Application of the Fe3O4@1,10‐phenanthroline‐5,6‐diol@Mn nano‐catalyst for the green synthesis of tetrazoles and its biological performance

The Fe₃O₄ magnetic particles were modified with 1,10‐phenanthroline‐5,6‐diol (Phen) and the related Mn complex (Fe₃O₄@Phen@Mn) synthesized as a heterogeneous catalyst to be used for the one‐pot three‐component synthesis of various tetrazoles. The catalysts were characterized by several methods, such as the elemental analysis, FT‐IR, X‐ray powder diffraction, dispersive X‐ray spectroscopy, scanning electron microscopy, transmission electron microscopy, dynamic light scattering, thermogravimetric‐differential thermal analysis, vibrating sample magnetometer and X‐ray photoelectron spectroscopy. In addition, the antioxidant and antibacterial activities of the catalyst and its Phen ligand were in vitro screened with 2,2‐diphenyl‐1‐picrylhydrazyl by free radical scavenging methods. Results showed that the synthesized compounds possess strong antioxidant activity (IC50; 0.172  ±  0.005 mg ml^?1) as well as a good antibacterial potential in comparison to standards.     

Transistor-Based Work-Function Measurement of Metal–Organic Frameworks for Ultra-Low-Power,Rationally Designed Chemical Sensors

A classic challenge in chemical sensing is selectivity. Metal–organic frameworks (MOFs) are an exciting class of materials because they can be tuned for selective chemical adsorption. Adsorption events trigger work-function shifts, which can be detected with a chemical-sensitive field-effect transistor (power ≈microwatts). In this work, several case studies were used towards generalizing the sensing mechanism, ultimately towards our metal-centric hypothesis. HKUST-1 was used as a proof-of-principle humidity sensor. The response is thickness independent, meaning the response is surface localized. ZIF-8 is demonstrated to be an NO₂-sensing material, and the response is dominated by adsorption at metal sites. Finally, MFM-300(In) shows how standard hard–soft acid–base theory can be used to qualitatively predict sensor responses. This paper sets the groundwork for using the tunability of metal–organic frameworks for chemical sensing with distributed, scalable devices.     

ZnSe and copper-doped ZnSe nanocrystals (NCs): Optical absorbance and precise determination of energy band gap beside their exact optical transition type and Urbach energy

The using of a reliable and accurate new method (called in literature as derivation of absorption spectrum fitting (DASF)) for evaluation of the optical band gap (E_g) and also the exact nature of charge carriers optical transitions, is investigated in ZnSe and ZnSe:Cu nanocrystals (NCs) synthesized by rapid microwave irradiation. This method can be performed by using the output of UV–Visible spectroscopy. The obtained E_g values are within the range of 2.985–3.261 eV, depending to the microwave irradiation time and Cu dopant percentage (decreasing trend with increasing of irradiation time and Cu content). The DASF-based obtained results for ZnSe and ZnSe:Cu nanoparticles, showed the more precise values of band gap, with the same trend of previously qualitative reported data on the same samples. Also, the direct gap nature of their optical transitions was justified. To perform the method, there is no any need to the concentration of solutions and merely one need the direct absorption or transmission spectra. In other word, DASF technique was employed on ZnSe NCs to confirm its validity and to avoid non-precise reports on optical band gap which can affect on the device optimizations based on these samples. Moreover, using the values of E_g, refractive index and dielectric constant of each sample were obtained at the absorption edge. Also, the width of the tailing states in the gap (Urbach energy: E_Tail) was estimated and were within the range of 0.049–0.122 eV, which their very small values in compare with E_g imply to the sharp valence and conduction band edges; it means the good crystallinity nature of the produced samples.     

Nuclephilic ring opening of epoxides promoted by multi-site phase-transfer catalyst:An efficient and eco-friendly route to synthesis of β-hydroxythiocyanate

A highly effective and mild protocol for ring opening of epoxides with NH4SCN in the presence of catalytic amount of a multisite phase-transfer catalyst,α,α′,α″-N-hexakis(triethylammoniummethylene chloride)-melamine,is developed.A variety ofβ-hydroxy thiocyanates as important intermediates in agricultural and pharmaceutical chemistry were obtained in high yields with excellent regioselectivity and in short reaction times.     

MAO-synthesized Al2O3-supported V2O5 nano-porous catalysts: Growth, characterization, and photoactivity

V₂O₅-loaded Al₂O₃ layers were successfully grown via micro-arc oxidation (MAO) process for the first time. Surface morphology and topography of the layers were investigated by scanning electron microscope (SEM) and atomic force microscope (AFM). It was found that the composite layers had a porous structure with a rough surface which is suitable for catalytic applications. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and energy dispersive X-ray spectroscopy (EDS) techniques were also employed to study phase structure and chemical composition of the composite layers. The layers consisted of γ-alumina, α-alumina, and vanadium pentoxide phases in which their relative contents varied with the applied voltage. Meanwhile, optical properties of the composite layers were investigated using UV-vis spectrophotometry technique, and the band gap energy was calculated as 3.15 eV. Furthermore, photocatalytic performance of the synthesized composite layers was determined by measuring the decomposition rate of methylene blue solution, as a model compound, on the surface of the layers under ultra violet photo-irradiation. It was found that more than 91% of the methylene blue was degraded after 120 min with a rate constant of k = 0.0192 min⁻¹.     

Thermal behavior of perfluoroalkylsiloxane monolayers on the oxidized Si(100) surface

The thermal stability of perfluoralkylsiloxane monolayers in a vacuum is investigated via X-ray photoelectron spectroscopy (XPS) for temperatures up to 600 degrees C. 1H,1H,2H,2H,-perfluorodecyltrichlorosilane (FDTS) monolayers are deposited on oxidized Si(100) surfaces from the vapor phase with various degrees of surface coverage. Significant monolayer desorption is observed to occur at temperatures below 300 degrees C regardless of the initial monolayer coverage. The desorption mechanism follows first-order kinetics and is independent of the initial coverage. Removal of FDTS is found to occur by the loss of the entire molecular chain, as evidenced by the fact that the CF(3)/CF(2) peak area ratios remain unaffected by the annealing process although CF(n)()/Si peak ratio declines with annealing. This is in sharp contrast to the behavior observed for octadecyltrichlorosilane monolayer for which elevated temperature leads to C-C bond breakage and successive shortening of the alkyl chain. It is also shown that the binding energy and the shape of the F 1s line are good indicators of the degree of disorder in the chain, as well as a measure of the interaction of the chain with the silicon surface.     

Electrospun electroactive nanofibers of gelatin‐oligoaniline/Poly (vinyl alcohol) templates for architecting of cardiac tissue with on‐demand drug release

In this study, grafted gelatin with oligoaniline (GelOA) was synthesized and then mixed with Poly (vinyl alcohol) (PVA). Several scaffolds with different ratio of PVA/GelOA were electrospun to fabricate electroactive scaffolds. GelOA was characterized using Fourier‐transform infrared spectroscopy (FTIR); moreover, nanofiber properties were evaluated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and scanning electron microscope (SEM) analyses. Nanofibers diameter was decreased with aniline oligomer increment form 300 to 150 nm because of the hydrophobic nature of the aniline oligomer. Aniline oligomer electroactivity was studied using cyclic voltammetry, which exhibited two redox peaks at 0.4 and 0.6. Moreover, aniline oligomer enhancement resulted in melting point increasing from 220°C to 230°C because of the crystallinity increment. To assess the biocompatibility of nanofibers, cell viability and cell adhesion were tracked using mesenchymal stem cell (MSCs). It was revealed that the presence of aniline oligomer leads to enhancing the conductivity, thermal properties and lowering the degradation rate and drug release. Among of different scaffolds, sample with high content of GelOA shows better behavior in physical and biological properties. Accumulative drug releases under applied electrical field at 40 minutes showed that the drug release for stimulated condition is about 33% more than the unapplied electrical field one.     

Silver nanoparticles‐tragacanth gel as a green membrane for effective extraction and determination of capecitabine

A novel eco‐friendly and effective electromembrane extraction method combining high‐performance liquid chromatography with UV detection was developed for the enrichment and determination of capecitabine. Tragacanth‐silver nanoparticles conjugated gel was prepared by dissolving the tragacanth powder in synthesized silver nanoparticles solution and was used as a green membrane in electromembrane extraction. The porosity and presence of silver nanoparticles in the gel were characterized by field emission scanning electron microscopy. This new electromembrane extraction approach uses neither organic solvent nor carrier agents to extract the target analyte. The best electromembrane extraction efficiency was obtained by using 4.0 mm membrane gel thickness containing 2.5% w/v of tragacanth gum, donor phase pH = 5.0, acceptor phase pH = 3.0, applied voltage 50 V, extraction time 20 min, and agitation rate 500 rpm. During method validation under the optimized conditions, good linearity dynamic range between 1 and 500 ng/mL with the coefficient of determination (R²) = 0.998 was obtained. Limit of detection and Limit of quantitation were estimated to be 0.84 and 1.0 ng/mL, respectively. Finally, the applicability of this method in real samples was confirmed by an acceptable performance in extraction and determination of capecitabine in human plasma samples.     

Thermodynamic study of complex formation between dibenzo-18-crown-6 and UO2 2+ cation in different non-aqueous binary solutions

In the present work the complexation process between UO₂ ²⁺ cation and the macrocyclic ligand, dibenzo-18-crown-6 (DB18C6) was studied in ethylacetate–dimethylformamide (EtOAc/DMF), ethylacetate–acetonitrile (EtOAc/AN), and ethylacetate–tetrahydrofuran (EtOAc/THF) and ethylacetate–propylencarbonate (EtOAc/PC) binary solutions at different temperatures using the conductometric method. The results show that the stoichiometry of the (DB18C6 . UO₂)²⁺ complex in all binary mixed solvents is 1:1. A non-linear behavior was observed for changes of log K_f of this complex versus the composition of the binary mixed solvents. The stability constant of (DB18C6 . UO₂)²⁺ complex in various neat solvents at 25 °C decreases in order: THF > EtOAc > PC > AN > DMF, and in the binary solvents at 25 °C is: THF–EtOAc > PC–EtOAc > DMF–EtOAc ≈ AN–EtOAc. The values of thermodynamic quantities (?H°_c, ?S°_c) for formation of this complex in the different binary solutions were obtained from temperature dependence of its stability constant and the results show that the thermodynamics of complexation reaction between UO₂ ²⁺ cation and DB18C6 is affected strongly by the nature and composition of the mixed solvents.     

Triplet Energy Transfer between the Primary Donor and Carotenoids in Rhodobacter sphaeroides R-26.1 Reaction Centers Incorporated with Spheroidene Analogs Having Different Extents of π-Electron Conjugation

Abstract— Three carotenoids, spheroidene, 3,4-dihydrospheroidene and 3,4,5,6-tetrahydrospheroidene, having 8, 9 and 10 conjugated carbon-carbon double bonds, respectively, were incorporated into Rhodobacter (Rb.) sphaeroides R-26.1 reaction centers. The extents of binding were found to be 95±5% for spheroidene, 65±5% for 3,4-dihydrospheroidene and 60±10% for 3,4,5,6-tetrahydrospheroidene. The dynamics of the triplet states of the primary donor and carotenoid were measured at room temperature by flash absorption spectroscopy. The carotenoid, spheroidene, was observed to quench the primary donor triplet state. The triplet state of spheroidene that was formed subsequently decayed to the ground state with a lifetime of 7.0±0.5 μs. The primary donor triplet lifetime in the Rb. sphaeroides R-26.1 reaction centers lacking carotenoids was 60±5 μs. Quenching of the primary donor triplet state by the carotenoid was not observed in the Rb. sphaeroides R-26.1 reaction centers containing 3,4-dihydrospheroidene nor in the R-26.1 reaction centers containing 3,4,5,6-tetrahydrospheroidene. Triplet-state electron paramagnetic resonance was also carried out on the samples. The experiments revealed carotenoid triple-state signals in the Rb. sphaeroides R-26.1 reaction centers incorporated with spheroidene, indicating that the primary donor triplet is quenched by the carotenoid. No carotenoid signals were observed from Rb. sphaeroides R-26.1 reaction centers incorporating 3,4-dihydrospheroidene nor in reaction centers incorporating 3,4,5,6-tetrahydrospheroidene. Circular dichroism, steady-state absorbance band shifts accompanying the primary photochemistry in the reaction center and singlet energy transfer from the carotenoid to the primary donor confirm that the carotenoids are bound in the reaction centers and interacting with the primary donor. These studies provide a systematic approach to exploring the effects of carotenoid structure and excited state energy on triplet transfer between the primary donor and carotenoids in reaction centers from photosynthetic bacteria.