Comparison of Penta and Tetra-pyridyl Cobalt-based Catalysts for Water Reduction: H2 Production Cycle,Solvent Response and Reduction Free Energy

Understanding water reduction towards H₂ generation is crucial to overcome today's renewable energy obstacles. Previous studies have shown the superior H₂ production performances of Cobalt based penta-pyridyl (CoaPPy) and tetra-pyridyl (CoaTPy) complexes in solution. We investigate H₂ production cycles of CoaPPy and CoaTPy complexes immersed in water solution by means of Ab-initio Molecular Dynamics and Density Functional Theory. We monitor dynamic properties of the systems, solvent response and structural changes occurring in the catalysts, by simulating all intermediate steps of the H₂ production cycle. Reduction free energies and reorganization energies are calculated. Our results show that, following the first electron injection, H₂ production proceeds with the singlet spin state. Following the first electron insertion, we observe a significant rearrangement of the hydrogen bonding network in the first solvation shell. The cobalt center turns out to be more accessible for the surrounding water molecules in the case of CoaTPy at all the intermediate steps, which explains its higher catalytic performance over CoaPPy. Following the first reduction reaction, a larger gain in reduction free energy is estimated for CoaTPy with respect to CoaPPy, with a difference of 0.14 eV, in line with the experiments. For the second reduction, instead, CoaPPy shows more negative reduction potential, by 0.41 eV.     

On the inheritance of the strongly π-extending property

In this article, we focus on modules with the property that every projection invariant submodule is essential in a fully invariant direct summand. In contrast to π-extending condition, it is shown that the former property is inherited by direct summands and Morita invariant. An application of our results yields that the endomorphism ring of a free module enjoys the property. Moreover, we characterize generalized triangular matrix rings with the aforementioned property and apply to somewhat special cases.     

Corrigendum to: on the inheritance of the strongly π-extending property

In this corrigendum, we provide correct versions of Theorem 2.8 and Corollary 3.2, retract two consequences of the previous form of the Theorem 2.8. To this end, the main results of the article remain after the aforementioned changes.     

Radiation induced copolymerization reactivity of different allyl monomers with styrene

Radiation induced copolymerizations of electron donating such as allyl phenol (AP) and electron withdrawing such as allyl isothiocyanate (AITC) monomers with styrene (Sty) as a comonomer were studied in order to correlate the electronic behavior with copolymerization yield and molecular weight. The allyl monomers and comonomer were mixed in the same mol ratios under Ar atmosphere and copolymerized by using gamma radiation in various absorbed doses (55, 110, 165 kGy) obtained from a Co-60 source. Poly(AP-co-Sty), and poly(AITC-co-Sty) could have been prepared at all of the absorbed doses. The maximum copolymerization yields were calculated as a 16.35 and 6.52 percent for poly(AP-co-Sty) and poly(AITC-co-Sty), respectively. The molecular weights of poly(AP-co-Sty) copolymers are found to be higher in comparison to those of poly(AITC-co-Sty). Both results indicate that, under the same irradiation conditions, AP is more reactive on styrene than AITC is. Thus, the monomers having electron withdrawing (EW) substituents attached to allyl group may result in better copolymerization yield and molecular weight than those with electron donating (ED) substituents. Thermal stabilities of the poly(AP-co-Sty) copolymers are also higher than those of poly(AITC-co-Sty).     

Anti-diabetic Properties of Calcium Channel Blockers: Inhibition Effects on Aldose Reductase Enzyme Activity

Applied Biochemistry and Biotechnology - Aldose reductase (AR) belongs to NADPH-dependent oxidoreductases and converts glucose to sorbitol in the polyol pathway. AR inhibition is essential to...     

Structural changes in Poly(lactic acid)–zeolite nanocomposites exposed to 60Co gamma rays

Poly(lactic acid) (PLA) nanocomposites containing 3%, 5% and 7% zeolite used in the present research study were prepared by solution casting. The PLA nanocomposites were structurally characterized by Scanning Electron Microscopy and Fourier-transform infrared spectroscopy. The effects of the gamma radiation at the absorbed doses of 10, 15 and 20?kGy on the structures and thermal properties of the nanocomposites were investigated in a tetrahydrofuran solvent. Thermodecomposition tests and analyses were carried within 30–500°C range at the rate of 10°C?min^?1 by thermogravimetric analysis (TG). The activation energies for thermal degradation of the nanocomposites were calculated from their TG data by Flynn–Wall–Ozawa method. The G values of the nanocomposites were calculated based on molecular weights which were measured by means of gel permeation chromatography before and after the gamma irradiation. The E_a and molecular weight results showed that addition of zeolite to the PLA affected the radiation resistance of the polymer.     

A study on densities of sets of points and lines

In this paper, firstly, our purpose is to give the relationship among the densities of the sets of collinear points, the relationship among the densities of the sets of noncollinear points, and the relationship among the densities of the sets of the intersecting lines in Euclidean plane, respectively. In addition to that, we define the density formulas for the sets of points and lines under the two‐parameter planar Euclidean motion. By means of these results, we obtain essential properties that explain the connection among the densities of the sets of points and among the densities of the sets of intersecting lines under the two‐parameter planar Euclidean motion.     

Cytotoxic effect,enzyme inhibition,and in silico studies of some novel N-substituted sulfonyl amides incorporating 1,3,4-oxadiazol structural motif

Molecular Diversity - The acetylcholinesterase and carbonic anhydrase inhibitors (AChEIs and hCAIs) remain key therapeutic agents for many bioactivities such as anti-Alzheimer and antiobesity...     

Stabilization of horseradish peroxidase by covalent conjugation with dextran aldehyde against temperature and pH changes

Stabilization of Horseradish Peroxidase (HRP; EC 1.11.1.7) against temperature and pH via the formation of the conjugates obtained by multipoint covalent bonding of dextran aldehyde (DA) to the enzyme were studied. Hence, three different molar weighted dextrans (17.5 kD, 75 kD, 188 kD) were covalently bonded to purified enzyme with different molar ratios (n_HRP/n_DA 20/1, 10/1, 1/1, 1/5, 1/10, 1/15, 1/20). The thermal stabilities of the obtained conjugates were evaluated with the activities determined at different temperatures (25, 30, 35, 40, 50, 60, 70, 80°C) applying 60 minutes incubation time. Conjugates formed were characterized by gel-permeation chromatography (GPC) and fluorescence techniques. The conjugate synthesized using dextran 75 kDa with n_HRP/n_DA 1/10 molar ratio showed better thermal stability than other conjugates and purified enzyme at pH 7. This conjugate also has wider activity pH range than purified enzyme. In addition, mentioned conjugate at pH 7 had very long storage lifetime compared to purified enzyme at +4°C and room temperature; which is considered a favorable feature for usage in practice.      

Comparative combustion study of some polymers with oil shale

In this study, the combustion kinetics of G?ynük oil shale, polyethylene, polyethylene glycol (PEG), polymethyl methacrylate (PMMA), polyvinyl chloride, and polymer?Coil shale blends were investigated by thermogravimetric analysis. Experiments were conducted at non-isothermal conditions with a heating rate of 5?K?min^?1 in the 298?C1173?K temperature interval under air atmosphere. An increase in the total conversion values with increasing mass percentage of polymers of the blends was observed. Differential thermogravimetric data were analyzed by an Arrhenius model. Effects of blending ratio of oil shale and polymer on the combustion kinetics were investigated. Kinetic parameters were determined and the results were discussed. An increase was observed in the frequency factor and activation energy values as the weight percentage of polymer in blends were increased. The minimum activation energy, 16.1?kJ?mol^?1, was calculated for PEG/oil shale with 2/3 blending ratio.