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1.
J Chem Phys ; 150(2): 024504, 2019 Jan 14.
Artículo en Inglés | MEDLINE | ID: mdl-30646699

RESUMEN

In the present work, we employ broadband dielectric spectroscopy to study the molecular dynamics of the prototypical glass former glycerol confined in two microporous zeolitic imidazolate frameworks (ZIF-8 and ZIF-11) with well-defined pore diameters of 1.16 and 1.46 nm, respectively. The spectra reveal information on the modified α relaxation of the confined supercooled liquid, whose temperature dependence exhibits clear deviations from the typical super-Arrhenius temperature dependence of the bulk material, depending on the temperature and pore size. This allows assigning well-defined cooperativity length scales of molecular motion to certain temperatures above the glass transition. We relate these and previous results on glycerol confined in other host systems to the temperature-dependent length scale deduced from nonlinear dielectric measurements. The combined experimental data can be consistently described by a critical divergence of this correlation length as expected within theoretical approaches assuming that the glass transition is due to an underlying phase transition.

2.
Sci Rep ; 7(1): 7463, 2017 08 07.
Artículo en Inglés | MEDLINE | ID: mdl-28785071

RESUMEN

Ionic liquids are promising candidates for electrolytes in energy-storage systems. We demonstrate that mixing two ionic liquids allows to precisely tune their physical properties, like the dc conductivity. Moreover, these mixtures enable the gradual modification of the fragility parameter, which is believed to be a measure of the complexity of the energy landscape in supercooled liquids. The physical origin of this index is still under debate; therefore, mixing ionic liquids can provide further insights. From the chemical point of view, tuning ionic liquids via mixing is an easy and thus an economic way. For this study, we performed detailed investigations by broadband dielectric spectroscopy and differential scanning calorimetry on two mixing series of ionic liquids. One series combines an imidazole based with a pyridine based ionic liquid and the other two different anions in an imidazole based ionic liquid. The analysis of the glass-transition temperatures and the thorough evaluations of the measured dielectric permittivity and conductivity spectra reveal that the dynamics in mixtures of ionic liquids are well defined by the fractions of their parent compounds.

3.
J Chem Phys ; 143(15): 154505, 2015 Oct 21.
Artículo en Inglés | MEDLINE | ID: mdl-26493913

RESUMEN

In this work, we examine the use of metal-organic framework (MOF) systems as host materials for the investigation of glassy dynamics in confined geometry. We investigate the confinement of the molecular glass former glycerol in three MFU-type MOFs with different pore sizes (MFU stands for "Metal-Organic Framework Ulm-University") and study the dynamics of the confined liquid via dielectric spectroscopy. In accord with previous reports on confined glass formers, we find different degrees of deviations from bulk behavior depending on pore size, demonstrating that MOFs are well-suited host systems for confinement investigations.

4.
Sci Rep ; 5: 13922, 2015 Sep 10.
Artículo en Inglés | MEDLINE | ID: mdl-26355037

RESUMEN

Ionic liquids (ILs) are salts that are liquid close to room temperature. Their possible applications are numerous, e.g., as solvents for green chemistry, in various electrochemical devices, and even for such "exotic" purposes as spinning-liquid mirrors for lunar telescopes. Here we concentrate on their use for new advancements in energy-storage and -conversion devices: Batteries, supercapacitors or fuel cells using ILs as electrolytes could be important building blocks for the sustainable energy supply of tomorrow. Interestingly, ILs show glassy freezing and the universal, but until now only poorly understood dynamic properties of glassy matter, dominate many of their physical properties. We show that the conductivity of ILs, an essential figure of merit for any electrochemical application, depends in a systematic way not only on their glass temperature but also on the so-called fragility, characterizing the non-canonical super-Arrhenius temperature dependence of their ionic mobility.

5.
J Vasc Surg ; 1(1): 84-95, 1984 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-6384562

RESUMEN

This report attempts to establish the place of real-time B-mode carotid imaging in the diagnosis of carotid artery disease through an analysis of the results of 3 years of experience in three major noninvasive vascular laboratories. Over 7000 patients were studied noninvasively with real-time B-mode carotid imaging and oculoplethysmography (OPG). Angiographic comparisons of 1723 vessels form the basis of this study. All tests were interpreted by physicians who had no knowledge of the angiograms. Images and x-ray films were classified by diameter of stenosis: grade I (0% to 39%), grade II (40% to 69%), grade III (70% to 99%), and grade IV (total occlusion). The effect of the imaging experience was determined by dividing the study into two periods. The results of image quality vs. accuracy and of combining the anatomic study (scan) and physiologic study (OPG) were also evaluated. The overall data show a specificity of 87% (985 of 1139), a sensitivity for grade II disease of 72% (193 of 267), a sensitivity for grade III of 66% (133 of 201), and a sensitivity for grade IV of 64% (74 of 116). With experience each center showed improvement of the imaging technique in diagnosing grade III (p greater than 0.1: not significant) and grade IV disease (p less than 0.0002: highly significant), although there was no improvement in the specificity and sensitivity of grade II disease. All scan errors were analyzed. Most errors were interpretation errors (27%: 90 of 338), scan/arteriogram mismatches (23%: 79 of 338), or poor-quality scans secondary to existing disease (22%: 75 of 338). There was a direct correlation of scan quality and accuracy, with a 97% specificity for grade I scans of good to excellent quality. When the scan and OPG agreed, there were uniform predictive values for all grades (88% to 93%). Sixteen of 79 scan/arteriogram mismatch vessels were operated on, and the scan proved more reliable in 86%. Real-time B-mode carotid imaging is a reliable technique for defining the normal carotid artery and is becoming increasingly sensitive in identifying existing disease. Despite its limitations, its strong points make it a valuable clinical tool.


Asunto(s)
Enfermedades de las Arterias Carótidas/diagnóstico , Ultrasonografía , Enfermedades de las Arterias Carótidas/diagnóstico por imagen , Angiografía Cerebral , Errores Diagnósticos , Humanos , Pletismografía
6.
Urology ; 18(2): 177-8, 1981 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-7269024

RESUMEN

Nitrofurantoin has been described as a cause of both hepatocellular cholestatic hepatic injury. A case report of a patient in whom granulomatous hepatitis developed attributed to nitrofurantoin is given.


Asunto(s)
Enfermedad Hepática Inducida por Sustancias y Drogas/etiología , Granuloma/inducido químicamente , Nitrofurantoína/efectos adversos , Femenino , Humanos , Persona de Mediana Edad , Infecciones Urinarias/tratamiento farmacológico
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