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At least 955 records · Page 53

Discovery of Dielectric Response and Forces in Sub-Nanoscale Objects (Final Technical Report)

This is the final technical report for DOE Award DE-SC0005132 entitled “Discovery of Dielectric Response and Forces in Sub-Nanoscale Objects.” This award originated on August 15, 2010 with Principle Investigator Prof. Phil Batson of Rutgers, The State University of New Jersey. Prof. Batson transitioned to Professor Emeritus status on January 31, 2023. At that time PI status was transferred to Prof. Robert Bartynski of the Department of Physics and Astronomy at Rutgers, The State University of New Jersey, and Director of the Rutgers Laboratory for Surface Modification. The central theme of the research performed under this award is develop and refine a NION aberration-corrected Scanning Transmission Electron Microscope to attain atomic spatial resolution and sub 10meV energy resolution in electron energy loss spectroscopy (EELS) performed on the transmitted electron beam. These capabilities allow examination of the excitation properties (primarily plasmonic and vibrational [ie., phonons] of nanoscale objects when excited with a highly-localized (~ Angstrom-scale) high energy (~ 60 keV) electron beam. Direct excitations (i.e., the response to electrons impinging directly on the sample) as well as excitations in response to the dynamic electric (and magnetic!) fields of an aloof electron beam (i.e., a beam that is close to but displaced from the target) have been studied. Our experimental work has benefited greatly from close collaborations with theoretical colleagues, but at Rutgers and from around the world, providing a much more complete understanding of the observed phenomena and suggesting avenues for further study and practical applications. This report summarizes the technical and scientific achievements accomplished during the entire award period. More extensive details are available in the Progress Reports that have already been filed with the Department of Energy. The report is divided into six sections. The first four sections focus on exploring, developing and understanding several unique capabilities and phenomena discovered and accessible owing to the high spatial- and energy-resolution we have been able to achieve. The latter two sections focus on applications of the STEM’s novel capabilities to study atomic- and nanometer-scale properties of solids, as well as broader applications to advanced and bio-materials.

47 OTHER INSTRUMENTATION↗

DNA Strand Displacement Driven Molecular Additive Manufacturing (DSD-MAM)

The goal of this project was to validate two-dimensional molecular printers, initially selfassembled from DNA and then actuated by externally driven cycles of DNA strand displacement, as prototype integrated nanosystems for molecular additive manufacturing. Novel functionalities of these nanomachines were explored during this project, including the following: nanometer-precision positioning mechanisms based on DNA strand displacement with multivalent interactions for discrete stepping or else diffusive capture; integration of independently moving layers of DNA origami to achieve 2D controllable motion; integration of spatial positioning with deposition functionality. The principal importance of this project was to provide an essential step in the development of a new technology for atomically precise manufacturing. Our first generation molecular 2D printer offers several advantages over conventional DNA-origami patterning, such as faster prototyping, faster dynamic rearrangement of patterns, and the ability to respond with feedback. We anticipate that our first-generation molecular printers may inspire future generations of molecular printers with iterative improvements in robustness and throughput. Potential applications of atomically precise manufacturing include the following: photovoltaics; photosynthetic and fuel cells; thermoelectrics and anisotropic heat spreaders; solid-state lighting; molecular electronic and plasmonic circuits; selectively preamble membranes; self-repairing materials with high strength-to-weight and fracture resistance.

36 MATERIALS SCIENCE↗

Zero-Power Wireless Infrared Digitizing Sensors for Large Scale Energy-Smart Farm

This project, funded by ARPA-E and led by Northeastern University, developed zeropower infrared digitizing sensors to optimize irrigation and enhance crop yields. Traditional water stress detection methods are costly and require frequent maintenance, limiting their effectiveness. Our research identified shortwave infrared (SWIR) transmittance as the most reliable indicator of plant water stress and developed plasmonically enhanced micromechanical photoswitches (PMPs) that operate with minimal power. The sensors offer low-cost, large-scale deployment, auto-calibration across different crops, and a 10-year battery life, significantly reducing maintenance costs. The system achieved 4x greater accuracy than conventional soil moisture sensors while ensuring economic feasibility. By enabling precision irrigation, this technology conserves water, enhances crop productivity, and lowers operational costs, making it a scalable solution for sustainable agriculture and global food security.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Prototyping of 2D and 3D photonic nanodevices by Electron Beam Lithography (CRADA Final Report)

Team developed a large area and fast electron beam lithographic for patterning visible wavelength optical materials to create 2 or 3 dimensional gratings and metasurfaces. Metasurfaces,are arrays of nanoantennas or optical resonators, are dielectric or plasmonic structures that allow control of the amplitude, phase, and polarization of light by locally modulating its wavefront The team was able to write a 1cm2 pattern with resolution better than 30 nm without visible discontinuities in the pattern. Performance to this specification allowed prototyping of optical lenses for production applications such as augmented reality goggles (optical displays) and other applications for visible light manipulations

36 MATERIALS SCIENCE↗

Microscale Thermophoresis (MST) as a Tool to Study Binding Interactions of Oxygen-Sensitive Biohybrids

Microscale thermophoresis (MST) is a technique used to measure the strength of molecular interactions. MST is a thermophoretic-based technique that monitors the change in fluorescence associated with the movement of fluorescent-labeled molecules in response to a temperature gradient triggered by an IR LASER. MST has advantages over other approaches for examining molecular interactions, such as isothermal titration calorimetry, nuclear magnetic resonance, biolayer interferometry, and surface plasmon resonance, requiring a small sample size that does not need to be immobilized and a high-sensitivity fluorescence detection. In addition, since the approach involves the loading of samples into capillaries that can be easily sealed, it can be adapted to analyze oxygen-sensitive samples. In this Bio-protocol, we describe the troubleshooting and optimization we have done to enable the use of MST to examine protein–protein interactions, protein–ligand interactions, and protein–nanocrystal interactions. The salient elements in the developed procedures include 1) loading and sealing capabilities in an anaerobic chamber for analysis using a NanoTemper MST located on the benchtop in air, 2) identification of the optimal reducing agents compatible with data acquisition with effective protection against trace oxygen, and 3) the optimization of data acquisition and analysis procedures. The procedures lay the groundwork to define the determinants of molecular interactions in these technically demanding systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Binding of Campylobacter jejuni FliW Adjacent to the CsrA RNA-Binding Pockets Modulates CsrA Regulatory Activity

Campylobacter jejuni CsrA is an mRNA-binding, post-transcriptional regulator that controls many metabolic- and virulence-related characteristics of this important pathogen. In contrast to E. coli CsrA, whose activity is modulated by binding to small non-coding RNAs (sRNAs), C. jejuni CsrA activity is controlled by binding to the CsrA antagonist FliW. In this study, we identified the FliW binding site on CsrA. Deletion of the C-terminus of C. jejuni CsrA, which is extended relative to sRNA-binding CsrA proteins, abrogated FliW binding. Bacterial two-hybrid experiments were used to assess the interaction of FliW with wild-type CsrA and mutants thereof, in which every amino acid was individually mutated. Two CsrA mutations (V51A and N55A) resulted in a significant decrease in FliW binding. The V51A and N55A mutants also showed a decrease in CsrA-FliW complex formation, as assessed by size-exclusion chromatography and surface plasmon resonance. These residues were highly conserved in bacterial species containing CsrA orthologs whose activities are predicted to be regulated by FliW. The location of FliW binding was immediately adjacent to the two RNA-binding sites of the CsrA homodimer, suggesting the model that FliW binding to CsrA modulates its ability to bind to its mRNA targets either by steric hindrance, electrostatic repulsion, or by altering the overall structure of the RNA-binding sites.

59 BASIC BIOLOGICAL SCIENCES↗

Recent Advances in Vertically Aligned Nanocomposites with Tunable Optical Anisotropy: Fundamentals and Beyond

Developing reliable and tunable metamaterials is fundamental to next-generation optical-based nanodevices and computing schemes. In this review, an overview of recent progress made with a unique group of ceramic-based functional nanocomposites, i.e., vertically aligned nanocomposites (VANs), is presented, with the focus on the tunable anisotropic optical properties. Using a self-assembling bottom-up deposition method, the as-grown VANs present great promise in terms of structural flexibility and property tunability. Such broad tunability of functionalities is achieved through VAN designs, material selection, growth control, and strain coupling. The as-grown multi-phase VAN films also present enormous advantages, including wafer scale integration, epitaxial quality, sharp atomic interface, as well as designable materials and geometries. This review also covers the research directions with practical device potentials, such as multiplex sensing, high-temperature plasmonics, magneto-optical switching, as well as photonic circuits.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electron Correlation and High-Temperature Superconductivity

Strong electron correlation plays a central role in the high-temperature superconductivity (HTSC) of cuprates. However, to date, research has focused only on its role in spin dynamics and related effects, even though it is becoming increasingly clear that spin alone may not be sufficient to create HTSC. Here, we discuss a possible role of electron correlation in the Bose–Einstein condensation (BEC) of Cooper pairs. Recently, we succeeded in observing dynamic electron correlation via inelastic X-ray scattering through results presented in real space. We discovered that electron correlations are strongly modified in the plasmon, proving that electron dynamics significantly affect electron correlation. Earlier, we found that in 4 He, the atom–atom distance in the BE condensate is 10% longer than that in the non-condensate. These results suggest the possibility that the reduction in electron-repulsion energy upon BEC is driving T c to high values. Thus, electron correlation itself could be the origin of the HTSC phenomenon.

Bose–Einstein condensation↗

Nonprecious Single Atom Catalyst for Methane Pyrolysis

The development of a suitable catalytic system for methane pyrolysis reactions requires a detailed investigation of the activation energy of C-H bonds on catalysts, as well as their stability against sintering and coke formation. In this work, both single-metal Ni atoms and small clusters of Ni atoms deposited on titanium nitride (TiN) plasmonic nanoparticles were characterized for the C-H bond activation of a methane pyrolysis reaction using ab initio spin-polarized density functional theory (DFT) calculations. The present work shows the complete reaction pathway, including energy barriers for C-H bond activation and dehydrogenated fragments, during the methane pyrolysis reaction on catalytic systems. Interestingly, the C-H bond activation barriers were low for both Ni single-atom and Ni-clusters, showing the energy barriers of ~1.10 eV and ~0.88 eV, respectively. Additionally, single-atom Ni-TiN showed weaker binding to adsorbates, and a net endothermic reaction pathway indicated that the single-atom Ni-TiN was expected to resist coke formation on its surface. However, these Ni single-atom catalysts can sinter, aggregate into a small cluster, and form a coke layer from the highly exothermic reaction pathway that the cluster takes despite the facile reaction pathway.

08 HYDROGEN↗

Gold Ion Beam Milled Gold Zero-Mode Waveguides

Zero-mode waveguides (ZMWs) are widely used in single molecule fluorescence microscopy for their enhancement of emitted light and the ability to study samples at physiological concentrations. ZMWs are typically produced using photo or electron beam lithography. We report a new method of ZMW production using focused ion beam (FIB) milling with gold ions. We demonstrate that ion-milled gold ZMWs with 200 nm apertures exhibit similar plasmon-enhanced fluorescence seen with ZMWs fabricated with traditional techniques such as electron beam lithography.

36 MATERIALS SCIENCE↗

Selected Area Deposition of High Purity Gold for Functional 3D Architectures

Selected area deposition of high purity gold films onto nanoscale 3D architectures is highly desirable as gold is conductive, inert, plasmonically active, and can be functionalized with thiol chemistries, which are useful in many biological applications. Here, we show that high-purity gold coatings can be selectively grown with the Me 2 Au (acac) precursor onto nanoscale 3D architectures via a pulsed laser pyrolytic chemical vapor deposition process. The selected area of deposition is achieved due to the high thermal resistance of the nanoscale geometries. Focused electron beam induced deposits (FEBID) and carbon nanofibers are functionalized with gold coatings, and we demonstrate the effects that laser irradiance, pulse width, and precursor pressure have on the growth rate. Furthermore, we demonstrate selected area deposition with a feature-targeting resolutions of ~100 and 5 µm, using diode lasers coupled to a multimode (915 nm) and single mode (785 nm) fiber optic, respectively. The experimental results are rationalized via finite element thermal modeling.

3-dimensional nanostructures↗

Femtosecond Laser-Induced Nano-Joining of Volatile Tellurium Nanotube Memristor

Nanowire/nanotube memristor devices provide great potential for random-access high-density resistance storage. However, fabricating high-quality and stable memristors is still challenging. This paper reports multileveled resistance states of tellurium (Te) nanotube based on the clean-room free femtosecond laser nano-joining method. The temperature for the entire fabrication process was maintained below 190 °C. A femtosecond laser joining technique was used to form nanowire memristor units with enhanced properties. Femtosecond (fs) laser-irradiated silver-tellurium nanotube-silver structures resulted in plasmonic-enhanced optical joining with minimal local thermal effects. This produced a junction between the Te nanotube and the silver film substrate with enhanced electrical contacts. Noticeable changes in memristor behavior were observed after fs laser irradiation. Capacitor-coupled multilevel memristor behavior was observed. Compared to previous metal oxide nanowire-based memristors, the reported Te nanotube memristor system displayed a nearly two-order stronger current response. The research displays that the multileveled resistance state is rewritable with a negative bias.

42 ENGINEERING↗

A Structural Basis for Inhibition of the Complement Initiator Protease C1r by Lyme Disease Spirochetes

Abstract Complement evasion is a hallmark of extracellular microbial pathogens such as Borrelia burgdorferi, the causative agent of Lyme disease. Lyme disease spirochetes express nearly a dozen outer surface lipoproteins that bind complement components and interfere with their native activities. Among these, BBK32 is unique in its selective inhibition of the classical pathway. BBK32 blocks activation of this pathway by selectively binding and inhibiting the C1r serine protease of the first component of complement, C1. To understand the structural basis for BBK32-mediated C1r inhibition, we performed crystallography and size-exclusion chromatography–coupled small angle X-ray scattering experiments, which revealed a molecular model of BBK32-C in complex with activated human C1r. Structure-guided site-directed mutagenesis was combined with surface plasmon resonance binding experiments and assays of complement function to validate the predicted molecular interface. Analysis of the structures shows that BBK32 inhibits activated forms of C1r by occluding substrate interaction subsites (i.e., S1 and S1’) and reveals a surprising role for C1r B loop–interacting residues for full inhibitory activity of BBK32. The studies reported in this article provide for the first time (to our knowledge) a structural basis for classical pathway–specific inhibition by a human pathogen.

Garrigues, Ryan J. (ORCID:0000000259233250)↗

Wave-wave interactions due to scattering by electrons.

The kinetic wave equation which describes the nonlinear wave-particle interaction in a plasma is considered, and a method which uses the picture of quantized plasmons interacting with particles for the description of nonlinear wave-particle interactions is briefly described. In this method an assumption is made of the Markoffian character of the equation. It is shown that the Markoffian assumption can be justified at least for the case when the plasma is close to a stable stationary state. The diagram method developed by Nishikawa (1966) is used to derive an explicit expression for the kinetic equation. The application of the result to the case of interaction between an electron-wave and an ion-wave is discussed.

Nishikawa, K.↗

Neutrino reactions in strong magnetic field

Presentation of the energy losses due to several neutrinos processes: (1) synchrotron neutrinos, (2) pair annihilation neutrinos, (3) plasmon neutrinos, and (4) photoneutrinos in the presence of a superstrong magnetic field. Numerical results are tabulated and illustrated for several values of densities and temperatures. In the low density regime, the presence of a magnetic field decreases the luminosity, whereas the opposite is true at higher densities. This last effect is, however, almost entirely due to the existence of a new process, the synchrotron neutrinos that disappear when H goes to zero. Even though the overall effect can only be quantitatively ascertained after a complete cooling computation is performed, one should however expect a much lower temperature for neutron star surface than the one computed in the case where H is zero.

Canuto, V.↗

Photoneutrino reactions in a superstrong magnetoactive plasma

The neutrino luminosity due to the photoneutrino process in the presence of a superstrong magnetoactive electron plasma appropriate for neutron stars is computed. The results indicate that for relatively low temperatures, between 100 million and 500 million K, the energy loss rate is significantly reduced both in the low-density regime below about 10 million g/cu cm (by the magnetic field) and in the high-density regime above that value (by plasmon excitations). These effects are temperature dependent, and they are less pronounced when the temperature is in the range from 500 million to 1 billion K.

Chou, C. K.↗

Intraband optical conductivity sigma/omega,T/ of Cu, Ag, and Au - Contribution from electron-electron scattering

The frequency and temperature dependence of the intraband optical conductivity of the noble metals Cu, Ag and Au is measured and contributions of electron-electron scattering are assessed. Optical measurements were performed at temperatures of 77, 295 and 425 K to obtain values of the Drude electron scattering rate with a linear dependence on temperature which may be attributed to electron-phonon scattering, and a quadratic dependence on photon energy, which is suggestive of electron-electron scattering but is a factor of two to three times greater than would be expected. Comparison of the optical data with dc electrical and thermal resistivity data which also show behavior attributed to electron-electron scattering reveals discrepancies of up to an order of magnitude. Other possible mechanisms for the frequency dependence, including absorptance, electron-surface plasmon interactions, a two-carrier model, and a structure dependence are considered, and it is concluded that the frequency dependence in the Drude scattering rates of the noble metals is not yet quantitatively understood

Parkins, G. R.↗