Measuring Conformational Dynamics of Single Biomolecules Using Nanoscale Electronic Devices

NASA Astrophysics Data System (ADS)

Akhterov, Maxim V.; Choi, Yongki; Sims, Patrick C.; Olsen, Tivoli J.; Gul, O. Tolga; Corso, Brad L.; Weiss, Gregory A.; Collins, Philip G.

2014-03-01

Molecular motion can be a rate-limiting step of enzyme catalysis, but motions are typically too quick to resolve with fluorescent single molecule techniques. Recently, we demonstrated a label-free technique that replaced fluorophores with nano-electronic circuits to monitor protein motions. The solid-state electronic technique used single-walled carbon nanotube (SWNT) transistors to monitor conformational motions of a single molecule of T4 lysozyme while processing its substrate, peptidoglycan. As lysozyme catalyzes the hydrolysis of glycosidic bonds, two protein domains undergo 8 Å hinge bending motion that generates an electronic signal in the SWNT transistor. We describe improvements to the system that have extended our temporal resolution to 2 μs . Electronic recordings at this level of detail directly resolve not just transitions between open and closed conformations but also the durations for those transition events. Statistical analysis of many events determines transition timescales characteristic of enzyme activity and shows a high degree of variability within nominally identical chemical events. The high resolution technique can be readily applied to other complex biomolecules to gain insights into their kinetic parameters and catalytic function.

A single arginine residue is required for the interaction of the electron transferring flavoprotein (ETF) with three of its dehydrogenase partners.

PubMed

Parker, Antony R

2003-12-01

The interaction of several dehydrogenases with the electron transferring flavoprotein (ETF) is a crucial step required for the successful transfer of electrons into the electron transport chain. The exact determinants regarding the interaction of ETF with its dehydrogenase partners are still unknown. Chemical modification of ETF with arginine-specific reagents resulted in the loss, to varying degrees, of activity with medium chain acyl-coenzyme A dehydrogenase (MCAD). The kinetic profiles showed the inactivations followed pseudo-first-order kinetics for all reagents used. For activity with MCAD, maximum inactivation of ETF was accomplished by 2,3-butanedione (4% residual activity after 120 min) and it was shown that modification of one arginine residue was responsible for the inactivation. Almost 100% restoration of this ETF activity was achieved upon incubation with free arginine. However, the same 2,3-butanedione modified ETF only possessed decreased activity with dimethylglycine-(DMGDH, 44%) and sarcosine- (SDH, 27%) dehydrogenases unlike the abolition with MCAD. Full protection of ETF from arginine modification by 2,3-butanedione was achieved using substrate-protected DMGDH, MCAD and SDH respectively. Cross-protection studies of ETF with the three dehydrogenases implied use of the same single arginine residue in the binding of all three dehydrogenases. These results lead us to conclude that this single arginine residue is essential in the binding of the ETF to MCAD, but only contributes partially to the binding of ETF to SDH and DMGDH and thus, the determinants of the dehydrogenase binding sites overlap but are not identical.

Optically programmable electron spin memory using semiconductor quantum dots.

PubMed

Kroutvar, Miro; Ducommun, Yann; Heiss, Dominik; Bichler, Max; Schuh, Dieter; Abstreiter, Gerhard; Finley, Jonathan J

2004-11-04

The spin of a single electron subject to a static magnetic field provides a natural two-level system that is suitable for use as a quantum bit, the fundamental logical unit in a quantum computer. Semiconductor quantum dots fabricated by strain driven self-assembly are particularly attractive for the realization of spin quantum bits, as they can be controllably positioned, electronically coupled and embedded into active devices. It has been predicted that the atomic-like electronic structure of such quantum dots suppresses coupling of the spin to the solid-state quantum dot environment, thus protecting the 'spin' quantum information against decoherence. Here we demonstrate a single electron spin memory device in which the electron spin can be programmed by frequency selective optical excitation. We use the device to prepare single electron spins in semiconductor quantum dots with a well defined orientation, and directly measure the intrinsic spin flip time and its dependence on magnetic field. A very long spin lifetime is obtained, with a lower limit of about 20 milliseconds at a magnetic field of 4 tesla and at 1 kelvin.

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Federal Register 2010, 2011, 2012, 2013, 2014

2011-09-27

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Single-handed helical carbonaceous nanotubes prepared using a pair of cationic low molecular weight gelators

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sun, Huayan; Wang, Qing; Guo, Yongmin

Highlights: • 3-aminophenol-formaldeyde resins were prepared through a templating method. • A pair of cationic gelators have been used as the templates. • Single-handed helical carbonaceous nanotubes were obtained after carbonization. • The carbonaceous nanotubes showed optical activity. - Abstract: We design a facile route to obtain enantiopure carbonaceous nanostructures, which have potential application as chiral sensors, electromagnetic wave absorbers, and asymmetric catalysts. A pair of cationic low molecular weight gelators was synthesized, which were able to self-assemble into twisted nanoribbons in ethanol at a concentration of 20 g L{sup −1} at 25 °C. Single-handed helical 3-aminophenol-formaldehyde resin nanotubes withmore » optical activity were prepared using the self-assembly of the low molecular weight gelators as templates. After carbonization, single-handed helical carbonaceous nanotubes were obtained and characterized using circular dichroism, wide-angle X-ray diffraction, field-emission scanning electron microscopy, transmission electron microscopy, and Raman spectroscopy. The results indicate that the walls of the nanotubes are amorphous carbon. Moreover, the left- and right-handed helical nanotubes exhibit opposite optical activity.« less

Single-Molecule Interfacial Electron Transfer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lu, H. Peter

This project is focused on the use of single-molecule high spatial and temporal resolved techniques to study molecular dynamics in condensed phase and at interfaces, especially, the complex reaction dynamics associated with electron and energy transfer rate processes. The complexity and inhomogeneity of the interfacial ET dynamics often present a major challenge for a molecular level comprehension of the intrinsically complex systems, which calls for both higher spatial and temporal resolutions at ultimate single-molecule and single-particle sensitivities. Combined single-molecule spectroscopy and electrochemical atomic force microscopy approaches are unique for heterogeneous and complex interfacial electron transfer systems because the static andmore » dynamic inhomogeneities can be identified and characterized by studying one molecule at a specific nanoscale surface site at a time. The goal of our project is to integrate and apply these spectroscopic imaging and topographic scanning techniques to measure the energy flow and electron flow between molecules and substrate surfaces as a function of surface site geometry and molecular structure. We have been primarily focusing on studying interfacial electron transfer under ambient condition and electrolyte solution involving both single crystal and colloidal TiO 2 and related substrates. The resulting molecular level understanding of the fundamental interfacial electron transfer processes will be important for developing efficient light harvesting systems and broadly applicable to problems in fundamental chemistry and physics. We have made significant advancement on deciphering the underlying mechanism of the complex and inhomogeneous interfacial electron transfer dynamics in dyesensitized TiO 2 nanoparticle systems that strongly involves with and regulated by molecule-surface interactions. We have studied interfacial electron transfer on TiO 2 nanoparticle surfaces by using ultrafast single-molecule spectroscopy and electrochemical AFM metal tip scanning microscopy, focusing on understanding the interfacial electron transfer dynamics at specific nanoscale electron transfer sites with high-spatially and temporally resolved topographic-and-spectroscopic characterization at individual molecule basis, characterizing single-molecule rate processes, reaction driving force, and molecule-substrate electronic coupling. One of the most significant characteristics of our new approach is that we are able to interrogate the complex interfacial electron transfer dynamics by actively pin-point energetic manipulation of the surface interaction and electronic couplings, beyond the conventional excitation and observation.« less

Single-Atom Catalyst of Platinum Supported on Titanium Nitride for Selective Electrochemical Reactions.

PubMed

Yang, Sungeun; Kim, Jiwhan; Tak, Young Joo; Soon, Aloysius; Lee, Hyunjoo

2016-02-05

As a catalyst, single-atom platinum may provide an ideal structure for platinum minimization. Herein, a single-atom catalyst of platinum supported on titanium nitride nanoparticles were successfully prepared with the aid of chlorine ligands. Unlike platinum nanoparticles, the single-atom active sites predominantly produced hydrogen peroxide in the electrochemical oxygen reduction with the highest mass activity reported so far. The electrocatalytic oxidation of small organic molecules, such as formic acid and methanol, also exhibited unique selectivity on the single-atom platinum catalyst. A lack of platinum ensemble sites changed the reaction pathway for the oxygen-reduction reaction toward a two-electron pathway and formic acid oxidation toward direct dehydrogenation, and also induced no activity for the methanol oxidation. This work demonstrates that single-atom platinum can be an efficient electrocatalyst with high mass activity and unique selectivity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Spatially-resolved mapping of history-dependent coupled electrochemical and electronical behaviors of electroresistive NiO

DOE PAGES

Sugiyama, Issei; Kim, Yunseok; Jesse, Stephen; ...

2014-10-22

Bias-induced oxygen ion dynamics underpins a broad spectrum of electroresistive and memristive phenomena in oxide materials. Although widely studied by device-level and local voltage-current spectroscopies, the relationship between electroresistive phenomena, local electrochemical behaviors, and microstructures remains elusive. Here, the interplay between history-dependent electronic transport and electrochemical phenomena in a NiO single crystalline thin film with a number of well-defined defect types is explored on the nanometer scale using an atomic force microscopy-based technique. A variety of electrochemically-active regions were observed and spatially resolved relationship between the electronic and electrochemical phenomena was revealed. The regions with pronounced electroresistive activity were furthermore » correlated with defects identified by scanning transmission electron microscopy. Using fully coupled mechanical-electrochemical modeling, we illustrate that the spatial distribution of strain plays an important role in electrochemical and electroresistive phenomena. In conclusion, these studies illustrate an approach for simultaneous mapping of the electronic and ionic transport on a single defective structure level such as dislocations or interfaces, and pave the way for creating libraries of defect-specific electrochemical responses.« less

The Energy Spectrum of Solar Energetic Electrons

NASA Astrophysics Data System (ADS)

Wang, L.; Yang, L.; Krucker, S.; Wimmer-Schweingruber, R. F.; Bale, S. D.

2015-12-01

Here we present a statistical survey of the energy spectrum of solar energetic electron events (SEEs) observed by the WIND 3DP instrument from 1995 though 2014. For SEEs with the minimum energy below 10 keV and the maximum energy above 100 keV, ~85% (~2%) have a double-power-law energy spectrum with a steepening (hardening) above the break energy, while ~13% have a single-power-law energy spectrum at all energies. The average spectral index is ~2.4 below the energy break and is ~4.0 above the energy break. For SEEs detected only at energies <10 keV (>20 keV), they generally show a single-power-law spectrum with the average index of ~3.0 (~3.3). The spectrum of SEEs detected only below 10 keV appears to get harder with increasing solar activity, but the spectrum of SEEs with higher-energy electrons shows no clear correlation with solar activity. We will also investigate whether the observed energy spectrum of SEEs at 1 AU mainly reflects the electron acceleration at the Sun or the electron transport in the interplanetary medium.

Interactions between C and Cu atoms in single-layer graphene: direct observation and modelling.

PubMed

Kano, Emi; Hashimoto, Ayako; Kaneko, Tomoaki; Tajima, Nobuo; Ohno, Takahisa; Takeguchi, Masaki

2016-01-07

Metal doping into the graphene lattice has been studied recently to develop novel nanoelectronic devices and to gain an understanding of the catalytic activities of metals in nanocarbon structures. Here we report the direct observation of interactions between Cu atoms and single-layer graphene by transmission electron microscopy. We document stable configurations of Cu atoms in the graphene sheet and unique transformations of graphene promoted by Cu atoms. First-principles calculations based on density functional theory reveal a reduction of energy barrier that caused rotation of C-C bonds near Cu atoms. We discuss two driving forces, electron irradiation and in situ heating, and conclude that the observed transformations were mainly promoted by electron irradiation. Our results suggest that individual Cu atoms can promote reconstruction of single-layer graphene.

Electron impact action spectroscopy of mass/charge selected macromolecular ions: Inner-shell excitation of ubiquitin protein

NASA Astrophysics Data System (ADS)

Ranković, Miloš Lj.; Giuliani, Alexandre; Milosavljević, Aleksandar R.

2016-02-01

We have performed inner-shell electron impact action spectroscopy of mass and charge selected macromolecular ions. For this purpose, we have coupled a focusing electron gun with a linear quadrupole ion trap mass spectrometer. This experiment represents a proof of principle that an energy-tunable electron beam can be used in combination with radio frequency traps as an activation method in tandem mass spectrometry (MS2) and allows performing action spectroscopy. Electron impact MS2 spectra of multiply protonated ubiquitin protein ion have been recorded at incident electron energies around the carbon 1 s excitation. Both MS2 and single ionization energy dependence spectra are compared with literature data obtained using the soft X-ray activation conditions.

A reversible single-molecule switch based on activated antiaromaticity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yin, Xiaodong; Zang, Yaping; Zhu, Liangliang

Single-molecule electronic devices provide researchers with an unprecedented ability to relate novel physical phenomena to molecular chemical structures. Typically, conjugated aromatic molecular backbones are relied upon to create electronic devices, where the aromaticity of the building blocks is used to enhance conductivity. We capitalize on the classical physical organic chemistry concept of Hückel antiaromaticity by demonstrating a single-molecule switch that exhibits low conductance in the neutral state and, upon electrochemical oxidation, reversibly switches to an antiaromatic high-conducting structure. We form single-molecule devices using the scanning tunneling microscope–based break-junction technique and observe an on/off ratio of ~70 for a thiophenylidene derivativemore » that switches to an antiaromatic state with 6-4-6-p electrons. Through supporting nuclear magnetic resonance measurements, we show that the doubly oxidized core has antiaromatic character and we use density functional theory calculations to rationalize the origin of the high-conductance state for the oxidized single-molecule junction. Together, our work demonstrates how the concept of antiaromaticity can be exploited to create single-molecule devices that are highly conducting.« less

A reversible single-molecule switch based on activated antiaromaticity

DOE PAGES

Yin, Xiaodong; Zang, Yaping; Zhu, Liangliang; ...

2017-10-27

Single-molecule electronic devices provide researchers with an unprecedented ability to relate novel physical phenomena to molecular chemical structures. Typically, conjugated aromatic molecular backbones are relied upon to create electronic devices, where the aromaticity of the building blocks is used to enhance conductivity. We capitalize on the classical physical organic chemistry concept of Hückel antiaromaticity by demonstrating a single-molecule switch that exhibits low conductance in the neutral state and, upon electrochemical oxidation, reversibly switches to an antiaromatic high-conducting structure. We form single-molecule devices using the scanning tunneling microscope–based break-junction technique and observe an on/off ratio of ~70 for a thiophenylidene derivativemore » that switches to an antiaromatic state with 6-4-6-p electrons. Through supporting nuclear magnetic resonance measurements, we show that the doubly oxidized core has antiaromatic character and we use density functional theory calculations to rationalize the origin of the high-conductance state for the oxidized single-molecule junction. Together, our work demonstrates how the concept of antiaromaticity can be exploited to create single-molecule devices that are highly conducting.« less

Electron attachment to DNA single strands: gas phase and aqueous solution.

PubMed

Gu, Jiande; Xie, Yaoming; Schaefer, Henry F

2007-01-01

The 2'-deoxyguanosine-3',5'-diphosphate, 2'-deoxyadenosine-3',5'-diphosphate, 2'-deoxycytidine-3',5'-diphosphate and 2'-deoxythymidine-3',5'-diphosphate systems are the smallest units of a DNA single strand. Exploring these comprehensive subunits with reliable density functional methods enables one to approach reasonable predictions of the properties of DNA single strands. With these models, DNA single strands are found to have a strong tendency to capture low-energy electrons. The vertical attachment energies (VEAs) predicted for 3',5'-dTDP (0.17 eV) and 3',5'-dGDP (0.14 eV) indicate that both the thymine-rich and the guanine-rich DNA single strands have the ability to capture electrons. The adiabatic electron affinities (AEAs) of the nucleotides considered here range from 0.22 to 0.52 eV and follow the order 3',5'-dTDP > 3',5'-dCDP > 3',5'-dGDP > 3',5'-dADP. A substantial increase in the AEA is observed compared to that of the corresponding nucleic acid bases and the corresponding nucleosides. Furthermore, aqueous solution simulations dramatically increase the electron attracting properties of the DNA single strands. The present investigation illustrates that in the gas phase, the excess electron is situated both on the nucleobase and on the phosphate moiety for DNA single strands. However, the distribution of the extra negative charge is uneven. The attached electron favors the base moiety for the pyrimidine, while it prefers the 3'-phosphate subunit for the purine DNA single strands. In contrast, the attached electron is tightly bound to the base fragment for the cytidine, thymidine and adenosine nucleotides, while it almost exclusively resides in the vicinity of the 3'-phosphate group for the guanosine nucleotides due to the solvent effects. The comparatively low vertical detachment energies (VDEs) predicted for 3',5'-dADP(-) (0.26 eV) and 3',5'-dGDP(-) (0.32 eV) indicate that electron detachment might compete with reactions having high activation barriers such as glycosidic bond breakage. However, the radical anions of the pyrimidine nucleotides with high VDE are expected to be electronically stable. Thus the base-centered radical anions of the pyrimidine nucleotides might be the possible intermediates for DNA single-strand breakage.

Mesh electronics: a new paradigm for tissue-like brain probes.

PubMed

Hong, Guosong; Yang, Xiao; Zhou, Tao; Lieber, Charles M

2018-06-01

Existing implantable neurotechnologies for understanding the brain and treating neurological diseases have intrinsic properties that have limited their capability to achieve chronically-stable brain interfaces with single-neuron spatiotemporal resolution. These limitations reflect what has been dichotomy between the structure and mechanical properties of living brain tissue and non-living neural probes. To bridge the gap between neural and electronic networks, we have introduced the new concept of mesh electronics probes designed with structural and mechanical properties such that the implant begins to 'look and behave' like neural tissue. Syringe-implanted mesh electronics have led to the realization of probes that are neuro-attractive and free of the chronic immune response, as well as capable of stable long-term mapping and modulation of brain activity at the single-neuron level. This review provides a historical overview of a 10-year development of mesh electronics by highlighting the tissue-like design, syringe-assisted delivery, seamless neural tissue integration, and single-neuron level chronic recording stability of mesh electronics. We also offer insights on unique near-term opportunities and future directions for neuroscience and neurology that now are available or expected for mesh electronics neurotechnologies. Copyright © 2017 The Authors. Published by Elsevier Ltd.. All rights reserved.

dc-plasma-sprayed electronic-tube device

DOEpatents

Meek, T.T.

1982-01-29

An electronic tube and associated circuitry which is produced by dc plasma arc spraying techniques is described. The process is carried out in a single step automated process whereby both active and passive devices are produced at very low cost. The circuitry is extremely reliable and is capable of functioning in both high radiation and high temperature environments. The size of the electronic tubes produced are more than an order of magnitude smaller than conventional electronic tubes.

Quasi-four-particle first-order Faddeev-Watson-Lovelace terms in proton-helium scattering

NASA Astrophysics Data System (ADS)

Safarzade, Zohre; Akbarabadi, Farideh Shojaei; Fathi, Reza; Brunger, Michael J.; Bolorizadeh, Mohammad A.

2017-06-01

The Faddeev-Watson-Lovelace equations, which are typically used for solving three-particle scattering problems, are based on the assumption of target having one active electron while the other electrons remain passive during the collision process. So, in the case of protons scattering from helium or helium-like targets, in which there are two bound-state electrons, the passive electron has a static role in the collision channel to be studied. In this work, we intend to assign a dynamic role to all the target electrons, as they are physically active in the collision. By including an active role for the second electron in proton-helium-like collisions, a new form of the Faddeev-Watson-Lovelace integral equations is needed, in which there is no disconnected kernel. We consider the operators and the wave functions associated with the electrons to obey the Pauli exclusion principle, as the electrons are indistinguishable. In addition, a quasi-three-particle collision is assumed in the initial channel, where the electronic cloud is represented as a single identity in the collision.

Active parallel redundancy for electronic integrator-type control circuits

NASA Technical Reports Server (NTRS)

Peterson, R. A.

1971-01-01

Circuit extends concept of redundant feedback control from type-0 to type-1 control systems. Inactive channels are slaves to the active channel, if latter fails, it is rejected and slave channel is activated. High reliability and elimination of single-component catastrophic failure are important in closed-loop control systems.

Theoretical aspects of femtosecond double-pump single-molecule spectroscopy. I. Weak-field regime.

PubMed

Palacino-González, Elisa; Gelin, Maxim F; Domcke, Wolfgang

2017-12-13

We present a theoretical description of double-pump femtosecond single-molecule signals with fluorescence detection. We simulate these signals in the weak-field regime for a model mimicking a chromophore with a Franck-Condon-active vibrational mode. We establish several signatures of these signals which are characteristic for the weak-field regime. The signatures include the quenching of vibrational beatings by electronic dephasing and a pronounced tilt of the phase-time profiles in the two-dimensional (2D) maps. We study how environment-induced slow modulations of the electronic dephasing and relevant chromophore parameters (electronic energy, orientation, vibrational frequency and relative shift of the potential energy surfaces) affect the signals.

Photoresponses in Gold Nanoparticle Single-Electron Transistors with Molecular Floating Gates

NASA Astrophysics Data System (ADS)

Noguchi, Yutaka; Yamamoto, Makoto; Ishii, Hisao; Ueda, Rieko; Terui, Toshifumi; Imazu, Keisuke; Tamada, Kaoru; Sakano, Takeshi; Matsuda, Kenji

2013-11-01

We have proposed a simple method of activating advanced functions in single-electron transistors (SETs) based on the specific properties of individual molecules. As a prototype, we fabricated a copper phthalocyanine (CuPc)-doped SET. The device consists of a gold-nanoparticle (GNP)-based SET doped with CuPc as a photoresponsive floating gate. In this paper, we report the details of the photoresponses of the CuPc-doped SET, such as conductance switching, sensitivity to the wavelength of the incident light, and multiple induced states.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Guanqun; Zou, Ningmu; Chen, Bo

Compared with their monometallic counterparts, bimetallic nanoparticles often show enhanced catalytic activity associated with the bimetallic interface. Direct quantitation of catalytic activity at the bimetallic interface is important for understanding the enhancement mechanism, but challenging experimentally. Here using single-molecule super-resolution catalysis imaging in correlation with electron microscopy, we report the first quantitative visualization of enhanced bimetallic activity within single bimetallic nanoparticles. We focus on heteronuclear bimetallic PdAu nanoparticles that present a well-defined Pd–Au bimetallic interface in catalyzing a photodriven fluorogenic disproportionation reaction. Our approach also enables a direct comparison between the bimetallic and monometallic regions within the same nanoparticle. Theoreticalmore » calculations further provide insights into the electronic nature of N–O bond activation of the reactant (resazurin) adsorbed on bimetallic sites. Subparticle activity correlation between bimetallic enhancement and monometallic activity suggests that the favorable locations to construct bimetallic sites are those monometallic sites with higher activity, leading to a strategy for making effective bimetallic nanocatalysts. Furthermore, the results highlight the power of super-resolution catalysis imaging in gaining insights that could help improve nanocatalysts.« less

Cucumber possesses a single terminal alternative oxidase gene that is upregulated by cold stress and in the mosaic (MSC) mitochondrial mutants

USDA-ARS?s Scientific Manuscript database

In plants alternative oxidase (AOX) is an important nuclear-encoded enzyme active in the mitochondrial electron-transport chain, transferring electrons from ubiquinol to alternative oxidase instead of the cytochrome pathway to yield ubiquinone and water. AOX protects against unexpected inhibition of...

Electron attachment to DNA single strands: gas phase and aqueous solution

PubMed Central

Gu, Jiande; Xie, Yaoming; Schaefer, Henry F.

2007-01-01

The 2′-deoxyguanosine-3′,5′-diphosphate, 2′-deoxyadenosine-3′,5′-diphosphate, 2′-deoxycytidine-3′,5′-diphosphate and 2′-deoxythymidine-3′,5′-diphosphate systems are the smallest units of a DNA single strand. Exploring these comprehensive subunits with reliable density functional methods enables one to approach reasonable predictions of the properties of DNA single strands. With these models, DNA single strands are found to have a strong tendency to capture low-energy electrons. The vertical attachment energies (VEAs) predicted for 3′,5′-dTDP (0.17 eV) and 3′,5′-dGDP (0.14 eV) indicate that both the thymine-rich and the guanine-rich DNA single strands have the ability to capture electrons. The adiabatic electron affinities (AEAs) of the nucleotides considered here range from 0.22 to 0.52 eV and follow the order 3′,5′-dTDP > 3′,5′-dCDP > 3′,5′-dGDP > 3′,5′-dADP. A substantial increase in the AEA is observed compared to that of the corresponding nucleic acid bases and the corresponding nucleosides. Furthermore, aqueous solution simulations dramatically increase the electron attracting properties of the DNA single strands. The present investigation illustrates that in the gas phase, the excess electron is situated both on the nucleobase and on the phosphate moiety for DNA single strands. However, the distribution of the extra negative charge is uneven. The attached electron favors the base moiety for the pyrimidine, while it prefers the 3′-phosphate subunit for the purine DNA single strands. In contrast, the attached electron is tightly bound to the base fragment for the cytidine, thymidine and adenosine nucleotides, while it almost exclusively resides in the vicinity of the 3′-phosphate group for the guanosine nucleotides due to the solvent effects. The comparatively low vertical detachment energies (VDEs) predicted for 3′,5′-dADP− (0.26 eV) and 3′,5′-dGDP− (0.32 eV) indicate that electron detachment might compete with reactions having high activation barriers such as glycosidic bond breakage. However, the radical anions of the pyrimidine nucleotides with high VDE are expected to be electronically stable. Thus the base-centered radical anions of the pyrimidine nucleotides might be the possible intermediates for DNA single-strand breakage. PMID:17660189

Development and application of accurate analytical models for single active electron potentials

NASA Astrophysics Data System (ADS)

Miller, Michelle; Jaron-Becker, Agnieszka; Becker, Andreas

2015-05-01

The single active electron (SAE) approximation is a theoretical model frequently employed to study scenarios in which inner-shell electrons may productively be treated as frozen spectators to a physical process of interest, and accurate analytical approximations for these potentials are sought as a useful simulation tool. Density function theory is often used to construct a SAE potential, requiring that a further approximation for the exchange correlation functional be enacted. In this study, we employ the Krieger, Li, and Iafrate (KLI) modification to the optimized-effective-potential (OEP) method to reduce the complexity of the problem to the straightforward solution of a system of linear equations through simple arguments regarding the behavior of the exchange-correlation potential in regions where a single orbital dominates. We employ this method for the solution of atomic and molecular potentials, and use the resultant curve to devise a systematic construction for highly accurate and useful analytical approximations for several systems. Supported by the U.S. Department of Energy (Grant No. DE-FG02-09ER16103), and the U.S. National Science Foundation (Graduate Research Fellowship, Grants No. PHY-1125844 and No. PHY-1068706).

Balancing single- and multi-reference correlation in the chemiluminescent reaction of dioxetanone using the anti-Hermitian contracted Schrödinger equation.

PubMed

Greenman, Loren; Mazziotti, David A

2011-05-07

Direct computation of energies and two-electron reduced density matrices (2-RDMs) from the anti-Hermitian contracted Schrödinger equation (ACSE) [D. A. Mazziotti, Phys. Rev. Lett. 97, 143002 (2006)], it is shown, recovers both single- and multi-reference electron correlation in the chemiluminescent reaction of dioxetanone especially in the vicinity of the conical intersection where strong correlation is important. Dioxetanone, the light-producing moiety of firefly luciferin, efficiently converts chemical energy into light by accessing its excited-state surface via a conical intersection. Our previous active-space 2-RDM study of dioxetanone [L. Greenman and D. A. Mazziotti, J. Chem. Phys. 133, 164110 (2010)] concluded that correlating 16 electrons in 13 (active) orbitals is required for realistic surfaces without correlating the remaining (inactive) orbitals. In this paper we pursue two complementary goals: (i) to correlate the inactive orbitals in 2-RDMs along dioxetanone's reaction coordinate and compare these results with those from multireference second-order perturbation theory (MRPT2) and (ii) to assess the size of the active space-the number of correlated electrons and orbitals-required by both MRPT2 and ACSE for accurate energies and surfaces. While MRPT2 recovers very different amounts of correlation with (4,4) and (16,13) active spaces, the ACSE obtains a similar amount of correlation energy with either active space. Nevertheless, subtle differences in excitation energies near the conical intersection suggest that the (16,13) active space is necessary to determine both energetic details and properties. Strong electron correlation is further assessed through several RDM-based metrics including (i) total and relative energies, (ii) the von Neumann entropy based on the 1-electron RDM, as well as the (iii) infinity and (iv) squared Frobenius norms based on the cumulant 2-RDM.

Probing Single Pt Atoms in Complex Intermetallic Al13Fe4.

PubMed

Yamada, Tsunetomo; Kojima, Takayuki; Abe, Eiji; Kameoka, Satoshi; Murakami, Yumi; Gille, Peter; Tsai, An Pang

2018-03-21

The atomic structure of a 0.2 atom % Pt-doped complex metallic alloy, monoclinic Al 13 Fe 4 , was investigated using a single crystal prepared by the Czochralski method. High-angle annular dark-field scanning transmission electron microscopy showed that the Pt atoms were dispersed as single atoms and substituted at Fe sites in Al 13 Fe 4 . Single-crystal X-ray structural analysis revealed that the Pt atoms preferentially substitute at Fe(1). Unlike those that have been reported, Pt single atoms in the surface layers showed lower activity and selectivity than those of Al 2 Pt and bulk Pt for propyne hydrogenation, indicating that the active state of a given single-atom Pt site is strongly dominated by the bonding to surrounding Al atoms.

In situ TEM observation of preferential amorphization in single crystal Si nanowire

NASA Astrophysics Data System (ADS)

Su, Jiangbin; Zhu, Xianfang

2018-06-01

The nanoinstability of a single crystal Si nanowire under electron beam irradiation was in situ investigated at room temperature by the transmission electron microscopy technique. It was observed that the Si nanowire amorphized preferentially from the surface towards the center, with the increasing of the electron dose. In contrast, in the center of the Si nanowire the amorphization seemed much more difficult, being accompanied by the rotation of crystal grains and the compression of d-spacing. Such a preferential amorphization, which is athermally induced by the electron beam irradiation, can be well accounted for by our proposed concepts of the nanocurvature effect and the energetic beam-induced athermal activation effect, while the classical knock-on mechanism and the electron beam heating effect seem inadequate to explain these processes. Furthermore, the findings revealed the difference of amorphization between a Si nanowire and a Si film under electron beam irradiation. Also, the findings have important implications for the nanoinstability and nanoprocessing of future Si nanowire-based devices.

In situ TEM observation of preferential amorphization in single crystal Si nanowire.

PubMed

Su, Jiangbin; Zhu, Xianfang

2018-06-08

The nanoinstability of a single crystal Si nanowire under electron beam irradiation was in situ investigated at room temperature by the transmission electron microscopy technique. It was observed that the Si nanowire amorphized preferentially from the surface towards the center, with the increasing of the electron dose. In contrast, in the center of the Si nanowire the amorphization seemed much more difficult, being accompanied by the rotation of crystal grains and the compression of d-spacing. Such a preferential amorphization, which is athermally induced by the electron beam irradiation, can be well accounted for by our proposed concepts of the nanocurvature effect and the energetic beam-induced athermal activation effect, while the classical knock-on mechanism and the electron beam heating effect seem inadequate to explain these processes. Furthermore, the findings revealed the difference of amorphization between a Si nanowire and a Si film under electron beam irradiation. Also, the findings have important implications for the nanoinstability and nanoprocessing of future Si nanowire-based devices.

Radiative one- and two-electron transitions into the empty K shell of He-like ions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kadrekar, Riddhi; Natarajan, L.

2011-12-15

The branching ratios between the single and double electron radiative transitions to empty K shell in He-like ions with 2s2p configuration are evaluated for 15 ions with 4{<=}Z{<=}26 using fully relativistic multiconfiguration Dirac-Fock wavefunctions in the active space approximation. The effects of configuration interaction and Breit contributions on the transition parameters have been analyzed in detail. Though the influence of Breit interaction on the electric dipole allowed one-electron radiative transitions is negligible, it substantially changes the spin-forbidden rates and the two-electron one-photon transition probabilities. Also, while the single electron transition rates are gauge independent, the correlated double-electron probabilities are foundmore » to be gauge sensitive. The probable uncertainties in the computed transition rates have been evaluated by considering the line strengths and the differences between the calculated and experimental transition energies as accuracy indicators. The present results are compared with other available experimental and theoretical data.« less

Long term effects of lipopolysaccharide on satellite glial cells in mouse dorsal root ganglia

DOE Office of Scientific and Technical Information (OSTI.GOV)

Blum, E.; Procacci, P.; Conte, V.

Lipopolysaccharide (LPS) has been used extensively to study neuroinflammation, but usually its effects were examined acutely (24 h<). We have shown previously that a single intraperitoneal LPS injection activated satellite glial cells (SGCs) in mouse dorsal root ganglia (DRG) and altered several functional parameters in these cells for at least one week. Here we asked whether the LPS effects would persist for 1 month. We injected mice with a single LPS dose and tested pain behavior, assessed SGCs activation in DRG using glial fibrillary acidic protein (GFAP) immunostaining, and injected a fluorescent dye intracellularly to study intercellular coupling. Electron microscopymore » was used to quantitate changes in gap junctions. We found that at 30 days post-LPS the threshold to mechanical stimulation was lower than in controls. GFAP expression, as well as the magnitude of dye coupling among SGCs were greater than in controls. Electron microscopy analysis supported these results, showing a greater number of gap junctions and an abnormal growth of SGC processes. These changes were significant, but less prominent than at 7 days post-LPS. We conclude that a single LPS injection exerts long-term behavioral and cellular changes. The results are consistent with the idea that SGC activation contributes to hyperalgesia. - Highlights: • A single lipopolysaccharides injection activated glia in mouse dorsal root ganglia for 30 days. • This was accompanied by increased communications by gap junctions among glia and by hyperalgesia. • Glial activation and coupling may contribute to chronic pain.« less

Project Physics Handbook 5, Models of the Atom.

ERIC Educational Resources Information Center

Harvard Univ., Cambridge, MA. Harvard Project Physics.

Five experiments and 19 activities are presented in this Unit 5 handbook. The experiments are related to electrolysis, charge-to-mass ratio, elementary charge determination, photoelectric effects, and spectroscopic analyses. The activities are concerned with Dalton's theory, water electrolysis, periodic tables, single-electron plating, cloud…

a New Method to Prepare the Novel Anatase TiO2

NASA Astrophysics Data System (ADS)

Cui, Guanjun; Xu, Zhanxia; Wang, Yan; Zhang, Min; Yang, Jianjun

In this paper, a kind of novel anatase TiO2 nanoparticle with single-electron-trapped oxygen vacancies was prepared by hydrothermal treated nanotube titanic acid. The morphology, structure, and properties of the products were characterized by transmission electron microscope, X-ray diffraction, electron spin resonance, and photoluminescence. Photocatalytic decolorization of the Methylene Blue solution was carried out in the visible light region and showed a high photocatalytic activity.

On the dynamical nature of the active center in a single-site photocatalyst visualized by 4D ultrafast electron microscopy

PubMed Central

Yoo, Byung-Kuk; Su, Zixue; Thomas, John Meurig; Zewail, Ahmed H.

2016-01-01

Understanding the dynamical nature of the catalytic active site embedded in complex systems at the atomic level is critical to developing efficient photocatalytic materials. Here, we report, using 4D ultrafast electron microscopy, the spatiotemporal behaviors of titanium and oxygen in a titanosilicate catalytic material. The observed changes in Bragg diffraction intensity with time at the specific lattice planes, and with a tilted geometry, provide the relaxation pathway: the Ti4+=O2− double bond transformation to a Ti3+−O1− single bond via the individual atomic displacements of the titanium and the apical oxygen. The dilation of the double bond is up to 0.8 Å and occurs on the femtosecond time scale. These findings suggest the direct catalytic involvement of the Ti3+−O1− local structure, the significance of nonthermal processes at the reactive site, and the efficient photo-induced electron transfer that plays a pivotal role in many photocatalytic reactions. PMID:26729878

75 FR 16817 - 2010 Scientific Meeting of the National Antimicrobial Resistance Monitoring System; Public...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-04-02

... resistance monitoring and research, including activities in other national programs. Date and Time: The... space available basis beginning at 8 a.m. on the day of the meeting. If you need special accommodations... electronic comments to http://www.regulations.gov . Submit a single copy of electronic comments or two paper...

Efficient numerical method for investigating diatomic molecules with single active electron subjected to intense and ultrashort laser fields

NASA Astrophysics Data System (ADS)

Kiss, Gellért Zsolt; Borbély, Sándor; Nagy, Ladislau

2017-12-01

We have presented here an efficient numerical approach for the ab initio numerical solution of the time-dependent Schrödinger Equation describing diatomic molecules, which interact with ultrafast laser pulses. During the construction of the model we have assumed a frozen nuclear configuration and a single active electron. In order to increase efficiency our system was described using prolate spheroidal coordinates, where the wave function was discretized using the finite-element discrete variable representation (FE-DVR) method. The discretized wave functions were efficiently propagated in time using the short-iterative Lanczos algorithm. As a first test we have studied here how the laser induced bound state dynamics in H2+ is influenced by the strength of the driving laser field.

Systematic Conversion of Single Walled Carbon Nanotubes into n-type Thermoelectric Materials by Molecular Dopants

PubMed Central

Nonoguchi, Yoshiyuki; Ohashi, Kenji; Kanazawa, Rui; Ashiba, Koji; Hata, Kenji; Nakagawa, Tetsuya; Adachi, Chihaya; Tanase, Tomoaki; Kawai, Tsuyoshi

2013-01-01

Thermoelectrics is a challenging issue for modern and future energy conversion and recovery technology. Carbon nanotubes are promising active thermoelectic materials owing to their narrow bandgap energy and high charge carrier mobility, and they can be integrated into flexible thermoelectrics that can recover any waste heat. We here report air-stable n-type single walled carbon nanotubes with a variety of weak electron donors in the range of HOMO level between ca. −4.4 eV and ca. −5.6 eV, in which partial uphill electron injection from the dopant to the conduction band of single walled carbon nanotubes is dominant. We display flexible films of the doped single walled carbon nanotubes possessing significantly large thermoelectric effect, which is applicable to flexible ambient thermoelectric modules. PMID:24276090

Electron attachment-induced DNA single-strand breaks at the pyrimidine sites

PubMed Central

Gu, Jiande; Wang, Jing; Leszczynski, Jerzy

2010-01-01

To elucidate the contribution of pyrimidine in DNA strand breaks caused by low-energy electrons (LEEs), theoretical investigations of the LEE attachment-induced C3′–O3′, and C5′–O5′ σ bond as well as N-glycosidic bond breaking of 2′-deoxycytidine-3′,5′-diphosphate and 2′-deoxythymidine-3′,5′-diphosphate were performed using the B3LYP/DZP++ approach. The base-centered radical anions are electronically stable enough to assure that either the C–O or glycosidic bond breaking processes might compete with the electron detachment and yield corresponding radical fragments and anions. In the gas phase, the computed glycosidic bond breaking activation energy (24.1 kcal/mol) excludes the base release pathway. The low-energy barrier for the C3′–O3′ σ bond cleavage process (∼6.0 kcal/mol for both cytidine and thymidine) suggests that this reaction pathway is the most favorable one as compared to other possible pathways. On the other hand, the relatively low activation energy barrier (∼14 kcal/mol) for the C5′–O5′ σ bond cleavage process indicates that this bond breaking pathway could be possible, especially when the incident electrons have relatively high energy (a few electronvolts). The presence of the polarizable medium greatly increases the activation energies of either C–O σ bond cleavage processes or the N-glycosidic bond breaking process. The only possible pathway that dominates the LEE-induced DNA single strands in the presence of the polarizable surroundings (such as in an aqueous solution) is the C3′–O3′ σ bond cleavage (the relatively low activation energy barrier, ∼13.4 kcal/mol, has been predicted through a polarizable continuum model investigation). The qualitative agreement between the ratio for the bond breaks of C5′–O5′, C3′–O3′ and N-glycosidic bonds observed in the experiment of oligonucleotide tetramer CGAT and the theoretical sequence of the bond breaking reaction pathways have been found. This consistency between the theoretical predictions and the experimental observations provides strong supportive evidences for the base-centered radical anion mechanism of the LEE-induced single-strand bond breaking around the pyrimidine sites of the DNA single strands. PMID:20430827

Avoided crossings, conical intersections, and low-lying excited states with a single reference method: the restricted active space spin-flip configuration interaction approach.

PubMed

Casanova, David

2012-08-28

The restricted active space spin-flip CI (RASCI-SF) performance is tested in the electronic structure computation of the ground and the lowest electronically excited states in the presence of near-degeneracies. The feasibility of the method is demonstrated by analyzing the avoided crossing between the ionic and neutral singlet states of LiF along the molecular dissociation. The two potential energy surfaces (PESs) are explored by means of the energies of computed adiabatic and approximated diabatic states, dipole moments, and natural orbital electronic occupancies of both states. The RASCI-SF methodology is also used to study the ground and first excited singlet surface crossing involved in the double bond isomerization of ethylene, as a model case. The two-dimensional PESs of the ground (S(0)) and excited (S(1)) states are calculated for the complete configuration space of torsion and pyramidalization molecular distortions. The parameters that define the state energetics in the vicinity of the S(0)/S(1) conical intersection region are compared to complete active space self-consistent field (CASSCF) results. These examples show that it is possible to describe strongly correlated electronic states using a single reference methodology without the need to expand the wavefunction to high levels of collective excitations. Finally, RASCI is also examined in the electronic structure characterization of the ground and 2(1)A(g)(-), 1(1)B(u)(+), 1(1)B(u)(-), and 1(3)B(u)(-) states of all-trans polyenes with two to seven double bonds and beyond. Transition energies are compared to configuration interaction singles, time-dependent density functional theory (TDDFT), CASSCF, and its second-order perturbation correction calculations, and to experimental data. The capability of RASCI-SF to describe the nature and properties of each electronic state is discussed in detail. This example is also used to expose the properties of different truncations of the RASCI wavefunction and to show the possibility to use an excitation operator with any number of α-to-β electronic promotions.

Distributions of methyl group rotational barriers in polycrystalline organic solids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Beckmann, Peter A., E-mail: pbeckman@brynmawr.edu, E-mail: wangxianlong@uestc.edu.cn; Conn, Kathleen G.; Division of Education and Human Services, Neumann University, One Neumann Drive, Aston, Pennsylvania 19014-1298

We bring together solid state {sup 1}H spin-lattice relaxation rate measurements, scanning electron microscopy, single crystal X-ray diffraction, and electronic structure calculations for two methyl substituted organic compounds to investigate methyl group (CH{sub 3}) rotational dynamics in the solid state. Methyl group rotational barrier heights are computed using electronic structure calculations, both in isolated molecules and in molecular clusters mimicking a perfect single crystal environment. The calculations are performed on suitable clusters built from the X-ray diffraction studies. These calculations allow for an estimate of the intramolecular and the intermolecular contributions to the barrier heights. The {sup 1}H relaxation measurements,more » on the other hand, are performed with polycrystalline samples which have been investigated with scanning electron microscopy. The {sup 1}H relaxation measurements are best fitted with a distribution of activation energies for methyl group rotation and we propose, based on the scanning electron microscopy images, that this distribution arises from molecules near crystallite surfaces or near other crystal imperfections (vacancies, dislocations, etc.). An activation energy characterizing this distribution is compared with a barrier height determined from the electronic structure calculations and a consistent model for methyl group rotation is developed. The compounds are 1,6-dimethylphenanthrene and 1,8-dimethylphenanthrene and the methyl group barriers being discussed and compared are in the 2–12 kJ mol{sup −1} range.« less

Single Molecule Enzymology via Nanoelectronic Circuits

NASA Astrophysics Data System (ADS)

Collins, Philip

Traditional single-molecule techniques rely on fluorescence or force transduction to monitor conformational changes and biochemical activity. Recent demonstrations of single-molecule monitoring with electronic transistors are poised to add to the single-molecule research toolkit. The transistor-based technique is sensitive to the motion of single charged side chain residues and can transduce those motions with microsecond resolution, opening the doors to single-molecule enzymology with unprecedented resolution. Furthermore, the solid-state platform provides opportunities for parallelization in arrays and long-duration monitoring of one molecule's activity or processivity, all without the limitations caused by photo-oxidation or mutagenic fluorophore incorporation. This presentation will review some of these advantages and their particular application to DNA polymerase I processing single-stranded DNA templates. This research was supported financially by the NIH NCI (R01 CA133592-01), the NIH NIGMS (1R01GM106957-01) and the NSF (DMR-1104629 and ECCS-1231910).

Dynamic defect correlations dominate activated electronic transport in SrTiO3

PubMed Central

Snijders, Paul C.; Şen, Cengiz; McConnell, Michael P.; Ma, Ying-Zhong; May, Andrew F.; Herklotz, Andreas; Wong, Anthony T.; Ward, T. Zac

2016-01-01

Strontium titanate (SrTiO3, STO) is a critically important material for the study of emergent electronic phases in complex oxides, as well as for the development of applications based on their heterostructures. Despite the large body of knowledge on STO, there are still many uncertainties regarding the role of defects in the properties of STO, including their influence on ferroelectricity in bulk STO and ferromagnetism in STO-based heterostructures. We present a detailed analysis of the decay of persistent photoconductivity in STO single crystals with defect concentrations that are relatively low but significantly affect their electronic properties. The results show that photo-activated electron transport cannot be described by a superposition of the properties due to independent point defects as current models suggest but is, instead, governed by defect complexes that interact through dynamic correlations. These results emphasize the importance of defect correlations for activated electronic transport properties of semiconducting and insulating perovskite oxides. PMID:27443503

Dynamic defect correlations dominate activated electronic transport in SrTiO 3

DOE PAGES

Snijders, Paul C.; Sen, Cengiz; McConnell, Michael P.; ...

2016-07-22

Strontium titanate (SrTiO 3, STO) is a critically important material for the study of emergent electronic phases in complex oxides, as well as for the development of applications based on their heterostructures. Despite the large body of knowledge on STO, there are still many uncertainties regarding the role of defects in the properties of STO, including their influence on ferroelectricity in bulk STO and ferromagnetism in STO-based heterostructures. In this paper, we present a detailed analysis of the decay of persistent photoconductivity in STO single crystals with defect concentrations that are relatively low but significantly affect their electronic properties. Themore » results show that photo-activated electron transport cannot be described by a superposition of the properties due to independent point defects as current models suggest but is, instead, governed by defect complexes that interact through dynamic correlations. In conclusion, these results emphasize the importance of defect correlations for activated electronic transport properties of semiconducting and insulating perovskite oxides.« less

Label-Free Direct Electronic Detection of Biomolecules with Amorphous Silicon Nanostructures

PubMed Central

Lund, John; Mehta, Ranjana; Parviz, Babak A.

2007-01-01

We present the fabrication and characterization of a nano-scale sensor made of amorphous silicon for the label-free, electronic detection of three classes of biologically important molecules: ions, oligonucleotides, and proteins. The sensor structure has an active element which is a 50 nm wide amorphous silicon semicircle and has a total footprint of less than 4 μm2. We demonstrate the functionalization of the sensor with receptor molecules and the electronic detection of three targets: H+ ions, short single-stranded DNAs, and streptavidin. The sensor is able to reliably distinguish single base-pair mismatches in 12 base long strands of DNA and monitor the introduction and identification of straptavidin in real-time. The versatile sensor structure can be readily functionalized with a wide range of receptor molecules and is suitable for integration with high-speed electronic circuits as a post-process on an integrated circuit chip. PMID:17292148

Peroxide Activation for Electrophilic Reactivity by the Binuclear Non-heme Iron Enzyme AurF

DOE PAGES

Park, Kiyoung; Li, Ning; Kwak, Yeonju; ...

2017-05-01

Binuclear non-heme iron enzymes activate O 2 for diverse chemistries that include oxygenation of organic substrates and hydrogen atom abstraction. This process often involves the formation of peroxo-bridged biferric intermediates, only some of which can perform electrophilic reactions. To elucidate the geometric and electronic structural requirements to activate peroxo reactivity, the active peroxo intermediate in 4-aminobenzoate N-oxygenase (AurF) has been characterized spectroscopically and computationally. A magnetic circular dichroism study of reduced AurF shows that its electronic and geometric structures are poised to react rapidly with O 2. Nuclear resonance vibrational spectroscopic definition of the peroxo intermediate formed in this reactionmore » shows that the active intermediate has a protonated peroxo bridge. Density functional theory computations on the structure established here show that the protonation activates peroxide for electrophilic/single-electron-transfer reactivity. As a result, this activation of peroxide by protonation is likely also relevant to the reactive peroxo intermediates in other binuclear non-heme iron enzymes.« less

Peroxide Activation for Electrophilic Reactivity by the Binuclear Non-heme Iron Enzyme AurF

DOE Office of Scientific and Technical Information (OSTI.GOV)

Park, Kiyoung; Li, Ning; Kwak, Yeonju

Binuclear non-heme iron enzymes activate O 2 for diverse chemistries that include oxygenation of organic substrates and hydrogen atom abstraction. This process often involves the formation of peroxo-bridged biferric intermediates, only some of which can perform electrophilic reactions. To elucidate the geometric and electronic structural requirements to activate peroxo reactivity, the active peroxo intermediate in 4-aminobenzoate N-oxygenase (AurF) has been characterized spectroscopically and computationally. A magnetic circular dichroism study of reduced AurF shows that its electronic and geometric structures are poised to react rapidly with O 2. Nuclear resonance vibrational spectroscopic definition of the peroxo intermediate formed in this reactionmore » shows that the active intermediate has a protonated peroxo bridge. Density functional theory computations on the structure established here show that the protonation activates peroxide for electrophilic/single-electron-transfer reactivity. As a result, this activation of peroxide by protonation is likely also relevant to the reactive peroxo intermediates in other binuclear non-heme iron enzymes.« less

Recent Developments in the Synthesis of Biomacromolecules and their Conjugates by Single Electron Transfer-Living Radical Polymerization.

PubMed

Lligadas, Gerard; Grama, Silvia; Percec, Virgil

2017-04-10

Single electron transfer-living radical polymerization (SET-LRP) represents a robust and versatile tool for the synthesis of vinyl polymers with well-defined topology and chain end functionality. The crucial step in SET-LRP is the disproportionation of the Cu(I)X generated by activation with Cu(0) wire, powder, or nascent Cu(0) generated in situ into nascent, extremely reactive Cu(0) atoms and nanoparticles and Cu(II)X 2 . Nascent Cu(0) activates the initiator and dormant chains via a homogeneous or heterogeneous outer-sphere single-electron transfer mechanism (SET-LRP). SET-LRP provides an ultrafast polymerization of a plethora of monomers (e.g., (meth)-acrylates, (meth)-acrylamides, styrene, and vinyl chloride) including hydrophobic and water insoluble to hydrophilic and water soluble. Some advantageous features of SET-LRP are (i) the use of Cu(0) wire or powder as readily available catalysts under mild reaction conditions, (ii) their excellent control over molecular weight evolution and distribution as well as polymer chain ends, (iii) their high functional group tolerance allowing the polymerization of commercial-grade monomers, and (iv) the limited purification required for the resulting polymers. In this Perspective, we highlight the recent advancements of SET-LRP in the synthesis of biomacromolecules and of their conjugates.

Cu1–xFexO: hopping transport and ferromagnetism

PubMed Central

Nasir, Mohd.; Islam, Rakibul; Ahmed, Md. A; Ayaz, Saniya; Kumar, Gautham; Kumar, Sunil; Prajapat, C. L.; Roussel, Frederick; Biring, Sajal

2017-01-01

Single phase, sol–gel prepared Cu1–xFexO (0 ≤ x ≤ 0.125) powders are characterized in terms of structural, electronic and magnetic properties. Using dielectric and magnetic studies we investigate the coupling of electron and spin. The electrical conductivities and activation energies are studied with increasing Fe content. Modelling of experimental conductivity data emphasizes a single hopping mechanism for all samples except x = 0.125, which have two activation energies. Hole doping is confirmed by confirming a majority Fe3+ substitution of Cu2+ in CuO from X-ray photoelectron spectroscopy studies (XPS). Such a substitution results in stabilized ferromagnetism. Fe substitution introduces variation in coercivity as an intrinsic magnetic property in Fe-doped CuO, and not as a secondary impurity phase. PMID:28989741

Carbene-catalysed reductive coupling of nitrobenzyl bromides and activated ketones or imines via single-electron-transfer process

NASA Astrophysics Data System (ADS)

Li, Bao-Sheng; Wang, Yuhuang; Proctor, Rupert S. J.; Zhang, Yuexia; Webster, Richard D.; Yang, Song; Song, Baoan; Chi, Yonggui Robin

2016-09-01

Benzyl bromides and related molecules are among the most common substrates in organic synthesis. They are typically used as electrophiles in nucleophilic substitution reactions. These molecules can also be activated via single-electron-transfer (SET) process for radical reactions. Representative recent progress includes α-carbon benzylation of ketones and aldehydes via photoredox catalysis. Here we disclose the generation of (nitro)benzyl radicals via N-heterocyclic carbene (NHC) catalysis under reductive conditions. The radical intermediates generated via NHC catalysis undergo formal 1,2-addition with ketones to eventually afford tertiary alcohol products. The overall process constitutes a formal polarity-inversion of benzyl bromide, allowing a direct coupling of two initially electrophilic carbons. Our study provides a new carbene-catalysed reaction mode that should enable unconventional transformation of (nitro)benzyl bromides under mild organocatalytic conditions.

Multi-state trajectory approach to non-adiabatic dynamics: General formalism and the active state trajectory approximation

NASA Astrophysics Data System (ADS)

Tao, Guohua

2017-07-01

A general theoretical framework is derived for the recently developed multi-state trajectory (MST) approach from the time dependent Schrödinger equation, resulting in equations of motion for coupled nuclear-electronic dynamics equivalent to Hamilton dynamics or Heisenberg equation based on a new multistate Meyer-Miller (MM) model. The derived MST formalism incorporates both diabatic and adiabatic representations as limiting cases and reduces to Ehrenfest or Born-Oppenheimer dynamics in the mean-field or the single-state limits, respectively. In the general multistate formalism, nuclear dynamics is represented in terms of a set of individual state-specific trajectories, while in the active state trajectory (AST) approximation, only one single nuclear trajectory on the active state is propagated with its augmented images running on all other states. The AST approximation combines the advantages of consistent nuclear-coupled electronic dynamics in the MM model and the single nuclear trajectory in the trajectory surface hopping (TSH) treatment and therefore may provide a potential alternative to both Ehrenfest and TSH methods. The resulting algorithm features in a consistent description of coupled electronic-nuclear dynamics and excellent numerical stability. The implementation of the MST approach to several benchmark systems involving multiple nonadiabatic transitions and conical intersection shows reasonably good agreement with exact quantum calculations, and the results in both representations are similar in accuracy. The AST treatment also reproduces the exact results reasonably, sometimes even quantitatively well, with a better performance in the adiabatic representation.

Self-referenced locking of optical coherence by single-detector electronic-frequency tagging

NASA Astrophysics Data System (ADS)

Shay, T. M.; Benham, Vincent; Spring, Justin; Ward, Benjamin; Ghebremichael, F.; Culpepper, Mark A.; Sanchez, Anthony D.; Baker, J. T.; Pilkington, D.; Berdine, Richard

2006-02-01

We report a novel coherent beam combining technique. This is the first actively phase locked optical fiber array that eliminates the need for a separate reference beam. In addition, only a single photodetector is required. The far-field central spot of the array is imaged onto the photodetector to produce the phase control loop signals. Each leg of the fiber array is phase modulated with a separate RF frequency, thus tagging the optical phase shift for each leg by a separate RF frequency. The optical phase errors for the individual array legs are separated in the electronic domain. In contrast with the previous active phase locking techniques, in our system the reference beam is spatially overlapped with all the RF modulated fiber leg beams onto a single detector. The phase shift between the optical wave in the reference leg and in the RF modulated legs is measured separately in the electronic domain and the phase error signal is feedback to the LiNbO 3 phase modulator for that leg to minimize the phase error for that leg relative to the reference leg. The advantages of this technique are 1) the elimination of the reference beam and beam combination optics and 2) the electronic separation of the phase error signals without any degradation of the phase locking accuracy. We will present the first theoretical model for self-referenced LOCSET and describe experimental results for a 3 x 3 array.

A comparative study of single-temperature and two-temperature accretion flows around black holes

NASA Astrophysics Data System (ADS)

Dihingia, Indu Kalpa; Das, Santabrata; Mandal, Samir

2018-02-01

We study the properties of sub-Keplerian accretion disk around a stationary black hole, considering bremsstrahlung, synchrotron and Comptonization of synchrotron photons as radiative cooling mechanisms active in the disk. We obtain the solutions of two-temperature global accretion flow (TTAF) and compare it with the results obtained from single-temperature (STAF) model. We observe that flow properties, in particular, the radial profile of electron and ion temperatures differ noticeably in the adopted models for flows with identical boundary conditions fixed at the outer edge of the disk. Since the electron temperature is one of the key factors to regulate the radiative processes, we argue that physically motivated description of electron temperature needs to be considered in studying the astrophysical phenomena around black holes.

Formation of a cytochrome c-nitrous oxide reductase complex is obligatory for N2O reduction by Paracoccus pantotrophus.

PubMed

Rasmussen, Tim; Brittain, Thomas; Berks, Ben C; Watmough, Nicholas J; Thomson, Andrew J

2005-11-07

Nitrous oxide reductase (N2OR) catalyses the final step of bacterial denitrification, the two-electron reduction of nitrous oxide (N2O) to dinitrogen (N2). N2OR contains two metal centers; a binuclear copper center, CuA, that serves to receive electrons from soluble donors, and a tetranuclear copper-sulfide center, CuZ, at the active site. Stopped flow experiments at low ionic strengths reveal rapid electron transfer (kobs=150 s-1) between reduced horse heart (HH) cytochrome c and the CuA center in fully oxidized N2OR. When fully reduced N2OR was mixed with oxidized cytochrome c, a similar rate of electron transfer was recorded for the reverse reaction, followed by a much slower internal electron transfer from CuZ to CuA(kobs=0.1-0.4 s-1). The internal electron transfer process is likely to represent the rate-determining step in the catalytic cycle. Remarkably, in the absence of cytochrome c, fully reduced N2OR is inert towards its substrate, even though sufficient electrons are stored to initiate a single turnover. However, in the presence of reduced cytochrome c and N2O, a single turnover occurs after a lag-phase. We propose that a conformational change in N2OR is induced by its specific interaction with cytochrome c that in turn either permits electron transfer between CuA and CuZ or controls the rate of N2O decomposition at the active site.

Tuning the Selectivity of Single-Site Supported Metal Catalysts with Ionic Liquids

DOE PAGES

Babucci, Melike; Fang, Chia -Yu; Hoffman, Adam S.; ...

2017-09-11

1,3-Dialkylimidazolium ionic liquid coatings act as electron donors, increasing the selectivity for partial hydrogenation of 1,3-butadiene catalyzed by iridium complexes supported on high-surface-area γ-Al 2O 3. High-energy-resolution fluorescence detection X-ray absorption near-edge structure (HERFD XANES) measurements quantify the electron donation and are correlated with the catalytic activity and selectivity. Furthermore, the results demonstrate broad opportunities to tune electronic environments and catalytic properties of atomically dispersed supported metal catalysts.

In Vivo Imaging of Tissue Physiological Function using EPR Spectroscopy | NCI Technology Transfer Center | TTC

Cancer.gov

Electron paramagnetic resonance (EPR) is a technique for studying chemical species that have one or more unpaired electrons.  The current invention describes Echo-based Single Point Imaging (ESPI), a novel EPR image formation strategy that allows in vivo imaging of physiological function.  The National Cancer Institute's Radiation Biology Branch is seeking statements of capability or interest from parties interested in in-licensing an in vivo imaging using Electron paramagnetic resonance (EPR) to measure active oxygen species.

Inelastic transport and low-bias rectification in a single-molecule diode.

PubMed

Hihath, Joshua; Bruot, Christopher; Nakamura, Hisao; Asai, Yoshihiro; Díez-Pérez, Ismael; Lee, Youngu; Yu, Luping; Tao, Nongjian

2011-10-25

Designing, controlling, and understanding rectification behavior in molecular-scale devices has been a goal of the molecular electronics community for many years. Here we study the transport behavior of a single molecule diode, and its nonrectifying, symmetric counterpart at low temperatures, and at both low and high biases to help elucidate the electron-phonon interactions and transport mechanisms in the rectifying system. We find that the onset of current rectification occurs at low biases, indicating a significant change in the elastic transport pathway. However, the peaks in the inelastic electron tunneling (IET) spectrum are antisymmetric about zero bias and show no significant changes in energy or intensity in the forward or reverse bias directions, indicating that despite the change in the elastic transmission probability there is little impact on the inelastic pathway. These results agree with first principles calculations performed to evaluate the IETS, which also allow us to identify which modes are active in the single molecule junction.

Molecular architecture of botulinum neurotoxin E revealed by single particle electron microscopy.

PubMed

Fischer, Audrey; Garcia-Rodriguez, Consuelo; Geren, Isin; Lou, Jianlong; Marks, James D; Nakagawa, Terunaga; Montal, Mauricio

2008-02-15

Clostridial botulinum neurotoxin (BoNT) causes a neuroparalytic condition recognized as botulism by arresting synaptic vesicle exocytosis. Although the crystal structures of full-length BoNT/A and BoNT/B holotoxins are known, the molecular architecture of the five other serotypes remains elusive. Here, we present the structures of BoNT/A and BoNT/E using single particle electron microscopy. Labeling of the particles with three different monoclonal antibodies raised against BoNT/E revealed the positions of their epitopes in the electron microscopy structure, thereby identifying the three hallmark domains of BoNT (protease, translocation, and receptor binding). Correspondingly, these antibodies selectively inhibit BoNT translocation activity as detected using a single molecule assay. The global structure of BoNT/E is strikingly different from that of BoNT/A despite strong sequence similarity. We postulate that the unique architecture of functionally conserved modules underlies the distinguishing attributes of BoNT/E and contributes to differences with BoNT/A.

Electron transport in ethanol & methanol absorbed defected graphene

NASA Astrophysics Data System (ADS)

Dandeliya, Sushmita; Srivastava, Anurag

2018-05-01

In the present paper, the sensitivity of ethanol and methanol molecules on surface of single vacancy defected graphene has been investigated using density functional theory (DFT). The changes in structural and electronic properties before and after adsorption of ethanol and methanol were analyzed and the obtained results show high adsorption energy and charge transfer. High adsorption happens at the active site with monovacancy defect on graphene surface. Present work confirms that the defected graphene increases the surface reactivity towards ethanol and methanol molecules. The presence of molecules near the active site affects the electronic and transport properties of defected graphene which makes it a promising choice for designing methanol and ethanol sensor.

Reflections on the value of electron microscopy in the study of heterogeneous catalysts

PubMed Central

2017-01-01

Electron microscopy (EM) is arguably the single most powerful method of characterizing heterogeneous catalysts. Irrespective of whether they are bulk and multiphasic, or monophasic and monocrystalline, or nanocluster and even single-atom and on a support, their structures in atomic detail can be visualized in two or three dimensions, thanks to high-resolution instruments, with sub-Ångstrom spatial resolutions. Their topography, tomography, phase-purity, composition, as well as the bonding, and valence-states of their constituent atoms and ions and, in favourable circumstances, the short-range and long-range atomic order and dynamics of the catalytically active sites, can all be retrieved by the panoply of variants of modern EM. The latter embrace electron crystallography, rotation and precession electron diffraction, X-ray emission and high-resolution electron energy-loss spectra (EELS). Aberration-corrected (AC) transmission (TEM) and scanning transmission electron microscopy (STEM) have led to a revolution in structure determination. Environmental EM is already playing an increasing role in catalyst characterization, and new advances, involving special cells for the study of solid catalysts in contact with liquid reactants, have recently been deployed. PMID:28265196

Structure of the Full-length VEGFR-1 Extracellular Domain in Complex with VEGF-A.

PubMed

Markovic-Mueller, Sandra; Stuttfeld, Edward; Asthana, Mayanka; Weinert, Tobias; Bliven, Spencer; Goldie, Kenneth N; Kisko, Kaisa; Capitani, Guido; Ballmer-Hofer, Kurt

2017-02-07

Vascular endothelial growth factors (VEGFs) regulate blood and lymph vessel development upon activation of three receptor tyrosine kinases: VEGFR-1, -2, and -3. Partial structures of VEGFR/VEGF complexes based on single-particle electron microscopy, small-angle X-ray scattering, and X-ray crystallography revealed the location of VEGF binding and domain arrangement of individual receptor subdomains. Here, we describe the structure of the full-length VEGFR-1 extracellular domain in complex with VEGF-A at 4 Å resolution. We combined X-ray crystallography, single-particle electron microscopy, and molecular modeling for structure determination and validation. The structure reveals the molecular details of ligand-induced receptor dimerization, in particular of homotypic receptor interactions in immunoglobulin homology domains 4, 5, and 7. Functional analyses of ligand binding and receptor activation confirm the relevance of these homotypic contacts and identify them as potential therapeutic sites to allosterically inhibit VEGFR-1 activity. Copyright © 2017 Elsevier Ltd. All rights reserved.

Anomalous single-electron transfer in common-gate quadruple-dot single-electron devices with asymmetric junction capacitances

NASA Astrophysics Data System (ADS)

Imai, Shigeru; Ito, Masato

2018-06-01

In this paper, anomalous single-electron transfer in common-gate quadruple-dot turnstile devices with asymmetric junction capacitances is revealed. That is, the islands have the same total number of excess electrons at high and low gate voltages of the swing that transfers a single electron. In another situation, two electrons enter the islands from the source and two electrons leave the islands for the source and drain during a gate voltage swing cycle. First, stability diagrams of the turnstile devices are presented. Then, sequences of single-electron tunneling events by gate voltage swings are investigated, which demonstrate the above-mentioned anomalous single-electron transfer between the source and the drain. The anomalous single-electron transfer can be understood by regarding the four islands as “three virtual islands and a virtual source or drain electrode of a virtual triple-dot device”. The anomalous behaviors of the four islands are explained by the normal behavior of the virtual islands transferring a single electron and the behavior of the virtual electrode.

An EBIC study of HEM polycrystalline silicon

NASA Technical Reports Server (NTRS)

Koch, T.; Ast, D.

1982-01-01

Low-cost silicon for solar cells grown by the heat exchanger method (HEM) was studied in the electron beam induced current (EBIC) mode of a scanning electron microscope (SEM). Comparisons were made between the defects observed optically and the recombination centers visible in EBIC. Much of the HEM material was single crystalline, but structural defects were found from areas near the corners of the grown material. Most of these defects consisted of linear twin boundaries and grain boundaries. The electrical activity of these boundaries was dependent on symmetry of the boundaries. Symmetric twin boundaries did not exhibit recombination activity while unsymmetric twin boundaries were electrically active.

Inkjet printing of single-crystal films.

PubMed

Minemawari, Hiromi; Yamada, Toshikazu; Matsui, Hiroyuki; Tsutsumi, Jun'ya; Haas, Simon; Chiba, Ryosuke; Kumai, Reiji; Hasegawa, Tatsuo

2011-07-13

The use of single crystals has been fundamental to the development of semiconductor microelectronics and solid-state science. Whether based on inorganic or organic materials, the devices that show the highest performance rely on single-crystal interfaces, with their nearly perfect translational symmetry and exceptionally high chemical purity. Attention has recently been focused on developing simple ways of producing electronic devices by means of printing technologies. 'Printed electronics' is being explored for the manufacture of large-area and flexible electronic devices by the patterned application of functional inks containing soluble or dispersed semiconducting materials. However, because of the strong self-organizing tendency of the deposited materials, the production of semiconducting thin films of high crystallinity (indispensable for realizing high carrier mobility) may be incompatible with conventional printing processes. Here we develop a method that combines the technique of antisolvent crystallization with inkjet printing to produce organic semiconducting thin films of high crystallinity. Specifically, we show that mixing fine droplets of an antisolvent and a solution of an active semiconducting component within a confined area on an amorphous substrate can trigger the controlled formation of exceptionally uniform single-crystal or polycrystalline thin films that grow at the liquid-air interfaces. Using this approach, we have printed single crystals of the organic semiconductor 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C(8)-BTBT) (ref. 15), yielding thin-film transistors with average carrier mobilities as high as 16.4 cm(2) V(-1) s(-1). This printing technique constitutes a major step towards the use of high-performance single-crystal semiconductor devices for large-area and flexible electronics applications.

Long-range ordering of composites for organic electronics: TIPS-pentacene single crystals with incorporated nano-fibers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Huanbin; Xue, Guobiao; Wu, Jiake

Multi-component active materials are widely used for organic electronic devices, with every component contributing complementary and synergistic optoelectronic functions. Mixing these components generally leads to lowered crystallinity and weakened charge transport. Therefore, preparing the active materials without substantially disrupting the crystalline lattice is highly desired. In this paper, we show that crystallization of TIPS-pentacene from solutions in the presence of fluorescent nanofibers of a perylene bisimide derivative (PBI) leads to formation of composites with nanofiber guest incorporated in the crystal host. In spite of the binary composite structure, the TIPS-pentacene maintains the single-crystalline nature. As a result, the incorporation ofmore » the PBI guest introduces additional fluorescence function but does not significantly reduce the charge transport property of the TIPS-pentacene host, exhibiting field-effect mobility as high as 3.34 cm 2 V -1 s -1 even though 26.4% of the channel area is taken over by the guest. Finally, as such, this work provides a facile approach toward high-performance multifunctional organic electronic materials.« less

Electron Reconfiguration and Enhanced Phonon Activation in the Superconducting State of a FeSe0.3Te0.7 Single Crystal, as Evidenced by Mössbauer Spectroscopy

NASA Astrophysics Data System (ADS)

Greculeasa, Simona; Miu, Lucica; Badica, Petre; Nie, Jiacai; Tolea, Mugurel; Kuncser, Victor

2015-01-01

The Mössbauer spectra of a FeSe0.3Te0.7 single crystal grown by the Bridgman method were analysed across the superconducting transition by considering the interplay between the structure and electron configuration of the transition metal. The magnetically determined superconducting critical temperature is TC ˜ 14 K. The 57Fe Mössbauer spectra collected in the temperature range from 5 to 200 K mainly have an asymmetric doublet pattern, which was conveniently fitted by the full Hamiltonian method. No effective magnetic moment ascribed to the superconducting phase was observed down to 5 K. The unusual behaviour observed below ˜17 K for the chemical isomer shift and quadrupole splitting may be associated with an electron reconfiguration process intimately related to an unusual lattice distortion accompanying the superconducting transition. The decreasing trend of the total absorption spectral area and second-order Doppler shift during cooling the sample below the critical temperature, point to enhanced phonon activation in the superconducting state.

Long-range ordering of composites for organic electronics: TIPS-pentacene single crystals with incorporated nano-fibers

DOE PAGES

Li, Huanbin; Xue, Guobiao; Wu, Jiake; ...

2017-08-18

Multi-component active materials are widely used for organic electronic devices, with every component contributing complementary and synergistic optoelectronic functions. Mixing these components generally leads to lowered crystallinity and weakened charge transport. Therefore, preparing the active materials without substantially disrupting the crystalline lattice is highly desired. In this paper, we show that crystallization of TIPS-pentacene from solutions in the presence of fluorescent nanofibers of a perylene bisimide derivative (PBI) leads to formation of composites with nanofiber guest incorporated in the crystal host. In spite of the binary composite structure, the TIPS-pentacene maintains the single-crystalline nature. As a result, the incorporation ofmore » the PBI guest introduces additional fluorescence function but does not significantly reduce the charge transport property of the TIPS-pentacene host, exhibiting field-effect mobility as high as 3.34 cm 2 V -1 s -1 even though 26.4% of the channel area is taken over by the guest. Finally, as such, this work provides a facile approach toward high-performance multifunctional organic electronic materials.« less

Theoretical study on the photocatalytic properties of graphene oxide with single Au atom adsorption

NASA Astrophysics Data System (ADS)

Ju, Lin; Dai, Ying; Wei, Wei; Li, Mengmeng; Jin, Cui; Huang, Baibiao

2018-03-01

The photocatalytic properties of graphene oxide (GO) with single Au atom adsorption are studied via the first-principles calculations based on the density functional theory. The present study addresses the origin of enhancement in photocatalytic efficiency of GO derived from single Au atom depositing. Compared with the clean one, the work function of the single Au atom adsorbed GO is lowered due to the charge transfer from Au to GO, indicating enhanced surface activity. The Au atom plays as an electron trapping center and a mediating role in charge transfer from photon excited GO to target species. The photogenerated electron-hole pairs can be separated effectively. For the GO configuration with atomic Au dispersion, there are some states introduced in the band gap, which are predominantly composed of Au 6s states. Through the in-gap state, the photo-generated electron transfer from the valence band of clean GO to the conductive band more easily. In addition, the reduction of the gap in the system is also presented in the current work, which indicates that the single Au atom adsorption improves light absorption for the GO based photocatalyst. These theoretical results are valuable for the future applications of GO materials as photocatalyst for water splitting.

Chiral Redox-Active Isosceles Triangles

DOE PAGES

Nalluri, Siva Krishna Mohan; Liu, Zhichang; Wu, Yilei; ...

2016-04-12

Designing small-molecule organic redox-active materials, with potential applications in energy storage, has received considerable interest of late. Herein, we report on the synthesis, characterization, and application of two rigid chiral triangles, each of which consist of non-identical pyromellitic diimide (PMDI) and naphthalene diimide (NDI)-based redox-active units. 1H and 13C NMR spectroscopic investigations in solution confirm the lower symmetry (C2 point group) associated with these two isosceles triangles. Single-crystal X-ray diffraction analyses reveal their rigid triangular prism-like geometries. Unlike previously investigated equilateral triangle containing three identical NDI subunits, both isosceles triangles do not choose to form one-dimensional supramolecular nanotubes by dintmore » of [C–H···O] interaction-driven columnar stacking. The rigid isosceles triangle, composed of one NDI and two PMDI subunits, forms—in the presence of N,N-dimethylformamide—two different types of intermolecular NDI–NDI and NDI–PMDI π–π stacked dimers with opposite helicities in the solid state. Cyclic voltammetry reveals that both isosceles triangles can accept reversibly up to six electrons. Continuous-wave electron paramagnetic resonance and electron–nuclear double-resonance spectroscopic investigations, supported by density functional theory calculations, on the single-electron reduced radical anions of the isosceles triangles confirm the selective sharing of unpaired electrons among adjacent redox-active NDI subunit(s) within both molecules. The isosceles triangles have been employed as electrode-active materials in organic rechargeable lithium-ion batteries. The evaluation of the structure–performance relationships of this series of diimide-based triangles reveals that the increase in the number of NDI subunits, replacing PMDI ones, within the molecules improves the electrochemical cell performance of the batteries.« less

High-resolution electron spectroscopy of lanthanide (Ce, Pr, and Nd) complexes of cyclooctatetraene: the role of 4f electrons.

PubMed

Kumari, Sudesh; Roudjane, Mourad; Hewage, Dilrukshi; Liu, Yang; Yang, Dong-Sheng

2013-04-28

Cerium, praseodymium, and neodymium complexes of 1,3,5,7-cyclooctatetraene (COT) complexes were produced in a laser-vaporization metal cluster source and studied by pulsed-field ionization zero electron kinetic energy spectroscopy and quantum chemical calculations. The computations included the second-order Møller-Plesset perturbation theory, the coupled cluster method with single, double, and perturbative triple excitations, and the state-average complete active space self-consistent field method. The spectrum of each complex exhibits multiple band systems and is assigned to ionization of several low-energy electronic states of the neutral complex. This observation is different from previous studies of M(COT) (M = Sc, Y, La, and Gd), for which a single band system was observed. The presence of the multiple low-energy electronic states is caused by the splitting of the partially filled lanthanide 4f orbitals in the ligand field, and the number of the low-energy states increases rapidly with increasing number of the metal 4f electrons. On the other hand, the 4f electrons have a small effect on the geometries and vibrational frequencies of these lanthanide complexes.

Symmetry breaking by quantum coherence in single electron attachment

NASA Astrophysics Data System (ADS)

Krishnakumar, E.; Prabhudesai, Vaibhav S.; Mason, Nigel J.

2018-02-01

Quantum coherence-induced effects in atomic and molecular systems are the basis of several proposals for laser-based control of chemical reactions. So far, these rely on coherent photon beams inducing coherent reaction pathways that may interfere with one another, to achieve the desired outcome. This concept has been successfully exploited for removing the inversion symmetry in the dissociation of homonuclear diatomic molecules, but it remains to be seen if such quantum coherent effects can also be generated by the interaction of incoherent electrons with such molecules. Here we show that resonant electron attachment to H2 and the subsequent dissociation into H (n = 2) + H- is asymmetric about the inter-nuclear axis, whereas the asymmetry in D2 is far less pronounced. We explain this observation as due to attachment of a single electron resulting in a coherent superposition of two resonances of opposite parity. In addition to exemplifying a new quantum coherent process, our observation of coherent quantum dynamics involves the active participation of all three electrons and two nuclei, which could provide new tools for studying electron correlations as a means to control chemical processes, and demonstrates the role of coherent effects in electron-induced chemistry.

Mirror Langmuir probe: a technique for real-time measurement of magnetized plasma conditions using a single Langmuir electrode.

PubMed

LaBombard, B; Lyons, L

2007-07-01

A new method for the real-time evaluation of the conditions in a magnetized plasma is described. The technique employs an electronic "mirror Langmuir probe" (MLP), constructed from bipolar rf transistors and associated high-bandwidth electronics. Utilizing a three-state bias wave form and active feedback control, the mirror probe's I-V characteristic is continuously adjusted to be a scaled replica of the "actual" Langmuir electrode immersed in a plasma. Real-time high-bandwidth measurements of the plasma's electron temperature, ion saturation current, and floating potential can thereby be obtained using only a single electrode. Initial tests of a prototype MLP system are reported, proving the concept. Fast-switching metal-oxide-semiconductor field-effect transistors produce the required three-state voltage bias wave form, completing a full cycle in under 1 mus. Real-time outputs of electron temperature, ion saturation current, and floating potential are demonstrated, which accurately track an independent computation of these values from digitally stored I-V characteristics. The MLP technique represents a significant improvement over existing real-time methods, eliminating the need for multiple electrodes and sampling all three plasma parameters at a single spatial location.

The convergence of complete active space self-consistent-field configuration interaction including all single and double excitation energies to the complete basis set limit

NASA Astrophysics Data System (ADS)

Petersson, George A.; Malick, David K.; Frisch, Michael J.; Braunstein, Matthew

2006-07-01

Examination of the convergence of full valence complete active space self-consistent-field configuration interaction including all single and double excitation (CASSCF-CISD) energies with expansion of the one-electron basis set reveals a pattern very similar to the convergence of single determinant energies. Calculations on the lowest four singlet states and the lowest four triplet states of N2 with the sequence of n-tuple-ζ augmented polarized (nZaP) basis sets (n =2, 3, 4, 5, and 6) are used to establish the complete basis set limits. Full configuration-interaction (CI) and core electron contributions must be included for very accurate potential energy surfaces. However, a simple extrapolation scheme that has no adjustable parameters and requires nothing more demanding than CAS(10e -,8orb)-CISD/3ZaP calculations gives the Re, ωe, ωeXe, Te, and De for these eight states with rms errors of 0.0006Å, 4.43cm-1, 0.35cm-1, 0.063eV, and 0.018eV, respectively.

Enhancing roll stability of heavy vehicle by LQR active anti-roll bar control using electronic servo-valve hydraulic actuators

NASA Astrophysics Data System (ADS)

Vu, Van Tan; Sename, Olivier; Dugard, Luc; Gaspar, Peter

2017-09-01

Rollover of heavy vehicle is an important road safety problem world-wide. Although rollovers are relatively rare events, they are usually deadly accidents when they occur. The roll stability loss is the main cause of rollover accidents in which heavy vehicles are involved. In order to improve the roll stability, most of modern heavy vehicles are equipped with passive anti-roll bars to reduce roll motion during cornering or riding on uneven roads. However these may be not sufficient to overcome critical situations. This paper introduces the active anti-roll bars made of four electronic servo-valve hydraulic actuators, which are modelled and integrated in a yaw-roll model of a single unit heavy vehicle. The control signal is the current entering the electronic servo-valve and the output is the force generated by the hydraulic actuator. The active control design is achieved solving a linear optimal control problem based on the linear quadratic regulator (LQR) approach. A comparison of several LQR controllers is provided to allow for tackling the considered multi-objective problems. Simulation results in frequency and time domains show that the use of two active anti-roll bars (front and rear axles) drastically improves the roll stability of the single unit heavy vehicle compared with the passive anti-roll bar.

Electrochemical studies of a truncated laccase produced in Pichia pastoris

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gelo-Pujic, M.; Kim, H.H.; Butlin, N.G.

1999-12-01

The cDNA that encodes an isoform is laccase from Trametes versicolor (LCCI), as well as a truncated version (LCCIa), was subcloned and expressed by using the yeast Pichia pastoris as the heterologous host. The amino acid sequence of LCCIa is identical to that of LCCI except that the final 11 amino acids at the C terminus of LCCI are replaced with a single cysteine residue. This modification was introduced for the purpose of improving the kinetics of electron transfer between an electrode and the copper-containing active site of laccase. The two laccases (LCCI and LCCIa) are compared in terms ofmore » their relative activity with two substrates that have different redox potentials. Results from electrochemical studies on solutions containing LCCI and LCCIa indicate that the redox potential of the active site of LCCIa is shifted to more negative values (411 mV versus normal hydrogen electrode voltage) than that found in other fungal laccases. In addition, replacing the 11 codons at the C terminus of the laccase gene with a single cysteine codon influences the rate of heterogeneous electron transfer between and electrode and the copper-containing active site. These results demonstrate for the first time that the rate of electron transfer between an oxidoreductase and an electrode can be enhanced by changes to the primary structure of a protein via site-directed mutagenesis.« less

Biointerfacial Property of Plasma-Treated Single-Walled Carbon Nanotube Film Electrodes for Electrochemical Biosensors

NASA Astrophysics Data System (ADS)

Kim, Joon Hyub; Lee, Jun-Yong; Jin, Joon-Hyung; Park, Eun Jin; Min, Nam Ki

2013-01-01

The single-walled carbon nanotube (SWCNT)-based thin film was spray-coated on the Pt support and functionalized using O2 plasma. The effects of plasma treatment on the biointerfacial properties of the SWCNT films were analyzed by cyclic voltammogram (CV), electrochemical impedance spectroscopy (EIS), and differential pulse voltammetry (DPV). The plasma-functionalized (pf) SWCNT electrodes modified with Legionella pneumophila-specific probe DNA strands showed a much higher peak current and a smaller peak separation in differential pulse voltammetry and a lower charge transfer resistance, compared to the untreated samples. These results suggest that the pf-SWCNT films have a better electrocatalytic character and an electron transfer capability faster than the untreated SWCNTs, due to the fact that the oxygen-containing functional groups promote direct electron transfer in the biointerfacial region of the electrocatalytic activity of redox-active biomolecules.

Phase transitions in trajectories of a superconducting single-electron transistor coupled to a resonator.

PubMed

Genway, Sam; Garrahan, Juan P; Lesanovsky, Igor; Armour, Andrew D

2012-05-01

Recent progress in the study of dynamical phase transitions has been made with a large-deviation approach to study trajectories of stochastic jumps using a thermodynamic formalism. We study this method applied to an open quantum system consisting of a superconducting single-electron transistor, near the Josephson quasiparticle resonance, coupled to a resonator. We find that the dynamical behavior shown in rare trajectories can be rich even when the mean dynamical activity is small, and thus the formalism gives insights into the form of fluctuations. The structure of the dynamical phase diagram found from the quantum-jump trajectories of the resonator is studied, and we see that sharp transitions in the dynamical activity may be related to the appearance and disappearance of bistabilities in the state of the resonator as system parameters are changed. We also demonstrate that for a fast resonator, the trajectories of quasiparticles are similar to the resonator trajectories.

Carbene-catalysed reductive coupling of nitrobenzyl bromides and activated ketones or imines via single-electron-transfer process

PubMed Central

Li, Bao-Sheng; Wang, Yuhuang; Proctor, Rupert S. J.; Zhang, Yuexia; Webster, Richard D.; Yang, Song; Song, Baoan; Chi, Yonggui Robin

2016-01-01

Benzyl bromides and related molecules are among the most common substrates in organic synthesis. They are typically used as electrophiles in nucleophilic substitution reactions. These molecules can also be activated via single-electron-transfer (SET) process for radical reactions. Representative recent progress includes α-carbon benzylation of ketones and aldehydes via photoredox catalysis. Here we disclose the generation of (nitro)benzyl radicals via N-heterocyclic carbene (NHC) catalysis under reductive conditions. The radical intermediates generated via NHC catalysis undergo formal 1,2-addition with ketones to eventually afford tertiary alcohol products. The overall process constitutes a formal polarity-inversion of benzyl bromide, allowing a direct coupling of two initially electrophilic carbons. Our study provides a new carbene-catalysed reaction mode that should enable unconventional transformation of (nitro)benzyl bromides under mild organocatalytic conditions. PMID:27671606

Pushing configuration-interaction to the limit: Towards massively parallel MCSCF calculations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vogiatzis, Konstantinos D.; Ma, Dongxia; Olsen, Jeppe

A new large-scale parallel multiconfigurational self-consistent field (MCSCF) implementation in the open-source NWChem computational chemistry code is presented. The generalized active space approach is used to partition large configuration interaction (CI) vectors and generate a sufficient number of batches that can be distributed to the available cores. Massively parallel CI calculations with large active spaces can be performed. The new parallel MCSCF implementation is tested for the chromium trimer and for an active space of 20 electrons in 20 orbitals, which can now routinely be performed. Unprecedented CI calculations with an active space of 22 electrons in 22 orbitals formore » the pentacene systems were performed and a single CI iteration calculation with an active space of 24 electrons in 24 orbitals for the chromium tetramer was possible. In conclusion, the chromium tetramer corresponds to a CI expansion of one trillion Slater determinants (914 058 513 424) and is the largest conventional CI calculation attempted up to date.« less

Pushing configuration-interaction to the limit: Towards massively parallel MCSCF calculations

DOE PAGES

Vogiatzis, Konstantinos D.; Ma, Dongxia; Olsen, Jeppe; ...

2017-11-14

A new large-scale parallel multiconfigurational self-consistent field (MCSCF) implementation in the open-source NWChem computational chemistry code is presented. The generalized active space approach is used to partition large configuration interaction (CI) vectors and generate a sufficient number of batches that can be distributed to the available cores. Massively parallel CI calculations with large active spaces can be performed. The new parallel MCSCF implementation is tested for the chromium trimer and for an active space of 20 electrons in 20 orbitals, which can now routinely be performed. Unprecedented CI calculations with an active space of 22 electrons in 22 orbitals formore » the pentacene systems were performed and a single CI iteration calculation with an active space of 24 electrons in 24 orbitals for the chromium tetramer was possible. In conclusion, the chromium tetramer corresponds to a CI expansion of one trillion Slater determinants (914 058 513 424) and is the largest conventional CI calculation attempted up to date.« less

Pushing configuration-interaction to the limit: Towards massively parallel MCSCF calculations

NASA Astrophysics Data System (ADS)

Vogiatzis, Konstantinos D.; Ma, Dongxia; Olsen, Jeppe; Gagliardi, Laura; de Jong, Wibe A.

2017-11-01

A new large-scale parallel multiconfigurational self-consistent field (MCSCF) implementation in the open-source NWChem computational chemistry code is presented. The generalized active space approach is used to partition large configuration interaction (CI) vectors and generate a sufficient number of batches that can be distributed to the available cores. Massively parallel CI calculations with large active spaces can be performed. The new parallel MCSCF implementation is tested for the chromium trimer and for an active space of 20 electrons in 20 orbitals, which can now routinely be performed. Unprecedented CI calculations with an active space of 22 electrons in 22 orbitals for the pentacene systems were performed and a single CI iteration calculation with an active space of 24 electrons in 24 orbitals for the chromium tetramer was possible. The chromium tetramer corresponds to a CI expansion of one trillion Slater determinants (914 058 513 424) and is the largest conventional CI calculation attempted up to date.

Pulsed-Plasma Physical Vapor Deposition Approach Toward the Facile Synthesis of Multilayer and Monolayer Graphene for Anticoagulation Applications.

PubMed

Vijayaraghavan, Rajani K; Gaman, Cezar; Jose, Bincy; McCoy, Anthony P; Cafolla, Tony; McNally, Patrick J; Daniels, Stephen

2016-02-01

We demonstrate the growth of multilayer and single-layer graphene on copper foil using bipolar pulsed direct current (DC) magnetron sputtering of a graphite target in pure argon atmosphere. Single-layer graphene (SG) and few-layer graphene (FLG) films are deposited at temperatures ranging from 700 °C to 920 °C within <30 min. We find that the deposition and post-deposition annealing temperatures influence the layer thickness and quality of the graphene films formed. The films were characterized using atomic force microscopy (AFM), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and optical transmission spectroscopy techniques. Based on the above studies, a diffusion-controlled mechanism was proposed for the graphene growth. A single-step whole blood assay was used to investigate the anticoagulant activity of graphene surfaces. Platelet adhesion, activation, and morphological changes on the graphene/glass surfaces, compared to bare glass, were analyzed using fluorescence microscopy and SEM techniques. We have found significant suppression of the platelet adhesion, activation, and aggregation on the graphene-covered surfaces, compared to the bare glass, indicating the anticoagulant activity of the deposited graphene films. Our production technique represents an industrially relevant method for the growth of SG and FLG for various applications including the biomedical field.

Quantitative structure-activity relationships for reactivities of sulfate and hydroxyl radicals with aromatic contaminants through single-electron transfer pathway.

PubMed

Luo, Shuang; Wei, Zongsu; Spinney, Richard; Villamena, Frederick A; Dionysiou, Dionysios D; Chen, Dong; Tang, Chong-Jian; Chai, Liyuan; Xiao, Ruiyang

2018-02-15

Sulfate radical anion (SO 4 •- ) and hydroxyl radical (OH) based advanced oxidation technologies has been extensively used for removal of aromatic contaminants (ACs) in waters. In this study, we investigated the Gibbs free energy (ΔG SET ∘ ) of the single electron transfer (SET) reactions for 76 ACs with SO 4 •- and OH, respectively. The result reveals that SO 4 •- possesses greater propensity to react with ACs through the SET channel than OH. We hypothesized that the electron distribution within the molecule plays an essential role in determining the ΔG SET ∘ and subsequent SET reactions. To test the hypothesis, a quantitative structure-activity relationship (QSAR) model was developed for predicting ΔG SET ∘ using the highest occupied molecular orbital energies (E HOMO ), a measure of electron distribution and donating ability. The standardized QSAR models are reported to be ΔG ° SET =-0.97×E HOMO - 181 and ΔG ° SET =-0.97×E HOMO - 164 for SO 4 •- and OH, respectively. The models were internally and externally validated to ensure robustness and predictability, and the application domain and limitations were discussed. The single-descriptor based models account for 95% of the variability for SO 4 •- and OH. These results provide the mechanistic insight into the SET reaction pathway of radical and non-radical bimolecular reactions, and have important applications for radical based oxidation technologies to remove target ACs in different waters. Copyright © 2017 Elsevier B.V. All rights reserved.

A real-time extension of density matrix embedding theory for non-equilibrium electron dynamics

NASA Astrophysics Data System (ADS)

Kretchmer, Joshua S.; Chan, Garnet Kin-Lic

2018-02-01

We introduce real-time density matrix embedding theory (DMET), a dynamical quantum embedding theory for computing non-equilibrium electron dynamics in strongly correlated systems. As in the previously developed static DMET, real-time DMET partitions the system into an impurity corresponding to the region of interest coupled to the surrounding environment, which is efficiently represented by a quantum bath of the same size as the impurity. In this work, we focus on a simplified single-impurity time-dependent formulation as a first step toward a multi-impurity theory. The equations of motion of the coupled impurity and bath embedding problem are derived using the time-dependent variational principle. The accuracy of real-time DMET is compared to that of time-dependent complete active space self-consistent field (TD-CASSCF) theory and time-dependent Hartree-Fock (TDHF) theory for a variety of quantum quenches in the single impurity Anderson model (SIAM), in which the Hamiltonian is suddenly changed (quenched) to induce a non-equilibrium state. Real-time DMET shows a marked improvement over the mean-field TDHF, converging to the exact answer even in the non-trivial Kondo regime of the SIAM. However, as expected from analogous behavior in static DMET, the constrained structure of the real-time DMET wavefunction leads to a slower convergence with respect to active space size, in the single-impurity formulation, relative to TD-CASSCF. Our initial results suggest that real-time DMET provides a promising framework to simulate non-equilibrium electron dynamics in which strong electron correlation plays an important role, and lays the groundwork for future multi-impurity formulations.

A real-time extension of density matrix embedding theory for non-equilibrium electron dynamics.

PubMed

Kretchmer, Joshua S; Chan, Garnet Kin-Lic

2018-02-07

We introduce real-time density matrix embedding theory (DMET), a dynamical quantum embedding theory for computing non-equilibrium electron dynamics in strongly correlated systems. As in the previously developed static DMET, real-time DMET partitions the system into an impurity corresponding to the region of interest coupled to the surrounding environment, which is efficiently represented by a quantum bath of the same size as the impurity. In this work, we focus on a simplified single-impurity time-dependent formulation as a first step toward a multi-impurity theory. The equations of motion of the coupled impurity and bath embedding problem are derived using the time-dependent variational principle. The accuracy of real-time DMET is compared to that of time-dependent complete active space self-consistent field (TD-CASSCF) theory and time-dependent Hartree-Fock (TDHF) theory for a variety of quantum quenches in the single impurity Anderson model (SIAM), in which the Hamiltonian is suddenly changed (quenched) to induce a non-equilibrium state. Real-time DMET shows a marked improvement over the mean-field TDHF, converging to the exact answer even in the non-trivial Kondo regime of the SIAM. However, as expected from analogous behavior in static DMET, the constrained structure of the real-time DMET wavefunction leads to a slower convergence with respect to active space size, in the single-impurity formulation, relative to TD-CASSCF. Our initial results suggest that real-time DMET provides a promising framework to simulate non-equilibrium electron dynamics in which strong electron correlation plays an important role, and lays the groundwork for future multi-impurity formulations.

Large-scale recording of thalamocortical circuits: in vivo electrophysiology with the two-dimensional electronic depth control silicon probe

PubMed Central

Fiáth, Richárd; Beregszászi, Patrícia; Horváth, Domonkos; Wittner, Lucia; Aarts, Arno A. A.; Ruther, Patrick; Neves, Hercules P.; Bokor, Hajnalka; Acsády, László

2016-01-01

Recording simultaneous activity of a large number of neurons in distributed neuronal networks is crucial to understand higher order brain functions. We demonstrate the in vivo performance of a recently developed electrophysiological recording system comprising a two-dimensional, multi-shank, high-density silicon probe with integrated complementary metal-oxide semiconductor electronics. The system implements the concept of electronic depth control (EDC), which enables the electronic selection of a limited number of recording sites on each of the probe shafts. This innovative feature of the system permits simultaneous recording of local field potentials (LFP) and single- and multiple-unit activity (SUA and MUA, respectively) from multiple brain sites with high quality and without the actual physical movement of the probe. To evaluate the in vivo recording capabilities of the EDC probe, we recorded LFP, MUA, and SUA in acute experiments from cortical and thalamic brain areas of anesthetized rats and mice. The advantages of large-scale recording with the EDC probe are illustrated by investigating the spatiotemporal dynamics of pharmacologically induced thalamocortical slow-wave activity in rats and by the two-dimensional tonotopic mapping of the auditory thalamus. In mice, spatial distribution of thalamic responses to optogenetic stimulation of the neocortex was examined. Utilizing the benefits of the EDC system may result in a higher yield of useful data from a single experiment compared with traditional passive multielectrode arrays, and thus in the reduction of animals needed for a research study. PMID:27535370

Disabling CNT Electronic Devices by Use of Electron Beams

NASA Technical Reports Server (NTRS)

Petkov, Mihail

2008-01-01

Bombardment with tightly focused electron beams has been suggested as a means of electrically disabling selected individual carbon-nanotubes (CNTs) in electronic devices. Evidence in support of the suggestion was obtained in an experiment in which a CNT field-effect transistor was disabled (see figure) by focusing a 1-keV electron beam on a CNT that served as the active channel of a field-effect transistor (FET). Such bombardment could be useful in the manufacture of nonvolatile-memory circuits containing CNT FETs. Ultimately, in order to obtain the best electronic performances in CNT FETs and other electronic devices, it will be necessary to fabricate the devices such that each one contains only a single CNT as an active element. At present, this is difficult because there is no way to grow a single CNT at a specific location and with a specific orientation. Instead, the common practice is to build CNTs into electronic devices by relying on spatial distribution to bridge contacts. This practice results in some devices containing no CNTs and some devices containing more than one CNT. Thus, CNT FETs have statistically distributed electronic characteristics (including switching voltages, gains, and mixtures of metallic and semiconducting CNTs). According to the suggestion, by using a 1-keV electron beam (e.g., a beam from a scanning electron microscope), a particular nanotube could be rendered electrically dysfunctional. This procedure could be repeated as many times as necessary on different CNTs in a device until all of the excess CNTs in the device had been disabled, leaving only one CNT as an active element (e.g., as FET channel). The physical mechanism through which a CNT becomes electrically disabled is not yet understood. On one hand, data in the literature show that electron kinetic energy >86 keV is needed to cause displacement damage in a CNT. On the other hand, inasmuch as a 1-keV beam focused on a small spot (typically a few tens of nanometers wide) deposits a significant amount of energy in a small volume, the energy density may suffice to thermally induce structural and/or electronic changes that disable the CNT. Research may be warranted to investigate this effect in detail.

A solvent-free microbial-activated air cathode battery paper platform made with pencil-traced graphite electrodes.

PubMed

Lee, Seung Ho; Ban, Ju Yeon; Oh, Chung-Hun; Park, Hun-Kuk; Choi, Samjin

2016-06-23

We present the fabrication of an ultra-low cost, disposable, solvent-free air cathode all-paper microbial fuel cell (MFC) that does not utilize any chemical treatments. The anode and cathode were fabricated by depositing graphite particles by drawing them on paper with a pencil (four strokes). Hydrophobic parchment paper was used as a proton exchange membrane (PEM) to allow only H(+) to pass. Air cathode MFC technology, where O2 was used as an electron acceptor, was implemented on the paper platform. The bioelectric current was generated by an electrochemical process involving the redox couple of microbial-activated extracellular electron transferred electrons, PEM-passed H(+), and O2 in the cathode. A fully micro-integrated pencil-traced MFC showed a fast start-time, producing current within 10 s after injection of bacterial cells. A single miniaturized all-paper air cathode MFC generated a maximum potential of 300 mV and a maximum current of 11 μA during 100 min after a single injection of Shewanella oneidensis. The micro-fabricated solvent-free air cathode all-paper MFC generated a power of 2,270 nW (5.68 mW/m(2)). The proposed solvent-free air cathode paper-based MFC device could be used for environmentally-friendly energy storage as well as in single-use medical power supplies that use organic matter.

A solvent-free microbial-activated air cathode battery paper platform made with pencil-traced graphite electrodes

PubMed Central

Lee, Seung Ho; Ban, Ju Yeon; Oh, Chung-Hun; Park, Hun-Kuk; Choi, Samjin

2016-01-01

We present the fabrication of an ultra-low cost, disposable, solvent-free air cathode all-paper microbial fuel cell (MFC) that does not utilize any chemical treatments. The anode and cathode were fabricated by depositing graphite particles by drawing them on paper with a pencil (four strokes). Hydrophobic parchment paper was used as a proton exchange membrane (PEM) to allow only H+ to pass. Air cathode MFC technology, where O2 was used as an electron acceptor, was implemented on the paper platform. The bioelectric current was generated by an electrochemical process involving the redox couple of microbial-activated extracellular electron transferred electrons, PEM-passed H+, and O2 in the cathode. A fully micro-integrated pencil-traced MFC showed a fast start-time, producing current within 10 s after injection of bacterial cells. A single miniaturized all-paper air cathode MFC generated a maximum potential of 300 mV and a maximum current of 11 μA during 100 min after a single injection of Shewanella oneidensis. The micro-fabricated solvent-free air cathode all-paper MFC generated a power of 2,270 nW (5.68 mW/m2). The proposed solvent-free air cathode paper-based MFC device could be used for environmentally-friendly energy storage as well as in single-use medical power supplies that use organic matter. PMID:27333815

A solvent-free microbial-activated air cathode battery paper platform made with pencil-traced graphite electrodes

NASA Astrophysics Data System (ADS)

Lee, Seung Ho; Ban, Ju Yeon; Oh, Chung-Hun; Park, Hun-Kuk; Choi, Samjin

2016-06-01

We present the fabrication of an ultra-low cost, disposable, solvent-free air cathode all-paper microbial fuel cell (MFC) that does not utilize any chemical treatments. The anode and cathode were fabricated by depositing graphite particles by drawing them on paper with a pencil (four strokes). Hydrophobic parchment paper was used as a proton exchange membrane (PEM) to allow only H+ to pass. Air cathode MFC technology, where O2 was used as an electron acceptor, was implemented on the paper platform. The bioelectric current was generated by an electrochemical process involving the redox couple of microbial-activated extracellular electron transferred electrons, PEM-passed H+, and O2 in the cathode. A fully micro-integrated pencil-traced MFC showed a fast start-time, producing current within 10 s after injection of bacterial cells. A single miniaturized all-paper air cathode MFC generated a maximum potential of 300 mV and a maximum current of 11 μA during 100 min after a single injection of Shewanella oneidensis. The micro-fabricated solvent-free air cathode all-paper MFC generated a power of 2,270 nW (5.68 mW/m2). The proposed solvent-free air cathode paper-based MFC device could be used for environmentally-friendly energy storage as well as in single-use medical power supplies that use organic matter.

Conductive Polymer Synthesis with Single-Crystallinity via a Novel Plasma Polymerization Technique for Gas Sensor Applications.

PubMed

Park, Choon-Sang; Kim, Dong Ha; Shin, Bhum Jae; Kim, Do Yeob; Lee, Hyung-Kun; Tae, Heung-Sik

2016-09-30

This study proposes a new nanostructured conductive polymer synthesis method that can grow the single-crystalline high-density plasma-polymerized nanoparticle structures by enhancing the sufficient nucleation and fragmentation of the pyrrole monomer using a novel atmospheric pressure plasma jet (APPJ) technique. Transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and field emission scanning electron microscopy (FE-SEM) results show that the plasma-polymerized pyrrole (pPPy) nanoparticles have a fast deposition rate of 0.93 µm·min -1 under a room-temperature process and have single-crystalline characteristics with porous properties. In addition, the single-crystalline high-density pPPy nanoparticle structures were successfully synthesized on the glass, plastic, and interdigitated gas sensor electrode substrates using a novel plasma polymerization technique at room temperature. To check the suitability of the active layer for the fabrication of electrochemical toxic gas sensors, the resistance variations of the pPPy nanoparticles grown on the interdigitated gas sensor electrodes were examined by doping with iodine. As a result, the proposed APPJ device could obtain the high-density and ultra-fast single-crystalline pPPy thin films for various gas sensor applications. This work will contribute to the design of highly sensitive gas sensors adopting the novel plasma-polymerized conductive polymer as new active layer.

Efficiency improvement of green light-emitting diodes by employing all-quaternary active region and electron-blocking layer

NASA Astrophysics Data System (ADS)

Usman, Muhammad; Saba, Kiran; Han, Dong-Pyo; Muhammad, Nazeer

2018-01-01

High efficiency of green GaAlInN-based light-emitting diode (LED) has been proposed with peak emission wavelength of ∼510 nm. By introducing quaternary quantum well (QW) along with the quaternary barrier (QB) and quaternary electron blocking layer (EBL) in a single structure, an efficiency droop reduction of up to 29% has been achieved in comparison to the conventional GaN-based LED. The proposed structure has significantly reduced electrostatic field in the active region. As a result, carrier leakage has been minimized and spontaneous emission rate has been doubled.

Powder-in-tube and thick-film methods of fabricating high temperature superconductors having enhanced biaxial texture

DOEpatents

Goyal, Amit; Kroeger, Donald M.

2003-11-11

A method for forming an electronically active biaxially textured article includes the steps of providing a substrate having a single crystal metal or metal alloy surface, deforming the substrate to form an elongated substrate surface having biaxial texture and depositing an epitaxial electronically active layer on the biaxially textured surface. The method can include at least one annealing step after the deforming step to produce the biaxially textured substrate surface. The invention can be used to form improved biaxially textured articles, such as superconducting wire and tape articles having improved J.sub.c values.

Monitoring Single-Molecule Protein Dynamics with a Carbon Nanotube Transistor

NASA Astrophysics Data System (ADS)

Collins, Philip G.

2014-03-01

Nanoscale electronic devices like field-effect transistors have long promised to provide sensitive, label-free detection of biomolecules. Single-walled carbon nanotubes press this concept further by not just detecting molecules but also monitoring their dynamics in real time. Recent measurements have demonstrated this premise by monitoring the single-molecule processivity of three different enzymes: lysozyme, protein Kinase A, and the Klenow fragment of DNA polymerase I. With all three enzymes, single molecules tethered to nanotube transistors were electronically monitored for 10 or more minutes, allowing us to directly observe a range of activity including rare transitions to chemically inactive and hyperactive conformations. The high bandwidth of the nanotube transistors further allow every individual chemical event to be clearly resolved, providing excellent statistics from tens of thousands of turnovers by a single enzyme. Initial success with three different enzymes indicates the generality and attractiveness of the nanotube devices as a new tool to complement other single-molecule techniques. Research on transduction mechanisms provides the design rules necessary to further generalize this architecture and apply it to other proteins. The purposeful incorporation of just one amino acid is sufficient to fabricate effective, single molecule sensors from a wide range of enzymes or proteins.

Innovative single-shot diagnostics for electrons from laser wakefield acceleration at FLAME

NASA Astrophysics Data System (ADS)

Bisesto, F. G.; Anania, M. P.; Cianchi, A.; Chiadroni, E.; Curcio, A.; Ferrario, M.; Pompili, R.; Zigler, A.

2017-07-01

Plasma wakefield acceleration is the most promising acceleration technique known nowadays, able to provide very high accelerating fields (> 100 GV/m), enabling acceleration of electrons to GeV energy in few centimeters. Here we present all the plasma related activities currently underway at SPARC_LAB exploiting the high power laser FLAME. In particular, we will give an overview of the single shot diagnostics employed: Electro Optic Sampling (EOS) for temporal measurement and Optical Transition Radiation (OTR) for an innovative one shot emittance measurements. In detail, the EOS technique has been employed to measure for the first time the longitudinal profile of electric field of fast electrons escaping from a solid target, driving the ions and protons acceleration, and to study the impact of using different target shapes. Moreover, a novel scheme for one shot emittance measurements based on OTR, developed and tested at SPARC_LAB LINAC, used in an experiment on electrons from laser wakefield acceleration still undergoing, will be shown.

Correlation of doping, structure, and carrier dynamics in a single GaN nanorod

NASA Astrophysics Data System (ADS)

Zhou, Xiang; Lu, Ming-Yen; Lu, Yu-Jung; Gwo, Shangjr; Gradečak, Silvija

2013-06-01

We report the nanoscale optical investigation of a single GaN p-n junction nanorod by cathodoluminescence (CL) in a scanning transmission electron microscope. CL emission characteristic of dopant-related transitions was correlated to doping and structural defect in the nanorod, and used to determine p-n junction position and minority carrier diffusion lengths of 650 nm and 165 nm for electrons and holes, respectively. Temperature-dependent CL study reveals an activation energy of 19 meV for non-radiative recombination in Mg-doped GaN nanorods. These results directly correlate doping, structure, carrier dynamics, and optical properties of GaN nanostructure, and provide insights for device design and fabrication.

Engineering Single-Atom Cobalt Catalysts toward Improved Electrocatalysis.

PubMed

Wan, Gang; Yu, Pengfei; Chen, Hangrong; Wen, Jianguo; Sun, Cheng-Jun; Zhou, Hua; Zhang, Nian; Li, Qianru; Zhao, Wanpeng; Xie, Bing; Li, Tao; Shi, Jianlin

2018-04-01

The development of cost-effective catalysts to replace noble metal is attracting increasing interests in many fields of catalysis and energy, and intensive efforts are focused on the integration of transition-metal sites in carbon as noble-metal-free candidates. Recently, the discovery of single-atom dispersed catalyst (SAC) provides a new frontier in heterogeneous catalysis. However, the electrocatalytic application of SAC is still subject to several theoretical and experimental limitations. Further advances depend on a better design of SAC through optimizing its interaction with adsorbates during catalysis. Here, distinctive from previous studies, favorable 3d electronic occupation and enhanced metal-adsorbates interactions in single-atom centers via the construction of nonplanar coordination is achieved, which is confirmed by advanced X-ray spectroscopic and electrochemical studies. The as-designed atomically dispersed cobalt sites within nonplanar coordination show significantly improved catalytic activity and selectivity toward the oxygen reduction reaction, approaching the benchmark Pt-based catalysts. More importantly, the illustration of the active sites in SAC indicates metal-natured catalytic sites and a media-dependent catalytic pathway. Achieving structural and electronic engineering on SAC that promotes its catalytic performances provides a paradigm to bridge the gap between single-atom catalysts design and electrocatalytic applications. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Femtosecond few- to single-electron point-projection microscopy for nanoscale dynamic imaging

PubMed Central

Bainbridge, A. R.; Barlow Myers, C. W.; Bryan, W. A.

2016-01-01

Femtosecond electron microscopy produces real-space images of matter in a series of ultrafast snapshots. Pulses of electrons self-disperse under space-charge broadening, so without compression, the ideal operation mode is a single electron per pulse. Here, we demonstrate femtosecond single-electron point projection microscopy (fs-ePPM) in a laser-pump fs-e-probe configuration. The electrons have an energy of only 150 eV and take tens of picoseconds to propagate to the object under study. Nonetheless, we achieve a temporal resolution with a standard deviation of 114 fs (equivalent to a full-width at half-maximum of 269 ± 40 fs) combined with a spatial resolution of 100 nm, applied to a localized region of charge at the apex of a nanoscale metal tip induced by 30 fs 800 nm laser pulses at 50 kHz. These observations demonstrate real-space imaging of reversible processes, such as tracking charge distributions, is feasible whilst maintaining femtosecond resolution. Our findings could find application as a characterization method, which, depending on geometry, could resolve tens of femtoseconds and tens of nanometres. Dynamically imaging electric and magnetic fields and charge distributions on sub-micron length scales opens new avenues of ultrafast dynamics. Furthermore, through the use of active compression, such pulses are an ideal seed for few-femtosecond to attosecond imaging applications which will access sub-optical cycle processes in nanoplasmonics. PMID:27158637

Molecular characterization of organic electronic films.

PubMed

DeLongchamp, Dean M; Kline, R Joseph; Fischer, Daniel A; Richter, Lee J; Toney, Michael F

2011-01-18

Organic electronics have emerged as a viable competitor to amorphous silicon for the active layer in low-cost electronics. The critical performance of organic electronic materials is closely related to their morphology and molecular packing. Unlike their inorganic counterparts, polymers combine complex repeat unit structure and crystalline disorder. This combination prevents any single technique from being able to uniquely solve the packing arrangement of the molecules. Here, a general methodology for combining multiple, complementary techniques that provide accurate unit cell dimensions and molecular orientation is described. The combination of measurements results in a nearly complete picture of the organic film morphology. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis, characterization and biological activities of semicarbazones and their copper complexes.

PubMed

Venkatachalam, Taracad K; Bernhardt, Paul V; Noble, Chris J; Fletcher, Nicholas; Pierens, Gregory K; Thurecht, Kris J; Reutens, David C

2016-09-01

Substituted semicarbazones/thiosemicarbazones and their copper complexes have been prepared and several single crystal structures examined. The copper complexes of these semicarbazone/thiosemicarbazones were prepared and several crystal structures examined. The single crystal X-ray structure of the pyridyl-substituted semicarbazone showed two types of copper complexes, a monomer and a dimer. We also found that the p-nitrophenyl semicarbazone formed a conventional 'magic lantern' acetate-bridged dimer. Electron Paramagnetic Resonance (EPR) of several of the copper complexes was consistent with the results of single crystal X-ray crystallography. The EPR spectra of the p-nitrophenyl semicarbazone copper complex in dimethylsulfoxide (DMSO) showed the presence of two species, confirming the structural information. Since thiosemicarbazones and semicarbazones have been reported to exhibit anticancer activity, we examined the anticancer activity of several of the derivatives reported in the present study and interestingly only the thiosemicarbazone showed activity while the semicarbazones were not active indicating that introduction of sulphur atom alters the biological profile of these thiosemicarbazones. Copyright © 2016 Elsevier Inc. All rights reserved.

Single-molecule imaging of DNA polymerase I (Klenow fragment) activity by atomic force microscopy

NASA Astrophysics Data System (ADS)

Chao, J.; Zhang, P.; Wang, Q.; Wu, N.; Zhang, F.; Hu, J.; Fan, C. H.; Li, B.

2016-03-01

We report a DNA origami-facilitated single-molecule platform that exploits atomic force microscopy to study DNA replication. We imaged several functional activities of the Klenow fragment of E. coli DNA polymerase I (KF) including binding, moving, and dissociation from the template DNA. Upon completion of these actions, a double-stranded DNA molecule was formed. Furthermore, the direction of KF activities was captured and then confirmed by shifting the KF binding sites on the template DNA.We report a DNA origami-facilitated single-molecule platform that exploits atomic force microscopy to study DNA replication. We imaged several functional activities of the Klenow fragment of E. coli DNA polymerase I (KF) including binding, moving, and dissociation from the template DNA. Upon completion of these actions, a double-stranded DNA molecule was formed. Furthermore, the direction of KF activities was captured and then confirmed by shifting the KF binding sites on the template DNA. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06544e

Identifying and counting point defects in carbon nanotubes.

PubMed

Fan, Yuwei; Goldsmith, Brett R; Collins, Philip G

2005-12-01

The prevailing conception of carbon nanotubes and particularly single-walled carbon nanotubes (SWNTs) continues to be one of perfectly crystalline wires. Here, we demonstrate a selective electrochemical method that labels point defects and makes them easily visible for quantitative analysis. High-quality SWNTs are confirmed to contain one defect per 4 microm on average, with a distribution weighted towards areas of SWNT curvature. Although this defect density compares favourably to high-quality, silicon single-crystals, the presence of a single defect can have tremendous electronic effects in one-dimensional conductors such as SWNTs. We demonstrate a one-to-one correspondence between chemically active point defects and sites of local electronic sensitivity in SWNT circuits, confirming the expectation that individual defects may be critical to understanding and controlling variability, noise and chemical sensitivity in SWNT electronic devices. By varying the SWNT synthesis technique, we further show that the defect spacing can be varied over orders of magnitude. The ability to detect and analyse point defects, especially at very low concentrations, indicates the promise of this technique for quantitative process analysis, especially in nanoelectronics development.

Nanoscale multireference quantum chemistry: full configuration interaction on graphical processing units.

PubMed

Fales, B Scott; Levine, Benjamin G

2015-10-13

Methods based on a full configuration interaction (FCI) expansion in an active space of orbitals are widely used for modeling chemical phenomena such as bond breaking, multiply excited states, and conical intersections in small-to-medium-sized molecules, but these phenomena occur in systems of all sizes. To scale such calculations up to the nanoscale, we have developed an implementation of FCI in which electron repulsion integral transformation and several of the more expensive steps in σ vector formation are performed on graphical processing unit (GPU) hardware. When applied to a 1.7 × 1.4 × 1.4 nm silicon nanoparticle (Si72H64) described with the polarized, all-electron 6-31G** basis set, our implementation can solve for the ground state of the 16-active-electron/16-active-orbital CASCI Hamiltonian (more than 100,000,000 configurations) in 39 min on a single NVidia K40 GPU.

Coherent control of single electrons: a review of current progress

NASA Astrophysics Data System (ADS)

Bäuerle, Christopher; Glattli, D. Christian; Meunier, Tristan; Portier, Fabien; Roche, Patrice; Roulleau, Preden; Takada, Shintaro; Waintal, Xavier

2018-05-01

In this report we review the present state of the art of the control of propagating quantum states at the single-electron level and its potential application to quantum information processing. We give an overview of the different approaches that have been developed over the last few years in order to gain full control over a propagating single-electron in a solid-state system. After a brief introduction of the basic concepts, we present experiments on flying qubit circuits for ensemble of electrons measured in the low frequency (DC) limit. We then present the basic ingredients necessary to realise such experiments at the single-electron level. This includes a review of the various single-electron sources that have been developed over the last years and which are compatible with integrated single-electron circuits. This is followed by a review of recent key experiments on electron quantum optics with single electrons. Finally we will present recent developments in the new physics that has emerged using ultrashort voltage pulses. We conclude our review with an outlook and future challenges in the field.

Single Electron Tunneling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ruggiero, Steven T.

Financial support for this project has led to advances in the science of single-electron phenomena. Our group reported the first observation of the so-called ''Coulomb Staircase'', which was produced by tunneling into ultra-small metal particles. This work showed well-defined tunneling voltage steps of width e/C and height e/RC, demonstrating tunneling quantized on the single-electron level. This work was published in a now well-cited Physical Review Letter. Single-electron physics is now a major sub-field of condensed-matter physics, and fundamental work in the area continues to be conducted by tunneling in ultra-small metal particles. In addition, there are now single-electron transistors thatmore » add a controlling gate to modulate the charge on ultra-small photolithographically defined capacitive elements. Single-electron transistors are now at the heart of at least one experimental quantum-computer element, and single-electron transistor pumps may soon be used to define fundamental quantities such as the farad (capacitance) and the ampere (current). Novel computer technology based on single-electron quantum dots is also being developed. In related work, our group played the leading role in the explanation of experimental results observed during the initial phases of tunneling experiments with the high-temperature superconductors. When so-called ''multiple-gap'' tunneling was reported, the phenomenon was correctly identified by our group as single-electron tunneling in small grains in the material. The main focus throughout this project has been to explore single electron phenomena both in traditional tunneling formats of the type metal/insulator/particles/insulator/metal and using scanning tunneling microscopy to probe few-particle systems. This has been done under varying conditions of temperature, applied magnetic field, and with different materials systems. These have included metals, semi-metals, and superconductors. Amongst a number of results, we have verified that clusters of down to one, two, and three metal atoms can be identified with single-electron techniques. We have also, extended the regime of single-electron phenomenology through the observation of single-electron effects in metal droplets in the high-conductance regime.« less

Evaluation of dual γ-ray imager with active collimator using various types of scintillators.

PubMed

Lee, Wonho; Lee, Taewoong; Jeong, Manhee; Kim, Ho Kyung

2011-10-01

The performance of a specialized dual γ-ray imager using both mechanical and electronic collimation was evaluated by Monte Carlo simulation (MCNP5). The dual imager consisted of an active collimator and a planar detector that were made from scintillators. The active collimator served not only as a coded aperture for mechanical collimation but also as a first detector for electronic collimation. Therefore, a single system contained both mechanical and electronic collimation. Various types of scintillators were tested and compared with each other in terms of their angular resolution, efficiency, and background noise. In general, a BGO active collimator had the best mechanical collimation performance, and an LaCl₃(Ce) active collimator provided the best electronic collimation performance. However, for low radiation energies, the mechanical collimation images made from both scintillators showed the same quality, and, for high radiation energies, electronic collimation images made from both scintillators also show similar quality. Therefore, if mechanical collimation is used to detect low-energy radiation and electronic collimation is applied to reconstruct a high-energy source, either LaCl₃(Ce) or BGO would be appropriate for the active collimator of a dual γ-ray imager. These results broaden the choice of scintillators for the active collimator of the dual γ-ray imager, which makes it possible to consider other factors, such as machinability and cost, in making the imager. As a planar detector, BGO showed better performance than other scintillators since its radiation detection efficiency was highest of all. Copyright © 2011 Elsevier Ltd. All rights reserved.

Highly mesoporous single-crystalline zeolite beta synthesized using a nonsurfactant cationic polymer as a dual-function template.

PubMed

Zhu, Jie; Zhu, Yihan; Zhu, Liangkui; Rigutto, Marcello; van der Made, Alexander; Yang, Chengguang; Pan, Shuxiang; Wang, Liang; Zhu, Longfeng; Jin, Yinying; Sun, Qi; Wu, Qinming; Meng, Xiangju; Zhang, Daliang; Han, Yu; Li, Jixue; Chu, Yueying; Zheng, Anmin; Qiu, Shilun; Zheng, Xiaoming; Xiao, Feng-Shou

2014-02-12

Mesoporous zeolites are useful solid catalysts for conversion of bulky molecules because they offer fast mass transfer along with size and shape selectivity. We report here the successful synthesis of mesoporous aluminosilicate zeolite Beta from a commercial cationic polymer that acts as a dual-function template to generate zeolitic micropores and mesopores simultaneously. This is the first demonstration of a single nonsurfactant polymer acting as such a template. Using high-resolution electron microscopy and tomography, we discovered that the resulting material (Beta-MS) has abundant and highly interconnected mesopores. More importantly, we demonstrated using a three-dimensional electron diffraction technique that each Beta-MS particle is a single crystal, whereas most previously reported mesoporous zeolites are comprised of nanosized zeolitic grains with random orientations. The use of nonsurfactant templates is essential to gaining single-crystalline mesoporous zeolites. The single-crystalline nature endows Beta-MS with better hydrothermal stability compared with surfactant-derived mesoporous zeolite Beta. Beta-MS also exhibited remarkably higher catalytic activity than did conventional zeolite Beta in acid-catalyzed reactions involving large molecules.

Innovative single-shot diagnostics for electrons accelerated through laser-plasma interaction at FLAME

NASA Astrophysics Data System (ADS)

Bisesto, F. G.; Anania, M. P.; Chiadroni, E.; Cianchi, A.; Costa, G.; Curcio, A.; Ferrario, M.; Galletti, M.; Pompili, R.; Schleifer, E.; Zigler, A.

2017-05-01

Plasma wakefield acceleration is the most promising acceleration technique known nowadays, able to provide very high accelerating fields (> 100 GV/m), enabling acceleration of electrons to GeV energy in few centimeters. Here we present all the plasma related activities currently underway at SPARC LAB exploiting the high power laser FLAME. In particular, we will give an overview of the single shot diagnostics employed: Electro Optic Sampling (EOS) for temporal measurement and optical transition radiation (OTR) for an innovative one shot emittance measurements. In detail, the EOS technique has been employed to measure for the first time the longitudinal profile of electric field of fast electrons escaping from a solid target, driving the ions and protons acceleration, and to study the impact of using different target shapes. Moreover, a novel scheme for one shot emittance measurements based on OTR, developed and tested at SPARC LAB LINAC, will be shown.

Electron source for a mini ion trap mass spectrometer

DOEpatents

Dietrich, Daniel D.; Keville, Robert F.

1995-01-01

An ion trap which operates in the regime between research ion traps which can detect ions with a mass resolution of better than 1:10.sup.9 and commercial mass spectrometers requiring 10.sup.4 ions with resolutions of a few hundred. The power consumption is kept to a minimum by the use of permanent magnets and a novel electron gun design. By Fourier analyzing the ion cyclotron resonance signals induced in the trap electrodes, a complete mass spectra in a single combined structure can be detected. An attribute of the ion trap mass spectrometer is that overall system size is drastically reduced due to combining a unique electron source and mass analyzer/detector in a single device. This enables portable low power mass spectrometers for the detection of environmental pollutants or illicit substances, as well as sensors for on board diagnostics to monitor engine performance or for active feedback in any process involving exhausting waste products.

Sketched oxide single-electron transistor

NASA Astrophysics Data System (ADS)

Cheng, Guanglei; Siles, Pablo F.; Bi, Feng; Cen, Cheng; Bogorin, Daniela F.; Bark, Chung Wung; Folkman, Chad M.; Park, Jae-Wan; Eom, Chang-Beom; Medeiros-Ribeiro, Gilberto; Levy, Jeremy

2011-06-01

Devices that confine and process single electrons represent an important scaling limit of electronics. Such devices have been realized in a variety of materials and exhibit remarkable electronic, optical and spintronic properties. Here, we use an atomic force microscope tip to reversibly `sketch' single-electron transistors by controlling a metal-insulator transition at the interface of two oxides. In these devices, single electrons tunnel resonantly between source and drain electrodes through a conducting oxide island with a diameter of ~1.5 nm. We demonstrate control over the number of electrons on the island using bottom- and side-gate electrodes, and observe hysteresis in electron occupation that is attributed to ferroelectricity within the oxide heterostructure. These single-electron devices may find use as ultradense non-volatile memories, nanoscale hybrid piezoelectric and charge sensors, as well as building blocks in quantum information processing and simulation platforms.

Support effects in single atom iron catalysts on adsorption characteristics of toxic gases (NO2, NH3, SO3 and H2S)

NASA Astrophysics Data System (ADS)

Gao, Zhengyang; Yang, Weijie; Ding, Xunlei; Lv, Gang; Yan, Weiping

2018-04-01

The effects of support on gas adsorption is crucial for single atom catalysts design and optimization. To gain insight into support effects on gas adsorption characteristics, a comprehensive theoretical study was performed to investigate the adsorption characteristics of toxic gases (NO2, NH3, SO3 and H2S) by utilizing single atom iron catalysts with three graphene-based supports. The adsorption geometry, adsorption energy, electronic and magnetic properties of the adsorption system have been explored. Additionally, the support effects have been analyzed through d-band center and Fermi softness, and thermodynamic analysis has been performed to consider the effect of temperature on gas adsorption. The support effects have a remarkable influence on the adsorption characteristics of four types of toxic gases which is determined by the electronic structure of graphene-based support, and the electronic structure can be characterized by Fermi softness of catalysts. Fermi softness and uplift height of Fe atom could be good descriptors for the adsorption activity of single atom iron catalysts with graphene-based supports. The findings can lay a foundation for the further study of graphene-based support effects in single atom catalysts and provide a guideline for development and design of new graphene-based support materials utilizing the idea of Fermi softness.

The Difference a Single Atom Can Make: Synthesis and Design at the Chemistry–Biology Interface

PubMed Central

2017-01-01

A Perspective of work in our laboratory on the examination of biologically active compounds, especially natural products, is presented. In the context of individual programs and along with a summary of our work, selected cases are presented that illustrate the impact single atom changes can have on the biological properties of the compounds. The examples were chosen to highlight single heavy atom changes that improve activity, rather than those that involve informative alterations that reduce or abolish activity. The examples were also chosen to illustrate that the impact of such single-atom changes can originate from steric, electronic, conformational, or H-bonding effects, from changes in functional reactivity, from fundamental intermolecular interactions with a biological target, from introduction of a new or altered functionalization site, or from features as simple as improvements in stability or physical properties. Nearly all the examples highlighted represent not only unusual instances of productive deep-seated natural product modifications and were introduced through total synthesis but are also remarkable in that they are derived from only a single heavy atom change in the structure. PMID:28945374

Single layers and multilayers of GaN and AlN in square-octagon structure: Stability, electronic properties, and functionalization

NASA Astrophysics Data System (ADS)

Gürbüz, E.; Cahangirov, S.; Durgun, E.; Ciraci, S.

2017-11-01

Further to planar single-layer hexagonal structures, GaN and AlN can also form free-standing, single-layer structures constructed from squares and octagons. We performed an extensive analysis of dynamical and thermal stability of these structures in terms of ab initio finite-temperature molecular dynamics and phonon calculations together with the analysis of Raman and infrared active modes. These single-layer square-octagon structures of GaN and AlN display directional mechanical properties and have wide, indirect fundamental band gaps, which are smaller than their hexagonal counterparts. These density functional theory band gaps, however, increase and become wider upon correction. Under uniaxial and biaxial tensile strain, the fundamental band gaps decrease and can be closed. The electronic and magnetic properties of these single-layer structures can be modified by adsorption of various adatoms, or by creating neutral cation-anion vacancies. The single-layer structures attain magnetic moment by selected adatoms and neutral vacancies. In particular, localized gap states are strongly dependent on the type of vacancy. The energetics, binding, and resulting electronic structure of bilayer, trilayer, and three-dimensional (3D) layered structures constructed by stacking the single layers are affected by vertical chemical bonds between adjacent layers. In addition to van der Waals interaction, these weak vertical bonds induce buckling in planar geometry and enhance their binding, leading to the formation of stable 3D layered structures. In this respect, these multilayers are intermediate between van der Waals solids and wurtzite crystals, offering a wide range of tunability.

Modeling Alkyl p-Methoxy Cinnamate (APMC) as UV absorber based on electronic transition using semiempirical quantum mechanics ZINDO/s calculation

NASA Astrophysics Data System (ADS)

Salmahaminati; Azis, Muhlas Abdul; Purwiandono, Gani; Arsyik Kurniawan, Muhammad; Rubiyanto, Dwiarso; Darmawan, Arif

2017-11-01

In this research, modeling several alkyl p-methoxy cinnamate (APMC) based on electronic transition by using semiempirical mechanical quantum ZINDO/s calculation is performed. Alkyl cinnamates of C1 (methyl) up to C7 (heptyl) homolog with 1-5 example structures of each homolog are used as materials. Quantum chemistry-package software Hyperchem 8.0 is used to simulate the drawing of the structure, geometry optimization by a semiempirical Austin Model 1 algorithm and single point calculation employing a semiempirical ZINDO/s technique. ZINDO/s calculations use a defined criteria that singly excited -Configuration Interaction (CI) where a gap of HOMO-LUMO energy transition and maximum degeneracy level are 7 and 2, respectively. Moreover, analysis of the theoretical spectra is focused on the UV-B (290-320 nm) and UV-C (200-290 nm) area. The results show that modeling of the compound can be used to predict the type of UV protection activity depends on the electronic transition in the UV area. Modification of the alkyl homolog relatively does not change the value of wavelength absorption to indicate the UV protection activity. Alkyl cinnamate compounds are predicted as UV-B and UV-C sunscreen.

Electrochemical Studies of a Truncated Laccase Produced in Pichia pastoris

PubMed Central

Gelo-Pujic, Mirjana; Kim, Hyug-Han; Butlin, Nathan G.; Palmore, G. Tayhas R.

1999-01-01

The cDNA that encodes an isoform of laccase from Trametes versicolor (LCCI), as well as a truncated version (LCCIa), was subcloned and expressed by using the yeast Pichia pastoris as the heterologous host. The amino acid sequence of LCCIa is identical to that of LCCI except that the final 11 amino acids at the C terminus of LCCI are replaced with a single cysteine residue. This modification was introduced for the purpose of improving the kinetics of electron transfer between an electrode and the copper-containing active site of laccase. The two laccases (LCCI and LCCIa) are compared in terms of their relative activity with two substrates that have different redox potentials. Results from electrochemical studies on solutions containing LCCI and LCCIa indicate that the redox potential of the active site of LCCIa is shifted to more negative values (411 mV versus normal hydrogen electrode voltage) than that found in other fungal laccases. In addition, replacing the 11 codons at the C terminus of the laccase gene with a single cysteine codon (i.e., LCCI→LCCIa) influences the rate of heterogeneous electron transfer between an electrode and the copper-containing active site (khet for LCCIa = 1.3 × 10−4 cm s−1). These results demonstrate for the first time that the rate of electron transfer between an oxidoreductase and an electrode can be enhanced by changes to the primary structure of a protein via site-directed mutagenesis. PMID:10584012

Sketched Oxide Single-Electron Transistor

NASA Astrophysics Data System (ADS)

Cheng, Guanglei

2012-02-01

Devices that confine and process single electrons represent an important scaling limit of electronics. Such devices have been realized in a variety of materials and exhibit remarkable electronic, optical and spintronic properties. Here, we use an atomic force microscope tip to reversibly ``sketch'' single-electron transistors by controlling a metal-insulator transition at the interface of two oxides.ootnotetextCheng et al., Nature Nanotechnology 6, 343 (2011). In these devices, single electrons tunnel resonantly between source and drain electrodes through a conducting oxide island with a diameter of ˜1.5 nm. We demonstrate control over the number of electrons on the island using bottom- and side-gate electrodes, and observe hysteresis in electron occupation that is attributed to ferroelectricity within the oxide heterostructure. These single-electron devices may find use as ultradense non-volatile memories, nanoscale hybrid piezoelectric and charge sensors, as well as building blocks in quantum information processing and simulation platforms.

Ultrafast electron transport across nano gaps in nanowire circuits

DOE Office of Scientific and Technical Information (OSTI.GOV)

Potma, Eric O.

In this Program we aim for a closer look at electron transfer through single molecules. To achieve this, we use ultrafast laser pulses to time stamp an electron tunneling event in a molecule that is connected between two metallic electrodes, while reading out the electron current. A key aspect of this project is the use of metallic substrates with plasmonic activity to efficiently manipulate the tunneling probability. The first Phase of this program is concerned with developing highly sensitive tools for the ultrafast optical manipulation of tethered molecules through the evanescent surface field of plasmonic substrates. The second Phase ofmore » the program aims to use these tools for exercising control over the electron tunneling probability.« less

Fabrication and single-electron-transfer operation of a triple-dot single-electron transistor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jo, Mingyu, E-mail: mingyujo@eis.hokudai.ac.jp; Uchida, Takafumi; Tsurumaki-Fukuchi, Atsushi

2015-12-07

A triple-dot single-electron transistor was fabricated on silicon-on-insulator wafer using pattern-dependent oxidation. A specially designed one-dimensional silicon wire having small constrictions at both ends was converted to a triple-dot single-electron transistor by means of pattern-dependent oxidation. The fabrication of the center dot involved quantum size effects and stress-induced band gap reduction, whereas that of the two side dots involved thickness modulation because of the complex edge structure of two-dimensional silicon. Single-electron turnstile operation was confirmed at 8 K when a 100-mV, 1-MHz square wave was applied. Monte Carlo simulations indicated that such a device with inhomogeneous tunnel and gate capacitances canmore » exhibit single-electron transfer.« less

Complete active space configuration interaction from state-averaged configuration interaction singles natural orbitals: Analytic first derivatives and derivative coupling vectors

NASA Astrophysics Data System (ADS)

Fales, B. Scott; Shu, Yinan; Levine, Benjamin G.; Hohenstein, Edward G.

2017-09-01

A new complete active space configuration interaction (CASCI) method was recently introduced that uses state-averaged natural orbitals from the configuration interaction singles method (configuration interaction singles natural orbital CASCI, CISNO-CASCI). This method has been shown to perform as well or better than state-averaged complete active space self-consistent field for a variety of systems. However, further development and testing of this method have been limited by the lack of available analytic first derivatives of the CISNO-CASCI energy as well as the derivative coupling between electronic states. In the present work, we present a Lagrangian-based formulation of these derivatives as well as a highly efficient implementation of the resulting equations accelerated with graphical processing units. We demonstrate that the CISNO-CASCI method is practical for dynamical simulations of photochemical processes in molecular systems containing hundreds of atoms.

Complete active space configuration interaction from state-averaged configuration interaction singles natural orbitals: Analytic first derivatives and derivative coupling vectors.

PubMed

Fales, B Scott; Shu, Yinan; Levine, Benjamin G; Hohenstein, Edward G

2017-09-07

A new complete active space configuration interaction (CASCI) method was recently introduced that uses state-averaged natural orbitals from the configuration interaction singles method (configuration interaction singles natural orbital CASCI, CISNO-CASCI). This method has been shown to perform as well or better than state-averaged complete active space self-consistent field for a variety of systems. However, further development and testing of this method have been limited by the lack of available analytic first derivatives of the CISNO-CASCI energy as well as the derivative coupling between electronic states. In the present work, we present a Lagrangian-based formulation of these derivatives as well as a highly efficient implementation of the resulting equations accelerated with graphical processing units. We demonstrate that the CISNO-CASCI method is practical for dynamical simulations of photochemical processes in molecular systems containing hundreds of atoms.

A tractable and accurate electronic structure method for static correlations: The perfect hextuples model

NASA Astrophysics Data System (ADS)

Parkhill, John A.; Head-Gordon, Martin

2010-07-01

We present the next stage in a hierarchy of local approximations to complete active space self-consistent field (CASSCF) model in an active space of one active orbital per active electron based on the valence orbital-optimized coupled-cluster (VOO-CC) formalism. Following the perfect pairing (PP) model, which is exact for a single electron pair and extensive, and the perfect quadruples (PQ) model, which is exact for two pairs, we introduce the perfect hextuples (PH) model, which is exact for three pairs. PH is an approximation to the VOO-CC method truncated at hextuples containing all correlations between three electron pairs. While VOO-CCDTQ56 requires computational effort scaling with the 14th power of molecular size, PH requires only sixth power effort. Our implementation also introduces some techniques which reduce the scaling to fifth order and has been applied to active spaces roughly twice the size of the CASSCF limit without any symmetry. Because PH explicitly correlates up to six electrons at a time, it can faithfully model the static correlations of molecules with up to triple bonds in a size-consistent fashion and for organic reactions usually reproduces CASSCF with chemical accuracy. The convergence of the PP, PQ, and PH hierarchy is demonstrated on a variety of examples including symmetry breaking in benzene, the Cope rearrangement, the Bergman reaction, and the dissociation of fluorine.

Selective scanning tunnelling microscope electron-induced reactions of single biphenyl molecules on a Si(100) surface.

PubMed

Riedel, Damien; Bocquet, Marie-Laure; Lesnard, Hervé; Lastapis, Mathieu; Lorente, Nicolas; Sonnet, Philippe; Dujardin, Gérald

2009-06-03

Selective electron-induced reactions of individual biphenyl molecules adsorbed in their weakly chemisorbed configuration on a Si(100) surface are investigated by using the tip of a low-temperature (5 K) scanning tunnelling microscope (STM) as an atomic size source of electrons. Selected types of molecular reactions are produced, depending on the polarity of the surface voltage during STM excitation. At negative surface voltages, the biphenyl molecule diffuses across the surface in its weakly chemisorbed configuration. At positive surface voltages, different types of molecular reactions are activated, which involve the change of adsorption configuration from the weakly chemisorbed to the strongly chemisorbed bistable and quadristable configurations. Calculated reaction pathways of the molecular reactions on the silicon surface, using the nudge elastic band method, provide evidence that the observed selectivity as a function of the surface voltage polarity cannot be ascribed to different activation energies. These results, together with the measured threshold surface voltages and the calculated molecular electronic structures via density functional theory, suggest that the electron-induced molecular reactions are driven by selective electron detachment (oxidation) or attachment (reduction) processes.

Large-scale recording of thalamocortical circuits: in vivo electrophysiology with the two-dimensional electronic depth control silicon probe.

PubMed

Fiáth, Richárd; Beregszászi, Patrícia; Horváth, Domonkos; Wittner, Lucia; Aarts, Arno A A; Ruther, Patrick; Neves, Hercules P; Bokor, Hajnalka; Acsády, László; Ulbert, István

2016-11-01

Recording simultaneous activity of a large number of neurons in distributed neuronal networks is crucial to understand higher order brain functions. We demonstrate the in vivo performance of a recently developed electrophysiological recording system comprising a two-dimensional, multi-shank, high-density silicon probe with integrated complementary metal-oxide semiconductor electronics. The system implements the concept of electronic depth control (EDC), which enables the electronic selection of a limited number of recording sites on each of the probe shafts. This innovative feature of the system permits simultaneous recording of local field potentials (LFP) and single- and multiple-unit activity (SUA and MUA, respectively) from multiple brain sites with high quality and without the actual physical movement of the probe. To evaluate the in vivo recording capabilities of the EDC probe, we recorded LFP, MUA, and SUA in acute experiments from cortical and thalamic brain areas of anesthetized rats and mice. The advantages of large-scale recording with the EDC probe are illustrated by investigating the spatiotemporal dynamics of pharmacologically induced thalamocortical slow-wave activity in rats and by the two-dimensional tonotopic mapping of the auditory thalamus. In mice, spatial distribution of thalamic responses to optogenetic stimulation of the neocortex was examined. Utilizing the benefits of the EDC system may result in a higher yield of useful data from a single experiment compared with traditional passive multielectrode arrays, and thus in the reduction of animals needed for a research study. Copyright © 2016 the American Physiological Society.

Single-electron random-number generator (RNG) for highly secure ubiquitous computing applications

NASA Astrophysics Data System (ADS)

Uchida, Ken; Tanamoto, Tetsufumi; Fujita, Shinobu

2007-11-01

Since the security of all modern cryptographic techniques relies on unpredictable and irreproducible digital keys generated by random-number generators (RNGs), the realization of high-quality RNG is essential for secure communications. In this report, a new RNG, which utilizes single-electron phenomena, is proposed. A room-temperature operating silicon single-electron transistor (SET) having nearby an electron pocket is used as a high-quality, ultra-small RNG. In the proposed RNG, stochastic single-electron capture/emission processes to/from the electron pocket are detected with high sensitivity by the SET, and result in giant random telegraphic signals (GRTS) on the SET current. It is experimentally demonstrated that the single-electron RNG generates extremely high-quality random digital sequences at room temperature, in spite of its simple configuration. Because of its small-size and low-power properties, the single-electron RNG is promising as a key nanoelectronic device for future ubiquitous computing systems with highly secure mobile communication capabilities.

Characterizing the response of a scintillator-based detector to single electrons.

PubMed

Sang, Xiahan; LeBeau, James M

2016-02-01

Here we report the response of a high angle annular dark field scintillator-based detector to single electrons. We demonstrate that care must be taken when determining the single electron intensity as significant discrepancies can occur when quantifying STEM images with different methods. To account for the detector response, we first image the detector using very low beam currents (∼8fA), and subsequently model the interval between consecutive single electrons events. We find that single electrons striking the detector present a wide distribution of intensities, which we show is not described by a simple function. Further, we present a method to accurately account for the electrons within the incident probe when conducting quantitative imaging. The role detector settings play on determining the single electron intensity is also explored. Finally, we extend our analysis to describe the response of the detector to multiple electron events within the dwell interval of each pixel. Copyright © 2015 Elsevier B.V. All rights reserved.

Single-electron thermal noise

NASA Astrophysics Data System (ADS)

Nishiguchi, Katsuhiko; Ono, Yukinori; Fujiwara, Akira

2014-07-01

We report the observation of thermal noise in the motion of single electrons in an ultimately small dynamic random access memory (DRAM). The nanometer-scale transistors that compose the DRAM resolve the thermal noise in single-electron motion. A complete set of fundamental tests conducted on this single-electron thermal noise shows that the noise perfectly follows all the aspects predicted by statistical mechanics, which include the occupation probability, the law of equipartition, a detailed balance, and the law of kT/C. In addition, the counting statistics on the directional motion (i.e., the current) of the single-electron thermal noise indicate that the individual electron motion follows the Poisson process, as it does in shot noise.

Single-electron thermal noise.

PubMed

Nishiguchi, Katsuhiko; Ono, Yukinori; Fujiwara, Akira

2014-07-11

We report the observation of thermal noise in the motion of single electrons in an ultimately small dynamic random access memory (DRAM). The nanometer-scale transistors that compose the DRAM resolve the thermal noise in single-electron motion. A complete set of fundamental tests conducted on this single-electron thermal noise shows that the noise perfectly follows all the aspects predicted by statistical mechanics, which include the occupation probability, the law of equipartition, a detailed balance, and the law of kT/C. In addition, the counting statistics on the directional motion (i.e., the current) of the single-electron thermal noise indicate that the individual electron motion follows the Poisson process, as it does in shot noise.

Highly water-dispersible, mixed ionic-electronic conducting, polymer acid-doped polyanilines as ionomers for direct methanol fuel cells.

PubMed

Murthy, Arun; Manthiram, Arumugam

2011-06-28

Highly water-dispersible polymer acid-doped polyanilines have been synthesized and evaluated as an alternative for expensive Nafion ionomers in the anode of direct methanol fuel cells (DMFC). These polymers as ionomers lead to higher performance in single cell DMFC compared to Nafion ionomers due to mixed ionic-electronic conduction, water dispersibility, and co-catalytic activity. This journal is © The Royal Society of Chemistry 2011

Cyclic Degradation Behavior of < 001 > -Oriented Fe-Mn-Al-Ni Single Crystals in Tension

NASA Astrophysics Data System (ADS)

Vollmer, M.; Kriegel, M. J.; Krooß, P.; Martin, S.; Klemm, V.; Weidner, A.; Chumlyakov, Y.; Biermann, H.; Rafaja, D.; Niendorf, T.

2017-12-01

In the present study, functional fatigue behavior of a near 〈001〉-oriented Fe-Mn-Al-Ni single crystal was investigated under tensile load. An incremental strain test up to 3.5% strain and cyclic tests up to 25 cycles revealed rapid pseudoelastic degradation. Progressive microstructural degradation was studied by in situ scanning electron microscopy. The results show a partially inhibited reactivation of previously formed martensite and proceeding activation of untransformed areas in subsequent cycles. The preferentially formed martensite variants were identified by means of Schmid factor calculation and the Kurdjumov-Sachs relationship. Post mortem transmission electron microscopy investigations shed light on the prevailing degradation mechanisms. Different types of dislocations were found promoting the progressive degradation during cyclic loading.

Synthesis and characterization of activated carbon from white lotus via single step chemical activation

NASA Astrophysics Data System (ADS)

Andas, Jeyashelly; Midon, Muhammad Dzulfiqar

2017-08-01

Highly porous activated carbon was successfully fabricated from the stalk of Nymphaea odorata via single step chemical activation. ZnCl2 was used as the chemical activating agent in the activation process. The raw material was preliminary characterized using Fourier Transform Infrared (FTIR), ultimate analysis (CHNS/O Analyzer) and Scanning Electron Microscope (SEM). The percentage yield, iodine number (IN) and the textural properties of the activated carbon were optimized under the influence of several synthesizing parameters such as impregnation ratio, activation temperature and activation time using ZnCl2. High IN (750.11 mg/g - 967.16 mg/g) was obtained from Sodium thiosulphate volumetric method and represents the porosity of the synthesized materials. Reduction in several functional groups was observed in the FTIR spectrum of the synthesized activated carbon. SEM analysis of the activated carbon verified the formation of highly porous surface compared to the raw Nymphaea odorata. This study provides a facile synthesis of activated carbon from waste natural resources at benign condition.

Single-electron pulses for ultrafast diffraction

PubMed Central

Aidelsburger, M.; Kirchner, F. O.; Krausz, F.; Baum, P.

2010-01-01

Visualization of atomic-scale structural motion by ultrafast electron diffraction and microscopy requires electron packets of shortest duration and highest coherence. We report on the generation and application of single-electron pulses for this purpose. Photoelectric emission from metal surfaces is studied with tunable ultraviolet pulses in the femtosecond regime. The bandwidth, efficiency, coherence, and electron pulse duration are investigated in dependence on excitation wavelength, intensity, and laser bandwidth. At photon energies close to the cathode’s work function, the electron pulse duration shortens significantly and approaches a threshold that is determined by interplay of the optical pulse width and the acceleration field. An optimized choice of laser wavelength and bandwidth results in sub-100-fs electron pulses. We demonstrate single-electron diffraction from polycrystalline diamond films and reveal the favorable influences of matched photon energies on the coherence volume of single-electron wave packets. We discuss the consequences of our findings for the physics of the photoelectric effect and for applications of single-electron pulses in ultrafast 4D imaging of structural dynamics. PMID:21041681

Electron-beam-induced-current and active secondary-electron voltage-contrast with aberration-corrected electron probes

DOE PAGES

Han, Myung-Geun; Garlow, Joseph A.; Marshall, Matthew S. J.; ...

2017-03-23

The ability to map out electrostatic potentials in materials is critical for the development and the design of nanoscale electronic and spintronic devices in modern industry. Electron holography has been an important tool for revealing electric and magnetic field distributions in microelectronics and magnetic-based memory devices, however, its utility is hindered by several practical constraints, such as charging artifacts and limitations in sensitivity and in field of view. In this article, we report electron-beam-induced-current (EBIC) and secondary-electron voltage-contrast (SE-VC) with an aberration-corrected electron probe in a transmission electron microscope (TEM), as complementary techniques to electron holography, to measure electric fieldsmore » and surface potentials, respectively. These two techniques were applied to ferroelectric thin films, multiferroic nanowires, and single crystals. Electrostatic potential maps obtained by off-axis electron holography were compared with EBIC and SE-VC to show that these techniques can be used as a complementary approach to validate quantitative results obtained from electron holography analysis.« less

CNTs threaded (001) exposed TiO2 with high activity in photocatalytic NO oxidation.

PubMed

Xiao, Shuning; Zhu, Wei; Liu, Peijue; Liu, Fanfan; Dai, Wenrui; Zhang, Dieqing; Chen, Wei; Li, Hexing

2016-02-07

A microwave-ionothermal strategy was developed for in situ synthesis of CNTs threaded TiO2 single crystal with a tunable percentage of surface exposed (001) active facets. The CNTs were used as microwave antennas to create local "super hot" dots to induce Ti(3+) adsorption and hydrolysis, thereby leading to a good assembly of (001) facets exposed single crystalline TiO2 threaded by the CNTs in the presence of Hmim[BF4] ionic liquid. Due to the high percentage of the active (001) facets of single crystal TiO2 and the direct electron transfer property of the CNTs, the as-prepared CNTs-TiO2 composite showed a photocatalytic NO removal ratio of up to 76.8% under UV irradiation. In addition, with self-doped Ti(3+), the CNTs-TiO2 composite also exhibited an enhanced activity under irradiation with either solar lights or visible lights, showing good potential in practical applications for environmental remediation.

Monitoring single protease activities on triple-helical collagen molecules

NASA Astrophysics Data System (ADS)

Harzar, Raj; Froberg, James; Srivastava, D. K.; Choi, Yongki

Matrix metalloproteinases (MMPs), a particular family of proteases, play a pivotal role in degrading the extracellular matrix (ECM). It has been known for more than 40 years that MMPs are closely involved in multiple human cancers during cell growth, invasion, and metastasis. However, the mechanisms of MMP activity are far from being understood. Here, we monitored enzymatic processing of MMPs with two complementary approaches, atomic force microscopy and nanocircuits measurements. AFM measurements demonstrated that incubation of collagen monomers with MMPs resulted in a single position cleavage, producing 3/4 and 1/4 collagen fragments. From electronic monitoring of single MMP nanocircuit measurements, we were able to capture a single cleavage event with a rate of 0.012 Hz, which were in good agreement with fluorescence assay measurements. This work was supported financially by the NIGMS/NIH (P30GM103332-02) and ND NASA EPSCoR RID Grant.

Major impact of N-methylation on cytotoxicity and hydrolysis of salan Ti(IV) complexes: sterics and electronics are intertwined.

PubMed

Meker, Sigalit; Manna, Cesar M; Peri, Dani; Tshuva, Edit Y

2011-10-14

A series of Ti(IV) complexes containing diamino bis(phenolato) "salan" type ligands with NH coordination were prepared, and their hydrolysis and cytotoxicity were analyzed and compared to the N-methylated analogues. Substituting methyl groups on the coordinative nitrogen donor of highly active and stable Ti(IV) salan complexes with H atoms has two main consequences: the hydrolysis rate increases and the cytotoxic activity diminishes. In addition, the small modification of a single replacement of Me with H leads to a different major hydrolysis product, where a dinuclear Ti(IV) complex with two bridging oxo ligands is obtained, as characterized by X-ray crystallography, rather than a trinuclear cluster. A partial hydrolysis product containing a single oxo bridge was also crystallographically analyzed. Investigation of a series of complexes with NH donors of different steric and electronic effects revealed that cytotoxicity may be restored by fine tuning these parameters even for complexes of low stability.

Impact of Mutations on the Midpoint Potential of the [4Fe-4S]+1,+2 Cluster and on Catalytic Activity in Electron Transfer Flavoprotein-ubiquinone Oxidoreductase (ETF-QO)†

PubMed Central

Usselman, Robert J.; Fielding, Alistair J.; Frerman, Frank E.; Watmough, Nicholas J.; Eaton, Gareth R.; Eaton, Sandra S.

2011-01-01

Electron transfer flavoprotein - ubiquinone oxidoreductase (ETF-QO) is an iron-sulfur flavoprotein that accepts electrons from electron-transfer flavoprotein (ETF) and reduces ubiquinone from the Q-pool. ETF-QO contains a single [4Fe-4S]2+,1+ cluster and one equivalent of FAD, which are diamagnetic in the isolated oxidized enzyme and can be reduced to paramagnetic forms by enzymatic donors or dithionite. Mutations were introduced by site-directed mutagenesis of amino acids in the vicinity of the iron-sulfur cluster of Rhodobacter sphaeroides ETF-QO. Y501 and T525 are equivalent to Y533 and T558 in the porcine ETF-QO. In the porcine protein, these residues are within hydrogen bonding distance of the Sγ of the cysteine ligands to the iron-sulfur cluster. Y501F, T525A, and Y501F/T525A substitutions were made to determine the effects on midpoint potential, activity, and EPR spectral properties of the cluster. The integrity of the mutated proteins was confirmed by optical spectra, EPR g-values, and spin-lattice relaxation rates, and the cluster to flavin point-dipole distance was determined by relaxation enhancement. Potentiometric titrations were monitored by changes in the CW EPR signals of the cluster and semiquinone. Single mutations decreased the mid-point potentials of the iron-sulfur cluster from +37 mV for wild type to −60 mV for Y501F and T525A and to −128 mV for Y501F/T525A. Lowering the midpoint potential resulted in a decrease in steady-state ubiquinone reductase activity and in ETF semiquinone disproportionation. The decrease in activity demonstrates that reduction of the iron-sulfur cluster is required for activity. There was no detectable effect of the mutations on the flavin midpoint potentials. PMID:18069858

Impact of mutations on the midpoint potential of the [4Fe-4S]+1,+2 cluster and on catalytic activity in electron transfer flavoprotein-ubiquinone oxidoreductase (ETF-QO).

PubMed

Usselman, Robert J; Fielding, Alistair J; Frerman, Frank E; Watmough, Nicholas J; Eaton, Gareth R; Eaton, Sandra S

2008-01-08

Electron-transfer flavoprotein-ubiquinone oxidoreductase (ETF-QO) is an iron-sulfur flavoprotein that accepts electrons from electron-transfer flavoprotein (ETF) and reduces ubiquinone from the Q-pool. ETF-QO contains a single [4Fe-4S]2+,1+ cluster and one equivalent of FAD, which are diamagnetic in the isolated oxidized enzyme and can be reduced to paramagnetic forms by enzymatic donors or dithionite. Mutations were introduced by site-directed mutagenesis of amino acids in the vicinity of the iron-sulfur cluster of Rhodobacter sphaeroides ETF-QO. Y501 and T525 are equivalent to Y533 and T558 in the porcine ETF-QO. In the porcine protein, these residues are within hydrogen-bonding distance of the Sgamma of the cysteine ligands to the iron-sulfur cluster. Y501F, T525A, and Y501F/T525A substitutions were made to determine the effects on midpoint potential, activity, and EPR spectral properties of the cluster. The integrity of the mutated proteins was confirmed by optical spectra, EPR g-values, and spin-lattice relaxation rates, and the cluster to flavin point-dipole distance was determined by relaxation enhancement. Potentiometric titrations were monitored by changes in the CW EPR signals of the cluster and semiquinone. Single mutations decreased the midpoint potentials of the iron-sulfur cluster from +37 mV for wild type to -60 mV for Y501F and T525A and to -128 mV for Y501F/T525A. Lowering the midpoint potential resulted in a decrease in steady-state ubiquinone reductase activity and in ETF semiquinone disproportionation. The decrease in activity demonstrates that reduction of the iron-sulfur cluster is required for activity. There was no detectable effect of the mutations on the flavin midpoint potentials.

An investigation into the feasibility of myoglobin-based single-electron transistors

PubMed Central

Li, Debin; Gannett, Peter M.; Lederman, David

2016-01-01

Myoglobin single-electron transistors were investigated using nanometer-gap platinum electrodes fabricated by electromigration at cryogenic temperatures. Apomyoglobin (myoglobin without heme group) was used as a reference. The results suggest single electron transport is mediated by resonant tunneling with the electronic and vibrational levels of the heme group in a single protein. They also represent a proof-of-principle that proteins with redox centers across nanometer-gap electrodes can be utilized to fabricate single-electron transistors. The protein orientation and conformation may significantly affect the conductance of these devices. Future improvements in device reproducibility and yield will require control of these factors. PMID:22972432

Active temporal multiplexing of indistinguishable heralded single photons

PubMed Central

Xiong, C.; Zhang, X.; Liu, Z.; Collins, M. J.; Mahendra, A.; Helt, L. G.; Steel, M. J.; Choi, D. -Y.; Chae, C. J.; Leong, P. H. W.; Eggleton, B. J.

2016-01-01

It is a fundamental challenge in quantum optics to deterministically generate indistinguishable single photons through non-deterministic nonlinear optical processes, due to the intrinsic coupling of single- and multi-photon-generation probabilities in these processes. Actively multiplexing photons generated in many temporal modes can decouple these probabilities, but key issues are to minimize resource requirements to allow scalability, and to ensure indistinguishability of the generated photons. Here we demonstrate the multiplexing of photons from four temporal modes solely using fibre-integrated optics and off-the-shelf electronic components. We show a 100% enhancement to the single-photon output probability without introducing additional multi-photon noise. Photon indistinguishability is confirmed by a fourfold Hong–Ou–Mandel quantum interference with a 91±16% visibility after subtracting multi-photon noise due to high pump power. Our demonstration paves the way for scalable multiplexing of many non-deterministic photon sources to a single near-deterministic source, which will be of benefit to future quantum photonic technologies. PMID:26996317

Nonequilibrium Chemical Effects in Single-Molecule SERS Revealed by Ab Initio Molecular Dynamics Simulations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fischer, Sean A.; Aprà, Edoardo; Govind, Niranjan

2017-02-03

Recent developments in nanophotonics have paved the way for achieving significant advances in the realm of single molecule chemical detection, imaging, and dynamics. In particular, surface-enhanced Raman scattering (SERS) is a powerful analytical technique that is now routinely used to identify the chemical identity of single molecules. Understanding how nanoscale physical and chemical processes affect single molecule SERS spectra and selection rules is a challenging task, and is still actively debated. Herein, we explore underappreciated chemical phenomena in ultrasensitive SERS. We observe a fluctuating excited electronic state manifold, governed by the conformational dynamics of a molecule (4,4’-dimercaptostilbene, DMS) interacting withmore » a metallic cluster (Ag20). This affects our simulated single molecule SERS spectra; the time trajectories of a molecule interacting with its unique local environment dictates the relative intensities of the observable Raman-active vibrational states. Ab initio molecular dynamics of a model Ag20-DMS system are used to illustrate both concepts in light of recent experimental results.« less

Correlation among Singlet-Oxygen Quenching, Free-Radical Scavenging, and Excited-State Intramolecular-Proton-Transfer Activities in Hydroxyflavones, Anthocyanidins, and 1-Hydroxyanthraquinones.

PubMed

Nagaoka, Shin-Ichi; Bandoh, Yuki; Nagashima, Umpei; Ohara, Keishi

2017-10-26

Singlet-oxygen ( 1 O 2 ) quenching, free-radical scavenging, and excited-state intramolecular proton-transfer (ESIPT) activities of hydroxyflavones, anthocyanidins, and 1-hydroxyanthraquinones were studied by means of laser, stopped-flow, and steady-state spectroscopies. In hydroxyflavones and anthocyanidins, the 1 O 2 quenching activity positively correlates to the free-radical scavenging activity. The reason for this correlation can be understood by considering that an early step of each reaction involves electron transfer from the unfused phenyl ring (B-ring), which is singly bonded to the bicyclic chromen or chromenylium moiety (A- and C-rings). Substitution of an electron-donating OH group at B-ring enhances the electron transfer leading to activation of the 1 O 2 quenching and free-radical scavenging. In 3-hydroxyflavones, the OH substitution at B-ring reduces the activity of ESIPT within C-ring, which can be explained in terms of the nodal-plane model. As a result, the 1 O 2 quenching and free-radical scavenging activities negatively correlate to the ESIPT activity. A catechol structure at B-ring is another factor that enhances the free-radical scavenging in hydroxyflavones. In contrast to these hydroxyflavones, 1-hydroxyanthraquinones having an electron-donating OH substituent adjacent to the O-H---O═C moiety susceptible to ESIPT do not show a simple correlation between their 1 O 2 quenching and ESIPT activities, because the OH substitution modulates these reactions.

A Structural Model of a P450-Ferredoxin Complex from Orientation-Selective Double Electron-Electron Resonance Spectroscopy.

PubMed

Bowen, Alice M; Johnson, Eachan O D; Mercuri, Francesco; Hoskins, Nicola J; Qiao, Ruihong; McCullagh, James S O; Lovett, Janet E; Bell, Stephen G; Zhou, Weihong; Timmel, Christiane R; Wong, Luet Lok; Harmer, Jeffrey R

2018-02-21

Cytochrome P450 (CYP) monooxygenases catalyze the oxidation of chemically inert carbon-hydrogen bonds in diverse endogenous and exogenous organic compounds by atmospheric oxygen. This C-H bond oxy-functionalization activity has huge potential in biotechnological applications. Class I CYPs receive the two electrons required for oxygen activation from NAD(P)H via a ferredoxin reductase and ferredoxin. The interaction of Class I CYPs with their cognate ferredoxin is specific. In order to reconstitute the activity of diverse CYPs, structural characterization of CYP-ferredoxin complexes is necessary, but little structural information is available. Here we report a structural model of such a complex (CYP199A2-HaPux) in frozen solution derived from distance and orientation restraints gathered by the EPR technique of orientation-selective double electron-electron resonance (os-DEER). The long-lived oscillations in the os-DEER spectra were well modeled by a single orientation of the CYP199A2-HaPux complex. The structure is different from the two known Class I CYP-Fdx structures: CYP11A1-Adx and CYP101A1-Pdx. At the protein interface, HaPux residues in the [Fe 2 S 2 ] cluster-binding loop and the α3 helix and the C-terminus residue interact with CYP199A2 residues in the proximal loop and the C helix. These residue contacts are consistent with biochemical data on CYP199A2-ferredoxin binding and electron transfer. Electron-tunneling calculations indicate an efficient electron-transfer pathway from the [Fe 2 S 2 ] cluster to the heme. This new structural model of a CYP-Fdx complex provides the basis for tailoring CYP enzymes for which the cognate ferredoxin is not known, to accept electrons from HaPux and display monooxygenase activity.

Size-dependent electronic structure controls activity for ethanol electro-oxidation at Ptn/indium tin oxide (n = 1 to 14).

PubMed

von Weber, Alexander; Baxter, Eric T; Proch, Sebastian; Kane, Matthew D; Rosenfelder, Michael; White, Henry S; Anderson, Scott L

2015-07-21

Understanding the factors that control electrochemical catalysis is essential to improving performance. We report a study of electrocatalytic ethanol oxidation - a process important for direct ethanol fuel cells - over size-selected Pt centers ranging from single atoms to Pt14. Model electrodes were prepared by soft-landing of mass-selected Ptn(+) on indium tin oxide (ITO) supports in ultrahigh vacuum, and transferred to an in situ electrochemical cell without exposure to air. Each electrode had identical Pt coverage, and differed only in the size of Pt clusters deposited. The small Ptn have activities that vary strongly, and non-monotonically with deposited size. Activity per gram Pt ranges up to ten times higher than that of 5 to 10 nm Pt particles dispersed on ITO. Activity is anti-correlated with the Pt 4d core orbital binding energy, indicating that electron rich clusters are essential for high activity.

Adiabatic and nonadiabatic responses of the radiation belt relativistic electrons to the external changes in solar wind dynamic pressure and interplanetary magnetic field

NASA Astrophysics Data System (ADS)

Li, L.

2013-12-01

By removing the influences of 'magnetopause shadowing' (r0>6.6RE) and geomagnetic activities, we investigated statistically the responses of magnetic field and relativistic (>0.5MeV) electrons at geosynchronous orbit to 201 interplanetary perturbations during 6 years from 2003 (solar maximum) to 2008 (solar minimum). The statistical results indicate that during geomagnetically quiet times (HSYM ≥-30nT, and AE<200nT), ~47.3% changes in the geosynchronous magnetic field and relativistic electron fluxes are caused by the combined actions of the enhancement of solar wind dynamic pressure (Pd) and the southward turning of interplanetary magnetic field (IMF) (ΔPd>0.4 nPa, and IMF Bz<0 nT), and only ~18.4% changes are due to single dynamic pressure increase (ΔPd >0.4 nPa, but IMF Bz>0 nT), and ~34.3% changes are due to single southward turning of IMF (IMF Bz<0 nT, but |ΔPd|<0.4 nPa). Although the responses of magnetic field and relativistic electrons to the southward turning of IMF are weaker than their responses to the dynamic pressure increase, the southward turning of IMF can cause the dawn-dusk asymmetric perturbations that the magnetic field and the relativistic electrons tend to increase on the dawnside (LT~00:00-12:00) but decrease on the duskside (LT~13:00-23:00). Furthermore, the variation of relativistic electron fluxes is adiabatically controlled by the magnitude and elevation angle changes of magnetic field during the single IMF southward turnings. However, the variation of relativistic electron fluxes is independent of the change in magnetic field in some compression regions during the enhancement of solar wind dynamic pressure (including the single pressure increases and the combined external perturbations), indicating that nonadiabatic dynamic processes of relativistic electrons occur there. Acknowledgments. This work is supported by NSFC (grants 41074119 and 40604018). Liuyuan Li is grateful to the staffs working for the data from GOES 8-12 satellites and OMNI database in CDAWeb.

A digital library for medical imaging activities

NASA Astrophysics Data System (ADS)

dos Santos, Marcelo; Furuie, Sérgio S.

2007-03-01

This work presents the development of an electronic infrastructure to make available a free, online, multipurpose and multimodality medical image database. The proposed infrastructure implements a distributed architecture for medical image database, authoring tools, and a repository for multimedia documents. Also it includes a peer-reviewed model that assures quality of dataset. This public repository provides a single point of access for medical images and related information to facilitate retrieval tasks. The proposed approach has been used as an electronic teaching system in Radiology as well.

Monitoring the dynamic photocatalytic activity of single CdS nanoparticles by lighting up H2 nanobubbles with fluorescent dyes† †Electronic supplementary information (ESI) available: Experimental details, Fig. S1–S13 and description of Movie S1. See DOI: 10.1039/c7sc04684g

PubMed Central

Su, Hua; Fang, Yimin; Chen, Fangyuan

2018-01-01

The capability of semiconductor nanomaterials to convert solar energy to chemical energy has led to many promising applications, for instance, photocatalyzed H2 generation. Studying this important photocatalytic reaction at the single nanocatalyst level provides a great opportunity to understand the microscopic reaction kinetics and mechanism by overcoming the chemical and structural heterogeneity among individuals. Here we report a fluorescence (FL) labeling strategy to visualize individual H2 nanobubbles that are generated at single CdS nanoparticles during photocatalysis. In operando imaging of nanobubble growth kinetics allows for determination of the photocatalytic activity of single nanocatalysts, which was found to randomly alternate among high activity, low activity and inactive states. In addition to H2 nanobubbles, the present labeling strategy is also suitable for other types of gas nanobubbles. Since nanomaterial-catalyzed gas generation is widely involved in many important photochemical (water splitting), electrochemical (electrolysis) and chemical (nanomotors) reactions, the present work is promising for the general applicability of single nanoparticle catalysis in broad basic and industrial fields by lighting up nanobubbles under commercial and conventional FL microscopes. PMID:29719679

Morphology evolution of single-crystalline hematite nanocrystals: magnetically recoverable nanocatalysts for enhanced facet-driven photoredox activity

NASA Astrophysics Data System (ADS)

Patra, Astam K.; Kundu, Sudipta K.; Bhaumik, Asim; Kim, Dukjoon

2015-12-01

We have developed a new green chemical approach for the shape-controlled synthesis of single-crystalline hematite nanocrystals in aqueous medium. FESEM, HRTEM and SAED techniques were used to determine the morphology and crystallographic orientations of each nanocrystal and its exposed facets. PXRD and HRTEM techniques revealed that the nanocrystals are single crystalline in nature; twins and stacking faults were not detected in these nanocrystals. The structural, vibrational, and electronic spectra of these nanocrystals were highly dependent on their shape. Different shaped hematite nanocrystals with distinct crystallographic planes have been synthesized under similar reaction conditions, which can be desired as a model for the purpose of properties comparison with the nanocrystals prepared under different reaction conditions. Here we investigated the photocatalytic performance of these different shaped-nanocrystals for methyl orange degradation in the presence of white light (λ > 420 nm). In this study, we found that the density of surface Fe3+ ions in particular facets was the key factor for the photocatalytic activity and was higher on the bitruncated-dodecahedron shape nanocrystals by coexposed {104}, {100} and {001} facets, attributing to higher catalytic activity. The catalytic activity of different exposed facet nanocrystals were as follows: {104} + {100} + {001} (bitruncated-dodecahedron) > {101} + {001} (bitruncated-octahedron) > {001} + {110} (nanorods) > {012} (nanocuboid) which provided the direct evidence of exposed facet-driven photocatalytic activity. The nanocrystals were easily recoverable using an external magnet and reused at least six times without significant loss of its catalytic activity.We have developed a new green chemical approach for the shape-controlled synthesis of single-crystalline hematite nanocrystals in aqueous medium. FESEM, HRTEM and SAED techniques were used to determine the morphology and crystallographic orientations of each nanocrystal and its exposed facets. PXRD and HRTEM techniques revealed that the nanocrystals are single crystalline in nature; twins and stacking faults were not detected in these nanocrystals. The structural, vibrational, and electronic spectra of these nanocrystals were highly dependent on their shape. Different shaped hematite nanocrystals with distinct crystallographic planes have been synthesized under similar reaction conditions, which can be desired as a model for the purpose of properties comparison with the nanocrystals prepared under different reaction conditions. Here we investigated the photocatalytic performance of these different shaped-nanocrystals for methyl orange degradation in the presence of white light (λ > 420 nm). In this study, we found that the density of surface Fe3+ ions in particular facets was the key factor for the photocatalytic activity and was higher on the bitruncated-dodecahedron shape nanocrystals by coexposed {104}, {100} and {001} facets, attributing to higher catalytic activity. The catalytic activity of different exposed facet nanocrystals were as follows: {104} + {100} + {001} (bitruncated-dodecahedron) > {101} + {001} (bitruncated-octahedron) > {001} + {110} (nanorods) > {012} (nanocuboid) which provided the direct evidence of exposed facet-driven photocatalytic activity. The nanocrystals were easily recoverable using an external magnet and reused at least six times without significant loss of its catalytic activity. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06509g

Single-molecule comparison of DNA Pol I activity with native and analog nucleotides

NASA Astrophysics Data System (ADS)

Gul, Osman; Olsen, Tivoli; Choi, Yongki; Corso, Brad; Weiss, Gregory; Collins, Philip

2014-03-01

DNA polymerases are critical enzymes for DNA replication, and because of their complex catalytic cycle they are excellent targets for investigation by single-molecule experimental techniques. Recently, we studied the Klenow fragment (KF) of DNA polymerase I using a label-free, electronic technique involving single KF molecules attached to carbon nanotube transistors. The electronic technique allowed long-duration monitoring of a single KF molecule while processing thousands of template strands. Processivity of up to 42 nucleotide bases was directly observed, and statistical analysis of the recordings determined key kinetic parameters for the enzyme's open and closed conformations. Subsequently, we have used the same technique to compare the incorporation of canonical nucleotides like dATP to analogs like 1-thio-2'-dATP. The analog had almost no affect on duration of the closed conformation, during which the nucleotide is incorporated. On the other hand, the analog increased the rate-limiting duration of the open conformation by almost 40%. We propose that the thiolated analog interferes with KF's recognition and binding, two key steps that determine its ensemble turnover rate.

Single-state electronic ballast with dimming feature and unity power factor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, T.F.; Yu, T.H.; Chiang, M.C.

1998-05-01

Analysis, design, and practical consideration of a single-stage electronic ballast with dimming feature and unity power factor are presented in this paper. The proposed single-stage ballast is the combination of a boost converter and a half-bridge series-resonant parallel-loaded inverter. The boost semistage working in the discontinuous conduction mode functions as a power factor corrector and the inverter semistage operated above resonance are employed to ballast the lamp. Replacing the lamp with the plasma model, analysis of the ballast is fulfilled. The dimming feature is carried out by pulse-width modulation (PWM) and variable-frequency controls simultaneously. The proposed single-stage ballast is suitablemore » for applications with moderate power level and low-line voltage while requiring a high-output voltage. It can save a controller, an active switch and its driver, reduce size, and possibly increase system reliability while requiring two additional diodes over a conventional two-stage system. A prototype was implemented to verify the theoretical discussion. The hardware measurements have shown that the desired performance can be achieved feasibly.« less

Multiconfiguration Pair-Density Functional Theory: A New Way To Treat Strongly Correlated Systems.

PubMed

Gagliardi, Laura; Truhlar, Donald G; Li Manni, Giovanni; Carlson, Rebecca K; Hoyer, Chad E; Bao, Junwei Lucas

2017-01-17

The electronic energy of a system provides the Born-Oppenheimer potential energy for internuclear motion and thus determines molecular structure and spectra, bond energies, conformational energies, reaction barrier heights, and vibrational frequencies. The development of more efficient and more accurate ways to calculate the electronic energy of systems with inherently multiconfigurational electronic structure is essential for many applications, including transition metal and actinide chemistry, systems with partially broken bonds, many transition states, and most electronically excited states. Inherently multiconfigurational systems are called strongly correlated systems or multireference systems, where the latter name refers to the need for using more than one ("multiple") configuration state function to provide a good zero-order reference wave function. This Account describes multiconfiguration pair-density functional theory (MC-PDFT), which was developed as a way to combine the advantages of wave function theory (WFT) and density functional theory (DFT) to provide a better treatment of strongly correlated systems. First we review background material: the widely used Kohn-Sham DFT (which uses only a single Slater determinant as reference wave function), multiconfiguration WFT methods that treat inherently multiconfigurational systems based on an active space, and previous attempts to combine multiconfiguration WFT with DFT. Then we review the formulation of MC-PDFT. It is a generalization of Kohn-Sham DFT in that the electron kinetic energy and classical electrostatic energy are calculated from a reference wave function, while the rest of the energy is obtained from a density functional. However, there are two main differences with respent to Kohn-Sham DFT: (i) The reference wave function is multiconfigurational rather than being a single Slater determinant. (ii) The density functional is a function of the total density and the on-top pair density rather than being a function of the spin-up and spin-down densities. In work carried out so far, the multiconfigurational wave function is a multiconfiguration self-consistent-field wave function. The new formulation has the advantage that the reference wave function has the correct spatial and spin symmetry and can describe bond dissociation (of both single and multiple bonds) and electronic excitations in a formally and physically correct way. We then review the formulation of density functionals in terms of the on-top pair density. Finally we review successful applications of the theory to bond energies and bond dissociation potential energy curves of main-group and transition metal bonds, to barrier heights (including pericyclic reactions), to proton affinities, to the hydrogen bond energy of water dimer, to ground- and excited-state charge transfer, to valence and Rydberg excitations of molecules, and to singlet-triplet splittings of radicals. We find that that MC-PDFT can give accurate results not only with complete-active-space multiconfiguration wave functions but also with generalized-active-space multiconfiguration wave functions, which are practical for larger numbers of active electrons and active orbitals than are complete-active-space wave functions. The separated-pair approximation, which is a special case of generalized active space self-consistent-field theory, is especially promising. MC-PDFT, because it requires much less computer time and storage than pure WFT methods, has the potential to open larger and more complex strongly correlated systems to accurate simulation.

Electronic, optical and photocatalytic behavior of Mn, N doped and co-doped TiO{sub 2}: Experiment and simulation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, Ya Fei; Li, Can, E-mail: canli1983@gmail.com; Lu, Song

2016-03-15

The crystal phase structure, surface morphology, chemical states and optical properties of Mn, N mono-doped and co-doped TiO{sub 2} nanoparticles were investigated by X-ray powder diffractometry, Raman spectra, scanning electron microscopy, X-ray photoelectron spectroscopy and UV–vis diffuse reflectance spectroscopy. Meanwhile, geometry structures, formation energies, electronic and optical properties of all systems have been also analyzed by density functional theory. The results showed that the band gap values and the carrier mobility in the valence band, conduction band and impurity levels have a synergetic influence on the visible-light absorption and photocatalytic activity of the doped TiO{sub 2}. The number and themore » carrier mobility of impurity level jointly influence the photocatalytic activity of catalyst under visible-light. Especially, the photocatalytic activity of Mn-2N co-doped TiO{sub 2} beyond three-fold than that of pure TiO{sub 2} under visible-light. - Graphical abstract: The ILs formed by N-2p orbital in N single doped specimen lie above the VB, while the ILs formed by Mn-3d orbital in Mn single doped specimen appear below the CB. However, a large amount of ILs formed by N-2p orbital and Mn-3d orbital in N and Mn codoped specimens. The band gap values and the carrier mobility in the valence band, conduction band and impurity levels have a synergetic influence on the visible-light absorption and photocatalytic activity of the doped TiO{sub 2}. The number and the carrier mobility of impurity level jointly influence the photocatalytic activity of catalyst under visible-light.« less

Localized electrical stimulation of in vitro neurons using an array of sub-cellular sized electrodes.

PubMed

Braeken, Dries; Huys, Roeland; Loo, Josine; Bartic, Carmen; Borghs, Gustaaf; Callewaert, Geert; Eberle, Wolfgang

2010-12-15

The investigation of single-neuron parameters is of great interest because many aspects in the behavior and communication of neuronal networks still remain unidentified. However, the present available techniques for single-cell measurements are slow and do not allow for a high-throughput approach. We present here a CMOS compatible microelectrode array with 84 electrodes (with diameters ranging from 1.2 to 4.2 μm) that are smaller than the size of cell, thereby supporting single-cell addressability. We show controllable electroporation of a single cell by an underlying electrode while monitoring changes in the intracellular membrane potential. Further, by applying a localized electrical field between two electrodes close to a neuron while recording changes in the intracellular calcium concentration, we demonstrate activation of a single cell (∼270%, DF/F(0)), followed by a network response of the neighboring cells. The technology can be easily scaled up to larger electrode arrays (theoretically up to 137,000 electrodes/mm(2)) with active CMOS electronics integration able to perform high-throughput measurements on single cells. Copyright © 2010 Elsevier B.V. All rights reserved.

Seebeck coefficient of one electron

DOE Office of Scientific and Technical Information (OSTI.GOV)

Durrani, Zahid A. K., E-mail: z.durrani@imperial.ac.uk

2014-03-07

The Seebeck coefficient of one electron, driven thermally into a semiconductor single-electron box, is investigated theoretically. With a finite temperature difference ΔT between the source and charging island, a single electron can charge the island in equilibrium, directly generating a Seebeck effect. Seebeck coefficients for small and finite ΔT are calculated and a thermally driven Coulomb staircase is predicted. Single-electron Seebeck oscillations occur with increasing ΔT, as one electron at a time charges the box. A method is proposed for experimental verification of these effects.

Comparison of Collisional and Electron-Based Dissociation Modes for Middle-Down Analysis of Multiply Glycosylated Peptides

NASA Astrophysics Data System (ADS)

Khatri, Kshitij; Pu, Yi; Klein, Joshua A.; Wei, Juan; Costello, Catherine E.; Lin, Cheng; Zaia, Joseph

2018-04-01

Analysis of singly glycosylated peptides has evolved to a point where large-scale LC-MS analyses can be performed at almost the same scale as proteomics experiments. While collisionally activated dissociation (CAD) remains the mainstay of bottom-up analyses, it performs poorly for the middle-down analysis of multiply glycosylated peptides. With improvements in instrumentation, electron-activated dissociation (ExD) modes are becoming increasingly prevalent for proteomics experiments and for the analysis of fragile modifications such as glycosylation. While these methods have been applied for glycopeptide analysis in isolated studies, an organized effort to compare their efficiencies, particularly for analysis of multiply glycosylated peptides (termed here middle-down glycoproteomics), has not been made. We therefore compared the performance of different ExD modes for middle-down glycopeptide analyses. We identified key features among the different dissociation modes and show that increased electron energy and supplemental activation provide the most useful data for middle-down glycopeptide analysis. [Figure not available: see fulltext.

Doping and vacancy effects of graphyne on SO2 adsorption.

PubMed

Kim, Sunkyung; Lee, Jin Yong

2017-05-01

The adsorption of sulfur dioxide (SO 2 ) on pristine and modified graphyne (including boron- or nitrogen- doping and introducing a single carbon atom defect) was investigated by density functional theory calculations. The structural, electronic, and magnetic properties of graphyne were changed according to the dopant atom site of doping and vacancy. SO 2 adsorption was obviously affected by modification of graphyne. SO 2 weakly interacted with pristine and nitrogen-doped graphynes. Boron doping at the sp-hybridized carbon site and introducing a single carbon atom vacancy in graphyne brought about a dramatic enhancement in SO 2 adsorption. The strongly chemisorbed SO 2 at these active sites caused deformation of the graphyne structure and electron redistribution, which induced changes in the conductivity and magnetism of graphynes. Copyright © 2017 Elsevier Inc. All rights reserved.

Harnessing redox activity for the formation of uranium tris(imido) compounds

NASA Astrophysics Data System (ADS)

Anderson, Nickolas H.; Odoh, Samuel O.; Yao, Yiyi; Williams, Ursula J.; Schaefer, Brian A.; Kiernicki, John J.; Lewis, Andrew J.; Goshert, Mitchell D.; Fanwick, Phillip E.; Schelter, Eric J.; Walensky, Justin R.; Gagliardi, Laura; Bart, Suzanne C.

2014-10-01

Classically, late transition-metal organometallic compounds promote multielectron processes solely through the change in oxidation state of the metal centre. In contrast, uranium typically undergoes single-electron chemistry. However, using redox-active ligands can engage multielectron reactivity at this metal in analogy to transition metals. Here we show that a redox-flexible pyridine(diimine) ligand can stabilize a series of highly reduced uranium coordination complexes by storing one, two or three electrons in the ligand. These species reduce organoazides easily to form uranium-nitrogen multiple bonds with the release of dinitrogen. The extent of ligand reduction dictates the formation of uranium mono-, bis- and tris(imido) products. Spectroscopic and structural characterization of these compounds supports the idea that electrons are stored in the ligand framework and used in subsequent reactivity. Computational analyses of the uranium imido products probed their molecular and electronic structures, which facilitated a comparison between the bonding in the tris(imido) structure and its tris(oxo) analogue.

High-order harmonic generation in solid slabs beyond the single-active-electron approximation

NASA Astrophysics Data System (ADS)

Hansen, Kenneth K.; Deffge, Tobias; Bauer, Dieter

2017-11-01

High-harmonic generation by a laser-driven solid slab is simulated using time-dependent density functional theory. Multiple harmonic plateaus up to very high harmonic orders are observed already at surprisingly low field strengths. The full all-electron harmonic spectra are, in general, very different from those of any individual Kohn-Sham orbital. Freezing the Kohn-Sham potential instead is found to be a good approximation for the laser intensities and harmonic orders considered. The origins of the plateau cutoffs are explained in terms of band gaps that can be reached by Kohn-Sham electrons and holes moving through the band structure.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sedlacek, J. A.; Kim, E.; Rittenhouse, S. T.

We investigate the (0001) surface of single crystal quartz with a submonolayer of Rb adsorbates. Using Rydberg atom electromagnetically induced transparency, we investigate the electric elds resulting from Rb adsorbed on the quartz surface, and measure the activation energy of the Rb adsorbates. We show that the Rb induces a negative electron affnity (NEA) on the quartz surface. The NEA surface allows for low energy electrons to bind to the surface and cancel the electric eld from the Rb adsorbates. Our results have implications for integrating Rydberg atoms into hybrid quantum systems and the fundamental study of atom-surface interactions, asmore » well as applications for electrons bound to a 2D surface.« less

Polarization effects in above-threshold ionization with a mid-infrared strong laser field

NASA Astrophysics Data System (ADS)

Kang, Hui-Peng; Xu, Song-Po; Wang, Yan-Lan; Yu, Shao-Gang; Zhao, Xiao-Yun; Hao, Xiao-Lei; Lai, Xuan-Yang; Pfeifer, Thomas; Liu, Xiao-Jun; Chen, Jing; Cheng, Ya; Xu, Zhi-Zhan

2018-05-01

Using a semiclassical approach, we theoretically study the above-threshold ionization of magnesium by intense, mid-infrared laser pulses. The formation of low-energy structures in the photoelectron spectrum is found to be enhanced by comparing with a calculation based on the single-active electron approximation. By performing electron trajectory and recollision-time distribution analysis, we demonstrate that this phenomenon is due to the laser-induced ionic core polarization effects on the recolliding electrons. We also show that the polarization effects should be experimentally detectable. Our finding provides new insight into ultrafast control of strong-field photoionization and imaging of polar molecules.

Electron source for a mini ion trap mass spectrometer

DOEpatents

Dietrich, D.D.; Keville, R.F.

1995-12-19

An ion trap is described which operates in the regime between research ion traps which can detect ions with a mass resolution of better than 1:10{sup 9} and commercial mass spectrometers requiring 10{sup 4} ions with resolutions of a few hundred. The power consumption is kept to a minimum by the use of permanent magnets and a novel electron gun design. By Fourier analyzing the ion cyclotron resonance signals induced in the trap electrodes, a complete mass spectra in a single combined structure can be detected. An attribute of the ion trap mass spectrometer is that overall system size is drastically reduced due to combining a unique electron source and mass analyzer/detector in a single device. This enables portable low power mass spectrometers for the detection of environmental pollutants or illicit substances, as well as sensors for on board diagnostics to monitor engine performance or for active feedback in any process involving exhausting waste products. 10 figs.

Interference experiment with asymmetric double slit by using 1.2-MV field emission transmission electron microscope.

PubMed

Harada, Ken; Akashi, Tetsuya; Niitsu, Kodai; Shimada, Keiko; Ono, Yoshimasa A; Shindo, Daisuke; Shinada, Hiroyuki; Mori, Shigeo

2018-01-17

Advanced electron microscopy technologies have made it possible to perform precise double-slit interference experiments. We used a 1.2-MV field emission electron microscope providing coherent electron waves and a direct detection camera system enabling single-electron detections at a sub-second exposure time. We developed a method to perform the interference experiment by using an asymmetric double-slit fabricated by a focused ion beam instrument and by operating the microscope under a "pre-Fraunhofer" condition, different from the Fraunhofer condition of conventional double-slit experiments. Here, pre-Fraunhofer condition means that each single-slit observation was performed under the Fraunhofer condition, while the double-slit observations were performed under the Fresnel condition. The interference experiments with each single slit and with the asymmetric double slit were carried out under two different electron dose conditions: high-dose for calculation of electron probability distribution and low-dose for each single electron distribution. Finally, we exemplified the distribution of single electrons by color-coding according to the above three types of experiments as a composite image.

Attosecond pulse carrier-envelope phase effects on ionized electron momentum and energy distributions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peng, L.-Y.; Starace, Anthony F.

2007-10-15

We analyze carrier-envelope phase (CEP) effects on electron wave-packet momentum and energy spectra produced by one or two few-cycle attosecond xuv pulses. The few-cycle attosecond pulses are assumed to have arbitrary phases. We predict CEP effects on ionized electron wave-packet momentum distributions produced by attosecond pulses having durations comparable to those obtained by Sansone et al. [Science 314, 443 (2006)]. The onset of significant CEP effects is predicted to occur for attosecond pulse field strengths close to those possible with current experimental capabilities. Our results are based on single-active-electron solutions of the three-dimensional, time-dependent Schroedinger equation including atomic potentials appropriatemore » for the H and He atoms.« less

Evidence that Additions of Grignard Reagents to Aliphatic Aldehydes Do Not Involve Single-Electron-Transfer Processes.

PubMed

Otte, Douglas A L; Woerpel, K A

2015-08-07

Addition of allylmagnesium reagents to an aliphatic aldehyde bearing a radical clock gave only addition products and no evidence of ring-opened products that would suggest single-electron-transfer reactions. The analogous Barbier reaction also did not provide evidence for a single-electron-transfer mechanism in the addition step. Other Grignard reagents (methyl-, vinyl-, t-Bu-, and triphenylmethylmagnesium halides) also do not appear to add to an alkyl aldehyde by a single-electron-transfer mechanism.

Bio-fabrication of nanomesh channels of single-walled carbon nanotubes for locally gated field-effect transistors

NASA Astrophysics Data System (ADS)

Byeon, Hye-Hyeon; Lee, Woo Chul; Kim, Wonbin; Kim, Seong Keun; Kim, Woong; Yi, Hyunjung

2017-01-01

Single-walled carbon nanotubes (SWNTs) are one of the promising electronic components for nanoscale electronic devices such as field-effect transistors (FETs) owing to their excellent device characteristics such as high conductivity, high carrier mobility and mechanical flexibility. Localized gating gemometry of FETs enables individual addressing of active channels and allows for better electrostatics via thinner dielectric layer of high k-value. For localized gating of SWNTs, it becomes critical to define SWNTs of controlled nanostructures and functionality onto desired locations in high precision. Here, we demonstrate that a biologically templated approach in combination of microfabrication processes can successfully produce a nanostructured channels of SWNTs for localized active devices such as local bottom-gated FETs. A large-scale nanostructured network, nanomesh, of SWNTs were assembled in solution using an M13 phage with strong binding affinity toward SWNTs and micrometer-scale nanomesh channels were defined using negative photolithography and plasma-etching processes. The bio-fabrication approach produced local bottom-gated FETs with remarkably controllable nanostructures and successfully enabled semiconducting behavior out of unsorted SWNTs. In addition, the localized gating scheme enhanced the device performances such as operation voltage and I on/I off ratio. We believe that our approach provides a useful and integrative method for fabricating electronic devices out of nanoscale electronic materials for applications in which tunable electrical properties, mechanical flexibility, ambient stability, and chemical stability are of crucial importance.

Evaluation of jamming efficiency for the protection of a single ground object

NASA Astrophysics Data System (ADS)

Matuszewski, Jan

2018-04-01

The electronic countermeasures (ECM) include methods to completely prevent or restrict the effective use of the electromagnetic spectrum by the opponent. The most widespread means of disorganizing the operation of electronic devices is to create active and passive radio-electronic jamming. The paper presents the way of jamming efficiency calculations for protecting ground objects against the radars mounted on the airborne platforms. The basic mathematical formulas for calculating the efficiency of active radar jamming are presented. The numerical calculations for ground object protection are made for two different electronic warfare scenarios: the jammer is placed very closely and in a determined distance from the protecting object. The results of these calculations are presented in the appropriate figures showing the minimal distance of effective jamming. The realization of effective radar jamming in electronic warfare systems depends mainly on the precise knowledge of radar and the jammer's technical parameters, the distance between them, the assumed value of the degradation coefficient, the conditions of electromagnetic energy propagation and the applied jamming method. The conclusions from these calculations facilitate making a decision regarding how jamming should be conducted to achieve high efficiency during the electronic warfare training.

Compendium of Current Single Event Effects for Candidate Spacecraft Electronics for NASA

NASA Technical Reports Server (NTRS)

O'Bryan, Martha V.; Label, Kenneth A.; Chen, Dakai; Campola, Michael J.; Casey, Megan C.; Lauenstein, Jean-Marie; Pellish, Jonathan A.; Ladbury, Raymond L.; Berg, Melanie D.

2015-01-01

NASA spacecraft are subjected to a harsh space environment that includes exposure to various types of ionizing radiation. The performance of electronic devices in a space radiation environment are often limited by their susceptibility to single event effects (SEE). Ground-based testing is used to evaluate candidate spacecraft electronics to determine risk to spaceflight applications. Interpreting the results of radiation testing of complex devices is and adequate understanding of the test condition is critical. Studies discussed herein were undertaken to establish the application-specific sensitivities of candidate spacecraft and emerging electronic devices to single-event upset (SEU), single-event latchup (SEL), single-event gate rupture (SEGR), single-event burnout (SEB), and single-event transient (SET). For total ionizing dose (TID) and displacement damage dose (DDD) results, see a companion paper submitted to the 2015 Institute of Electrical and Electronics Engineers (IEEE) Nuclear and Space Radiation Effects Conference (NSREC) Radiation Effects Data Workshop (REDW) entitled "compendium of Current Total Ionizing Dose and Displacement Damage for Candidate Spacecraft Electronics for NASA by M. Campola, et al.

A low-cost approach to electronic excitation energies based on the driven similarity renormalization group

NASA Astrophysics Data System (ADS)

Li, Chenyang; Verma, Prakash; Hannon, Kevin P.; Evangelista, Francesco A.

2017-08-01

We propose an economical state-specific approach to evaluate electronic excitation energies based on the driven similarity renormalization group truncated to second order (DSRG-PT2). Starting from a closed-shell Hartree-Fock wave function, a model space is constructed that includes all single or single and double excitations within a given set of active orbitals. The resulting VCIS-DSRG-PT2 and VCISD-DSRG-PT2 methods are introduced and benchmarked on a set of 28 organic molecules [M. Schreiber et al., J. Chem. Phys. 128, 134110 (2008)]. Taking CC3 results as reference values, mean absolute deviations of 0.32 and 0.22 eV are observed for VCIS-DSRG-PT2 and VCISD-DSRG-PT2 excitation energies, respectively. Overall, VCIS-DSRG-PT2 yields results with accuracy comparable to those from time-dependent density functional theory using the B3LYP functional, while VCISD-DSRG-PT2 gives excitation energies comparable to those from equation-of-motion coupled cluster with singles and doubles.

Monolayer PtSe₂, a New Semiconducting Transition-Metal-Dichalcogenide, Epitaxially Grown by Direct Selenization of Pt.

PubMed

Wang, Yeliang; Li, Linfei; Yao, Wei; Song, Shiru; Sun, J T; Pan, Jinbo; Ren, Xiao; Li, Chen; Okunishi, Eiji; Wang, Yu-Qi; Wang, Eryin; Shao, Yan; Zhang, Y Y; Yang, Hai-tao; Schwier, Eike F; Iwasawa, Hideaki; Shimada, Kenya; Taniguchi, Masaki; Cheng, Zhaohua; Zhou, Shuyun; Du, Shixuan; Pennycook, Stephen J; Pantelides, Sokrates T; Gao, Hong-Jun

2015-06-10

Single-layer transition-metal dichalcogenides (TMDs) receive significant attention due to their intriguing physical properties for both fundamental research and potential applications in electronics, optoelectronics, spintronics, catalysis, and so on. Here, we demonstrate the epitaxial growth of high-quality single-crystal, monolayer platinum diselenide (PtSe2), a new member of the layered TMDs family, by a single step of direct selenization of a Pt(111) substrate. A combination of atomic-resolution experimental characterizations and first-principle theoretic calculations reveals the atomic structure of the monolayer PtSe2/Pt(111). Angle-resolved photoemission spectroscopy measurements confirm for the first time the semiconducting electronic structure of monolayer PtSe2 (in contrast to its semimetallic bulk counterpart). The photocatalytic activity of monolayer PtSe2 film is evaluated by a methylene-blue photodegradation experiment, demonstrating its practical application as a promising photocatalyst. Moreover, circular polarization calculations predict that monolayer PtSe2 has also potential applications in valleytronics.

Inter-ring rotations of AAA ATPase p97 revealed by electron cryomicroscopy

PubMed Central

Yeung, Heidi O.; Förster, Andreas; Bebeacua, Cecilia; Niwa, Hajime; Ewens, Caroline; McKeown, Ciarán; Zhang, Xiaodong; Freemont, Paul S.

2014-01-01

The type II AAA+ protein p97 is involved in numerous cellular activities, including endoplasmic reticulum-associated degradation, transcription activation, membrane fusion and cell-cycle control. These activities are at least in part regulated by the ubiquitin system, in which p97 is thought to target ubiquitylated protein substrates within macromolecular complexes and assist in their extraction or disassembly. Although ATPase activity is essential for p97 function, little is known about how ATP binding or hydrolysis is coupled with p97 conformational changes and substrate remodelling. Here, we have used single-particle electron cryomicroscopy (cryo-EM) to study the effect of nucleotides on p97 conformation. We have identified conformational heterogeneity within the cryo-EM datasets from which we have resolved two major p97 conformations. A comparison of conformations reveals inter-ring rotations upon nucleotide binding and hydrolysis that may be linked to the remodelling of target protein complexes. PMID:24598262

Robust and Soft Elastomeric Electronics Tolerant to Our Daily Lives.

PubMed

Sekiguchi, Atsuko; Tanaka, Fumiaki; Saito, Takeshi; Kuwahara, Yuki; Sakurai, Shunsuke; Futaba, Don N; Yamada, Takeo; Hata, Kenji

2015-09-09

Clothes represent a unique textile, as they simultaneously provide robustness against our daily activities and comfort (i.e., softness). For electronic devices to be fully integrated into clothes, the devices themselves must be as robust and soft as the clothes themselves. However, to date, no electronic device has ever possessed these properties, because all contain components fabricated from brittle materials, such as metals. Here, we demonstrate robust and soft elastomeric devices where every component possesses elastomeric characteristics with two types of single-walled carbon nanotubes added to provide the necessary electronic properties. Our elastomeric field effect transistors could tolerate every punishment our clothes experience, such as being stretched (elasticity: ∼ 110%), bent, compressed (>4.0 MPa, by a car and heels), impacted (>6.26 kg m/s, by a hammer), and laundered. Our electronic device provides a novel design principle for electronics and wide range applications even in research fields where devices cannot be used.

Flocking from a quantum analogy: spin-orbit coupling in an active fluid

NASA Astrophysics Data System (ADS)

Loewe, Benjamin; Souslov, Anton; Goldbart, Paul M.

2018-01-01

Systems composed of strongly interacting self-propelled particles can form a spontaneously flowing polar active fluid. The study of the connection between the microscopic dynamics of a single such particle and the macroscopic dynamics of the fluid can yield insights into experimentally realizable active flows, but this connection is well understood in only a few select cases. We introduce a model of self-propelled particles based on an analogy with the motion of electrons that have strong spin-orbit coupling. We find that, within our model, self-propelled particles are subject to an analog of the Heisenberg uncertainty principle that relates translational and rotational noise. Furthermore, by coarse-graining this microscopic model, we establish expressions for the coefficients of the Toner-Tu equations—the hydrodynamic equations that describe an active fluid composed of these ‘active spins.’ The connection between stochastic self-propelled particles and quantum particles with spin may help realize exotic phases of matter using active fluids via analogies with systems composed of strongly correlated electrons.

Challenges for single molecule electronic devices with nanographene and organic molecules. Do single molecules offer potential as elements of electronic devices in the next generation?

NASA Astrophysics Data System (ADS)

Enoki, Toshiaki; Kiguchi, Manabu

2018-03-01

Interest in utilizing organic molecules to fabricate electronic materials has existed ever since organic (molecular) semiconductors were first discovered in the 1950s. Since then, scientists have devoted serious effort to the creation of various molecule-based electronic systems, such as molecular metals and molecular superconductors. Single-molecule electronics and the associated basic science have emerged over the past two decades and provided hope for the development of highly integrated molecule-based electronic devices in the future (after the Si-based technology era has ended). Here, nanographenes (nano-sized graphene) with atomically precise structures are among the most promising molecules that can be utilized for electronic/spintronic devices. To manipulate single small molecules for an electronic device, a single molecular junction has been developed. It is a powerful tool that allows even small molecules to be utilized. External electric, magnetic, chemical, and mechanical perturbations can change the physical and chemical properties of molecules in a way that is different from bulk materials. Therefore, the various functionalities of molecules, along with changes induced by external perturbations, allows us to create electronic devices that we cannot create using current top-down Si-based technology. Future challenges that involve the incorporation of condensed matter physics, quantum chemistry calculations, organic synthetic chemistry, and electronic device engineering are expected to open a new era in single-molecule device electronic technology.

Single Molecule Electronics and Devices

PubMed Central

Tsutsui, Makusu; Taniguchi, Masateru

2012-01-01

The manufacture of integrated circuits with single-molecule building blocks is a goal of molecular electronics. While research in the past has been limited to bulk experiments on self-assembled monolayers, advances in technology have now enabled us to fabricate single-molecule junctions. This has led to significant progress in understanding electron transport in molecular systems at the single-molecule level and the concomitant emergence of new device concepts. Here, we review recent developments in this field. We summarize the methods currently used to form metal-molecule-metal structures and some single-molecule techniques essential for characterizing molecular junctions such as inelastic electron tunnelling spectroscopy. We then highlight several important achievements, including demonstration of single-molecule diodes, transistors, and switches that make use of electrical, photo, and mechanical stimulation to control the electron transport. We also discuss intriguing issues to be addressed further in the future such as heat and thermoelectric transport in an individual molecule. PMID:22969345

Enhanced Oxidative Bioremediation of cis-Dichloroethene (cis-DCE) and Vinyl Chloride (VC) using Electron Shuttles

DTIC Science & Technology

2010-02-01

Analyses on a single grain of soil or a single crystal of a precipitate were accomplished using an EMP. Not only can analyses be made on particles as small...24Fe+32 (OH)12[ CO3 ] 54.5% Fe, 41.6% O, 2.0% C 6Fe+2 + CO3 -2 + 12H2O → [Fe+24Fe+32 (OH)12][ CO3 ] (s) + 12H+ + 2e- Mixed ferrous/ferric iron...400 mV DCE: 2,000 Sulfate: ញ mg/L VC: 63 µg/L Seneca Army Depot Activity (Ash Landfill site), New York October-06 Single Double- Wide

A role for catalase-peroxidase large loop 2 revealed by deletion mutagenesis: control of active site water and ferric enzyme reactivity.

PubMed

Kudalkar, Shalley N; Njuma, Olive J; Li, Yongjiang; Muldowney, Michelle; Fuanta, N Rene; Goodwin, Douglas C

2015-03-03

Catalase-peroxidases (KatGs), the only catalase-active members of their superfamily, all possess a 35-residue interhelical loop called large loop 2 (LL2). It is essential for catalase activity, but little is known about its contribution to KatG function. LL2 shows weak sequence conservation; however, its length is nearly identical across KatGs, and its apex invariably makes contact with the KatG-unique C-terminal domain. We used site-directed and deletion mutagenesis to interrogate the role of LL2 and its interaction with the C-terminal domain in KatG structure and catalysis. Single and double substitutions of the LL2 apex had little impact on the active site heme [by magnetic circular dichroism or electron paramagnetic resonance (EPR)] and activity (catalase or peroxidase). Conversely, deletion of a single amino acid from the LL2 apex reduced catalase activity by 80%. Deletion of two or more apex amino acids or all of LL2 diminished catalase activity by 300-fold. Peroxide-dependent but not electron donor-dependent kcat/KM values for deletion variant peroxidase activity were reduced 20-200-fold, and kon for cyanide binding diminished by 3 orders of magnitude. EPR spectra for deletion variants were all consistent with an increase in the level of pentacoordinate high-spin heme at the expense of hexacoordinate high-spin states. Together, these data suggest a shift in the distribution of active site waters, altering the reactivity of the ferric state, toward, among other things, compound I formation. These results identify the importance of LL2 length conservation for maintaining an intersubunit interaction that is essential for an active site water distribution that facilitates KatG catalytic activity.

Topics in Nanophotonic Devices for Nitrogen-Vacancy Color Centers in Diamond

ERIC Educational Resources Information Center

Babinec, Thomas Michael

2012-01-01

Recently, developments in novel and high-purity materials allow for the presence of a single, solitary crystalline defect to define the electronic, magnetic, and optical functionality of a device. The discrete nature of the active dopant, whose properties are defined by a quantum mechanical description of its structure, enables radically new…

TEMPO-promoted Pauson-Khand reaction. Single-electron activation of cobalt-carbonyl bonds?

PubMed

Lagunas, Anna; Mairata I Payeras, Antoni; Jimeno, Ciril; Pericàs, Miquel A

2005-07-07

[reaction: see text] The Pauson-Khand reaction is notably accelerated by TEMPO. According to DFT calculations, TEMPO could trigger a radical, low-energy pathway for the reaction by facilitating the decarbonylation of doublet complexes arising either from a CO/nitroxide exchange or from nitroxide addition to a CO ligand.

Activity inhibition on municipal activated sludge by single-walled carbon nanotubes

NASA Astrophysics Data System (ADS)

Parise, Alex; Thakor, Harshrajsinh; Zhang, Xiaoqi

2014-01-01

The objective of this study was to evaluate the respiratory activity inhibition of activated sludge used in a typical wastewater treatment plant by single-walled carbon nanotubes (SWCNTs) with different length and functionality. Four types of SWCNTs were evaluated: short, functionalized short, long, and functionalized long. Based on the effective concentration (EC50) values obtained, we determined that functionalized SWCNTs resulted in a higher microbial respiratory inhibition than non-functionalized nanotubes, and long SWCNTs gave a higher microbial respiratory inhibition than their short counterparts. Among the four types of SWCNTs studied, functionalized long exhibited the highest respiration inhibition. Scanning electron microscopy imaging indicates that the long SWCNTs dispersed more favorably after sonication than the short variety. The findings demonstrated that the toxicity of CNTs (exhibited by respiratory inhibition) is related to their physical properties; the length and functionality of SWCNTs affected the toxicity of SWCNTs in a mixed-cultured biologic system.

Test Result of 650 MHz, Beta 0.61 Single Cell Niobium Cavity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Seth, Sudeshna; Bhattacharyya, Pranab; Dutta Gupta, Anjan

VECC has been involved in the design, analysis and development of 650 MHz, beta 0.61 (LB650), elliptical Superconducting RF linac cavity, as part of research and development activities on SRF cavities and associated technologies under Indian Institutions Fermilab Collaboration (IIFC). A single-cell niobium cavity has been indigenously designed and developed at VECC, with the help of Electron Beam Welding (EBW) facility at IUAC, New Delhi. Various measurements, processing and testing at 2K in Vertical Test Stand (VTS) of the single-cell cavity was carried out at ANL and Fermilab, USA, with active participation of VECC engineers. It achieved a maximum acceleratingmore » gradient(Eacc) of 34.5 MV/m with Quality Factor of 2·10⁹ and 30 MV/m with Quality Factor of 1.5·10¹⁰. This is probably the highest accelerating gradient achieved so far in the world for LB650 cavities. This paper describes the design, fabrication and measurement of the single cell niobium cavity. Cavity processing and test results of Vertical Test of the single-cell niobium cavity are also presented.« less

Repetitive readout of a single electronic spin via quantum logic with nuclear spin ancillae.

PubMed

Jiang, L; Hodges, J S; Maze, J R; Maurer, P; Taylor, J M; Cory, D G; Hemmer, P R; Walsworth, R L; Yacoby, A; Zibrov, A S; Lukin, M D

2009-10-09

Robust measurement of single quantum bits plays a key role in the realization of quantum computation and communication as well as in quantum metrology and sensing. We have implemented a method for the improved readout of single electronic spin qubits in solid-state systems. The method makes use of quantum logic operations on a system consisting of a single electronic spin and several proximal nuclear spin ancillae in order to repetitively readout the state of the electronic spin. Using coherent manipulation of a single nitrogen vacancy center in room-temperature diamond, full quantum control of an electronic-nuclear system consisting of up to three spins was achieved. We took advantage of a single nuclear-spin memory in order to obtain a 10-fold enhancement in the signal amplitude of the electronic spin readout. We also present a two-level, concatenated procedure to improve the readout by use of a pair of nuclear spin ancillae, an important step toward the realization of robust quantum information processors using electronic- and nuclear-spin qubits. Our technique can be used to improve the sensitivity and speed of spin-based nanoscale diamond magnetometers.

Dependence of magnetic field and electronic transport of Mn4 Single-molecule magnet in a Single-Electron Transistor

NASA Astrophysics Data System (ADS)

Rodriguez, Alvar; Singh, Simranjeet; Haque, Firoze; Del Barco, Enrique; Nguyen, Tu; Christou, George

2012-02-01

Dependence of magnetic field and electronic transport of Mn4 Single-molecule magnet in a Single-Electron Transistor A. Rodriguez, S. Singh, F. Haque and E. del Barco Department of Physics, University of Central Florida, 4000 Central Florida Blvd., Orlando, Florida 32816 USA T. Nguyen and G. Christou Department of Chemistry, University of Florida, Gainesville, Florida 32611 USA Abstract We have performed single-electron transport measurements on a series of Mn-based low-nuclearity single-molecule magnets (SMM) observing Coulomb blockade. SMMs with well isolated and low ground spin states, i.e. S = 9/2 (Mn4) and S = 6 (Mn3) were chosen for these studies, such that the ground spin multiplet does not mix with levels of other excited spin states for the magnetic fields (H = 0-8 T) employed in the experiments. Different functionalization groups were employed to change the mechanical, geometrical and transport characteristics of the molecules when deposited from liquid solution on the transistors. Electromigration-broken three-terminal single-electron transistors were used. Results obtained at temperatures down to 240 mK and in the presence of high magnetic fields will be shown.

Using DFT Methods to Study Activators in Optical Materials

DOE PAGES

Du, Mao-Hua

2015-08-17

Density functional theory (DFT) calculations of various activators (ranging from transition metal ions, rare-earth ions, ns 2 ions, to self-trapped and dopant-bound excitons) in phosphors and scintillators are reviewed. As a single-particle ground-state theory, DFT calculations cannot reproduce the experimentally observed optical spectra, which involve transitions between multi-electronic states. However, DFT calculations can generally provide sufficiently accurate structural relaxation and distinguish different hybridization strengths between an activator and its ligands in different host compounds. This is important because the activator-ligand interaction often governs the trends in luminescence properties in phosphors and scintillators, and can be used to search for newmore » materials. DFT calculations of the electronic structure of the host compound and the positions of the activator levels relative to the host band edges in scintillators are also important for finding optimal host-activator combinations for high light yields and fast scintillation response. Mn 4+ activated red phosphors, scintillators activated by Ce 3+, Eu 2+, Tl +, and excitons are shown as examples of using DFT calculations in phosphor and scintillator research.« less

Interfacial Energy Alignment at the ITO/Ultra-Thin Electron Selective Dielectric Layer Interface and Its Effect on the Efficiency of Bulk-Heterojunction Organic Solar Cells.

PubMed

Itoh, Eiji; Goto, Yoshinori; Saka, Yusuke; Fukuda, Katsutoshi

2016-04-01

We have investigated the photovoltaic properties of an inverted bulk heterojunction (BHJ) cell in a device with an indium-tin-oxide (ITO)/electron selective layer (ESL)/P3HT:PCBM active layer/MoOx/Ag multilayered structure. The insertion of only single layer of poly(diallyl-dimethyl-ammonium chloride) (PDDA) cationic polymer film (or poly(ethyleneimine) (PEI) polymeric interfacial dipole layer) and titanium oxide nanosheet (TN) films as an ESL effectively improved cell performance. Abnormal S-shaped curves were observed in the inverted BHJ cells owing to the contact resistance across the ITO/active layer interface and the ITO/PDDA/TN/active layer interface. The series resistance across the ITO/ESL interface in the inverted BHJ cell was successfully reduced using an interfacial layer with a positively charged surface potential with respect to ITO base electrode. The positive dipole in PEI and the electronic charge phenomena at the electrophoretic deposited TN (ED-TN) films on ITO contributed to the reduction of the contact resistance at the electrode interface. The surface potential measurement revealed that the energy alignment by the transfer of electronic charges from the ED-TN to the base electrodes. The insertion of the ESL with a large positive surface potential reduced the potential barrier for the electron injection at ITO/TN interface and it improved the photovoltaic properties of the inverted cell with an ITO/TN/active layer/MoOx/Ag structure.

The merger of electrochemistry and molecular electronics.

PubMed

McCreery, Richard L

2012-02-01

Molecular Electronics has the potential to greatly enhance existing silicon-based microelectronics to realize new functions, higher device density, lower power consumption, and lower cost. Although the investigation of electron transport through single molecules and molecular monolayers in "molecular junctions" is a recent development, many of the relevant concepts and phenomena are derived from electrochemistry, as practiced for the past several decades. The past 10+ years have seen an explosion of research activity directed toward how the structure of molecules affects electron transport in molecular junctions, with the ultimate objective of "rational design" of molecular components with new electronic functions, such as chemical sensing, interactions with light, and low-cost, low-power consumer electronics. In order to achieve these scientifically and commercially important objectives, the factors controlling charge transport in molecules "connected" to conducting contacts must be understood, and methods for massively parallel manufacturing of molecular circuits must be developed. This Personal Account describes the development of reproducible and robust molecular electronic devices, starting with modified electrodes used in electrochemistry and progressing to manufacturable molecular junctions. Although the field faced some early difficulties in reliability and characterization, the pieces are now in place for rapid advances in understanding charge transport at the molecular level. Inherent in the field of Molecular Electronics are many electrochemical concepts, including tunneling, redox exchange, activated electron transfer, and electron coupling between molecules and conducting contacts. Copyright © 2012 The Japan Chemical Journal Forum and Wiley Periodicals, Inc.

Bioelectronic neural pixel: Chemical stimulation and electrical sensing at the same site

PubMed Central

Jonsson, Amanda; Inal, Sahika; Uguz, Ilke; Williamson, Adam J.; Kergoat, Loïg; Rivnay, Jonathan; Khodagholy, Dion; Berggren, Magnus; Bernard, Christophe; Malliaras, George G.

2016-01-01

Local control of neuronal activity is central to many therapeutic strategies aiming to treat neurological disorders. Arguably, the best solution would make use of endogenous highly localized and specialized regulatory mechanisms of neuronal activity, and an ideal therapeutic technology should sense activity and deliver endogenous molecules at the same site for the most efficient feedback regulation. Here, we address this challenge with an organic electronic multifunctional device that is capable of chemical stimulation and electrical sensing at the same site, at the single-cell scale. Conducting polymer electrodes recorded epileptiform discharges induced in mouse hippocampal preparation. The inhibitory neurotransmitter, γ-aminobutyric acid (GABA), was then actively delivered through the recording electrodes via organic electronic ion pump technology. GABA delivery stopped epileptiform activity, recorded simultaneously and colocally. This multifunctional “neural pixel” creates a range of opportunities, including implantable therapeutic devices with automated feedback, where locally recorded signals regulate local release of specific therapeutic agents. PMID:27506784

Four-electron deoxygenative reductive coupling of carbon monoxide at a single metal site

NASA Astrophysics Data System (ADS)

Buss, Joshua A.; Agapie, Theodor

2016-01-01

Carbon dioxide is the ultimate source of the fossil fuels that are both central to modern life and problematic: their use increases atmospheric levels of greenhouse gases, and their availability is geopolitically constrained. Using carbon dioxide as a feedstock to produce synthetic fuels might, in principle, alleviate these concerns. Although many homogeneous and heterogeneous catalysts convert carbon dioxide to carbon monoxide, further deoxygenative coupling of carbon monoxide to generate useful multicarbon products is challenging. Molybdenum and vanadium nitrogenases are capable of converting carbon monoxide into hydrocarbons under mild conditions, using discrete electron and proton sources. Electrocatalytic reduction of carbon monoxide on copper catalysts also uses a combination of electrons and protons, while the industrial Fischer-Tropsch process uses dihydrogen as a combined source of electrons and electrophiles for carbon monoxide coupling at high temperatures and pressures. However, these enzymatic and heterogeneous systems are difficult to probe mechanistically. Molecular catalysts have been studied extensively to investigate the elementary steps by which carbon monoxide is deoxygenated and coupled, but a single metal site that can efficiently induce the required scission of carbon-oxygen bonds and generate carbon-carbon bonds has not yet been documented. Here we describe a molybdenum compound, supported by a terphenyl-diphosphine ligand, that activates and cleaves the strong carbon-oxygen bond of carbon monoxide, enacts carbon-carbon coupling, and spontaneously dissociates the resulting fragment. This complex four-electron transformation is enabled by the terphenyl-diphosphine ligand, which acts as an electron reservoir and exhibits the coordinative flexibility needed to stabilize the different intermediates involved in the overall reaction sequence. We anticipate that these design elements might help in the development of efficient catalysts for converting carbon monoxide to chemical fuels, and should prove useful in the broader context of performing complex multi-electron transformations at a single metal site.

Prediction of Spin-Polarization Effects in Quantum Wire Transport

NASA Astrophysics Data System (ADS)

Fasol, Gerhard; Sakaki, Hiroyuki

1994-01-01

We predict a new effect for transport in quantum wires: spontaneous spin polarization. Most work on transport in mesoscopic devices has assumed a model of non interacting, spin-free electrons. We introduce spin, electron pair scattering and microscopic crystal properties into the design of mesoscopic devices. The new spin polarization effect results from the fact that in a single mode quantum wire, electron and hole bands still have two spin subbands. In general, these two spin subbands are expected to be split even in zero magnetic field. At sufficiently low temperatures the electron pair scattering rates for one spin subband ( e.g., the spin-down) can be much larger than for the other spin subband. This effect can be used for an active spin polarizer device: hot electrons in one subband ( e.g., `spin up') pass with weak pair scattering, while electrons in the opposite subband ( e.g., `spin down'), have high probability of scattering into the `spin-up' subband, resulting in spin polarization of a hot electron beam.

Molecular electronics with single molecules in solid-state devices.

PubMed

Moth-Poulsen, Kasper; Bjørnholm, Thomas

2009-09-01

The ultimate aim of molecular electronics is to understand and master single-molecule devices. Based on the latest results on electron transport in single molecules in solid-state devices, we focus here on new insights into the influence of metal electrodes on the energy spectrum of the molecule, and on how the electron transport properties of the molecule depend on the strength of the electronic coupling between it and the electrodes. A variety of phenomena are observed depending on whether this coupling is weak, intermediate or strong.

Room-temperature current blockade in atomically defined single-cluster junctions

NASA Astrophysics Data System (ADS)

Lovat, Giacomo; Choi, Bonnie; Paley, Daniel W.; Steigerwald, Michael L.; Venkataraman, Latha; Roy, Xavier

2017-11-01

Fabricating nanoscopic devices capable of manipulating and processing single units of charge is an essential step towards creating functional devices where quantum effects dominate transport characteristics. The archetypal single-electron transistor comprises a small conducting or semiconducting island separated from two metallic reservoirs by insulating barriers. By enabling the transfer of a well-defined number of charge carriers between the island and the reservoirs, such a device may enable discrete single-electron operations. Here, we describe a single-molecule junction comprising a redox-active, atomically precise cobalt chalcogenide cluster wired between two nanoscopic electrodes. We observe current blockade at room temperature in thousands of single-cluster junctions. Below a threshold voltage, charge transfer across the junction is suppressed. The device is turned on when the temporary occupation of the core states by a transiting carrier is energetically enabled, resulting in a sequential tunnelling process and an increase in current by a factor of ∼600. We perform in situ and ex situ cyclic voltammetry as well as density functional theory calculations to unveil a two-step process mediated by an orbital localized on the core of the cluster in which charge carriers reside before tunnelling to the collector reservoir. As the bias window of the junction is opened wide enough to include one of the cluster frontier orbitals, the current blockade is lifted and charge carriers can tunnel sequentially across the junction.

Foundation for Integrating Employee Health Activities for Active Duty Personnel in the Department of Defense

DTIC Science & Technology

2009-01-01

the intent of DoD’s electronic health record, AHLTA, which will eventually contain all health uti - lization information in a single record. However...service) Health monitoring Serum sample Prescription medications Immunizations Pregnancy test Health monitoring Required (varies by service) Periodic...FedEx in 2002, but it should be noted that these are unpublished. FedEx reports that the HCM program has reduced costs and uti - lization of heath-care

High-energy electron emission from metallic nano-tips driven by intense single-cycle terahertz pulses

PubMed Central

Li, Sha; Jones, R. R.

2016-01-01

Electrons ejected from atoms and subsequently driven to high energies in strong laser fields enable techniques from attosecond pulse generation to imaging with rescattered electrons. Analogous processes govern strong-field electron emission from nanostructures, where long wavelength radiation and large local field enhancements hold the promise for producing electrons with substantially higher energies, allowing for higher resolution time-resolved imaging. Here we report on the use of single-cycle terahertz pulses to drive electron emission from unbiased nano-tips. Energies exceeding 5 keV are observed, substantially greater than previously attained at higher drive frequencies. Despite large differences in the magnitude of the respective local fields, we find that the maximum electron energies are only weakly dependent on the tip radius, for 10 nm

Single-Nanoparticle Photoelectrochemistry at a Nanoparticulate TiO2 -Filmed Ultramicroelectrode.

PubMed

Peng, Yue-Yi; Ma, Hui; Ma, Wei; Long, Yi-Tao; Tian, He

2018-03-26

An ultrasensitive photoelectrochemical method for achieving real-time detection of single nanoparticle collision events is presented. Using a micrometer-thick nanoparticulate TiO 2 -filmed Au ultra-microelectrode (TiO 2 @Au UME), a sub-millisecond photocurrent transient was observed for an individual N719-tagged TiO 2 (N719@TiO 2 ) nanoparticle and is due to the instantaneous collision process. Owing to a trap-limited electron diffusion process as the rate-limiting step, a random three-dimensional diffusion model was developed to simulate electron transport dynamics in TiO 2 film. The combination of theoretical simulation and high-resolution photocurrent measurement allow electron-transfer information of a single N719@TiO 2 nanoparticle to be quantified at single-molecule accuracy and the electron diffusivity and the electron-collection efficiency of TiO 2 @Au UME to be estimated. This method provides a test for studies of photoinduced electron transfer at the single-nanoparticle level. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Organic photovoltaic devices with a single layer geometry (Conference Presentation)

NASA Astrophysics Data System (ADS)

Kolesov, Vladimir A.; Fuentes-Hernandez, Canek; Aizawa, Naoya; Larrain, Felipe A.; Chou, Wen-Fang; Perrotta, Alberto; Graham, Samuel; Kippelen, Bernard

2016-09-01

Organic photovoltaics (OPV) can lead to a low cost and short energy payback time alternative to existing photovoltaic technologies. However, to fulfill this promise, power conversion efficiencies must be improved and simultaneously the architecture of the devices and their processing steps need to be further simplified. In the most efficient devices to date, the functions of photocurrent generation, and hole/electron collection are achieved in different layers adding complexity to the device fabrication. In this talk, we present a novel approach that yields devices in which all these functions are combined in a single layer. Specifically, we report on bulk heterojunction devices in which amine-containing polymers are first mixed in the solution together with the donor and acceptor materials that form the active layer. A single-layer coating yields a self-forming bottom electron-collection layer comprised of the amine-containing polymer (e.g. PEIE). Hole-collection is achieved by subsequent immersion of this single layer in a solution of a polyoxometalate (e.g. phosphomolybdic acid (PMA)) leading to an electrically p-doped region formed by the diffusion of the dopant molecules into the bulk. The depth of this doped region can be controlled with values up to tens of nm by varying the immersion time. Devices with a single 500 nm-thick active layer of P3HT:ICBA processed using this method yield power conversion efficiency (PCE) values of 4.8 ± 0.3% at 1 sun and demonstrate a performance level superior to that of benchmark three-layer devices with separate layers of PEIE/P3HT:ICBA/MoOx (4.1 ± 0.4%). Devices remain stable after shelf lifetime experiments carried-out at 60 °C over 280 h.

Convergence of Cortical and Sensory Driver Inputs on Single Thalamocortical Cells

PubMed Central

Groh, Alexander; Bokor, Hajnalka; Mease, Rebecca A.; Plattner, Viktor M.; Hangya, Balázs; Stroh, Albrecht; Deschenes, Martin; Acsády, László

2014-01-01

Ascending and descending information is relayed through the thalamus via strong, “driver” pathways. According to our current knowledge, different driver pathways are organized in parallel streams and do not interact at the thalamic level. Using an electron microscopic approach combined with optogenetics and in vivo physiology, we examined whether driver inputs arising from different sources can interact at single thalamocortical cells in the rodent somatosensory thalamus (nucleus posterior, POm). Both the anatomical and the physiological data demonstrated that ascending driver inputs from the brainstem and descending driver inputs from cortical layer 5 pyramidal neurons converge and interact on single thalamocortical neurons in POm. Both individual pathways displayed driver properties, but they interacted synergistically in a time-dependent manner and when co-activated, supralinearly increased the output of thalamus. As a consequence, thalamocortical neurons reported the relative timing between sensory events and ongoing cortical activity. We conclude that thalamocortical neurons can receive 2 powerful inputs of different origin, rather than only a single one as previously suggested. This allows thalamocortical neurons to integrate raw sensory information with powerful cortical signals and transfer the integrated activity back to cortical networks. PMID:23825316

Antibacterial Activity of Electrochemically Synthesized Colloidal Silver Nanoparticles Against Hospital-Acquired Infections

NASA Astrophysics Data System (ADS)

Thuc, Dao Tri; Huy, Tran Quang; Hoang, Luc Huy; Hoang, Tran Huy; Le, Anh-Tuan; Anh, Dang Duc

2017-06-01

This study evaluated the antibacterial activity of electrochemically synthesized colloidal silver nanoparticles (AgNPs) against hospital-acquired infections. Colloidal AgNPs were synthesized via a single process using bulk silver bars, bi-distilled water, trisodium citrate, and direct current voltage at room temperature. Colloidal AgNPs were characterized by transmission electron microscopy, field-emission scanning electron microscopy, and energy-dispersive x-ray analyses. The antibacterial activity of colloidal AgNPs against four bacterial strains isolated from clinical samples, including methicillin-resistant Staphylococcus aureus, Escherichia coli O157:H7, multidrug-resistant Pseudomonas aeruginosa, and carbapenem-resistant Klebsiella pneumonia, was evaluated by disc diffusion, minimum inhibitory concentration (MIC), and ultrathin sectioning electron microscopy. The results showed that the prepared AgNPs were 19.7 ± 4.3 nm in size, quasi-spherical, and of high purity. Zones of inhibition approximately 6-10 mm in diameter were found, corresponding to AgNPs concentrations of 50 μg/mL to 100 μg/mL. The MIC results revealed that the antibacterial activity of the prepared AgNPs was strongly dependent on the concentration and strain of the tested bacteria.

Ag/CuO nanoparticles prepared from a novel trinuclear compound [Cu(Imdz)4(Ag(CN)2)2] (Imdz = imidazole) by a pyrolysis display excellent antimicrobial activity

NASA Astrophysics Data System (ADS)

Adhikary, Jaydeep; Das, Balaram; Chatterjee, Sourav; Dash, Sandeep Kumar; Chattopadhyay, Sourav; Roy, Somenath; Chen, Jeng-Wei; Chattopadhyay, Tanmay

2016-06-01

One copper and two silver containing one hetero tri-nuclear precursor compound [Cu(Imdz)4(Ag(CN)2)2] (1) (Imdz = Imidazole) has been synthesized and characterized by single crystal X-ray diffraction. Simple pyrolysis of the complex at 550 °C for 4 h afforded Ag/CuO nanoparticles (NPs). The synthesized nanoparticles were characterized by ultraviolet-visible (UV-Vis), Fourier transform infrared (FT-IR), X-ray powder diffraction (XRPD), dynamic light scattering (DLS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray (EDX) and X-ray photo electron spectroscopy (XPS). Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli) have been employed as model microbial species to study the anti-microbial activity of the synthesized NPs. The NPs showed potent anti-microbial activity evidenced from the Minimum Inhibitory Concentration (MIC) and Minimum Bactericidal Concentration (MBC) values. Very high level of cell uptake and then generation of reactive oxygen species (ROS) are the origin of such strong antimicrobial activity for the NPs. However, the cytotoxicity level of the NPs towards normal human cell is very low.

Ion resonances and ELF wave production by an electron beam injected into the ionosphere - ECHO 6

NASA Astrophysics Data System (ADS)

Winckler, J. R.; Steffen, J. E.; Malcolm, P. R.; Erickson, K. N.; Abe, Y.; Swanson, R. L.

1984-09-01

Two effects observed with electron antennas ejected from a sounding rocket launched into the ionosphere in March 1983 carrying electron beam guns are discussed. The sensor packages were ejected and travelled parallel to the vehicle trajectory. Electric potentials were measured between the single probes and a plasma diagnostic package while the gun injected electrons into the ionosphere in perpendicular and parallel 1 kHz directions. Signal pulses over the dc-1250 kHz range were detected. A kHz gun frequency caused a signal that decreased by two orders of magnitude between 45-90 m from the beam field line. However, the signal was detectable at 1 mV/m at 120 m, supporting earlier data that indicated that pulsed electron beams can cause ELF waves in space. Beam injection parallel to the magnetic field produced an 840 Hz resonance that could be quenched by activation of a transverse beam.

Robust activation method for negative electron affinity photocathodes

DOEpatents

Mulhollan, Gregory A [Dripping Springs, TX; Bierman, John C [Austin, TX

2011-09-13

A method by which photocathodes(201), single crystal, amorphous, or otherwise ordered, can be surface modified to a robust state of lowered and in best cases negative, electron affinity has been discovered. Conventional methods employ the use of Cs(203) and an oxidizing agent(207), typically carried by diatomic oxygen or by more complex molecules, for example nitrogen trifluoride, to achieve a lowered electron affinity(404). In the improved activation method, a second alkali, other than Cs(205), is introduced onto the surface during the activation process, either by co-deposition, yo-yo, or sporadic or intermittent application. Best effect for GaAs photocathodes has been found through the use of Li(402) as the second alkali, though nearly the same effect can be found by employing Na(406). Suitable photocathodes are those which are grown, cut from boules, implanted, rolled, deposited or otherwise fabricated in a fashion and shape desired for test or manufacture independently supported or atop a support structure or within a framework or otherwise affixed or suspended in the place and position required for use.

Charge transport with single molecules--an electrochemical approach.

PubMed

Li, Chen; Mishchenko, Artem; Pobelov, Ilya; Wandlowski, Thomas

2010-01-01

After an introduction and brief review of charge transport in nanoscale molecular systems we report on experimental studies in gold / (single) molecule / gold junctions at solid / liquid interfaces employing a scanning tunneling microscopy (STM)-based 'break junction' technique. We demonstrate attempts in developing basic relationships between molecular structure, conductance properties and nanoscale electrochemical concepts based on four case studies from our own work. In experiments with alpha, omega-alkanedithiol and biphenyldithiol molecular junctions we address the role of sulfur-gold couplings and molecular conformation, such as gauche defects in the alkyl chains and the torsion angle between two phenyl rings. Combination with quantum chemistry calculations enabled a detailed molecular-level understanding of the electronic structure and transport characteristics of both systems. Employing the concept of 'electrolyte gating' with redox-active molecules, such as thiol-terminated derivatives of viologens (HS-6V6-SH or (HS-6V6)) we demonstrate the construction of symmetric and asymmetric active molecular junctions with transistor- or diode-like behavior upon polarization in an electrochemical environment. The experimental data could be represented quantitatively by the Kutznetsov/Ulstrup model assuming a two-step electron transfer with partial vibration relaxation. Finally, we show that surface-immobilized gold nanoparticles with a diameter of (2.4 +/- 0.5) nm exhibit features of locally addressable multi-state electronic switching upon electrolyte gating, which appears to be reminiscent of a sequential charging through several 'oxidation/reduction states'.

Radio-frequency reflectometry on an undoped AlGaAs/GaAs single electron transistor

DOE Office of Scientific and Technical Information (OSTI.GOV)

MacLeod, S. J.; See, A. M.; Keane, Z. K.

2014-01-06

Radio frequency reflectometry is demonstrated in a sub-micron undoped AlGaAs/GaAs device. Undoped single electron transistors (SETs) are attractive candidates to study single electron phenomena, due to their charge stability and robust electronic properties after thermal cycling. However, these devices require a large top-gate, which is unsuitable for the fast and sensitive radio frequency reflectometry technique. Here, we demonstrate that rf reflectometry is possible in an undoped SET.

Compendium of Single Event Effects, Total Ionizing Dose, and Displacement Damage for Candidate Spacecraft Electronics for NASA

NASA Technical Reports Server (NTRS)

LaBel, Kenneth A.; OBryan, Martha V.; Chen, Dakai; Campola, Michael J.; Casey, Megan C.; Pellish, Jonathan A.; Lauenstein, Jean-Marie; Wilcox, Edward P.; Topper, Alyson D.; Ladbury, Raymond L.;

Structural, Optical, and Photocatalytic Properties of Quasi-One-Dimensional Nanocrystalline ZnO, ZnOC:nC Composites, and C-doped ZnO

NASA Astrophysics Data System (ADS)

Shalaeva, E. V.; Gyrdasova, O. I.; Krasilnikov, V. N.; Melkozerova, M. A.; Baklanova, I. V.; Buldakova, L. Yu.

Various thermolysis rotes of zinc glicolate complexes are considered for the synthesis of quasi-one-dimensional nanostructured aggregates ZnO and Zn-O-C used as photocatalysts. Structural features of quasi-one-dimensional aggregates Zn-O-C and ZnO are investigated in detail. Transmission electron microscopy, Raman spectroscopy, and electron paramagnetic resonance spectroscopy methods demonstrate that the aggregates Zn-O-C have either composite structure (ZnO crystallites in amorphous carbon matrix) or a C-doped ZnO single-phase structure depending on heat treatment conditions, and that all the aggregates exhibit as a rule a tubular morphology, a nanocrystalline structure with a high specific surface area, and a high concentration of singly charged oxygen vacancies. The mechanism of the nanocrystalline structure formation is discussed and the effect of thermolysis condition on the formation of the textured structure of aggregates is investigated. The results of examination of the photocatalytic and optical absorption properties of the synthesized aggregates are presented. The photocatalytic activity for the hydroquinone oxidation reaction under ultraviolet and visible light increases in the series: the reference ZnO powder, quasi-one-dimensional ZnO, quasi-one-dimensional aggregates C-doped ZnO, and this tendency correlates with the reduction of the optical gap width. As a result of our studies, we have arrived at an important conclusion that thermal treatment of ZnO:nC composites allows a C-doped ZnO with high catalytic activity. This increasing photoactivity of C-doped ZnO aggregates is attributed to the optimal specific surface area and electron-energy spectrum restructuring to be produced owing to the presence of singly charged oxygen vacancies and carbon dissolved in the ZnO lattice.

Influence of heme-thiolate in shaping the catalytic properties of a bacterial nitric-oxide synthase.

PubMed

Hannibal, Luciana; Somasundaram, Ramasamy; Tejero, Jesús; Wilson, Adjele; Stuehr, Dennis J

2011-11-11

Nitric-oxide synthases (NOS) are heme-thiolate enzymes that generate nitric oxide (NO) from L-arginine. Mammalian and bacterial NOSs contain a conserved tryptophan (Trp) that hydrogen bonds with the heme-thiolate ligand. We mutated Trp(66) to His and Phe (W66H, W66F) in B. subtilis NOS to investigate how heme-thiolate electronic properties control enzyme catalysis. The mutations had opposite effects on heme midpoint potential (-302, -361, and -427 mV for W66H, wild-type (WT), and W66F, respectively). These changes were associated with rank order (W66H < WT < W66F) changes in the rates of oxygen activation and product formation in Arg hydroxylation and N-hydroxyarginine (NOHA) oxidation single turnover reactions, and in the O(2) reactivity of the ferrous heme-NO product complex. However, enzyme ferrous heme-O(2) autoxidation showed an opposite rank order. Tetrahydrofolate supported NO synthesis by WT and the mutant NOS. All three proteins showed similar extents of product formation (L-Arg → NOHA or NOHA → citrulline) in single turnover studies, but the W66F mutant showed a 2.5 times lower activity when the reactions were supported by flavoproteins and NADPH. We conclude that Trp(66) controls several catalytic parameters by tuning the electron density of the heme-thiolate bond. A greater electron density (as in W66F) improves oxygen activation and reactivity toward substrate, but decreases heme-dioxy stability and lowers the driving force for heme reduction. In the WT enzyme the Trp(66) residue balances these opposing effects for optimal catalysis.

Mechanism of hole injection enhancement in light-emitting diodes by inserting multiple hole-reservoir layers in electron blocking layer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, Yukun; Wang, Shuai; Feng, Lungang

In this study, gallium nitride (GaN) based light-emitting diodes (LEDs) with single and multiple hole-reservoir layers (HRLs) inserted in the electron-blocking layer (EBL) have been investigated numerically and experimentally. According to simulation results, a better electron confinement and a higher hole injection level can be achieved by the multiple HRLs inserted in the EBL region. To further reveal the underlying mechanism of hole injection enhancement experimentally, the active regions were intentionally designed to emit photons with three different wavelengths of 440 nm, 460 nm, and 480 nm, respectively. Based on the experimental results of photoluminescence (PL) and time-resolved PL (TRPL) measurements conducted atmore » 298 K, the remarkable enhancement (148%) of PL intensities and significant increase in the decay times of the quantum wells close to p-GaN can be obtained. Therefore, the mechanism is proposed that carriers are able to reserve in the EBL region with multiple HRLs for a much longer time. Meanwhile, carriers could diffuse into the active region by tunnelling and/or thermo-electronic effect and then recombine efficiently, leading to the better carrier reservoir effect and higher hole injection in LEDs. As a result, by inserting multiple HRLs in the EBL region instead of single HRL, the experimental external quantum efficiency is enhanced by 19.8%, while the serious droop ratio is markedly suppressed from 37.0% to 27.6% at the high current injection of 100 A/cm{sup 2}.« less

A Method for 3D-Reconstruction of a Muscle Thick Filament Using the Tilt Series Images of a Single Filament Electron Tomogram

PubMed Central

Márquez, G.; Pinto, A.; Alamo, L.; Baumann, B.; Ye, F.; Winkler, H.; Taylor, K.; Padrón, R.

2014-01-01

Summary Myosin interacting-heads (MIH) motifs are visualized in 3D-reconstructions of thick filaments from striated muscle. These reconstructions are calculated by averaging methods using images from electron micrographs of grids prepared using numerous filament preparations. Here we propose an alternative method to calculate the 3D-reconstruction of a single thick filament using only a tilt series images recorded by electron tomography. Relaxed thick filaments, prepared from tarantula leg muscle homogenates, were negatively stained. Single-axis tilt series of single isolated thick filaments were obtained with the electron microscope at a low electron dose, and recorded on a CCD camera by electron tomography. An IHRSR 3D-recontruction was calculated from the tilt series images of a single thick filament. The reconstruction was enhanced by including in the search stage dual tilt image segments while only single tilt along the filament axis is usually used, as well as applying a band pass filter just before the back projection. The reconstruction from a single filament has a 40 Å resolution and clearly shows the presence of MIH motifs. In contrast, the electron tomogram 3D-reconstruction of the same thick filament –calculated without any image averaging and/or imposition of helical symmetry- only reveals MIH motifs infrequently. This is –to our knowledge- the first application of the IHRSR method to calculate a 3D reconstruction from tilt series images. This single filament IHRSR reconstruction method (SF-IHRSR) should provide a new tool to assess structural differences between well-ordered thick (or thin) filaments in a grid by recording separately their electron tomograms. PMID:24727133

A method for 3D-reconstruction of a muscle thick filament using the tilt series images of a single filament electron tomogram.

PubMed

Márquez, G; Pinto, A; Alamo, L; Baumann, B; Ye, F; Winkler, H; Taylor, K; Padrón, R

2014-05-01

Myosin interacting-heads (MIH) motifs are visualized in 3D-reconstructions of thick filaments from striated muscle. These reconstructions are calculated by averaging methods using images from electron micrographs of grids prepared using numerous filament preparations. Here we propose an alternative method to calculate the 3D-reconstruction of a single thick filament using only a tilt series images recorded by electron tomography. Relaxed thick filaments, prepared from tarantula leg muscle homogenates, were negatively stained. Single-axis tilt series of single isolated thick filaments were obtained with the electron microscope at a low electron dose, and recorded on a CCD camera by electron tomography. An IHRSR 3D-recontruction was calculated from the tilt series images of a single thick filament. The reconstruction was enhanced by including in the search stage dual tilt image segments while only single tilt along the filament axis is usually used, as well as applying a band pass filter just before the back projection. The reconstruction from a single filament has a 40 Å resolution and clearly shows the presence of MIH motifs. In contrast, the electron tomogram 3D-reconstruction of the same thick filament - calculated without any image averaging and/or imposition of helical symmetry - only reveals MIH motifs infrequently. This is - to our knowledge - the first application of the IHRSR method to calculate a 3D reconstruction from tilt series images. This single filament IHRSR reconstruction method (SF-IHRSR) should provide a new tool to assess structural differences between well-ordered thick (or thin) filaments in a grid by recording separately their electron tomograms. Copyright © 2014 Elsevier Inc. All rights reserved.

3D simulation of electron and ion transmission of GEM-based detectors

NASA Astrophysics Data System (ADS)

Bhattacharya, Purba; Mohanty, Bedangadas; Mukhopadhyay, Supratik; Majumdar, Nayana; da Luz, Hugo Natal

2017-10-01

Time Projection Chamber (TPC) has been chosen as the main tracking system in several high-flux and high repetition rate experiments. These include on-going experiments such as ALICE and future experiments such as PANDA at FAIR and ILC. Different R&D activities were carried out on the adoption of Gas Electron Multiplier (GEM) as the gas amplification stage of the ALICE-TPC upgrade version. The requirement of low ion feedback has been established through these activities. Low ion feedback minimizes distortions due to space charge and maintains the necessary values of detector gain and energy resolution. In the present work, Garfield simulation framework has been used to study the related physical processes occurring within single, triple and quadruple GEM detectors. Ion backflow and electron transmission of quadruple GEMs, made up of foils with different hole pitch under different electromagnetic field configurations (the projected solutions for the ALICE TPC) have been studied. Finally a new triple GEM detector configuration with low ion backflow fraction and good electron transmission properties has been proposed as a simpler GEM-based alternative suitable for TPCs for future collider experiments.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lehtola, Susi; Parkhill, John; Head-Gordon, Martin

Novel implementations based on dense tensor storage are presented here for the singlet-reference perfect quadruples (PQ) [J. A. Parkhill et al., J. Chem. Phys. 130, 084101 (2009)] and perfect hextuples (PH) [J. A. Parkhill and M. Head-Gordon, J. Chem. Phys. 133, 024103 (2010)] models. The methods are obtained as block decompositions of conventional coupled-cluster theory that are exact for four electrons in four orbitals (PQ) and six electrons in six orbitals (PH), but that can also be applied to much larger systems. PQ and PH have storage requirements that scale as the square, and as the cube of the numbermore » of active electrons, respectively, and exhibit quartic scaling of the computational effort for large systems. Applications of the new implementations are presented for full-valence calculations on linear polyenes (C nH n+2), which highlight the excellent computational scaling of the present implementations that can routinely handle active spaces of hundreds of electrons. The accuracy of the models is studied in the π space of the polyenes, in hydrogen chains (H 50), and in the π space of polyacene molecules. In all cases, the results compare favorably to density matrix renormalization group values. With the novel implementation of PQ, active spaces of 140 electrons in 140 orbitals can be solved in a matter of minutes on a single core workstation, and the relatively low polynomial scaling means that very large systems are also accessible using parallel computing.« less

Controlled chain polymerisation and chemical soldering for single-molecule electronics.

PubMed

Okawa, Yuji; Akai-Kasaya, Megumi; Kuwahara, Yuji; Mandal, Swapan K; Aono, Masakazu

2012-05-21

Single functional molecules offer great potential for the development of novel nanoelectronic devices with capabilities beyond today's silicon-based devices. To realise single-molecule electronics, the development of a viable method for connecting functional molecules to each other using single conductive polymer chains is required. The method of initiating chain polymerisation using the tip of a scanning tunnelling microscope (STM) is very useful for fabricating single conductive polymer chains at designated positions and thereby wiring single molecules. In this feature article, developments in the controlled chain polymerisation of diacetylene compounds and the properties of polydiacetylene chains are summarised. Recent studies of "chemical soldering", a technique enabling the covalent connection of single polydiacetylene chains to single functional molecules, are also introduced. This represents a key step in advancing the development of single-molecule electronics.

A singly charged ion source for radioactive {sup 11}C ion acceleration

DOE Office of Scientific and Technical Information (OSTI.GOV)

Katagiri, K.; Noda, A.; Nagatsu, K.

2016-02-15

A new singly charged ion source using electron impact ionization has been developed to realize an isotope separation on-line system for simultaneous positron emission tomography imaging and heavy-ion cancer therapy using radioactive {sup 11}C ion beams. Low-energy electron beams are used in the electron impact ion source to produce singly charged ions. Ionization efficiency was calculated in order to decide the geometric parameters of the ion source and to determine the required electron emission current for obtaining high ionization efficiency. Based on these considerations, the singly charged ion source was designed and fabricated. In testing, the fabricated ion source wasmore » found to have favorable performance as a singly charged ion source.« less

Chloroplast ATP Synthase Modulation of the Thylakoid Proton Motive Force: Implications for Photosystem I and Photosystem II Photoprotection

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kanazawa, Atsuko; Ostendorf, Elisabeth; Kohzuma, Kaori

In wild type plants, decreasing CO 2 lowers the activity of the chloroplast ATP synthase, slowing proton efflux from the thylakoid lumen resulting in buildup of thylakoid proton motive force (pmf). The resulting acidification of the lumen regulates both light harvesting, via the qE mechanism, and photosynthetic electron transfer through the cytochrome b 6f complex. Here in this paper, we show that the cfq mutant of Arabidopsis, harboring single point mutation in its γ-subunit of the chloroplast ATP synthase, increases the specific activity of the ATP synthase and disables its down-regulation under low CO 2. The increased thylakoid proton conductivitymore » (g H +) in cfq results in decreased pmf and lumen acidification, preventing full activation of qE and more rapid electron transfer through the b6f complex, particularly under low CO 2 and fluctuating light. These conditions favor the accumulation of electrons on the acceptor side of PSI, and result in severe loss of PSI activity. Comparing the current results with previous work on the pgr5 mutant suggests a general mechanism where increased PSI photodamage in both mutants is caused by loss of pmf, rather than inhibition of CEF per se. Overall, our results support a critical role for ATP synthase regulation in maintaining photosynthetic control of electron transfer to prevent photodamage.« less

Chloroplast ATP Synthase Modulation of the Thylakoid Proton Motive Force: Implications for Photosystem I and Photosystem II Photoprotection

DOE PAGES

Kanazawa, Atsuko; Ostendorf, Elisabeth; Kohzuma, Kaori; ...

2017-05-03

In wild type plants, decreasing CO 2 lowers the activity of the chloroplast ATP synthase, slowing proton efflux from the thylakoid lumen resulting in buildup of thylakoid proton motive force (pmf). The resulting acidification of the lumen regulates both light harvesting, via the qE mechanism, and photosynthetic electron transfer through the cytochrome b 6f complex. Here in this paper, we show that the cfq mutant of Arabidopsis, harboring single point mutation in its γ-subunit of the chloroplast ATP synthase, increases the specific activity of the ATP synthase and disables its down-regulation under low CO 2. The increased thylakoid proton conductivitymore » (g H +) in cfq results in decreased pmf and lumen acidification, preventing full activation of qE and more rapid electron transfer through the b6f complex, particularly under low CO 2 and fluctuating light. These conditions favor the accumulation of electrons on the acceptor side of PSI, and result in severe loss of PSI activity. Comparing the current results with previous work on the pgr5 mutant suggests a general mechanism where increased PSI photodamage in both mutants is caused by loss of pmf, rather than inhibition of CEF per se. Overall, our results support a critical role for ATP synthase regulation in maintaining photosynthetic control of electron transfer to prevent photodamage.« less

An ab initio study of the C3(+) cation using multireference methods

NASA Technical Reports Server (NTRS)

Taylor, Peter R.; Martin, J. M. L.; Francois, J. P.; Gijbels, R.

1991-01-01

The energy difference between the linear 2 sigma(sup +, sub u) and cyclic 2B(sub 2) structures of C3(+) has been investigated using large (5s3p2d1f) basis sets and multireference electron correlation treatments, including complete active space self consistent fields (CASSCF), multireference configuration interaction (MRCI), and averaged coupled-pair functional (ACPF) methods, as well as the single-reference quadratic configuration interaction (QCISD(T)) method. Our best estimate, including a correction for basis set incompleteness, is that the linear form lies above the cyclic from by 5.2(+1.5 to -1.0) kcal/mol. The 2 sigma(sup +, sub u) state is probably not a transition state, but a local minimum. Reliable computation of the cyclic/linear energy difference in C3(+) is extremely demanding of the electron correlation treatment used: of the single-reference methods previously considered, CCSD(T) and QCISD(T) perform best. The MRCI + Q(0.01)/(4s2p1d) energy separation of 1.68 kcal/mol should provide a comparison standard for other electron correlation methods applied to this system.

Single-Site Active Iron-Based Bifunctional Oxygen Catalyst for a Compressible and Rechargeable Zinc-Air Battery.

PubMed

Ma, Longtao; Chen, Shengmei; Pei, Zengxia; Huang, Yan; Liang, Guojin; Mo, Funian; Yang, Qi; Su, Jun; Gao, Yihua; Zapien, Juan Antonio; Zhi, Chunyi

2018-02-27

The exploitation of a high-efficient, low-cost, and stable non-noble-metal-based catalyst with oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) simultaneously, as air electrode material for a rechargeable zinc-air battery is significantly crucial. Meanwhile, the compressible flexibility of a battery is the prerequisite of wearable or/and portable electronics. Herein, we present a strategy via single-site dispersion of an Fe-N x species on a two-dimensional (2D) highly graphitic porous nitrogen-doped carbon layer to implement superior catalytic activity toward ORR/OER (with a half-wave potential of 0.86 V for ORR and an overpotential of 390 mV at 10 mA·cm -2 for OER) in an alkaline medium. Furthermore, an elastic polyacrylamide hydrogel based electrolyte with the capability to retain great elasticity even under a highly corrosive alkaline environment is utilized to develop a solid-state compressible and rechargeable zinc-air battery. The creatively developed battery has a low charge-discharge voltage gap (0.78 V at 5 mA·cm -2 ) and large power density (118 mW·cm -2 ). It could be compressed up to 54% strain and bent up to 90° without charge/discharge performance and output power degradation. Our results reveal that single-site dispersion of catalytic active sites on a porous support for a bifunctional oxygen catalyst as cathode integrating a specially designed elastic electrolyte is a feasible strategy for fabricating efficient compressible and rechargeable zinc-air batteries, which could enlighten the design and development of other functional electronic devices.

Synthesis, X-ray crystallography, spectroscopic characterization and spectroscopic/electrochemical evidence of formation of phenoxy free radical in active center analogs of galactose oxidase - [Cu(Salgly)H₂O] and [Cu(Salphenylalanine)H₂O].

PubMed

Das, Biva; Medhi, Okhil K

2013-03-01

The formation of phenolate free radical is the factor of high turnover for catalytic activity of galactose oxidase (GO) compared to that by inorganic complexes. A new active center analog of GO, [Cu(II)(Salphenylalanine)H(2)O] have been synthesized and its single crystal X-ray analysis was done. In aqueous surfactant micellar solution chemical oxidation as well as electrochemical oxidation of structural models of galactose oxidase - [Cu(II)Salgly·H(2)O] and [Cu(II)(Salphenylalanine)·H(2)O], have been found to generate free radical originating at the phenolate group. Formation of the free radical have been proved by electron paramagnetic resonance spectroscopy, electronic spectroscopy and electrochemistry. Copyright © 2012 Elsevier B.V. All rights reserved.

On the formation of nanocrystalline active zinc oxide from zinc hydroxide carbonate

NASA Astrophysics Data System (ADS)

Moezzi, Amir; Cortie, Michael; Dowd, Annette; McDonagh, Andrew

2014-04-01

The decomposition of zinc hydroxide carbonate, Zn5(CO3)2(OH)6 (ZHC), into the high surface area form of ZnO known as "active zinc oxide" is examined. In particular, the nucleation and evolution of the ZnO nanocrystals is of interest as the size of these particles controls the activity of the product. The decomposition process was studied using X-ray diffraction, thermogravimetric analysis, scanning electron microscopy, transmission electron microscopy and BET surface area measurements. At about 240 °C ZHC decomposes to porous ZnO in a single step. The product material has a specific surface area in the range of 47-65 m2 g-1 and initially has a crystallite size that is of the order of 10 nm. A further increase in temperature, however, causes the particles to coarsen to over 25 nm in diameter. In principle, the coarsening phenomenon may be interrupted to control the particle size.

Single-Electron Detection and Spectroscopy via Relativistic Cyclotron Radiation.

PubMed

Asner, D M; Bradley, R F; de Viveiros, L; Doe, P J; Fernandes, J L; Fertl, M; Finn, E C; Formaggio, J A; Furse, D; Jones, A M; Kofron, J N; LaRoque, B H; Leber, M; McBride, E L; Miller, M L; Mohanmurthy, P; Monreal, B; Oblath, N S; Robertson, R G H; Rosenberg, L J; Rybka, G; Rysewyk, D; Sternberg, M G; Tedeschi, J R; Thümmler, T; VanDevender, B A; Woods, N L

2015-04-24

It has been understood since 1897 that accelerating charges must emit electromagnetic radiation. Although first derived in 1904, cyclotron radiation from a single electron orbiting in a magnetic field has never been observed directly. We demonstrate single-electron detection in a novel radio-frequency spectrometer. The relativistic shift in the cyclotron frequency permits a precise electron energy measurement. Precise beta electron spectroscopy from gaseous radiation sources is a key technique in modern efforts to measure the neutrino mass via the tritium decay end point, and this work demonstrates a fundamentally new approach to precision beta spectroscopy for future neutrino mass experiments.

Ultrafast lattice dynamics of single crystal and polycrystalline gold nanofilms☆

NASA Astrophysics Data System (ADS)

Hu, Jianbo; Karam, Tony E.; Blake, Geoffrey A.; Zewail, Ahmed H.

2017-09-01

Ultrafast electron diffraction is employed to spatiotemporally visualize the lattice dynamics of 11 nm-thick single-crystal and 2 nm-thick polycrystalline gold nanofilms. Surprisingly, the electron-phonon coupling rates derived from two temperature simulations of the data reveal a faster interaction between electrons and the lattice in the case of the single-crystal sample. We interpret this unexpected behavior as arising from quantum confinement of the electrons in the 2 nm-thick gold nanofilm, as supported by absorption spectra, an effect that counteracts the expected increase in the electron scattering off surfaces and grain boundaries in the polycrystalline materials.

Dopant-controlled single-electron pumping through a metallic island

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wenz, Tobias, E-mail: tobias.wenz@ptb.de; Hohls, Frank, E-mail: frank.hohls@ptb.de; Jehl, Xavier

We investigate a hybrid metallic island/single dopant electron pump based on fully depleted silicon-on-insulator technology. Electron transfer between the central metallic island and the leads is controlled by resonant tunneling through single phosphorus dopants in the barriers. Top gates above the barriers are used to control the resonance conditions. Applying radio frequency signals to the gates, non-adiabatic quantized electron pumping is achieved. A simple deterministic model is presented and confirmed by comparing measurements with simulations.

Digital processing with single electrons for arbitrary waveform generation of current

NASA Astrophysics Data System (ADS)

Okazaki, Yuma; Nakamura, Shuji; Onomitsu, Koji; Kaneko, Nobu-Hisa

2018-03-01

We demonstrate arbitrary waveform generation of current using a GaAs-based single-electron pump. In our experiment, a digital processing algorithm known as delta-sigma modulation is incorporated into single-electron pumping to generate a density-modulated single-electron stream, by which we demonstrate the generation of arbitrary waveforms of current including sinusoidal, square, and triangular waves with a peak-to-peak amplitude of approximately 10 pA and an output bandwidth ranging from dc to close to 1 MHz. The developed current generator can be used as the precise and calculable current reference required for measurements of current noise in low-temperature experiments.

Using granular film to suppress charge leakage in a single-electron latch.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Orlov, A. O.; Luo, X.; Yadavalli, K. K.

2008-01-01

A single-electron latch is a device that can be used as a building block for quantum-dot cellular automata circuits. It consists of three nanoscale metal 'dots' connected in series by tunnel junctions; charging of the dots is controlled by three electrostatic gates. One very important feature of a single-electron latch is its ability to store ('latch') information represented by the location of a single electron within the three dots. To obtain latching, the undesirable leakage of charge during the retention time must be suppressed. Previously, to achieve this goal, multiple tunnel junctions were used to connect the three dots. However,more » this method of charge leakage suppression requires an additional compensation of the background charges affecting each parasitic dot in the array of junctions. We report a single-electron latch where a granular metal film is used to fabricate the middle dot in the latch which concurrently acts as a charge leakage suppressor. This latch has no parasitic dots, therefore the background charge compensation procedure is greatly simplified. We discuss the origins of charge leakage suppression and possible applications of granular metal dots for various single-electron circuits.« less

Single-Nanowire Electrochemical Probe Detection for Internally Optimized Mechanism of Porous Graphene in Electrochemical Devices.

PubMed

Hu, Ping; Yan, Mengyu; Wang, Xuanpeng; Han, Chunhua; He, Liang; Wei, Xiujuan; Niu, Chaojiang; Zhao, Kangning; Tian, Xiaocong; Wei, Qiulong; Li, Zijia; Mai, Liqiang

2016-03-09

Graphene has been widely used to enhance the performance of energy storage devices due to its high conductivity, large surface area, and excellent mechanical flexibility. However, it is still unclear how graphene influences the electrochemical performance and reaction mechanisms of electrode materials. The single-nanowire electrochemical probe is an effective tool to explore the intrinsic mechanisms of the electrochemical reactions in situ. Here, pure MnO2 nanowires, reduced graphene oxide/MnO2 wire-in-scroll nanowires, and porous graphene oxide/MnO2 wire-in-scroll nanowires are employed to investigate the capacitance, ion diffusion coefficient, and charge storage mechanisms in single-nanowire electrochemical devices. The porous graphene oxide/MnO2 wire-in-scroll nanowire delivers an areal capacitance of 104 nF/μm(2), which is 4.0 and 2.8 times as high as those of reduced graphene oxide/MnO2 wire-in-scroll nanowire and MnO2 nanowire, respectively, at a scan rate of 20 mV/s. It is demonstrated that the reduced graphene oxide wrapping around the MnO2 nanowire greatly increases the electronic conductivity of the active materials, but decreases the ion diffusion coefficient because of the shielding effect of graphene. By creating pores in the graphene, the ion diffusion coefficient is recovered without degradation of the electron transport rate, which significantly improves the capacitance. Such single-nanowire electrochemical probes, which can detect electrochemical processes and behavior in situ, can also be fabricated with other active materials for energy storage and other applications in related fields.

Aligned carbon nanotube, graphene and graphite oxide thin films via substrate-directed rapid interfacial deposition

NASA Astrophysics Data System (ADS)

D'Arcy, Julio M.; Tran, Henry D.; Stieg, Adam Z.; Gimzewski, James K.; Kaner, Richard B.

2012-05-01

A procedure for depositing thin films of carbon nanostructures is described that overcomes the limitations typically associated with solution based methods. Transparent and conductively continuous carbon coatings can be grown on virtually any type of substrate within seconds. Interfacial surface tension gradients result in directional fluid flow and film spreading at the water/oil interface. Transparent films of carbon nanostructures are produced including aligned ropes of single-walled carbon nanotubes and assemblies of single sheets of chemically converted graphene and graphite oxide. Process scale-up, layer-by-layer deposition, and a simple method for coating non-activated hydrophobic surfaces are demonstrated.A procedure for depositing thin films of carbon nanostructures is described that overcomes the limitations typically associated with solution based methods. Transparent and conductively continuous carbon coatings can be grown on virtually any type of substrate within seconds. Interfacial surface tension gradients result in directional fluid flow and film spreading at the water/oil interface. Transparent films of carbon nanostructures are produced including aligned ropes of single-walled carbon nanotubes and assemblies of single sheets of chemically converted graphene and graphite oxide. Process scale-up, layer-by-layer deposition, and a simple method for coating non-activated hydrophobic surfaces are demonstrated. Electronic supplementary information (ESI) available: Droplet coalescence, catenoid formation, mechanism of film growth, scanning electron micrographs showing carbon nanotube alignment, flexible transparent films of SWCNTs, AFM images of a chemically converted graphene film, and SEM images of SWCNT free-standing thin films. See DOI: 10.1039/c2nr00010e

Synthesis of mesoporous zeolite single crystals with cheap porogens

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tao Haixiang; Li Changlin; Ren Jiawen

2011-07-15

Mesoporous zeolite (silicalite-1, ZSM-5, TS-1) single crystals have been successfully synthesized by adding soluble starch or sodium carboxymethyl cellulose (CMC) to a conventional zeolite synthesis system. The obtained samples were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), nitrogen sorption analysis, {sup 27}Al magic angle spinning nuclear magnetic resonance ({sup 27}Al MAS NMR), temperature-programmed desorption of ammonia (NH{sub 3}-TPD) and ultraviolet-visible spectroscopy (UV-vis). The SEM images clearly show that all zeolite crystals possess the similar morphology with particle size of about 300 nm, the TEM images reveal that irregular intracrystalmore » pores are randomly distributed in the whole crystal. {sup 27}Al MAS NMR spectra indicate that nearly all of the Al atoms are in tetrahedral co-ordination in ZSM-5, UV-vis spectra confirm that nearly all of titanium atoms are incorporated into the framework of TS-1. The catalytic activity of meso-ZSM-5 in acetalization of cyclohexanone and meso-TS-1 in hydroxylation of phenol was also studied. The synthesis method reported in this paper is cost-effective and environmental friendly, can be easily expended to prepare other hierarchical structured zeolites. - Graphical abstract: Mesoporous zeolite single crystals were synthesized by using cheap porogens as template. Highlights: > Mesoporous zeolite (silicalite-1, ZSM-5, TS-1) single crystals were synthesized. > Soluble starch or sodium carboxymethyl cellulose (CMC) was used as porogens. > The mesoporous zeolites had connected mesopores although closed pores existed. > Higher catalytic activities were obtained.« less

Wavelength dependence and multiple-induced states in photoresponses of copper phthalocyanine-doped gold nanoparticle single-electron device

NASA Astrophysics Data System (ADS)

Yamamoto, Makoto; Ueda, Rieko; Terui, Toshifumi; Imazu, Keisuke; Tamada, Kaoru; Sakano, Takeshi; Matsuda, Kenji; Ishii, Hisao; Noguchi, Yutaka

2014-01-01

We have proposed a gold nanoparticle (GNP)-based single-electron transistor (SET) doped with a dye molecule, where the molecule works as a photoresponsive floating gate. Here, we examined the source-drain current (I_{\\text{SD}}) at a constant drain voltage under light irradiation with various wavelengths ranging from 400 to 700 nm. Current change was enhanced at the wavelengths of 600 and 700 nm, corresponding to the optical absorption band of the doped molecule (copper phthalocyanine: CuPc). Moreover, several peaks appear in the histograms of I_{\\text{SD}} during light irradiation, indicating that multiple discrete states were induced in the device. The results suggest that the current change was initiated by the light absorption of CuPc and multiple CuPc molecules near the GNP working as a floating gate. Molecular doping can activate advanced device functions in GNP-based SETs.

Foundry fabricated photonic integrated circuit optical phase lock loop.

PubMed

Bałakier, Katarzyna; Fice, Martyn J; Ponnampalam, Lalitha; Graham, Chris S; Wonfor, Adrian; Seeds, Alwyn J; Renaud, Cyril C

2017-07-24

This paper describes the first foundry-based InP photonic integrated circuit (PIC) designed to work within a heterodyne optical phase locked loop (OPLL). The PIC and an external electronic circuit were used to phase-lock a single-line semiconductor laser diode to an incoming reference laser, with tuneable frequency offset from 4 GHz to 12 GHz. The PIC contains 33 active and passive components monolithically integrated on a single chip, fully demonstrating the capability of a generic foundry PIC fabrication model. The electronic part of the OPLL consists of commercially available RF components. This semi-packaged system stabilizes the phase and frequency of the integrated laser so that an absolute frequency, high-purity heterodyne signal can be generated when the OPLL is in operation, with phase noise lower than -100 dBc/Hz at 10 kHz offset from the carrier. This is the lowest phase noise level ever demonstrated by monolithically integrated OPLLs.

Mini ion trap mass spectrometer

DOEpatents

Dietrich, Daniel D.; Keville, Robert F.

1995-01-01

An ion trap which operates in the regime between research ion traps which can detect ions with a mass resolution of better than 1:10.sup.9 and commercial mass spectrometers requiring 10.sup.4 ions with resolutions of a few hundred. The power consumption is kept to a minimum by the use of permanent magnets and a novel electron gun design. By Fourier analyzing the ion cyclotron resonance signals induced in the trap electrodes, a complete mass spectra in a single combined structure can be detected. An attribute of the ion trap mass spectrometer is that overall system size is drastically reduced due to combining a unique electron source and mass analyzer/detector in a single device. This enables portable low power mass spectrometers for the detection of environmental pollutants or illicit substances, as well as sensors for on board diagnostics to monitor engine performance or for active feedback in any process involving exhausting waste products.

Mini ion trap mass spectrometer

DOEpatents

Dietrich, D.D.; Keville, R.F.

1995-09-19

An ion trap is described which operates in the regime between research ion traps which can detect ions with a mass resolution of better than 1:10{sup 9} and commercial mass spectrometers requiring 10{sup 4} ions with resolutions of a few hundred. The power consumption is kept to a minimum by the use of permanent magnets and a novel electron gun design. By Fourier analyzing the ion cyclotron resonance signals induced in the trap electrodes, a complete mass spectra in a single combined structure can be detected. An attribute of the ion trap mass spectrometer is that overall system size is drastically reduced due to combining a unique electron source and mass analyzer/detector in a single device. This enables portable low power mass spectrometers for the detection of environmental pollutants or illicit substances, as well as sensors for on board diagnostics to monitor engine performance or for active feedback in any process involving exhausting waste products. 10 figs.

Higher Performance of DSSC with Dyes from Cladophora sp. as Mixed Cosensitizer through Synergistic Effect

PubMed Central

Haji Manaf, Noramaliyana; Tennakoon, Kushan; Chandrakanthi, R. L. N.; Lim, Linda Biaw Leng; Bandara, J. M. R. Sarath; Ekanayake, Piyasiri

2015-01-01

Chlorophyll and xanthophyll dyes extracted from a single source of filamentous freshwater green algae (Cladophora sp.) were used to sensitize dye sensitized solar cells and their performances were investigated. A more positive interaction is expected as the derived dyes come from a single natural source because they work mutually in nature. Cell sensitized with mixed chlorophyll and xanthophyll showed synergistic activity with improved cell performance of 1.5- to 2-fold higher than that sensitized with any individual dye. The effect of temperature and the stability of these dyes were also investigated. Xanthophyll dye was found to be more stable compared to chlorophyll that is attributed in the ability of xanthophyll to dissipate extra energy via reversible structural changes. Mixing the dyes resulted to an increase in effective electron life time and reduced the process of electron recombination during solar cell operation, hence exhibiting a synergistic effect. PMID:25688266

Higher Performance of DSSC with Dyes from Cladophora sp. as Mixed Cosensitizer through Synergistic Effect.

PubMed

Lim, Andery; Haji Manaf, Noramaliyana; Tennakoon, Kushan; Chandrakanthi, R L N; Lim, Linda Biaw Leng; Bandara, J M R Sarath; Ekanayake, Piyasiri

2015-01-01

Chlorophyll and xanthophyll dyes extracted from a single source of filamentous freshwater green algae (Cladophora sp.) were used to sensitize dye sensitized solar cells and their performances were investigated. A more positive interaction is expected as the derived dyes come from a single natural source because they work mutually in nature. Cell sensitized with mixed chlorophyll and xanthophyll showed synergistic activity with improved cell performance of 1.5- to 2-fold higher than that sensitized with any individual dye. The effect of temperature and the stability of these dyes were also investigated. Xanthophyll dye was found to be more stable compared to chlorophyll that is attributed in the ability of xanthophyll to dissipate extra energy via reversible structural changes. Mixing the dyes resulted to an increase in effective electron life time and reduced the process of electron recombination during solar cell operation, hence exhibiting a synergistic effect.

Mechanism-Based Condition Screening for Sustainable Catalysis in Single-Electron Steps by Cyclic Voltammetry.

PubMed

Liedtke, Theresa; Spannring, Peter; Riccardi, Ludovico; Gansäuer, Andreas

2018-04-23

A cyclic-voltammetry-based screening method for Cp 2 TiX-catalyzed reactions is introduced. Our mechanism-based approach enables the study of the influence of various additives on the electrochemically generated active catalyst Cp 2 TiX, which is in equilibrium with catalytically inactive [Cp 2 TiX 2 ] - . Thioureas and ureas are most efficient in the generation of Cp 2 TiX in THF. Knowing the precise position of the equilibrium between Cp 2 TiX and [Cp 2 TiX 2 ] - allowed us to identify reaction conditions for the bulk electrolysis of Cp 2 TiX 2 complexes and for Cp 2 TiX-catayzed radical arylations without having to carry out the reactions. Our time- and resource-efficient approach is of general interest for the design of catalytic reactions that proceed in single-electron steps. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Band structures in coupled-cluster singles-and-doubles Green's function (GFCCSD)

NASA Astrophysics Data System (ADS)

Furukawa, Yoritaka; Kosugi, Taichi; Nishi, Hirofumi; Matsushita, Yu-ichiro

2018-05-01

We demonstrate that the coupled-cluster singles-and-doubles Green's function (GFCCSD) method is a powerful and prominent tool drawing the electronic band structures and the total energies, which many theoretical techniques struggle to reproduce. We have calculated single-electron energy spectra via the GFCCSD method for various kinds of systems, ranging from ionic to covalent and van der Waals, for the first time: the one-dimensional LiH chain, one-dimensional C chain, and one-dimensional Be chain. We have found that the bandgap becomes narrower than in HF due to the correlation effect. We also show that the band structures obtained from the GFCCSD method include both quasiparticle and satellite peaks successfully. Besides, taking one-dimensional LiH as an example, we discuss the validity of restricting the active space to suppress the computational cost of the GFCCSD method. We show that the calculated results without bands that do not contribute to the chemical bonds are in good agreement with full-band calculations. With the GFCCSD method, we can calculate the total energies and spectral functions for periodic systems in an explicitly correlated manner.

Monolayer PtSe 2 , a New Semiconducting Transition-Metal-Dichalcogenide, Epitaxially Grown by Direct Selenization of Pt

DOE PAGES

Wang, Yeliang; Li, Linfei; Yao, Wei; ...

2015-05-21

For single-layer transition-metal dichalcogenides (TMDs) receive significant attention due to their intriguing physical properties for both fundamental research and potential applications in electronics, optoelectronics, spintronics, catalysis, and so on. Here, we demonstrate the epitaxial growth of high-quality single-crystal, monolayer platinum diselenide (PtSe2), a new member of the layered TMDs family, by a single step of direct selenization of a Pt(111) substrate. We found that a combination of atomic-resolution experimental characterizations and first-principle theoretic calculations reveals the atomic structure of the monolayer PtSe2/Pt(111). Angle-resolved photoemission spectroscopy measurements confirm for the first time the semiconducting electronic structure of monolayer PtSe2 (in contrastmore » to its semimetallic bulk counterpart). The photocatalytic activity of monolayer PtSe2 film is evaluated by a methylene-blue photodegradation experiment, demonstrating its practical application as a promising photocatalyst. Moreover, circular polarization calculations predict that monolayer PtSe2 has also potential applications in valleytronics.« less

Quantum logic readout and cooling of a single dark electron spin

NASA Astrophysics Data System (ADS)

Shi, Fazhan; Zhang, Qi; Naydenov, Boris; Jelezko, Fedor; Du, Jiangfeng; Reinhard, Friedemann; Wrachtrup, Jörg

2013-05-01

We study a single dark N2 electron spin defect in diamond, which is magnetically coupled to a nearby nitrogen-vacancy (NV) center. We perform pulsed electron spin resonance on this single spin by mapping its state to the NV center spin and optically reading out the latter. Moreover, we show that the NV center's spin polarization can be transferred to the electron spin by combined two decoupling control-NOT gates. These two results allow us to extend the NV center's two key properties—optical spin polarization and detection—to any electron spin in its vicinity. This enables dark electron spins to be used as local quantum registers and engineerable memories.

GAGG:ce single crystalline films: New perspective scintillators for electron detection in SEM.

PubMed

Bok, Jan; Lalinský, Ondřej; Hanuš, Martin; Onderišinová, Zuzana; Kelar, Jakub; Kučera, Miroslav

2016-04-01

Single crystal scintillators are frequently used for electron detection in scanning electron microscopy (SEM). We report gadolinium aluminum gallium garnet (GAGG:Ce) single crystalline films as a new perspective scintillators for the SEM. For the first time, the epitaxial garnet films were used in a practical application: the GAGG:Ce scintillator was incorporated into a SEM scintillation electron detector and it showed improved image quality. In order to prove the GAGG:Ce quality accurately, the scintillation properties were examined using electron beam excitation and compared with frequently used scintillators in the SEM. The results demonstrate excellent emission efficiency of the GAGG:Ce single crystalline films together with their very fast scintillation decay useful for demanding SEM applications. Copyright © 2016 Elsevier B.V. All rights reserved.

Observations of Interchange Between Acceleration and Thermalization Processes in Auroral Electrons. Ph.D. Thesis

NASA Technical Reports Server (NTRS)

Pongratz, M. B.

1972-01-01

The results of high time-resolution measurements of energetic electrons in an auroral break up are presented. Electrons with energies from 500 eV to over 100 keV and pitch angles from 0 to 150 deg were detected with two detectors onboard sounding rocket 18:63 UE. Complete energy spectra were taken every 0.1 seconds. The procedure for cleaning and activating the BeCu dynodes of a small, rugged, high gain electron multiplier is described. A theoretical study of the energy-angular response of a spherical plate electrostatic analyzer is compared to experimental results. An energy spectrum unfolding technique which does not require the assumption of a histogram-type energy spectrum is presented. A method of determining sounding rocket orientation from the output of a single magnetometer is described.

Spectral characteristics of plasma sheet ion and electron populations during disturbed geomagnetic conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Christon, S.P., Williams, D.J.; Mitchell, D.G.; Huang, C.Y.

1991-01-01

The authors have determined the spectral characteristics of central plasma sheet ions and electrons observed during 71 hours when geomagnetic activity was at moderate to high levels (AE {ge} 100nT). Particle data from the low-energy proton and electron differential energy analyzer and the medium energy particle instrument on ISEE 1 are combined to obtain differential energy spectra (measured in units of particles/cm{sup 2} s sr keV) in the kinetic energy range {approximately}30 eV/e to {approximately}1 MeV at geocentric radial distances >12R{sub e}. Nearly isotropic central plasma sheet total ion and electron populations were chosen for analysis and were measured tomore » be continuous particle distributions from the lowest to highest energies. During these high AE periods the >24 keV particle fluxes and the temperature of the entire particle distribution kT are significantly higher than during low AE periods (AE < 100 nT). The temperatures kT{sub i} and kT{sub e} are highly correlated during both quiet and disturbed periods. The active period spectral shape appears softer for ions and somewhat harder for electrons than during quiet periods. They find that the observed active period spectrum typically is complex and cannot be represented in general by a single functional form, as during quiet periods when it can be represented by the kappa distribution function. In a limited energy range near the knee of the ion spectra, the spectral shape can often be fit with a Maxwellian form, thus rolling over faster than the typical quiet time spectrum. Electron spectra also display this spectral characteristic, although at a lower occurence frequency than for ions. The electron spectra are predominantly kappalike at energies near and above the knee. The authors conclude that both ions and electrons participate in at least two separate accerlation mechanisms as geomagnetic activity evolves from low AE to high AE values.« less

Electronic components embedded in a single graphene nanoribbon.

PubMed

Jacobse, P H; Kimouche, A; Gebraad, T; Ervasti, M M; Thijssen, J M; Liljeroth, P; Swart, I

2017-07-25

The use of graphene in electronic devices requires a band gap, which can be achieved by creating nanostructures such as graphene nanoribbons. A wide variety of atomically precise graphene nanoribbons can be prepared through on-surface synthesis, bringing the concept of graphene nanoribbon electronics closer to reality. For future applications it is beneficial to integrate contacts and more functionality directly into single ribbons by using heterostructures. Here, we use the on-surface synthesis approach to fabricate a metal-semiconductor junction and a tunnel barrier in a single graphene nanoribbon consisting of 5- and 7-atom wide segments. We characterize the atomic scale geometry and electronic structure by combined atomic force microscopy, scanning tunneling microscopy, and conductance measurements complemented by density functional theory and transport calculations. These junctions are relevant for developing contacts in all-graphene nanoribbon devices and creating diodes and transistors, and act as a first step toward complete electronic devices built into a single graphene nanoribbon.Adding functional electronic components to graphene nanoribbons requires precise control over their atomic structure. Here, the authors use a bottom-up approach to build a metal-semiconductor junction and a tunnel barrier directly into a single graphene nanoribbon, an exciting development for graphene-based electronic devices.

Suppression of shot noise and spontaneous radiation in electron beams

DOE Office of Scientific and Technical Information (OSTI.GOV)

Litvinenko,V.

2009-08-23

Shot noise in the electron beam distribution is the main source of noise in high-gain FEL amplifiers, which may affect applications ranging from single- and multi-stage HGHG FELs to an FEL amplifier for coherent electron cooling. This noise also imposes a fundamental limit of about 10{sup 6} on FEL gain, after which SASE FELs saturate. There are several advantages in strongly suppressing this shot noise in the electron beam, and the corresponding spontaneous radiation. For more than a half-century, a traditional passive method has been used successfully in practical low-energy microwave electronic devices to suppress shot noise. Recently, it wasmore » proposed for this purpose in FELs. However, being passive, the method has some significant limitations and is hardly suitable for the highly inhomogeneous beams of modern high-gain FELs. I present a novel active method of suppressing, by many orders-of-magnitude, the shot noise in relativistic electron beams. I give a theoretical description of the process, and detail its fundamental limitation.« less

Photosensitizing Electron Transfer Processes of Fullerenes, Carbon Nanotubes, and Carbon Nanohorns.

PubMed

Ito, Osamu

2017-03-01

In this account, studies on the photosensitizing electron transfer of nanocarbons, such as fullerenes, single-walled carbon nanotubes (SWCNTs), and carbon nanohorns (CNH), performed in our laboratory for about 15 years in the early 21st century have been briefly reviewed. These novel nanocarbons act as excellent electron acceptors, when they are linked to light-absorbing electron donors, such as porphyrins or phthalocyanines. For such molecule-nanocarbon hybrids, the direct confirmation of fast, transient, electron-transfer phenomena must be performed with time-resolved spectroscopic methods, such as transient absorption spectral measurements, in addition to fluorescence time-profile measurements in the wide-wavelength regions. Careful use of these methods affords useful information to understand photoinduced electron-transfer mechanisms. In addition, kinetic data obtained by these methods can assist in the construction of light-active devices, such as photovoltaic cells and solar H 2 -generation systems. © 2017 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electron and hole transport in ambipolar, thin film pentacene transistors

NASA Astrophysics Data System (ADS)

Saudari, Sangameshwar R.; Kagan, Cherie R.

2015-01-01

Solution-processed, ambipolar, thin-film pentacene field-effect transistors were employed to study both electron and hole transport simultaneously in a single, organic solid-state device. Electron and hole mobilities were extracted from the respective unipolar saturation regimes and show thermally activated behavior and gate voltage dependence. We fit the gate voltage dependent saturation mobility to a power law to extract the characteristic Meyer-Neldel (MN) energy, a measure of the width of the exponential distribution of localized states extending into the energy gap of the organic semiconductor. The MN energy is ˜78 and ˜28 meV for electrons and holes, respectively, which reflects a greater density of localized tail states for electrons than holes. This is consistent with the lower measured electron than hole mobility. For holes, the well-behaved linear regime allows for four-point probe measurement of the contact resistance independent mobility and separate characterization of the width of the localized density of states, yielding a consistent MN energy of 28 meV.

High-resolution, high-throughput imaging with a multibeam scanning electron microscope.

PubMed

Eberle, A L; Mikula, S; Schalek, R; Lichtman, J; Knothe Tate, M L; Zeidler, D

2015-08-01

Electron-electron interactions and detector bandwidth limit the maximal imaging speed of single-beam scanning electron microscopes. We use multiple electron beams in a single column and detect secondary electrons in parallel to increase the imaging speed by close to two orders of magnitude and demonstrate imaging for a variety of samples ranging from biological brain tissue to semiconductor wafers. © 2015 The Authors Journal of Microscopy © 2015 Royal Microscopical Society.

Temperature dependency of the emission properties from positioned In(Ga)As/GaAs quantum dots

DOE Office of Scientific and Technical Information (OSTI.GOV)

Braun, T.; Schneider, C.; Maier, S.

In this letter we study the influence of temperature and excitation power on the emission linewidth from site-controlled InGaAs/GaAs quantum dots grown on nanoholes defined by electron beam lithography and wet chemical etching. We identify thermal electron activation as well as direct exciton loss as the dominant intensity quenching channels. Additionally, we carefully analyze the effects of optical and acoustic phonons as well as close-by defects on the emission linewidth by means of temperature and power dependent micro-photoluminescence on single quantum dots with large pitches.

N2O + CO reaction over single Ga or Ge atom embedded graphene: A DFT study

NASA Astrophysics Data System (ADS)

Esrafili, Mehdi D.; Vessally, Esmail

2018-01-01

The possibility of using a single Ga or Ge atom embedded graphene as an efficient catalyst for the reduction of N2O molecule by CO is examined. We perform density functional theory calculations to calculate adsorption energies as well as analysis of the structural and electronic properties of different species involved in the N2O + CO reaction. The large activation energy for the diffusion of the single Ga or Ge atom on the C vacancy site of graphene shows the high stability of both Ga- and Ge-embedded graphene sheets in the N2O reduction. The activation energy needed for the decomposition of N2O is calculated to be 18.4 and 14.1 kcal/mol over Ga- and Ge-embedded graphene, respectively. The results indicate that the Ge-embedded graphene may serve as an effective catalyst for the N2O reduction. Moreover, the activation energy for the disproportionation of N2O molecules that generates N2 and O2 is relatively high; so, the generation of these side products may be hindered by decreasing the temperature.

Polarized excitons and optical activity in single-wall carbon nanotubes

NASA Astrophysics Data System (ADS)

Chang, Yao-Wen; Jin, Bih-Yaw

2018-05-01

The polarized excitons and optical activity of single-wall carbon nanotubes (SWNTs) are studied theoretically by π -electron Hamiltonian and helical-rotational symmetry. By taking advantage of the symmetrization, the single-particle energy and properties of a SWNT are characterized with the corresponding helical band structure. The dipole-moment matrix elements, magnetic-moment matrix elements, and the selection rules can also be derived. Based on different selection rules, the optical transitions can be assigned as the parallel-polarized, left-handed circularly-polarized, and right-handed circularly-polarized transitions, where the combination of the last two gives the cross-polarized transition. The absorption and circular dichroism (CD) spectra are simulated by exciton calculation. The calculated results are well comparable with the reported measurements. Built on the foundation, magnetic-field effects on the polarized excitons and optical activity of SWNTs are studied. Dark-bright exciton splitting and interband Faraday effect in the CD spectrum of SWNTs under an axial magnetic field are predicted. The Faraday rotation dispersion can be analyzed according to the selection rules of circular polarizations and the helical band structure.

Metal to insulator transition in Sb doped SnO2 monocrystalline nanowires thin films

NASA Astrophysics Data System (ADS)

Costa, I. M.; Bernardo, E. P.; Marangoni, B. S.; Leite, E. R.; Chiquito, A. J.

2016-12-01

We report on the growth and transport properties of single crystalline Sb doped SnO2 wires grown from chemical vapour deposition. While undoped samples presented semiconducting behaviour, doped ones clearly undergo a transition from an insulating state ( d R /d T <0 ) to a metallic one ( d R /d T >0 ) around 130 -150 K depending on the doping level. Data analysis in the framework of the metal-to-insulator transition theories allowed us to investigate the underlying physics: electron-electron and electron-phonon interactions were identified as the scattering mechanisms present in the metallic phase, while the conduction mechanism of the semiconducting phase (undoped sample) was characterized by thermal activation and variable range hopping mechanisms.

A Dose-Rate Effect in Single-Particle Electron Microscopy

PubMed Central

Chen, James Z.; Sachse, Carsten; Xu, Chen; Mielke, Thorsten; Spahn, Christian M. T.; Grigorieff, Nikolaus

2008-01-01

A low beam-intensity, low electron-dose imaging method has been developed for single-particle electron cryo-microscopy (cryo-EM). Experiments indicate that the new technique can reduce beam-induced specimen movement and secondary radiolytic effects, such as “bubbling”. The improvement in image quality, especially for multiple-exposure data collection, will help single-particle cryo-EM to reach higher resolution. PMID:17977018

Targeting excited states in all-trans polyenes with electron-pair states.

PubMed

Boguslawski, Katharina

2016-12-21

Wavefunctions restricted to electron pair states are promising models for strongly correlated systems. Specifically, the pair Coupled Cluster Doubles (pCCD) ansatz allows us to accurately describe bond dissociation processes and heavy-element containing compounds with multiple quasi-degenerate single-particle states. Here, we extend the pCCD method to model excited states using the equation of motion (EOM) formalism. As the cluster operator of pCCD is restricted to electron-pair excitations, EOM-pCCD allows us to target excited electron-pair states only. To model singly excited states within EOM-pCCD, we modify the configuration interaction ansatz of EOM-pCCD to contain also single excitations. Our proposed model represents a simple and cost-effective alternative to conventional EOM-CC methods to study singly excited electronic states. The performance of the excited state models is assessed against the lowest-lying excited states of the uranyl cation and the two lowest-lying excited states of all-trans polyenes. Our numerical results suggest that EOM-pCCD including single excitations is a good starting point to target singly excited states.

UAVSAR Active Electronically-Scanned Array

NASA Technical Reports Server (NTRS)

Sadowy, Gregory; Brown, Kyle; Chamberlain, Neil; Figueroa, Harry; Fisher, Charlie; Grando, Maurio; Hamilton, Gary; Vorperian, Vatche; Zawadzki, Mark

2010-01-01

The Uninhabited Airborne Vehicle Synthetic Aperture Radar (UAVSAR) L-band (1.2-1.3 GHz) repeat pass, interferometric synthetic aperture radar (InSAR) used for Earth science applications. Using complex radar images collected during separate passes on time scales of hours to years, changes in surface topography can be measured. The repeat-pass InSAR technique requires that the radar look angle be approximately the same on successive passes. Due to variations in aircraft attitude between passes, antenna beam steering is required to replicate the radar look angle. This paper describes an active, electronically steered array (AESA) that provides beam steering capability in the antenna azimuth plane. The array contains 24 transmit/receive modules generating 2800 W of radiated power and is capable of pulse-to-pulse beam steering and polarization agility. Designed for high reliability as well as serviceability, all array electronics are contained in single 178cm x 62cm x 12 cm air-cooled panel suitable for operation up 60,000 ft altitude.

Inhibited proton transfer enhances Au-catalyzed CO2-to-fuels selectivity.

PubMed

Wuttig, Anna; Yaguchi, Momo; Motobayashi, Kenta; Osawa, Masatoshi; Surendranath, Yogesh

2016-08-09

CO2 reduction in aqueous electrolytes suffers efficiency losses because of the simultaneous reduction of water to H2 We combine in situ surface-enhanced IR absorption spectroscopy (SEIRAS) and electrochemical kinetic studies to probe the mechanistic basis for kinetic bifurcation between H2 and CO production on polycrystalline Au electrodes. Under the conditions of CO2 reduction catalysis, electrogenerated CO species are irreversibly bound to Au in a bridging mode at a surface coverage of ∼0.2 and act as kinetically inert spectators. Electrokinetic data are consistent with a mechanism of CO production involving rate-limiting, single-electron transfer to CO2 with concomitant adsorption to surface active sites followed by rapid one-electron, two-proton transfer and CO liberation from the surface. In contrast, the data suggest an H2 evolution mechanism involving rate-limiting, single-electron transfer coupled with proton transfer from bicarbonate, hydronium, and/or carbonic acid to form adsorbed H species followed by rapid one-electron, one-proton, or H recombination reactions. The disparate proton coupling requirements for CO and H2 production establish a mechanistic basis for reaction selectivity in electrocatalytic fuel formation, and the high population of spectator CO species highlights the complex heterogeneity of electrode surfaces under conditions of fuel-forming electrocatalysis.

Engineering highly organized and aligned single walled carbon nanotube networks for electronic device applications: Interconnects, chemical sensor, and optoelectronics

NASA Astrophysics Data System (ADS)

Kim, Young Lae

For 20 years, single walled carbon nanotubes (SWNTs) have been studied actively due to their unique one-dimensional nanostructure and superior electrical, thermal, and mechanical properties. For these reasons, they offer the potential to serve as building blocks for future electronic devices such as field effect transistors (FETs), electromechanical devices, and various sensors. In order to realize these applications, it is crucial to develop a simple, scalable, and reliable nanomanufacturing process that controllably places aligned SWNTs in desired locations, orientations, and dimensions. Also electronic properties (semiconducting/metallic) of SWNTs and their organized networks must be controlled for the desired performance of devices and systems. These fundamental challenges are significantly limiting the use of SWNTs for future electronic device applications. Here, we demonstrate a strategy to fabricate highly controlled micro/nanoscale SWNT network structures and present the related assembly mechanism to engineer the SWNT network topology and its electrical transport properties. A method designed to evaluate the electrical reliability of such nano- and microscale SWNT networks is also presented. Moreover, we develop and investigate a robust SWNT based multifunctional selective chemical sensor and a range of multifunctional optoelectronic switches, photo-transistors, optoelectronic logic gates and complex optoelectronic digital circuits.

Ultrashort electron pulses as a four-dimensional diagnosis of plasma dynamics.

PubMed

Zhu, P F; Zhang, Z C; Chen, L; Li, R Z; Li, J J; Wang, X; Cao, J M; Sheng, Z M; Zhang, J

2010-10-01

We report an ultrafast electron imaging system for real-time examination of ultrafast plasma dynamics in four dimensions. It consists of a femtosecond pulsed electron gun and a two-dimensional single electron detector. The device has an unprecedented capability of acquiring a high-quality shadowgraph image with a single ultrashort electron pulse, thus permitting the measurement of irreversible processes using a single-shot scheme. In a prototype experiment of laser-induced plasma of a metal target under moderate pump intensity, we demonstrated its unique capability of acquiring high-quality shadowgraph images on a micron scale with a-few-picosecond time resolution.

Single electron beam rf feedback free electron laser

DOEpatents

Brau, C.A.; Stein, W.E.; Rockwood, S.D.

1981-02-11

A free electron laser system and electron beam system for a free electron laser which uses rf feedback to enhance efficiency are described. Rf energy is extracted from a single electron beam by decelerating cavities and energy is returned to accelerating cavities using rf returns, such as rf waveguides, rf feedthroughs, resonant feedthroughs, etc. This rf energy is added to rf klystron energy to reduce the required input energy and thereby enhance energy efficiency of the system.

Advance of Mechanically Controllable Break Junction for Molecular Electronics.

PubMed

Wang, Lu; Wang, Ling; Zhang, Lei; Xiang, Dong

2017-06-01

Molecular electronics stands for the ultimate size of functional elements, keeping up with an unstoppable trend over the past few decades. As a vital component of molecular electronics, single molecular junctions have attracted significant attention from research groups all over the world. Due to its pronounced superiority, the mechanically controllable break junctions (MCBJ) technique has been widely applied to characterize the dynamic performance of single molecular junctions. This review presents a system analysis for single-molecule junctions and offers an overview of four test-beds for single-molecule junctions, thus offering more insight into the mechanisms of electron transport. We mainly focus on the development of state-of-the-art mechanically controlled break junctions. The three-terminal gated MCBJ approaches are introduced to manipulate the electron transport of molecules, and MCBJs are combined with characterization techniques. Additionally, applications of MCBJs and remarkable properties of single molecules are addressed. Finally, the challenges and perspective for the mechanically controllable break junctions technique are provided.

Preparation of Coaxial-Line and Hollow Mn2O3 Nanofibers by Single-Nozzle Electrospinning and Their Catalytic Performances for Thermal Decomposition of Ammonium Perchlorate.

PubMed

Liang, Jiyuan; Yang, Jie; Cao, Weiguo; Guo, Xiangke; Guo, Xuefeng; Ding, Weiping

2015-09-01

Coaxial-line and hollow Mn2O3 nanofibers have been synthesized by a simple single-nozzle electrospinning method without using a complicated coaxial jet head, combined with final calcination. The crystal structure and morphology of the Mn2O3 nanofibers were investigated by using the X-ray diffraction, scanning electron microscopy and transmission electron microscopy. The results indicate that the electrospinning distance has important influence on the morphology and structure of the obtained Mn2O3 nanofibers, which changes from hollow fibers for short electrospinning distance to coaxial-line structure for long electrospinning distance after calcination in the air. The formation mechanisms of different structured Mn2O3 fibers are discussed in detail. This facile and effective method is easy to scale up and may be versatile for constructing coaxial-line and hollow fibers of other metal oxides. The catalytic activity of the obtained Mn2O3 nanofibers on thermal decomposition of ammonium perchlorate (AP) was studied by differential scanning calorimetry (DSC). The results show that the hollow Mn2O3 nanofibers have good catalytic activity to promote the thermal decomposition of AP.

Programmable single-cell mammalian biocomputers.

PubMed

Ausländer, Simon; Ausländer, David; Müller, Marius; Wieland, Markus; Fussenegger, Martin

2012-07-05

Synthetic biology has advanced the design of standardized control devices that program cellular functions and metabolic activities in living organisms. Rational interconnection of these synthetic switches resulted in increasingly complex designer networks that execute input-triggered genetic instructions with precision, robustness and computational logic reminiscent of electronic circuits. Using trigger-controlled transcription factors, which independently control gene expression, and RNA-binding proteins that inhibit the translation of transcripts harbouring specific RNA target motifs, we have designed a set of synthetic transcription–translation control devices that could be rewired in a plug-and-play manner. Here we show that these combinatorial circuits integrated a two-molecule input and performed digital computations with NOT, AND, NAND and N-IMPLY expression logic in single mammalian cells. Functional interconnection of two N-IMPLY variants resulted in bitwise intracellular XOR operations, and a combinatorial arrangement of three logic gates enabled independent cells to perform programmable half-subtractor and half-adder calculations. Individual mammalian cells capable of executing basic molecular arithmetic functions isolated or coordinated to metabolic activities in a predictable, precise and robust manner may provide new treatment strategies and bio-electronic interfaces in future gene-based and cell-based therapies.

Single-step One-pot Synthesis of TiO2 Nanosheets Doped with Sulfur on Reduced Graphene Oxide with Enhanced Photocatalytic Activity.

PubMed

Wang, Weilin; Wang, Zhaofeng; Liu, Jingjing; Luo, Zhu; Suib, Steven L; He, Peng; Ding, Guqiao; Zhang, Zhengguo; Sun, Luyi

2017-04-21

A hybrid photocatalyst based on anatase TiO 2 was designed by doping TiO 2 with sulfur and incorporating reduced graphene oxide (TiO 2 -S/rGO hybrid), with an aim to narrow the band gap to potentially make use of visible light and decrease the recombination of excitons, respectively. This TiO 2 -S/rGO hybrid was successfully synthesized using a one-pot hydrothermal method via single-step reaction. The structure and morphology of the TiO 2 -S/rGO hybrid catalyst was carefully characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). Its photocatalytic reactivity was evaluated by the degradation of methyl blue. The results showed that both the doping of sulfur and the introduction of rGO worked as designed, and the TiO 2 -S/rGO hybrid exhibited high photocatalytic activity under simulated sunlight. Considering both the facile and scalable reaction to synthesize TiO 2 -S/rGO hybrid, and its excellent photocatalytic performance, such TiO 2 -S/rGO hybrids are expect to find practical applications in environmental and energy sectors.

Single-step One-pot Synthesis of TiO2 Nanosheets Doped with Sulfur on Reduced Graphene Oxide with Enhanced Photocatalytic Activity

NASA Astrophysics Data System (ADS)

Wang, Weilin; Wang, Zhaofeng; Liu, Jingjing; Luo, Zhu; Suib, Steven L.; He, Peng; Ding, Guqiao; Zhang, Zhengguo; Sun, Luyi

2017-04-01

A hybrid photocatalyst based on anatase TiO2 was designed by doping TiO2 with sulfur and incorporating reduced graphene oxide (TiO2-S/rGO hybrid), with an aim to narrow the band gap to potentially make use of visible light and decrease the recombination of excitons, respectively. This TiO2-S/rGO hybrid was successfully synthesized using a one-pot hydrothermal method via single-step reaction. The structure and morphology of the TiO2-S/rGO hybrid catalyst was carefully characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). Its photocatalytic reactivity was evaluated by the degradation of methyl blue. The results showed that both the doping of sulfur and the introduction of rGO worked as designed, and the TiO2-S/rGO hybrid exhibited high photocatalytic activity under simulated sunlight. Considering both the facile and scalable reaction to synthesize TiO2-S/rGO hybrid, and its excellent photocatalytic performance, such TiO2-S/rGO hybrids are expect to find practical applications in environmental and energy sectors.

High quality single shot ultrafast MeV electron diffraction from a photocathode radio-frequency gun

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fu, Feichao; Liu, Shengguang; Zhu, Pengfei

2014-08-15

A compact ultrafast electron diffractometer, consisting of an s-band 1.6 cell photocathode radio-frequency gun, a multi-function changeable sample chamber, and a sensitive relativistic electron detector, was built at Shanghai Jiao Tong University. High-quality single-shot transmission electron diffraction patterns have been recorded by scattering 2.5 MeV electrons off single crystalline gold and polycrystalline aluminum samples. The high quality diffraction pattern indicates an excellent spatial resolution, with the ratio of the diffraction ring radius over the ring rms width beyond 10. The electron pulse width is estimated to be about 300 fs. The high temporal and spatial resolution may open new opportunities inmore » various areas of sciences.« less

High quality single shot ultrafast MeV electron diffraction from a photocathode radio-frequency gun.

PubMed

Fu, Feichao; Liu, Shengguang; Zhu, Pengfei; Xiang, Dao; Zhang, Jie; Cao, Jianming

2014-08-01

A compact ultrafast electron diffractometer, consisting of an s-band 1.6 cell photocathode radio-frequency gun, a multi-function changeable sample chamber, and a sensitive relativistic electron detector, was built at Shanghai Jiao Tong University. High-quality single-shot transmission electron diffraction patterns have been recorded by scattering 2.5 MeV electrons off single crystalline gold and polycrystalline aluminum samples. The high quality diffraction pattern indicates an excellent spatial resolution, with the ratio of the diffraction ring radius over the ring rms width beyond 10. The electron pulse width is estimated to be about 300 fs. The high temporal and spatial resolution may open new opportunities in various areas of sciences.

Real-time single-molecule electronic DNA sequencing by synthesis using polymer-tagged nucleotides on a nanopore array

PubMed Central

Fuller, Carl W.; Kumar, Shiv; Porel, Mintu; Chien, Minchen; Bibillo, Arek; Stranges, P. Benjamin; Dorwart, Michael; Tao, Chuanjuan; Li, Zengmin; Guo, Wenjing; Shi, Shundi; Korenblum, Daniel; Trans, Andrew; Aguirre, Anne; Liu, Edward; Harada, Eric T.; Pollard, James; Bhat, Ashwini; Cech, Cynthia; Yang, Alexander; Arnold, Cleoma; Palla, Mirkó; Hovis, Jennifer; Chen, Roger; Morozova, Irina; Kalachikov, Sergey; Russo, James J.; Kasianowicz, John J.; Davis, Randy; Roever, Stefan; Church, George M.; Ju, Jingyue

2016-01-01

DNA sequencing by synthesis (SBS) offers a robust platform to decipher nucleic acid sequences. Recently, we reported a single-molecule nanopore-based SBS strategy that accurately distinguishes four bases by electronically detecting and differentiating four different polymer tags attached to the 5′-phosphate of the nucleotides during their incorporation into a growing DNA strand catalyzed by DNA polymerase. Further developing this approach, we report here the use of nucleotides tagged at the terminal phosphate with oligonucleotide-based polymers to perform nanopore SBS on an α-hemolysin nanopore array platform. We designed and synthesized several polymer-tagged nucleotides using tags that produce different electrical current blockade levels and verified they are active substrates for DNA polymerase. A highly processive DNA polymerase was conjugated to the nanopore, and the conjugates were complexed with primer/template DNA and inserted into lipid bilayers over individually addressable electrodes of the nanopore chip. When an incoming complementary-tagged nucleotide forms a tight ternary complex with the primer/template and polymerase, the tag enters the pore, and the current blockade level is measured. The levels displayed by the four nucleotides tagged with four different polymers captured in the nanopore in such ternary complexes were clearly distinguishable and sequence-specific, enabling continuous sequence determination during the polymerase reaction. Thus, real-time single-molecule electronic DNA sequencing data with single-base resolution were obtained. The use of these polymer-tagged nucleotides, combined with polymerase tethering to nanopores and multiplexed nanopore sensors, should lead to new high-throughput sequencing methods. PMID:27091962

Modification of a single tryptophan residue in human Cu,Zn-superoxide dismutase by peroxynitrite in the presence of bicarbonate.

PubMed

Yamakura, F; Matsumoto, T; Fujimura, T; Taka, H; Murayama, K; Imai, T; Uchida, K

2001-07-09

Human recombinant Cu,Zn-SOD was reacted with peroxynitrite in a reaction mixture containing 150 mM potassium phosphate buffer (pH 7.4) 25 mM sodium bicarbonate, and 0.1 mM diethylenetriamine pentaacetic acid. Disappearance of fluorescence emission at 350 nm, which could be attributed to modification of a single tryptophan residue, was observed in the modified enzyme with a pH optimum of around 8.4. A fluorescence decrease with the same pH optimum was also observed without sodium bicarbonate, but with less efficiency. Amino acid contents of the modified enzyme showed no significant difference in all amino acids except the loss of a single tryptophan residue of the enzyme. The peroxynitrite-modified enzyme showed an increase in optical absorption around 350 nm and 30% reduced enzyme activity based on the copper contents. The modified enzyme showed the same electron paramagnetic resonance spectrum as that of the control enzyme. The modified Cu,Zn-SOD showed a single protein band in sodium dodecyl sulfate--polyacrylamide gel electrophoresis (SDS--PAGE) and five protein bands in non-denaturing PAGE. From this evidence, we conclude that nitration and/or oxidation of the single tryptophan 32 and partial inactivation of the enzyme activity of Cu,Zn-SOD is caused by a peroxynitrite-carbon dioxide adduct without perturbation of the active site copper integrity.

Diffusion of One-Dimensional Crystals in Channels of Single-Walled Carbon Nanotubes

NASA Astrophysics Data System (ADS)

Zhigalina, V. G.; Kumskov, A. S.; Falaleev, N. S.; Vasiliev, A. L.; Kiselev, N. A.

2018-05-01

The transport of one-dimensional CuI crystals in channels of single-walled carbon nanotubes (SWCNTs) has been studied by high resolution electron microscopy. The diffusion kinetics has been investigated by counting the number of CuI atoms escaping from the nanotube channel. The diffusivity is calculated to be 6.8 × 10-21 m2/s, which corresponds to an activation-barrier height of 1 eV/atom. A comparison with the theoretically estimated height of the energy barrier for molecular transport through a graphene layer is indicative of mass transfer through vacancy defects in graphene.

Theoretical Investigations of the Electrochemical Reduction of CO on Single Metal Atoms Embedded in Graphene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kirk, Charlotte; Chen, Leanne D.; Siahrostami, Samira

Single transition metal atoms embedded at single vacancies of graphene provide a unique paradigm for catalytic reactions. We present a density functional theory study of such systems for the electrochemical reduction of CO. Theoretical investigations of CO electrochemical reduction are particularly challenging in that electrochemical activation energies are a necessary descriptor of activity. We determined the electrochemical barriers for key proton–electron transfer steps using a state-of-the-art, fully explicit solvent model of the electrochemical interface. The accuracy of GGA-level functionals in describing these systems was also benchmarked against hybrid methods. We find the first proton transfer to form CHO from COmore » to be a critical step in C 1 product formation. On these single atom sites, the corresponding barrier scales more favorably with the CO binding energy than for 211 and 111 transition metal surfaces, in the direction of improved activity. Intermediates and transition states for the hydrogen evolution reaction were found to be less stable than those on transition metals, suggesting a higher selectivity for CO reduction. We present a rate volcano for the production of methane from CO. We identify promising candidates with high activity, stability, and selectivity for the reduction of CO. As a result, this work highlights the potential of these systems as improved electrocatalysts over pure transition metals for CO reduction.« less

Theoretical Investigations of the Electrochemical Reduction of CO on Single Metal Atoms Embedded in Graphene

DOE PAGES

Kirk, Charlotte; Chen, Leanne D.; Siahrostami, Samira; ...

2017-12-18

Single transition metal atoms embedded at single vacancies of graphene provide a unique paradigm for catalytic reactions. We present a density functional theory study of such systems for the electrochemical reduction of CO. Theoretical investigations of CO electrochemical reduction are particularly challenging in that electrochemical activation energies are a necessary descriptor of activity. We determined the electrochemical barriers for key proton–electron transfer steps using a state-of-the-art, fully explicit solvent model of the electrochemical interface. The accuracy of GGA-level functionals in describing these systems was also benchmarked against hybrid methods. We find the first proton transfer to form CHO from COmore » to be a critical step in C 1 product formation. On these single atom sites, the corresponding barrier scales more favorably with the CO binding energy than for 211 and 111 transition metal surfaces, in the direction of improved activity. Intermediates and transition states for the hydrogen evolution reaction were found to be less stable than those on transition metals, suggesting a higher selectivity for CO reduction. We present a rate volcano for the production of methane from CO. We identify promising candidates with high activity, stability, and selectivity for the reduction of CO. As a result, this work highlights the potential of these systems as improved electrocatalysts over pure transition metals for CO reduction.« less

Three-terminal graphene single-electron transistor fabricated using feedback-controlled electroburning

DOE Office of Scientific and Technical Information (OSTI.GOV)

Puczkarski, Paweł; Gehring, Pascal, E-mail: pascal.gehring@materials.ox.ac.uk; Lau, Chit S.

2015-09-28

We report room-temperature Coulomb blockade in a single layer graphene three-terminal single-electron transistor fabricated using feedback-controlled electroburning. The small separation between the side gate electrode and the graphene quantum dot results in a gate coupling up to 3 times larger compared to the value found for the back gate electrode. This allows for an effective tuning between the conductive and Coulomb blocked state using a small side gate voltage of about 1 V. The technique can potentially be used in the future to fabricate all-graphene based room temperature single-electron transistors or three terminal single molecule transistors with enhanced gate coupling.

Single-electron detection and spectroscopy via relativistic cyclotron radiation

DOE PAGES

Asner, D. M.; Bradley, R. F.; de Viveiros, L.; ...

2015-04-20

Since 1897, we've understood that accelerating charges must emit electromagnetic radiation. Cyclotron radiation, the particular form of radiation emitted by an electron orbiting in a magnetic field, was first derived in 1904. Despite the simplicity of this concept, and the enormous utility of electron spectroscopy in nuclear and particle physics, single-electron cyclotron radiation has never been observed directly. We demonstrate single-electron detection in a novel radiofrequency spec- trometer. Here, we observe the cyclotron radiation emitted by individual magnetically-trapped electrons that are produced with mildly-relativistic energies by a gaseous radioactive source. The relativistic shift in the cyclotron frequency permits a precisemore » electron energy measurement. Precise beta electron spectroscopy from gaseous radiation sources is a key technique in modern efforts to measure the neutrino mass via the tritium decay endpoint, and this work demonstrates a fundamentally new approach to precision beta spectroscopy for future neutrino mass experiments.« less

Dose rate effect on micronuclei induction in human blood lymphocytes exposed to single pulse and multiple pulses of electrons.

PubMed

Acharya, Santhosh; Bhat, N N; Joseph, Praveen; Sanjeev, Ganesh; Sreedevi, B; Narayana, Y

2011-05-01

The effects of single pulses and multiple pulses of 7 MV electrons on micronuclei (MN) induction in cytokinesis-blocked human peripheral blood lymphocytes (PBLs) were investigated over a wide range of dose rates per pulse (instantaneous dose rate). PBLs were exposed to graded doses of 2, 3, 4, 6, and 8 Gy of single electron pulses of varying pulse widths at different dose rates per pulse, ranging from 1 × 10(6) Gy s(-1) to 3.2 × 10(8) Gy s(-1). Different dose rates per pulse were achieved by changing the dose per electron pulse by adjusting the beam current and pulse width. MN yields per unit absorbed dose after irradiation with single electron pulses were compared with those of multiple pulses of electrons. A significant decrease in the MN yield with increasing dose rates per pulse was observed, when dose was delivered by a single electron pulse. However, no reduction in the MN yield was observed when dose was delivered by multiple pulses of electrons. The decrease in the yield at high dose rates per pulse suggests possible radical recombination, which leads to decreased biological damage. Cellular response to the presence of very large numbers of chromosomal breaks may also alter the damage.

Optical activity and electronic absorption spectra of some simple nucleosides related to cytidine and uridine: all-valence-shell molecular orbital calculations.

PubMed Central

Miles, D W; Redington, P K; Miles, D L; Eyring, H

1981-01-01

The circular dichroism and electronic absorption of three simple model systems for cytidine and uridine have been measured to 190 nm. The molecular spectral properties (excitation wavelengths, oscillator strengths, rotational strengths, and polarization directions) and electronic transitional patterns were investigated by using wave functions of the entire nucleoside with the goal of establishing the reliability of the theoretical method. The computed electronic absorption quantities were shown to be in satisfactory agreement with experimental data. It was found that the computed optical rotatory strengths of the B2u and E1u electronic transitions and lowest observed n-pi transition are in good agreement with experimental values. Electronic transitions were characterized by their electronic transitional patterns derived from population analysis of the transition density matrix. The theoretical rotational strengths associated with the B2u and E1u transitions stabilize after the use of just a few singly excited configurations in the configuration interaction basis and, hypothetically, are more reliable as indicators of conformation in pyrimidine nucleosides related to cytidine. PMID:6950393

Heterogeneous Single-Atom Catalyst for Visible-Light-Driven High-Turnover CO2 Reduction: The Role of Electron Transfer.

PubMed

Gao, Chao; Chen, Shuangming; Wang, Ying; Wang, Jiawen; Zheng, Xusheng; Zhu, Junfa; Song, Li; Zhang, Wenkai; Xiong, Yujie

2018-03-01

Visible-light-driven conversion of CO 2 into chemical fuels is an intriguing approach to address the energy and environmental challenges. In principle, light harvesting and catalytic reactions can be both optimized by combining the merits of homogeneous and heterogeneous photocatalysts; however, the efficiency of charge transfer between light absorbers and catalytic sites is often too low to limit the overall photocatalytic performance. In this communication, it is reported that the single-atom Co sites coordinated on the partially oxidized graphene nanosheets can serve as a highly active and durable heterogeneous catalyst for CO 2 conversion, wherein the graphene bridges homogeneous light absorbers with single-atom catalytic sites for the efficient transfer of photoexcited electrons. As a result, the turnover number for CO production reaches a high value of 678 with an unprecedented turnover frequency of 3.77 min -1 , superior to those obtained with the state-of-the-art heterogeneous photocatalysts. This work provides fresh insights into the design of catalytic sites toward photocatalytic CO 2 conversion from the angle of single-atom catalysis and highlights the role of charge kinetics in bridging the gap between heterogeneous and homogeneous photocatalysts. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Toward single-mode active crystal fibers for next-generation high-power fiber devices.

PubMed

Lai, Chien-Chih; Gao, Wan-Ting; Nguyen, Duc Huy; Ma, Yuan-Ron; Cheng, Nai-Chia; Wang, Shih-Chang; Tjiu, Jeng-Wei; Huang, Chun-Ming

2014-08-27

We report what we believe to be the first demonstration of a facile approach with controlled geometry for the production of crystal-core ceramic-clad hybrid fibers for scaling fiber devices to high average powers. The process consists of dip coating a solution of polycrystalline alumina onto a high-crystallinity 40-μm-diameter Ti:sapphire single-crystalline core followed by thermal treatments. Comparison of the measured refractive index with high-resolution transmission electron microscopy reveals that a Ca/Si-rich intragranular layer is precipitated at grain boundaries by impurity segregation and liquid-phase formation due to the relief of misfit strain energy in the Al2O3 matrix, slightly perturbing the refractive index and hence the optical properties. Additionally, electron backscatter diffractions supply further evidence that the Ti:sapphire single-crystalline core provides the template for growth into a sacrificial polycrystalline cladding, bringing the core and cladding into a direct bond. The thus-prepared doped crystal core with the undoped crystal cladding was achieved through the abnormal grain-growth process. The presented results provide a general guideline both for controlling crystal growth and for the performance of hybrid materials and provides insights into how one might design single-mode high-power crystal fiber devices.

Tracing Single Electrons in a Disordered Polymer Film at Room Temperature.

PubMed

Wilma, Kevin; Issac, Abey; Chen, Zhijian; Würthner, Frank; Hildner, Richard; Köhler, Jürgen

2016-04-21

The transport of charges lies at the heart of essentially all modern (opto-) electronic devices. Although inorganic semiconductors built the basis for current technologies, organic materials have become increasingly important in recent years. However, organic matter is often highly disordered, which directly impacts the charge carrier dynamics. To understand and optimize device performance, detailed knowledge of the transport mechanisms of charge carriers in disordered matter is therefore of crucial importance. Here we report on the observation of the motion of single electrons within a disordered polymer film at room temperature, using single organic chromophores as probe molecules. The migration of a single electron gives rise to a varying electric field in its vicinity, which is registered via a shift of the emission spectra (Stark shift) of a chromophore. The spectral shifts allow us to determine the electron mobility and reveal for each nanoenvironment a distinct number of different possible electron-transfer pathways within the rugged energy landscape of the disordered polymer matrix.

Giant current fluctuations in an overheated single-electron transistor

NASA Astrophysics Data System (ADS)

Laakso, M. A.; Heikkilä, T. T.; Nazarov, Yuli V.

2010-11-01

Interplay of cotunneling and single-electron tunneling in a thermally isolated single-electron transistor leads to peculiar overheating effects. In particular, there is an interesting crossover interval where the competition between cotunneling and single-electron tunneling changes to the dominance of the latter. In this interval, the current exhibits anomalous sensitivity to the effective electron temperature of the transistor island and its fluctuations. We present a detailed study of the current and temperature fluctuations at this interesting point. The methods implemented allow for a complete characterization of the distribution of the fluctuating quantities, well beyond the Gaussian approximation. We reveal and explore the parameter range where, for sufficiently small transistor islands, the current fluctuations become gigantic. In this regime, the optimal value of the current, its expectation value, and its standard deviation differ from each other by parametrically large factors. This situation is unique for transport in nanostructures and for electron transport in general. The origin of this spectacular effect is the exponential sensitivity of the current to the fluctuating effective temperature.

Cost-effective description of strong correlation: Efficient implementations of the perfect quadruples and perfect hextuples models

DOE PAGES

Lehtola, Susi; Parkhill, John; Head-Gordon, Martin

2016-10-07

Novel implementations based on dense tensor storage are presented here for the singlet-reference perfect quadruples (PQ) [J. A. Parkhill et al., J. Chem. Phys. 130, 084101 (2009)] and perfect hextuples (PH) [J. A. Parkhill and M. Head-Gordon, J. Chem. Phys. 133, 024103 (2010)] models. The methods are obtained as block decompositions of conventional coupled-cluster theory that are exact for four electrons in four orbitals (PQ) and six electrons in six orbitals (PH), but that can also be applied to much larger systems. PQ and PH have storage requirements that scale as the square, and as the cube of the numbermore » of active electrons, respectively, and exhibit quartic scaling of the computational effort for large systems. Applications of the new implementations are presented for full-valence calculations on linear polyenes (C nH n+2), which highlight the excellent computational scaling of the present implementations that can routinely handle active spaces of hundreds of electrons. The accuracy of the models is studied in the π space of the polyenes, in hydrogen chains (H 50), and in the π space of polyacene molecules. In all cases, the results compare favorably to density matrix renormalization group values. With the novel implementation of PQ, active spaces of 140 electrons in 140 orbitals can be solved in a matter of minutes on a single core workstation, and the relatively low polynomial scaling means that very large systems are also accessible using parallel computing.« less

Cost-effective description of strong correlation: Efficient implementations of the perfect quadruples and perfect hextuples models

NASA Astrophysics Data System (ADS)

Lehtola, Susi; Parkhill, John; Head-Gordon, Martin

2016-10-01

Novel implementations based on dense tensor storage are presented for the singlet-reference perfect quadruples (PQ) [J. A. Parkhill et al., J. Chem. Phys. 130, 084101 (2009)] and perfect hextuples (PH) [J. A. Parkhill and M. Head-Gordon, J. Chem. Phys. 133, 024103 (2010)] models. The methods are obtained as block decompositions of conventional coupled-cluster theory that are exact for four electrons in four orbitals (PQ) and six electrons in six orbitals (PH), but that can also be applied to much larger systems. PQ and PH have storage requirements that scale as the square, and as the cube of the number of active electrons, respectively, and exhibit quartic scaling of the computational effort for large systems. Applications of the new implementations are presented for full-valence calculations on linear polyenes (CnHn+2), which highlight the excellent computational scaling of the present implementations that can routinely handle active spaces of hundreds of electrons. The accuracy of the models is studied in the π space of the polyenes, in hydrogen chains (H50), and in the π space of polyacene molecules. In all cases, the results compare favorably to density matrix renormalization group values. With the novel implementation of PQ, active spaces of 140 electrons in 140 orbitals can be solved in a matter of minutes on a single core workstation, and the relatively low polynomial scaling means that very large systems are also accessible using parallel computing.

Antibacterial activity of moxifloxacin on bacteria associated with periodontitis within a biofilm.

PubMed

Tsaousoglou, Phoebus; Nietzsche, Sandor; Cachovan, Georg; Sculean, Anton; Eick, Sigrun

2014-02-01

The activity of moxifloxacin was compared with ofloxacin and doxycycline against bacteria associated with periodontitis within a biofilm (single strain and mixed population) in vitro. MICs and minimal bactericidal concentrations (MBCs) of moxifloxacin, ofloxacin and doxycyline were determined against single strains and mixed populations in a planktonic state. Single-species biofilms of two Porphyromonas gingivalis and two Aggregatibacter actinomycetemcomitans strains and a multispecies biofilm consisting of 12 species were formed for 3 days. The minimal biofilm eradication concentrations (MBECs) were determined after exposing the biofilms to the antibacterials (0.002-512 µg ml(-1)) for 18 h, addition of nutrient broth for 3 days and subsequent subcultivation. Photographs were taken using confocal laser-scanning microscopy and scanning electron microscopy. The MICs and MBCs did not differ between ofloxacin and moxifloxacin against A. actinomycetemcomitans, whilst moxifloxacin was more active than the other tested antibacterials against anaerobes and the mixed population. The single-species biofilms were eradicated by moderate concentrations of the antibacterials, and the lowest MBECs were always found for moxifloxacin (2-8 µg ml(-1)). MBECs against the multispecies biofilms were 128, >512 and >512 µg ml(-1) for moxifloxacin, ofloxacin and doxycycline, respectively. In summary, moxifloxacin in a topical formulation may have potential as an adjunct to mechanical removal of the biofilms.

Exploring biorthonormal transformations of pair-correlation functions in atomic structure variational calculations

NASA Astrophysics Data System (ADS)

Verdebout, S.; Jönsson, P.; Gaigalas, G.; Godefroid, M.; Froese Fischer, C.

2010-04-01

Multiconfiguration expansions frequently target valence correlation and correlation between valence electrons and the outermost core electrons. Correlation within the core is often neglected. A large orbital basis is needed to saturate both the valence and core-valence correlation effects. This in turn leads to huge numbers of configuration state functions (CSFs), many of which are unimportant. To avoid the problems inherent to the use of a single common orthonormal orbital basis for all correlation effects in the multiconfiguration Hartree-Fock (MCHF) method, we propose to optimize independent MCHF pair-correlation functions (PCFs), bringing their own orthonormal one-electron basis. Each PCF is generated by allowing single- and double-excitations from a multireference (MR) function. This computational scheme has the advantage of using targeted and optimally localized orbital sets for each PCF. These pair-correlation functions are coupled together and with each component of the MR space through a low dimension generalized eigenvalue problem. Nonorthogonal orbital sets being involved, the interaction and overlap matrices are built using biorthonormal transformation of the coupled basis sets followed by a counter-transformation of the PCF expansions. Applied to the ground state of beryllium, the new method gives total energies that are lower than the ones from traditional complete active space (CAS)-MCHF calculations using large orbital active sets. It is fair to say that we now have the possibility to account for, in a balanced way, correlation deep down in the atomic core in variational calculations.

REVIEWS OF TOPICAL PROBLEMS Electron-vibration interaction in tunneling processes through single molecules

NASA Astrophysics Data System (ADS)

Arseev, Petr I.; Maslova, N. S.

2011-02-01

It is shown how effective Hamiltonians are constructed in the framework of the adiabatic approach to the electron-vibration interaction in electron tunneling through single molecules. Methods for calculating tunneling characteristics are discussed and possible features resulting from the electron-vibration coupling are described. The intensity of vibrations excited by a tunneling current in various systems is examined.

Enhanced visible light photocatalytic activity of copper-doped titanium oxide-zinc oxide heterojunction for methyl orange degradation

NASA Astrophysics Data System (ADS)

Dorraj, Masoumeh; Alizadeh, Mahdi; Sairi, Nor Asrina; Basirun, Wan Jefrey; Goh, Boon Tong; Woi, Pei Meng; Alias, Yatimah

2017-08-01

A novel Cu-doped TiO2 coupled with ZnO nanoparticles (Cu-TiO2/ZnO) was prepared by sol-gel method and subsequent precipitation for methyl orange (MO) photodegradation under visible light irradiation. The compositions and shapes of the as-prepared Cu-TiO2/ZnO nanocomposites were characterized by photoluminescence spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, field emission scanning electron microscopy, transmission electron microscopy, UV-vis diffuse reflectance spectra and Brunauer-Emmett-Teller adsorption isotherm techniques. The Cu-TiO2/ZnO nanocomposites showed considerably higher photocatalytic activity for MO removal from water under visible light irradiation than that of single-doped semiconductors. The effects of Cu-TiO2 and ZnO mass ratios on the photocatalytic reaction were also studied. A coupling percentage of 30% ZnO exhibited the highest photocatalytic activity. The enhanced photocatalytic activity of the Cu-TiO2/ZnO nanocomposites was mainly attributed to heterojunction formation, which allowed the efficient separation of photoinduced electron-hole pairs at the interface. Moreover, these novel nanocomposites could be recycled during MO degradation in a three-cycle experiment without evident deactivation, which is particularly important in environmental applications.

Single electron counting using a dual MCP assembly

NASA Astrophysics Data System (ADS)

Yang, Yuzhen; Liu, Shulin; Zhao, Tianchi; Yan, Baojun; Wang, Peiliang; Yu, Yang; Lei, Xiangcui; Yang, Luping; Wen, Kaile; Qi, Ming; Heng, Yuekun

2016-09-01

The gain, pulse height resolution and peak-to-valley ratio of single electrons detected by using a Chevron configured Microchannel Plate (MCP) assembly are studied. The two MCPs are separated by a 280 μm gap and are biased by four electrodes. The purpose of the study is to determine the optimum bias voltage arrangements for single electron counting. By comparing the results of various bias voltage combinations, we conclude that good performance for the electron counting can be achieved by operating the MCP assembly in saturation mode. In addition, by applying a small reverse bias voltage across the gap while adjusting the bias voltages of the MCPs, optimum performance of electron counting can be obtained.

DNA-Based Single-Molecule Electronics: From Concept to Function.

PubMed

Wang, Kun

2018-01-17

Beyond being the repository of genetic information, DNA is playing an increasingly important role as a building block for molecular electronics. Its inherent structural and molecular recognition properties render it a leading candidate for molecular electronics applications. The structural stability, diversity and programmability of DNA provide overwhelming freedom for the design and fabrication of molecular-scale devices. In the past two decades DNA has therefore attracted inordinate amounts of attention in molecular electronics. This review gives a brief survey of recent experimental progress in DNA-based single-molecule electronics with special focus on single-molecule conductance and I-V characteristics of individual DNA molecules. Existing challenges and exciting future opportunities are also discussed.

DNA-Based Single-Molecule Electronics: From Concept to Function

PubMed Central

2018-01-01

Beyond being the repository of genetic information, DNA is playing an increasingly important role as a building block for molecular electronics. Its inherent structural and molecular recognition properties render it a leading candidate for molecular electronics applications. The structural stability, diversity and programmability of DNA provide overwhelming freedom for the design and fabrication of molecular-scale devices. In the past two decades DNA has therefore attracted inordinate amounts of attention in molecular electronics. This review gives a brief survey of recent experimental progress in DNA-based single-molecule electronics with special focus on single-molecule conductance and I–V characteristics of individual DNA molecules. Existing challenges and exciting future opportunities are also discussed. PMID:29342091

Demonstration of Single-Shot Picosecond Time-Resolved MeV Electron Imaging Using a Compact Permanent Magnet Quadrupole Based Lens

NASA Astrophysics Data System (ADS)

Cesar, D.; Maxson, J.; Musumeci, P.; Sun, Y.; Harrison, J.; Frigola, P.; O'Shea, F. H.; To, H.; Alesini, D.; Li, R. K.

2016-07-01

We present the results of an experiment where a short focal length (˜1.3 cm ), permanent magnet electron lens is used to image micron-size features (of a metal sample) with a single shot from an ultrahigh brightness picosecond-long 4 MeV electron beam emitted by a radio-frequency photoinjector. Magnification ratios in excess of 30 × were obtained using a triplet of compact, small gap (3.5 mm), Halbach-style permanent magnet quadrupoles with nearly 600 T /m field gradients. These results pave the way towards single-shot time-resolved electron microscopy and open new opportunities in the applications of high brightness electron beams.

Efficient Nitrogen Fixation via a Redox-Flexible Single-Iron Site with Reverse-Dative Iron → Boron σ Bonding.

PubMed

Lu, Jun-Bo; Ma, Xue-Lu; Wang, Jia-Qi; Liu, Jin-Cheng; Xiao, Hai; Li, Jun

2018-05-10

Model systems of the FeMo cofactor of nitrogenase have been explored extensively in catalysis to gain insights into their ability for nitrogen fixation that is of vital importance to the human society. Here we investigate the trigonal pyramidal borane-ligand Fe complex by first-principles calculations, and find that the variation of oxidation state of Fe along the reaction path correlates with that of the reverse-dative Fe → B bonding. The redox-flexibility of the reverse-dative Fe → B bonding helps to provide an electron reservoir that buffers and stabilizes the evolution of Fe oxidation state, which is essential for forming the key intermediates of N 2 activation. Our work provides insights for understanding and optimizing homogeneous and surface single-atom catalysts with reverse-dative donating ligands for efficient dinitrogen fixation. The extension of this kind of molecular catalytic active center to heterogeneous catalysts with surface single-clusters is also discussed.

Cathodoluminescent characteristics and light technical parameters of thin-film screens based on oxides and oxysulfides of rare-earth elements

NASA Astrophysics Data System (ADS)

Bondar, Vyacheslav D.; Grytsiv, Myroslav; Groodzinsky, Arkady; Vasyliv, Mykhailo

1995-11-01

Results on creation of thin-film single-crystal high-resolution screens with energy control of luminescence color are presented. In order to create phosphor films ion-plasma technology for deposition of yttrium and lanthanum oxides and oxysulfides activated by rare earth elements has been developed. The screen consists of phosphor film on phosphor substrate with different colors of luminescence (e.g. Y2O3-Eu film with red color on Y3Al5O12- Tb, Ce substrate with green color of luminescence). Electron irradiation causes luminescence with color that depends on energy of the electron beam. The physical reason for color change is that electron beam energy defines electron penetration depth. If the energy is weak, only the film is excited. More powerful beam penetrates into the substrate and thus changes the color of luminescence.

Layer-by-Layer Assembly of Glucose Oxidase on Carbon Nanotube Modified Electrodes.

PubMed

Suroviec, Alice H

2017-01-01

The use of enzymatically modified electrodes for the detection of glucose or other non-electrochemically active analytes is becoming increasingly common. Direct heterogeneous electron transfer to glucose oxidase has been shown to be kinetically difficult, which is why electron transfer mediators or indirect detection is usually used for monitoring glucose with electrochemical sensors. It has been found, however, that electrodes modified with single or multi-walled carbon nanotubes (CNTs) demonstrate fast heterogeneous electron transfer kinetics as compared to that found for traditional electrodes. Incorporating CNTs into the assembly of electrochemical glucose sensors, therefore, affords the possibility of facile electron transfer to glucose oxidase, and a more direct determination of glucose. This chapter describes the methods used to use CNTs in a layer-by-layer structure along with glucose oxidase to produce an enzymatically modified electrode with high turnover rates, increased stability and shelf-life.

Silica-supported isolated gallium sites as highly active, selective and stable propane dehydrogenation catalysts† †Electronic supplementary information (ESI) available: Experimental details, material characterization data, catalytic measurement details and crystallographic details. CCDC 1499756. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6sc05178b Click here for additional data file. Click here for additional data file.

PubMed Central

Searles, Keith; Siddiqi, Georges; Safonova, Olga V.

2017-01-01

Single-site gallium centers on the surface of silica are prepared via grafting of [Ga(OSi(OtBu)3)3(THF)] on SiO2–700 followed by a thermolysis step. The resulting surface species corresponds to well-defined tetra-coordinate gallium single-sites, [( 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 SiO)3Ga(XOSi)] (X = –H or Si) according to IR, X-ray absorption near-edge structure and extended X-ray absorption fine structure analysis. These gallium sites show high activity, selectivity and stability for propane dehydrogenation with an initial turnover frequency of 20 per h per gallium center, propylene selectivity of ≥93% and remarkable stability over 20 h. The stability of the catalyst probably results from site-isolation of the active site on a non-reducible support such as silica, diminishing facile reduction typical of Ga2O3-based catalysts. PMID:28553501

Single-crystalline nanogap electrodes: enhancing the nanowire-breakdown process with a gaseous environment.

PubMed

Suga, Hiroshi; Sumiya, Touru; Furuta, Shigeo; Ueki, Ryuichi; Miyazawa, Yosuke; Nishijima, Takuya; Fujita, Jun-ichi; Tsukagoshi, Kazuhito; Shimizu, Tetsuo; Naitoh, Yasuhisa

2012-10-24

A method for fabricating single-crystalline nanogaps on Si substrates was developed. Polycrystalline Pt nanowires on Si substrates were broken down by current flow under various gaseous environments. The crystal structure of the nanogap electrode was evaluated using scanning electron microscopy and transmission electron microscopy. Nanogap electrodes sandwiched between Pt-large-crystal-grains were obtained by the breakdown of the wire in an O(2) or H(2) atmosphere. These nanogap electrodes show intense spots in the electron diffraction pattern. The diffraction pattern corresponds to Pt (111), indicating that single-crystal grains are grown by the electrical wire breakdown process in an O(2) or H(2) atmosphere. The Pt wires that have (111)-texture and coherent boundaries can be considered ideal as interconnectors for single molecular electronics. The simple method for fabrication of a single-crystalline nanogap is one of the first steps toward standard nanogap electrodes for single molecular instruments and opens the door to future research on physical phenomena in nanospaces.

Single shot spin readout using a cryogenic high-electron-mobility transistor amplifier at sub-Kelvin temperatures

NASA Astrophysics Data System (ADS)

Tracy, L. A.; Luhman, D. R.; Carr, S. M.; Bishop, N. C.; Ten Eyck, G. A.; Pluym, T.; Wendt, J. R.; Lilly, M. P.; Carroll, M. S.

2016-02-01

We use a cryogenic high-electron-mobility transistor circuit to amplify the current from a single electron transistor, allowing for demonstration of single shot readout of an electron spin on a single P donor in Si with 100 kHz bandwidth and a signal to noise ratio of ˜9. In order to reduce the impact of cable capacitance, the amplifier is located adjacent to the Si sample, at the mixing chamber stage of a dilution refrigerator. For a current gain of ˜ 2.7 × 10 3 , the power dissipation of the amplifier is 13 μW, the bandwidth is ˜ 1.3 MHz, and for frequencies above 300 kHz the current noise referred to input is ≤ 70 fA/ √{ Hz } . With this amplification scheme, we are able to observe coherent oscillations of a P donor electron spin in isotopically enriched 28Si with 96% visibility.

Technology of silicon charged-particle detectors developed at the Institute of Electron Technology (ITE)

NASA Astrophysics Data System (ADS)

Wegrzecka, Iwona; Panas, Andrzej; Bar, Jan; Budzyński, Tadeusz; Grabiec, Piotr; Kozłowski, Roman; Sarnecki, Jerzy; Słysz, Wojciech; Szmigiel, Dariusz; Wegrzecki, Maciej; Zaborowski, Michał

2013-07-01

The paper discusses the technology of silicon charged-particle detectors developed at the Institute of Electron Technology (ITE). The developed technology enables the fabrication of both planar and epiplanar p+-ν-n+ detector structures with an active area of up to 50 cm2. The starting material for epiplanar structures are silicon wafers with a high-resistivity n-type epitaxial layer ( ν layer - ρ < 3 kΩcm) deposited on a highly doped n+-type substrate (ρ< 0,02Ωcm) developed and fabricated at the Institute of Electronic Materials Technology. Active layer thickness of the epiplanar detectors (νlayer) may range from 10 μm to 150 μm. Imported silicon with min. 5 kΩcm resistivity is used to fabricate planar detectors. Active layer thickness of the planar detectors (ν) layer) may range from 200 μm to 1 mm. This technology enables the fabrication of both discrete and multi-junction detectors (monolithic detector arrays), such as single-sided strip detectors (epiplanar and planar) and double-sided strip detectors (planar). Examples of process diagrams for fabrication of the epiplanar and planar detectors are presented in the paper, and selected technological processes are discussed.

Crystallization and growth of Ni-Si alloy thin films on inert and on silicon substrates

NASA Astrophysics Data System (ADS)

Grimberg, I.; Weiss, B. Z.

1995-04-01

The crystallization kinetics and thermal stability of NiSi2±0.2 alloy thin films coevaporated on two different substrates were studied. The substrates were: silicon single crystal [Si(100)] and thermally oxidized silicon single crystal. In situ resistance measurements, transmission electron microscopy, x-ray diffraction, Auger electron spectroscopy, and Rutherford backscattering spectroscopy were used. The postdeposition microstructure consisted of a mixture of amorphous and crystalline phases. The amorphous phase, independent of the composition, crystallizes homogeneously to NiSi2 at temperatures lower than 200 °C. The activation energy, determined in the range of 1.4-2.54 eV, depends on the type of the substrate and on the composition of the alloyed films. The activation energy for the alloys deposited on the inert substrate was found to be lower than for the alloys deposited on silicon single crystal. The lowest activation energy was obtained for nonstoichiometric NiSi2.2, the highest for NiSi2—on both substrates. The crystallization mode depends on the structure of the as-deposited films, especially the density of the existing crystalline nuclei. Substantial differences were observed in the thermal stability of the NiSi2 compound on both substrates. With the alloy films deposited on the Si substrate, only the NiSi2 phase was identified after annealing to temperatures up to 800 °C. In the films deposited on the inert substrate, NiSi and NiSi2 phases were identified when the Ni content in the alloy exceeded 33 at. %. The effects of composition and the type of substrate on the crystallization kinetics and thermal stability are discussed.

Experimental realization of a Szilard engine with a single electron.

PubMed

Koski, Jonne V; Maisi, Ville F; Pekola, Jukka P; Averin, Dmitri V

2014-09-23

The most succinct manifestation of the second law of thermodynamics is the limitation imposed by the Landauer principle on the amount of heat a Maxwell demon (MD) can convert into free energy per single bit of information obtained in a measurement. We propose and realize an electronic MD based on a single-electron box operated as a Szilard engine, where kBT ln 2 of heat is extracted from the reservoir at temperature T per one bit of created information. The information is encoded in the position of an extra electron in the box.

Electric field imaging of single atoms

PubMed Central

Shibata, Naoya; Seki, Takehito; Sánchez-Santolino, Gabriel; Findlay, Scott D.; Kohno, Yuji; Matsumoto, Takao; Ishikawa, Ryo; Ikuhara, Yuichi

2017-01-01

In scanning transmission electron microscopy (STEM), single atoms can be imaged by detecting electrons scattered through high angles using post-specimen, annular-type detectors. Recently, it has been shown that the atomic-scale electric field of both the positive atomic nuclei and the surrounding negative electrons within crystalline materials can be probed by atomic-resolution differential phase contrast STEM. Here we demonstrate the real-space imaging of the (projected) atomic electric field distribution inside single Au atoms, using sub-Å spatial resolution STEM combined with a high-speed segmented detector. We directly visualize that the electric field distribution (blurred by the sub-Å size electron probe) drastically changes within the single Au atom in a shape that relates to the spatial variation of total charge density within the atom. Atomic-resolution electric field mapping with single-atom sensitivity enables us to examine their detailed internal and boundary structures. PMID:28555629

Universal quantum gates on electron-spin qubits with quantum dots inside single-side optical microcavities.

PubMed

Wei, Hai-Rui; Deng, Fu-Guo

2014-01-13

We present some compact quantum circuits for a deterministic quantum computing on electron-spin qubits assisted by quantum dots inside single-side optical microcavities, including the CNOT, Toffoli, and Fredkin gates. They are constructed by exploiting the giant optical Faraday rotation induced by a single-electron spin in a quantum dot inside a single-side optical microcavity as a result of cavity quantum electrodynamics. Our universal quantum gates have some advantages. First, all the gates are accomplished with a success probability of 100% in principle. Second, our schemes require no additional electron-spin qubits and they are achieved by some input-output processes of a single photon. Third, our circuits for these gates are simple and economic. Moreover, our devices for these gates work in both the weak coupling and the strong coupling regimes, and they are feasible in experiment.

Activating "Invisible" Glue: Using Electron Beam for Enhancement of Interfacial Properties of Graphene-Metal Contact.

PubMed

Kim, Songkil; Russell, Michael; Kulkarni, Dhaval D; Henry, Mathias; Kim, Steve; Naik, Rajesh R; Voevodin, Andrey A; Jang, Seung Soon; Tsukruk, Vladimir V; Fedorov, Andrei G

2016-01-26

Interfacial contact of two-dimensional graphene with three-dimensional metal electrodes is crucial to engineering high-performance graphene-based nanodevices with superior performance. Here, we report on the development of a rapid "nanowelding" method for enhancing properties of interface to graphene buried under metal electrodes using a focused electron beam induced deposition (FEBID). High energy electron irradiation activates two-dimensional graphene structure by generation of structural defects at the interface to metal contacts with subsequent strong bonding via FEBID of an atomically thin graphitic interlayer formed by low energy secondary electron-assisted dissociation of entrapped hydrocarbon contaminants. Comprehensive investigation is conducted to demonstrate formation of the FEBID graphitic interlayer and its impact on contact properties of graphene devices achieved via strong electromechanical coupling at graphene-metal interfaces. Reduction of the device electrical resistance by ∼50% at a Dirac point and by ∼30% at the gate voltage far from the Dirac point is obtained with concurrent improvement in thermomechanical reliability of the contact interface. Importantly, the process is rapid and has an excellent insertion potential into a conventional fabrication workflow of graphene-based nanodevices through single-step postprocessing modification of interfacial properties at the buried heterogeneous contact.

Substrate co-doping modulates electronic metal–support interactions and significantly enhances single-atom catalysis

DOE PAGES

Shi, Jinlei; Wu, Jinghe; Zhao, Xingju; ...

2016-10-07

Transitional metal nanoparticles or atoms deposited on appropriate substrates can lead to highly economical, efficient, and selective catalysis. One of the greatest challenges is to control the electronic metal–support interactions (EMSI) between the supported metal atoms and the substrate so as to optimize their catalytic performance. Here, from first-principles calculations, we show that an otherwise inactive Pd single adatom on TiO 2(110) can be tuned into a highly effective catalyst, e.g. for O 2 adsorption and CO oxidation, by purposefully selected metal–nonmetal co-dopant pairs in the substrate. Such an effect is proved here to result unambiguously from a significantly enhancedmore » EMSI. A nearly linear correlation is noted between the strength of the EMSI and the activation of the adsorbed O 2 molecule, as well as the energy barrier for CO oxidation. Particularly, the enhanced EMSI shifts the frontier orbital of the deposited Pd atom upward and largely enhances the hybridization and charge transfer between the O 2 molecule and the Pd atom. Upon co-doping, the activation barrier for CO oxidation on the Pd monomer is also reduced to a level comparable to that on the Pd dimer which was experimentally reported to be highly efficient for CO oxidation. The present findings provide new insights into the understanding of the EMSI in heterogeneous catalysis and can open new avenues to design and fabricate cost-effective single-atom-sized and/or nanometer-sized catalysts.« less

High-power green and blue electron-beam pumped surface-emitting lasers using dielectric and epitaxial distributed Bragg reflectors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Klein, T., E-mail: tklein@ifp.uni-bremen.de; Klembt, S.; Institut Néel, Université Grenoble Alpes and CNRS, B.P. 166, 38042 Grenoble

2015-03-21

ZnSe-based electron-beam pumped vertical-cavity surface-emitting lasers for the green (λ = 530 nm) and blue (λ = 462 nm) spectral region have been realized. Structures with and without epitaxial bottom distributed Bragg reflector have been fabricated and characterized. The samples consist of an active region containing 20 quantum wells with a cavity length varying between an optical thickness of 10 λ to 20 λ. The active material is ZnCdSSe in case of the green devices and ZnSe for the blue ones. Room temperature single mode lasing for structures with and without epitaxial bottom mirror with a maximum output power up to 5.9 W (green) and 3.3 W (blue)more » is achieved, respectively.« less

In situ growth of lamellar ZnTiO3 nanosheets on TiO2 tubular array with enhanced photocatalytic activity.

PubMed

Cai, Yunyu; Ye, Yixing; Tian, Zhenfei; Liu, Jun; Liu, Yishu; Liang, Changhao

2013-12-14

We report a self-sacrificed in situ growth design toward preparation of ZnTiO3-TiO2 heterojunction structure. Highly reactive zinc oxide colloidal particles derived by laser ablation in liquids can react with TiO2 nanotubes to form a lamellar ZnTiO3 nanosheet structure in a hydrothermal-treatment process. Such hybrid structural product was characterized by X-ray diffraction, scanning and transmission electron microscopy, UV-vis diffuse reflection spectroscopy and X-ray photoelectron spectroscopy. The enhanced photocatalytic activity of the hybrid structure toward degradation of methyl orange (MO) and pentachlorophenol (PCP) molecules was demonstrated and compared with single phase TiO2, as a result of the efficient separation of light excited electrons and holes at the hetero-interfaces in the two semiconductors.

Tuning the Activity of Carbon for Electrocatalytic Hydrogen Evolution via an Iridium-Cobalt Alloy Core Encapsulated in Nitrogen-Doped Carbon Cages.

PubMed

Jiang, Peng; Chen, Jitang; Wang, Changlai; Yang, Kang; Gong, Shipeng; Liu, Shuai; Lin, Zhiyu; Li, Mengsi; Xia, Guoliang; Yang, Yang; Su, Jianwei; Chen, Qianwang

2018-03-01

Graphene, a 2D material consisting of a single layer of sp 2 -hybridized carbon, exhibits inert activity as an electrocatalyst, while the incorporation of heteroatoms (such as N) into the framework can tune its electronic properties. Because of the different electronegativity between N and C atoms, electrons will transfer from C to N in N-doped graphene nanosheets, changing inert C atoms adjacent to the N-dopants into active sites. Notwithstanding the achieved progress, its intrinsic activity in acidic media is still far from Pt/C. Here, a facile annealing strategy is adopted for Ir-doped metal-organic frameworks to synthesize IrCo nanoalloys encapsulated in N-doped graphene layers. The highly active electrocatalyst, with remarkably reduced Ir loading (1.56 wt%), achieves an ultralow Tafel slope of 23 mV dec -1 and an overpotential of only 24 mV at a current density of 10 mA cm -2 in 0.5 m sulfuric acid solution. Such superior performance is even superior to the noble-metal catalyst Pt. Surface structural and computational studies reveal that the superior behavior originates from the decreased ΔG H* for HER induced by the electrons transferred from the alloy core to the graphene layers, which is beneficial for enhancing CH binding. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Observing microscopic structures of a relativistic object using a time-stretch strategy.

PubMed

Roussel, E; Evain, C; Le Parquier, M; Szwaj, C; Bielawski, S; Manceron, L; Brubach, J-B; Tordeux, M-A; Ricaud, J-P; Cassinari, L; Labat, M; Couprie, M-E; Roy, P

2015-05-28

Emission of light by a single electron moving on a curved trajectory (synchrotron radiation) is one of the most well-known fundamental radiation phenomena. However experimental situations are more complex as they involve many electrons, each being exposed to the radiation of its neighbors. This interaction has dramatic consequences, one of the most spectacular being the spontaneous formation of spatial structures inside electrons bunches. This fundamental effect is actively studied as it represents one of the most fundamental limitations in electron accelerators, and at the same time a source of intense terahertz radiation (Coherent Synchrotron Radiation, or CSR). Here we demonstrate the possibility to directly observe the electron bunch microstructures with subpicosecond resolution, in a storage ring accelerator. The principle is to monitor the terahertz pulses emitted by the structures, using a strategy from photonics, time-stretch, consisting in slowing-down the phenomena before recording. This opens the way to unpreceeded possibilities for analyzing and mastering new generation high power coherent synchrotron sources.

Observing microscopic structures of a relativistic object using a time-stretch strategy

NASA Astrophysics Data System (ADS)

Roussel, E.; Evain, C.; Le Parquier, M.; Szwaj, C.; Bielawski, S.; Manceron, L.; Brubach, J.-B.; Tordeux, M.-A.; Ricaud, J.-P.; Cassinari, L.; Labat, M.; Couprie, M.-E.; Roy, P.

2015-05-01

Emission of light by a single electron moving on a curved trajectory (synchrotron radiation) is one of the most well-known fundamental radiation phenomena. However experimental situations are more complex as they involve many electrons, each being exposed to the radiation of its neighbors. This interaction has dramatic consequences, one of the most spectacular being the spontaneous formation of spatial structures inside electrons bunches. This fundamental effect is actively studied as it represents one of the most fundamental limitations in electron accelerators, and at the same time a source of intense terahertz radiation (Coherent Synchrotron Radiation, or CSR). Here we demonstrate the possibility to directly observe the electron bunch microstructures with subpicosecond resolution, in a storage ring accelerator. The principle is to monitor the terahertz pulses emitted by the structures, using a strategy from photonics, time-stretch, consisting in slowing-down the phenomena before recording. This opens the way to unpreceeded possibilities for analyzing and mastering new generation high power coherent synchrotron sources.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Saudari, Sangameshwar R.; Kagan, Cherie R.; Department of Electrical and Systems Engineering, University of Pennsylvania, Philadelphia, Pennsylvania 19104

Solution-processed, ambipolar, thin-film pentacene field-effect transistors were employed to study both electron and hole transport simultaneously in a single, organic solid-state device. Electron and hole mobilities were extracted from the respective unipolar saturation regimes and show thermally activated behavior and gate voltage dependence. We fit the gate voltage dependent saturation mobility to a power law to extract the characteristic Meyer-Neldel (MN) energy, a measure of the width of the exponential distribution of localized states extending into the energy gap of the organic semiconductor. The MN energy is ∼78 and ∼28 meV for electrons and holes, respectively, which reflects a greater densitymore » of localized tail states for electrons than holes. This is consistent with the lower measured electron than hole mobility. For holes, the well-behaved linear regime allows for four-point probe measurement of the contact resistance independent mobility and separate characterization of the width of the localized density of states, yielding a consistent MN energy of 28 meV.« less

Physics and Engineering Design of the ITER Electron Cyclotron Emission Diagnostic

NASA Astrophysics Data System (ADS)

Rowan, W. L.; Austin, M. E.; Houshmandyar, S.; Phillips, P. E.; Beno, J. H.; Ouroua, A.; Weeks, D. A.; Hubbard, A. E.; Stillerman, J. A.; Feder, R. E.; Khodak, A.; Taylor, G.; Pandya, H. K.; Danani, S.; Kumar, R.

2015-11-01

Electron temperature (Te) measurements and consequent electron thermal transport inferences will be critical to the non-active phases of ITER operation and will take on added importance during the alpha heating phase. Here, we describe our design for the diagnostic that will measure spatial and temporal profiles of Te using electron cyclotron emission (ECE). Other measurement capability includes high frequency instabilities (e.g. ELMs, NTMs, and TAEs). Since results from TFTR and JET suggest that Thomson Scattering and ECE differ at high Te due to driven non-Maxwellian distributions, non-thermal features of the ITER electron distribution must be documented. The ITER environment presents other challenges including space limitations, vacuum requirements, and very high-neutron-fluence. Plasma control in ITER will require real-time Te. The diagnosic design that evolved from these sometimes-conflicting needs and requirements will be described component by component with special emphasis on the integration to form a single effective diagnostic system. Supported by PPPL/US-DA via subcontract S013464-C to UT Austin.

Electron transport in single molecules: from benzene to graphene.

PubMed

Chen, F; Tao, N J

2009-03-17

Electron movement within and between molecules--that is, electron transfer--is important in many chemical, electrochemical, and biological processes. Recent advances, particularly in scanning electrochemical microscopy (SECM), scanning-tunneling microscopy (STM), and atomic force microscopy (AFM), permit the study of electron movement within single molecules. In this Account, we describe electron transport at the single-molecule level. We begin by examining the distinction between electron transport (from semiconductor physics) and electron transfer (a more general term referring to electron movement between donor and acceptor). The relation between these phenomena allows us to apply our understanding of single-molecule electron transport between electrodes to a broad range of other electron transfer processes. Electron transport is most efficient when the electron transmission probability via a molecule reaches 100%; the corresponding conductance is then 2e(2)/h (e is the charge of the electron and h is the Planck constant). This ideal conduction has been observed in a single metal atom and a string of metal atoms connected between two electrodes. However, the conductance of a molecule connected to two electrodes is often orders of magnitude less than the ideal and strongly depends on both the intrinsic properties of the molecule and its local environment. Molecular length, means of coupling to the electrodes, the presence of conjugated double bonds, and the inclusion of possible redox centers (for example, ferrocene) within the molecular wire have a pronounced effect on the conductance. This complex behavior is responsible for diverse chemical and biological phenomena and is potentially useful for device applications. Polycyclic aromatic hydrocarbons (PAHs) afford unique insight into electron transport in single molecules. The simplest one, benzene, has a conductance much less than 2e(2)/h due to its large LUMO-HOMO gap. At the other end of the spectrum, graphene sheets and carbon nanotubes--consisting of infinite numbers of aromatic rings--have small or even zero energy gaps between the conduction and valence bands. Between these two limits are intermediate molecules with rich properties, such as perylene derivatives made of seven aromatic rings; the properties of these types of molecules have yet to be fully explored. Studying PAHs is important not only in answering fundamental questions about electron transport but also in the ongoing quest for molecular-scale electronic devices. This line of research also helps bridge the gap between electron transfer phenomena in small redox molecules and electron transport properties in nanostructures.

Atomic Scale Structure-Chemistry Relationships at Oxide Catalyst Surfaces and Interfaces

NASA Astrophysics Data System (ADS)

McBriarty, Martin E.

Oxide catalysts are integral to chemical production, fuel refining, and the removal of environmental pollutants. However, the atomic-scale phenomena which lead to the useful reactive properties of catalyst materials are not sufficiently understood. In this work, the tools of surface and interface science and electronic structure theory are applied to investigate the structure and chemical properties of catalytically active particles and ultrathin films supported on oxide single crystals. These studies focus on structure-property relationships in vanadium oxide, tungsten oxide, and mixed V-W oxides on the surfaces of alpha-Al2O3 and alpha-Fe2O 3 (0001)-oriented single crystal substrates, two materials with nearly identical crystal structures but drastically different chemical properties. In situ synchrotron X-ray standing wave (XSW) measurements are sensitive to changes in the atomic-scale geometry of single crystal model catalyst surfaces through chemical reaction cycles, while X-ray photoelectron spectroscopy (XPS) reveals corresponding chemical changes. Experimental results agree with theoretical calculations of surface structures, allowing for detailed electronic structure investigations and predictions of surface chemical phenomena. The surface configurations and oxidation states of V and W are found to depend on the coverage of each, and reversible structural shifts accompany chemical state changes through reduction-oxidation cycles. Substrate-dependent effects suggest how the choice of oxide support material may affect catalytic behavior. Additionally, the structure and chemistry of W deposited on alpha-Fe 2O3 nanopowders is studied using X-ray absorption fine structure (XAFS) measurements in an attempt to bridge single crystal surface studies with real catalysts. These investigations of catalytically active material surfaces can inform the rational design of new catalysts for more efficient and sustainable chemistry.

Development of multi-layer crystal detector and related front end electronics

NASA Astrophysics Data System (ADS)

Cardarelli, R.; Di Ciaccio, A.; Paolozzi, L.

2014-05-01

A crystal (diamond) particle detector has been developed and tested, whose constitute elements are a multi-layer polycrystalline diamond and a pick-up system capable of collecting in parallel the charge produced in the layers. The charge is read with a charge-to-voltage amplifier (5-6 mV/fC) realized with bipolar junction transistors in order to minimize the effect of the detector capacitance. The tests performed with cosmic rays and at the beam test facility of Frascati with 500 MeV electrons in single electron mode operation have shown that a detector with 4-5 layers of 250 μm thickness each and 9 mm2 active area exhibits an upper limit of 150 ps time resolution for minimum ionizing particles at an operating voltage of about 350 V.

Covalent lanthanide(III) macrocyclic complexes: the bonding nature and optical properties of a promising single antenna molecule.

PubMed

Rabanal-León, Walter A; Páez-Hernández, Dayán; Arratia-Pérez, Ramiro

2014-12-21

The present work is focused on the elucidation of the electronic structure, bonding nature and optical properties of a series of low symmetry (C2) coordination compounds of type [Ln(III)HAM](3+), where "Ln(III)" are the trivalent lanthanide ions: La(3+), Ce(3+), Eu(3+) and Lu(3+), while "HAM" is the neutral six-nitrogen donor macrocyclic ligand [C22N6H26]. This systematic study has been performed in the framework of the Relativistic Density Functional Theory (R-DFT) and also using a multi-reference approach via the Complete Active Space (CAS) wavefunction treatment with the aim of analyzing their ground state and excited state electronic structures as well as electronic correlation. Furthermore, the use of the energy decomposition scheme proposed by Morokuma-Ziegler and the electron localization function (ELF) allows us to characterize the bonding between the lanthanide ions and the macrocyclic ligand, obtaining as a result a dative-covalent interaction. Due to a great deal of lanthanide optical properties and their technological applications, the absorption spectra of this set of coordination compounds were calculated using the time-dependent density functional theory (TD-DFT), where the presence of the intense Ligand to Metal Charge Transfer (LMCT) bands in the ultraviolet and visible region and the inherent f-f electronic transitions in the Near-Infra Red (NIR) region for some lanthanide ions allow us to propose these systems as "single antenna molecules" with potential applications in NIR technologies.

Development and Applications of Advanced Electronic Structure Methods

NASA Astrophysics Data System (ADS)

Bell, Franziska

This dissertation contributes to three different areas in electronic structure theory. The first part of this thesis advances the fundamentals of orbital active spaces. Orbital active spaces are not only essential in multi-reference approaches, but have also become of interest in single-reference methods as they allow otherwise intractably large systems to be studied. However, despite their great importance, the optimal choice and, more importantly, their physical significance are still not fully understood. In order to address this problem, we studied the higher-order singular value decomposition (HOSVD) in the context of electronic structure methods. We were able to gain a physical understanding of the resulting orbitals and proved a connection to unrelaxed natural orbitals in the case of Moller-Plesset perturbation theory to second order (MP2). In the quest to find the optimal choice of the active space, we proposed a HOSVD for energy-weighted integrals, which yielded the fastest convergence in MP2 correlation energy for small- to medium-sized active spaces to date, and is also potentially transferable to coupled-cluster theory. In the second part, we studied monomeric and dimeric glycerol radical cations and their photo-induced dissociation in collaboration with Prof. Leone and his group. Understanding the mechanistic details involved in these processes are essential for further studies on the combustion of glycerol and carbohydrates. To our surprise, we found that in most cases, the experimentally observed appearance energies arise from the separation of product fragments from one another rather than rearrangement to products. The final chapters of this work focus on the development, assessment, and application of the spin-flip method, which is a single-reference approach, but capable of describing multi-reference problems. Systems exhibiting multi-reference character, which arises from the (near-) degeneracy of orbital energies, are amongst the most interesting in chemistry, biology and materials science, yet amongst the most challenging to study with electronic structure methods. In particular, we explored a substituted dimeric BPBP molecule with potential tetraradical character, which gained attention as one of the most promising candidates for an organic conductor. Furthermore, we extended the spin-flip approach to include variable orbital active spaces and multiple spin-flips. This allowed us to perform wave-function-based studies of ground- and excited-states of polynuclear metal complexes, polyradicals, and bond-dissociation processes involving three or more bonds.

Control of single-electron charging of metallic nanoparticles onto amorphous silicon surface.

PubMed

Weis, Martin; Gmucová, Katarína; Nádazdy, Vojtech; Capek, Ignác; Satka, Alexander; Kopáni, Martin; Cirák, Július; Majková, Eva

2008-11-01

Sequential single-electron charging of iron oxide nanoparticles encapsulated in oleic acid/oleyl amine envelope and deposited by the Langmuir-Blodgett technique onto Pt electrode covered with undoped hydrogenated amorphous silicon film is reported. Single-electron charging (so-called quantized double-layer charging) of nanoparticles is detected by cyclic voltammetry as current peaks and the charging effect can be switched on/off by the electric field in the surface region induced by the excess of negative/positive charged defect states in the amorphous silicon layer. The particular charge states in amorphous silicon are created by the simultaneous application of a suitable bias voltage and illumination before the measurement. The influence of charged states on the electric field in the surface region is evaluated by the finite element method. The single-electron charging is analyzed by the standard quantized double layer model as well as two weak-link junctions model. Both approaches are in accordance with experiment and confirm single-electron charging by tunnelling process at room temperature. This experiment illustrates the possibility of the creation of a voltage-controlled capacitor for nanotechnology.

Common electronic origin of superconductivity in (Li,Fe)OHFeSe bulk superconductor and single-layer FeSe/SrTiO3 films.

PubMed

Zhao, Lin; Liang, Aiji; Yuan, Dongna; Hu, Yong; Liu, Defa; Huang, Jianwei; He, Shaolong; Shen, Bing; Xu, Yu; Liu, Xu; Yu, Li; Liu, Guodong; Zhou, Huaxue; Huang, Yulong; Dong, Xiaoli; Zhou, Fang; Liu, Kai; Lu, Zhongyi; Zhao, Zhongxian; Chen, Chuangtian; Xu, Zuyan; Zhou, X J

2016-02-08

The mechanism of high-temperature superconductivity in the iron-based superconductors remains an outstanding issue in condensed matter physics. The electronic structure plays an essential role in dictating superconductivity. Recent revelation of distinct electronic structure and high-temperature superconductivity in the single-layer FeSe/SrTiO3 films provides key information on the role of Fermi surface topology and interface in inducing or enhancing superconductivity. Here we report high-resolution angle-resolved photoemission measurements on the electronic structure and superconducting gap of an FeSe-based superconductor, (Li0.84Fe0.16)OHFe0.98Se, with a Tc at 41 K. We find that this single-phase bulk superconductor shows remarkably similar electronic behaviours to that of the superconducting single-layer FeSe/SrTiO3 films in terms of Fermi surface topology, band structure and the gap symmetry. These observations provide new insights in understanding high-temperature superconductivity in the single-layer FeSe/SrTiO3 films and the mechanism of superconductivity in the bulk iron-based superconductors.

Effect of copper on the recombination activity of extended defects in silicon

DOE Office of Scientific and Technical Information (OSTI.GOV)

Feklisova, O. V., E-mail: feklisov@iptm.ru; Yakimov, E. B.

2015-06-15

The effect of copper atoms introduced by high-temperature diffusion on the recombination properties of dislocations and dislocation trails in p-type single-crystal silicon is studied by the electron-beam-induced current technique. It is shown that, in contrast to dislocations, dislocation trails exhibit an increase in recombination activity after the introduction of copper. Bright contrast appearance in the vicinity of dislocation trails is detected after the diffusion of copper and quenching of the samples. The contrast depends on the defect density in these trails.

Size-dependent single electron transfer and semi-metal-to-insulator transitions in molecular metal oxide electronics

NASA Astrophysics Data System (ADS)

Balliou, Angelika; Bouroushian, Mirtat; Douvas, Antonios M.; Skoulatakis, George; Kennou, Stella; Glezos, Nikos

2018-07-01

All-inorganic self-arranged molecular transition metal oxide hyperstructures based on polyoxometalate molecules (POMs) are fabricated and tested as electronically tunable components in emerging electronic devices. POM hyperstructures reveal great potential as charging nodes of tunable charging level for molecular memories and as enhancers of interfacial electron/hole injection for photovoltaic stacks. STM, UPS, UV–vis spectroscopy and AFM measurements show that this functionality stems from the films’ ability to structurally tune their HOMO–LUMO levels and electron localization length at room temperature. By adapting POM nanocluster size in solution, self-doping and current modulation of four orders of magnitude is monitored on a single nanocluster on SiO2 at voltages as low as 3 Volt. Structurally driven insulator-to-semi-metal transitions and size-dependent current regulation through single electron tunneling are demonstrated and examined with respect to the stereochemical and electronic structure of the molecular entities. This extends the value of self-assembly as a tool for correlation length and electronic properties tuning and demonstrate POM hyperstructures’ plausibility for on-chip molecular electronics operative at room temperature.

Size-dependent single electron transfer and semi-metal-to-insulator transitions in molecular metal oxide electronics.

PubMed

Balliou, Angelika; Bouroushian, Mirtat; Douvas, Antonios M; Skoulatakis, George; Kennou, Stella; Glezos, Nikos

2018-07-06

All-inorganic self-arranged molecular transition metal oxide hyperstructures based on polyoxometalate molecules (POMs) are fabricated and tested as electronically tunable components in emerging electronic devices. POM hyperstructures reveal great potential as charging nodes of tunable charging level for molecular memories and as enhancers of interfacial electron/hole injection for photovoltaic stacks. STM, UPS, UV-vis spectroscopy and AFM measurements show that this functionality stems from the films' ability to structurally tune their HOMO-LUMO levels and electron localization length at room temperature. By adapting POM nanocluster size in solution, self-doping and current modulation of four orders of magnitude is monitored on a single nanocluster on SiO 2 at voltages as low as 3 Volt. Structurally driven insulator-to-semi-metal transitions and size-dependent current regulation through single electron tunneling are demonstrated and examined with respect to the stereochemical and electronic structure of the molecular entities. This extends the value of self-assembly as a tool for correlation length and electronic properties tuning and demonstrate POM hyperstructures' plausibility for on-chip molecular electronics operative at room temperature.

The research of single intersection sensor signal control based on section data

NASA Astrophysics Data System (ADS)

Liu, Yunxiang; Huang, Yue; Wang, Hao

2016-12-01

Propose a sensing signal intersection control design electronic license based on the design by setting the intersection readers to interact with active electronic tags equipped vehicles, vehicle information obtained on the road section. In the vehicle detection sensor may control the green density as evaluation criteria are extended when the vehicle is higher than the threshold, the green density continuity, whereas the switching phases. Induction showed improved control strategy can achieve real-time traffic signal control effectively in high saturation intersection, to overcome the traditional sensor control failure at high saturation drawbacks and improve the utilization of urban Intersection comparative analysis by simulation.

Development of the Internet-Enabled System for Exercise Telerehabilitation and Cardiovascular Training.

PubMed

Dedov, Vadim N; Dedova, Irina V

2015-07-01

Sustained exercise training could significantly improve patient rehabilitation and management of noncommunicable diseases in the community. This study aimed to develop a universal telecare system for delivery of exercise rehabilitation and cardiovascular training services at home. An innovative bilateral leg training device was equipped with an electronic system for the ongoing measurement of training activities with the device. A single-item parameter reflecting the intensity of training was monitored using several modern telecommunication technologies. According to the application protocol, eight volunteers first tried the device for 30-60 min to determine their personal training capacity. Then, they were provided with equipment to use at home for 4 weeks. Adherence to daily training was assessed by the number of training days per week, training intensity, and duration of training sessions. The system provided reliable recording of training activities with the device using (1) long-term data logging without an ongoing connection to the computer, (2) wireless monitoring and recording of training activities on a stand-alone computer, and (3) a secure cloud-based monitoring over the Internet connection using electronic devices, including smartphones. Overall analysis of recordings and phone feedbacks to participants took only approximately 5 h for the duration of study. This study, although of a pilot nature, described the comprehensive exercise telerehabilitation system integrating mobile training equipment with personalized training protocols and remote monitoring. A single-item electronic parameter of the system usage facilitated time-effective data management. Wireless connection allowed various locations of device application and several monitoring arrangements ranging from real-time monitoring to long-term recording of exercise activities. A cloud-based software platform enabled management of multiple users at distance. Implementation of this model may facilitate both accessibility and availability of personalized exercise telerehabilitation services. Further studies would validate it in the clinical and healthcare environment.

Faster Electron Injection and More Active Sites for Efficient Photocatalytic H2 Evolution in g-C3 N4 /MoS2 Hybrid.

PubMed

Shi, Xiaowei; Fujitsuka, Mamoru; Kim, Sooyeon; Majima, Tetsuro

2018-03-01

Herein, the structural effect of MoS 2 as a cocatalyst of photocatalytic H 2 generation activity of g-C 3 N 4 under visible light irradiation is studied. By using single-particle photoluminescence (PL) and femtosecond time-resolved transient absorption spectroscopies, charge transfer kinetics between g-C 3 N 4 and two kinds of nanostructured MoS 2 (nanodot and monolayer) are systematically investigated. Single-particle PL results show the emission of g-C 3 N 4 is quenched by MoS 2 nanodots more effectively than MoS 2 monolayers. Electron injection rate and efficiency of g-C 3 N 4 /MoS 2 -nanodot hybrid are calculated to be 5.96 × 10 9 s -1 and 73.3%, respectively, from transient absorption spectral measurement, which are 4.8 times faster and 2.0 times higher than those of g-C 3 N 4 /MoS 2 -monolayer hybrid. Stronger intimate junction between MoS 2 nanodots and g-C 3 N 4 is suggested to be responsible for faster and more efficient electron injection. In addition, more unsaturated terminal sulfur atoms can serve as the active site in MoS 2 nanodot compared with MoS 2 monolayer. Therefore, g-C 3 N 4 /MoS 2 nanodot exhibits a 7.9 times higher photocatalytic activity for H 2 evolution (660 µmol g- 1 h -1 ) than g-C 3 N 4 /MoS 2 monolayer (83.8 µmol g -1 h -1 ). This work provides deep insight into charge transfer between g-C 3 N 4 and nanostructured MoS 2 cocatalysts, which can open a new avenue for more rationally designing MoS 2 -based catalysts for H 2 evolution. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Optical impedance spectroscopy with single-mode electro-active-integrated optical waveguides.

PubMed

Han, Xue; Mendes, Sergio B

2014-02-04

An optical impedance spectroscopy (OIS) technique based on a single-mode electro-active-integrated optical waveguide (EA-IOW) was developed to investigate electron-transfer processes of redox adsorbates. A highly sensitive single-mode EA-IOW device was used to optically follow the time-dependent faradaic current originated from a submonolayer of cytochrome c undergoing redox exchanges driven by a harmonic modulation of the electric potential at several dc bias potentials and at several frequencies. To properly retrieve the faradaic current density from the ac-modulated optical signal, we introduce here a mathematical formalism that (i) accounts for intrinsic changes that invariably occur in the optical baseline of the EA-IOW device during potential modulation and (ii) provides accurate results for the electro-chemical parameters. We are able to optically reconstruct the faradaic current density profile against the dc bias potential in the working electrode, identify the formal potential, and determine the energy-width of the electron-transfer process. In addition, by combining the optically reconstructed faradaic signal with simple electrical measurements of impedance across the whole electrochemical cell and the capacitance of the electric double-layer, we are able to determine the time-constant connected to the redox reaction of the adsorbed protein assembly. For cytochrome c directly immobilized onto the indium tin oxide (ITO) surface, we measured a reaction rate constant of 26.5 s(-1). Finally, we calculate the charge-transfer resistance and pseudocapacitance associated with the electron-transfer process and show that the frequency dependence of the redox reaction of the protein submonolayer follows as expected the electrical equivalent of an RC-series admittance diagram. Above all, we show here that OIS with single-mode EA-IOW's provide strong analytical signals that can be readily monitored even for small surface-densities of species involved in the redox process (e.g., fmol/cm(2), 0.1% of a full protein monolayer). This experimental approach, when combined with the analytical formalism described here, brings additional sensitivity, accuracy, and simplicity to electro-chemical analysis and is expected to become a useful tool in investigations of redox processes.

Experimental determination of the elastic cotunneling rate in a hybrid single-electron box

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sun, Chia-Heng; Tai, Po-Chen; Chen, Yung-Fu, E-mail: yfuchen@ncu.edu.tw

2014-06-09

We report measurements of charge configurations and charge transfer dynamics in a hybrid single-electron box composed of aluminum and copper. We used two single-electron transistors (SETs) to simultaneously read out different parts of the box, enabling us to map out stability diagrams of the box and identify various charge transfer processes in the box. We further characterized the elastic cotunneling in the box, which is an important source of error in electron turnstiles consisting of hybrid SETs, and found that the rate was as low as 1 Hz at degeneracy and compatible with theoretical estimates for electron tunneling via virtual statesmore » in the central superconducting island of the box.« less

Bogolon-mediated electron capture by impurities in hybrid Bose-Fermi systems

NASA Astrophysics Data System (ADS)

Boev, M. V.; Kovalev, V. M.; Savenko, I. G.

2018-04-01

We investigate the processes of electron capture by a Coulomb impurity center residing in a hybrid system consisting of spatially separated two-dimensional layers of electron and Bose-condensed dipolar exciton gases coupled via the Coulomb forces. We calculate the probability of the electron capture accompanied by the emission of a single Bogoliubov excitation (bogolon), similar to regular phonon-mediated scattering in solids. Furthermore, we study the electron capture mediated by the emission of a pair of bogolons in a single capture event and show that these processes not only should be treated in the same order of the perturbation theory, but also they give a more important contribution than single-bogolon-mediated capture, in contrast with regular phonon scattering.

Structure analysis of the single-domain Si(111)4 × 1-In surface by μ-probe Auger electron diffraction and μ-probe reflection high energy electron diffraction

NASA Astrophysics Data System (ADS)

Nakamura, N.; Anno, K.; Kono, S.

1991-10-01

A single-domain Si(111)4 × 1-In surface has been studied by μ-probe reflection high-energy electron diffraction (RHEED) to elucidate the symmetry of the 4 × 1 surface. Azimuthal diffraction patterns of In MNN Auger electron have been obtained by a μ-probe Auger electron diffraction (AED) apparatus from the single-domain Si(111)4 × 1-In surface. On the basis of information from scanning tunneling microscopy [J. Microsc. 152 (1988) 727] and under the assumption that the 4 × 1 surface is composed of In-overlayers, the μ-probe AED patterns were kinematically analyzed to reach a concrete model of indium arrangement.

Demonstration of Single-Shot Picosecond Time-Resolved MeV Electron Imaging Using a Compact Permanent Magnet Quadrupole Based Lens.

PubMed

Cesar, D; Maxson, J; Musumeci, P; Sun, Y; Harrison, J; Frigola, P; O'Shea, F H; To, H; Alesini, D; Li, R K

2016-07-08

We present the results of an experiment where a short focal length (∼1.3  cm), permanent magnet electron lens is used to image micron-size features (of a metal sample) with a single shot from an ultrahigh brightness picosecond-long 4 MeV electron beam emitted by a radio-frequency photoinjector. Magnification ratios in excess of 30× were obtained using a triplet of compact, small gap (3.5 mm), Halbach-style permanent magnet quadrupoles with nearly 600  T/m field gradients. These results pave the way towards single-shot time-resolved electron microscopy and open new opportunities in the applications of high brightness electron beams.

Fabrication of Tunnel Junctions For Direct Detector Arrays With Single-Electron Transistor Readout Using Electron-Beam Lithography

NASA Technical Reports Server (NTRS)

Stevenson, T. R.; Hsieh, W.-T.; Li, M. J.; Stahle, C. M.; Rhee, K. W.; Teufel, J.; Schoelkopf, R. J.

2002-01-01

This paper will describe the fabrication of small aluminum tunnel junctions for applications in astronomy. Antenna-coupled superconducting tunnel junctions with integrated single-electron transistor readout have the potential for photon-counting sensitivity at sub-millimeter wavelengths. The junctions for the detector and single-electron transistor can be made with electron-beam lithography and a standard self-aligned double-angle deposition process. However, high yield and uniformity of the junctions is required for large-format detector arrays. This paper will describe how measurement and modification of the sensitivity ratio in the resist bilayer was used to greatly improve the reliability of forming devices with uniform, sub-micron size, low-leakage junctions.

Maxwell's demons realized in electronic circuits

NASA Astrophysics Data System (ADS)

Koski, Jonne V.; Pekola, Jukka P.

2016-12-01

We review recent progress in making the former gedanken experiments of Maxwell's demon [1] into real experiments in a lab. In particular, we focus on realizations based on single-electron tunneling in electronic circuits. We first present how stochastic thermodynamics can be investigated in these circuits. Next we review recent experiments on an electron-based Szilard engine. Finally, we report on experiments on single-electron tunneling-based cooling, overviewing the recent realization of a Coulomb gap refrigerator, as well as an autonomous Maxwell's demon.

Photo-activation of Single Molecule Magnet Behavior in a Manganese-based Complex

NASA Astrophysics Data System (ADS)

Fetoh, Ahmed; Cosquer, Goulven; Morimoto, Masakazu; Irie, Masahiro; El-Gammal, Ola; El-Reash, Gaber Abu; Breedlove, Brian K.; Yamashita, Masahiro

2016-03-01

A major roadblock to fully realizing molecular electronic devices is the ability to control the properties of each molecule in the device. Herein we report the control of the magnetic properties of single-molecule magnets (SMMs), which can be used in memory devices, by using a photo-isomerizable diarthylenthene ligand. Photo-isomerization of the diarylethene ligand bridging two manganese salen complexes with visible light caused a significant change in the SMM behavior due to opening of the six-membered ring of diarylethene ligand, accompanied by reorganization of the entire molecule. The ring-opening activated the frequency-dependent magnetization of the complex. Our results are a major step towards the realization of molecular memory devices composed of SMMs because the SMM behaviour can be turned on and off simply by irradiating the molecule.

The electronic structures and work functions of (100) surface of typical binary and doped REB6 single crystals

NASA Astrophysics Data System (ADS)

Liu, Hongliang; Zhang, Xin; Xiao, Yixin; Zhang, Jiuxing

2018-03-01

The density function theory been used to calculate the electronic structures of binary and doped rare earth hexaborides (REB6), which exhibits the large density of states (DOS) near Fermi level. The d orbital elections of RE element contribute the electronic states of election emission near the Fermi level, which imply that the REB6 (RE = La, Ce, Gd) with wide distribution of high density d orbital electrons could provide a lower work function and excellent emission properties. Doping RE elements into binary REB6 can adjust DOS and the position of the Fermi energy level. The calculated work functions of considered REB6 (100) surface show that the REB6 (RE = La, Ce, Gd) have lower work function and doping RE elements with active d orbital electrons can significantly reduce work function of binary REB6. The thermionic emission test results are basically accordant with the calculated value, proving the first principles calculation could provide a good theoretical guidance for the study of electron emission properties of REB6.

Bio-integrated electronics and sensor systems

NASA Astrophysics Data System (ADS)

Yeo, Woon-Hong; Webb, R. Chad; Lee, Woosik; Jung, Sungyoung; Rogers, John A.

2013-05-01

Skin-mounted epidermal electronics, a strategy for bio-integrated electronics, provide an avenue to non-invasive monitoring of clinically relevant physiological signals for healthcare applications. Current conventional systems consist of single-point sensors fastened to the skin with adhesives, and sometimes with conducting gels, which limits their use outside of clinical settings due to loss of adhesion and irritation to the user. In order to facilitate extended use of skin-mounted healthcare sensors without disrupting everyday life, we envision electronic monitoring systems that integrate seamlessly with the skin below the notice of the user. This manuscript reviews recent significant results towards our goal of wearable electronic sensor systems for long-term monitoring of physiological signals. Ultra-thin epidermal electronic systems (EES) are demonstrated for extended use on the skin, in a conformal manner, including during everyday bathing and sleeping activities. We describe the assessment of clinically relevant physiological parameters, such as electrocardiograms (ECG), electromyograms (EMG), electroencephalograms (EEG), temperature, mechanical strain and thermal conductivity, using examples of multifunctional EES devices. Additionally, we demonstrate capability for real life application of EES by monitoring the system functionality, which has no discernible change, during cyclic fatigue testing.

Low-energy electron-impact single ionization of helium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Colgan, J.; Pindzola, M. S.; Childers, G.

2006-04-15

A study is made of low-energy electron-impact single ionization of ground-state helium. The time-dependent close-coupling method is used to calculate total integral, single differential, double differential, and triple differential ionization cross sections for impact electron energies ranging from 32 to 45 eV. For all quantities, the calculated cross sections are found to be in very good agreement with experiment, and for the triple differential cross sections, good agreement is also found with calculations made using the convergent close-coupling technique.

Resonant scattering of energetic electrons in the outer radiation belt by HAARP-induced ELF/VLF waves

NASA Astrophysics Data System (ADS)

Chang, Shanshan; Zhu, Zhengping; Ni, Binbin; Cao, Xing; Luo, Weihua

2016-10-01

Several extremely low-frequency (ELF)/very low-frequency (VLF) wave generation experiments have been performed successfully at High-Frequency Active Auroral Research Program (HAARP) heating facility and the artificial ELF/VLF signals can leak into the outer radiation belt and contribute to resonant interactions with energetic electrons. Based on the artificial wave properties revealed by many of in situ observations, we implement test particle simulations to evaluate the effects of energetic electron resonant scattering driven by the HAARP-induced ELF/VLF waves. The results indicate that for both single-frequency/monotonic wave and multi-frequency/broadband waves, the behavior of each electron is stochastic while the averaged diffusion effect exhibits temporal linearity in the wave-particle interaction process. The computed local diffusion coefficients show that, the local pitch-angle scattering due to HARRP-induced single-frequency ELF/VLF whistlers with an amplitude of ∼10 pT can be intense near the loss cone with a rate of ∼10-2 rad2 s-1, suggesting the feasibility of HAARP-induced ELF/VLF waves for removal of outer radiation belt energetic electrons. In contrast, the energy diffusion of energetic electrons is relatively weak, which confirms that pitch-angle scattering by artificial ELF/VLF waves can dominantly lead to the precipitation of energetic electrons. Moreover, diffusion rates of the discrete, broadband waves, with the same amplitude of each discrete frequency as the monotonic waves, can be much larger, which suggests that it is feasible to trigger a reasonable broadband wave instead of the monotonic wave to achieve better performance of controlled precipitation of energetic electrons. Moreover, our test particle scattering simulation show good agreement with the predictions of the quasi-linear theory, confirming that both methods are applied to evaluate the effects of resonant interactions between radiation belt electrons and artificially generated discrete ELF/VLF waves.

Charge Transport Processes in Molecular Junctions

NASA Astrophysics Data System (ADS)

Smith, Christopher Eugene

Molecular electronics (ME) has evolved into a rich area of exploration that combines the fields of chemistry, materials, electronic engineering and computational modeling to explore the physics behind electronic conduction at the molecular level. Through studying charge transport properties of single molecules and nanoscale molecular materials the field has gained the potential to bring about new avenues for the miniaturization of electrical components where quantum phenomena are utilized to achieve solid state molecular device functionality. Molecular junctions are platforms that enable these studies and consist of a single molecule or a small group of molecules directly connected to electrodes. The work presented in this thesis has built upon the current understanding of the mechanisms of charge transport in ordered junctions using self-assembled monolayer (SAM) molecular thin films. Donor and acceptor compounds were synthesized and incorporated into SAMs grown on metal substrates then the transport properties were measured with conducting probe atomic force microscopy (CP-AFM). In addition to experimentally measured current-voltage (I-V) curves, the transport properties were addressed computationally and modeled theoretically. The key objectives of this project were to 1) investigate the impact of molecular structure on hole and electron charge transport, 2) understand the nature of the charge carriers and their structure-transport properties through long (<4 nm) conjugated molecular wires, and 3) quantitatively extract interfacial properties characteristic to macroscopic junctions, such as energy level alignment and molecule-contact electronic coupling from experimental I-V curves. Here, we lay ground work for creating a more complete picture of charge transport in macroscopically ordered molecular junctions of controlled architecture, length and charge carrier. The polaronic nature of hopping transport has been predicted in long, conjugated molecular wires. Using quantum-based calculations, we modeled 'p-type' polaron transport through oligophenylenethiophene (OPTI) wires and assigned transport activation energies to specific modes of nuclear motion. We also show control over 'n-type', LUMO-mediated transport in short ( 2 nm) redox-active perylenediimide (PDI) SAMs bound to contacts through isocyano linkers. By changing the contact work function (φ) and temperature, we were able to verify thermally-assisted LUMO transport. Transition voltage spectroscopy and the single level model was employed to fit the experimental I-V curves and extract the electronic coupling (epsilon) and the EF-LUMO offset (epsilonl). It was found that epsilonl does not change with φ (LUMO pinning), while Gamma changes with both φ and temperature. Further, the PDI SAMs could be reversibly chemically gated to modulate the transport. These results help advance our understanding of transport behavior in semiconducting molecular thin films, and open opportunities to engineer improved electronic functionality into molecular devices.

Single electron relativistic clock interferometer

NASA Astrophysics Data System (ADS)

Bushev, P. A.; Cole, J. H.; Sholokhov, D.; Kukharchyk, N.; Zych, M.

2016-09-01

Although time is one of the fundamental notions in physics, it does not have a unique description. In quantum theory time is a parameter ordering the succession of the probability amplitudes of a quantum system, while according to relativity theory each system experiences in general a different proper time, depending on the system's world line, due to time dilation. It is therefore of fundamental interest to test the notion of time in the regime where both quantum and relativistic effects play a role, for example, when different amplitudes of a single quantum clock experience different magnitudes of time dilation. Here we propose a realization of such an experiment with a single electron in a Penning trap. The clock can be implemented in the electronic spin precession and its time dilation then depends on the radial (cyclotron) state of the electron. We show that coherent manipulation and detection of the electron can be achieved already with present day technology. A single electron in a Penning trap is a technologically ready platform where the notion of time can be probed in a hitherto untested regime, where it requires a relativistic as well as quantum description.

Nuclear-driven electron spin rotations in a coupled silicon quantum dot and single donor system

NASA Astrophysics Data System (ADS)

Harvey-Collard, Patrick; Jacobson, Noah Tobias; Rudolph, Martin; Ten Eyck, Gregory A.; Wendt, Joel R.; Pluym, Tammy; Lilly, Michael P.; Pioro-Ladrière, Michel; Carroll, Malcolm S.

Single donors in silicon are very good qubits. However, a central challenge is to couple them to one another. To achieve this, many proposals rely on using a nearby quantum dot (QD) to mediate an interaction. In this work, we demonstrate the coherent coupling of electron spins between a single 31P donor and an enriched 28Si metal-oxide-semiconductor few-electron QD. We show that the electron-nuclear spin interaction can drive coherent rotations between singlet and triplet electron spin states. Moreover, we are able to tune electrically the exchange interaction between the QD and donor electrons. The combination of single-nucleus-driven rotations and voltage-tunable exchange provides all elements for future all-electrical control of a spin qubit, and requires only a single dot and no additional magnetic field gradients. This work was performed, in part, at the Center for Integrated Nanotechnologies, an Office of Science User Facility operated for the U.S. Department of Energy (DOE) Office of Science. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. DOE's National Nuclear Security Administration under Contract DE-AC04-94AL85000.

Defects induced in cerium dioxide single crystals by electron irradiation

DOE PAGES

Costantini, Jean-Marc; Miro, Sandrine; Touati, Nadia; ...

2018-01-12

In this work, Micro-Raman spectroscopy, X-band electron paramagnetic resonance (EPR) spectroscopy, and UV-visible optical absorption spectroscopy were used to study the damage production in cerium dioxide (CeO 2) single crystals by electron irradiation for three energies (1.0, 1.4, and 2.5 MeV). The Raman-active T 2g peak was left unchanged after 2.5-MeV electron irradiation at a high fluence. This shows that no structural modifications occurred for the cubic fluorite structure. UV-visible optical absorption spectra exhibited a characteristic sub band-gap tail for 1.4-MeV and 2.5-MeV energies, but not for 1.0 MeV. Narrow EPR lines were recorded near liquid-helium temperature after 2.5-MeV electronmore » irradiation; whereas no such signal was found for the virgin un-irradiated crystal or after 1.0-MeV irradiation for the same fluence. The angular variation of these lines in the {111} plane revealed a weak g-factor anisotropy assigned to Ce 3+ ions (with the 4f 1 configuration) in a high-symmetry local environment. Finally, it is concluded that Ce 3+ ions may be produced by a reduction resulting from the displacement damage process. However, no evidence of F + or F 0 center or hole center formation due to irradiation was found from the present EPR and optical absorption spectra.« less

Defects induced in cerium dioxide single crystals by electron irradiation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Costantini, Jean-Marc; Miro, Sandrine; Touati, Nadia

In this work, Micro-Raman spectroscopy, X-band electron paramagnetic resonance (EPR) spectroscopy, and UV-visible optical absorption spectroscopy were used to study the damage production in cerium dioxide (CeO 2) single crystals by electron irradiation for three energies (1.0, 1.4, and 2.5 MeV). The Raman-active T 2g peak was left unchanged after 2.5-MeV electron irradiation at a high fluence. This shows that no structural modifications occurred for the cubic fluorite structure. UV-visible optical absorption spectra exhibited a characteristic sub band-gap tail for 1.4-MeV and 2.5-MeV energies, but not for 1.0 MeV. Narrow EPR lines were recorded near liquid-helium temperature after 2.5-MeV electronmore » irradiation; whereas no such signal was found for the virgin un-irradiated crystal or after 1.0-MeV irradiation for the same fluence. The angular variation of these lines in the {111} plane revealed a weak g-factor anisotropy assigned to Ce 3+ ions (with the 4f 1 configuration) in a high-symmetry local environment. Finally, it is concluded that Ce 3+ ions may be produced by a reduction resulting from the displacement damage process. However, no evidence of F + or F 0 center or hole center formation due to irradiation was found from the present EPR and optical absorption spectra.« less

Single-Molecule Bioelectronics

PubMed Central

Rosenstein, Jacob K.; Lemay, Serge G.; Shepard, Kenneth L.

2014-01-01

Experimental techniques which interface single biomolecules directly with microelectronic systems are increasingly being used in a wide range of powerful applications, from fundamental studies of biomolecules to ultra-sensitive assays. Here we review several technologies which can perform electronic measurements of single molecules in solution: ion channels, nanopore sensors, carbon nanotube field-effect transistors, electron tunneling gaps, and redox cycling. We discuss the shared features among these techniques that enable them to resolve individual molecules, and discuss their limitations. Recordings from each of these methods all rely on similar electronic instrumentation, and we discuss the relevant circuit implementations and potential for scaling these single-molecule bioelectronic interfaces to high-throughput arrayed sensing platforms. PMID:25529538

Electron paramagnetic resonance study of radiation-induced paramagnetic centers in succinic anhydride single crystal

NASA Astrophysics Data System (ADS)

Caliskan, Betul; Caliskan, Ali Cengiz; Er, Emine

2017-09-01

Succinic anhydride single crystals were exposed to 60Co-gamma irradiation at room temperature. The irradiated single crystals were investigated at 125 K by Electron Paramagnetic Resonance (EPR) Spectroscopy. The investigation of EPR spectra of irradiated single crystals of succinic anhydride showed the presence of two succinic anhydride anion radicals. The anion radicals observed in gamma-irradiated succinic anhydride single crystal were created by the scission of the carbon-oxygen double bond. The structure of EPR spectra demonstrated that the hyperfine splittings arise from the same radical species. The reduction of succinic anhydride was identified which is formed by the addition of an electron to oxygen of the Csbnd O bond. The g values, the hyperfine structure constants and direction cosines of the radiation damage centers observed in succinic anhydride single crystal were obtained.

Structural changes induced by lattice-electron interactions: SiO2 stishovite and FeTiO3 ilmenite.

PubMed

Yamanaka, Takamitsu

2005-09-01

The bright source and highly collimated beam of synchrotron radiation offers many advantages for single-crystal structure analysis under non-ambient conditions. The structure changes induced by the lattice-electron interaction under high pressure have been investigated using a diamond anvil pressure cell. The pressure dependence of electron density distributions around atoms is elucidated by a single-crystal diffraction study using deformation electron density analysis and the maximum entropy method. In order to understand the bonding electrons under pressure, diffraction intensity measurements of FeTiO3 ilmenite and gamma-SiO2 stishovite single crystals at high pressures were made using synchrotron radiation. Both diffraction studies describe the electron density distribution including bonding electrons and provide the effective charge of the cations. In both cases the valence electrons are more localized around the cations with increasing pressure. This is consistent with molecular orbital calculations, proving that the bonding electron density becomes smaller with pressure. The thermal displacement parameters of both samples are reduced with increasing pressure.

One-Pot Solvothermal in Situ Growth of 1D Single-Crystalline NiSe on Ni Foil as Efficient and Stable Transparent Conductive Oxide Free Counter Electrodes for Dye-Sensitized Solar Cells.

PubMed

Bao, Chao; Li, Faxin; Wang, Jiali; Sun, Panpan; Huang, Niu; Sun, Yihua; Fang, Liang; Wang, Lei; Sun, Xiaohua

2016-12-07

One-dimensional single-crystal nanostructural nickel selenides were successfully in situ grown on metal nickel foils by two simple one-step solvothermal methods, which formed NiSe/Ni counter electrodes (CEs) for dye-sensitized solar cells (DSSCs). The nickel foil acted as the nickel source in the reaction process, a supporting substrate, and an electron transport "speedway". Electrochemical testing indicated that the top 1D single-crystal NiSe exhibited prominent electrocatalytic activity for I 3 - reduction. Due to the metallic conductivity of Ni substrate and the outstanding electrocatalytic activity of single-crystal NiSe, the DSSC based on a NiSe/Ni CE exhibited higher fill factor (FF) and larger short-circuit current density (J sc ) than the DSSC based on Pt/FTO CE. The corresponding power conversion efficiency (6.75%) outperformed that of the latter (6.18%). Moreover, the NiSe/Ni CEs also showed excellent electrochemical stability in the I - /I 3 - redox electrolyte. These findings indicated that single-crystal NiSe in situ grown on Ni substrate was a potential candidate to replace Pt/TCO as a cheap and highly efficient counter electrode of DSSC.

Co-adsorption of Trichloroethylene and Arsenate by Iron-Impregnated Granular Activated Carbon.

PubMed

Deng, Baolin; Kim, Eun-Sik

2016-05-01

Co-adsorption of trichloroethylene (TCE) and arsenate [As(V)] was investigated using modified granular activated carbons (GAC): untreated, sodium hypochlorite-treated (NaClO-GAC), and NaClO with iron-treated GAC (NaClO/Fe-GAC). Batch experiments of single- [TCE or As(V)] and binary- [TCE and As(V)] components solutions are evaluated through Langmuir and Freundlich isotherm models and adsorption kinetic tests. In the single-component system, the adsorption capacity of As(V) was increased by the NaClO-GAC and the NaClO/Fe-GAC. The untreated GAC showed a low adsorption capacity for As(V). Adsorption of TCE by the NaClO/Fe-GAC was maximized, with an increased Freundlich constant. Removal of TCE in the binary-component system was decreased 15% by the untreated GAC, and NaClO- and NaClO/Fe-GAC showed similar efficiency to the single-component system because of the different chemical status of the GAC surfaces. Results of the adsorption isotherms of As(V) in the binary-component system were similar to adsorption isotherms of the single-component system. The adsorption affinities of single- and binary-component systems corresponded with electron transfer, competitive adsorption, and physicochemical properties.

A hierarchical nanostructure consisting of amorphous MnO 2, Mn 3O 4 nanocrystallites, and single-crystalline MnOOH nanowires for supercapacitors

NASA Astrophysics Data System (ADS)

Hu, Chi-Chang; Hung, Ching-Yun; Chang, Kuo-Hsin; Yang, Yi-Lin

In this communication, a porous hierarchical nanostructure consisting of amorphous MnO 2 (a-MnO 2), Mn 3O 4 nanocrystals, and single-crystalline MnOOH nanowires is designed for the supercapacitor application, which is prepared by a simple two-step electrochemical deposition process. Because of the gradual co-transformation of Mn 3O 4 nanocrystals and a-MnO 2 nanorods into an amorphous manganese oxide, the cycle stability of a-MnO 2 is obviously enhanced by adding Mn 3O 4. This unique ternary oxide nanocomposite with 100-cycle CV activation exhibits excellent capacitive performances, i.e., excellent reversibility, high specific capacitances (470 F g -1 in CaCl 2), high power property, and outstanding cycle stability. The highly porous microstructures of this composite before and after the 10,000-cycle CV test are examined by means of scanning electron microscopy (SEM) and transmission electron microscopy (TEM).

Single walled carbon nanotube-based stochastic resonance device with molecular self-noise source

NASA Astrophysics Data System (ADS)

Fujii, Hayato; Setiadi, Agung; Kuwahara, Yuji; Akai-Kasaya, Megumi

2017-09-01

Stochastic resonance (SR) is an intrinsic noise usage system for small-signal sensing found in various living creatures. The noise-enhanced signal transmission and detection system, which is probabilistic but consumes low power, has not been used in modern electronics. We demonstrated SR in a summing network based on a single-walled carbon nanotube (SWNT) device that detects small subthreshold signals with very low current flow. The nonlinear current-voltage characteristics of this SWNT device, which incorporated Cr electrodes, were used as the threshold level of signal detection. The adsorption of redox-active polyoxometalate molecules on SWNTs generated additional noise, which was utilized as a self-noise source. To form a summing network SR device, a large number of SWNTs were aligned parallel to each other between the electrodes, which increased the signal detection ability. The functional capabilities of the present small-size summing network SR device, which rely on dense nanomaterials and exploit intrinsic spontaneous noise at room temperature, offer a glimpse of future bio-inspired electronic devices.

Structural behavior of Tl-exchanged natrolite at high pressure depending on the composition of pressure-transmitting medium

NASA Astrophysics Data System (ADS)

Seryotkin, Yu. V.; Bakakin, V. V.; Likhacheva, A. Yu.; Dementiev, S. N.; Rashchenko, S. V.

2017-10-01

The structural evolution of Tl-exchanged natrolite with idealized formula Tl2[Al2Si3O10]·2H2O, compressed in penetrating (water:ethanol 1:1) and non-penetrating (paraffin) media, was studied up to 4 GPa. The presence of Tl+ with non-bonded electron lone pairs, which can be either stereo-chemically active or passive, determines distinctive features of the high-pressure behavior of the Tl-form. The effective volume of assemblages Tl+(O,H2O) n depends on the E-pairs activity: single-sided coordination correlates with smaller volumes. At ambient conditions, there are two types of Tl positions, only one of them having a nearly single-sided coordination as a characteristic of stereo-activity of the Tl+ E pair. Upon the compression in paraffin, a phase transition occurs: a 5% volume contraction of flexible natrolite framework is accompanied by the conversion of all the Tl+ cations into stereo-chemically active state with a single-sided coordination. This effect requires the reconstruction of all the extra-framework subsystems with the inversion of the cation and H2O positions. The compression in water-containing medium leads to the increase of H2O content up to three molecules pfu through the filling of partly vacant positions. This hinders a single-sided coordination of Tl ions and preserves the configuration of their ion-molecular subsystem. It is likely that the extra-framework subsystem is responsible for the super-structure modulation.

Fully Screen-Printed, Large-Area, and Flexible Active-Matrix Electrochromic Displays Using Carbon Nanotube Thin-Film Transistors.

PubMed

Cao, Xuan; Lau, Christian; Liu, Yihang; Wu, Fanqi; Gui, Hui; Liu, Qingzhou; Ma, Yuqiang; Wan, Haochuan; Amer, Moh R; Zhou, Chongwu

2016-11-22

Semiconducting single-wall carbon nanotubes are ideal semiconductors for printed electronics due to their advantageous electrical and mechanical properties, intrinsic printability in solution, and desirable stability in air. However, fully printed, large-area, high-performance, and flexible carbon nanotube active-matrix backplanes are still difficult to realize for future displays and sensing applications. Here, we report fully screen-printed active-matrix electrochromic displays employing carbon nanotube thin-film transistors. Our fully printed backplane shows high electrical performance with mobility of 3.92 ± 1.08 cm 2 V -1 s -1 , on-off current ratio I on /I off ∼ 10 4 , and good uniformity. The printed backplane was then monolithically integrated with an array of printed electrochromic pixels, resulting in an entirely screen-printed active-matrix electrochromic display (AMECD) with good switching characteristics, facile manufacturing, and long-term stability. Overall, our fully screen-printed AMECD is promising for the mass production of large-area and low-cost flexible displays for applications such as disposable tags, medical electronics, and smart home appliances.

Arc-melting preparation of single crystal LaB.sub.6 cathodes

DOEpatents

Gibson, Edwin D.; Verhoeven, John D.

1977-06-21

A method for preparing single crystals of lanthanum hexaboride (LaB.sub.6) by arc melting a rod of compacted LaB.sub.6 powder. The method is especially suitable for preparing single crystal LaB.sub.6 cathodes for use in scanning electron microscopes (SEM) and scanning transmission electron microscopes (STEM).

Single gate p-n junctions in graphene-ferroelectric devices

NASA Astrophysics Data System (ADS)

Hinnefeld, J. Henry; Xu, Ruijuan; Rogers, Steven; Pandya, Shishir; Shim, Moonsub; Martin, Lane W.; Mason, Nadya

2016-05-01

Graphene's linear dispersion relation and the attendant implications for bipolar electronics applications have motivated a range of experimental efforts aimed at producing p-n junctions in graphene. Here we report electrical transport measurements of graphene p-n junctions formed via simple modifications to a PbZr0.2Ti0.8O3 substrate, combined with a self-assembled layer of ambient environmental dopants. We show that the substrate configuration controls the local doping region, and that the p-n junction behavior can be controlled with a single gate. Finally, we show that the ferroelectric substrate induces a hysteresis in the environmental doping which can be utilized to activate and deactivate the doping, yielding an "on-demand" p-n junction in graphene controlled by a single, universal backgate.

Genomic, proteomic, and biochemical analysis of the organohalide respiratory pathway in Desulfitobacterium dehalogenans.

PubMed

Kruse, Thomas; van de Pas, Bram A; Atteia, Ariane; Krab, Klaas; Hagen, Wilfred R; Goodwin, Lynne; Chain, Patrick; Boeren, Sjef; Maphosa, Farai; Schraa, Gosse; de Vos, Willem M; van der Oost, John; Smidt, Hauke; Stams, Alfons J M

2015-03-01

Desulfitobacterium dehalogenans is able to grow by organohalide respiration using 3-chloro-4-hydroxyphenyl acetate (Cl-OHPA) as an electron acceptor. We used a combination of genome sequencing, biochemical analysis of redox active components, and shotgun proteomics to study elements of the organohalide respiratory electron transport chain. The genome of Desulfitobacterium dehalogenans JW/IU-DC1(T) consists of a single circular chromosome of 4,321,753 bp with a GC content of 44.97%. The genome contains 4,252 genes, including six rRNA operons and six predicted reductive dehalogenases. One of the reductive dehalogenases, CprA, is encoded by a well-characterized cprTKZEBACD gene cluster. Redox active components were identified in concentrated suspensions of cells grown on formate and Cl-OHPA or formate and fumarate, using electron paramagnetic resonance (EPR), visible spectroscopy, and high-performance liquid chromatography (HPLC) analysis of membrane extracts. In cell suspensions, these components were reduced upon addition of formate and oxidized after addition of Cl-OHPA, indicating involvement in organohalide respiration. Genome analysis revealed genes that likely encode the identified components of the electron transport chain from formate to fumarate or Cl-OHPA. Data presented here suggest that the first part of the electron transport chain from formate to fumarate or Cl-OHPA is shared. Electrons are channeled from an outward-facing formate dehydrogenase via menaquinones to a fumarate reductase located at the cytoplasmic face of the membrane. When Cl-OHPA is the terminal electron acceptor, electrons are transferred from menaquinones to outward-facing CprA, via an as-yet-unidentified membrane complex, and potentially an extracellular flavoprotein acting as an electron shuttle between the quinol dehydrogenase membrane complex and CprA. Copyright © 2015, American Society for Microbiology. All Rights Reserved.

Genomic, Proteomic, and Biochemical Analysis of the Organohalide Respiratory Pathway in Desulfitobacterium dehalogenans

PubMed Central

van de Pas, Bram A.; Atteia, Ariane; Krab, Klaas; Hagen, Wilfred R.; Goodwin, Lynne; Chain, Patrick; Boeren, Sjef; Maphosa, Farai; Schraa, Gosse; de Vos, Willem M.; van der Oost, John; Smidt, Hauke

2014-01-01

Desulfitobacterium dehalogenans is able to grow by organohalide respiration using 3-chloro-4-hydroxyphenyl acetate (Cl-OHPA) as an electron acceptor. We used a combination of genome sequencing, biochemical analysis of redox active components, and shotgun proteomics to study elements of the organohalide respiratory electron transport chain. The genome of Desulfitobacterium dehalogenans JW/IU-DC1T consists of a single circular chromosome of 4,321,753 bp with a GC content of 44.97%. The genome contains 4,252 genes, including six rRNA operons and six predicted reductive dehalogenases. One of the reductive dehalogenases, CprA, is encoded by a well-characterized cprTKZEBACD gene cluster. Redox active components were identified in concentrated suspensions of cells grown on formate and Cl-OHPA or formate and fumarate, using electron paramagnetic resonance (EPR), visible spectroscopy, and high-performance liquid chromatography (HPLC) analysis of membrane extracts. In cell suspensions, these components were reduced upon addition of formate and oxidized after addition of Cl-OHPA, indicating involvement in organohalide respiration. Genome analysis revealed genes that likely encode the identified components of the electron transport chain from formate to fumarate or Cl-OHPA. Data presented here suggest that the first part of the electron transport chain from formate to fumarate or Cl-OHPA is shared. Electrons are channeled from an outward-facing formate dehydrogenase via menaquinones to a fumarate reductase located at the cytoplasmic face of the membrane. When Cl-OHPA is the terminal electron acceptor, electrons are transferred from menaquinones to outward-facing CprA, via an as-yet-unidentified membrane complex, and potentially an extracellular flavoprotein acting as an electron shuttle between the quinol dehydrogenase membrane complex and CprA. PMID:25512312

Distinguishing the Roles of Thylakoid Respiratory Terminal Oxidases in the Cyanobacterium Synechocystis sp. PCC 6803.

PubMed

Ermakova, Maria; Huokko, Tuomas; Richaud, Pierre; Bersanini, Luca; Howe, Christopher J; Lea-Smith, David J; Peltier, Gilles; Allahverdiyeva, Yagut

2016-06-01

Various oxygen-utilizing electron sinks, including the soluble flavodiiron proteins (Flv1/3), and the membrane-localized respiratory terminal oxidases (RTOs), cytochrome c oxidase (Cox) and cytochrome bd quinol oxidase (Cyd), are present in the photosynthetic electron transfer chain of Synechocystis sp. PCC 6803. However, the role of individual RTOs and their relative importance compared with other electron sinks are poorly understood, particularly under light. Via membrane inlet mass spectrometry gas exchange, chlorophyll a fluorescence, P700 analysis, and inhibitor treatment of the wild type and various mutants deficient in RTOs, Flv1/3, and photosystem I, we investigated the contribution of these complexes to the alleviation of excess electrons in the photosynthetic chain. To our knowledge, for the first time, we demonstrated the activity of Cyd in oxygen uptake under light, although it was detected only upon inhibition of electron transfer at the cytochrome b6f site and in ∆flv1/3 under fluctuating light conditions, where linear electron transfer was drastically inhibited due to impaired photosystem I activity. Cox is mostly responsible for dark respiration and competes with P700 for electrons under high light. Only the ∆cox/cyd double mutant, but not single mutants, demonstrated a highly reduced plastoquinone pool in darkness and impaired gross oxygen evolution under light, indicating that thylakoid-based RTOs are able to compensate partially for each other. Thus, both electron sinks contribute to the alleviation of excess electrons under illumination: RTOs continue to function under light, operating on slower time ranges and on a limited scale, whereas Flv1/3 responds rapidly as a light-induced component and has greater capacity. © 2016 American Society of Plant Biologists. All Rights Reserved.

Dicopper(II) metallacyclophanes as multifunctional magnetic devices: a joint experimental and computational study.

PubMed

Castellano, María; Ruiz-García, Rafael; Cano, Joan; Ferrando-Soria, Jesús; Pardo, Emilio; Fortea-Pérez, Francisco R; Stiriba, Salah-Eddine; Julve, Miguel; Lloret, Francesc

2015-03-17

Metallosupramolecular complexes constitute an important advance in the emerging fields of molecular spintronics and quantum computation and a useful platform in the development of active components of spintronic circuits and quantum computers for applications in information processing and storage. The external control of chemical reactivity (electro- and photochemical) and physical properties (electronic and magnetic) in metallosupramolecular complexes is a current challenge in supramolecular coordination chemistry, which lies at the interface of several other supramolecular disciplines, including electro-, photo-, and magnetochemistry. The specific control of current flow or spin delocalization through a molecular assembly in response to one or many input signals leads to the concept of developing a molecule-based spintronics that can be viewed as a potential alternative to the classical molecule-based electronics. A great variety of factors can influence over these electronically or magnetically coupled, metallosupramolecular complexes in a reversible manner, electronic or photonic external stimuli being the most promising ones. The response ability of the metal centers and/or the organic bridging ligands to the application of an electric field or light irradiation, together with the geometrical features that allow the precise positioning in space of substituent groups, make these metal-organic systems particularly suitable to build highly integrated molecular spintronic circuits. In this Account, we describe the chemistry and physics of dinuclear copper(II) metallacyclophanes with oxamato-containing dinucleating ligands featuring redox- and photoactive aromatic spacers. Our recent works on dicopper(II) metallacyclophanes and earlier ones on related organic cyclophanes are now compared in a critical manner. Special focus is placed on the ligand design as well as in the combination of experimental and computational methods to demonstrate the multifunctionality nature of these metallosupramolecular complexes. This new class of oxamato-based dicopper(II) metallacyclophanes affords an excellent synthetic and theoretical set of models for both chemical and physical fundamental studies on redox- and photo-triggered, long-distance electron exchange phenomena, which are two major topics in molecular magnetism and molecular electronics. Apart from their use as ground tests for the fundamental research on the relative importance of the spin delocalization and spin polarization mechanisms of the electron exchange interaction through extended π-conjugated aromatic ligands in polymetallic complexes, oxamato-based dicopper(II) metallacyclophanes possessing spin-containing electro- and chromophores at the metal and/or the ligand counterparts emerge as potentially active (magnetic and electronic) molecular components to build a metal-based spintronic circuit. They are thus unique examples of multifunctional magnetic complexes to get single-molecule spintronic devices by controlling and allowing the spin communication, when serving as molecular magnetic couplers and wires, or by exhibiting bistable spin behavior, when acting as molecular magnetic rectifiers and switches. Oxamato-based dicopper(II) metallacyclophanes also emerge as potential candidates for the study of coherent electron transport through single molecules, both experimentally and theoretically. The results presented herein, which are a first step in the metallosupramolecular approach to molecular spintronics, intend to attract the attention of physicists and materials scientists with a large expertice in the manipulation and measurement of single-molecule electron transport properties, as well as in the processing and addressing of molecules on different supports.

Redox-Active Bis(phenolate) N-Heterocyclic Carbene [OCO] Pincer Ligands Support Cobalt Electron Transfer Series Spanning Four Oxidation States.

PubMed

Harris, Caleb F; Bayless, Michael B; van Leest, Nicolaas P; Bruch, Quinton J; Livesay, Brooke N; Bacsa, John; Hardcastle, Kenneth I; Shores, Matthew P; de Bruin, Bas; Soper, Jake D

2017-10-16

A new family of low-coordinate Co complexes supported by three redox-noninnocent tridentate [OCO] pincer-type bis(phenolate) N-heterocyclic carbene (NHC) ligands are described. Combined experimental and computational data suggest that the charge-neutral four-coordinate complexes are best formulated as Co(II) centers bound to closed-shell [OCO] 2- dianions, of the general formula [(OCO)Co II L] (where L is a solvent-derived MeCN or THF). Cyclic voltammograms of the [(OCO)Co II L] complexes reveal three oxidations accessible at potentials below 1.2 V vs Fc + /Fc, corresponding to generation of formally Co(V) species, but the true physical/spectroscopic oxidation states are much lower. Chemical oxidations afford the mono- and dications of the imidazoline NHC-derived complex, which were examined by computational and magnetic and spectroscopic methods, including single-crystal X-ray diffraction. The metal and ligand oxidation states of the monocationic complex are ambiguous; data are consistent with formulation as either [( S OCO)Co III (THF) 2 ] + containing a closed-shell [ S OCO] 2- diphenolate ligand bound to a S = 1 Co(III) center, or [( S OCO • )Co II (THF) 2 ] + with a low-spin Co(II) ion ferromagnetically coupled to monoanionic [ S OCO • ] - containing a single unpaired electron distributed across the [OCO] framework. The dication is best described as [( S OCO 0 )Co II (THF) 3 ] 2+ , with a single unpaired electron localized on the d 7 Co(II) center and a doubly oxidized, charge-neutral, closed-shell S OCO 0 ligand. The combined data provide for the first time unequivocal and structural evidence for [OCO] ligand redox activity. Notably, varying the degree of unsaturation in the NHC backbone shifts the ligand-based oxidation potentials by up to 400 mV. The possible chemical origins of this unexpected shift, along with the potential utility of the [OCO] pincer ligands for base-metal-mediated organometallic coupling catalysis, are discussed.

Single shot spin readout with a cryogenic high-electron-mobility transistor amplifier at sub-Kelvin temperatures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tracy, Lisa A.; Luhman, Dwight R.; Carr, Stephen M.

We use a cryogenic high-electron-mobility transistor circuit to amplify the current from a single electron transistor, allowing for demonstration of single shot readout of an electron spin on a single P donor in Si with 100 kHz bandwidth and a signal to noise ratio of ~9. In order to reduce the impact of cable capacitance, the amplifier is located adjacent to the Si sample, at the mixing chamber stage of a dilution refrigerator. For a current gain of ~2.7 x 10 3 the power dissipation of the amplifier is 13 μW, the bandwidth is ~1.3 MHz, and for frequencies abovemore » 300 kHz the current noise referred to input is ≤ 70 fA/√Hz. Furthermore, with this amplification scheme, we are able to observe coherent oscillations of a P donor electron spin in isotopically enriched 28Si with 96% visibility.« less

Single shot spin readout with a cryogenic high-electron-mobility transistor amplifier at sub-Kelvin temperatures

DOE PAGES

Tracy, Lisa A.; Luhman, Dwight R.; Carr, Stephen M.; ...

2016-02-08

We use a cryogenic high-electron-mobility transistor circuit to amplify the current from a single electron transistor, allowing for demonstration of single shot readout of an electron spin on a single P donor in Si with 100 kHz bandwidth and a signal to noise ratio of ~9. In order to reduce the impact of cable capacitance, the amplifier is located adjacent to the Si sample, at the mixing chamber stage of a dilution refrigerator. For a current gain of ~2.7 x 10 3 the power dissipation of the amplifier is 13 μW, the bandwidth is ~1.3 MHz, and for frequencies abovemore » 300 kHz the current noise referred to input is ≤ 70 fA/√Hz. Furthermore, with this amplification scheme, we are able to observe coherent oscillations of a P donor electron spin in isotopically enriched 28Si with 96% visibility.« less

Quantum-Sequencing: Fast electronic single DNA molecule sequencing

NASA Astrophysics Data System (ADS)

Casamada Ribot, Josep; Chatterjee, Anushree; Nagpal, Prashant

2014-03-01

A major goal of third-generation sequencing technologies is to develop a fast, reliable, enzyme-free, high-throughput and cost-effective, single-molecule sequencing method. Here, we present the first demonstration of unique ``electronic fingerprint'' of all nucleotides (A, G, T, C), with single-molecule DNA sequencing, using Quantum-tunneling Sequencing (Q-Seq) at room temperature. We show that the electronic state of the nucleobases shift depending on the pH, with most distinct states identified at acidic pH. We also demonstrate identification of single nucleotide modifications (methylation here). Using these unique electronic fingerprints (or tunneling data), we report a partial sequence of beta lactamase (bla) gene, which encodes resistance to beta-lactam antibiotics, with over 95% success rate. These results highlight the potential of Q-Seq as a robust technique for next-generation sequencing.

Probe-based measurement of lateral single-electron transfer between individual molecules

PubMed Central

Steurer, Wolfram; Fatayer, Shadi; Gross, Leo; Meyer, Gerhard

2015-01-01

The field of molecular electronics aims at using single molecules as functional building blocks for electronics components, such as switches, rectifiers or transistors. A key challenge is to perform measurements with atomistic control over the alignment of the molecule and its contacting electrodes. Here we use atomic force microscopy to examine charge transfer between weakly coupled pentacene molecules on insulating films with single-electron sensitivity and control over the atomistic details. We show that, in addition to the imaging capability, the probe tip can be used to control the charge state of individual molecules and to detect charge transfers to/from the tip, as well as between individual molecules. Our approach represents a novel route for molecular charge transfer studies with a host of opportunities, especially in combination with single atom/molecule manipulation and nanopatterning techniques. PMID:26387533

Conditional Dispersive Readout of a CMOS Single-Electron Memory Cell

NASA Astrophysics Data System (ADS)

Schaal, S.; Barraud, S.; Morton, J. J. L.; Gonzalez-Zalba, M. F.

2018-05-01

Quantum computers require interfaces with classical electronics for efficient qubit control, measurement, and fast data processing. Fabricating the qubit and the classical control layer using the same technology is appealing because it will facilitate the integration process, improving feedback speeds and offering potential solutions to wiring and layout challenges. Integrating classical and quantum devices monolithically, using complementary metal-oxide-semiconductor (CMOS) processes, enables the processor to profit from the most mature industrial technology for the fabrication of large-scale circuits. We demonstrate a CMOS single-electron memory cell composed of a single quantum dot and a transistor that locks charge on the quantum-dot gate. The single-electron memory cell is conditionally read out by gate-based dispersive sensing using a lumped-element L C resonator. The control field-effect transistor (FET) and quantum dot are fabricated on the same chip using fully depleted silicon-on-insulator technology. We obtain a charge sensitivity of δ q =95 ×10-6e Hz-1 /2 when the quantum-dot readout is enabled by the control FET, comparable to results without the control FET. Additionally, we observe a single-electron retention time on the order of a second when storing a single-electron charge on the quantum dot at millikelvin temperatures. These results demonstrate first steps towards time-based multiplexing of gate-based dispersive readout in CMOS quantum devices opening the path for the development of an all-silicon quantum-classical processor.

Availability of surface boron species in improved oxygen reduction activity of Pt catalysts: A first-principles study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Libo; Zhou, Gang, E-mail: gzhou@mail.buct.edu.cn

2016-04-14

The oxidation process of boron (B) species on the Pt(111) surface and the beneficial effects of boron oxides on the oxygen reduction activity are investigated by first-principles calculations. The single-atom B anchored on the Pt surface has a great attraction for the oxygen species in the immediate environment. With the dissociation of molecular oxygen, a series of boron oxides is formed in succession, both indicating exothermic oxidation reactions. After BO{sub 2} is formed, the subsequent O atom immediately participates in the oxygen reduction reaction. The calculated O adsorption energy is appreciably decreased as compared to Pt catalysts, and more approximatemore » to the optimal value of the volcano plot, from which is clear that O hydrogenation kinetics is improved. The modulation mechanism is mainly based on the electron-deficient nature of stable boron oxides, which normally reduces available electronic states of surface Pt atoms that bind the O by facilitating more electron transfer. This modification strategy from the exterior opens the new way, different from the alloying, to efficient electrocatalyst design for PEMFCs.« less

Synthesis of a Ni2P/Ni12P5 bi-phase nanocomposite for the efficient catalytic reduction of 4-nitrophenol based on the unique n-n heterojunction effects.

PubMed

Tian, Feng-Yu; Hou, Dongfang; Zhang, Wei-Min; Qiao, Xiu-Qing; Li, Dong-Sheng

2017-10-24

A novel heterostructure catalyst of Ni 2 P/Ni 12 P 5 has been fabricated through a simple solvothermal method by modifying the molar ratio of the initial raw materials. The products are characterized by X-ray powder diffraction (XRD), field emission scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HRTEM), nitrogen adsorption and X-ray photoelectron spectroscopy (XPS). It is found that the two phases, Ni 2 P and Ni 12 P 5 , are interlaced with one another in the as-formed nanocomposite, resulting in more interfaces. The bi-phase catalyst exhibits a markedly enhanced catalytic activity in the reduction of 4-nitrophenol, as compared to that of single Ni 2 P or Ni 12 P 5 . The enhanced catalytic activity can be attributed to the unique n-n series effects, which result in the increased ease of electron transfer over the Ni 2 P/Ni 12 P 5 bi-phase catalyst.

Shedding light on cell compartmentation in the candidate phylum Poribacteria by high resolution visualisation and transcriptional profiling

NASA Astrophysics Data System (ADS)

Jahn, Martin T.; Markert, Sebastian M.; Ryu, Taewoo; Ravasi, Timothy; Stigloher, Christian; Hentschel, Ute; Moitinho-Silva, Lucas

2016-10-01

Assigning functions to uncultivated environmental microorganisms continues to be a challenging endeavour. Here, we present a new microscopy protocol for fluorescence in situ hybridisation-correlative light and electron microscopy (FISH-CLEM) that enabled, to our knowledge for the first time, the identification of single cells within their complex microenvironment at electron microscopy resolution. Members of the candidate phylum Poribacteria, common and uncultivated symbionts of marine sponges, were used towards this goal. Cellular 3D reconstructions revealed bipolar, spherical granules of low electron density, which likely represent carbon reserves. Poribacterial activity profiles were retrieved from prokaryotic enriched sponge metatranscriptomes using simulation-based optimised mapping. We observed high transcriptional activity for proteins related to bacterial microcompartments (BMC) and we resolved their subcellular localisation by combining FISH-CLEM with immunohistochemistry (IHC) on ultra-thin sponge tissue sections. In terms of functional relevance, we propose that the BMC-A region may be involved in 1,2-propanediol degradation. The FISH-IHC-CLEM approach was proven an effective toolkit to combine -omics approaches with functional studies and it should be widely applicable in environmental microbiology.

Non-metal single/dual doped carbon quantum dots: a general flame synthetic method and electro-catalytic properties

NASA Astrophysics Data System (ADS)

Han, Yuzhi; Tang, Di; Yang, Yanmei; Li, Chuanxi; Kong, Weiqian; Huang, Hui; Liu, Yang; Kang, Zhenhui

2015-03-01

A combustion flame method is developed for the convenient and scalable fabrication of single- and dual-doped carbon quantum dots (CQDs) (N-CQDs, B-CQDs, P-CQDs, and S-CQDs and dual-doped B,N-CQDs, P,N-CQDs, and S,N-CQDs), and the doping contents can be easily adjusted by simply changing the concentrations of precursors in ethanol. These single/dual-doped CQDs, especially B,N-CQDs, show high catalytic activities for the oxygen reduction reaction.A combustion flame method is developed for the convenient and scalable fabrication of single- and dual-doped carbon quantum dots (CQDs) (N-CQDs, B-CQDs, P-CQDs, and S-CQDs and dual-doped B,N-CQDs, P,N-CQDs, and S,N-CQDs), and the doping contents can be easily adjusted by simply changing the concentrations of precursors in ethanol. These single/dual-doped CQDs, especially B,N-CQDs, show high catalytic activities for the oxygen reduction reaction. Electronic supplementary information (ESI) available: TEM images, UV-Vis absorption, PL, Raman, FTIR, XPS, CV, and LSV data of single/dual doped CQDs, a table for the calculated mass concentrations of different atoms in various B, N, P or S containing CQDs and a table for summary of the ORR performance of various catalysts in an O2-saturated 0.1 M KOH solution. See DOI: 10.1039/c4nr07116f

Review of Electronics Based on Single-Walled Carbon Nanotubes.

PubMed

Cao, Yu; Cong, Sen; Cao, Xuan; Wu, Fanqi; Liu, Qingzhou; Amer, Moh R; Zhou, Chongwu

2017-08-14

Single-walled carbon nanotubes (SWNTs) are extremely promising materials for building next-generation electronics due to their unique physical and electronic properties. In this article, we will review the research efforts and achievements of SWNTs in three electronic fields, namely analog radio-frequency electronics, digital electronics, and macroelectronics. In each SWNT-based electronic field, we will present the major challenges, the evolutions of the methods to overcome these challenges, and the state-of-the-art of the achievements. At last, we will discuss future directions which could lead to the broad applications of SWNTs. We hope this review could inspire more research on SWNT-based electronics, and accelerate the applications of SWNTs.

Generation and characterization of ultra-short electron beams for single spike infrared FEL radiation at SPARC_LAB

NASA Astrophysics Data System (ADS)

Villa, F.; Anania, M. P.; Artioli, M.; Bacci, A.; Bellaveglia, M.; Bisesto, F. G.; Biagioni, A.; Carpanese, M.; Cardelli, F.; Castorina, G.; Chiadroni, E.; Cianchi, A.; Ciocci, F.; Croia, M.; Curcio, A.; Dattoli, G.; Gallo, A.; Di Giovenale, D.; Di Palma, E.; Di Pirro, G.; Ferrario, M.; Filippi, F.; Giannessi, L.; Giribono, A.; Marocchino, A.; Massimo, F.; Mostacci, A.; Petralia, A.; Petrarca, M.; Petrillo, V.; Piersanti, L.; Pioli, S.; Pompili, R.; Romeo, S.; Rossi, A. R.; Scifo, J.; Shpakov, V.; Vaccarezza, C.

2017-09-01

The technique for producing and measuring few tens of femtosecond electron beams, and the consequent generation of few tens femtoseconds single spike FEL radiation pulses at SPARC_LAB is presented. The undulator has been used in the double role of radiation source and diagnostic tool for the characterization of the electron beam. The connection between the electron bunch length and the radiation bandwidth is analyzed.

Two-screen single-shot electron spectrometer for laser wakefield accelerated electron beams.

PubMed

Soloviev, A A; Starodubtsev, M V; Burdonov, K F; Kostyukov, I Yu; Nerush, E N; Shaykin, A A; Khazanov, E A

2011-04-01

The laser wakefield acceleration electron beams can essentially deviate from the axis of the system, which distinguishes them greatly from beams of conventional accelerators. In case of energy measurements by means of a permanent-magnet electron spectrometer, the deviation angle can affect accuracy, especially for high energies. A two-screen single-shot electron spectrometer that correctly allows for variations of the angle of entry is considered. The spectrometer design enables enhancing accuracy of measuring narrow electron beams significantly as compared to a one-screen spectrometer with analogous magnetic field, size, and angular acceptance. © 2011 American Institute of Physics

System for cooling hybrid vehicle electronics, method for cooling hybrid vehicle electronics

DOEpatents

France, David M.; Yu, Wenhua; Singh, Dileep; Zhao, Weihuan

2017-11-21

The invention provides a single radiator cooling system for use in hybrid electric vehicles, the system comprising a surface in thermal communication with electronics, and subcooled boiling fluid contacting the surface. The invention also provides a single radiator method for simultaneously cooling electronics and an internal combustion engine in a hybrid electric vehicle, the method comprising separating a coolant fluid into a first portion and a second portion; directing the first portion to the electronics and the second portion to the internal combustion engine for a time sufficient to maintain the temperature of the electronics at or below 175.degree. C.; combining the first and second portion to reestablish the coolant fluid; and treating the reestablished coolant fluid to the single radiator for a time sufficient to decrease the temperature of the reestablished coolant fluid to the temperature it had before separation.

Photon Counting Imaging with an Electron-Bombarded Pixel Image Sensor

PubMed Central

Hirvonen, Liisa M.; Suhling, Klaus

2016-01-01

Electron-bombarded pixel image sensors, where a single photoelectron is accelerated directly into a CCD or CMOS sensor, allow wide-field imaging at extremely low light levels as they are sensitive enough to detect single photons. This technology allows the detection of up to hundreds or thousands of photon events per frame, depending on the sensor size, and photon event centroiding can be employed to recover resolution lost in the detection process. Unlike photon events from electron-multiplying sensors, the photon events from electron-bombarded sensors have a narrow, acceleration-voltage-dependent pulse height distribution. Thus a gain voltage sweep during exposure in an electron-bombarded sensor could allow photon arrival time determination from the pulse height with sub-frame exposure time resolution. We give a brief overview of our work with electron-bombarded pixel image sensor technology and recent developments in this field for single photon counting imaging, and examples of some applications. PMID:27136556

Molecular Diode Studies Based on a Highly Sensitive Molecular Measurement Technique.

PubMed

Iwane, Madoka; Fujii, Shintaro; Kiguchi, Manabu

2017-04-26

In 1974, molecular electronics pioneers Mark Ratner and Arieh Aviram predicted that a single molecule could act as a diode, in which electronic current can be rectified. The electronic rectification property of the diode is one of basic functions of electronic components and since then, the molecular diode has been investigated as a first single-molecule device that would have a practical application. In this review, we first describe the experimental fabrication and electronic characterization techniques of molecular diodes consisting of a small number of molecules or a single molecule. Then, two main mechanisms of the rectification property of the molecular diode are discussed. Finally, representative results for the molecular diode are reviewed and a brief outlook on crucial issues that need to be addressed in future research is discussed.

Molecular Diode Studies Based on a Highly Sensitive Molecular Measurement Technique

PubMed Central

Iwane, Madoka; Fujii, Shintaro; Kiguchi, Manabu

2017-01-01

In 1974, molecular electronics pioneers Mark Ratner and Arieh Aviram predicted that a single molecule could act as a diode, in which electronic current can be rectified. The electronic rectification property of the diode is one of basic functions of electronic components and since then, the molecular diode has been investigated as a first single-molecule device that would have a practical application. In this review, we first describe the experimental fabrication and electronic characterization techniques of molecular diodes consisting of a small number of molecules or a single molecule. Then, two main mechanisms of the rectification property of the molecular diode are discussed. Finally, representative results for the molecular diode are reviewed and a brief outlook on crucial issues that need to be addressed in future research is discussed. PMID:28445393

Single-step One-pot Synthesis of TiO 2 Nanosheets Doped with Sulfur on Reduced Graphene Oxide with Enhanced Photocatalytic Activity

DOE PAGES

Wang, Weilin; Wang, Zhaofeng; Liu, Jingjing; ...

2017-04-21

A hybrid photocatalyst based on anatase TiO 2 was designed by doping TiO 2 with sulfur and incorporating reduced graphene oxide (TiO 2-S/rGO hybrid), with an aim to narrow the band gap to potentially make use of visible light and decrease the recombination of excitons, respectively. This TiO 2-S/rGO hybrid was successfully synthesized using a one-pot hydrothermal method via single-step reaction. The structure and morphology of the TiO 2-S/rGO hybrid catalyst was carefully characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). Its photocatalytic reactivity was evaluated by the degradation ofmore » methyl blue. The results showed that both the doping of sulfur and the introduction of rGO worked as designed, and the TiO 2-S/rGO hybrid exhibited high photocatalytic activity under simulated sunlight. Finally, considering both the facile and scalable reaction to synthesize TiO 2-S/rGO hybrid, and its excellent photocatalytic performance, such TiO 2-S/rGO hybrids are expect to find practical applications in environmental and energy sectors.« less

Chirality of Single-Handed Twisted Titania Tubular Nanoribbons Prepared Through Sol-gel Transcription.

PubMed

Wang, Sibing; Zhang, Chuanyong; Li, Yi; Li, Baozong; Yang, Yonggang

2015-08-01

Single-handed twisted titania tubular nanoribbons were prepared through sol-gel transcription using a pair of enantiomers. Handedness was controlled by that of the template. The obtained samples were characterized using field-emission electron microscopy, transmission electron microscopy, diffuse reflectance circular dichroism (DRCD), and X-ray diffraction. The DRCD spectra indicated that the titania nanotubes exhibit optical activity. Although the tubular structure was destroyed after being calcined at 700 °C for 2.0 h, DRCD signals were still identified. However, the DRCD signals disappeared after being calcined at 1000 °C for 2.0 h. The optical activity of titania was proposed to be due to chiral defects. Previous results showed that straight titania tubes could be used as asymmetric autocatalysts, indicating that titania exhibit chirality at the angstrom level. Herein, it was found that they also exhibit DRCD signals, indicating that there are no obvious relationships between morphology at the nano level and chirality at the angstrom level. The nanotube chirality should originate from the chiral defects on the nanotube inner surface. The Fourier transform infrared spectra indicated that the chirality of the titania was transferred from the gelators through the hydrogen bonding between N-H and Ti-OH. © 2015 Wiley Periodicals, Inc.

Single-step One-pot Synthesis of TiO2 Nanosheets Doped with Sulfur on Reduced Graphene Oxide with Enhanced Photocatalytic Activity

PubMed Central

Wang, Weilin; Wang, Zhaofeng; Liu, Jingjing; Luo, Zhu; Suib, Steven L.; He, Peng; Ding, Guqiao; Zhang, Zhengguo; Sun, Luyi

2017-01-01

A hybrid photocatalyst based on anatase TiO2 was designed by doping TiO2 with sulfur and incorporating reduced graphene oxide (TiO2-S/rGO hybrid), with an aim to narrow the band gap to potentially make use of visible light and decrease the recombination of excitons, respectively. This TiO2-S/rGO hybrid was successfully synthesized using a one-pot hydrothermal method via single-step reaction. The structure and morphology of the TiO2-S/rGO hybrid catalyst was carefully characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). Its photocatalytic reactivity was evaluated by the degradation of methyl blue. The results showed that both the doping of sulfur and the introduction of rGO worked as designed, and the TiO2-S/rGO hybrid exhibited high photocatalytic activity under simulated sunlight. Considering both the facile and scalable reaction to synthesize TiO2-S/rGO hybrid, and its excellent photocatalytic performance, such TiO2-S/rGO hybrids are expect to find practical applications in environmental and energy sectors. PMID:28429736

Electron Detachment Dissociation of Underivatized Chloride-Adducted Oligosaccharides

NASA Astrophysics Data System (ADS)

Kornacki, James R.; Adamson, Julie T.; Håkansson, Kristina

2012-11-01

Chloride anion attachment has previously been shown to aid determination of saccharide anomeric configuration and generation of linkage information in negative ion post-source decay MALDI tandem mass spectrometry. Here, we employ electron detachment dissociation (EDD) and collision activated dissociation (CAD) for the structural characterization of underivatized oligosaccharides bearing a chloride ion adduct. Both neutral and sialylated oligosaccharides are examined, including maltoheptaose, an asialo biantennary glycan (NA2), disialylacto- N-tetraose (DSLNT), and two LS tetrasaccharides (LSTa and LSTb). Gas-phase chloride-adducted species are generated by negative ion mode electrospray ionization. EDD and CAD spectra of chloride-adducted oligosaccharides are compared to the corresponding spectra for doubly deprotonated species not containing a chloride anion to assess the role of chloride adduction in the stimulation of alternative fragmentation pathways and altered charge locations allowing detection of additional product ions. In all cases, EDD of singly chloridated and singly deprotonated species resulted in an increase in observed cross-ring cleavages, which are essential to providing saccharide linkage information. Glycosidic cleavages also increased in EDD of chloride-adducted oligosaccharides to reveal complementary structural information compared to traditional (non-chloride-assisted) EDD and CAD. Results indicate that chloride adduction is of interest in alternative anion activation methods such as EDD for oligosaccharide structural characterization.

Imaging active topological defects in carbon nanotubes

NASA Astrophysics Data System (ADS)

Suenaga, Kazu; Wakabayashi, Hideaki; Koshino, Masanori; Sato, Yuta; Urita, Koki; Iijima, Sumio

2007-06-01

A single-walled carbon nanotube (SWNT) is a wrapped single graphene layer, and its plastic deformation should require active topological defects-non-hexagonal carbon rings that can migrate along the nanotube wall. Although in situ transmission electron microscopy (TEM) has been used to examine the deformation of SWNTs, these studies deal only with diameter changes and no atomistic mechanism has been elucidated experimentally. Theory predicts that some topological defects can form through the Stone-Wales transformation in SWNTs under tension at 2,000 K, and could act as a dislocation core. We demonstrate here, by means of high-resolution (HR)-TEM with atomic sensitivity, the first direct imaging of pentagon-heptagon pair defects found in an SWNT that was heated at 2,273 K. Moreover, our in situ HR-TEM observation reveals an accumulation of topological defects near the kink of a deformed nanotube. This result suggests that dislocation motions or active topological defects are indeed responsible for the plastic deformation of SWNTs.

Functional links between stability and reactivity of strontium ruthenate single crystals during oxygen evolution

NASA Astrophysics Data System (ADS)

Chang, Seo Hyoung; Danilovic, Nemanja; Chang, Kee-Chul; Subbaraman, Ram; Paulikas, Arvydas P.; Fong, Dillon D.; Highland, Matthew J.; Baldo, Peter M.; Stamenkovic, Vojislav R.; Freeland, John W.; Eastman, Jeffrey A.; Markovic, Nenad M.

2014-06-01

In developing cost-effective complex oxide materials for the oxygen evolution reaction, it is critical to establish the missing links between structure and function at the atomic level. The fundamental and practical implications of the relationship on any oxide surface are prerequisite to the design of new stable and active materials. Here we report an intimate relationship between the stability and reactivity of oxide catalysts in exploring the reaction on strontium ruthenate single-crystal thin films in alkaline environments. We determine that for strontium ruthenate films with the same conductance, the degree of stability, decreasing in the order (001)>(110)>(111), is inversely proportional to the activity. Both stability and reactivity are governed by the potential-induced transformation of stable Ru4+ to unstable Run>4+. This ordered(Ru4+)-to-disordered(Run>4+) transition and the development of active sites for the reaction are determined by a synergy between electronic and morphological effects.

Larvicidal study of tetrahydropyrimidine scaffolds against Anopheles arabiensis and structural insight by single crystal X-ray studies.

PubMed

Bairagi, Keshab M; Venugopala, Katharigatta N; Mondal, Pradip Kumar; Gleiser, Raquel M; Chopra, Deepak; García, Daniel; Odhav, Bharti; Nayak, Susanta K

2018-06-20

A series of methyl or ethyl 4-(substitutedphenyl/pyridyl)-6-methyl-2-oxo/thioxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate (HPM) analogues 4a-g was synthesized and evaluated for larvicidal activity against Anopheles arabiensis. These newly synthesized compounds were characterized by spectral studies such as FT-IR, NMR ( 1 H and 13 C), LC-MS and elemental analysis. The conformational features and supramolecular assembly of molecules 4a, 4b and 4e were further analyzed from single crystal X-ray study. The larvicidal activity of these tetrahydropyrimidine pharmacophore series were analyzed based on their relative substituent's. Among the synthesized HPM analogous from the series, compounds 4d and 4e both having electron withdrawing chlorine group on phenyl ring at the fourth position of the tetrahydropyrimidine pharmacophore exhibited the most promising larvicidal activity. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

Electronic Structure Analysis of the Oxygen-Activation Mechanism by FeII- and α-Ketoglutarate (αKG)-Dependent Dioxygenases

PubMed Central

Ye, Shengfa; Riplinger, Christoph; Hansen, Andreas; Krebs, Carsten; Bollinger, J. Martin; Neese, Frank

2014-01-01

α-Ketoglutarate (αKG)-dependent nonheme iron enzymes utilize a high-spin (HS) ferrous center to couple the activation of oxygen to the decarboxylation of the cosubstrate αKG to yield succinate and CO2, and to generate a high-valent ferryl species that then acts as an oxidant to functionalize the target C–H bond. Herein a detailed analysis of the electronic-structure changes that occur in the oxygen activation by this enzyme was performed. The rate-limiting step, which is identical on the septet and quintet surfaces, is the nucleophilic attack of the distal O atom of the O2 adduct on the carbonyl group in αKG through a bicyclic transition state (5,7TS1). Due to the different electronic structures in 5,7TS1, the decay of 7TS1 leads to a ferric oxyl species, which undergoes a rapid intersystem crossing to form the ferryl intermediate. By contrast, a HS ferrous center ligated by a peroxosuccinate is obtained on the quintet surface following 5TS1. Thus, additional two single-electron transfer steps are required to afford the same FeIV–oxo species. However, the triplet reaction channel is catalytically irrelevant. The biological role of αKG played in the oxygen-activation reaction is dual. The αKG LUMO (C=O π*) serves as an electron acceptor for the nucleophilic attack of the superoxide monoanion. On the other hand, the αKG HOMO (C1–C2 σ) provides the second and third electrons for the further reduction of the superoxide. In addition to density functional theory, high-level ab initio calculations have been used to calculate the accurate energies of the critical points on the alternative potential-energy surfaces. Overall, the results delivered by the ab initio calculations are largely parallel to those obtained with the B3LYP density functional, thus lending credence to our conclusions. PMID:22511515

Single Molecule Spectroelectrochemistry of Interfacial Charge Transfer Dynamics In Hybrid Organic Solar Cell

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pan, Shanlin

2014-11-16

Our research under support of this DOE grant is focused on applied and fundamental aspects of model organic solar cell systems. Major accomplishments are: 1) we developed a spectroelectorchemistry technique of single molecule single nanoparticle method to study charge transfer between conjugated polymers and semiconductor at the single molecule level. The fluorescence of individual fluorescent polymers at semiconductor surfaces was shown to exhibit blinking behavior compared to molecules on glass substrates. Single molecule fluorescence excitation anisotropy measurements showed the conformation of the polymer molecules did not differ appreciably between glass and semiconductor substrates. The similarities in molecular conformation suggest thatmore » the observed differences in blinking activity are due to charge transfer between fluorescent polymer and semiconductor, which provides additional pathways between states of high and low fluorescence quantum efficiency. Similar spectroelectrochemistry work has been done for small organic dyes for understand their charge transfer dynamics on various substrates and electrochemical environments; 2) We developed a method of transferring semiconductor nanoparticles (NPs) and graphene oxide (GO) nanosheets into organic solvent for a potential electron acceptor in bulk heterojunction organic solar cells which employed polymer semiconductor as the electron donor. Electron transfer from the polymer semiconductor to semiconductor and GO in solutions and thin films was established through fluorescence spectroscopy and electroluminescence measurements. Solar cells containing these materials were constructed and evaluated using transient absorption spectroscopy and dynamic fluorescence techniques to understand the charge carrier generation and recombination events; 3) We invented a spectroelectorchemistry technique using light scattering and electroluminescence for rapid size determination and studying electrochemistry of single NPs in an electrochemical cell. For example, we are able to use this technique to track electroluminescence of single Au NPs, and the electrodeposition of individual Ag NPs in-situ. These metallic NPs are useful to enhance light harvesting in organic photovoltaic systems. The scattering at the surface of an indium tin oxide (ITO) working electrode was measured during a potential sweep. Utilizing Mie scattering theory and high resolution scanning electron microscopy (SEM), the scattering data were used to calculate current-potential curves depicting the electrodeposition of individual Ag NPs. The oxidation of individual presynthesized and electrodeposited Ag NPs was also investigated using fluorescence and DFS microscopies. Our work has produced 1 US provisional patent, 15 published manuscripts, 1 submitted and two additional in-writing manuscripts. 5 graduate students, 1 postdoctoral student, 1 visiting professor, and two undergraduate students have received research training in the area of electrochemistry and optical spectroscopy under support of this award.« less

First principles numerical model of avalanche-induced arc discharges in electron-irradiated dielectrics

NASA Technical Reports Server (NTRS)

Beers, B. L.; Pine, V. W.; Hwang, H. C.; Bloomberg, H. W.; Lin, D. L.; Schmidt, M. J.; Strickland, D. J.

1979-01-01

The model consists of four phases: single electron dynamics, single electron avalanche, negative streamer development, and tree formation. Numerical algorithms and computer code implementations are presented for the first three phases. An approach to developing a code description of fourth phase is discussed. Numerical results are presented for a crude material model of Teflon.

Economic analysis of crystal growth in space

NASA Technical Reports Server (NTRS)

Ulrich, D. R.; Chung, A. M.; Yan, C. S.; Mccreight, L. R.

1972-01-01

Many advanced electronic technologies and devices for the 1980's are based on sophisticated compound single crystals, i.e. ceramic oxides and compound semiconductors. Space processing of these electronic crystals with maximum perfection, purity, and size is suggested. No ecomonic or technical justification was found for the growth of silicon single crystals for solid state electronic devices in space.

Spatial Control of Laser Wakefield Accelerated Electron Beams

NASA Astrophysics Data System (ADS)

Maksimchuk, A.; Behm, K.; Zhao, T.; Joglekar, A. S.; Hussein, A.; Nees, J.; Thomas, A. G. R.; Krushelnick, K.; Elle, J.; Lucero, A.; Samarin, G. M.; Sarry, G.; Warwick, J.

2017-10-01

The laser wakefield experiments to study and control spatial properties of electron beams were performed using HERCULES laser at the University of Michigan at power of 100 TW. In the first experiment multi-electron beam generation was demonstrated using co-propagating, parallel laser beams with a π-phase shift mirror and showing that interaction between the wakefields can cause injection to occur for plasma and laser parameters in which a single wakefield displays no significant injection. In the second experiment a magnetic triplet quadrupole system was used to refocus and stabilize electron beams at the distance of 60 cm from the interaction region. This produced a 10-fold increase in remote gamma-ray activation of 63Cu using a lead converter. In the third experiment measurements of un-trapped electrons with high transverse momentum produce a 500 mrad (FWHM) ring. This ring is formed by electrons that receive a forward momentum boost by traversing behind the bubble and its size is inversely proportional to the plasma density. The characterization of divergence and charge of this electron ring may reveal information about the wakefield structure and trapping potential. Supported by U.S. Department of Energy and the National Nuclear Security Administration and Air Force Office of Scientific Research.

Facile approach to prepare Pt decorated SWNT/graphene hybrid catalytic ink

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mayavan, Sundar, E-mail: sundarmayavan@cecri.res.in; Department of Nuclear and Quantum Engineering, Korea Advanced Institute of Science and Technology, Daejeon, 305-701; Mandalam, Aditya

Highlights: • Pt NPs were in situ synthesized onto CNT–graphene support in aqueous solution. • The as-prepared material was used directly as a catalyst ink without further treatment. • Catalyst ink is active toward methanol oxidation. • This approach realizes both scalable and greener production of hybrid catalysts. - Abstract: Platinum nanoparticles were in situ synthesized onto hybrid support involving graphene and single walled carbon nanotube in aqueous solution. We investigate the reduction of graphene oxide, and platinum nanoparticle functionalization on hybrid support by X-ray photoelectron spectroscopy, Raman spectroscopy, X-ray diffraction, scanning electron microscopy and transmission electron microscopy. The as-preparedmore » platinum on hybrid support was used directly as a catalyst ink without further treatment and is active toward methanol oxidation. This work realizes both scalable and greener production of highly efficient hybrid catalysts, and would be valuable for practical applications of graphene based fuel cell catalysts.« less

Magnetic decoupling of the linac in a low field biplanar linac-MR system.

PubMed

St Aubin, J; Steciw, S; Fallone, B G

2010-09-01

The integration of a low field biplanar magnetic resonance (MR) imager and linear accelerator (linac) causes magnetic interference at the linac due to the MR fringe fields. In order to eliminate this interference, passive and active magnetic shielding designs are investigated. The optimized design of passive magnetic shielding was performed using the finite element method. The design was required to achieve no greater than a 20% electron beam loss within the linac waveguide and electron gun, no greater than 0.06 T at the multileaf collimator (MLC) motors, and generate a distortion of the main MR imaging volume of no greater than 300 ppm. Through the superposition of the analytical solution for a single current carrying wire loop, active shielding designs in the form of three and four sets of coil pairs surrounding the linac waveguide and electron gun were also investigated. The optimized current and coil center locations that yielded the best cancellation of the MR fringe fields at the linac were determined using sequential quadratic programming. Optimized passive shielding in the form of two steel cylinders was designed to meet the required constraints. When shielding the MLC motors along with the waveguide and electron gun, the thickness of the cylinders was less than 1 mm. If magnetically insensitive MLC motors are used, no MLC shielding would be required and the waveguide shield (shielding the waveguide and electron gun) became 1.58 mm thick. In addition, the optimized current and coil spacing for active shielding was determined for both three and four coil pair configurations. The results of the active shielding optimization produced no beam loss within the waveguide and electron gun and a maximum MR field distortion of 91 ppm over a 30 cm diameter spherical volume. Very simple passive and active shielding designs have been shown to magnetically decouple the linac from the MR imager in a low field biplanar linac-MR system. The MLC passive shielding produced the largest distortion of the MR field over the imaging volume. With the use of magnetically insensitive motors, the MR field distortion drops substantially since no MLC shield is required. The active shielding designs yielded no electron beam loss within the linac.

Common electronic origin of superconductivity in (Li,Fe)OHFeSe bulk superconductor and single-layer FeSe/SrTiO3 films

PubMed Central

Zhao, Lin; Liang, Aiji; Yuan, Dongna; Hu, Yong; Liu, Defa; Huang, Jianwei; He, Shaolong; Shen, Bing; Xu, Yu; Liu, Xu; Yu, Li; Liu, Guodong; Zhou, Huaxue; Huang, Yulong; Dong, Xiaoli; Zhou, Fang; Liu, Kai; Lu, Zhongyi; Zhao, Zhongxian; Chen, Chuangtian; Xu, Zuyan; Zhou, X. J.

2016-01-01

The mechanism of high-temperature superconductivity in the iron-based superconductors remains an outstanding issue in condensed matter physics. The electronic structure plays an essential role in dictating superconductivity. Recent revelation of distinct electronic structure and high-temperature superconductivity in the single-layer FeSe/SrTiO3 films provides key information on the role of Fermi surface topology and interface in inducing or enhancing superconductivity. Here we report high-resolution angle-resolved photoemission measurements on the electronic structure and superconducting gap of an FeSe-based superconductor, (Li0.84Fe0.16)OHFe0.98Se, with a Tc at 41 K. We find that this single-phase bulk superconductor shows remarkably similar electronic behaviours to that of the superconducting single-layer FeSe/SrTiO3 films in terms of Fermi surface topology, band structure and the gap symmetry. These observations provide new insights in understanding high-temperature superconductivity in the single-layer FeSe/SrTiO3 films and the mechanism of superconductivity in the bulk iron-based superconductors. PMID:26853801

Antioxidant, phenolic and antifungal profiles of Acanthus mollis (Acanthaceae).

PubMed

Jara, Carlos; Leyton, Miguel; Osorio, Mauricio; Silva, Viviana; Fleming, Francisco; Paz, Marilyn; Madrid, Alejandro; Mellado, Marco

2017-10-01

Acanthus mollis is used as ornamental and medicinal plant. The ethnopharmacology reports indicate that extracts have anti-inflammatory activity. Phytoconstituents profile was evaluated by estimating the content of anthraquinones, flavonoids and phenols. In addition, the antioxidant activity was evaluated using four methods: Hydrogen atoms transfer (TRAP, ORAC and DPPH assays), and single electron transfer (FRAP assay). Finally, antifungal activity was determined by the M27-A2 test. The results shown that ethanol extracts have the highest concentration of phenols, anthraquinones and flavonoids. Total antioxidant capacity, extracts of ethyl acetate and ethanol are those with the highest activity, which correlates strongly with the presence of phenols. The antifungal activity measured in various strains of Candida is concentrated in ethyl acetate extracts of flower and leaf ethanol, a phenomenon may be related to antioxidant activity.

Current-voltage characteristics and transition voltage spectroscopy of individual redox proteins.

PubMed

Artés, Juan M; López-Martínez, Montserrat; Giraudet, Arnaud; Díez-Pérez, Ismael; Sanz, Fausto; Gorostiza, Pau

2012-12-19

Understanding how molecular conductance depends on voltage is essential for characterizing molecular electronics devices. We reproducibly measured current-voltage characteristics of individual redox-active proteins by scanning tunneling microscopy under potentiostatic control in both tunneling and wired configurations. From these results, transition voltage spectroscopy (TVS) data for individual redox molecules can be calculated and analyzed statistically, adding a new dimension to conductance measurements. The transition voltage (TV) is discussed in terms of the two-step electron transfer (ET) mechanism. Azurin displays the lowest TV measured to date (0.4 V), consistent with the previously reported distance decay factor. This low TV may be advantageous for fabricating and operating molecular electronic devices for different applications. Our measurements show that TVS is a helpful tool for single-molecule ET measurements and suggest a mechanism for gating of ET between partner redox proteins.

Indirect-detection single-photon-counting x-ray detector for breast tomosynthesis

NASA Astrophysics Data System (ADS)

Jiang, Hao; Kaercher, Joerg; Durst, Roger

2016-03-01

X-ray mammography is a crucial screening tool for early identification of breast cancer. However, the overlap of anatomical features present in projection images often complicates the task of correctly identifying suspicious masses. As a result, there has been increasing interest in acquisition of volumetric information through digital breast tomosynthesis (DBT) which, compared to mammography, offers the advantage of depth information. Since DBT requires acquisition of many projection images, it is desirable that the noise in each projection image be dominated by the statistical noise of the incident x-ray quanta and not by the additive noise of the imaging system (referred to as quantum-limited imaging) and that the cumulative dose be as low as possible (e.g., no more than for a mammogram). Unfortunately, the electronic noise (~2000 electrons) present in current DBT systems based on active matrix, flat-panel imagers (AMFPIs) is still relatively high compared with modest x-ray gain of the a-Se and CsI:Tl x-ray converters often used. To overcome the modest signal-to-noise ratio (SNR) limitations of current DBT systems, we have developed a large-area x-ray imaging detector with the combination of an extremely low noise (~20 electrons) active-pixel CMOS and a specially designed high resolution scintillator. The high sensitivity and low noise of such system provides better SNR by at least an order of magnitude than current state-of-art AMFPI systems and enables x-ray indirect-detection single photon counting (SPC) at mammographic energies with the potential of dose reduction.

Academic impact of a public electronic health database: bibliometric analysis of studies using the general practice research database.

PubMed

Chen, Yu-Chun; Wu, Jau-Ching; Haschler, Ingo; Majeed, Azeem; Chen, Tzeng-Ji; Wetter, Thomas

2011-01-01

Studies that use electronic health databases as research material are getting popular but the influence of a single electronic health database had not been well investigated yet. The United Kingdom's General Practice Research Database (GPRD) is one of the few electronic health databases publicly available to academic researchers. This study analyzed studies that used GPRD to demonstrate the scientific production and academic impact by a single public health database. A total of 749 studies published between 1995 and 2009 with 'General Practice Research Database' as their topics, defined as GPRD studies, were extracted from Web of Science. By the end of 2009, the GPRD had attracted 1251 authors from 22 countries and been used extensively in 749 studies published in 193 journals across 58 study fields. Each GPRD study was cited 2.7 times by successive studies. Moreover, the total number of GPRD studies increased rapidly, and it is expected to reach 1500 by 2015, twice the number accumulated till the end of 2009. Since 17 of the most prolific authors (1.4% of all authors) contributed nearly half (47.9%) of GPRD studies, success in conducting GPRD studies may accumulate. The GPRD was used mainly in, but not limited to, the three study fields of "Pharmacology and Pharmacy", "General and Internal Medicine", and "Public, Environmental and Occupational Health". The UK and United States were the two most active regions of GPRD studies. One-third of GRPD studies were internationally co-authored. A public electronic health database such as the GPRD will promote scientific production in many ways. Data owners of electronic health databases at a national level should consider how to reduce access barriers and to make data more available for research.

High quality single shot diffraction patterns using ultrashort megaelectron volt electron beams from a radio frequency photoinjector.

PubMed

Musumeci, P; Moody, J T; Scoby, C M; Gutierrez, M S; Bender, H A; Wilcox, N S

2010-01-01

Single shot diffraction patterns using a 250-fs-long electron beam have been obtained at the UCLA Pegasus laboratory. High quality images with spatial resolution sufficient to distinguish closely spaced peaks in the Debye-Scherrer ring pattern have been recorded by scattering the 1.6 pC 3.5 MeV electron beam generated in the rf photoinjector off a 100-nm-thick Au foil. Dark current and high emittance particles are removed from the beam before sending it onto the diffraction target using a 1 mm diameter collimating hole. These results open the door to the study of irreversible phase transformations by single shot MeV electron diffraction.

Spray printing of organic semiconducting single crystals

NASA Astrophysics Data System (ADS)

Rigas, Grigorios-Panagiotis; Payne, Marcia M.; Anthony, John E.; Horton, Peter N.; Castro, Fernando A.; Shkunov, Maxim

2016-11-01

Single-crystal semiconductors have been at the forefront of scientific interest for more than 70 years, serving as the backbone of electronic devices. Inorganic single crystals are typically grown from a melt using time-consuming and energy-intensive processes. Organic semiconductor single crystals, however, can be grown using solution-based methods at room temperature in air, opening up the possibility of large-scale production of inexpensive electronics targeting applications ranging from field-effect transistors and light-emitting diodes to medical X-ray detectors. Here we demonstrate a low-cost, scalable spray-printing process to fabricate high-quality organic single crystals, based on various semiconducting small molecules on virtually any substrate by combining the advantages of antisolvent crystallization and solution shearing. The crystals' size, shape and orientation are controlled by the sheer force generated by the spray droplets' impact onto the antisolvent's surface. This method demonstrates the feasibility of a spray-on single-crystal organic electronics.

Active pixel sensor array as a detector for electron microscopy.

PubMed

Milazzo, Anna-Clare; Leblanc, Philippe; Duttweiler, Fred; Jin, Liang; Bouwer, James C; Peltier, Steve; Ellisman, Mark; Bieser, Fred; Matis, Howard S; Wieman, Howard; Denes, Peter; Kleinfelder, Stuart; Xuong, Nguyen-Huu

2005-09-01

A new high-resolution recording device for transmission electron microscopy (TEM) is urgently needed. Neither film nor CCD cameras are systems that allow for efficient 3-D high-resolution particle reconstruction. We tested an active pixel sensor (APS) array as a replacement device at 200, 300, and 400 keV using a JEOL JEM-2000 FX II and a JEM-4000 EX electron microscope. For this experiment, we used an APS prototype with an area of 64 x 64 pixels of 20 microm x 20 microm pixel pitch. Single-electron events were measured by using very low beam intensity. The histogram of the incident electron energy deposited in the sensor shows a Landau distribution at low energies, as well as unexpected events at higher absorbed energies. After careful study, we concluded that backscattering in the silicon substrate and re-entering the sensitive epitaxial layer a second time with much lower speed caused the unexpected events. Exhaustive simulation experiments confirmed the existence of these back-scattered electrons. For the APS to be usable, the back-scattered electron events must be eliminated, perhaps by thinning the substrate to less than 30 microm. By using experimental data taken with an APS chip with a standard silicon substrate (300 microm) and adjusting the results to take into account the effect of a thinned silicon substrate (30 microm), we found an estimate of the signal-to-noise ratio for a back-thinned detector in the energy range of 200-400 keV was about 10:1 and an estimate for the spatial resolution was about 10 microm.

Work function and temperature dependence of electron tunneling through an N-type perylene diimide molecular junction with isocyanide surface linkers.

PubMed

Smith, Christopher E; Xie, Zuoti; Bâldea, Ioan; Frisbie, C Daniel

2018-01-18

Conducting probe atomic force microscopy (CP-AFM) was employed to examine electron tunneling in self-assembled monolayer (SAM) junctions. A 2.3 nm long perylene tetracarboxylic acid diimide (PDI) acceptor molecule equipped with isocyanide linker groups was synthesized, adsorbed onto Ag, Au and Pt substrates, and the current-voltage (I-V) properties were measured by CP-AFM. The dependence of the low-bias resistance (R) on contact work function indicates that transport is LUMO-assisted ('n-type behavior'). A single-level tunneling model combined with transition voltage spectroscopy (TVS) was employed to analyze the experimental I-V curves and to extract the effective LUMO position ε l = E LUMO - E F and the effective electronic coupling (Γ) between the PDI redox core and the contacts. This analysis revealed a strong Fermi level (E F ) pinning effect in all the junctions, likely due to interface dipoles that significantly increased with increasing contact work function, as revealed by scanning Kelvin probe microscopy (SKPM). Furthermore, the temperature (T) dependence of R was found to be substantial. For Pt/Pt junctions, R varied more than two orders of magnitude in the range 248 K < T < 338 K. Importantly, the R(T) data are consistent with a single step electron tunneling mechanism and allow independent determination of ε l , giving values compatible with estimates of ε l based on analysis of the full I-V data. Theoretical analysis revealed a general criterion to unambiguously rule out a two-step transport mechanism: namely, if measured resistance data exhibit a pronounced Arrhenius-type temperature dependence, a two-step electron transfer scenario should be excluded in cases where the activation energy depends on contact metallurgy. Overall, our results indicate (1) the generality of the Fermi level pinning phenomenon in molecular junctions, (2) the utility of employing the single level tunneling model for determining essential electronic structure parameters (ε l and Γ), and (3) the importance of changing the nature of the contacts to verify transport mechanisms.

Biorthogonal moment expansions in coupled-cluster theory: Review of key concepts and merging the renormalized and active-space coupled-cluster methods

NASA Astrophysics Data System (ADS)

Shen, Jun; Piecuch, Piotr

2012-06-01

After reviewing recent progress in the area of the development of coupled-cluster (CC) methods for quasi-degenerate electronic states that are characterized by stronger non-dynamical correlation effects, including new generations of single- and multi-reference approaches that can handle bond breaking and excited states dominated by many-electron transitions, and after discussing the key elements of the left-eigenstate completely renormalized (CR) CC and equation-of-motion (EOM) CC methods, and the underlying biorthogonal method of moments of CC (MMCC) equations [P. Piecuch, M. Włoch, J. Chem. Phys. 123 (2005) 224105; P. Piecuch, M. Włoch, J.R. Gour, A. Kinal, Chem. Phys. Lett. 418 (2006) 467; M. Włoch, M.D. Lodriguito, P. Piecuch, J.R. Gour, Mol. Phys. 104 (2006) 2149], it is argued that it is beneficial to merge the CR-CC/EOMCC and active-space CC/EOMCC [P. Piecuch, Mol. Phys. 108 (2010) 2987, and references therein] theories into a single formalism. In order to accomplish this goal, the biorthogonal MMCC theory, which provides compact many-body expansions for the differences between the full configuration interaction and CC or, in the case of excited states, EOMCC energies, obtained using conventional truncation schemes in the cluster operator T and excitation operator Rμ, is generalized, so that one can correct the CC/EOMCC energies obtained with arbitrary truncations in T and Rμ for the selected many-electron correlation effects of interest. The resulting moment expansions, defining the new, Flexible MMCC (Flex-MMCC) formalism, and the ensuing CC(P; Q) hierarchy, proposed in the present work, enable one to correct energies obtained in the active-space CC and EOMCC calculations, in which one selects higher many-body components of T and Rμ via active orbitals and which recover much of the relevant non-dynamical and some dynamical electron correlation effects in applications involving potential energy surfaces (PESs) along bond breaking coordinates, for the effects of higher-order, primarily dynamical, correlations missing in the active-space CC/EOMCC considerations. The Flex-MMCC corrections to the active-space CC/EOMCC energies are mathematically similar to the non-iterative energy corrections defining the existing left-eigenstate CR-CC and CR-EOMCC methods, such as CR-CC(2, 3) and CR-EOMCC(2, 3). The potential advantages of the Flex-MMCC and CC(P; Q) formalisms are illustrated by describing the initial implementation and numerical tests of the novel CC hybrid scheme, abbreviated as CC(t; 3), in which one corrects the results of the CC calculations with singles, doubles, and active-space triples, termed CCSDt, for the remaining effects due to connected triple excitations that are missing in the CCSDt considerations, but are present in the MMCC-based CR-CC(2, 3) approach. By examining bond breaking in the HF, F2, and F2+ molecules, it is demonstrated that the CC(t; 3) method improves the CCSDt and CR-CC(2, 3) results, providing PESs that agree with those obtained with the full CC theory with singles, doubles, and triples (CCSDT) to within small fractions of a millihartree, at the fraction of the computer costs of the CCSDT calculations. Different strategies for defining active-space triples within the CC(t; 3) scheme and the underlying CCSDt method are discussed. When limited to the ground-state problem, the CC(t; 3) approach can be regarded as an improved and rigorously derived extension of the recently proposed CCSD(T)-h method [J. Shen, E. Xu, Z. Kou, S. Li, J. Chem. Phys. 132 (2010) 114115], in which triples corrections of the CCSD(T) type are replaced by their more robust CR-CC(2, 3)-style analogs.

New Insights on the Rheology of Olivine Deformed under Lithospheric Temperature Conditions

NASA Astrophysics Data System (ADS)

Cordier, P.; Demouchy, S. A.; Mussi, A.; Tommasi, A.

2014-12-01

Rheology of mantle rocks at lithospheric temperatures remains poorly constrained, since most experimental studies on creep mechanisms of olivine single crystals ((MgFe)2SiO4, Pbnm) and polycrystalline olivine aggregates were performed at high-temperatures (T >> 1200oC). In this study, we report results from deformation experiments on oriented single crystals of San Carlos olivine and polycrystalline olivine aggregate at temperatures relevant of the uppermost mantle (ranging from 800o to 1090oC) in tri-axial compression. The experiments were carried out at a confining pressure of 300 MPa in a high-resolution gas-medium mechanical testing apparatus at various constant strain rates (from 7 x 10-6 s-1 to 1 x 10-4 s-1). Mechanical tests show that mantle lithosphere is actually weaker than previously inferred from the extrapolation of high-temperature experiments. In this study, we present characterization of dislocation microstructures based on transmission electron microscopy and electron tomography. It is shown that below 1000°C, dislocation activity is restricted to [001] glide with a strong predominance of {110} as glide planes. We observe recovery mechanisms which suggest that the mechanical properties observed in laboratory experiments represent an upper bound for the actual behavior of olivine under lithospheric mantle conditions. Moreover, the drastic reduction in slip system activity observed questions the ability of deforming olivine aggregates in the ductile regime at such temperatures. We show that ductility is preserved thanks to the activation of alternative deformation mechanisms in grain boundaries involving disclinations.

Conditioning of BPM pickup signals for operations of the Duke storage ring with a wide range of single-bunch current

NASA Astrophysics Data System (ADS)

Xu, Wei; Li, Jing-Yi; Huang, Sen-Lin; Z. Wu, W.; Hao, H.; P., Wang; K. Wu, Y.

2014-10-01

The Duke storage ring is a dedicated driver for the storage ring based oscillator free-electron lasers (FELs), and the High Intensity Gamma-ray Source (HIGS). It is operated with a beam current ranging from about 1 mA to 100 mA per bunch for various operations and accelerator physics studies. High performance operations of the FEL and γ-ray source require a stable electron beam orbit, which has been realized by the global orbit feedback system. As a critical part of the orbit feedback system, the electron beam position monitors (BPMs) are required to be able to precisely measure the electron beam orbit in a wide range of the single-bunch current. However, the high peak voltage of the BPM pickups associated with high single-bunch current degrades the performance of the BPM electronics, and can potentially damage the BPM electronics. A signal conditioning method using low pass filters is developed to reduce the peak voltage to protect the BPM electronics, and to make the BPMs capable of working with a wide range of single-bunch current. Simulations and electron beam based tests are performed. The results show that the Duke storage ring BPM system is capable of providing precise orbit measurements to ensure highly stable FEL and HIGS operations.

Nanowire active-matrix circuitry for low-voltage macroscale artificial skin.

PubMed

Takei, Kuniharu; Takahashi, Toshitake; Ho, Johnny C; Ko, Hyunhyub; Gillies, Andrew G; Leu, Paul W; Fearing, Ronald S; Javey, Ali

2010-10-01

Large-scale integration of high-performance electronic components on mechanically flexible substrates may enable new applications in electronics, sensing and energy. Over the past several years, tremendous progress in the printing and transfer of single-crystalline, inorganic micro- and nanostructures on plastic substrates has been achieved through various process schemes. For instance, contact printing of parallel arrays of semiconductor nanowires (NWs) has been explored as a versatile route to enable fabrication of high-performance, bendable transistors and sensors. However, truly macroscale integration of ordered NW circuitry has not yet been demonstrated, with the largest-scale active systems being of the order of 1 cm(2) (refs 11,15). This limitation is in part due to assembly- and processing-related obstacles, although larger-scale integration has been demonstrated for randomly oriented NWs (ref. 16). Driven by this challenge, here we demonstrate macroscale (7×7 cm(2)) integration of parallel NW arrays as the active-matrix backplane of a flexible pressure-sensor array (18×19 pixels). The integrated sensor array effectively functions as an artificial electronic skin, capable of monitoring applied pressure profiles with high spatial resolution. The active-matrix circuitry operates at a low operating voltage of less than 5 V and exhibits superb mechanical robustness and reliability, without performance degradation on bending to small radii of curvature (2.5 mm) for over 2,000 bending cycles. This work presents the largest integration of ordered NW-array active components, and demonstrates a model platform for future integration of nanomaterials for practical applications.

Conical Fourier shell correlation applied to electron tomograms.

PubMed

Diebolder, C A; Faas, F G A; Koster, A J; Koning, R I

2015-05-01

The resolution of electron tomograms is anisotropic due to geometrical constraints during data collection, such as the limited tilt range and single axis tilt series acquisition. Acquisition of dual axis tilt series can decrease these effects. However, in cryo-electron tomography, to limit the electron radiation damage that occurs during imaging, the total dose should not increase and must be fractionated over the two tilt series. Here we set out to determine whether it is beneficial fractionate electron dose for recording dual axis cryo electron tilt series or whether it is better to perform single axis acquisition. To assess the quality of tomographic reconstructions in different directions here we introduce conical Fourier shell correlation (cFSCe/o). Employing cFSCe/o, we compared the resolution isotropy of single-axis and dual-axis (cryo-)electron tomograms using even/odd split data sets. We show that the resolution of dual-axis simulated and cryo-electron tomograms in the plane orthogonal to the electron beam becomes more isotropic compared to single-axis tomograms and high resolution peaks along the tilt axis disappear. cFSCe/o also allowed us to compare different methods for the alignment of dual-axis tomograms. We show that different tomographic reconstruction programs produce different anisotropic resolution in dual axis tomograms. We anticipate that cFSCe/o can also be useful for comparisons of acquisition and reconstruction parameters, and different hardware implementations. Copyright © 2015 Elsevier Inc. All rights reserved.

Current Single Event Effects Results for Candidate Spacecraft Electronics for NASA

NASA Technical Reports Server (NTRS)

OBryan, Martha V.; Seidleck, Christina M.; Carts, Martin A.; LaBel, Kenneth A.; Marshall, Cheryl J.; Reed, Robert A.; Sanders, Anthony B.; Hawkins, Donald K.; Cox, Stephen R.; Kniffin, Scott D.

2004-01-01

We present data on the vulnerability of a variety of candidate spacecraft electronics to proton and heavy ion induced single event effects. Devices tested include digital, analog, linear bipolar, and hybrid devices, among others.

Single Event Effects Results for Candidate Spacecraft Electronics for NASA

NASA Technical Reports Server (NTRS)

O'Bryan, Martha; LaBel, Kenneth A.; Kniffin, Scott D.; Howard, James W., Jr.; Poivey, Christian; Ladbury, Ray L.; Buchner, Stephen P.; Xapsos, Michael; Reed, Robert A.; Sanders, Anthony B.

2003-01-01

We present data on the vulnerability of a variety of candidate spacecraft electronics to proton and heavy ion induced single event effects. Devices tested include digital, analog, linear bipolar, and hybrid devices, among others.

Heterogeneous Monolithic Integration of Single-Crystal Organic Materials.

PubMed

Park, Kyung Sun; Baek, Jangmi; Park, Yoonkyung; Lee, Lynn; Hyon, Jinho; Koo Lee, Yong-Eun; Shrestha, Nabeen K; Kang, Youngjong; Sung, Myung Mo

2017-02-01

Manufacturing high-performance organic electronic circuits requires the effective heterogeneous integration of different nanoscale organic materials with uniform morphology and high crystallinity in a desired arrangement. In particular, the development of high-performance organic electronic and optoelectronic devices relies on high-quality single crystals that show optimal intrinsic charge-transport properties and electrical performance. Moreover, the heterogeneous integration of organic materials on a single substrate in a monolithic way is highly demanded for the production of fundamental organic electronic components as well as complex integrated circuits. Many of the various methods that have been designed to pattern multiple heterogeneous organic materials on a substrate and the heterogeneous integration of organic single crystals with their crystal growth are described here. Critical issues that have been encountered in the development of high-performance organic integrated electronics are also addressed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dopant induced single electron tunneling within the sub-bands of single silicon NW tri-gate junctionless n-MOSFET

NASA Astrophysics Data System (ADS)

Uddin, Wasi; Georgiev, Yordan M.; Maity, Sarmistha; Das, Samaresh

2017-09-01

We report 1D electron transport of silicon junctionless tri-gate n-type transistor at 4.2 K. The step like curve observed in the current voltage characteristic suggests 1D transport. Besides the current steps for 1D transport, we found multiple spikes within individual steps, which we relate to inter-band single electron tunneling, mediated by the charged dopants available in the channel region. Clear Coulomb diamonds were observed in the stability diagram of the device. It is shown that a uniformly doped silicon nanowire can provide us the window for the single electron tunnelling. Back-gate versus front-gate color plot, where current is in a color scale, shows a crossover of the increased conduction region. This is a clear indication of the dopant-dopant interaction. It has been shown that back-gate biasing can be used to tune the coupling strength between the dopants.

Factor VIII organisation on nanodiscs with different lipid composition.

PubMed

Grushin, Kirill; Miller, Jaimy; Dalm, Daniela; Stoilova-McPhie, Svetla

2015-04-01

Nanodiscs (ND) are lipid bilayer membrane patches held by amphiphilic scaffolding proteins (MSP) of ~10 nm in diameter. Nanodiscs have been developed as lipid nanoplatforms for structural and functional studies of membrane and membrane associated proteins. Their size and monodispersity have rendered them unique for electron microscopy (EM) and single particle analysis studies of proteins and complexes either spanning or associated to the ND membrane. Binding of blood coagulation factors and complexes, such as the Factor VIII (FVIII) and the Factor VIIIa - Factor IXa (intrinsic tenase) complex to the negatively charged activated platelet membrane is required for normal haemostasis. In this study we present our work on optimising ND, specifically designed to bind FVIII at close to physiological conditions. The binding of FVIII to the negatively charged ND rich in phosphatidylserine (PS) was followed by electron microscopy at three different PS compositions and two different membrane scaffolding protein (MSP1D1) to lipid ratios. Our results show that the ND with highest PS content (80 %) and lowest MSP1D1 to lipid ratio (1:47) are the most suitable for structure determination of the membrane-bound FVIII by single particle EM. Our preliminary FVIII 3D reconstruction as bound to PS containing ND demonstrates the suitability of the optimised ND for structural studies by EM. Further assembly of the activated FVIII form (FVIIIa) and the whole FVIIIa-FIXa complex on ND, followed by EM and single particle reconstruction will help to identify the protein-protein and protein-membrane interfaces critical for the intrinsic tenase complex assembly and function.

Surface conduction of topological Dirac electrons in bulk insulating Bi2Se3

NASA Astrophysics Data System (ADS)

Fuhrer, Michael

2013-03-01

The three dimensional strong topological insulator (STI) is a new phase of electronic matter which is distinct from ordinary insulators in that it supports on its surface a conducting two-dimensional surface state whose existence is guaranteed by topology. I will discuss experiments on the STI material Bi2Se3, which has a bulk bandgap of 300 meV, much greater than room temperature, and a single topological surface state with a massless Dirac dispersion. Field effect transistors consisting of thin (3-20 nm) Bi2Se3 are fabricated from mechanically exfoliated from single crystals, and electrochemical and/or chemical gating methods are used to move the Fermi energy into the bulk bandgap, revealing the ambipolar gapless nature of transport in the Bi2Se3 surface states. The minimum conductivity of the topological surface state is understood within the self-consistent theory of Dirac electrons in the presence of charged impurities. The intrinsic finite-temperature resistivity of the topological surface state due to electron-acoustic phonon scattering is measured to be ~60 times larger than that of graphene largely due to the smaller Fermi and sound velocities in Bi2Se3, which will have implications for topological electronic devices operating at room temperature. As samples are made thinner, coherent coupling of the top and bottom topological surfaces is observed through the magnitude of the weak anti-localization correction to the conductivity, and, in the thinnest Bi2Se3 samples (~ 3 nm), in thermally-activated conductivity reflecting the opening of a bandgap.

Electron Information in Single- and Dual-Frequency Capacitive Discharges at Atmospheric Pressure.

PubMed

Park, Sanghoo; Choe, Wonho; Moon, Se Youn; Shi, Jian Jun

2018-05-14

Determining the electron properties of weakly ionized gases, particularly in a high electron-neutral collisional condition, is a nontrivial task; thus, the mechanisms underlying the electron characteristics and electron heating structure in radio-frequency (rf) collisional discharges remain unclear. Here, we report the electrical characteristics and electron information in single-frequency (4.52 MHz and 13.56 MHz) and dual-frequency (a combination of 4.52 MHz and 13.56 MHz) capacitive discharges within the abnormal α-mode regime at atmospheric pressure. A continuum radiation-based electron diagnostic method is employed to estimate the electron density (n e ) and temperature (T e ). Our experimental observations reveal that time-averaged n e (7.7-14 × 10 11  cm -3 ) and T e (1.75-2.5 eV) can be independently controlled in dual-frequency discharge, whereas such control is nontrivial in single-frequency discharge, which shows a linear increase in n e and little to no change in T e with increases in the rf input power. Furthermore, the two-dimensional spatiotemporal evolution of neutral bremsstrahlung and associated electron heating structures is demonstrated. These results reveal that a symmetric structure in electron heating becomes asymmetric (via a local suppression of electron temperature) as two-frequency power is simultaneously introduced.

Ultrafast electron microscopy: Instrument response from the single-electron to high bunch-charge regimes

NASA Astrophysics Data System (ADS)

Plemmons, Dayne A.; Flannigan, David J.

2017-09-01

We determine the instrument response of an ultrafast electron microscope equipped with a conventional thermionic electron gun and absent modifications beyond the optical ports. Using flat, graphite-encircled LaB6 cathodes, we image space-charge effects as a function of photoelectron-packet population and find that an applied Wehnelt bias has a negligible effect on the threshold levels (>103 electrons per pulse) but does appear to suppress blurring at the upper limits (∼105 electrons). Using plasma lensing, we determine the instrument-response time for 700-fs laser pulses and find that single-electron packets are laser limited (1 ps), while broadening occurs well below the space-charge limit.

Use of single scatter electron monte carlo transport for medical radiation sciences

DOEpatents

Svatos, Michelle M.

2001-01-01

The single scatter Monte Carlo code CREEP models precise microscopic interactions of electrons with matter to enhance physical understanding of radiation sciences. It is designed to simulate electrons in any medium, including materials important for biological studies. It simulates each interaction individually by sampling from a library which contains accurate information over a broad range of energies.

Spin Measurements of an Electron Bound to a Single Phosphorous Donor in Silicon

NASA Astrophysics Data System (ADS)

Luhman, D. R.; Nguyen, K.; Tracy, L. A.; Carr, S. M.; Borchardt, J.; Bishop, N. C.; Ten Eyck, G. A.; Pluym, T.; Wendt, J.; Carroll, M. S.; Lilly, M. P.

2014-03-01

The spin of an electron bound to a single donor implanted in silicon is potentially useful for quantum information processing. We report on our efforts to measure and manipulate the spin of an electron bound to a single P donor in silicon. A low number of P donors are implanted using a self-aligned process into a silicon substrate in close proximity to a single-electron-transistor (SET) defined by lithographically patterned polysilicon gates. The SET is used to sense the occupancy of the electron on the donor and for spin read-out. An adjacent transmission line allows the application of microwave pulses to rotate the spin of the electron. We will present data from various experiments designed to exploit these capabilities. This work was performed, in part, at the Center for Integrated Nanotechnologies, a U.S. DOE Office of Basic Energy Sciences user facility. The work was supported by Sandia National Laboratories Directed Research and Development Program. Sandia National Laboratories is a multi-program laboratory operated by Sandia Corporation, a Lockheed-Martin Company, for the U. S. Department of Energy under Contract No. DE-AC04-94AL85000.

Multifunctional Diketopyrrolopyrrole-Based Conjugated Polymers with Perylene Bisimide Side Chains.

PubMed

Li, Cheng; Yu, Changshi; Lai, Wenbin; Liang, Shijie; Jiang, Xudong; Feng, Guitao; Zhang, Jianqi; Xu, Yunhua; Li, Weiwei

2017-11-24

Two conjugated polymers based on diketopyrrolopyrrole (DPP) in the main chain with different content of perylene bisimide (PBI) side chains are developed. The influence of PBI side chain on the photovoltaic performance of these DPP-based conjugated polymers is systematically investigated. This study suggests that the PBI side chains can not only alter the absorption spectrum and energy level but also enhance the crystallinity of conjugated polymers. As a result, such polymers can act as electron donor, electron acceptor, and single-component active layer in organic solar cells. These findings provide a new guideline for the future molecular design of multifunctional conjugated polymers. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

All-optical photochromic spatial light modulators based on photoinduced electron transfer in rigid matrices

NASA Technical Reports Server (NTRS)

Beratan, David N. (Inventor); Perry, Joseph W. (Inventor)

1991-01-01

A single material (not a multi-element structure) spatial light modulator may be written to, as well as read out from, using light. The device has tailorable rise and hold times dependent on the composition and concentration of the molecular species used as the active components. The spatial resolution of this device is limited only by light diffraction as in volume holograms. The device may function as a two-dimensional mask (transmission or reflection) or as a three-dimensional volume holographic medium. This device, based on optically-induced electron transfer, is able to perform incoherent to coherent image conversion or wavelength conversion over a wide spectral range (ultraviolet, visible, or near-infrared regions).

High-Fidelity Rapid Initialization and Read-Out of an Electron Spin via the Single Donor D(-) Charge State.

PubMed

Watson, T F; Weber, B; House, M G; Büch, H; Simmons, M Y

2015-10-16

We demonstrate high-fidelity electron spin read-out of a precision placed single donor in silicon via spin selective tunneling to either the D(+) or D(-) charge state of the donor. By performing read-out at the stable two electron D(0)↔D(-) charge transition we can increase the tunnel rates to a nearby single electron transistor charge sensor by nearly 2 orders of magnitude, allowing faster qubit read-out (1 ms) with minimum loss in read-out fidelity (98.4%) compared to read-out at the D(+)↔D(0) transition (99.6%). Furthermore, we show that read-out via the D(-) charge state can be used to rapidly initialize the electron spin qubit in its ground state with a fidelity of F(I)=99.8%.

FOB-SH: Fragment orbital-based surface hopping for charge carrier transport in organic and biological molecules and materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Spencer, J.; Gajdos, F.; Blumberger, J., E-mail: j.blumberger@ucl.ac.uk

2016-08-14

We introduce a fragment orbital-based fewest switches surface hopping method, FOB-SH, designed to efficiently simulate charge carrier transport in strongly fluctuating condensed phase systems such as organic semiconductors and biomolecules. The charge carrier wavefunction is expanded and the electronic Hamiltonian constructed in a set of singly occupied molecular orbitals of the molecular sites that mediate the charge transfer. Diagonal elements of the electronic Hamiltonian (site energies) are obtained from a force field, whereas the off-diagonal or electronic coupling matrix elements are obtained using our recently developed analytic overlap method. We derive a general expression for the exact forces on themore » adiabatic ground and excited electronic state surfaces from the nuclear gradients of the charge localized electronic states. Applications to electron hole transfer in a model ethylene dimer and through a chain of ten model ethylenes validate our implementation and demonstrate its computational efficiency. On the larger system, we calculate the qualitative behaviour of charge mobility with change in temperature T for different regimes of the intermolecular electronic coupling. For small couplings, FOB-SH predicts a crossover from a thermally activated regime at low temperatures to a band-like transport regime at higher temperatures. For higher electronic couplings, the thermally activated regime disappears and the mobility decreases according to a power law. This is interpreted by a gradual loss in probability for resonance between the sites as the temperature increases. The polaron hopping model solved for the same system gives a qualitatively different result and underestimates the mobility decay at higher temperatures. Taken together, the FOB-SH methodology introduced here shows promise for a realistic investigation of charge carrier transport in complex organic, aqueous, and biological systems.« less

FOB-SH: Fragment orbital-based surface hopping for charge carrier transport in organic and biological molecules and materials

NASA Astrophysics Data System (ADS)

Spencer, J.; Gajdos, F.; Blumberger, J.

2016-08-01

We introduce a fragment orbital-based fewest switches surface hopping method, FOB-SH, designed to efficiently simulate charge carrier transport in strongly fluctuating condensed phase systems such as organic semiconductors and biomolecules. The charge carrier wavefunction is expanded and the electronic Hamiltonian constructed in a set of singly occupied molecular orbitals of the molecular sites that mediate the charge transfer. Diagonal elements of the electronic Hamiltonian (site energies) are obtained from a force field, whereas the off-diagonal or electronic coupling matrix elements are obtained using our recently developed analytic overlap method. We derive a general expression for the exact forces on the adiabatic ground and excited electronic state surfaces from the nuclear gradients of the charge localized electronic states. Applications to electron hole transfer in a model ethylene dimer and through a chain of ten model ethylenes validate our implementation and demonstrate its computational efficiency. On the larger system, we calculate the qualitative behaviour of charge mobility with change in temperature T for different regimes of the intermolecular electronic coupling. For small couplings, FOB-SH predicts a crossover from a thermally activated regime at low temperatures to a band-like transport regime at higher temperatures. For higher electronic couplings, the thermally activated regime disappears and the mobility decreases according to a power law. This is interpreted by a gradual loss in probability for resonance between the sites as the temperature increases. The polaron hopping model solved for the same system gives a qualitatively different result and underestimates the mobility decay at higher temperatures. Taken together, the FOB-SH methodology introduced here shows promise for a realistic investigation of charge carrier transport in complex organic, aqueous, and biological systems.

Electrocatalytic interface based on novel carbon nanomaterials for advanced electrochemical sensors

DOE PAGES

Zhou, Ming; Guo, Shaojun

2015-07-17

The rapid development of nanoscience and nanotechnology provides new opportunities for the sustainable progress of nanoscale catalysts (i.e., nanocatalysts). The introduction of nanocatalysts into electronic devices implants their novel functions into electronic sensing systems, resulting in the testing of many advanced electrochemical sensors and the fabrication of some highly sensitive, selective, and stable sensing platforms. In this Review, we will summarize recent significant progress on exploring advanced carbon nanomaterials (such as carbon nanotubes, graphene, highly ordered mesoporous carbons, and electron cyclotron resonance sputtered nanocarbon film) as nanoscale electrocatalysts (i.e., nanoelectrocatalysts) for constructing the catalytic nanointerfaces of electronic devices to achievemore » high-sensitivity and high-selectivity electrochemical sensors. Furthermore, different mechanisms for the extraordinary and unique electrocatalytic activities of these carbon nanomaterials will be also highlighted, compared and discussed. An outlook on the future trends and developments in this area will be provided at the end. Notably, to elaborate the nature of carbon nanomaterial, we will mainly focus on the electrocatalysis of single kind of carbon materials rather than their hybrid composite materials. As a result, we expect that advanced carbon nanomaterials with unique electrocatalytic activities will continue to attract increasing research interest and lead to new opportunities in various fields of research.« less

Electrocatalytic interface based on novel carbon nanomaterials for advanced electrochemical sensors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou, Ming; Guo, Shaojun

The rapid development of nanoscience and nanotechnology provides new opportunities for the sustainable progress of nanoscale catalysts (i.e., nanocatalysts). The introduction of nanocatalysts into electronic devices implants their novel functions into electronic sensing systems, resulting in the testing of many advanced electrochemical sensors and the fabrication of some highly sensitive, selective, and stable sensing platforms. In this Review, we will summarize recent significant progress on exploring advanced carbon nanomaterials (such as carbon nanotubes, graphene, highly ordered mesoporous carbons, and electron cyclotron resonance sputtered nanocarbon film) as nanoscale electrocatalysts (i.e., nanoelectrocatalysts) for constructing the catalytic nanointerfaces of electronic devices to achievemore » high-sensitivity and high-selectivity electrochemical sensors. Furthermore, different mechanisms for the extraordinary and unique electrocatalytic activities of these carbon nanomaterials will be also highlighted, compared and discussed. An outlook on the future trends and developments in this area will be provided at the end. Notably, to elaborate the nature of carbon nanomaterial, we will mainly focus on the electrocatalysis of single kind of carbon materials rather than their hybrid composite materials. As a result, we expect that advanced carbon nanomaterials with unique electrocatalytic activities will continue to attract increasing research interest and lead to new opportunities in various fields of research.« less

Silver nanocrystal-decorated polyoxometalate single-walled nanotubes as nanoreactors for desulfurization catalysis at room temperature.

PubMed

Zhang, Hao; Xu, Xiaobin; Lin, Haifeng; Ud Din, Muhammad Aizaz; Wang, Haiqing; Wang, Xun

2017-09-14

Ultrathin nanocrystals generally provide a remarkable catalytic performance due to their high specific surface area and exposure of certain active sites. However, deactivation caused by growth and gathering limits the catalytic application of ultrathin nanocrystals. Here we report Ag nanocrystal-decorated polyoxometalate (Ag-POM) single-walled nanotubes assembled via a concise, surfactant-free soaking method as a new kind of well-defined core-sheath nanoreactor. The diameter of Ag nanocrystals inside polyoxometalate nanotubes can be controlled via simply adjusting the reactant concentration. Ag-POM provided outstanding oxidative desulfurization (ODS) catalytic performance for aromatic sulfocompounds at room temperature. It was suggested that Ag nanocrystals decorated on the inner surface played a key role in adjusting the electronic distribution and enhancing the catalytic activity. The as-prepared Ag-POM nanotubes are promising candidate catalysts with enhanced performance for practical catalytic applications in the gasoline desulfurization industry.

Inference of Heating Properties from "Hot" Non-flaring Plasmas in Active Region Cores. I. Single Nanoflares

NASA Astrophysics Data System (ADS)

Barnes, W. T.; Cargill, P. J.; Bradshaw, S. J.

2016-09-01

The properties that are expected of “hot” non-flaring plasmas due to nanoflare heating in active regions are investigated using hydrodynamic modeling tools, including a two-fluid development of the Enthalpy Based Thermal Evolution of Loops code. Here we study a single nanoflare and show that while simple models predict an emission measure distribution extending well above 10 MK, which is consistent with cooling by thermal conduction, many other effects are likely to limit the existence and detectability of such plasmas. These include: differential heating between electrons and ions, ionization non-equilibrium, and for short nanoflares, the time taken for the coronal density to increase. The most useful temperature range to look for this plasma, often called the “smoking gun” of nanoflare heating, lies between 106.6 and 107 K. Signatures of the actual heating may be detectable in some instances.

"Hot" Non-flaring Plasmas in Active Region Cores Heated by Single Nanoflares

NASA Astrophysics Data System (ADS)

Barnes, Will Thomas; Cargill, Peter; Bradshaw, Stephen

2016-05-01

We use hydrodynamic modeling tools, including a two-fluid development of the EBTEL code, to investigate the properties expected of "hot" (i.e. between 106.7 and 107.2 K) non-flaring plasmas due to nanoflare heating in active regions. Here we focus on single nanoflares and show that while simple models predict an emission measure distribution extending well above 10 MK that is consistent with cooling by thermal conduction, many other effects are likely to limit the existence and detectability of such plasmas. These include: differential heating between electrons and ions, ionization non-equilibrium and, for short nanoflares, the time taken for the coronal density to increase. The most useful temperature range to look for this plasma, often called the "smoking gun" of nanoflare heating, lies between 1 MK and 10 MK. Signatures of the actual heating may be detectable in some instances.

Vibrational spectroscopy and imaging for concurrent cellular trafficking of co-localized doxorubicin and deuterated phospholipid vesicles

NASA Astrophysics Data System (ADS)

Misra, S. K.; Mukherjee, P.; Ohoka, A.; Schwartz-Duval, A. S.; Tiwari, S.; Bhargava, R.; Pan, D.

2016-01-01

Simultaneous tracking of nanoparticles and encapsulated payload is of great importance and visualizing their activity is arduous. Here we use vibrational spectroscopy to study the in vitro tracking of co-localized lipid nanoparticles and encapsulated drug employing a model system derived from doxorubicin-encapsulated deuterated phospholipid (dodecyl phosphocholine-d38) single tailed phospholipid vesicles.Simultaneous tracking of nanoparticles and encapsulated payload is of great importance and visualizing their activity is arduous. Here we use vibrational spectroscopy to study the in vitro tracking of co-localized lipid nanoparticles and encapsulated drug employing a model system derived from doxorubicin-encapsulated deuterated phospholipid (dodecyl phosphocholine-d38) single tailed phospholipid vesicles. Electronic supplementary information (ESI) available: Raman and confocal images of the Deuto-DOX-NPs in cells, materials and details of methods. See DOI: 10.1039/c5nr07975f

Simultaneous transcranial magnetic stimulation and single neuron recording in alert non-human primates

PubMed Central

Mueller, Jerel K.; Grigsby, Erinn M.; Prevosto, Vincent; Petraglia, Frank W.; Rao, Hrishikesh; Deng, Zhi-De; Peterchev, Angel V.; Sommer, Marc A.; Egner, Tobias; Platt, Michael L.; Grill, Warren M.

2014-01-01

Transcranial magnetic stimulation (TMS) is a widely used, noninvasive method for stimulating nervous tissue, yet its mechanisms of effect are poorly understood. Here we report novel methods for studying the influence of TMS on single neurons in the brain of alert non-human primates. We designed a TMS coil that focuses its effect near the tip of a recording electrode and recording electronics that enable direct acquisition of neuronal signals at the site of peak stimulus strength minimally perturbed by stimulation artifact in intact, awake monkeys (Macaca mulatta). We recorded action potentials within ~1 ms after 0.4 ms TMS pulses and observed changes in activity that differed significantly for active stimulation as compared to sham stimulation. The methodology is compatible with standard equipment in primate laboratories, allowing for easy implementation. Application of these new tools will facilitate the refinement of next generation TMS devices, experiments, and treatment protocols. PMID:24974797

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hushur, Anwar; Manghnani, Murli H.; Werheit, Helmut

Single-crystal B4.3C boron carbide is investigated concerning the pressure-dependence of optical properties and of Raman-active phonons up to ~70 GPa. The high concentration of structural defects determining the electronic properties of boron carbide at ambient conditions initially decrease and finally vanish with pressure increasing. We obtain this immediately from transparency photos, allowing to estimate the pressure-dependent variation of the absorption edge rapidly increasing around 55 GPa. Glass-like transparency at pressures exceeding 60 GPa indicate that the width of the band exceeds ~3.1 eV thus making boron carbide a wide-gap semiconductor. Furthermore, the spectra of Raman–active phonons indicate a pressure-dependent phasemore » transition in single-crystal natB4.3C boron carbide near 35 GPa., particularly related to structural changes in connection with the C-B-C chains, while the basic icosahedral structure remains largely unaffected.« less

Emerging behavior in electronic bidding.

PubMed

Yang, I; Jeong, H; Kahng, B; Barabási, A-L

2003-07-01

We characterize the statistical properties of a large number of agents on two major online auction sites. The measurements indicate that the total number of bids placed in a single category and the number of distinct auctions frequented by a given agent follow power-law distributions, implying that a few agents are responsible for a significant fraction of the total bidding activity on the online market. We find that these agents exert an unproportional influence on the final price of the auctioned items. This domination of online auctions by an unusually active minority may be a generic feature of all online mercantile processes.

Emerging behavior in electronic bidding

NASA Astrophysics Data System (ADS)

Yang, I.; Jeong, H.; Kahng, B.; Barabási, A.-L.

2003-07-01

We characterize the statistical properties of a large number of agents on two major online auction sites. The measurements indicate that the total number of bids placed in a single category and the number of distinct auctions frequented by a given agent follow power-law distributions, implying that a few agents are responsible for a significant fraction of the total bidding activity on the online market. We find that these agents exert an unproportional influence on the final price of the auctioned items. This domination of online auctions by an unusually active minority may be a generic feature of all online mercantile processes.

In situ characterization of cofacial Co(IV) centers in Co4O4 cubane: Modeling the high-valent active site in oxygen-evolving catalysts.

PubMed

Brodsky, Casey N; Hadt, Ryan G; Hayes, Dugan; Reinhart, Benjamin J; Li, Nancy; Chen, Lin X; Nocera, Daniel G

2017-04-11

The Co 4 O 4 cubane is a representative structural model of oxidic cobalt oxygen-evolving catalysts (Co-OECs). The Co-OECs are active when residing at two oxidation levels above an all-Co(III) resting state. This doubly oxidized Co(IV) 2 state may be captured in a Co(III) 2 (IV) 2 cubane. We demonstrate that the Co(III) 2 (IV) 2 cubane may be electrochemically generated and the electronic properties of this unique high-valent state may be probed by in situ spectroscopy. Intervalence charge-transfer (IVCT) bands in the near-IR are observed for the Co(III) 2 (IV) 2 cubane, and spectroscopic analysis together with electrochemical kinetics measurements reveal a larger reorganization energy and a smaller electron transfer rate constant for the doubly versus singly oxidized cubane. Spectroelectrochemical X-ray absorption data further reveal systematic spectral changes with successive oxidations from the cubane resting state. Electronic structure calculations correlated to experimental data suggest that this state is best represented as a localized, antiferromagnetically coupled Co(IV) 2 dimer. The exchange coupling in the cofacial Co(IV) 2 site allows for parallels to be drawn between the electronic structure of the Co 4 O 4 cubane model system and the high-valent active site of the Co-OEC, with specific emphasis on the manifestation of a doubly oxidized Co(IV) 2 center on O-O bond formation.

In situ characterization of cofacial Co(IV) centers in Co 4O 4 cubane: Modeling the high-valent active site in oxygen-evolving catalysts

DOE PAGES

Brodsky, Casey N.; Hadt, Ryan G.; Hayes, Dugan; ...

2017-03-27

The Co 4O 4 cubane is a representative structural model of oxidic cobalt oxygen evolving catalysts (Co-OECs). The Co-OECs are active when residing at two oxidation levels above an all Co(III) resting state. This doubly oxidized Co(IV) 2 state may be captured in a Co(III) 2(IV) 2 cubane. We demonstrate that the Co(III) 2(IV) 2 cubane may be electrochemically generated and the electronic properties of this unique high-valent state may be probed by in situ spectroscopy. Intervalence charge transfer (IVCT) bands in the near-IR are observed for the Co(III) 2(IV) 2 cubane, and spectroscopic analysis together with electrochemical kinetics measurementsmore » reveal a larger reorganization energy and a smaller electron transfer rate constant for the doubly versus singly oxidized cubane. Spectroelectrochemical X-ray absorption data further reveal systematic spectral changes with successive oxidations from the cubane resting state. Electronic structure calculations correlated to experimental data suggest that this state is best represented as a localized, antiferromagnetically coupled Co(IV) 2 dimer. The exchange coupling in the cofacial Co(IV) 2 site allows for parallels to be drawn between the electronic structure of the Co 4O 4 cubane model system and the high valent active site of the Co-OEC, with specific emphasis on the manifestation of a doubly oxidized Co(IV) 2 center on O–O bond formation.« less

Automated data collection in single particle electron microscopy

PubMed Central

Tan, Yong Zi; Cheng, Anchi; Potter, Clinton S.; Carragher, Bridget

2016-01-01

Automated data collection is an integral part of modern workflows in single particle electron microscopy (EM) research. This review surveys the software packages available for automated single particle EM data collection. The degree of automation at each stage of data collection is evaluated, and the capabilities of the software packages are described. Finally, future trends in automation are discussed. PMID:26671944

Where is crystallography going?

PubMed Central

Ashton, Alun W.; Sorensen, Thomas

2018-01-01

Macromolecular crystallography (MX) has been a motor for biology for over half a century and this continues apace. A series of revolutions, including the production of recombinant proteins and cryo-crystallography, have meant that MX has repeatedly reinvented itself to dramatically increase its reach. Over the last 30 years synchrotron radiation has nucleated a succession of advances, ranging from detectors to optics and automation. These advances, in turn, open up opportunities. For instance, a further order of magnitude could perhaps be gained in signal to noise for general synchrotron experiments. In addition, X-ray free-electron lasers offer to capture fragments of reciprocal space without radiation damage, and open up the subpicosecond regime of protein dynamics and activity. But electrons have recently stolen the limelight: so is X-ray crystallography in rude health, or will imaging methods, especially single-particle electron microscopy, render it obsolete for the most interesting biology, whilst electron diffraction enables structure determination from even the smallest crystals? We will lay out some information to help you decide. PMID:29533241

Numerical Investigation on Electron and Ion Transmission of GEM-based Detectors

NASA Astrophysics Data System (ADS)

Bhattacharya, Purba; Sahoo, Sumanya Sekhar; Biswas, Saikat; Mohanty, Bedangadas; Majumdar, Nayana; Mukhopadhyay, Supratik

2018-02-01

ALICE at the LHC is planning a major upgrade of its detector systems, including the TPC, to cope with an increase of the LHC luminosity after 2018. Different R&D activities are currently concentrated on the adoption of the Gas Electron Multiplier (GEM) as the gas amplification stage of the ALICE-TPC upgrade version. The major challenge is to have low ion feedback in the drift volume as well as to ensure a collection of good percentage of primary electrons in the signal generation process. In the present work, Garfield simulation framework has been adopted to numerically estimate the electron transparency and ion backflow fraction of GEM-based detectors. In this process, extensive simulations have been carried out to enrich our understanding of the complex physical processes occurring within single, triple and quadruple GEM detectors. A detailed study has been performed to observe the effect of detector geometry, field configuration and magnetic field on the above mentioned characteristics.

Experimental demonstration of a single-spike hard-X-ray free-electron laser starting from noise

DOE PAGES

Marinelli, A.; MacArthur, J.; Emma, P.; ...

2017-10-09

In this letter, we report the experimental demonstration of single-spike hard-X-ray free-electron laser pulses starting from noise with multi-eV bandwidth. Here, this is accomplished by shaping a low-charge electron beam with a slotted emittance spoiler and by adjusting the transport optics to optimize the beam-shaping accuracy. Based on elementary free-electron laser scaling laws, we estimate the pulse duration to be less than 1 fs full-width at half-maximum.

Experimental demonstration of a single-spike hard-X-ray free-electron laser starting from noise

DOE Office of Scientific and Technical Information (OSTI.GOV)

Marinelli, A.; MacArthur, J.; Emma, P.

In this letter, we report the experimental demonstration of single-spike hard-X-ray free-electron laser pulses starting from noise with multi-eV bandwidth. Here, this is accomplished by shaping a low-charge electron beam with a slotted emittance spoiler and by adjusting the transport optics to optimize the beam-shaping accuracy. Based on elementary free-electron laser scaling laws, we estimate the pulse duration to be less than 1 fs full-width at half-maximum.

Performance optimization of detector electronics for millimeter laser ranging

NASA Technical Reports Server (NTRS)

Cova, Sergio; Lacaita, A.; Ripamonti, Giancarlo

1993-01-01

The front-end electronic circuitry plays a fundamental role in determining the performance actually obtained from ultrafast and highly sensitive photodetectors. We deal here with electronic problems met working with microchannel plate photomultipliers (MCP-PMTs) and single photon avalanche diodes (SPADs) for detecting single optical photons and measuring their arrival time with picosecond resolution. The performance of available fast circuits is critically analyzed. Criteria for selecting the most suitable electronics are derived and solutions for exploiting the detector performance are presented and discussed.

Redox activity distinguishes solid-state electron transport from solution-based electron transfer in a natural and artificial protein: cytochrome C and hemin-doped human serum albumin.

PubMed

Amdursky, Nadav; Ferber, Doron; Pecht, Israel; Sheves, Mordechai; Cahen, David

2013-10-28

Integrating proteins in molecular electronic devices requires control over their solid-state electronic transport behavior. Unlike "traditional" electron transfer (ET) measurements of proteins that involve liquid environments and a redox cycle, no redox cofactor is needed for solid-state electron transport (ETp) across the protein. Here we show the fundamental difference between these two approaches by macroscopic area measurements, which allow measuring ETp temperature dependence down to cryogenic temperatures, via cytochrome C (Cyt C), an ET protein with a heme (Fe-porphyrin) prosthetic group as a redox centre. We compare the ETp to electrochemical ET measurements, and do so also for the protein without the Fe (with metal-free porphyrin) and without porphyrin. As removing the porphyrin irreversibly alters the protein's conformation, we repeat these measurements with human serum albumin (HSA), 'doped' (by non-covalent binding) with a single hemin equivalent, i.e., these natural and artificial proteins share a common prosthetic group. ETp via Cyt C and HSA-hemin are very similar in terms of current magnitude and temperature dependence, which suggests similar ETp mechanisms via these two systems, thermally activated hopping (with ~0.1 eV activation energy) >190 K and tunneling by superexchange <190 K. Also, ET rates to and from the Fe redox centres (Fe(2+) <=> Fe(3+) + e(-)), measured by electrochemistry of HSA-hemin are only 4 times lower than those for Cyt C. However, while removing the Fe redox centre from the porphyrin ring markedly affects the ET rate, it hardly changes the ETp currents through these proteins, while removing the macrocycle (from HSA, which retains its conformation) significantly reduces ETp efficiency. These results show that solid-state ETp across proteins does not require the presence of a redox cofactor, and that while for ET the Fe ion is the main electron mediator, for ETp the porphyrin ring has this function.

Efficient creation of electron vortex beams for high resolution STEM imaging.

PubMed

Béché, A; Juchtmans, R; Verbeeck, J

2017-07-01

The recent discovery of electron vortex beams carrying quantised angular momentum in the TEM has led to an active field of research, exploring a variety of potential applications including the possibility of mapping magnetic states at the atomic scale. A prerequisite for this is the availability of atomic sized electron vortex beams at high beam current and mode purity. In this paper we present recent progress showing that by making use of the Aharonov-Bohm effect near the tip of a long single domain ferromagnetic Nickel needle, a very efficient aperture for the production of electron vortex beams can be realised. The aperture transmits more than 99% of all electrons and provides a vortex mode purity of up to 92%. Placing this aperture in the condenser plane of a state of the art Cs corrected microscope allows us to demonstrate atomic resolution HAADF STEM images with spatial resolution better than 1 Angström, in agreement with theoretical expectations and only slightly inferior to the performance of a non-vortex probe on the same instrument. Copyright © 2016 Elsevier B.V. All rights reserved.

Electron microscopy study of gold nanoparticles deposited on transition metal oxides.

PubMed

Akita, Tomoki; Kohyama, Masanori; Haruta, Masatake

2013-08-20

Many researchers have investigated the catalytic performance of gold nanoparticles (GNPs) supported on metal oxides for various catalytic reactions of industrial importance. These studies have consistently shown that the catalytic activity and selectivity depend on the size of GNPs, the kind of metal oxide supports, and the gold/metal oxide interface structure. Although researchers have proposed several structural models for the catalytically active sites and have identified the specific electronic structures of GNPs induced by the quantum effect, recent experimental and theoretical studies indicate that the perimeter around GNPs in contact with the metal oxide supports acts as an active site in many reactions. Thus, it is of immense importance to investigate the detailed structures of the perimeters and the contact interfaces of gold/metal oxide systems by using electron microscopy at an atomic scale. This Account describes our investigation, at the atomic scale using electron microscopy, of GNPs deposited on metal oxides. In particular, high-resolution transmission electron microscopy (HRTEM) and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) are valuable tools to observe local atomic structures, as has been successfully demonstrated for various nanoparticles, surfaces, and material interfaces. TEM can be applied to real powder catalysts as received without making special specimens, in contrast to what is typically necessary to observe bulk materials. For precise structure analyses at an atomic scale, model catalysts prepared by using well-defined single-crystalline substrates are also adopted for TEM observations. Moreover, aberration-corrected TEM, which has high spatial resolution under 0.1 nm, is a promising tool to observe the interface structure between GNPs and metal oxide supports including oxygen atoms at the interfaces. The oxygen atoms in particular play an important role in the behavior of gold/metal oxide interfaces, because they may participate in catalytic reaction steps. Detailed information about the interfacial structures between GNPs and metal oxides provides valuable structure models for theoretical calculations which can elucidate the local electronic structure effective for activating a reactant molecule. Based on our observations with HRTEM and HAADF-STEM, we report the detailed structure of gold/metal oxide interfaces.

Highly oxygenated ent-pimarane-type diterpenoids from the Chinese liverwort Pedinophyllum interruptum and their allelopathic activities.

PubMed

Liu, Na; Li, Rui-Juan; Wang, Xiao-Ning; Zhu, Rong-Xiu; Wang, Lei; Lin, Zhao-Min; Zhao, Yu; Lou, Hong-Xiang

2013-09-27

Ten highly oxygenated ent-pimarane-type diterpenoids, pedinophyllols A-J (1-10), were isolated from the Chinese liverwort Pedinophyllum interruptum. Their structures were determined by comprehensive analysis of spectroscopic data together with single-crystal X-ray diffraction analysis. The absolute configurations were elucidated by comparison of experimental and theoretically calculated electronic circular dichroism spectra. Allelopathic testing showed that several new diterpenoids inhibited germination of Arabidopsis thaliana seeds.

Scanning ultrafast electron microscopy.

PubMed

Yang, Ding-Shyue; Mohammed, Omar F; Zewail, Ahmed H

2010-08-24

Progress has been made in the development of four-dimensional ultrafast electron microscopy, which enables space-time imaging of structural dynamics in the condensed phase. In ultrafast electron microscopy, the electrons are accelerated, typically to 200 keV, and the microscope operates in the transmission mode. Here, we report the development of scanning ultrafast electron microscopy using a field-emission-source configuration. Scanning of pulses is made in the single-electron mode, for which the pulse contains at most one or a few electrons, thus achieving imaging without the space-charge effect between electrons, and still in ten(s) of seconds. For imaging, the secondary electrons from surface structures are detected, as demonstrated here for material surfaces and biological specimens. By recording backscattered electrons, diffraction patterns from single crystals were also obtained. Scanning pulsed-electron microscopy with the acquired spatiotemporal resolutions, and its efficient heat-dissipation feature, is now poised to provide in situ 4D imaging and with environmental capability.

Toward single-chirality carbon nanotube device arrays.

PubMed

Vijayaraghavan, Aravind; Hennrich, Frank; Stürzl, Ninette; Engel, Michael; Ganzhorn, Marc; Oron-Carl, Matti; Marquardt, Christoph W; Dehm, Simone; Lebedkin, Sergei; Kappes, Manfred M; Krupke, Ralph

2010-05-25

The large-scale integration of devices consisting of individual single-walled carbon nanotubes (SWCNT), all of the same chirality, is a critical step toward their electronic, optoelectronic, and electromechanical application. Here, the authors realize two related goals, the first of which is the fabrication of high-density, single-chirality SWCNT device arrays by dielectrophoretic assembly from monodisperse SWCNT solution obtained by polymer-mediated sorting. Such arrays are ideal for correlating measurements using various techniques across multiple identical devices, which is the second goal. The arrays are characterized by voltage-contrast scanning electron microscopy, electron transport, photoluminescence (PL), and Raman spectroscopy and show identical signatures as expected for single-chirality SWCNTs. In the assembled nanotubes, a large D peak in Raman spectra, a large dark-exciton peak in PL spectra as well as lowered conductance and slow switching in electron transport are all shown to be correlated to each other. By comparison to control samples, we conclude that these are the result of scattering from electronic and not structural defects resulting from the polymer wrapping, similar to what has been predicted for DNA wrapping.

Single-Photon, Double Photodetachment of Nickel Phthalocyanine Tetrasulfonic Acid 4- Anions.

PubMed

Daly, Steven; Girod, Marion; Vojkovic, Marin; Giuliani, Alexandre; Antoine, Rodolphe; Nahon, Laurent; O'Hair, Richard A J; Dugourd, Philippe

2016-07-07

Single-photon, two-electron photodetachment from nickel phthalocyanine tetrasulfonic acid tetra anions, [NiPc](4-), was examined in the gas-phase using a linear ion trap coupled to the DESIRS VUV beamline of the SOLEIL Synchrotron. This system was chosen since it has a low detachment energy, known charge localization, and well-defined geometrical and electronic structures. A threshold for two-electron loss is observed at 10.2 eV, around 1 eV lower than previously observed double detachment thresholds on multiple charged protein anions. The photodetachment energy of [NiPc](4-) has been previously determined to be 3.5 eV and the photodetachment energy of [NiPc](3-•) is determined in this work to be 4.3 eV. The observed single photon double electron detachment threshold is hence 5.9 eV higher than the energy required for sequential single electron loss. Possible mechanisms are for double photodetachment are discussed. These observations pave the way toward new, exciting experiments for probing double photodetachment at relatively low energies, including correlation measurements on emitted photoelectrons.

Two-dimensional collective electron magnetotransport, oscillations, and chaos in a semiconductor superlattice

NASA Astrophysics Data System (ADS)

Bonilla, L. L.; Carretero, M.; Segura, A.

2017-12-01

When quantized, traces of classically chaotic single-particle systems include eigenvalue statistics and scars in eigenfuntions. Since 2001, many theoretical and experimental works have argued that classically chaotic single-electron dynamics influences and controls collective electron transport. For transport in semiconductor superlattices under tilted magnetic and electric fields, these theories rely on a reduction to a one-dimensional self-consistent drift model. A two-dimensional theory based on self-consistent Boltzmann transport does not support that single-electron chaos influences collective transport. This theory agrees with existing experimental evidence of current self-oscillations, predicts spontaneous collective chaos via a period doubling scenario, and could be tested unambiguously by measuring the electric potential inside the superlattice under a tilted magnetic field.

Inequivalence of single-particle and population lifetimes in a cuprate superconductor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Shuolong; Sobota, J. A.; Leuenberger, D.

2015-06-15

We study optimally doped Bi-2212 (T c=96 K) using femtosecond time- and angle-resolved photoelectron spectroscopy. Energy-resolved population lifetimes are extracted and compared with single-particle lifetimes measured by equilibrium photoemission. The population lifetimes deviate from the single-particle lifetimes in the low excitation limit by 1–2 orders of magnitude. Fundamental considerations of electron scattering unveil that these two lifetimes are in general distinct, yet for systems with only electron-phonon scattering they should converge in the low-temperature, low-fluence limit. As a result, the qualitative disparity in our data, even in this limit, suggests that scattering channels beyond electron-phonon interactions play a significant rolemore » in the electron dynamics of cuprate superconductors.« less

Extreme anisotropy and anomalous transport properties of heavily electron doped Lix(NH3)yFe2Se2 single crystals

NASA Astrophysics Data System (ADS)

Sun, Shanshan; Wang, Shaohua; Yu, Rong; Lei, Hechang

2017-08-01

We report the growth of heavily electron doped Li-NH3 intercalated FeSe single crystals that are free of material complexities and allow access to the intrinsic superconducting properties. Lix(NH3)yFe2Se2 single crystals show extremely large electronic anisotropy in both normal and superconducting states. They also exhibit anomalous transport properties in the normal state, which are believed to possibly be related to the anisotropy of relaxation time and/or temperature-dependent electron carrier concentration. Taking into account the great chemical flexibility of intercalants in the system, our findings provide a platform to understanding the origin of superconductivity in FeSe-related superconductors.

Two-dimensional collective electron magnetotransport, oscillations, and chaos in a semiconductor superlattice.

PubMed

Bonilla, L L; Carretero, M; Segura, A

2017-12-01

When quantized, traces of classically chaotic single-particle systems include eigenvalue statistics and scars in eigenfuntions. Since 2001, many theoretical and experimental works have argued that classically chaotic single-electron dynamics influences and controls collective electron transport. For transport in semiconductor superlattices under tilted magnetic and electric fields, these theories rely on a reduction to a one-dimensional self-consistent drift model. A two-dimensional theory based on self-consistent Boltzmann transport does not support that single-electron chaos influences collective transport. This theory agrees with existing experimental evidence of current self-oscillations, predicts spontaneous collective chaos via a period doubling scenario, and could be tested unambiguously by measuring the electric potential inside the superlattice under a tilted magnetic field.

New Equations for Calculating Principal and Fine-Structure Atomic Spectra for Single and Multi-Electron Atoms

DOE Office of Scientific and Technical Information (OSTI.GOV)

Surdoval, Wayne A.; Berry, David A.; Shultz, Travis R.

A set of equations are presented for calculating atomic principal spectral lines and fine-structure energy splits for single and multi-electron atoms. Calculated results are presented and compared to the National Institute of Science and Technology database demonstrating very good accuracy. The equations do not require fitted parameters. The only experimental parameter required is the Ionization energy for the electron of interest. The equations have comparable accuracy and broader applicability than the single electron Dirac equation. Three Appendices discuss the origin of the new equations and present calculated results. New insights into the special relativistic nature of the Dirac equation andmore » its relationship to the new equations are presented.« less

The physics of a single-event upset in integrated circuits: A review and critique of analytical models for charge collection

NASA Technical Reports Server (NTRS)

Vonroos, O.; Zoutendyk, J.

1983-01-01

When an energetic particle (kinetic energy 0.5 MeV) originating from a radioactive decay or a cosmic ray transverse the active regions of semiconductor devices used in integrated circuit (IC) chips, it leaves along its track a high density electron hole plasma. The subsequent decay of this plasma by drift and diffusion leads to charge collection at the electrodes large enough in most cases to engender a false reading, hence the name single-event upset (SEU). The problem of SEU's is particularly severe within the harsh environment of Jupiter's radiation belts and constitutes therefore a matter of concern for the Galileo mission. The physics of an SEU event is analyzed in some detail. Owing to the predominance of nonlinear space charge effects and the fact that positive (holes) and negative (electrons) charges must be treated on an equal footing, analytical models for the ionized-charge collection and their corresponding currents as a function of time prove to be inadequate even in the simplest case of uniformly doped, abrupt p-n junctions in a one-dimensional geometry. The necessity for full-fledged computer simulation of the pertinent equations governing the electron-hole plasma therefore becomes imperative.

Surface Proton Transfer Promotes Four-Electron Oxygen Reduction on Gold Nanocrystal Surfaces in Alkaline Solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lu, Fang; Zhang, Yu; Liu, Shizhong

Four-electron oxygen reduction reaction (4e-ORR), as a key pathway in energy conversion, is preferred over the two-electron reduction pathway that falls short in dissociating dioxygen molecules. Gold (Au) surfaces exhibit high sensitivity of the ORR pathway to its atomic structures. The long-standing puzzle remains unsolved why the Au surfaces with {100} sub-facets were exceptionally capable to catalyze the 4e-ORR in alkaline solution, though limited within a narrow potential window. Herein we report the discovery of a dominant 4e-ORR over the whole potential range on {310} surface of Au nanocrystal shaped as truncated ditetragonal prism (TDP). In contrast, ORR pathways onmore » single-crystalline facets of shaped nanoparticles, including {111} on nano-octahedra and {100} on nano-cubes, are similar to their single-crystal counterparts. Combining our experimental results with density functional theory calculations, we elucidate the key role of surface proton transfers from co-adsorbed H 2O molecules in activating the facet- and potential-dependent 4e ORR on Au in alkaline solutions. These results elucidate how surface atomic structures determine the reaction pathways via bond scission and formation among weakly adsorbed water and reaction intermediates. The new insight helps in developing facet-specific nanocatalysts for various reactions.« less

Binding of the human "electron transferring flavoprotein" (ETF) to the medium chain acyl-CoA dehydrogenase (MCAD) involves an arginine and histidine residue.

PubMed

Parker, Antony R

2003-10-01

The interaction between the "electron transferring flavoprotein" (ETF) and medium chain acyl-CoA dehydrogenase (MCAD) enables successful flavin to flavin electron transfer, crucial for the beta-oxidation of fatty acids. The exact biochemical determinants for ETF binding to MCAD are unknown. Here we show that binding of human ETF, to MCAD, was inhibited by 2,3-butanedione and diethylpyrocarbonate (DEPC) and reversed by incubation with free arginine and hydroxylamine respectively. Spectral analyses of native ETF vs modified ETF suggested that flavin binding was not affected and that the loss of ETF activity with MCAD involved modification of one ETF arginine residue and one ETF histidine residue respectively. MCAD and octanoyl-CoA protected ETF against inactivation by both 2,3-butanedione and DEPC indicating that the arginine and histidine residues are present in or around the MCAD binding site. Comparison of exposed arginine and histidine residues among different ETF species, however, indicates that arginine residues are highly conserved but that histidine residues are not. These results lead us to conclude that this single arginine residue is essential for the binding of ETF to MCAD, but that the single histidine residue, although involved, is not.

O2 adsorbed on Ptn clusters: Structure and optical absorption

NASA Astrophysics Data System (ADS)

Wang, Ruiying; Zhao, Liang; Jia, Jianfeng; Wu, Hai-Shun

2018-03-01

The interaction of O2 with Ptn and the optical absorption properties of PtnO2 were explored under the framework of density functional theory. The Ptn (n= 2, 4, 6, 9, 10, 14, 18, 22, and 27) clusters were selected, which were reported as magnetic number Ptn clusters in reference (V. Kumar and Y. Kawazoe, Phys. Rev. B 77(20), 205418 (2008)). The single Pt atom was also considered. The longest O2 bonds were found for Pt27O2, Pt6O2 and Pt14O2, while PtO2 and Pt2O2 have the shortest O2 bonds. This result showed that the single Pt atom was not preferred for O2 activation. The O2 bond length was closely related to the electron transfer from Ptn to O2. The optical absorptions of PtnO2 were investigated with time-dependent density functional theory method. A new term of charge transfer strength was defined to estimate the further electron transfer from Ptn to O2 caused by the optical absorption in the visible light range. Our calculations showed that with the increasing n, the further electron transfer from Ptn to O2 caused by optical absorption will become very weak.

Surface Proton Transfer Promotes Four-Electron Oxygen Reduction on Gold Nanocrystal Surfaces in Alkaline Solution

DOE PAGES

Lu, Fang; Zhang, Yu; Liu, Shizhong; ...

2017-05-11

Four-electron oxygen reduction reaction (4e-ORR), as a key pathway in energy conversion, is preferred over the two-electron reduction pathway that falls short in dissociating dioxygen molecules. Gold (Au) surfaces exhibit high sensitivity of the ORR pathway to its atomic structures. The long-standing puzzle remains unsolved why the Au surfaces with {100} sub-facets were exceptionally capable to catalyze the 4e-ORR in alkaline solution, though limited within a narrow potential window. Herein we report the discovery of a dominant 4e-ORR over the whole potential range on {310} surface of Au nanocrystal shaped as truncated ditetragonal prism (TDP). In contrast, ORR pathways onmore » single-crystalline facets of shaped nanoparticles, including {111} on nano-octahedra and {100} on nano-cubes, are similar to their single-crystal counterparts. Combining our experimental results with density functional theory calculations, we elucidate the key role of surface proton transfers from co-adsorbed H 2O molecules in activating the facet- and potential-dependent 4e ORR on Au in alkaline solutions. These results elucidate how surface atomic structures determine the reaction pathways via bond scission and formation among weakly adsorbed water and reaction intermediates. The new insight helps in developing facet-specific nanocatalysts for various reactions.« less

Growth, morphological properties and pulsed photo response of MoTe2 single crystal synthesized by DVT technique

NASA Astrophysics Data System (ADS)

Dixit, Vijay; Vyas, Chirag; Patel, Abhishek; Pathak, V. M.; Solanki, G. K.; Patel, K. D.

2018-05-01

Molybednum Di Telluride of group VI belongs to the family of layered transition metal di-chalcogenides (TMDCs). These TMDCs show good potential for applications in the field of optoelectronic devices as they are chemically inert trilayered structure of MX2 type. In the present investigation crystals of MoTe2 are grown by direct vapor transport technique in a dual zone horizontal furnace. The grown crystals were characterized by Energy Dispersive Analysis of X-rays (EDAX) to study its elemental and stoichiometric composition, Selected Area Electron Diffraction (SAED) confirms the hexagonal structure. Spot pattern of electron diffraction shows formation of single phase. Scanning Electron Microscope (SEM) shows the layer by layer growth of the crystals, Thermo Electric Power (TEP) reflects the p-type semiconducting nature of the grown crystals. As this material is photosensitive material having band gap of approximately 1.0 eV, a transient photo response against polychromatic radiation (40 mW/cm2) of photodetector is also measured which showed slow decay in generated photocurrent due to low trapping density within the active area of the prepared device. Thus, it shows that this material can be a good photovoltaic material for constructing a solar cell also.

UWALK: the development of a multi-strategy, community-wide physical activity program.

PubMed

Jennings, Cally A; Berry, Tanya R; Carson, Valerie; Culos-Reed, S Nicole; Duncan, Mitch J; Loitz, Christina C; McCormack, Gavin R; McHugh, Tara-Leigh F; Spence, John C; Vallance, Jeff K; Mummery, W Kerry

2017-03-01

UWALK is a multi-strategy, multi-sector, theory-informed, community-wide approach using e and mHealth to promote physical activity in Alberta, Canada. The aim of UWALK is to promote physical activity, primarily via the accumulation of steps and flights of stairs, through a single over-arching brand. This paper describes the development of the UWALK program. A social ecological model and the social cognitive theory guided the development of key strategies, including the marketing and communication activities, establishing partnerships with key stakeholders, and e and mHealth programs. The program promotes the use of physical activity monitoring devices to self-monitor physical activity. This includes pedometers, electronic devices, and smartphone applications. In addition to entering physical activity data manually, the e and mHealth program provides the function for objective data to be automatically uploaded from select electronic devices (Fitbit®, Garmin and the smartphone application Moves) The RE-AIM framework is used to guide the evaluation of UWALK. Funding for the program commenced in February 2013. The UWALK brand was introduced on April 12, 2013 with the official launch, including the UWALK website on September 20, 2013. This paper describes the development and evaluation framework of a physical activity promotion program. This program has the potential for population level dissemination and uptake of an ecologically valid physical activity promotion program that is evidence-based and theoretically framed.

Electron-helium S-wave model benchmark calculations. I. Single ionization and single excitation

NASA Astrophysics Data System (ADS)

Bartlett, Philip L.; Stelbovics, Andris T.

2010-02-01

A full four-body implementation of the propagating exterior complex scaling (PECS) method [J. Phys. B 37, L69 (2004)] is developed and applied to the electron-impact of helium in an S-wave model. Time-independent solutions to the Schrödinger equation are found numerically in coordinate space over a wide range of energies and used to evaluate total and differential cross sections for a complete set of three- and four-body processes with benchmark precision. With this model we demonstrate the suitability of the PECS method for the complete solution of the full electron-helium system. Here we detail the theoretical and computational development of the four-body PECS method and present results for three-body channels: single excitation and single ionization. Four-body cross sections are presented in the sequel to this article [Phys. Rev. A 81, 022716 (2010)]. The calculations reveal structure in the total and energy-differential single-ionization cross sections for excited-state targets that is due to interference from autoionization channels and is evident over a wide range of incident electron energies.

Reduction of nitrogen oxides (NOx) by superalkalis

NASA Astrophysics Data System (ADS)

Srivastava, Ambrish Kumar

2018-03-01

NOx are major air pollutants, having negative impact on environment and consequently, human health. We propose here the single-electron reduction of NOx (x = 1, 2) using superalkalis. We study the interaction of NOx with FLi2, OLi3 and NLi4 superalkalis using density functional and single-point CCSD(T) calculations, which lead to stable superalkali-NOx ionic complexes with negatively charged NOx. This clearly reveals that the NOx can successfully be reduced to NOx- anion due to electron transfer from superalkalis. It has been also noticed that the size of superalkalis plays a crucial in the single-electron reduction of NOx.

From few-cycle femtosecond pulse to single attosecond pulse-controlling and tracking electron dynamics with attosecond precision

NASA Astrophysics Data System (ADS)

Wang, He

The few-cycle femtosecond laser pulse has proved itself to be a powerful tool for controlling the electron dynamics inside atoms and molecules. By applying such few-cycle pulses as a driving field, single isolated attosecond pulses can be produced through the high-order harmonic generation process, which provide a novel tool for capturing the real time electron motion. The first part of the thesis is devoted to the state of the art few-cycle near infrared (NIR) laser pulse development, which includes absolute phase control (carrier-envelope phase stabilization), amplitude control (power stabilization), and relative phase control (pulse compression and shaping). Then the double optical gating (DOG) method for generating single attosecond pulses and the attosecond streaking experiment for characterizing such pulses are presented. Various experimental limitations in the attosecond streaking measurement are illustrated through simulation. Finally by using the single attosecond pulses generated by DOG, an attosecond transient absorption experiment is performed to study the autoionization process of argon. When the delay between a few-cycle NIR pulse and a single attosecond XUV pulse is scanned, the Fano resonance shapes of the argon autoionizing states are modified by the NIR pulse, which shows the direct observation and control of electron-electron correlation in the temporal domain.

Too Hot for Photon-Assisted Transport: Hot-Electrons Dominate Conductance Enhancement in Illuminated Single-Molecule Junctions.

PubMed

Fung, E-Dean; Adak, Olgun; Lovat, Giacomo; Scarabelli, Diego; Venkataraman, Latha

2017-02-08

We investigate light-induced conductance enhancement in single-molecule junctions via photon-assisted transport and hot-electron transport. Using 4,4'-bipyridine bound to Au electrodes as a prototypical single-molecule junction, we report a 20-40% enhancement in conductance under illumination with 980 nm wavelength radiation. We probe the effects of subtle changes in the transmission function on light-enhanced current and show that discrete variations in the binding geometry result in a 10% change in enhancement. Importantly, we prove theoretically that the steady-state behavior of photon-assisted transport and hot-electron transport is identical but that hot-electron transport is the dominant mechanism for optically induced conductance enhancement in single-molecule junctions when the wavelength used is absorbed by the electrodes and the hot-electron relaxation time is long. We confirm this experimentally by performing polarization-dependent conductance measurements of illuminated 4,4'-bipyridine junctions. Finally, we perform lock-in type measurements of optical current and conclude that currents due to laser-induced thermal expansion mask optical currents. This work provides a robust experimental framework for studying mechanisms of light-enhanced transport in single-molecule junctions and offers tools for tuning the performance of organic optoelectronic devices by analyzing detailed transport properties of the molecules involved.

A diagnostic for determining the quality of single-reference electron correlation methods

NASA Technical Reports Server (NTRS)

Lee, Timothy J.; Taylor, Peter R.

1989-01-01

It was recently proposed that the Euclidian norm of the t(sub 1) vector of the coupled cluster wave function (normalized by the number of electrons included in the correlation procedure) could be used to determine whether a single-reference-based electron correlation procedure is appopriate. This diagnostic, T(sub 1) is defined for use with self-consistent-field molecular orbitals and is invariant to the same orbital rotations as the coupled cluster energy. T(sub 1) is investigated for several different chemical systems which exhibit a range of multireference behavior, and is shown to be an excellent measure of the importance of non-dynamical electron correlation and is far superior to C(sub 0) from a singles and doubles configuration interaction wave function. It is further suggested that when the aim is to recover a large fraction of the dynamical electron correlation energy, a large T(sub 1) (i.e., greater than 0.02) probably indicates the need for a multireference electron correlation procedure.

A diagnostic for determining the quality of single-reference electron correlation methods

NASA Technical Reports Server (NTRS)

Lee, Timothy J.; Taylor, Peter R.

1989-01-01

It was recently proposed that the Euclidian norm of the t sub 1 vector of the coupled cluster wave function (normalized by the number of electrons included in the correlation procedure) could be used to determine whether a single-reference-based electron correlation procedure is appropriate. This diagnostic, T sub 1, is defined for use with self consistent field molecular orbitals and is invariant to the same orbital rotations as the coupled cluster energy. T sub 1 is investigated for several different chemical systems which exhibit a range of multireference behavior, and is shown to be an excellent measure of the importance of nondynamical electron correlation and is far superior to C sub 0 from a singles and doubles configuration interaction wave function. It is further suggested that when the aim is to recover a large fraction of the dynamical electron correlation energy, a large T sub 1 (i.e., greater than 0.02) probably indicates the need for a multireference electron correlation procedure.

Single-molecule electronics: Cooling individual vibrational modes by the tunneling current.

PubMed

Lykkebo, Jacob; Romano, Giuseppe; Gagliardi, Alessio; Pecchia, Alessandro; Solomon, Gemma C

2016-03-21

Electronic devices composed of single molecules constitute the ultimate limit in the continued downscaling of electronic components. A key challenge for single-molecule electronics is to control the temperature of these junctions. Controlling heating and cooling effects in individual vibrational modes can, in principle, be utilized to increase stability of single-molecule junctions under bias, to pump energy into particular vibrational modes to perform current-induced reactions, or to increase the resolution in inelastic electron tunneling spectroscopy by controlling the life-times of phonons in a molecule by suppressing absorption and external dissipation processes. Under bias the current and the molecule exchange energy, which typically results in heating of the molecule. However, the opposite process is also possible, where energy is extracted from the molecule by the tunneling current. Designing a molecular "heat sink" where a particular vibrational mode funnels heat out of the molecule and into the leads would be very desirable. It is even possible to imagine how the vibrational energy of the other vibrational modes could be funneled into the "cooling mode," given the right molecular design. Previous efforts to understand heating and cooling mechanisms in single molecule junctions have primarily been concerned with small models, where it is unclear which molecular systems they correspond to. In this paper, our focus is on suppressing heating and obtaining current-induced cooling in certain vibrational modes. Strategies for cooling vibrational modes in single-molecule junctions are presented, together with atomistic calculations based on those strategies. Cooling and reduced heating are observed for two different cooling schemes in calculations of atomistic single-molecule junctions.

Automated Construction of Molecular Active Spaces from Atomic Valence Orbitals.

PubMed

Sayfutyarova, Elvira R; Sun, Qiming; Chan, Garnet Kin-Lic; Knizia, Gerald

2017-09-12

We introduce the atomic valence active space (AVAS), a simple and well-defined automated technique for constructing active orbital spaces for use in multiconfiguration and multireference (MR) electronic structure calculations. Concretely, the technique constructs active molecular orbitals capable of describing all relevant electronic configurations emerging from a targeted set of atomic valence orbitals (e.g., the metal d orbitals in a coordination complex). This is achieved via a linear transformation of the occupied and unoccupied orbital spaces from an easily obtainable single-reference wave function (such as from a Hartree-Fock or Kohn-Sham calculations) based on projectors to targeted atomic valence orbitals. We discuss the premises, theory, and implementation of the idea, and several of its variations are tested. To investigate the performance and accuracy, we calculate the excitation energies for various transition-metal complexes in typical application scenarios. Additionally, we follow the homolytic bond breaking process of a Fenton reaction along its reaction coordinate. While the described AVAS technique is not a universal solution to the active space problem, its premises are fulfilled in many application scenarios of transition-metal chemistry and bond dissociation processes. In these cases the technique makes MR calculations easier to execute, easier to reproduce by any user, and simplifies the determination of the appropriate size of the active space required for accurate results.

Electronic structure changes during the on-surface synthesis of nitrogen-doped chevron-shaped graphene nanoribbons

NASA Astrophysics Data System (ADS)

Maaß, Friedrich; Utecht, Manuel; Stremlau, Stephan; Gille, Marie; Schwarz, Jutta; Hecht, Stefan; Klamroth, Tillmann; Tegeder, Petra

2017-07-01

Utilizing suitable precursor molecules, a thermally activated and surface-assisted synthesis results in the formation of defect-free graphene nanoribbons (GNRs), which exhibit electronic properties that are not present in extended graphene. Most importantly, they have a band gap in the order of a few electron volts, depending on the nanoribbon width. In this study, we investigate the electronic structure changes during the formation of GNRs, nitrogen-doped (singly and doubly N-doped) as well as non-N-doped chevron-shaped CGNRs on Au(111). Thus we determine the optical gaps of the precursor molecules, the intermediate nonaromatic polymers, and finally the aromatic GNRs, using high-resolution electron energy loss spectroscopy and density functional theory calculations. As expected, we find no influence of N-doping on the size of the optical gaps. The gap of the precursor molecules is around 4.5 eV. Polymerization leads to a reduction of the gap to a value of 3.2 eV due to elongation and thus enhanced delocalization. The CGNRs exhibit a band gap of 2.8 eV, thus the gap is further reduced in the nanoribbons, since they exhibit an extended delocalized π -electron system.

A 120kV IGBT modulator for driving a pierce electron gun

DOE Office of Scientific and Technical Information (OSTI.GOV)

Earley, L. M.; Brown, R. W.; Carlson, R. L.

2004-01-01

An IGBT modulator has been developed to drive a 120 kV, 23 A Pierce electron gun. The modulator is capable of producing pulses up to 10 {mu}s in width at repetition rates up to 10Hz with no active reset. The pulse rise time on the electron gun will be approximately 2 {mu}s and the remaining 8 {mu}s of flattop is tuned to have a ripple of less than 1 percent rms. The modulator technology was developed from a previous 50 kV prototype. The modulator consists of six boards, each with one EUPEC IGBT that drives a single common step-up transformermore » wound on METGLAS 2605SC cores. The six transformer cores share a common bi-filar output secondary winding. The modulator uses a fiber optic trigger system and has a high voltage cable output with an epoxy receptacle on the oil end and a ceramic receptacle on the vacuum end. The 120 kV electron gun was manufactured by MDS Co. and will be used to generate sheet electron beams from the standard pencil beam produced by the Pierce electron gun.« less

Enhancing and optimizing electronic transport in biphenyl derivative single-molecule junctions attached to carbon nanotubes electrodes

NASA Astrophysics Data System (ADS)

Reis-Silva, J. C.; Ferreira, D. F. S.; Leal, J. F. P.; Pinheiro, F. A.; Del Nero, J.

2017-02-01

We investigate, by means of ab initio calculations based on non-equilibrium Green's function method coupled to density function theory, electronic transport in molecular junctions composed of biphenyl (BP) and biphenyl within (-2H+) defect (BP2D) molecules attached to metallic (9,0) carbon nanotubes. We demonstrate that the BP2D junction exhibits unprecedented electronic transport properties, and that its conductance can be up to three orders of magnitude higher than biphenyl single-molecule junctions. These findings are explained in terms of the non-planar molecular conformation of BP2D, and of the stronger electronic coupling between the BP2D molecule and the organic electrodes, which confers high stability to the junction. Our results suggest that BP2D attached to carbon nanotubes can be explored as an efficient and highly stable platform in single-molecule electronics with extraordinary transport properties.

Epitaxial growth of thermally stable cobalt films on Au(111)

NASA Astrophysics Data System (ADS)

Haag, N.; Laux, M.; Stöckl, J.; Kollamana, J.; Seidel, J.; Großmann, N.; Fetzer, R.; Kelly, L. L.; Wei, Z.; Stadtmüller, B.; Cinchetti, M.; Aeschlimann, M.

2016-10-01

Ferromagnetic thin films play a fundamental role in spintronic applications as a source for spin polarized carriers and in fundamental studies as ferromagnetic substrates. However, it is challenging to produce such metallic films with high structural quality and chemical purity on single crystalline substrates since the diffusion barrier across the metal-metal interface is usually smaller than the thermal activation energy necessary for smooth surface morphologies. Here, we introduce epitaxial thin Co films grown on an Au(111) single crystal surface as a thermally stable ferromagnetic thin film. Our structural investigations reveal an identical growth of thin Co/Au(111) films compared to Co bulk single crystals with large monoatomic Co terraces with an average width of 500 Å, formed after thermal annealing at 575 K. Combining our results from photoemission and Auger electron spectroscopy, we provide evidence that no significant diffusion of Au into the near surface region of the Co film takes place for this temperature and that no Au capping layer is formed on top of Co films. Furthermore, we show that the electronic valence band is dominated by a strong spectral contribution from a Co 3d band and a Co derived surface resonance in the minority band. Both states lead to an overall negative spin polarization at the Fermi energy.

Rapid genotyping of common MeCP2 mutations with an electronic DNA microchip using serial differential hybridization.

PubMed

Thistlethwaite, William A; Moses, Linda M; Hoffbuhr, Kristen C; Devaney, Joseph M; Hoffman, Eric P

2003-05-01

Rett syndrome is a neurodevelopmental disorder that affects females almost exclusively, and in which eight common point mutations on the X-linked MeCP2 gene are knows to cause over 70% of mutation-positive cases. We explored the use of a novel platform to detect the eight common mutations in Rett syndrome patients to expedite and simplify the process of identification of known genotypes. The Nanogen workstation consists of a two-color assay based on electric hybridization and thermal discrimination, all performed on an electronically active NanoChip. This genotyping platform was tested on 362 samples of a pre-determined genotype, which had been previously identified by a combination of DHPLC (denaturing high performance liquid chromatography) and direct sequencing. This genotyping technique proved to be rapid, facile, and displayed a specificity of 100% with 3% ambiguity. In addition, we present consecutive testing of seven mutations on a single pad of the NanoChip. This was accomplished by tagging down two amplimers together and serially hybridizing for seven different loci, allowing us to genotype samples for seven of the eight common Rett mutations on a single pad. This novel method displayed the same level of specificity and accuracy as the single amplimer reactions, and proved to be faster and more economical.

Metal-insulator transition characteristics of VO2 thin films grown on Ge(100) single crystals

NASA Astrophysics Data System (ADS)

Yang, Z.; Ko, C.; Ramanathan, S.

2010-10-01

Phase transitions exhibited by correlated oxides could be of potential relevance to the emerging field of oxide electronics. We report on the synthesis of high-quality VO2 thin films grown on single crystal Ge(100) substrates by physical vapor deposition and their metal-insulator transition (MIT) properties. Thermally triggered MIT is demonstrated with nearly three orders of magnitude resistance change across the MIT with transition temperatures of 67 °C (heating) and 61 °C (cooling). Voltage-triggered hysteretic MIT is observed at room temperature at threshold voltage of ˜2.1 V for ˜100 nm thickness VO2 films. Activation energies for electron transport in the insulating and conducting states are obtained from variable temperature resistance measurements. We further compare the properties of VO2 thin films grown under identical conditions on Si(100) single crystals. The VO2 thin films grown on Ge substrate show higher degree of crystallinity, slightly reduced compressive strain, larger resistance change across MIT compared to those grown on Si. Depth-dependent x-ray photoelectron spectroscopy measurements were performed to provide information on compositional variation trends in the two cases. These results suggest Ge could be a suitable substrate for further explorations of switching phenomena and devices for thin film functional oxides.

RANKING TEM CAMERAS BY THEIR RESPONSE TO ELECTRON SHOT NOISE

PubMed Central

Grob, Patricia; Bean, Derek; Typke, Dieter; Li, Xueming; Nogales, Eva; Glaeser, Robert M.

2013-01-01

We demonstrate two ways in which the Fourier transforms of images that consist solely of randomly distributed electrons (shot noise) can be used to compare the relative performance of different electronic cameras. The principle is to determine how closely the Fourier transform of a given image does, or does not, approach that of an image produced by an ideal camera, i.e. one for which single-electron events are modeled as Kronecker delta functions located at the same pixels where the electrons were incident on the camera. Experimentally, the average width of the single-electron response is characterized by fitting a single Lorentzian function to the azimuthally averaged amplitude of the Fourier transform. The reciprocal of the spatial frequency at which the Lorentzian function falls to a value of 0.5 provides an estimate of the number of pixels at which the corresponding line-spread function falls to a value of 1/e. In addition, the excess noise due to stochastic variations in the magnitude of the response of the camera (for single-electron events) is characterized by the amount to which the appropriately normalized power spectrum does, or does not, exceed the total number of electrons in the image. These simple measurements provide an easy way to evaluate the relative performance of different cameras. To illustrate this point we present data for three different types of scintillator-coupled camera plus a silicon-pixel (direct detection) camera. PMID:23747527

Emerging Carbon and Post-Carbon Nanomaterial Inks for Printed Electronics.

PubMed

Secor, Ethan B; Hersam, Mark C

2015-02-19

Carbon and post-carbon nanomaterials present desirable electrical, optical, chemical, and mechanical attributes for printed electronics, offering low-cost, large-area functionality on flexible substrates. In this Perspective, recent developments in carbon nanomaterial inks are highlighted. Monodisperse semiconducting single-walled carbon nanotubes compatible with inkjet and aerosol jet printing are ideal channels for thin-film transistors, while inkjet, gravure, and screen-printable graphene-based inks are better-suited for electrodes and interconnects. Despite the high performance achieved in prototype devices, additional effort is required to address materials integration issues encountered in more complex systems. In this regard, post-carbon nanomaterial inks (e.g., electrically insulating boron nitride and optically active transition-metal dichalcogenides) present promising opportunities. Finally, emerging work to extend these nanomaterial inks to three-dimensional printing provides a path toward nonplanar devices. Overall, the superlative properties of these materials, coupled with versatile assembly by printing techniques, offer a powerful platform for next-generation printed electronics.

Solar powered hybrid sensor module program

NASA Technical Reports Server (NTRS)

Johnson, J. M.; Holmes, H. K.

1985-01-01

Geo-orbital systems of the near future will require more sophisticated electronic and electromechanical monitoring and control systems than current satellite systems with an emphasis in the design on the electronic density and autonomy of the subsystem components. Results of a project to develop, design, and implement a proof-of-concept sensor system for space applications, with hybrids forming the active subsystem components are described. The design of the solar power hybrid sensor modules is discussed. Module construction and function are described. These modules combined low power CMOS electronics, GaAs solar cells, a crystal oscillatory standard UART data formatting, and a bidirectional optical data link into a single 1.25 x 1.25 x 0.25 inch hybrid package which has no need for electrical input or output. Several modules were built and tested. Applications of such a system for future space missions are also discussed.

Measurement of precipitation induced FUV emission and Geocoronal Lyman Alpha from the IMI mission

NASA Technical Reports Server (NTRS)

Mende, Stephen B.; Fuselier, S. A.; Rairden, R. L.

1995-01-01

This final report describes the activities of the Lockheed Martin Palo Alto Research Laboratory in studying the measurement of ion and electron precipitation induced Far Ultra-Violet (FUV) emissions and Geocoronal Lyman Alpha for the NASA Inner Magnetospheric Imager (IMI) mission. this study examined promising techniques that may allow combining several FUV instruments that would separately measure proton aurora, electron aurora, and geocoronal Lyman alpha into a single instrument operated on a spinning spacecraft. The study consisted of two parts. First, the geocoronal Lyman alpha, proton aurora, and electron aurora emissions were modeled to determine instrument requirements. Second, several promising techniques were investigated to determine if they were suitable for use in an IMI-type mission. Among the techniques investigated were the Hydrogen gas cell for eliminating cold geocoronal Lyman alpha emissions, and a coded aperture spectrometer with sufficient resolution to separate Doppler shifted Lyman alpha components.

The Non-innocent Phenalenyl Unit: An Electronic Nest to Modulate the Catalytic Activity in Hydroamination Reaction

PubMed Central

Mukherjee, Arup; Sen, Tamal K.; Ghorai, Pradip Kr; Mandal, Swadhin K.

2013-01-01

The phenalenyl unit has played intriguing role in different fields of research spanning from chemistry, material chemistry to device physics acting as key electronic reservoir which has not only led to the best organic single component conductor but also created the spin memory device of next generation. Now we show the non-innocent behaviour of phenalenyl unit in modulating the catalytic behaviour in a homogeneous organic transformation. The present study establishes that the cationic state of phenalenyl unit can act as an organic Lewis acceptor unit to influence the catalytic outcome of intermolecular hydroamination reaction of carbodiimides. For the present study, we utilized organoaluminum complexes of phenalenyl ligands in which the phenalenyl unit maintains the closed shell electronic state. The DFT calculation reveals that the energy of LUMO of the catalyst is mainly controlled by phenalenyl ligands which in turn determines the outcome of the catalysis. PMID:24084653

Electronic properties of 8 - Pmmn borophene

DOE PAGES

Lopez-Bezanilla, Alejandro; Littlewood, Peter B.

2016-06-15

First-principles calculations on monolayer 8-Pmmn borophene are reported to reveal unprecedented electronic properties in a two-dimensional material. Based on a Born effective charge analysis, 8-Pmmn borophene is the first single-element-based monolayered material exhibiting two sublattices with substantial ionic features. We observed Dirac cones are actually formed by the p(z) orbitals of one of the inequivalent sublattices composed of uniquely four atoms, yielding an underlying hexagonal network topologically equivalent to distorted graphene. One significant physical outcome of this effect includes the possibility of converting metallic 8-Pmmn borophene into an indirect band gap semiconductor by means of external shear stress. Furthermore, themore » stability of the strained structures are supported by a phonon frequency analysis. The Dirac cones are sensitive to the formation of vacancies only in the inequivalent sublattice electronically active at the Fermi level.« less

Magneto-optical fingerprints of distinct graphene multilayers using the giant infrared Kerr effect

NASA Astrophysics Data System (ADS)

Ellis, Chase T.; Stier, Andreas V.; Kim, Myoung-Hwan; Tischler, Joseph G.; Glaser, Evan R.; Myers-Ward, Rachael L.; Tedesco, Joseph L.; Eddy, Charles R.; Gaskill, D. Kurt; Cerne, John

2013-11-01

The remarkable electronic properties of graphene strongly depend on the thickness and geometry of graphene stacks. This wide range of electronic tunability is of fundamental interest and has many applications in newly proposed devices. Using the mid-infrared, magneto-optical Kerr effect, we detect and identify over 18 interband cyclotron resonances (CR) that are associated with ABA and ABC stacked multilayers as well as monolayers that coexist in graphene that is epitaxially grown on 4H-SiC. Moreover, the magnetic field and photon energy dependence of these features enable us to explore the band structure, electron-hole band asymmetries, and mechanisms that activate a CR response in the Kerr effect for various multilayers that coexist in a single sample. Surprisingly, we find that the magnitude of monolayer Kerr effect CRs is not temperature dependent. This unexpected result reveals new questions about the underlying physics that makes such an effect possible.

Structural and Functional Hierarchy in Photosynthetic Energy Conversion—from Molecules to Nanostructures

NASA Astrophysics Data System (ADS)

Szabó, Tibor; Magyar, Melinda; Hajdu, Kata; Dorogi, Márta; Nyerki, Emil; Tóth, Tünde; Lingvay, Mónika; Garab, Győző; Hernádi, Klára; Nagy, László

2015-12-01

Basic principles of structural and functional requirements of photosynthetic energy conversion in hierarchically organized machineries are reviewed. Blueprints of photosynthesis, the energetic basis of virtually all life on Earth, can serve the basis for constructing artificial light energy-converting molecular devices. In photosynthetic organisms, the conversion of light energy into chemical energy takes places in highly organized fine-tunable systems with structural and functional hierarchy. The incident photons are absorbed by light-harvesting complexes, which funnel the excitation energy into reaction centre (RC) protein complexes containing redox-active chlorophyll molecules; the primary charge separations in the RCs are followed by vectorial transport of charges (electrons and protons) in the photosynthetic membrane. RCs possess properties that make their use in solar energy-converting and integrated optoelectronic systems feasible. Therefore, there is a large interest in many laboratories and in the industry toward their use in molecular devices. RCs have been bound to different carrier matrices, with their photophysical and photochemical activities largely retained in the nano-systems and with electronic connection to conducting surfaces. We show examples of RCs bound to carbon-based materials (functionalized and non-functionalized single- and multiwalled carbon nanotubes), transitional metal oxides (ITO) and conducting polymers and porous silicon and characterize their photochemical activities. Recently, we adapted several physical and chemical methods for binding RCs to different nanomaterials. It is generally found that the P+(QAQB)- charge pair, which is formed after single saturating light excitation is stabilized after the attachment of the RCs to the nanostructures, which is followed by slow reorganization of the protein structure. Measuring the electric conductivity in a direct contact mode or in electrochemical cell indicates that there is an electronic interaction between the protein and the inorganic carrier matrices. This can be a basis of sensing element of bio-hybrid device for biosensor and/or optoelectronic applications.

Ultrathin solution-processed single crystals of thiophene-phenylene co-oligomers for organic field-effect devices

NASA Astrophysics Data System (ADS)

Glushkova, Anastasia V.; Poimanova, Elena Yu.; Bruevich, Vladimir V.; Luponosov, Yuriy N.; Ponomarenko, Sergei A.; Paraschuk, Dmitry Yu.

2017-08-01

Thiophene-phenylene co-oligomers (TPCO) single crystals are promising materials for organic light-emitting devices, e.g., light-emitting transistors (OLETs), due to their ability to combine high luminescence and efficient charge transport. However, optical confinement in platy single crystals strongly decreases light emission from their top surface degrading the device performance. To avoid optical waveguiding, single crystals thinner than 100 nm would be beneficial. Herein, we report on solution-processed ultrathin single crystals of TPCO and study their charge transport properties. As materials we used 1,4-bis(5'-hexyl-2,2'-bithiophene-5-yl)benzene (DH-TTPTT) and 1,4-bis(5'-decyl-2,2'-bithiophene-5-yl)benzene (DD-TTPTT). The ultrathin single crystals were studied by optical polarization, atomic-force, and transmission electron microscopies, and as active layers in organic field effect transistors (OFET). The OFET hole mobility was increased tenfold for the oligomer with longer alkyl substituents (DD-TTPTT) reaching 0.2 cm2/Vs. Our studies of crystal growth indicate that if the substrate is wetted, it has no significant effect on the crystal growth. We conclude that solution-processed ultrathin TPCO single crystals are a promising platform for organic optoelectronic field-effect devices.

Ratios of double to single ionization of He and Ne by strong 400-nm laser pulses using the quantitative rescattering theory

NASA Astrophysics Data System (ADS)

Chen, Zhangjin; Li, Xiaojin; Zatsarinny, Oleg; Bartschat, Klaus; Lin, C. D.

2018-01-01

We present numerical simulations of the ratio between double and single ionization of He and Ne by intense laser pulses at wavelengths of 390 and 400 nm, respectively. The yields of doubly charged ions due to nonsequential double ionization (NSDI) are obtained by employing the quantitative rescattering (QRS) model. In this model, the NSDI ionization probability is expressed as a product of the returning electron wave packet (RWP) and the total scattering cross sections for laser-free electron impact excitation and electron impact ionization of the parent ion. According to the QRS theory, the same RWP is also responsible for the emission of high-energy above-threshold ionization photoelectrons. To obtain absolute double-ionization yields, the RWP is generated by solving the time-dependent Schrödinger equation (TDSE) within a one-electron model. The same TDSE results can also be taken to obtain single-ionization yields. By using the TDSE results to calibrate single ionization and the RWP obtained from the strong-field approximation, we further simplify the calculation such that the nonuniform laser intensity distribution in the focused laser beam can be accounted for. In addition, laser-free electron impact excitation and ionization cross sections are calculated using the state-of-the-art many-electron R -matrix theory. The simulation results for double-to-single-ionization ratios are found to compare well with experimental data and support the validity of the nonsequential double-ionization mechanism for the covered intensity region.

Microscopic Electronic and Mechanical Properties of Ultra-Thin Layered Materials

DTIC Science & Technology

2016-07-25

Graphene single layers grown by chemical vapor deposition on single crystal Cu substrates are subject to nonuniform physisorption strains that...the observed highly nonuniform strains. 4. Connecting dopant bond type with electronic structure in N-doped graphene (reference [4]) Robust methods

Electron spin resonance of an irradiated single crystal of potassium hydrogen maleate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Iwasaki, Machio; Itoh, Koichi

1963-09-15

Electron spin resonance absorptions of x-irradiated single crystals of potassium hydrogen maleate and potassium deuterium maleate were observed. Both compounds gave the same hyperfine structures, although the slightly sharper line widths were observed for the deuterium exchanged compound.

Oxygen activation in flavoprotein oxidases: the importance of being positive.

PubMed

Gadda, Giovanni

2012-04-03

The oxidation of flavin hydroquinones by O(2) in solution is slow, with second-order rate constants of ~250 M(-1) s(-1). This is due to the obligatory, single-electron transfer that initiates the reaction being thermodynamically unfavored and poorly catalyzed. Notwithstanding considerations of O(2) accessibility to the reaction site, its desolvation and geometry and other factors that can also contribute to further rate acceleration, flavoprotein oxidases must activate O(2) for reaction with flavin hydroquinones to be able to achieve the 100-1000-fold rate enhancements typically observed. Protein positive charges have been identified in glucose oxidase, monomeric sarcosine oxidase, N-methyltryptophan oxidase and fructosamine oxidase that electrostatically stabilize the transition state for the initial single electron transfer that generates the O(2)(-•)/flavin semiquinone radical pair. In choline oxidase despite the presence of three histidines in the active site, the trimethylammonium group of the reaction product provides such an electrostatic stabilization. A nonpolar site proximal to the flavin C(4a) atom in choline oxidase has also been identified, which contributes to the geometry and desolvation of the O(2) reaction site. The relevance of O(2) activation by product charges to other flavoprotein oxidases, such as for example those catalyzing amine oxidations, is discussed in this review. A nonpolar site close to the flavin C(4a) atom and a positive charge is identified through structural analysis in several flavoprotein oxidases. Mutagenesis has disclosed nonpolar sites in O(2)-reducing enzymes that utilize copper/TPQ or iron. It is predicted that classes of O(2)-reducing enzymes utilizing other cofactors also contain a similar catalytic motif.

Length-dependent thermal transport in one-dimensional self-assembly of planar π-conjugated molecules

NASA Astrophysics Data System (ADS)

Tang, Hao; Xiong, Yucheng; Zu, Fengshuo; Zhao, Yang; Wang, Xiaomeng; Fu, Qiang; Jie, Jiansheng; Yang, Juekuan; Xu, Dongyan

2016-06-01

This work reports a thermal transport study in quasi-one-dimensional organic nanostructures self-assembled from conjugated planar molecules via π-π interactions. Thermal resistances of single crystalline copper phthalocyanine (CuPc) and perylenetetracarboxylic diimide (PTCDI) nanoribbons are measured via a suspended thermal bridge method. We experimentally observed the deviation from the linear length dependence for the thermal resistance of single crystalline β-phase CuPc nanoribbons, indicating possible subdiffusion thermal transport. Interestingly, a gradual transition to the linear length dependence is observed with the increase of the lateral dimensions of CuPc nanoribbons. The measured thermal resistance of single crystalline CuPc nanoribbons shows an increasing trend with temperature. However, the trend of temperature dependence of thermal resistance is reversed after electron irradiation, i.e., decreasing with temperature, indicating that the single crystalline CuPc nanoribbons become `amorphous'. Similar behavior is also observed for PTCDI nanoribbons after electron irradiation, proving that the electron beam can induce amorphization of single crystalline self-assembled nanostructures of planar π-conjugated molecules. The measured thermal resistance of the `amorphous' CuPc nanoribbon demonstrates a roughly linear dependence on the nanoribbon length, suggesting that normal diffusion dominates thermal transport.This work reports a thermal transport study in quasi-one-dimensional organic nanostructures self-assembled from conjugated planar molecules via π-π interactions. Thermal resistances of single crystalline copper phthalocyanine (CuPc) and perylenetetracarboxylic diimide (PTCDI) nanoribbons are measured via a suspended thermal bridge method. We experimentally observed the deviation from the linear length dependence for the thermal resistance of single crystalline β-phase CuPc nanoribbons, indicating possible subdiffusion thermal transport. Interestingly, a gradual transition to the linear length dependence is observed with the increase of the lateral dimensions of CuPc nanoribbons. The measured thermal resistance of single crystalline CuPc nanoribbons shows an increasing trend with temperature. However, the trend of temperature dependence of thermal resistance is reversed after electron irradiation, i.e., decreasing with temperature, indicating that the single crystalline CuPc nanoribbons become `amorphous'. Similar behavior is also observed for PTCDI nanoribbons after electron irradiation, proving that the electron beam can induce amorphization of single crystalline self-assembled nanostructures of planar π-conjugated molecules. The measured thermal resistance of the `amorphous' CuPc nanoribbon demonstrates a roughly linear dependence on the nanoribbon length, suggesting that normal diffusion dominates thermal transport. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr09043a

A 3% Measurement of the Beam Normal Single Spin Asymmetry in Forward Angle Elastic Electron-Proton Scattering using the Qweak Setup

DOE Office of Scientific and Technical Information (OSTI.GOV)

Waidyawansa, Dinayadura Buddhini

2013-08-01

The beam normal single spin asymmetry generated in the scattering of transversely polarized electrons from unpolarized nucleons is an observable of the imaginary part of the two-photon exchange process. Moreover, it is a potential source of false asymmetry in parity violating electron scattering experiments. The Q{sub weak} experiment uses parity violating electron scattering to make a direct measurement of the weak charge of the proton. The targeted 4% measurement of the weak charge of the proton probes for parity violating new physics beyond the Standard Model. The beam normal single spin asymmetry at Q{sub weak} kinematics is at least threemore » orders of magnitude larger than 5 ppb precision of the parity violating asymmetry. To better understand this parity conserving background, the Q{sub weak} Collaboration has performed elastic scattering measurements with fully transversely polarized electron beam on the proton and aluminum. This dissertation presents the analysis of the 3% measurement (1.3% statistical and 2.6% systematic) of beam normal single spin asymmetry in electronproton scattering at a Q2 of 0.025 (GeV/c)2. It is the most precise existing measurement of beam normal single spin asymmetry available at the time. A measurement of this precision helps to improve the theoretical models on beam normal single spin asymmetry and thereby our understanding of the doubly virtual Compton scattering process.« less

Two-Electron Transfer Pathways.

PubMed

Lin, Jiaxing; Balamurugan, D; Zhang, Peng; Skourtis, Spiros S; Beratan, David N

2015-06-18

The frontiers of electron-transfer chemistry demand that we develop theoretical frameworks to describe the delivery of multiple electrons, atoms, and ions in molecular systems. When electrons move over long distances through high barriers, where the probability for thermal population of oxidized or reduced bridge-localized states is very small, the electrons will tunnel from the donor (D) to acceptor (A), facilitated by bridge-mediated superexchange interactions. If the stable donor and acceptor redox states on D and A differ by two electrons, it is possible that the electrons will propagate coherently from D to A. While structure-function relations for single-electron superexchange in molecules are well established, strategies to manipulate the coherent flow of multiple electrons are largely unknown. In contrast to one-electron superexchange, two-electron superexchange involves both one- and two-electron virtual intermediate states, the number of virtual intermediates increases very rapidly with system size, and multiple classes of pathways interfere with one another. In the study described here, we developed simple superexchange models for two-electron transfer. We explored how the bridge structure and energetics influence multielectron superexchange, and we compared two-electron superexchange interactions to single-electron superexchange. Multielectron superexchange introduces interference between singly and doubly oxidized (or reduced) bridge virtual states, so that even simple linear donor-bridge-acceptor systems have pathway topologies that resemble those seen for one-electron superexchange through bridges with multiple parallel pathways. The simple model systems studied here exhibit a richness that is amenable to experimental exploration by manipulating the multiple pathways, pathway crosstalk, and changes in the number of donor and acceptor species. The features that emerge from these studies may assist in developing new strategies to deliver multiple electrons in condensed-phase redox systems, including multiple-electron redox species, multimetallic/multielectron redox catalysts, and multiexciton excited states.

Early-Late Heterobimetallic Complexes Linked by Phosphinoamide Ligands. Tuning Redox Potentials and Small Molecule Activation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thomas, Christine M.

2015-08-01

Recent attention in the chemical community has been focused on the energy efficient and environmentally benign conversion of abundant small molecules (CO2, H2O, etc.) to useful liquid fuels. This project addresses these goals by examining fundamental aspects of catalyst design to ultimately access small molecule activation processes under mild conditions. Specifically, Thomas and coworkers have targetted heterobimetallic complexes that feature metal centers with vastly different electronic properties, dictated both by their respective positions on the periodic table and their coordination environment. Unlike homobimetallic complexes featuring identical or similar metals, the bonds between metals in early/late heterobimetallics are more polarized, withmore » the more electron-rich late metal center donating electron density to the more electron-deficient early metal center. While metal-metal bonds pose an interesting strategy for storing redox equivalents and stabilizing reactive metal fragments, the polar character of metal-metal bonds in heterobimetallic complexes renders these molecules ideally poised to react with small molecule substrates via cleavage of energy-rich single and double bonds. In addition, metal-metal interactions have been shown to dramatically affect redox potentials and promote multielectron redox activity, suggesting that metal-metal interactions may provide a mechanism to tune redox potentials and access substrate reduction/activation at mild overpotentials. This research project has provided a better fundamental understanding of how interactions between transition metals can be used as a strategy to promote and/or control chemical transformations related to the clean production of fuels. While this project focused on the study of homogeneous systems, it is anticipated that the broad conclusions drawn from these investigations will be applicable to heterogeneous catalysis as well, particularly on heterogeneous processes that occur at interfaces in multicomponent systems.« less

A multireference perturbation method using non-orthogonal Hartree-Fock determinants for ground and excited states

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yost, Shane R.; Kowalczyk, Tim; Van Voorhis, Troy, E-mail: tvan@mit.edu

2013-11-07

In this article we propose the ΔSCF(2) framework, a multireference strategy based on second-order perturbation theory, for ground and excited electronic states. Unlike the complete active space family of methods, ΔSCF(2) employs a set of self-consistent Hartree-Fock determinants, also known as ΔSCF states. Each ΔSCF electronic state is modified by a first-order correction from Møller-Plesset perturbation theory and used to construct a Hamiltonian in a configuration interactions like framework. We present formulas for the resulting matrix elements between nonorthogonal states that scale as N{sub occ}{sup 2}N{sub virt}{sup 3}. Unlike most active space methods, ΔSCF(2) treats the ground and excited statemore » determinants even-handedly. We apply ΔSCF(2) to the H{sub 2}, hydrogen fluoride, and H{sub 4} systems and show that the method provides accurate descriptions of ground- and excited-state potential energy surfaces with no single active space containing more than 10 ΔSCF states.« less

Preparation, characterization and activity evaluation of heterostructure In(2)O(3)/In(OH)(3) photocatalyst.

PubMed

Shifu, Chen; Xiaoling, Yu; Huaye, Zhang; Wei, Liu

2010-08-15

In this paper, the heterostructure In(2)O(3)/In(OH)(3) photocatalyst was prepared by programmed thermal treatment of In(OH)(3) using In(NO(3))(3).9H(2)O as the precursor. Various characterization methods such as X-ray power diffraction (XRD), UV-vis diffuse reflectance spectroscopy (DRS), Fourier transform infrared spectrometry (FT-IR) and transmission electron microscopy (TEM) were employed to investigate the structure, morphologies, and optical properties. Terephthalic acid was used as a probe molecule to detect the generation of hydroxyl radicals (OH) on the surface of UV-illuminated photocatalyst by a photoluminescence (PL) technique. The results showed that the photocatalytic activity of the heterostructure In(2)O(3)/In(OH)(3) was higher than that of single In(2)O(3) or In(OH)(3). The increased photocatalytic activity may be attributed to the formation of the heterojunction between In(2)O(3) and In(OH)(3), which suppresses the recombination of photoexcited electrons-hole pairs. Copyright 2010 Elsevier B.V. All rights reserved.

Cryo-electron microscopy structure of human peroxiredoxin-3 filament reveals the assembly of a putative chaperone.

PubMed

Radjainia, Mazdak; Venugopal, Hariprasad; Desfosses, Ambroise; Phillips, Amy J; Yewdall, N Amy; Hampton, Mark B; Gerrard, Juliet A; Mitra, Alok K

2015-05-05

Peroxiredoxins (Prxs) are a ubiquitous class of thiol-dependent peroxidases that play an important role in the protection and response of cells to oxidative stress. The catalytic unit of typical 2-Cys Prxs are homodimers, which can self-associate to form complex assemblies that are hypothesized to have signaling and chaperone activity. Mitochondrial Prx3 forms dodecameric toroids, which can further stack to form filaments, the so-called high-molecular-weight (HMW) form that has putative holdase activity. We used single-particle analysis and helical processing of electron cryomicroscopy images of human Prx3 filaments induced by low pH to generate a ∼7-Å resolution 3D structure of the HMW form, the first such structure for a 2-Cys Prx. The pseudo-atomic model reveals interactions that promote the stacking of the toroids and shows that unlike previously reported data, the structure can accommodate a partially folded C terminus. The HMW filament lumen displays hydrophobic patches, which we hypothesize bestow holdase activity. Copyright © 2015 Elsevier Ltd. All rights reserved.

Thermal-Error Regime in High-Accuracy Gigahertz Single-Electron Pumping

NASA Astrophysics Data System (ADS)

Zhao, R.; Rossi, A.; Giblin, S. P.; Fletcher, J. D.; Hudson, F. E.; Möttönen, M.; Kataoka, M.; Dzurak, A. S.

2017-10-01

Single-electron pumps based on semiconductor quantum dots are promising candidates for the emerging quantum standard of electrical current. They can transfer discrete charges with part-per-million (ppm) precision in nanosecond time scales. Here, we employ a metal-oxide-semiconductor silicon quantum dot to experimentally demonstrate high-accuracy gigahertz single-electron pumping in the regime where the number of electrons trapped in the dot is determined by the thermal distribution in the reservoir leads. In a measurement with traceability to primary voltage and resistance standards, the averaged pump current over the quantized plateau, driven by a 1-GHz sinusoidal wave in the absence of a magnetic field, is equal to the ideal value of e f within a measurement uncertainty as low as 0.27 ppm.

Instrumental requirements for the detection of electron beam-induced object excitations at the single atom level in high-resolution transmission electron microscopy.

PubMed

Kisielowski, C; Specht, P; Gygax, S M; Barton, B; Calderon, H A; Kang, J H; Cieslinski, R

2015-01-01

This contribution touches on essential requirements for instrument stability and resolution that allows operating advanced electron microscopes at the edge to technological capabilities. They enable the detection of single atoms and their dynamic behavior on a length scale of picometers in real time. It is understood that the observed atom dynamic is intimately linked to the relaxation and thermalization of electron beam-induced sample excitation. Resulting contrast fluctuations are beam current dependent and largely contribute to a contrast mismatch between experiments and theory if not considered. If explored, they open the possibility to study functional behavior of nanocrystals and single molecules at the atomic level in real time. Copyright © 2014 Elsevier Ltd. All rights reserved.

Strong spin-photon coupling in silicon

NASA Astrophysics Data System (ADS)

Samkharadze, N.; Zheng, G.; Kalhor, N.; Brousse, D.; Sammak, A.; Mendes, U. C.; Blais, A.; Scappucci, G.; Vandersypen, L. M. K.

2018-03-01

Long coherence times of single spins in silicon quantum dots make these systems highly attractive for quantum computation, but how to scale up spin qubit systems remains an open question. As a first step to address this issue, we demonstrate the strong coupling of a single electron spin and a single microwave photon. The electron spin is trapped in a silicon double quantum dot, and the microwave photon is stored in an on-chip high-impedance superconducting resonator. The electric field component of the cavity photon couples directly to the charge dipole of the electron in the double dot, and indirectly to the electron spin, through a strong local magnetic field gradient from a nearby micromagnet. Our results provide a route to realizing large networks of quantum dot–based spin qubit registers.