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1.
Chem Commun (Camb) ; 50(89): 13718-21, 2014 Nov 18.
Artículo en Inglés | MEDLINE | ID: mdl-25248514

RESUMEN

This communication reports a novel sandwich-like rotaxane shuttle, which exhibits a unique mode of potential-controlled behaviour. Two dynamic processes occur simultaneously - conformational "unfolding" of the DADA stack accompanies translocation of the ring over the rotaxane's axle.

2.
Anal Bioanal Chem ; 398(4): 1651-60, 2010 Oct.
Artículo en Inglés | MEDLINE | ID: mdl-20658283

RESUMEN

Nanostructured bioelectrodes were designed and assembled into a biofuel cell with no separating membrane. The glassy carbon electrodes were modified with mediator-functionalized carbon nanotubes. Ferrocene (Fc) and 2,2'-azino-bis (3-ethylbenzothiazoline-6-sulfonate) diammonium salt (ABTS) bound chemically to the carbon nanotubes were found useful as mediators of the enzyme catalyzed electrode processes. Glucose oxidase from Aspergillus niger AM-11 and laccase from Cerrena unicolor C-139 were incorporated in a liquid-crystalline matrix-monoolein cubic phase. The carbon nanotubes-nanostructured electrode surface was covered with the cubic phase film containing the enzyme and acted as the catalytic surface for the oxidation of glucose and reduction of oxygen. Thanks to the mediating role of derivatized nanotubes the catalysis was almost ten times more efficient than on the GCE electrodes: catalytic current of glucose oxidation was 1 mA cm(-2) and oxygen reduction current exceeded 0.6 mA cm(-2). The open circuit voltage of the biofuel cell was 0.43 V. Application of carbon nanotubes increased the maximum power output of the constructed biofuel cell to 100 µW cm(-2) without stirring of the solution which was ca. 100 times more efficient than using the same bioelectrodes without nanotubes on the electrode surface.


Asunto(s)
Fuentes de Energía Bioeléctrica , Técnicas Biosensibles/instrumentación , Electroquímica/instrumentación , Proteínas Fúngicas/química , Glucosa Oxidasa/química , Lacasa/química , Nanotubos de Carbono/química , Aspergillus niger/enzimología , Técnicas Biosensibles/métodos , Catálisis , Coriolaceae/enzimología , Electroquímica/métodos , Electrodos , Oxidación-Reducción
3.
Bioelectrochemistry ; 80(1): 73-80, 2010 Nov.
Artículo en Inglés | MEDLINE | ID: mdl-20609634

RESUMEN

Single-walled carbon nanotubes (SWCNTs) were covalently modified with a redox mediator derived from 2,2'-azino-bis-(3-ethylbenzothiazoline)-6-sulfonic acid (ABTS), and implemented in the construction of electrodes for biocatalytic oxygen reduction. The procedure is based on: covalent bonding of mediator to nanotubes, placing the nanotubes directly on the carbon electrode surface and covering the nanostructured electrode with a Nafion film containing laccase as the biocatalyst. The modified electrode is stable and the problem of mediator (ABTS) leaking from the film is eliminated by binding it covalently to the nanotubes. Three different synthetic approaches were used to obtain ABTS-modified carbon nanotubes. Nanotubes were modified at ends/defect sites or on the nanotube sidewalls and characterized by Raman spectroscopy, TGA and electrochemistry. The accessibility of differently located ABTS units by the laccase active center and mediation of electron transfer were studied by cyclic voltammetry. The surface concentrations of ABTS groups electrically connected with the electrode were compared for each of the electrodes based on the charges of the voltammetric peaks recorded in the deaerated solution. The nanotube modification procedure giving the best parameters of the catalytic process was selected.


Asunto(s)
Técnicas Biosensibles/métodos , Nanotubos de Carbono/química , Oxígeno/química , Benzotiazoles/química , Biocatálisis , Electrodos , Polímeros de Fluorocarbono/química , Lacasa/química , Lacasa/metabolismo , Oxidación-Reducción , Oxígeno/metabolismo , Plata/química , Compuestos de Plata/química , Espectrometría Raman , Ácidos Sulfónicos/química , Termogravimetría
4.
Otolaryngol Pol ; 61(3): 325-8, 2007.
Artículo en Polaco | MEDLINE | ID: mdl-17847791

RESUMEN

INTRODUCTION: Malignant fibrohistiocytoma is one of the rare neoplasms of the larynx. It has nonepithelial origin. The most common sites of the neoplasm are: limbs, trunk and retroperitoneal space. Other localizations within head and neck are very rare. There are 5 histologic types. The most common is pleomorphic type. It is built of histiocytes, fibroblasts and multinuclear giant cells. An examination of the neoplasms consists of microscopic and immunohistologic examination with identification specific tissue markers and intermediate filaments of proteins. Treatment methods of the neoplasms are radical surgery, radiotherapy, chemiotherapy and associate methods of therapy. Prognosis is very bad. MATERIAL AND METHODS: [corrected] We present 71 years old man with croak for four mounths. The tumor of the larynx was examined in laryngoscopy. Biopsy of the tumor confirmed malignant fibrohistiocytoma. Laser surgery (chordectomy) was used to treatment this tumor without radiotherapy. RESULTS: One year observation of the patient didn't show recurrence of neoplasm, but he had only croak. CONCLUSIONS: Malignant fibrohistiocytoma of the larynx doesn't differ from other malignant neoplasms of the larynx. Malignant fibrohistiocytoma of the larynx is very rare malignant neoplasms of the larynx.


Asunto(s)
Histiocitoma Fibroso Maligno/patología , Histiocitoma Fibroso Maligno/cirugía , Neoplasias Laríngeas/patología , Neoplasias Laríngeas/cirugía , Laringe/patología , Anciano , Biopsia , Histiocitoma Fibroso Maligno/diagnóstico , Humanos , Inmunohistoquímica , Neoplasias Laríngeas/diagnóstico , Laringectomía/métodos , Laringoscopía , Terapia por Láser , Masculino , Enfermedades Raras , Estroboscopía , Resultado del Tratamiento
5.
J Am Chem Soc ; 123(38): 9356-66, 2001 Sep 26.
Artículo en Inglés | MEDLINE | ID: mdl-11562218

RESUMEN

[2]Catenane systems containing copper(II) and nickel(II) as metal centers have been self-assembled using tetraazamacrocyclic complexes and benzo-24-crown-8 as building blocks. A variety of methods, including X-ray crystallography, ESI mass spectrometry, (13)C and (1)H NMR, and electrochemistry, were applied to characterize these new face-to-face bismacrocyclic systems. Weak pi...pi interactions introduced by interlocking transition metal complexes with benzocrown moieties were shown to increase the communication (cooperativity) of metal centers. Introduction of the benzocrown increases the stability of the mixed valence state of the macrocyclic complex, which is reflected in high values of conproportionation constants. Moreover, this effect was found to be stronger than that obtained by shortening the length of the spacer between the two tetraazamacrocyclic subunits in the parent bismacrocycles. The extent of communication is larger for the nickel catenane than for the copper one.

6.
Chem Phys Lipids ; 105(1): 71-91, 2000 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-10727114

RESUMEN

The synthesis and surface behavior of a series of nine new hydrogenated nonionic surfactants and their fluorinated analogs, derived from D-mannitol are described. Adsorption monolayers (Gibbs monolayers) were studied by surface pressure (H) measurements as a function of time. For the spread monolayers (Langmuir monolayers), the measurements of surface pressure versus molecular area (A) were performed. For the most hydrophobic amphiphiles at low concentrations, the adsorption at the air/water interface from the bulk solution required extremely long times to attain equilibrium. The A values for two compounds which could be studied in both adsorbed and spread monolayers provided data allowing a direct comparison of the properties of the two types of films formed at the air/water interface. In spite of different mechanisms of formation of Langmuir and Gibbs monolayers, their characteristic parameters were identical, proving the equivalence of these two types of structures.


Asunto(s)
Compuestos de Flúor/síntesis química , Manitol/análogos & derivados , Tensoactivos/síntesis química , Espectroscopía de Resonancia Magnética , Estructura Molecular , Presión , Propiedades de Superficie , Tensión Superficial
7.
Environ Pollut ; 74(2): 89-100, 1991.
Artículo en Inglés | MEDLINE | ID: mdl-15092066

RESUMEN

Cadmium toxicity to the green alga Stichococcus bacillaris was investigated in media of pH 3-9. A significant decrease of cadmium toxicity occurred in both the acidic and alkaline ranges of pH. In media of pH 3 and 9, cadmium did not affect the dry mass content substantially. Maximum toxicity of cadmium was noticed at pH 6-7. Voltametric investigations showed a significant effect of pH on electrochemically measured cadmium content in the culture media. Hydrolysis of the medium components and formation of cadmium complexes with OH(-) ions caused a considerable decrease in amounts of electrochemically measured cadmium in the alkaline range of pH.

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