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1.
Chemistry ; 17(4): 1122-7, 2011 Jan 24.
Artículo en Inglés | MEDLINE | ID: mdl-21243678

RESUMEN

We have developed a novel triphenylmethane-based hexanuclear zinc complex that exhibits peculiar photochemical and photophysical properties. Upon UV irradiation, the compound turned from colorless to reddish purple, while the color of emission turned from blue to red. The color change was attributed to an oxidation of the ligand part. It was suggested that an intramolecular energy-transfer mechanism operates to give rise to the red emission. The UV treatment of a single crystal results in simultaneous emission of orthogonally polarized blue and red light. This color switching, namely linear dichroic emission was so distinct that one can recognize with by sight through optical microscope. The columnar arrangement of molecules in the crystal clearly accounts for the observed polarization of the emission.

2.
J Phys Chem B ; 110(51): 26033-9, 2006 Dec 28.
Artículo en Inglés | MEDLINE | ID: mdl-17181254

RESUMEN

Adsorption of glucose oxidase (GOD) onto plasma-polymerized thin films (PPF) with nanoscale thickness was characterized by atomic force microscopy (AFM), quartz crystal microbalance (QCM), and electrochemical measurements. The PPF surface is very flat (less than 1-nm roughness), and its properties (charge and wettability) can be easily changed while retaining the backbone structure. We focused on three types of surfaces: (1) the pristine surface of hexamethyldisiloxane (HMDS) PPF (hydrophobic and neutral surface), (2) an HMDS PPF surface with nitrogen-plasma treatment (hydrophilic and positive-charged surface), and (3) an HMDS PPF surface treated with oxygen plasma (hydrophilic and negative-charged surface). The AFM image showed that the GOD molecules were densely adsorbed onto surface 2 and that individual GOD molecules could be observed. The longer axis of GOD ellipsoid molecules were aligned parallel to the surface, called the "lying position", because of electrostatic association. On surface 1, clusters of GOD molecules did not completely cover the original PPF surface (surface coverage was ca. 60%). The 10-nm-size step height between the GOD clusters and the PPF surface suggests that the longer axes of individual GOD molecules were aligned perpendicular to the surface, called the "standing position". On surface 3, only a few of the GOD molecules were adsorbed because of electrostatic repulsion. These results indicate that the plasma polymerization process can facilitate enhancement or reduction of protein adsorption. The AFM images show a corresponding tendency with the QCM profiles. The QCM data indicate that the adsorption behavior obeys the Langmuir isotherm equation. The amperometric biosensor characteristics of the GOD-adsorbed PPF on a platinum electrode showed an increment in the current because of enzymatic reaction with glucose addition, indicating that enzyme activity was mostly retained in spite of irreversible adsorption.


Asunto(s)
Glucosa Oxidasa/química , Polímeros/química , Cuarzo/química , Adsorción , Microscopía de Fuerza Atómica
3.
J Physiol Anthropol Appl Human Sci ; 24(4): 483-6, 2005 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-16079603

RESUMEN

We present a conceptual framework for applying techniques of SNP genotyping as a molecular biological approach and remote sensing as an ecological approach to elucidation of the contribution of polygene and environmental factors to inter-individual variation in skin pigmentation phenotype. Additionally, we discuss the obstacles that frustrate our efforts to identify how the human genome encodes the complex phenotype and suggest the use of computational methods designed for knowledge discovery within hereditary database.


Asunto(s)
Biología Computacional/métodos , Ambiente , Variación Genética , Genoma Humano , Polimorfismo de Nucleótido Simple/genética , Pigmentación de la Piel/genética , Atmósfera/análisis , Bases de Datos Genéticas , Genotipo , Humanos , Espectrofotometría/métodos , Telemetría/métodos
4.
J Am Chem Soc ; 124(46): 13731-6, 2002 Nov 20.
Artículo en Inglés | MEDLINE | ID: mdl-12431103

RESUMEN

The cooperative action of multiple Cu(II) nuclear centers is shown to be effective and selective in the hydrolysis of 2'-5' and 3'-5' ribonucleotides. Reported herein is the specific catalysis by two trinuclear Cu(II) complexes of L3A and L3B. Pseudo first-order kinetic studies reveal that the L3A trinuclear Cu(II) complex effects hydrolysis of Up(2'-5')U with a rate constant of 28 x 10(-)(4) min(-)(1) and Up(3'-5')U with a rate constant of 0.5 x 10(-)(4) min(-)(1). The hydrolyses of Ap(3'-5')A and Ap(2'-5')A proceed with rate constants of 24 x 10(-)(4) min(-)(1) and 0.5 x 10(-)(4) min(-)(1) respectively. The L3A trinuclear Cu(II) complex demonstrates high specificity for Up(2'-5')U and Ap(3'-5')A. Similar studies with the more rigid L3B trinuclear Cu(II) complex shows no selectivity and yields lower rate constants for hydrolysis. The selectivity observed with the L3A ligand is attributed to the geometry of the ligand-bound diribonucleotide which ultimately dictates the proximity of the attacking hydroxyl and the phosphoester to a Cu(II) center for activation and subsequent hydrolysis.


Asunto(s)
Nucleótidos de Adenina/química , Cobre/química , Fosfatos de Dinucleósidos/química , Compuestos Organometálicos/química , Ribonucleótidos/química , Cristalografía por Rayos X , Hidrólisis , Cinética , Ligandos , Especificidad por Sustrato
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