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1.
Neuroimage ; 59(3): 2994-3002, 2012 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-22032947

RESUMO

Correlations between spontaneous fluctuations in the blood oxygenation level dependent (BOLD) signal measured with functional MRI are finding increasing use as measures of functional connectivity in the brain, where differences can potentially predict cognitive performance and diagnose disease. Caffeine, which is a widely consumed neural stimulant and vasoactive agent, has been found to decrease the amplitude and correlation of resting-state BOLD fluctuations, and hence is an important factor to consider in functional connectivity studies. However, because the BOLD signal is sensitive to neural and vascular factors, the physiological mechanisms by which caffeine alters spontaneous BOLD fluctuations remain unclear. Resting-state functional connectivity has traditionally been assessed using stationary measures, such as the correlation coefficient between BOLD signals measured across the length of a scan. However, recent work has shown that the correlation of resting-state networks can vary considerably over time, with periods as short as 10 s. In this study, we used a sliding window correlation analysis to assess temporal variations in resting-state functional connectivity of the motor cortex before and after caffeine ingestion. We found that the temporal variability of BOLD correlation was significantly higher following a caffeine dose, with transient periods of strong correlation alternating with periods of low or negative correlation. This phenomenon was primarily due to increased variability in the phase difference between BOLD time courses in the left and right motor cortices. These results indicate that caffeine may cause underlying spontaneous neural fluctuations to go in and out of coherence more frequently, and emphasizes the need to consider non-stationary measures when studying changes in functional connectivity.


Assuntos
Cafeína/farmacologia , Estimulantes do Sistema Nervoso Central/farmacologia , Córtex Motor/efeitos dos fármacos , Vias Neurais/efeitos dos fármacos , Oxigênio/sangue , Adulto , Algoritmos , Artefatos , Mapeamento Encefálico , Circulação Cerebrovascular/efeitos dos fármacos , Interpretação Estatística de Dados , Feminino , Dedos/fisiologia , Hemodinâmica/fisiologia , Humanos , Processamento de Imagem Assistida por Computador , Modelos Lineares , Imageamento por Ressonância Magnética , Masculino , Mecânica Respiratória , Imagem Corporal Total , Adulto Jovem
2.
ChemistryOpen ; 11(6): e202200077, 2022 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-35642133

RESUMO

Transition-metal-(TM-)doped TiO2 has been considered as promising electrode material for the oxygen evolution reaction (OER). OER activity is expected to depend on the coordination of the surface atoms. In this study, we theoretically investigate the stability of low-index surfaces of TM-doped rutile, (110), (100), (101) and (001), with 50 % of the Ti atoms substituted by Sc, Y, V, Nb or Ta. For Sc and Y, we also consider models with O vacancies providing the most stable oxidation state of Sc and Y. Surface energies are calculated with DFT(+U). Based on the Gibbs-Wulff theorem, the shape of the single crystals is predicted. It is observed that p-doping leads to spontaneous oxygen loss and O vacancies cause surface reconstruction. The Wulff shapes of n-doped TiO2 have smaller contributions of the (110) facet and, for Nb and Ta, larger contributions of other facets. Given the higher coordinative unsaturation of the TM atoms in the latter, a higher catalytic activity is expected.

3.
ChemSusChem ; 14(21): 4708-4717, 2021 Nov 04.
Artigo em Inglês | MEDLINE | ID: mdl-34498408

RESUMO

Metal carbides are promising materials for electrocatalytic reactions such as water electrolysis. However, for application in catalysis for the oxygen evolution reaction (OER), protection against oxidative corrosion, a high surface area with facile electrolyte access, and control over the exposed active surface sites are highly desirable. This study concerns a new method for the synthesis of porous tungsten carbide films with template-controlled porosity that are surface-modified with thin layers of nickel oxide (NiO) to obtain active and stable OER catalysts. The method relies on the synthesis of soft-templated mesoporous tungsten oxide (mp. WOx ) films, a pseudomorphic transformation into mesoporous tungsten carbide (mp. WCx ), and a subsequent shape-conformal deposition of finely dispersed NiO species by atomic layer deposition (ALD). As theoretically predicted by density functional theory (DFT) calculations, the highly conductive carbide support promotes the conversion of Ni2+ into Ni3+ , leading to remarkably improved utilization of OER-active sites in alkaline medium. The obtained Ni mass-specific activity is about 280 times that of mesoporous NiOx (mp. NiOx ) films. The NiO-coated WCx catalyst achieves an outstanding mass-specific activity of 1989 A gNi -1 in a rotating-disc electrode (RDE) setup at 25 °C using 0.1 m KOH as the electrolyte.

4.
Neuroimage ; 46(1): 56-63, 2009 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-19457356

RESUMO

In resting-state functional magnetic resonance imaging (fMRI), correlations between spontaneous low-frequency fluctuations in the blood oxygenation level dependent (BOLD) signal are used to assess functional connectivity between different brain regions. Changes in resting-state BOLD connectivity measures are typically interpreted as changes in coherent neural activity across spatially distinct brain regions. However, this interpretation can be complicated by the complex dependence of the BOLD signal on both neural and vascular factors. For example, prior studies have shown that vasoactive agents that alter baseline cerebral blood flow, such as caffeine and carbon dioxide, can significantly alter the amplitude and dynamics of the task-related BOLD response. In this study, we examined the effect of caffeine (200 mg dose) on resting-state BOLD connectivity in the motor cortex across a sample of healthy young subjects (N=9). We found that caffeine significantly (p<0.05) reduced measures of resting-state BOLD connectivity in the motor cortex. Baseline cerebral blood flow and spectral energy in the low-frequency BOLD fluctuations were also significantly decreased by caffeine. These results suggest that caffeine usage should be carefully considered in the design and interpretation of resting-state BOLD fMRI studies.


Assuntos
Cafeína/farmacologia , Estimulantes do Sistema Nervoso Central/farmacologia , Imageamento por Ressonância Magnética , Córtex Motor/efeitos dos fármacos , Vias Neurais/efeitos dos fármacos , Adulto , Circulação Cerebrovascular/efeitos dos fármacos , Feminino , Humanos , Interpretação de Imagem Assistida por Computador , Masculino , Córtex Motor/irrigação sanguínea , Descanso
5.
J Diabetes Sci Technol ; 7(6): 1436-45, 2013 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-24351170

RESUMO

Input from continuous glucose monitors (CGMs) is a critical component of artificial pancreas (AP) systems, but CGM performance issues continue to limit progress in AP research. While G4 PLATINUM has been integrated into AP systems around the world and used in many successful AP controller feasibility studies, this system was designed to address the needs of ambulatory CGM users as an adjunctive use system. Dexcom and the University of Padova have developed an advanced CGM, called G4AP, to specifically address the heightened performance requirements for future AP studies. The G4AP employs the same sensor and transmitter as the G4 PLATINUM but contains updated denoising and calibration algorithms for improved accuracy and reliability. These algorithms were applied to raw data from an existing G4 PLATINUM clinical study using a simulated prospective procedure. The results show that mean absolute relative difference (MARD) compared with venous plasma glucose was improved from 13.2% with the G4 PLATINUM to 11.7% with the G4AP. Accuracy improvements were seen over all days of sensor wear and across the plasma glucose range (40-400 mg/dl). The greatest improvements occurred in the low glucose range (40-80 mg/dl), in euglycemia (80-120 mg/dl), and on the first day of sensor use. The percentage of sensors with a MARD <15% increased from 69% to 80%. Metrics proposed by the AP research community for addressing specific AP requirements were also computed. The G4AP consistently exhibited improved sensor performance compared with the G4 PLATINUM. These improvements are expected to enable further advances in AP research.


Assuntos
Glicemia/metabolismo , Diabetes Mellitus Tipo 1/sangue , Diabetes Mellitus Tipo 1/terapia , Monitorização Fisiológica/instrumentação , Pacientes Ambulatoriais , Pâncreas Artificial , Tecnologia de Sensoriamento Remoto/instrumentação , Algoritmos , Desenho de Equipamento , Humanos , Insulina/administração & dosagem , Insulina/uso terapêutico , Monitorização Fisiológica/métodos , Tecnologia de Sensoriamento Remoto/métodos , Reprodutibilidade dos Testes
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