Evaluation of oxalic acid extraction and quantification methods in the different purslane (Portulaca oleracea L.) matrices and spinach (Spinacea oleracea).

Purslane (Portulaca oleracea) and spinach (Spinacea oleracea) are species with elevated levels of oxalic acid, an antinutrient that interferes in the bioaccessibility of minerals such as calcium and iron. Evaluating methods to determine oxalic acid content with reduced matrix interference, such as employing Flame Atomic Absorption Spectrometry (FAAS), can enhance the specificity of determinations. The different matrices of purslane (whole plant, leaves, and juice) and spinach (whole plant) were tested using three extraction methods (M1, M2, and M3). The oxalic acid content was evaluated by UV-vis spectrophotometry and FAAS (Flame Atomic Absorption Spectrometry). The absence of the precipitation step in M1 resulted in high levels of oxalic acid in the investigated matrices. The quantification of oxalic acid by FAAS for M2 (6M HCl for 1 hour at 100°C) and M3 (0.25N HCl for 15 minutes at 100°C) in the samples of purslane leaves and spinach whole plants yielded statistically similar results. However, the analysis by UV-vis spectrophotometry for M2 and M3 showed significant discrepancies in all evaluated samples, suggesting interference from colored compounds in the food matrix.•Comparison of methods of extraction•Comparison of UV-vis spectrophotometer and FAAS in the quantification of oxalic acid•Analysis of antinutrients in plant matrices.

Antibacterial Efficacy and Characterization of Silver Nanoparticles Synthesized via Methanolic Extract of Fomes fomentarius L. Fr.

Green synthesis employs environmentally friendly, biodegradable substances for the production of nanomaterials. This study aims to develop an innovative method for synthesizing silver nanoparticles (AgNPs) using a methanolic extract of Fomes fomentarius L. Fr. as the reducing agent and to assess the potential antibacterial properties of the resulting nanoparticles. The successful synthesis of AgNPs was confirmed through characterization techniques such as UV-visible (UV-Vis) spectrophotometry, Fourier-transform infrared spectroscopy (FT-IR), and powder X-ray diffraction (PXRD). The UV-Vis analysis revealed an absorption peak at 423 nm, while FT-IR identified key phytochemical compounds involved in the reduction process. PXRD analysis indicated a face-centered cubic (fcc) structure with prominent peaks observed at 2θ = 38°, 44.6°, 64.6°, and 78°, confirming the crystalline nature of the AgNPs, with a crystallite diameter of approximately 24 nm, consistent with TEM analysis. The synthesized AgNPs demonstrated significant antibacterial activity, particularly against S. aureus, with higher efficacy against gram-positive bacteria.

Comparative performance of liquid chromatography and spectrophotometry in determining metformin hydrochloride within pharmaceutical formulations.

The present study compared the performance of Ultra-high performance liquid chromatography (UHPLC) and UV-Vis spectrophotometry for the quantification of metformin hydrochloride in five commercially available metformin hydrochloride products with different strengths. The metformin hydrochloride was measured in the UHPLC with a mobile phase consisting of a mixture of 0.05 M phosphate buffer solution and methanol (35:65, v/v) with a pH of 3.6. Metformin hydrochloride was determined spectrophotometrically at 234 nm using a mixture of methanol and water as a blank. The methods' linearity for metformin hydrochloride was within the concentration range of (2.5-40 µg/ml) in both techniques. The validation process encompassed assessments of specificity, selectivity, linearity, accuracy, precision, the lower limit of quantification (LLOQ), the lower limit of detection (LLOD), robustness, and system suitability. For the UHPLC validation method, the repeatability and reproducibility (expressed as relative standard deviation) were less than 1.578 and 2.718 %, respectively. The LLOQ for metformin hydrochloride was 0.625 µg/ml, and the LLOD was 0.156 µg/ml. For the UV-Vis spectrophotometric validation method, the repeatability and reproducibility (stated as relative standard deviation) were less than 3.773 and 1.988 %, respectively. The percentage recovery results for the five brands of metformin hydrochloride tablets were (98-101 %) and (92-104 %) for the UHPLC and UV-Vis spectrophotometric methods, respectively. In conclusion, the described methodologies were successfully employed for the quantitative analysis of metformin hydrochloride in different pharmaceutical tablet products.

Comparative Analysis of Laboratory-Based and Spectroscopic Methods Used to Estimate the Algal Density of Chlorella vulgaris.

Chlorella vulgaris is of great importance in numerous exploratory or industrial applications (e.g., medicals, food, and feed additives). Rapid quantification of algal biomass is crucial in photobioreactors for the optimization of nutrient management and the estimation of production. The main goal of this study is to provide a simple, rapid, and not-resource-intensive estimation method for determining the algal density of C. vulgaris according to the measured parameters using UV-Vis spectrophotometry. Comparative assessment measurements were conducted with seven different methods (e.g., filtration, evaporation, chlorophyll a extraction, and detection of optical density and fluorescence) to determine algal biomass. By analyzing the entire spectra of diluted algae samples, optimal wavelengths were determined through a stepwise series of linear regression analyses by a novel correlation scanning method, facilitating accurate parameter estimation. Nonlinear formulas for spectrometry-based estimation processes were derived for each parameter. As a result, a general formula for biomass concentration estimation was developed, with recommendations for suitable measuring devices based on algae concentration levels. New values for magnesium content and the average single-cell weight of C. vulgaris were established, in addition to the development of a rapid, semiautomated cell counting method, improving efficiency and accuracy in algae quantification for cultivation and biotechnology applications.

A Comprehensive Examination of UV-VIS Spectrophotometric Methods in Pharmaceutical Analysis Between 2015-2023.

BACKGROUND: Quality control is a system of validated procedures in which many samples, including active pharmaceutical ingredients and final products, are analyzed using standard or validated analytical methods. METHOD: Analytical methods used in analyzing active pharmaceutical ingredients or final products in the pharmaceutical industry can be methods registered in pharmacopeias and developed by the company itself. For this reason, published papers related to pharmaceutical analysis attract analysts and researchers' attention. In this study, pharmaceutical analysis and bioanalysis studies carried out between 2015 and 2023 were examined using Google Scholar, and the recent trends were determined for pharmaceutical analysis. Among the published papers performing conventional analytical techniques for pharmaceutical analysis, those applying UV-VIS spectrophotometry method were selected to predict a future perspective in this study. In addition to the data obtained, the current situation of the pharmaceutical industry was considered to correlate with the obtained data for pharmaceutical analysis. RESULTS: The results were presented with comparative tables and summarizing graphs. Interpreting the results allowed us to determine the trends that pharmaceutical analysis studies will lead in the future. This study can be helpful for researchers working on pharmaceutical analysis in both the industry and academia to predict future trends in pharmaceutical analysis. As a result of the literature research covering the dates 2015-2023, 56% of UV-VIS Spectrophotometric methods are used on pharmaceutical dosage forms, 27% are bulk, 16% are pure, 2% are biological materials, and 0.4% are herbal. Made from materials. Of these studies, 28% were conducted in the 200-240 nm range, 27% were conducted in the 240-300 nm range, and only 44% were conducted at >300 nm. Interpreting the results allowed us to determine the trends that pharmaceutical analysis studies will lead in the future. CONCLUSION: This study can be helpful for researchers working on pharmaceutical analysis in both the industry and academy side to predict future trends for pharmaceutical analysis.

Dispersive micro-solid phase extraction (D-µSPE) of nickel on activated nanodiamonds@Bi2WO6 nanocomposite from water and food samples.

This study presents an original nano-sorbent using activated nanodiamonds@Bi2WO6 to separate and enrich nickel ions from water and food samples. FTIR, XRD, FE-SEM, FE-SEM-EDX, EDS-TEAM, TGA, and BET were used to characterize the nanocomposite. It has a large surface area, active functional groups, and better reactivity. Ni(II) ions were determined as Ni(II)-PADAP chelates using UV-VIS spectroscopy. The parameters were studied and optimized, including pH (6), eluent type and volume (1 mL), ligand quantity (10 µg), sorbent dosage (20 mg), and contact time (1 min). The method has a low limit of detection (LOD) of 1.6 µg L-1, a limit of quantification (LOQ) of 5.3 µg L-1, a relative standard deviation of 4.5%, and a preconcentration factor of 10. The method was validated by applying to certified reference materials (BCR estuarine water 505 and 1573a NIST). The method was successfully applied to tap waters, industrial waste waters, and vegetables.

Exploring the interaction of biologically active compounds with DNA through the application of the SwitchSense technique, UV-Vis spectroscopy, and computational methods.

DNA is a key target for anticancer and antimicrobial drugs. Assessing the bioactivity of compounds involves in silico and instrumental studies to determine their affinity for biomolecules like DNA. This study explores the potential of the switchSense technique in rapidly evaluating compound bioactivity towards DNA. By combining switchSense with computational methods and UV-Vis spectrophotometry, various bioactive compounds' interactions with DNA were analyzed. The objects of the study were: netropsin (as a model compound that binds in the helical groove), as well as derivatives of pyrazine (PTCA), sulfonamide (NbutylS), and anthraquinone (AQ-NetOH). Though no direct correlation was found between switchSense kinetics and binding modes, this research suggests the technique's broader utility in assessing new compounds' interactions with DNA. used as analytes whose interactions with DNA have not been yet fully described in the literature.

Determination of seawater COD spectra using double-loop contraction and sorted frog optimization.

This study develops a novel double-loop contraction and C value sorting selection-based shrinkage frog-leaping algorithm (double-contractive cognitive random field [DC-CRF]) to mitigate the interference of complex salts and ions in seawater on the ultraviolet-visible (UV-Vis) absorbance spectra for chemical oxygen demand (COD) quantification. The key innovations of DC-CRF are introducing variable importance evaluation via C value to guide wavelength selection and accelerate convergence; a double-loop structure integrating random frog (RF) leaping and contraction attenuation to dynamically balance convergence speed and efficiency. Utilizing seawater samples from Jiaozhou Bay, DC-CRF-partial least squares regression (PLSR) reduced the input variables by 97.5% after 1,600 iterations relative to full-spectrum PLSR, RF-PLSR, and CRF-PLSR. It achieved a test R2 of 0.943 and root mean square error of 1.603, markedly improving prediction accuracy and efficiency. This work demonstrates the efficacy of DC-CRF-PLSR in enhancing UV-Vis spectroscopy for rapid COD analysis in intricate seawater matrices, providing an efficient solution for optimizing seawater spectra.

Development of UV-Vis spectroscopy-based analysis method for determination of tin(IV) in epilobium parviflorum (hoary willowherb) tea using deep eutectic solvent based preconcentration.

In this study, a UV-Vis Spectroscopy-based method was developed for the determination of tin(IV) in epilobium parviflorum tea samples after preconcentration. The preconcentration process was carried out using the liquid-liquid microextraction technique. Before starting the analysis, optimization studies were carried out for the variables likely to affect the experimental results. As a result of the analyzes performed under optimum conditions, the detection limit of our method was calculated as 16.83 µg/L. The percent relative standard deviation value was calculated as 1.25% (n = 8) and linearity was found in the range of 10-1000 µg/L. Recovery experiments were performed on epilobium parviflorum tea samples using the matrix matching method. As a result of the analyzes made on teas belonging to three different brands, recovery results ranging from 92 to 117% were obtained.

A UV-Vis spectroscopic detection method for cobalt ions in zinc sulfate solution based on discrete wavelet transform and extreme gradient boosting.

Zinc is a crucial strategic metal resource. The concentration of cobalt ions in zinc refining solution significantly impacts the efficiency of zinc electrolysis production. The traditional method of detecting cobalt ions in zinc solution is time-consuming, labor-intensive and ineffective. However, optical detection offers the advantage of high efficiency and low cost, making it a potential replacement for the traditional method. In this study, the spectral curve of cobalt ions in zinc solution is detected by ultraviolet-visible (UV-Vis) spectrophotometry. Additionally, we propose a model for the concentration-absorbance relationship of cobalt ions in zinc solution based on discrete wavelet transform and extreme gradient boosting (DWT-XGBoost) algorithms. First, the spectral curve's information region is denoised by using Savitzky-Golay (S-G) smoothing. Then, the denoised spectra is utilized to extract features through discrete wavelet transform and principal component analysis. These features are used as inputs to the XGBoost model to establish prediction models for low and high cobalt ions in zinc solution. Bayesian optimization is implemented to adjust the model's hyperparameters, including learning rate, feature sampling ratio, to enhance the prediction performance. Finally, applying the model to zinc solution samples from a zinc smelter and compared with other state-of-the-art algorithms, the DWT-XGBoost algorithm exhibits the lowest RMSE, MAE and MAPE, with values of 0.034 mg/L, 0.025 mg/L, 6.983 % for low cobalt and with values of 0.231 mg/L, 0.067 mg/L and 0.472 % for high cobalt. The experimental results demonstrate that the DWT-XGBoost model exhibits significantly superior prediction performance.

Development of Visible Spectrophotometric Methods for the Determination of Tricyclic Antidepressants Based on Formation of Molecular Complexes with p-Benzoquinones.

Tricyclic antidepressants are commonly employed in the management of major depressive disorders. The present work describes two visible (VIS) spectrophotometric techniques that utilize the formation of charge transfer complexes between four antidepressant compounds, namely, amitriptyline hydrochloride (AMI), imipramine hydrochloride (IMI), clomipramine hydrochloride (CLO), and trimipramine maleate (TRI) acting as electron donors and two p-benzoquinones, namely, p-chloranilic acid (pCA) and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), serving as electron acceptors. The stoichiometry of the compounds produced exhibited a consistent 1:1 ratio in all instances, as established by Job's method. Molar absorptivities, equilibrium association constants, and several other spectroscopic properties were determined for all complexes. The developed spectrophotometric techniques were validated intra-laboratory and successfully applied for quantitative assessment of the four antidepressant active ingredients in several commercial pharmaceutical formulations. The methods are relatively simple, fast, and use readily available laboratory instrumentation, making them easily applicable by most quality control laboratories worldwide.

Residue behaviour and health risk assessment of chlorpyrifos and mancozeb in apple fruits and soil.

Mancozeb residue estimation was done using second derivative ultraviolet spectroscopy by Shimadzu ultraviolet-visible spectrophotometer, and chlorpyrifos was estimated by QuEChERS technique using GC-FPD. The persistence for chlorpyrifos was carried out at two locations, and for mancozeb, persistence studies were carried out at four locations. Initial deposits of mancozeb on apple fruits ranged from 1.33 to 1.63 mg/kg at the recommended dose and from 2.55 to 3.26 mg/kg at double the recommended dose at all four locations. Chlorpyrifos residues in apple fruits had an initial deposit of 0.94-0.99 mg/kg at recommended dose and 1.75-1.92 mg/kg at double the recommended dose. Mancozeb residues in apple fruit were below the detection limit (BDL) after 20 days at recommended dose and after 25 days at double the recommended dose at two locations, while mancozeb residue at the other two locations and the residues of chlorpyrifos at all locations reached BDL after 15 and 20 days at recommended and double the recommended doses, respectively. Half-life of mancozeb varied from 3.07 to 4.02 days at recommended dose and from 3.30 to 4.32 days at double the recommended dose, whereas chlorpyrifos residues dissipated to half their initial concentration on 2.33-2.35 days at recommended dose and 2.89-2.90 days at double the recommended dose. The soil samples showed no presence of residues of chlorpyrifos and mancozeb at harvest. The risk assessment revealed that hazard quotient for the intake of mancozeb was in the range of 0.06-0.13% and 0.20-0.44% for rural and urban population, while for the intake of chlorpyrifos, hazard quotient was in the range of 0.10-0.12% for rural population and 0.33-0.38% for urban population, and theoretical maximum dietary intake (9.67 × 10-5 mg/person and 3.18 × 10-4 mg/person for rural population and urban population in case of mancozeb and 3.22 × 10-5 mg/person and 1.06 × 10-4 mg/person for rural population and urban population in case of chlorpyrifos) was also found to be less than maximum permissible intake (1.38 mg/kg for mancozeb and 0.60 mg/kg for chlorpyrifos). The results of risk assessment thereby indicated that apple consumption does not pose a risk to human health.

UV-Vis absorption spectrophotometry and LC-DAD-MS-ESI(+)-ESI(-) coupled to chemometrics analysis of the monitoring of sulfamethoxazole degradation by chlorination, photodegradation, and chlorination/photodegradation.

Sulfamethoxazole (SMX) is one of the most widely used antibiotics worldwide and has been detected at high concentrations in wastewater treatment plant effluents and river waters. In this study, the SMX degradation process combining the simultaneous chlorine oxidation and UV photodegradation is assessed and compared with both photodegradation and chlorine oxidation processes individually. Photodegradation and Chlorine/UV tests were performed using Suntest CPS equipment. Different experimental techniques, including UV-Visible spectrophotometry and liquid chromatography coupled to a diode array detector and positive and negative ionization mass spectrometry (LC-DAD-MS-ESI(+)-ESI(-)), were used to evaluate the degradation reaction of SMX. All the analytical data generated have been processed with the Multivariate Curve Resolution-Alternating Least Squares (MCR-ALS) method to monitor, resolve, and identify the several transformation products generated during the studied degradation processes. A new data fusion analysis strategy is proposed to examine the three processes simultaneously (with only photodegradation, only chlorination, and simultaneous chlorination+photodegradation). Combined with the analysis of different analytical techniques individually (spectrophotometry, LC-DAD, and LC-MS), the fusion of all generated data improved the description of the degradation processes. Detection using DAD allowed a better correspondence among the species monitored spectrophotometrically (UV-Vis) with those analyzed chromatographically. On the other side, detection using MS in both positive and negative acquisition modes allowed resolving a larger number of chemical compounds (specially SMX degradation subproducts) that could not be detected by UV-Vis spectrometry. The results obtained permitted the comparison of the effects produced by the three different degradation processes.

Development of gold plasmonic nanoparticles for detection of polydiallyldimethylammonium chloride at Umgeni water treatment plants: An optimised study and case application.

Background: Polydiallyldimethylammonium chloride (poly-(DADMAC) is used in many drinking water treatment plants in most parts of the world as a flocculant to remove suspended solids from raw water. However, it is very important that residual poly-(DADMAC) is monitored because it disintegrates into a carcinogenic compound known as N-nitrosodimethylamine (NDMA) during the treatment of drinking water. Methods: In this work, the gold nanoparticle method is optimised for the detection of poly-(DADMAC), where the gold nanoparticles were stabilised with trisodium citrate and then used in quantifying poly-(DADMAC) by Ultraviolet-Visible-Near Infrared spectrophotometry. The optimised method was able to measure poly-(DADMAC) at low concentrations of 1.000 µg L-1 in drinking water with limits of detection and limits of quantification of 0.3302 and 1.101 µg L-1, respectively. Significant results: The method was applied to two different water treatment plants and the concentration of poly-(DADMAC) found during stages of the water treatment process ranged from 1.013 to 33.63 µg L-1. The average poly-(DADMAC) concentrate concentration that is dosed for coagulation in Umgeni Water plant A was 7.889 µg L-1 while in plant B was 19.28 µg L-1. Residual poly-(DADMAC) concentration in drinking water was within the accepted limit of 50.00 µg L-1, regulated by the World Health Organisation (WHO).

Application of Red Onion Peel Extract for Green Synthesis of Silver Nanoparticles in Hydrogels Exhibiting Antimicrobial Properties.

UV-initiated green synthesis of metal nanoparticles by using plant extracts as photoreducing agents is of particular interest since it is an environmentally friendly, easy-to-maintain, and cost-effective method. Plant molecules that act as reducing agents are assembled in a highly controlled way which makes them suitable for metal nanoparticle synthesis. Depending on the plant species, their application for green synthesis of metal nanoparticles for diverse applications may contribute to the mediation/reduction in organic waste amounts, thus enabling the implementation of the circular economy concept. In this work, UV-initiated green synthesis of Ag nanoparticles in hydrogels and hydrogel's thin films containing gelatin (matrix), red onion peel extract of different concentrations, water, and a small amount of 1 M AgNO3 have been investigated and characterized using UV-Vis spectroscopy, SEM and EDS analysis, XRD technique, performing swelling experiments and antimicrobial tests using bacteria (Staphylococcus aureus, Acinetobacter baumannii, Pseudomonas aeruginosa), yeasts (Candida parapsilosis, Candida albicans) and microscopic fungi (Aspergillus flavus, Aspergillus fumigatus). It was found that the antimicrobial effectiveness of the silver-enriched red onion peel extract-gelatin films was higher at lower AgNO3 concentrations as compared to those usually used in the commercially available antimicrobial products. The enhancement of the antimicrobial effectiveness was analyzed and discussed, assuming the synergy between photoreducing agent (red onion peel extract) and silver nitrate (AgNO3) in the initial gel solutions leading to the intensification of Ag nanoparticles production.

Development and validation of an eco-compatible UV-Vis spectrophotometric method for the determination of Cu2+ in aqueous matrices.

Cu2+ are ubiquitous ions in the ecosystem and are responsible of serious environmental pollution. Indeed, the development of sensitive methods for Cu2+ detection is an urgent demand. In this work, we proposed a new spectrophotometric method for Cu2+ determination in different water matrices (distilled water, drinking water, wastewater, and river water). The method employs a bio-based organic ligand namely tetrasodium iminodisuccinate (IDS) able to form a stable complex with the analyte with a maximum absorption at 710 nm. Within the linear range of 6.3-381 mg L-1, the limit of detection (LOD) was determined to be as 1.43 mg L-1. Moreover, the recovery data of the spiked analysis of drinking/river/wastewater water samples were also satisfactory and verified the feasibility of the method for the analysis of Cu2+ in natural conditions. Finally, the AGREE assessment tool was used for a quantitative evaluation of the proposed method and reference method, in agreement with the green analytical chemistry principles. The results showed the lower environmental impact of the proposed method and the suitability of this novel approach for Cu2+ in water matrices.

Aqueous Two-Phase Systems Based on Cationic and Anionic Surfactants Mixture for Rapid Extraction and Colorimetric Determination of Synthetic Food Dyes.

In this study, aqueous two-phase systems (ATPSs) containing a cationic and anionic surfactants mixture were used for the preconcentration of the synthetic food dyes Allura Red AC, Azorubine, Sunset Yellow, Tartrazine, and Fast Green FCF. A rapid, simple, low cost, affordable, and environmentally friendly methodology based on microextraction in ATPSs, followed by spectrophotometric/colorimetric determination of the dyes, is proposed. The ATPSs are formed in mixtures of benzethonium chloride (BztCl) and sodium N-lauroylsarcosinate (NaLS) or sodium dihexylsulfosuccinate (NaDHSS) under the molar ratio close to equimolar at the total surfactant concentration of 0.01-0.20 M. The density, viscosity, polarity, and water content in the surfactant-rich phases at an equimolar ratio BztCl:NaA were determined. The effects of pH, total surfactant concentration, dye concentration, and time of extraction/centrifugation were investigated, and the optimum conditions for the quantitative extraction of dyes were established. The smartphone-based colorimetric determination was employed directly in the extract without separating the aqueous phase. The analytical performance (calibration linearity, precision, limits of detection and quantification, reproducibility, and preconcentration factor) and comparison of the spectrophotometric and smartphone-based colorimetric determination of dyes were evaluated. The method was applied to the determination of dyes in food samples and food-processing industrial wastewater.

Clofazimine pKa Determination by Potentiometry and Spectrophotometry: Reverse Cosolvent Dependence as an Indicator of the Presence of Dimers in Aqueous Solutions.

The weakly basic antibiotic and anti-inflammatory drug, clofazimine (CFZ), was first described in 1957. It has been used therapeutically, most notably in the treatment of leprosy. However, the compound is extremely insoluble in aqueous media, and, indeed, there is poor consensus about what its intrinsic solubility is since the reported values range from 0.04 to 11 ng/mL. To understand the speciation and solubilization of CFZ as a function of pH, it is of paramount importance to know the true aqueous pKa. However, there is also poor consensus about the value of the pKa (reported measured values range from 6.08 to 9.11). In the present study, we report the determination of the CFZ ionization constant using two independent techniques. A state-of-the-art potentiometric analysis was performed, drawing on titration data in methanol-water solutions (46-75 wt % MeOH) of CFZ, using the bias-reducing consensus of two different procedures of extrapolating the apparent psKa values to zero cosolvent to approximate the true aqueous pKa as 9.43 ± 0.12 (25 °C, I = 0.15 M reference ionic strength). In parallel, spectrophotometric UV/vis titration data were acquired (250-600 nm at different pH) in 10 mM HEPES buffer solutions containing up to 54 wt % MeOH. The alternating least squares (ALS) method was used in the analysis of the absorbance-pH spectra. Uncharacteristically, the cosolvent UV/vis data in our study showed reverse cosolvent dependence (apparent pKa values increased with increasing cosolvent) which could be explained by a dimerization of the free base. The analysis of UV/vis data obtained from 54 wt % MeOH-water solution containing 20 µM CFZ yielded the apparent pKa 9.51 ± 0.17 (I ≈ 0.005 M). To assess whether self-assembly of CFZ was energetically feasible, density functional theory (DFT) calculations were used to study the putative CFZ dimers in aqueous and methanol media. The DFT-optimized geometries and infrared spectra of CFZ dimers using water and methanol as solvents were calculated and analyzed. Based on the lack of negative frequencies in calculated infrared spectra, it was confirmed that optimized geometries correspond to the true energetic minima. Visual analysis of optimized structures indicates the presence of stacking interactions between two CFZ molecules. The protonation site (the imine nitrogen atom) was determined by 1H NMR spectroscopy.

Synthesis of magnetic molecular imprinted polymer with a new functional monomer for dispersive micro solid phase extraction of captopril from wastewater and biological samples and determination by UV-Vis spectrophotometry.

A magnetic molecularly imprinted polymer (MMIP) was fabricated for captopril by surface polymerization of Fe3O4@SiO2 nanoparticles using a new functional monomer of N-(allylcarbamothioyl)-2-chlorobenzamide. It was then employed as a selective nanosorbent for dispersive magnetic micro solid phase extraction (DM-µ-SPE) of captopril from biological and wastewater samples. To characterize the physicochemical properties of the MMIP, different analytical methods such as the vibrating sample magnetometer, field emission scanning electron microscopy, Brunauer-Emmett-Teller, and Fourier transform infrared spectroscopy were utilized. To gain the maximum extraction recovery of captopril, the influence of various operating conditions was investigated and experimental settings optimized. After the extraction step, the concentration of captopril was measured by UV-Vis spectrophotometer at 245 nm. The assessments demonstrated that the MMIP provides higher extraction efficiency in comparison to magnetic non-imprinted polymer, suggesting the establishment of selective recognition binding sites at the MMIP surface. The method depicted desirable figures of merit of a low detection limit of 0.16 µg L-1, a limit of quantification of 0.50 µg L-1, a linear dynamic range of 0.50-22.0 µg L-1, and an acceptable preconcentration factor of 333. The magnetic MIP was successfully employed for preconcentration and extraction of trace amounts of captopril in real samples, such as human blood serum, urine, and wastewater samples, with recoveries in the range 95.7 to 102.6% and relative standard deviations < 5%.

Synthesis of molecularly imprinted polymer as a nanosorbent for dispersive magnetic micro solid-phase extraction and determination of valsartan in biological samples by UV-Vis Spectrophotometry: Isotherm, kinetics, and thermodynamic studies.

A magnetic molecularly imprinted polymer (MIP) was synthesized by precipitation polymerization utilizing Fe3O4@SiO2-MPS as a magnetic core, itaconic acid as a functional monomer, azobisisobutyronitrile as an initiator, and ethylene glycol dimethacrylate as a cross linker. It was then applied as a nanosorbent for dispersive magnetic micro solid phase extraction (DM-µ-SPE) and determination of valsartan in biological fluids. The morphology and structure of magnetic MIP were characterized by Fourier-transform infrared spectroscopy, Field Emission Scanning electron microscopy, Vibrating sample magnetometer, Energy dispersive x-ray analysis, and Thermogravimetric analysis. The influence of operation conditions on sorption, such as pH (4-10), contact time (10-25 min), initial concentration (1-30 mg L-1), and temperature (25-40 °C) was investigated. After the extraction step, the valsartan concentration was determined by UV-Vis spectrophotometer at 253 nm. The isotherm and kinetic of valsartan sorption were best fitted by the Langmuir model (R2 = 0.987) and the Pseudo second-order kinetic model (R2 = 0.971), respectively. The maximum monolayer sorption capacity for magnetic MIP was obtained to be 4.56 mg g-1. The analytical approach demonstrated favorable figures of merit, with a linear dynamic range of 10-100 µg L-1, a low detection limit of 0.56 µg L-1, and an acceptable preconcentration factor of 5 acquired in optimum conditions. The recoveries of the suggested technique at three spiked levels of analysis were in the range of 101 %-102 %. Valsartan was extracted from various real samples (urine and human blood plasma samples) utilizing the proposed magnetic nanosorbent, and the results exhibited that magnetic MIP was favorable for extraction and measurement of trace amounts of valsartan in biological samples.