Nanodiamonds exhibit exceptional colloidal properties in aqueous media that lead to a wide range of applications in nanomedicine and other fields. Nevertheless, the role of surface chemistry on the hydration of nanodiamonds remains poorly understood. Here, we probed the water hydrogen bond network in aqueous dispersions of nanodiamonds by infrared, Raman, and X-ray absorption spectroscopies applied in situ in aqueous environment. Aqueous dispersions of nanodiamonds with hydrogenated, carboxylated, hydroxylated, and polyfunctional surface terminations were compared. A different hydrogen bond network was found in hydrogenated nanodiamonds dispersions compared to dispersions of nanodiamonds with other surface terminations. Although no hydrogen bonds are formed between water and hydrogenated surface groups, a long-range disruption of the water hydrogen bond network is evidenced in hydrogenated nanodiamonds dispersion. We propose that this unusual hydration structure results from electron accumulation at the diamond–water interface.
1 June 2012 in Earth and Planetary Science Letters
Methods to probe the molecular structure of living cells are of paramount importance in understanding drug interactions and environmental influences in these complex dynamical systems. The coupling of an acoustic levitation device with a micro-Raman spectrometer provides a direct molecular probe of cellular chemistry in a containerless environment minimizing signal attenuation and eliminating the affects of adhesion to walls and interfaces. We show that the Raman acoustic levitation spectroscopic (RALS) approach can be used to monitor the heme dynamics of a levitated 5 µL suspension of red blood cells and to detect hemozoin in malaria infected cells. The spectra obtained have an excellent signal-to-noise ratio and demonstrate for the first time the utility of the technique as a diagnostic and monitoring tool for minute sample volumes of living animal cells.
Zinc oxide is a prevalent industrial-age pigment that readily reacts with fatty acids in oil-based paints to form zinc carboxylates. Zinc stearate aggregates are associated with deterioration in late nineteenth and twentieth century paintings. The current study uses both conventional and synchrotron Fourier transform infrared spectroscopy (FT-IR) to investigate metal carboxylate composition in a range of naturally aged artists' oil paints and reference paint film draw-downs. The paints contain zinc oxide alone or in combination with lead white, titanium white, and aluminum stearate and are prepared with linseed and safflower oils. Attenuated total reflectance (ATR)-FT-IR using the conventional source identifies marked differences in carboxylate profiles between exposed and protected surfaces in a large number of samples. Synchrotron FT-IR microspectroscopy of thin paint cross-sections maps metal carboxylate distributions at high spatial resolution and resolves broad concentration gradients and micrometer-scale phase separation of carboxylate species. Aluminum stearate, a common paint additive, is found to influence the distribution of zinc carboxylates more strongly than pigment composition or oil type. The presence of aluminum stearate results in higher concentrations and more pronounced separation of saturated C16 and C18 chain zinc carboxylates in the margin of paint nearest the polyester substrate. The presence of aluminum stearate in association with zinc oxide has a clear influence on zinc carboxylate formation and distribution, with potential implications for long term stability of vulnerable paintings.