Principal active species of horseradish peroxidase, compound I: a hybrid quantum mechanical/molecular mechanical study

The active species, Compound I, of horseradish peroxidase (HRP) has been investigated by quantum mechanical/molecular mechanical (QM/MM) calculations using 10 different QM regions. In accord with experimental data, the lowest doublet and quartet states are found to be virtually degenerate, with two unpaired electrons on the FeO moiety and one localized on the porphyrin in an a(2u)-dominant orbital with a minor, but nonnegligible, a(1u) component. The proximal ligand appears to be imidazole rather than imidazolate. The hydrogen-bonding network around the FeO moiety (i.e., Arg38 and His42) has significant influence on the axial bonds and the spin density distribution in the FeO moiety. Including this network in the QM region was found to be essential for reproducing the experimental M?ssbauer parameters. The protein environment shapes most of the subtle features of Compound I of HRP.     

Photoinduced carbon monoxide migration in a synthetic heme-copper complex

Time-resolved infrared (TRIR) flash photolytic techniques have been employed to initiate and observe the efficient dissociation of CO from a synthetic heme-CO/copper complex, [((6)L)Fe(II)(CO)..Cu(I)](+) (2), in CH(3)CN and acetone at room temperature. In CH(3)CN, a significant fraction of the photodissociated CO molecules transiently bind to copper (nu(CO)(Cu) = 2091 cm(-)(1)) giving [((6)L)Fe(II)..Cu(I)(CO)](+) (4), with an observed rate constant, k(1) = 1.5 x 10(5) s(-)(1). That is followed by a slower direct transfer of CO from the copper moiety back to the heme (nu(CO)(Fe) = 1975 cm(-)(1)) with k(2) = 1600 s(-)(1). Additional transient absorption (TA) UV-vis spectroscopic experiments have been performed monitoring the CO-transfer reaction by following the Soret band. Eyring analysis of the temperature-dependent data yields DeltaH(double dagger) = 43.9 kJ mol(-)(1) for the 4-to-2 transformation, similar to that for CO dissociation from [Cu(I)(tmpa)(CO)](+) in CH(3)CN (DeltaH(double dagger) = 43.6 kJ mol(-)(1)), suggesting CO dissociation from copper regulates the binding of small molecules to the heme within [((6)L)Fe(II)..Cu(I)](+)(3). Our observations are analagous to those observed for the heme(a3)/Cu(B) active site of cytochrome c oxidase, where photodissociated CO from the heme(a3) site immediately (ps) transfers to Cu(B) followed by millisecond transfer back to the heme.     

Antibacterial properties of Ag nanoparticle loaded multilayers and formation of magnetically directed antibacterial microparticles

Antibacterial coatings based on hydrogen-bonded multilayers containing in situ synthesized Ag nanoparticles were created on planar surfaces and on magnetic colloidal particles. We report the antibacterial properties of these coatings, determined using a disk-diffusion (Kirby-Bauer) test, as a function of the film thickness and the concentration of Ag nanoparticles in the hydrogen-bonded multilayers. The zone of inhibition (ZoI) determined by the disk-diffusion test increases as the thickness of the multilayer film is increased. Results obtained for the values of the ZoI as a function of film thickness can be described adequately with a simple diffusion model (i.e., the square of the zone of inhibition (ZoI) depended linearly on the logarithm of the thickness of the silver-loaded films). This observation suggests that, in order to incrementally increase the ZoI, an exponentially increasing amount of Ag is required within the multilayers. In general, there was no statistically significant correlation between the zone of inhibition and the number of Ag loading and reduction cycles. The duration of sustained release of antibacterial Ag ions from these coatings, however, could be prolonged by increasing the total supply of zerovalent silver in the films via multiple loading and reduction cycles. These results indicate that the release of silver is controlled by an oxidation mechanism at the surface of the nanoparticles and that repeated loading and reduction of silver leads preferentially to growth of the existing silver nanoparticles in the film as opposed to nucleation of new Ag nanoparticles. We also show that magnetic microspheres coated with silver nanoparticle loaded hydrogen-bonded multilayer thin films can be used to deliver antibacterial agents to specific locations. The minimum inhibitory concentration (MIC) of nanocomposite coated microspheres was determined by the agar dilution technique: antibacterial magnetic microspheres with higher concentrations of Ag nanoparticles exhibited lower MIC values.     

Organization-induced charge redistribution in self-assembled organic monolayers on gold

The charge redistribution that occurs within dipolar molecules as they self-assemble into organized organic monolayer films has been studied. The extent of charge transfer is probed by work function measurements, using low-energy photoelectron spectroscopy (LEPS), contact potential difference (CPD), and X-ray photoelectron spectroscopy (XPS), with the latter providing fine details about the internal charge distribution along the molecule. In addition, two-photon photoelectron spectroscopy is applied to investigate the electronic structure of the adsorbed layers. We show that charge transfer acts to reduce the dipole-dipole interaction between the molecules but may either decrease or increase the molecule-to-surface dipole moment.     

A comparison of two models of theρ-meson

A renormalization of the-propagator is presented. It is shown that if the-wave, isovector - amplitude is assumed to be dominated by this renormalized, many scattering parameters are predicted that agree well with experimental data. The model is compared with one presented by Tschang and Parkinson. It is shown that the predictions of the two models are the same, but that the renormalization model does not contain some of the theoretical problems of the Tschang and Parkinson scheme.Research partially supported by NSF Institutional Grant No. GU3220 and a grant from the Research Corporation.     

Application of an auditory model to speech recognition

Some aspects of auditory processing are incorporated in a front end for the IBM speech-recognition system [F. Jelinek, "Continuous speech recognition by statistical methods," Proc. IEEE 64 (4), 532-556 (1976)]. This new process includes adaptation, loudness scaling, and mel warping. Tests show that the design is an improvement over previous algorithms.     

Actions of Commutative Hopf Algebras

We show that actions of finite-dimensional semisimple commutativeHopf algebras H on H-module algebras A are essentially group-gradings.Moreover we show that the centralizer of H in the smash productA # H equals A^H H. Using these we invoke results about groupgraded algebras and results about centralizers of separablesubalgebras to give connections between the ideal structureof A, A^H and A # H. Examples of the above occur naturally when one considers: (1) finite abelian groups G of automorphisms of an algebra Awith | G |^–1 A; (2) G-graded algebras, for finite groups G; (3) finite-dimensional restricted Lie algebras L, with semisimplerestricted enveloping algebra u(L), acting as derivations onan algebra A.     

Microplate assay for determination of cathepsin D activity based on quantification of a specific and stable peptide released from hemoglobin: VV-hemorphin-7

Cathepsins are key enzymes in mediating turnover of cytosolic proteins. In the context of cancer progression, those most actively studied include cathepsins D and B which have been implicated in processes such as growth and metastasis of many types of cancer. For more than 10 years, their roles as tumor marker and prognostic indicators have been studied, especially in breast cancer. Most of the studies relating the role of cathepsin D in cancer used immunological detection methods to determine the level of enzyme but do not reflect enzyme activity. Moreover, one of the problems in understanding cathepsin D clinical studies is that immunoassays may employ antibodies against the different form of the antigen. As an alternative, this work describes an indirect method to assess the active form of cathepsin D based on ELISA quantification of a specific and stable product of hemoglobin hydrolysis: VV-hemorphin-7. The procedure described here allows a low detection limit (ca. 5×10⁻⁹ M) and thus can represent an original approach to evaluate cathepsin D activity in biological samples.