Accelerating Surface Photoreactions Using MoS2-FeS2 Nanoadsorbents: Photoreduction of Cr(VI) to Cr(III) and Photodegradation of Methylene Blue.

Nanocubic MoS2-FeS2, as a photocatalyst, was synthesized with high catalytic active edges and high specific surface areas with the capability of absorbing visible light. The results showed that the photocatalytic efficiency of nanocubic MoS2-FeS2 for adsorption/degradation of methylene blue (MB) as well as the reduction of Cr(VI) was high. The adsorption process was found to follow a kinetic model of a pseudo-second-order kind (Qe.cal = 464 mg g-1) along with an isotherm described by the Langmuir model with Qe.cal = 340 mg g-1. The photodegradation process was achieved by holes. It was found that the photodegradation rate constant of MB by MoS2-FeS2 (0.203 min-1) was about 22 times higher than that of MoS2 (0.0091 min-1). The percent apparent quantum yield for photoreduction of Cr(VI) to Cr(III) using MoS2-FeS2 (5.7%) was about 33 times higher than utilizing MoS2 (0.1709%). Therefore, the synergistically prolonged visible-light harvesting as well as the photocarrier diffusion length proved that MoS2-FeS2 nanotubes can effectively be utilized in environmental pollutant's remediation.

Introducing hierarchical hollow MnO2 microspheres as nanozymes for colorimetric determination of captopril.

A simple sensor was developed for the colorimetric determination of captopril (CPT). Herein, hierarchical hollow MnO2 microspheres (HH-MnO2) were applied as nanozymes with peroxidase-mimetic activity. Free cation radicals with a strong absorption signal (λmax at 653 nm) were generated via a redox reaction between 3, 3', 5, 5'-tetramethylbenzidine (TMB) and HH-MnO2. Captopril could successfully prevent the generation of blue-colored free cation radicals. The influence of CPT concentration on the absorption of the generated radicals was monitored by UV-Vis spectroscopy. The corresponding linear concentration range was from 1.0 to 30.0 µg mL-1 (4.6-138.1 µmol L-1), and the detection limit was found to be 0.26 µg mL-1 (1.2 µmol L-1). As a practical usage, the developed sensor was effectively utilized to measure the content of CPT in pharmaceutical formulations.

A novel selective and sensitive multinanozyme colorimetric method for glutathione detection by using an indamine polymer.

A sensitive and selective novel multinanozyme colorimetric method for glutathione (GSH) detection was developed. MnO2-nanozymes can catalyze the oxidation reaction of 3, 3՛-diaminobenzidine (DAB) and produce a brown indamine polymer. In the presence of GSH, this reaction slowly proceeds. When Au-nanozymes was used as peroxidase mimic along with MnO2-nanozymes, the analytical signal and selectivity (particularly, over Cys and AA) were significantly improved for GSH detection. Therefore, this novel multinanozyme system was further developed through optimization for the colorimetric detection of GSH. The calibration curve presented two wide linear range from 0.05 to 0.19 and 0.19-11.35 mg L̶ 1 with a very low detection limit of 0.02 mg L̶ 1 (5 nM) for GSH. The developed method was employed for human serum analysis without any dilution and any deproteinization.

A field-applicable colorimetric assay for notorious explosive triacetone triperoxide through nanozyme-catalyzed irreversible oxidation of 3, 3'-diaminobenzidine.

A field-applicable colorimetric assay for fast detection of notorious explosive triacetone triperoxide (TATP) has been developed through the selective irreversible oxidation of 3, 3'-diaminobenzidine by hydrogen peroxide (HP) liberated during the acidic hydrolysis/degradation of TATP in the presence of MnO2 nanozymes. The generated HP was detected by probing the absorbance of the product (indamine polymer) of the 3, 3'-diaminobenzidine (DAB) oxidation reaction at 460.0 nm. The UV-Vis measurements provided a linear range from 1.57 to 10.50 mg L-1 TATP with a detection limit of 0.34 mg L-1. The oxidation of DAB cannot proceed by molecular oxygen, thus it is selectively oxidized by H2O2; this prevents false-positive results from laundry detergents (containing O2-releasing substances). Moreover, a naked-eye field test was developed, and a fast spot test analyzing time of 5 s was achieved. The selectivity of the assay was checked by analyzing some synthetic samples prepared with a laundry detergent as camouflage. The results of the developed assay revealed quantitative recoveries for TATP whereas the standard nanozyme-based method showed significant false-positive results. Graphical abstract.

Employment of a natural deep eutectic solvent as a sustainable mobile phase additive for improving the isolation of four crucial cardiovascular drugs by micellar liquid chromatography.

Modification of micellar liquid chromatography (MLC) with a natural deep eutectic solvent (NADES) and butanol was effectively performed for analysis of four crucial cardiovascular drugs namely aspirin, atorvastatin, metformin, and metoprolol. The multivariate software tools were employed for screening and optimizing the primary experimental parameters including sodium dodecyl sulphate concentration ([SDS]) as well as the volume percentages of NADES, butanol, and glacial acetic acid (GAC). By using the desirability function, the optimal framework of the mobile phase was obtained at volume ratio of 83:10:3.5:3.5, respectively, for SDS (0.09 mol L-1), butanol, NADES, and GAC. Moreover, the curvature and effect plots were applied for evaluating the robustness of the procedure. At the optimal conditions, the drugs were excellently separated within a total analysis time of 12 min when the flow rate of the mobile phase was 1 mL min-1. To certify the performance of the developed procedure, the Food and Drug Administration guidelines for bioanalytical analysis have been implemented. The designed MLC system was successfully utilized for the quantification of the drugs in urine and plasma samples.

Electrochemical sensing of hydrogen peroxide using a glassy carbon electrode modified with multiwalled carbon nanotubes and zein nanoparticle composites: application to HepG2 cancer cell detection.

A nanobiocomposite was prepared from multiwalled carbon nanotubes and zein nanoparticles. It was dispersed in water/ethanol and drop cast onto a glassy carbon electrode. The modified electrode can be used for electroreduction of H2O2 (typically at a working potential of -0.71 V vs. Ag/AgCl). The electrochemical properties of the electrode were investigated by cyclic voltammetry, linear sweep voltammetry, chronoamperometry and electrochemical impedance spectroscopy. Response to H2O2 is linear in the 0.049 to 22 µM concentration range, and the detection limit is 35 nM at pH 7.0. The sensor was successfully utilized for the measurement of H2O2 in a synthetic urine sample, and for monitoring the release of H2O2 from human dermal fibroblasts and human hepatocellular carcinoma cells. Graphical abstractSchematic representation of a novel metal- and enzyme-free electrochemical nanosensor. A glassy carbon electrode was modified with a nanocomposite prepared from multiwalled carbon nanotubes and zein nanoparticles. It was applied to the identification of liver cancer cells via sensing of H2O2 and has a very low detection limit.

Designing a sustainable mobile phase composition for melamine monitoring in milk samples based on micellar liquid chromatography and natural deep eutectic solvent.

Modified micellar liquid chromatography (MLC) with a natural deep eutectic solvent (NADES), produced from choline chloride (ChCl) and ethylene glycol (EG), was employed for melamine (MEL) monitoring in milk matrix. This sustainable mobile phase was attained through chemometrical optimization of crucial variables including concentration of sodium dodecyl sulphate ([SDS]) along with volume percentages of both NADES and glacial acetic acid (GAC). The desirability function and central composite design were utilized as chemometrical tools. Retention time (tR-MEL), and chromatographic peak width of MEL at 50% of its height (W50%-MEL) were considered for finding the best possible arrangement of the influential factors in the configuration of the mobile phase. Under the optimal experimental conditions of 0.10 mol L-1 SDS, 4% (v/v) NADES, and 4% (v/v) GAC, the results showed that both tR-MEL and W50%-MEL drastically decreased when NADES was a part of the mobile phase composition. This indicated that ChCl-EG-based NADES had a significant impact on improving the chromatographic behaviour of an ionizable polar compound, MEL. At the optimal point, MEL was eluted in approximately 10 min without being interfered by coexisting proteins and endogenous species in milk. The practical performance of the mobile phase was established through direct injection of milk samples into the MLC system. The eligibility criteria of the United State-Food and Drug Administration (US-FDA) were considered for validation of the introduced methodology.

Quantitative structure-retention relationship for chromatographic behaviour of anthraquinone derivatives through considering organic modifier features in micellar liquid chromatography.

A simple and informative quantitative structure-retention relationship (QSRR) model has been introduced for prediction of retention times in some anthraquinone derivatives using reversed-phase micellar liquid chromatography (MLC) technique. In the developed multiple linear regression model, the structural descriptors of analytes as well as the empirical parameters of organic modifiers in the applied MLC systems have been considered. Retention times of 77 chromatographic samples (16 anthraquinones were evaluated by using 6 different organic modifiers) were experimentally determined and utilized as the independent variables of the QSRR model. Five small-chain alcohols (methanol, ethanol, propanol, butanol, and pentanol) as well as acetonitrile were used as the eluent modifiers. A five-parametric model was attained for the logarithm of the retention time values which covered about 96 and 95% variance of the chromatographic data in training and cross-validation, respectively. The presence of an excellent correlation coefficient for external validation test (= 0.94) and a well-applicable domain proved the prediction ability of the constructed model. Both validity and reliability of the formulated model were examined through its application on diverse random-selected training and test sets. Moreover, quantum chemical calculations were performed in the framework of density functional theory to simulate the interactions between AQs and modifiers and gain mechanistic details about the retention behavior in the MLC system.

Analysis of malondialdehyde in human plasma samples through derivatization with 2,4-dinitrophenylhydrazine by ultrasound-assisted dispersive liquid-liquid microextraction-GC-FID approach.

A sensitive and reliable ultrasound-assisted dispersive liquid-liquid microextraction (UA-DLLME) procedure was developed and validated for extraction and analysis of malondialdehyde (MDA) as an important lipids-peroxidation biomarker in human plasma. In this methodology, to achieve an applicable extraction procedure, the whole optimization processes were performed in human plasma. To convert MDA into readily extractable species, it was derivatized to hydrazone structure-base by 2,4-dinitrophenylhydrazine (DNPH) at 40 °C within 60 min. Influences of experimental variables on the extraction process including type and volume of extraction and disperser solvents, amount of derivatization agent, temperature, pH, ionic strength, sonication and centrifugation times were evaluated. Under the optimal experimental conditions, the enhancement factor and extraction recovery were 79.8 and 95.8%, respectively. The analytical signal linearly (R2 = 0.9988) responded over a concentration range of 5.00-4000 ng mL-1 with a limit of detection of 0.75 ng mL-1 (S/N = 3) in the plasma sample. To validate the developed procedure, the recommend guidelines of Food and Drug Administration for bioanalytical analysis have been employed.

Simultaneous determination of captopril and hydrochlorothiazide by using a carbon ionic liquid electrode modified with copper hydroxide nanoparticles.

A carbon electrode modified with the ionic liquid octylpyridinium hexafluorophosphate and copper hydroxide nanoparticles was employed in an electrochemical assay for simultaneous determination of captopril (CPT) and hydrochlorothiazide (HCT). The electrode showed two well-defined oxidation peaks for CPT (at 0.22 V) and HCT (at 0.73 V, both vs. Ag/AgCl) at pH 8.0 using square wave voltammetry. Calibration plots are linear in the concentration ranges of 0.7-70 µM (CPT) and 3-600 µM (HCT), with detection limits of 12 and 60 nM, respectively. The electrode was repeatedly applied to simultaneous determination of CPT and HCT in pharmaceutical formulation without showing any fouling. Graphical abstract Application of carbon ionic liquid electrode (CILE) modified with Cu(OH)2 nanoparticles (Cu(OH)2NP/CILE) for the simultaneous determination of captopril (CPT) and hydrochlorothiazide (HCT) in pharmaceutical formulation is presented.

Green-modified micellar liquid chromatography for isocratic isolation of some cardiovascular drugs with different polarities through experimental design approach.

Bilayer pseudo-stationary phase micellar liquid chromatography (MLC) was developed for simultaneous isocratic isolation of hydrochlorothiazide, as a basic-polar (hydrophilic) cardiovascular drug, as well as triamterene and losartan potassium, as acidic-nonpolar (hydrophobic) cardiovascular drugs. Utilizing a deep eutectic solvent (DES), as a novel green mobile phase additive in combination with acetonitrile (ACN) and acetic acid (ACA), drastically improved the chromatographic behavior of the drugs. Concentration of sodium dodecyl sulphate (SDS), as well as volume percentages of ACN, DES, and ACA were optimized by using a central composite design. The optimal composition of the mobile phase (0.12 mol L-1 SDS, 5% ACN, 4% DES, and 2% ACA) was chosen through the desirability function. The chromatographic peaks of both hydrophilic and hydrophobic drugs, respectively, emerged at high and low retention time values in the shortest total analysis time of 20 min (at a flow rate of 2 mL min-1). Analytical characterization of the developed approach was investigated through Food and Drug Administration (FDA) guidelines. Applicability of the method was evaluated by analysing of human plasma samples which were directly injected into the system.

Chiral recognition of tryptophan enantiomers using chitosan-capped silver nanoparticles: Scanometry and spectrophotometry approaches.

A new, fast and inexpensive colorimetric sensor was developed for chiral recognition of tryptophan enantiomers using chitosan-capped silver nanoparticles. The function of the sensor was based on scanometry and spectrophotometry of the colored product of a reaction solution containing a mixture of chitosan-capped silver nanoparticles, phosphate buffer and tryptophan enantiomers. The image of the colored solution was taken using the scanometer and the corresponding color values were obtained using Photoshop software which subsequently were used for optimization of the experimental parameters as the analytical signal. Two types of color values system were investigated: RGB (red, green and blue values) and CMYK (cyan, magenta, yellow and black values). The color values indicated that L-tryptophan had better interaction than D-tryptophan with chitosan-capped silver nanoparticles. A linear relationship between the analytical signal and the concentration of L-tryptophan was obtained in the concentration range of 1.3 × 10-5-4.6 × 10-4molL-1. Detection limits, were obtained to be 2.1 × 10-6, 2.4 × 10-6 and 3.8 × 10-6molL-1 for L-tryptophan based on R (red), G (green) and B (blue) values, respectively.

Chiral recognition of naproxen enantiomers based on fluorescence quenching of bovine serum albumin-stabilized gold nanoclusters.

A simple, fast and green method for chiral recognition of S- and R-naproxen has been introduced. The method was based on quenching of the fluorescence intensity of bovine serum albumin-stabilized gold nanoclusters in the presence of naproxen enantiomers. The quenching intensity in the presence of S-naproxen was higher than R-naproxen when phosphate buffer solution at pH7.0 was used. The chiral recognition occurred due to steric effect between bovine serum albumin conformation and naproxen enantiomers. Two linear determination range were established as 7.4×10-7-9.1×10-6 and 9.1×10-6-3.1×10-5molL-1 for both enantiomers and detection limits of 7.4×10-8molL-1 and 9.5×10-8molL-1 were obtained for S- and R-naproxen, respectively. The developed method showed good repeatability and reproducibility for the analysis of a synthetic sample. To make the procedure applicable to biological samples, the removal of heavy metals from the sample is suggested before any analytical attempt.

Gas-assisted dispersive liquid-phase microextraction using ionic liquid as extracting solvent for spectrophotometric speciation of copper.

Gas-assisted dispersive liquid-phase microextraction (GA-DLPME) has been developed for preconcentration and spectrophotometric determination of copper ion in different water samples. The ionic liquid 1-hexyl-3-methylimidazolium hexafluorophosphate and argon gas, respectively, were used as the extracting solvent and disperser. The procedure was based on direct reduction of Cu(II) to Cu(I) by hydroxylamine hydrochloride, followed by extracting Cu(I) into ionic liquid phase by using neocuproine as the chelating agent. Several experimental variables that affected the GA-DLPME efficiency were investigated and optimized. Under the optimum experimental conditions (IL volume, 50µL; pH, 6.0; acetate buffer, 1.5molL(-1); reducing agent concentration, 0.2molL(-1); NC concentration, 120µgmL(-1); Ar gas bubbling time, 6min; argon flow rate, 1Lmin(-1); NaCl concentration, 6% w/w; and centrifugation time, 3min), the calibration graph was linear over the concentration range of 0.30-2.00µgmL(-1) copper ion with a limit of detection of 0.07µgmL(-1). Relative standard deviation for five replicate determinations of 1.0µgmL(-1) copper ion was found to be 3.9%. The developed method was successfully applied to determination of both Cu(I) and Cu(II) species in water samples.

A rapid and sensitive assay for determination of doxycycline using thioglycolic acid-capped cadmium telluride quantum dots.

A rapid, simple and inexpensive spectrofluorimetric sensor for determination of doxycycline based on its interaction with thioglycolic acid-capped cadmium telluride quantum dots (TGA/CdTe QDs) has been developed. Under the optimum experimental conditions, the sensor exhibited a fast response time of <10s. The results revealed that doxycycline could quench the fluorescence of TGA/CdTe QDs via electron transfer from the QDs to doxycycline through a dynamic quenching mechanism. The sensor permitted determination of doxycycline in a concentration range of 1.9×10(-6)-6.1×10(-5)molL(-1) with a detection limit of 1.1×10(-7)molL(-1). The sensor was applied for determination of doxycycline in honey and human serum samples.

A comparative study for adsorption of lysozyme from aqueous samples onto Fe3O4 magnetic nanoparticles using different ionic liquids as modifier.

In this paper, nanoparticles of Fe3O4 as well as their modified forms with different ionic liquids (IL-Fe3O4) were prepared and used for adsorption of lysozyme. The mean size and the surface morphology of the nanoparticles were characterized by TEM, XRD and FTIR techniques. Adsorption studies of lysozyme were performed under different experimental conditions in batch system on different modified magnetic nanoparticles such as, lysozyme concentration, pH of the solution, and contact time. Experimental results were obtained under the optimum operational conditions of pH 9.0 and a contact time of 10 min when initial protein concentrations of 0.05-2.0 mg mL(-1) were used. The isotherm evaluations revealed that the Langmuir model attained better fits to the equilibrium data than the Freundlich model. The maximum obtained adsorption capacities were 370.4, 400.0 500.0 and 526.3 mg of lysozyme for adsorption onto Fe3O4 and modified magnetic nanoparticles by [C4MIM][Br], [C6MIM][Br] and [C8MIM][Br] per gram of adsorbent, respectively. The Langmuir adsorption constants were 0.004, 0.019, 0.024 and 0.012 L mg(-1) for adsorptions of lysozyme onto Fe3O4 and modified magnetic nanoparticles by [C4MIM][Br], [C6MIM][Br] and [C8MIM][Br], respectively. The adsorption capacity of lysozyme was found to be dependent on its chemical structure, pH of the solution, temperature and type of ionic liquid as modifier. The applicability of two kinetic models including pseudo-first order and pseudo-second order model was estimated. Furthermore, the thermodynamic parameters were calculated. Protein could desorb from IL-Fe3O4 nanoparticles by using NaCl solution at pH 9.5 and was reused.

Highly sensitive colorimetric determination of amoxicillin in pharmaceutical formulations based on induced aggregation of gold nanoparticles.

A novel, simple and highly sensitive colorimetric method is developed for determination of Amoxicillin (AMX). The system is based on aggregation of citrate-capped gold nanoparticles (AuNP) in acetate buffer (pH=4.5) in the presence of the degradation product of Amoxicillin (DPAMX). It was found that the color of gold nanoparticles changed from red to purple and the intensity of surface plasmon resonance (SPR) peak of AuNPs decreased. A new absorption band was appeared in the wavelength range of 600-700nm upon addition of DPAMX. The absorbance ratio at the wavelength of 660 and 525nm (A660/A525) was chosen as the analytical signal indirectly related to AMX concentration. The linearity of the calibration graph was found over the concentration range of 0.3-4.5µM AMX with a correlation coefficient of 0.9967. Under the optimum experimental conditions, the detection limit was found to be 0.15µM. The applicability of the method was successfully demonstrated by analysis of AMX in pharmaceutical formulations including capsules and oral suspensions.

Photodegradation study of nystatin by UV-Vis spectrophotometry and chemometrics modeling.

Nystatin, one of the tetraene antifungal antibiotics, is very sensitive to light. Thus, when nystatin is exposed to natural daylight, it is photodegraded to products of lower biological activity. In this work, the photodegradation kinetics of nystatin was monitored by a UV-Vis spectrophotometry method. The absorbance spectra of the nystatin, exposed to a 366 nm UV lamp, were recorded at different periods of time. By application of factor analysis to the absorbance data matrix, three absorbing chemical species, coexisting in the reaction system, were detected. The soft-modeling multivariate curve resolution-alternating least squares analysis of the evolutionary absorbance data revealed that nystatin undergoes photodegradation in a two-step consecutive manner. Hard-modeling data analysis suggested that reaction has first-order kinetics in the first step and zero-order kinetics in the second step. The reaction rate constants of the first and second steps were estimated as 0.0929 (+/-0.0076) and 0.0052 (+/-0.0016)/min, respectively. Finally, the pure spectra of the resolved chemical species were calculated.

A novel methodology for analysis of enantiomers through determination of their critical micelle concentrations using spectrophotometric method.

A novel methodology for analysis of enantiomer composition of chiral compounds based on measuring of their critical micelle concentration by using spectrophotometric technique is introduced. The proposed method does not require any chiral selector and the corresponding process is simple, fast, reproducible, and inexpensive. The procedure was successfully applied for analysis of naproxen. The critical micelle concentration data showed that (R)-naproxen could be determined with an RSD of 1.1% and a relative error of -5.6% when a real sample containing the racemic mixture of naproxen with a total concentration of 0.04 mM was tested.

Characterization of a novel organic solvent tolerant protease from a moderately halophilic bacterium and its behavior in ionic liquids.

An extracellular protease was purified from a novel moderately halophilic bacterium Salinivibrio sp. strain MS-7 by the combination of an acetone precipitation (40-80 %) step and a DEAE-cellulose anion exchange column chromatography. Kinetic parameters of the enzyme exhibited V(max) and K(m) of 130 U/mg and 1.14 mg/ml, respectively, using casein as a substrate. The biochemical properties of the enzyme revealed that the 21-kDa protease had a temperature and pH optimum of 50 °C and 8.0, respectively. The enzyme was strongly inhibited by phenylmethylsulfonyl fluoride, Pefabloc SC, chymostatin, and also EDTA, indicating that it belongs to the class of serine metalloproteases. Interestingly, Ba(2+) and Ca(2+) (2 mM) strongly enhanced the enzyme activity, while Fe(2+) and Mg(2+) activated moderately and Zn(2+), Ni(2+), and Hg(2+) decreased the enzyme activity. The effect of organic solvents with different logP on the purified protease revealed complete stability in toluene, ethyl acetate, chloroform, and n-hexane at 10 and 50 % (v/v) and moderate stability even in 50 % of DMSO and ethanol. The behavior of the MS-7 protease in three imidazolium-based ionic liquids exhibited suitable activity in these green solvent systems, especially in 1-hexyl-3-methylimidazolium hexafluorophosphate ([C(6)MIM][PF(6)]). Comparison of the purified protease with other previously reported proteases suggests that strain MS-7 secrets a novel organic solvent-tolerant protease with outstanding activity in organic solvents and imidazolium-based ionic liquids, which could be applied in low water synthetic section of industrial biotechnology.