Temperature studies of dielectric permittivity and mass density pretransitional anomalies in binary mixtures

Results of temperature studies of dielectric permittivity and mass density in binary mixtures are presented. The anomaly of dielectric permittivity as a function of temperature in nitrobenzene-n-alkanes binary mixtures has been studied. Molar dielectric permittivity which takes into account the anomaly of dielectric permittivity and the mass density anomaly has been introduced.     

Approximate Hermitian–Einstein connections on principal bundles over a compact Riemann surface

Let $X$ be a compact connected Riemann surface and $G$ a connected reductive complex affine algebraic group. Given a holomorphic principal $G$ -bundle $E_G$ over $X$ , we construct a $C^\infty $ Hermitian structure on $E_G$ together with a $1$ -parameter family of $C^\infty $ automorphisms $\{F_t\}_{t\in \mathbb R }$ of the principal $G$ -bundle $E_G$ with the following property: Let $\nabla ^t$ be the connection on $E_G$ corresponding to the Hermitian structure and the new holomorphic structure on $E_G$ constructed using $F_t$ from the original holomorphic structure. As $t\rightarrow -\infty $ , the connection $\nabla ^t$ converges in $C^\infty $ Fréchet topology to the connection on $E_G$ given by the Hermitian–Einstein connection on the polystable principal bundle associated to $E_G$ . In particular, as $t\rightarrow -\infty $ , the curvature of $\nabla ^t$ converges in $C^\infty $ Fréchet topology to the curvature of the connection on $E_G$ given by the Hermitian–Einstein connection on the polystable principal bundle associated to $E_G$ . The family $\{F_t\}_{t\in \mathbb R }$ is constructed by generalizing the method of [6]. Given a holomorphic vector bundle $E$ on $X$ , in [6] a $1$ -parameter family of $C^\infty $ automorphisms of $E$ is constructed such that as $t\rightarrow -\infty $ , the curvature converges, in $C^0$ topology, to the curvature of the Hermitian–Einstein connection of the associated graded bundle.     

Trapping of a Highly Reactive Oxoiron(IV) Complex in the Catalytic Epoxidation of Olefins by Hydrogen Peroxide

The generation of a nonheme oxoiron(IV) intermediate, [(cyclam)Fe^IV(O)(CH₃CN)]²⁺ ( 2 ; cyclam=1,4,8,11‐tetraazacyclotetradecane), is reported in the reactions of [(cyclam)Fe^II]²⁺ with aqueous hydrogen peroxide (H₂O₂) or a soluble iodosylbenzene (sPhIO) as a rare example of an oxoiron(IV) species that shows a preference for epoxidation over allylic oxidation in the oxidation of cyclohexene. Complex 2 is kinetically and catalytically competent to perform the epoxidation of olefins with high stereo‐ and regioselectivity. More importantly, 2 is likely to be the reactive intermediate involved in the catalytic epoxidation of olefins by [(cyclam)Fe^II]²⁺ and H₂O₂. In spite of the predominance of the oxoiron(IV) cores in biology, the present study is a rare example of high‐yield isolation and spectroscopic characterization of a catalytically relevant oxoiron(IV) intermediate in chemical oxidation reactions.     

Spontaneous Resolution by Crystallization of an Octanuclear Iron(III) Complex Using Only Racemic Reagents

The P and M enantiomers of the octanuclear [Fe₈(μ₄‐O)₄(μ‐4‐Cl‐pz)₁₂Cl₄] complex, having T symmetry, were resolved by temporary substitution of chloride ligands by racemic 4‐^sBu‐phenolates and subsequent crystallization, where the (S)‐ and (R)‐phenolates coordinate selectively to the M and P complexes, respectively. The complexes were characterized by circular dichroism analysis and X‐ray structure determination. This work constitutes a rare example of enantiomeric recognition resulting in spontaneous resolution upon crystallization.     

Multicomponent access to novel proline/cyclized cysteine tethered monastrol conjugates as potential anticancer agents

The versatility of multicomponent Biginelli’s reaction is exploited in the development of proline and cyclized cysteine tethered conjugates of monastrol, a kinesin Eg5 inhibitor. Ten new conjugates are synthesized focusing on structural replacement of the ester moiety (C-5 position) of the monastrol backbone with amino acid based amide moieties. On cytotoxic evaluation, conjugate 24 has shown promising in vitro cytotoxic activity against leukemia. Molecular docking studies revealed that the conjugates 19 and 24 exhibit better interaction at kinesin Eg5 receptor compared to monastrol. Moreover, computational calculations and predictions of important molecular properties suggest that these new amino acid based conjugates could be further improved to provide potential anticancer agents.     

Semi‐heterogeneous Dual Nickel/Photocatalysis using Carbon Nitrides: Esterification of Carboxylic Acids with Aryl Halides

Cross‐coupling reactions mediated by dual nickel/photocatalysis are synthetically attractive but rely mainly on expensive, non‐recyclable noble‐metal complexes as photocatalysts. Heterogeneous semiconductors, which are commonly used for artificial photosynthesis and wastewater treatment, are a sustainable alternative. Graphitic carbon nitrides, a class of metal‐free polymers that can be easily prepared from bulk chemicals, are heterogeneous semiconductors with high potential for photocatalytic organic transformations. Here, we demonstrate that graphitic carbon nitrides in combination with nickel catalysis can induce selective C?O cross‐couplings of carboxylic acids with aryl halides, yielding the respective aryl esters in excellent yield and selectivity. The heterogeneous organic photocatalyst exhibits a broad substrate scope, is able to harvest green light, and can be recycled multiple times. In situ FTIR was used to track the reaction progress to study this transformation at different irradiation wavelengths and reaction scales.     

Superconducting energy gap and c-axis plasma frequency of (Nd,Sm)FeAsO0.82F0.18 superconductors from infrared ellipsometry

We present far-infrared ellipsometric measurements of polycrystalline samples of the pnictide superconductor RFeAsO0.82F0.18 (R=Nd and Sm). We find evidence that the electronic properties are strongly anisotropic such that the optical spectra are dominated by the weakly conducting c-axis response similar to the cuprate high-temperature superconductors. We deduce an upper limit of the c-axis superconducting plasma frequency of omega pl,c(SC)< or =260 cm(-1) corresponding to a lower limit of the c-axis magnetic penetration depth of lambda c > or =6 microm and lambda c/lambda ab > or =30 as compared to lambda ab=185 nm from muon spin rotation [A. Drew, arXiv:0805.1042 [Phys. Rev. Lett. (to be published)]]. We also observe a gaplike suppression of the conductivity in the superconducting state with a shoulderlike feature at omegaSC* approximately 300 cm(-1) and spectral shape which is consistent with an unconventional order parameter with 2Delta approximately omegaSC* approximately 37 meV.     

Entropy of MgO based on the Stacey equation of state

In the present communication we have modified the earlier calculations for the compression dependence of entropy of MgO using recent experimental data and more accurate equation of state. We have estimated the thermal expansivity with the help of the Anderson–Isaak equation at different compressions and selected temperatures up to the melting temperature of the solid. P–V relationship and compression dependence of isothermal bulk modulus are computed with the help of the Stacey equation of state. The results have been compared with those recommended by Cynn et al. [J. Phys. Chem. 99/19 (1995) 7813]. It is found that the entropy decreases with increasing compression along an isotherm.