We present here the first fabrication of hollow cobalt oxide nanoparticles produced by a protein-regulated site-specific reconstitution process in aqueous solution and describe the metal growth mechanism in the ferritin interior.
Horse spleen ferritin (HoSF) containing 800-1500 cobalt or 250-1200 manganese atoms as Co(O)OH and Mn(O)OH mineral cores within the HoSF interior (Co-HoSF and Mn-HoSF) was synthesized, and the chemical reactivity, kinetics of reduction, and the reduction potentials were measured. Microcoulometric and chemical reduction of HoSF containing the M(O)OH mineral core (M = Co or Mn) was rapid and quantitative with a reduction stoichiometry of 1.05 +/- 0.10 e/M forming a stable M(OH)(2) mineral core. At pH 9.0, ascorbic acid (AH(2)), a two-electron reductant, effectively reduced the mineral cores; however, the reaction was incomplete and rapidly reached equilibrium. The addition of excess AH(2) shifted the reaction to completion with a M(3+)/AH(2) stoichiometry of 1.9-2.1, consistent with a single electron per metal atom reduction. The rate of reaction between M(O)OH and excess AH(2) was measured by monitoring the decrease in mineral core absorbance with time. The reaction was first order in each reactant with second-order rate constants of 0.53 and 4.74 M(-1) min(-1), respectively, for Co- and Mn-HoSF at pH 9.0. From the variation of absorbance with increasing AH(2) concentration, equilibrium constants at pH 9.0 of 5.0 +/- 1.9 for Co-HoSF and 2.9 +/- 0.9 for Mn-HoSF were calculated for 2M(O)OH + AH(2) = 2M(OH)(2) + D, where AH(2) and D are ascorbic acid and dehydroascorbic acid, respectively. Consistent with these equilibrium constants, the standard potential for the reduction of Co(III)-HoSF is 42 mV more positive than that of the ascorbic acid reaction, while the standard potential of Mn(III)-HoSF is 27 mV positive relative to AH(2). Fe(2+) in solution with Co- and Mn-HoSF under anaerobic conditions was oxidized to form Fe(O)OH within the HoSF interior, resulting in partial displacement of the Co or Mn by iron.
Quantum logic gates (QLGs) or other logic systems are based on quantum-dots (QD) with a stringent requirement of size uniformity. The QD are widely known building units for QLGs. The size control of QD is a critical issue in quantum-dot fabrication. The work presented here offers a new method to develop quantum-dots using a bio-template, called ferritin, that ensures QD production in uniform size of nano-scale proportion. This technology is essential for NASA, DoD, and industrial nanotechnology applications such as: ultra-high density data storage, quantum electronic devices, biomedical nanorobots, molecular tagging, terahertz radiation sources, nanoelectromechanical systems (NEMS), etc. The bio-template for uniform yield of QD is based on a ferritin protein that allows reconstitution of core material through the reduction and chelation processes. By either the magnetic or electrical property of reconstituted core materials, the QD can be used for logic gates which are fundamental building blocks for quantum computing. However, QLGs are in an incubation stage and still have many potential obstacles that need to be addressed, such as an error collection, a decoherence, and a hardware architecture. One of the biggest challenges for developing QLG is the requirement of ordered and uniform size of QD for arrays on a substrate with nanometer precision. The other methods known so far, such as self-assembled QD grown in the Stranski-Krastanov mode, are usually randomly organized. The QD development by bio-template includes the electrochemical/chemical reconstitution of ferritins with different core materials, such as iron, cobalt, manganese, platinum, and nickel. The other bio-template method used in our laboratory is dendrimers, precisely defined chemical structures. With ferritin-templated QD, we fabricated the heptagon-shaped patterned array via direct nano manipulation of the ferritin molecules with a tip of atomic force microscope (AFM). We also designed various nanofabrication methods of QD arrays using a wide range manipulation techniques. The precise control of the ferritin-templated QD for a patterned arrangement are offered by various methods, such as a site-specific immobilization of thiolated ferritins through local oxidation using the AFM tip, ferritin, arrays induced by gold nanoparticle manipulation, thiolated ferritin positioning by shaving method, etc. In the signal measurements, the current-voltage curve is obtained by measuring the current through the ferritin, between the tip and the substrate for potential sweeping or at constant potential. The measured resistance near zero bias was 1.8 teraohm for single holoferritin and 5.7 teraohm for single apoferritin, respectively.
The concept of a bio-nanobattery is based on ferritin, an iron storage protein that naturally exists in most biological systems. Biomineralization allows ferritins to reconstitute iron cove-with various metallic cores. When the ferritin half cells are integrated into a complete battery system, the fabrication of well-organized ferritin arrays is necessary and very important to enhance the overall battery performance, improving the battery power density, the power discharge rate, the compactness of battery size, etc. In this work, a spin self-assembly (SA) method was used for producing a thin-film array structure of ferritins. The spin SA deposition was repeated until two bilayers of cationized and native ferritins or 4 alternating ferritin layers were achieved. High-resolution field-emission scanning electron microscopy (FESEM), atomic force microscopy (AFM) and variable angle spectroscopic ellipsometry (VASE) were used to characterize the multilayered ferritin arrays. The thickness of ferritin multilayer increased linearly as the spin SA deposition was repeated. The spin SA deposition method produced well-organized, uniform, and flat ferritin layers in a much shorter period of time, compared with Langmuir-Blodgett or dipping deposition methods. Such enhancement can be attributed to a strong electrostatic attraction that holds the ferritin layer on the substrate during the spin-coating process while hydrodynamic drag and centrifugal forces remove loosely-bound ferritins.
Currently available power storage systems, such as those used to supply-power to microelectronic devices, typically consist of a single centralized canister and a series of wires to supply electrical power to where it is needed in a circuit. As the size of electrical circuits and components become smaller, there exists a need for a distributed power. system to reduce Joule heating, wiring, and to allow autonomous operation of the various functions performed by the circuit. Our research is being conducted to develop a bio-nanobattery using ferritins reconstituted with both an iron core (Fe-ferritin) and a cobalt core (Co-ferritin). Both Co-ferritin and Fe-ferritin were synthesized and characterized as candidates for the bio-nanobattery. The reducing capability was determined as well as the half-cell electrical potentials, indicating an electrical output of nearly 0.5-V for the battery cell. Ferritins having other metallic cores are also being investigated, in order to increase the overall electrical output. Two dimensional ferritin arrays were also produced on various substrates, demonstrating the necessary building blocks for the bio-nanobattery. The bio-nanobattery will play a key role in moving to a distributed power storage system for electronic applications.
Platinum-cored ferritins were synthesized as electrocatalysts by electrochemical biomineralization of immobilized apoferritin with platinum. The platinum cored ferritin was fabricated by exposing the immobilized apoferritin to platinum ions at a reduction potential. On the platinum-cored ferritin, oxygen is reduced to water with four protons and four electrons generated from the anode. The ferritin acts as a nano-scale template, a biocompatible cage, and a separator between the nanoparticles. This results in a smaller catalyst loading of the electrodes for fuel cells or other electrochemical devices. In addition, the catalytic activity of the ferritin-stabilized platinum nanoparticles is enhanced by the large surface area and particle size phenomena. The work presented herein details the immobilization of ferritin with various surface modifications, the electrochemical biomineralization of ferritin with different inorganic cores, and the fabrication of self-assembled 2-D arrays with thiolated ferritin.
The concept of microwave-driven smart membrane actuators is envisioned as the best option to alleviate the complexity associated with hard-wired control circuitry. A large, ultra lightweight space structure, such as solar sails and Gossamer spacecrafts, requires a distributed power source to alleviate wire networks, unlike the localized on-board power infrastructures typically found in most small spacecrafts. A rectenna array based on a patch configuration for high voltage output was developed to drive membrane actuators. Networked patch rectenna array receives and converts microwave power into a DC power for an array of smart actuators. To use microwave power effectively, the concept of a power allocation and distribution (PAD) logic circuit is being adopted for networking a rectenna/actuator patch array. Use of thin-film patch rectennas adds a significant amount of rigidity to membrane flexibility. Therefore, dipole rectennas that offer flexibility and are lighter weight are being considered for thin-film membrane actuators. Preliminary design and fabrication of PAD circuitry that consists of a few nodal elements were made for laboratory testing. The networked actuators were tested to correlate the network coupling effect, power allocation and distribution, and response time.
An experimental study of a smart‐materials actuator driven by a microwave is presented in this paper. A proof‐of‐concept experiment using a smart material, such as thin layer composite unimorph ferroelectric driver and sensor (THUNDER), has been demonstrated with wirelessly transmitted microwave power. Such an advance system will offer a new class of smart devices that are remotely controlled via wirelessly transmitted power. Thus, a system of this nature autonomously functions without an onboard power infrastructure. Potential applications are integrated sensors, actuators, and smart flight control in space applications, as well as biologically‐inspired systems. © 2003 Wiley Periodicals, Inc. Microwave Opt Technol Lett 36: 331–333, 2003; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/mop.10757
NASA''s Next Generation Space Telescope (NGST) has a large deployable, fragmented optical surface (</- 8 m in diameter) that requires autonomous correction of deployment misalignments and thermal effects. Its high and stringent resolution requirement imposes a great deal of challenge for optical correction. The threshold value for optical corrections is dictated by N/20 (30 nm for NGST optics). Control of an adaptive optics array consisting of a large number of optical elements and smart material actuators is so complex that power distribution for activation and control of actuators must be done by other than hard-wired circuitry. The concept of microwave-driven smart actuators is envisioned as the best option to alleviate the complexity associated with hard-wiring. A microwave-driven actuator was studied to realize such a concept for future applications. Piezoelectric material was used as an actuator that shows dimensional change with high electric field. The actuators were coupled with microwave rectenna and tested to correlate the coupling effect of electromagnetic wave. In experiments, a 3x3 rectenna patch array generated more than 50 volts which is a threshold voltage for 30-nm displacement of a single piezoelectric material. Overall, the test results indicate that the microwave-driven actuator concept can be adopted for NGST applications.