Energy Dependence of Gold Nanoparticle Radiosensitization in Plasmid DNA

Gold nanoparticles (GNPs) are of considerable interest for use as a radiosensitizer, because of their biocompatibility and their ability to increase dose deposited because of their high mass energy absorption coefficient. Their sensitizing properties have been verified experimentally, but a discrepancy between the experimental results and theoretical predictions suggests that the sensitizing effect does not depend solely on gold's superior absorption of energetic photons. This work presents the results of three sets of experiments that independently mapped out the energy dependence of the radiosensitizing effects of GNPs on plasmid DNA suspended in water. Incident photon energy was varied from 11.8 to 80 keV through the use of monochromatic synchrotron and broadband X-rays. These results depart significantly from the theoretical predictions in two ways: First, the sensitization is significantly larger than would be predicted; second, it does not vary with energy as would be predicted from energy absorption coefficients. These results clearly demonstrate that the effects of GNP-enhanced therapies cannot be predicted by considering additional dose alone and that a greater understanding of the processes involved is necessary for the development of future therapeutics.

Nanodosimetric effects of gold nanoparticles in megavoltage radiation therapy

Background and purpose: The addition of gold nanoparticles (GNPs) to tumours leads to an increase in dose due to their high density and energy absorption coefficient, making it a potential radiosensitiser. However, experiments have observed radiosensitisations significantly larger than the increase in dose alone, including at megavoltage energies where gold's relative energy absorption is lowest. This work investigates whether GNPs create dose inhomogeneities on a sub-cellular scale which combine with non-linear dose dependence of cell survival to be the source of radiosensitisation at megavoltage energies.

Physical basis and biological mechanisms of gold nanoparticle radiosensitization

The unique properties of nanomaterials, in particular gold nanoparticles (GNPs) have applications for a wide range of biomedical applications. GNPs have been proposed as novel radiosensitizing agents due to their strong photoelectric absorption coefficient. Experimental evidence supporting the application of GNPs as radiosensitizing agents has been provided from extensive in vitro investigation and a relatively limited number of in vivo studies. Whilst these studies provide experimental evidence for the use of GNPs in combination with ionising radiation, there is an apparent disparity between the observed experimental findings and the level of radiosensitization predicted by mass energy absorption and GNP concentration. This review summarises experimental findings and attempts to highlight potential underlying biological mechanisms of response in GNP radiosensitization.

Catalysis of CO electrooxidation at Pt, Ru, and PtRu alloy. An in situ FTIR study

A comparative study of CO electrooxidation on different catalysts using in situ FTIR spectroscopy is presented. As electrode materials, polycrystalline Pt and Ru and a PtRu (50:50) alloy are used. The latter is one of the well-known active alloys for CO oxidation. The potential dependence of the band frequencies for the CO stretch indicates the formation of relatively compact islands at pure Pt and Ru, and a loose adlayer structure at the alloy. This loose structure has a positive effect on the rate of oxidative desorption. CO submonolayer coverages are obtained by integrating the absorption bands for CO produced upon oxidation of adsorbed CO. The band intensities measured at Pt, Ru, and PtRu indicate an influence of the substrate on the absorption coefficient of the CO stretch. It is shown that for a correct description of the catalyst properties toward CO electrooxidation, it must be distinguished between bulk and adsorbed CO. In contrast to the statement of most of the recent papers that a PtRu alloy (50:50) is the material with the highest activity for CO oxidation, it is demonstrated and rationalized in the present paper that for bulk CO oxidation pure Ru is the best catalyst. © 1999 American Chemical Society.

INTERPLAY OF CAF2 SUBSTRATE ROUGHENING AND FILM DEPOSITION RATE ON RADIATIVE SCATTERING OF SURFACE-PLASMON POLARITONS FROM AG FILMS

The radiative decay of surface plasmon polaritons has been investigated in an attempt to characterize the surface roughness of Ag films prepared under different conditions. The polaritons were excited by the method of attenuated total reflection of light. The films were deposited on the face of a 60-degrees BK-7 glass prism at a rate that was deliberately fixed in two different ranges (centred on 0.1 and 10 nm s-1) and in some cases a CaF2 underlayer was used to roughen the film surfaces. The intensity of the scattered light emitted from the opposite face of the films was measured as a function of direction for each using the same sensitivity scale and was correlated with the preparation of the film. It was found that on nominally smooth substrates fast-deposited thinner films give out more light and are deduced to have greater short wavelength (300-600 nm) roughness amplitude. There is also evidence for long wavelenth (7 mum) periodic roughness due to the prism substrate itself. On CaF2 roughened surfaces the light output from the films is further increased and the peak intensity is backward directed with respect to the exciting laser beam direction. Here roughness on a lateral scale of 350 nm is responsible. Also, elastic scattering of surface plasmon polaritons at grain boundaries reduces the light output from fast deposited, small grain, films on CaF2 roughened surfaces. Overall, a consistent picture of roughness induced radiative polariton decay emerges for all cases studied.

Optimisation of singlet oxygen production from photosensitiser-incorporated, medically-relevant hydrogels

Photodynamic therapy and photodynamic antimicrobial chemotherapy are widely used, but despite this, the relationships between fluence, wavelength of irradiation and singlet oxygen (1O2) production are poorly understood. To establish the relationships between these factors in medically-relevant materials, the effect of fluence on 1O2 production from a tetrakis(4-N-methylpyridyl)porphyrin (TMPyP)-incorporated 2-hydroxyethyl methacrylate: methyl methacrylate: methacrylic acid (HEMA:MMA:MAA) copolymer, a total energy of 50.48 J/cm², was applied at varying illumination power, and times. 1O2 production was characterised using anthracene-9,10-dipropionic acid, disodium salt (ADPA) using a recently described method. Using two light sources, a white LED array and a white halogen source, the LED array was found to produce less 1O2 than the halogen source when the same power (over 500-600 nm) and time conditions were applied. Importantly, it showed that the longest wavelength Q band (590 nm) is primarily responsible for 1O2 generation, and that a linear relationship exists between increasing power and time and the production of singlet oxygen.

Optimization of singlet oxygen production from photosensitizer-incorporated, medically relevant hydrogels

Photodynamic therapy and photodynamic antimicrobial chemotherapy are widely used, but despite this, the relationships between fluence, wavelength of irradiation and singlet oxygen ((1) O2 ) production are poorly understood. To establish the relationships between these factors in medically relevant materials, the effect of fluence on (1) O2 production from a tetrakis(4-N-methylpyridyl)porphyrin (TMPyP)-incorporated 2-hydroxyethyl methacrylate: methyl methacrylate: methacrylic acid (HEMA: MMA:MAA) copolymer, a total energy of 50.48 J/cm(2) , was applied at varying illumination power, and times. (1) O2 production was characterized using anthracene-9,10-dipropionic acid, disodium salt (ADPA) using a recently described method. Using two light sources, a white LED array and a white halogen source, the LED array was found to produce less (1) O2 than the halogen source when the same power (over 500 - 600 nm) and time conditions were applied. Importantly, it showed that the longest wavelength Q band (590 nm) is primarily responsible for (1) O2 generation, and that a linear relationship exists between increasing power and time and the production of singlet oxygen. 

Structure and dynamics of aqueous 2-propanol: A THz-TDS, NMR and neutron diffraction study

Aqueous liquid mixtures, in particular, those involving amphiphilic species, play an important role in many physical, chemical and biological processes. Of particular interest are alcohol/water mixtures; however, the structural dynamics of such systems are still not fully understood. Herein, a combination of terahertz time-domain spectroscopy (THz-TDS) and NMR relaxation time analysis has been applied to investigate 2-propanol/water mixtures across the entire composition range; while neutron diffraction studies have been carried out at two specific concentrations. Excellent agreement is seen between the techniques with a maximum in both the relative absorption coefficient and the activation energy to molecular motion occurring at ∼90 mol% H₂O. Furthermore, this is the same value at which well-established excess thermodynamic functions exhibit a maximum/minimum. Additionally, both neutron diffraction and THz-TDS have been used to provide estimates of the size of the hydration shell around 2-propanol in solution. Both methods determine that between 4 and 5 H₂O molecules per 2-propanol are found in the 2-propanol/water clusters at 90 mol% H₂O. Based on the acquired data, a description of the structure of 2-propanol/water across the composition range is presented.