We report a study of the effects of confinement in multi-walled carbon nanotubes and mesoporous silica glasses (SBA-15) on the solid structure and melting of both H(2)O and D(2)O ice, using differential scanning calorimetry, dielectric relaxation spectroscopy, and neutron diffraction. Multi-walled nanotubes of 2.4, 3.9 and 10 nm are studied, and the SBA-15 studied has pores of mean diameter 3.9 nm; temperatures ranging from approximately 110 to 290 K were studied. We find that the melting point is depressed relative to the bulk water for all systems studied, with the depression being greater in the case of the silica mesopores. These results are shown to be consistent with molecular simulation studies of freezing in silica and carbon materials. The neutron diffraction data show that the cubic phase of ice is stabilized by the confinement in carbon nanotubes, as well as in silica mesopores, and persists up to temperatures of about 240 K, above which there is a transition to the hexagonal ice structure.
This study provides deep insight into the adsorption process of doxorubicin onto different types of carbon nanotubes that have been proved to show attractive properties as a drug delivery system. The main aim of the work was to propose probable adsorption mechanisms and interactions between the anticancer drug and surface of modified and pristine carbon nanotubes at blood pH. The carbon nanotubes were oxidized to optimize the absorbance efficiency relative to that of pristine multiwalled carbon nanotubes. The adsorption isotherm of the modified system was well described by the Temkin equation. It confirms that the adsorption in the system studied involves also hydrogen and covalent bonding and is exothermic in nature. The experimental kinetic curves of adsorption were fitted to different mathematical models to check if the kinetics of doxorubicin adsorption onto the modified multiwalled carbon nanotubes follows a pseudo-second-order model and the chemical sorption is bound to be the rate-limiting. On the basis of the molecular dynamics simulation, it was shown that in vacuo the aggregation tendency of doxorubicin molecules is far more favorable than their adsorption on pristine carbon nanotubes (CNTs). It suggests that only functionalization of the nanotube surface can affect the interaction between doxorubicin and functional groups of the carriers and increases the efficiency of the drug loading process.
We report dielectric relaxation spectroscopy measurements of the melting point of carbon tetrachloride confined within open-tip multi-walled carbon nanotubes with two different pore diameters, 4.0 and 2.8 nm. In both cases, a single transition temperature well above the bulk melting point was obtained for confined CCl4. These results contrast with what was obtained in our previous measurements using carbon nanotubes with a pore diameter of 5.0 nm, where multiple transition temperatures both above and below the bulk melting point of CCl4 were observed. Our experimental measurements are consistent with our recent molecular simulation results (F. R. Hung, B. Coasne, E. E. Santiso, K. E. Gubbins, F. R. Siperstein and M. Sliwinska-Bartkowiak, J. Chem. Phys., 2005, 122, 144706). Although the simulations overestimate the temperatures in which melting upon confinement occurs, both simulations and experiments suggest that all regions of adsorbate freeze at the same temperature, and that freezing occurs at higher temperatures upon reduction of the pore diameter.
We report experimental results on the structure and melting behavior of ice confined in multi-walled carbon nanotubes and ordered mesoporous carbon CMK-3, which is the carbon replica of a SBA-15 silica template. The silica template has cylindrical mesopores with micropores connecting the walls of neighboring mesopores. The structure of the carbon replica material CMK-3 consists of carbon rods connected by smaller side-branches, with quasi-cylindrical mesopores of average pore size 4.9 nm and micropores of 0.6 nm. Neutron diffraction and differential scanning calorimetry have been used to determine the structure of the confined ice and the solid-liquid transition temperature. The results are compared with the behavior of water in multi-walled carbon nanotubes of inner diameters of 2.4 nm and 4 nm studied by the same methods. For D(2)O in CMK-3 we find evidence of the existence of nanocrystals of cubic ice and ice IX; the diffraction results also suggest the presence of ice VIII, although this is less conclusive. We find evidence of cubic ice in the case of the carbon nanotubes. For bulk water these crystal forms only occur at temperatures below 170 K in the case of cubic ice, and at pressures of hundreds or thousands of MPa in the case of ice VIII and IX. These phases appear to be stabilized by the confinement.
We report X-ray diffraction studies of water and carbon tetrachloride adsorbed in nanoporous activated carbon fibres. The fibres are built of turbostratic nanoparticles separated by quasi two-dimensional voids, forming narrow slit-shaped pores. In order to determine the structure of water within the pores and its influence on the fibres' structure, mean interatomic and intermolecular distances have been estimated from the positions of the maxima of the normalized angular distribution functions obtained by X-ray diffraction. We observe a cluster arrangement of the water molecules, as well as significant changes in the interlayer distance of the carbon nanoparticles upon adsorption of both water and carbon tetrachloride. The results suggest that very high pressures arise within the pores, as has been observed in molecular simulations, and this may give rise to the large change in electronic properties of the fibres after adsorption of guest molecules. The in-pore pressure normal to the pore walls is estimated from the experimental data, and is found to be positive and of the order 4000 bar. Molecular simulation results for the normal pressure component are presented for both water and carbon tetrachloride in carbon slit pores, and are in general agreement with the experiments. For both fluids the normal pressure is an oscillating function of pore width.
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