Here we wish to demonstrate a unique property of nanomaterials: energy deposition with nanometer precision from low-energy electrons released from these nanostructures interacting with hard X-ray radiation in aqueous solution. Three effects combine to cause this phenomenon: (1) localized absorption of X-rays by nanostructures, (2) effective release of low-energy electrons from small nanostructures, and (3) efficient deposition of energy in water in the form of radicals and electrons. This combination creates localized X-ray absorption and localized energy deposition of nanometer precision. We confirmed the theoretically predicted nanoscale energy deposition distribution by measuring hydroxyl radical-induced DNA strand breaks, and observed enhanced damage to a 5600-bp DNA molecule from approximately 10 chemically conjugated small gold nanoparticles under X-ray radiation. These results provide a general guidance to applications of this new concept in many fields including radiation chemistry, radiology, radiation oncology, biochemistry, biology, and nanotechnology.

We report here a new phenomenon of dynamic enhancement of chemical reactions by nanomaterials under hard X-ray irradiation. The nanomaterials were gold and platinum nanoparticles, and the chemical reaction employed was the hydroxylation of coumarin carboxylic acid. The reaction yield was enhanced 2000 times over that predicted on the basis of the absorption of X-rays only by the nanoparticles, and the enhancement was found for the first time to depend on the X-ray dose rate. The maximum turnover frequency was measured at 1 × 10(-4) s(-1) Gy(-1). We call this process chemical enhancement, which is defined as the increased yield of a chemical reaction due to the chemical properties of the added materials. The chemical enhancement described here is believed to be ubiquitous and may significantly alter the outcome of chemical reactions under X-ray irradiation with the assistance of nanomaterials.

A theorem is established to show that nanoscale energy deposition in water by X-rays can be greatly enhanced via the geometry of nanostructures. The calculated results show that enhancement over background water can reach over 60 times for a single nanoshell made of gold. Other geometries and nanostructures are investigated, and it is found that a shell of gold nanoparticles can generate similar enhancement. The concepts of composition, matrix, and satellite effects are established and studied, all of which can further increase the enhancement of the effect of X-rays.

The structural characteristics of alpha-helices in poly-alanine-based peptides have been investigated via molecular dynamics simulation with the goal of understanding the basic features of peptide simulations within the context of a model system, classical molecular dynamics with generalized Born (GB) solvation, and to shed insight into the formation and stabilization of alpha-helices in short peptides. The effects of peptide length, terminal charges, proline substitution, and temperature on the alpha-helical secondary structure have been studied. The simulations have shown that distinct secondary structure begins to develop in peptides with lengths approaching 10 residues while ambiguous structures occur in shorter peptides. The helical content of peptides with lengths > or =10 amino acids is observed to be nearly constant up to (Ala)(40). Interestingly, terminal charges and proline in the second position from the N-terminus alter the secondary structure locally with little effect on the overall alpha-helical content of the peptide. The free energy profile of helix formation was also investigated. A large increase in free energy accompanying the formation of helices with more than two consecutive hydrogen bonds in the (i, i + 4) pattern was observed while the free energy increases linearly with additional hydrogen bonds. Values for the change in enthalpy and entropy of helix nucleation and propagation are reported. Additionally the results obtained from the GB model are compared to explicit solvent simulations of two synthetic alanine-based peptides.

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