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26 records · Page 2

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NASA NTRS1997

Surface Plasmon Resonance Evaluation of Colloidal Metal Aerogel Filters

Surface plasmon resonance imaging has in the past been applied to the characterization of thin films. In this study we apply the surface plasmon technique not to determine macroscopic spatial variations but rather to determine average microscopic information. Specifically, we deduce the dielectric properties of the surrounding gel matrix and information concerning the dynamics of the gelation process from the visible absorption characteristics of colloidal metal nanoparticles contained in aerogel pores. We have fabricated aerogels containing gold and silver nanoparticles. Because the dielectric constant of the metal particles is linked to that of the host matrix at the surface plasmon resonance, any change 'in the dielectric constant of the material surrounding the metal nanoparticles results in a shift in the surface plasmon wavelength. During gelation the surface plasmon resonance shifts to the red as the average or effective dielectric constant of the matrix increases. Conversely, formation of an aerogel or xerogel through supercritical extraction or evaporation of the solvent produces a blue shift in the resonance indicating a decrease in the dielectric constant of the matrix. From the magnitude of this shift we deduce the average fraction of air and of silica in contact with the metal particles. The surface area of metal available for catalytic gas reaction may thus be determined.

Smith, David D.↗

NASA NTRS1998

Noble Metal Immersion Spectroscopy of Silica Alcogels and Aerogels

We have fabricated aerogels containing gold and silver nanoparticles for gas catalysis applications. By applying the concept of an average or effective dielectric constant to the heterogeneous interlayer surrounding each particle, we extend the technique of immersion spectroscopy to porous or heterogeneous media. Specifically, we apply the predominant effective medium theories for the determination of the average fractional composition of each component in this inhomogeneous layer. Hence, the surface area of metal available for catalytic gas reaction is determined. The technique is satisfactory for statistically random metal particle distributions but needs further modification for aggregated or surfactant modified systems. Additionally, the kinetics suggest that collective particle interactions in coagulated clusters are perturbed during silica gelation resulting in a change in the aggregate geometry.

Smith, David D.↗

NASA NTRS2008

Near-Field Spectroscopy with Nanoparticles Deposited by AFM

An alternative approach to apertureless near-field optical spectroscopy involving an atomic-force microscope (AFM) entails less complexity of equipment than does a prior approach. The alternative approach has been demonstrated to be applicable to apertureless near-field optical spectroscopy of the type using an AFM and surface enhanced Raman scattering (SERS), and is expected to be equally applicable in cases in which infrared or fluorescence spectroscopy is used. Apertureless near-field optical spectroscopy is a means of performing spatially resolved analyses of chemical compositions of surface regions of nanostructured materials. In apertureless near-field spectroscopy, it is common practice to utilize nanostructured probe tips or nanoparticles (usually of gold) having shapes and dimensions chosen to exploit plasmon resonances so as to increase spectroscopic-signal strengths. To implement the particular prior approach to which the present approach is an alternative, it is necessary to integrate a Raman spectrometer with an AFM and to utilize a special SERS-active probe tip. The resulting instrumentation system is complex, and the tasks of designing and constructing the system and using the system to acquire spectro-chemical information from nanometer-scale regions on a surface are correspondingly demanding.

Anderson, Mark S.↗

NASA NTRSDate not supplied

Radiocatalyst for Radiation Protection and Microbial Control

Radiocatalysts are materials that reduce the activation energy required to split water into hydrogen and reactive oxygen species (ROS). They are activated by radiation and can be used to improve the ability of water to act as a radiation barrier. This paper reports the results of an experimental evaluation of a gold radiocatalyst. This work provides a preliminary evaluation of the ability of these types of catalysts to increase the efficiency of water hydrolysis when exposed to different types of radiation (GCR). Although the radiation exposure devices used in this testing were not capable of generating radiation as diverse as is commonly found in space, the testing is useful in evaluating the function of these radiocatalytic nanoparticles when exposed to a a subset of the types of radiation that are found in GCR. The results are relevant to evaluating the use of this material for both space radiation protection and the production of useful byproducts, such as ROS, which can be used to maintain the sterility of stored water supplies. Radiocatalysts are materials typically used in radiation cancer therapy to improve the kill rate of tumors. These nanoparticles can be directly injected into tumors or functionalized to enter tumor cells via the blood stream. When they are exposed to radiation, they produce ROS. ROS are water hydrolysis products such as OH¯, O¯, O3, H2O2. This study used radiocatalytic 1.8 nm gold nanoparticles functionalized with citrate. These nanoparticles were tested through exposure to Xrays, 56Fe particles and gamma rays to demonstrate activity to a variety of radiation sources. The results demonstrate that radiocatalysts can improve the radiation absorption of water by a factor of 3 to 8 and can effectively kill bacteria at radiation levels above 1 Gy.

radiocatalyst radiation protection biocide↗

NASA NTRS1997

Surface Plasmon Resonance Evaluation of Colloidal Metal Aerogel Filters

We have fabricated aerogels containing gold, silver, and platinum nanoparticles for gas catalysis applications. By applying the concept of an average or effective dielectric constant to the heterogeneous interlayer surrounding each particle, we extend the technique of immersion spectroscopy to porous or heterogeneous media. Specifically, we apply the predominant effective medium theories for the determination of the average fractional composition of each component in this inhomogeneous layer. Hence, the surface area of metal available for catalytic gas reaction is determined. The technique is satisfactory for statistically random metal particle distributions but needs further modification for aggregated or surfactant modified systems. Additionally, the kinetics suggest that collective particle interactions in coagulated clusters are perturbed during silica gelation resulting in a change in the aggregate geometry.

Smith, David D.↗

NASA NTRS2004

Biologically Derived Nanoparticle Arrays via a Site-Specific Reconstitution of Ferritin and their Electrochemistry

Nanoparticle arrays biologically derived from an electrochemically-controlled site-specific biomineralization were fabricated on a gold substrate through the immobilization process of biomolecules. The work reported herein includes the immobilization of ferritin with various surface modifications, the electrochemical biomineralization of ferritins with different inorganic cores, the fabrication of self-assembled arrays with the immobilized ferritin, and the electrochemical characterization of various core materials. Protein immobilization on the substrate is achieved by anchoring ferritins with dithiobis-N-succinimidyl propionate (DTSP). A reconstitution process of electrochemical site-specific biomineralization with a protein cage loads ferritins with different core materials such as Pt, Co, Mn, and Ni. The ferritin acts as a nano-scale template, a biocompatible cage, and a separator between the nanoparticles. The nano-sized metalcored ferritins on a gold substrate displayed a good electrochemical activity for the electron transport and storage, which is suitable for bioelectronics applications such as biofuel cell, bionanobattery, biosensors, etc. Keywords: Ferritin, immobilization, site-specific reconstitution, biomineralization, and bioelectronics

Kim, Jae-Woo↗

NASA NTRS2007

Electrochemically Controlled Reconstitution of Immobilized Ferritins for Bioelectronic Applications

Site-specific reconstituted nanoparticles were fabricated via electrochemically-controlled biomineralization through the immobilization of biomolecules. The work reported herein includes the immobilization of ferritin with various surface modifications, the electrochemical biomineralization of ferritins with different inorganic cores, and the electrocatalytic reduction of oxygen on the reconstituted Pt-cored ferritins. Protein immobilization on the substrate is achieved by anchoring ferritins with dithiobis-N-succinimidyl propionate (DTSP). A reconstitution process of site-specific electrochemical biomineralization with a protein cage loads ferritins with different core materials. The ferritin acts as a nano-scale template, a biocompatible cage, and a separator between the nanoparticles. This first demonstration of electrochemically controlled site-specific reconstitution of biomolecules provides a new tool for biomineralization and opens the way to produce the bio-templated nanoparticles by electrochemical control. The nanosized platinum-cored ferritins on gold displayed good catalytic activity for the electrochemical reduction of oxygen, which is applicable to biofuel cell applications. This results in a smaller catalyst loading on the electrodes for fuel cells or other bioelectronic devices.

Kim, Jae-Woo↗

NASA NTRS2002

Ordered nanoparticle arrays formed on engineered chaperonin protein templates

Traditional methods for fabricating nanoscale arrays are usually based on lithographic techniques. Alternative new approaches rely on the use of nanoscale templates made of synthetic or biological materials. Some proteins, for example, have been used to form ordered two-dimensional arrays. Here, we fabricated nanoscale ordered arrays of metal and semiconductor quantum dots by binding preformed nanoparticles onto crystalline protein templates made from genetically engineered hollow double-ring structures called chaperonins. Using structural information as a guide, a thermostable recombinant chaperonin subunit was modified to assemble into chaperonins with either 3 nm or 9 nm apical pores surrounded by chemically reactive thiols. These engineered chaperonins were crystallized into two-dimensional templates up to 20 microm in diameter. The periodic solvent-exposed thiols within these crystalline templates were used to size-selectively bind and organize either gold (1.4, 5 or 10nm) or CdSe-ZnS semiconductor (4.5 nm) quantum dots into arrays. The order within the arrays was defined by the lattice of the underlying protein crystal. By combining the self-assembling properties of chaperonins with mutations guided by structural modelling, we demonstrate that quantum dots can be manipulated using modified chaperonins and organized into arrays for use in next-generation electronic and photonic devices.

Chaperonins/chemistry/ultrastructure↗