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At least 505 records · Page 28

MO-FG-BRA-05: Next Generation Radiotherapy Biomaterials Loaded With Gold Nanoparticles

Purpose: It has been proposed that routinely used inert radiotherapy (RT) biomaterials (e.g. fiducials, spacers) can be upgraded to smarter ones by coating/loading them with radiosensitizing gold nanoparticles (GNPs), for sustained in-situ release after implantation to enhance RT. In this work, we developed prototypes of such RT biomaterials and investigated the sustained release of GNPs from the biomaterials as a function of design parameters. Methods: Prototype smart biomaterials were produced by incorporating the GNPs in poly(D,L-lactide-co-glycolide) (PLGA) polymer millirods during the gel phase of production. For comparison, commercially available spacers were also coated with a polymer film loaded with fluorescent GNP. Optical/spectroscopy methods were used to monitor in vitro release of GNPs over time as a function of different design parameters: polymer weighting, type, and initial (loading) GNP concentrations. Inductively coupled plasma mass spectrometry was employed to verify GNP release. Results: Results showed that gold nanoparticles could be successfully loaded in the new RT biomaterial prototypes. Burst release of GNPs could be achieved within 1 to 25 days depending on the preparation approach. Burst release was followed by sustained release profile over time. The amount of released GNP increased with increasing loading concentration as expected. The release profiles could also be customized as a function of polymer weighting, or preparation approaches. Conclusion: Considered together, our results highlight potential for the development of next generation RT biomaterials loaded with GNPs customizable to different RT schedules. Such biomaterials could be employed as needed instead of currently used inert spacers/fiducials at no additional inconvenience to patients, to enhance RT.

60 APPLIED LIFE SCIENCES↗

MO-FG-BRA-08: A Preliminary Study of Gold Nanoparticles Enhanced Diffuse Optical Tomography

Purpose: To develop an imaging method by using gold nanoparticles (GNP) to enhance diffuse optical tomography (DOT) for better tumor detection. Methods: Experiments were performed on a tissue-simulating cylindrical optical phantom (30mm diameter, 60mm length). The GNP used are gold nanorods (10nm diameter, 44nm length) with peak light absorption at 840nm. 0.085ml GNP colloid of 96nM concentration was loaded into a 6mm diameter cylindrical hole in the phantom. An 856nm laser beam (14mW) was used as light source to irradiate the phantom at multiple locations through rotating and elevating the phantom. A CCD camera captured the light transmission through the phantom for each irradiation with total 40 projections (8 rotation angles in 45degree steps and 5 elevations with 3mm apart). Cone beam CT of the phantom was used to generate the three-dimensional mesh for DOT reconstruction and to identify the true location of the GNP volume. A forward simulation was performed with known phantom optical properties to establish a relationship between the absorption coefficient and concentration of the GNP by matching the simulated and measured transmission. DOT image reconstruction was performed to restore the GNP within the phantom. In addition, a region-constrained reconstruction was performed by confining the solutions within the GNP volume detected from CT. Results: The position of the GNP volume was reconstructed with <2mm error. The reconstructed average GNP concentration within an identical volume was 104nM, 8% difference from the truth. When the CT was used as “a priori”, the reconstructed average GNP concentration was 239nM, about 2.5 times of the true concentration. Conclusion: This study is the first to demonstrate GNP enhanced DOT with phantom imaging. The GNP can be differentiated from their surrounding background. However, the reconstruction methods needs to be improved for better spatial and quantification accuracy.

60 APPLIED LIFE SCIENCES↗

TU-F-CAMPUS-T-05: Dose Escalation to Biological Tumor Volumes of Prostate Cancer Patients Using Gold Nanoparticles

Purpose: Studies have shown that radiation boosting could help reduce prostate cancer (PCa) recurrence. Biological tumor volumes (BTV) are a high priority for such radiation boosting. The purpose of this study is to investigate the potential of radiation boosting of real patient BTVs using gold nanoparticles (GNP) released from gold-loaded brachytherapy spacers (GBS) during brachytherapy. Methods: The BTVs of 12 patients having prostate adenocarcinoma identified with positron emission tomography (PET) and CT scanner using C-11 labeled tracer [11C]acetate were investigated. The initial GNP concentration and time to achieve a dose enhancement effect (DEF) of 2 was simulated using the freely downloadable software RAID APP. The investigations were carried out for low dose rate (LDR) brachytherapy sources (BTS) described in AAPM Task Group report 43: Cs-131, I-125, and Pd-103. In first case, we used 7 mg/g and 18 mg/g of GNP initial concentrations to estimate the time needed for released GNP to achieve a DEF of 2 for the different BTS, and compare with clinically relevant treatment times. In second case, we calculated the initial concentration of GNPs needed to achieve a DEF of 2 during the time the BTS would typically deliver 50%, 70% and 90% of the total dose. Results: For an initial concentration of 18 mg/g, when using Cs-131, and Pd-103, a DEF of 2 could only be achieved for BTV of 3.3 cm3 and 1 cm3 respectively. Meanwhile a DEF of 2 could be achieved for all 12 BTVs when using I-125. To achieve a DEF of 2 for all patients using Cs-131 and Pd-103, much higher initial concentrations would have to be used than have been typically employed in pre-clinical studies. Conclusion: The I-125 is the most viable BTS that can be employed with GBS to guide dose painting treatment planning for localized PCa.

60 APPLIED LIFE SCIENCES↗

Measurement of gold nanofilm dose enhancement using unlaminated radiochromic film

Purpose: Bombarding high-Z material with x-ray radiation releases Auger electrons and Coster–Kronig electrons, along with deeper penetrating fluorescent x-rays and photoelectrons. The Auger and Coster–Kronig electron penetration distance is on the order of nanometers to micrometers in water or tissue, creating a large dose enhancement accompanied by a RBE greater than 1 at the cellular level. The authors’ aim is to measure the gold nanofilm dose enhancement factor (DEF) at the cellular level with unlaminated radiochromic film via primary 50 kVp tungsten x-ray spectrum interaction, similar to an electronic brachytherapy spectrum. Methods: Unlaminated Gafchromic{sup ®} EBT2 film and Monte Carlo modeling were combined to derive DEF models. Gold film of thickness 23.1 ± 4.3 nm and surface roughness of 1.2 ± 0.2 nm was placed in contact with unlaminated radiochromic film in a downstream orientation and exposed to a 50 kVp tungsten bremsstrahlung, mean energy 19.2 keV. Film response correction factors were derived by Monte Carlo modeling of electron energy deposition in the film’s active layer, and by measuring film energy dependence from 4.5 keV to 50 kVp. Results: The measured DEF within a 13.6 μm thick water layer was 0.29 with a mean dose of 94 ± 9.4 cGy from Au emissions and 324 ± 32.4 cGy from the 50 kVp primary beam. Monte Carlo derived correction factors allowed determination of Au contributed dose in shallower depths at 0.25 μm intervals. Maximum DEF of 18.31 was found in the first 0.25 μm water depth. Conclusions: Dose enhancement from Au nanofilm can be measured at the cellular level using unlaminated radiochromic film. Complementing the measured dose value with Monte Carlo calculations allows estimation of dose enhancement at depth increments within the cellular range.

60 APPLIED LIFE SCIENCES↗

SU-G-TeP3-03: Dose Enhancement of Gold Nanoparticle in Proton Therapy: A Monte Carlo Study Based On the Transmission Electron Microscopy Imaging

Purpose: Gold nanoparticle (GNP) is a promising radiosensitizer that selectively boosts tumor dose in radiotherapy. Transmission electron microscopy (TEM) imaging observations recently revealed for the first time that GNP exists in vivo in the form of highly localized vesicles, instead of hypothetical uniform distribution. This work investigates the corresponding difference of energy deposition in proton therapy. Methods: First, single vesicles of various radii were constructed by packing GNPs (as Φ50 nm gold spheres) in spheres and were simulated, as well as a single GNP. The radial energy depositions (REDs) were scored using 100 concentric spherical shells from 0.1µm to 10µm, 0.1µm thickness each, for both vesicles and GNP, and compared. TEM images, 8 days after injection in a PC3 prostate cancer murine model, were used to extract position/dimension of vesicles, as well as contours of cytoplasmic and nucleus membranes. Vesicles were then constructed based on the TEM images. A 100 MeV proton beam was studied by using the Geant4-DNA code, which simulates all energy deposition events. Results: The vesicle REDs, normalized to the same proton energy loss as in a single GNP, are larger (smaller) than that of a single GNP when radius >2µm (<2µm). The peak increase (at about 3µm radius) is about 10% and 18% for Φ1µm and Φ1.6µm vesicles respectively, relative to a single GNP. The TEM-based simulation resulted in a larger energy deposition (by about one order of magnitude) that follows completely different pattern from that of hypothetical GNP distributions (regular dotted pattern in extracellular and/or extranucleus regions). Conclusion: The in vivo energy deposition, both in pattern and magnitude, of proton therapy is greatly affected by the true distribution of the GNP, as illustrated by the presence of GNP vesicles compared to hypothetical scenarios. Work supported by NSERC Discovery Grant #435510, Canada.

60 APPLIED LIFE SCIENCES↗

SU-G-TeP3-13: The Role of Nanoscale Energy Deposition in the Development of Gold Nanoparticle-Enhanced Radiotherapy

Purpose: Gold nanoparticles (GNPs) can enhance radiotherapy effects. The high photoelectric cross section of gold relative to tissue, particularly at lower energies, leads to localized dose enhancement. However in a clinical context, photon energies must also be sufficient to reach a target volume at a given depth. These properties must be balanced to optimize such a therapy. Given that nanoscale energy deposition patterns around GNPs play a role in determining biological outcomes, in this work we seek to establish their role in this optimization process. Methods: The PENELOPE Monte Carlo code was used to generate spherical dose deposition kernels in 1000 nm diameter spheres around 50 nm diameter GNPs in response to monoenergetic photons incident on the GNP. Induced “lesions” were estimated by either a local effect model (LEM) or a mean dose model (MDM). The ratio of these estimates was examined for a range of photon energies (10 keV to 2 MeV), for three sets of linear-quadratic parameters. Results: The models produce distinct differences in expected lesion values, the lower the alpha-beta ratio, the greater the difference. The ratio of expected lesion values remained constant within 5% for energies of 40 keV and above across all parameter sets and rose to a difference of 35% for lower energies only for the lowest alpha-beta ratio. Conclusion: Consistent with other work, these calculations suggest nanoscale energy deposition patterns matter in predicting biological response to GNP-enhanced radiotherapy. However the ratio of expected lesions between the different models is largely independent of energy, indicating that GNP-enhanced radiotherapy scenarios can be optimized in photon energy without consideration of the nanoscale patterns. Special attention may be warranted for energies of 20 keV or below and low alpha-beta ratios.

60 APPLIED LIFE SCIENCES↗

Sci-Sat AM: Radiation Dosimetry and Practical Therapy Solutions - 02: Dosimetric effects of gold nanoparticle surface coatings

Introduction: Gold nanoparticles (GNPs) can enhance radiation therapy within a tumour, increasing local energy deposition under irradiation, but experimental evidence suggests the enhancement is not as large as predicted by dose enhancement alone. Many studies neglect to account for surface coatings that are frequently used to optimize GNP uptake and biological distribution. This study uses Monte Carlo methods to investigate the consequences on local dose enhancement due to including these surface coatings. Methods: Using the PENELOPE Monte Carlo code system, GNP irradiation was simulated both with and without surface coatings of polyethylene glycol (PEG) of various molecular weights. Dose was scored to the gold, coating, and surrounding water, and the dosimetric differences between these scenarios were examined. Results: The simulated PEG coating absorbs a large portion of the energy that would otherwise be deposited in the medium. The mean dose to water was reduced by up to 2.5, 3.5, and 4.5% for GNPs of diameters 50, 20, and 10 nm, respectively. This effect was more pronounced for smaller GNPs, thicker coatings, and low photon source energies where the enhancement due to GNPs is the greatest. The molecular weight of the coating material did not have a significant impact on the dose. Conclusions: The inclusion of a coating material in GNP enhanced radiation may reduce the dose enhancement due to the nanoparticles. Both the composition and size of the coating play a role in the level of this reduction and should be considered carefully.

60 APPLIED LIFE SCIENCES↗

Concentration of energy inside laser-irradiated gold and silver plasmon nanoparticles in air

We simulated laser-intensity distribution inside spherical gold and silver nanoparticles with radii between 10 and 100 nm, which are exposed to laser radiation at 400, 532, and 800 nm in air, and analyzed the results. The effect of high energy concentration inside illuminated (front) and shadowed (back) hemispheres of gold and silver nanoparticles is established for several nanoparticle sizes and laser wavelengths. The results can be used in nanophotonics of new plasmon devices (concentrators, antennas, etc.) and photon components.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Surface plasmon polaritons in a composite system of porous silicon and gold

A composite system of silicon quantum dots and gold particles with properties periodically changing along the surface (i.e., a system exhibiting the properties of a diffraction grating) is obtained by a one-step metal-assisted chemical etching. The spectral and angular dependences of the photoresponse for the composite system on single-crystal silicon are studied. The photoresponse peaks were observed, which behavior (the dependence on the parameters of the diffraction grating, wavelength and incidence angles of light) is attributed to the excitation of plasmon-polariton modes at the surface of the composite system with the diffraction grating. At the same time, the obtained values of the wave vectors for these modes are smaller than those calculated for plasmon polaritons excited at the interface between air and metal (gold) diffraction grating.

36 MATERIALS SCIENCE↗

Double-Lattice Magnetoplasmonic Structures Based on BIG and Perforated Gold Films

A method of manufacturing double-lattice magnetoplasmonic crystals with the structure (Au/BIG){sup 2}, in which the plasmon gold lattices are displaced relative to each other by half a period, has been presented. Gold films with thicknesses of about 40 nm have been formed by the ion-beam sputtering–deposition method, while the adhesive properties of the films allow the dimensional etching by a sharp-focused ion beam. It has been shown that the formation of the second plasmon lattice located on top of the 100 nm thick garnet layer allows the preserving of the periodicity of the first Au lattice. However, there is a significant influence of diffusion spreading on the lower lattice material, which leads to a decrease in its density. The dependence of the intensity magnetooptical effect in the geometry on the transmission as a function of the thickness of the upper lattice and presence of an additional layer of Ta{sub 2}O{sub 5} has been studied.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Plasmonic gold-cellulose nanofiber aerogels

Assembly of plasmonic nanomaterials into a low refractive index medium, such as an aerogel, holds a great promise for optical metamaterials, optical sensors, and photothermal energy converters. However, conventional plasmonic aerogels are opaque and optically isotropic composites, impeding them from being used as low-loss or polarization-dependent optical materials. Here we demonstrate a plasmonic-cellulose nanofiber composite aerogel that comprises of well-dispersed gold nanorods within a cellulose nanofiber network. The cellulose aerogel host is highly transparent owing to the small scattering cross-section of the nanofibers and forms a nematic liquid crystalline medium with strong optical birefringence. We find that the longitudinal surface plasmon resonance peak of gold nanorods shows a dramatic shift when probed for the cellulose aerogel compared with the wet gels. Simulations reveal the shift of surface plasmon resonance peak with gel drying can be attributed to the change of the effective refractive index of the gels. This composite material may provide a platform for three- dimensional plasmonic devices ranging from optical sensors to metamaterials.

36 MATERIALS SCIENCE↗

Evaluation of Pad 18 Spent Mercury Gold Trap Stainless Steel Container Failure

Failure of the Pad 18 spent mercury gold trap stainless steel waste container is principally attributed to corrosion induced by degradation of plasticized polyvinyl chloride (pPVC) waste packaging material. Dehydrochlorination of pPVC polymer by thermal and/or radiolytic degradation is well-known to evolve HCl gas, which is highly corrosive to stainless steel and other metals in the presence of moisture. Degradation of the pPVC packaging material was likely caused by radiolysis in the presence of tritium gas within the waste container, though other degradation mechanisms (aging, thermo-oxidation, plasticizer migration) over 30 years storage may have contributed. Corrosion was also likely enhanced by the crevice in the container weld design, and may have been enhanced by the presence of tritiated water. Similar non-failed spent mercury gold trap waste containers did not show radiographic evidence of plastic packaging or trapped free liquid within the container. Therefore, those containers are not expected to exhibit similar failures. Halogenated polymers such as pPVC subject to degradation can evolve halide gases such as HCl, which is corrosive in the presence of moisture and can generate pressure in sealed systems.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Preparation of Nanocomposite Plasmonic Films Made from Cellulose Nanocrystals or Mesoporous Silica Decorated with Unidirectionally Aligned Gold Nanorods

Using liquid crystalline self-assembly of cellulose nanocrystals, we achieve long-range alignment of anisotropic metal nanoparticles in colloidal nanocrystal dispersions that are then used to deposit thin structured films with ordering features highly dependent on the deposition method. These hybrid films are comprised of gold nanorods unidirectionally aligned in a matrix that can be made of ordered cellulose nanocrystals or silica nanostructures obtained by using cellulose-based nanostructures as a replica. The ensuing long-range alignment of gold nanorods in both cellulose-based and nanoporous silica films results in a polarization-sensitive surface plasmon resonance. The demonstrated device-scale bulk nanoparticle alignment may enable engineering of new material properties arising from combining the orientational ordering of host nanostructures and properties of the anisotropic plasmonic metal nanoparticles. Our approach may also allow for scalable fabrication of plasmonic polarizers and nanoporous silica structures with orientationally ordered anisotropic plasmonic nanoinclusions.

mesoporous silica↗

Preliminary Results, Analysis, and Overview of Part-1 of the GOLD Experiment

The Ground/Orbiter Lasercomm Demonstration (GOLD) is an optical communications demonstraton between the Japanese Engineering Test Satellite (ETS-VI) and an optical ground transmitting and receiving station at the Table Mountain Facility. GOLD was an experiment that demonstrated real-time international collaboration.

optical communications ETS-VI GOLD Table Mountain ↗

Gold and palladium adsorption from leached electronic scrap using ordered mesoporous carbon nanoscaffolds

Ordered mesoporous carbon (OMC) nanoscaffolds are engineered agglomerates of carbon nanotubes held together by small carbon nanofibers with uniform pore sizes, high pore volume, and high channel permeability. These materials exhibit very high affinity for the adsorption of gold from aqueous acidic mixtures. The efficiency of gold recovery is comparable to those typically accomplished using biopolymer-based adsorbents. The adsorption efficiency for other precious metals such as palladium and platinum is lower. Studies on the precious metal (Au, Pd) adsorption on OMC materials from actual liquors of leached electronics will be presented. Adsorption properties will be compared for several different sorbents used for the recovery of precious metals. The leach liquor compositions for three different types of electronic scrap materials (personal computer board, cell phone and tv input/output board) will be presented. The sorption efficiencies for Au, Pd, together with a spectrum of competing and non-competing metals, from such leach mixtures will be compared.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Oscillatory and Collective Dynamics of Gold‐Nanoparticle‐Laden Droplets Driven by Photothermal‐Induced Thermocapillarity

Droplets have long intrigued researchers due to their ability to exhibit complex and fascinating behavior when subjected to external stimuli. Here, a coupled oscillatory behavior of gold-nanoparticle-surfactant-laden aqueous droplets is investigated at an oil-oil interface stimulated by light. This study shows that the interaction between light and the droplets gives rise to a range of oscillatory modes, including bouncing and clustering, where droplets exhibit collective movement. From experiment and numerical simulations, this study elucidates the underlying mechanism: upon laser irradiation, gold nanoparticles convert light into heat, generating asymmetric thermal gradients that drive upward thermocapillary flows and a hydrodynamic force from photothermal convection. These forces compete with gravity and buoyancy to induce droplet bouncing, while the resulting asymmetric flow fields bias neighboring droplets toward the illuminated droplet, leading to clustering. These findings not only expand the library of dynamic droplet behavior but also offer insights into the potential applications of light-driven systems in materials science, soft robotics, and microfluidics.

Marangoni effect↗

Self-assembly of DNA functionalized gold nanoparticles at the liquid-vapor interface

Here, surface sensitive synchrotron X-ray scattering and spectroscopy are used to monitor and characterize the spontaneous formation of 2D Gibbs monolayers of thiolated single-stranded DNA-functionalized gold nanoparticles (ssDNAAuNPs) at the vapor–solution interface by manipulating salt concentrations. Grazing incidence small-angle X-ray scattering and X-ray refl ectivity show that the noncomplementary ssDNA-AuNPs dispersed in aqueous solution spontaneously accumulate at the vapor–liquid interface in the form of a single layer by increasing MgCl 2 or CaCl 2 concentrations. Furthermore, the monoparticle layer undergoes a transformation from short- to long-range (hexagonal) order above a threshold salt-concentration. Using various salts at similar ionic strength to those of MgCl 2 or CaCl 2 such as, NaCl or LaCl 3 , it is found that surface adsorbed NPs lack any order. X-ray fluorescence near total reflection of the same samples provides direct evidence of interfacial gold and more importantly a significant surface enrichment of the cations. Quantitative analysis reveals that divalent cations screen the charge of ssDNA, and that the hydrophobic hexyl-thiol group, commonly used to functionalize the ssDNA (for capping the AuNPs), is likely the driving force for the accumulation of the NPs at the interface.

36 MATERIALS SCIENCE↗

A simple primary amide for the selective recovery of gold from secondary resources

Waste electrical and electronic equipment (WEEE) such as mobile phones contains a plethora of metals of which gold is by far the most valuable. Herein a simple primary amide is described that achieves the selective separation of gold from a mixture of metals typically found in mobile phones by extraction into toluene from an aqueous HCl solution; unlike current processes, reverse phase transfer is achieved simply using water. Phase transfer occurs by dynamic assembly of protonated and neutral amides with [AuCl 4 ]– ions through hydrogen bonding in the organic phase, as shown by EXAFS, mass spectrometry measurements, and computational calculations, and supported by distribution coefficient analysis. In conclusion, the fundamental chemical understanding gained herein should be integral to the development of metal-recovery processes, in particular through the use of dynamic assembly processes to build complexity from simplicity.

36 MATERIALS SCIENCE↗