 1.7 µM in DMSO/HEPES (7:3, v/v, pH = 7.0), respectively. [MQDA-Eu3+] demonstrated sensitive detection of TCs in environmental and food samples with satisfactory recoveries and exhibited excellent imaging capabilities for TCs in living cells and zebrafish with low cytotoxicity. The proposed approach demonstrated considerable potential for the quantitative detection of TCs.

Integrated assessment of the spatial distribution, sources, degradation, and human risk of tetracyclines in honey in China.

Tetracyclines are widely used in Chinese apiculture. However, limited information is available on the presence of tetracycline residues in honey and the sources, degradation patterns, and associated health risks of these compounds. In this study, the presence of tetracyclines in honey samples across China was investigated over a four-year period. Additionally, the risks of dietary intake, as well as the sources and degradation patterns of tetracyclines in honey, were assessed. The three-dimensional spatial distributions (floral region, geographical region and entomological origin) of tetracyclines contamination varied significantly. Tetracycline residues in honey posed a moderate risk to children aged 3-10 years in Northwest China. Source analysis indicated that colony migration serves as the primary source of tetracyclines in honey. Based on the degradation patterns of tetracyclines in honey within colonies and during storage, oxytetracycline is more readily degraded than other tetracyclines. The main degradation products of tetracyclines are epimers and dehydration products, and the effects of these products on human health and the environment should be further evaluated in future studies. This comprehensive investigation provides valuable insights into the safe use and regulation of tetracyclines in Chinese apiculture.

Deep learning assisted logic gates for real-time identification of natural tetracycline antibiotics.

The overuse and misuse of tetracycline (TCs) antibiotics, including tetracycline (TTC), oxytetracycline (OTC), doxycycline (DC), and chlortetracycline (CTC), pose a serious threat to human health. However, current rapid sensing platforms for tetracyclines can only quantify the total amount of TCs mixture, lacking real-time identification of individual components. To address this challenge, we integrated a deep learning strategy with fluorescence and colorimetry-based multi-mode logic gates in our self-designed smartphone-integrated toolbox for the real-time identification of natural TCs. Our ratiometric fluorescent probe (CD-Au NCs@ZIF-8) encapsulated carbon dots and Au NCs in ZIF-8 to prevent false negative or positive results. Additionally, our independently developed WeChat app enabled linear quantification of the four natural TCs using the fluorescence channels. The colorimetric channels were also utilized as outputs of logic gates to achieve real-time identification of the four individual natural tetracyclines. We anticipate this strategy could provide a new perspective for effective control of antibiotics.

Covalent organic framework aerogel for high-performance solid-phase extraction of tetracycline antibiotics: Experiment and simulated calculation on adsorption behavior.

Three-dimensional sponge-architecture covalent organic frameworks (COFs)-aerogel was successfully designed and synthesized via a freeze-drying template approach, and utilized as an efficient sorbent in solid-phase extraction (SPE). A method for selective enrichment of pharmaceutical contaminants including tetracycline, chlortetracycline, methacycline and oxytetracycline in the environment and food samples was proposed by combining with high performance liquid chromatography (HPLC). To understand the adsorption mechanism, selectivity test and molecular dynamics (MD) simulated calculation were both carried out. The experimental and in-silico results demonstrated that the COFs-aerogel possessed high selectivity for contaminants with H bond acceptors/donors and good efficiency with maximum adsorption capacity up to 294.1 mg/g. The SPE-based HPLC method worked well in the range of 8-1000 ng/mL, with the need of little dose of adsorbent and sample volume while no need of spectrometer, outgoing the reported adsorbents. Under the optimized conditions, the intra-day and inter-day relative standard deviations (RSD) of repeatability were within 2.78-6.29 % and 2.44-8.42 % (n = 5). The results meet the current detection requirement for practical applications, and could be extended for further design of promising adsorbents.

Quantitative determination of tetracyclines in medicated feed for food-producing animals by HPLC-DAD.

Tetracyclines are a group of antibiotic substances largely administered through medicated feed to control diseases in food-producing animals. Fine dosing of antibiotics contained in medicated feed is crucial for the success of the treatment as well as minimising potential threats such as the spread of antimicrobial resistance and the transfer of antibiotic residues in food. A rapid analytical method based on HPLC with diode array detection (HPLC-DAD) was developed to quantify oxytetracycline, chlortetracycline and doxycycline in medicated feed. The reported method underwent in-house validation and was found to be suitable for the quantification of three target tetracyclines within the concentration range of 40-1000 mg kg-1 in official routine analysis. The method was applied to 103 official samples in the framework of the Italian National Plan on animal feed during the years 2021-2023 and nine non-compliant concentrations were identified in swine and fish feed samples.

An asynchronous response fluorescence sensor combines machine learning theory to qualitatively and quantitatively detect tetracyclines.

Excess use of tetracyclines poses significant health risks arising from animal-derived foods, meaning simple and sensitive methods to detect tetracyclines would be beneficial given current laboratory methods are complex and expensive. Herein, we describe an asynchronous response fluorescence sensor constructed based on Zn-based metal-organic framework and Ru(bpy)32+ (denoted as Ru@Zn-BTEC) for the qualitative and quantitative detection of tetracyclines in foods. Under excitation at 365 nm, the sensor emitted red fluorescence at 609 nm. When tetracyclines were present, these molecules aggregated in the Ru@Zn-BTEC framework, causing green fluorescence emission at 528 nm. The developed sensing system accurately distinguished the different categories of tetracyclines with a classifier accuracy of 94 %. The Ru@Zn-BTEC sensor demonstrated a detection limit of 0.012 µM and satisfactory recovery (87.81 %-113.84 %) for tetracyclines in food samples. This work provides a pathway for constructing asynchronous response fluorescence sensors for food analysis.

Comprehensive Assessment of Environmental Emissions, Fate, and Risks of Veterinary Antibiotics in China: An Environmental Fate Modeling Approach.

China is one of the major global consumers of veterinary antibiotics. Insufficient recognition of emissions and environmental contamination hamper global efforts to prevent antibiotic resistance development. This pioneering study combined empirical data and modeling approaches to predict total 2010-2020 emissions of 80 veterinary antibiotics ranging from 23,110 to 40,850 tonnes/year, after 36-50% antibiotic removal by manure treatment. Following an initial increase of 10% from 2010 to 2015, emissions declined thereafter by 43%. While 85% of emissions discharged into soils, approximately 56%, 23%, and 18% of environmental residue were ultimately distributed in soils, freshwaters, and seawaters under steady-state conditions. In 2020, 657 (319-1470) tonnes entered the ocean from inland freshwaters. Median ∑antibiotics concentrations were estimated at 4.7 × 103 ng/L in freshwaters and 2.9 ng/g in soils, with tetracyclines and sulfonamides as the predominant components. We identified 44 veterinary antibiotics potentially posing high risks of resistance development in freshwaters, with seven exhibiting high risks in >10% of Chinese freshwater areas. Tetracyclines were the category with the most antibiotics exhibiting elevated risks; however, sulfamethylthiazole demonstrated the highest individual compound risk. The Haihe River Basin displayed the highest susceptibility overall. The findings offer valuable support for control of veterinary antibiotic contamination in China.

Tetracyclines contamination in European aquatic environments: A comprehensive review of occurrence, fate, and removal techniques.

Tetracyclines are among the most commonly used antibiotics for the treatment of bacterial infections and the improvement of agricultural growth and feed efficiency. All compounds in the group of tetracyclines (tetracycline, chlorotetracycline, doxycycline, and oxytetracycline) are excreted in an unchanged form in urine at a rate of more than 70%. They enter the aquatic environment in altered and unaltered forms which affect aquatic micro- and macroorganisms. This study reviews the occurrence, fate, and removal techniques of tetracycline contamination in Europe. The average level of tetracycline contamination in water ranged from 0 to 20 ng/L. However, data regarding environmental contamination by tetracyclines are still insufficient. Despite the constant presence and impact of tetracyclines in the environment, there are no legal restrictions regarding the discharge of tetracyclines into the aquatic environment. To address these challenges, various removal techniques, including advanced oxidation, adsorption, and UV treatment, are being critically evaluated and compared. The summarized data contributes to a better understanding of the current state of Europe's waters and provides insight into potential strategies for future environmental management and policy development. Further research on the pollution and effects of tetracyclines in aquatic environments is therefore required.

Prediction of antibiotic sorption in soil with machine learning and analysis of global antibiotic resistance risk.

Although the sorption of antibiotics in soil has been extensively studied, their spatial distribution patterns and sorption mechanisms still need to be clarified, which hinders the assessment of antibiotic resistance risk. In this study, machine learning was employed to develop the models for predicting the soil sorption behavior of three classes of antibiotics (sulfonamides, tetracyclines, and fluoroquinolones) in 255 soils with 2203 data points. The optimal independent models obtained an accurate predictive performance with R2 of 0.942 to 0.977 and RMSE of 0.051 to 0.210 on test sets compared to combined models. Besides, a global map of the antibiotic sorption capacity of soil predicted with the optimal models revealed that the sorption potential of fluoroquinolones was the highest, followed by tetracyclines and sulfonamides. Additionally, 14.3% of regions had higher antibiotic sorption potential, mainly in East and South Asia, Central Siberia, Western Europe, South America, and Central North America. Moreover, a risk index calculated with the antibiotic sorption capacity of soil and population density indicated that about 3.6% of soils worldwide have a high risk of resistance, especially in South and East Asia with high population densities. This work has significant implications for assessing the antibiotic contamination potential and resistance risk.

Sensitive dual-signal detection and effective removal of tetracycline antibiotics in honey based on a hollow triple-metal organic framework nanozymes.

In this work, a colorimetric/fluorescent dual-signal mode sensor is proposed for the sensitive, selective and accurate detection and removal of tetracycline antibiotics (TCs). A triple-metal MOF of NiCoFe is successfully synthesized and controllable adjusted the shape of the hollow structure for the first time, and then modified with TCs aptamer. The as-prepared triple-atom MOF (apt-NiCoFe-MOF-74) exhibits well-defined hollow morphology, high crystallinity, and high surface areas endow their alluring adsorption and removal performances for TCs. More attractively, this triple-metal MOF show a good peroxidase-like activity and strong fluorescence property at 540 nm of apt-NiCoFe-MOF-74 when excitation wavelength was 370 nm. Inspire by this, a dual-signal output biosensor is constructed and the linear absorbance response is well correlated with wide range and low LOD for TCs. The biosensor provided an universal method with satisfactory sensitivity and accuracy for TCs analysis in real food samples.

Highly efficient removal of tetracyclines from water by a superelastic MOF-based aerogel: Mechanism quantitative analysis and dynamic adsorption.

Metal-organic frameworks (MOFs) were promising adsorbents for removing antibiotics, but the inherent poor recyclability of MOF powders limits further application. Moreover, the dominant adsorption mechanisms and their quantitative assessment are less studied. Here, ultrahigh adsorption capacities of 821.51 and 931.87 mg g-1 for tetracycline (TC) and oxytetracycline (OTC), respectively, were realised by a novel adsorbents (biochar loaded with MIL-88B(Fe), denoted as BC@MIL-88B(Fe)), which were further immobilised in a 3D porous gelatin (GA) substrate. The obtained BCM/GA200 showed superior adsorption performance under wide pH ranges and under the interference of humic acid. Moreover, it can survive >8 cycles and even maintain high adsorption efficiency in different actual water samples. Notably, BCM/GA200 can selectively remove tetracyclines in a multivariate system containing other kinds of antibiotics and from a dynamic adsorption system. Most importantly, the results of X-ray photoelectron spectroscopy, 2D Fourier transform infrared correlation spectroscopy (2D-FTIR-COS) and density functional theory techniques revealed that (1) for TC adsorption, at pH < 4.0, the contribution of complexation was 25 %-45 %, whereas pore filling and hydrogen bonding accounted for 39 %-72 % of the total uptake. At 4.0 < pH < 10.0, the contribution of complexation increased to 60 %-82 %, whereas electrostatic attraction and π-π interaction were 4 %-13 % and 2 %-10 %, respectively. (2) For OTC adsorption, complexation was dominant at 3.0 < pH < 10.0, accounting for 55 %-86 % of the total uptake, and electrostatic attraction and π-π interactions caused 3 %-10 % and 3 %-15 %, respectively. (3) At pH > 10.0, pore filling dominated TC and OTC adsorption. Finally, the reaction sequences of the main adsorption mechanisms were also probed by 2D-FTIR-COS. This work solves the poor recyclability of MOF powders and provides a mechanistic insight into antibiotic removal by MOFs.

Green hairy basil seed mucilage biosorbent for dispersive solid phase extraction enrichment of tetracyclines in bovine milk samples followed by HPLC analysis.

Unmodified hairy basil seed mucilage (Ocimum basilicum L.), with attractive features as structural functionality and adsorption capacity, was employed as a green biosorbent for dispersive solid phase extraction and enrichment of oxytetracycline, tetracycline, and doxycycline before quantitation by HPLC-UV for the first time. Hairy basil crushed seed increased the contacting surface area and was completely dispersed in the sample solution to extract tetracyclines under acidic condition with the assistance of ultrasonic waves. The analytes in the extraction phase were separated on a C18 column under isocratic condition with a mobile phase consisted of acetonitrile and trifluoroacetic acid. Influence of chemical and physical variables on the extraction efficiency of the developed method was investigated and optimized systematically. Under the optimal condition of all experimental parameters, good linear ranges were obtained at 15.0-500 µg L-1 for tetracyclines with determination coefficients more than 0.9994. Limits of detection (LODs) and limits of quantitation (LOQs) ranged 5.0-7.0 and 15.0 µg L-1, respectively. Relative standard deviations (RSDs) of the proposed method at 100 and 300 µg L-1 for TCs were less than 13 % and 10 %, respectively with percentage TC recoveries from spiked standard ranging 83.1-109.9 %. This simple, reliable, cost-effective, and environmentally friendly method was successfully applied for the analysis of tetracycline residues in milk. The greenness of the proposed method was assessed using the Analytical Eco-Scale and AGREE protocol.