Naked five-coordinate Fe(III)(NO) porphyrin complexes: vibrational and reactivity features

Model ferric heme nitrosyl complexes, [Fe(TPP)(NO)](+) and [Fe(TPFPP)(NO)](+), where TPP is the dianion of 5,10,15,20-tetrakis-phenyl-porphyrin and TPFPP is the dianion of 5,10,15,20-tetrakis-pentafluorophenyl-porphyrin, have been obtained as isolated species by the gas phase reaction of NO with [Fe(III)(TPP)](+) and [Fe(III) (TPFPP)](+) ions delivered in the gas phase by electrospray ionization, respectively. The so-formed nitrosyl complexes have been characterized by vibrational spectroscopy also exploiting (15)N-isotope substitution in the NO ligand. The characteristic NO stretching frequency is observed at 1825 and 1859 cm(-1) for [Fe(III)(TPP)(NO)](+) and [Fe(III)(TPFPP)(NO)](+) ions, respectively, providing reference values for genuine five-coordinate Fe(III)(NO) porphyrin complexes differing only for the presence of either phenyl or pentafluorophenyl substituents on the meso positions of the porphyrin ligand. The vibrational assignment is aided by hybrid density functional theory (DFT) calculations of geometry and electronic structure and frequency analysis which clearly support a singlet spin electronic state for both [Fe(TPP)(NO)](+) and [Fe(TPFPP)(NO)](+) complexes. Both TD-DFT and CASSCF calculations suggest that the singlet ground state is best described as Fe(II)(NO(+)) and that the open-shell AFC bonding scheme contribute for a high-energy excited state. The kinetics of the NO addition reaction in the gas phase are faster for [Fe(III)(TPFPP)](+) ions by a relatively small factor, though highly reliable because of a direct comparative evaluation. The study was aimed at gaining vibrational and reactivity data on five-coordinate Fe(III)(NO) porphyrin complexes, typically transient species in solution, ultimately to provide insights into the nature of the Fe(NO) interaction in heme proteins.     

Carbene-mediated transformations of 1-(benzylideneamino)benzimidazoles

Carbene-mediated transformations of N-(3-butylbenzimidazol-3-ium-1-yl)-1-arylmethanimine iodides with carbon disulfide and benzoyl isothiocyanate gave the corresponding NHC·CS(2) betaines in 68-85% and benzoyl-[1-butyl-3-[(E)-(aryl)methyleneamino]benzimidazol-1-ium-2-carbothioyl]azanides, respectively, in 74-85% yields. However, reaction with excess isopropyl isothiocyanate in NaH/THF at room temperature yielded the 1-butyl-1',3'-diisopropyl-3-[(E)-(aryl)methyleneamino]spiro[benzimidazole-2,5'-imidazolidine]-2',4'-dithiones (74-77%).     

Femtosecond excited-state dynamics of 4-nitrophenyl pyrrolidinemethanol: evidence of twisted intramolecular charge transfer and intersystem crossing involving the nitro group

Ultrafast excited-state relaxation dynamics of a nonlinear optical (NLO) dye, (S)-(-)-1-(4-nitrophenyl)-2-pyrrolidinemethanol (NPP), was carried out under the regime of femtosecond fluorescence up-conversion measurements in augmentation with quantum chemical calculations. The primary concern was to trace the relaxation pathways which guide the depletion of the first singlet excited state upon photoexcitation, in such a way that it is virtually nonfluorescent. Ground- and excited-state (singlet and triplet) potential energy surfaces were calculated as a function of the -NO(2) torsional coordinate, which revealed the perpendicular orientation of -NO(2) in the excited state relative to the planar ground-state conformation. The fluorescence transients in the femtosecond regime show biexponential decay behavior. The first time component of a few hundred femtoseconds was ascribed to the ultrafast twisted intramolecular charge transfer (TICT). The occurrence of charge transfer (CT) is substantiated by the large dipole moment change during excitation. The construction of intensity- and area-normalized time-resolved emission spectra (TRES and TRANES) of NPP in acetonitrile exhibited a two-state emission on behalf of decay of the locally excited (LE) state and rise of the CT state with a Stokes shift of 2000 cm(-1) over a time scale of 1 ps. The second time component of a few picoseconds is attributed to the intersystem crossing (isc). In highly polar solvents both the processes occur on a much faster time scale compared to that in nonpolar solvents, credited to the differential stability of energy states in different polarity solvents. The shape of frontier molecular orbitals in the excited state dictates the shift of electron density from the phenyl ring to the -NO(2) group and is attributed to the charge-transfer process taking place in the molecule. The viscosity dependence of relaxation dynamics augments the proposition of considering the -NO(2) group torsional motion as the main excited-state relaxation coordinate.     

Development of a novel reporter gene vector for cell based angiogenic studies

Angiogenesis is a promising area of research that targets key therapeutic areas like cancer; wound healing, inflammatory diseases, etc. There is an increasing demand for screening of potential angiogenic and anti-angiogenic agents using sensitive, robust cell-based assays. We have developed a reporter vector containing cis-acting elements that respond to growth factors/angiogenic ligands for use in a cell-based luciferase reporter assay. We performed transient transfection of our reporter gene vector in MCF-7 cells to establish its application for screening of potential pro/anti-angiogenic agents. Reporter gene transactivation studies with different concentrations of fetal bovine serum clearly indicated that the vector is functionally responsive to the angiogenic signals mediated by serum growth factors. We also used endostatin to inhibit transactivation and prove responsiveness to the anti-angiogenic agent. This vector is a promising tool for studying angiogenesis using cell-based reporter gene assays.     

Methyl hydrogen peroxide dimer: A structural study

Methyl hydrogen peroxide (MHP) exhibits a tendency to form a stable dimer by hydrogen-bonding. Ab initio theoretical investigations on methyl hydrogen peroxide dimer (MHPD) carried out herein lead to several energetically stable structures that have a direct bearing on the reactivity of the monomer in terms of its molecular electrostatic potential (MESP). To gauge the role played by the electron-correlation in lending stability to MHP and its dimer, we employ the density functional theory (DFT) (as implemented by B3LYP-functional), and subsequently second order Møller-Plesset (MP2) perturbation theory, using the basis sets 6-31G(d, p) and 6-311++G(2d, 2p). Simulated infra-red vibrational spectra lead to spectral intensity redistribution upon dimerization. Energetically the lowest MHPD is endowed with inversion symmetry and has two hydrogen bonds, while three other structures emerge: one energetically very close with two H-bonds, and the two others, with three H-bonds each, yet higher by about 2 kcal mol⁻¹.     

Matrix multiplication operators on Banach function spaces

In this paper, we study the matrix multiplication operators on Banach function spaces and discuss their applications in semigroups for solving the abstract Cauchy problem.     

The multicomponent reaction of dimethoxycarbene, dimethyl butynedioate and electrophilic styrenes: an unprecedented synthesis of highly substituted cyclopentenone acetals

The zwitterionic species generated by the addition of dimethoxycarbene to dimethyl butynedioate is trapped by arylidenemalononitrile to yield cyclopentenone derivatives.     

A simple synthesis of thioketonemolybdenum carbonyl complexes. An example of geometric isomerism

Thioketones react with molybdenum hexacarbonyl in tetrahydrofuran (60–65°C, 2–3 h) to give molybdenum pentacarbonyl complexes in 52–80% yield. Geometric isomers were isolated in the case of thiocamphor.     

Composition operators on Banach function spaces

We study the boundedness and the compactness of composition operators on some Banach function spaces such as absolutely continuous Banach function spaces on a -finite measure space, Lorentz function spaces on a -finite measure space and rearrangement invariant spaces on a resonant measure space. In addition, we study some properties of the spectra of a composition operator on the general Banach function spaces.