Zeolitic imidazolate frameworks (ZIFs) have been widely investigated for numerous applications including energy storage, heterogeneous catalysis, and greenhouse gas adsorption. Much of the early work has focused on the bulk properties of microcrystalline ZIFs. Herein, we focus on identifying the nature of the surface of ZIF-8 by studying a supported ZIF-8 nanoparticle film using surface characterization techniques. We have experimentally identified the presence of a zinc-rich surface terminated by carbonates and water/hydroxyl groups (in addition to the expected methylimidazole terminations) using X-ray photoelectron spectroscopy (XPS). The thermal stability of ZIF-8 thin films was also investigated using scanning electron microscopy (SEM) and temperature-programmed reaction spectroscopy (TPRS). We determined the onset of decomposition of ZIF-8 thin films to be approximately 630 K using TPRS in an ultrahigh vacuum (UHV) environment. This work presents the first characterization steps needed to study the evolution of ZIF surfaces in situ using surface characterization techniques. Such techniques are capable of determining reaction products and tracking intermediates and surface evolution in gas adsorption/reaction studies of thin films.
Although multivariate analytic techniques might identify diagnostic patterns that are not captured by univariate methods, they have rarely been used to study the neural correlates of Alzheimer's disease (AD) or cognitive impairment. Nonquantitative PET scans were acquired during rest in 17 probable AD subjects selected for mild severity [mean-modified Mini Mental Status Examination (mMMS) 46/57; SD 5.1], 16 control subjects (mMMS 54; SD 2.5) and 23 subjects with minimal to mild cognitive impairment but no dementia (mMMS 53; SD 2.8). Expert clinical reading had low success in discriminating AD and controls. There were no significant mean flow differences among groups in traditional univariate SPM Voxel-wise analyses or region of interest (ROI) analyses. A covariance pattern was identified whose mean expression was significantly higher in the AD as compared to controls (P = 0.03; sensitivity 76-94%; specificity 63-81%). Sites of increased concomitant flow included insula, cuneus, pulvinar, lingual, fusiform, superior occipital and parahippocampal gyri, whereas decreased concomitant flow was found in cingulate, inferior parietal lobule, middle and inferior frontal, supramarginal and precentral gyri. The covariance analysis-derived pattern was then prospectively applied to the cognitively impaired subjects: as compared to subjects with Clinical Dementia Rating (CDR) = 0, subjects with CDR = 0.5 had significantly higher mean covariance pattern expression (P = 0.009). Expression of this pattern correlated inversely with Selective Reminding Test total recall (r = −0.401, P = 0.002), delayed recall (r = −0.351, P = 0.008) and mMMS scores (r = −0.401, P = 0.002) in all three groups combined. We conclude that patients with AD may differentially express resting cerebral blood flow covariance patterns even at very early disease stages. Significant alterations in expression of resting flow covariance patterns occur even for subjects with cognitive impairment. Expression of covariance patterns correlates with cognitive and functional performance measures, holding promise for meaningful associations with underlying biopathological processes.
Background: Associations between the APOE genotype and various medical conditions have been documented at a very young age. The association between the APOE genotype and cognitive performance varies at different ages. APOE related changes in brain activation have been recently reported for middle aged and elderly subjects. Objective: To explore APOE related alterations during cognitive activation in a population of young adults. Methods: Using H 2 15 O positron emission tomography (PET), imaging was carried out in 20 healthy young adults (age 19 to 28 years; four e4 carriers and 16 non-e4 carriers) during a non-verbal memory task. Voxel-wise multiple regression analyses were undertaken, with the activation difference PET counts as the dependent variable and the APOE genotype as the independent variable. Results: Brain regions were identified where e4 carriers showed significantly lower or higher activation than noncarriers. Conclusions:The results suggest that APOE dependent modulation of cerebral flow may be present even at a young age. This may reflect an APOE related physiological heterogeneity which may or may not predispose to brain disease in the ensuing decades or, less likely, the effect of very early Alzheimer's disease related pathological changes.
Brain regions where systematic relationships (slopes) between subjects' education-IQ and brain activation differ as a function of disease status may mediate the differential ability to cope with (ie, delay or modify) clinical manifestations of AD.
The adsorption of CO 2 and H 2 O by ZIF-8 thin films was investigated using X-ray photoelectron spectroscopy (XPS) and temperature-programmed desorption (TPD) in situ under low-temperature, low-pressure conditions. Using these two techniques, we demonstrate the ability to clearly distinguish molecules that exhibit significant adsorption in the pore structure of ZIF-8, from molecules that adsorb predominantly at outer surface sites. In particular, CO 2 was found to penetrate into the pore structure, while H 2 O resided predominantly at the surface. CO 2 uptake was quantified, and mobility within the films was investigated. The ability to distinguish surface processes from those that primarily occur in the bulk is key to understanding the properties of nanoporous materials.
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