How to Build Prussian Blue Based Water Oxidation Catalytic Assemblies: Common Trends and Strategies

Prussian blue (PB) and its analogues (PBAs) have at least a three-century-long history in coordination chemistry. Recently, cobalt-based PBAs have been acknowledged as efficient and robust water oxidation catalysts. Given the flexibility in their synthesis, the structure and morphology of cobalt-based PBAs have been modified for enhanced catalytic activity under electrochemical (EC), photocatalytic (PC), and photoelectrochemical (PEC) conditions. Here, in this review, the work on cobalt-based PBAs is presented in four sections: i) electrocatalytic water oxidation with bare PBAs, ii) photocatalytic processes in the presence of a photosensitizer (PS), iii) photoelectrochemical water oxidation by coupling PBAs to proper semiconductors (SCs), and iv) the utilization of PBA-PS assemblies coated on SCs for the dye-sensitized photoelectrochemical water oxidation. This review will guide readers through the structure and catalytic activity relationship in cobalt-based PBAs by describing the role of each structural component. Furthermore, this review aims to provide insight into common strategies to enhance the catalytic activity of PBAs.     

Revisiting roaming trajectories in ketene isomerization at higher dimensionality

Roaming dynamics have been observed in a three-dimensional model of the ketene isomerization reaction. The roaming trajectories sample the region between the outer potential barriers closest to the respective ketene isomers and involve turning points along the reaction coordinate in a polar representation. These roaming trajectories avoid the intrinsic reaction coordinate and the intermediates to which it is associated. Thus, one-dimensional transition state theory (TST) is generally insufficient as has been confirmed through an analysis of the reactive flux along the dividing surface (DS). A global representation of the DS, however, leads to accurate TST rate constants. The exact and TST microcanonical rates of isomerization have been obtained for the three-dimensional model and compare well to experiment. The global DS is therefore particularly important for obtaining rates in reactions that exhibit roaming. This work thus confirms the findings of our previous two-dimensional treatment of ketene isomerization (Ulusoy et al. in J. Phys. Chem. A 117:7553–7560, 2013).     

q‐Voronovskaya type theorems for q‐Baskakov operators

In the present paper, we prove quantitative q‐Voronovskaya type theorems for q‐Baskakov operators in terms of weighted modulus of continuity. We also present a new form of Voronovskaya theorem, that is, q‐Grüss‐Voronovskaya type theorem for q‐Baskakov operators in quantitative mean. Hence, we describe the rate of convergence and upper bound for the error of approximation, simultaneously. Our results are valid for the subspace of continuous functions although classical ones is valid for differentiable functions. Copyright © 2015 John Wiley & Sons, Ltd.     

Approximation by modified Szász-Durrmeyer operators

The main goal of this paper is to introduce Durrmeyer modifications for the generalized Szász–Mirakyan operators defined in (Aral et al., in Results Math 65:441–452, 2014). The construction of the new operators is based on a function \(\rho \) which is continuously differentiable \(\infty \) times on \( \left[ 0,\infty \right) ,\) such that \(\rho \left( 0\right) =0\) and \( \inf _{x\in \left[ 0,\infty \right) }\rho ^{\prime }\left( x\right) \ge 1.\) Involving the weighted modulus of continuity constructed using the function \( \rho \), approximation properties of the operators are explored: uniform convergence over unbounded intervals is established and a quantitative Voronovskaya theorem is given. Moreover, we obtain direct approximation properties of the operators in terms of the moduli of smoothness. Our results show that the new operators are sensitive to the rate of convergence to f,  depending on the selection of \(\rho .\) For the particular case \(\rho \left( x\right) =x\), the previous results for classical Szász-Durrmeyer operators are captured.     

Synthesis,characterization and thermal study of some tetradentate Schiff base transition metal complexes

Several mononuclear Co(II), Ni(II), Cu(II), and Fe(II) complexes of tetradentate salpren-type diimine, obtained from 3,5-di-tert-butyl-2-hydroxybenzaldehyde and 1,3-diaminopropane have been prepared and characterized by analytical, spectroscopic (FT-IR, UV–VIS) techniques, magnetic susceptibility measurements and thermogravimetric analyses (TG). The thermodynamic and thermal properties of complexes have been investigated. For further characterization Direct Insertion Probe-Mass Spectrometry (DIP-MS) was used and the fragmentation pattern and also stability of the ions were evaluated. The characterization of the end products of the decomposition was achieved by X-ray diffraction. The thermal stabilities of metal complexes of N,N′-bis(3,5-di-t-butylsalicylidene)-1,3-propanediamine ligand (L) were found as Ni(II) > Cu(II) > Co(II) > Fe(II).     

Development of a cloud point extraction and preconcentration method for chromium(III) and total chromium prior to flame atomic absorption spectrometry

A sensitive and selective method has been developed for the determination of chromium in water samples based on using cloud point extraction (CPE) preconcentration and determination by flame atomic absorption spectrometry (FAAS). The method is based on the complexation of Cr(III) ions with Brilliant Cresyl Blue (BCB) in the presence of non-ionic surfactant Triton X-114. Under the optimum conditions, the preconcentration of 50 mL of water sample in the presence of 0.5 g/L Triton X-114 and 1.2 × 10⁻⁵ M BCB permitted the detection of 0.42 μg/L chromium(III). The calibration graph was linear in the range of 1.5–70 μg/L, and the recovery of more than 99% was achieved. The proposed method was used in FAAS determination of Cr(III) in water samples and certified water samples. In addition, the developed CPE-FAAS method was also used for speciation of the inorganic chromium species after reduction of Cr(VI) to Cr(III) using a thiosulphate solution of 120 mg/L in the presence of Hg(II) ion as a stabilizer.     

Existence and uniqueness for a nonlinear inverse reaction‐diffusion problem with a nonlinear source in higher dimensions

This paper analyzes the existence and the uniqueness problem for an n‐dimensional nonlinear inverse reaction‐diffusion problem with a nonlinear source. A transformation is used to obtain a new inverse coefficient problem. Then, a parabolic differential operator L_λ is defined to establish the relation between the solution of L_λ = 0 and the new inverse problem. Following this, it is shown that the inverse problem has at least one solution in the class of admissible coefficients. Furthermore, it is proved that this solution is the unique solution of the undertaken inverse problem. A numerical example is given to illustrate ill‐posedness of the inverse problem. Copyright © 2013 John Wiley & Sons, Ltd.     

New 6-(4-Bromophenyl)-imidazo[2,1- b ]thiazole Derivatives: Synthesis and Antimicrobial Activity

 New 4-alkyl/aryl-1-((6-(4-bromophenyl)-imidazo[2,1-b]thiazol-3-yl)-acetyl)-3-thiosemicarbazides and 3-alkyl/aryl-2-(((6-(4-bromophenyl)-imidazo[2,1-b]thiazol-3-yl)-acetyl)-hydrazono)-4-thiazolidinones were synthesized from 6-(4-bromophenyl)-imidazo[2,1-b]thiazole-3-acetic acid hydrazide. Their structures were elucidated by elemental analyses and spectroscopic data. All compounds were tested for antibacterial and antifungal activities. The antimicrobial activities of the compounds were assessed by the microbroth dilution technique. The compounds were also evaluated for antituberculosis activity against Mycobacterium tuberculosis H₃₇Rv (ATCC 27294); they exhibited varying degrees of inhibition in the in vitro primary screening at 6.25 μg · cm⁻³. The most active compound was 3-(4-nitrophenyl)-2-(((6-(4-bromophenyl)-imidazo[2,1-b]thiazol-3-yl)-acetyl)-hydrazono)-4-thiazolidinone.