Metal-free carbon-based anode for electrochemical degradation of tetracycline and metronidazole in wastewater.

Degradation of antibiotics through electrocatalytic oxidation has recently been comprehended as a promising strategy in wastewater treatment. Herein, nitrogen and sulphur doped graphene oxide (N,S-rGO) nanosheets were synthesized and employed as metal-free anodic material for electrochemical degradation of antibiotics, viz. metronidazole (MNZ) and tetracycline (TC). The synthesized anodic material was characterized using various spectral techniques and further the electrochemical behaviour of N,S-rGO was thoroughly examined. Thereafter, the N,S-rGO material was then employed as the anode material towards the electrocatalytic degradation of antibiotics. Parameters such as initial concentration of the antibiotics and current densities were varied and their effect towards the degradation of MNZ and TC were probed. Notably, the N,S-rGO based anode has shown impressive removal efficiency of 99% and 98.5%, after 120 min of reaction time for MNZ and TC, respectively, under optimized conditions. The obtained results including the kinetic parameters, removal efficiency and electrical efficiency ensure that the prepared anodic material has huge prospective towards real-time application for removal of antibiotics from water.

Bimetal-oxide (Fe/Co) modified bagasse-waste carbon coated on lead oxide-battery electrode for metronidazole removal.

Current study covers the preparation and application of a commercial modified lead oxide battery electrode (LBE) in electrochemical oxidation (ECO) of metronidazole (MNZ) in an aqueous phase. Modified electrode is prepared by doping of bimetal-oxide (Fe and Zn) nanoparticles (NPs) & single metal-oxide (Fe/Zn) on bagasse-waste carbon (bwc) which is further coated on LBE. The modified LBE electrode surface was examined for metal-oxide NPs through X-ray diffraction analysis (XRD). Different electrodes are prepared by varying combinations of two metal-oxide based on molar ratio and tested for electrochemical characterization and MNZ removal test. Based on large oxygen evolution potential in a linear sweep volumetry (LSV) analysis and high MNZ removal rate, the best electrode has been represented as Fe1:Co2-bwc/LBE which contains Fe & Co molar ratio of 1:2. Moreover, equilibrium attained at faster rate in degradation process of MNZ, where pseudo first order kinetics of 2.29 × 10-2 min-1 was obtained under optimized condition of (MNZ:100 mg/L, pH:7, CD: 30 mA/cm2 and electrolyte: 0.05 M Na2SO4). Maximum MNZ removal, total organic carbon removal (TOC), mineralization current efficiency (MCE) & energy consumption (EC) of 98.7%, 85.3%, 62.2% & 96.143 kW h/kg-TOC removed are found in 180 min of treatment time for Fe1:Co2-bwc/LBE electrode. Accelerated service life test confirms that the stability of modified electrode is enhanced by 1.5 times compared to pristine LBE. Repeatability test confirms that modified LBE (Fe1:Co2-bwc/LBE) can be utilized up to 3 times.

Efficient detection of metronidazole by a glassy carbon electrode modified with a composite of a cyclotriveratrylene-based metal-organic framework and multi-walled carbon nanotubes.

Constructing a sensitive and efficient sensor for determination of metronidazole (MNZ) is crucial in food field. Herein, a new cyclotriveratrylene-based metal-organic framework (MOF), namely, [Cd6L2(cyclen)2(H2O)2] (1), was constructed by self-assembly of functionalized 5,6,12,13,19,20-hexacarboxy-propoxy-cyclotriveratrylene (H6L), 1,4,7,10-tetraazacyclododecane (cyclen) and Cd(II) cation under solvothermal condition. In 1, adjacent Cd(II) cations are linked by L6- to produce a 2D polymeric structure with carboxylate and phenolic oxygen atoms. To enhance conductivity of 1, it was combined with conducting carbon materials, including mesoporous carbon (MC), reduced graphene oxide (RGO) and multi-walled carbon nanotubes (MWCNT), respectively, producing a series of composite materials. Remarkably, electrochemical tests showed that 1@MWCNT(1:1) featured a much better electrochemical detection performance for metronidazole (MNZ) than 1@MC and 1@RGO. The linear range for the detection of MNZ is up to 0.4-500 µM and the limit of detection (LOD) for MNZ reached 0.25 µM. Importantly, the fabricated sensor 1@MWCNT(1:1) was employed for the detection of MNZ in honey and egg with satisfactory result. High-performance liquid chromatography (HPLC) validated the high accuracy of the electrochemical method for the determination of honey and egg.

Inner filter effect-based near-infrared fluorescent probe for detection of metronidazole on a smartphone-integrated analytical platform.

Antibiotic residues pose a serious threat to ecosystems and food safety. Developing convenient, visual, and on-site detection methods is therefore in high demand and has a practical purpose. In this work, a near-infrared (NIR) fluorescent probe with an analysis platform based on a smartphone has been constructed for quantitative and on-site detection of metronidazole (MNZ). CdTe quantum dots with NIR emission at 710 nm (QD710) were prepared by using a simple hydrothermal method and showed good properties. A spectral overlap between absorption of MNZ and excitation of QD710 resulted in an effective inner filter effect (IFE) between QD710 and MNZ. Because of the IFE, the fluorescence of QD710 decreased gradually with increasing concentrations of MNZ. Based on the fluorescence response, quantitative detection and visualization of MNZ was achieved. NIR fluorescence analysis and the special IFE between probe and target can improve sensitivity and selectivity for MNZ. Additionally, these were also utilized for quantitative detection of MNZ in real food samples and the results were reliable and satisfactory. Meanwhile, a portable visual analysis platform in a smartphone was constructed for on-site analysis of MNZ, which can be used as an alternative method for detection of MNZ residues in situations with limited instrumental conditions. Therefore, this work provides a convenient, visual, and real-time analysis method for detection of MNZ and the analysis platform shows great potential for commercialization.

Green synthesis of Ag nanoparticles from Argemone mexicana L. leaf extract coated with MOF-5 for the removal of metronidazole antibiotics from aqueous solution.

There are growing concerns about the toxicity of metronidazole (MNZ) antibiotics in wastewater, which must be removed. This study used AgN/MOF-5 (1:3) to investigate the adsorptive removal of MNZ antibiotics from wastewater. Green synthesis of Ag-nanoparticles was from Argemone mexicana leaf aqueous extract blended with the synthesized MOF-5 in 1:3 by proportion. The adsorption materials were characterized by scanning electron microscope (SEM), N2 adsorption-desorption analysis, X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD). The surface area increased due to the appearance of micropores. Besides, the efficiency of AgN/MOF-5 (1:3) for MNZ removal was evaluated by adsorption properties, including key influential parameters (adsorbent dosage, pH, contact time, etc.) and adsorption mechanism, kinetics/isotherms. The results from the adsorption process conformed to pseudo-second-order kinetics (R2 = 0.998) and well fitted with the Langmuir isotherm having 191.1 mg/g maximum adsorption capacity. The adsorption mechanism of AgN/MOF-5 (1:3) was due to the interactions of π-π stacking, Ag-N-MOF covalent bonding and hydrogen bonding. Thus, AgN/MOF-5 (1:3) is a potential adsorbent for the removal of aqueous MNZ. The adsorption process is endothermic, spontaneous, and feasible based on the obtained thermodynamic parameter of ΔHO and ΔSO having 14.72 and 0.129 kJ/mol respectively.

Effect of Mn-based magnetic biochar /PS reaction system on oxidation of metronidazole.

In order to fully exploit the potential of magnetic biochar-based persulfate (PS) systems, Mn was utilized to modify the magnetic biochar-based catalysts through impregnation-pyrolysis method. Taking metronidazole (MNZ), a typical antifungal drug, as the target contaminant, the reactivity of the synthesized magnetic biochar (MMBC) catalyst was evaluated. The degradation efficiency of MNZ in MMBC/persulfate system was 95.6%, which was 13.0 times higher than that in MBC/PS system. The characterization experiments confirmed the degradation of metronidazole by surface binding free radicals, the ·OH and 1O2 played the key role in remove of MNZ in the system of MMBC/PS. Physicochemical characterization, Fe(II) semi-quantitative analysis and masking experiments confirmed that the doping of MBC with Mn increased its Fe(II) content (43.0 mg/g), approximately 7.8 times higher than that of pristine MBC. The increase of Fe(II) content in MBC is the key reason to improve the optimization of MBC modified with Mn. Simultaneously, both Fe(II) and Mn(II) were the key components of PS activation by magnetic biochar. This paper presents a method to optimize the high efficiency of PS activation by magnetic biochar.

Chromatographic analysis of ciprofloxacin and metronidazole in real human plasma: green analytical chemistry perspective.

Background: Ciprofloxacin and metronidazole are beneficial for treating mixed aerobic/anaerobic infections. Methods: Following the oral administration of ciprofloxacin and metronidazole in healthy volunteers, TLC and HPLC methods were described for their analysis in plasma samples. In the first method, a stationary phase of silica gel TLC F254 plates was used using acetone/water/triethylamine/glacial acetic acid (8:2:0.25:0.1 v/v). The second approach used a C18 column and methanol/aqueous 0.05% triethylamine (25:75 v/v), with a flow rate of 1 ml/min and detection at 325 nm. Four green metrics were used to evaluate the approaches' environmental impact. Conclusion: The study provided the sensitivity required for determination of the two drugs in the collected samples. The findings showed that results were within permitted ranges with minimal environmental impact.

Seasonal distribution and dynamic evolution of antibiotics and evaluation of their resistance selection potential and ecotoxicological risk at a wastewater treatment plant in Jinan, China.

The seasonal distribution and dynamic evolution of antibiotics in wastewater from main treatment areas and in sludge and their resistance selection potential and ecotoxicological risk were studied at a municipal wastewater treatment plant in Jinan, East China. Ten antibiotics were selected, and all were detected in wastewater and sludge samples, with fluoroquinolones showing the highest detection concentrations and frequencies. Seasonal fluctuations in the antibiotic concentrations in the influent, effluent, and sludge were observed, with the highest values in winter in most cases. The dynamic evolution of antibiotics during the treatment process differed among the seasons. The antibiotic removal efficiencies were incomplete, ranging from - 40.47 to 100%. Mass balance analysis showed that sulfonamides, roxithromycin, and metronidazole were mainly removed through biological processing, whereas fluoroquinolones, doxycycline, and chloramphenicol were removed through sludge adsorption. Levofloxacin, as well as a mixture of the 10 antibiotics from the effluent, could pose a low ecotoxicological risk to Daphnia in the receiving waters. Additionally, levofloxacin and ciprofloxacin in the effluent and ciprofloxacin and metronidazole in the sludge may facilitate the selection of antibiotic-resistant bacteria in the environment.

Effects of a milk oligosaccharide biosimilar on fecal characteristics, microbiota, and bile acid, calprotectin, and immunoglobulin concentrations of healthy adult dogs treated with metronidazole.

In recent dog and cat experiments, a novel milk oligosaccharide biosimilar (GNU100) positively modulated fecal microbiota and metabolite profiles, suggesting benefits to gastrointestinal health. The objective of this study was to investigate the effects of GNU100 on the fecal characteristics, microbiota, and bile acid (BA) concentrations of healthy adult dogs treated with antibiotics. Twelve healthy adult female dogs (mean age: 3.74 ± 2.4 yr) were used in an 8-wk crossover design study (dogs underwent both treatments). All dogs were fed a control diet during a 2-wk baseline, then randomly allotted to 1 of 2 treatments (diet only or diet + 1% GNU100) for another 6 wk. From weeks 2 to 4, dogs were orally administered metronidazole (20 mg/kg BW) twice daily. Fecal scores were recorded daily and fresh fecal samples were collected at weeks 2, 4, 5, 6, and 8 for measurement of pH, dry matter, microbiota populations, and BA, immunoglobulin A, and calprotectin concentrations. On weeks 0, 4, and 8, blood samples were collected for serum chemistry and hematology analysis. All data were analyzed as repeated measures using the Mixed Models procedure of SAS version 9.4, with significance considered P < 0.05. Metronidazole increased (P < 0.0001) fecal scores (looser stools) and modified (P < 0.05) fecal microbiota and BA profiles. Using qPCR, metronidazole reduced fecal Blautia, Fusobacterium, Turicibacter, Clostridium hiranonis, and Faecalibacterium abundances, and increased fecal Streptococcus and Escherichia coli abundances. DNA sequencing analysis demonstrated that metronidazole reduced microbial alpha diversity and influenced the relative abundance of 20 bacterial genera and families. Metronidazole also increased primary BA and reduced secondary BA concentrations. Most antibiotic-induced changes returned to baseline by week 8. Fecal scores were more stable (P = 0.01) in GNU100-fed dogs than controls after antibiotic administration. GNU100 also influenced fecal microbiota and BA profiles, reducing (P < 0.05) the influence of metronidazole on microbial alpha diversity and returning some fecal microbiota and secondary BA to baseline levels at a quicker (P < 0.05) rate than controls. In conclusion, our results suggest that GNU100 supplementation provides benefits to dogs treated with antibiotics, providing more stable fecal scores, maintaining microbial diversity, and allowing for quicker recovery of microbiota and secondary BA profiles which play an essential role in gut health.

Our objective was to test the effects of a novel milk oligosaccharide biosimilar (GNU100) on the fecal characteristics, microbiota, and bile acid (BA) concentrations of healthy adult dogs treated with antibiotics. Dogs were fed a control diet during a 2-wk baseline, then randomly allotted to 1 of 2 treatments (diet only or diet + 1% GNU100) for another 6 wk. From weeks 2 to 4, dogs were given an oral antibiotic. Fecal scores were recorded and fresh fecal samples were collected over time to assess fecal characteristics, microbiota populations, and BA concentrations. The antibiotic was shown to increase fecal scores (looser stools) and modify fecal microbiota populations (altered diversity and ~20 bacterial genera and families) and BA profiles (increased primary and reduced secondary BA). Most antibiotic-induced changes returned to baseline by week 8. In dogs fed GNU100, fecal scores were more stable and changes to microbial diversity were lower than controls after antibiotic administration. Fecal microbiota and secondary BA of GNU100-fed dogs also returned to baseline levels at a quicker rate than controls. These results suggest that GNU100 provides benefits to dogs given antibiotics, providing more stable fecal scores, maintaining microbial diversity, and allowing for quicker recovery of microbiota and BA profiles.

Study on the photocatalytic degradation of metronidazole antibiotic in aqueous media with TiO2 under lab and pilot scale.

Nowadays, the increased consumption of antibiotics, such as metronidazole (MTZ), leads to their introduction in wastewater as well as in the receiving surface waters due to their incomplete removal by conventional wastewater treatment plants. Heterogeneous photocatalysis is a versatile technology that can efficiently degrade such organic contaminants. In the present research, the photocatalytic degradation of MTZ with TiO2 P25 was studied under lab and pilot (CPC reactor) conditions. The antibiotic was efficiently removed at high rates in both cases (100 % and 91 %) following pseudo-first order kinetics with rate constants equal to 0.0452 min-1 (±RSD% = 0.68 % - 2.57 %) and 0.0462 L KJ-1 (±RSD% = 8.94 % - 21.64 %) respectively. Also, by scavenging lab scale experiments, the contribution of the generated reactive species was investigated and hydroxy radicals (HO•) were proposed as the predominant species. By applying high resolution mass spectrometry techniques, the transformation products (TPs) were identified and possible transformation pathways were proposed. The ecotoxicity of the TPs was assessed in silico using the ECOSAR software with the results revealing that most of them were less toxic than the parent compound. Similarly, the mutagenicity, developmental toxicity and bioconcentration factors of the TPs were predicted by utilizing the T.E.S.T. software and in their majority, were found to be less mutagenic and developmentally toxic than MTZ. The ecotoxicity monitoring with the Vibrio fischeri bioassay in both laboratory and pilot scale experiments indicated that through heterogeneous photocatalysis it is possible to reduce the toxicity of wastewater containing MTZ. Finally, the stability and reusability of the photocatalyst was investigated through three consecutive catalytic cycles with the results showing that the performance of TiO2 decreased after each use. For the heterogeneous photocatalysis with TiO2 to be a "real life" applicable technique, further studies focusing on catalyst regeneration and optimization of the catalytic conditions must be conducted.

A novel sensing platform for electrochemical detection of metronidazole antibiotic based on green-synthesized magnetic Fe3O4 nanoparticles.

The spread of antibiotic resistant genes has become a serious global concern. Thus, the development of efficient antibiotic monitoring systems to reduce their environmental risks is of great importance. Here, a potent electrochemical sensor was fabricated to detect metronidazole (MNZ) on the basis of green synthesis of Fe3O4 nanoparticles (NPs) using Sambucus ebulus L. leaves alcoholic plant extract as a safe and impressive reducing and stabilizing agent. Several analyses such as X-ray diffraction (XRD), Fourier transform infrared spectrophotometer (FTIR), thermogravimetric analysis (TGA), field emission scanning electron microscope (FESEM), energy dispersive X-ray spectroscopy (EDX), and dynamic light scattering (DLS) confirmed the production of homogeneous, monodisperse, regular, and stable magnetite NPs with a spherical morphology. The as-prepared Fe3O4NPs were afterwards applied to evaluate the electrochemical activity of MNZ by merging them with graphene nanosheets (GR NSs) on the glassy carbon electrode (GCE). The GR/Fe3O4NPs/GCE represented extraordinary catalytic activity toward MNZ with two dynamic ranges of 0.05-5 µM and 5-120 µM, limit of detection (LOD) of 0.23 nM, limit of quantification (LOQ) of 0.76 nM, and sensitivity of 7.34 µA µM-1 cm-2. The fabricated sensor was further employed as a practical tool for electrochemical detection of MNZ in real aqueous samples.

Effects of metronidazole on mesophilic and thermophilic fermentation: Biodegradation mechanisms, microbial communities, and reversibility.

Metronidazole (MNZ), an antibiotic that is specifically used for the treatment of anaerobic infections, may inhibit anaerobic fermentation. This work was designed to understand the fate and effects of MNZ in mesophilic fermentation (MF) and thermophilic fermentation (TF), respectively. The results showed that the removal of MNZ mainly occurred via biodegradation, rather than adsorption, and that MNZ could be completely degraded by opening the imidazole ring. MFs were more strongly inhibited by MNZ than TFs. MNZ concentration increased from 0 to 25 mg/L, hydrogen yield (HY) decreased from 167.5 to 16.8 mL/g glucose (90.0% decrease), and butyrate yield almost completely disappeared in MFs, whereas in TFs, HY decreased only from 101.1 to 89.3 mL/g glucose (11.7% decrease), and ethanol yield increased by 39.8%. Illumina MiSeq sequencing analysis showed that MNZ reduced the abundance of hydrogen-producing bacteria. Furthermore, the inhibition of MNZ on anaerobic fermentation was reversible.

Identification of the major photodegradant in metronidazole by LC-PDA-MS and its reveal in compendial methods.

Metronidazole in aqueous solution is sensitive to light and UV irradiation, leading to the formation of N-(2-hydroxyethyl)-5-methyl-l,2,4-oxadiazole-3-carboxamide. This is revealed here by liquid chromatography with tandem photo diode array detection and mass spectrometry (LC-PDA-MS) and further verified by comparison with the corresponding reference substance and proton nuclear magnetic resonance (1H-NMR). However, in current compendial tests for related substances/organic impurities of metronidazole, the above photolytic degradant could not be detected. Thus, when photodegradation of metronidazole occurs, it could not be demonstrated. In our study, an improved LC method was developed and validated, which includes a detection at a wavelength of 230 nm and optimization of mobile phase composition thereby a better separation was obtained.

Graphene-based materials for metronidazole degradation: A comprehensive review.

Due to its cytotoxic effect, metronidazole (MNZ) is a drug commonly used to treat bacterial, protozoal, and microaerophilic bacterial infections. After consumption, it undergoes a series of metamorphic reactions that lead to the degradation of oxidized, acetylated, and hydrolyzed metabolites in the environment. To eliminate such pollutants, due to their high potential, adsorption and photocatalysis extensive processes are used in which graphene can be used to improve efficiency. This review analyses the use of graphene as an absorbent and catalyst with a focus on absorption and photocatalytic degradation of MNZ by graphene-based materials (GBMs). The parameters affecting the adsorption, and photocatalytic degradation of MNZ are investigated and discussed. Besides, the basic mechanisms occurring in these processes are summarized and analyzed. This work provides a theoretical framework that can direct future research in the field of MNZ removal from aqueous solutions.

A dye encapsulated zinc-based metal-organic framework as a dual-emission sensor for highly sensitive detection of antibiotics.

Self-assembly of two Zn-MOFs, [Zn2L(DMF)3]·H2O·5DMF (1) and [Zn2L(H2O)2]·4H2O·3DMF (2), was achieved with an amide-functionalized tetracarboxylate ligand under similar conditions. Incorporated amide groups make the tetratopic linkers exhibit different configurations, tetrahedron and square, and subsequently combine tetrahedral [Zn2(CO2)4] clusters or square paddle-well [Zn2(CO2)4] clusters to afford a lon net for 1 and a nbo net for 2. Remarkably, 2 demonstrated high porosity and amide group decorated cages, and thereby proved to be a good capturing agent for a fluorescent dye molecule (DMASM). Consequently, a dual-emitting DMASM@2 sensor was successfully fabricated based on effective energy transfer from the host framework to DMASM with the variable luminescent color being visible to the naked eye. DMASM@2 could be used for the detection of metronidazole (MDZ) and dimetridazole (DTZ) with high sensitivity and remarkable recyclability.

Enhanced metronidazole removal by binary-species photoelectrogenic biofilm of microaglae and anoxygenic phototrophic bacteria.

High efficient removal of antibiotics during nutriments recovery for biomass production poses a major technical challenge for photosynthetic microbial biofilm-based wastewater treatment since antibiotics are always co-exist with nutriments in wastewater and resist biodegradation due to their strong biotoxicity and recalcitrance. In this study, we make a first attempt to enhance metronidazole (MNZ) removal from wastewater using electrochemistry-activated binary-species photosynthetic biofilm of Rhodopseudomonas Palustris (R. Palustris) and Chlorella vulgaris (C. vulgaris) by cultivating them under different applied potentials. The results showed that application of external potentials of -0.3, 0 and 0.2 V led to 11, 33 and 26-fold acceleration in MNZ removal, respectively, as compared to that of potential free. The extent of enhancement in MNZ removal was positively correlated to the intensities of photosynthetic current produced under different externally applied potentials. The binary-species photoelectrogenic biofilm exhibited 18 and 6-fold higher MNZ removal rate than that of single-species of C. vulgaris and R. Palustris, respectively, due to the enhanced metabolic interaction between them. Application of an external potential of 0V significantly promoted the accumulation of tryptophan and tyrosine-like compounds as well as humic acid in extracellular polymeric substance, whose concentrations were 7.4, 7.1 and 2.0-fold higher than those produced at potential free, contributing to accelerated adsorption and reductive and photosensitive degradation of MNZ.

Validity of caregivers' reports on prior use of antibacterials in children under five years presenting to health facilities in Gulu, northern Uganda.

INTRODUCTION: Given the frequent initiation of antibacterial treatment at home by caregivers of children under five years in low-income countries, there is a need to find out whether caregivers' reports of prior antibacterial intake by their children before being brought to the healthcare facility are accurate. The aim of this study was to describe and validate caregivers' reported use of antibacterials by their children prior to seeking care at the healthcare facility. METHODS: A cross sectional study was conducted among children under five years seeking care at healthcare facilities in Gulu district, northern Uganda. Using a researcher administered questionnaire, data were obtained from caregivers regarding reported prior antibacterial intake in their children. These reports were validated by comparing them to common antibacterial agents detected in blood and urine samples from the children using liquid chromatography with tandem mass spectrometry (LC-MS/MS) methods. RESULTS: A total of 355 study participants had a complete set of data on prior antibacterial use collected using both self-report and LC-MS/MS. Of the caregivers, 14.4% (51/355, CI: 10.9-18.5%) reported giving children antibacterials prior to visiting the healthcare facility. However, LC-MS/MS detected antibacterials in blood and urine samples in 63.7% (226/355, CI: 58.4-68.7%) of the children. The most common antibacterials detected from the laboratory analysis were cotrimoxazole (29%, 103/355), ciprofloxacin (13%, 46/355), and metronidazole (9.9%, 35/355). The sensitivity, specificity, positive predictive value (PPV), negative predictive value and agreement of self-reported antibacterial intake prior to healthcare facility visit were 17.3% (12.6-22.8), 90.7% (84.3-95.1), 76.5% (62.5-87.2), 38.5% (33.0-44.2) and 43.9% (k 0.06) respectively. CONCLUSION: There is low validity of caregivers' reports on prior intake of antibacterials by these children. There is need for further research to understand the factors associated with under reporting of prior antibacterial use.

The influence of injection volume on efficiency of microbore liquid chromatography columns for gradient and isocratic elution.

The injection volume and the associated column volume overload is one of the most common issues in miniaturized chromatography. The injection volume should not exceed 10% of the effective column volume. A further reduction of the injection volume leads to an increase in chromatographic efficiency. However, the signal intensity must be above a certain threshold to generate a chromatographic peak that can be detected. Therefore, the injection volume has to be optimized to reach the ideal balance between chromatographic efficiency and sensitivity. This study examined the general influence of the injection volume for both isocratic and gradient elution, depending on the retention factor and peak standard deviation. For this purpose, substances of different polarity were selected to represent a broad elution spectrum. Besides the model analyte naphthalene, these were mainly pharmaceuticals. For all measurements a microbore column with an ID of 300 µm and packed with 1.9 µm fully porous particles was used. For isocratic elution, the injection volume was varied between 4 and 16% of the effective column volume. The retention factors were adjusted between 2 and 10. For gradient elution, the injection volume was varied between 4 and 160% of the effective column volume. The observed effects were further investigated using the gradient kinetic plot theory. In isocratic elution, a loss in plate height up to 50% was observed for components that elute near the void time. A significant reduction of the chromatographic efficiency was noticed up to a retention factor of 4. In gradient elution, a reduction in peak capacity could only be observed if the injection volume exceeded 40% of the effective column volume. For some substances, only a slight loss in peak capacity was noticed even with a volume overload of 160%.

Crystal morphology control of synthetic giniite for enhanced photo-Fenton activity against the emerging pollutant metronidazole.

Metronidazole (MNZ) is a recalcitrant antibiotic with toxic and carcinogenic effects in aquatic environments. In this work, Fe5(PO4)4(OH)3·2H2O (giniite) particles were synthesised with three different alkaline cations (Li+, Na+ and K+) and used as Fenton catalysts for MNZ removal. It is shown that the addition of different cations during the hydrothermal synthesis process promote different morphologies from asterisk-like to flower-like and branches-like, maintaining the crystalline structure of pure giniite. The photo-Fenton activity of these particles was then evaluated through the degradation of MNZ under sunlight radiation for 9 h. The results indicate that the alkaline cation has a predominant role in the photo-Fenton efficiency, as demonstrated by the superior degradation efficiencies of Na@giniite particles (91.2% and 72.5% with giniite concentration of 0.2 g L-1 and 0.07 g L-1, respectively), related with its high surface area (10.7 m2 g-1). Thus, it is demonstrated the suitability of Na@giniite particles as Fenton catalyst for MNZ removal from water.

Poly(alizarin red S) modified glassy carbon electrode for square wave adsorptive stripping voltammetric determination of metronidazole in tablet formulation.

Potentiodynamically fabricated poly(alizarin red s) modified GCE was characterized using CV and EIS techniques. In contrast to the cyclic voltammetric response of the unmodified GCE for metronidazole, an irreversible reduction peak with three-folds of current enhancement and reduced overpotential at the poly(alizarin red s) modified GCE showed the catalytic effect of the modifier towards reduction of metronidazole. While observed peak potential shift with increasing pH (4.0-10.0) indicated the involvement of protons during the reduction of metronidazole, peak potential shift with scan rate (20-300 mV s-1) confirmed the irreversibility of the reduction reaction of metronidazole at the modified GCE. A better correlation for the dependence of peak current on scan rate (r2 = 0.9883) than on square root of scan rate (r2 = 0.9740) supplemented by slope value of 0.38 for plot of log(current) versus log(scan rate) indicated the reduction reaction of metronidazole at the surface of the modified electrode was predominantly adsorption controlled. Under the optimized method and solution parameters, reductive current response of tablet sample showed linear dependence on spiked standard concentration in a wide range (0-125 µM) with excellent determination coefficient r2, LoD and LoQ of 0.9991, 0.38, and 1.25 µM, respectively. Spike recovery of 97.9% and interference recovery of 96.2-97.5% in the presence of 21.28 and 31.92 µM of uric acid and ascorbic acid validated the applicability of the present method for determination of metronidazole in tablet formulation. The metronidazole content of the tested tablet formulation using standard addition method was found to be 97.6% of what is claimed by the tablet manufacturer making the developed method an excellent potential candidate for its applicability to determine metronidazole in real samples with complex matrix.