Green adsorbents for pharmaceutics removal from urine: Analysis of isotherms, kinetics, adsorption interactions, cost estimation, and environmental impact.

Husks of rice (RH), coffee (CH), and cholupa (CLH) were used to produce natural adsorbents. The natural adsorbents were used to remove pharmaceuticals such as diclofenac, ciprofloxacin, and acetaminophen in a mixture of distilled water. However, CH stood out for its efficiency in removing ciprofloxacin (74%) due to the higher concentration of acidic groups, as indicated by the Boehm method. In addition, CH removed 86% of ciprofloxacin individually. Therefore, CH was selected and used to remove other fluoroquinolones, such as levofloxacin and Norfloxacin. Although electrostatic interactions favored removals, better removal was observed for ciprofloxacin due to its smaller molecular volume. Then, ciprofloxacin was selected, and the effect of pH, matrix, and adsorbent doses were evaluated. In this way, using a pH of 6.2 in urine with a dose of 1.5 g L-1, it is possible to adsorb CIP concentrations in the range (0.0050-0.42 mmol L-1). Subsequently, the high R2 values and low percentages of APE and Δq indicated better fits for pseudo-second-order kinetics, suggesting a two-stage adsorption. At the same time, the Langmuir isotherm recommends a monolayer adsorption with a Qm of 25.2 mg g-1. In addition, a cost of 0.373 USD/g CIP was estimated for the process, where the material can be reused up to 4 times with a CIP removal in the urine of 51%. Consequently, thermodynamics analysis showed an exothermic and spontaneous process with high disorder. Furthermore, changes in FTIR analysis after adsorption suggest that CH in removing CIP in urine involves electrostatic attractions, hydrogen bonds and π-π interactions. In addition, the life cycle analysis presents, for the 11 categories evaluated, a lower environmental impact of the CIP removal in urine with CH than for the preparation of adsorbent, confirming that the adsorption process is more environmentally friendly than materials synthesis or other alternatives of treatments. Furthermore, future directions of the study based on real applications were proposed.

Selective adsorption of antibiotics from human urine using biochar modified by dimethyl sulfoxide, deep eutectic solvent, and ionic liquid.

Antibiotics present in human urine pose significant challenges for the use of urine-based fertilizers in agriculture. This study introduces a novel two-stage approach utilizing distinct biochar types to mitigate this concern. Initially, a modified biochar selectively adsorbed azithromycin (AZ), ciprofloxacin (CPX), sulfamethoxazole (SMX), trimethoprim (TMP), and tetracycline (TC) from human urine. Subsequently, a separate pristine biochar was employed to capture nutrients. Biochar, derived from sewage sludge and pyrolyzed at 550 and 700 °C, was modified using dimethyl sulfoxide, deep eutectic solvent, and ionic liquid to enhance antibiotic removal in the first stage. The modifications introduced hydrophilic functional groups (-OH/-COOH), which favor antibiotic adsorption. Adsorption kinetics followed the pseudo-second-order model, with the Langmuir isotherm model best describing the adsorption data. The maximum adsorption capacities for AZ, CPX, SMX, TMP, and TC after the modification were 196.08, 263.16, 81.30, 370.37, and 833.33 µg/g, respectively. Pristine biochar exhibited a superior ammonia adsorption capacity compared to the modified biochar. Hydrogen bonding, electrostatic attraction, and chemisorption drove antibiotic adsorption on the modified biochar. Regeneration efficiency declined due to solvent accumulation and potential byproduct formation on the biochar surface (<30% removal capacity after three cycles). This study presents innovative biochar modification strategies for selective antibiotic adsorption, laying the groundwork for environmentally friendly urine-based fertilizers in agriculture.

Amperometric detection of antibiotic drug ciprofloxacin using cobalt-iron Prussian blue analogs capped on carbon nitride.

Ciprofloxacin (CIP) electrochemical sensor was constructed using cobalt-iron Prussian blue analogs decorated on carbon nitride (Co-Fe-PBA@CN). Co-Fe-PBA decorated on CN was fabricated using a simple sonication-assisted hydrothermal method to prepare the composite to obtain a cube-shaped structure decorated on CN sheets. The fabricated Co-Fe-PBA@CN was physically characterized using XRD and SEM analysis. Then, the fabricated composite was electrochemically studied to sense antibiotic drug ciprofloxacin (CIP). The electrochemical behavior was investigated using tools such as cyclic voltammetry (CV) and amperometric I-t studies. The Co-Fe-PBA@CN modified electrode displays a wide linear range (0.005-300 and 325-741 µM) with a low detection limit (0.7389 and 1.0313 nM) and good sensitivity (0.3157 and 0.2263 µA.µM-1cm-2) toward CIP. The Co-Fe-PBA@CN modified electrode also exhibits good selectivity, reproducibility, and repeatability toward CIP. The proposed sensor was validated with real sample analysis, biological samples like urine and blood serum containing commercially available ciprofloxacin tablets were studied, and the results demonstrate good viability.

Collection and Separation of Fleroxacin and Ciprofloxacin in Ultrasound-Assisted Ionic Liquid Salting-Out Microextraction System.

An ultrasound-assisted ionic liquid (IL) salting-out microextraction system was developed and applied for the extraction of quinolone antibiotics from urine. A precipitate was formed from the salt and IL, and it acted as the sorbent for the analytes. The precipitate containing the analyte was separated by filtration, redissolved, and the solution then was evaporated. The resulting extract was redissolved for high-performance liquid chromatographic analysis. Several parameters, including type and volume of IL, the type and amount of salts, sample pH, temperature and extraction time were optimized. Under the optimal experimental conditions, the limits of detection for fleroxacin and ciprofloxacin were 3.12 and 4.97 µg L-1, respectively. When the present method was applied to real urine sample analysis, the analyte recoveries ranged from 82.3 to 106.8%. This ultrasound-assisted IL salting-out microextraction system had the characteristics of high recoveries, shorter separation time and easy-to-perform collection procedure, which yielded the method to have potential for wide application.

A turn-on fluorescence probe Eu3+ functionalized Ga-MOF integrated with logic gate operation for detecting ppm-level ciprofloxacin (CIP) in urine.

The threatening of antibiotic drugs for human and environment is being paid more and more attention. Ciprofloxacin (CIP), a strong quinolone antibiotic drug widely used in therapeutic treatments, is the most frequently detected in surface waters among the fluoroquinolones, which represents animal and human health risks. A novel highly fluorescent Ga-based hybrid (Eu3+@1) has been synthesized based on metal-organic framework (MOF) by encapsulating lanthanide cations Eu3+ in its channels. The as-synthesized compound possesses excellent water and pH-independent stability. It displays week red luminescence of Eu3+ in itself and can sense the CIP concentration as turn-on fluorescent probe in the human urine. With addition of CIP, the evident luminescence enhancement is clearly observed from the Eu3+@1. Linear correlation between the fluorescence intensity and the concentration of CIP is investigated, proving the excellent performance of Eu3+@1 in the detection of CIP with linear range (0.01-0.2 mg/mL) and low detection limit (2.4 ppm or 2.4 µg/mL). The response time is also very quick, less than 3 min. Based on these findings, we introduce AND logic gate strategy to the probe. The input of the logic gates (0, 1), (0, 1, 1), (1, 1, 1) cause the different outputs of CIP determination "LOW" (<25 ppm),"NORMAL" (25-76 ppm), "HIGH" (>76 ppm), respectively. The novel strategy can be applied for a real-time CIP concentration evaluation by intelligent discrimination.

Simultaneous determination of levofloxacin and ciprofloxacin in human urine by ionic-liquid-based, dual-template molecularly imprinted coated graphene oxide monolithic solid-phase extraction.

A novel method was developed to simultaneously determine the ciprofloxacin and levofloxacin levels in human urine using an ionic-liquid-based, dual-molecularly imprinted polymer-coated graphene oxide solid-phase extraction monolithic column coupled with high-performance liquid chromatography. The molecularly imprinted monolithic column was prepared using ciprofloxacin and levofloxacin as templates, 1-vinyl-3-ethylimidazolium bromide as the functional monomer, and graphene oxide as the core material. The resulting imprinted monoliths were characterized by scanning electron microscopy and fourier transform-infrared spectroscopy. The efficiency and capacity of the ionic-liquid-based imprinted monolithic column were investigated by varying the synthesis conditions (ciprofloxacin/levofloxacin ratio and template/functional monomer/cross-linker ratio). The solid-phase extraction process was optimized by changing the washing and eluting conditions. The results suggested that the proposed ionic-liquid-based molecularly imprinted solid-phase extraction monolithic-high-performance liquid chromatography method could separate ciprofloxacin and levofloxacin efficiently and simultaneously from human urine. The mean recoveries of ciprofloxacin and levofloxacin ranged from 89.2 to 93.8 and 86.7 to 94.6%, respectively. The intra- and interday relative standard deviation ranged from 0.9 to 3.2 and 0.8 to 2.9%, respectively. Under the optimized conditions, the recoveries of ciprofloxacin and levofloxacin were more than 93.8%.

UPLC-MS/MS method validation of ciprofloxacin in human urine: Application to biodegradability study in microbial fuel cell.

To enable the reliable quantification of ciprofloxacin in human urine, a sensitive and selective assay based on liquid chromatography-tandem mass spectrometry was developed. The chromatographic separation of the ciprofloxacin was carried out on a Zorbex Eclipse C18 column using methanol and ammonium acetate as a mobile phase by the gradient elution method. The developed assay covered a wide range of concentrations (1.56-100 ng/mL) with a lower limit of detection of 0.76 ng/mL. Quantification was performed using the multiple reaction monitoring transitions 331.8/231 for ciprofloxacin and 362/318 for ofloxacin (internal standard). This assay was validated for linearity, accuracy, precision and recovery. The validated method was then applied to the biodegradability of ciprofloxacin (99%) from human urine in the microbial fuel cell.

Rethinking urinary antibiotic breakpoints: analysis of urinary antibiotic concentrations to treat multidrug resistant organisms.

OBJECTIVE: The present study analyzed whether renally eliminated antibiotics achieve sufficient urinary concentrations based on their pharmacokinetic/pharmacodynamic principles to effectively eradicate organisms deemed resistant by automated susceptibility testing. RESULTS: Lower median minimum inhibitory concentrations against enterobacteriaceae were noted for ceftriaxone, cefepime, and doripenem when comparing Etest® to Vitek®. All Pseudomonas aeruginosa isolates were susceptible to cefepime, ciprofloxacin, and doripenem with both susceptibility methods, but higher median minimum inhibitory concentrations were observed with Etest®. Urine concentrations/time profiles were calculated for standard doses of ceftriaxone, cefepime, doripenem, and ciprofloxacin. The data presented in the current study suggests high urine concentrations of antibiotics may effectively eradicate bacteria which were determined to be resistant per in vitro susceptibility testing.

Direct Biological Sample Analyses by Laserspray Ionization Miniature Mass Spectrometry.

With improved performances, miniature mass spectrometers are becoming suitable for more practical applications. At the same time, the coupling of an approximate ionization source is essential in terms of minimizing sample preparation and broadening the range of samples that could be analyzed. In this study, an atmospheric pressure laserspray ionization (AP-LSI) source was coupled with our home developed miniature ion trap mass spectrometer. The whole system is compact in size, and biological samples could be directly analyzed with minimum sample preparation. Direct detections of peptides, proteins, drugs in whole blood, and urine could be achieved with high sensitivity. The analyses of tissue sections were demonstrated, and different regions in a tissue section could be differentiated based on their lipid profiles. Results suggest that the coupling of AP-LSI with miniature mass spectrometer is a powerful technique, which could potentially benefit target molecule analysis in biological and medical applications.

Urinary excretion of ciprofloxacin after administration of extended release tablets in healthy volunteers. Swellable drug-polyelectrolyte matrix versus bilayer tablets.

This paper builds on a previous paper in which new ciprofloxacin extended-release tablets were developed based on a ciprofloxacin-based swellable drug polyelectrolyte matrix (SDPM-CIP). The matrix contains a molecular dispersion of ciprofloxacin ionically bonded to the acidic groups of carbomer, forming the polyelectrolyte-drug complex CB-CIP. This formulation showed that the release profile of the ciprofloxacin bilayer tablets currently commercialised can be achieved with a simpler strategy. Thus, since ciprofloxacin urine concentrations are associated with the clinical cure of urinary tract infections, the goal of this work was to compare the urinary excretion of SDPM-CIP tablets with those of the CIPRO XR® bilayer tablets. A batch of SDPM-CIP tablets was manufactured by the wet granulation method and the CB-CIP ionic complex was obtained in situ. Fasted healthy volunteers received a single oral dose of 500 mg ciprofloxacin of either formulation in a randomised crossover study. Urinary concentrations were assessed by HPLC at intervals up to 36 h. Pharmacokinetic parameters (rate of urinary excretion, maximum urine excretion rate, tmax, area under the curve, amount and percentage of the ciprofloxacin dose excreted in urine) showed no statistical differences between both formulations at any of the time intervals of collection. The processing conditions to obtain SDPM-CIP tablets are easy to scale up since they involve technology currently employed in the pharmaceutical industry and the process is less challenging to implement. In addition, SDPM-CIP tablets met pharmacopoeial quality specifications.

Simultaneous determination of paracetamol and ciprofloxacin in biological fluid samples using a glassy carbon electrode modified with graphene oxide and nickel oxide nanoparticles.

A simple and highly selective electrochemical method using a glassy carbon electrode (GCE) modified with graphene oxide (GO) and nickel oxide nanoparticles (NiONPs) was developed for the simultaneous determination of paracetamol (PAR) and ciprofloxacin (CIP). The electrochemical characterisation of the modified GCE was performed by cyclic voltammetry and electrochemical impedance spectroscopy. The morphological characterisation of the GO and NiONPs was performed by scanning electron microscopy and transmission electron microscopy. Under optimised conditions, using square wave voltammetry, the simultaneous determination of PAR and CIP using the NiONPs-GO-CTS: EPH/GCE sensor shows a linear concentration range from 0.10 to 2.9µmolL-1 and 0.040-0.97µmolL-1, with detection limits of 6.7 and 6.0 nmol L-1, respectively. The NiONPs-GO-CTS: EPH/GCE sensor showed good reproducibility, repeatability and stability. Furthermore, the proposed method was successfully applied for the simultaneous determination of PAR and CIP in synthetic biological fluid samples.

Assessment of urinary pharmacokinetics and pharmacodynamics of orbifloxacin in healthy dogs with ex vivo modelling.

PURPOSE: The aim of this study was to investigate the urinary pharmacokinetics (PK) of orbifloxacin (OBFX) administered at 5 mg kg-1 in six healthy dogs. A further aim was to use an ex vivo model to evaluate the urinary PK and pharmacodynamics (PD) of OBFX to determine its urinary bactericidal titre (UBT), which represents the maximal dilution of urine allowing bactericidal activity. METHODOLOGY: Fourteen urinary tract infection (UTI) pathogenic strains of five bacterial species (Escherichia coli, Pseudomonas aeruginosa, Klebsiella pneumoniae, Proteus mirabilis and Staphylococcuspseudintermedius) were used. Urine samples were obtained every 4 h for the first 24 h after OBFX administration, for measurement of urine drug concentration and UBT.Results/Key findings. The urine OBFX concentration peaked at 0-4, 4-8 or 4-8 h after administration, with a maximum concentration of 383±171 µg ml-1. Overall, the fluctuation in median UBT closely correlated with that of the mean urine OBFX concentration. In addition, the median areas under the UBT-time curves (AUBTs) were significantly inversely correlated with the MICs for OBFX in the tested strains (P<0.01). Notably, median UBTs and AUBTs were extremely low (0-0.5 and 2-5, respectively) in OBFX-resistant E. coli strains with MIC ≥8 µg ml-1. CONCLUSION: The fluctuation of UBTs closely correlated with that of urine concentration, and UBT values depended on the susceptibility of the bacterial strains to OBFX. We believe that ex vivo modelling to determine UBTs is useful to evaluate the urinary PK/PD of antimicrobials indicated for UTIs in dogs.

Detection of Ciprofloxacin in Urine through Sensitized Lanthanide Luminescence.

Ciprofloxacin, a fluoroquinolone antibiotic, is widely used for the treatment of bacterial infection in humans due to its broad antibacterial spectrum. An excessive use or overdose of ciprofloxacin on the other hand can cause several adverse effects not only to humans but also to microorganisms. Unabsorbed ciprofloxacin in the body is mostly excreted through urine and finally goes to the environment, providing a drug resistance pressure on bacteria. Hence a simple and efficient detection method of ciprofloxacin is necessary, which, for example, can be used to analyze ciprofloxacin content in urine. Although ciprofloxacin itself shows inherent fluorescence, direct fluorescent detection of ciprofloxacin in raw urine sample is difficult due to autofluorescence of urine by other components. Herein we report that a Tb(III) complex of DO3A (1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid) can be efficiently sensitized by ciprofloxacin to emit luminescence separately from the urine autofluorescence wavelength region. Tb-DO3A shows excellent sensitivity with a detection limit of three parts per billion in aqueous buffer solution. Further, Tb-DO3A is used to detect ciprofloxacin with high sensitivity and selectivity in a raw urine sample without any purification or separation procedures in the concentrations ranging from 1 µg·mL-1 to 50 µg·mL-1. The direct measurement of ciprofloxacin excreted in urine may be used to control overdose of the drug.

Molecularly imprinted macroporous monoliths for solid-phase extraction: Effect of pore size and column length on recognition properties.

The series of macroporous monolithic molecularly imprinted monoliths differed by pore size, column length (volume) and amount of template used for imprinting was synthesized using methacrylic acid and glycerol dimethacrylate as co-monomers and antibiotic ciprofloxacin as a template. The prepared monoliths were characterized regarding to their permeability, pore size, porosity, and resistance to the flow of a mobile phase. The surface morphology was also analyzed. The slight dependence of imprinting factor on flow rate, as well as its independence on pore size of macroporous molecularly imprinted monolithic media was observed. The column obtained at different conditions exhibited different affinity of ciprofloxacin to the imprinted sites that was characterized with Kdiss values in the range of 10(-5)-10(-4)M. The solid-phase extraction of ciprofloxacin from such biological liquids as human blood serum, human urine and cow milk serum was performed using the developed monolithic columns. In all cases, the extraction was found to be 95.0-98.6%. Additionally, the comparison of extraction of three fluoroqinolone analogues, e.g. ciprofloxacin, levofloxacin and moxifloxacin, from human blood plasma was carried out. Contrary to ciprofloxacin extracted with more than 95%, this parameter did not exceed 40% for its analogues.

A Simple DNA-based Electrochemical Biosensor for Highly Sensitive Detection of Ciprofloxacin Using Disposable Graphene.

In this work we exploited the electrostatic interaction of double stranded DNA (dsDNA) with drug components to construct a simple, but highly sensitive, DNA-electrochemical sensor for detecting ciprofloxacin. The following straightforward three-step procedure was performed to determine ciprofloxacin: (i) dsDNA-layer immobilization on the surface of the working graphene-modified screen-printed carbon electrode; (ii) dsDNA-ciprofloxacin interaction for 2 min; and (iii) electrochemical measurement using square-wave voltammetry. An increased oxidation of the guanine component was observed, at +1.0 V, as a result of the electrostatic interaction of positively charged ciprofloxacin with the negatively charged nucleic acid sugar phosphate. Based on the International Conference on Harmonization Guidelines, a linear relationship between the guanine oxidation peak and ciprofloxacin concentration (0.1 to 100 µM) was obtained with a detection limit of 0.1 µM. Our developed sensor is straightforward to construct and use, requiring no multi-step time-consuming preconditioning of electrodes. It is highly sensitive and selective in the detection of ciprofloxacin, and has the potential to be useful in the future fabrication of rapid and portable on-site food safety analysis devices.

Preparation, degradation and in vitro release of ciprofloxacin-eluting ureteral stents for potential antibacterial application.

Drug-eluting stents with biodegradable polymers as reservoirs have shown great potential in the application of interventional therapy due to their capability of local drug delivery. Herein, poly(l-lactide-co-ε-caprolactone) (PLCL) with three different compositions as carriers for ciprofloxacin lactate (CIP) was coated on ureteral stents by the dipping method. To simulate a body environment, degradation behavior of PLCL as both the bulk film and the stent coating was evaluated in artificial urine (AU, pH6.20) respectively at 37°C for 120days by tracing their weight/Mn loss, water absorption and surface morphologies. Furthermore, the release profile of the eluting drug CIP on each stent exhibited a three-stage pattern, which was greatly affected by the degradation behavior of PLCL except for the burst stage. Interestingly, the degradation results on both macroscopic and molecular level indicated that the release mechanism at stage I was mainly controlled by chain scission instead of the weight loss or morphological changes of the coatings. While for stage II, the release profile was dominated by erosion resulting from the hydrolysis reaction autocatalyzed by acidic degradation residues. In addition, ciprofloxacin-loaded coatings displayed a significant bacterial resistance against E. coli and S. aureus without obvious cytotoxicity to Human foreskin fibroblasts (HFFs). Our results suggested that PLCL copolymers with tunable degradation rate as carriers for ciprofloxacin lactate could be used as a promising long-term antibacterial coating for ureteral stents.

The nanocrystalline coordination polymer of AMT-Ag for an effective detection of ciprofloxacin hydrochloride in pharmaceutical formulation and biological fluid.

The present report highlights a cost effective and portable AMT-Ag nanocrystalline coordination polymer (NCCP) based electrochemical sensor for an efficient sensing of biologically active drug molecule ciprofloxacin hydrochloride (CFX). The AMT-Ag NCCP, is synthesized using an easily accessible organic ligand 2-amino-5-mercapto-1,3,4-thiadiazole (AMT) with silver nitrate. In the infinite polymer array of AMT-Ag, silver (I) centers are bridged by tecton AMT through the exocyclic thiol and amino linkage. A successful ultra‒trace detection of CFX has been achieved due to the prominent electron channeling through the pores of polymeric nano-crystallites. The efficient charge transfer arises at the interface of electrolyte and AMT-Ag nano-crystals anchored electrode through hydrophobic interaction and π-π electron coupling. The voltammogram reveals the critical redox features of CFX and provides a clear representation about the steps involved in the AMT-Ag assisted oxidation of CFX. This specific signature further applied in the voltammetric assay of CFX in pharmaceutical formulation (eye drops) and biological fluid (urine) by a significantly high sensitivity (0.002µA/µM and 0.007µA/µM) and detection limit (22nM and 60nM) respectively without any interference. Therefore, the developed AMT-Ag NCCP could serve as a highly valuable platform for the fabrication of high-performance electrochemical sensors for the detection of biologically important drug molecules.

Spectrophotometric and chemometric methods for determination of imipenem, ciprofloxacin hydrochloride, dexamethasone sodium phosphate, paracetamol and cilastatin sodium in human urine.

New accurate, sensitive and selective spectrophotometric and chemometric methods were developed and subsequently validated for determination of Imipenem (IMP), ciprofloxacin hydrochloride (CIPRO), dexamethasone sodium phosphate (DEX), paracetamol (PAR) and cilastatin sodium (CIL) in human urine. These methods include a new derivative ratio method, namely extended derivative ratio (EDR), principal component regression (PCR) and partial least-squares (PLS) methods. A novel EDR method was developed for the determination of these drugs, where each component in the mixture was determined by using a mixture of the other four components as divisor. Peak amplitudes were recorded at 293.0 nm, 284.0 nm, 276.0 nm, 257.0 nm and 221.0 nm within linear concentration ranges 3.00-45.00, 1.00-15.00, 4.00-40.00, 1.50-25.00 and 4.00-50.00 µg mL(-1) for IMP, CIPRO, DEX, PAR and CIL, respectively. PCR and PLS-2 models were established for simultaneous determination of the studied drugs in the range of 3.00-15.00, 1.00-13.00, 4.00-12.00, 1.50-9.50, and 4.00-12.00 µg mL(-1) for IMP, CIPRO, DEX, PAR and CIL, respectively, by using eighteen mixtures as calibration set and seven mixtures as validation set. The suggested methods were validated according to the International Conference of Harmonization (ICH) guidelines and the results revealed that they were accurate, precise and reproducible. The obtained results were statistically compared with those of the published methods and there was no significant difference.

In-tube magnetic solid phase microextraction of some fluoroquinolones based on the use of sodium dodecyl sulfate coated Fe3O4 nanoparticles packed tube.

In-tube magnetic solid phase microextraction (in-tube MSPME) of fluoroquinolones from water and urine samples based on the use of sodium dodecyl sulfate (SDS) coated Fe3O4 nanoparticles packed tube has been reported. After the preparation of Fe3O4 nanoparticles (NPs) by a batch synthesis, these NPs were introduced into a stainless steel tube by a syringe and then a strong magnet was placed around the tube, so that the Fe3O4 NPs were remained in the tube and the tube was used in the in-tube SPME-HPLC/UV for the analysis of fluoroquinolones in water and urine samples. Plackett-Burman design was employed for screening the variables significantly affecting the extraction efficiency. Then, the significant factors were more investigated by Box-Behnken design. Calibration curves were linear (R(2)>0.990) in the range of 0.1-1000µgL(-1) for ciprofloxacin (CIP) and 0.5-500µgL(-1) for enrofloxacin (ENR) and ofloxacin (OFL), respectively. LODs for all studied fluoroquinolones ranged from 0.01 to 0.05µgL(-1). The main advantages of this method were rapid and easy automation and analysis, short extraction time, high sensitivity, possibility of fully sorbent collection after analysis, wide linear range and no need to organic solvents in extraction.

On the performance of multiway methods for simultaneous quantification of two fluoroquinolones in urine samples by fluorescence spectroscopy and second-order calibration strategies.

In the present work, the analytical performance of three multi-way algorithms has been evaluated. The proposed analytical problem was the simultaneous determination of moxifloxacin and ciprofloxacin in human urine samples using fluorescence spectroscopy. Parallel factor analysis (PARAFAC), self-weighted alternating trilinear decomposition (SWATLD) and unfolded partial least squares combined with the residual bilinearization procedure (U-PLS/RBL) have been compared, regarding their ability to solve the proposed problem. In this study, "second-order advantage" was also exploited for the mentioned algorithms through different calibration strategies. The three-way data was obtained via fluorescence spectroscopy, so that excitation-emission matrices (EEM) of the samples were recorded as the analytical signals. The accuracy and precision of each individual algorithm for analyzing the drugs in urine samples were compared using root mean square error of prediction (RMSEP), recovery and elliptical joint confidence region (EJCR) plots. The results revealed that each of the three algorithms could be applied for determination of moxifloxacin and ciprofloxacin, despite different EEM subsets and calibration strategies. However, better analytical performances were observed through PARAFAC and U-PLS/RBL modeling for MOX and CIP, respectively. So, by coupling the multi-way decomposition algorithms with fluorescence spectroscopy, a main part of preliminary sample preparation steps can be eliminated and experimental procedure might be significantly simplified, while achieving desirable analytical performance.