DFT exploration of adsorptive performances of borophene to small sulfur-containing gases.

Density functional theory (DFT) calculations were applied to study the ability of B36 to adsorb H2S, SO2, SO3, CH3SH, (CH3)2S, and C4H4S gases. Several exchange-correlation including B97D, PBE, B3LYP, M062X, and WB97XD were utilized to evaluate adsorption energies. The initial results showed that boundary boron atoms are the most appropriate interaction sites. The adsorption energies, electron density, electron localized function, and differential charge density plots confirmed the formation of chemical covalent bonds only between SOx and B36. The results of thermochemistry analysis revealed the exothermic nature of the adsorption of sulfur-containing gases on B36; the highest values of ∆H298 were found for SO3/B36 and SO2/B36 systems. The electronic absorption spectra and DOS of B36 did not exhibit significant variations after gases adsorption, while the modeled CD spectra showed a remarkable change in the case of the SOx/B36 system. Accordingly, B36 is not suggested for detecting the studied gases. The effect of imposing mono vacancy defect and external electric field to the adsorption of titled gases on the sorbent showed, while the former did not affect the adsorption energies significantly the later improved the adsorption of gas molecules on the B36 system. The results of the current study could provide deeper molecular insight on the removal of SOx gases by B36 system.

Automated hollow-fiber liquid-phase microextraction followed by liquid chromatography with mass spectrometry for the determination of benzodiazepine drugs in biological samples.

In this study, two-phase hollow-fiber liquid-phase microextraction and three-phase hollow-fiber liquid-phase microextraction based on two immiscible organic solvents were compared for extraction of oxazepam and Lorazepam. Separations were performed on a liquid chromatography with mass spectrometry instrument. Under optimal conditions, three-phase hollow-fiber liquid-phase microextraction based on two immiscible organic solvents has a better extraction efficiency. In a urine sample, for three-phase hollow fiber liquid-phase microextraction based on two immiscible organic solvents, the calibration curves were found to be linear in the range of 0.6-200 and 0.9-200 µg L(-1) and the limits of detection were 0.2 and 0.3 µg L(-1) for oxazepam and lorazepam, respectively. For two-phase hollow fiber liquid-phase microextraction, the calibration curves were found to be linear in the range of 1-200 and 1.5-200 µg L(-1) and the limits of detection were 0.3 and 0.5 µg L(-1) for oxazepam and lorazepam, respectively. In a urine sample, for three-phase hollow-fiber-based liquid-phase microextraction based on two immiscible organic solvents, relative standard deviations in the range of 4.2-4.5% and preconcentration factors in the range of 70-180 were obtained for oxazepam and lorazepam, respectively. Also for the two-phase hollow-fiber liquid-phase microextraction, preconcentration factors in the range of 101-257 were obtained for oxazepam and lorazepam, respectively.

Development of a localized surface plasmon resonance-based gold nanobiosensor for the determination of prolactin hormone in human serum.

A localized surface plasmon resonance immunoassay has been developed to determine prolactin hormone in human serum samples. Gold nanoparticles were synthesized, and the probe was prepared by electrostatic adsorption of antibody on the surfaces of gold nanoparticles. The pH and the antibody-to-gold nanoparticle ratio, as the factors affecting the probe functions, were optimized. The constructed nanobiosensor was characterized by dynamic light scattering. The sensor was applied for the determination of prolactin antigen concentration based on the amount of localized surface plasmon resonance peak shift. A linear dynamic range of 1-40 ng ml(-1), a detection limit of 0.8 ng ml(-1), and sensitivity of 10 pg ml(-1) were obtained. Finally, the nanobiosensor was applied for the determination of prolactin in human control serum sample.

Silica-encapsulated magnetic nanoparticles: enzyme immobilization and cytotoxic study.

Silica-encapsulated magnetic nanoparticles (MNPs) were prepared via microemulsion method. The products were characterized by high resolution transmission electron microscopy (HRTEM) and energy-dispersive X-ray spectrum (EDS). MNPs with no observed cytotoxic activity against human lung carcinoma cell and brine shrimp lethality were used as suitable support for glucose oxidase (GOD) immobilization. Binding of GOD onto the support was confirmed by the FTIR spectra. The amount of immobilized GODs was 95 mg/g. Storage stability study showed that the immobilized GOD retained 98% of its initial activity after 45 days and 90% of the activity was also remained after 12 repeated uses. Considerable enhancements in thermal stabilities were observed for the immobilized GOD at elevated temperatures up to 80°C and the activity of immobilized enzyme was less sensitive to pH changes in solution.

Synthesis and characterization of novel ion-imprinted polymeric nanoparticles for very fast and highly selective recognition of copper(II) ions.

This work reports the preparation of new Cu(2+) ion-imprinted polymeric nanoparticles using 1-hydroxy-4-(prop-2'-enyloxy)-9,10-anthraquinone (AQ) as a vinylated chelating agent. The Cu(2+) ion found to form a stable 1:1 complex with AQ in methanol solution. The resulting Cu(2+)-AQ complex was copolymerized with ethyleneglycol dimethacrylate, as a cross-linking monomer, via precipitation polymerization method. The imprint copper ion was removed from the polymeric matrix using a 0.1 mol L(-1) HNO(3) solution. The Cu(2+)-imprinted polymeric nanoparticles were characterized by IR spectroscopy, scanning electron microscopy (SEM) and N(2) adsorption-desorption isotherms. The SEM micrographs showed colloidal nanoparticles of 60-100 nm in diameter and slightly irregular in shape. Optimum pH for maximum sorption was 7.0. Sorption and desorption of Cu(2+) ion on the IIP nanoparticles were quite fast and achieved completely over entire investigated time periods of 2-30 min. Maximum sorbent capacity and enrichment factor of the prepared IIP for Cu(2+) were 73.8 µmol g(-1) and 56.5, respectively. The relative standard deviation and limit of detection (C(LOD)=3S(b)/m) of the method were evaluated as 2.6% and 0.1 ng mL(-1), using inductively coupled plasma-atomic emission spectrometry, respectively. It was found that the imprinting technology results in increased affinity of the prepared material toward Cu(2+) ion over other metal ions with the same charge and close ionic radius. The relative standard deviations for six and twenty replicates with the same nanoparticles were found to be 1.7% and 2.1%, respectively.

A stoichiometric imprinted chelating resin for selective recognition of copper(II) ions in aqueous media.

This work reports the preparation of a new copper(II) ion-imprinted polymer (IIP) material, using 5,6;14,15-dibenzo-1,4-dioxa-8,12-diazacyclopentadecane-5,14-diene (DBDA15C4) and 2-vinylpyridine (VP) as a non-vinylated chelating agent and a functional vinyl monomer, respectively. The Cu2+ ion can form stable complexes with DBDA15C4 and VP. The stoichiometries of Cu2+-DBDA15C4 and ternary Cu2+-DBDA15C4-VP complexes were elucidated using conductometric and spectrophotometric methods, and found to be Cu2+ (DBDA15C4), Cu2+ (DBDA15C4)2 and Cu2+ (DBDA15C4)(VP)2. The results obtained from solution studies were also supported by ab initio theoretical calculations. The resulting ternary complex Cu2+ (DBDA15C4)(VP)2 was copolymerized with ethyleneglycoldimethacrylate, as a cross-linking monomer, via bulk polymerization method. The imprinted copper ion was removed from the polymeric matrix by 0.1 M HNO3. The Cu2+-imprinted polymer particles were characterized by IR spectroscopy and elemental analysis. Optimum pH range for rebinding of Cu2+ on the IIP and equilibrium binding time were 7.0-7.5 and 45 min, respectively. Sorbent capacity and enrichment factor for Cu2+ were obtained as 75.3+/-1.9 micromol g(-1) and 100, respectively. In selectivity study, it was found that imprinting results in increased affinity of the material toward Cu2+ ion over other competitor metal ions with the same charge and close ionic radius. The prepared IIPs were repeatedly used and regenerated for five times without a significant decrease in polymer binding affinities.

Grafting of ion-imprinted polymers on the surface of silica gel particles through covalently surface-bound initiators: a selective sorbent for uranyl ion.

A new ion imprinted polymer coated silica gel sorbent has been prepared using the radical "grafting from" polymerization method through surface-bound azo initiators for selective uranyl uptake. The introduction of azo initiator onto the silica surface was achieved by the reaction of surface amino groups with 4,4'-azobis(4-cyanopentanoic acid chloride). The grafting step was then carried out in a stirred solution of initiator-modified silica particles in the presence of uranyl ion and functional and cross-linking monomers. The prepared sorbent was characterized using FT-IR spectroscopy, scanning electron microscopy (SEM), elemental analysis (EA), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and BET adsorption isotherm analysis. The influence of the uranyl concentration, pH, and flow rate of solution on the grafted polymer affinity has been investigated. Maximum uptake of uranyl ion was observed at a pH 3.0. The rebinding behavior of the sorbent has been successfully described by the Langmuir-Freundlich isotherm. The dynamic column capacity of sorbent and enrichment factor for uranyl ion were 52.9 +/- 3.4 micromol g(-1) and 52, respectively. It was found that imprinting results in increased affinity of the sorbent toward uranyl ion over strong competitor metal ions such as Fe(III) and Th(IV). The sorbent was repeatedly used and regenerated for 3 months without any significant decrease in polymer binding affinities. Finally the sorbent was applied to the preconcentration and determination of uranyl ion in real water samples.

Imprinted polymer particles for selenium uptake: synthesis, characterization and analytical applications.

This work reports the preparation of molecularly imprinted polymer (MIP) particles for selective extraction and determination of selenium ions from aqueous media. Polymerization was achieved in a glass tube containing SeO(2), o-phenylenediamine, 2-vinylpyridine (VP), ethyleneglycoldimethacrylate (EDMA), 2,2'-azobisisobutyronitrile (AIBN). The polymer block obtained was ground and sieved (55-75 microm) and the Se-o-phenylenediamine complex was removed from polymer particles by leaching with 2M of HCl, which leaves a cavity in the polymer particles. The polymer particles both prior to and after leaching have been characterized by IR and thermogravimetric (TG) studies. The effect of different parameters, such as pH, extraction time, type and least amount of eluent for elution of complex from polymer were evaluated. Extraction efficiencies >99% were obtained by elution of the polymers with 15 mL of methanol-acetonitrile mixture (1:2, v/v). The limit of detection of the proposed method followed by hydride generation atomic absorption spectroscopy (HG-AAS) was found to be 3.3 microg L(-1) and a dynamic linear range (DLR) of 10-200 microg L(-1) was obtained. The relative standard deviations (R.S.D.s) at 30.0 microg L(-1) of Se were below than 8.1%. The influence of various cationic interferences on percent recovery of complex was studied. The method was applied to the recovery and determination of selenium in different real samples.