Radiation-induced polymerization for the immobilization of penicillin acylase

The immobilization ofEscherichia coli penicillin acylase (EC 3.5.1.11) was investigated by radiation-induced polymerization of 2-hydroxyethyl methacrylate at low temperature. A leak-proof composite that does not swell in water was obtained by adding the crosslinking agent trimethylolpropane trimethacrylate to the monomer-aqueous enzyme mixture. Penicillin acylase, which was immobilized with greater than 70% yield, possessed a higherK _m value toward the substrate 6-nitro-3-phenylacetamidobenzoic acid than the free enzyme form (K _m = 1.7 × 10⁻⁵ and 1 × 10⁻⁵M, respectively). The structural stability of immobilized penicillin acylase, as assessed by heat, guanidinium chloride, and pH denaturation profiles, was very similar to that of the free-enzyme form, thus suggesting that penicillin acylase was entrapped in its native state into aqueous free spaces of the polymer matrix.     

Counteranion dependent protonation and aggregation of tetrakis(4-sulfonatophenyl)porphyrin in organic solvents

The tetrabutylammonium salt of 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (TPPS) is soluble in dichloromethane, and the general properties of this compound have been investigated as function of various added acids HX (X = Cl, Br, I, CF(3)COO, CF(3)SO(3), TFPB) through UV-vis absorption spectroscopy, steady state fluorescence emission, and resonance light-scattering (RLS) techniques. Upon addition of HX, the initial monomeric free base TPPS is readily converted in an aggregated species, whose spectroscopic features are independent of the nature of the counteranion X. All the spectroscopic evidence suggest a J-type arrangement of chromophores in this aggregate, involving strong hydrogen bonds, electrostatic, and dispersive interactions. In the specific case of chloride and bromide, in the presence of a TBAX excess, the addition of the corresponding acid leads to a monomeric ion-pair between the TBA cations and the diacid TPPS, whose central core is strongly interacting with the halide. On further increasing the acid concentration in these latter solutions, fully protonated species are formed that eventually start to aggregate.     

Platinum(II) complexes bearing 1,1'-bis(diphenylphosphino)ferrocene as building blocks for functionalized redox active porphyrins

Reactions of the cationic complex ions [PtMe(Me2SO)(PP)]+ (PP = dppf (1,1'-bis(diphenylphosphino)ferrocene) and dppe (1,2-bis(diphenylphosphino)ethane)) with 5,10,15,20-tetrakis(4-pyridyl)-21H,23H-porphyrin (TpyP) led to the formation of the symmetrical tetraplatinated porphyrin complexes, [PtMe(PP)]4TpyP.X4 (PP = dppf, X = CF3SO3-, 3, and PP = dppe, X = BF4-, 5) containing the organometallic fragment [PtMe(PP)]. The precursor sulfoxide platinum complexes [PtMe(Me2SO)(dppf)]CF3SO3, 2 and [PtMe(Me2SO)(dppe)]BF4, 4, were prepared by halide abstraction from [PtMeCl(dppf)], 1, and by controlled protonolysis of [PtMe2(dppe)] respectively, in the presence of a small amount of dimethyl sulfoxide. All these starting platinum(II) compounds, as well as the porphyrin derivatives 3 and 5, were fully characterized through elemental analysis, 1H NMR mono- and bidimensional, 31P[1H], 31P-1H HMBC, UV/Vis absorption and photophysical measurements. The X-ray crystal structure of complex 1 has been determined. In order to ascertain the electronic influence of ferrocene, the spectroscopic and redox properties of 3 were compared with those of TPyP and of the analogous 5. Cyclic voltammetry (CV), differential pulse voltammetry (DPV), 1H and 31P NMR data, and UV/Vis data, all suggest a certain degree of communication between the central porphyrin and the peripheral hetero-bimetallic fragments. In contrast, no detectable interaction among these peripheral groups seem to come into play. Unlikely from the porphyrin derivative 5, formation of well defined fluorescent mesoscopic ring structures was easily achieved by simple evaporation from diluted dichloromethane solutions of 3.     

Porphyrin deposition induced by UV irradiation

Simple irradiation by UV light of porphyrin TpyP and its zinc(II) and manganese(III) metal derivatives in chlorinated solvents leads to the deposition on silica of mesoscale aggregates. The process is due to the photochemical decomposition of the solvent with generation of HCl, which causes the precipitation of a protonated form. The morphology of the resulting objects is driven by the nature of the inserted metal ion.     

Electron-hole drops in A2B6 compounds with blende type structure

Evidence of electron-hole drops (EHD) in ZnTe, ZnSe and ZnS single crystalsof blende type structure based on studies of luminescence and optical gain measurements under laser excitation is presented. It is established that at T =4.2 K the luminescence and the inverse population of the most pure crystals near the self-absorption edge is due to the radiative recombination of EHD. The main parameters of the drops in these materials are obtained by comparison of experimental and theoretical luminescence spectra.     

Spiro[2.2]pentane as a dissymmetric scaffold for conformationally constrained analogues of glutamic acid: focus on racemic 1-aminospiro[2.2]pentyl-1,4-dicarboxylic acids

In search for novel conformationally constrained analogues of L-glutamic acid, a diastereodivergent synthesis of the four 1-aminospiro[2.2]pentyl-1,4-dicarboxylic acid racemic pairs is reported along with their stereochemical assignment, conformational analysis, and preliminary biological evaluation as potential glutamate (ionotropic and metabotropic) ligands.