Characterization and reactivity study of non-heme high-valent iron–hydroxo complexes

A terminal Fe^IIIOH complex, [Fe^III(L)(OH)]²⁻ (1), has been synthesized and structurally characterized (H₄L = 1,2-bis(2-hydroxy-2-methylpropanamido)benzene). The oxidation reaction of 1 with one equiv. of tris(4-bromophenyl)ammoniumyl hexachloroantimonate (TBAH) or ceric ammonium nitrate (CAN) in acetonitrile at −45 °C results in the formation of a Fe^IIIOH ligand radical complex, [Fe^III(L˙)(OH)]⁻ (2), which is hereby characterized by UV-visible, ¹H nuclear magnetic resonance, electron paramagnetic resonance, and X-ray absorption spectroscopy techniques. The reaction of 2 with a triphenylcarbon radical further gives triphenylmethanol and mimics the so-called oxygen rebound step of Cpd II of cytochrome P450. Furthermore, the reaction of 2 was explored with different 4-substituted-2,6-di-tert-butylphenols. Based on kinetic analysis, a hydrogen atom transfer (HAT) mechanism has been established. A pK_a value of 19.3 and a BDFE value of 78.2 kcal/mol have been estimated for complex 2.

One-electron oxidation of an Fe^III–OH complex (1) results in the formation of a Fe^III–OH ligand radical complex (2). Its reaction with (C₆H₅)₃C˙ results in the formation of (C₆H₅)₃COH, which is a functional mimic of compound II of cytochrome P450.     

Effects of different composition ratio on the dielectric relaxation and dynamic mechanical properties of poly(ω‐dodecalactam‐co‐ε‐caprolactam‐co‐propylene oxide) copolymers

The molecular dynamics of new poly (ω‐dodecalactam‐co‐ε‐caprolactam‐co‐propylene oxide) copolymers (DL/CL/PAC) has been investigated by using dynamic mechanical thermal analysis (DMTA) and dielectric relaxation spectroscopy (DRS) measurements. The copolymers were synthesized via anionic polymerization of relevant lactams activated with carbamoyl derivatives of telechelic hydroxyl terminated polypropylene oxide with isophorone diisocyanate (PAC). The calorimetric, X‐ray diffraction, and DMTA measurements were performed to recognize the influence of the composition ratio and the type of PAC on the physical, thermal, and mechanical properties of the synthesized copolymers. The DRS was used to study the frequency dependence of the dielectric permittivity of some isotherms from ?110 to 145 °C. Copolymerization of ε‐caprolactam with about 10 wt % ω‐dodecalactam results in a copolymer that has lower water absorption, a melting point close to that of polyamide 6 and has a high enough degree of crystallinity in respect to high storage modulus. Five dielectric relaxations have been observed in the dielectric spectra, three at lower temperature and two at higher temperature. The copolymers have two glass transition temperatures for polyamide segments and polyether blocks, indicating microphase separation in the copolymers. Other studies directed toward molecular dynamics of polyamide DL/CL/PAC copolymers have not been reported. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

Existence of unimodular elements in a projective module

(1) Let R be an affine algebra over an algebraically closed field of characteristic 0 with $\dim (R)=n$. Let P be a projective $A=R[T_1,?,T_k]$-module of rank n with determinant L. Suppose I is an ideal of A of height n such that there are two surjections $\alpha :P?I$ and $?:L\oplus A^{n?1}?I$. Assume that either (a) $k=1$ and $n\ge 3$ or (b) k is arbitrary but $n\ge 4$ is even. Then P has a unimodular element (see 4.1, 4.3).(2) Let R be a ring containing $\mathbb{Q}$ of even dimension n with height of the Jacobson radical of $R\ge 2$. Let P be a projective $R[T,T^{?1}]$-module of rank n with trivial determinant. Assume that there exists a surjection $\alpha :P?I$, where $I?R[T,T^{?1}]$ is an ideal of height n such that I is generated by n elements. Then P has a unimodular element (see 3.4).     

A hydrogen peroxide-responsive hyperpolarized 13C MRI contrast agent

We report a new reaction-based approach for the detection of hydrogen peroxide (H(2)O(2)) using hyperpolarized (13)C magnetic resonance imaging ((13)C MRI) and the H(2)O(2)-mediated oxidation of α-ketoacids to carboxylic acids. (13)C-Benzoylformic acid reacts selectively with H(2)O(2) over other reactive oxygen species to generate (13)C-benzoic acid and can be hyperpolarized using dynamic nuclear polarization, providing a method for dual-frequency detection of H(2)O(2). Phantom images collected using frequency-specific imaging sequences demonstrate the efficacy of this responsive contrast agent to monitor H(2)O(2) at pre-clinical field strengths. The combination of reaction-based detection chemistry and hyperpolarized (13)C MRI provides a potentially powerful new methodology for non-invasive multi-analyte imaging in living systems.     

Effect of Second Order Chemical Reaction on MHD Free Convective Radiating Flow over an Impulsively Started Vertical Plate

An attempt has been made to study laminar convective heat and mass transfer flow of an incompressible, viscous and electrically conducting fluid over an impulsively started vertical plate with conduction-radiation embedded in a porous medium in presence of transverse magnetic field. The influence of both second order chemical reaction and heat generation are taken into account. The governing coupled partial differential equations are solved by Crank-Nicolson method. The effects of important physical parameters on the velocity, temperature and concentration have been analyzed through graphs. The results of the present study agree well with the previous solutions. Applications of the present study are shown in material processing systems and different industries. The important findings of present study are: chemical reaction parameter acts as resistive force to reduce the velocity whereas heat source parameter enhances the velocity.     

Further results on the Drazin inverse of even‐order tensors

The notion of the Drazin inverse of an even‐order tensors with the Einstein product was introduced, very recently [J. Ji and Y. Wei. Comput. Math. Appl., 75(9), (2018), pp. 3402‐3413]. In this article, we further elaborate this theory by establishing a few characterizations of the Drazin inverse and $\mathrm{??}$‐weighted Drazin inverse of tensors. In addition to these, we compute the Drazin inverse of tensors using different types of generalized inverses and full rank decomposition of tensors. We also address the solution of multilinear systems by using the Drazin inverse and iterative (higher order Gauss‐Seidel) method of tensors. Besides these, the convergence analysis of the iterative technique is also investigated within the framework of the Einstein product.     

The effect of mass transfer on MHD free convective radiating flow over an impulsively started vertical plate embedded in a porous medium

The laminar convective heat and mass transfer flow of an incompressible, viscous, electrically conducting fluid over an impulsively started vertical plate with conduction-radiation embedded in a porous medium in presence of transverse magnetic eld has been studied. An exact solution is derived by solving the dimensionless governing coupled partial differential equations. As the equations are nonlinear, so Laplace transform technique is used to solve it. The eects of important physical parameters on the velocity, temperature, concentration, skin friction, Nusselt number and Sherwood number have been analyzed through graphs. The results of the present study agree well with the previous solutions obtained without mass transfer. After the consideration of mass transfer, some dierent results are noticed. Applications of the present study arise in material processing systems and different industries.     

Antioxidant and antibacterial activities of bark extracts from Commiphora berryi and Commiphora caudata

This study investigates the in vitro antioxidant and antimicrobial activities of eight extracts obtained from the dried barks of Commiphora berryi and Commiphora caudata (Burseraceae). The radical scavenging activity was assessed by 1,1-diphenyl-2-picryl hydrazyl (DPPH) and nitric oxide assays. The methanolic extracts of C. berryi and C. caudata showed significant DPPH radical scavenging activity, with IC?? values of 26.92 and 21.16?μg?mL?1, respectively, and low radical scavenging activity against the nitric oxide assay. The antimicrobial activity of the plants was tested against the Gram-positive and Gram-negative bacteria. The ethyl acetate, chloroform and petroleum ether extracts of C. berryi showed good antibacterial activity against Pseudomonas aeruginosa, with a minimum inhibitory concentration (MIC) of 0.26?mg?mL?1, whereas the ethyl acetate and methanol extracts of C. caudata showed moderate antimicrobial activity with an MIC of more than 2.0?mg?mL?1 against P. aeruginosa compared to the petroleum ether and chloroform extracts, which showed an MIC of 1.1?mg?mL?1. The methanolic extracts of C. berryi and C. caudata also showed moderate cytotoxic activity against a human mammary carcinoma cell line (MCF-7), with values IC?? of 82.6 and 88.4?μg?mL?1, respectively.     

Estimation of slow diffusion rates in confined systems: CCl4 in zeolite NaA

Often the rate of passage of gaseous molecules through model zeolites is too small to be computed directly. An estimate for the rate of passage of CCl₄ through the 8-ring window in a model of zeolite A has been obtained by combining a direct evaluation of the free energy profile and an adaptation of the rare events method. First the free energy profile is found from a direct evaluation of the canonical partition function at high dilution and the transition state theory rate constant obtained. The dynamic correction factor is then estimated from molecular dynamics runs and used to compute the actual rate k_eff. The method is used to estimate the rate of passage through the 8-ring window in a rigid model of zeolite A, and the results are compared with those obtained from rigid models with expanded windows and from the flexible model. Even a small expansion in the 8-ring window diameter increases the rate significantly, but the changes associated with a flexible cage are small.