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LDRD final report on adaptive-responsive nanostructures for sensing applications.

Description: Functional organic nanostructures such as well-formed tubes or fibers that can easily be fabricated into electronic and photonic devices are needed in many applications. Especially desirable from a national security standpoint are nanostructures that have enhanced sensitivity for the detection of chemicals and biological (CB) agents and other environmental stimuli. We recently discovered the first class of highly responsive and adaptive porphyrin-based nanostructures that may satisfy these requirements. These novel porphyrin nanostructures, which are formed by ionic self-assembly of two oppositely charged porphyrins, may function as conductors, semiconductors, or photoconductors, and they have additional properties that make them suitable for device fabrication (e.g., as ultrasensitive colorimetric CB microsensors). Preliminary studies with porphyrin nanotubes have shown that these nanostructures have novel optical and electronic properties, including strong resonant light scattering, quenched fluorescence, and electrical conductivity. In addition, they are photochemically active and capable of light-harvesting and photosynthesis; they may also have nonlinear optical properties. Remarkably, the nanotubes and potentially other porphyrin nanostructure are mechanically responsive and adaptive (e.g., the rigidity of the micrometers-long nanotubes is altered by light, ultrasound, or chemicals) and they self-heal upon removal the environmental stimulus. Given the tremendous degree of structural variation possible in the porphyrin subunits, additional types of nanostructures and greater control over their morphology can be anticipated. Molecular modification also provides a means of controlling their electronic, photonic, and other functional properties. In this work, we have greatly broadened the range of ionic porphyrin nanostructures that can be made, and determined the optical and responsivity properties of the nanotubes and other porphyrin nanostructures. We have also explored means for controlling their morphology, size, and placement on surfaces. The research proposed will lay the groundwork for the use of these remarkable porphyrin nanostructures in micro- and nanoscale devices, by providing a more detailed understanding of ...
Date: November 1, 2005
Creator: Shelnutt, John Allen; van Swol, Frank B.; Wang, Zhongchun & Medforth, Craig J.
Partner: UNT Libraries Government Documents Department

Nonplanarity and the protonation behavior of porphyrins

Description: {sup 1}H NMR studies of the protonation of highly nonplanar porphyrins with strong acids reveal the presence of the previously elusive monocation, and show that its stability can be related to the amount of saddle distortion induced by protonation; the amount of saddle distortion for a porphyrin dication is also found to correlate well with the rate of intermolecular proton transfer.
Date: March 21, 2000
Partner: UNT Libraries Government Documents Department

LDRD final report on imaging self-organization of proteins in membranes by photocatalytic nano-tagging.

Description: We have developed a new nanotagging technology for detecting and imaging the self-organization of proteins and other components of membranes at nanometer resolution for the purpose of investigating cell signaling and other membrane-mediated biological processes. We used protein-, lipid-, or drug-bound porphyrin photocatalysts to grow in-situ nanometer-sized metal particles, which reveal the location of the porphyrin-labeled molecules by electron microscopy. We initially used photocatalytic nanotagging to image assembled multi-component proteins and to monitor the distribution of lipids and porphyrin labels in liposomes. For example, by exchanging the heme molecules in hemoproteins with a photocatalytic tin porphyrin, a nanoparticle was grown at each heme site of the protein. The result obtained from electron microscopy for a tagged multi-subunit protein such as hemoglobin is a symmetric constellation of a specific number of nanoparticle tags, four in the case of the hemoglobin tetramer. Methods for covalently linking photocatalytic porphyrin labels to lipids and proteins were also developed to detect and image the self-organization of lipids, protein-protein supercomplexes, and membrane-protein complexes. Procedures for making photocatalytic porphyrin-drug, porphyrin-lipid, and porphyrin-protein hybrids for non-porphyrin-binding proteins and membrane components were pursued and the first porphyrin-labeled lipids was investigated in liposomal membrane models. Our photocatalytic nanotagging technique may ultimately allow membrane self-organization and cell signaling processes to be imaged in living cells. Fluorescence and plasmonic spectra of the tagged proteins might also provide additional information about protein association and membrane organization. In addition, a porphyrin-aspirin or other NSAID hybrid may be used to grow metal nanotags for the pharmacologically important COX enzymes in membranes so that the distribution of the protein can be imaged at the nanometer scale.
Date: November 1, 2005
Creator: Zavadil, Kevin Robert; Shelnutt, John Allen; Sasaki, Darryl Yoshio; Song, Yujiang & Medforth, Craig J.
Partner: UNT Libraries Government Documents Department

LDRD final report on nanovehicle light-driven propulsion.

Description: Having demonstrated the possibility of constructing nanoscale metallic vehicular bodies as described in last year's proposal, our goals have been to make uniform preparations of the metallized lipid assemblies and to determine the feasibility of powering these nanostructures with biological motors that are activated and driven by visible light. We desired that the propulsion system be constructed entirely by self-assembly and powered by a photocatalytic process partially already built into the nanovehicle. The nanovehicle we desire to build is composed of both natural biological components (ATPase, kinesin-microtubules) and biomimetic components (platinized liposomes, photosynthetic membrane) as functional units. The vehicle's body was originally envisioned to be composed of a surfactant liposomal bilayer coated with platinum nanoparticles, but instead of the expected nanoparticles we were able to grow dendritic 2-nm thick platinum sheets on the liposomes. Now, we have shown that it is possible to completely enclose the liposomes with sheeting to form porous platinum spheres, which show good structural stability as evidenced by their ability to survive the stresses of electron-microscopy sample preparation. Our goals were to control the synthesis of the platinized liposomes well enough to make uniform preparations of the coated individual liposomes and to develop the propulsion system for these nanovehicles a hydrogen-evolving artificial photosynthetic system in the liposomal bilayer that generates the pH gradient across the membrane that is necessary to drive the synthesis of ATP by ATP-synthase incorporated in the membrane. ATP produced would fuel the molecular motor (kinesin) attached to the vehicle, needing only light, storable ADP, phosphate, and an electron donor to be produced by ATP-synthase in the membrane. These research goals appear to be attainable, but growing the uniform preparations of the liposomes coated with dendritic platinum sheeting, a necessary accomplishment that would simplify the task of incorporating and verifying the photosynthetic function ...
Date: December 1, 2004
Creator: Singh, Anup K.; van Swol, Frank B.; Shelnutt, John Allen; Medforth, Craig J. & Song, Yujiang
Partner: UNT Libraries Government Documents Department

A nonplanar porphyrin-based receptor molecule for chiral amine ligands

Description: A novel porphyrin-based receptor molecule for chiral amine ligands is described in which nonplanarity of the porphyrin macrocycle is used to orient the ligand and to enhance porphyrin-ligand interactions. The porphyrin macrocycle provides a versatile platform upon which to build elaborate superstructures, and this feature coupled with a rich and well-developed synthetic chemistry has led to the synthesis of many elegant models of heme protein active sites and numerous porphyrin-based receptor molecules. One design feature which is not usually considered in the design of porphyrin-based receptor molecules is nonplanarity of the porphyrin ring, although there are a few systems such as the pyridine sensitive Venus Flytrap and the chirality-memory molecule which illustrate that nonplanar porphyrin-based receptors can display unique and interesting behavior. Given the novel properties of these receptors and the continuing interest in the effects of nonplanarity on the properties of porphyrins the authors decided to investigate in more detail the potential applications of nonplanarity in the design of porphyrin-based receptors. Herein, they describe the design, synthesis, and characterization of a new kind of nonplanar porphyrin-based receptor molecule for chiral amines.
Date: March 6, 2000
Partner: UNT Libraries Government Documents Department

Synthesis and Characterization of a New Perhalogenated Porphyrin

Description: The first synthesis of an octahalotetraalkylporphyrin [2,3,7,8,12,13,17,18 -octabromo-5,10,15,20- tetrakis(trifluoromethyl)porphinato nickel(II)] is reported; this perhalogenated porphyrin has several novel properties including a very nonplanar ruffled structure with an unusually short Ni- N distance, an extremely red-shifted optical spectrum, and hindered rotation of the trifluoromethyl groups ({Delta}G<sub>278K</sub> =47 kJ mol<sup>-1</sup>).
Date: May 19, 1999
Creator: Jia, Songling; Medforth, Craig J.; Nelson, Nora Y.; Nurco, Daniel J.; Shelnutt, John & Smith, Kevin M.
Partner: UNT Libraries Government Documents Department

Synthesis and unusual properties of the first 2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetraalkylporphyrin

Description: The new perhalogenated porphyrin 2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetrakis(trifluoromethyl)porphinato-nickel(II) exhibits several striking features, including an extremely ruffled macrocycle with a very short Ni-N distance, an unusually red-shifted optical spectrum, and, surprisingly, hindered rotation of the meso-trifluoromethyl substituents ({Delta}G{sub 278}{sup +} = 47 kJ/mol).
Date: March 6, 2000
Partner: UNT Libraries Government Documents Department

Novel Dodecaarylporphyrins: Synthesis and Variable Temperature NMR Studies

Description: An investigation of the synthesis of novel dodecaarylporphyrins using the Suzuki coupling reaction of arylboronic acids with octabromotetraarylporphyrins is reported. Studies of the dynamic properties of these new porphyrins using variable temperature (VT) <SUP>1</SUP>H NMR spectroscopy and molecular mechanics provide interesting insights into their dynamic properties, including the first determination of {beta} aryl rotation in a porphyrin system.
Date: May 5, 1999
Creator: Cancilla, Mark; Lebrilla, Carlito; Ma, Jian-Guo; Medforth, Craig J.; Muzzi, Cinzia M.; Shelnutt, John A. et al.
Partner: UNT Libraries Government Documents Department

LDRD final report on light-powered nanovehicles.

Description: We have investigated the possibility of constructing nanoscale metallic vehicles powered by biological motors or flagella that are activated and powered by visible light. The vehicle's body is to be composed of the surfactant bilayer of a liposome coated with metallic nanoparticles or nanosheets grown together into a porous single crystal. The diameter of the rigid metal vesicles is from about 50 nm to microns. Illumination with visible light activates a photosynthetic system in the bilayer that can generate a pH gradient across the liposomal membrane. The proton gradient can fuel a molecular motor that is incorporated into the membrane. Some molecular motors require ATP to fuel active transport. The protein ATP synthase, when embedded in the membrane, will use the pH gradient across the membrane to produce ATP from ADP and inorganic phosphate. The nanoscale vehicle is thus composed of both natural biological components (ATPase, flagellum; actin-myosin, kinesin-microtubules) and biomimetic components (metal vehicle casing, photosynthetic membrane) as functional units. Only light and storable ADP, phosphate, water, and weak electron donor are required fuel components. These nano-vehicles are being constructed by self-assembly and photocatalytic and autocatalytic reactions. The nano-vehicles can potentially respond to chemical gradients and other factors such as light intensity and field gradients, in a manner similar to the way that magnetic bacteria navigate. The delivery package might include decision-making and guidance components, drugs or other biological and chemical agents, explosives, catalytic reactors, and structural materials. We expected in one year to be able only to assess the problems and major issues at each stage of construction of the vehicle and the likely success of fabricating viable nanovehicles with our biomimetic photocatalytic approach. Surprisingly, we have been able to demonstrate that metallized photosynthetic liposomes can indeed be made. We have completed the synthesis of metallized liposomes with photosynthetic ...
Date: November 1, 2003
Creator: Shelnutt, John Allen; van Swol, Frank B.; Miller, James Edward; Pereira, Eulalia; Qiu, Yan; Jiang, Ying-Bing et al.
Partner: UNT Libraries Government Documents Department

DOE/BES/NSET annual report on growth of metal and semiconductor nanostructures using localized photocatalysts.

Description: Our overall goal is to understand and develop a novel light-driven approach to the controlled growth of unique metal and semiconductor nanostructures and nanomaterials. In this photochemical process, bio-inspired porphyrin-based photocatalysts reduce metal salts in aqueous solutions at ambient temperatures to provide metal nucleation and growth centers. Photocatalyst molecules are pre-positioned at the nanoscale to control the location and morphology of the metal nanostructures grown. Self-assembly, chemical confinement, and molecular templating are some of the methods used for nanoscale positioning of the photocatalyst molecules. When exposed to light, the photocatalyst molecule repeatedly reduces metal ions from solution, leading to deposition and the synthesis of the new nanostructures and nanostructured materials. Studies of the photocatalytic growth process and the resulting nanostructures address a number of fundamental biological, chemical, and environmental issues and draw on the combined nanoscience characterization and multi-scale simulation capabilities of the new DOE Center for Integrated Nanotechnologies, the University of New Mexico, and Sandia National Laboratories. Our main goals are to elucidate the processes involved in the photocatalytic growth of metal nanomaterials and provide the scientific basis for controlled synthesis. The nanomaterials resulting from these studies have applications in nanoelectronics, photonics, sensors, catalysis, and micromechanical systems. The proposed nanoscience concentrates on three thematic research areas: (1) the creation of nanoscale structures for realizing novel phenomena and quantum control, (2) understanding nanoscale processes in the environment, and (3) the development and use of multi-scale, multi-phenomena theory and simulation. Our goals for FY03 have been to understand the role of photocatalysis in the synthesis of dendritic platinum nanostructures grown from aqueous surfactant solutions under ambient conditions. The research is expected to lead to highly nanoengineered materials for catalysis mediated by platinum, palladium, and potentially other catalytically important metals. The nanostructures made also have potential applications in nanoelectronics, nanophotonics, and nanomagnetic ...
Date: October 1, 2003
Creator: Haddad, Raid Edward; Brinker, C. Jeffrey; Shelnutt, John Allen; Yang, Yi; Nuttall, H. Eric; Watt, Richard K. et al.
Partner: UNT Libraries Government Documents Department