The aggregation behavior of the newly synthesized gadofullerene magnetic resonance imaging (MRI) contrast agent, i.e., Gd@C(82)O(6)(OH)(16)(NHCH(2)CH(2)COOH)(8) (abbreviated as AAD-EMF), was studied in detail by dynamic light scattering, scanning electron microscopy, T(1)-weighted magnetic resonance, and atomic force microscopy. It was revealed that the AAD-EMF aggregation in aqueous solution is pH-dependent. At pH 2, the AAD-EMF first self-assemble to form ca. 30 nm small clusters, and then dozens of the small clusters further aggregate to form large grapelike particles. At pH 7, the aggregates are also ca. 30 nm small clusters, but they are hard to further aggregate except for forming some cluster dimers or trimers, so AAD-EMF aggregates have a narrow size distribution by this time. At pH 9, the AAD-EMF aggregations cover a large range of continuous hydrodynamic diameters from 30 to 2000 nm. On the basis of the above observations, the aggregating mechanism of AAD-EMF under different pH values was proposed by concurrently considering the hydrogen-bonding effect and the dipolar interactions between AAD-EMF. 相似文献
Spectroscopic (FT-IR, FT-Raman, UV–vis, and NMR) techniques have been extensively used for structural elucidation of compounds along with the study of geometrical and vibrational properties. Herein, 2-acetyl-5-methylfuran, a derivative of furan, was experimentally characterized and analyzed in details using FT-IR, FT-Raman, UV–vis, and 1H NMR spectroscopic techniques conducted in different solvents. The experimentally analyzed spectral results were carefully compared with theoretical values obtained using density functional theory (DFT) calculations at the B3LYP/6–311?+?+?G (d, p) method to support, validate, and provide more insights on the structural characterizations of the titled compound. The correlated experimental and theoretical structural vibrational assignments along with their potential energy distributions (PEDs) and all the spectroscopic spectral investigations of the titled structure were observed to be in good agreements with calculated results.
ESR dating of fluvial terraces is usually based on the assumption of sunlight resetting of the Al centres in quartz. Very long bleaching times (months of sunlight exposure) are required to reset this centre to a stable, non-zero ESR intensity. Considering that highly light sensitive optically stimulated luminescence (OSL) analyses of fluvial samples often indicate partial bleaching, ESR dating should be extremely difficult. Two samples were analysed, a fluvial sediment from a Chinese river terrace and an Australian granite. Using a Höhnle sunlight simulator, the Ti centres of both samples were completely bleached within 1 to 65 h, while the Al centre required extreme bleaching times to reach stable residual intensities (∼1000 h). As an alternative to light resetting, tumbler experiments were carried out to simulate fluvial action. The samples were treated under OSL sample preparation conditions. After relatively short tumbling times, corresponding to a few km of fluvial transport, both Al- and Ti-centres were partially reset. In a granite sample, the tumbling reduced the intensity of the Al centre more effectively than light exposure. 相似文献
Geometrical optimizations of two fullerenes, C60 and C70, have been performed by means of density-functional theory techniques. Based on the Gelius model, ultraviolet photoelectron spectra (UPS) of C60 and C70 have been simulated. We have shown how the different local arrangements of carbon atoms of C70 are responsible for the spectra. Our calculated spectra are in good agreement with the experimental counterparts. 相似文献
The formation mechanism of metallofullerene Y@C82 was investigated by ab initio calculations with two theoretical models. The first model is a traditional Y@C80 + C2 "fullerene-road" growing mechanism, in which the Y@C82 is assumed to form by combining Y@C80 and C2 fragments, and the second model involves formation by an unclosed C76 and a C6Y fragment. The calculated results showed that the second mechanism is much more energetically favorable. 相似文献
We report a combined experimental and theoretical investigation on the regiochemistry of a series of TNT endohedral fullerenes ScxGd3-xN@C80 (x = 0-3) in 1,3-dipolar cycloadditions, which demonstrates that the regioselectivity of the TNT-based endohedral fullerenes ScxGd3-xN@C80 (x = 0-3) in the exohedral cycloadditions depends remarkably on the size of the encaged cluster. 相似文献
Two new water-soluble Gd-containing endohedral metallofullerenes [ScxGd3-xN@C80OmOHn (x = 1, 2; m approximately 12; n approximately 26)] were synthesized in a simple one-step reaction and characterized by Fourier transform (FT)-IR as well as X-ray photoelectron spectroscopy (XPS). Their observed longitudinal relaxivities (R1) for water protons are 20.7 and 17.6 mM(-1) s(-1), respectively, which are significantly higher than that of the commercial magnetic resonance imaging (MRI) contrast agent (Gd-DTPA, 3.2 mM(-1) s(-1)). These results indicate these trimetallic nitride endohedral fullerenols are potential next-generation high-efficiency MRI contrast agents. 相似文献