Rapid Determination of Pentazocine in Human Plasma and Urine by a Potentiometric Method

Abstract

A fast potentiometric determination method has been reported for pentazocine in human plasma without complicated pretreatments using a coated-wire potentiometric selective electrode. The sensing membrane was made by incorporating of ion-association complexes of pentazocine cation and sodium tetraphenyl borate (NaTPB) in a polyvinyl chloride. The sensor exhibited fast, stable, and linear Nernstian response over the range of 5 × 10^?5 to 0.1 mol L^?1 pentazocine with a slope of 57.8 mV per decade and with detection limit of 3.2 × 10^?5 mol L^?1. The proposed sensor has been used for determination of pentazocine in human plasma and urine.     

A Simple,Cost‐effective,and Environmentally Friendly Method for Determination of Ciprofloxacin in Drugs and Urine Samples Based on Electrogenerated Chemiluminescence

Ciprofloxacin is an antibiotic that belongs to the class of drugs known as quinolones and it is frequently used to treat a variety of bacterial infections. The present work aims the development of a simple, cost‐effective, and environmentally friendly method for the determination of ciprofloxacin in drugs and artificial urine samples due to the high importance of this antibiotic for the human health. The proposed method is based on the electrogenerated chemiluminescence (ECL) resulting from the reaction between the ciprofloxacin and the tris(2,2′‐bipyridyl)ruthenium(II) complex. This method exploits a screen‐printed carbon electrode positioned in an ECL cell with capacity to 50 μL of electrolytic solution. The ECL intensity was monitored with the aid of a photodiode. The ECL signal was simultaneously registered to the voltammetric measurements. Under optimized experimental conditions, the ECL method presented a linear response range for ciprofloxacin between 0.5 and 500 μmol L^?1 (or 0.0005 and 0.5 mmol L^?1). The proposed method presented a detection limit of 0.5 μmol L^?1 and it was successfully applied for the ciprofloxacin determination in drugs and artificial urine samples, with good accuracy and precision.     

Synthesis of ractopamine molecularly imprinted membrane and its application in the rapid determination of three β‐agonists in porcine urine samples

A novel molecularly imprinted membrane (MIM) with ractopamine (RAC) as the template and the hydrophilic PVDF membrane as the support was synthesized for the selective absorption of RAC and its structure analogues. The absorption behavior and selectivity of the MIM were studied. The experimental results showed that the MIM had the good selectivity to three β‐agonists including RAC, RIT, and formoterol (FOM) than that of nonimprinted membrane. The adsorption capacity for three compounds was above 1.88 μg/cm² of per membrane. Based on the clean‐up and enrichment of porcine urine samples with the MIM, a sensitive determination method of three β‐agonists in porcine urine samples by using MIM followed ultra performance chromatography coupled MS/MS detection was developed. The LOD and LOQ for RAC, RIT, and FOM were below 0.006 and 0.02 ng/mL, respectively. The mean recoveries, repeatability, and reproducibility of three compounds in porcine urine samples varied from 67.9 to 86.3%, from 3.3 to 10.8%, and from 5.3 to 8.5%, respectively. The presented method was applied to test 50 real porcine urine samples. It was demonstrated to be more sensitive and robust for the determination of RAC, RIT, and FOM in porcine urine.     

Determination of 5‐fluorocytosine, 5‐fluorouracil,and 5‐fluorouridine in hospital wastewater by liquid chromatography–mass spectrometry

Chemotherapeutics are pharmaceutical compounds the occurrence of which in the environment is of growing concern because of the increase in treatments against cancer diseases. They can reach the aquatic ecosystems after passing through wastewater treatment plants without complete removal. One of the most frequently used chemotherapeutics is 5‐fluorouracil which exhibits a strong cytostatic effect. In this paper, an analytical methodology was developed, validated, and applied to determine 5‐fluorouracil, its precursor, 5‐fluorocytosine, and its major active metabolite, 5‐fluorouridine, in hospital wastewater samples. Due to the expected low concentrations after dilution and interferences present in such a complex matrix, a very selective and sensitive detection method is required. Moreover, an extraction method must be implemented prior to the determination in order to purify the sample extract and preconcentrate the target analytes at micrograms per liter concentration levels. Solid‐phase extraction followed by liquid chromatography with tandem mass spectrometry was the combination of choice and all included parameters were studied. Under optimized conditions for wastewater samples analysis, recoveries from 63 to 108% were obtained, while intraday and interday relative standard deviations never exceeded 20 and 25%, respectively. Limits of detection between 61 and 620 ng/L were achieved. Finally, the optimized method was applied to samples from hospital wastewater effluents.     

Functionalization of Reduced Graphene Oxide with β‐cyclodextrin Modified Palladium Nanoparticles for the Detection of Hydrazine in Environmental Water Samples

A sensitive and selective hydrazine sensor was developed by β‐cyclodextrin modified palladium nanoparticles decorated reduced graphene oxide (PdNPs‐β‐CD/rGO) nanocomposite. The PdNPs‐β‐CD/rGO hybrid material was prepared by simple electrochemical method. The hydrophobic cavity of β‐CD ineracts with palladium nanoparticles by hydrophobic interaction and further it is uniformly assembled on the rGO surface through hydrogen bond formation, which is clearly confirmed by FT‐IR, FESEM and TEM. The high electrocatalytic activity of hydrazine oxidation was observed at −0.05 V (vs. Ag/AgCl) on PdNPs‐β‐CD/rGO modified electrode; due to the excellent stabilization, high catalytic activity and large surface area of the PdNPs‐β‐CD/rGO composite. The PdNPs‐β‐CD/rGO fabricated hydrazine sensor exhibited an excellent analytical performance, including high sensitivity (1.95 μA μM⁻¹ cm⁻²), lower detection limit (28 nM) and a wide linear range (0.05 to 1600 μM). We also demonstrated that the PdNPs‐β‐CD/rGO nanocomposite modified electrode is a highly selective and sensitive sensor towards detection of hydrazine among the various interfering species. Hence, the proposed hydrazine sensor is able to determine hydrazine in different water samples.     

Extractionless HPLC Method for the Determination of Naproxen in Human Plasma and Urine

Abstract

A simple and rapid (extractionless) high-performance liquid chromatographic method with ultraviolet detection, at 278 nm, is described for the determination of naproxen in human plasma and urine. Niflumic acid is used as internal standard. The chromatographic system consists of a reversed-phase C18-Spherisorb column with acetonitrile/0.1 M sodium acetate (35:65 v/v, pH 6.14) as the mobile phase. The retention time is 3.0 min for naproxen and 3.8 min for niflumic acid. The total run time is 5 min and the typical assay time is 10 min. The method is sufficiently sensitive for biopharmaceutical studies, after the oral administration of a single sustained release dose.     

Asymmetric Diels–Alder Reaction of α‐Substituted and β,β‐Disubstituted α,β‐Enals via Diarylprolinol Silyl Ether for the Construction of All‐Carbon Quaternary Stereocenters

The asymmetric Diels–Alder reaction of α‐substituted acrolein proceeds in the presence of the trifluoroacetic acid salt of trifluoromethyl‐substituted diarylprolinol silyl ether to afford the exo‐isomer with both excellent diastereoselectivity and high enantioselectivity. In the Diels–Alder reaction of a β,β‐disubstituted α,β‐unsaturated aldehyde, good exo‐selectivity and excellent enantioselectivity was obtained when the perchloric acid salt of the bulky triisopropyl silyl ether of trifluoromethyl substituted diarylprolinol was employed as an organocatalyst in the presence of water. In both cases, all‐carbon quaternary stereocenters are constructed enantioselectively.     

Novel adsorptive materials by adenosine 5ʹ‐triphosphate imprinted‐polymer over the surface of polystyrene nanospheres for selective separation of adenosine 5ʹ‐triphosphate biomarker from urine

In this study, we have developed a method to assess adenosine 5?‐triphosphate by adsorptive extraction using surface adenosine 5′‐triphosphate‐imprinted polymer over polystyrene nanoparticles (412 ± 16 nm) for selective recognition/separation from urine. Molecularly imprinted polymer was synthesized by emulsion copolymerization reaction using adenosine 5′‐triphosphate as a template, functional monomers (methacrylic acid, N‐isopropyl acrylamide, and dimethylamino ethylmethacrylate) and a crosslinker, methylenebisacrylamide. The binding capacities of imprinted and non‐imprinted polymers were measured using high‐performance liquid chromatography with UV detection with a detection limit of 1.6 ± 0.02 µM of adenosine 5′‐triphosphate in the urine. High binding affinity (Q_MIP, 42.65 µmol/g), and high selectivity and specificity to adenosine 5′‐triphosphate compared to other competitive nucleotides including adenosine 5?‐diphosphate, adenosine 5?‐monophosphate, and analogs such as adenosine, adenine, uridine, uric acid, and creatinine were observed. The imprinting efficiency of imprinted polymer is 2.11 for urine (Q_MIP, 100.3 µmol/g) and 2.51 for synthetic urine (Q_MIP, 48.5 µmol/g). The extraction protocol was successfully applied to the direct extraction of adenosine 5′‐triphosphate from spiked human urine indicating that this synthesized molecularly imprinted polymer allowed adenosine 5′‐triphosphate to be preconcentrated while simultaneously interfering compounds were removed from the matrix. These submicron imprinted polymers over nano polystyrene spheres have a potential in the pharmaceutical industries and clinical analysis applications.     

Application of Bar Adsorptive Microextraction for the Determination of Levels of Tricyclic Antidepressants in Urine Samples

This work entailed the development, optimization, validation, and application of a novel analytical approach, using the bar adsorptive microextraction technique (BAμE), for the determination of the six most common tricyclic antidepressants (TCAs; amitriptyline, mianserin, trimipramine, imipramine, mirtazapine and dosulepin) in urine matrices. To achieve this goal, we employed, for the first time, new generation microextraction devices coated with convenient sorbent phases, polymers and novel activated carbons prepared from biomaterial waste, in combination with large-volume-injection gas chromatography-mass spectrometry operating in selected-ion monitoring mode (LVI-GC-MS(SIM)). Preliminary assays on sorbent coatings, showed that the polymeric phases present a much more effective performance, as the tested biosorbents exhibited low efficiency for application in microextraction techniques. By using BAμE coated with C₁₈ polymer, under optimized experimental conditions, the detection limits achieved for the six TCAs ranged from 0.2 to 1.6 μg L⁻¹ and, weighted linear regressions resulted in remarkable linearity (r² > 0.9960) between 10.0 and 1000.0 μg L⁻¹. The developed analytical methodology (BAμE(C18)/LVI-GC-MS(SIM)) provided suitable matrix effects (90.2–112.9%, RSD ≤ 13.9%), high recovery yields (92.3–111.5%, RSD ≤ 12.3%) and a remarkable overall process efficiency (ranging from 84.9% to 124.3%, RSD ≤ 13.9%). The developed and validated methodology was successfully applied for screening the six TCAs in real urine matrices. The proposed analytical methodology proved to be an eco-user-friendly approach to monitor trace levels of TCAs in complex urine matrices and an outstanding analytical alternative in comparison with other microextraction-based techniques.     

Determination of betaine,l‐carnitine,and choline in human urine using a self‐packed column and column‐switching ion chromatography with nonsuppressed conductivity detection

A simple method for the determination of betaine, l ‐carnitine, and choline in human urine was developed based on column‐switching ion chromatography coupled with nonsuppressed conductivity detection by using a self‐packed column. A pretreatment column (50 mm × 4.6 mm, id) packed with poly(glycidyl methacrylate‐divinylbenzene) microspheres was used for the extraction and cleanup of analytes. Chromatographic separation was achieved within 10 min on a cationic exchange column (150 mm × 4.6 mm, id) using maleic anhydride modified poly(glycidyl methacrylate‐divinylbenzene) as the particles for packing. The detection was performed by ion chromatography with nonsuppressed conductivity detection. Parameters including column‐switching time, eluent type, flow rates of eluent, and interfering effects were optimized. Linearity (r ² ≥ 0.99) was obtained for the concentration range of 0.50–100, 0.75–100, and 0.25–100 μg/mL for betaine, l ‐carnitine, and choline, respectively. Detection limits were 0.12, 0.20, and 0.05 μg/mL for betaine, l ‐carnitine, and choline, respectively. The intra‐ and interday accuracy and precision for all quality controls were within ±10.11%. Satisfactory recovery was observed between 92.5 and 105.0%. The validated method was successfully applied for the determination of betaine, l ‐carnitine, and choline in urine samples from healthy people.     

Novel Electrochemically Treated Graphite Pencil Electrode Surfaces for the Determination of Trace α‐Naphthol in Water Samples

An electrochemically treated graphite pencil electrode (PGPE) has been simply prepared for trace level determination of α‐naphthol. The pretreatment of GPE surfaces is conducted in 0.8 M NaOH by cycling the potential between +1.3 and +1.9 V for 50 CV segments at a scan rate of 100 mV s^?1. The influence of the pretreatment is studied extensively, and optimum conditions are obtained. Linear sweep anodic stripping voltammetry (LSASV) is used for the determination of α‐naphthol. Based on the constructed calibration curve, a linear range of 0.01 μM to 2.0 μM with a detection limit of 1.5 nM (S/N=3) is obtained. The results reveal that the electrochemical treatment of the GPE surface improves its electrochemical catalytic activity with reference to surfaces of the non‐treated GPE. The present method is applied for the determination of trace α‐naphthol in real water samples.     

A Nanoporous Supramolecular Metal–Organic Framework Based on a Nucleotide: Interplay of the π···π Interactions Directing Assembly and Geometric Matching of Aromatic Tails

Self-assembly is the most powerful force for creating ordered supramolecular architectures from simple components under mild conditions. π···π stacking interactions have been widely explored in modern supramolecular chemistry as an attractive reversible noncovalent tool for the nondestructive fabrication of materials for different applications. Here, we report on the self-assembly of cytidine 5’-monophosphate (CMP) nucleotide and copper metal ions for the preparation of a rare nanoporous supramolecular metal-organic framework in water. π···π stacking interactions involving the aromatic groups of the ancillary 2,2’-bipyridine (bipy) ligands drive the self-assemblies of hexameric pseudo-amphiphilic [Cu6(bipy)6(CMP)2(µ-O)Br4]²⁺ units. Owing to the supramolecular geometric matching between the aromatic tails, a nanoporous crystalline phase with hydrophobic and hydrophilic chiral pores of 1.2 and 0.8 nanometers, respectively, was successfully synthesized. The encoded chiral information, contained on the enantiopure building blocks, is transferred to the final supramolecular structure, assembled in the very unusual topology 8T6. These kinds of materials, owing to chiral channels with chiral active sites from ribose moieties, where the enantioselective recognition can occur, are, in principle, good candidates to carry out efficient separation of enantiomers, better than traditional inorganic and organic porous materials.     

Dating Sediments by EPR Using Al-h Centre: A Comparison between the Properties of Fine (4–11 µm) and Coarse (>63 µm) Quartz Grains

The possibility of EPR dating for sediments using Al-h signals of fine (4–11 μm) grains of quartz has not been previously discussed. Here, the Al-h and peroxy EPR spectra of fine (4–11 μm) and coarse (63–90, 125–180 μm) sedimentary quartz from thoroughly investigated loess sites in Eastern Europe were examined. By comparing experimental spectra with a simulated signal, we evaluated the overestimation observed when using the standard approach established by Toyoda and Falguères to measure Al-h intensity for different doses of radiation, up to 40,000 Gy. This overestimation, caused by the presence of peroxy signals, was much more pronounced for fine grains. Fine grains exhibited some additional dose-dependent signals, which, for some samples, caused a complete distortion of the Al-h spectra at high doses, making it impossible to measure the standard amplitude. We propose a new approach to measuring Al-h signal intensity, focusing on the peak-to-baseline amplitude of the part of the signal at g ≈ 2.0603, which is not affected by the peroxy signals and therefore has the potential of providing more accurate results. The shapes of dose response curves constructed for coarse and fine grains using the new approach show considerable similarity, suggesting that Al-h centre formation in fine and coarse grains upon artificial radiation at room temperature follows the same pattern.     

Electrochemical Sensor‐Based Ruthenium Nanoparticles on Reduced Graphene Oxide for the Simultaneous Determination of Ethinylestradiol and Amoxicillin

The composite material of reduced graphene and Ru nanoparticles (rGO/RuNP) was obtained by electrochemical oxidation of ruthenium nanoparticles immobilised on the glassy carbon electrode (GCE) surface and used for simultaneous electroanalysis of drugs. There are many discussions in the scientific community about the decrease in therapeutic efficacy of contraceptives when associated with antibiotics. The antibiotic effect of the antagonist can increase the contraceptive excretion levels in urine, indicating a reduction in the body and thus a decrease in the desired effect. Using the DPV technique, it was possible to quantify ethinylestradiol (EE2) and amoxicillin (AMX) with a linear response range, 5.50x10⁻⁸ – 1.20x10⁻⁶ mol L⁻¹, and LOD, 2.04 nmol L⁻¹ and 1.63 nmol L⁻¹, respectively. The results for the electrochemical behaviour of EE2 and AMX using GCE/rGO/RuNP were compared with GCE/rGO and GCE. The GCE/rGO/RuNP showed greater stability and separation anodic peak currents, suitable for the quantification of organic molecules in samples of environmental interest, as well as clinical and food samples.     

Formation and Rearrangement of Homoserine Depsipeptides and Depsiproteins in the α‐Ketoacid–Hydroxylamine Ligation with 5‐Oxaproline

The primary products of the chemical ligation of α‐ketoacids and 5‐oxaproline peptides are esters, rather than the previously reported amides. The depsipeptide product rapidly rearranges to the amide in basic buffers. The formation of esters sheds light on possible mechanisms for the type II KAHA ligations and opens an avenue for the chemical synthesis of depsiproteins.     

Diphenylprolinol Silyl Ether as a Catalyst in an Enantioselective,Catalytic Michael Reaction for the Formation of α,α‐Disubstituted α‐Amino Acid Derivatives

Direct and enantioselective : Diphenylprolinol silyl ether was found to catalyze the direct, asymmetric Michael reaction of 4‐substituted 2‐aryl‐2‐oxazoline‐5‐one and α,β‐unsaturated aldehydes, affording the chiral α,α‐disubstituted α‐amino acid derivatives with excellent enantioselectivity.

     

Umpolung Strategy for α‐Functionalization of Aldehydes for the Addition of Thiols and other Nucleophiles

Nucleophile–nucleophile coupling is a challenging transformation in organic chemistry. Herein we present a novel umpolung strategy for α‐functionalization of aldehydes with nucleophiles. The strategy uses organocatalytic enamine activation and quinone‐promoted oxidation to access O‐bound quinol‐intermediates that undergo nucleophilic substitution reactions. These quinol‐intermediates react with different classes of nucleophiles. The focus is on an unprecedented organocatalytic oxidative α‐thiolation of aldehydes. The reaction scope is demonstrated for a broad range of thiols and extended to chemoselective bioconjugation, and applicable to a large variety of aldehydes. This strategy can also encompass organocatalytic enantioselective coupling of α‐branched aldehydes with thiols forming quaternary thioethers. Studies indicate a stereoselective formation of the intermediate followed by a stereospecific nucleophilic substitution reaction at a quaternary stereocenter, with inversion of configuration.     

Micelle-Enhanced Spectrofluorimetric Method for the Determination of Antibacterial Trovafloxacin in Human Urine and Serum

A spectrofluorimetric method for the determination of trace amounts of the antibacterial trovafloxacin has been developed based on its native fluorescence in a micellar solution of sodium dodecyl sulfate (SDS). The wavelengths of excitation and emission were 270 nm and 410 nm, respectively. The optimised method allows the determination of 3.0–40.0 ng mL⁻¹ of trovafloxacin in 8 mM SDS solution and 0.1 M acetic acid-sodium acetate buffer solution (pH 5.5), with a relative standard deviation of 1.5% (for a level of 12.0 ng mL⁻¹) and a detection limit of 0.8 ng mL⁻¹. The method was applied to the determination of trovafloxacin in human urine and serum samples. It was validated using HPLC as a reference method. Recovery levels of the method reached 100% in all cases.     

Method for the Determination of DES,Hexestrol and Dienestrol Residues in Bovine Urine Using GC-MSD

Abstract

A method is described to determine Diethylestilbestrol, Hexestrol and Dienestrol residues in bovine urine, using GC-MSD, working with the SIM system. The urine was centrifuged and the pH adjusted to 9 with 32% NaOH, then subjected to a solid phase extraction procedure using C-18 columns (Baker, spe-500). These columns were eluted with methanol, the alcohol extract was evaporated to obtain a solid residue. The derivation of the stilbene was performed with BSTFA:TMCS 99:1, incubated 15 min at 70°C. The final extracts were dissolved in acetonitrile and injected in a GC-MSD apparatus (quadrupol electronic impact). Three characteristic ions were monitored for each product studied. The detection limit achieved is 2 ppb for Diethylestilbestrol and Hexestrol and 3 ppb for Dienestrol.     

Octadecyl Bonded Silica Membrane Disk Modified with Cyanex302 for Preconcentration and Determination of Traces of Cobalt in Urine by Flame Atomic Absorption Spectrometry

Abstract

Octadecyl bonded silica membrane disk was impregnated with Cyanex302 for flame atomic absorption spectrometric determination of traces of cobalt(II) in urine. The solid phase extraction method developed using the modified disk was systematically investigated for sorption-desorption of cobalt(II). Cobalt(II) was quantitatively sorbed on the disk at pH 6.0 and eluted using 15 cm³ of 1 × 10^?3 M HCl. The lower limit of detection for cobalt(II) was 1.5 µg dm^?3 and the preconcentration factor 133 with a precision in terms of relative standard deviation (% R. S. D.) 0.6. The reusability of the modified disk was ≥35 cycles.