Manipulating interfacial thermal transport is important for many technologies including nanoelectronics, solid-state lighting, energy generation and nanocomposites. Here, we demonstrate the use of a strongly bonding organic nanomolecular monolayer (NML) at model metal/dielectric interfaces to obtain up to a fourfold increase in the interfacial thermal conductance, to values as high as 430 MW m(-2) K(-1) in the copper-silica system. We also show that the approach of using an NML can be implemented to tune the interfacial thermal conductance in other materials systems. Molecular dynamics simulations indicate that the remarkable enhancement we observe is due to strong NML-dielectric and NML-metal bonds that facilitate efficient heat transfer through the NML. Our results underscore the importance of interfacial bond strength as a means to describe and control interfacial thermal transport in a variety of materials systems.
Phosphonic acids are increasingly being used for controlling surface and interface properties in hybrid or composite materials, (opto)electronic devices and in the synthesis of nanomaterials. In this perspective article, a concise survey of phosphonate coupling molecules is first presented, including details on their coordination chemistry, their use in the surface modification of inorganic substrates with self-assembled monolayers, and the analytical techniques available to characterize their environment in nanomaterials. Then, some of their recent applications in the development of organic electronic devices, photovoltaic cells, biomaterials, biosensors, supported catalysts and sorbents, corrosion inhibitors, and nanostructured composite materials, are presented. In the last part of the article, a brief overview of recent progress in the use of phosphonate ligands for the preparation of molecular nanomaterials like metal organic frameworks and functionalized polyoxometalates is given.
The incorporation of Mg in hydroxyapatite (HA) was investigated using multinuclear solid state NMR, X-ray absorption spectroscopy (XAS) and computational modeling. High magnetic field 43 Ca solid state NMR and Ca K-edge XAS of a ~10% Mg-substituted HA were performed, bringing direct evidence of the preferential substitution of Mg in the Ca(II) position. 1 H and 31 P solid state NMR show that the environment of the anions is disordered in this substituted apatite phase. Both Density Functional Theory (DFT) and interatomic potential computations of Mg-substituted HA structures are in agreement with these observations. Indeed, the incorporation of low levels of Mg in the Ca(II) site is found to be more favourable energetically, and the NMR parameters calculated from these optimized structures are consistent with the experimental data. Calculations provide direct insight in the structural modifications of the HA lattice, due to the strong contraction of the M•••O distances around Mg. Finally, extensive interatomic potential calculations also suggest that a local clustering of Mg within the HA lattice is likely to occur.
Natural abundance (43)Ca solid-state NMR of hydroxyapatite (Ca(10)(PO(4))(6)(OH)(2)) was performed at three different fields (8.45, 14.1 and 18.8 T). The two crystallographically distinct calcium sites of the apatite structure were spectroscopically resolved at 18.8 T. The (43)Ca NMR interaction parameters (delta(iso), C(Q) and eta(Q)) of each site were determined by multiple magnetic-field simulations. The peaks with delta(iso) = 11.2 +/- 0.8 and - 1.8 +/- 0.8 ppm, both with C(Q) = 2.6 +/- 0.4 MHz, were assigned to the Ca(II) and Ca(I) sites, respectively, on the basis of their relative intensities.
International audienceDespite the numerous studies of bone mineral, there are still many questions regarding the exact structure and composition of the mineral phase, and how the mineral crystals become organised with respect to each other and the collagen matrix. Bone mineral is commonly formulated as hydroxyapatite, albeit with numerous substitutions, and has previously been studied by 31P and 1H NMR, which has given considerable insight into the complexity of the mineral structure. However, to date, there has been no report of an NMR investigation of the other major component of bone mineral, calcium, nor of common minority cations like sodium. Here, direct analysis of the local environment of calcium in two biological apatites, equine bone (HB) and bovine tooth (CT), was carried out using both 43Ca solid state NMR and Ca K-edge X-ray absorption spectroscopy, revealing important structural information about the calcium coordination shell. The 43Ca diso in HB and CT is found to correlate with the average Ca–O bond distance measured by Ca K-edge EXAFS, and the 43Ca NMR linewidths show that there is a greater distribution in chemical bonding around calcium in HB and CT, compared to synthetic apatites. In the case of sodium, 23Na MAS NMR, high resolution 3Q-MAS NMR, as well as 23Na{31P} REDOR and 1H{23Na} R3-HMQC correlation experiments give the first direct evidence that some sodium is located inside the apatite phase in HB and CT, but with a greater distribution of environments compared to a synthetic sodium substituted apatite (Na-HA)
The interfaces within bones, teeth and other hybrid biomaterials are of paramount importance but remain particularly difficult to characterize at the molecular level because both sensitive and selective techniques are mandatory. Here, it is demonstrated that unprecedented insights into calcium environments, for example the differentiation of surface and core species of hydroxyapatite nanoparticles, can be obtained using solid-state NMR, when combined with dynamic nuclear polarization. Although calcium represents an ideal NMR target here (and de facto for a large variety of calcium-derived materials), its stable NMR-active isotope, calcium-43, is a highly unreceptive probe. Using the sensitivity gains from dynamic nuclear polarization, not only could calcium-43 NMR spectra be obtained easily, but natural isotopic abundance 2D correlation experiments could be recorded for calcium-43 in short experimental time. This opens perspectives for the detailed study of interfaces in nanostructured materials of the highest biological interest as well as calcium-based nanosystems in general.
The reaction of gold nanoparticles with benzimididazol-2-ylidene ligands leads to the formation of well-defined bis-carbene gold(i) complexes, as shown by characterization techniques such as powder XRD and solid state NMR.
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