Tissue-like Neural Probes for Understanding and Modulating the Brain.

PubMed

Hong, Guosong; Viveros, Robert D; Zwang, Theodore J; Yang, Xiao; Lieber, Charles M

2018-03-19

Electrophysiology tools have contributed substantially to understanding brain function, yet the capabilities of conventional electrophysiology probes have remained limited in key ways because of large structural and mechanical mismatches with respect to neural tissue. In this Perspective, we discuss how the general goal of probe design in biochemistry, that the probe or label have a minimal impact on the properties and function of the system being studied, can be realized by minimizing structural, mechanical, and topological differences between neural probes and brain tissue, thus leading to a new paradigm of tissue-like mesh electronics. The unique properties and capabilities of the tissue-like mesh electronics as well as future opportunities are summarized. First, we discuss the design of an ultraflexible and open mesh structure of electronics that is tissue-like and can be delivered in the brain via minimally invasive syringe injection like molecular and macromolecular pharmaceuticals. Second, we describe the unprecedented tissue healing without chronic immune response that leads to seamless three-dimensional integration with a natural distribution of neurons and other key cells through these tissue-like probes. These unique characteristics lead to unmatched stable long-term, multiplexed mapping and modulation of neural circuits at the single-neuron level on a year time scale. Last, we offer insights on several exciting future directions for the tissue-like electronics paradigm that capitalize on their unique properties to explore biochemical interactions and signaling in a "natural" brain environment.

Signature properties of water: Their molecular electronic origins

PubMed Central

Jones, Andrew P.; Cipcigan, Flaviu S.; Crain, Jason; Martyna, Glenn J.

2015-01-01

Water challenges our fundamental understanding of emergent materials properties from a molecular perspective. It exhibits a uniquely rich phenomenology including dramatic variations in behavior over the wide temperature range of the liquid into water’s crystalline phases and amorphous states. We show that many-body responses arising from water’s electronic structure are essential mechanisms harnessed by the molecule to encode for the distinguishing features of its condensed states. We treat the complete set of these many-body responses nonperturbatively within a coarse-grained electronic structure derived exclusively from single-molecule properties. Such a “strong coupling” approach generates interaction terms of all symmetries to all orders, thereby enabling unique transferability to diverse local environments such as those encountered along the coexistence curve. The symmetries of local motifs that can potentially emerge are not known a priori. Consequently, electronic responses unfiltered by artificial truncation are then required to embody the terms that tip the balance to the correct set of structures. Therefore, our fully responsive molecular model produces, a simple, accurate, and intuitive picture of water’s complexity and its molecular origin, predicting water’s signature physical properties from ice, through liquid–vapor coexistence, to the critical point. PMID:25941394

Silver nanoplates with ground or metastable structures obtained from template-free two-phase aqueous/organic synthesis

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

Zhelev, Doncho V., E-mail: dontcho.jelev@nih.gov; Zheleva, Tsvetanka S.

2014-01-28

Silver has unique electrical, catalytic, and plasmonic characteristics and has been widely sought for fabrication of nanostructures. The properties of silver nanostructures are intimately coupled to the structure of silver crystals. Two crystal structures are known for silver: the stable (ground) state cubic face centered 3C-Ag structure and the metastable hexagonal 4H-Ag structure. Recently, Chackraborty et al. [J. Phys.: Condens. Matter 23, 325401 (2011)] discovered a low density, highly reactive metastable hexagonal 2H-Ag structure accessible during electrodeposition of silver nanowires in porous anodic alumina templates. This 2H-Ag structure has enhanced electrical and catalytic characteristics. In the present work we reportmore » template-free synthesis of silver nanoplates with the metastable 2H-Ag crystal structure, which appears together with the ground 3C-Ag and the metastable 4H-Ag structures in a two-phase solution synthesis with citric acid as the capping agent. The capacity of citric acid to stabilize both the stable and the metastable structures is explained by its preferential binding to the close packed facets of Ag crystals, which are the (111) planes for 3C-Ag and the (0001) planes for 4H-Ag and 2H-Ag. Nanoplate morphology and structure are characterized using scanning electron microscopy, X-ray diffraction, and transmission electron microscopy. The synthesized nanoplates have thickness from 15 to 17 nm and edge length from 1 to 10 μm. Transmission electron microscopy selected area electron diffraction is used to uniquely identify and distinguish between nanoplates with 2H-Ag or 4H-Ag or 3C-Ag structures.« less

Cryo-EM structures of two bovine adenovirus type 3 intermediates

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

Cheng, Lingpeng; Huang, Xiaoxing; Li, Xiaomin

2014-02-15

Adenoviruses (Ads) infect hosts from all vertebrate species and have been investigated as vaccine vectors. We report here near-atomic structures of two bovine Ad type 3 (BAd3) intermediates obtained by cryo-electron microscopy. A comparison between the two intermediate structures reveals that the differences are localized in the fivefold vertex region, while their facet structures are identical. The overall facet structure of BAd3 exhibits a similar structure to human Ads; however, BAd3 protein IX has a unique conformation. Mass spectrometry and cryo-electron tomography analyses indicate that one intermediate structure represents the stage during DNA encapsidation, whilst the other intermediate structure representsmore » a later stage. These results also suggest that cleavage of precursor protein VI occurs during, rather than after, the DNA encapsidation process. Overall, our results provide insights into the mechanism of Ad assembly, and allow the first structural comparison between human and nonhuman Ads at backbone level. - Highlights: • First structure of bovine adenovirus type 3. • Some channels are located at the vertex of intermediate during DNA encapsidation. • Protein IX exhibits a unique conformation of trimeric coiled–coiled structure. • Cleavage of precursor protein VI occurs during the DNA encapsidation process.« less

C12A7 Electride Hollow Cathode

DTIC Science & Technology

2013-03-01

due to its unique charged lattice structure (Kim, Toda , et al, 2006) (Medvedeva, Teasley, & Hoffman, 2007) ( Toda , et al., 2004). If the 0.6 eV work...formation of the lattice, which then evacuate upon cooling leaving behind their electrons (Kim, Toda , et al, 2006).     Figure 1: Structure of C12A7...electride in which an electron is clathrated within the positively charged lattice framework ( Toda , et al., 2007). Distribution A: Approved for

LSMS

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

Eisenbach, Markus; Li, Ying Wai; Liu, Xianglin

2017-12-01

LSMS is a first principles, Density Functional theory based, electronic structure code targeted mainly at materials applications. LSMS calculates the local spin density approximation to the diagonal part of the electron Green's function. The electron/spin density and energy are easily determined once the Green's function is known. Linear scaling with system size is achieved in the LSMS by using several unique properties of the real space multiple scattering approach to the Green's function.

Electronic structure and superconductivity of FeSe-related superconductors.

PubMed

Liu, Xu; Zhao, Lin; He, Shaolong; He, Junfeng; Liu, Defa; Mou, Daixiang; Shen, Bing; Hu, Yong; Huang, Jianwei; Zhou, X J

2015-05-13

FeSe superconductors and their related systems have attracted much attention in the study of iron-based superconductors owing to their simple crystal structure and peculiar electronic and physical properties. The bulk FeSe superconductor has a superconducting transition temperature (Tc) of ~8 K and it can be dramatically enhanced to 37 K at high pressure. On the other hand, its cousin system, FeTe, possesses a unique antiferromagnetic ground state but is non-superconducting. Substitution of Se with Te in the FeSe superconductor results in an enhancement of Tc up to 14.5 K and superconductivity can persist over a large composition range in the Fe(Se,Te) system. Intercalation of the FeSe superconductor leads to the discovery of the AxFe2-ySe2 (A = K, Cs and Tl) system that exhibits a Tc higher than 30 K and a unique electronic structure of the superconducting phase. A recent report of possible high temperature superconductivity in single-layer FeSe/SrTiO3 films with a Tc above 65 K has generated much excitement in the community. This pioneering work opens a door for interface superconductivity to explore for high Tc superconductors. The distinct electronic structure and superconducting gap, layer-dependent behavior and insulator-superconductor transition of the FeSe/SrTiO3 films provide critical information in understanding the superconductivity mechanism of iron-based superconductors. In this paper, we present a brief review of the investigation of the electronic structure and superconductivity of the FeSe superconductor and related systems, with a particular focus on the FeSe films.

Lighting system with thermal management system

DOEpatents

Arik, Mehmet; Weaver, Stanton Earl; Stecher, Thomas Elliot; Seeley, Charles Erklin; Kuenzler, Glenn Howard; Wolfe, Jr., Charles Franklin; Utturkar, Yogen Vishwas; Sharma, Rajdeep; Prabhakaran, Satish; Icoz, Tunc

2015-02-24

Lighting systems having unique configurations are provided. For instance, the lighting system may include a light source, a thermal management system and driver electronics, each contained within a housing structure. The light source is configured to provide illumination visible through an opening in the housing structure. The thermal management system is configured to provide an air flow, such as a unidirectional air flow, through the housing structure in order to cool the light source. The driver electronics are configured to provide power to each of the light source and the thermal management system.

Lighting system with thermal management system

DOEpatents

Arik, Mehmet; Weaver, Stanton Earl; Stecher, Thomas Elliot; Seeley, Charles Erklin; Kuenzler, Glenn Howard; Wolfe, Jr., Charles Franklin; Utturkar, Yogen Vishwas; Sharma, Rajdeep; Prabhakaran, Satish; Icoz, Tunc

2015-08-25

Lighting systems having unique configurations are provided. For instance, the lighting system may include a light source, a thermal management system and driver electronics, each contained within a housing structure. The light source is configured to provide illumination visible through an opening in the housing structure. The thermal management system is configured to provide an air flow, such as a unidirectional air flow, through the housing structure in order to cool the light source. The driver electronics are configured to provide power to each of the light source and the thermal management system.

Lighting system with thermal management system

DOEpatents

Arik, Mehmet; Weaver, Stanton; Stecher, Thomas; Seeley, Charles; Kuenzler, Glenn; Wolfe, Jr., Charles; Utturkar, Yogen; Sharma, Rajdeep; Prabhakaran, Satish; Icoz, Tunc

2013-05-07

Lighting systems having unique configurations are provided. For instance, the lighting system may include a light source, a thermal management system and driver electronics, each contained within a housing structure. The light source is configured to provide illumination visible through an opening in the housing structure. The thermal management system is configured to provide an air flow, such as a unidirectional air flow, through the housing structure in order to cool the light source. The driver electronics are configured to provide power to each of the light source and the thermal management system.

Lighting system with thermal management system

DOEpatents

Arik, Mehmet; Weaver, Stanton Earl; Stecher, Thomas Elliot; Seeley, Charles Erklin; Kuenzler, Glenn Howard; Wolfe, Jr, Charles Franklin; Utturkar, Yogen Vishwas; Sharma, Rajdeep; Prabhakaran, Satish; Icoz, Tunc

2016-10-11

Lighting systems having unique configurations are provided. For instance, the lighting system may include a light source, a thermal management system and driver electronics, each contained within a housing structure. The light source is configured to provide illumination visible through an opening in the housing structure. The thermal management system is configured to provide an air flow, such as a unidirectional air flow, through the housing structure in order to cool the light source. The driver electronics are configured to provide power to each of the light source and the thermal management system.

Hole doping, hybridization gaps, and electronic correlation in graphene on a platinum substrate

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

Hwang, Jinwoong; Hwang, Hwihyeon; Kim, Min-Jeong

The interaction between graphene and substrates provides a viable route to enhance the functionality of both materials. Depending on the nature of electronic interaction at the interface, the electron band structure of graphene is strongly influenced, allowing us to make use of the intrinsic properties of graphene or to design additional functionalities in graphene. In this paper, we present an angle-resolved photoemission study on the interaction between graphene and a platinum substrate. The formation of an interface between graphene and platinum leads to a strong deviation in the electronic structure of graphene not only from its freestanding form but alsomore » from the behavior observed on typical metals. Finally, the combined study on the experimental and theoretical electron band structure unveils the unique electronic properties of graphene on a platinum substrate, which singles out graphene/platinum as a model system investigating graphene on a metallic substrate with strong interaction.« less

Hole doping, hybridization gaps, and electronic correlation in graphene on a platinum substrate

DOE PAGES

Hwang, Jinwoong; Hwang, Hwihyeon; Kim, Min-Jeong; ...

2017-08-02

The interaction between graphene and substrates provides a viable route to enhance the functionality of both materials. Depending on the nature of electronic interaction at the interface, the electron band structure of graphene is strongly influenced, allowing us to make use of the intrinsic properties of graphene or to design additional functionalities in graphene. In this paper, we present an angle-resolved photoemission study on the interaction between graphene and a platinum substrate. The formation of an interface between graphene and platinum leads to a strong deviation in the electronic structure of graphene not only from its freestanding form but alsomore » from the behavior observed on typical metals. Finally, the combined study on the experimental and theoretical electron band structure unveils the unique electronic properties of graphene on a platinum substrate, which singles out graphene/platinum as a model system investigating graphene on a metallic substrate with strong interaction.« less

Fractal design concepts for stretchable electronics.

PubMed

Fan, Jonathan A; Yeo, Woon-Hong; Su, Yewang; Hattori, Yoshiaki; Lee, Woosik; Jung, Sung-Young; Zhang, Yihui; Liu, Zhuangjian; Cheng, Huanyu; Falgout, Leo; Bajema, Mike; Coleman, Todd; Gregoire, Dan; Larsen, Ryan J; Huang, Yonggang; Rogers, John A

2014-01-01

Stretchable electronics provide a foundation for applications that exceed the scope of conventional wafer and circuit board technologies due to their unique capacity to integrate with soft materials and curvilinear surfaces. The range of possibilities is predicated on the development of device architectures that simultaneously offer advanced electronic function and compliant mechanics. Here we report that thin films of hard electronic materials patterned in deterministic fractal motifs and bonded to elastomers enable unusual mechanics with important implications in stretchable device design. In particular, we demonstrate the utility of Peano, Greek cross, Vicsek and other fractal constructs to yield space-filling structures of electronic materials, including monocrystalline silicon, for electrophysiological sensors, precision monitors and actuators, and radio frequency antennas. These devices support conformal mounting on the skin and have unique properties such as invisibility under magnetic resonance imaging. The results suggest that fractal-based layouts represent important strategies for hard-soft materials integration.

Fractal design concepts for stretchable electronics

NASA Astrophysics Data System (ADS)

Fan, Jonathan A.; Yeo, Woon-Hong; Su, Yewang; Hattori, Yoshiaki; Lee, Woosik; Jung, Sung-Young; Zhang, Yihui; Liu, Zhuangjian; Cheng, Huanyu; Falgout, Leo; Bajema, Mike; Coleman, Todd; Gregoire, Dan; Larsen, Ryan J.; Huang, Yonggang; Rogers, John A.

2014-02-01

Stretchable electronics provide a foundation for applications that exceed the scope of conventional wafer and circuit board technologies due to their unique capacity to integrate with soft materials and curvilinear surfaces. The range of possibilities is predicated on the development of device architectures that simultaneously offer advanced electronic function and compliant mechanics. Here we report that thin films of hard electronic materials patterned in deterministic fractal motifs and bonded to elastomers enable unusual mechanics with important implications in stretchable device design. In particular, we demonstrate the utility of Peano, Greek cross, Vicsek and other fractal constructs to yield space-filling structures of electronic materials, including monocrystalline silicon, for electrophysiological sensors, precision monitors and actuators, and radio frequency antennas. These devices support conformal mounting on the skin and have unique properties such as invisibility under magnetic resonance imaging. The results suggest that fractal-based layouts represent important strategies for hard-soft materials integration.

Theoretical study of the zero-gap organic conductor α-(BEDT-TTF)2I3

PubMed Central

Kobayashi, Akito; Katayama, Shinya; Suzumura, Yoshikazu

2009-01-01

The quasi-two-dimensional molecular conductor α-(BEDT-TTF)2I3 exhibits anomalous transport phenomena where the temperature dependence of resistivity is weak but the ratio of the Hall coefficient at 10 K to that at room temperature is of the order of 104. These puzzling phenomena were solved by predicting massless Dirac fermions, whose motions are described using the tilted Weyl equation with anisotropic velocity. α-(BEDT-TTF)2I3 is a unique material among several materials with Dirac fermions, i.e. graphene, bismuth, and quantum wells such as HgTe, from the view-points of both the structure and electronic states described as follows. α-(BEDT-TTF)2I3 has the layered structure with highly two-dimensional massless Dirac fermions. The anisotropic velocity and incommensurate momenta of the contact points, ±k0, originate from the inequivalency of the BEDT-TTF sites in the unit cell, where ±k0 moves in the first Brillouin zone with increasing pressure. The massless Dirac fermions exist in the presence of the charge disproportionation and are robust against the increase in pressure. The electron densities on those inequivalent BEDT-TTF sites exhibit anomalous momentum distributions, reflecting the angular dependences of the wave functions around the contact points. Those unique electronic properties affect the spatial oscillations of the electron densities in the vicinity of an impurity. A marked behavior of the Hall coefficient, where the sign of the Hall coefficient reverses sharply but continuously at low temperatures around 5 K, is investigated by treating the interband effects of the magnetic field exactly. It is shown that such behavior is possible by assuming the existence of the extremely small amount of electron doping. The enhancement of the orbital diamagnetism is also expected. The results of the present research shed light on a new aspect of Dirac fermion physics, i.e. the emergence of unique electronic properties owing to the structure of the material. PMID:27877282

Edge mixing dynamics in graphene p–n junctions in the quantum Hall regime

PubMed Central

Matsuo, Sadashige; Takeshita, Shunpei; Tanaka, Takahiro; Nakaharai, Shu; Tsukagoshi, Kazuhito; Moriyama, Takahiro; Ono, Teruo; Kobayashi, Kensuke

2015-01-01

Massless Dirac electron systems such as graphene exhibit a distinct half-integer quantum Hall effect, and in the bipolar transport regime co-propagating edge states along the p–n junction are realized. Additionally, these edge states are uniformly mixed at the junction, which makes it a unique structure to partition electrons in these edge states. Although many experimental works have addressed this issue, the microscopic dynamics of electron partition in this peculiar structure remains unclear. Here we performed shot-noise measurements on the junction in the quantum Hall regime as well as at zero magnetic field. We found that, in sharp contrast with the zero-field case, the shot noise in the quantum Hall regime is finite in the bipolar regime, but is strongly suppressed in the unipolar regime. Our observation is consistent with the theoretical prediction and gives microscopic evidence that the edge states are uniquely mixed along the p–n junction. PMID:26337445

Unique spin-polarized transmission effects in a QD ring structure

NASA Astrophysics Data System (ADS)

Hedin, Eric; Joe, Yong

2010-10-01

Spintronics is an emerging field in which the spin of the electron is used for switching purposes and to communicate information. In order to obtain spin-polarized electron transmission, the Zeeman effect is employed to produce spin-split energy states in quantum dots which are embedded in the arms of a mesoscopic Aharonov-Bohm (AB) ring heterostructure. The Zeeman splitting of the QD energy levels can be induced by a parallel magnetic field, or by a perpendicular field which also produces AB-effects. The combination of these effects on the transmission resonances of the structure is studied analytically and several parameter regimes are identified which produce a high degree of spin-polarized output. Contour and line plots of the weighted spin polarization as a function of electron energy and magnetic field are presented to visualize the degree of spin-polarization. Taking advantage of these unique parameter regimes shows the potential promise of such devices for producing spin-polarized currents.

Optical, photonic and optoelectronic properties of graphene, h-NB and their hybrid materials

NASA Astrophysics Data System (ADS)

Wang, Jingang; Ma, Fengcai; Liang, Wenjie; Wang, Rongming; Sun, Mengtao

2017-06-01

Because of the linear dispersion relation and the unique structure of graphene's Dirac electrons, which can be tuned the ultra-wide band, this enables more applications in photonics, electronics and plasma optics. As a substrate, hexagonal boron nitride (h-BN) has an atomic level flat surface without dangling bonds, a weak doping effect and a response in the far ultraviolet area. So the graphene/h-BN heterostructure is very attractive due to its unique optical electronics characteristics. Graphene and h-BN which are stacked in different ways could open the band gap of graphene, and form a moiré pattern for graphene on h-BN and the superlattice in the Brillouin zone, which makes it possible to build photoelectric devices.

Graphene based biosensors

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

Gürel, Hikmet Hakan, E-mail: hhakan.gurel@kocaeli.edu.tr; Salmankurt, Bahadır

2016-03-25

Nanometer-sized graphene as a 2D material has unique chemical and electronic properties. Because of its unique physical, chemical, and electronic properties, its interesting shape and size make it a promising nanomaterial in many biological applications. It is expected that biomaterials incorporating graphene will be developed for the graphene-based drug delivery systems and biomedical devices. The interactions of biomolecules and graphene are long-ranged and very weak. Development of new techniques is very desirable for design of bioelectronics sensors and devices. In this work, we present first-principles calculations within density functional theory to calculate effects of charging on nucleobases on graphene. Itmore » is shown that how modify structural and electronic properties of nucleobases on graphene by applied charging.« less

Atomic structure solution of the complex quasicrystal approximant Al77Rh15Ru8 from electron diffraction data.

PubMed

Samuha, Shmuel; Mugnaioli, Enrico; Grushko, Benjamin; Kolb, Ute; Meshi, Louisa

2014-12-01

The crystal structure of the novel Al77Rh15Ru8 phase (which is an approximant of decagonal quasicrystals) was determined using modern direct methods (MDM) applied to automated electron diffraction tomography (ADT) data. The Al77Rh15Ru8 E-phase is orthorhombic [Pbma, a = 23.40 (5), b = 16.20 (4) and c = 20.00 (5) Å] and has one of the most complicated intermetallic structures solved solely by electron diffraction methods. Its structural model consists of 78 unique atomic positions in the unit cell (19 Rh/Ru and 59 Al). Precession electron diffraction (PED) patterns and high-resolution electron microscopy (HRTEM) images were used for the validation of the proposed atomic model. The structure of the E-phase is described using hierarchical packing of polyhedra and a single type of tiling in the form of a parallelogram. Based on this description, the structure of the E-phase is compared with that of the ε6-phase formed in Al-Rh-Ru at close compositions.

Pressure tuning the lattice and optical response of silver sulfide

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

Zhao, Zhao, E-mail: zhaozhao@stanford.edu; Wei, Hua; Mao, Wendy L.

2016-06-27

Binary transition metal chalcogenides have attracted increasing attention for their unique structural and electronic properties. High pressure is a powerful tool for tuning the lattice and electronic structure of transition metal chalcogenides away from their pristine states. In this work, we systematically studied the in situ structural and optical behavior of silver sulfide (Ag{sub 2}S) under pressure by synchrotron X-ray diffraction and infrared spectroscopy measurements in a diamond anvil cell. Upon compression, Ag{sub 2}S undergoes structural symmetrization accompanied by a series of structural transitions while the crystallographic inequivalence of the two Ag sites is maintained. Electronically, pressure effectively tunes themore » ambient semiconducting Ag{sub 2}S into a metal at ∼22 GPa. Drude model analysis shows that the optical conductivity evolves significantly, reaching the highest value of 100 Ω{sup −1} cm{sup −1} at ∼40 GPa. Our results highlight the structural and electronic tunability of silver chalcogenides as a function of pressure and suggest the potential of Ag{sub 2}S as a platform for developing optical and opto-electronic applications.« less

Effect of ammonia and methane adsorption on the electronic structure of undoped and Fe-doped 2D silica: a first-principles calculation

NASA Astrophysics Data System (ADS)

Chibisov, A. N.; Chibisova, M. A.

2018-05-01

Two-dimensional silicon oxide (2D SiO2) is a unique surface phase with interesting optical, structural and electronic properties. In this study, important novel results on the effect of Fe on the structural and electronic properties of 2D SiO2 during adsorption of CH4 and NH3 molecules are presented. Density functional theory calculations are used to investigate the interaction of CH4 and NH3 molecules with silica. The electronic structure and molecules adsorption energy are studied in detail for undoped and Fe-doped surfaces. The results show that adsorption of CH4 and NH3 molecules on the surface decreases the spin polarization of Fe/SiO2. The results are relevant to understanding the adsorption physics of 2D SiO2 for practical usage in modern nanoelectronic sensors for nanotechnology and optoelectronics.

Observation of van Hove Singularities in Twisted Silicene Multilayers.

PubMed

Li, Zhi; Zhuang, Jincheng; Chen, Lan; Ni, Zhenyi; Liu, Chen; Wang, Li; Xu, Xun; Wang, Jiaou; Pi, Xiaodong; Wang, Xiaolin; Du, Yi; Wu, Kehui; Dou, Shi Xue

2016-08-24

Interlayer interactions perturb the electronic structure of two-dimensional materials and lead to new physical phenomena, such as van Hove singularities and Hofstadter's butterfly pattern. Silicene, the recently discovered two-dimensional form of silicon, is quite unique, in that silicon atoms adopt competing sp(2) and sp(3) hybridization states leading to a low-buckled structure promising relatively strong interlayer interaction. In multilayer silicene, the stacking order provides an important yet rarely explored degree of freedom for tuning its electronic structures through manipulating interlayer coupling. Here, we report the emergence of van Hove singularities in the multilayer silicene created by an interlayer rotation. We demonstrate that even a large-angle rotation (>20°) between stacked silicene layers can generate a Moiré pattern and van Hove singularities due to the strong interlayer coupling in multilayer silicene. Our study suggests an intriguing method for expanding the tunability of the electronic structure for electronic applications in this two-dimensional material.

The Electrical Structure of Discharges Modified by Electron Beams

NASA Astrophysics Data System (ADS)

Haas, F. A.; Braithwaite, N. St. J.

1997-10-01

Injection of an electron beam into a low pressure plasma modifies both the electrical structure and the distributions of charged particle energies. The electrical structure is investigated here in a one-dimensional model by representing the discharge as two collisionless sheaths with a monenergetic electron beam, linked by a quasi-neutral collisional region. The latter is modelled by fluid equations in which the beam current decreases with position. Since the electrodes are connected by an external conductor this implies through Kirchoff's laws that the thermal electron current must correspondingly increase with position. Given the boundary conditions and beam input at the first electrode then the rest of the system is uniquely described. The model reveals the dependence of the sheath potentials at the emitting and absorbing surfaces on the beam current. The model is relevant to externally injected beams and to electron beams originating from secondary processes on surfaces exposed to the plasma.

Thermal Skin fabrication technology

NASA Technical Reports Server (NTRS)

Milam, T. B.

1972-01-01

Advanced fabrication techniques applicable to Thermal Skin structures were investigated, including: (1) chemical machining; (2) braze bonding; (3) diffusion bonding; and (4) electron beam welding. Materials investigated were nickel and nickel alloys. Sample Thermal Skin panels were manufactured using the advanced fabrication techniques studied and were structurally tested. Results of the program included: (1) development of improved chemical machining processes for nickel and several nickel alloys; (2) identification of design geometry limits; (3) identification of diffusion bonding requirements; (4) development of a unique diffusion bonding tool; (5) identification of electron beam welding limits; and (6) identification of structural properties of Thermal Skin material.

Using Quantum Confinement to Uniquely Identify Devices

PubMed Central

Roberts, J.; Bagci, I. E.; Zawawi, M. A. M.; Sexton, J.; Hulbert, N.; Noori, Y. J.; Young, M. P.; Woodhead, C. S.; Missous, M.; Migliorato, M. A.; Roedig, U.; Young, R. J.

2015-01-01

Modern technology unintentionally provides resources that enable the trust of everyday interactions to be undermined. Some authentication schemes address this issue using devices that give a unique output in response to a challenge. These signatures are generated by hard-to-predict physical responses derived from structural characteristics, which lend themselves to two different architectures, known as unique objects (UNOs) and physically unclonable functions (PUFs). The classical design of UNOs and PUFs limits their size and, in some cases, their security. Here we show that quantum confinement lends itself to the provision of unique identities at the nanoscale, by using fluctuations in tunnelling measurements through quantum wells in resonant tunnelling diodes (RTDs). This provides an uncomplicated measurement of identity without conventional resource limitations whilst providing robust security. The confined energy levels are highly sensitive to the specific nanostructure within each RTD, resulting in a distinct tunnelling spectrum for every device, as they contain a unique and unpredictable structure that is presently impossible to clone. This new class of authentication device operates with minimal resources in simple electronic structures above room temperature. PMID:26553435

Syringe injectable electronics

PubMed Central

Hong, Guosong; Zhou, Tao; Jin, Lihua; Duvvuri, Madhavi; Jiang, Zhe; Kruskal, Peter; Xie, Chong; Suo, Zhigang; Fang, Ying; Lieber, Charles M.

2015-01-01

Seamless and minimally-invasive three-dimensional (3D) interpenetration of electronics within artificial or natural structures could allow for continuous monitoring and manipulation of their properties. Flexible electronics provide a means for conforming electronics to non-planar surfaces, yet targeted delivery of flexible electronics to internal regions remains difficult. Here, we overcome this challenge by demonstrating syringe injection and subsequent unfolding of submicrometer-thick, centimeter-scale macroporous mesh electronics through needles with a diameter as small as 100 micrometers. Our results show that electronic components can be injected into man-made and biological cavities, as well as dense gels and tissue, with > 90% device yield. We demonstrate several applications of syringe injectable electronics as a general approach for interpenetrating flexible electronics with 3D structures, including (i) monitoring of internal mechanical strains in polymer cavities, (ii) tight integration and low chronic immunoreactivity with several distinct regions of the brain, and (iii) in vivo multiplexed neural recording. Moreover, syringe injection enables delivery of flexible electronics through a rigid shell, delivery of large volume flexible electronics that can fill internal cavities and co-injection of electronics with other materials into host structures, opening up unique applications for flexible electronics. PMID:26053995

Syringe-injectable electronics.

PubMed

Liu, Jia; Fu, Tian-Ming; Cheng, Zengguang; Hong, Guosong; Zhou, Tao; Jin, Lihua; Duvvuri, Madhavi; Jiang, Zhe; Kruskal, Peter; Xie, Chong; Suo, Zhigang; Fang, Ying; Lieber, Charles M

2015-07-01

Seamless and minimally invasive three-dimensional interpenetration of electronics within artificial or natural structures could allow for continuous monitoring and manipulation of their properties. Flexible electronics provide a means for conforming electronics to non-planar surfaces, yet targeted delivery of flexible electronics to internal regions remains difficult. Here, we overcome this challenge by demonstrating the syringe injection (and subsequent unfolding) of sub-micrometre-thick, centimetre-scale macroporous mesh electronics through needles with a diameter as small as 100 μm. Our results show that electronic components can be injected into man-made and biological cavities, as well as dense gels and tissue, with >90% device yield. We demonstrate several applications of syringe-injectable electronics as a general approach for interpenetrating flexible electronics with three-dimensional structures, including (1) monitoring internal mechanical strains in polymer cavities, (2) tight integration and low chronic immunoreactivity with several distinct regions of the brain, and (3) in vivo multiplexed neural recording. Moreover, syringe injection enables the delivery of flexible electronics through a rigid shell, the delivery of large-volume flexible electronics that can fill internal cavities, and co-injection of electronics with other materials into host structures, opening up unique applications for flexible electronics.

Syringe-injectable electronics

NASA Astrophysics Data System (ADS)

Liu, Jia; Fu, Tian-Ming; Cheng, Zengguang; Hong, Guosong; Zhou, Tao; Jin, Lihua; Duvvuri, Madhavi; Jiang, Zhe; Kruskal, Peter; Xie, Chong; Suo, Zhigang; Fang, Ying; Lieber, Charles M.

2015-07-01

Seamless and minimally invasive three-dimensional interpenetration of electronics within artificial or natural structures could allow for continuous monitoring and manipulation of their properties. Flexible electronics provide a means for conforming electronics to non-planar surfaces, yet targeted delivery of flexible electronics to internal regions remains difficult. Here, we overcome this challenge by demonstrating the syringe injection (and subsequent unfolding) of sub-micrometre-thick, centimetre-scale macroporous mesh electronics through needles with a diameter as small as 100 μm. Our results show that electronic components can be injected into man-made and biological cavities, as well as dense gels and tissue, with >90% device yield. We demonstrate several applications of syringe-injectable electronics as a general approach for interpenetrating flexible electronics with three-dimensional structures, including (1) monitoring internal mechanical strains in polymer cavities, (2) tight integration and low chronic immunoreactivity with several distinct regions of the brain, and (3) in vivo multiplexed neural recording. Moreover, syringe injection enables the delivery of flexible electronics through a rigid shell, the delivery of large-volume flexible electronics that can fill internal cavities, and co-injection of electronics with other materials into host structures, opening up unique applications for flexible electronics.

Temperature-driven topological transition in 1T'-MoTe2

NASA Astrophysics Data System (ADS)

Berger, Ayelet Notis; Andrade, Erick; Kerelsky, Alexander; Edelberg, Drew; Li, Jian; Wang, Zhijun; Zhang, Lunyong; Kim, Jaewook; Zaki, Nader; Avila, Jose; Chen, Chaoyu; Asensio, Maria C.; Cheong, Sang-Wook; Bernevig, Bogdan A.; Pasupathy, Abhay N.

2018-01-01

The topology of Weyl semimetals requires the existence of unique surface states. Surface states have been visualized in spectroscopy measurements, but their connection to the topological character of the material remains largely unexplored. 1T'-MoTe2, presents a unique opportunity to study this connection. This material undergoes a phase transition at 240 K that changes the structure from orthorhombic (putative Weyl semimetal) to monoclinic (trivial metal), while largely maintaining its bulk electronic structure. Here, we show from temperature-dependent quasiparticle interference measurements that this structural transition also acts as a topological switch for surface states in 1T'-MoTe2. At low temperature, we observe strong quasiparticle scattering, consistent with theoretical predictions and photoemission measurements for the surface states in this material. In contrast, measurements performed at room temperature show the complete absence of the scattering wavevectors associated with the trivial surface states. These distinct quasiparticle scattering behaviors show that 1T'-MoTe2 is ideal for separating topological and trivial electronic phenomena via temperature-dependent measurements.

Combined experimental and ab initio study of the electronic structure of narrow-diameter single-wall carbon nanotubes with predominant (6,4),(6,5) chirality

NASA Astrophysics Data System (ADS)

de Blauwe, K.; Mowbray, D. J.; Miyata, Y.; Ayala, P.; Shiozawa, H.; Rubio, A.; Hoffmann, P.; Kataura, H.; Pichler, T.

2010-09-01

Narrow diameter tubes and especially (6,5) tubes with a diameter of 0.75 nm are currently one of the most studied carbon nanotubes because their unique optical and especially luminescence response makes them exceptionally suited for biomedical applications. Here we report on a detailed analysis of the electronic structure of nanotubes with (6,5) and (6,4) chiralities using a combined experimental and theoretical approach. From high-energy spectroscopy involving x-ray absorption and photoemission spectroscopy the detailed valence- and conduction-band response of these narrow diameter tubes is studied. The observed electronic structure is in sound agreement with state of the art ab initio calculations using density-functional theory.

Chemically derived graphene oxide: towards large-area thin-film electronics and optoelectronics.

PubMed

Eda, Goki; Chhowalla, Manish

2010-06-11

Chemically derived graphene oxide (GO) possesses a unique set of properties arising from oxygen functional groups that are introduced during chemical exfoliation of graphite. Large-area thin-film deposition of GO, enabled by its solubility in a variety of solvents, offers a route towards GO-based thin-film electronics and optoelectronics. The electrical and optical properties of GO are strongly dependent on its chemical and atomic structure and are tunable over a wide range via chemical engineering. In this Review, the fundamental structure and properties of GO-based thin films are discussed in relation to their potential applications in electronics and optoelectronics.

Resonant inelastic soft x-ray scattering of CdS: a two-dimensional electronic structure map approach

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

Weinhardt, L.; Fuchs, O.; Fleszar, A.

2008-09-24

Resonant inelastic x-ray scattering (RIXS) with soft x-rays is uniquely suited to study the elec-tronic structure of a variety of materials, but is currently limited by low (fluorescence yield) count rates. This limitation is overcome with a new high-transmission spectrometer that allows to measure soft x-ray RIXS"maps." The S L2,3 RIXS map of CdS is discussed and compared with density functional calculations. The map allows the extraction of decay channel-specific"absorp-tion spectra," giving detailed insight into the wave functions of occupied and unoccupied elec-tronic states.

Bowl Inversion and Electronic Switching of Buckybowls on Gold.

PubMed

Fujii, Shintaro; Ziatdinov, Maxim; Higashibayashi, Shuhei; Sakurai, Hidehiro; Kiguchi, Manabu

2016-09-21

Bowl-shaped π-conjugated compounds, or buckybowls, are a novel class of sp(2)-hybridized nanocarbon materials. In contrast to tubular carbon nanotubes and ball-shaped fullerenes, the buckybowls feature structural flexibility. Bowl-to-bowl structural inversion is one of the unique properties of the buckybowls in solutions. Bowl inversion on a surface modifies the metal-molecule interactions through bistable switching between bowl-up and bowl-down states on the surface, which makes surface-adsorbed buckybowls a relevant model system for elucidation of the mechano-electronic properties of nanocarbon materials. Here, we report a combination of scanning tunneling microscopy (STM) measurements and ab initio atomistic simulations to identify the adlayer structure of the sumanene buckybowl on Au(111) and reveal its unique bowl inversion behavior. We demonstrate that the bowl inversion can be induced by approaching the STM tip toward the molecule. By tuning the local metal-molecule interaction using the STM tip, the sumanene buckybowl exhibits structural bistability with a switching rate that is two orders of magnitude faster than that of the stochastic inversion process.

The Experimental Study of Novel Pseudospark Hollow Cathode Plasma Electron Gun

NASA Astrophysics Data System (ADS)

Gu, Xiaowei; Meng, Lin; Sun, Yiqin; Yu, Xinhua

2008-11-01

The high-power microwave devices with plasma-filled have unique properties. One of the major problems associated with plasma-filled microwave sources is that ions from the plasma drift toward the gun regions of the tube. This bombardment is particularly dangerous for the gun, where high-energy ion impacts can damage the cathode surface and degrade its electron emission capabilities. One of the techniques investigated to mitigate this issue is to replace the material cathode with plasma cathode. Now, we study the novel electron gun (E-gun) that can be suitable for high power microwave device applications, adopting two forms of discharge channel, 1: a single hole channel, the structure can produce a solid electron beam; 2: porous holes channel, the structure can generate multiple electronic injection which is similar to the annular electron beam.

Surface electronic structure of the topological Kondo-insulator candidate correlated electron system SmB6.

PubMed

Neupane, M; Alidoust, N; Xu, S-Y; Kondo, T; Ishida, Y; Kim, D J; Liu, Chang; Belopolski, I; Jo, Y J; Chang, T-R; Jeng, H-T; Durakiewicz, T; Balicas, L; Lin, H; Bansil, A; Shin, S; Fisk, Z; Hasan, M Z

2013-01-01

The Kondo insulator SmB6 has long been known to exhibit low-temperature transport anomalies whose origin is of great interest. Here we uniquely access the surface electronic structure of the anomalous transport regime by combining state-of-the-art laser and synchrotron-based angle-resolved photoemission techniques. We observe clear in-gap states (up to ~4 meV), whose temperature dependence is contingent on the Kondo gap formation. In addition, our observed in-gap Fermi surface oddness tied with the Kramers' point topology, their coexistence with the two-dimensional transport anomaly in the Kondo hybridization regime, as well as their robustness against thermal recycling, taken together, collectively provide strong evidence for protected surface metallicity with a Fermi surface whose topology is consistent with the theoretically predicted topological Fermi surface. Our observations of systematic surface electronic structure provide the fundamental electronic parameters for the anomalous Kondo ground state of correlated electron material SmB6.

Graphitic carbon nitride based nanocomposites: a review

NASA Astrophysics Data System (ADS)

Zhao, Zaiwang; Sun, Yanjuan; Dong, Fan

2014-11-01

Graphitic carbon nitride (g-C3N4), as an intriguing earth-abundant visible light photocatalyst, possesses a unique two-dimensional structure, excellent chemical stability and tunable electronic structure. Pure g-C3N4 suffers from rapid recombination of photo-generated electron-hole pairs resulting in low photocatalytic activity. Because of the unique electronic structure, the g-C3N4 could act as an eminent candidate for coupling with various functional materials to enhance the performance. According to the discrepancies in the photocatalytic mechanism and process, six primary systems of g-C3N4-based nanocomposites can be classified and summarized: namely, the g-C3N4 based metal-free heterojunction, the g-C3N4/single metal oxide (metal sulfide) heterojunction, g-C3N4/composite oxide, the g-C3N4/halide heterojunction, g-C3N4/noble metal heterostructures, and the g-C3N4 based complex system. Apart from the depiction of the fabrication methods, heterojunction structure and multifunctional application of the g-C3N4-based nanocomposites, we emphasize and elaborate on the underlying mechanisms in the photocatalytic activity enhancement of g-C3N4-based nanocomposites. The unique functions of the p-n junction (semiconductor/semiconductor heterostructures), the Schottky junction (metal/semiconductor heterostructures), the surface plasmon resonance (SPR) effect, photosensitization, superconductivity, etc. are utilized in the photocatalytic processes. Furthermore, the enhanced performance of g-C3N4-based nanocomposites has been widely employed in environmental and energetic applications such as photocatalytic degradation of pollutants, photocatalytic hydrogen generation, carbon dioxide reduction, disinfection, and supercapacitors. This critical review ends with a summary and some perspectives on the challenges and new directions in exploring g-C3N4-based advanced nanomaterials.

Focused-electron-beam-induced processing (FEBIP) for emerging applications in carbon nanoelectronics

NASA Astrophysics Data System (ADS)

Fedorov, Andrei G.; Kim, Songkil; Henry, Mathias; Kulkarni, Dhaval; Tsukruk, Vladimir V.

2014-12-01

Focused-electron-beam-induced processing (FEBIP), a resist-free additive nanomanufacturing technique, is an actively researched method for "direct-write" processing of a wide range of structural and functional nanomaterials, with high degree of spatial and time-domain control. This article attempts to critically assess the FEBIP capabilities and unique value proposition in the context of processing of electronics materials, with a particular emphasis on emerging carbon (i.e., based on graphene and carbon nanotubes) devices and interconnect structures. One of the major hurdles in advancing the carbon-based electronic materials and device fabrication is a disjoint nature of various processing steps involved in making a functional device from the precursor graphene/CNT materials. Not only this multi-step sequence severely limits the throughput and increases the cost, but also dramatically reduces the processing reproducibility and negatively impacts the quality because of possible between-the-step contamination, especially for impurity-susceptible materials such as graphene. The FEBIP provides a unique opportunity to address many challenges of carbon nanoelectronics, especially when it is employed as part of an integrated processing environment based on multiple "beams" of energetic particles, including electrons, photons, and molecules. This avenue is promising from the applications' prospective, as such a multi-functional (electron/photon/molecule beam) enables one to define shapes (patterning), form structures (deposition/etching), and modify (cleaning/doping/annealing) properties with locally resolved control on nanoscale using the same tool without ever changing the processing environment. It thus will have a direct positive impact on enhancing functionality, improving quality and reducing fabrication costs for electronic devices, based on both conventional CMOS and emerging carbon (CNT/graphene) materials.

Manipulation of Dirac cones in intercalated epitaxial graphene

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

Kim, Minsung; Tringides, Michael C.; Hershberger, Matthew T.

Graphene is an intriguing material in view of its unique Dirac quasi-particles, and the manipulation of its electronic structure is important in material design and applications. Here, we theoretically investigate the electronic band structure of epitaxial graphene on SiC with intercalation of rare earth metal ions (e.g., Yb and Dy) using first-principles calculations. We can use the intercalation to control the coupling of the constituent components (buffer layer, graphene, and substrate), resulting in strong modification of the graphene band structure. We also demonstrate that the metal-intercalated epitaxial graphene has tunable band structures by controlling the energies of Dirac cones asmore » well as the linear and quadratic band dispersion depending on the intercalation layer and density. Thus, the metal intercalation is a viable method to manipulate the electronic band structure of the epitaxial graphene, which can enhance the functional utility and controllability of the material.« less

Manipulation of Dirac cones in intercalated epitaxial graphene

DOE PAGES

Kim, Minsung; Tringides, Michael C.; Hershberger, Matthew T.; ...

2017-07-12

Graphene is an intriguing material in view of its unique Dirac quasi-particles, and the manipulation of its electronic structure is important in material design and applications. Here, we theoretically investigate the electronic band structure of epitaxial graphene on SiC with intercalation of rare earth metal ions (e.g., Yb and Dy) using first-principles calculations. We can use the intercalation to control the coupling of the constituent components (buffer layer, graphene, and substrate), resulting in strong modification of the graphene band structure. We also demonstrate that the metal-intercalated epitaxial graphene has tunable band structures by controlling the energies of Dirac cones asmore » well as the linear and quadratic band dispersion depending on the intercalation layer and density. Thus, the metal intercalation is a viable method to manipulate the electronic band structure of the epitaxial graphene, which can enhance the functional utility and controllability of the material.« less

Single-shot mega-electronvolt ultrafast electron diffraction for structure dynamic studies of warm dense matter

NASA Astrophysics Data System (ADS)

Mo, M. Z.; Shen, X.; Chen, Z.; Li, R. K.; Dunning, M.; Sokolowski-Tinten, K.; Zheng, Q.; Weathersby, S. P.; Reid, A. H.; Coffee, R.; Makasyuk, I.; Edstrom, S.; McCormick, D.; Jobe, K.; Hast, C.; Glenzer, S. H.; Wang, X.

2016-11-01

We have developed a single-shot mega-electronvolt ultrafast-electron-diffraction system to measure the structural dynamics of warm dense matter. The electron probe in this system is featured by a kinetic energy of 3.2 MeV and a total charge of 20 fC, with the FWHM pulse duration and spot size at sample of 350 fs and 120 μm respectively. We demonstrate its unique capability by visualizing the atomic structural changes of warm dense gold formed from a laser-excited 35-nm freestanding single-crystal gold foil. The temporal evolution of the Bragg peak intensity and of the liquid signal during solid-liquid phase transition are quantitatively determined. This experimental capability opens up an exciting opportunity to unravel the atomic dynamics of structural phase transitions in warm dense matter regime.

Development of High-Gradient Dielectric Laser-Driven Particle Accelerator Structures

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

Byer, Robert L.

2013-11-07

The thrust of Stanford's program is to conduct research on high-gradient dielectric accelerator structures driven with high repetition-rate, tabletop infrared lasers. The close collaboration between Stanford and SLAC (Stanford Linear Accelerator Center) is critical to the success of this project, because it provides a unique environment where prototype dielectric accelerator structures can be rapidly fabricated and tested with a relativistic electron beam.

Atomic structure and bonding of the interfacial bilayer between Au nanoparticles and epitaxially regrown MgAl{sub 2}O{sub 4} substrates

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

Zhu, Guo-zhen; Canadian Centre of Electron Microscopy and Department of Materials Science and Engineering, McMaster University, 1280 Main Street West, Hamilton, Ontario L8S 4M1; Majdi, Tahereh

2014-12-08

A unique metal/oxide interfacial bilayer formed between Au nanoparticles and MgAl{sub 2}O{sub 4} substrates following thermal treatment is reported. Associated with the formation of the bilayer was the onset of an abnormal epitaxial growth of the substrate under the nanoparticle. According to the redistribution of atoms and the changes of their electronic structure probed across the interface by a transmission electron microscopy, we suggest two possible atomic models of the interfacial bilayer.

Structural and electronic properties of monolayer group III monochalcogenides

NASA Astrophysics Data System (ADS)

Demirci, S.; Avazlı, N.; Durgun, E.; Cahangirov, S.

2017-03-01

We investigate the structural, mechanical, and electronic properties of the two-dimensional hexagonal structure of group III-VI binary monolayers, M X (M =B , Al, Ga, In and X =O , S, Se, Te) using first-principles calculations based on the density functional theory. The structural optimization calculations and phonon spectrum analysis indicate that all of the 16 possible binary compounds are thermally stable. In-plane stiffness values cover a range depending on the element types and can be as high as that of graphene, while the calculated bending rigidity is found to be an order of magnitude higher than that of graphene. The obtained electronic band structures show that M X monolayers are indirect band-gap semiconductors. The calculated band gaps span a wide optical spectrum from deep ultraviolet to near infrared. The electronic structure of oxides (M O ) is different from the rest because of the high electronegativity of oxygen atoms. The dispersions of the electronic band edges and the nature of bonding between atoms can also be correlated with electronegativities of constituent elements. The unique characteristics of group III-VI binary monolayers can be suitable for high-performance device applications in nanoelectronics and optics.

A facile bacterial assisted electrochemical self-assembly of polypyrrole micro-pillars: towards underwater low adhesive superoleophobicity

NASA Astrophysics Data System (ADS)

Cheng, Zhe; Ding, Chunmei; Liu, Huan; Zhu, Ying; Jiang, Lei

2013-12-01

By taking advantage of bacterial extracellular electron transfer behavior, a facile method was developed to fabricate oriented polypyrrole micro-pillars (PPy-MP) with nanoscale surface roughness. Microbes acted as a living conductive template on which PPy was in situ polymerized. The as-prepared PPy-MP exhibit the distinctive underwater low adhesive superoleophobicity which is attributable to the unique hierarchical micro/nano-structures and the high surface energy by doping with inorganic small anions.By taking advantage of bacterial extracellular electron transfer behavior, a facile method was developed to fabricate oriented polypyrrole micro-pillars (PPy-MP) with nanoscale surface roughness. Microbes acted as a living conductive template on which PPy was in situ polymerized. The as-prepared PPy-MP exhibit the distinctive underwater low adhesive superoleophobicity which is attributable to the unique hierarchical micro/nano-structures and the high surface energy by doping with inorganic small anions. Electronic supplementary information (ESI) available: The shape of a water drop on PPy-MPA and cauliflower-like PPy film in air. See DOI: 10.1039/c3nr03788f

Evolution and Control of Electronic Structures near the Interface of Complex Oxide Heterostructure SmTiO3/SrTiO3

NASA Astrophysics Data System (ADS)

Mori, Ryo; Marshall, Patrick; Isaac, Brandon; Denlinger, Jonathan; Stemmer, Susanne; Lanzara, Alessandra

The confined electron system in the quantum well of the transition metal oxide, SrTiO3, embedded in the rare earth titanate, SmTiO3, shows unique properties, such as high carrier density, fermi liquid to non-fermi liquid transition, and pseudo-gap, which can be controlled by changing the shape of the quantum well. We will present a distinct difference in the electronic structures between the different quantum well structures obtained by angle-resolved photoemission spectroscopy (ARPES) measurements, suggesting the possibility to control the orbital character and the electron correlation near the interface as well as carrier density. The work was supported by the Quantum Materials Program at LBNL, funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Materials Sciences and Engineering Division, under Contract No. DE-AC02-05CH11231.

Nanodiamond Landmarks for Subcellular Multimodal Optical and Electron Imaging

PubMed Central

Zurbuchen, Mark A.; Lake, Michael P.; Kohan, Sirus A.; Leung, Belinda; Bouchard, Louis-S.

2013-01-01

There is a growing need for biolabels that can be used in both optical and electron microscopies, are non-cytotoxic, and do not photobleach. Such biolabels could enable targeted nanoscale imaging of sub-cellular structures, and help to establish correlations between conjugation-delivered biomolecules and function. Here we demonstrate a sub-cellular multi-modal imaging methodology that enables localization of inert particulate probes, consisting of nanodiamonds having fluorescent nitrogen-vacancy centers. These are functionalized to target specific structures, and are observable by both optical and electron microscopies. Nanodiamonds targeted to the nuclear pore complex are rapidly localized in electron-microscopy diffraction mode to enable “zooming-in” to regions of interest for detailed structural investigations. Optical microscopies reveal nanodiamonds for in-vitro tracking or uptake-confirmation. The approach is general, works down to the single nanodiamond level, and can leverage the unique capabilities of nanodiamonds, such as biocompatibility, sensitive magnetometry, and gene and drug delivery. PMID:24036840

Dioxygen in Polyoxometalate Mediated Reactions.

PubMed

Weinstock, Ira A; Schreiber, Roy E; Neumann, Ronny

2018-03-14

In this review article, we consider the use of molecular oxygen in reactions mediated by polyoxometalates. Polyoxometalates are anionic metal oxide clusters of a variety of structures that are soluble in liquid phases and therefore amenable to homogeneous catalytic transformations. Often, they are active for electron transfer oxidations of a myriad of substrates and upon reduction can be reoxidized by molecular oxygen. For example, the phosphovanadomolybdate, H 5 PV 2 Mo 10 O 40 , can oxidize Pd(0) thereby enabling aerobic reactions catalyzed by Pd and H 5 PV 2 Mo 10 O 40 . In a similar vein, polyoxometalates can stabilize metal nanoparticles, leading to additional transformations. Furthermore, electron transfer oxidation of other substrates such as halides and sulfur-containing compounds is possible. More uniquely, H 5 PV 2 Mo 10 O 40 and its analogues can mediate electron transfer-oxygen transfer reactions where oxygen atoms are transferred from the polyoxometalate to the substrate. This unique property has enabled correspondingly unique transformations involving carbon-carbon, carbon-hydrogen, and carbon-metal bond activation. The pathway for the reoxidation of vanadomolybdates with O 2 appears to be an inner-sphere reaction, but the oxidation of one-electron reduced polyoxotungstates has been shown through intensive research to be an outer-sphere reaction. Beyond electron transfer and electron transfer-oxygen transfer aerobic transformations, there a few examples of apparent dioxygenase activity where both oxygen atoms are donated to a substrate.

Platinum replica electron microscopy: Imaging the cytoskeleton globally and locally.

PubMed

Svitkina, Tatyana M

2017-05-01

Structural studies reveal how smaller components of a system work together as a whole. However, combining high resolution of details with full coverage of the whole is challenging. In cell biology, light microscopy can image many cells in their entirety, but at a lower resolution, whereas electron microscopy affords very high resolution, but usually at the expense of the sample size and coverage. Structural analyses of the cytoskeleton are especially demanding, because cytoskeletal networks are unresolvable by light microscopy due to their density and intricacy, whereas their proper preservation is a challenge for electron microscopy. Platinum replica electron microscopy can uniquely bridge the gap between the "comfort zones" of light and electron microscopy by allowing high resolution imaging of the cytoskeleton throughout the entire cell and in many cells in the population. This review describes the principles and applications of platinum replica electron microscopy for studies of the cytoskeleton. Copyright © 2017 Elsevier Ltd. All rights reserved.

Platinum Replica Electron Microscopy: Imaging the Cytoskeleton Globally and Locally

PubMed Central

SVITKINA, Tatyana M.

2017-01-01

Structural studies reveal how smaller components of a system work together as a whole. However, combining high resolution of details with full coverage of the whole is challenging. In cell biology, light microscopy can image many cells in their entirety, but at a lower resolution, whereas electron microscopy affords very high resolution, but usually at the expense of the sample size and coverage. Structural analyses of the cytoskeleton are especially demanding, because cytoskeletal networks are unresolvable by light microscopy due to their density and intricacy, whereas their proper preservation is a challenge for electron microscopy. Platinum replica electron microscopy can uniquely bridge the gap between the “comfort zones” of light and electron microscopy by allowing high resolution imaging of the cytoskeleton throughout the entire cell and in many cells in the population. This review describes the principles and applications of platinum replica electron microscopy for studies of the cytoskeleton. PMID:28323208

Observation of van Hove Singularities in Twisted Silicene Multilayers

PubMed Central

2016-01-01

Interlayer interactions perturb the electronic structure of two-dimensional materials and lead to new physical phenomena, such as van Hove singularities and Hofstadter’s butterfly pattern. Silicene, the recently discovered two-dimensional form of silicon, is quite unique, in that silicon atoms adopt competing sp2 and sp3 hybridization states leading to a low-buckled structure promising relatively strong interlayer interaction. In multilayer silicene, the stacking order provides an important yet rarely explored degree of freedom for tuning its electronic structures through manipulating interlayer coupling. Here, we report the emergence of van Hove singularities in the multilayer silicene created by an interlayer rotation. We demonstrate that even a large-angle rotation (>20°) between stacked silicene layers can generate a Moiré pattern and van Hove singularities due to the strong interlayer coupling in multilayer silicene. Our study suggests an intriguing method for expanding the tunability of the electronic structure for electronic applications in this two-dimensional material. PMID:27610412

Valence Band Control of Metal Silicide Films via Stoichiometry.

PubMed

Streller, Frank; Qi, Yubo; Yang, Jing; Mangolini, Filippo; Rappe, Andrew M; Carpick, Robert W

2016-07-07

The unique electronic and mechanical properties of metal silicide films render them interesting for advanced materials in plasmonic devices, batteries, field-emitters, thermoelectric devices, transistors, and nanoelectromechanical switches. However, enabling their use requires precisely controlling their electronic structure. Using platinum silicide (PtxSi) as a model silicide, we demonstrate that the electronic structure of PtxSi thin films (1 ≤ x ≤ 3) can be tuned between metallic and semimetallic by changing the stoichiometry. Increasing the silicon content in PtxSi decreases the carrier density according to valence band X-ray photoelectron spectroscopy and theoretical density of states (DOS) calculations. Among all PtxSi phases, Pt3Si offers the highest DOS due to the modest shift of the Pt5d manifold away from the Fermi edge by only 0.5 eV compared to Pt, rendering it promising for applications. These results, demonstrating tunability of the electronic structure of thin metal silicide films, suggest that metal silicides can be designed to achieve application-specific electronic properties.

Conducting Polymeric Hydrogel Electrolyte Based on Carboxymethylcellulose and Polyacrylamide/Polyaniline for Supercapacitor Applications

NASA Astrophysics Data System (ADS)

Suganya, N.; Jaisankar, V.; Sivakumar, E. K. T.

Conducting polymer hydrogels represent a unique class of materials that possess enormous application in flexible electronic devices. In the present work, conducting carboxymethylcellulose (CMC)-co-polyacrylamide (PAAm)/polyaniline was synthesized by a two-step interpenetrating network solution polymerization technique. The synthesized CMC-co-PAAm/polyaniline with interpenetrating network structure was prepared by in situ polymerization of aniline to enhance conductivity. The molecular structure and morphology of the copolymer hydrogels were characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. The novel conducting polymer hydrogels show good electrical and electrochemical behavior, which makes them potentially useful in electronic devices such as supercapacitors, biosensors, bioelectronics, solar cells and memory devices.

Two-Dimensional Stoichiometric Boron Oxides as a Versatile Platform for Electronic Structure Engineering.

PubMed

Zhang, Ruiqi; Li, Zhenyu; Yang, Jinlong

2017-09-21

Oxides of two-dimensional (2D) atomic crystals have been widely studied due to their unique properties. In most 2D oxides, oxygen acts as a functional group, which makes it difficult to control the degree of oxidation. Because borophene is an electron-deficient system, it is expected that oxygen will be intrinsically incorporated into the basal plane of borophene, forming stoichiometric 2D boron oxide (BO) structures. By using first-principles global optimization, we systematically explore structures and properties of 2D BO systems with well-defined degrees of oxidation. Stable B-O-B and OB 3 tetrahedron structure motifs are identified in these structures. Interesting properties, such as strong linear dichroism, Dirac node-line (DNL) semimetallicity, and negative differential resistance, have been predicted for these systems. Our results demonstrate that 2D BO represents a versatile platform for electronic structure engineering via tuning the stoichiometric degree of oxidation, which leads to various technological applications.

Structural basis for energy transduction by respiratory alternative complex III.

PubMed

Sousa, Joana S; Calisto, Filipa; Langer, Julian D; Mills, Deryck J; Refojo, Patrícia N; Teixeira, Miguel; Kühlbrandt, Werner; Vonck, Janet; Pereira, Manuela M

2018-04-30

Electron transfer in respiratory chains generates the electrochemical potential that serves as energy source for the cell. Prokaryotes can use a wide range of electron donors and acceptors and may have alternative complexes performing the same catalytic reactions as the mitochondrial complexes. This is the case for the alternative complex III (ACIII), a quinol:cytochrome c/HiPIP oxidoreductase. In order to understand the catalytic mechanism of this respiratory enzyme, we determined the structure of ACIII from Rhodothermus marinus at 3.9 Å resolution by single-particle cryo-electron microscopy. ACIII presents a so-far unique structure, for which we establish the arrangement of the cofactors (four iron-sulfur clusters and six c-type hemes) and propose the location of the quinol-binding site and the presence of two putative proton pathways in the membrane. Altogether, this structure provides insights into a mechanism for energy transduction and introduces ACIII as a redox-driven proton pump.

Single-shot mega-electronvolt ultrafast electron diffraction for structure dynamic studies of warm dense matter

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

Mo, M. Z., E-mail: mmo09@slac.stanford.edu; Shen, X.; Chen, Z.

We have developed a single-shot mega-electronvolt ultrafast-electron-diffraction system to measure the structural dynamics of warm dense matter. The electron probe in this system is featured by a kinetic energy of 3.2 MeV and a total charge of 20 fC, with the FWHM pulse duration and spot size at sample of 350 fs and 120 μm respectively. We demonstrate its unique capability by visualizing the atomic structural changes of warm dense gold formed from a laser-excited 35-nm freestanding single-crystal gold foil. The temporal evolution of the Bragg peak intensity and of the liquid signal during solid-liquid phase transition are quantitatively determined.more » This experimental capability opens up an exciting opportunity to unravel the atomic dynamics of structural phase transitions in warm dense matter regime.« less

Single-shot mega-electronvolt ultrafast electron diffraction for structure dynamic studies of warm dense matter

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

Mo, M. Z.; Shen, X.; Chen, Z.

We have developed a single-shot mega-electronvolt ultrafast-electron-diffraction system to measure the structural dynamics of warm dense matter. The electron probe in this system is featured by a kinetic energy of 3.2 MeV and a total charge of 20 fC, with the FWHM pulse duration and spot size at sample of 350 fs and 120 µm respectively. We demonstrate its unique capability by visualizing the atomic structural changes of warm dense gold formed from a laser-excited 35-nm freestanding single-crystal gold foil. The temporal evolution of the Bragg peak intensity and of the liquid signal during solid-liquid phase transition are quantitatively determined.more » This experimental capability opens up an exciting opportunity to unravel the atomic dynamics of structural phase transitions in warm dense matter regime« less

Self-assembled ultrathin nanotubes on diamond (100) surface

NASA Astrophysics Data System (ADS)

Lu, Shaohua; Wang, Yanchao; Liu, Hanyu; Miao, Mao-Sheng; Ma, Yanming

2014-04-01

Surfaces of semiconductors are crucially important for electronics, especially when the devices are reduced to the nanoscale. However, surface structures are often elusive, impeding greatly the engineering of devices. Here we develop an efficient method that can automatically explore the surface structures using structure swarm intelligence. Its application to a simple diamond (100) surface reveals an unexpected surface reconstruction featuring self-assembled carbon nanotubes arrays. Such a surface is energetically competitive with the known dimer structure under normal conditions, but it becomes more favourable under a small compressive strain or at high temperatures. The intriguing covalent bonding between neighbouring tubes creates a unique feature of carrier kinetics (that is, one dimensionality of hole states, while two dimensionality of electron states) that could lead to novel design of superior electronics. Our findings highlight that the surface plays vital roles in the fabrication of nanodevices by being a functional part of them.

Single-shot mega-electronvolt ultrafast electron diffraction for structure dynamic studies of warm dense matter

DOE PAGES

Mo, M. Z.; Shen, X.; Chen, Z.; ...

2016-08-04

We have developed a single-shot mega-electronvolt ultrafast-electron-diffraction system to measure the structural dynamics of warm dense matter. The electron probe in this system is featured by a kinetic energy of 3.2 MeV and a total charge of 20 fC, with the FWHM pulse duration and spot size at sample of 350 fs and 120 µm respectively. We demonstrate its unique capability by visualizing the atomic structural changes of warm dense gold formed from a laser-excited 35-nm freestanding single-crystal gold foil. The temporal evolution of the Bragg peak intensity and of the liquid signal during solid-liquid phase transition are quantitatively determined.more » This experimental capability opens up an exciting opportunity to unravel the atomic dynamics of structural phase transitions in warm dense matter regime« less

Anomalous electronic structure and magnetoresistance in TaAs2

NASA Astrophysics Data System (ADS)

Luo, Yongkang; McDonald, R. D.; Rosa, P. F. S.; Scott, B.; Wakeham, N.; Ghimire, N. J.; Bauer, E. D.; Thompson, J. D.; Ronning, F.

2016-06-01

The change in resistance of a material in a magnetic field reflects its electronic state. In metals with weakly- or non-interacting electrons, the resistance typically increases upon the application of a magnetic field. In contrast, negative magnetoresistance may appear under some circumstances, e.g., in metals with anisotropic Fermi surfaces or with spin-disorder scattering and semimetals with Dirac or Weyl electronic structures. Here we show that the non-magnetic semimetal TaAs2 possesses a very large negative magnetoresistance, with an unknown scattering mechanism. Density functional calculations find that TaAs2 is a new topological semimetal [ℤ2 invariant (0;111)] without Dirac dispersion, demonstrating that a negative magnetoresistance in non-magnetic semimetals cannot be attributed uniquely to the Adler-Bell-Jackiw chiral anomaly of bulk Dirac/Weyl fermions.

Anomalous electronic structure and magnetoresistance in TaAs2

PubMed Central

Luo, Yongkang; McDonald, R. D.; Rosa, P. F. S.; Scott, B.; Wakeham, N.; Ghimire, N. J.; Bauer, E. D.; Thompson, J. D.; Ronning, F.

2016-01-01

The change in resistance of a material in a magnetic field reflects its electronic state. In metals with weakly- or non-interacting electrons, the resistance typically increases upon the application of a magnetic field. In contrast, negative magnetoresistance may appear under some circumstances, e.g., in metals with anisotropic Fermi surfaces or with spin-disorder scattering and semimetals with Dirac or Weyl electronic structures. Here we show that the non-magnetic semimetal TaAs2 possesses a very large negative magnetoresistance, with an unknown scattering mechanism. Density functional calculations find that TaAs2 is a new topological semimetal [ℤ2 invariant (0;111)] without Dirac dispersion, demonstrating that a negative magnetoresistance in non-magnetic semimetals cannot be attributed uniquely to the Adler-Bell-Jackiw chiral anomaly of bulk Dirac/Weyl fermions. PMID:27271852

An organoboron compound with a wide absorption spectrum for solar cell applications.

PubMed

Liu, Fangbin; Ding, Zicheng; Liu, Jun; Wang, Lixiang

2017-11-09

Organoboron compounds offer new approaches to tune the electronic structures of π-conjugated molecules. In this work, an electron acceptor (M-BNBP4P-1) is developed by endcapping an organoboron core unit with two strong electron-withdrawing groups. M-BNBP4P-1 exhibits a unique wide absorption spectrum with two strong absorption bands in the long wavelength region (λ max = 771 nm) and the short wavelength region (λ max = 502 nm), which indicate superior sunlight harvesting capability. This is due to its special electronic structure, i.e. a delocalized LUMO and a localized HOMO. Prototype solution-processed organic solar cells based on M-BNBP4P-1 show a power conversion efficiency of 7.06% and a wide photoresponse from 350 nm to 880 nm.

Atomistic simulations of highly conductive molecular transport junctions under realistic conditions

NASA Astrophysics Data System (ADS)

French, William R.; Iacovella, Christopher R.; Rungger, Ivan; Souza, Amaury Melo; Sanvito, Stefano; Cummings, Peter T.

2013-04-01

We report state-of-the-art atomistic simulations combined with high-fidelity conductance calculations to probe structure-conductance relationships in Au-benzenedithiolate (BDT)-Au junctions under elongation. Our results demonstrate that large increases in conductance are associated with the formation of monatomic chains (MACs) of Au atoms directly connected to BDT. An analysis of the electronic structure of the simulated junctions reveals that enhancement in the s-like states in Au MACs causes the increases in conductance. Other structures also result in increased conductance but are too short-lived to be detected in experiment, while MACs remain stable for long simulation times. Examinations of thermally evolved junctions with and without MACs show negligible overlap between conductance histograms, indicating that the increase in conductance is related to this unique structural change and not thermal fluctuation. These results, which provide an excellent explanation for a recently observed anomalous experimental result [Bruot et al., Nat. Nanotechnol., 2012, 7, 35-40], should aid in the development of mechanically responsive molecular electronic devices.We report state-of-the-art atomistic simulations combined with high-fidelity conductance calculations to probe structure-conductance relationships in Au-benzenedithiolate (BDT)-Au junctions under elongation. Our results demonstrate that large increases in conductance are associated with the formation of monatomic chains (MACs) of Au atoms directly connected to BDT. An analysis of the electronic structure of the simulated junctions reveals that enhancement in the s-like states in Au MACs causes the increases in conductance. Other structures also result in increased conductance but are too short-lived to be detected in experiment, while MACs remain stable for long simulation times. Examinations of thermally evolved junctions with and without MACs show negligible overlap between conductance histograms, indicating that the increase in conductance is related to this unique structural change and not thermal fluctuation. These results, which provide an excellent explanation for a recently observed anomalous experimental result [Bruot et al., Nat. Nanotechnol., 2012, 7, 35-40], should aid in the development of mechanically responsive molecular electronic devices. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr00459g

Pressure-induced structural and electronic transitions, metallization, and enhanced visible-light responsiveness in layered rhenium disulphide

NASA Astrophysics Data System (ADS)

Wang, Pei; Wang, Yonggang; Qu, Jingyu; Zhu, Qiang; Yang, Wenge; Zhu, Jinlong; Wang, Liping; Zhang, Weiwei; He, Duanwei; Zhao, Yusheng

2018-06-01

Triclinic rhenium disulphide (Re S2 ) is a promising candidate for postsilicon electronics because of its unique optic-electronic properties. The electrical and optical properties of Re S2 under high pressure, however, remain unclear. Here we present a joint experimental and theoretical study on the structure, electronic, and vibrational properties, and visible-light responses of Re S2 up to 50 GPa. There is a direct-to-indirect band-gap transition in 1 T -Re S2 under low-pressure regime up to 5 GPa. Upon further compression, 1 T -Re S2 undergoes a structural transition to distorted-1 T' phase at 7.7 GPa, followed by the isostructural metallization at 38.5 GPa. Both in situ Raman spectrum and electronic structure analysis reveal that interlayer sulfur-sulfur interaction is greatly enhanced during compression, leading to the remarkable modifications on the electronic properties observed in our subsequent experimental measurements, such as band-gap closure and enhanced photoresponsiveness. This study demonstrates the critical role of pressure in tuning materials properties and the potential usage of layered Re S2 for pressure-responsive optoelectronic applications.

Effects of increasing number of rings on the ion sensing ability of CdSe quantum dots: a theoretical study

NASA Astrophysics Data System (ADS)

Malik, Pragati; Kakkar, Rita

2018-04-01

A computational study on the structural and electronic properties of a special class of artificial atoms, known as quantum dots, has been carried out. These are semiconductors with unique optical and electronic properties and have been widely used in various applications, such as bio-sensing, bio-imaging, and so on. We have considered quantum dots belonging to II-VI types of semiconductors, due to their wide band gap, possession of large exciton binding energies and unique optical and electronic properties. We have studied their applications as chemical ion sensors by beginning with the study of the ion sensing ability of (CdSe) n ( n = 3, 6, 9 which are in the size range of 0.24, 0.49, 0.74 nm, respectively) quantum dots for cations of the zinc triad, namely Zn2+, Cd2+, Hg2+, and various anions of biological and environmental importance, and studied the effect of increasing number of rings on their ion sensing ability. The various structural, electronic, and optical properties, their interaction energies, and charge transfer on interaction with metal ions and anions have been calculated and reported. Our studies indicate that the CdSe quantum dots can be employed as sensors for both divalent cations and anions, but they can sense cations better than anions.

Study of rare earth local moment magnetism and strongly correlated phenomena in various crystal structures

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

Kong, Tai

Benefiting from unique properties of 4f electrons, rare earth based compounds are known for offering a versatile playground for condensed matter physics research as well as industrial applications. This thesis focuses on three specific examples that further explore the rare earth local moment magnetism and strongly correlated phenomena in various crystal structures.

Stretchable and Tunable Microtectonic ZnO-Based Sensors and Photonics.

PubMed

Gutruf, Philipp; Zeller, Eike; Walia, Sumeet; Nili, Hussein; Sriram, Sharath; Bhaskaran, Madhu

2015-09-16

The concept of realizing electronic applications on elastically stretchable "skins" that conform to irregularly shaped surfaces is revolutionizing fundamental research into mechanics and materials that can enable high performance stretchable devices. The ability to operate electronic devices under various mechanically stressed states can provide a set of unique functionalities that are beyond the capabilities of conventional rigid electronics. Here, a distinctive microtectonic effect enabled oxygen-deficient, nanopatterned zinc oxide (ZnO) thin films on an elastomeric substrate are introduced to realize large area, stretchable, transparent, and ultraportable sensors. The unique surface structures are exploited to create stretchable gas and ultraviolet light sensors, where the functional oxide itself is stretchable, both of which outperform their rigid counterparts under room temperature conditions. Nanoscale ZnO features are embedded in an elastomeric matrix function as tunable diffraction gratings, capable of sensing displacements with nanometre accuracy. These devices and the microtectonic oxide thin film approach show promise in enabling functional, transparent, and wearable electronics. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Temperature-induced band shift in bulk γ-InSe by angle-resolved photoemission spectroscopy

NASA Astrophysics Data System (ADS)

Xu, Huanfeng; Wang, Wei; Zhao, Yafei; Zhang, Xiaoqian; Feng, Yue; Tu, Jian; Gu, Chenyi; Sun, Yizhe; Liu, Chang; Nie, Yuefeng; Edmond Turcu, Ion C.; Xu, Yongbing; He, Liang

2018-05-01

Indium selenide (InSe) has recently become popular research topics because of its unique layered crystal structure, direct band gap and high electron mobilities. In this work, we have acquired the electronic structure of bulk γ-InSe at various temperatures using angle-resolved photoemission spectroscopy (ARPES). We have also found that as the temperature decreases, the valence bands of γ-InSe exhibit a monotonic shift to lower binding energies. This band shift is attributed to the change of lattice parameters and has been validated by variable temperature X-ray diffraction measurements and theoretical calculations.

Materials discovery guided by data-driven insights

NASA Astrophysics Data System (ADS)

Klintenberg, Mattias

As the computational power continues to grow systematic computational exploration has become an important tool for materials discovery. In this presentation the Electronic Structure Project (ESP/ELSA) will be discussed and a number of examples presented that show some of the capabilities of a data-driven methodology for guiding materials discovery. These examples include topological insulators, detector materials and 2D materials. ESP/ELSA is an initiative that dates back to 2001 and today contain many tens of thousands of materials that have been investigated using a robust and high accuracy electronic structure method (all-electron FP-LMTO) thus providing basic materials first-principles data for most inorganic compounds that have been structurally characterized. The web-site containing the ESP/ELSA data has as of today been accessed from more than 4,000 unique computers from all around the world.

Parameterizing A Surface Water Model for Multiwalled Carbon Nanotubes

EPA Science Inventory

The unique electronic, mechanical, and structural properties of carbon nanotubes (CNTs) has lead to increasing production of these versatile materials; currently, the use of carbon-based nanomaterials in consumer products is second only to that of nano-scale silver. Although ther...

Metabolomic Analysis of Liver Cells Exposed to Carbon Nanotubes and Graphene Oxide

EPA Science Inventory

Carbon nanotubes (CNTs) and other graphenic nanomaterials are being used extensively in industrial, consumer, and mechanical applications based in part on their unique structural, optical and electronic properties. Due to the widespread use of these nanoparticles (NPs), human and...

Pressure induced metallization with absence of structural transition in layered molybdenum diselenide

PubMed Central

Zhao, Zhao; Zhang, Haijun; Yuan, Hongtao; Wang, Shibing; Lin, Yu; Zeng, Qiaoshi; Xu, Gang; Liu, Zhenxian; Solanki, G. K.; Patel, K. D.; Cui, Yi; Hwang, Harold Y.; Mao, Wendy L.

2015-01-01

Layered transition-metal dichalcogenides have emerged as exciting material systems with atomically thin geometries and unique electronic properties. Pressure is a powerful tool for continuously tuning their crystal and electronic structures away from the pristine states. Here, we systematically investigated the pressurized behavior of MoSe2 up to ∼60 GPa using multiple experimental techniques and ab-initio calculations. MoSe2 evolves from an anisotropic two-dimensional layered network to a three-dimensional structure without a structural transition, which is a complete contrast to MoS2. The role of the chalcogenide anions in stabilizing different layered patterns is underscored by our layer sliding calculations. MoSe2 possesses highly tunable transport properties under pressure, determined by the gradual narrowing of its band-gap followed by metallization. The continuous tuning of its electronic structure and band-gap in the range of visible light to infrared suggest possible energy-variable optoelectronics applications in pressurized transition-metal dichalcogenides. PMID:26088416

Pressure induced metallization with absence of structural transition in layered molybdenum diselenide

DOE PAGES

Zhao, Zhao; Zhang, Haijun; Yuan, Hongtao; ...

2015-06-19

Layered transition-metal dichalcogenides have emerged as exciting material systems with atomically thin geometries and unique electronic properties. Pressure is a powerful tool for continuously tuning their crystal and electronic structures away from the pristine states. Here, we systematically investigated the pressurized behavior of MoSe 2 up to ~60 GPa using multiple experimental techniques and ab-initio calculations. MoSe 2 evolves from an anisotropic two-dimensional layered network to a three-dimensional structure without a structural transition, which is a complete contrast to MoS 2. The role of the chalcogenide anions in stabilizing different layered patterns is underscored by our layer sliding calculations. MoSemore » 2 possesses highly tunable transport properties under pressure, determined by the gradual narrowing of its band-gap followed by metallization. The continuous tuning of its electronic structure and band-gap in the range of visible light to infrared suggest possible energy-variable optoelectronics applications in pressurized transition-metal dichalcogenides.« less

Effective tuning of electron charge and spin distribution in a dot-ring nanostructure at the ZnO interface

NASA Astrophysics Data System (ADS)

Chakraborty, Tapash; Manaselyan, Aram; Barseghyan, Manuk

2018-05-01

Electronic states and the Aharonov-Bohm effect in ZnO quantum dot-ring nanostructures containing few interacting electrons reveal several unique features. We have shown here that in contrast to the dot-rings made of conventional semiconductors, such as InAs or GaAs, the dot-rings in ZnO heterojunctions demonstrate several unique characteristics due to the unusual properties of quantum dots and rings in ZnO. In particular the energy spectra of the ZnO dot-ring and the Aharnov-Bohm oscillations are strongly dependant on the electron number in the dot or in the ring. Therefore even small changes of the confinement potential, sizes of the dot-ring or the magnetic field can drastically change the energy spectra and the behavior of Aharonov-Bohm oscillations in the system. Due to this interesting phenomena it is possible to effectively control with high accuracy the electron charge and spin distribution inside the dot-ring structure. This controlling can be achieved either by changing the magnetic field or the confinement potentials.

Structural characterization of the novel aminoglycoside phosphotransferase AphVIII from Streptomyces rimosus with enzymatic activity modulated by phosphorylation

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

Boyko, Konstantin M., E-mail: kmb@inbi.ras.ru; National Research Center “Kurchatov Institute”, Kurchatov Complex of NBICS-technologies, Akad. Kurchatova sqr., 1, Moscow, 123182; Gorbacheva, Marina A.

2016-09-02

Aminoglycoside phosphotransferases represent a broad class of enzymes that promote bacterial resistance to aminoglycoside antibiotics via the phosphorylation of hydroxyl groups in the latter. Here we report the spatial structure of the 3′-aminoglycoside phosphotransferase of novel VIII class (AphVIII) solved by X-ray diffraction method with a resolution of 2.15 Å. Deep analysis of APHVIII structure and its comparison with known structures of aminoglycoside phosphotransferases of various types reveals that AphVIII has a typical two-domain fold and, however, possesses some unique characteristics that distinguish the enzyme from its known homologues. The most important difference is the presence of the activation loop withmore » unique Ser146 residue. We demonstrate that in the apo-state of the enzyme the activation loop does not interact with other parts of the enzyme and seems to adopt catalytically competent state only after substrate binding. - Highlights: • 3D structure of the novel aminoglycoside phosphotransferase AphVIII was obtained. • AphVIII activation loop is clearly identified in the electron density. • AphVIII has some unique structural features in its substrate C-ring binding pocket.« less

Determination of the structural phase and octahedral rotation angle in halide perovskites

NASA Astrophysics Data System (ADS)

dos Reis, Roberto; Yang, Hao; Ophus, Colin; Ercius, Peter; Bizarri, Gregory; Perrodin, Didier; Shalapska, Tetiana; Bourret, Edith; Ciston, Jim; Dahmen, Ulrich

2018-02-01

A key to the unique combination of electronic and optical properties in halide perovskite materials lies in their rich structural complexity. However, their radiation sensitive nature limits nanoscale structural characterization requiring dose efficient microscopic techniques in order to determine their structures precisely. In this work, we determine the space-group and directly image the Br halide sites of CsPbBr3, a promising material for optoelectronic applications. Based on the symmetry of high-order Laue zone reflections of convergent-beam electron diffraction, we identify the tetragonal (I4/mcm) structural phase of CsPbBr3 at cryogenic temperature. Electron ptychography provides a highly sensitive phase contrast measurement of the halide positions under low electron-dose conditions, enabling imaging of the elongated Br sites originating from the out-of-phase octahedral rotation viewed along the [001] direction of I4/mcm persisting at room temperature. The measurement of these features and comparison with simulations yield an octahedral rotation angle of 6.5°(±1.5°). The approach demonstrated here opens up opportunities for understanding the atomic scale structural phenomena applying advanced characterization tools on a wide range of radiation sensitive halide-based all-inorganic and hybrid organic-inorganic perovskites.

Strain-induced phase transition and electron spin-polarization in graphene spirals

PubMed Central

Zhang, Xiaoming; Zhao, Mingwen

2014-01-01

Spin-polarized triangular graphene nanoflakes (t-GNFs) serve as ideal building blocks for the long-desired ferromagnetic graphene superlattices, but they are always assembled to planar structures which reduce its mechanical properties. Here, by joining t-GNFs in a spiral way, we propose one-dimensional graphene spirals (GSs) with superior mechanical properties and tunable electronic structures. We demonstrate theoretically the unique features of electron motion in the spiral lattice by means of first-principles calculations combined with a simple Hubbard model. Within a linear elastic deformation range, the GSs are nonmagnetic metals. When the axial tensile strain exceeds an ultimate strain, however, they convert to magnetic semiconductors with stable ferromagnetic ordering along the edges. Such strain-induced phase transition and tunable electron spin-polarization revealed in the GSs open a new avenue for spintronics devices. PMID:25027550

Strain-induced phase transition and electron spin-polarization in graphene spirals.

PubMed

Zhang, Xiaoming; Zhao, Mingwen

2014-07-16

Spin-polarized triangular graphene nanoflakes (t-GNFs) serve as ideal building blocks for the long-desired ferromagnetic graphene superlattices, but they are always assembled to planar structures which reduce its mechanical properties. Here, by joining t-GNFs in a spiral way, we propose one-dimensional graphene spirals (GSs) with superior mechanical properties and tunable electronic structures. We demonstrate theoretically the unique features of electron motion in the spiral lattice by means of first-principles calculations combined with a simple Hubbard model. Within a linear elastic deformation range, the GSs are nonmagnetic metals. When the axial tensile strain exceeds an ultimate strain, however, they convert to magnetic semiconductors with stable ferromagnetic ordering along the edges. Such strain-induced phase transition and tunable electron spin-polarization revealed in the GSs open a new avenue for spintronics devices.

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

Gürel, Hikmet Hakan, E-mail: hhakan.gurel@kocaeli.edu.tr; Salmankurt, Bahadır

Graphene as a 2D material has unique chemical and electronic properties. Because of its unique physical, chemical, and electronic properties, its interesting shape and size make it a promising nanomaterial in many biological applications. However, the lower water-solubility and the irreversible aggregation due to the strong π-π stacking hinder the wide application of graphene nanosheets in biomedical field. Thus, graphene oxide (GO), one derivative of graphene, has been used more frequently in the biological system owing to its relatively higher water solubility and biocompatibility. Recently, it has been demonstrated that nanomaterials with different functional groups on the surface can bemore » used to bind the drug molecules with high affinity. GO has different functional groups such as H, OH and O on its surface; it can be a potential candidate as a drug carrier. The interactions of biomolecules and graphene like structures are long-ranged and very weak. Development of new techniques is very desirable for design of bioelectronics sensors and devices. In this work, we present first-principles spin polarized calculations within density functional theory to calculate effects of charging on DNA/RNA nucleobases on graphene oxide. It is shown that how modify structural and electronic properties of nucleobases on graphene oxide by applied charging.« less

Gate-dependent Pseudospin Mixing in Graphene/boron Nitride Moire Superlattices

DTIC Science & Technology

2014-08-31

LETTERS PUBLISHED ONLINE: 31 AUGUST 2014 | DOI : 10.1038/NPHYS3075 Gate-dependent pseudospin mixing in graphene/boron nitride moiré superlattices... Dirac –Weyl spinors with a two-component pseudospin1–12. The unique pseudospin structure of Dirac electrons leads to emerging phenomena such as the...massless Dirac cone2, anomalous quantum Hall eect2,3, and Klein tunnelling4,5 in graphene. The capability to manipulate electron pseudospin is highly

Parameterizing water quality analysis and simulation program (WASP) for carbon-based nanomaterials

EPA Science Inventory

Carbon nanotubes (CNT) and graphenes are among the most popular carbon-based nanomaterials due to their unique electronic, mechanic and structural properties. Exposure modeling of these nanomaterials in the aquatic environment is necessary to predict the fate of these materials. ...

Biomarker analysis of liver cells exposed to surfactant-wrapped and oxidized multi-walled carbon nanotubes (MWCNTs)

EPA Science Inventory

Carbon nanotubes (CNTs) have great potential in industrial, consumer, and mechanical applications, based partly on their unique structural, optical and electronic properties. CNTs are commonly oxidized or treated with surfactants to facilitate aqueous solution processing, and the...

Design, hydrothermal synthesis and electrochemical properties of porous birnessite-type manganese dioxide nanosheets on graphene as a hybrid material for supercapacitors

NASA Astrophysics Data System (ADS)

Liu, Ying; Yan, De; Zhuo, Renfu; Li, Shuankui; Wu, Zhiguo; Wang, Jun; Ren, Pingyuan; Yan, Pengxun; Geng, Zhongrong

2013-11-01

MnO2-graphene hybrid with a unique structure of porous birnessite-type manganese dioxide (MnO2) nanosheets on graphene has been designed and synthesized by a simple hydrothermal method. The formation mechanism of the hybrid is discussed based on a series of time-dependent experiments. Electrochemical measurements reveal that the MnO2-graphene electrode exhibits much higher specific capacitance (315 F g-1 at a current density of 0.2 A g-1) and better rate capability (even 193 F g-1 at 6 A g-1) compared with both the graphene and MnO2 electrodes. Moreover, the capacitance of MnO2-graphene electrode is still 87% retained after 2000 cycles at a charging rate of 3 A g-1. The superior capacitive performance of the hybrid is attributed to its unique structure, which provides good electronic conductivity, fast electron and ion transport, and high utilization of MnO2.

All-benzene carbon nanocages: size-selective synthesis, photophysical properties, and crystal structure.

PubMed

Matsui, Katsuma; Segawa, Yasutomo; Itami, Kenichiro

2014-11-19

The design and synthesis of a series of carbon nanocages consisting solely of benzene rings are described. Carbon nanocages are appealing molecules not only because they represent junction unit structures of branched carbon nanotubes, but also because of their potential utilities as unique optoelectronic π-conjugated materials and guest-encapsulating hosts. Three sizes of strained, conjugated [n.n.n]carbon nanocages (1, n = 4; 2, n = 5; 3, n = 6) were synthesized with perfect size-selectivity. Cyclohexane-containing units and 1,3,5-trisubstituted benzene-containing units were assembled to yield the minimally strained bicyclic precursors, which were successfully converted into the corresponding carbon nanocages via acid-mediated aromatization. X-ray crystallography of 1 confirmed the cage-shaped structure with an approximately spherical void inside the cage molecule. The present studies revealed the unique properties of carbon nanocages, including strain energies, size-dependent absorption and fluorescence, as well as unique size-dependency for the electronic features of 1-3.

Reaction Dynamics at Liquid Interfaces

NASA Astrophysics Data System (ADS)

Benjamin, Ilan

2015-04-01

The liquid interface is a narrow, highly anisotropic region, characterized by rapidly varying density, polarity, and molecular structure. I review several aspects of interfacial solvation and show how these affect reactivity at liquid/liquid interfaces. I specifically consider ion transfer, electron transfer, and SN2 reactions, showing that solvent effects on these reactions can be understood by examining the unique structure and dynamics of the liquid interface region.

Structure-Function, Stability, and Chemical Modification of the Cyanobacterial Cytochrome b6f Complex from Nostoc sp. PCC 7120*

PubMed Central

Baniulis, Danas; Yamashita, Eiki; Whitelegge, Julian P.; Zatsman, Anna I.; Hendrich, Michael P.; Hasan, S. Saif; Ryan, Christopher M.; Cramer, William A.

2009-01-01

The crystal structure of the cyanobacterial cytochrome b6f complex has previously been solved to 3.0-Å resolution using the thermophilic Mastigocladus laminosus whose genome has not been sequenced. Several unicellular cyanobacteria, whose genomes have been sequenced and are tractable for mutagenesis, do not yield b6f complex in an intact dimeric state with significant electron transport activity. The genome of Nostoc sp. PCC 7120 has been sequenced and is closer phylogenetically to M. laminosus than are unicellular cyanobacteria. The amino acid sequences of the large core subunits and four small peripheral subunits of Nostoc are 88 and 80% identical to those in the M. laminosus b6f complex. Purified b6f complex from Nostoc has a stable dimeric structure, eight subunits with masses similar to those of M. laminosus, and comparable electron transport activity. The crystal structure of the native b6f complex, determined to a resolution of 3.0Å (PDB id: 2ZT9), is almost identical to that of M. laminosus. Two unique aspects of the Nostoc complex are: (i) a dominant conformation of heme bp that is rotated 180° about the α- and γ-meso carbon axis relative to the orientation in the M. laminosus complex and (ii) acetylation of the Rieske iron-sulfur protein (PetC) at the N terminus, a post-translational modification unprecedented in cyanobacterial membrane and electron transport proteins, and in polypeptides of cytochrome bc complexes from any source. The high spin electronic character of the unique heme cn is similar to that previously found in the b6f complex from other sources. PMID:19189962

Structure-Function, Stability, and Chemical Modification of the Cyanobacterial Cytochrome b[subscript 6]f Complex from Nostoc sp. PCC 7120

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

Baniulis, Danas; Yamashita, Eiki; Whitelegge, Julian P.

2009-06-08

The crystal structure of the cyanobacterial cytochrome b{sub 6}f complex has previously been solved to 3.0-{angstrom} resolution using the thermophilic Mastigocladus laminosus whose genome has not been sequenced. Several unicellular cyanobacteria, whose genomes have been sequenced and are tractable for mutagenesis, do not yield b{sub 6}f complex in an intact dimeric state with significant electron transport activity. The genome of Nostoc sp. PCC 7120 has been sequenced and is closer phylogenetically to M. laminosus than are unicellular cyanobacteria. The amino acid sequences of the large core subunits and four small peripheral subunits of Nostoc are 88 and 80% identical tomore » those in the M. laminosus b{sub 6}f complex. Purified b{sub 6}f complex from Nostoc has a stable dimeric structure, eight subunits with masses similar to those of M. laminosus, and comparable electron transport activity. The crystal structure of the native b{sub 6}f complex, determined to a resolution of 3.0{angstrom} (PDB id: 2ZT9), is almost identical to that of M. laminosus. Two unique aspects of the Nostoc complex are: (i) a dominant conformation of heme b{sub p} that is rotated 180 deg. about the {alpha}- and {gamma}-meso carbon axis relative to the orientation in the M. laminosus complex and (ii) acetylation of the Rieske iron-sulfur protein (PetC) at the N terminus, a post-translational modification unprecedented in cyanobacterial membrane and electron transport proteins, and in polypeptides of cytochrome bc complexes from any source. The high spin electronic character of the unique heme cn is similar to that previously found in the b{sub 6}f complex from other sources.« less

Thomson backscattering diagnostics of nanosecond electron bunches in high space charge regime

NASA Astrophysics Data System (ADS)

Plachinda, Pavel

The trend over the last 50 years of down-scaling the silicon transistor to achieve faster computations has led to doubling of the number of transistors and computation speed over about every two years. However, this trend cannot be maintained due to the fundamental limitations of silicon as the main material for the semiconducting industry. Therefore, there is an active search for exploration of alternate materials. Among the possible candidates that can may be able to replace silicon is graphene which has recently gained the most attention. Unique properties of graphene include exceedingly high carrier mobility, tunable band gap, huge optical density of a monolayer, anomalous quantum Hall effect, and many others. To be suitable for microelectronic applications the material should be semiconductive, i.e. have a non-zero band gap. Pristine graphene is a semimetal, but by the virtue of doping the graphene surface with different molecules and radicals a band gap can be opened. Because the electronic properties of all materials are intimately related to their atomic structure, characterization of molecular and electronic structure of functionalizing groups is of high interest. The ab-inito (from the first principles) calculations provide a unique opportunity to study the influence of the dopants and thus allow exploration of the physical phenomena in functionalized graphene structures. This ability paves the road to probe the properties based on the intuitive structural information only. A great advantage of this approach lies in the opportunity for quick screening of various atomic structures. We conducted a series of ab-inito investigations of graphene functionalized with covalently and hapticly bound groups, and demonstrated possible practical usage of functionalized graphene for microelectronic and optical applications. This investigation showed that it is possible produce band gaps in graphene (i.e., produce semiconducting graphene) of about 1 eV, without degrading the carrier mobility. This was archived by considering the influence of those adducts on electronic band structure and conductivity properties.

Neutral-current weak interactions at an EIC

DOE PAGES

Zhao, Y. X.; Deshpande, A.; Huang, J.; ...

2017-03-21

Here, a simulation study of measurements of neutral current structure functions of the nucleon at the future high-energy and high-luminosity polarized electron-ion collider (EIC) is presented. A new series of γ-Z interference structure functions, F γZ 1, F γZ 3, g γZ 1, g γZ 5 become accessible via parity-violating asymmetries in polarized electron-nucleon deep inelastic scattering (DIS). Within the context of the quark-parton model, they provide a unique and, in some cases, yet-unmeasured combination of unpolarized and polarized parton distribution functions. The uncertainty projections for these structure functions using electron-proton collisions are considered for various EIC beam energy configurations.more » Also presented are uncertainty projections for measurements of the weak mixing angle sin 2θ W using electron-deuteron collisions which cover a much higher Q 2 than that accessible in fixed target measurements. QED and QCD radiative corrections and effects of detector smearing are included with the calculations.« less

Electron-density descriptors as predictors in quantitative structure--activity/property relationships and drug design.

PubMed

Matta, Chérif F; Arabi, Alya A

2011-06-01

The use of electron density-based molecular descriptors in drug research, particularly in quantitative structure--activity relationships/quantitative structure--property relationships studies, is reviewed. The exposition starts by a discussion of molecular similarity and transferability in terms of the underlying electron density, which leads to a qualitative introduction to the quantum theory of atoms in molecules (QTAIM). The starting point of QTAIM is the topological analysis of the molecular electron-density distributions to extract atomic and bond properties that characterize every atom and bond in the molecule. These atomic and bond properties have considerable potential as bases for the construction of robust quantitative structure--activity/property relationships models as shown by selected examples in this review. QTAIM is applicable to the electron density calculated from quantum-chemical calculations and/or that obtained from ultra-high resolution x-ray diffraction experiments followed by nonspherical refinement. Atomic and bond properties are introduced followed by examples of application of each of these two families of descriptors. The review ends with a study whereby the molecular electrostatic potential, uniquely determined by the density, is used in conjunction with atomic properties to elucidate the reasons for the biological similarity of bioisosteres.

Structural and electronic properties of the alkali metal incommensurate phases

NASA Astrophysics Data System (ADS)

Woolman, Gavin; Naden Robinson, Victor; Marqués, Miriam; Loa, Ingo; Ackland, Graeme J.; Hermann, Andreas

2018-05-01

Under pressure, the alkali elements sodium, potassium, and rubidium adopt nonperiodic structures based on two incommensurate interpenetrating lattices. While all elements form the same "host" lattice, their "guest" lattices are all distinct. The physical mechanism that stabilizes these phases is not known, and detailed calculations are challenging due to the incommensurability of the lattices. Using a series of commensurate approximant structures, we tackle this issue using density functional theory calculations. In Na and K, the calculations prove accurate enough to reproduce not only the stability of the host-guest phases, but also the complicated pressure dependence of the host-guest ratio and the two guest-lattice transitions. We find Rb-IV to be metastable at all pressures, and suggest it is a high-temperature phase. The electronic structure of these materials is unique: they exhibit two distinct, coexisting types of electride behavior, with both fully localized pseudoanions and electrons localized in 1D wells in the host lattice, leading to low conductivity. While all phases feature pseudogaps in the electronic density of states, the perturbative free-electron picture applies to Na, but not to K and Rb, due to significant d -orbital population in the latter.

Dirac electron in a chiral space-time crystal created by counterpropagating circularly polarized plane electromagnetic waves

NASA Astrophysics Data System (ADS)

Borzdov, G. N.

2017-10-01

The family of solutions to the Dirac equation for an electron moving in an electromagnetic lattice with the chiral structure created by counterpropagating circularly polarized plane electromagnetic waves is obtained. At any nonzero quasimomentum, the dispersion equation has two solutions which specify bispinor wave functions describing electron states with different energies and mean values of momentum and spin operators. The inversion of the quasimomentum results in two other linearly independent solutions. These four basic wave functions are uniquely defined by eight complex scalar functions (structural functions), which serve as convenient building blocks of the relations describing the electron properties. These properties are illustrated in graphical form over a wide range of quasimomenta. The superpositions of two basic wave functions describing different spin states and corresponding to (i) the same quasimomentum (unidirectional electron states with the spin precession) and (ii) the two equal-in-magnitude but oppositely directed quasimomenta (bidirectional electron states) are also treated.

Surface determination through atomically resolved secondary-electron imaging

PubMed Central

Ciston, J.; Brown, H. G.; D'Alfonso, A. J.; Koirala, P.; Ophus, C.; Lin, Y.; Suzuki, Y.; Inada, H.; Zhu, Y.; Allen, L. J.; Marks, L. D.

2015-01-01

Unique determination of the atomic structure of technologically relevant surfaces is often limited by both a need for homogeneous crystals and ambiguity of registration between the surface and bulk. Atomically resolved secondary-electron imaging is extremely sensitive to this registration and is compatible with faceted nanomaterials, but has not been previously utilized for surface structure determination. Here we report a detailed experimental atomic-resolution secondary-electron microscopy analysis of the c(6 × 2) reconstruction on strontium titanate (001) coupled with careful simulation of secondary-electron images, density functional theory calculations and surface monolayer-sensitive aberration-corrected plan-view high-resolution transmission electron microscopy. Our work reveals several unexpected findings, including an amended registry of the surface on the bulk and strontium atoms with unusual seven-fold coordination within a typically high surface coverage of square pyramidal TiO5 units. Dielectric screening is found to play a critical role in attenuating secondary-electron generation processes from valence orbitals. PMID:26082275

Surface determination through atomically resolved secondary-electron imaging

DOE PAGES

Ciston, J.; Brown, H. G.; D’Alfonso, A. J.; ...

2015-06-17

We report that unique determination of the atomic structure of technologically relevant surfaces is often limited by both a need for homogeneous crystals and ambiguity of registration between the surface and bulk. Atomically resolved secondary-electron imaging is extremely sensitive to this registration and is compatible with faceted nanomaterials, but has not been previously utilized for surface structure determination. Here we show a detailed experimental atomic-resolution secondary-electron microscopy analysis of the c(6 x 2) reconstruction on strontium titanate (001) coupled with careful simulation of secondary-electron images, density functional theory calculations and surface monolayer-sensitive aberration-corrected plan-view high-resolution transmission electron microscopy. Our workmore » reveals several unexpected findings, including an amended registry of the surface on the bulk and strontium atoms with unusual seven-fold coordination within a typically high surface coverage of square pyramidal TiO 5 units. Lastly, dielectric screening is found to play a critical role in attenuating secondary-electron generation processes from valence orbitals.« less

Recent advances in the fabrication and structure-specific applications of graphene-based inorganic hybrid membranes.

PubMed

Zhao, Xinne; Zhang, Panpan; Chen, Yuting; Su, Zhiqiang; Wei, Gang

2015-03-12

The preparation and applications of graphene (G)-based materials are attracting increasing interests due to their unique electronic, optical, magnetic, thermal, and mechanical properties. Compared to G-based hybrid and composite materials, G-based inorganic hybrid membrane (GIHM) offers enormous advantages ascribed to their facile synthesis, planar two-dimensional multilayer structure, high specific surface area, and mechanical stability, as well as their unique optical and mechanical properties. In this review, we report the recent advances in the technical fabrication and structure-specific applications of GIHMs with desirable thickness and compositions. In addition, the advantages and disadvantages of the methods utilized for creating GIHMs are discussed in detail. Finally, the potential applications and key challenges of GIHMs for future technical applications are mentioned.

Robust Production, Crystallization, Structure Determination, and Analysis of [Fe-S] Proteins: Uncovering Control of Electron Shuttling and Gating in the Respiratory Metabolism of Molybdopterin Guanine Dinucleotide Enzymes.

PubMed

Tsai, Chi-Lin; Tainer, John A

2018-01-01

[Fe-S] clusters are essential cofactors in all domains of life. They play many biological roles due to their unique abilities for electron transfer and conformational control. Yet, producing and analyzing Fe-S proteins can be difficult and even misleading if not done anaerobically. Due to unique redox properties of [Fe-S] clusters and their oxygen sensitivity, they pose multiple challenges and can lose enzymatic activity or cause their component proteins to be structurally disordered due to [Fe-S] cluster oxidation and loss in air. Here we highlight tested protocols and strategies enabling efficient and stable [Fe-S] protein production, purification, crystallization, X-ray diffraction data collection, and structure determination. From multiple high-resolution anaerobic crystal structures, we furthermore analyze exemplary data defining [Fe-S] clusters, substrate entry, and product exit for the functional oxidation states of type II molybdo-bis(molybdopterin guanine dinucleotide) (Mo-bisMGD) enzymes. Notably, these enzymes perform electron shuttling between quinone pools and specific substrates to catalyze respiratory metabolism. The identified structure-activity relationships for this enzyme class have broad implications germane to perchlorate environments on Earth and Mars extending to an alternative mechanism underlying metabolic origins for the evolution of the oxygen atmosphere. Integrated structural analyses of type II Mo-bisMGD enzymes unveil novel distinctive shared molecular mechanisms for dynamic control of substrate entry and product release gated by hydrophobic residues. Collective findings support a prototypic model for type II Mo-bisMGD enzymes including insights for a fundamental molecular mechanistic understanding of selectivity and regulation by a conformationally gated channel with general implications for [Fe-S] cluster respiratory enzymes. © 2018 Elsevier Inc. All rights reserved.

Synthesis and CV Studies of Dithiol-terminated Metal Terpyridine Complexes

NASA Technical Reports Server (NTRS)

Asano, Sylvia; Fan, Wendy; Ng, Hou-Tee; Han, Jie; Meyyappan, M.

2003-01-01

Transition metal coordination complexes possess unique electronic structures that should be a good model for studying electronic transport behavior at a molecular level. The discrete, multiple redox states, low redox potential and the superb ability to establish contact with other molecular and electronic components by coordination chemistry have made this a subject of investigation for their possible application as active electronic components in molecular devices. We present the synthesis and electrochemical characterization of 4'-thioacetylphenyl-2'2:6',2"-terpyridine iron(II) complex and compare it with a model bis-terpyridine iron(II) complex by cyclic voltammetry. With the use of different working electrodes, the behavior of these complexes show different electron transfer rates.

3D structural fluctuation of IgG1 antibody revealed by individual particle electron tomography

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

Zhang, Xing; Zhang, Lei; Tong, Huimin

2015-05-05

Commonly used methods for determining protein structure, including X-ray crystallography and single-particle reconstruction, often provide a single and unique three-dimensional (3D) structure. However, in these methods, the protein dynamics and flexibility/fluctuation remain mostly unknown. Here, we utilized advances in electron tomography (ET) to study the antibody flexibility and fluctuation through structural determination of individual antibody particles rather than averaging multiple antibody particles together. Through individual-particle electron tomography (IPET) 3D reconstruction from negatively-stained ET images, we obtained 120 ab-initio 3D density maps at an intermediate resolution (~1–3 nm) from 120 individual IgG1 antibody particles. Using these maps as a constraint, wemore » derived 120 conformations of the antibody via structural flexible docking of the crystal structure to these maps by targeted molecular dynamics simulations. Statistical analysis of the various conformations disclosed the antibody 3D conformational flexibility through the distribution of its domain distances and orientations. This blueprint approach, if extended to other flexible proteins, may serve as a useful methodology towards understanding protein dynamics and functions.« less

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.

Ordered water structure at hydrophobic graphite interfaces observed by 4D, ultrafast electron crystallography

PubMed Central

Yang, Ding-Shyue; Zewail, Ahmed H.

2009-01-01

Interfacial water has unique properties in various functions. Here, using 4-dimensional (4D), ultrafast electron crystallography with atomic-scale spatial and temporal resolution, we report study of structure and dynamics of interfacial water assembly on a hydrophobic surface. Structurally, vertically stacked bilayers on highly oriented pyrolytic graphite surface were determined to be ordered, contrary to the expectation that the strong hydrogen bonding of water on hydrophobic surfaces would dominate with suppressed interfacial order. Because of its terrace morphology, graphite plays the role of a template. The dynamics is also surprising. After the excitation of graphite by an ultrafast infrared pulse, the interfacial ice structure undergoes nonequilibrium “phase transformation” identified in the hydrogen-bond network through the observation of structural isosbestic point. We provide the time scales involved, the nature of ice-graphite structural dynamics, and relevance to properties related to confined water. PMID:19246378

Electronic shell structure in Ga12 icosahedra and the relation to the bulk forms of gallium.

PubMed

Schebarchov, D; Gaston, N

2012-07-28

The electronic structure of known cluster compounds with a cage-like icosahedral Ga(12) centre is studied by first-principles theoretical methods, based on density functional theory. We consider these hollow metalloid nanostructures in the context of the polymorphism of the bulk, and identify a close relation to the α phase of gallium. This previously unrecognised connection is established using the electron localisation function, which reveals the ubiquitous presence of radially-pointing covalent bonds around the Ga(12) centre--analogous to the covalent bonds between buckled deltahedral planes in α-Ga. Furthermore, we find prominent superatom shell structure in these clusters, despite their hollow icosahedral motif and the presence of covalent bonds. The exact nature of the electronic shell structure is contrasted with simple electron shell models based on jellium, and we demonstrate how the interplay between gallium dimerisation, ligand- and crystal-field effects can alter the splitting of the partially filled 1F shell. Finally, in the unique compound where the Ga(12) centre is bridged by six phosphorus ligands, the electronic structure most closely resembles that of δ-Ga and there are no well-defined superatom orbitals. The results of this comprehensive study bring new insights into the nature of chemical bonding in metalloid gallium compounds and the relation to bulk gallium metal, and they may also guide the development of more general models for ligand-protected clusters.

Spirally Structured Conductive Composites for Highly Stretchable, Robust Conductors and Sensors.

PubMed

Wu, Xiaodong; Han, Yangyang; Zhang, Xinxing; Lu, Canhui

2017-07-12

Flexible and stretchable electronics are highly desirable for next generation devices. However, stretchability and conductivity are fundamentally difficult to combine for conventional conductive composites, which restricts their widespread applications especially as stretchable electronics. Here, we innovatively develop a new class of highly stretchable and robust conductive composites via a simple and scalable structural approach. Briefly, carbon nanotubes are spray-coated onto a self-adhesive rubber film, followed by rolling up the film completely to create a spirally layered structure within the composites. This unique spirally layered structure breaks the typical trade-off between stretchability and conductivity of traditional conductive composites and, more importantly, restrains the generation and propagation of mechanical microcracks in the conductive layer under strain. Benefiting from such structure-induced advantages, the spirally layered composites exhibit high stretchability and flexibility, good conductive stability, and excellent robustness, enabling the composites to serve as highly stretchable conductors (up to 300% strain), versatile sensors for monitoring both subtle and large human activities, and functional threads for wearable electronics. This novel and efficient methodology provides a new design philosophy for manufacturing not only stretchable conductors and sensors but also other stretchable electronics, such as transistors, generators, artificial muscles, etc.

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

dos Reis, Roberto; Yang, Hao; Ophus, Colin

A key to the unique combination of electronic and optical properties in halide perovskite materials lies in their rich structural complexity. However, their radiation sensitive nature limits nanoscale structural characterization requiring dose efficient microscopic techniques in order to determine their structures precisely. In this work, we determine the space-group and directly image the Br halide sites of CsPbBr 3, a promising material for optoelectronic applications. Based on the symmetry of high-order Laue zone reflections of convergent-beam electron diffraction, we identify the tetragonal (I4/mcm) structural phase of CsPbBr 3 at cryogenic temperature. Electron ptychography provides a highly sensitive phase contrast measurementmore » of the halide positions under low electron-dose conditions, enabling imaging of the elongated Br sites originating from the out-of-phase octahedral rotation viewed along the [001] direction of I4/mcm persisting at room temperature. The measurement of these features and comparison with simulations yield an octahedral rotation angle of 6.5°(±1.5°). Finally, the approach demonstrated here opens up opportunities for understanding the atomic scale structural phenomena applying advanced characterization tools on a wide range of radiation sensitive halide-based all-inorganic and hybrid organic-inorganic perovskites.« less

Disordered Zinc in Zn4Sb3 with Phonon-Glass and Electron-Crystal Thermoelectric Properties

NASA Technical Reports Server (NTRS)

Snyder, G. Jeffrey; Christensen, Mogens; Nishibori, Eiji; Caillat, Thierry; Brummerstedt Iversen, Bo

2004-01-01

By converting waste heat into electricity, thermoelectric generators could be an important part of the solution to today's energy challenges. The compound Zn4Sb3 is one of the most efficient thermoelectric materials known. Its high efficiency results from an extraordinarily low thermal conductivity in conjunction with the electronic structure of a heavily doped semiconductor. Previous structural studies have been unable to explain this unusual combination of properties. Here, we show through a comprehensive structural analysis using single-crystal X-ray and powder-synchrotron-radiation diffraction methods, that both the electronic and thermal properties of Zn4Sb3 can be understood in terms of unique structural features that have been previously overlooked. The identification of Sb3- ions and Sb-2(4-) dimers reveals that Zn4Sb3 is a valence semiconductor with the ideal stoichiometry Zn13Sb10. In addition, the structure contains significant disorder, with zinc atoms distributed over multiple positions. The discovery of glass-like interstitial sites uncovers a highly effective mechanism for reducing thermal conductivity. Thus Zn4Sb3 is in many ways an ideal 'phonon glass, electron crystal' thermoelectric material.

The gj factor of a bound electron and the hyperfine structure splitting in hydrogenlike ions

NASA Astrophysics Data System (ADS)

Beier, Thomas

2000-12-01

The comparison between theory and experiment of the hyperfine structure splitting and the electronic gj factor in heavy highly charged ions provides a unique testing ground for quantum electrodynamics in the presence of strong electric and magnetic fields. A theoretical evaluation is presented of all quantum electrodynamical contributions to the ground-state hfs splitting in hydrogenlike and lithiumlike atoms as well as to the gj factor. Binding and nuclear effects are discussed as well. A comparison with the available experimental data is performed, and a detailed discussion of theoretical sources of uncertainty is included which is mainly due to insufficiently known nuclear properties.

Vibronic structure and coupling of higher excited electronic states in carotenoids

NASA Astrophysics Data System (ADS)

Krawczyk, Stanisław; Luchowski, Rafał

2013-03-01

Absorption spectra of all-trans carotenoids (lycopene, violaxanthin, ζ-carotene) at low temperature exhibit peculiar features in the UV range. The transition to the 11Ag+ state ('cis-band') weakens on cooling, indicating that it is induced by thermal deformations of the conjugated chain. The higher energy band has unique vibrational structure indicating the vibronic coupling of nBu with another electronic state. The electroabsorption spectra point to the electric field-induced mixing of the nBu state with the vibrational continuum of a lower-lying excited state (Fano effect). These observations widen the basis for elucidation of the vibronic coupling effects in the lower excited states.

Enhanced photoelectrochemical activity in all-oxide heterojunction devices based on correlated "metallic" oxides.

PubMed

Apgar, Brent A; Lee, Sungki; Schroeder, Lauren E; Martin, Lane W

2013-11-20

n-n Schottky, n-n ohmic, and p-n Schottky heterojunctions based on TiO2 /correlated "metallic" oxide couples exhibit strong solar-light absorption driven by the unique electronic structure of the "metallic" oxides. Photovoltaic and photocatalytic responses are driven by hot electron injection from the "metallic" oxide into the TiO2 , enabling new modalities of operation for energy systems. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Functional conjugated pyridines via main-group element tuning.

PubMed

Stolar, Monika; Baumgartner, Thomas

2018-03-29

Pyridine-based materials have seen widespread attention for the development of n-type organic materials. In recent years, the incorporation of main-group elements has also explored significant advantages for the development and tunability of organic conjugated materials. The unique chemical and electronic structure of main-group elements has led to several enhancements in conventional organic materials. This Feature article highlights recent main-group based pyridine materials by discussing property enhancements and application in organic electronics.

Exploring the Electronic Structure and Chemical Homogeneity of Individual Bi2Te3 Nanowires by Nano-Angle-Resolved Photoemission Spectroscopy.

PubMed

Krieg, Janina; Chen, Chaoyu; Avila, José; Zhang, Zeying; Sigle, Wilfried; Zhang, Hongbin; Trautmann, Christina; Asensio, Maria Carmen; Toimil-Molares, Maria Eugenia

2016-07-13

Due to their high surface-to-volume ratio, cylindrical Bi2Te3 nanowires are employed as model systems to investigate the chemistry and the unique conductive surface states of topological insulator nanomaterials. We report on nanoangle-resolved photoemission spectroscopy (nano-ARPES) characterization of individual cylindrical Bi2Te3 nanowires with a diameter of 100 nm. The nanowires are synthesized by electrochemical deposition inside channels of ion-track etched polymer membranes. Core level spectra recorded with submicron resolution indicate a homogeneous chemical composition along individual nanowires, while nano-ARPES intensity maps reveal the valence band structure at the single nanowire level. First-principles electronic structure calculations for chosen crystallographic orientations are in good agreement with those revealed by nano-ARPES. The successful application of nano-ARPES on single one-dimensional nanostructures constitutes a new avenue to achieve a better understanding of the electronic structure of topological insulator nanomaterials.

Band Structure Engineering and Thermoelectric Properties of Charge-Compensated Filled Skutterudites

PubMed Central

Shi, Xiaoya; Yang, Jiong; Wu, Lijun; Salvador, James R.; Zhang, Cheng; Villaire, William L.; Haddad, Daad; Yang, Jihui; Zhu, Yimei; Li, Qiang

2015-01-01

Thermoelectric properties of semiconductors are intimately related to their electronic band structure, which can be engineered via chemical doping. Dopant Ga in the cage-structured skutterudite Co4Sb12 substitutes Sb sites while occupying the void sites. Combining quantitative scanning transmission electron microscopy and first-principles calculations, we show that Ga dual-site occupancy breaks the symmetry of the Sb-Sb network, splits the deep triply-degenerate conduction bands, and drives them downward to the band edge. The charge-compensating nature of the dual occupancy Ga increases overall filling fraction limit. By imparting this unique band structure feature, and judiciously doping the materials by increasing the Yb content, we promote the Fermi level to a point where carriers are in energetic proximity to these features. Increased participation of these heavier bands in electronic transport leads to increased thermopower and effective mass. Further, the localized distortion from Ga/Sb substitution enhances the phonon scattering to reduce the thermal conductivity effectively. PMID:26456013

The physics and chemistry of graphene-on-surfaces.

PubMed

Zhao, Guoke; Li, Xinming; Huang, Meirong; Zhen, Zhen; Zhong, Yujia; Chen, Qiao; Zhao, Xuanliang; He, Yijia; Hu, Ruirui; Yang, Tingting; Zhang, Rujing; Li, Changli; Kong, Jing; Xu, Jian-Bin; Ruoff, Rodney S; Zhu, Hongwei

2017-07-31

Graphene has demonstrated great potential in next-generation electronics due to its unique two-dimensional structure and properties including a zero-gap band structure, high electron mobility, and high electrical and thermal conductivity. The integration of atom-thick graphene into a device always involves its interaction with a supporting substrate by van der Waals forces and other intermolecular forces or even covalent bonding, and this is critical to its real applications. Graphene films on different surfaces are expected to exhibit significant differences in their properties, which lead to changes in their morphology, electronic structure, surface chemistry/physics, and surface/interface states. Therefore, a thorough understanding of the surface/interface properties is of great importance. In this review, we describe the major "graphene-on-surface" structures and examine the roles of their properties and related phenomena in governing the overall performance for specific applications including optoelectronics, surface catalysis, anti-friction and superlubricity, and coatings and composites. Finally, perspectives on the opportunities and challenges of graphene-on-surface systems are discussed.

Band structure engineering and thermoelectric properties of charge-compensated filled skutterudites

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

Shi, Xiaoya; Yang, Jiong; Wu, Lijun

2015-10-12

Thermoelectric properties of semiconductors are intimately related to their electronic band structure, which can be engineered via chemical doping. Dopant Ga in the cage-structured skutterudite Co 4Sb 12 substitutes Sb sites while occupying the void sites. Combining quantitative scanning transmission electron microscopy and first-principles calculations, we show that Ga dual-site occupancy breaks the symmetry of the Sb-Sb network, splits the deep triply-degenerate conduction bands, and drives them downward to the band edge. The charge-compensating nature of the dual occupancy Ga increases overall filling fraction limit. By imparting this unique band structure feature, and judiciously doping the materials by increasing themore » Yb content, we promote the Fermi level to a point where carriers are in energetic proximity to these features. Increased participation of these heavier bands in electronic transport leads to increased thermopower and effective mass. Further, the localized distortion from Ga/Sb substitution enhances the phonon scattering to reduce the thermal conductivity effectively.« less

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.

Band Structure Engineering and Thermoelectric Properties of Charge-Compensated Filled Skutterudites

NASA Astrophysics Data System (ADS)

Shi, Xiaoya; Yang, Jiong; Wu, Lijun; Salvador, James R.; Zhang, Cheng; Villaire, William L.; Haddad, Daad; Yang, Jihui; Zhu, Yimei; Li, Qiang

2015-10-01

Thermoelectric properties of semiconductors are intimately related to their electronic band structure, which can be engineered via chemical doping. Dopant Ga in the cage-structured skutterudite Co4Sb12 substitutes Sb sites while occupying the void sites. Combining quantitative scanning transmission electron microscopy and first-principles calculations, we show that Ga dual-site occupancy breaks the symmetry of the Sb-Sb network, splits the deep triply-degenerate conduction bands, and drives them downward to the band edge. The charge-compensating nature of the dual occupancy Ga increases overall filling fraction limit. By imparting this unique band structure feature, and judiciously doping the materials by increasing the Yb content, we promote the Fermi level to a point where carriers are in energetic proximity to these features. Increased participation of these heavier bands in electronic transport leads to increased thermopower and effective mass. Further, the localized distortion from Ga/Sb substitution enhances the phonon scattering to reduce the thermal conductivity effectively.

(Charge separation in photoredox reactions). Informal annual technical progress report, October 1, 1981-October 1, 1982. [N,N,N',N'tetramethylbenzidine

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

Kevan, L.

1982-10-21

During this period work has focused on the structural aspects of photoinduced charge separation in micellar media with initial forays into vesicular media. The primary techniques utilized are electron spin resonance and electron spin echo spectrometry. The analysis of electron spin echo modulation gives a unique handle on very weak hyperfine interactions thus providing a new structural tool for this general problem. Electron spin resonance and electron spin echo studies of the photoionization of N,N,N',N'tetramethylbenzidine (TMB) to give the cation radical have been carried out in anionic, cationic and nonionic micellar solutions frozen to 77/sup 0/K. The photoionization efficiency ofmore » TMB has also been studied in micelles with varying alkyl chain lengths of the surfactant. Stearic acid nitroxide spin probes have also been used to determine some structural aspects of the location of the neutral TMB molecule in anionic micelles before photoionization. The nitroxide work in which the nitroxide is acting as an electron acceptor also shows that a suitable electron acceptor can be located within the micellar structure. The effect of inorganic solutes on the efficiency of the photoionization of TMB in frozen micelles has also been studied. A series of electron scavenger studies have been initiated to study the effect on TMB photoionization efficiency. Electron spin echo detection of laser photogenerated TMB cation in liquid sodium dodecyl sulfate solutions at room temperature has recently been observed.« less

CeO2/rGO/Pt sandwich nanostructure: rGO-enhanced electron transmission between metal oxide and metal nanoparticles for anodic methanol oxidation of direct methanol fuel cells.

PubMed

Yu, Xue; Kuai, Long; Geng, Baoyou

2012-09-21

Pt-based nanocomposites have been of great research interest. In this paper, we design an efficient MO/rGO/Pt sandwich nanostructure as an anodic electrocatalyst for DMFCs with combination of the merits of rigid structure of metallic oxides (MOs) and excellent electronic conductivity of reduced oxidized graphene (rGO) as well as overcoming their shortcomings. In this case, the CeO(2)/rGO/Pt sandwich nanostructure is successfully fabricated through a facile hydrothermal approach in the presence of graphene oxide and CeO(2) nanoparticles. This structure has a unique building architecture where rGO wraps up the CeO(2) nanoparticles and Pt nanoparticles are homogeneously dispersed on the surface of rGO. This novel structure endows this material with great electrocatalytic performance in methanol oxidation: it reduces the overpotential of methanol oxidation significantly and its electrocatalytic activity and stability are much enhanced compared with Pt/rGO, CeO(2)/Pt and Pt/C catalysts. This work supplies a unique MO/rGO/Pt sandwich nanostructure as an efficient way to improve the electrocatalytic performance, which will surely shed some light on the exploration of some novel structures of electrocatalyst for DMFCs.

Engineered unique elastic modes at a BaTiO 3/2x1-Ge(001) interface

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

Kumah, D. P.; Dogan, M.; Ngai, J. H.

Here, the strong interaction at an interface between a substrate and thin film leads to epitaxy and provides a means of inducing structural changes in the epitaxial film. These induced material phases often exhibit technologically relevant electronic, magnetic, and functional properties. The 2×1 surface of a Ge(001) substrate applies a unique type of epitaxial constraint on thin films of the perovskite oxide BaTiO 3 where a change in bonding and symmetry at the interface leads to a non-bulk-like crystal structure of the BaTiO 3. While the complex crystal structure is predicted using first-principles theory, it is further shown that themore » details of the structure are a consequence of hidden phases found in the bulk elastic response of the BaTiO 3 induced by the symmetry of forces exerted by the germanium substrate.« less

Engineered Unique Elastic Modes at a BaTiO 3 / ( 2 × 1 ) - Ge ( 001 ) Interface

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

Kumah, D. P.; Dogan, M.; Ngai, J. H.

The strong interaction at an interface between a substrate and thin film leads to epitaxy and provides a means of inducing structural changes in the epitaxial film. These induced material phases often exhibit technologically relevant electronic, magnetic, and functional properties. The 2×1 surface of a Ge(001) substrate applies a unique type of epitaxial constraint on thin films of the perovskite oxide BaTiO3 where a change in bonding and symmetry at the interface leads to a non-bulk-like crystal structure of the BaTiO3. While the complex crystal structure is predicted using first-principles theory, it is further shown that the details of themore » structure are a consequence of hidden phases found in the bulk elastic response of the BaTiO3 induced by the symmetry of forces exerted by the germanium substrate.« less

Engineered unique elastic modes at a BaTiO 3/2x1-Ge(001) interface

DOE PAGES

Kumah, D. P.; Dogan, M.; Ngai, J. H.; ...

2016-03-07

Here, the strong interaction at an interface between a substrate and thin film leads to epitaxy and provides a means of inducing structural changes in the epitaxial film. These induced material phases often exhibit technologically relevant electronic, magnetic, and functional properties. The 2×1 surface of a Ge(001) substrate applies a unique type of epitaxial constraint on thin films of the perovskite oxide BaTiO 3 where a change in bonding and symmetry at the interface leads to a non-bulk-like crystal structure of the BaTiO 3. While the complex crystal structure is predicted using first-principles theory, it is further shown that themore » details of the structure are a consequence of hidden phases found in the bulk elastic response of the BaTiO 3 induced by the symmetry of forces exerted by the germanium substrate.« less

Anomalous electronic structure and magnetoresistance in TaAs 2

DOE PAGES

Luo, Yongkang; McDonald, R. D.; Rosa, P. F. S.; ...

2016-01-01

We report that the change in resistance of a material in a magnetic field reflects its electronic state. In metals with weakly- or non-interacting electrons, the resistance typically increases upon the application of a magnetic field. In contrast, negative magnetoresistance may appear under some circumstances, e.g., in metals with anisotropic Fermi surfaces or with spin-disorder scattering and semimetals with Dirac or Weyl electronic structures. Here we show that the non-magnetic semimetal TaAs 2 possesses a very large negative magnetoresistance, with an unknown scattering mechanism. In conclusion, density functional calculations find that TaAs 2 is a new topological semimetal [Z 2more » invariant (0;111)] without Dirac dispersion, demonstrating that a negative magnetoresistance in non-magnetic semimetals cannot be attributed uniquely to the Adler-Bell-Jackiw chiral anomaly of bulk Dirac/Weyl fermions.« less

Dislocation structures and electrical conduction properties of low angle tilt grain boundaries in LiNbO{sub 3}

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

Furushima, Yuho; Nakamura, Atsutomo, E-mail: nakamura@numse.nagoya-u.ac.jp; Toyoura, Kazuaki

Dislocations in crystalline materials constitute unique, atomic-scale, one-dimensional structure and have a potential to induce peculiar physical properties that are not found in the bulk. In this study, we fabricated LiNbO{sub 3} bicrystals with low angle tilt grain boundaries and investigated the relationship between the atomic structure of the boundary dislocations and their electrical conduction properties. Observations by using transmission electron microscopy revealed that dislocation structures at the (0001) low angle tilt grain boundaries depend on the tilt angle of the boundaries. Specifically, the characteristic dislocation structures with a large Burgers vector were formed in the boundary with the tiltmore » angle of 2°. It is noteworthy that only the grain boundary of 2° exhibits distinct electrical conductivity after reduction treatment, although LiNbO{sub 3} is originally insulating. This unique electrical conductivity is suggested to be due to the characteristic dislocation structures with a large Burgers vector.« less

76 FR 20953 - Application(s) for Duty-Free Entry of Scientific Instruments

Federal Register 2010, 2011, 2012, 2013, 2014

2011-04-14

...., 9700 South Cass Ave., Lemont, IL 60439. Instrument: Mythen 1K Detector System. Manufacturer: Dectris... (RIXS) to study the electronic structure of highly correlated systems. This instrument is unique in that... dynamic range; and a small, lightweight and compact design. Justification for Duty-Free Entry: There are...

The change in prevalence of Campylobacter on chicken carcasses during processing: A systematic review

USDA-ARS?s Scientific Manuscript database

A systematic review was conducted to evaluate the change in prevalence of Campylobacter on chicken carcasses during processing. A structured literature search of eight electronic databases using keywords for “Campylobacter,” “chicken,” and “processing” identified 1,734 unique citations. Abstracts ...

Nondestructive detection and measurement of hydrogen embrittlement

DOEpatents

Alex, Franklin; Byrne, Joseph Gerald

1977-01-01

A nondestructive system and method for the determination of the presence and extent of hydrogen embrittlement in metals, alloys, and other crystalline structures subject thereto. Positron annihilation characteristics of the positron-electron annihilation within the tested material provide unique energy distribution curves for each type of material tested at each respective stage of hydrogen embrittlement. Gamma radiation resulting from such annihilation events is detected and statistically summarized by appropriate instrumentation to reveal the variations of electron activity within the tested material caused by hydrogen embrittlement therein. Such data from controlled tests provides a direct indication of the relative stages of hydrogen embrittlement in the form of unique energy distribution curves which may be utilized as calibration curves for future comparison with field tests to give on-site indication of progressive stages of hydrogen embrittlement.

A direct electron detector for time-resolved MeV electron microscopy

DOE PAGES

Vecchione, T.; Denes, P.; Jobe, R. K.; ...

2017-03-15

The introduction of direct electron detectors enabled the structural biology revolution of cryogenic electron microscopy. Direct electron detectors are now expected to have a similarly dramatic impact on time-resolved MeV electron microscopy, particularly by enabling both spatial and temporal jitter correction. Here in this paper, we report on the commissioning of a direct electron detector for time-resolved MeV electron microscopy. The direct electron detector demonstrated MeV single electron sensitivity and is capable of recording megapixel images at 180 Hz. The detector has a 15-bit dynamic range, better than 30-μm spatial resolution and less than 20 analogue-to-digital converter count RMS pixelmore » noise. The unique capabilities of the direct electron detector and the data analysis required to take advantage of these capabilities are presented. The technical challenges associated with generating and processing large amounts of data are also discussed.« less

A direct electron detector for time-resolved MeV electron microscopy

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

Vecchione, T.; Denes, P.; Jobe, R. K.

The introduction of direct electron detectors enabled the structural biology revolution of cryogenic electron microscopy. Direct electron detectors are now expected to have a similarly dramatic impact on time-resolved MeV electron microscopy, particularly by enabling both spatial and temporal jitter correction. Here in this paper, we report on the commissioning of a direct electron detector for time-resolved MeV electron microscopy. The direct electron detector demonstrated MeV single electron sensitivity and is capable of recording megapixel images at 180 Hz. The detector has a 15-bit dynamic range, better than 30-μm spatial resolution and less than 20 analogue-to-digital converter count RMS pixelmore » noise. The unique capabilities of the direct electron detector and the data analysis required to take advantage of these capabilities are presented. The technical challenges associated with generating and processing large amounts of data are also discussed.« less

Phase stability and large in-plane resistivity anisotropy in the 112-type iron-based superconductor Ca 1 - x La x FeAs 2

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

Kang, Chang-Jong; Birol, Turan; Kotliar, Gabriel

The recently discovered high-T c superconductor Ca 1-xLa xFeAs 2 is a unique compound not just because of its low-symmetry crystal structure but also because of its electronic structure, which hosts Dirac-like metallic bands resulting from (spacer) zigzag As chains. We present a comprehensive first-principles theoretical study of the electronic and crystal structures of Ca 1-xLa xFeAs 2. After discussing the connection between the crystal structure of the 112 family, which Ca 1-xLa xFeAs 2 is a member of, with the other known structures of Fe pnictide superconductors, we check the thermodynamic phase stability of CaFeAs 2, and similar hyphotheticalmore » compounds SrFeAs 2 and BaFeAs 2 which, we find, are slightly higher in energy. We calculate the optical conductivity of Ca 1-xLa xFeAs 2 using the DFT+DMFT method and predict a large in-plane resistivity anisotropy in the normal phase, which does not originate from electronic nematicity, but is enhanced by the electronic correlations. In particular, we predict a 0.34 eV peak in the yy component of the optical conductivity of the 30% La-doped compound, which corresponds to coherent interband transitions within a fast-dispersing band arising from the zigzag As chains, which are unique to this compound. We also study the Landau free energy for Ca 1-xLa xFeAs 2 including the order parameter relevant for the nematic transition and find that the free energy does not have any extra terms that could induce ferro-orbital order. This explains why the presence of As chains does not broaden the nematic transition in Ca 1-xLa xFeAs 2.« less

Phase stability and large in-plane resistivity anisotropy in the 112-type iron-based superconductor Ca 1 - x La x FeAs 2

DOE PAGES

Kang, Chang-Jong; Birol, Turan; Kotliar, Gabriel

2017-01-17

The recently discovered high-T c superconductor Ca 1-xLa xFeAs 2 is a unique compound not just because of its low-symmetry crystal structure but also because of its electronic structure, which hosts Dirac-like metallic bands resulting from (spacer) zigzag As chains. We present a comprehensive first-principles theoretical study of the electronic and crystal structures of Ca 1-xLa xFeAs 2. After discussing the connection between the crystal structure of the 112 family, which Ca 1-xLa xFeAs 2 is a member of, with the other known structures of Fe pnictide superconductors, we check the thermodynamic phase stability of CaFeAs 2, and similar hyphotheticalmore » compounds SrFeAs 2 and BaFeAs 2 which, we find, are slightly higher in energy. We calculate the optical conductivity of Ca 1-xLa xFeAs 2 using the DFT+DMFT method and predict a large in-plane resistivity anisotropy in the normal phase, which does not originate from electronic nematicity, but is enhanced by the electronic correlations. In particular, we predict a 0.34 eV peak in the yy component of the optical conductivity of the 30% La-doped compound, which corresponds to coherent interband transitions within a fast-dispersing band arising from the zigzag As chains, which are unique to this compound. We also study the Landau free energy for Ca 1-xLa xFeAs 2 including the order parameter relevant for the nematic transition and find that the free energy does not have any extra terms that could induce ferro-orbital order. This explains why the presence of As chains does not broaden the nematic transition in Ca 1-xLa xFeAs 2.« less

Analysis of Multilayer Devices for Superconducting Electronics by High-Resolution Scanning Transmission Electron Microscopy and Energy Dispersive Spectroscopy

DOE PAGES

Missert, Nancy; Kotula, Paul G.; Rye, Michael; ...

2017-02-15

We used a focused ion beam to obtain cross-sectional specimens from both magnetic multilayer and Nb/Al-AlOx/Nb Josephson junction devices for characterization by scanning transmission electron microscopy (STEM) and energy dispersive X-ray spectroscopy (EDX). An automated multivariate statistical analysis of the EDX spectral images produced chemically unique component images of individual layers within the multilayer structures. STEM imaging elucidated distinct variations in film morphology, interface quality, and/or etch artifacts that could be correlated to magnetic and/or electrical properties measured on the same devices.

Determination of the structural phase and octahedral rotation angle in halide perovskites

DOE PAGES

dos Reis, Roberto; Yang, Hao; Ophus, Colin; ...

2018-02-12

A key to the unique combination of electronic and optical properties in halide perovskite materials lies in their rich structural complexity. However, their radiation sensitive nature limits nanoscale structural characterization requiring dose efficient microscopic techniques in order to determine their structures precisely. In this work, we determine the space-group and directly image the Br halide sites of CsPbBr 3, a promising material for optoelectronic applications. Based on the symmetry of high-order Laue zone reflections of convergent-beam electron diffraction, we identify the tetragonal (I4/mcm) structural phase of CsPbBr 3 at cryogenic temperature. Electron ptychography provides a highly sensitive phase contrast measurementmore » of the halide positions under low electron-dose conditions, enabling imaging of the elongated Br sites originating from the out-of-phase octahedral rotation viewed along the [001] direction of I4/mcm persisting at room temperature. The measurement of these features and comparison with simulations yield an octahedral rotation angle of 6.5°(±1.5°). Finally, the approach demonstrated here opens up opportunities for understanding the atomic scale structural phenomena applying advanced characterization tools on a wide range of radiation sensitive halide-based all-inorganic and hybrid organic-inorganic perovskites.« less

Full-potential theoretical investigations of electron inelastic mean free paths and extended x-ray absorption fine structure in molybdenum.

PubMed

Chantler, C T; Bourke, J D

2014-04-09

X-ray absorption fine structure (XAFS) spectroscopy is one of the most robust, adaptable, and widely used structural analysis tools available for a range of material classes from bulk solids to aqueous solutions and active catalytic structures. Recent developments in XAFS theory have enabled high-accuracy calculations of spectra over an extended energy range using full-potential cluster modelling, and have demonstrated particular sensitivity in XAFS to a fundamental electron transport property-the electron inelastic mean free path (IMFP). We develop electron IMFP theory using a unique hybrid model that simultaneously incorporates second-order excitation losses, while precisely accounting for optical transitions dictated by the complex band structure of the solid. These advances are coupled with improved XAFS modelling to determine wide energy-range absorption spectra for molybdenum. This represents a critical test case of the theory, as measurements of molybdenum K-edge XAFS represent the most accurate determinations of XAFS spectra for any material. We find that we are able to reproduce an extended range of oscillatory structure in the absorption spectrum, and demonstrate a first-time theoretical determination of the absorption coefficient of molybdenum over the entire extended XAFS range utilizing a full-potential cluster model.

Ripple-modulated electronic structure of a 3D topological insulator.

PubMed

Okada, Yoshinori; Zhou, Wenwen; Walkup, D; Dhital, Chetan; Wilson, Stephen D; Madhavan, V

2012-01-01

Three-dimensional topological insulators host linearly dispersing states with unique properties and a strong potential for applications. An important ingredient in realizing some of the more exotic states in topological insulators is the ability to manipulate local electronic properties. Direct analogy to the Dirac material graphene suggests that a possible avenue for controlling local properties is via a controlled structural deformation such as the formation of ripples. However, the influence of such ripples on topological insulators is yet to be explored. Here we use scanning tunnelling microscopy to determine the effects of one-dimensional buckling on the electronic properties of Bi(2)Te(3.) By tracking spatial variations of the interference patterns generated by the Dirac electrons we show that buckling imposes a periodic potential, which locally modulates the surface-state dispersion. This suggests that forming one- and two-dimensional ripples is a viable method for creating nanoscale potential landscapes that can be used to control the properties of Dirac electrons in topological insulators.

X-ray free electron laser: opportunities for drug discovery.

PubMed

Cheng, Robert K Y; Abela, Rafael; Hennig, Michael

2017-11-08

Past decades have shown the impact of structural information derived from complexes of drug candidates with their protein targets to facilitate the discovery of safe and effective medicines. Despite recent developments in single particle cryo-electron microscopy, X-ray crystallography has been the main method to derive structural information. The unique properties of X-ray free electron laser (XFEL) with unmet peak brilliance and beam focus allow X-ray diffraction data recording and successful structure determination from smaller and weaker diffracting crystals shortening timelines in crystal optimization. To further capitalize on the XFEL advantage, innovations in crystal sample delivery for the X-ray experiment, data collection and processing methods are required. This development was a key contributor to serial crystallography allowing structure determination at room temperature yielding physiologically more relevant structures. Adding the time resolution provided by the femtosecond X-ray pulse will enable monitoring and capturing of dynamic processes of ligand binding and associated conformational changes with great impact to the design of candidate drug compounds. © 2017 The Author(s). Published by Portland Press Limited on behalf of the Biochemical Society.

Navigating 3D electron microscopy maps with EM-SURFER.

PubMed

Esquivel-Rodríguez, Juan; Xiong, Yi; Han, Xusi; Guang, Shuomeng; Christoffer, Charles; Kihara, Daisuke

2015-05-30

The Electron Microscopy DataBank (EMDB) is growing rapidly, accumulating biological structural data obtained mainly by electron microscopy and tomography, which are emerging techniques for determining large biomolecular complex and subcellular structures. Together with the Protein Data Bank (PDB), EMDB is becoming a fundamental resource of the tertiary structures of biological macromolecules. To take full advantage of this indispensable resource, the ability to search the database by structural similarity is essential. However, unlike high-resolution structures stored in PDB, methods for comparing low-resolution electron microscopy (EM) density maps in EMDB are not well established. We developed a computational method for efficiently searching low-resolution EM maps. The method uses a compact fingerprint representation of EM maps based on the 3D Zernike descriptor, which is derived from a mathematical series expansion for EM maps that are considered as 3D functions. The method is implemented in a web server named EM-SURFER, which allows users to search against the entire EMDB in real-time. EM-SURFER compares the global shapes of EM maps. Examples of search results from different types of query structures are discussed. We developed EM-SURFER, which retrieves structurally relevant matches for query EM maps from EMDB within seconds. The unique capability of EM-SURFER to detect 3D shape similarity of low-resolution EM maps should prove invaluable in structural biology.

Magnetic structure and local lattice distortion in giant negative thermal expansion material Mn3Cu1-xGexN

NASA Astrophysics Data System (ADS)

Iikubo, S.; Kodama, K.; Takenaka, K.; Takagi, H.; Shamoto, S.

2010-11-01

Magnetic and local structures in an antiperovskite system, Mn3Cu1-xGexN, with a giant negative thermal expansion have been studied by neutron powder diffraction measurement. We discuss (1) an importance of an averaged cubic crystal structure and a ΓG5g antiferromagnetic spin structure for the large magneto-volume effect (MVE) in this itinerant electron system, (2) an unique role of a local lattice distortion well described by the low temperature tetragonal structure of Mn3GeN for the broadening of MVE.

Quantum dot behavior in transition metal dichalcogenides nanostructures

NASA Astrophysics Data System (ADS)

Luo, Gang; Zhang, Zhuo-Zhi; Li, Hai-Ou; Song, Xiang-Xiang; Deng, Guang-Wei; Cao, Gang; Xiao, Ming; Guo, Guo-Ping

2017-08-01

Recently, transition metal dichalcogenides (TMDCs) semiconductors have been utilized for investigating quantum phenomena because of their unique band structures and novel electronic properties. In a quantum dot (QD), electrons are confined in all lateral dimensions, offering the possibility for detailed investigation and controlled manipulation of individual quantum systems. Beyond the definition of graphene QDs by opening an energy gap in nanoconstrictions, with the presence of a bandgap, gate-defined QDs can be achieved on TMDCs semiconductors. In this paper, we review the confinement and transport of QDs in TMDCs nanostructures. The fabrication techniques for demonstrating two-dimensional (2D) materials nanostructures such as field-effect transistors and QDs, mainly based on e-beam lithography and transfer assembly techniques are discussed. Subsequently, we focus on electron transport through TMDCs nanostructures and QDs. With steady improvement in nanoscale materials characterization and using graphene as a springboard, 2D materials offer a platform that allows creation of heterostructure QDs integrated with a variety of crystals, each of which has entirely unique physical properties.

Organic-Inorganic Perovskites: Structural Versatility for Functional Materials Design.

PubMed

Saparov, Bayrammurad; Mitzi, David B

2016-04-13

Although known since the late 19th century, organic-inorganic perovskites have recently received extraordinary research community attention because of their unique physical properties, which make them promising candidates for application in photovoltaic (PV) and related optoelectronic devices. This review will explore beyond the current focus on three-dimensional (3-D) lead(II) halide perovskites, to highlight the great chemical flexibility and outstanding potential of the broader class of 3-D and lower dimensional organic-based perovskite family for electronic, optical, and energy-based applications as well as fundamental research. The concept of a multifunctional organic-inorganic hybrid, in which the organic and inorganic structural components provide intentional, unique, and hopefully synergistic features to the compound, represents an important contemporary target.

A Facile Method for Synthesizing Dendritic Core–Shell Structured Ternary Metallic Aerogels and Their Enhanced Electrochemical Performances

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

Shi, Qiurong; Zhu, Chengzhou; Li, Yijing

2016-11-08

Currently, three dimensional self-supported metallic structures are attractive for their unique properties of high porosity, low density, excellent conductivity etc. that promote their wide application in fuel cells. Here, for the first time, we report a facile synthesis of dendritic core-shell structured Au/Pt3Pd ternary metallic aerogels via a one-pot self-assembly gelation strategy. The as-prepared Au/Pt3Pd ternary metallic aerogels demonstrated superior electrochemical performances toward oxygen reduction reaction compared to commercial Pt/C. The unique dendritic core-shell structures, Pt3Pd alloyed shells and the cross-linked network structures are beneficial for the electrochemical oxygen reduction reaction performances of the Pt-based materials via the electronic effect,more » geometric effect and synergistic effect. This strategy of fabrication of metallic hydrogels and aerogels as well as their exceptional properties hold great promise in a variety of applications.« less

Synthesis and Characterization of Monodisperse Core-shell Lanthanide Upconversion Nanoparticles NaYF4: Yb,Tm/SiO2

NASA Astrophysics Data System (ADS)

Manurung, R. V.; Wiranto, G.; Hermida, I. D. P.

2018-05-01

Lanthanide up-converting luminescent nanoparticles (UCNPs) are exciting and promising materials for optical bioimaging, biosensor and theranostic due to their unique and advantageous optical and chemical properties. The UCNPs absorb low energy near-infrared (NIR) light and emit high-energy shorter wavelength photons (visible light). Their unique features allow them to overcome various problems associated with conventional imaging probes such as photostability, lack of toxicity, and to provide versatility for creating nanoplatforms with both imaging and therapeutic modalities. This paper reports synthesis and characterization of core-shell structured of NaYF4:Yb,Tm/SiO2 microspheres. The synthesis of lanthanide upconversion nanoparticles NaYF4:Yb,Tm was prepared by thermal decomposition process which involves dissolving organic precursors in high-boiling-point solvents oleic acid (OA) and octadecene (ODE). After that, the NaYF4:Yb,Tm phosphors was coated by silica via reverse microemulsion process to obtain core-shell structured NaYF4:Yb,Tm/SiO2. Scanning electron microscopy, transmission electron microscopy, specific area electron diffraction, and photoluminescence were applied to characterize these samples. The obtained core-shell structured NaYF4:Yb,Tm/SiO2 phosphors exhibit a perfect cubic morphology with narrow size distribution and smooth surface. Upon IR excitation at 980 nm, the NaYF4:Yb,Tm/SiO2 samples exhibit whitish blue upconversion (UC) luminescence, respectively. These phosphors show potential applications in the displaying on biological fields and biosensing.

Controlling electron beam-induced structure modifications and cation exchange in cadmium sulfide-copper sulfide heterostructured nanorods.

PubMed

Zheng, Haimei; Sadtler, Bryce; Habenicht, Carsten; Freitag, Bert; Alivisatos, A Paul; Kisielowski, Christian

2013-11-01

The atomic structure and interfaces of CdS/Cu2S heterostructured nanorods are investigated with the aberration-corrected TEAM 0.5 electron microscope operated at 80 kV and 300 kV applying in-line holography and complementary techniques. Cu2S exhibits a low-chalcocite structure in pristine CdS/Cu2S nanorods. Under electron beam irradiation the Cu2S phase transforms into a high-chalcocite phase while the CdS phase maintains its wurtzite structure. Time-resolved experiments reveal that Cu(+)-Cd(2+) cation exchange at the CdS/Cu2S interfaces is stimulated by the electron beam and proceeds within an undisturbed and coherent sulfur sub-lattice. A variation of the electron beam current provides an efficient way to control and exploit such irreversible solid-state chemical processes that provide unique information about system dynamics at the atomic scale. Specifically, we show that the electron beam-induced copper-cadmium exchange is site specific and anisotropic. A resulting displacement of the CdS/Cu2S interfaces caused by beam-induced cation interdiffusion equals within a factor of 3-10 previously reported Cu diffusion length measurements in heterostructured CdS/Cu2S thin film solar cells with an activation energy of 0.96 eV. © 2013 Elsevier B.V. All rights reserved.

Dislocation loop formation by swift heavy ion irradiation of metals.

PubMed

Khara, Galvin S; Murphy, Samuel T; Duffy, Dorothy M

2017-07-19

A coupled two-temperature, molecular dynamics methodology is used to simulate the structural evolution of bcc metals (Fe and W) and fcc metals (Cu and Ni) following irradiation by swift heavy ions. Electronic temperature dependent electronic specific heat capacities and electron-phonon coupling strengths are used to capture the full effects of the variation in the electronic density of states. Tungsten is found to be significantly more resistant to damage than iron, due both to the higher melting temperature and the higher thermal conductivity. Very interesting defect structures, quite different from defects formed in cascades, are found to be created by swift heavy ion irradiation in the bcc metals. Isolated vacancies form a halo around elongated interstitial dislocation loops that are oriented along the ion path. Such configurations are formed by rapid recrystallization of the molten cylindrical region that is created by the energetic ion. Vacancies are created at the recrystallization front, resulting in excess atoms at the core which form interstitial dislocation loops on completion of crystallization. These unique defect structures could, potentially, be used to create metal films with superior mechanical properties and interesting nanostructures.

Dislocation loop formation by swift heavy ion irradiation of metals

NASA Astrophysics Data System (ADS)

Khara, Galvin S.; Murphy, Samuel T.; Duffy, Dorothy M.

2017-07-01

A coupled two-temperature, molecular dynamics methodology is used to simulate the structural evolution of bcc metals (Fe and W) and fcc metals (Cu and Ni) following irradiation by swift heavy ions. Electronic temperature dependent electronic specific heat capacities and electron-phonon coupling strengths are used to capture the full effects of the variation in the electronic density of states. Tungsten is found to be significantly more resistant to damage than iron, due both to the higher melting temperature and the higher thermal conductivity. Very interesting defect structures, quite different from defects formed in cascades, are found to be created by swift heavy ion irradiation in the bcc metals. Isolated vacancies form a halo around elongated interstitial dislocation loops that are oriented along the ion path. Such configurations are formed by rapid recrystallization of the molten cylindrical region that is created by the energetic ion. Vacancies are created at the recrystallization front, resulting in excess atoms at the core which form interstitial dislocation loops on completion of crystallization. These unique defect structures could, potentially, be used to create metal films with superior mechanical properties and interesting nanostructures.

Origin of High Electronic Quality in Solar Cell Absorber CH3NH3PbI3

NASA Astrophysics Data System (ADS)

Yin, Wanjian; Shi, Tingting; Wei, Suhua; Yan, Yanfa

Thin-film solar cells based on CH3NH3PbI3 halide perovskites have recently shown remarkable performance. First-principle calculations and molecular dynamic simulations show that the structure of pristine CH3NH3PbI3 is much more disordered than the inorganic archetypal thin-film semiconductor CdTe. However, the structural disorders from thermal fluctuation, point defects and grain boundaries introduce rare deep defect states within the bandgaps; therefore, the material has high electronic quality. We have further shown that this unusually high electronic quality is attributed to the unique electronic structures of halide perovskite: the strong coupling between cation lone-pair Pb s orbitals and anion p orbitals and the large atomic size of constitute cation atoms. We further found that although CH3NH3PbI3 GBs do not introduce a deep gap state, the defect level close to the VBM can still act as a shallow hole trap state. Cl and O can spontaneously segregate into GBs and passivate those defect levels and deactivate the trap state.

Self‐Assembled Graphene‐Based Architectures and Their Applications

PubMed Central

Yuan, Zhongke; Xiao, Xiaofen; Li, Jing; Zhao, Zhe

2017-01-01

Abstract Due to unique planar structures and remarkable thermal, electronic, and mechanical properties, chemically modified graphenes (CMGs) such as graphene oxides, reduced graphene oxides, and the related derivatives are recognized as the attractive building blocks for “bottom‐up” nanotechnology, while self‐assembly of CMGs has emerged as one of the most promising approaches to construct advanced functional materials/systems based on graphene. By virtue of a variety of noncovalent forces like hydrogen bonding, van der Waals interaction, metal‐to‐ligand bonds, electrostatic attraction, hydrophobic–hydrophilic interactions, and π–π interactions, the CMGs bearing various functional groups are highly desirable for the assemblies with themselves and a variety of organic and/or inorganic species which can yield various hierarchical nanostructures and macroscopic composites endowed with unique structures, properties, and functions for widespread technological applications such as electronics, optoelectronics, electrocatalysis/photocatalysis, environment, and energy storage and conversion. In this review, significant recent advances concerning the self‐assembly of CMGs are summarized, and the broad applications of self‐assembled graphene‐based materials as well as some future opportunities and challenges in this vibrant area are elucidated. PMID:29619311

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

Dolyniuk, Juli-Anna; Zaikina, Julia V.; Kaseman, Derrick C.

A new clathrate type has been discovered in the Ba/Cu/Zn/P system. The crystal structure of the Ba 8M 24P 28+δ (M=Cu/Zn) clathrate is composed of the pentagonal dodecahedra common to clathrates along with a unique 22-vertex polyhedron with two hexagonal faces capped by additional partially occupied phosphorus sites. This is the first example of a clathrate compound where the framework atoms are not in tetrahedral or trigonal-pyramidal coordination. In Ba 8M 24P 28+δ a majority of the framework atoms are five- and six-coordinated, a feature more common to electron-rich intermetallics. The crystal structure of this new clathrate was determined bymore » a combination of X-ray and neutron diffraction and was confirmed with solid-state 31P NMR spectroscopy. Based on chemical bonding analysis, the driving force for the formation of this new clathrate is the excess of electrons generated by a high concentration of Zn atoms in the framework. The rattling of guest atoms in the large cages results in a very low thermal conductivity, a unique feature of the clathrate family of compounds.« less

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

Xu, Shao-Gang; Liao, Ji-Hai; Zhao, Yu-Jun

The unique electronic property induced diversified structure of boron (B) cluster has attracted much interest from experimentalists and theorists. B{sub 30–40} were reported to be planar fragments of triangular lattice with proper concentrations of vacancies recently. Here, we have performed high-throughput screening for possible B clusters through the first-principles calculations, including various shapes and distributions of vacancies. As a result, we have determined the structures of B{sub n} clusters with n = 30–51 and found a stable planar cluster of B{sub 49} with a double-hexagon vacancy. Considering the 8-electron rule and the electron delocalization, a concise model for the distributionmore » of the 2c–2e and 3c–2e bonds has been proposed to explain the stability of B planar clusters, as well as the reported B cages.« less

High-Throughput Synthesis and Structure of Zeolite ZSM-43 with Two-Directional 8-Ring Channels.

PubMed

Willhammar, Tom; Su, Jie; Yun, Yifeng; Zou, Xiaodong; Afeworki, Mobae; Weston, Simon C; Vroman, Hilda B; Lonergan, William W; Strohmaier, Karl G

2017-08-07

The aluminosilicate zeolite ZSM-43 (where ZSM = Zeolite Socony Mobil) was first synthesized more than 3 decades ago, but its chemical structure remained unsolved because of its poor crystallinity and small crystal size. Here we present optimization of the ZSM-43 synthesis using a high-throughput approach and subsequent structure determination by the combination of electron crystallographic methods and powder X-ray diffraction. The synthesis required the use of a combination of both inorganic (Cs + and K + ) and organic (choline) structure-directing agents. High-throughput synthesis enabled a screening of the synthesis conditions, which made it possible to optimize the synthesis, despite its complexity, in order to obtain a material with significantly improved crystallinity. When both rotation electron diffraction and high-resolution transmission electron microscopy imaging techniques are applied, the structure of ZSM-43 could be determined. The structure of ZSM-43 is a new zeolite framework type and possesses a unique two-dimensional channel system limited by 8-ring channels. ZSM-43 is stable upon calcination, and sorption measurements show that the material is suitable for adsorption of carbon dioxide as well as methane.

Polarized XANES Monitors Femtosecond Structural Evolution of Photoexcited Vitamin B 12

DOE PAGES

Miller, Nicholas A.; Deb, Aniruddha; Alonso-Mori, Roberto; ...

2017-01-30

Ultrafast, polarization-selective time-resolved X-ray absorption near-edge structure (XANES) was used to characterize the photochemistry of vitamin B 12, cyanocobalamin (CNCbl), in solution. Cobalamins are important biological cofactors involved in methyl transfer, radical rearrangement, and light-activated gene regulation, while also holding promise as light-activated agents for spatiotemporal controlled delivery of therapeutics. We introduce polarized femtosecond XANES, combined with UV–visible spectroscopy, to reveal sequential structural evolution of CNCbl in the excited electronic state. Femtosecond polarized XANES provides the crucial structural dynamics link between computed potential energy surfaces and optical transient absorption spectroscopy. Polarization selectivity can be used to uniquely identify electronic contributionsmore » and structural changes, even in isotropic samples when well-defined electronic transitions are excited. Our XANES measurements reveal that the structural changes upon photoexcitation occur mainly in the axial direction, where elongation of the axial Co–CN bond and Co–N Im bond on a 110 fs time scale is followed by corrin ring relaxation on a 260 fs time scale. In conclusion, these observations expose features of the potential energy surfaces controlling cobalamin reactivity and deactivation.« less

Polarized XANES Monitors Femtosecond Structural Evolution of Photoexcited Vitamin B 12

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

Miller, Nicholas A.; Deb, Aniruddha; Alonso-Mori, Roberto

Ultrafast, polarization-selective time-resolved X-ray absorption near-edge structure (XANES) was used to characterize the photochemistry of vitamin B 12, cyanocobalamin (CNCbl), in solution. Cobalamins are important biological cofactors involved in methyl transfer, radical rearrangement, and light-activated gene regulation, while also holding promise as light-activated agents for spatiotemporal controlled delivery of therapeutics. We introduce polarized femtosecond XANES, combined with UV–visible spectroscopy, to reveal sequential structural evolution of CNCbl in the excited electronic state. Femtosecond polarized XANES provides the crucial structural dynamics link between computed potential energy surfaces and optical transient absorption spectroscopy. Polarization selectivity can be used to uniquely identify electronic contributionsmore » and structural changes, even in isotropic samples when well-defined electronic transitions are excited. Our XANES measurements reveal that the structural changes upon photoexcitation occur mainly in the axial direction, where elongation of the axial Co–CN bond and Co–N Im bond on a 110 fs time scale is followed by corrin ring relaxation on a 260 fs time scale. In conclusion, these observations expose features of the potential energy surfaces controlling cobalamin reactivity and deactivation.« less

Sculpting Nanoscale Functional Channels in Complex Oxides Using Energetic Ions and Electrons

DOE PAGES

Sachan, Ritesh; Zarkadoula, Eva; Ou, Xin; ...

2018-04-26

The formation of metastable phases has attracted significant attention because of their unique properties and potential functionalities. In the present study, we demonstrate the phase conversion of energetic-ion-induced amorphous nanochannels/tracks into a metastable defect fluorite in A 2B 2O 7 structured complex oxides by electron irradiation. Through in situ electron irradiation experiments in a scanning transmission electron microscope, we observe electron-induced epitaxial crystallization of the amorphous nanochannels in Yb 2Ti 2O 7 into the defect fluorite. This energetic-electron-induced phase transformation is attributed to the coupled effect of ionization-induced electronic excitations and local heating, along with subthreshold elastic energy transfers. Wemore » also show the role of ionic radii of A-site cations (A = Yb, Gd, and Sm) and B-site cations (Ti and Zr) in facilitating the electron-beam-induced crystallization of the amorphous phase to the defect-fluorite structure. The formation of the defect-fluorite structure is eased by the decrease in the difference between ionic radii of A- and B-site cations in the lattice. Molecular dynamics simulations of thermal annealing of the amorphous phase nanochannels in A 2B 2O 7 draw parallels to the electron-irradiation-induced crystallization and confirm the role of ionic radii in lowering the barrier for crystallization. Furthermore, these results suggest that employing guided electron irradiation with atomic precision is a useful technique for selected area phase formation in nanoscale printed devices.« less

Sculpting Nanoscale Functional Channels in Complex Oxides Using Energetic Ions and Electrons

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

Sachan, Ritesh; Zarkadoula, Eva; Ou, Xin

The formation of metastable phases has attracted significant attention because of their unique properties and potential functionalities. In the present study, we demonstrate the phase conversion of energetic-ion-induced amorphous nanochannels/tracks into a metastable defect fluorite in A 2B 2O 7 structured complex oxides by electron irradiation. Through in situ electron irradiation experiments in a scanning transmission electron microscope, we observe electron-induced epitaxial crystallization of the amorphous nanochannels in Yb 2Ti 2O 7 into the defect fluorite. This energetic-electron-induced phase transformation is attributed to the coupled effect of ionization-induced electronic excitations and local heating, along with subthreshold elastic energy transfers. Wemore » also show the role of ionic radii of A-site cations (A = Yb, Gd, and Sm) and B-site cations (Ti and Zr) in facilitating the electron-beam-induced crystallization of the amorphous phase to the defect-fluorite structure. The formation of the defect-fluorite structure is eased by the decrease in the difference between ionic radii of A- and B-site cations in the lattice. Molecular dynamics simulations of thermal annealing of the amorphous phase nanochannels in A 2B 2O 7 draw parallels to the electron-irradiation-induced crystallization and confirm the role of ionic radii in lowering the barrier for crystallization. Furthermore, these results suggest that employing guided electron irradiation with atomic precision is a useful technique for selected area phase formation in nanoscale printed devices.« less

Understanding boron through size-selected clusters: structure, chemical bonding, and fluxionality.

PubMed

Sergeeva, Alina P; Popov, Ivan A; Piazza, Zachary A; Li, Wei-Li; Romanescu, Constantin; Wang, Lai-Sheng; Boldyrev, Alexander I

2014-04-15

Boron is an interesting element with unusual polymorphism. While three-dimensional (3D) structural motifs are prevalent in bulk boron, atomic boron clusters are found to have planar or quasi-planar structures, stabilized by localized two-center-two-electron (2c-2e) σ bonds on the periphery and delocalized multicenter-two-electron (nc-2e) bonds in both σ and π frameworks. Electron delocalization is a result of boron's electron deficiency and leads to fluxional behavior, which has been observed in B13(+) and B19(-). A unique capability of the in-plane rotation of the inner atoms against the periphery of the cluster in a chosen direction by employing circularly polarized infrared radiation has been suggested. Such fluxional behaviors in boron clusters are interesting and have been proposed as molecular Wankel motors. The concepts of aromaticity and antiaromaticity have been extended beyond organic chemistry to planar boron clusters. The validity of these concepts in understanding the electronic structures of boron clusters is evident in the striking similarities of the π-systems of planar boron clusters to those of polycyclic aromatic hydrocarbons, such as benzene, naphthalene, coronene, anthracene, or phenanthrene. Chemical bonding models developed for boron clusters not only allowed the rationalization of the stability of boron clusters but also lead to the design of novel metal-centered boron wheels with a record-setting planar coordination number of 10. The unprecedented highly coordinated borometallic molecular wheels provide insights into the interactions between transition metals and boron and expand the frontier of boron chemistry. Another interesting feature discovered through cluster studies is boron transmutation. Even though it is well-known that B(-), formed by adding one electron to boron, is isoelectronic to carbon, cluster studies have considerably expanded the possibilities of new structures and new materials using the B(-)/C analogy. It is believed that the electronic transmutation concept will be effective and valuable in aiding the design of new boride materials with predictable properties. The study of boron clusters with intermediate properties between those of individual atoms and bulk solids has given rise to a unique opportunity to broaden the frontier of boron chemistry. Understanding boron clusters has spurred experimentalists and theoreticians to find new boron-based nanomaterials, such as boron fullerenes, nanotubes, two-dimensional boron, and new compounds containing boron clusters as building blocks. Here, a brief and timely overview is presented addressing the recent progress made on boron clusters and the approaches used in the authors' laboratories to determine the structure, stability, and chemical bonding of size-selected boron clusters by joint photoelectron spectroscopy and theoretical studies. Specifically, key findings on all-boron hydrocarbon analogues, metal-centered boron wheels, and electronic transmutation in boron clusters are summarized.

Understanding Boron through Size-Selected Clusters: Structure, Chemical Bonding, and Fluxionality

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

Sergeeva, Alina P.; Popov, Ivan A.; Piazza, Zachary A.

Conspectus Boron is an interesting element with unusual polymorphism. While three-dimensional (3D) structural motifs are prevalent in bulk boron, atomic boron clusters are found to have planar or quasi-planar structures, stabilized by localized two-center–two-electron (2c–2e) σ bonds on the periphery and delocalized multicenter–two-electron (nc–2e) bonds in both σ and π frameworks. Electron delocalization is a result of boron’s electron deficiency and leads to fluxional behavior, which has been observed in B13+ and B19–. A unique capability of the in-plane rotation of the inner atoms against the periphery of the cluster in a chosen direction by employing circularly polarized infrared radiationmore » has been suggested. Such fluxional behaviors in boron clusters are interesting and have been proposed as molecular Wankel motors. The concepts of aromaticity and antiaromaticity have been extended beyond organic chemistry to planar boron clusters. The validity of these concepts in understanding the electronic structures of boron clusters is evident in the striking similarities of the π-systems of planar boron clusters to those of polycyclic aromatic hydrocarbons, such as benzene, naphthalene, coronene, anthracene, or phenanthrene. Chemical bonding models developed for boron clusters not only allowed the rationalization of the stability of boron clusters but also lead to the design of novel metal-centered boron wheels with a record-setting planar coordination number of 10. The unprecedented highly coordinated borometallic molecular wheels provide insights into the interactions between transition metals and boron and expand the frontier of boron chemistry. Another interesting feature discovered through cluster studies is boron transmutation. Even though it is well-known that B–, formed by adding one electron to boron, is isoelectronic to carbon, cluster studies have considerably expanded the possibilities of new structures and new materials using the B–/C analogy. It is believed that the electronic transmutation concept will be effective and valuable in aiding the design of new boride materials with predictable properties. The study of boron clusters with intermediate properties between those of individual atoms and bulk solids has given rise to a unique opportunity to broaden the frontier of boron chemistry. Understanding boron clusters has spurred experimentalists and theoreticians to find new boron-based nanomaterials, such as boron fullerenes, nanotubes, two-dimensional boron, and new compounds containing boron clusters as building blocks. Here, a brief and timely overview is presented addressing the recent progress made on boron clusters and the approaches used in the authors’ laboratories to determine the structure, stability, and chemical bonding of size-selected boron clusters by joint photoelectron spectroscopy and theoretical studies. Specifically, key findings on all-boron hydrocarbon analogues, metal-centered boron wheels, and electronic transmutation in boron clusters are summarized.« less

Structural correlations in the generation of polaron pairs in low-bandgap polymers for photovoltaics

NASA Astrophysics Data System (ADS)

Tautz, Raphael; da Como, Enrico; Limmer, Thomas; Feldmann, Jochen; Egelhaaf, Hans-Joachim; von Hauff, Elizabeth; Lemaur, Vincent; Beljonne, David; Yilmaz, Seyfullah; Dumsch, Ines; Allard, Sybille; Scherf, Ullrich

2012-07-01

Polymeric semiconductors are materials where unique optical and electronic properties often originate from a tailored chemical structure. This allows for synthesizing conjugated macromolecules with ad hoc functionalities for organic electronics. In photovoltaics, donor-acceptor co-polymers, with moieties of different electron affinity alternating on the chain, have attracted considerable interest. The low bandgap offers optimal light-harvesting characteristics and has inspired work towards record power conversion efficiencies. Here we show for the first time how the chemical structure of donor and acceptor moieties controls the photogeneration of polaron pairs. We show that co-polymers with strong acceptors show large yields of polaron pair formation up to 24% of the initial photoexcitations as compared with a homopolymer (η=8%). π-conjugated spacers, separating the donor and acceptor centre of masses, have the beneficial role of increasing the recombination time. The results provide useful input into the understanding of polaron pair photogeneration in low-bandgap co-polymers for photovoltaics.

Fine structure constant defines visual transparency of graphene.

PubMed

Nair, R R; Blake, P; Grigorenko, A N; Novoselov, K S; Booth, T J; Stauber, T; Peres, N M R; Geim, A K

2008-06-06

There are few phenomena in condensed matter physics that are defined only by the fundamental constants and do not depend on material parameters. Examples are the resistivity quantum, h/e2 (h is Planck's constant and e the electron charge), that appears in a variety of transport experiments and the magnetic flux quantum, h/e, playing an important role in the physics of superconductivity. By and large, sophisticated facilities and special measurement conditions are required to observe any of these phenomena. We show that the opacity of suspended graphene is defined solely by the fine structure constant, a = e2/hc feminine 1/137 (where c is the speed of light), the parameter that describes coupling between light and relativistic electrons and that is traditionally associated with quantum electrodynamics rather than materials science. Despite being only one atom thick, graphene is found to absorb a significant (pa = 2.3%) fraction of incident white light, a consequence of graphene's unique electronic structure.

Pressure-induced multiband superconductivity in pyrite PtB i2 with perfect electron-hole compensation

NASA Astrophysics Data System (ADS)

Chen, Xuliang; Shao, Dexi; Gu, Chuanchuan; Zhou, Yonghui; An, Chao; Zhou, Ying; Zhu, Xiangde; Chen, Tong; Tian, Mingliang; Sun, Jian; Yang, Zhaorong

2018-05-01

We report on the discovery of pressure-induced superconductivity in the compensated semimetal pyrite PtB i2 , which exhibits extreme magnetoresistance (XMR) and nontrivial band structure at ambient pressure. The appearance of superconductivity, first observed at PC˜13 GPa with an onset critical temperature TC of ˜2.2 K , is accompanied by a pronounced enhancement of the density of electrons and holes based on Hall-effect measurements. Upon further compression, TC remains almost unchanged up to 50.0 GPa; remarkably, the perfect electron-hole compensation still holds, while the carrier mobility greatly reduces. No evident trace of structural phase transitions is detected through synchrotron x-ray diffraction over the measured pressure range of 1.5-51.2 GPa. These results highlight a multiband characteristic of the observed superconductivity, making pyrite PtB i2 unique among the compensated XMR materials where the pressure-induced superconductivity usually links to structural transitions and carrier imbalance.

Crystal structures of virus-like photosystem I complexes from the mesophilic cyanobacterium Synechocystis PCC 6803

PubMed Central

Mazor, Yuval; Nataf, Daniel; Toporik, Hila; Nelson, Nathan

2014-01-01

Oxygenic photosynthesis supports virtually all life forms on earth. Light energy is converted by two photosystems—photosystem I (PSI) and photosystem II (PSII). Globally, nearly 50% of photosynthesis takes place in the Ocean, where single cell cyanobacteria and algae reside together with their viruses. An operon encoding PSI was identified in cyanobacterial marine viruses. We generated a PSI that mimics the salient features of the viral complex, named PSIPsaJF. PSIPsaJF is promiscuous for its electron donors and can accept electrons from respiratory cytochromes. We solved the structure of PSIPsaJF and a monomeric PSI, with subunit composition similar to the viral PSI, providing for the first time a detailed description of the reaction center and antenna system from mesophilic cyanobacteria, including red chlorophylls and cofactors of the electron transport chain. Our finding extends the understanding of PSI structure, function and evolution and suggests a unique function for the viral PSI. DOI: http://dx.doi.org/10.7554/eLife.01496.001 PMID:24473073

Crystal structures of virus-like photosystem I complexes from the mesophilic cyanobacterium Synechocystis PCC 6803.

PubMed

Mazor, Yuval; Nataf, Daniel; Toporik, Hila; Nelson, Nathan

2013-01-01

Oxygenic photosynthesis supports virtually all life forms on earth. Light energy is converted by two photosystems-photosystem I (PSI) and photosystem II (PSII). Globally, nearly 50% of photosynthesis takes place in the Ocean, where single cell cyanobacteria and algae reside together with their viruses. An operon encoding PSI was identified in cyanobacterial marine viruses. We generated a PSI that mimics the salient features of the viral complex, named PSI(PsaJF). PSI(PsaJF) is promiscuous for its electron donors and can accept electrons from respiratory cytochromes. We solved the structure of PSI(PsaJF) and a monomeric PSI, with subunit composition similar to the viral PSI, providing for the first time a detailed description of the reaction center and antenna system from mesophilic cyanobacteria, including red chlorophylls and cofactors of the electron transport chain. Our finding extends the understanding of PSI structure, function and evolution and suggests a unique function for the viral PSI. DOI: http://dx.doi.org/10.7554/eLife.01496.001.

Symmetry and novelty in the electronic and geometric structure of nanoalloys:. the case of Ag27Cu7

NASA Astrophysics Data System (ADS)

Ortigoza, M. Alcántara; Rahman, T. S.

2008-04-01

Nanoparticles of bimetallic alloys have been shown to possess composition dependent characteristics which distinguish themselves from the corresponding bulk alloys. Taking the 34-atom nanoalloy of Ag and Cu (Ag27Cu7), we show using first principles electronic structure calculations that this core-shell alloy indeed has perfect D5h symmetry and consists of only 6 non-equivalent (2 Cu and 4 Ag) atoms. Analysis of the interatomic bond lengths and detailed electronic structure further reveal that the Cu atoms play a major role in controlling the characteristics of the nanoalloy. The higher cohesive energy, together with shorter bond length for Cu, compared to Ag, conspire to produce a hierarchy in the relative strengths of the Ag - Cu, Ag - Ag, and Cu - Cu bonds and corresponding interatomic bond lengths, point to the uniqueness in the characteristics of this nanoalloy. Charge density plots of Ag27Cu7 provide further insights into the relative strengths of the various interatomic bonds.

One-Dimensional Perovskite Manganite Oxide Nanostructures: Recent Developments in Synthesis, Characterization, Transport Properties, and Applications

NASA Astrophysics Data System (ADS)

Li, Lei; Liang, Lizhi; Wu, Heng; Zhu, Xinhua

2016-03-01

One-dimensional nanostructures, including nanowires, nanorods, nanotubes, nanofibers, and nanobelts, have promising applications in mesoscopic physics and nanoscale devices. In contrast to other nanostructures, one-dimensional nanostructures can provide unique advantages in investigating the size and dimensionality dependence of the materials' physical properties, such as electrical, thermal, and mechanical performances, and in constructing nanoscale electronic and optoelectronic devices. Among the one-dimensional nanostructures, one-dimensional perovskite manganite nanostructures have been received much attention due to their unusual electron transport and magnetic properties, which are indispensable for the applications in microelectronic, magnetic, and spintronic devices. In the past two decades, much effort has been made to synthesize and characterize one-dimensional perovskite manganite nanostructures in the forms of nanorods, nanowires, nanotubes, and nanobelts. Various physical and chemical deposition techniques and growth mechanisms are explored and developed to control the morphology, identical shape, uniform size, crystalline structure, defects, and homogenous stoichiometry of the one-dimensional perovskite manganite nanostructures. This article provides a comprehensive review of the state-of-the-art research activities that focus on the rational synthesis, structural characterization, fundamental properties, and unique applications of one-dimensional perovskite manganite nanostructures in nanotechnology. It begins with the rational synthesis of one-dimensional perovskite manganite nanostructures and then summarizes their structural characterizations. Fundamental physical properties of one-dimensional perovskite manganite nanostructures are also highlighted, and a range of unique applications in information storages, field-effect transistors, and spintronic devices are discussed. Finally, we conclude this review with some perspectives/outlook and future researches in these fields.

One-Dimensional Perovskite Manganite Oxide Nanostructures: Recent Developments in Synthesis, Characterization, Transport Properties, and Applications.

PubMed

Li, Lei; Liang, Lizhi; Wu, Heng; Zhu, Xinhua

2016-12-01

One-dimensional nanostructures, including nanowires, nanorods, nanotubes, nanofibers, and nanobelts, have promising applications in mesoscopic physics and nanoscale devices. In contrast to other nanostructures, one-dimensional nanostructures can provide unique advantages in investigating the size and dimensionality dependence of the materials' physical properties, such as electrical, thermal, and mechanical performances, and in constructing nanoscale electronic and optoelectronic devices. Among the one-dimensional nanostructures, one-dimensional perovskite manganite nanostructures have been received much attention due to their unusual electron transport and magnetic properties, which are indispensable for the applications in microelectronic, magnetic, and spintronic devices. In the past two decades, much effort has been made to synthesize and characterize one-dimensional perovskite manganite nanostructures in the forms of nanorods, nanowires, nanotubes, and nanobelts. Various physical and chemical deposition techniques and growth mechanisms are explored and developed to control the morphology, identical shape, uniform size, crystalline structure, defects, and homogenous stoichiometry of the one-dimensional perovskite manganite nanostructures. This article provides a comprehensive review of the state-of-the-art research activities that focus on the rational synthesis, structural characterization, fundamental properties, and unique applications of one-dimensional perovskite manganite nanostructures in nanotechnology. It begins with the rational synthesis of one-dimensional perovskite manganite nanostructures and then summarizes their structural characterizations. Fundamental physical properties of one-dimensional perovskite manganite nanostructures are also highlighted, and a range of unique applications in information storages, field-effect transistors, and spintronic devices are discussed. Finally, we conclude this review with some perspectives/outlook and future researches in these fields.

Characterization of TEM Moiré Patterns Originating from Two Monolayer Graphenes Grown on the Front and Back Sides of a Copper Substrate by CVD Method

NASA Astrophysics Data System (ADS)

Yamazaki, Kenji; Maehara, Yosuke; Gohara, Kazutoshi

2018-06-01

The number of layers affects the electronic properties of graphene owing to its unique band structure, called the Dirac corn. Raman spectroscopy is a key diagnostic tool for identifying the number of graphene layers and for determining their physical properties. Here, we observed moiré structures in transmission electron microscopy (TEM) observations; these are signature patterns in multilayer, although Raman spectra showed the typical intensity of the 2D/G peak in the monolayer. We also performed a multi-slice TEM image simulation to compare the 3D atomic structures of the two graphene membranes with experimental TEM images. We found that the experimental moiré image was constructed with a 9-12 Å interlayer distance between graphene membranes. This structure was constructed by transferring CVD-grown graphene films that formed on both sides of the Cu substrate at once.

Lighting system with thermal management system having point contact synthetic jets

DOEpatents

Arik, Mehmet; Weaver, Stanton Earl; Kuenzler, Glenn Howard; Wolfe, Jr., Charles Franklin; Sharma, Rajdeep

2013-12-10

Lighting system having unique configurations are provided. For instance, the lighting system may include a light source, a thermal management system and driver electronics, each contained within a housing structure. The light source is configured to provide illumination visible through an opening in the housing structure. The thermal management system includes a plurality of synthetic jets. The synthetic jets are arranged within the lighting system such that they are secured at contact points.

Lighting system with thermal management system having point contact synthetic jets

DOEpatents

Arik, Mehmet; Weaver, Stanton Earl; Kuenzler, Glenn Howard; Wolfe, Jr, Charles Franklin; Sharma, Rajdeep

2016-08-30

Lighting systems having unique configurations are provided. For instance, the lighting system may include a light source, a thermal management system and driver electronics, each contained within a housing structure. The light source is configured to provide illumination visible through an opening in the housing structure. The thermal management system includes a plurality of synthetic jets. The synthetic jets are arranged within the lighting system such that they are secured at contact points.

Lighting system with thermal management system having point contact synthetic jets

DOEpatents

Arik, Mehmet; Weaver, Stanton Earl; Kuenzler, Glenn Howard; Wolfe, Jr., Charles Franklin; Sharma, Rajdeep

2016-08-23

Lighting systems having unique configurations are provided. For instance, the lighting system may include a light source, a thermal management system and driver electronics, each contained within a housing structure. The light source is configured to provide illumination visible through an opening in the housing structure. The thermal management system includes a plurality of synthetic jets. The synthetic jets are arranged within the lighting system such that they are secured at contact points.

Electrochemistry at Edge of Single Graphene Layer in a Nanopore

PubMed Central

Banerjee, Shouvik; Shim, Jiwook; Rivera, Jose; Jin, Xiaozhong; Estrada, David; Solovyeva, Vita; You, Xiuque; Pak, James; Pop, Eric; Aluru, Narayana; Bashir, Rashid

2013-01-01

We study the electrochemistry of single layer graphene edges using a nanopore-based structure consisting of stacked graphene and Al2O3 dielectric layers. Nanopores, with diameters ranging from 5 to 20 nm, are formed by an electron beam sculpting process on the stacked layers. This leads to unique edge structure which, along with the atomically thin nature of the embedded graphene electrode, demonstrates electrochemical current densities as high as 1.2 × 104 A/cm2. The graphene edge embedded structure offers a unique capability to study the electrochemical exchange at an individual graphene edge, isolated from the basal plane electrochemical activity. We also report ionic current modulation in the nanopore by biasing the embedded graphene terminal with respect to the electrodes in the fluid. The high electrochemical specific current density for a graphene nanopore-based device can have many applications in sensitive chemical and biological sensing, and energy storage devices. PMID:23249127

Measurement of GEP/GMP to Q2 = 5.6 GEV2 via Recoil Polarization at Jefferson Lab

NASA Astrophysics Data System (ADS)

Gayou, Olivier

2001-10-01

The measurement of the elastic form factors is a key ingredient to any complete understanding of the internal structure of the nucleons, and ultimately of the strong force. Precise data are essential to impose stringent tests on any QCD-based theory. The electromagnetic interaction provides a unique tool to investigate these form factors. In elastic electron scattering off a proton, the electron interacts with the nucleon exchanging a virtual photon. The electron-photon interaction is fully understood from QED, hence making the hadron vertex the only unknown of the reaction...

Synthesis of one-dimensional metal-containing insulated molecular wire with versatile properties directed toward molecular electronics materials.

PubMed

Masai, Hiroshi; Terao, Jun; Seki, Shu; Nakashima, Shigeto; Kiguchi, Manabu; Okoshi, Kento; Fujihara, Tetsuaki; Tsuji, Yasushi

2014-02-05

We report, herein, the design, synthesis, and properties of new materials directed toward molecular electronics. A transition metal-containing insulated molecular wire was synthesized through the coordination polymerization of a Ru(II) porphyrin with an insulated bridging ligand of well-defined structure. The wire displayed not only high linearity and rigidity, but also high intramolecular charge mobility. Owing to the unique properties of the coordination bond, the interconversion between the monomer and polymer states was realized under a carbon monoxide atmosphere or UV irradiation. The results demonstrated a high potential of the metal-containing insulated molecular wire for applications in molecular electronics.

All-carbon sp-sp2 hybrid structures: Geometrical properties, current rectification, and current amplification

PubMed Central

Zhang, Zhenhua; Zhang, Junjun; Kwong, Gordon; Li, Ji; Fan, Zhiqiang; Deng, Xiaoqing; Tang, Guiping

2013-01-01

All-carbon sp-sp2 hybrid structures comprised of a zigzag-edged trigonal graphene (ZTG)and carbon chains are proposed and constructed as nanojunctions. It has been found that such simple hybrid structures possess very intriguing propertiesapp:addword:intriguing. The high-performance rectifying behaviors similar to macroscopic p-n junction diodes, such as a nearly linear positive-bias I-V curve (metallic behavior), a very small leakage current under negative bias (insulating behavior), a rather low threshold voltage, and a large bias region contributed to a rectification, can be predicted. And also, a transistor can be built by such a hybrid structure, which can show an extremely high current amplification. This is because a sp-hybrid carbon chain has a special electronic structure which can limit the electronic resonant tunneling of the ZTG to a unique and favorable situation. These results suggest that these hybrid structures might promise importantly potential applications for developing nano-scale integrated circuits. PMID:23999318

Periodicity in Attachment Organelle Revealed by Electron Cryotomography Suggests Conformational Changes in Gliding Mechanism of Mycoplasma pneumoniae

PubMed Central

Kawamoto, Akihiro; Matsuo, Lisa; Kato, Takayuki; Yamamoto, Hiroki

2016-01-01

ABSTRACT Mycoplasma pneumoniae, a pathogenic bacterium, glides on host surfaces using a unique mechanism. It forms an attachment organelle at a cell pole as a protrusion comprised of knoblike surface structures and an internal core. Here, we analyzed the three-dimensional structure of the organelle in detail by electron cryotomography. On the surface, knoblike particles formed a two-dimensional array, albeit with limited regularity. Analyses using a nonbinding mutant and an antibody showed that the knoblike particles correspond to a naplike structure that has been observed by negative-staining electron microscopy and is likely to be formed as a complex of P1 adhesin, the key protein for binding and gliding. The paired thin and thick plates feature a rigid hexagonal lattice and striations with highly variable repeat distances, respectively. The combination of variable and invariant structures in the internal core and the P1 adhesin array on the surface suggest a model in which axial extension and compression of the thick plate along a rigid thin plate is coupled with attachment to and detachment from the substrate during gliding. PMID:27073090

Lithiation Mechanism of Tunnel-Structured MnO 2 Electrode Investigated by In Situ Transmission Electron Microscopy

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

Lee, Seung-Yong; Wu, Lijun; Poyraz, Altug S.

Manganese oxide (α-MnO 2) has been considered as a promising energy material, including as a lithium-based battery electrode candidate, due to its environmental friendliness. Thanks to its unique 1D [2 × 2] tunnel structure, α-MnO 2 can be applied to a cathode by insertion reaction and to an anode by conversion reaction in corresponding voltage ranges, in a lithium-based battery. Numerous reports have attributed its remarkable performance to its unique tunnel structure; however, the precise electrochemical reaction mechanism remains unknown. In this study, finding of the lithiation mechanism of α-MnO 2 nanowire by in situ transmission electron microscopy (TEM) ismore » reported. By elaborately modifying the existing in situ TEM experimental technique, rapid lithium-ion diffusion through the tunnels is verified. Furthermore, by tracing the full lithiation procedure, the evolution of the MnO intermediate phase and the development of the MnO and Li 2O phases with preferred orientations is demonstrated, which explains how the conversion reaction occurs in α-MnO 2 material. This study provides a comprehensive understanding of the electrochemical lithiation process and mechanism of α-MnO 2 material, in addition to the introduction of an improved in situ TEM biasing technique.« less

Lithiation Mechanism of Tunnel-Structured MnO 2 Electrode Investigated by In Situ Transmission Electron Microscopy

DOE PAGES

Lee, Seung-Yong; Wu, Lijun; Poyraz, Altug S.; ...

2017-10-06

Manganese oxide (α-MnO 2) has been considered as a promising energy material, including as a lithium-based battery electrode candidate, due to its environmental friendliness. Thanks to its unique 1D [2 × 2] tunnel structure, α-MnO 2 can be applied to a cathode by insertion reaction and to an anode by conversion reaction in corresponding voltage ranges, in a lithium-based battery. Numerous reports have attributed its remarkable performance to its unique tunnel structure; however, the precise electrochemical reaction mechanism remains unknown. In this study, finding of the lithiation mechanism of α-MnO 2 nanowire by in situ transmission electron microscopy (TEM) ismore » reported. By elaborately modifying the existing in situ TEM experimental technique, rapid lithium-ion diffusion through the tunnels is verified. Furthermore, by tracing the full lithiation procedure, the evolution of the MnO intermediate phase and the development of the MnO and Li 2O phases with preferred orientations is demonstrated, which explains how the conversion reaction occurs in α-MnO 2 material. This study provides a comprehensive understanding of the electrochemical lithiation process and mechanism of α-MnO 2 material, in addition to the introduction of an improved in situ TEM biasing technique.« less

Plasticity and Kinky Chemistry of Carbon Nanotubes

NASA Technical Reports Server (NTRS)

Srivastava, Deepak; Dzegilenko, Fedor

2000-01-01

Since their discovery in 1991, carbon nanotubes have been the subject of intense research interest based on early predictions of their unique mechanical, electronic, and chemical properties. Materials with the predicted unique properties of carbon nanotubes are of great interest for use in future generations of aerospace vehicles. For their structural properties, carbon nanotubes could be used as reinforcing fibers in ultralight multifunctional composites. For their electronic properties, carbon nanotubes offer the potential of very high-speed, low-power computing elements, high-density data storage, and unique sensors. In a continuing effort to model and predict the properties of carbon nanotubes, Ames accomplished three significant results during FY99. First, accurate values of the nanomechanics and plasticity of carbon nanotubes based on quantum molecular dynamics simulations were computed. Second, the concept of mechanical deformation catalyzed-kinky-chemistry as a means to control local chemistry of nanotubes was discovered. Third, the ease of nano-indentation of silicon surfaces with carbon nanotubes was established. The elastic response and plastic failure mechanisms of single-wall nanotubes were investigated by means of quantum molecular dynamics simulations.

Bioinspired peptide nanotubes: deposition technology, basic physics and nanotechnology applications.

PubMed

Rosenman, G; Beker, P; Koren, I; Yevnin, M; Bank-Srour, B; Mishina, E; Semin, S

2011-02-01

Synthetic peptide monomers can self-assemble into PNM such as nanotubes, nanospheres, hydrogels, etc. which represent a novel class of nanomaterials. Molecular recognition processes lead to the formation of supramolecular PNM ensembles containing crystalline building blocks. Such low-dimensional highly ordered regions create a new physical situation and provide unique physical properties based on electron-hole QC phenomena. In the case of asymmetrical crystalline structure, basic physical phenomena such as linear electro-optic, piezoelectric, and nonlinear optical effects, described by tensors of the odd rank, should be explored. Some of the PNM crystalline structures permit the existence of spontaneous electrical polarization and observation of ferroelectricity. The PNM crystalline arrangement creates highly porous nanotubes when various residues are packed into structural network with specific wettability and electrochemical properties. We report in this review on a wide research of PNM intrinsic physical properties, their electronic and optical properties related to QC effect, unique SHG, piezoelectricity and ferroelectric spontaneous polarization observed in PNT due to their asymmetric structure. We also describe PNM wettability phenomenon based on their nanoporous structure and its influence on electrochemical properties in PNM. The new bottom-up large scale technology of PNT physical vapor deposition and patterning combined with found physical effects at nanoscale, developed by us, opens the avenue for emerging nanotechnology applications of PNM in novel fields of nanophotonics, nanopiezotronics and energy storage devices. Copyright © 2010 European Peptide Society and John Wiley & Sons, Ltd.

Structure-dependent performance of TiO 2/C as anode material for Na-ion batteries

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

He, Hanna; Gan, Qingmeng; Wang, Haiyan

The performance of energy storage materials is highly dependent on their nanostructures. Herein, hierarchical rod-in-tube TiO 2 with a uniform carbon coating is synthesized as the anode material for sodium-ion batteries by a facile solvothermal method. This unique structure consists of a tunable nanorod core, interstitial hollow spaces, and a functional nanotube shell assembled from two-dimensional nanosheets. By adjusting the types of solvents used and reaction time, the morphologies of TiO 2/C composites can be tuned to nanoparticles, microrods, rod-in-tube structures, or microtubes. Among these materials, rod-in-tube TiO 2 with a uniform carbon coating shows the highest electronic conductivity, specificmore » surface area (336.4 m(2) g(-1)), and porosity, and these factors lead to the best sodium storage capability. Benefiting from the unique structural features and improved electronic/ionic conductivity, the as-obtained rod-in-tube TiO2/C in coin cell tests exhibits a high discharge capacity of 277.5 and 153.9 mAh g(-1) at 50 and 5000 mA g(-1), respectively, and almost 100% capacity retention over 14,000 cycles at 5000 mA g(-1). In operando high-energy X-ray diffraction further confirms the stable crystal structure of the rod-in-tube TiO 2/C during Na+ insertion/extraction. This work highlights that nanostructure design is an effective strategy to achieve advanced energy storage materials.« less

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.

Exploring electronic structure of one-atom thick polycrystalline graphene films: A nano angle resolved photoemission study

PubMed Central

Avila, José; Razado, Ivy; Lorcy, Stéphane; Fleurier, Romain; Pichonat, Emmanuelle; Vignaud, Dominique; Wallart, Xavier; Asensio, María C.

2013-01-01

The ability to produce large, continuous and defect free films of graphene is presently a major challenge for multiple applications. Even though the scalability of graphene films is closely associated to a manifest polycrystalline character, only a few numbers of experiments have explored so far the electronic structure down to single graphene grains. Here we report a high resolution angle and lateral resolved photoelectron spectroscopy (nano-ARPES) study of one-atom thick graphene films on thin copper foils synthesized by chemical vapor deposition. Our results show the robustness of the Dirac relativistic-like electronic spectrum as a function of the size, shape and orientation of the single-crystal pristine grains in the graphene films investigated. Moreover, by mapping grain by grain the electronic dynamics of this unique Dirac system, we show that the single-grain gap-size is 80% smaller than the multi-grain gap recently reported by classical ARPES. PMID:23942471

Structural, electronic and magnetic properties of carbon doped boron nitride nanowire: Ab initio study

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

Jalilian, Jaafar, E-mail: JaafarJalilian@gmail.com; Kanjouri, Faramarz, E-mail: kanjouri@khu.ac.ir

2016-11-15

Using spin-polarized density functional theory calculations, we demonstrated that carbon doped boron nitride nanowire (C-doped BNNW) has diverse electronic and magnetic properties depending on position of carbon atoms and their percentages. Our results show that only when one carbon atom is situated on the edge of the nanowire, C-doped BNNW is transformed into half-metal. The calculated electronic structure of the C-doped BNNW suggests that doping carbon can induce localized edge states around the Fermi level, and the interaction among localized edge states leads to semiconductor to half-metal transition. Overall, the bond reconstruction causes of appearance of different electronic behavior suchmore » as semiconducting, half-metallicity, nonmagnetic metallic, and ferromagnetic metallic characters. The formation energy of the system shows that when a C atom is doped on surface boron site, system is more stable than the other positions of carbon impurity. Our calculations show that C-doped BNNW may offer unique opportunities for developing nanoscale spintronic materials.« less

A Framework for Evaluating Science and Technology Electronic Reference Books: A Comparison of Five Platforms in Chemistry

ERIC Educational Resources Information Center

Lafferty, Meghan

2009-01-01

This article examines what is desirable in online reference books in science and technology and outlines a framework for evaluating their interfaces. The framework considers factors unique to these subject areas like chemical structures and numerical data. Criteria in three categories, navigability, searchability, and results, were applied to five…

Diels-Alder Trapping of Photochemically Generated o-Xylenols: Application in the Synthesis of Novel Organic Molecules and Polymers

NASA Technical Reports Server (NTRS)

Meador, Michael A.

2003-01-01

Bis(o-xylenol) equivalents are useful synthetic intermediates in the construction of polymers and hydroxyl substituted organic molecules which can organize by hydrogen bonded self-assembly into unique supramolecular structures. These polymers and supramolecular materials have potential use as coatings and thin films in aerospace, electronic and biomedical applications.

Similarity and diversity of translational GTPase factors EF-G, EF4, and BipA: From structure to function.

PubMed

Ero, Rya; Kumar, Veerendra; Chen, Yun; Gao, Yong-Gui

2016-12-01

EF-G, EF4, and BipA are members of the translation factor family of GTPases with a common ribosome binding mode and GTPase activation mechanism. However, topological variations of shared as well as unique domains ensure different roles played by these proteins during translation. Recent X-ray crystallography and cryo-electron microscopy studies have revealed the structural basis for the involvement of EF-G domain IV in securing the movement of tRNAs and mRNA during translocation as well as revealing how the unique C-terminal domains of EF4 and BipA interact with the ribosome and tRNAs contributing to the regulation of translation under certain conditions. EF-G, EF-4, and BipA are intriguing examples of structural variations on a common theme that results in diverse behavior and function. Structural studies of translational GTPase factors have been greatly facilitated by the use of antibiotics, which have revealed their mechanism of action.

N-doped yolk-shell hollow carbon sphere wrapped with graphene as sulfur host for high-performance lithium-sulfur batteries

NASA Astrophysics Data System (ADS)

Zhang, Yongzheng; Sun, Kai; Liang, Zhan; Wang, Yanli; Ling, Licheng

2018-01-01

N-doped yolk-shell hollow carbon sphere wrapped with reduced graphene oxide (rGO/N-YSHCS) is designed and fabricated as sulfur host for lithium-sulfur batteries. The shuttle effect of polysulfides can be suppressed effectively by the porous yolk-shell structure, graphene layer and N-doping. A good conductivity network is provided for electron transportation through the graphene layer coupled with the unique yolk-shell carbon matrix. Such unique structure offers the synthesized rGO/N-YSHCS/S electrode with a high reversible capacity (800 mAh g-1 at 0.2 C after 100 cycles) and good high-rate capability (636 mAh g-1 at 1 C and 540 mAh g-1 at 2 C).

Stretchable Platinum Network-Based Transparent Electrodes for Highly Sensitive Wearable Electronics.

PubMed

Wang, Yuting; Cheng, Jing; Xing, Yan; Shahid, Muhammad; Nishijima, Hiroki; Pan, Wei

2017-07-01

A platinum network-based transparent electrode has been fabricated by electrospinning. The unique nanobelt structured electrode demonstrates low sheet resistance (about 16 Ω sq -1 ) and high transparency of 80% and excellent flexibility. One of the most interesting demonstrations of this Pt nanobelt electrode is its excellent reversibly resilient characteristic. The electric conductivity of the flexible Pt electrode can recover to its initial value after 160% extending and this performance is repeatable and stable. The good linear relationship between the resistance and strain of the unique structured Pt electrode makes it possible to assemble a wearable high sensitive strain sensor. Present reported Pt nanobelt electrode also reveals potential applications in electrode for flexible fuel cells and highly transparent ultraviolet (UV) sensors. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis, properties and applications of 2D layered MIIIXVI (M = Ga, In; X = S, Se, Te) materials.

PubMed

Xu, Kai; Yin, Lei; Huang, Yun; Shifa, Tofik Ahmed; Chu, Junwei; Wang, Feng; Cheng, Ruiqing; Wang, Zhenxing; He, Jun

2016-09-29

Group III-VI compounds M III X VI (M = Ga, In; X = S, Se, Te) are one class of important 2D layered materials and are currently attracting increasing interest due to their unique electronic and optoelectronic properties and their great potential applications in various other fields. Similar to 2D layered transition metal dichalcogenides (TMDs), M III X VI also have the significant merits of ultrathin thickness, ultrahigh surface-to-volume ratio, and high compatibility with flexible devices. More impressively, in contrast with TMDCs, M III X VI demonstrate many superior properties, such as direct band gap electronic structure, high carrier mobility, rare p-type electronic behaviors, high charge density, and so on. These unique characteristics cause high-performance device applications in electronics, optoelectronics, and optics. In this review, we aim to provide a summary of the state-of-the-art of research activities in 2D layered M III X VI materials. The scope of the review covers the synthesis and properties of 2D layered M III X VI materials and their van der Waals heterostructures. We especially focus on the applications in electronics and optoelectronics. Moreover, the review concludes with some perspectives on future developments in this field.

Electronic coupling through natural amino acids.

PubMed

Berstis, Laura; Beckham, Gregg T; Crowley, Michael F

2015-12-14

Myriad scientific domains concern themselves with biological electron transfer (ET) events that span across vast scales of rate and efficiency through a remarkably fine-tuned integration of amino acid (AA) sequences, electronic structure, dynamics, and environment interactions. Within this intricate scheme, many questions persist as to how proteins modulate electron-tunneling properties. To help elucidate these principles, we develop a model set of peptides representing the common α-helix and β-strand motifs including all natural AAs within implicit protein-environment solvation. Using an effective Hamiltonian strategy with density functional theory, we characterize the electronic coupling through these peptides, furthermore considering side-chain dynamics. For both motifs, predictions consistently show that backbone-mediated electronic coupling is distinctly sensitive to AA type (aliphatic, polar, aromatic, negatively charged and positively charged), and to side-chain orientation. The unique properties of these residues may be employed to design activated, deactivated, or switch-like superexchange pathways. Electronic structure calculations and Green's function analyses indicate that localized shifts in the electron density along the peptide play a role in modulating these pathways, and further substantiate the experimentally observed behavior of proline residues as superbridges. The distinct sensitivities of tunneling pathways to sequence and conformation revealed in this electronic coupling database help improve our fundamental understanding of the broad diversity of ET reactivity and provide guiding principles for peptide design.

Nanoroses of nickel oxides: synthesis, electron tomography study, and application in CO oxidation and energy storage.

PubMed

Fihri, Aziz; Sougrat, Rachid; Rakhi, Raghavan Baby; Rahal, Raed; Cha, Dongkyu; Hedhili, Mohamed Nejib; Bouhrara, Mohamed; Alshareef, Husam N; Polshettiwar, Vivek

2012-07-01

Nickel oxide and mixed-metal oxide structures were fabricated by using microwave irradiation in pure water. The nickel oxide self-assembled into unique rose-shaped nanostructures. These nickel oxide roses were studied by performing electron tomography with virtual cross-sections through the particles to understand their morphology from their interior to their surface. These materials exhibited promising performance as nanocatalysts for CO oxidation and in energy storage devices. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electronic and magnetic properties of small rhodium clusters

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

Soon, Yee Yeen; Yoon, Tiem Leong; Lim, Thong Leng

2015-04-24

We report a theoretical study of the electronic and magnetic properties of rhodium-atomic clusters. The lowest energy structures at the semi-empirical level of rhodium clusters are first obtained from a novel global-minimum search algorithm, known as PTMBHGA, where Gupta potential is used to describe the atomic interaction among the rhodium atoms. The structures are then re-optimized at the density functional theory (DFT) level with exchange-correlation energy approximated by Perdew-Burke-Ernzerhof generalized gradient approximation. For the purpose of calculating the magnetic moment of a given cluster, we calculate the optimized structure as a function of the spin multiplicity within the DFT framework.more » The resultant magnetic moments with the lowest energies so obtained allow us to work out the magnetic moment as a function of cluster size. Rhodium atomic clusters are found to display a unique variation in the magnetic moment as the cluster size varies. However, Rh{sub 4} and Rh{sub 6} are found to be nonmagnetic. Electronic structures of the magnetic ground-state structures are also investigated within the DFT framework. The results are compared against those based on different theoretical approaches available in the literature.« less

Stabilization of Small Boron Cage by Transition Metal Encapsulation

NASA Astrophysics Data System (ADS)

Zhang, Lijun; Lv, Jian; Wang, Yanchao; Ma, Yanming

2015-03-01

The discovery of chemically stable fullerene-like structures formed by elements other than carbon has been long-standing desired. On this aspect significant efforts have centered around boron, only one electron deficient compared with carbon. However, during the past decade a large number of experimental and theoretical studies have established that small boron clusters are either planar/quasi-planar or forming double-ring tubular structures. Until recently, two all-boron fullerenes have been independently discovered: B38 proposed by our structure searching calculations and B40 observed in a joint experimental and theoretical study. Here we extend our work to the even smaller boron clusters and propose an effective routine to stabilize them by transition metal encapsulation. By combining swarm-intelligence structure searching and first-principles calculations, we have systematically investigated the energy landscapes of transition-metal-doped MB24 clusters (M = Ti, Zr, Hf, Cr, Mo, W, Fe, Ru and Os). Two stable symmetric endohedral boron cages, MoB24 and WB24 are identified. The stability of them can be rationalized in terms of their unique 18-electron closed-shell electronic structures. Funded by Recruitment Program of Global Experts of China and China Postdoctoral Science Foundation.

Polyaniline nanofiber/large mesoporous carbon composites as electrode materials for supercapacitors

NASA Astrophysics Data System (ADS)

Liu, Huan; Xu, Bin; Jia, Mengqiu; Zhang, Mei; Cao, Bin; Zhao, Xiaonan; Wang, Yu

2015-03-01

A composite of polyaniline nanofiber/large mesoporous carbon (PANI-F/LMC) hybrid was prepared by an in situ chemical oxidative polymerization of aniline monomer with nano-CaCO3 templated LMC as host matrix for supercapacitors. The morphology, composition and electronic structure of the composites (PANI-F/LMC) together with pure PANI nanofibers and the LMC were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), FT-IR, X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). It is found that the PANI nanofibers were incorporated into the large mesochannels of LMC with interpenetrating framework formed. Such unique structure endows the PANI-F/LMC composite with a high capacitance of 473 F g-1 at a current load of 0.1 A g-1 with good rate performance and cycling stability, suggesting its potential application in the electrode material for supercapacitors.

Magnetic phase diagram and electronic structure of UPt 2 Si 2 at high magnetic fields: A possible field-induced Lifshitz transition

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

Grachtrup, D. Schulze; Steinki, N.; Süllow, S.

2017-04-14

We have measured Hall effect, magnetotransport and magnetostriction on the field induced phases of single crystalline UPt2Si2 in magnetic fields up to 60T at temperatures down to 50mK, this way firmly establishing the phase diagram for magnetic fields Bka and c axes. Moreover, for Bkc axis we observe strong changes in the Hall effect at the phase boundaries. From a comparison to band structure calculations utilizing the concept of a dual nature of the uranium 5f electrons, we propose that these represent field induced topological changes of the Fermi surface due to at least one Lifshitz transition. Furthermore, we findmore » a unique history dependence of the magnetotransport and magnetostriction data, indicating that the proposed Lifshitz type transition is of a discontinuous nature, as predicted for interacting electron systems.« less

Atomic-Scale Characterization of Oxide Interfaces and Superlattices Using Scanning Transmission Electron Microscopy

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

Spurgeon, Steven R.; Chambers, Scott A.

Scanning transmission electron microscopy (STEM) has become one of the fundamental tools to characterize oxide interfaces and superlattices. Atomic-scale structure, chemistry, and composition mapping can now be conducted on a wide variety of materials systems thanks to the development of aberration-correctors and advanced detectors. STEM imaging and diffraction, coupled with electron energy loss (EELS) and energy-dispersive X-ray (EDS) spectroscopies, offer unparalleled, high-resolution analysis of structure-property relationships. In this chapter we highlight investigations into key phenomena, including interfacial conductivity in oxide superlattices, charge screening effects in magnetoelectric heterostructures, the design of high-quality iron oxide interfaces, and the complex physics governing atomic-scalemore » chemical mapping. These studies illustrate how unique insights from STEM characterization can be integrated with other techniques and first-principles calculations to develop better models for the behavior of functional oxides.« less

Coaxial carbon plasma gun deposition of amorphous carbon films

NASA Technical Reports Server (NTRS)

Sater, D. M.; Gulino, D. A.; Rutledge, S. K.

1984-01-01

A unique plasma gun employing coaxial carbon electrodes was used in an attempt to deposit thin films of amorphous diamond-like carbon. A number of different structural, compositional, and electrical characterization techniques were used to characterize these films. These included scanning electron microscopy, scanning transmission electron microscopy, X ray diffraction and absorption, spectrographic analysis, energy dispersive spectroscopy, and selected area electron diffraction. Optical absorption and electrical resistivity measurements were also performed. The films were determined to be primarily amorphous, with poor adhesion to fused silica substrates. Many inclusions of particulates were found to be present as well. Analysis of these particulates revealed the presence of trace impurities, such as Fe and Cu, which were also found in the graphite electrode material. The electrodes were the source of these impurities. No evidence of diamond-like crystallite structure was found in any of the film samples. Details of the apparatus, experimental procedure, and film characteristics are presented.

Counter-ion and dopant effects on charge carriers in intrinsically conductive polymer

NASA Astrophysics Data System (ADS)

Ogle, Jonathan; Yehulie, Mandefro; Boehme, Christoph; Whittaker-Brooks, Luisa

Recently, a significant amount of attention has been devoted to the optimization and applications of organic electronics. In particular, intrinsically conductive polymers have seen a strong continued interest for their use in thermoelectric and photovoltaic devices. With conductivities ranging from 10-8 to 103 S cm-1, the conductive polymer poly(3,4-ethylenedioxythiophene) -PEDOT is one of the most studied solution-processable polymer material due to its unique optical and electronic properties. While charge carriers at lower conductivities have been identified as polarons, an understanding of the electronic structure of PEDOT as its conductivity increases is not well understood. We have investigated the effect that counter-ion exchange and doping has on the polaron concentration of PEDOT via electron paramagnetic resonance, ultraviolet photoelectron spectroscopy, and X-ray absorption fine structure spectroscopy studies. Such studies have allowed us to correlate charge carriers concentrations and the real and virtual electronic states in PEDOT as a function of various dopants. As discussed in our talk, we believe our findings could be extended to the understanding of other polymeric materials.

Electronic evidence of temperature-induced Lifshitz transition and topological nature in ZrTe5

PubMed Central

Zhang, Yan; Wang, Chenlu; Yu, Li; Liu, Guodong; Liang, Aiji; Huang, Jianwei; Nie, Simin; Sun, Xuan; Zhang, Yuxiao; Shen, Bing; Liu, Jing; Weng, Hongming; Zhao, Lingxiao; Chen, Genfu; Jia, Xiaowen; Hu, Cheng; Ding, Ying; Zhao, Wenjuan; Gao, Qiang; Li, Cong; He, Shaolong; Zhao, Lin; Zhang, Fengfeng; Zhang, Shenjin; Yang, Feng; Wang, Zhimin; Peng, Qinjun; Dai, Xi; Fang, Zhong; Xu, Zuyan; Chen, Chuangtian; Zhou, X. J.

2017-01-01

The topological materials have attracted much attention for their unique electronic structure and peculiar physical properties. ZrTe5 has host a long-standing puzzle on its anomalous transport properties manifested by its unusual resistivity peak and the reversal of the charge carrier type. It is also predicted that single-layer ZrTe5 is a two-dimensional topological insulator and there is possibly a topological phase transition in bulk ZrTe5. Here we report high-resolution laser-based angle-resolved photoemission measurements on the electronic structure and its detailed temperature evolution of ZrTe5. Our results provide direct electronic evidence on the temperature-induced Lifshitz transition, which gives a natural understanding on underlying origin of the resistivity anomaly in ZrTe5. In addition, we observe one-dimensional-like electronic features from the edges of the cracked ZrTe5 samples. Our observations indicate that ZrTe5 is a weak topological insulator and it exhibits a tendency to become a strong topological insulator when the layer distance is reduced. PMID:28534501

Electron localization in rod-shaped triicosahedral gold nanocluster

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

Zhou, Meng; Jin, Renxi; Sfeir, Matthew Y.

Atomically precise gold nanocluster based on linear assembly of repeating icosahedrons (clusters of clusters) is a unique type of linear nanostructure, which exhibits strong near-infrared absorption as their free electrons are confined in a one-dimensional quantum box. There is little known about the carrier dynamics in these nanoclusters, which limit their energy-related applications. We reported the observation of exciton localization in triicosahedral Au37 nanoclusters (0.5 nm in diameter and 1.6 nm in length) by measuring femtosecond and nanosecond carrier dynamics. Upon photoexcitation to S1 electronic state, electrons in Au37 undergo ~100-ps localization from the two vertexes of three icosahedrons tomore » one vertex, forming a long-lived S1* state. Such phenomenon is not observed in Au25 (dimer) and Au13 (monomer) consisting of two and one icosahedrons, respectively. We have further observed temperature dependence on the localization process, which proves it is thermally driven. Two excited-state vibration modes with frequencies of 20 and 70 cm -1 observed in the kinetic traces are assigned to the axial and radial breathing modes, respectively. The electron localization is ascribed to the structural distortion of Au37 in the excited state induced by the strong coherent vibrations. The electron localization phenomenon we observed provides unique physical insight into one-dimensional gold nanoclusters and other nanostructures, which will advance their applications in solar-energy storage and conversion.« less

Electron localization in rod-shaped triicosahedral gold nanocluster

DOE PAGES

Zhou, Meng; Jin, Renxi; Sfeir, Matthew Y.; ...

2017-05-30

Atomically precise gold nanocluster based on linear assembly of repeating icosahedrons (clusters of clusters) is a unique type of linear nanostructure, which exhibits strong near-infrared absorption as their free electrons are confined in a one-dimensional quantum box. There is little known about the carrier dynamics in these nanoclusters, which limit their energy-related applications. We reported the observation of exciton localization in triicosahedral Au37 nanoclusters (0.5 nm in diameter and 1.6 nm in length) by measuring femtosecond and nanosecond carrier dynamics. Upon photoexcitation to S1 electronic state, electrons in Au37 undergo ~100-ps localization from the two vertexes of three icosahedrons tomore » one vertex, forming a long-lived S1* state. Such phenomenon is not observed in Au25 (dimer) and Au13 (monomer) consisting of two and one icosahedrons, respectively. We have further observed temperature dependence on the localization process, which proves it is thermally driven. Two excited-state vibration modes with frequencies of 20 and 70 cm -1 observed in the kinetic traces are assigned to the axial and radial breathing modes, respectively. The electron localization is ascribed to the structural distortion of Au37 in the excited state induced by the strong coherent vibrations. The electron localization phenomenon we observed provides unique physical insight into one-dimensional gold nanoclusters and other nanostructures, which will advance their applications in solar-energy storage and conversion.« less

Focusing the view on nature's water-splitting catalyst.

PubMed

Zein, Samir; Kulik, Leonid V; Yano, Junko; Kern, Jan; Pushkar, Yulia; Zouni, Athina; Yachandra, Vittal K; Lubitz, Wolfgang; Neese, Frank; Messinger, Johannes

2008-03-27

Nature invented a catalyst about 3Gyr ago, which splits water with high efficiency into molecular oxygen and hydrogen equivalents (protons and electrons). This reaction is energetically driven by sunlight and the active centre contains relatively cheap and abundant metals: manganese and calcium. This biological system therefore forms the paradigm for all man-made attempts for direct solar fuel production, and several studies are underway to determine the electronic and geometric structures of this catalyst. In this report we briefly summarize the problems and the current status of these efforts and propose a density functional theory-based strategy for obtaining a reliable high-resolution structure of this unique catalyst that includes both the inorganic core and the first ligand sphere.

Focusing the view on nature's water-splitting catalyst

PubMed Central

Zein, Samir; Kulik, Leonid V; Yano, Junko; Kern, Jan; Pushkar, Yulia; Zouni, Athina; Yachandra, Vittal K; Lubitz, Wolfgang; Neese, Frank; Messinger, Johannes

2007-01-01

Nature invented a catalyst about 3 Gyr ago, which splits water with high efficiency into molecular oxygen and hydrogen equivalents (protons and electrons). This reaction is energetically driven by sunlight and the active centre contains relatively cheap and abundant metals: manganese and calcium. This biological system therefore forms the paradigm for all man-made attempts for direct solar fuel production, and several studies are underway to determine the electronic and geometric structures of this catalyst. In this report we briefly summarize the problems and the current status of these efforts and propose a density functional theory-based strategy for obtaining a reliable high-resolution structure of this unique catalyst that includes both the inorganic core and the first ligand sphere. PMID:17989003

Topological RPdBi half-Heusler semimetals: A new family of noncentrosymmetric magnetic superconductors.

PubMed

Nakajima, Yasuyuki; Hu, Rongwei; Kirshenbaum, Kevin; Hughes, Alex; Syers, Paul; Wang, Xiangfeng; Wang, Kefeng; Wang, Renxiong; Saha, Shanta R; Pratt, Daniel; Lynn, Jeffrey W; Paglione, Johnpierre

2015-06-01

We report superconductivity and magnetism in a new family of topological semimetals, the ternary half-Heusler compound RPdBi (R: rare earth). In this series, tuning of the rare earth f-electron component allows for simultaneous control of both lattice density via lanthanide contraction and the strength of magnetic interaction via de Gennes scaling, allowing for a unique tuning of the normal-state band inversion strength, superconducting pairing, and magnetically ordered ground states. Antiferromagnetism with ordering vector (½,½,½) occurs below a Néel temperature that scales with de Gennes factor dG, whereas a superconducting transition is simultaneously supressed with increasing dG. With superconductivity appearing in a system with noncentrosymmetric crystallographic symmetry, the possibility of spin-triplet Cooper pairing with nontrivial topology analogous to that predicted for the normal-state electronic structure provides a unique and rich opportunity to realize both predicted and new exotic excitations in topological materials.

The structure of PccH from Geobactersulfurreducens-a novel low reduction potential monoheme cytochrome essential for accepting electrons from an electrode

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

Dantas, Joana; Campelo, Luisa M.; Duke, Norma E. C.

The structure of cytochrome c (GSU3274) designated as PccH from Geobactersulfurreducens was determined at a resolution of 2.0 angstrom. PccH is a small (15kDa) cytochrome containing one c-type heme, found to be essential for the growth of G.sulfurreducens with respect to accepting electrons from graphite electrodes poised at -300mV versus standard hydrogen electrode. with fumarate as the terminal electron acceptor. The structure of PccH is unique among the monoheme cytochromes described to date. The structural fold of PccH can be described as forming two lobes with the heme sandwiched in a cleft between the two lobes. In addition, PccH hasmore » a low reduction potential of -24mV at pH7, which is unusual for monoheme cytochromes. Based on difference in structure, together with sequence phylogenetic analysis, we propose that PccH can be regarded as a first characterized example of a new subclass of class I monoheme cytochromes. The low reduction potential of PccH may enable the protein to be redox active at the typically negative potential ranges encountered by G. sulfurreducens. Because PccH is predicted to be located in the periplasm of this bacterium, it could not be involved in the first step of accepting electrons from the electrode but is very likely involved in the downstream electron transport events in the periplasm.« less

The structure of PccH from Geobacter sulfurreducens  - a novel low reduction potential monoheme cytochrome essential for accepting electrons from an electrode

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

Dantas, Joana M.; Campelo, Luísa M.; Duke, Norma E. C.

2015-04-10

The structure of cytochrome-c (GSU3274) designated as PccH from Geobacter sulfurreducens was determined at 2.0 Å resolution. PccH is a small (15 kDa) cytochrome containing one c-type heme, found to be essential for growth of G. sulfurreducens accepting electrons from graphite electrodes poised at -300 mV versus SHE with fumarate as the terminal electron acceptor. The structure of PccH is unique among the monoheme cytochromes described to date. The structural fold of PccH can be described as forming two lobes with the heme sandwiched in a cleft between the two lobes. In addition, PccH has a low reduction potential ofmore » -24 mV at pH 7, which is unusual for monoheme cytochromes. Based on difference in structure together with sequence phylogenetic analysis we propose that PccH can be regarded as a first characterized example of a new subclass of class I monoheme cytochromes. The low reduction potential of PccH may enable the protein to be redox active at the typically negative potential ranges encountered by this bacterium. Because PccH is predicted to be located in the periplasm of G. sulfurreducens, it could not be involved in the first step of accepting electrons from the electrode but very likely involved in the downstream electron transport events in the periplasm.« less

Electronic structure of the unique [4Fe-3S] cluster in O2-tolerant hydrogenases characterized by 57Fe Mössbauer and EPR spectroscopy

PubMed Central

Pandelia, Maria-Eirini; Bykov, Dmytro; Izsak, Robert; Infossi, Pascale; Giudici-Orticoni, Marie-Thérèse; Bill, Eckhard; Neese, Frank; Lubitz, Wolfgang

2013-01-01

Iron–sulfur clusters are ubiquitous electron transfer cofactors in hydrogenases. Their types and redox properties are important for H2 catalysis, but, recently, their role in a protection mechanism against oxidative inactivation has also been recognized for a [4Fe-3S] cluster in O2-tolerant group 1 [NiFe] hydrogenases. This cluster, which is uniquely coordinated by six cysteines, is situated in the proximity of the catalytic [NiFe] site and exhibits unusual redox versatility. The [4Fe-3S] cluster in hydrogenase (Hase) I from Aquifex aeolicus performs two redox transitions within a very small potential range, forming a superoxidized state above +200 mV vs. standard hydrogen electrode (SHE). Crystallographic data has revealed that this state is stabilized by the coordination of one of the iron atoms to a backbone nitrogen. Thus, the proximal [4Fe-3S] cluster undergoes redox-dependent changes to serve multiple purposes beyond classical electron transfer. In this paper, we present field-dependent 57Fe-Mössbauer and EPR data for Hase I, which, in conjunction with spectroscopically calibrated density functional theory (DFT) calculations, reveal the distribution of Fe valences and spin-coupling schemes for the iron–sulfur clusters. The data demonstrate that the electronic structure of the [4Fe-3S] core in its three oxidation states closely resembles that of corresponding conventional [4Fe-4S] cubanes, albeit with distinct differences for some individual iron sites. The medial and distal iron–sulfur clusters have similar electronic properties as the corresponding cofactors in standard hydrogenases, although their redox potentials are higher. PMID:23267108

Redox-dependent complex formation by an ATP-dependent activator of the corrinoid/iron-sulfur protein

PubMed Central

Hennig, Sandra E.; Jeoung, Jae-Hun; Goetzl, Sebastian; Dobbek, Holger

2012-01-01

Movement, cell division, protein biosynthesis, electron transfer against an electrochemical gradient, and many more processes depend on energy conversions coupled to the hydrolysis of ATP. The reduction of metal sites with low reduction potentials (E0′ < -500 mV) is possible by connecting an energetical uphill electron transfer with the hydrolysis of ATP. The corrinoid-iron/sulfur protein (CoFeSP) operates within the reductive acetyl-CoA pathway by transferring a methyl group from methyltetrahydrofolate bound to a methyltransferase to the [Ni-Ni-Fe4S4] cluster of acetyl-CoA synthase. Methylation of CoFeSP only occurs in the low-potential Co(I) state, which can be sporadically oxidized to the inactive Co(II) state, making its reductive reactivation necessary. Here we show that an open-reading frame proximal to the structural genes of CoFeSP encodes an ATP-dependent reductive activator of CoFeSP. Our biochemical and structural analysis uncovers a unique type of reductive activator distinct from the electron-transferring ATPases found to reduce the MoFe-nitrogenase and 2-hydroxyacyl-CoA dehydratases. The CoFeSP activator contains an ASKHA domain (acetate and sugar kinases, Hsp70, and actin) harboring the ATP-binding site, which is also present in the activator of 2-hydroxyacyl-CoA dehydratases and a ferredoxin-like [2Fe-2S] cluster domain acting as electron donor. Complex formation between CoFeSP and its activator depends on the oxidation state of CoFeSP, which provides evidence for a unique strategy to achieve unidirectional electron transfer between two redox proteins. PMID:22431597

Electronic structure description of the cis-MoOS unit in models for molybdenum hydroxylases.

PubMed

Doonan, Christian J; Rubie, Nick D; Peariso, Katrina; Harris, Hugh H; Knottenbelt, Sushilla Z; George, Graham N; Young, Charles G; Kirk, Martin L

2008-01-09

The molybdenum hydroxylases catalyze the oxidation of numerous aromatic heterocycles and simple organics and, unlike other hydroxylases, utilize water as the source of oxygen incorporated into the product. The electronic structures of the cis-MoOS units in CoCp2[TpiPrMoVOS(OPh)] and TpiPrMoVIOS(OPh) (TpiPr = hydrotris(3-isopropylpyrazol-1-yl)borate), new models for molybdenum hydroxylases, have been studied in detail using S K-edge X-ray absorption spectroscopy, vibrational spectroscopy, and detailed bonding calculations. The results show a highly delocalized Mo=S pi* LUMO redox orbital that is formally Mo(dxy) with approximately 35% sulfido ligand character. Vibrational spectroscopy has been used to quantitate Mo-Ssulfido bond order changes in the cis-MoOS units as a function of redox state. Results support a redox active molecular orbital that has a profound influence on MoOS bonding through changes to the relative electro/nucleophilicity of the terminal sulfido ligand accompanying oxidation state changes. The bonding description for these model cis-MoOS systems supports enzyme mechanisms that are under orbital control and dominantly influenced by the unique electronic structure of the cis-MoOS site. The electronic structure of the oxidized enzyme site is postulated to play a role in polarizing a substrate carbon center for nucleophilic attack by metal activated water and acting as an electron sink in the two-electron oxidation of substrates.

Novel electric double-layer capacitor with a coaxial fiber structure.

PubMed

Chen, Xuli; Qiu, Longbin; Ren, Jing; Guan, Guozhen; Lin, Huijuan; Zhang, Zhitao; Chen, Peining; Wang, Yonggang; Peng, Huisheng

2013-11-26

A coaxial electric double-layer capacitor fiber is developed from the aligned carbon nanotube fiber and sheet, which functions as two electrodes with a polymer gel sandwiched between them. The unique coaxial structure enables a rapid transportation of ions between the two electrodes with a high electrochemical performance. These energy storage fibers are also flexible and stretchable, and can be woven into and widely used for electronic textiles. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Antropov, Vladimir P; Antonov, Victor N

We present a first-principles investigation of the electronic structure and physical properties of doped lithium nitridometalates Li 2(Li 1-xM x)N (LiMN) with M = Cr, Mn, Fe, Co, and Ni. The diverse properties include the equilibrium magnetic moments, magneto-crystalline anisotropy, magneto-optical Kerr spectra, and x-ray magnetic circular dichroism. We explain the colossal magnetic anisotropy in LiFeN by its unique electronic structure which ultimately leads to a series of unusual physical properties. The most unique property is a complete suppression of relativistic effects and freezing of orbital moments for in-plane orientation of the magnetization. This leads to the colossal spatial anisotropymore » of many magnetic properties including energy, Kerr, and dichroism effects. LiFeN is identified as an ultimate single-ion anisotropy system where a nearly insulating state can be produced by a spin orbital coupling alone. A very nontrivial strongly fluctuating and sign changing character of the magnetic anisotropy with electronic 3d-atomic doping is predicted theoretically. A large and highly anisotropic Kerr effect due to the interband transitions between atomic-like Fe 3d bands is found for LiFeN. A giant anisotropy of the x-ray magnetic circular dichroism for the Fe K spectrum and a very weak one for the Fe L 2,3 spectra in LiFeN are also predicted.« less

Reusable glucose sensing using carbon nanotube-based self-assembly

NASA Astrophysics Data System (ADS)

Bhattacharyya, Tamoghna; Samaddar, Sarbani; Dasgupta, Anjan Kr.

2013-09-01

Lipid functionalized single walled carbon nanotube-based self assembly forms a super-micellar structure. This assemblage has been exploited to trap glucose oxidase in a molecular cargo for glucose sensing. The advantage of such a molecular trap is that all components of this unique structure (both the trapping shell and the entrapped enzyme) are reusable and rechargeable. The unique feature of this sensing method lies in the solid state functionalization of single walled carbon nanotubes that facilitates liquid state immobilization of the enzyme. The method can be used for soft-immobilization (a new paradigm in enzyme immobilization) of enzymes with better thermostability that is imparted by the strong hydrophobic environment provided through encapsulation by the nanotubes.Lipid functionalized single walled carbon nanotube-based self assembly forms a super-micellar structure. This assemblage has been exploited to trap glucose oxidase in a molecular cargo for glucose sensing. The advantage of such a molecular trap is that all components of this unique structure (both the trapping shell and the entrapped enzyme) are reusable and rechargeable. The unique feature of this sensing method lies in the solid state functionalization of single walled carbon nanotubes that facilitates liquid state immobilization of the enzyme. The method can be used for soft-immobilization (a new paradigm in enzyme immobilization) of enzymes with better thermostability that is imparted by the strong hydrophobic environment provided through encapsulation by the nanotubes. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr02609d

Ultrafast Structural Dynamics in Combustion Relevant Model Systems

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

Weber, Peter M.

2014-03-31

The research project explored the time resolved structural dynamics of important model reaction system using an array of novel methods that were developed specifically for this purpose. They include time resolved electron diffraction, time resolved relativistic electron diffraction, and time resolved Rydberg fingerprint spectroscopy. Toward the end of the funding period, we also developed time-resolved x-ray diffraction, which uses ultrafast x-ray pulses at LCLS. Those experiments are just now blossoming, as the funding period expired. In the following, the time resolved Rydberg Fingerprint Spectroscopy is discussed in some detail, as it has been a very productive method. The binding energymore » of an electron in a Rydberg state, that is, the energy difference between the Rydberg level and the ground state of the molecular ion, has been found to be a uniquely powerful tool to characterize the molecular structure. To rationalize the structure sensitivity we invoke a picture from electron diffraction: when it passes the molecular ion core, the Rydberg electron experiences a phase shift compared to an electron in a hydrogen atom. This phase shift requires an adjustment of the binding energy of the electron, which is measurable. As in electron diffraction, the phase shift depends on the molecular, geometrical structure, so that a measurement of the electron binding energy can be interpreted as a measurement of the molecule’s structure. Building on this insight, we have developed a structurally sensitive spectroscopy: the molecule is first elevated to the Rydberg state, and the binding energy is then measured using photoelectron spectroscopy. The molecule’s structure is read out as the binding energy spectrum. Since the photoionization can be done with ultrafast laser pulses, the technique is inherently capable of a time resolution in the femtosecond regime. For the purpose of identifying the structures of molecules during chemical reactions, and for the analysis of molecular species in the hot environments of combustion processes, there are several features that make the Rydberg ionization spectroscopy uniquely useful. First, the Rydberg electron’s orbit is quite large and covers the entire molecule for most molecular structures of combustion interest. Secondly, the ionization does not change vibrational quantum numbers, so that even complicated and large molecules can be observed with fairly well resolved spectra. In fact, the spectroscopy is blind to vibrational excitation of the molecule. This has the interesting consequence for the study of chemical dynamics, where the molecules are invariably very energetic, that the molecular structures are observed unobstructed by the vibrational congestion that dominates other spectroscopies. This implies also that, as a tool to probe the time-dependent structural dynamics of chemically interesting molecules, Rydberg spectroscopy may well be better suited than electron or x-ray diffraction. With recent progress in calculating Rydberg binding energy spectra, we are approaching the point where the method can be evolved into a structure determination method. To implement the Rydberg ionization spectroscopy we use a molecular beam based, time-resolved pump-probe multi-photon ionization/photoelectron scheme in which a first laser pulse excites the molecule to a Rydberg state, and a probe pulse ionizes the molecule. A time-of-flight detector measures the kinetic energy spectrum of the photoelectrons. The photoelectron spectrum directly provides the binding energy of the electron, and thereby reveals the molecule’s time-dependent structural fingerprint. Only the duration of the laser pulses limits the time resolution. With a new laser system, we have now reached time resolutions better than 100 fs, although very deep UV wavelengths (down to 190 nm) have slightly longer instrument functions. The structural dynamics of molecules in Rydberg-excited states is obtained by delaying the probe ionization photon from the pump photon; the structural dynamics of molecules in their ground state or excited valence states is measured by inducing the dynamics using a near UV laser pulse, and employing a multi-photon ionization scheme via the Rydberg states as a probe process. Thus, the technique is capable of measuring the reaction dynamics in any electronic state of neutral molecules.« less

Structural phase transitions and time-resolved dynamics of solid-supported interfacial methanol observed by reflection electron diffraction

NASA Astrophysics Data System (ADS)

Yang, Ding-Shyue; He, Xing; Wu, Chengyi

Due to their large scattering cross sections with matter, electrons are suitable for contactless probing of solid-supported surface assemblies, especially in a reflection geometry. Direct visualization of assembly structures through electron diffraction further enables studies of ultrafast structural dynamics through the pump-probe scheme as well as discoveries of hidden phase changes in equilibrium that have been obscure in spectroscopic measurements. In this presentation, we report our first observation of unique two-stage transformations of interfacial methanol on smooth hydrophobic surfaces. The finding may reconcile the inconsistent previous reports of the crystallization temperature using various indirect methods. Dynamically, energy transfer across a solid-molecule interface following photoexcitation of the substrate is found to be highly dependent on the structure of interfacial methanol. If it is only 2-dimensionally ordered, as the film thickness increases, a prolonged time in the decrease of diffraction intensity is seen, signifying an inefficient vibrational coupling in the surface normal direction. Implications of the dynamics results and an outlook of interfacial studies using time-resolved and averaged electron diffraction will be discussed. We gratefully acknowledge the support from the R. A. Welch Foundation (Grant No. E-1860), the Donors of the American Chemical Society Petroleum Research Fund (ACS-PRF), and the University of Houston.

Anterior lens epithelium in intumescent white cataracts - scanning and transmission electron microscopy study.

PubMed

Andjelic, Sofija; Drašlar, Kazimir; Hvala, Anastazija; Hawlina, Marko

2016-02-01

Our purpose was to study the structure of the lens epithelial cells (LECs) of intumescent white cataracts (IC) in comparison with nuclear cataracts (NC) in order to investigate possible structural reasons for development of IC. The anterior lens capsule (aLC: basement membrane and associated LECs) were obtained from cataract surgery and prepared for scanning electron microscopy (SEM) and transmission electron microscopy (TEM). We observed by SEM that in IC, LEC swelling was pronounced with the clefts surrounding the groups of LECs. Another structural feature was spherical formations, that were observed on the apical side of LEC's, towards the fibre cell layer, both by SEM and TEM. Development of these structures, bulging out from the apical cell membrane of the LEC's and disrupting it, could be followed in steps towards the sphere formation. The degeneration of the lens epithelium and the structures of the aLC in IC similar to Morgagnian globules were also observed. None of these structural changes were observed in NC. We show by SEM and TEM that, in IC, LECs have pronounced structural features not observed in NC. This supports the hypothesis that the disturbed structure of LECs plays a role in water accumulation in the IC lens. We also suggest that, in IC, LECs produce bulging spheres that represent unique structures of degenerated material, extruded from the LEC.

A unique iron-sulfur cluster is crucial for oxygen tolerance of a [NiFe]-hydrogenase.

PubMed

Goris, Tobias; Wait, Annemarie F; Saggu, Miguel; Fritsch, Johannes; Heidary, Nina; Stein, Matthias; Zebger, Ingo; Lendzian, Friedhelm; Armstrong, Fraser A; Friedrich, Bärbel; Lenz, Oliver

2011-05-01

Hydrogenases are essential for H(2) cycling in microbial metabolism and serve as valuable blueprints for H(2)-based biotechnological applications. However, most hydrogenases are extremely oxygen sensitive and prone to inactivation by even traces of O(2). The O(2)-tolerant membrane-bound [NiFe]-hydrogenase of Ralstonia eutropha H16 is one of the few examples that can perform H(2) uptake in the presence of ambient O(2). Here we show that O(2) tolerance is crucially related to a modification of the internal electron-transfer chain. The iron-sulfur cluster proximal to the active site is surrounded by six instead of four conserved coordinating cysteines. Removal of the two additional cysteines alters the electronic structure of the proximal iron-sulfur cluster and renders the catalytic activity sensitive to O(2) as shown by physiological, biochemical, spectroscopic and electrochemical studies. The data indicate that the mechanism of O(2) tolerance relies on the reductive removal of oxygenic species guided by the unique architecture of the electron relay rather than a restricted access of O(2) to the active site.

Electronic and phononic modulation of MoS2 under biaxial strain

NASA Astrophysics Data System (ADS)

Moghadasi, A.; Roknabadi, M. R.; Ghorbani, S. R.; Modarresi, M.

2017-12-01

Dichalcogenides of transition metals are attractive material due to its unique properties. In this work, it has been investigated the electronic band structure, phonon spectrum and heat capacity of MoS2 under the applied tensile and compressive biaxial strain using the density functional theory. The Molybdenum disulfide under compressive (tensile) strain up to 6% (10%) has stable atomic structure without any negative frequency in the phonon dispersion curves. The tensile biaxial strain reduces the energy gap in the electronic band structure and the optical-acoustic gap in phonon dispersion curves. The tensile biaxial strain also increases the specific heat capacity. On the other hand, the compressive biaxial strain in this material increases phonon gap and reduces the heat capacity and the electronic band gap. The phonon softening/hardening is reported for tensile/compressive biaxial strain in MoS2. We report phonon hardening for out of plane ZA mode in the presence of both tensile and compressive strains. Results show that the linear variation of specific heat with strain (CV ∝ε) and square dependency of specific heat with the temperature (CV ∝T2) for low temperature regime. The results demonstrate that the applied biaxial strain tunes the electronic energy gap and modifies the phonon spectrum of MoS2.

Low energy electron catalyst: the electronic origin of catalytic strategies.

PubMed

Davis, Daly; Sajeev, Y

2016-10-12

Using a low energy electron (LEE) as a catalyst, the electronic origin of the catalytic strategies corresponding to substrate selectivity, reaction specificity and reaction rate enhancement is investigated for a reversible unimolecular elementary reaction. An electronic energy complementarity between the catalyst and the substrate molecule is the origin of substrate selectivity and reaction specificity. The electronic energy complementarity is induced by tuning the electronic energy of the catalyst. The energy complementarity maximizes the binding forces between the catalyst and the molecule. Consequently, a new electronically metastable high-energy reactant state and a corresponding new low barrier reaction path are resonantly created for a specific reaction of the substrate through the formation of a catalyst-substrate transient adduct. The LEE catalysis also reveals a fundamental structure-energy correspondence in the formation of the catalyst-substrate transient adduct. Since the energy complementarities corresponding to the substrate molecules of the forward and the backward steps of the reversible reactions are not the same due to their structural differences, the LEE catalyst exhibits a unique one-way catalytic strategy, i.e., the LEE catalyst favors the reversible reaction more effectively in one direction. A characteristic stronger binding of the catalyst to the transition state of the reaction than in the initial reactant state and the final product state is the molecular origin of barrier lowering.

Intense Current Structures Observed at Electron Kinetic Scales in the Near-Earth Magnetotail During Dipolarization and Substorm Current Wedge Formation

NASA Astrophysics Data System (ADS)

Grigorenko, E. E.; Dubyagin, S.; Malykhin, A. Yu.; Khotyaintsev, Yu V.; Kronberg, E. A.; Lavraud, B.; Ganushkina, N. Yu

2018-01-01

We use data from the 2013-2014 Cluster Inner Magnetosphere Campaign, with its uniquely small spacecraft separations (less than or equal to electron inertia length, λe), to study multiscale magnetic structures in 14 substorm-related prolonged dipolarizations in the near-Earth magnetotail. Three time scales of dipolarization are identified: (i) a prolonged growth of the BZ component with duration ≤20 min; (ii) BZ pulses with durations ≤1 min during the BZ growth; and (iii) strong magnetic field gradients with durations ≤2 s during the dipolarization growth. The values of these gradients observed at electron scales are several dozen times larger than the corresponding values of magnetic gradients simultaneously detected at ion scales. These nonlinear features in magnetic field gradients denote the formation of intense and localized (approximately a few λe) current structures during the dipolarization and substorm current wedge formation. These observations highlight the importance of electron scale processes in the formation of a 3-D substorm current system.

Theoretical study of dynamic electron-spin-polarization via the doublet-quartet quantum-mixed state and time-resolved ESR spectra of the quartet high-spin state.

PubMed

Teki, Yoshio; Matsumoto, Takafumi

2011-04-07

The mechanism of the unique dynamic electron polarization of the quartet (S = 3/2) high-spin state via a doublet-quartet quantum-mixed state and detail theoretical calculations of the population transfer are reported. By the photo-induced electron transfer, the quantum-mixed charge-separate state is generated in acceptor-donor-radical triad (A-D-R). This mechanism explains well the unique dynamic electron polarization of the quartet state of A-D-R. The generation of the selectively populated quantum-mixed state and its transfer to the strongly coupled pure quartet and doublet states have been treated both by a perturbation approach and by exact numerical calculations. The analytical solutions show that generation of the quantum-mixed states with the selective populations after de-coherence and/or accompanying the (complete) dephasing during the charge-recombination are essential for the unique dynamic electron polarization. Thus, the elimination of the quantum coherence (loss of the quantum information) is the key process for the population transfer from the quantum-mixed state to the quartet state. The generation of high-field polarization on the strongly coupled quartet state by the charge-recombination process can be explained by a polarization transfer from the quantum-mixed charge-separate state. Typical time-resolved ESR patterns of the quantum-mixed state and of the strongly coupled quartet state are simulated based on the generation mechanism of the dynamic electron polarization. The dependence of the spectral pattern of the quartet high-spin state has been clarified for the fine-structure tensor and the exchange interaction of the quantum-mixed state. The spectral pattern of the quartet state is not sensitive towards the fine-structure tensor of the quantum-mixed state, because this tensor contributes only as a perturbation in the population transfer to the spin-sublevels of the quartet state. Based on the stochastic Liouville equation, it is also discussed why the selective population in the quantum-mixed state is generated for the "finite field" spin-sublevels. The numerical calculations of the elimination of the quantum coherence (de-coherence and/or dephasing) are demonstrated. A new possibility of the enhanced intersystem crossing pathway in solution is also proposed.

Low-dose patterning of platinum nanoclusters on carbon nanotubes by focused-electron-beam-induced deposition as studied by TEM

PubMed Central

Bittencourt, Carla; Bals, Sara; Van Tendeloo, Gustaaf

2013-01-01

Summary Focused-electron-beam-induced deposition (FEBID) is used as a direct-write approach to decorate ultrasmall Pt nanoclusters on carbon nanotubes at selected sites in a straightforward maskless manner. The as-deposited nanostructures are studied by transmission electron microscopy (TEM) in 2D and 3D, demonstrating that the Pt nanoclusters are well-dispersed, covering the selected areas of the CNT surface completely. The ability of FEBID to graft nanoclusters on multiple sides, through an electron-transparent target within one step, is unique as a physical deposition method. Using high-resolution TEM we have shown that the CNT structure can be well preserved thanks to the low dose used in FEBID. By tuning the electron-beam parameters, the density and distribution of the nanoclusters can be controlled. The purity of as-deposited nanoclusters can be improved by low-energy electron irradiation at room temperature. PMID:23399584

Attosecond electron bunches from a nanofiber driven by Laguerre-Gaussian laser pulses.

PubMed

Hu, Li-Xiang; Yu, Tong-Pu; Sheng, Zheng-Ming; Vieira, Jorge; Zou, De-Bin; Yin, Yan; McKenna, Paul; Shao, Fu-Qiu

2018-05-08

Generation of attosecond bunches of energetic electrons offers significant potential from ultrafast physics to novel radiation sources. However, it is still a great challenge to stably produce such electron beams with lasers, since the typical subfemtosecond electron bunches from laser-plasma interactions either carry low beam charge, or propagate for only several tens of femtoseconds. Here we propose an all-optical scheme for generating dense attosecond electron bunches via the interaction of an intense Laguerre-Gaussian (LG) laser pulse with a nanofiber. The dense bunch train results from the unique field structure of a circularly polarized LG laser pulse, enabling each bunch to be phase-locked and accelerated forward with low divergence, high beam charge and large beam-angular-momentum. This paves the way for wide applications in various fields, e.g., ultrabrilliant attosecond x/γ-ray emission.

Policy and system strategies in promoting child health information systems, including the role of Medicaid, the state children's health insurance program, and public financing.

PubMed

MacTaggart, Patricia; Bagley, Bruce

2009-01-01

Government, through its unique roles as regulator, purchaser, provider, and facilitator, has an opportunity and an obligation to play a major role in accelerating the implementation of electronic health record systems and electronic health information exchange. Providers, who are expected to deliver appropriate care at designated locations at an appropriate cost, are dependent on health information technology for efficient effective health care. As state and federal governments move forward with health care purchasing reforms, they must take the opportunity to leverage policy and structure and to align incentives that enhance the potential for provider engagement in electronic health record adoption.

Protein crystal screening and characterization for serial femtosecond nanocrystallography

PubMed Central

Darmanin, Connie; Strachan, Jamie; Adda, Christopher G.; Ve, Thomas; Kobe, Bostjan; Abbey, Brian

2016-01-01

The recent development of X-ray free electron lasers (XFELs) has spurred the development of serial femtosecond nanocrystallography (SFX) which, for the first time, is enabling structure retrieval from sub-micron protein crystals. Although there are already a growing number of structures published using SFX, the technology is still very new and presents a number of unique challenges as well as opportunities for structural biologists. One of the biggest barriers to the success of SFX experiments is the preparation and selection of suitable protein crystal samples. Here we outline a protocol for preparing and screening for suitable XFEL targets. PMID:27139248

Dioxygen Binding, Activation, and Reduction to H2O by Cu Enzymes.

PubMed

Solomon, Edward I

2016-07-05

Oxygen intermediates in copper enzymes exhibit unique spectroscopic features that reflect novel geometric and electronic structures that are key to reactivity. This perspective will describe: (1) the bonding origin of the unique spectroscopic features of the coupled binuclear copper enzymes and how this overcomes the spin forbiddenness of O2 binding and activates monooxygenase activity, (2) how the difference in exchange coupling in the non-coupled binuclear Cu enzymes controls the reaction mechanism, and (3) how the trinuclear Cu cluster present in the multicopper oxidases leads to a major structure/function difference in enabling the irreversible reductive cleavage of the O-O bond with little overpotential and generating a fully oxidized intermediate, different from the resting enzyme studied by crystallography, that is key in enabling fast PCET in the reductive half of the catalytic cycle.

Spin-polarized surface resonances accompanying topological surface state formation

PubMed Central

Jozwiak, Chris; Sobota, Jonathan A.; Gotlieb, Kenneth; Kemper, Alexander F.; Rotundu, Costel R.; Birgeneau, Robert J.; Hussain, Zahid; Lee, Dung-Hai; Shen, Zhi-Xun; Lanzara, Alessandra

2016-01-01

Topological insulators host spin-polarized surface states born out of the energetic inversion of bulk bands driven by the spin-orbit interaction. Here we discover previously unidentified consequences of band-inversion on the surface electronic structure of the topological insulator Bi2Se3. By performing simultaneous spin, time, and angle-resolved photoemission spectroscopy, we map the spin-polarized unoccupied electronic structure and identify a surface resonance which is distinct from the topological surface state, yet shares a similar spin-orbital texture with opposite orientation. Its momentum dependence and spin texture imply an intimate connection with the topological surface state. Calculations show these two distinct states can emerge from trivial Rashba-like states that change topology through the spin-orbit-induced band inversion. This work thus provides a compelling view of the coevolution of surface states through a topological phase transition, enabled by the unique capability of directly measuring the spin-polarized unoccupied band structure. PMID:27739428

Synthesis and high catalytic properties of mesoporous Pt nanowire array by novel conjunct template method

NASA Astrophysics Data System (ADS)

Zhong, Yi; Xu, Cai-Ling; Kong, Ling-Bin; Li, Hu-Lin

2008-12-01

A novel conjunct template method for fabricating mesoporous Pt nanowire array through direct current (DC) electrodeposition of Pt into the pores of anodic aluminum oxide (AAO) template on Ti/Si substrate from hexagonal structured lyotropic liquid crystalline phase is demonstrated in this paper. The morphology and structure of as-prepared Pt nanowire array are characterized by field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD). The electrocatalytic properties of Pt nanowire array for methanol are also investigated in detail. The results indicate that Pt nanowire array has the unique mesoporous structure of approximate 40-50 nm in diameter, which resulted in the high surface area and greatly improved electrocatalytic activity for methanol. The mesoporous Pt nanowire array synthesized by the new conjunct template method has a very promising application in portable fuel cell power sources.

Electromers of the benzene dimer radical cation.

PubMed

Błoch-Mechkour, Anna; Bally, Thomas

2015-04-28

The well-studied benzene dimer radical cation, which is prototypical for this class of species, has been reinvestigated computationally. Thereby it turned out that both the σ-hemibonded and the half-shifted sandwich structures of the benzene dimer cation, which had been independently proposed, represent stationary points on the B2PLYP-D potential energy surfaces. However, these structures belong to distinct electronic states, both of which are associated with potential surfaces that are very flat with regard to rotation of the two benzene rings in an opposite sense relative to each other. The surfaces of these two "electromers" of the benzene dimer cation are separated by only 3-4 kcal mol(-1) and do not intersect along the rotation coordinate, which represents a rather unique electronic structure situation. When moving on either of the two surfaces the title complex is an extremely fluxional species, in spite of its being bound by over 20 kcal mol(-1).

Photoisomerization-induced manipulation of single-electron tunneling for novel Si-based optical memory.

PubMed

Hayakawa, Ryoma; Higashiguchi, Kenji; Matsuda, Kenji; Chikyow, Toyohiro; Wakayama, Yutaka

2013-11-13

We demonstrated optical manipulation of single-electron tunneling (SET) by photoisomerization of diarylethene molecules in a metal-insulator-semiconductor (MIS) structure. Stress is placed on the fact that device operation is realized in the practical device configuration of MIS structure and that it is not achieved in structures based on nanogap electrodes and scanning probe techniques. Namely, this is a basic memory device configuration that has the potential for large-scale integration. In our device, the threshold voltage of SET was clearly modulated as a reversible change in the molecular orbital induced by photoisomerization, indicating that diarylethene molecules worked as optically controllable quantum dots. These findings will allow the integration of photonic functionality into current Si-based memory devices, which is a unique feature of organic molecules that is unobtainable with inorganic materials. Our proposed device therefore has enormous potential for providing a breakthrough in Si technology.

First principles study on structural, lattice dynamical and thermal properties of BaCeO3

NASA Astrophysics Data System (ADS)

Zhang, Qingping; Ding, Jinwen; He, Min

2017-09-01

BaCeO3 exhibits impressive application potentials on solid oxide fuel cell electrolyte, hydrogen separation membrane and photocatalyst, owing to its unique ionic and electronic properties. In this article, the electronic structures, phonon spectra and thermal properties of BaCeO3 in orthorhombic, rhombohedral and cubic phases are investigated based on density functional theory. Comparisons with reported experimental results are also presented. The calculation shows that orthorhombic structure is both energetically and dynamically stable under ground state, which is supported by the experiment. Moreover, charge transfer between cations and anions accompanied with phase transition is observed, which is responsible for the softened phonon modes in rhombohedral and cubic phases. Besides, thermal properties are discussed. Oxygen atoms contribute most to the specific heat. The calculated entropy and specific heat at constant pressure fit well with the experimental ones within the measured temperature range.

Phase shift of oscillatory magnetoresistance in a double-cross thin film structure of La0.3Pr0.4Ca0.3MnO3 via strain-engineered elongation of electronic domains

NASA Astrophysics Data System (ADS)

Alagoz, H. S.; Prasad, B.; Jeon, J.; Blamire, M. G.; Chow, K. H.; Jung, J.

2018-02-01

The subtle balance between the competing electronic phases in manganites due to complex interplay between spin, charge, and orbital degrees of freedom could allow one to modify the properties of electronically phase separated systems. In this paper, we show that the phase shift in the oscillatory magnetoresistance ρ (θ ) can be modified by engineering strain driven elongation of electronic domains in La0.3Pr0.4Ca0.3MnO3 (LPCMO) thin films. Strain-driven elongation of magnetic domains can produce different percolation paths and hence different anisotropic magnetoresistance responses. This tunability provides a unique control that is unattainable in conventional 3 d ferromagnetic metals and alloys.

Structural analysis, electronic properties, and band gaps of a graphene nanoribbon: A new 2D materials

NASA Astrophysics Data System (ADS)

Dass, Devi

2018-03-01

Graphene nanoribbon (GNR), a new 2D carbon nanomaterial, has some unique features and special properties that offer a great potential for interconnect, nanoelectronic devices, optoelectronics, and nanophotonics. This paper reports the structural analysis, electronic properties, and band gaps of a GNR considering different chirality combinations obtained using the pz orbital tight binding model. In structural analysis, the analytical expressions for GNRs have been developed and verified using the simulation for the first time. It has been found that the total number of unit cells and carbon atoms within an overall unit cell and molecular structure of a GNR have been changed with the change in their chirality values which are similar to the values calculated using the developed analytical expressions thus validating both the simulation as well as analytical results. Further, the electronic band structures at different chirality values have been shown for the identification of metallic and semiconductor properties of a GNR. It has been concluded that all zigzag edge GNRs are metallic with very small band gaps range whereas all armchair GNRs show both the metallic and semiconductor nature with very small and high band gaps range. Again, the total number of subbands in each electronic band structure is equal to the total number of carbon atoms present in overall unit cell of the corresponding GNR. The semiconductors GNRs can be used as a channel material in field effect transistor suitable for advanced CMOS technology whereas the metallic GNRs could be used for interconnect.

Electronic Structure and Band Gap of Fullerenes on Tungsten Surfaces: Transition from a Semiconductor to a Metal Triggered by Annealing.

PubMed

Monazami, Ehsan; McClimon, John B; Rondinelli, James; Reinke, Petra

2016-12-21

The understanding and control of molecule-metal interfaces is critical to the performance of molecular electronics and photovoltaics devices. We present a study of the interface between C 60 and W, which is a carbide-forming transition metal. The complex solid-state reaction at the interface can be exploited to adjust the electronic properties of the molecule layer. Scanning tunneling microscopy/spectroscopy measurements demonstrate the progression of this reaction from wide band gap (>2.5 eV) to metallic molecular surface during annealing from 300 to 800 K. Differential conduction maps with 10 4 scanning tunneling spectra are used to quantify the transition in the density of states and the reduction of the band gap during annealing with nanometer spatial resolution. The electronic transition is spatially homogeneous, and the surface band gap can therefore be adjusted by a targeted annealing step. The modified molecules, which we call nanospheres, are quite resistant to ripening and coalescence, unlike any other metallic nanoparticle of the same size. Densely packed C 60 and isolated C 60 molecules show the same transition in electronic structure, which confirms that the transformation is controlled by the reaction at the C 60 -W interface. Density functional theory calculations are used to develop possible reaction pathways in agreement with experimentally observed electronic structure modulation. Control of the band gap by the choice of annealing temperature is a unique route to tailoring molecular-layer electronic properties.

Direct visualization of quasi-ordered oxygen chain structures on Au(110)-(1 × 2)

NASA Astrophysics Data System (ADS)

Hiebel, F.; Montemore, M. M.; Kaxiras, E.; Friend, C. M.

2016-08-01

The Au(110) surface offers unique advantages for atomically-resolved model studies of catalytic oxidation processes on gold. We investigate the adsorption of oxygen on Au(110) using a combination of scanning tunneling microscopy (STM) and density functional theory (DFT) methods. We identify the typical (empty-states) STM contrast resulting from adsorbed oxygen as atomic-sized dark features of electronic origin. DFT-based image simulations confirm that chemisorbed oxygen is generally detected indirectly, from the binding-induced electronic structure modification of gold. STM images show that adsorption occurs without affecting the general structure of the pristine Au(110) missing-row reconstruction. The tendency to form one-dimensional structures is observed already at low coverage (< 0.05 ML), with oxygen adsorbing on alternate sides of the reconstruction ridges. Consistently, calculations yield preferred adsorption on the (111) facets of the reconstruction, on a 3-fold coordination site, with increased stability when adsorbed in chains. Gold atoms with two oxygen neighbors exhibit enhanced electronic hybridization with the O states. Finally, the species observed are reactive to CO oxidation at 200 K and desorption of CO2 leaves a clean and ordered gold surface.

Thermal stability of MBE-grown epitaxial MoSe2 and WSe2 thin films

NASA Astrophysics Data System (ADS)

Chang, Young Jun; Choy, Byoung Ki; Phark, Soo-Hyon; Kim, Minu

Layered transition metal dichalcogenides (TMDs) draw much attention, because of its unique optical properties and band structures depending on the layer thicknesses. However, MBE growth of epitaxial films demands information about thermal stability of stoichiometry and related electronic structure for high temperature range. We grow epitaxial MoSe2 and WSe2 ultrathin films by using molecular beam epitaxy (MBE). We characterize stoichiometry of films grown at various growth temperature by using various methods, XPS, EDX, and TOF-MEIS. We further test high temperature stability of electronic structure for those films by utilizing in-situ ellipsometry attached to UHV chamber. We discuss threshold temperatures up to 700~1000oC, at which electronic phases changes from semiconductor to metal due to selenium deficiency. This information can be useful for potential application of TMDs for fabrication of Van der Waals multilayers and related devices. This research was supported by Nano.Material Technology Development Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT and Future Planning. (2009-0082580), NRF-2014R1A1A1002868.

Tuning the electronic properties of gated multilayer phosphorene: A self-consistent tight-binding study

NASA Astrophysics Data System (ADS)

Li, L. L.; Partoens, B.; Peeters, F. M.

2018-04-01

By taking account of the electric-field-induced charge screening, a self-consistent calculation within the framework of the tight-binding approach is employed to obtain the electronic band structure of gated multilayer phosphorene and the charge densities on the different phosphorene layers. We find charge density and screening anomalies in single-gated multilayer phosphorene and electron-hole bilayers in dual-gated multilayer phosphorene. Due to the unique puckered lattice structure, both intralayer and interlayer charge screenings are important in gated multilayer phosphorene. We find that the electric-field tuning of the band structure of multilayer phosphorene is distinctively different in the presence and absence of charge screening. For instance, it is shown that the unscreened band gap of multilayer phosphorene decreases dramatically with increasing electric-field strength. However, in the presence of charge screening, the magnitude of this band-gap decrease is significantly reduced and the reduction depends strongly on the number of phosphorene layers. Our theoretical results of the band-gap tuning are compared with recent experiments and good agreement is found.

Facile synthesis of 3D few-layered MoS2 coated TiO2 nanosheet core-shell nanostructures for stable and high-performance lithium-ion batteries

NASA Astrophysics Data System (ADS)

Chen, Biao; Zhao, Naiqin; Guo, Lichao; He, Fang; Shi, Chunsheng; He, Chunnian; Li, Jiajun; Liu, Enzuo

2015-07-01

Uniform transition metal sulfide deposition on a smooth TiO2 surface to form a coating structure is a well-known challenge, caused mainly due to their poor affinities. Herein, we report a facile strategy for fabricating mesoporous 3D few-layered (<4 layers) MoS2 coated TiO2 nanosheet core-shell nanocomposites (denoted as 3D FL-MoS2@TiO2) by a novel two-step method using a smooth TiO2 nanosheet as a template and glucose as a binder. The core-shell structure has been systematically examined and corroborated by transmission electron microscopy, scanning transmission electron microscopy, and X-ray photoelectron spectroscopy analyses. It is found that the resultant 3D FL-MoS2@TiO2 as a lithium-ion battery anode delivers an outstanding high-rate capability with an excellent cycling performance, relating to the unique structure of 3D FL-MoS2@TiO2. The 3D uniform coverage of few-layered (<4 layers) MoS2 onto the TiO2 can remarkably enhance the structure stability and effectively shortens the transfer paths of both lithium ions and electrons, while the strong synergistic effect between MoS2 and TiO2 can significantly facilitate the transport of ions and electrons across the interfaces, especially in the high-rate charge-discharge process. Moreover, the facile fabrication strategy can be easily extended to design other oxide/carbon-sulfide/oxide core-shell materials for extensive applications.Uniform transition metal sulfide deposition on a smooth TiO2 surface to form a coating structure is a well-known challenge, caused mainly due to their poor affinities. Herein, we report a facile strategy for fabricating mesoporous 3D few-layered (<4 layers) MoS2 coated TiO2 nanosheet core-shell nanocomposites (denoted as 3D FL-MoS2@TiO2) by a novel two-step method using a smooth TiO2 nanosheet as a template and glucose as a binder. The core-shell structure has been systematically examined and corroborated by transmission electron microscopy, scanning transmission electron microscopy, and X-ray photoelectron spectroscopy analyses. It is found that the resultant 3D FL-MoS2@TiO2 as a lithium-ion battery anode delivers an outstanding high-rate capability with an excellent cycling performance, relating to the unique structure of 3D FL-MoS2@TiO2. The 3D uniform coverage of few-layered (<4 layers) MoS2 onto the TiO2 can remarkably enhance the structure stability and effectively shortens the transfer paths of both lithium ions and electrons, while the strong synergistic effect between MoS2 and TiO2 can significantly facilitate the transport of ions and electrons across the interfaces, especially in the high-rate charge-discharge process. Moreover, the facile fabrication strategy can be easily extended to design other oxide/carbon-sulfide/oxide core-shell materials for extensive applications. Electronic supplementary information (ESI) available: Supplementary SEM, TEM, XPS and EIS analyses. See DOI: 10.1039/c5nr03334a

Bionic Nanosystems

NASA Astrophysics Data System (ADS)

Sebastian Mannoor, Manu

Direct multidimensional integration of functional electronics and mechanical elements with viable biological systems could allow for the creation of bionic systems and devices possessing unique and advanced capabilities. For example, the ability to three dimensionally integrate functional electronic and mechanical components with biological cells and tissue could enable the creation of bionic systems that can have tremendous impact in regenerative medicine, prosthetics, and human-machine interfaces. However, as a consequence of the inherent dichotomy in material properties and limitations of conventional fabrication methods, the attainment of truly seamless integration of electronic and/or mechanical components with biological systems has been challenging. Nanomaterials engineering offers a general route for overcoming these dichotomies, primarily due to the existence of a dimensional compatibility between fundamental biological functional units and abiotic nanomaterial building blocks. One area of compelling interest for bionic systems is in the field of biomedical sensing, where the direct interfacing of nanosensors onto biological tissue or the human body could stimulate exciting opportunities such as on-body health quality monitoring and adaptive threat detection. Further, interfacing of antimicrobial peptide based bioselective probes onto the bionic nanosensors could offer abilities to detect pathogenic bacteria with bio-inspired selectivity. Most compellingly, when paired with additive manufacturing techniques such as 3D printing, these characteristics enable three dimensional integration and merging of a variety of functional materials including electronic, structural and biomaterials with viable biological cells, in the precise anatomic geometries of human organs, to form three dimensionally integrated, multi-functional bionic hybrids and cyborg devices with unique capabilities. In this thesis, we illustrate these approaches using three representative bionic systems: 1) Bionic Nanosensors: featuring bio-integrated graphene nanosensors for ubiquitous sensing, 2) Bionic Organs: featuring 3D printed bionic ears with three dimensionally integrated electronics and 3) Bionic Leaves: describing ongoing work in the direction of the creation of a bionic leaf enabled by the integration of plant derived photosynthetic functional units with electronic materials and components into a leaf-shaped hierarchical structure for harvesting photosynthetic bioelectricity.

Electronic coupling through natural amino acids

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

Berstis, Laura; Beckham, Gregg T., E-mail: michael.crowley@nrel.gov, E-mail: gregg.beckham@nrel.gov; Crowley, Michael F., E-mail: michael.crowley@nrel.gov, E-mail: gregg.beckham@nrel.gov

2015-12-14

Myriad scientific domains concern themselves with biological electron transfer (ET) events that span across vast scales of rate and efficiency through a remarkably fine-tuned integration of amino acid (AA) sequences, electronic structure, dynamics, and environment interactions. Within this intricate scheme, many questions persist as to how proteins modulate electron-tunneling properties. To help elucidate these principles, we develop a model set of peptides representing the common α-helix and β-strand motifs including all natural AAs within implicit protein-environment solvation. Using an effective Hamiltonian strategy with density functional theory, we characterize the electronic coupling through these peptides, furthermore considering side-chain dynamics. For bothmore » motifs, predictions consistently show that backbone-mediated electronic coupling is distinctly sensitive to AA type (aliphatic, polar, aromatic, negatively charged and positively charged), and to side-chain orientation. The unique properties of these residues may be employed to design activated, deactivated, or switch-like superexchange pathways. Electronic structure calculations and Green’s function analyses indicate that localized shifts in the electron density along the peptide play a role in modulating these pathways, and further substantiate the experimentally observed behavior of proline residues as superbridges. The distinct sensitivities of tunneling pathways to sequence and conformation revealed in this electronic coupling database help improve our fundamental understanding of the broad diversity of ET reactivity and provide guiding principles for peptide design.« less

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

Sorokina, Veronika, E-mail: ansonika@mail.ru; Nikiforov, Konstantin, E-mail: knikiforov@cc.spbu.ru

Studying emission characteristics of nanotubes is extremely important for development of electronics. Compared to other electron sources nanotube-based field emitters allow obtaining significant emission currents at relatively low values of the applied field. It is possible due to their unique structure. This article is devoted to theoretical investigation how external electric field effects several samples of open single-wall nanotubes from carbon and silicon carbide. Total energies, dipole moments and band gaps for five types of nanotubes were calculated from the first principles. The numerical experiment results indicate the adequacy of modeling. It was concluded that considered configurations of achiral carbonmore » nanotubes should be semiconductors.« less

Helium Ion Secondary Electron Mode Microscopy For Interconnect Material Imaging

NASA Astrophysics Data System (ADS)

Ogawa, Shinichi; Thompson, William; Stern, Lewis; Scipioni, Larry; Notte, John; Farkas, Lou; Barriss, Louise

2010-04-01

The recently developed helium ion microscope (HIM) is now capable of 0.35 nm secondary electron (SE) mode image resolution. When low-k dielectrics or copper interconnects in ultra large scale integrated circuits (ULSI) interconnect structures were imaged in this mode, it was found that unique pattern dimension and fidelity information at sub-nanometer resolution was available for the first time. This paper will discuss the helium ion microscope architecture and the SE imaging techniques that make the HIM observation method of particular value to the low-k dielectric and dual damascene copper interconnect technologies.

Scanning tunnelling microscope for boron surface studies

NASA Astrophysics Data System (ADS)

Trenary, Michael

1990-10-01

The equipment purchased is to be used in an experimental study of the relationship between atomic structure and chemical reactivity for boron and carbon surfaces. This research is currently being supported by grant AFOSR-88-0111. A renewal proposal is currently pending with AFOSR to continue these studies. Carbon and boron are exceptionally stable, covalently bonded solids with highly unique crystal structures. The specific reactions to be studied are loosely related to the problems of oxidation and oxidation inhibition of carbon/carbon composites. The main experimental instrument to be used is a scanning tunneling microscope (STM) purchased under grant number AFSOR-89-0146. Other techniques to be used include Auger electron spectroscopy, X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), low energy electron diffraction (LEED), temperature programmed desorption (TPD) and scanning tunneling microscopy (STM).

Evidence of sharp and diffuse domain walls in BiFeO3 by means of unit-cell-wise strain and polarization maps obtained with high resolution scanning transmission electron microscopy.

PubMed

Lubk, A; Rossell, M D; Seidel, J; He, Q; Yang, S Y; Chu, Y H; Ramesh, R; Hÿtch, M J; Snoeck, E

2012-07-27

Domain walls (DWs) substantially influence a large number of applications involving ferroelectric materials due to their limited mobility when shifted during polarization switching. The discovery of greatly enhanced conduction at BiFeO(3) DWs has highlighted yet another role of DWs as a local material state with unique properties. However, the lack of precise information on the local atomic structure is still hampering microscopical understanding of DW properties. Here, we examine the atomic structure of BiFeO(3) 109° DWs with pm precision by a combination of high-angle annular dark-field scanning transmission electron microscopy and a dedicated structural analysis. By measuring simultaneously local polarization and strain, we provide direct experimental proof for the straight DW structure predicted by ab initio calculations as well as the recently proposed theory of diffuse DWs, thus resolving a long-standing discrepancy between experimentally measured and theoretically predicted DW mobilities.

Boron Nitride Nanostructures: Fabrication, Functionalization and Applications.

PubMed

Yin, Jun; Li, Jidong; Hang, Yang; Yu, Jin; Tai, Guoan; Li, Xuemei; Zhang, Zhuhua; Guo, Wanlin

2016-06-01

Boron nitride (BN) structures are featured by their excellent thermal and chemical stability and unique electronic and optical properties. However, the lack of controlled synthesis of quality samples and the electrically insulating property largely prevent realizing the full potential of BN nanostructures. A comprehensive overview of the current status of the synthesis of two-dimensional hexagonal BN sheets, three dimensional porous hexagonal BN materials and BN-involved heterostructures is provided, highlighting the advantages of different synthetic methods. In addition, structural characterization, functionalizations and prospective applications of hexagonal BN sheets are intensively discussed. One-dimensional BN nanoribbons and nanotubes are then discussed in terms of structure, fabrication and functionality. In particular, the existing routes in pursuit of tunable electronic and magnetic properties in various BN structures are surveyed, calling upon synergetic experimental and theoretical efforts to address the challenges for pioneering the applications of BN into functional devices. Finally, the progress in BN superstructures and novel B/N nanostructures is also briefly introduced. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A review on the synthesis, crystal growth, structure and physical properties of rare earth based quaternary intermetallic compounds

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

Mumbaraddi, Dundappa; Sarkar, Sumanta; Peter, Sebastian C., E-mail: sebastiancp@jncasr.ac.in

2016-04-15

This review highlights the synthesis and crystal growth of quaternary intermetallic compounds based on rare earth metals. In the first part of this review, we highlight briefly about intermetallics and their versatile properties in comparison to the constituent elements. In the next part, we have discussed about various synthesis techniques with more focus on the metal flux technique towards the well shaped crystal growth of novel compounds. In the subsequent parts, several disordered quaternary compounds have been reviewed and then outlined most known ordered quaternary compounds with their complex structure. A special attention has been given to the ordered compoundsmore » with structural description and relation to the parent binary and ternary compounds. The importance of electronic and structural feature is highlighted as the key roles in designing these materials for emerging applications. - Graphical abstract: Rare earth based quaternary intermetallic compounds crystallize in complex novel crystal structures. The diversity in the crystal structure may induce unique properties and can be considered them as future materials. - Highlights: • Crystal growth and crystal structure of quaternary rare earth based intermetallics. • Structural complexity of quaternary compounds in comparison to the parent compounds. • Novel quaternary compounds display unique crystal structure.« less

Elaiophores in Gomesa bifolia (Sims) M.W. Chase & N.H. Williams (Oncidiinae: Cymbidieae: Orchidaceae): structure and oil secretion

PubMed Central

Aliscioni, Sandra S.; Torretta, Juan P.; Bello, Mariano E.; Galati, Beatriz G.

2009-01-01

Background and Aims Oils are an unusual floral reward in Orchidaceae, being produced by specialized glands called elaiophores. Such glands have been described in subtribe Oncidiinae for a few species. The aims of the present study were to identify the presence of elaiophores in Gomesa bifolia, to study their structure and to understand how the oil is secreted. Additionally, elaiophores of G. bifolia were compared with those of related taxa within the Oncidiinae. Methods Elaiophores were identified using Sudan III. Their structure was examined by using light, scanning electron and transmission electron microscopy. Key Results Secretion of oils was from the tips of callus protrusions. The secretory cells each had a large, centrally located nucleus, highly dense cytoplasm, abundant plastids containing lipid globules associated with starch grains, numerous mitochondria, an extensive system of rough and smooth endoplasmatic reticulum, and electron-dense dictyosomes. The outer tangential walls were thick, with a loose cellulose matrix and a few, sparsely distributed inconspicuous cavities. Electron-dense structures were observed in the cell wall and formed a lipid layer that covered the cuticle of the epidermal cells. The cuticle as viewed under the scanning electron microscope was irregularly rugose. Conclusions The elaiophores of G. bifolia are of the epithelial type. The general structure of the secretory cells resembles that described for other species of Oncidiinae, but some unique features were encountered for this species. The oil appears to pass through the outer tangential wall and the cuticle, covering the latter without forming cuticular blisters. PMID:19692391

The Nature of Metastable AA’ Graphite: Low Dimensional Nano- and Single-Crystalline Forms

PubMed Central

Lee, Jae-Kap; Kim, Jin-Gyu; Hembram, K. P. S. S.; Kim, Yong-Il; Min, Bong-Ki; Park, Yeseul; Lee, Jeon-Kook; Moon, Dong Ju; Lee, Wooyoung; Lee, Sang-Gil; John, Phillip

2016-01-01

Over the history of carbon, it is generally acknowledged that Bernal AB stacking of the sp2 carbon layers is the unique crystalline form of graphite. The universal graphite structure is synthesized at 2,600~3,000 °C and exhibits a micro-polycrystalline feature. In this paper, we provide evidence for a metastable form of graphite with an AA’ structure. The non-Bernal AA’ allotrope of graphite is synthesized by the thermal- and plasma-treatment of graphene nanopowders at ~1,500 °C. The formation of AA’ bilayer graphene nuclei facilitates the preferred texture growth and results in single-crystal AA’ graphite in the form of nanoribbons (1D) or microplates (2D) of a few nm in thickness. Kinetically controlled AA’ graphite exhibits unique nano- and single-crystalline feature and shows quasi-linear behavior near the K-point of the electronic band structure resulting in anomalous optical and acoustic phonon behavior. PMID:28000780

Visualization of HIV T Cell Virological Synapses and Virus-Containing Compartments by Three-Dimensional Correlative Light and Electron Microscopy

PubMed Central

Wang, Lili; Eng, Edward T.; Law, Kenneth; Gordon, Ronald E.; Rice, William J.

2016-01-01

ABSTRACT Virological synapses (VS) are adhesive structures that form between infected and uninfected cells to enhance the spread of HIV-1. During T cell VS formation, viral proteins are actively recruited to the site of cell-cell contact where the viral material is efficiently translocated to target cells into heterogeneous, protease-resistant, antibody-inaccessible compartments. Using correlative light and electron microscopy (CLEM), we define the membrane topography of the virus-containing compartments (VCC) where HIV is found following VS-mediated transfer. Focused ion beam scanning electron microscopy (FIB-SEM) and serial sectioning transmission electron microscopy (SS-TEM) were used to better resolve the fluorescent Gag-containing structures within the VCC. We found that small punctate fluorescent signals correlated with single viral particles in enclosed vesicular compartments or surface-localized virus particles and that large fluorescent signals correlated with membranous Gag-containing structures with unknown pathological function. CLEM imaging revealed distinct pools of newly deposited viral proteins within endocytic and nonendocytic compartments in VS target T cells. IMPORTANCE This study directly correlates individual virus-associated objects observed in light microscopy with ultrastructural features seen by electron microscopy in the HIV-1 virological synapse. This approach elucidates which infection-associated ultrastructural features represent bona fide HIV protein complexes. We define the morphology of some HIV cell-to-cell transfer intermediates as true endocytic compartments and resolve unique synapse-associated viral structures created by transfer across virological synapses. PMID:27847357

Mottness Collapse in 1 T -TaS2 -xSex Transition-Metal Dichalcogenide: An Interplay between Localized and Itinerant Orbitals

NASA Astrophysics Data System (ADS)

Qiao, Shuang; Li, Xintong; Wang, Naizhou; Ruan, Wei; Ye, Cun; Cai, Peng; Hao, Zhenqi; Yao, Hong; Chen, Xianhui; Wu, Jian; Wang, Yayu; Liu, Zheng

2017-10-01

The layered transition-metal dichalcogenide 1 T -TaS2 has been recently found to undergo a Mott-insulator-to-superconductor transition induced by high pressure, charge doping, or isovalent substitution. By combining scanning tunneling microscopy measurements and first-principles calculations, we investigate the atomic scale electronic structure of the 1 T -TaS2 Mott insulator and its evolution to the metallic state upon isovalent substitution of S with Se. We identify two distinct types of orbital textures—one localized and the other extended—and demonstrate that the interplay between them is the key factor that determines the electronic structure. In particular, we show that the continuous evolution of the charge gap visualized by scanning tunneling microscopy is due to the immersion of the localized-orbital-induced Hubbard bands into the extended-orbital-spanned Fermi sea, featuring a unique evolution from a Mott gap to a charge-transfer gap. This new mechanism of Mottness collapse revealed here suggests an interesting route for creating novel electronic states and designing future electronic devices.

Disorder and defects are not intrinsic to boron carbide

NASA Astrophysics Data System (ADS)

Mondal, Swastik; Bykova, Elena; Dey, Somnath; Ali, Sk Imran; Dubrovinskaia, Natalia; Dubrovinsky, Leonid; Parakhonskiy, Gleb; van Smaalen, Sander

2016-01-01

A unique combination of useful properties in boron-carbide, such as extreme hardness, excellent fracture toughness, a low density, a high melting point, thermoelectricity, semi-conducting behavior, catalytic activity and a remarkably good chemical stability, makes it an ideal material for a wide range of technological applications. Explaining these properties in terms of chemical bonding has remained a major challenge in boron chemistry. Here we report the synthesis of fully ordered, stoichiometric boron-carbide B13C2 by high-pressure-high-temperature techniques. Our experimental electron-density study using high-resolution single-crystal synchrotron X-ray diffraction data conclusively demonstrates that disorder and defects are not intrinsic to boron carbide, contrary to what was hitherto supposed. A detailed analysis of the electron density distribution reveals charge transfer between structural units in B13C2 and a new type of electron-deficient bond with formally unpaired electrons on the C-B-C group in B13C2. Unprecedented bonding features contribute to the fundamental chemistry and materials science of boron compounds that is of great interest for understanding structure-property relationships and development of novel functional materials.

Metal oxides for optoelectronic applications.

PubMed

Yu, Xinge; Marks, Tobin J; Facchetti, Antonio

2016-04-01

Metal oxides (MOs) are the most abundant materials in the Earth's crust and are ingredients in traditional ceramics. MO semiconductors are strikingly different from conventional inorganic semiconductors such as silicon and III-V compounds with respect to materials design concepts, electronic structure, charge transport mechanisms, defect states, thin-film processing and optoelectronic properties, thereby enabling both conventional and completely new functions. Recently, remarkable advances in MO semiconductors for electronics have been achieved, including the discovery and characterization of new transparent conducting oxides, realization of p-type along with traditional n-type MO semiconductors for transistors, p-n junctions and complementary circuits, formulations for printing MO electronics and, most importantly, commercialization of amorphous oxide semiconductors for flat panel displays. This Review surveys the uniqueness and universality of MOs versus other unconventional electronic materials in terms of materials chemistry and physics, electronic characteristics, thin-film fabrication strategies and selected applications in thin-film transistors, solar cells, diodes and memories.

Metal oxides for optoelectronic applications

NASA Astrophysics Data System (ADS)

Yu, Xinge; Marks, Tobin J.; Facchetti, Antonio

2016-04-01

Metal oxides (MOs) are the most abundant materials in the Earth's crust and are ingredients in traditional ceramics. MO semiconductors are strikingly different from conventional inorganic semiconductors such as silicon and III-V compounds with respect to materials design concepts, electronic structure, charge transport mechanisms, defect states, thin-film processing and optoelectronic properties, thereby enabling both conventional and completely new functions. Recently, remarkable advances in MO semiconductors for electronics have been achieved, including the discovery and characterization of new transparent conducting oxides, realization of p-type along with traditional n-type MO semiconductors for transistors, p-n junctions and complementary circuits, formulations for printing MO electronics and, most importantly, commercialization of amorphous oxide semiconductors for flat panel displays. This Review surveys the uniqueness and universality of MOs versus other unconventional electronic materials in terms of materials chemistry and physics, electronic characteristics, thin-film fabrication strategies and selected applications in thin-film transistors, solar cells, diodes and memories.

First-Principles Estimation of Electronic Temperature from X-Ray Thomson Scattering Spectrum of Isochorically Heated Warm Dense Matter

NASA Astrophysics Data System (ADS)

Mo, Chongjie; Fu, Zhenguo; Kang, Wei; Zhang, Ping; He, X. T.

2018-05-01

Through the perturbation formula of time-dependent density functional theory broadly employed in the calculation of solids, we provide a first-principles calculation of x-ray Thomson scattering spectrum of isochorically heated aluminum foil, as considered in the experiments of Sperling et al. [Phys. Rev. Lett. 115, 115001 (2015), 10.1103/PhysRevLett.115.115001], where ions were constrained near their lattice positions. From the calculated spectra, we find that the electronic temperature cannot exceed 2 eV, much smaller than the previous estimation of 6 eV via the detailed balance relation. Our results may well be an indication of unique electronic properties of warm dense matter, which can be further illustrated by future experiments. The lower electronic temperature predicted partially relieves the concern on the heating of x-ray free electron laser to the sample when used in structure measurement.

p-π Conjugated Polymers Based on Stable Triarylborane with n-Type Behavior in Optoelectronic Devices.

PubMed

Meng, Bin; Ren, Yi; Liu, Jun; Jäkle, Frieder; Wang, Lixiang

2018-02-19

p-π conjugation with embedded heteroatoms offers unique opportunities to tune the electronic structure of conjugated polymers. An approach is presented to form highly electron-deficient p-π conjugated polymers based on triarylboranes, demonstrate their n-type behavior, and explore device applications. By combining alternating [2,4,6-tris(trifluoromethyl)phenyl]di(thien-2-yl)borane (FBDT) and electron-deficient isoindigo (IID)/pyridine-flanked diketopyrrolopyrrole (DPPPy) units, we achieve low-lying lowest unoccupied molecular orbital (LUMO) and highest occupied molecular orbital (HOMO) energy levels, high electron mobilities, and broad absorptions in the visible region. All-polymer solar cells with these polymers as electron acceptors exhibit encouraging photovoltaic performance with power conversion efficiencies of up to 2.83 %. These results unambiguously prove the n-type behavior and demonstrate the photovoltaic applications of p-π conjugated polymers based on triarylborane. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electronic reconstruction of doped Mott insulator heterojunctions

NASA Astrophysics Data System (ADS)

Charlebois, M.; Hassan, S. R.; Karan, R.; Dion, M.; Senechal, D.; Tremblay, A.-M. S.

2012-02-01

Correlated electron heterostructures became a possible alternative when thin-film deposition techniques achieved structures with a sharp interface transition [1]. Soon thereafter, Okamoto & Millis introduced the concept of ``electronic reconstruction'' [2]. We study here the electronic reconstruction of doped Mott insulator heterostructures based on a Cluster Dynamical Mean Field Theory (CDMFT) calculations of the Hubbard model in the limit where electrostatic energy dominates over the kinetic energy associated with transport across layers. The grand potential of individual layers is first computed within CDMFT and then the electrostatic potential energy is taken into account in the Hartree approximation. The charge reconstruction in an ensemble of stacked planes of different nature can lead to a distribution of electron charge and to transport properties that are unique to doped-Mott insulators.[4pt] [1] J. Mannhart, D. G. Schlom, Science 327, 1607 (2010).[0pt] [2] S. Okamoto and A. J. Millis, Nature 428, 630 (2004).

Toward all-carbon electronics: fabrication of graphene-based flexible electronic circuits and memory cards using maskless laser direct writing.

PubMed

Liang, Jiajie; Chen, Yongsheng; Xu, Yanfei; Liu, Zhibo; Zhang, Long; Zhao, Xin; Zhang, Xiaoliang; Tian, Jianguo; Huang, Yi; Ma, Yanfeng; Li, Feifei

2010-11-01

Owing to its extraordinary electronic property, chemical stability, and unique two-dimensional nanostructure, graphene is being considered as an ideal material for the highly expected all-carbon-based micro/nanoscale electronics. Herein, we present a simple yet versatile approach to constructing all-carbon micro/nanoelectronics using solution-processing graphene films directly. From these graphene films, various graphene-based microcosmic patterns and structures have been fabricated using maskless computer-controlled laser cutting. Furthermore, a complete system involving a prototype of a flexible write-once-read-many-times memory card and a fast data-reading system has been demonstrated, with infinite data retention time and high reliability. These results indicate that graphene could be the ideal material for fabricating the highly demanded all-carbon and flexible devices and electronics using the simple and efficient roll-to-roll printing process when combined with maskless direct data writing.

X-ray circular dichroism signals: a unique probe of local molecular chirality

DOE PAGES

Zhang, Yu; Rouxel, Jeremy R.; Autschbach, Jochen; ...

2017-06-26

Core-resonant circular dichroism (CD) signals are induced by molecular chirality and vanish for achiral molecules and racemic mixtures. The highly localized nature of core excitations makes them ideal probes of local chirality within molecules. Simulations of the circular dichroism spectra of several molecular families illustrate how these signals vary with the electronic coupling to substitution groups, the distance between the X-ray chromophore and the chiral center, geometry, and chemical structure. As a result, clear insight into the molecular structure is obtained through analysis of the X-ray CD spectra.

X-ray circular dichroism signals: a unique probe of local molecular chirality

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

Zhang, Yu; Rouxel, Jeremy R.; Autschbach, Jochen

Core-resonant circular dichroism (CD) signals are induced by molecular chirality and vanish for achiral molecules and racemic mixtures. The highly localized nature of core excitations makes them ideal probes of local chirality within molecules. Simulations of the circular dichroism spectra of several molecular families illustrate how these signals vary with the electronic coupling to substitution groups, the distance between the X-ray chromophore and the chiral center, geometry, and chemical structure. As a result, clear insight into the molecular structure is obtained through analysis of the X-ray CD spectra.

Electronic structure, magnetism, and antisite disorder in CoFeCrGe and CoMnCrAl quaternary Heusler alloys

DOE PAGES

Enamullah, .; Venkateswara, Y.; Gupta, Sachin; ...

2015-12-10

In this study, we present a combined theoretical and experimental study of two quaternary Heusler alloys CoFeCrGe (CFCG) and CoMnCrAl (CMCA), promising candidates for spintronics applications. Magnetization measurement shows the saturation magnetization and transition temperature to be 3 μ B, 866 K and 0.9 μ B, 358 K for CFCG and CMCA respectively. The magnetization values agree fairly well with our theoretical results and also obey the Slater-Pauling rule, a prerequisite for half metallicity. A striking difference between the two systems is their structure; CFCG crystallizes in fully ordered Y-type structure while CMCA has L2 1 disordered structure. The antisitemore » disorder adds a somewhat unique property to the second compound, which arises due to the probabilistic mutual exchange of Al positions with Cr/Mn and such an effect is possibly expected due to comparable electronegativities of Al and Cr/Mn. Ab initio simulation predicted a unique transition from half metallic ferromagnet to metallic antiferromagnet beyond a critical excess concentration of Al in the alloy.« less

Flexible supercapacitors with high areal capacitance based on hierarchical carbon tubular nanostructures

NASA Astrophysics Data System (ADS)

Zhang, Haitao; Su, Hai; Zhang, Lei; Zhang, Binbin; Chun, Fengjun; Chu, Xiang; He, Weidong; Yang, Weiqing

2016-11-01

Hierarchical structure design can greatly enhance the unique properties of primary material(s) but suffers from complicated preparation process and difficult self-assembly of materials with different dimensionalities. Here we report on the growth of single carbon tubular nanostructures with hierarchical structure (hCTNs) through a simple method based on direct conversion of carbon dioxide. Resorting to in-situ transformation and self-assembly of carbon micro/nano-structures, the obtained hCTNs are blood-like multichannel hierarchy composed of one large channel across the hCTNs and plenty of small branches connected to each other. Due to the unique pore structure and high surface area, these hCTN-based flexible supercapacitors possess the highest areal capacitance of ∼320 mF cm-2, as well as good rate-capability and excellent cycling stability (95% retention after 2500 cycles). It was established that this method can control the morphology, size, and density of hCTNs and effectively construct hCTNs well anchored to the various substrates. Our work unambiguously demonstrated the potential of hCTNs for large flexible supercapacitors and integrated energy management electronics.

TiO 2 nanotube arrays for photocatalysis: Effects of crystallinity, local order, and electronic structure

DOE PAGES

Liu, Jing; Hosseinpour, Pegah M.; Luo, Si; ...

2014-11-19

To furnish insight into correlations of electronic and local structure and photoactivity, arrays of short and long TiO₂ nanotubes were synthesized by electrochemical anodization of Ti foil, followed by thermal treatment in O₂ (oxidizing), Ar (inert), and H₂ (reducing) environments. The physical and electronic structures of these nanotubes were probed with x-ray diffraction, scanning electron microscopy, and synchrotron-based x-ray absorption spectroscopy, and correlated with their photocatalytic properties. The photocatalytic activity of the nanotubes was evaluated by monitoring the degradation of methyl orange under UV-VIS light irradiation. Results show that upon annealing at 350 °C all as-anodized amorphous TiO₂ nanotube samplesmore » partially transform to the anatase structure, with variations in the degree of crystallinity and in the concentration of local defects near the nanotubes' surface (~5 nm) depending on the annealing conditions. Degradation of methyl orange was not detectable for the as-anodized TiO₂ nanotubes regardless of their length. The annealed long nanotubes demonstrated detectable catalytic activity, which was more significant with the H₂-annealed nanotubes than with the Ar- and O₂-annealed nanotube samples. This enhanced photocatalytic response of the H₂-annealed long nanotubes relative to the other samples is positively correlated with the presence of a larger concentration of lattice defects (such as Ti 3+ and anticipated oxygen vacancies) and a slightly lower degree of crystallinity near the nanotube surface. These physical and electronic structural attributes impact the efficacy of visible light absorption; moreover, the increased concentration of surface defects is postulated to promote the generation of hydroxyl radicals and thus accelerate the photodegradation of the methyl orange. The information obtained from this study provides unique insight into the role of the near-surface electronic and defect structure, crystal structure, and the local chemical environment on the photocatalytic activity and may be employed for tailoring the materials' properties for photocatalysis and other energy-related applications.« less

Synthesis and Cs-Corrected Scanning Transmission Electron Microscopy Characterization of Multimetallic Nanoparticles

NASA Astrophysics Data System (ADS)

Khanal, Subarna; Bhattarai, Nabraj; Velázquez-Salazar, Jesus; Jose-Yacaman, Miguel; Subarna Khanal Team

2014-03-01

Multimetallic nanoparticles have been attracted greater attention both in materials science and nanotechnology due to its unique electronic, optical, biological, and catalytic properties lead by physiochemical interactions among different atoms and phases. The distinct features of multimetallic nanoparticles enhanced synergetic properties, large surface to volume ratio and quantum size effects ultimately lead to novel and wide range of possibilities for different applications than monometallic counterparts. For instance, PtPd, Pt/Cu, Au-Au3Cu, AgPd/Pt, AuCu/Pt and many other multimetallic nanoparticles have raised interest for their various applications in fuel cells, ethanol and methanol oxidation reactions, hydrogen storage, and so on. The nanostructures were analyzed by transmission electron microscopy (TEM) and by aberration-corrected scanning transmission electron microscopy (Cs-corrected STEM), in combination with high angle annular dark field (HAADF), bright field (BF), energy dispersive X-ray spectroscopy (EDS), and electron energy loss spectroscopy (EELS) detectors. These techniques allowed us to probe the structure at the atomic level of the nanoparticles revealing new structural information and elemental composition of the nanoparticles. The authors would like to acknowledge NSF grants DMR-1103730, ``Alloys at the Nanoscale: The Case of Nanoparticles Second Phase'' and NSF PREM Grant # DMR 0934218.

Inside-in, alternative paradigms for sound spatialization

NASA Astrophysics Data System (ADS)

Bahn, Curtis; Moore, Stephan

2003-04-01

Arrays of widely spaced mono-directional loudspeakers (P.A.-style stereo configurations or ``outside-in'' surround-sound systems) have long provided the dominant paradigms for electronic sound diffusion. So prevalent are these models that alternatives have largely been ignored and electronic sound, regardless of musical aesthetic, has come to be inseparably associated with single-channel speakers, or headphones. We recognize the value of these familiar paradigms, but believe that electronic sound can and should have many alternative, idiosyncratic voices. Through the design and construction of unique sound diffusion structures, one can reinvent the nature of electronic sound; when allied with new sensor technologies, these structures offer alternative modes of interaction with techniques of sonic computation. This paper describes several recent applications of spherical speakers (multichannel, outward-radiating geodesic speaker arrays) and Sensor-Speaker-Arrays (SenSAs: combinations of various sensor devices with outward-radiating multi-channel speaker arrays). This presentation introduces the development of four generations of spherical speakers-over a hundred individual speakers of various configurations-and their use in many different musical situations including live performance, recording, and sound installation. We describe the design and construction of these systems, and, more generally, the new ``voices'' they give to electronic sound.

Continuous wave superconducting radio frequency electron linac for nuclear physics research

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

Reece, Charles E.

CEBAF, the Continuous Electron Beam Accelerator Facility, has been actively serving the nuclear physics research community as a unique forefront international resource since 1995. This cw electron linear accelerator (linac) at the U.S. Department of Energy’s Thomas Jefferson National Accelerator Facility (Jefferson Lab) has continued to evolve as a precision tool for discerning the structure and dynamics within nuclei. Superconducting rf (SRF) technology has been the essential foundation for CEBAF, first as a 4 GeV machine, then 6 GeV, and currently capable of 12 GeV. Lastly, we review the development, implementation, and performance of SRF systems for CEBAF from itsmore » early beginnings to the commissioning of the 12 GeV era.« less

Continuous wave superconducting radio frequency electron linac for nuclear physics research

DOE PAGES

Reece, Charles E.

2016-12-28

CEBAF, the Continuous Electron Beam Accelerator Facility, has been actively serving the nuclear physics research community as a unique forefront international resource since 1995. This cw electron linear accelerator (linac) at the U.S. Department of Energy’s Thomas Jefferson National Accelerator Facility (Jefferson Lab) has continued to evolve as a precision tool for discerning the structure and dynamics within nuclei. Superconducting rf (SRF) technology has been the essential foundation for CEBAF, first as a 4 GeV machine, then 6 GeV, and currently capable of 12 GeV. Lastly, we review the development, implementation, and performance of SRF systems for CEBAF from itsmore » early beginnings to the commissioning of the 12 GeV era.« less

Analysis of Black Bearing Balls from a Space Shuttle Body Flap Actuator

NASA Technical Reports Server (NTRS)

Sovinski, Marjorie F.; Street, Kenneth W.

2005-01-01

A significantly deteriorated ball bearing mechanism from a body flap actuator on Space Shuttle OV-103 was disassembled and the balls submitted for analysis in conjunction with Return to Flight activities. The OV-103 balls, referred to as the "black balls", were subjected to X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FT-IR) and Raman micro spectroscopy, surface profilometry, and optical and electron microscopy. The spectroscopic results in combination with microscopy analysis allowed a determination of the lubricant degradation pathway. The chemical attack mechanism does not adequately explain the unique visual appearance of the black balls. Numerous efforts have unsuccessfully focused on duplication of the phenomena causing this unique surface structure and appearance of the black balls. Further detail will be presented supporting these conclusions along with plausible explanations of the unique black appearance to the balls.

Failure of the Hume-Rothery stabilization mechanism in the Ag(5)Li(8) gamma-brass studied by first-principles FLAPW electronic structure calculations.

PubMed

Mizutani, U; Asahi, R; Sato, H; Noritake, T; Takeuchi, T

2008-07-09

The first-principles FLAPW (full potential linearized augmented plane wave) electronic structure calculations were performed for the Ag(5)Li(8) gamma-brass, which contains 52 atoms in a unit cell and has been known for many years as one of the most structurally complex alloy phases. The calculations were also made for its neighboring phase AgLi B2 compound. The main objective in the present work is to examine if the Ag(5)Li(8) gamma-brass is stabilized at the particular electrons per atom ratio e/a = 21/13 in the same way as some other gamma-brasses like Cu(5)Zn(8) and Cu(9)Al(4), obeying the Hume-Rothery electron concentration rule. For this purpose, the e/a value for the Ag(5)Li(8) gamma-brass as well as the AgLi B2 compound was first determined by means of the FLAPW-Fourier method we have developed. It proved that both the gamma-brass and the B2 compound possess an e/a value equal to unity instead of 21/13. Moreover, we could demonstrate why the Hume-Rothery stabilization mechanism fails for the Ag(5)Li(8) gamma-brass and proposed a new stability mechanism, in which the unique gamma-brass structure can effectively lower the band-structure energy by forming heavily populated bonding states near the bottom of the Ag-4d band.

Plasma Waves and Structures Associated with Magnetic Reconnection

NASA Astrophysics Data System (ADS)

Ergun, R.; Wilder, F. D.; Ahmadi, N.; Goodrich, K.; Holmes, J.; Newman, D. L.; Burch, J.; Torbert, R. B.; Le Contel, O.; Giles, B. L.; Strangeway, R. J.; Lindqvist, P. A.

2017-12-01

Space observations of magnetic reconnection indicate a variety of plasma wave modes and structures in the vicinity of the electron diffusion region including electromagnetic whistler waves, quasi-electrostatic whistler waves, electron phase-space holes, double layers, electron acoustic waves, lower hybrid waves, upper hybrid waves, and electromagnetic drift waves. These waves and plasma structures are seen in magnetotail reconnection and subsolar reconnection. The MMS mission has the unique ability to unequivocally identify the electron diffusion region and distinguish waves in the EDR from those in the extended separatrix. Such a distinction is critical since some of the observed waves may be involved the reconnection process while others may result from subsequent or associated events and do not directly influence the reconnection process. For example, some of the largest amplitude (> 100 mV/m) electrostatic waves have been identified as electron acoustic waves and upper hybrid waves. These waves are likely generated as a result of reconnection and do not appear to strongly influence the reconnection process. On the other hand, large-amplitude electrostatic whistler waves have been observed very near the X-line, are seen in simulations, and may be participating in reconnection physics. Electromagnetic drift waves almost always appear in cases of asymmetric reconnection and may lead to a more turbulent process. We summarize wave observations by MMS and discuss the relative their possible role in magnetic reconnection physics, concentrating on recent magnetotail observations.

Characterization of pi-Conjugated Polymers for Transistor and Photovoltaic Applications

NASA Astrophysics Data System (ADS)

Paulsen, Bryan D.

pi-Conjugated polymers represent a unique class of optoelectronic materials. Being polymers, they are solution processable and inherently "soft" materials. This makes them attractive candidates for the production of roll-to-roll printed electronic devices on flexible substrates. The optical and electronic properties of pi-conjugated polymers are synthetically tunable allowing material sets to be tailored to specific applications. Two of the most heavily researched applications are the thin film transistor, the building block of electronic circuits, and the bulk heterojunction solar cell, which holds great potential as a renewable energy source. Key to developing commercially feasible pi-conjugated polymer devices is a thorough understanding of the electronic structure and charge transport behavior of these materials in relationship with polymer structure. Here this structure property relationship has been investigated through electrical and electrochemical means in concert with a variety of other characterization techniques and device test beds. The tunability of polymer optical band gap and frontier molecular orbital energy level was investigated in systems of vinyl incorporating statistical copolymers. Energy levels and band gaps are crucial parameters in developing efficient photovoltaic devices, with control of these parameters being highly desirable. Additionally, charge transport and density of electronic states were investigated in pi-conjugated polymers at extremely high electrochemically induced charge density. Finally, the effects of molecular weight on pi-conjugated polymer optical properties, energy levels, charge transport, morphology, and photovoltaic device performance was examined.

Comparative study of energetic heliospheric electrons at wind and geotail

NASA Technical Reports Server (NTRS)

Chaizy, P. A.; Lanzerotti, L. J.; Lin, R. P.; Lepping, R. P.; Kokubun, S. K.; Bosqued, J.-M.; Sanderson, T. R.; Yamamoto, T.

1997-01-01

The current fleet of both heliospheric and magnetospheric spacecraft provides a unique opportunity of studying spatio-temporal plasma phenomena. Among the numerous topics that can be addressed by such a fleet, figures the 3D study of energetic (greater than 20 keV) solar electron) solar electron events. WIND and GEOTAIL are particulary interesting for such analysis: more than two years of data; up to 3/4 continuous days spent by GEOTAIL in the solar wind; and comparable experiments. During solar electron events, rapid electron flux changes can be associated with these structures. Sometimes they are seen at both spacecraft with a time difference corresponding to the convection time, but sometimes they are observed at one spacecraft but not at the other. Several preliminary conclusions can be drawn from such events: (1) there is direct evidence that, within distances lower than 1.5 x 10(exp 6) km at 1 A (approximately 7000 km at the sun), there are significant spatial variations of (a) the magnetic field line connections to the source region and probably of (b) the particle propagation features; (2) magnetic field lines inside and outside particle propagation structures can keep distinct access to the source region for more than one hour; (3) flux waves, of probable local origin, were observed; and (4) within one hour, spatial flux discrepancies, separated by magnetic structures, may remain or disappear.

Enhanced photovoltaic properties of perovskite solar cells by TiO2 homogeneous hybrid structure

PubMed Central

Su, Pengyu; Yao, Huizhen; Liu, Li; Ding, Dong; Feng, Fei; Feng, Shuang; Xue, Yebin; Liu, Xizhe; Yang, Haibin

2017-01-01

In this paper, we fabricated a TiO2 homogeneous hybrid structure for application in perovskite solar cells (PSCs) under ambient conditions. Under the standard air mass 1.5 global (AM 1.5G) illumination, PSCs based on homogeneous hybrid structure present a maximum power conversion efficiency of 5.39% which is higher than that of pure TiO2 nanosheets. The enhanced properties can be explained by the better contact of TiO2 nanosheets/nanoparticles with CH3NH3PbI3 and fewer pinholes in electron transport materials. The advent of such unique structure opens up new avenues for the future development of high-efficiency photovoltaic cells. PMID:29134092

Selected Topics on the Synthesis, Properties and Applications of Multiwalled Carbon Nanotubes

PubMed Central

Stoner, B.R.; Brown, B.; Glass, J.T.

2014-01-01

Summary In summary, MWCNTs have been examined for a variety of electronic applications due to their unique structure and chemistry. Electrodes for field emission, energy and sensor applications hold particular interest. MWCNTs provide a very high surface area, relatively easy methods of surface modification, controllable and high concentration of reactive surface sites, and high specific capacitance. Combining MWCNTs with graphene structures, oxide and metal nanoparticles and certain polymers extends their performance and functionality. Such hybrid structures have been produced in situ during CNT growth and in two-step processes. Excellent progress on understanding the mechanisms of CNT growth has enabled numerous growth methods to all yield MWCNT structures in a variety of morphologies. PMID:24910503

Enhanced photovoltaic properties of perovskite solar cells by TiO2 homogeneous hybrid structure.

PubMed

Su, Pengyu; Fu, Wuyou; Yao, Huizhen; Liu, Li; Ding, Dong; Feng, Fei; Feng, Shuang; Xue, Yebin; Liu, Xizhe; Yang, Haibin

2017-10-01

In this paper, we fabricated a TiO 2 homogeneous hybrid structure for application in perovskite solar cells (PSCs) under ambient conditions. Under the standard air mass 1.5 global (AM 1.5G) illumination, PSCs based on homogeneous hybrid structure present a maximum power conversion efficiency of 5.39% which is higher than that of pure TiO 2 nanosheets. The enhanced properties can be explained by the better contact of TiO 2 nanosheets/nanoparticles with CH 3 NH 3 PbI 3 and fewer pinholes in electron transport materials. The advent of such unique structure opens up new avenues for the future development of high-efficiency photovoltaic cells.

Wood-Derived Materials for Green Electronics, Biological Devices, and Energy Applications.

PubMed

Zhu, Hongli; Luo, Wei; Ciesielski, Peter N; Fang, Zhiqiang; Zhu, J Y; Henriksson, Gunnar; Himmel, Michael E; Hu, Liangbing

2016-08-24

With the arising of global climate change and resource shortage, in recent years, increased attention has been paid to environmentally friendly materials. Trees are sustainable and renewable materials, which give us shelter and oxygen and remove carbon dioxide from the atmosphere. Trees are a primary resource that human society depends upon every day, for example, homes, heating, furniture, and aircraft. Wood from trees gives us paper, cardboard, and medical supplies, thus impacting our homes, school, work, and play. All of the above-mentioned applications have been well developed over the past thousands of years. However, trees and wood have much more to offer us as advanced materials, impacting emerging high-tech fields, such as bioengineering, flexible electronics, and clean energy. Wood naturally has a hierarchical structure, composed of well-oriented microfibers and tracheids for water, ion, and oxygen transportation during metabolism. At higher magnification, the walls of fiber cells have an interesting morphology-a distinctly mesoporous structure. Moreover, the walls of fiber cells are composed of thousands of fibers (or macrofibrils) oriented in a similar angle. Nanofibrils and nanocrystals can be further liberated from macrofibrils by mechanical, chemical, and enzymatic methods. The obtained nanocellulose has unique optical, mechanical, and barrier properties and is an excellent candidate for chemical modification and reconfiguration. Wood is naturally a composite material, comprised of cellulose, hemicellulose, and lignin. Wood is sustainable, earth abundant, strong, biodegradable, biocompatible, and chemically accessible for modification; more importantly, multiscale natural fibers from wood have unique optical properties applicable to different kinds of optoelectronics and photonic devices. Today, the materials derived from wood are ready to be explored for applications in new technology areas, such as electronics, biomedical devices, and energy. The goal of this study is to review the fundamental structures and chemistries of wood and wood-derived materials, which are essential for a wide range of existing and new enabling technologies. The scope of the review covers multiscale materials and assemblies of cellulose, hemicellulose, and lignin as well as other biomaterials derived from wood, in regard to their major emerging applications. Structure-properties-application relationships will be investigated in detail. Understanding the fundamental properties of these structures is crucial for designing and manufacturing products for emerging applications. Today, a more holistic understanding of the interplay between the structure, chemistry, and performance of wood and wood-derived materials is advancing historical applications of these materials. This new level of understanding also enables a myriad of new and exciting applications, which motivate this review. There are excellent reviews already on the classical topic of woody materials, and some recent reviews also cover new understanding of these materials as well as potential applications. This review will focus on the uniqueness of woody materials for three critical applications: green electronics, biological devices, and energy storage and bioenergy.

Wood-Derived Materials for Green Electronics, Biological Devices, and Energy Applications

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

Zhu, Hongli; Luo, Wei; Ciesielski, Peter N.

With the arising of global climate change and resource shortage, in recent years, increased attention has been paid to environmentally friendly materials. Trees are sustainable and renewable materials, which give us shelter and oxygen and remove carbon dioxide from the atmosphere. Trees are a primary resource that human society depends upon every day, for example, homes, heating, furniture, and aircraft. Wood from trees gives us paper, cardboard, and medical supplies, thus impacting our homes, school, work, and play. All of the above-mentioned applications have been well developed over the past thousands of years. However, trees and wood have much moremore » to offer us as advanced materials, impacting emerging high-tech fields, such as bioengineering, flexible electronics, and clean energy. Wood naturally has a hierarchical structure, composed of well-oriented microfibers and tracheids for water, ion, and oxygen transportation during metabolism. At higher magnification, the walls of fiber cells have an interesting morphology--a distinctly mesoporous structure. Moreover, the walls of fiber cells are composed of thousands of fibers (or macrofibrils) oriented in a similar angle. Nanofibrils and nanocrystals can be further liberated from macrofibrils by mechanical, chemical, and enzymatic methods. The obtained nanocellulose has unique optical, mechanical, and barrier properties and is an excellent candidate for chemical modification and reconfiguration. Wood is naturally a composite material, comprised of cellulose, hemicellulose, and lignin. Wood is sustainable, earth abundant, strong, biodegradable, biocompatible, and chemically accessible for modification; more importantly, multiscale natural fibers from wood have unique optical properties applicable to different kinds of optoelectronics and photonic devices. Today, the materials derived from wood are ready to be explored for applications in new technology areas, such as electronics, biomedical devices, and energy. The goal of this study is to review the fundamental structures and chemistries of wood and wood-derived materials, which are essential for a wide range of existing and new enabling technologies. The scope of the review covers multiscale materials and assemblies of cellulose, hemicellulose, and lignin as well as other biomaterials derived from wood, in regard to their major emerging applications. Structure-properties-application relationships will be investigated in detail. Understanding the fundamental properties of these structures is crucial for designing and manufacturing products for emerging applications. Today, a more holistic understanding of the interplay between the structure, chemistry, and performance of wood and wood-derived materials is advancing historical applications of these materials. This new level of understanding also enables a myriad of new and exciting applications, which motivate this review. There are excellent reviews already on the classical topic of woody materials, and some recent reviews also cover new understanding of these materials as well as potential applications. This review will focus on the uniqueness of woody materials for three critical applications: green electronics, biological devices, and energy storage and bioenergy.« less

Sea spray aerosol structure and composition using cryogenic transmission electron microscopy

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

Patterson, Joseph P.; Collins, Douglas B.; Michaud, Jennifer M.

The surface properties of atmospheric aerosol particles largely control their impact on climate by affecting their ability to uptake water, react heterogeneously, and nucleate ice in clouds. However, in the vacuum of a conventional electron microscope, the native surface structure often undergoes chemical rearrangement resulting in surfaces that are quite different from their atmospheric configurations. Herein, we report the development of a cryo-TEM approach where sea spray aerosol particles are flash frozen in their native state and then probed by electron microscopy. This unique approach allows for the detection of not only mixed salts, but also soft materials including wholemore » hydrated bacteria, diatoms, virus particles, marine vesicles, as well as gel networks within hydrated salt droplets. As a result, we anticipate this method will open up a new avenue of analysis for aerosol particles, not only for ocean-derived aerosols, but for those produced from other sources where there is interest in the transfer of organic or biological species from the biosphere to the atmosphere.« less

Stacking sequence and interlayer coupling in few-layer graphene revealed by in situ imaging

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

Wang, Zhu-Jun; Dong, Jichen; Cui, Yi

In the transition from graphene to graphite, the addition of each individual graphene layer modifies the electronic structure and produces a different material with unique properties. Controlled growth of few-layer graphene is therefore of fundamental interest and will provide access to materials with engineered electronic structure. Here we combine isothermal growth and etching experiments with in situ scanning electron microscopy to reveal the stacking sequence and interlayer coupling strength in few-layer graphene. The observed layer-dependent etching rates reveal the relative strength of the graphene graphene and graphene substrate interaction and the resulting mode of adlayer growth. Scanning tunnelling microscopy andmore » density functional theory calculations confirm a strong coupling between graphene edge atoms and platinum. Simulated etching confirms that etching can be viewed as reversed growth. This work demonstrates that real-time imaging under controlled atmosphere is a powerful method for designing synthesis protocols for sp2 carbon nanostructures in between graphene and graphite.« less

Sea spray aerosol structure and composition using cryogenic transmission electron microscopy

DOE PAGES

Patterson, Joseph P.; Collins, Douglas B.; Michaud, Jennifer M.; ...

2016-01-15

The surface properties of atmospheric aerosol particles largely control their impact on climate by affecting their ability to uptake water, react heterogeneously, and nucleate ice in clouds. However, in the vacuum of a conventional electron microscope, the native surface structure often undergoes chemical rearrangement resulting in surfaces that are quite different from their atmospheric configurations. Herein, we report the development of a cryo-TEM approach where sea spray aerosol particles are flash frozen in their native state and then probed by electron microscopy. This unique approach allows for the detection of not only mixed salts, but also soft materials including wholemore » hydrated bacteria, diatoms, virus particles, marine vesicles, as well as gel networks within hydrated salt droplets. As a result, we anticipate this method will open up a new avenue of analysis for aerosol particles, not only for ocean-derived aerosols, but for those produced from other sources where there is interest in the transfer of organic or biological species from the biosphere to the atmosphere.« less

Interlaced crystals having a perfect Bravais lattice and complex chemical order revealed by real-space crystallography

DOE PAGES

Shen, Xiao; Hernandez-Pagan, Emil; Zhou, Wu; ...

2014-11-14

The search for optimal thermoelectric materials aims for structures in which the crystalline order is disrupted to lower the thermal conductivity without degradation of the electron conductivity. Here we report the synthesis and characterization of ternary nanoparticles (two cations and one anion) that exhibit a new form of crystal-line order: an uninterrupted, perfect, global Bravais lattice, in which the two cations exhibit a wide array of distinct ordering patterns within the cation sublattice, form-ing interlaced domains and phases. Partitioning into domains and phases is not unique; the corresponding boundaries have no structural defects or strain and entail no energy cost.more » We call this form of crystalline order “interlaced crystals” and present the example of hexagonal-CuInS 2. Interlacing is possible in multi-cation tetrahedral-ly-bonded compound with an average of two electrons per bond. Interlacing has min-imal effect on electronic properties, but should strongly reduce phonon transport, making interlaced crystals attractive for thermoelectric applications.« less

Stacking sequence and interlayer coupling in few-layer graphene revealed by in situ imaging

DOE PAGES

Wang, Zhu-Jun; Dong, Jichen; Cui, Yi; ...

2016-10-19

In the transition from graphene to graphite, the addition of each individual graphene layer modifies the electronic structure and produces a different material with unique properties. Controlled growth of few-layer graphene is therefore of fundamental interest and will provide access to materials with engineered electronic structure. Here we combine isothermal growth and etching experiments with in situ scanning electron microscopy to reveal the stacking sequence and interlayer coupling strength in few-layer graphene. The observed layer-dependent etching rates reveal the relative strength of the graphene graphene and graphene substrate interaction and the resulting mode of adlayer growth. Scanning tunnelling microscopy andmore » density functional theory calculations confirm a strong coupling between graphene edge atoms and platinum. Simulated etching confirms that etching can be viewed as reversed growth. This work demonstrates that real-time imaging under controlled atmosphere is a powerful method for designing synthesis protocols for sp2 carbon nanostructures in between graphene and graphite.« less

Electronic and optoelectronic device applications based on ReS2

NASA Astrophysics Data System (ADS)

Liu, Erfu; Long, Mingsheng; Wang, Yaojia; Pan, Yiming; Ho, Chinghwa; Wang, Baigeng; Miao, Feng

Rhenium disulfide (ReS2) is a unique semiconducting TMD with distorted 1T structure and weak interlayer coupling. We have previously investigated its in-plane anisotropic property and electronic applications on FET and digital inverters. In this talk, we will present high responsivity phototransistors based on few-layer ReS2. Depending on the back gate voltage, source drain bias and incident optical light intensity, the maximum attainable photoresponsivity can reach as high as 88,600 A W-1, which is one of the highest value among individual two-dimensional materials with similar device structures. Such high photoresponsivity is attributed to the increased light absorption as well as the gain enhancement due to the existence of trap states in the few-layer ReS2 flakes. The existence of trap states is proved by temperature dependent transport measurements. It further enables the detection of weak signals. Our studies underscore ReS2 as a promising material for future electronic and sensitive optoelectronic applications.

Stacking sequence and interlayer coupling in few-layer graphene revealed by in situ imaging

PubMed Central

Wang, Zhu-Jun; Dong, Jichen; Cui, Yi; Eres, Gyula; Timpe, Olaf; Fu, Qiang; Ding, Feng; Schloegl, R.; Willinger, Marc-Georg

2016-01-01

In the transition from graphene to graphite, the addition of each individual graphene layer modifies the electronic structure and produces a different material with unique properties. Controlled growth of few-layer graphene is therefore of fundamental interest and will provide access to materials with engineered electronic structure. Here we combine isothermal growth and etching experiments with in situ scanning electron microscopy to reveal the stacking sequence and interlayer coupling strength in few-layer graphene. The observed layer-dependent etching rates reveal the relative strength of the graphene–graphene and graphene–substrate interaction and the resulting mode of adlayer growth. Scanning tunnelling microscopy and density functional theory calculations confirm a strong coupling between graphene edge atoms and platinum. Simulated etching confirms that etching can be viewed as reversed growth. This work demonstrates that real-time imaging under controlled atmosphere is a powerful method for designing synthesis protocols for sp2 carbon nanostructures in between graphene and graphite. PMID:27759024

Orbitally-driven giant phonon anharmonicity in SnSe

DOE PAGES

Li, Chen W.; Hong, Jiawang; May, Andrew F.; ...

2015-10-19

We understand that elementary excitations and their couplings in condensed matter systems is critical to develop better energy-conversion devices. In thermoelectric materials, the heat-to-electricity conversion efficiency is directly improved by suppressing the propagation of phonon quasiparticles responsible for macroscopic thermal transport. The material with the current record for thermoelectric conversion efficiency, SnSe, achieves an ultra-low thermal conductivity, but the mechanism enabling this strong phonon scattering remains largely unknown. Using inelastic neutron scattering measurements and first-principles simulations, we mapped the four-dimensional phonon dispersion surfaces of SnSe, and revealed the origin of ionic-potential anharmonicity responsible for the unique properties of SnSe. Wemore » show that the giant phonon scattering arises from an unstable electronic structure, with orbital interactions leading to a ferroelectric-like lattice instability. Our results provide a microscopic picture connecting electronic structure and phonon anharmonicity in SnSe, and offers precious insights on how electron-phonon and phononphonon interactions may lead to the realization of ultra-low thermal conductivity.« less

Development of scanning electron and x-ray microscope

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

Matsumura, Tomokazu, E-mail: tomokzau.matsumura@etd.hpk.co.jp; Hirano, Tomohiko, E-mail: tomohiko.hirano@etd.hpk.co.jp; Suyama, Motohiro, E-mail: suyama@etd.hpk.co.jp

We have developed a new type of microscope possessing a unique feature of observing both scanning electron and X-ray images under one unit. Unlike former X-ray microscopes using SEM [1, 2], this scanning electron and X-ray (SELX) microscope has a sample in vacuum, thus it enables one to observe a surface structure of a sample by SEM mode, to search the region of interest, and to observe an X-ray image which transmits the region. For the X-ray observation, we have been focusing on the soft X-ray region from 280 eV to 3 keV to observe some bio samples and softmore » materials. The resolutions of SEM and X-ray modes are 50 nm and 100 nm, respectively, at the electron energy of 7 keV.« less

Electride and superconductivity behaviors in Mn5Si3-type intermetallics

NASA Astrophysics Data System (ADS)

Zhang, Yaoqing; Wang, Bosen; Xiao, Zewen; Lu, Yangfan; Kamiya, Toshio; Uwatoko, Yoshiya; Kageyama, Hiroshi; Hosono, Hideo

2017-08-01

Electrides are unique in the sense that they contain localized anionic electrons in the interstitial regions. Yet they exist with a diversity of chemical compositions, especially under extreme conditions, implying generalized underlying principles for their existence. What is rarely observed is the combination of electride state and superconductivity within the same material, but such behavior would open up a new category of superconductors. Here, we report a hexagonal Nb5Ir3 phase of Mn5Si3-type structure that falls into this category and extends the electride concept into intermetallics. The confined electrons in the one-dimensional cavities are reflected by the characteristic channel bands in the electronic structure. Filling these free spaces with foreign oxygen atoms serves to engineer the band topology and increase the superconducting transition temperature to 10.5 K in Nb5Ir3O. Specific heat analysis indicates the appearance of low-lying phonons and two-gap s-wave superconductivity. Strong electron-phonon coupling is revealed to be the pairing glue with an anomalously large ratio between the superconducting gap Δ0 and Tc, 2Δ0/kBTc = 6.12. The general rule governing the formation of electrides concerns the structural stability against the cation filling/extraction in the channel site.

Synthesis, Structure, and Molecular Recognition of S6 - and (SO2 )6 -Corona[6](het)arenes: Control of Macrocyclic Conformation and Properties by the Oxidation State of the Bridging Heteroatoms.

PubMed

Guo, Qing-Hui; Zhao, Liang; Wang, Mei-Xiang

2016-05-10

We report herein the synthesis, structure, and molecular recognition of S6 - and (SO2 )6 -corona[6](het)arenes, and demonstrate a unique and efficient strategy of regulating macrocyclic conformation and properties by adjusting the oxidation state of the heteroatom linkages. The one-pot nucleophilic aromatic substitution reaction of 1,4-benzenedithiol derivatives, biphenyl-4,4'-dithiol and 9,9-dipropyl-9H-fluorene-2,7-dithiol with 3,6-dichlorotetrazine afforded S6 -corona[3]arene[3]tetrazines. These compounds underwent inverse-electron-demand Diels-Alder reaction with enamines and norbornadiene to produce S6 -corona[3]arene[3]pyridazines. Facile oxidation of sulfide linkages yielded (SO2 )6 -corona[3]arene[3]pyridazines. All corona[6](het)arenes adopted generally hexagonal macrocyclic ring structures; however, their electronic properties and conformation could be fine-tuned by altering the oxidation state of the sulfur linkages. Whereas (SO2 )6 -corona[3]arene[3]pyridazines were electron-deficient, S6 -corona[3]arene[3]pyridazines acted as electron-rich macrocyclic hosts that recognized various organic cations in both aqueous and organic solutions. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bonding properties of FCC-like Au 44 (SR) 28 clusters from X-ray absorption spectroscopy

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

Yang, Rui; Chevrier, Daniel M.; Zeng, Chenjie

Thiolate-protected gold clusters with precisely controlled atomic composition have recently emerged as promising candidates for a variety of applications because of their unique optical, electronic, and catalytic properties. The recent discovery of the Au44(SR)28 total structure is considered as an interesting finding in terms of the face-centered cubic (FCC)-like core structure in small gold-thiolate clusters. Herein, the unique bonding properties of Au44(SR)28 is analyzed using temperature-dependent X-ray absorption spectroscopy (XAS) measurements at the Au L3-edge and compared with other FCC-like clusters such as Au36(SR)24 and Au28(SR)20. A negative thermal expansion was detected for the Au–Au bonds of the metal coremore » (the first Au–Au shell) and was interpreted based on the unique Au core structure consisting of the Au4 units. EXAFS fitting results from Au28(SR)20, Au36(SR)24, and Au44(SR)28 show a size-dependent negative thermal expansion behavior in the first Au–Au shell, further highlighting the importance of the Au4 units in determining the Au core bonding properties and shedding light on the growth mechanism of these FCC-like Au clusters.« less

Scalable Synthesis of Freestanding Sandwich-structured Graphene/Polyaniline/Graphene Nanocomposite Paper for Flexible All-Solid-State Supercapacitor

NASA Astrophysics Data System (ADS)

Xiao, Fei; Yang, Shengxiong; Zhang, Zheye; Liu, Hongfang; Xiao, Junwu; Wan, Lian; Luo, Jun; Wang, Shuai; Liu, Yunqi

2015-03-01

We reported a scalable and modular method to prepare a new type of sandwich-structured graphene-based nanohybrid paper and explore its practical application as high-performance electrode in flexible supercapacitor. The freestanding and flexible graphene paper was firstly fabricated by highly reproducible printing technique and bubbling delamination method, by which the area and thickness of the graphene paper can be freely adjusted in a wide range. The as-prepared graphene paper possesses a collection of unique properties of highly electrical conductivity (340 S cm-1), light weight (1 mg cm-2) and excellent mechanical properties. In order to improve its supercapacitive properties, we have prepared a unique sandwich-structured graphene/polyaniline/graphene paper by in situ electropolymerization of porous polyaniline nanomaterials on graphene paper, followed by wrapping an ultrathin graphene layer on its surface. This unique design strategy not only circumvents the low energy storage capacity resulting from the double-layer capacitor of graphene paper, but also enhances the rate performance and cycling stability of porous polyaniline. The as-obtained all-solid-state symmetric supercapacitor exhibits high energy density, high power density, excellent cycling stability and exceptional mechanical flexibility, demonstrative of its extensive potential applications for flexible energy-related devices and wearable electronics.

Scalable Synthesis of Freestanding Sandwich-structured Graphene/Polyaniline/Graphene Nanocomposite Paper for Flexible All-Solid-State Supercapacitor

PubMed Central

Xiao, Fei; Yang, Shengxiong; Zhang, Zheye; Liu, Hongfang; Xiao, Junwu; Wan, Lian; Luo, Jun; Wang, Shuai; Liu, Yunqi

2015-01-01

We reported a scalable and modular method to prepare a new type of sandwich-structured graphene-based nanohybrid paper and explore its practical application as high-performance electrode in flexible supercapacitor. The freestanding and flexible graphene paper was firstly fabricated by highly reproducible printing technique and bubbling delamination method, by which the area and thickness of the graphene paper can be freely adjusted in a wide range. The as-prepared graphene paper possesses a collection of unique properties of highly electrical conductivity (340 S cm−1), light weight (1 mg cm−2) and excellent mechanical properties. In order to improve its supercapacitive properties, we have prepared a unique sandwich-structured graphene/polyaniline/graphene paper by in situ electropolymerization of porous polyaniline nanomaterials on graphene paper, followed by wrapping an ultrathin graphene layer on its surface. This unique design strategy not only circumvents the low energy storage capacity resulting from the double-layer capacitor of graphene paper, but also enhances the rate performance and cycling stability of porous polyaniline. The as-obtained all-solid-state symmetric supercapacitor exhibits high energy density, high power density, excellent cycling stability and exceptional mechanical flexibility, demonstrative of its extensive potential applications for flexible energy-related devices and wearable electronics. PMID:25797022

Scalable synthesis of freestanding sandwich-structured graphene/polyaniline/graphene nanocomposite paper for flexible all-solid-state supercapacitor.

PubMed

Xiao, Fei; Yang, Shengxiong; Zhang, Zheye; Liu, Hongfang; Xiao, Junwu; Wan, Lian; Luo, Jun; Wang, Shuai; Liu, Yunqi

2015-03-23

We reported a scalable and modular method to prepare a new type of sandwich-structured graphene-based nanohybrid paper and explore its practical application as high-performance electrode in flexible supercapacitor. The freestanding and flexible graphene paper was firstly fabricated by highly reproducible printing technique and bubbling delamination method, by which the area and thickness of the graphene paper can be freely adjusted in a wide range. The as-prepared graphene paper possesses a collection of unique properties of highly electrical conductivity (340 S cm(-1)), light weight (1 mg cm(-2)) and excellent mechanical properties. In order to improve its supercapacitive properties, we have prepared a unique sandwich-structured graphene/polyaniline/graphene paper by in situ electropolymerization of porous polyaniline nanomaterials on graphene paper, followed by wrapping an ultrathin graphene layer on its surface. This unique design strategy not only circumvents the low energy storage capacity resulting from the double-layer capacitor of graphene paper, but also enhances the rate performance and cycling stability of porous polyaniline. The as-obtained all-solid-state symmetric supercapacitor exhibits high energy density, high power density, excellent cycling stability and exceptional mechanical flexibility, demonstrative of its extensive potential applications for flexible energy-related devices and wearable electronics.

Improving hole injection and carrier distribution in InGaN light-emitting diodes by removing the electron blocking layer and including a unique last quantum barrier

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

Cheng, Liwen, E-mail: lwcheng@yzu.edu.cn; Chen, Haitao; Wu, Shudong

2015-08-28

The effects of removing the AlGaN electron blocking layer (EBL), and using a last quantum barrier (LQB) with a unique design in conventional blue InGaN light-emitting diodes (LEDs), were investigated through simulations. Compared with the conventional LED design that contained a GaN LQB and an AlGaN EBL, the LED that contained an AlGaN LQB with a graded-composition and no EBL exhibited enhanced optical performance and less efficiency droop. This effect was caused by an enhanced electron confinement and hole injection efficiency. Furthermore, when the AlGaN LQB was replaced with a triangular graded-composition, the performance improved further and the efficiency droopmore » was lowered. The simulation results indicated that the enhanced hole injection efficiency and uniform distribution of carriers observed in the quantum wells were caused by the smoothing and thinning of the potential barrier for the holes. This allowed a greater number of holes to tunnel into the quantum wells from the p-type regions in the proposed LED structure.« less

Alcohol dehydrogenase of acetic acid bacteria: structure, mode of action, and applications in biotechnology.

PubMed

Yakushi, Toshiharu; Matsushita, Kazunobu

2010-05-01

Pyrroquinoline quinone-dependent alcohol dehydrogenase (PQQ-ADH) of acetic acid bacteria is a membrane-bound enzyme involved in the acetic acid fermentation by oxidizing ethanol to acetaldehyde coupling with reduction of membranous ubiquinone (Q), which is, in turn, re-oxidized by ubiquinol oxidase, reducing oxygen to water. PQQ-ADHs seem to have co-evolved with the organisms fitting to their own habitats. The enzyme consists of three subunits and has a pyrroloquinoline quinone, 4 heme c moieties, and a tightly bound Q as the electron transfer mediators. Biochemical, genetic, and electrochemical studies have revealed the unique properties of PQQ-ADH since it was purified in 1978. The enzyme is unique to have ubiquinol oxidation activity in addition to Q reduction. This mini-review focuses on the molecular properties of PQQ-ADH, such as the roles of the subunits and the cofactors, particularly in intramolecular electron transport of the enzyme from ethanol to Q. Also, we summarize biotechnological applications of PQQ-ADH as to enantiospecific oxidations for production of the valuable chemicals and bioelectrocatalysis for sensors and fuel cells using indirect and direct electron transfer technologies and discuss unsolved issues and future prospects related to this elaborate enzyme.

Boron Nitride Nanotubes for Engineering Applications

NASA Technical Reports Server (NTRS)

Hurst, Janet; Hull, David; Gorican, Daniel

2005-01-01

Boron nitride nanotubes (BNNT) are of significant interest to the scientific and technical communities for many of the same reasons that carbon nanotubes (CNT) have attracted wide attention. Both materials have potentially unique and important properties for structural and electronic applications. However of even more consequence than their similarities may be the complementary differences between carbon and boron nitride nanotubes While BNNT possess a very high modulus similar to CNT, they also possess superior chemical and thermal stability. Additionally, BNNT have more uniform electronic properties, with a uniform band gap of 5.5 eV while CNT vary from semi-conductive to highly conductive behavior. Boron nitride nanotubes have been synthesized both in the literature and at NASA Glenn Research Center, by a variety of methods such as chemical vapor deposition, arc discharge and reactive milling. Consistent large scale production of a reliable product has proven difficult. Progress in the reproducible synthesis of 1-2 gram sized batches of boron nitride nanotubes will be discussed as well as potential uses for this unique material.

Synthesis of Boron Nitride Nanotubes for Engineering Applications

NASA Technical Reports Server (NTRS)

Hurst, Janet; Hull, David; Gorican, Dan

2005-01-01

Boron Nitride nanotubes (BNNT) are of interest to the scientific and technical communities for many of the same reasons that carbon nanotubes (CNT) have attracted large amounts of attention. Both materials have potentially unique and significant properties which may have important structural and electronic applications in the future. However of even more interest than their similarities may be the differences between carbon and boron nanotubes. Whilt boron nitride nanotubes possess a very high modulus similaar to CNT, they are also more chemically and thermally inert. Additionally BNNT possess more uniform electronic properties, having a uniform band gap of approximately 5.5 eV while CNT vary from semi-conductin to conductor behavior. Boron Nitride nanotubes have been synthesized by a variety of methods such as chemical vapor deposition, arc discharge and reactive milling. Consistently producing a reliable product has proven difficult. Progress in synthesis of 1-2 gram sized batches of Boron Nitride nanotubes will be discussed as well as potential uses for this unique material.

Gas chromatographic-mass spectrometric characterization of thebaol, an opium constituent, and its structural analogs.

PubMed

Megutnishvili, Levan; Todua, Nino; Stein, Stephen; Mikaia, Anzor

2018-05-18

A GC-MS method is described for the characterization of thebaol, a component of opium poppy. The method includes preliminary sample derivatization to TMS, TBDMS, TFA, PFP and HFB substituted products. Fragmentation of resulting derivatives is unique under electron ionization, and proceeds via consecutive loss of two radicals that violate the "even-electron rule". Peaks of [M-2CH 3 ] +. and [M-C 4 H 9 -CH 3 ] +. ions show maximum intensities in the spectra of trimethyl- and tert-butyldimethylsilyl-thebaols. Elimination of perfluoroalkyl and methyl radicals from M +. is characteristic for TFA, PFP and HFB thebaols. The same fragmentation peculiarity is characteristic for derivatives prepared from related natural compounds containing vicinal 2-methoxyphenol moieties. The unique fragmentation of trialkylsilyl and perfluoroacyl derivatives of thebaol can be successfully used for thebaol determination within complex mixtures. This is part 4 from the series "Analytical derivatives in mass spectrometry", parts 1, 2 and 3 see [1-3]. Copyright © 2018 Elsevier B.V. All rights reserved.

Integrated digital inverters based on two-dimensional anisotropic ReS₂ field-effect transistors

DOE PAGES

Liu, Erfu; Fu, Yajun; Wang, Yaojia; ...

2015-05-07

Semiconducting two-dimensional transition metal dichalcogenides are emerging as top candidates for post-silicon electronics. While most of them exhibit isotropic behaviour, lowering the lattice symmetry could induce anisotropic properties, which are both scientifically interesting and potentially useful. Here we present atomically thin rhenium disulfide (ReS₂) flakes with unique distorted 1T structure, which exhibit in-plane anisotropic properties. We fabricated monolayer and few-layer ReS₂ field-effect transistors, which exhibit competitive performance with large current on/off ratios (~10⁷) and low subthreshold swings (100 mV per decade). The observed anisotropic ratio along two principle axes reaches 3.1, which is the highest among all known two-dimensional semiconductingmore » materials. Furthermore, we successfully demonstrated an integrated digital inverter with good performance by utilizing two ReS₂ anisotropic field-effect transistors, suggesting the promising implementation of large-scale two-dimensional logic circuits. Our results underscore the unique properties of two-dimensional semiconducting materials with low crystal symmetry for future electronic applications.« less

Acentric 2-D ensembles of D-br-A electron-transfer chromophores via vectorial orientation within amphiphilic n-helix bundle peptides for photovoltaic device applications.

PubMed

Koo, Jaseung; Park, Jaehong; Tronin, Andrey; Zhang, Ruili; Krishnan, Venkata; Strzalka, Joseph; Kuzmenko, Ivan; Fry, H Christopher; Therien, Michael J; Blasie, J Kent

2012-02-14

We show that simply designed amphiphilic 4-helix bundle peptides can be utilized to vectorially orient a linearly extended donor-bridge-acceptor (D-br-A) electron transfer (ET) chromophore within its core. The bundle's interior is shown to provide a unique solvation environment for the D-br-A assembly not accessible in conventional solvents and thereby control the magnitudes of both light-induced ET and thermal charge recombination rate constants. The amphiphilicity of the bundle's exterior was employed to vectorially orient the peptide-chromophore complex at a liquid-gas interface, and its ends were tailored for subsequent covalent attachment to an inorganic surface, via a "directed assembly" approach. Structural data, combined with evaluation of the excited state dynamics exhibited by these peptide-chromophore complexes, demonstrate that densely packed, acentrically ordered 2-D monolayer ensembles of such complexes at high in-plane chromophore densities approaching 1/200 Å(2) offer unique potential as active layers in binary heterojunction photovoltaic devices.

In situ template synthesis of hollow nanospheres assembled from NiCo2S4@C ultrathin nanosheets with high electrochemical activities for lithium storage and ORR catalysis.

PubMed

Wu, Xiaoyu; Li, Songmei; Wang, Bo; Liu, Jianhua; Yu, Mei

2017-05-10

Transition-metal sulfide hollow nanostructures have received intensive attention in energy-related applications due to their unique structural features and high electrochemical activities. Here, a well-designed composite of NiCo 2 S 4 @C is successfully fabricated using a facile in situ template removal method. The obtained composite shows unique microstructures of hollow nanospheres (∼650 nm in diameter) assembled from ultrathin NiCo 2 S 4 @C nanosheets, in which numerous scattered NiCo 2 S 4 nanoparticles are embedded in ultrathin carbon nanosheets, exhibiting mesoporous features with a high surface area of 247.25 m 2 g -1 . When used as anode materials for LIBs, NiCo 2 S 4 @C hollow nanospheres exhibit a high reversible capacity of 1592 mA h g -1 at a current density of 500 mA g -1 , enhanced cycling performance maintaining a capacity of 1178 mA h g -1 after 200 cycles, and a remarkable rate capability. Meanwhile, the hollow nanospheres display excellent catalytic activity as ORR catalysts with a four-electron pathway and superior durability to that of commercial Pt/C catalysts. Their excellent lithium storage and ORR catalysis performance can be attributed to the rational incorporation of high-activity NiCo 2 S 4 and ultrathin carbon nanosheets, as well as unique hollow microstructures, which offer efficient electron/ion transport, an enhanced electroactive material/electrolyte contact area, numerous active sites, and excellent structural stability.

High resolution three-dimensional reconstruction of fibrotic skeletal muscle extracellular matrix.

PubMed

Gillies, Allison R; Chapman, Mark A; Bushong, Eric A; Deerinck, Thomas J; Ellisman, Mark H; Lieber, Richard L

2017-02-15

Fibrosis occurs secondary to many skeletal muscle diseases and injuries, and can alter muscle function. It is unknown how collagen, the most abundant extracellular structural protein, alters its organization during fibrosis. Quantitative and qualitative high-magnification electron microscopy shows that collagen is organized into perimysial cables which increase in number in a model of fibrosis, and cables have unique interactions with collagen-producing cells. Fibrotic muscles are stiffer and have a higher concentration of collagen-producing cells. These results improve our understanding of the organization of fibrotic skeletal muscle extracellular matrix and identify novel structures that might be targeted by antifibrotic therapy. Skeletal muscle extracellular matrix (ECM) structure and organization are not well understood, yet the ECM plays an important role in normal tissue homeostasis and disease processes. Fibrosis is common to many muscle diseases and is typically quantified based on an increase in ECM collagen. Through the use of multiple imaging modalities and quantitative stereology, we describe the structure and composition of wild-type and fibrotic ECM, we show that collagen in the ECM is organized into large bundles of fibrils, or collagen cables, and the number of these cables (but not their size) increases in desmin knockout muscle (a fibrosis model). The increase in cable number is accompanied by increased muscle stiffness and an increase in the number of collagen producing cells. Unique interactions between ECM cells and collagen cables were also observed and reconstructed by serial block face scanning electron microscopy. These results demonstrate that the muscle ECM is more highly organized than previously reported. Therapeutic strategies for skeletal muscle fibrosis should consider the organization of the ECM to target the structures and cells contributing to fibrotic muscle function. © 2016 Rehabilitation Institute of Chicago. The Journal of Physiology © 2016 The Physiological Society.

High resolution three‐dimensional reconstruction of fibrotic skeletal muscle extracellular matrix

PubMed Central

Gillies, Allison R.; Chapman, Mark A.; Bushong, Eric A.; Deerinck, Thomas J.; Ellisman, Mark H.

2016-01-01

Key points Fibrosis occurs secondary to many skeletal muscle diseases and injuries, and can alter muscle function.It is unknown how collagen, the most abundant extracellular structural protein, alters its organization during fibrosis.Quantitative and qualitative high‐magnification electron microscopy shows that collagen is organized into perimysial cables which increase in number in a model of fibrosis, and cables have unique interactions with collagen‐producing cells.Fibrotic muscles are stiffer and have a higher concentration of collagen‐producing cells.These results improve our understanding of the organization of fibrotic skeletal muscle extracellular matrix and identify novel structures that might be targeted by antifibrotic therapy. Abstract Skeletal muscle extracellular matrix (ECM) structure and organization are not well understood, yet the ECM plays an important role in normal tissue homeostasis and disease processes. Fibrosis is common to many muscle diseases and is typically quantified based on an increase in ECM collagen. Through the use of multiple imaging modalities and quantitative stereology, we describe the structure and composition of wild‐type and fibrotic ECM, we show that collagen in the ECM is organized into large bundles of fibrils, or collagen cables, and the number of these cables (but not their size) increases in desmin knockout muscle (a fibrosis model). The increase in cable number is accompanied by increased muscle stiffness and an increase in the number of collagen producing cells. Unique interactions between ECM cells and collagen cables were also observed and reconstructed by serial block face scanning electron microscopy. These results demonstrate that the muscle ECM is more highly organized than previously reported. Therapeutic strategies for skeletal muscle fibrosis should consider the organization of the ECM to target the structures and cells contributing to fibrotic muscle function. PMID:27859324

Microscopy image segmentation tool: Robust image data analysis

NASA Astrophysics Data System (ADS)

Valmianski, Ilya; Monton, Carlos; Schuller, Ivan K.

2014-03-01

We present a software package called Microscopy Image Segmentation Tool (MIST). MIST is designed for analysis of microscopy images which contain large collections of small regions of interest (ROIs). Originally developed for analysis of porous anodic alumina scanning electron images, MIST capabilities have been expanded to allow use in a large variety of problems including analysis of biological tissue, inorganic and organic film grain structure, as well as nano- and meso-scopic structures. MIST provides a robust segmentation algorithm for the ROIs, includes many useful analysis capabilities, and is highly flexible allowing incorporation of specialized user developed analysis. We describe the unique advantages MIST has over existing analysis software. In addition, we present a number of diverse applications to scanning electron microscopy, atomic force microscopy, magnetic force microscopy, scanning tunneling microscopy, and fluorescent confocal laser scanning microscopy.

Electronic, magnetic, and magnetocrystalline anisotropy properties of light lanthanides

DOE PAGES

Hackett, Timothy A.; Baldwin, D. J.; Paudyal, Durga

2017-05-17

Theoretical understanding of interactions between localized and mobile electrons and the crystal environment in light lanthanides is important because of their key role in much needed magnetic anisotropy in permanent magnet materials that have a great impact in automobile and wind turbine applications. We report electronic, magnetic, and magnetocrystalline properties of these basic light lanthanide elements studied from advanced density functional theory (DFT) calculations. We find that the inclusion of onsite 4f electron correlation and spin orbit coupling within the full-potential band structure is needed to understand the unique magnetocrystalline properties of these light lanthanides. The onsite electron correlation, spinmore » orbit coupling, and full potential for the asphericity of charge densities must be taken into account for the proper treatment of 4f states. We find the variation of total energy as a function of lattice constants that indicate multiple structural phases in Ce contrasting to a single stable structure obtained in other light lanthanides. The 4f orbital magnetic moments are partially quenched as a result of crystalline electric field splitting that leads to magnetocrystalline anisotropy. The charge density plots have similar asphericity and environment in Pr and Nd indicating similar magnetic anisotropy. However, Ce and Sm show completely different asphericity and environment as both orbital moments are significantly quenched. In addition, the Fermi surface structures exemplified in Nd indicate structural stability and unravel a cause of anisotropy. The calculated magnetocrystalline anisotropy energy (MAE) reveals competing c-axis and in-plane anisotropies, and also predicts possibilities of unusual structural deformations in light lanthanides. The uniaxial magnetic anisotropy is obtained in the double hexagonal closed pack structures of the most of the light lanthanides, however, the anisotropy is reduced or turned to planar in the low symmetry structures. As a result, through crystal field calculations we also illustrate the crystal field ground state 4f multiplets of light lanthanides.« less

Electronic, magnetic, and magnetocrystalline anisotropy properties of light lanthanides

NASA Astrophysics Data System (ADS)

Hackett, Timothy A.; Baldwin, D. J.; Paudyal, D.

2017-11-01

Theoretical understanding of interactions between localized and mobile electrons and the crystal environment in light lanthanides is important because of their key role in much needed magnetic anisotropy in permanent magnet materials that have a great impact in automobile and wind turbine applications. We report electronic, magnetic, and magnetocrystalline properties of these basic light lanthanide elements studied from advanced density functional theory (DFT) calculations. We find that the inclusion of onsite 4f electron correlation and spin orbit coupling within the full-potential band structure is needed to understand the unique magnetocrystalline properties of these light lanthanides. The onsite electron correlation, spin orbit coupling, and full potential for the asphericity of charge densities must be taken into account for the proper treatment of 4f states. We find the variation of total energy as a function of lattice constants that indicate multiple structural phases in Ce contrasting to a single stable structure obtained in other light lanthanides. The 4f orbital magnetic moments are partially quenched as a result of crystalline electric field splitting that leads to magnetocrystalline anisotropy. The charge density plots have similar asphericity and environment in Pr and Nd indicating similar magnetic anisotropy. However, Ce and Sm show completely different asphericity and environment as both orbital moments are significantly quenched. In addition, the Fermi surface structures exemplified in Nd indicate structural stability and unravel a cause of anisotropy. The calculated magnetocrystalline anisotropy energy (MAE) reveals competing c-axis and in-plane anisotropies, and also predicts possibilities of unusual structural deformations in light lanthanides. The uniaxial magnetic anisotropy is obtained in the double hexagonal closed pack structures of the most of the light lanthanides, however, the anisotropy is reduced or turned to planar in the low symmetry structures. Through crystal field calculations we also illustrate the crystal field ground state 4f multiplets of light lanthanides.

Electronic, magnetic, and magnetocrystalline anisotropy properties of light lanthanides

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

Hackett, Timothy A.; Baldwin, D. J.; Paudyal, Durga

Theoretical understanding of interactions between localized and mobile electrons and the crystal environment in light lanthanides is important because of their key role in much needed magnetic anisotropy in permanent magnet materials that have a great impact in automobile and wind turbine applications. We report electronic, magnetic, and magnetocrystalline properties of these basic light lanthanide elements studied from advanced density functional theory (DFT) calculations. We find that the inclusion of onsite 4f electron correlation and spin orbit coupling within the full-potential band structure is needed to understand the unique magnetocrystalline properties of these light lanthanides. The onsite electron correlation, spinmore » orbit coupling, and full potential for the asphericity of charge densities must be taken into account for the proper treatment of 4f states. We find the variation of total energy as a function of lattice constants that indicate multiple structural phases in Ce contrasting to a single stable structure obtained in other light lanthanides. The 4f orbital magnetic moments are partially quenched as a result of crystalline electric field splitting that leads to magnetocrystalline anisotropy. The charge density plots have similar asphericity and environment in Pr and Nd indicating similar magnetic anisotropy. However, Ce and Sm show completely different asphericity and environment as both orbital moments are significantly quenched. In addition, the Fermi surface structures exemplified in Nd indicate structural stability and unravel a cause of anisotropy. The calculated magnetocrystalline anisotropy energy (MAE) reveals competing c-axis and in-plane anisotropies, and also predicts possibilities of unusual structural deformations in light lanthanides. The uniaxial magnetic anisotropy is obtained in the double hexagonal closed pack structures of the most of the light lanthanides, however, the anisotropy is reduced or turned to planar in the low symmetry structures. As a result, through crystal field calculations we also illustrate the crystal field ground state 4f multiplets of light lanthanides.« less

Carbon Nanotubes by CVD and Applications

NASA Technical Reports Server (NTRS)

Cassell, Alan; Delzeit, Lance; Nguyen, Cattien; Stevens, Ramsey; Han, Jie; Meyyappan, M.; Arnold, James O. (Technical Monitor)

2001-01-01

Carbon nanotube (CNT) exhibits extraordinary mechanical and unique electronic properties and offers significant potential for structural, sensor, and nanoelectronics applications. An overview of CNT, growth methods, properties and applications is provided. Single-wall, and multi-wall CNTs have been grown by chemical vapor deposition. Catalyst development and optimization has been accomplished using combinatorial optimization methods. CNT has also been grown from the tips of silicon cantilevers for use in atomic force microscopy.

Importance of σ Bonding Electrons for the Accurate Description of Electron Correlation in Graphene.

PubMed

Zheng, Huihuo; Gan, Yu; Abbamonte, Peter; Wagner, Lucas K

2017-10-20

Electron correlation in graphene is unique because of the interplay between the Dirac cone dispersion of π electrons and long-range Coulomb interaction. Because of the zero density of states at Fermi level, the random phase approximation predicts no metallic screening at long distance and low energy, so one might expect that graphene should be a poorly screened system. However, empirically graphene is a weakly interacting semimetal, which leads to the question of how electron correlations take place in graphene at different length scales. We address this question by computing the equal time and dynamic structure factor S(q) and S(q,ω) of freestanding graphene using ab initio fixed-node diffusion Monte Carlo simulations and the random phase approximation. We find that the σ electrons contribute strongly to S(q,ω) for relevant experimental values of ω even at distances up to around 80 Å. These findings illustrate how the emergent physics from underlying Coulomb interactions results in the observed weakly correlated semimetal.

ultraLM and miniLM: Locator tools for smart tracking of fluorescent cells in correlative light and electron microscopy.

PubMed

Brama, Elisabeth; Peddie, Christopher J; Wilkes, Gary; Gu, Yan; Collinson, Lucy M; Jones, Martin L

2016-12-13

In-resin fluorescence (IRF) protocols preserve fluorescent proteins in resin-embedded cells and tissues for correlative light and electron microscopy, aiding interpretation of macromolecular function within the complex cellular landscape. Dual-contrast IRF samples can be imaged in separate fluorescence and electron microscopes, or in dual-modality integrated microscopes for high resolution correlation of fluorophore to organelle. IRF samples also offer a unique opportunity to automate correlative imaging workflows. Here we present two new locator tools for finding and following fluorescent cells in IRF blocks, enabling future automation of correlative imaging. The ultraLM is a fluorescence microscope that integrates with an ultramicrotome, which enables 'smart collection' of ultrathin sections containing fluorescent cells or tissues for subsequent transmission electron microscopy or array tomography. The miniLM is a fluorescence microscope that integrates with serial block face scanning electron microscopes, which enables 'smart tracking' of fluorescent structures during automated serial electron image acquisition from large cell and tissue volumes.

COMPUTATIONAL METHODOLOGIES for REAL-SPACE STRUCTURAL REFINEMENT of LARGE MACROMOLECULAR COMPLEXES

PubMed Central

Goh, Boon Chong; Hadden, Jodi A.; Bernardi, Rafael C.; Singharoy, Abhishek; McGreevy, Ryan; Rudack, Till; Cassidy, C. Keith; Schulten, Klaus

2017-01-01

The rise of the computer as a powerful tool for model building and refinement has revolutionized the field of structure determination for large biomolecular systems. Despite the wide availability of robust experimental methods capable of resolving structural details across a range of spatiotemporal resolutions, computational hybrid methods have the unique ability to integrate the diverse data from multimodal techniques such as X-ray crystallography and electron microscopy into consistent, fully atomistic structures. Here, commonly employed strategies for computational real-space structural refinement are reviewed, and their specific applications are illustrated for several large macromolecular complexes: ribosome, virus capsids, chemosensory array, and photosynthetic chromatophore. The increasingly important role of computational methods in large-scale structural refinement, along with current and future challenges, is discussed. PMID:27145875

Exciton scattering approach for optical spectra calculations in branched conjugated macromolecules

NASA Astrophysics Data System (ADS)

Li, Hao; Wu, Chao; Malinin, Sergey V.; Tretiak, Sergei; Chernyak, Vladimir Y.

2016-12-01

The exciton scattering (ES) technique is a multiscale approach based on the concept of a particle in a box and developed for efficient calculations of excited-state electronic structure and optical spectra in low-dimensional conjugated macromolecules. Within the ES method, electronic excitations in molecular structure are attributed to standing waves representing quantum quasi-particles (excitons), which reside on the graph whose edges and nodes stand for the molecular linear segments and vertices, respectively. Exciton propagation on the linear segments is characterized by the exciton dispersion, whereas exciton scattering at the branching centers is determined by the energy-dependent scattering matrices. Using these ES energetic parameters, the excitation energies are then found by solving a set of generalized "particle in a box" problems on the graph that represents the molecule. Similarly, unique energy-dependent ES dipolar parameters permit calculations of the corresponding oscillator strengths, thus, completing optical spectra modeling. Both the energetic and dipolar parameters can be extracted from quantum-chemical computations in small molecular fragments and tabulated in the ES library for further applications. Subsequently, spectroscopic modeling for any macrostructure within a considered molecular family could be performed with negligible numerical effort. We demonstrate the ES method application to molecular families of branched conjugated phenylacetylenes and ladder poly-para-phenylenes, as well as structures with electron donor and acceptor chemical substituents. Time-dependent density functional theory (TD-DFT) is used as a reference model for electronic structure. The ES calculations accurately reproduce the optical spectra compared to the reference quantum chemistry results, and make possible to predict spectra of complex macromolecules, where conventional electronic structure calculations are unfeasible.

Creation of an Accurate Algorithm to Detect Snellen Best Documented Visual Acuity from Ophthalmology Electronic Health Record Notes.

PubMed

Mbagwu, Michael; French, Dustin D; Gill, Manjot; Mitchell, Christopher; Jackson, Kathryn; Kho, Abel; Bryar, Paul J

2016-05-04

Visual acuity is the primary measure used in ophthalmology to determine how well a patient can see. Visual acuity for a single eye may be recorded in multiple ways for a single patient visit (eg, Snellen vs. Jäger units vs. font print size), and be recorded for either distance or near vision. Capturing the best documented visual acuity (BDVA) of each eye in an individual patient visit is an important step for making electronic ophthalmology clinical notes useful in research. Currently, there is limited methodology for capturing BDVA in an efficient and accurate manner from electronic health record (EHR) notes. We developed an algorithm to detect BDVA for right and left eyes from defined fields within electronic ophthalmology clinical notes. We designed an algorithm to detect the BDVA from defined fields within 295,218 ophthalmology clinical notes with visual acuity data present. About 5668 unique responses were identified and an algorithm was developed to map all of the unique responses to a structured list of Snellen visual acuities. Visual acuity was captured from a total of 295,218 ophthalmology clinical notes during the study dates. The algorithm identified all visual acuities in the defined visual acuity section for each eye and returned a single BDVA for each eye. A clinician chart review of 100 random patient notes showed a 99% accuracy detecting BDVA from these records and 1% observed error. Our algorithm successfully captures best documented Snellen distance visual acuity from ophthalmology clinical notes and transforms a variety of inputs into a structured Snellen equivalent list. Our work, to the best of our knowledge, represents the first attempt at capturing visual acuity accurately from large numbers of electronic ophthalmology notes. Use of this algorithm can benefit research groups interested in assessing visual acuity for patient centered outcome. All codes used for this study are currently available, and will be made available online at https://phekb.org.

Creation of an Accurate Algorithm to Detect Snellen Best Documented Visual Acuity from Ophthalmology Electronic Health Record Notes

PubMed Central

French, Dustin D; Gill, Manjot; Mitchell, Christopher; Jackson, Kathryn; Kho, Abel; Bryar, Paul J

2016-01-01

Background Visual acuity is the primary measure used in ophthalmology to determine how well a patient can see. Visual acuity for a single eye may be recorded in multiple ways for a single patient visit (eg, Snellen vs. Jäger units vs. font print size), and be recorded for either distance or near vision. Capturing the best documented visual acuity (BDVA) of each eye in an individual patient visit is an important step for making electronic ophthalmology clinical notes useful in research. Objective Currently, there is limited methodology for capturing BDVA in an efficient and accurate manner from electronic health record (EHR) notes. We developed an algorithm to detect BDVA for right and left eyes from defined fields within electronic ophthalmology clinical notes. Methods We designed an algorithm to detect the BDVA from defined fields within 295,218 ophthalmology clinical notes with visual acuity data present. About 5668 unique responses were identified and an algorithm was developed to map all of the unique responses to a structured list of Snellen visual acuities. Results Visual acuity was captured from a total of 295,218 ophthalmology clinical notes during the study dates. The algorithm identified all visual acuities in the defined visual acuity section for each eye and returned a single BDVA for each eye. A clinician chart review of 100 random patient notes showed a 99% accuracy detecting BDVA from these records and 1% observed error. Conclusions Our algorithm successfully captures best documented Snellen distance visual acuity from ophthalmology clinical notes and transforms a variety of inputs into a structured Snellen equivalent list. Our work, to the best of our knowledge, represents the first attempt at capturing visual acuity accurately from large numbers of electronic ophthalmology notes. Use of this algorithm can benefit research groups interested in assessing visual acuity for patient centered outcome. All codes used for this study are currently available, and will be made available online at https://phekb.org. PMID:27146002

The molecular and crystal structure of dextrans: a combined electron and X-ray diffraction study. II. A low temperature, hydrated polymorph.

PubMed

Guizard, C; Chanzy, H; Sarko, A

1985-06-05

The crystal and molecular structure of a dextran hydrate has been determined through combined electron and X-ray diffraction analysis, aided by stereochemical model refinement. A total of 65 hk0 electron diffraction intensities were measured on frozen single crystals held at the temperature of liquid nitrogen, to a resolution limit of 1.6 A. The X-ray intensities were measured from powder patterns recorded from collections of the single crystals. The structure crystallizes in a monoclinic unit cell with parameters a = 25.71 A, b = 10.21 A, c (chain axis) = 7.76 A and beta = 91.3 degrees. The space group is P2(1) with b axis unique. The unit cell contains six chains and eight water molecules, with three chains of the same polarity and four water molecules constituting the asymmetric unit. Along the chain direction the asymmetric unit is a dimer residue; however, the individual glucopyranose residues are very nearly related by a molecular 2-fold screw axis. The conformation of the chain is very similar to that in the anhydrous structure, but the chain packing differs in the two structures in that the rotational positions of the chains about the helix axes (the chain setting angles) are considerably different. The chains still pack in the form of sheets that are separated by water molecules. The difference in the chain setting angles between the anhydrous and hydrate structures corresponds to the angle between like unit cell axes observed in the diffraction diagrams recorded from hybrid crystals containing both polymorphs. Despite some beam damage effects, the structure was determined to a satisfactory degree of agreement, with the residuals R''(electron diffraction) = 0.258 and R(X-ray) = 0.127.

Cryo-transmission electron microscopy structure of a gigadalton peptide fiber of de novo design

PubMed Central

Sharp, Thomas H.; Bruning, Marc; Mantell, Judith; Sessions, Richard B.; Thomson, Andrew R.; Zaccai, Nathan R.; Brady, R. Leo; Verkade, Paul; Woolfson, Derek N.

2012-01-01

Nature presents various protein fibers that bridge the nanometer to micrometer regimes. These structures provide inspiration for the de novo design of biomimetic assemblies, both to address difficulties in studying and understanding natural systems, and to provide routes to new biomaterials with potential applications in nanotechnology and medicine. We have designed a self-assembling fiber system, the SAFs, in which two small α-helical peptides are programmed to form a dimeric coiled coil and assemble in a controlled manner. The resulting fibers are tens of nm wide and tens of μm long, and, therefore, comprise millions of peptides to give gigadalton supramolecular structures. Here, we describe the structure of the SAFs determined to approximately 8 Å resolution using cryotransmission electron microscopy. Individual micrographs show clear ultrastructure that allowed direct interpretation of the packing of individual α-helices within the fibers, and the construction of a 3D electron density map. Furthermore, a model was derived using the cryotransmission electron microscopy data and side chains taken from a 2.3 Å X-ray crystal structure of a peptide building block incapable of forming fibers. This was validated using single-particle analysis techniques, and was stable in prolonged molecular-dynamics simulation, confirming its structural viability. The level of self-assembly and self-organization in the SAFs is unprecedented for a designed peptide-based material, particularly for a system of considerably reduced complexity compared with natural proteins. This structural insight is a unique high-resolution description of how α-helical fibrils pack into larger protein fibers, and provides a basis for the design and engineering of future biomaterials. PMID:22847414

Electronic structure of the [MNH2]+ (M = Sc-Cu) complexes.

PubMed

Hendrickx, Marc F A; Clima, Sergiu

2006-11-23

B3LYP geometry optimizations for the [MNH2]+ complexes of the first-row transition metal cations (Sc+-Cu+) were performed. Without any exception the ground states of these unsaturated amide complexes were calculated to possess planar geometries. CASPT2 binding energies that were corrected for zero-point energies and including relativistic effects show a qualitative trend across the series that closely resembles the experimental observations. The electronic structures for the complexes of the early and middle transition metal cations (Sc+-Co+) differ from the electronic structures derived for the complexes of the late transition metal cations (Ni+ and Cu+). For the former complexes the relative higher position of the 3d orbitals above the singly occupied 2p(pi) HOMO of the uncoordinated NH2 induces an electron transfer from the 3d shell to 2p(pi). The stabilization of the 3d orbitals from the left to the right along the first-row transition metal series causes these orbitals to become situated below the HOMO of the NH2 ligand for Ni+ and Cu+, preventing a transfer from occurring in the [MNH2]+ complexes of these metal cations. Analysis of the low-lying states of the amide complexes revealed a rather unique characteristic of their electronic structures that was found across the entire series. Rather exceptionally for the whole of chemistry, pi-type interactions were calculated to be stronger than the corresponding sigma-type interactions. The origin of this extraordinary behavior can be ascribed to the low-lying sp2 lone pair orbital of the NH2 ligand with respect to the 3d level.

Studies of the pedestal structure and inter-ELM pedestal evolution in JET with the ITER-like wall

NASA Astrophysics Data System (ADS)

Maggi, C. F.; Frassinetti, L.; Horvath, L.; Lunniss, A.; Saarelma, S.; Wilson, H.; Flanagan, J.; Leyland, M.; Lupelli, I.; Pamela, S.; Urano, H.; Garzotti, L.; Lerche, E.; Nunes, I.; Rimini, F.; Contributors, JET

2017-11-01

The pedestal structure of type I ELMy H-modes has been analysed for JET with the ITER-like Wall (JET-ILW). The electron pressure pedestal width is independent of ρ * and increases proportionally to  √β pol,PED. Additional broadening of the width is observed, at constant β pol, PED, with increasing ν * and/or neutral gas injection and the contribution of atomic physics effects in setting the pedestal width cannot as yet be ruled out. Neutral penetration alone does not determine the shape of the edge density profile in JET-ILW. The ratio of electron density to electron temperature scale lengths in the edge transport barrier region, η e, is of order 2-3 within experimental uncertainties. Existing understanding, represented in the stationary linear peeling-ballooning mode stability and the EPED pedestal structure models, is extended to the dynamic evolution between ELM crashes in JET-ILW, in order to test the assumptions underlying these two models. The inter-ELM temporal evolution of the pedestal structure in JET-ILW is not unique, but depends on discharge conditions, such as heating power and gas injection levels. The strong reduction in p e,PED with increasing D 2 gas injection at high power is primarily due to clamping of \

Scalable synthesis of Na3V2(PO4)(3)/C porous hollow spheres as a cathode for Na-ion batteries

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

Mao, JF; Luo, C; Gao, T

2015-01-01

Na3V2(PO4)(3) (NVP) has been considered as a very promising cathode material for sodium-ion batteries (SIBs) due to its typical NASICON structure, which provides an open and three dimensional (3D) framework for Na+ migration. However, the low electronic conductivity of NVP limits its rate capability and cycling ability. In this study, carbon coated hollow structured NVP/C composites are synthesized via a template-free and scalable ultrasonic spray pyrolysis process, where the carbon coated NVP particles are uniformly decorated on the inner and outer surfaces of the porous hollow carbon spheres. When evaluated as a cathode material for SIBs, the unique NVP/C porousmore » hollow sphere cathode delivers an initial discharge capacity of 99.2 mA h g(-1) and retains 89.3 mA h g(-1) after 300 charge/discharge cycles with a very low degradation rate of 0.035% per cycle. For comparison, the NVP/C composite, prepared by the traditional sol-gel method, delivers a lower initial discharge capacity of 97.4 mA h g(-1) and decreases significantly to 71.5 mA h g(-1) after 300 cycles. The superior electrochemical performance of NVP/C porous hollow spheres is attributed to their unique porous, hollow and spherical structures, as well as the carbon-coating layer, which provides a high contact area between electrode/electrolyte, high electronic conductivity, and high mechanical strength.« less

Lifetime of a Chemically Bound Helium Compound

NASA Technical Reports Server (NTRS)

Chaban, Galina M.; Lundell, Jan; Gerber, R. Benny; Kwak, Dochan (Technical Monitor)

2001-01-01

The rare-gas atoms are chemically inert, to an extent unique among all elements. This is due to the stable electronic structure of the atoms. Stable molecules with chemically bound rare-gas atoms are, however, known. A first such compound, XePtF6, W2S prepared in 1962 and since then a range of molecules containing radon, xenon and krypton have been obtained. Most recently, a first stable chemically bound compound of argon was prepared, leaving neon and helium as the only elements for which stable chemically bound molecules are not yet known. Electronic structure calculations predict that a metastable species HHeF exists, but significance of the result depends on the unknown lifetime. Here we report quantum dynamics calculations of the lifetime of HHeF, using accurate interactions computed from electronic structure theory. HHeF is shown to disintegrate by tunneling through energy barriers into He + HF and H + He + F the first channel greatly dominating. The lifetime of HHeF is more than 120 picoseconds, that of DHeF is 14 nanoseconds. The relatively long lifetimes are encouraging for the preparation prospects of this first chemically bound helium compound.

Morphology, stoichiometry, and crystal structure control via post-annealing for Pt-ZnO nanograin Schottky barrier interfaces

NASA Astrophysics Data System (ADS)

Chan, Yuet Ching; Yu, Jerry; Ho, Derek

2018-06-01

Nanointerfaces have attracted intensive research effort for advanced electronics due to their unique and tunable semiconducting properties made possible by metal-contacted oxide structures at the nanoscale. Although much work has been on the adjustment of fabrication parameters to achieve high-quality interfaces, little work has experimentally obtained the various correlations between material parameters and Schottky barrier electronic properties to accurately probe the underlying phenomenon. In this work, we investigate the control of Pt-ZnO nanograin interfaces properties by thermal annealing. Specifically, we quantitatively analyze the correlation between material parameters (such as surface morphology, crystallographic structure, and stoichiometry) and Schottky diode parameters (Schottky barrier height, ideality factor, and contact resistance). Results revealed strong dependencies of Schottky barrier characteristics on oxygen vacancies, surface roughness, grain density, d-spacing, and crystallite size. I-V-T data shows that annealing at 600 °C produces a nanograin based interface with the most rectifying diode characteristics. These dependencies, which have not been previously reported holistically, highlight the close relationship between material properties and Schottky barrier characteristics, and are instrumental for the performance optimization of nanostructured metal-semiconductor interfaces in advanced electronic devices.

Zn(II)-PEG 300 globules as soft template for the synthesis of hexagonal ZnO micronuts by the hydrothermal reaction method.

PubMed

Shi, Xixi; Pan, Lingling; Chen, Shuoping; Xiao, Yong; Liu, Qiaoyun; Yuan, Liangjie; Sun, Jutang; Cai, Lintao

2009-05-19

Hexagonal ZnO micronuts (HZMNs) have been successfully synthesized with the assistance of poly(ethylene glycol) (PEG) 300 via a hydrothermal method. The structure and morphology of the HZMNs were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and selected area electron diffraction (SAED). An individual ZnO micronut is revealed as twinned crystals. Time-dependent investigation shows that the growth of HZMNs involves a dissolution-recrystallization process followed by Ostwald ripening, in which is the first formed solid ZnO particles dissolve and transform to HZMNs with hollow structure. PEG 300 has been found to play a crucial role in the growth of this unique hollow structure. TEM observations show that the PEG chains aggregate to globules in water, which then have interaction with the dissolved zinc species to form the globules in a coiled state under hydrothermal conditions. These Zn(II)-PEG 300 globules act as soft template for the growth of HZMNs, and the possible growth mechanism is proposed. The room-temperature photoluminescence (PL) spectrum shows red emission around 612 nm with a full width at half-maximum (fwhm) only about 13 nm.

An Innovative Electrolysis Approach for the Synthesis of Metal Matrix Bulk Nanocomposites: A Case Study on Copper-Niobium System

NASA Astrophysics Data System (ADS)

Shokrvash, Hussein; Rad, Rahim Yazdani; Massoudi, Abouzar

2018-04-01

Design and synthesis of a prototype Cu-Nb nanocomposite are presented. Oxygen-free Cu-Nb nanocomposites were prepared using an electrolysis facility with special emphasis on the cathodic deoxidation of Cu and nanometric Nb2O5 blends in a molten NaCl-CaCl2 electrolyte. The as-prepared nanocomposites were characterized by X-ray diffraction and energy-dispersive X-ray spectroscopy. The elemental analysis of the Cu matrix and Nb phase revealed the high solubility of Nb in the Cu structure (0.85 at. pct) and Cu in the Nb structure (10.59 at. pct) over short synthesis times (4-5 hours). Furthermore, precise analysis using field emission scanning electron microscopy and transmission electron microscopy confirmed the unique structure and nanocomposite morphology of the Cu-Nb nanocomposite. The successful synthesis of Cu-Nb nanocomposites offers a new conceptual and empirical outlook on the generation of bulk nanostructures of immiscible bimetals using electro-synthesis.

Spin-polarized surface resonances accompanying topological surface state formation

DOE PAGES

Jozwiak, Chris; Sobota, Jonathan A.; Gotlieb, Kenneth; ...

2016-10-14

Topological insulators host spin-polarized surface states born out of the energetic inversion of bulk bands driven by the spin-orbit interaction. Here we discover previously unidentified consequences of band-inversion on the surface electronic structure of the topological insulator Bi 2Se 3. By performing simultaneous spin, time, and angle-resolved photoemission spectroscopy, we map the spin-polarized unoccupied electronic structure and identify a surface resonance which is distinct from the topological surface state, yet shares a similar spin-orbital texture with opposite orientation. Its momentum dependence and spin texture imply an intimate connection with the topological surface state. Calculations show these two distinct states canmore » emerge from trivial Rashba-like states that change topology through the spin-orbit-induced band inversion. As a result, this work thus provides a compelling view of the coevolution of surface states through a topological phase transition, enabled by the unique capability of directly measuring the spin-polarized unoccupied band structure.« less

Molecular dynamics-based refinement and validation for sub-5 Å cryo-electron microscopy maps.

PubMed

Singharoy, Abhishek; Teo, Ivan; McGreevy, Ryan; Stone, John E; Zhao, Jianhua; Schulten, Klaus

2016-07-07

Two structure determination methods, based on the molecular dynamics flexible fitting (MDFF) paradigm, are presented that resolve sub-5 Å cryo-electron microscopy (EM) maps with either single structures or ensembles of such structures. The methods, denoted cascade MDFF and resolution exchange MDFF, sequentially re-refine a search model against a series of maps of progressively higher resolutions, which ends with the original experimental resolution. Application of sequential re-refinement enables MDFF to achieve a radius of convergence of ~25 Å demonstrated with the accurate modeling of β-galactosidase and TRPV1 proteins at 3.2 Å and 3.4 Å resolution, respectively. The MDFF refinements uniquely offer map-model validation and B-factor determination criteria based on the inherent dynamics of the macromolecules studied, captured by means of local root mean square fluctuations. The MDFF tools described are available to researchers through an easy-to-use and cost-effective cloud computing resource on Amazon Web Services.

Direct observation of charged domain walls in hybrid improper ferroelectric (Ca,Sr)3Ti2O7

NASA Astrophysics Data System (ADS)

Kurushima, Kousuke; Yoshimoto, Wataru; Ishii, Yui; Cheong, Sang-Wook; Mori, Shigeo

2017-10-01

We investigated ferroelectric (FE) domain wall structures including “charged domain walls” of hybrid improper FE (Ca,Sr)3Ti2O7 at the subatomic resolution by dark-field transmission electron microscopy (TEM) and high-resolution state-of-the-art aberration-corrected high-angle annular-dark-field (HAADF) scanning transmission electron microscopy (STEM). Dark-field TEM and high-resolution HAADF-STEM images obtained in the FE phase of single crystals of Ca2.46Sr0.54Ti2O7 revealed the formation of abundant charged domain walls with the head-to-head and tail-to-tail configurations in the FE domain structure, in addition to the FE 180° domain structure. The charged domain walls with the head-to-head and tail-to-tail FE polarizations exist stably and can be characterized as the unique double arc-type displacement of Ca/Sr ions in a unit cell without charge accumulation.

Near-Atomic Resolution Structure of a Plant Geminivirus Determined by Electron Cryomicroscopy.

PubMed

Hipp, Katharina; Grimm, Clemens; Jeske, Holger; Böttcher, Bettina

2017-08-01

African cassava mosaic virus is a whitefly-transmitted geminivirus which forms unique twin particles of incomplete icosahedra that are joined at five-fold vertices, building an unusual waist. How its 22 capsomers interact within a half-capsid or across the waist is unknown thus far. Using electron cryo-microscopy and image processing, we determined the virion structure with a resolution of 4.2 Å and built an atomic model for its capsid protein. The inter-capsomer contacts mediated by the flexible N termini and loop regions differed within the half-capsids and at the waist, explaining partly the unusual twin structure. The tip of the pentameric capsomer is sealed by a plug formed by a turn region harboring the evolutionary conserved residue Y193. Basic amino acid residues inside the capsid form a positively charged pocket next to the five-fold axis of the capsomer suitable for binding DNA. Within this pocket, density most likely corresponding to DNA was resolved. Copyright © 2017 Elsevier Ltd. All rights reserved.

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.

Report on the Installation and Preparedness of a Protochips Fusion in-situ Heating Holder for TEM

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

Edmondson, Philip D.

2017-03-01

This brief report documents the procurement and installation of a Protochips Fusion (formerly Aduro) high-temperature, high stability transmission electron microscopy (TEM) specimen holder that allows for the high spatial resolution characterization of material specimens at high temperature in situ of an electron microscope. This specimen holder was specifically procured for use with The FEI Talos F200X Scanning/Transmission Electron Microscope (STEM) in Oak Ridge National Laboratory’s (ORNL’s) Low Activation Materials Development and Analysis (LAMDA) Laboratory. The Protochips Fusion holder will enable high-resolution structural and chemical analysis of irradiated materials at high temperature, becoming a unique capability worldwide, and would encourage high-qualitymore » in situ experiments to be conducted on irradiated materials.« less

Segmented nanowires displaying locally controllable properties

DOEpatents

Sutter, Eli Anguelova; Sutter, Peter Werner

2013-03-05

Vapor-liquid-solid growth of nanowires is tailored to achieve complex one-dimensional material geometries using phase diagrams determined for nanoscale materials. Segmented one-dimensional nanowires having constant composition display locally variable electronic band structures that are determined by the diameter of the nanowires. The unique electrical and optical properties of the segmented nanowires are exploited to form electronic and optoelectronic devices. Using gold-germanium as a model system, in situ transmission electron microscopy establishes, for nanometer-sized Au--Ge alloy drops at the tips of Ge nanowires (NWs), the parts of the phase diagram that determine their temperature-dependent equilibrium composition. The nanoscale phase diagram is then used to determine the exchange of material between the NW and the drop. The phase diagram for the nanoscale drop deviates significantly from that of the bulk alloy.

Ultrathin 2D Photocatalysts: Electronic-Structure Tailoring, Hybridization, and Applications.

PubMed

Di, Jun; Xiong, Jun; Li, Huaming; Liu, Zheng

2018-01-01

As a sustainable technology, semiconductor photocatalysis has attracted considerable interest in the past several decades owing to the potential to relieve or resolve energy and environmental-pollution issues. By virtue of their unique structural and electronic properties, emerging ultrathin 2D materials with appropriate band structure show enormous potential to achieve efficient photocatalytic performance. Here, the state-of-the-art progress on ultrathin 2D photocatalysts is reviewed and a critical appraisal of the classification, controllable synthesis, and formation mechanism of ultrathin 2D photocatalysts is presented. Then, different strategies to tailor the electronic structure of ultrathin 2D photocatalysts are summarized, including component tuning, thickness tuning, doping, and defect engineering. Hybridization with the introduction of a foreign component and maintaining the ultrathin 2D structure is presented to further boost the photocatalytic performance, such as quantum dots/2D materials, single atoms/2D materials, molecular/2D materials, and 2D-2D stacking materials. More importantly, the advancement of versatile photocatalytic applications of ultrathin 2D photocatalysts in the fields of water oxidation, hydrogen evolution, CO 2 reduction, nitrogen fixation, organic syntheses, and removal pollutants is discussed. Finally, the future opportunities and challenges regarding ultrathin 2D photocatalysts to bring about new opportunities for future research in the field of photocatalysis are also presented. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

First Principles Study of Electronic and Magnetic Structures in Double Perovskites

NASA Astrophysics Data System (ADS)

Ball, Molly

At present, electronic devices are reaching their storage and processing limit causing a major push to find materials that can be used in the next generation of devices. Double perovskites with A2BB'O 6 stoichiometry form one of the leading classes of materials currently being studied as a potential candidate because of their extremely wide range and tunability of functional properties, along with economic and highly scalable synthesis routes. Having a thorough understanding of their electronic and magnetic structure and their dependence on composition and local structure is the basis for targeted development of novel and optimized double perovskites. While the body of knowledge and rules within the field of materials chemistry has enabled many previous discoveries, recent developments within density functional theory (DFT) allow by now a rather realistic description of the electronic and magnetic properties of materials and especially identification of their origin from geometry and orbital structure. This thesis details computational work based on DFT within several collaborative studies to better understand the electronic and magnetic properties of double perovskites and related materials that show promise for future use in multifunctional devices. First, we will begin with a general introduction to the double perovskite structure, their properties, and the computational methods used to study them. In the next section, we will look at the case of the antiferromagnetic, insulating double perovskite Sr2CoOsO6, where measurements showed that the transition metal ions in the two sublattices undergo magnetic ordering independently of each other, indicating weak magnetic short-range coupling and a dominance of longer-range interactions, which has previously not been observed. Here, we performed DFT calculations to extract the exchange strengths between the ions and explain this unique dominance of the long-range interactions. Then, we will look at studies done on thin films of Sr2CrReO 6, where our experimental collaborators found extraordinarily large anisotropy fields and record-breaking strain-tunable magnetocrystalline anisotropy (MCA). We employed first principles calculations that examine the dependence of MCA on strain and could identify orbital magnetism on the Re atoms as the origin of this unique phenomenon. In the last section, we introduce double perovskites as novel lead-free halide solar cell materials, with current focus on Cs2AgBiBr 6 and Cs2AgBiCl6. While organic Pb based halides that can be synthesized without expensive clean rooms have achieved within record time efficiencies that rival that of traditional semiconductor based materials, creating quite a buzz within the field of photovoltaics, their Pb content and lacking air stability represented severe roadblocks towards market introduction. Here, we show with band structure calculations that spin-orbit coupling is a much more dominant interaction than in traditional semiconductors and thus needs to be considered when designing novel materials for maximum efficiency. The results of this study have given momentum to investigate additional halides double perovskites. Finally, we will summarize and discuss the importance of computational modeling in order to explore the wide and to date little explored composition space of double perovskites, one of the currently most promising materials classes for novel devices with unique and extremely tunable properties.

Injectable 3-D Fabrication of Medical Electronics at the Target Biological Tissues

NASA Astrophysics Data System (ADS)

Jin, Chao; Zhang, Jie; Li, Xiaokang; Yang, Xueyao; Li, Jingjing; Liu, Jing

2013-12-01

Conventional transplantable biomedical devices generally request sophisticated surgery which however often causes big trauma and serious pain to the patients. Here, we show an alternative way of directly making three-dimensional (3-D) medical electronics inside the biological body through sequential injections of biocompatible packaging material and liquid metal ink. As the most typical electronics, a variety of medical electrodes with different embedded structures were demonstrated to be easily formed at the target tissues. Conceptual in vitro experiments provide strong evidences for the excellent performances of the injectable electrodes. Further in vivo animal experiments disclosed that the formed electrode could serve as both highly efficient ECG (Electrocardiograph) electrode and stimulator electrode. These findings clarified the unique features and practicability of the liquid metal based injectable 3-D fabrication of medical electronics. The present strategy opens the way for directly manufacturing electrophysiological sensors or therapeutic devices in situ via a truly minimally invasive approach.

Carrier generation and electronic properties of a single-component pure organic metal

NASA Astrophysics Data System (ADS)

Kobayashi, Yuka; Terauchi, Takeshi; Sumi, Satoshi; Matsushita, Yoshitaka

2017-01-01

Metallic conduction generally requires high carrier concentration and wide bandwidth derived from strong orbital interaction between atoms or molecules. These requisites are especially important in organic compounds because a molecule is fundamentally an insulator; only multi-component salts with strong intermolecular interaction--namely, only charge transfer complexes and conducting polymers--have demonstrated intrinsic metallic behaviour. Herein we report a single-component electroactive molecule, zwitterionic tetrathiafulvalene(TTF)-extended dicarboxylate radical (TED), exhibiting metallic conduction even at low temperatures. TED exhibits d.c. conductivities of 530 S cm-1 at 300 K and 1,000 S cm-1 at 50 K with copper-like electronic properties. Spectroscopic and theoretical investigations of the carrier-generation mechanism and the electronic states of this single molecular species reveal a unique electronic structure with a spin-density gradient in the extended TTF moieties that becomes, in itself, a metallic state.

Controlling competing orders via nonequilibrium acoustic phonons: Emergence of anisotropic effective electronic temperature

NASA Astrophysics Data System (ADS)

Schütt, Michael; Orth, Peter P.; Levchenko, Alex; Fernandes, Rafael M.

2018-01-01

Ultrafast perturbations offer a unique tool to manipulate correlated systems due to their ability to promote transient behaviors with no equilibrium counterpart. A widely employed strategy is the excitation of coherent optical phonons, as they can cause significant changes in the electronic structure and interactions on short time scales. One of the issues, however, is the inevitable heating that accompanies these resonant excitations. Here, we explore a promising alternative route: the nonequilibrium excitation of acoustic phonons, which, due to their low excitation energies, generally lead to less heating. We demonstrate that driving acoustic phonons leads to the remarkable phenomenon of a momentum-dependent effective temperature, by which electronic states at different regions of the Fermi surface are subject to distinct local temperatures. Such an anisotropic effective electronic temperature can have a profound effect on the delicate balance between competing ordered states in unconventional superconductors, opening a so far unexplored avenue to control correlated phases.

Electronic Transport in Two-Dimensional Materials

NASA Astrophysics Data System (ADS)

Sangwan, Vinod K.; Hersam, Mark C.

2018-04-01

Two-dimensional (2D) materials have captured the attention of the scientific community due to the wide range of unique properties at nanometer-scale thicknesses. While significant exploratory research in 2D materials has been achieved, the understanding of 2D electronic transport and carrier dynamics remains in a nascent stage. Furthermore, because prior review articles have provided general overviews of 2D materials or specifically focused on charge transport in graphene, here we instead highlight charge transport mechanisms in post-graphene 2D materials, with particular emphasis on transition metal dichalcogenides and black phosphorus. For these systems, we delineate the intricacies of electronic transport, including band structure control with thickness and external fields, valley polarization, scattering mechanisms, electrical contacts, and doping. In addition, electronic interactions between 2D materials are considered in the form of van der Waals heterojunctions and composite films. This review concludes with a perspective on the most promising future directions in this fast-evolving field.

Conformational gating of DNA conductance

PubMed Central

Artés, Juan Manuel; Li, Yuanhui; Qi, Jianqing; Anantram, M. P.; Hihath, Joshua

2015-01-01

DNA is a promising molecule for applications in molecular electronics because of its unique electronic and self-assembly properties. Here we report that the conductance of DNA duplexes increases by approximately one order of magnitude when its conformation is changed from the B-form to the A-form. This large conductance increase is fully reversible, and by controlling the chemical environment, the conductance can be repeatedly switched between the two values. The conductance of the two conformations displays weak length dependencies, as is expected for guanine-rich sequences, and can be fit with a coherence-corrected hopping model. These results are supported by ab initio electronic structure calculations that indicate that the highest occupied molecular orbital is more disperse in the A-form DNA case. These results demonstrate that DNA can behave as a promising molecular switch for molecular electronics applications and also provide additional insights into the huge dispersion of DNA conductance values found in the literature. PMID:26648400

Conformational gating of DNA conductance.

PubMed

Artés, Juan Manuel; Li, Yuanhui; Qi, Jianqing; Anantram, M P; Hihath, Joshua

2015-12-09

DNA is a promising molecule for applications in molecular electronics because of its unique electronic and self-assembly properties. Here we report that the conductance of DNA duplexes increases by approximately one order of magnitude when its conformation is changed from the B-form to the A-form. This large conductance increase is fully reversible, and by controlling the chemical environment, the conductance can be repeatedly switched between the two values. The conductance of the two conformations displays weak length dependencies, as is expected for guanine-rich sequences, and can be fit with a coherence-corrected hopping model. These results are supported by ab initio electronic structure calculations that indicate that the highest occupied molecular orbital is more disperse in the A-form DNA case. These results demonstrate that DNA can behave as a promising molecular switch for molecular electronics applications and also provide additional insights into the huge dispersion of DNA conductance values found in the literature.

Quasiparticle Interference Studies of Quantum Materials.

PubMed

Avraham, Nurit; Reiner, Jonathan; Kumar-Nayak, Abhay; Morali, Noam; Batabyal, Rajib; Yan, Binghai; Beidenkopf, Haim

2018-06-03

Exotic electronic states are realized in novel quantum materials. This field is revolutionized by the topological classification of materials. Such compounds necessarily host unique states on their boundaries. Scanning tunneling microscopy studies of these surface states have provided a wealth of spectroscopic characterization, with the successful cooperation of ab initio calculations. The method of quasiparticle interference imaging proves to be particularly useful for probing the dispersion relation of the surface bands. Herein, how a variety of additional fundamental electronic properties can be probed via this method is reviewed. It is demonstrated how quasiparticle interference measurements entail mesoscopic size quantization and the electronic phase coherence in semiconducting nanowires; helical spin protection and energy-momentum fluctuations in a topological insulator; and the structure of the Bloch wave function and the relative insusceptibility of topological electronic states to surface potential in a topological Weyl semimetal. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

How cryo‐electron microscopy and X‐ray crystallography complement each other

PubMed Central

Wang, Jia‐Wei

2016-01-01

Abstract With the ability to resolve structures of macromolecules at atomic resolution, X‐ray crystallography has been the most powerful tool in modern structural biology. At the same time, recent technical improvements have triggered a resolution revolution in the single particle cryo‐EM method. While the two methods are different in many respects, from sample preparation to structure determination, they both have the power to solve macromolecular structures at atomic resolution. It is important to understand the unique advantages and caveats of the two methods in solving structures and to appreciate the complementary nature of the two methods in structural biology. In this review we provide some examples, and discuss how X‐ray crystallography and cryo‐EM can be combined in deciphering structures of macromolecules for our full understanding of their biological mechanisms. PMID:27543495

How cryo-electron microscopy and X-ray crystallography complement each other.

PubMed

Wang, Hong-Wei; Wang, Jia-Wei

2017-01-01

With the ability to resolve structures of macromolecules at atomic resolution, X-ray crystallography has been the most powerful tool in modern structural biology. At the same time, recent technical improvements have triggered a resolution revolution in the single particle cryo-EM method. While the two methods are different in many respects, from sample preparation to structure determination, they both have the power to solve macromolecular structures at atomic resolution. It is important to understand the unique advantages and caveats of the two methods in solving structures and to appreciate the complementary nature of the two methods in structural biology. In this review we provide some examples, and discuss how X-ray crystallography and cryo-EM can be combined in deciphering structures of macromolecules for our full understanding of their biological mechanisms. © 2016 The Protein Society.

Nuclear resonance scattering of synchrotron radiation as a unique electronic, structural and thermodynamic probe

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

Alp, E. Ercan; Sturhahn, Wolfgang; Toellner, Thomas S.

2012-05-09

Discovery of Moessbauer effect in a nuclear transition was a remarkable development. It revealed how long-lived nuclear states with relatively low energies in the kiloelectron volt (keV) region can be excited without recoil. This new effect had a unique feature involving a coupling between nuclear physics and solid-state physics, both in terms of physics and sociology. Physics coupling originates from the fact that recoilless emission and absorption or resonance is only possible if the requirement that nuclei have to be bound in a lattice with quantized vibrational states is fulfilled, and that the finite electron density on the nucleus couplesmore » to nuclear degrees of freedom leading to hyperfine interactions. thus, Moessbauer spectroscopy allows peering into solid-state effects using unique nuclear transitions. Sociological aspects of this coupling had been equally startling and fruitful. The interaction between diverse scientific communities, who learned to use Moessbauer spectroscopy proved to be very valuable. For example, biologists, geologists, chemists, physics, materials scientists, and archeologists, all sharing a common spectroscopic technique, also learned to appreciate the beauty and intricacies of each other's fields. As a laboratory-based technique, Moessbauer spectroscopy matured by the end of the 1970s. Further exciting developments took place when accelerator-based techniques were employed, like synchrotron radiation or 'in-beam'Moessbauer experiments with implanted radioactive ions. More recently, two Moessbauer spectrometers on the surface of the Mars kept the technique vibrant and viable up until present time. In this chapter, the authors look into some of the unique aspects of nuclear resonance excited with synchrotron radiation as a probe of condensed matter, including magnetism, valence, vibrations, and lattice dynamics, and review the development of nuclear resonance inelastic x-ray scattering (NRIXS) and synchrotron Moessbauer spectroscopy (SMS). However, to place these two techniques into some perspective with respect to other methods that yield related information, they display their version of a frequently used map of momentum and energy transfer diagram in figure 17.1. Here, various probes like electrons, neutrons, or light, i.e., Brillouin or Raman, and relatively newer forms of X-ray scattering are placed according to their range of energy and momentum transfer taking place during the measurements. Accordingly, NRIXS is a method that needs to be considered as a complementary probe to inelastic neutron and X-ray scattering, while SMS occupies a unique space due to its sensitivity to magnetism, structural deformations, valence, and spin states.« less

Gamma ray irradiated silicon nanowires: An effective model to investigate defects at the interface of Si/SiOx

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

Yin, Kui; Zhao, Yi; Liu, Liangbin

2014-01-20

The effect of gamma ray irradiation on silicon nanowires was investigated. Here, an additional defect emerged in the gamma-ray-irradiated silicon nanowires and was confirmed with electron spin resonance spectra. {sup 29}Si nuclear magnetic resonance spectroscopy showed that irradiation doses had influence on the Q{sup 4} unit structure. This phenomenon indicated that the unique core/shell structure of silicon nanowires might contribute to induce metastable defects under gamma ray irradiation, which served as a satisfactory model to investigate defects at the interface of Si/SiOx.

Dynamics of the penetration boundaries of solar protons during a strong magnetic storm

NASA Technical Reports Server (NTRS)

Glukhov, G. A.; Kratenko, Y. P.; Mineev, Y. V.

1985-01-01

The variations in the equatorial penetration boundary of solar protons with E sub p = 0.9 to 8.0 MeV during a strong magnetic storm of April 3 to 5, were analyzed. The dynamics of this boundary is compared with the dynamics of the outer trapping boundary of electrons with E sub e = - 0.3 to 0.6 MeV. The solar-proton penetration and the structure of the real magnetic field are studied. The unique data on the thin structure of development of a magnetospheric substorm were obtained for the first time.

Development of structure in natural silk spinning and poly(vinyl alcohol) hydrogel formation

NASA Astrophysics Data System (ADS)

Willcox, Patricia Jeanene

This research involves the characterization of structure and structure formation in aqueous systems. Particularly, these studies investigate the effect of various processing variables on the structure formation that occurs upon conversion from aqueous solution to fiber or hydrogel. The two processes studied include natural silk fiber spinning and physical gelation of poly(vinyl alcohol), PVOH, in water. The techniques employed combine cryogenic technology for sample preparation and direct observation by transmission electron microscopy with electron diffraction, atomic force microscopy, optical rheometry, X-ray scattering and optical microscopy. In order to explore the full range of structure formation in natural silk spinning, studies are conducted in vivo and in vitro. In vivo structural investigations are accomplished through the cryogenic quenching and subsequent microtoming of live silk-spinning animals, Nephila clavipes (spider) and Bombyx mori (silkworm). Observations made using transmission electron microscopy, electron diffraction and atomic force microscopy indicate a cholesteric liquid crystalline mesophase of aqueous silk fibroin in both species. The mechanism of structure formation in solution is studied in vitro using optical rheometry on aqueous solutions made from regenerated Bombyx mori cocoon silk. Concentrated solutions exhibit birefringence under flow, with a wormlike conformation of the silk molecules in concentrated salt solution. Changes in salt concentration and pH of the aqueous silk solutions result in differing degrees of alignment and aggregation. These results suggest that structural control in the natural silk spinning process is accomplished by chemical manipulation of the electrostatic interactions and hydrogen bonding between chains. Application of cryogenic methods in transmission electron microscopy also provides a unique look at hydration-dependent structures in gels of poly(vinyl alcohol) produced by freeze-thaw processing. Morphologies ranging from circular pores to fibrillar networks are observed in gels formed from aqueous PVOH solutions subjected to cycles of freezing and thawing. These morphologies can be directly associated with the progressive nature of the mechanism of gelation as it proceeds from liquid-liquid phase separation to crystallization with increased cycling. A comparison of the structures produced by cycling and by aging suggests that there is a similarity in structural changes, but a superposition of the effects of cycling and aging is not possible.

Cell walls of the dimorphic fungal pathogens Sporothrix schenckii and Sporothrix brasiliensis exhibit bilaminate structures and sloughing of extensive and intact layers

PubMed Central

Walker, Louise A.; Niño-Vega, Gustavo; Mora-Montes, Héctor M.; Neves, Gabriela W. P.; Villalobos-Duno, Hector; Barreto, Laura; Garcia, Karina; Franco, Bernardo; Martínez-Álvarez, José A.; Munro, Carol A.; Gow, Neil A. R.

2018-01-01

Sporotrichosis is a subcutaneous mycosis caused by pathogenic species of the Sporothrix genus. A new emerging species, Sporothrix brasiliensis, is related to cat-transmitted sporotrichosis and has severe clinical manifestations. The cell wall of pathogenic fungi is a unique structure and impacts directly on the host immune response. We reveal and compare the cell wall structures of Sporothrix schenckii and S. brasiliensis using high-pressure freezing electron microscopy to study the cell wall organization of both species. To analyze the components of the cell wall, we also used infrared and 13C and 1H NMR spectroscopy and the sugar composition was determined by quantitative high-performance anion-exchange chromatography. Our ultrastructural data revealed a bi-layered cell wall structure for both species, including an external microfibrillar layer and an inner electron-dense layer. The inner and outer layers of the S. brasiliensis cell wall were thicker than those of S. schenckii, correlating with an increase in the chitin and rhamnose contents. Moreover, the outer microfibrillar layer of the S. brasiliensis cell wall had longer microfibrils interconnecting yeast cells. Distinct from those of other dimorphic fungi, the cell wall of Sporothrix spp. lacked α-glucan component. Interestingly, glycogen α-particles were identified in the cytoplasm close to the cell wall and the plasma membrane. The cell wall structure as well as the presence of glycogen α-particles varied over time during cell culture. The structural differences observed in the cell wall of these Sporothrix species seemed to impact its uptake by monocyte-derived human macrophages. The data presented here show a unique cell wall structure of S. brasiliensis and S. schenckii during the yeast parasitic phase. A new cell wall model for Sporothrix spp. is therefore proposed that suggests that these fungi molt sheets of intact cell wall layers. This observation may have significant effects on localized and disseminated immunopathology. PMID:29522522

Accessing protein conformational ensembles using room-temperature X-ray crystallography

PubMed Central

Fraser, James S.; van den Bedem, Henry; Samelson, Avi J.; Lang, P. Therese; Holton, James M.; Echols, Nathaniel; Alber, Tom

2011-01-01

Modern protein crystal structures are based nearly exclusively on X-ray data collected at cryogenic temperatures (generally 100 K). The cooling process is thought to introduce little bias in the functional interpretation of structural results, because cryogenic temperatures minimally perturb the overall protein backbone fold. In contrast, here we show that flash cooling biases previously hidden structural ensembles in protein crystals. By analyzing available data for 30 different proteins using new computational tools for electron-density sampling, model refinement, and molecular packing analysis, we found that crystal cryocooling remodels the conformational distributions of more than 35% of side chains and eliminates packing defects necessary for functional motions. In the signaling switch protein, H-Ras, an allosteric network consistent with fluctuations detected in solution by NMR was uncovered in the room-temperature, but not the cryogenic, electron-density maps. These results expose a bias in structural databases toward smaller, overpacked, and unrealistically unique models. Monitoring room-temperature conformational ensembles by X-ray crystallography can reveal motions crucial for catalysis, ligand binding, and allosteric regulation. PMID:21918110

Structure of the TRPV1 ion channel determined by electron cryo-microscopy.

PubMed

Liao, Maofu; Cao, Erhu; Julius, David; Cheng, Yifan

2013-12-05

Transient receptor potential (TRP) channels are sensors for a wide range of cellular and environmental signals, but elucidating how these channels respond to physical and chemical stimuli has been hampered by a lack of detailed structural information. Here we exploit advances in electron cryo-microscopy to determine the structure of a mammalian TRP channel, TRPV1, at 3.4 Å resolution, breaking the side-chain resolution barrier for membrane proteins without crystallization. Like voltage-gated channels, TRPV1 exhibits four-fold symmetry around a central ion pathway formed by transmembrane segments 5-6 (S5-S6) and the intervening pore loop, which is flanked by S1-S4 voltage-sensor-like domains. TRPV1 has a wide extracellular 'mouth' with a short selectivity filter. The conserved 'TRP domain' interacts with the S4-S5 linker, consistent with its contribution to allosteric modulation. Subunit organization is facilitated by interactions among cytoplasmic domains, including amino-terminal ankyrin repeats. These observations provide a structural blueprint for understanding unique aspects of TRP channel function.

Structure of the TRPV1 ion channel determined by electron cryo-microscopy

PubMed Central

Liao, Maofu; Cao, Erhu; Julius, David; Cheng, Yifan

2014-01-01

Transient receptor potential (TRP) channels are sensors for a wide range of cellular and environmental signals, but elucidating how these channels respond to physical and chemical stimuli has been hampered by a lack of detailed structural information. Here, we exploit advances in electron cryo-microscopy to determine the structure of a mammalian TRP channel, TRPV1, at 3.4Å resolution, breaking the side-chain resolution barrier for membrane proteins without crystallization. Like voltage-gated channels, TRPV1 exhibits four-fold symmetry around a central ion pathway formed by transmembrane helices S5–S6 and the intervening pore loop, which is flanked by S1–S4 voltage sensor-like domains. TRPV1 has a wide extracellular ‘mouth’ with short selectivity filter. The conserved ‘TRP domain’ interacts with the S4–S5 linker, consistent with its contribution to allosteric modulation. Subunit organization is facilitated by interactions among cytoplasmic domains, including N-terminal ankyrin repeats. These observations provide a structural blueprint for understanding unique aspects of TRP channel function. PMID:24305160

Formation of Tellurium Nanocrystals during Anaerobic Growth of Bacteria That Use Te Oxyanions as Respiratory Electron Acceptors▿

PubMed Central

Baesman, Shaun M.; Bullen, Thomas D.; Dewald, James; Zhang, Donghui; Curran, Seamus; Islam, Farhana S.; Beveridge, Terry J.; Oremland, Ronald S.

2007-01-01

Certain toxic elements support the metabolism of diverse prokaryotes by serving as respiratory electron acceptors for growth. Here, we demonstrate that two anaerobes previously shown to be capable of respiring oxyanions of selenium also achieve growth by reduction of either tellurate [Te(VI)] or tellurite [Te(IV)] to elemental tellurium [Te(0)]. This reduction achieves a sizeable stable-Te-isotopic fractionation (isotopic enrichment factor [ɛ] = −0.4 to −1.0 per ml per atomic mass unit) and results in the formation of unique crystalline Te(0) nanoarchitectures as end products. The Te(0) crystals occur internally within but mainly externally from the cells, and each microorganism forms a distinctly different structure. Those formed by Bacillus selenitireducens initially are nanorods (∼10-nm diameter by 200-nm length), which cluster together, forming larger (∼1,000-nm) rosettes composed of numerous individual shards (∼100-nm width by 1,000-nm length). In contrast, Sulfurospirillum barnesii forms extremely small, irregularly shaped nanospheres (diameter < 50 nm) that coalesce into larger composite aggregates. Energy-dispersive X-ray spectroscopy and selected area electron diffraction indicate that both biominerals are composed entirely of Te and are crystalline, while Raman spectroscopy confirms that they are in the elemental state. These Te biominerals have specific spectral signatures (UV-visible light, Raman) that also provide clues to their internal structures. The use of microorganisms to generate Te nanomaterials may be an alternative for bench-scale syntheses. Additionally, they may also generate products with unique properties unattainable by conventional physical/chemical methods. PMID:17277198

Formation of tellurium nanocrystals during anaerobic growth of bacteria that use Te oxyanions as respiratory electron acceptors

USGS Publications Warehouse

Baesman, S.M.; Bullen, T.D.; Dewald, J.; Zhang, Dongxiao; Curran, S.; Islam, F.S.; Beveridge, T.J.; Oremland, R.S.

2007-01-01

Certain toxic elements support the metabolism of diverse prokaryotes by serving as respiratory electron acceptors for growth. Here, we demonstrate that two anaerobes previously shown to be capable of respiring oxyanions of selenium also achieve growth by reduction of either tellurate [Te(VI)] or tellurite [Te(IV)] to elemental tellurium [Te(0)]. This reduction achieves a sizeable stable-Te-isotopic fractionation (isotopic enrichment factor [??] = -0.4 to -1.0 per ml per atomic mass unit) and results in the formation of unique crystalline Te(0) nanoarchitectures as end products. The Te(0) crystals occur internally within but mainly externally from the cells, and each microorganism forms a distinctly different structure. Those formed by Bacillus selenitireducens initially are nanorods (???10-nm diameter by 200-nm length), which cluster together, forming larger (???1,000-nm) rosettes composed of numerous individual shards (???100-nm width by 1,000-nm length). In contrast, Sulfurospirillium barnesii forms extremely small, irregularly shaped nanospheres (diameter < 50 nm) that coalesce into larger composite aggregates. Energy-dispersive X-ray spectroscopy and selected area electron diffraction indicate that both biominerals are composed entirely of Te and are crystalline, while Raman spectroscopy confirms that they are in the elemental state. These Te biominerals have specific spectral signatures (UV-visible light, Raman) that also provide clues to their internal structures. The use of microorganisms to generate Te nanomaterials may be an alternative for bench-scale syntheses. Additionally, they may also generate products with unique properties unattainable by conventional physical/chemical methods. Copyright ?? 2007, American Society for Microbiology. All Rights Reserved.

Localization of electrons due to orbitally ordered bi-stripes in the bilayer manganite La(2-2x)Sr(1+2x)Mn2O7 (x ~ 0.59).

PubMed

Sun, Z; Wang, Q; Fedorov, A V; Zheng, H; Mitchell, J F; Dessau, D S

2011-07-19

Electronic phases with stripe patterns have been intensively investigated for their vital roles in unique properties of correlated electronic materials. How these real-space patterns affect the conductivity and other properties of materials (which are usually described in momentum space) is one of the major challenges of modern condensed matter physics. By studying the electronic structure of La(2-2x)Sr(1+2x)Mn(2)O(7) (x ∼ 0.59) and in combination with earlier scattering measurements, we demonstrate the variation of electronic properties accompanying the melting of so-called bi-stripes in this material. The static bi-stripes can strongly localize the electrons in the insulating phase above T(c) ∼ 160 K, while the fraction of mobile electrons grows, coexisting with a significant portion of localized electrons when the static bi-stripes melt below T(c). The presence of localized electrons below T(c) suggests that the melting bi-stripes exist as a disordered or fluctuating counterpart. From static to melting, the bi-stripes act as an atomic-scale electronic valve, leading to a "colossal" metal-insulator transition in this material.

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

McCormac, Kathleen; Byrd, Ian; Brannen, Rodney

We prepared highly porous Si/TiO 2 composite nanofibres using a unique sulphur-templating method combined with electrospinning. The structure, morphology, surface area, phase and composition of these nanofibres were characterized using Raman spectroscopy, scanning electron microscopy, powder X-ray diffraction, surface area analyser and thermogravimetric analyser. The specific surface area of Si/TiO 2 porous NFs is as large as 387m 2g -1, whose silicon capacity can be maintained above 1580mAhg -1 in 180 cycles.

Well-Known Mediators of Selective Oxidation with Unknown Electronic Structure: Metal-Free Generation and EPR Study of Imide-N-oxyl Radicals.

PubMed

Krylov, Igor B; Kompanets, Mykhailo O; Novikova, Katerina V; Opeida, Iosip O; Kushch, Olga V; Shelimov, Boris N; Nikishin, Gennady I; Levitsky, Dmitri O; Terent'ev, Alexander O

2016-01-14

Nitroxyl radicals are widely used in chemistry, materials sciences, and biology. Imide-N-oxyl radicals are subclass of unique nitroxyl radicals that proved to be useful catalysts and mediators of selective oxidation and CH-functionalization. An efficient metal-free method was developed for the generation of imide-N-oxyl radicals from N-hydroxyimides at room temperature by the reaction with (diacetoxyiodo)benzene. The method allows for the production of high concentrations of free radicals and provides high resolution of their EPR spectra exhibiting the superhyperfine structure from benzene ring protons distant from the radical center. An analysis of the spectra shows that, regardless of the electronic effects of the substituents in the benzene ring, the superhyperfine coupling constant of an unpaired electron with the distant protons at positions 4 and 5 of the aromatic system is substantially greater than that with the protons at positions 3 and 6 that are closer to the N-oxyl radical center. This is indicative of an unusual character of the spin density distribution of the unpaired electron in substituted phthalimide-N-oxyl radicals. Understanding of the nature of the electron density distribution in imide-N-oxyl radicals may be useful for the development of commercial mediators of oxidation based on N-hydroxyimides.

Characteristics of gradient-interface-structured ZnCdSSe quantum dots with modified interface and its application to quantum-dot-sensitized solar cells

NASA Astrophysics Data System (ADS)

Jeong, Da-Woon; Kim, Jae-Yup; Seo, Han Wook; Lim, Kyoung-Mook; Ko, Min Jae; Seong, Tae-Yeon; Kim, Bum Sung

2018-01-01

Colloidal quantum dots (QDs) are attractive materials for application in photovoltaics, LEDs, displays, and bio devices owing to their unique properties. In this study, we synthesized gradient-interface-structured ZnCdSSe QDs and modified the interface based on a thermodynamic simulation to investigate its optical and physical properties. In addition, the interface was modified by increasing the molar concentration of Se. QDs at the modified interface were applied to QD-sensitized solar cells, which showed a 25.5% increase in photoelectric conversion efficiency owing to the reduced electron confinement effect. The increase seems to be caused by the excited electrons being relatively easily transferred to the level of TiO2 owing to the reduced electron confinement effect. Consequently, the electron confinement effect was observed to be reduced by increasing the ZnSe (or Zn1-xCdxSe)-rich phase at the interface. This means that, based on the thermodynamic simulation, the interface between the core QDs and the surface of the QDs can be controlled. The improvement of optical and electronic properties by controlling interfaces and surfaces during the synthesis of QDs, as reported in this work, can be useful for many applications beyond solar cells.

Localized versus itinerant states created by multiple oxygen vacancies in SrTiO3

NASA Astrophysics Data System (ADS)

Jeschke, Harald O.; Shen, Juan; Valentí, Roser

2015-02-01

Oxygen vacancies in strontium titanate surfaces (SrTiO3) have been linked to the presence of a two-dimensional electron gas with unique behavior. We perform a detailed density functional theory study of the lattice and electronic structure of SrTiO3 slabs with multiple oxygen vacancies, with a main focus on two vacancies near a titanium dioxide terminated SrTiO3 surface. We conclude based on total energies that the two vacancies preferably inhabit the first two layers, i.e. they cluster vertically, while in the direction parallel to the surface, the vacancies show a weak tendency towards equal spacing. Analysis of the nonmagnetic electronic structure indicates that oxygen defects in the surface TiO2 layer lead to population of Ti {{t}2g} states and thus itinerancy of the electrons donated by the oxygen vacancy. In contrast, electrons from subsurface oxygen vacancies populate Ti eg states and remain localized on the two Ti ions neighboring the vacancy. We find that both the formation of a bound oxygen-vacancy state composed of hybridized Ti 3eg and 4p states neighboring the oxygen vacancy as well as the elastic deformation after extracting oxygen contribute to the stabilization of the in-gap state.

Kinetic consequences of introducing a proximal selenocysteine ligand into cytochrome P450cam.

PubMed

Vandemeulebroucke, An; Aldag, Caroline; Stiebritz, Martin T; Reiher, Markus; Hilvert, Donald

2015-11-10

The structural, electronic, and catalytic properties of cytochrome P450cam are subtly altered when the cysteine that coordinates to the heme iron is replaced with a selenocysteine. To map the effects of the sulfur-to-selenium substitution on the individual steps of the catalytic cycle, we conducted a comparative kinetic analysis of the selenoenzyme and its cysteine counterpart. Our results show that the more electron-donating selenolate ligand has only negligible effects on substrate, product, and oxygen binding, electron transfer, catalytic turnover, and coupling efficiency. Off-pathway reduction of oxygen to give superoxide is the only step significantly affected by the mutation. Incorporation of selenium accelerates this uncoupling reaction approximately 50-fold compared to sulfur, but because the second electron transfer step is much faster, the impact on overall catalytic turnover is minimal. Density functional theory calculations with pure and hybrid functionals suggest that superoxide formation is governed by a delicate interplay of spin distribution, spin state, and structural effects. In light of the remarkably similar electronic structures and energies calculated for the sulfur- and selenium-containing enzymes, the ability of the heavier atom to enhance the rate of spin crossover may account for the experimental observations. Because the selenoenzyme closely mimics wild-type P450cam, even at the level of individual steps in the reaction cycle, selenium represents a unique mechanistic probe for analyzing the role of the proximal ligand and spin crossovers in P450 chemistry.

Sea Spray Aerosol Structure and Composition Using Cryogenic Transmission Electron Microscopy

PubMed Central

2016-01-01

The composition and surface properties of atmospheric aerosol particles largely control their impact on climate by affecting their ability to uptake water, react heterogeneously, and nucleate ice in clouds. However, in the vacuum of a conventional electron microscope, the native surface and internal structure often undergo physicochemical rearrangement resulting in surfaces that are quite different from their atmospheric configurations. Herein, we report the development of cryogenic transmission electron microscopy where laboratory generated sea spray aerosol particles are flash frozen in their native state with iterative and controlled thermal and/or pressure exposures and then probed by electron microscopy. This unique approach allows for the detection of not only mixed salts, but also soft materials including whole hydrated bacteria, diatoms, virus particles, marine vesicles, as well as gel networks within hydrated salt droplets—all of which will have distinct biological, chemical, and physical processes. We anticipate this method will open up a new avenue of analysis for aerosol particles, not only for ocean-derived aerosols, but for those produced from other sources where there is interest in the transfer of organic or biological species from the biosphere to the atmosphere. PMID:26878061

Role of 4 f electrons in crystallographic and magnetic complexity

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

Pathak, Arjun K.; Paudyal, Durga; Mudryk, Yaroslav

2017-08-09

Here, the functionality of many magnetic materials critically depends on first manipulating and then taking advantage of highly nonlinear changes of properties that occur during phase transformations. Unique to lanthanides, property-defining 4f electrons are highly localized and, as commonly accepted, play little to no role in chemical bonding. Yet here we demonstrate that the competition between 4f-electron energy landscapes of Dy (4f 9) and Er (4f 11) is the key element of the puzzle required to explain complex interplay of magnetic and structural features observed in Er 1–xDy xCo 2, and likely many other mixed lanthanide systems. Unlike the parentmore » binaries—DyCo 2 and ErCo 2—Er 1–xDy xCo 2 exhibits two successive magnetostructural transitions: a first order at TC, followed by a second order in the ferrimagnetically ordered state. Supported by first-principles calculations, our results offer new opportunities for targeted design of magnetic materials with multiple functionalities, and also provide a critical insight into the role of 4f electrons in controlling the magnetism and structure of lanthanide intermetallics.« less

Excitonic Properties of Chemically Synthesized 2D Organic-Inorganic Hybrid Perovskite Nanosheets.

PubMed

Zhang, Qi; Chu, Leiqiang; Zhou, Feng; Ji, Wei; Eda, Goki

2018-05-01

2D organic-inorganic hybrid perovskites (OIHPs) represent a unique class of materials with a natural quantum-well structure and quasi-2D electronic properties. Here, a versatile direct solution-based synthesis of mono- and few-layer OIHP nanosheets and a systematic study of their electronic structure as a function of the number of monolayers by photoluminescence and absorption spectroscopy are reported. The monolayers of various OIHPs are found to exhibit high electronic quality as evidenced by high quantum yield and negligible Stokes shift. It is shown that the ground exciton peak blueshifts by ≈40 meV when the layer thickness reduces from bulk to monolayer. It is also shown that the exciton binding energy remains effectively unchanged for (C 6 H 5 (CH 2 ) 2 NH 3 ) 2 PbI 4 with the number of layers. Similar trends are observed for (C 4 H 9 NH 3 ) 2 PbI 4 in contrast to the previous report. Further, the photoluminescence lifetime is found to decrease with the number of monolayers, indicating the dominant role of surface trap states in nonradiative recombination of the electron-hole pairs. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Atomic Scale Control of Competing Electronic Phases in Ultrathin Correlated Oxides

NASA Astrophysics Data System (ADS)

Shen, Kyle

2015-03-01

Ultrathin epitaxial thin films offer a number of unique advantages for engineering the electronic properties of correlated transition metal oxides. For example, atomically thin films can be synthesized to artificially confine electrons in two dimensions. Furthermore, using a substrate with a mismatched lattice constant can impose large biaxial strains of larger than 3% (Δa / a), much larger than can achieved in bulk single crystals. Since these dimensionally confined or strained systems may necessarily be less than a few unit cells thick, investigating their properties and electronic structure can be particularly challenging. We employ a combination of reactive oxide molecular beam epitaxy (MBE) and angle-resolved photoemission spectroscopy (ARPES) to investigate how dimensional confinement and epitaxial strain can be used to manipulate electronic properties and structure in correlated transition metal oxide thin films. We describe some of our recent work manipulating and studying the electronic structure of ultrathin LaNiO3 through a thickness-driven metal-insulator transition between three and two unit cells (Nature Nanotechnology 9, 443, 2014), where coherent Fermi liquid-like quasiparticles are suppressed at the metal-insulator transition observed in transport. We also will describe some recent unpublished work using epitaxial strain to drive a Lifshitz transition in atomically thin films of the spin-triplet ruthenate superconductor Sr2RuO4, where we also can dramatically alter the quasiparticle scattering rates and drive the system towards non-Fermi liquid behavior near the critical point (B. Burganov, C. Adamo, in preparation). Funding provided by the Office of Naval Research and Air Force Office of Scientific Research.

Computational Discovery of New Materials Under Pressure

NASA Astrophysics Data System (ADS)

Zurek, Eva

The pressure variable opens the door towards the synthesis of materials with unique properties, ie. superconductivity, hydrogen storage media, high-energy density and superhard materials, to name a few. Indeed, recently superconductivity has been observed below 203 K and 103 K in samples of compressed sulfur dihydride and phosphine, respectively. Under pressure elements that would not normally combine may form stable compounds, or may mix in novel proportions. As a result using our chemical intuition developed at 1 atm to theoretically predict stable phases is bound to fail. In order to enable our search for superconducting hydrogen-rich systems under pressure, we have developed XtalOpt, an open-source evolutionary algorithm for crystal structure prediction. New advances in XtalOpt that enable the prediction of unit cells with greater complexity will be described. XtalOpt has been employed to find the most stable structures of hydrides with unique stoichiometries under pressure. The electronic structure and bonding of the predicted phases has been analyzed by detailed first-principles calculations based on density functional theory. The results of our computational experiments are helping us to build chemical and physical intuition for compressed solids.

Fabrication and characterization of ordered arrays of nanostructures

NASA Astrophysics Data System (ADS)

Larson, Preston

2005-11-01

Nanostructures are currently of great interest because of their unique properties and potential applications in a wide range of areas such as opto-electronic and biomedical devices. Current research in nanotechnology involves fabrication and characterization of these structures, as well as theoretical and experimental studies to explore their unique and novel properties. Not only do nanostructures have the potential to be both evolutionary (state-of-the-art ICs have more and more features on the nanoscale) but revolutionary (quantum computing) as well. In this thesis, a combination of bottom-up and top-down approaches is explored to fabricate ordered arrays of nanostrucutures. The bottom-up approach involves the growth of self-organized porous anodic aluminum oxide (AAO) films. AAO films consist of a well ordered hexagonal array of close-packed pores with diameters and spacings ranging from around 5 to 500 nm. Via a top-down approach, these AAO films are then used as masks or templates to fabricate ordered arrays of nanostructures (i.e. dots, holes, meshes, pillars, rings, etc.) of various materials using conventional deposition and/or etching techniques. Using AAO films as masks allows a simple and economical method to fabricate arrays of structures with nano-scale dimensions. Furthermore, they allow the fabrication of large areas (many millimeters on a side) of highly uniform and well-ordered arrays of nanostructures, a crucial requirement for most characterization techniques and applications. Characterization of these nanostructures using various techniques (electron microscopy, atomic force microscopy, UV-Vis absorption spectroscopy, photoluminescence, capacitance-voltage measurements, magnetization hysteresis curves, etc.) will be presented. Finally, these structures provide a unique opportunity to determine the single and collective properties of nanostructure arrays and will have various future applications including but not limited to: data storage, light emitting or sensing devices, nano-tribological coatings for surfaces, bio-sensors, filters, and more.

Investigating the effect of background magnetic field on the resonance condition between EMIC waves and relativistic electrons

NASA Astrophysics Data System (ADS)

Woodger, L. A.; Millan, R. M.

2017-12-01

Balloon-borne x-ray detectors observe bremsstrahlung from precipitating electrons, offering a unique opportunity to observe sustained precipitation from a quasi-geosynchronous platform. Recent balloon observations of duskside relativistic electron precipitation (REP) on BARREL confirm that Electro-Magnetic Ion Cyclotron (EMIC) waves cause electron precipitation [e.g. Li et al., 2014]. However, BARREL observations show precipitation does not occur everywhere that waves are observed; precipitation is confined to narrow magnetic local time (MLT) regions in the duskside magnetosphere [Blum et al., 2015]. Furthermore, modulation of relativistic electron precipitation on Ultra Low Frequency (ULF) wave (f < 20 mHz) timescales has been reported in several events from balloon X-ray observations [Foat et al., 1998; Millan et al., 2002]. Wave-particle interaction between relativistic electrons and EMIC waves is a highly debated loss processes contributing to the dynamics of Earth's radiation belts. We present REP from balloon x-ray observations in the context of precipitation driven by EMIC waves. We investigate how background magnetic field strength could drive the localization, distribution, and temporal structure of the precipitating electrons.

Morphology control, defect engineering and photoactivity tuning of ZnO crystals by graphene oxide--a unique 2D macromolecular surfactant.

PubMed

Pan, Xiaoyang; Yang, Min-Quan; Xu, Yi-Jun

2014-03-28

Zinc oxide (ZnO) nanostructured materials have received significant attention because of their unique physicochemical and electronic properties. In particular, the functional properties of ZnO are strongly dependent on its morphology and defect structure, particularly for a semiconductor ZnO-based photocatalyst. Here, we demonstrate a simple strategy for simultaneous morphology control, defect engineering and photoactivity tuning of semiconductor ZnO by utilizing the unique surfactant properties of graphene oxide (GO) in a liquid phase. By varying the amount of GO added during the synthesis process, the morphology of ZnO gradually evolves from a one dimensional prismatic rod to a hexagonal tube-like architecture while GO is converted into reduced GO (RGO). In addition, the introduction of GO can create oxygen vacancies in the lattice of ZnO crystals. As a result, the absorption edge of the wide band gap semiconductor ZnO is effectively extended to the visible light region, which thus endows the RGO-ZnO nanocomposites with visible light photoactivity; in contrast, the bare ZnO nanorod is only UV light photoactive. The synergistic integration of the unique morphology and the presence of oxygen vacancies imparts the RGO-ZnO nanocomposite with remarkably enhanced visible light photoactivity as compared to bare ZnO and its counterpart featuring different structural morphologies and the absence of oxygen vacancies. Our promising results highlight the versatility of the 2D GO as a solution-processable macromolecular surfactant to fabricate RGO-semiconductor nanocomposites with tunable morphology, defect structure and photocatalytic performance in a system-materials-engineering way.

Multifunctional Nanostructured Conductive Polymer Gels: Synthesis, Properties, and Applications

DOE PAGES

Zhao, Fei; Shi, Ye; Pan, Lijia; ...

2017-06-26

Conductive polymers have attracted significant interest over the past few decades because they synergize the advantageous features of conventional polymeric materials and organic conductors. With rationally designed nanostructures, conductive polymers can further exhibit exceptional mechanical, electrical, and optical properties because of their confined dimensions at the nanoscale level. Among various nanostructured conductive polymers, conductive polymer gels (CPGs) with synthetically tunable hierarchical 3D network structures show great potential for a wide range of applications, such as bioelectronics, and energy storage/conversion devices owing to their structural features. CPGs retain the properties of nanosized conductive polymers during the assembly of the nanobuilding blocksmore » into a monolithic macroscopic structure while generating structure-derived features from the highly cross-linked network. In this Account, we review our recent progress on the synthesis, properties, and novel applications of dopant cross-linked CPGs. We first describe the synthetic strategies, in which molecules with multiple functional groups are adopted as cross-linkers to cross-link conductive polymer chains into a 3D molecular network. These cross-linking molecules also act as dopants to improve the electrical conductivity of the gel network. The microstructure and physical/chemical properties of CPGs can be tuned by controlling the synthetic conditions such as species of monomers and cross-linkers, reaction temperature, and solvents. By incorporating other functional polymers or particles into the CPG matrix, hybrid gels have been synthesized with tailored structures. These hybrid gel materials retain the functionalities from each component, as well as enable synergic effects to improve mechanical and electrical properties of CPGs. We then introduce the unique structure-derived properties of the CPGs. The network facilitates both electronic and ionic transport owing to the continuous pathways for electrons and hierarchical pores for ion diffusion. CPGs also provide high surface area and solvent compatibility, similar to natural gels. With these improved properties, CPGs have been explored to enable novel conceptual devices in diverse applications from smart electronics and ultrasensitive biosensors, to energy storage and conversion devices. CPGs have also been adopted for developing hybrid materials with multifunctionalities, such as stimuli responsiveness, self-healing properties, and super-repellency to liquid. With synthetically tunable physical/chemical properties, CPGs emerge as a unique material platform to develop novel multifunctional materials that have the potential to impact electronics, energy, and environmental technologies. Our hope is that this Account promotes further efforts toward synthetic control, fundamental investigation, and application exploration of CPGs.« less

Multifunctional Nanostructured Conductive Polymer Gels: Synthesis, Properties, and Applications

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

Zhao, Fei; Shi, Ye; Pan, Lijia

Conductive polymers have attracted significant interest over the past few decades because they synergize the advantageous features of conventional polymeric materials and organic conductors. With rationally designed nanostructures, conductive polymers can further exhibit exceptional mechanical, electrical, and optical properties because of their confined dimensions at the nanoscale level. Among various nanostructured conductive polymers, conductive polymer gels (CPGs) with synthetically tunable hierarchical 3D network structures show great potential for a wide range of applications, such as bioelectronics, and energy storage/conversion devices owing to their structural features. CPGs retain the properties of nanosized conductive polymers during the assembly of the nanobuilding blocksmore » into a monolithic macroscopic structure while generating structure-derived features from the highly cross-linked network. In this Account, we review our recent progress on the synthesis, properties, and novel applications of dopant cross-linked CPGs. We first describe the synthetic strategies, in which molecules with multiple functional groups are adopted as cross-linkers to cross-link conductive polymer chains into a 3D molecular network. These cross-linking molecules also act as dopants to improve the electrical conductivity of the gel network. The microstructure and physical/chemical properties of CPGs can be tuned by controlling the synthetic conditions such as species of monomers and cross-linkers, reaction temperature, and solvents. By incorporating other functional polymers or particles into the CPG matrix, hybrid gels have been synthesized with tailored structures. These hybrid gel materials retain the functionalities from each component, as well as enable synergic effects to improve mechanical and electrical properties of CPGs. We then introduce the unique structure-derived properties of the CPGs. The network facilitates both electronic and ionic transport owing to the continuous pathways for electrons and hierarchical pores for ion diffusion. CPGs also provide high surface area and solvent compatibility, similar to natural gels. With these improved properties, CPGs have been explored to enable novel conceptual devices in diverse applications from smart electronics and ultrasensitive biosensors, to energy storage and conversion devices. CPGs have also been adopted for developing hybrid materials with multifunctionalities, such as stimuli responsiveness, self-healing properties, and super-repellency to liquid. With synthetically tunable physical/chemical properties, CPGs emerge as a unique material platform to develop novel multifunctional materials that have the potential to impact electronics, energy, and environmental technologies. Our hope is that this Account promotes further efforts toward synthetic control, fundamental investigation, and application exploration of CPGs.« less

Multifunctional Nanostructured Conductive Polymer Gels: Synthesis, Properties, and Applications.

PubMed

Zhao, Fei; Shi, Ye; Pan, Lijia; Yu, Guihua

2017-07-18

Conductive polymers have attracted significant interest over the past few decades because they synergize the advantageous features of conventional polymeric materials and organic conductors. With rationally designed nanostructures, conductive polymers can further exhibit exceptional mechanical, electrical, and optical properties because of their confined dimensions at the nanoscale level. Among various nanostructured conductive polymers, conductive polymer gels (CPGs) with synthetically tunable hierarchical 3D network structures show great potential for a wide range of applications, such as bioelectronics, and energy storage/conversion devices owing to their structural features. CPGs retain the properties of nanosized conductive polymers during the assembly of the nanobuilding blocks into a monolithic macroscopic structure while generating structure-derived features from the highly cross-linked network. In this Account, we review our recent progress on the synthesis, properties, and novel applications of dopant cross-linked CPGs. We first describe the synthetic strategies, in which molecules with multiple functional groups are adopted as cross-linkers to cross-link conductive polymer chains into a 3D molecular network. These cross-linking molecules also act as dopants to improve the electrical conductivity of the gel network. The microstructure and physical/chemical properties of CPGs can be tuned by controlling the synthetic conditions such as species of monomers and cross-linkers, reaction temperature, and solvents. By incorporating other functional polymers or particles into the CPG matrix, hybrid gels have been synthesized with tailored structures. These hybrid gel materials retain the functionalities from each component, as well as enable synergic effects to improve mechanical and electrical properties of CPGs. We then introduce the unique structure-derived properties of the CPGs. The network facilitates both electronic and ionic transport owing to the continuous pathways for electrons and hierarchical pores for ion diffusion. CPGs also provide high surface area and solvent compatibility, similar to natural gels. With these improved properties, CPGs have been explored to enable novel conceptual devices in diverse applications from smart electronics and ultrasensitive biosensors, to energy storage and conversion devices. CPGs have also been adopted for developing hybrid materials with multifunctionalities, such as stimuli responsiveness, self-healing properties, and super-repellency to liquid. With synthetically tunable physical/chemical properties, CPGs emerge as a unique material platform to develop novel multifunctional materials that have the potential to impact electronics, energy, and environmental technologies. We hope that this Account promotes further efforts toward synthetic control, fundamental investigation, and application exploration of CPGs.

Diazonium functionalized graphene: microstructure, electric, and magnetic properties.

PubMed

Huang, Ping; Jing, Long; Zhu, Huarui; Gao, Xueyun

2013-01-15

The unique honeycomb lattice structure of graphene gives rise to its outstanding electronic properties such as ultrahigh carrier mobility, ballistic transport, and more. However, a crucial obstacle to its use in the electronics industry is its lack of an energy bandgap. A covalent chemistry strategy could overcome this problem, and would have the benefits of being highly controllable and stable in the ambient environment. One possible approach is aryl diazonium functionalization. In this Account, we investigate the micromolecular/lattice structure, electronic structure, and electron-transport properties of nitrophenyl-diazonium-functionalized graphene. We find that nitrophenyl groups mainly adopt random and inhomogeneous configurations on the graphene basal plane, and that their bonding with graphene carbon atoms leads to slight elongation of the graphene lattice spacing. By contrast, hydrogenated graphene has a compressed lattice. Low levels of functionalization suppressed the electric conductivity of the resulting functionalized graphene, while highly functionalized graphene showed the opposite effect. This difference arises from the competition between the charge transfer effect and the scattering enhancement effect introduced by nitrophenyl groups bonding with graphene carbon atoms. Detailed electron transport measurements revealed that the nitrophenyl diazonium functionalization locally breaks the symmetry of graphene lattice, which leads to an increase in the density of state near the Fermi level, thus increasing the carrier density. On the other hand, the bonded nitrophenyl groups act as scattering centers, lowering the mean free path of the charge carriers and suppressing the carrier mobility. In rare cases, we observed ordered configurations of nitrophenyl groups in local domains on graphene flakes due to fluctuations in the reaction processes. We describe one example of such a superlattice, with a lattice constant nearly twice of that of pristine graphene. We performed comprehensive theoretical calculations to investigate the lattice and the electronic structure of the superlattice structure. Our results reveal that it is a thermodynamically stable, spin-polarized semiconductor with a bandgap of ∼0.5 eV. Our results demonstrate the possibility of controlling graphene's electronic properties using aryl diazonium functionalization. Asymmetric addition of aryl groups to different sublattices of graphene is a promising approach for producing ferromagnetic, semiconductive graphene, which will have broad applications in the electronic industry.

On the release of cppxfel for processing X-ray free-electron laser images.

PubMed

Ginn, Helen Mary; Evans, Gwyndaf; Sauter, Nicholas K; Stuart, David Ian

2016-06-01

As serial femtosecond crystallography expands towards a variety of delivery methods, including chip-based methods, and smaller collected data sets, the requirement to optimize the data analysis to produce maximum structure quality is becoming increasingly pressing. Here cppxfel , a software package primarily written in C++, which showcases several data analysis techniques, is released. This software package presently indexes images using DIALS (diffraction integration for advanced light sources) and performs an initial orientation matrix refinement, followed by post-refinement of individual images against a reference data set. Cppxfel is released with the hope that the unique and useful elements of this package can be repurposed for existing software packages. However, as released, it produces high-quality crystal structures and is therefore likely to be also useful to experienced users of X-ray free-electron laser (XFEL) software who wish to maximize the information extracted from a limited number of XFEL images.

New materials graphyne, graphdiyne, graphone, and graphane: review of properties, synthesis, and application in nanotechnology.

PubMed

Peng, Qing; Dearden, Albert K; Crean, Jared; Han, Liang; Liu, Sheng; Wen, Xiaodong; De, Suvranu

2014-01-01

Plenty of new two-dimensional materials including graphyne, graphdiyne, graphone, and graphane have been proposed and unveiled after the discovery of the "wonder material" graphene. Graphyne and graphdiyne are two-dimensional carbon allotropes of graphene with honeycomb structures. Graphone and graphane are hydrogenated derivatives of graphene. The advanced and unique properties of these new materials make them highly promising for applications in next generation nanoelectronics. Here, we briefly review their properties, including structural, mechanical, physical, and chemical properties, as well as their synthesis and applications in nanotechnology. Graphyne is better than graphene in directional electronic properties and charge carriers. With a band gap and magnetism, graphone and graphane show important applications in nanoelectronics and spintronics. Because these materials are close to graphene and will play important roles in carbon-based electronic devices, they deserve further, careful, and thorough studies for nanotechnology applications.

Amorphous Red Phosphorus Embedded in Sandwiched Porous Carbon Enabling Superior Sodium Storage Performances.

PubMed

Wu, Ying; Liu, Zheng; Zhong, Xiongwu; Cheng, Xiaolong; Fan, Zhuangjun; Yu, Yan

2018-03-01

The red P anode for sodium ion batteries has attracted great attention recently due to the high theoretical capacity, but the poor intrinsic electronic conductivity and large volume expansion restrain its widespread applications. Herein, the red P is successfully encapsulated into the cube shaped sandwich-like interconnected porous carbon building (denoted as P@C-GO/MOF-5) via the vaporization-condensation method. Superior cycling stability (high capacity retention of about 93% at 2 A g -1 after 100 cycles) and excellent rate performance (502 mAh g -1 at 10 A g -1 ) can be obtained for the P@C-GO/MOF-5 electrode. The superior electrochemical performance can be ascribed to the successful incorporation of red P into the unique carbon matrix with large surface area and pore volume, interconnected porous structure, excellent electronic conductivity and superior structural stability. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Giant piezoelectricity of monolayer group IV monochalcogenides

NASA Astrophysics Data System (ADS)

Fei, Ruixiang; Li, Wenbin; Li, Ju; Yang, Li

We predict enormous, anisotropic piezoelectric effects in intrinsic monolayer group IV monochalcogenides (MX, M =Sn or Ge, X =Se or S), including SnSe, SnS, GeSe, and GeS. Using first-principle simulations based on the modern theory of polarization, we find that their piezoelectric coefficients are about one to two orders of magnitude larger than those of other 2D materials, such as MoS2 and GaSe, and bulk quartz and AlN which are widely used in industry. This enhancement is a result of the unique ``puckered'' C2v symmetry and electronic structure of monolayer group IV monochalcogenides. Given the achieved experimental advances in the fabrication of monolayers, their flexible character, and ability to withstand enormous strain, these 2D structures with giant piezoelectric effects may be promising for a broad range of applications such as nano-sized sensors, piezotronics, and energy harvesting in portable electronic devices.

Fabrication of anodic aluminium oxide templates on curved surfaces.

PubMed

Yin, Aijun; Guico, Rodney S; Xu, Jimmy

2007-01-24

Aluminium anodization provides a simple and inexpensive way to obtain nanoporous templates with uniform and controllable pore diameters and periods over a wide range. Moreover, one of the interesting possibilities afforded by the anodization process is that the anodization can take place on arbitrary surfaces, such as curved surfaces, which has not yet been well studied or applied in nanofabrication. In this paper, we characterize the anodization of Al films on silicon substrates with a curved top surface. The structures of the resultant anodic aluminium oxide (AAO) films are examined by scanning electron microscopy. Unique features including cessation, bending, and branching of pore channels are observed in the curved area. Possible growth mechanisms are proposed, which can also contribute to the understanding of the self-organization mechanism in the formation of porous AAO membranes. The new structures may open new opportunities in optical, electronic and electrochemical applications.

Pre-Town Meeting on spin physics at an Electron-Ion Collider

NASA Astrophysics Data System (ADS)

Aschenauer, Elke-Caroline; Balitsky, Ian; Bland, Leslie; Brodsky, Stanley J.; Burkardt, Matthias; Burkert, Volker; Chen, Jian-Ping; Deshpande, Abhay; Diehl, Markus; Gamberg, Leonard; Grosse Perdekamp, Matthias; Huang, Jin; Hyde, Charles; Ji, Xiangdong; Jiang, Xiaodong; Kang, Zhong-Bo; Kubarovsky, Valery; Lajoie, John; Liu, Keh-Fei; Liu, Ming; Liuti, Simonetta; Melnitchouk, Wally; Mulders, Piet; Prokudin, Alexei; Tarasov, Andrey; Qiu, Jian-Wei; Radyushkin, Anatoly; Richards, David; Sichtermann, Ernst; Stratmann, Marco; Vogelsang, Werner; Yuan, Feng

2017-04-01

A polarized ep/ eA collider (Electron-Ion Collider, or EIC), with polarized proton and light-ion beams and unpolarized heavy-ion beams with a variable center-of-mass energy √{s} ˜ 20 to ˜ 100 GeV (upgradable to ˜ 150 GeV) and a luminosity up to ˜ 10^{34} cm-2s-1, would be uniquely suited to address several outstanding questions of Quantum Chromodynamics, and thereby lead to new qualitative and quantitative information on the microscopic structure of hadrons and nuclei. During this meeting at Jefferson Lab we addressed recent theoretical and experimental developments in the spin and the three-dimensional structure of the nucleon (sea quark and gluon spatial distributions, orbital motion, polarization, and their correlations). This mini-review contains a short update on progress in these areas since the EIC White paper (A. Accardi et al., Eur. Phys. J. A 52, 268 (2016)).

Atom Probe Tomography Studies on the Cu(In,Ga)Se2 Grain Boundaries

PubMed Central

Cojocaru-Mirédin, Oana; Schwarz, Torsten; Choi, Pyuck-Pa; Herbig, Michael; Wuerz, Roland; Raabe, Dierk

2013-01-01

Compared with the existent techniques, atom probe tomography is a unique technique able to chemically characterize the internal interfaces at the nanoscale and in three dimensions. Indeed, APT possesses high sensitivity (in the order of ppm) and high spatial resolution (sub nm). Considerable efforts were done here to prepare an APT tip which contains the desired grain boundary with a known structure. Indeed, site-specific sample preparation using combined focused-ion-beam, electron backscatter diffraction, and transmission electron microscopy is presented in this work. This method allows selected grain boundaries with a known structure and location in Cu(In,Ga)Se2 thin-films to be studied by atom probe tomography. Finally, we discuss the advantages and drawbacks of using the atom probe tomography technique to study the grain boundaries in Cu(In,Ga)Se2 thin-film solar cells. PMID:23629452

New materials graphyne, graphdiyne, graphone, and graphane: review of properties, synthesis, and application in nanotechnology

PubMed Central

Peng, Qing; Dearden, Albert K; Crean, Jared; Han, Liang; Liu, Sheng; Wen, Xiaodong; De, Suvranu

2014-01-01

Plenty of new two-dimensional materials including graphyne, graphdiyne, graphone, and graphane have been proposed and unveiled after the discovery of the “wonder material” graphene. Graphyne and graphdiyne are two-dimensional carbon allotropes of graphene with honeycomb structures. Graphone and graphane are hydrogenated derivatives of graphene. The advanced and unique properties of these new materials make them highly promising for applications in next generation nanoelectronics. Here, we briefly review their properties, including structural, mechanical, physical, and chemical properties, as well as their synthesis and applications in nanotechnology. Graphyne is better than graphene in directional electronic properties and charge carriers. With a band gap and magnetism, graphone and graphane show important applications in nanoelectronics and spintronics. Because these materials are close to graphene and will play important roles in carbon-based electronic devices, they deserve further, careful, and thorough studies for nanotechnology applications. PMID:24808721

Nanostructural features degrading the performance of superconducting radio frequency niobium cavities revealed by transmission electron microscopy and electron energy loss spectroscopy

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

Trenikhina, Y.; Romanenko, A.; Kwon, J.

Nanoscale defect structure within the magnetic penetration depth of ~100 nm is key to the performance limitations of niobium superconducting radio frequency cavities. Using a unique combination of advanced thermometry during cavity RF measurements, and TEM structural and compositional characterization of the samples extracted from cavity walls, we discover the existence of nanoscale hydrides in electropolished cavities limited by the high field Q slope, and show the decreased hydride formation in the electropolished cavity after 120°C baking. Furthermore, we demonstrate that adding 800°C hydrogen degassing followed by light buffered chemical polishing restores the hydride formation to the pre-120°C bake level.more » We also show absence of niobium oxides along the grain boundaries and the modifications of the surface oxide upon 120°C bake.« less

Nanostructural features degrading the performance of superconducting radio frequency niobium cavities revealed by transmission electron microscopy and electron energy loss spectroscopy

DOE PAGES

Trenikhina, Y.; Romanenko, A.; Kwon, J.; ...

2015-04-21

Nanoscale defect structure within the magnetic penetration depth of ~100 nm is key to the performance limitations of niobium superconducting radio frequency cavities. Using a unique combination of advanced thermometry during cavity RF measurements, and TEM structural and compositional characterization of the samples extracted from cavity walls, we discover the existence of nanoscale hydrides in electropolished cavities limited by the high field Q slope, and show the decreased hydride formation in the electropolished cavity after 120°C baking. Furthermore, we demonstrate that adding 800°C hydrogen degassing followed by light buffered chemical polishing restores the hydride formation to the pre-120°C bake level.more » We also show absence of niobium oxides along the grain boundaries and the modifications of the surface oxide upon 120°C bake.« less

Nanostructural features degrading the performance of superconducting radio frequency niobium cavities revealed by transmission electron microscopy and electron energy loss spectroscopy

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

Trenikhina, Y., E-mail: yuliatr@fnal.gov; Fermi National Accelerator Laboratory, Batavia, Illinois 60510; Romanenko, A., E-mail: aroman@fnal.gov

Nanoscale defect structure within the magnetic penetration depth of ∼100 nm is key to the performance limitations of niobium superconducting radio frequency cavities. Using a unique combination of advanced thermometry during cavity RF measurements, and TEM structural and compositional characterization of the samples extracted from cavity walls, we discover the existence of nanoscale hydrides in electropolished cavities limited by the high field Q slope, and show the decreased hydride formation in the electropolished cavity after 120 °C baking. Furthermore, we demonstrate that adding 800 °C hydrogen degassing followed by light buffered chemical polishing restores the hydride formation to the pre-120 °C bake level. Wemore » also show absence of niobium oxides along the grain boundaries and the modifications of the surface oxide upon 120 °C bake.« less

Novel Catalysis by Gold: A Modern Alchemy

NASA Astrophysics Data System (ADS)

Haruta, Masatake

Gold has long been neglected as a catalyst because of its chemical inertness. However, when gold is deposited as nanoparticles on carbon and polymer materials as well as on base metal oxides and hydroxides, it exhibits unique catalytic properties for many reactions such as CO oxidation at a temperature as low as 200 K, gas phase direct epoxidation of propylene, and aerobic oxidation of glucose to gluconic acid. The structure-catalytic activity correlations are discussed with emphasis on the contact structure, support selection, and the size control of gold particles. Gold clusters with diameters smaller than 2 nm are expected to exhibit novel properties in catalysis, optics, and electronics depending on the size (number of atoms), shape, and the electronic and chemical interaction with the support materials. The above achievements and attempts can be regarded as a modern alchemy that creates valuables by means of the noblest element with little practical use.

On the release of cppxfel for processing X-ray free-electron laser images

DOE PAGES

Ginn, Helen Mary; Evans, Gwyndaf; Sauter, Nicholas K.; ...

2016-05-11

As serial femtosecond crystallography expands towards a variety of delivery methods, including chip-based methods, and smaller collected data sets, the requirement to optimize the data analysis to produce maximum structure quality is becoming increasingly pressing. Herecppxfel, a software package primarily written in C++, which showcases several data analysis techniques, is released. This software package presently indexes images using DIALS (diffraction integration for advanced light sources) and performs an initial orientation matrix refinement, followed by post-refinement of individual images against a reference data set.Cppxfelis released with the hope that the unique and useful elements of this package can be repurposed formore » existing software packages. However, as released, it produces high-quality crystal structures and is therefore likely to be also useful to experienced users of X-ray free-electron laser (XFEL) software who wish to maximize the information extracted from a limited number of XFEL images.« less

Poly(trifluoromethyl)azulenes: structures and acceptor properties

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

Clikeman, Tyler T.; Bukovsky, Eric V.; Kuvychko, Igor V.

2014-07-10

Azulene is a non-alternant, non-benzenoid aromatic hydrocarbon with an intense blue colour, a dipole moment of 1.0 D,1 positive electron affinity, and an “anomalous” emission from the second excited state in violation of Kasha’s rule.2,3 Azulene’s unique properties have potential uses in molecular switches,4,5 molecular diodes,6 organic photovoltaics,7 and charge transfer complexes.8-12 Introduction of electron-withdrawing groups to the azulenic core, such as CN,8,13,14 halogens,15-19 and CF3,20,21 can enhance certain electrical and photophysical properties. In this work, we report six new trifluoromethyl derivatives of azulene (AZUL), three isomers of AZUL(CF3)3 and three isomers of AZUL(CF3)4, and the first X-ray structure ofmore » a π-stacked donor-acceptor complex of a trifluoromethyl azulene with donor pyrene.« less

A facile synthesis of zinc oxide/multiwalled carbon nanotube nanocomposite lithium ion battery anodes by sol-gel method

NASA Astrophysics Data System (ADS)

Köse, Hilal; Karaal, Şeyma; Aydın, Ali Osman; Akbulut, Hatem

2015-11-01

Free standing zinc oxide (ZnO) and multiwalled carbon nanotube (MWCNT) nanocomposite materials are prepared by a sol gel technique giving a new high capacity anode material for lithium ion batteries. Free-standing ZnO/MWCNT nanocomposite anodes with two different chelating agent additives, triethanolamine (TEA) and glycerin (GLY), yield different electrochemical performances. Field emission gun scanning electron microscopy (FEG-SEM), energy dispersive X-ray spectrometer (EDS), high resolution transmission electron microscopy (HRTEM) and X-ray diffraction (XRD) analyses reveal the produced anode electrodes exhibit a unique structure of ZnO coating on the MWCNT surfaces. Li-ion cell assembly using a ZnO/MWCNT/GLY free-standing anode and Li metal cathode possesses the best discharge capacity, remaining as high as 460 mAh g-1 after 100 cycles. This core-shell structured anode can offer increased energy storage and performance over conventional anodes in Li-ion batteries.

Three-dimensional graphdiyne as a topological nodal-line semimetal

NASA Astrophysics Data System (ADS)

Nomura, Takafumi; Habe, Tetsuro; Sakamoto, Ryota; Koshino, Mikito

2018-05-01

We study the electronic band structure of three-dimensional ABC-stacked (rhombohedral) graphdiyne, which is a new planar carbon allotrope recently fabricated. Using first-principles calculation, we show that the system is a nodal-line semimetal, in which the conduction band and valence band cross at a closed ring in the momentum space. We derive the minimum tight-binding model and the low-energy effective Hamiltonian in a 4 ×4 matrix form. The nodal line is protected by a nontrivial winding number, and it ensures the existence of the topological surface state in a finite-thickness slab. The Fermi surface of the doped system exhibits a peculiar, self-intersecting hourglass structure, which is quite different from the torus or pipe shape in the previously proposed nodal semimetals. Despite its simple configuration, three-dimensional graphdiyne offers unique electronic properties distinct from any other carbon allotropes.

Exotic Physics and Chemistry of Two-Dimensional Phosphorus: Phosphorene.

PubMed

Chowdhury, Chandra; Datta, Ayan

2017-07-06

Phosphorene, the monolayer form of black phosphorus, is the most recent addition to graphene-like van der Waals two-dimensional (2D) systems. Due to its several interesting properties, namely its tunable direct band gap, high carrier mobility, and unique in-plane anisotropy, it has emerged as a promising candidate for electronic and optoelectronic devices. Phosphorene (Pn) reveals a much richer phase diagram than graphene, and it comprises the two forms namely the stapler-clip like (black Pn, α form) and chairlike (blue Pn, β form) structures. Regardless of its favorable properties, black Pn suffers from instability in oxygen and water, which limits its successful applications in electronic devices. In this Perspective, the cause of structural diversity of Pn, which leads to different properties of both black and blue Pn, is discussed. We provide possible solutions for protecting phosphorene from chemical degradation and its applications in the field of energy storage namely for Li and Na ion batteries.

Anomalous Stretchable Conductivity Using an Engineered Tricot Weave.

PubMed

Lee, Yong-Hee; Kim, Yoonseob; Lee, Tae-Ik; Lee, Inhwa; Shin, Jaeho; Lee, Hyun Soo; Kim, Taek-Soo; Choi, Jang Wook

2015-12-22

Robust electric conduction under stretching motions is a key element in upcoming wearable electronic devices but is fundamentally very difficult to achieve because percolation pathways in conductive media are subject to collapse upon stretching. Here, we report that this fundamental challenge can be overcome by using a parameter uniquely available in textiles, namely a weaving structure. A textile structure alternately interwoven with inelastic and elastic yarns, achieved via a tricot weave, possesses excellent elasticity (strain up to 200%) in diagonal directions. When this textile is coated with conductive nanomaterials, proper textile engineering allows the textile to obtain an unprecedented 7-fold conductivity increase, with conductivity reaching 33,000 S cm(-1), even at 130% strain, due to enhanced interyarn contacts. The observed stretching conductivity can be described well using a modified 3D percolation theory that reflects the weaving effect and is also utilized for stretchable electronic interconnects and supercapacitors with high performance.

Hollow raspberry-like PdAg alloy nanospheres: High electrocatalytic activity for ethanol oxidation in alkaline media

NASA Astrophysics Data System (ADS)

Peng, Cheng; Hu, Yongli; Liu, Mingrui; Zheng, Yixiong

2015-03-01

Palladium-silver (PdAg) alloy nanospheres with unique structure were prepared using a one-pot procedure based on the galvanic replacement reaction. Their electrocatalytic activity for ethanol oxidation in alkaline media was evaluated. The morphology and crystal structure of the samples were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD). Electrochemical characterization techniques, including cyclic voltammetry (CV) and chronoamperometry (CA) measurements were used to analyze the electrochemical performance of the PdAg alloy nanospheres. The SEM and TEM images showed that the PdAg alloy nanospheres exhibit a hierarchical nanostructure with hollow interiors and porous walls. Compared to the commercial Pd/C catalyst, the as-prepared PdAg alloy nanospheres exhibit superior electrocatalytic activity and stability towards ethanol electro-oxidation in alkaline media, showing its potential as a new non-Pt electro-catalyst for direct alcohol fuel cells (DAFCs).

Ferromagnetism in the Hubbard Model with a Gapless Nearly-Flat Band

NASA Astrophysics Data System (ADS)

Tanaka, Akinori

2018-01-01

We present a version of the Hubbard model with a gapless nearly-flat lowest band which exhibits ferromagnetism in two or more dimensions. The model is defined on a lattice obtained by placing a site on each edge of the hypercubic lattice, and electron hopping is assumed to be only between nearest and next nearest neighbor sites. The lattice, where all the sites are identical, is simple, and the corresponding single-electron band structure, where two cosine-type bands touch without an energy gap, is also simple. We prove that the ground state of the model is unique and ferromagnetic at half-filling of the lower band, if the lower band is nearly flat and the strength of on-site repulsion is larger than a certain value which is independent of the lattice size. This is the first example of ferromagnetism in three dimensional non-singular models with a gapless band structure.

Japanese power electronics inverter technology and its impact on the American air conditioning industry

NASA Astrophysics Data System (ADS)

Ushimaru, Kenji

1990-08-01

Since 1983, technological advances and market growth of inverter-driven variable-speed heat pumps in Japan have been dramatic. The high level of market penetration was promoted by a combination of political, economic, and trade policies in Japan. A unique environment was created in which the leading domestic industries, microprocessor manufacturing, compressors for air conditioning and refrigerators, and power electronic devices, were able to direct the development and market success of inverter-driven heat pumps. As a result, leading U.S. variable-speed heat pump manufacturers should expect a challenge from the Japanese producers of power devices and microprocessors. Because of the vertically-integrated production structure in Japan, in contrast to the out-sourcing culture of the United States, price competition at the component level (such as inverters, sensors, and controls) may impact the structure of the industry more severely than final product sales.

Electronic Structure Calculations and Adaptation Scheme in Multi-core Computing Environments

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

Seshagiri, Lakshminarasimhan; Sosonkina, Masha; Zhang, Zhao

2009-05-20

Multi-core processing environments have become the norm in the generic computing environment and are being considered for adding an extra dimension to the execution of any application. The T2 Niagara processor is a very unique environment where it consists of eight cores having a capability of running eight threads simultaneously in each of the cores. Applications like General Atomic and Molecular Electronic Structure (GAMESS), used for ab-initio molecular quantum chemistry calculations, can be good indicators of the performance of such machines and would be a guideline for both hardware designers and application programmers. In this paper we try to benchmarkmore » the GAMESS performance on a T2 Niagara processor for a couple of molecules. We also show the suitability of using a middleware based adaptation algorithm on GAMESS on such a multi-core environment.« less

Freely Suspended Two-Dimensional Electron Gases.

NASA Astrophysics Data System (ADS)

Blick, Robert; Monzon, Franklin; Roukes, Michael; Wegscheider, Werner; Stern, Frank

1998-03-01

We present a new technique that has allowed us to build the first freely suspended two-dimensional electron gas devices from AlGaAs/GaAs/AlAs heterostructures. This technique is based upon specially MBE grown structures that include a sacrificial layer. In order to design the MBE layer sequence, the conduction band lineup for these samples was modelled numerically. The overall focus of this work is to provide a new approach for studies of the quantum mechanical properties of nanomachined structures. Our current experiments are directed toward use of these techniques for research on very high frequency nanomechanical resonators. The high mobility 2DEG system provides a unique approach to realizing wideband, extremely sensitive displacement detection, using the piezoelectric properties of GaAs to modulate a suspended nanometer-scale HEMT. This approach offers promise for sensitive displacement detectors with sub-nanometer resolution and bandwidths into the microwave range.

Infrared fingerprints of few-layer black phosphorus.

PubMed

Zhang, Guowei; Huang, Shenyang; Chaves, Andrey; Song, Chaoyu; Özçelik, V Ongun; Low, Tony; Yan, Hugen

2017-01-06

Black phosphorus is an infrared layered material. Its bandgap complements other widely studied two-dimensional materials: zero-gap graphene and visible/near-infrared gap transition metal dichalcogenides. Although highly desirable, a comprehensive infrared characterization is still lacking. Here we report a systematic infrared study of mechanically exfoliated few-layer black phosphorus, with thickness ranging from 2 to 15 layers and photon energy spanning from 0.25 to 1.36 eV. Each few-layer black phosphorus exhibits a thickness-dependent unique infrared spectrum with a series of absorption resonances, which reveals the underlying electronic structure evolution and serves as its infrared fingerprints. Surprisingly, unexpected absorption features, which are associated with the forbidden optical transitions, have been observed. Furthermore, we unambiguously demonstrate that controllable uniaxial strain can be used as a convenient and effective approach to tune the electronic structure of few-layer black phosphorus. Our study paves the way for black phosphorus applications in infrared photonics and optoelectronics.

Pre-Town Meeting on spin physics at an Electron-Ion Collider

DOE PAGES

Aschenauer, Elke-Caroline; Balitsky, Ian; Bland, Leslie; ...

2017-04-14

A polarized ep/eA collider (Electron-Ion Collider, or EIC), with polarized proton and light-ion beams and unpolarized heavy-ion beams with a variable center-of-mass energy √s ~ 20 to ~ 100 GeV (upgradable to ~ 150 GeV) and a luminosity up to ~10 34 cm -2s -1, would be uniquely suited to address several outstanding questions of Quantum Chromodynamics, and thereby lead to new qualitative and quantitative information on the microscopic structure of hadrons and nuclei. During this meeting at Jefferson Lab we addressed recent theoretical and experimental developments in the spin and the three-dimensional structure of the nucleon (sea quark andmore » gluon spatial distributions, orbital motion, polarization, and their correlations). Finally, this mini-paper contains a short update on progress in these areas since the EIC White paper (A. Accardi et al., Eur. Phys. J. A 52, 268 (2016)).« less

Unconventional molecule-resolved current rectification in diamondoid–fullerene hybrids

PubMed Central

Randel, Jason C.; Niestemski, Francis C.; Botello-Mendez, Andrés R.; Mar, Warren; Ndabashimiye, Georges; Melinte, Sorin; Dahl, Jeremy E. P.; Carlson, Robert M. K.; Butova, Ekaterina D.; Fokin, Andrey A.; Schreiner, Peter R.; Charlier, Jean-Christophe; Manoharan, Hari C.

2014-01-01

The unimolecular rectifier is a fundamental building block of molecular electronics. Rectification in single molecules can arise from electron transfer between molecular orbitals displaying asymmetric spatial charge distributions, akin to p–n junction diodes in semiconductors. Here we report a novel all-hydrocarbon molecular rectifier consisting of a diamantane–C60 conjugate. By linking both sp3 (diamondoid) and sp2 (fullerene) carbon allotropes, this hybrid molecule opposingly pairs negative and positive electron affinities. The single-molecule conductances of self-assembled domains on Au(111), probed by low-temperature scanning tunnelling microscopy and spectroscopy, reveal a large rectifying response of the molecular constructs. This specific electronic behaviour is postulated to originate from the electrostatic repulsion of diamantane–C60 molecules due to positively charged terminal hydrogen atoms on the diamondoid interacting with the top electrode (scanning tip) at various bias voltages. Density functional theory computations scrutinize the electronic and vibrational spectroscopic fingerprints of this unique molecular structure and corroborate the unconventional rectification mechanism. PMID:25202942

Simultaneous Correlative Scanning Electron and High-NA Fluorescence Microscopy

PubMed Central

Liv, Nalan; Zonnevylle, A. Christiaan; Narvaez, Angela C.; Effting, Andries P. J.; Voorneveld, Philip W.; Lucas, Miriam S.; Hardwick, James C.; Wepf, Roger A.; Kruit, Pieter; Hoogenboom, Jacob P.

2013-01-01

Correlative light and electron microscopy (CLEM) is a unique method for investigating biological structure-function relations. With CLEM protein distributions visualized in fluorescence can be mapped onto the cellular ultrastructure measured with electron microscopy. Widespread application of correlative microscopy is hampered by elaborate experimental procedures related foremost to retrieving regions of interest in both modalities and/or compromises in integrated approaches. We present a novel approach to correlative microscopy, in which a high numerical aperture epi-fluorescence microscope and a scanning electron microscope illuminate the same area of a sample at the same time. This removes the need for retrieval of regions of interest leading to a drastic reduction of inspection times and the possibility for quantitative investigations of large areas and datasets with correlative microscopy. We demonstrate Simultaneous CLEM (SCLEM) analyzing cell-cell connections and membrane protrusions in whole uncoated colon adenocarcinoma cell line cells stained for actin and cortactin with AlexaFluor488. SCLEM imaging of coverglass-mounted tissue sections with both electron-dense and fluorescence staining is also shown. PMID:23409024

Doping of Ga in antiferromagnetic semiconductor α-Cr2O3 and its effects on magnetic and electronic properties

NASA Astrophysics Data System (ADS)

Bhowmik, R. N.; Venkata Siva, K.; Ranganathan, R.; Mazumdar, Chandan

2017-06-01

The samples of Ga-doped Cr2O3 have been prepared using chemical co-precipitation route. X-ray diffraction pattern and Raman spectra have indicated rhombohedral crystal structure with space group R 3 bar C. Magnetic measurements indicated diluted antiferromagnetic (AFM) spin order in Ga-doped α-Cr2O3 and ferrimagnetic ordering of spins at about 50-60 K is confirmed from the analysis of the temperature dependence of dc magnetization and ac susceptibility data. Apart from magnetic dilution effect, the samples have shown superparamagnetic behavior below 50 K due to frustrated surface spins of the nano-sized grains. The samples have shown non-linear electronic properties. The current-voltage (I-V) characteristics of the Ga-doped α-Cr2O3 samples are remarkably different from α-Cr2O3 sample. The bi-stable electronic states and negative differential resistance are some of the unique non-linear electronic properties that the I-V curves of Ga-doped samples have exhibited. Optical study revealed three electronic transitions in the samples associated with band gap energy at about 2.67-2.81 eV, 1.91-2.11 eV, 1.28-1.35 eV, respectively. The results indicated multi-level electronic structure in Ga-doped α-Cr2O3 system.

Multiple sites of retardation of electron transfer in Photosystem II after hydrolysis of phosphatidylglycerol.

PubMed

Kim, Eun-Ha; Razeghifard, Reza; Anderson, Jan M; Chow, Wah Soon

2007-01-01

Phosphatidylglycerol (PG), containing the unique fatty acid Delta3, trans-16:1-hexadecenoic acid, is a minor but ubiquitous lipid component of thylakoid membranes of chloroplasts and cyanobacteria. We investigated its role in electron transfers and structural organization of Photosystem II (PSII) by treating Arabidopsis thaliana thylakoids with phospholipase A(2) to decrease the PG content. Phospholipase A(2) treatment of thylakoids (a) inhibited electron transfer from the primary quinone acceptor Q(A) to the secondary quinone acceptor Q(B), (b) retarded electron transfer from the manganese cluster to the redox-active tyrosine Z, (c) decreased the extent of flash-induced oxidation of tyrosine Z and dark-stable tyrosine D in parallel, and (d) inhibited PSII reaction centres such that electron flow to silicomolybdate in continuous light was inhibited. In addition, phospholipase A(2) treatment of thylakoids caused the partial dissociation of (a) PSII supercomplexes into PSII dimers that do not have the complete light-harvesting complex of PSII (LHCII); (b) PSII dimers into monomers; and (c) trimers of LHCII into monomers. Thus, removal of PG by phospholipase A(2) brings about profound structural changes in PSII, leading to inhibition/retardation of electron transfer on the donor side, in the reaction centre, and on the acceptor side. Our results broaden the simple view of the predominant effect being on the Q(B)-binding site.

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

Brodsky, Casey N.; Hadt, Ryan G.; Hayes, Dugan

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

Graphene-based electrochemical energy conversion and storage: fuel cells, supercapacitors and lithium ion batteries.

PubMed

Hou, Junbo; Shao, Yuyan; Ellis, Michael W; Moore, Robert B; Yi, Baolian

2011-09-14

Graphene has attracted extensive research interest due to its strictly 2-dimensional (2D) structure, which results in its unique electronic, thermal, mechanical, and chemical properties and potential technical applications. These remarkable characteristics of graphene, along with the inherent benefits of a carbon material, make it a promising candidate for application in electrochemical energy devices. This article reviews the methods of graphene preparation, introduces the unique electrochemical behavior of graphene, and summarizes the recent research and development on graphene-based fuel cells, supercapacitors and lithium ion batteries. In addition, promising areas are identified for the future development of graphene-based materials in electrochemical energy conversion and storage systems. This journal is © the Owner Societies 2011

Binary ionic porphyrin nanosheets: electronic and light-harvesting properties regulated by crystal structure

NASA Astrophysics Data System (ADS)

Tian, Yongming; M. Beavers, Christine; Busani, Tito; Martin, Kathleen E.; Jacobsen, John L.; Mercado, Brandon Q.; Swartzentruber, Brian S.; van Swol, Frank; Medforth, Craig J.; Shelnutt, John A.

2012-02-01

Crystalline solids self-assembled from anionic and cationic porphyrins provide a new class of multifunctional optoelectronic micro- and nanomaterials. A 1 : 1 combination of zinc(ii) tetra(4-sulfonatophenyl)porphyrin (ZnTPPS) and tin(iv) tetra(N-methyl-4-pyridiniumyl)porphyrin (SnTNMePyP) gives porphyrin nanosheets with high aspect ratios and varying thickness. The room temperature preparation of the nanosheets has provided the first X-ray crystal structure of a cooperative binary ionic (CBI) solid. The unit cell contains one and one-half molecules of aquo-ZnTPPS4- (an electron donor) and three half molecules of dihydroxy-SnTNMePyP4+ (an electron acceptor). Charge balance in the solid is reached without any non-porphyrinic ions, as previously determined for other CBI nanomaterials by non-crystallographic means. The crystal structure reveals a complicated molecular arrangement with slipped π-π stacking only occurring in isolated dimers of one of the symmetrically unique zinc porphyrins. Consistent with the crystal structure, UV-visible J-aggregate bands indicative of exciton delocalization and extended π-π stacking are not observed. XRD measurements show that the structure of the Zn/Sn nanosheets is distinct from that of Zn/Sn four-leaf clover-like CBI solids reported previously. In contrast with the Zn/Sn clovers that do exhibit J-aggregate bands and are photoconductive, the nanosheets are not photoconductive. Even so, the nanosheets act as light-harvesting structures in an artificial photosynthesis system capable of reducing water to hydrogen but not as efficiently as the Zn/Sn clovers.Crystalline solids self-assembled from anionic and cationic porphyrins provide a new class of multifunctional optoelectronic micro- and nanomaterials. A 1 : 1 combination of zinc(ii) tetra(4-sulfonatophenyl)porphyrin (ZnTPPS) and tin(iv) tetra(N-methyl-4-pyridiniumyl)porphyrin (SnTNMePyP) gives porphyrin nanosheets with high aspect ratios and varying thickness. The room temperature preparation of the nanosheets has provided the first X-ray crystal structure of a cooperative binary ionic (CBI) solid. The unit cell contains one and one-half molecules of aquo-ZnTPPS4- (an electron donor) and three half molecules of dihydroxy-SnTNMePyP4+ (an electron acceptor). Charge balance in the solid is reached without any non-porphyrinic ions, as previously determined for other CBI nanomaterials by non-crystallographic means. The crystal structure reveals a complicated molecular arrangement with slipped π-π stacking only occurring in isolated dimers of one of the symmetrically unique zinc porphyrins. Consistent with the crystal structure, UV-visible J-aggregate bands indicative of exciton delocalization and extended π-π stacking are not observed. XRD measurements show that the structure of the Zn/Sn nanosheets is distinct from that of Zn/Sn four-leaf clover-like CBI solids reported previously. In contrast with the Zn/Sn clovers that do exhibit J-aggregate bands and are photoconductive, the nanosheets are not photoconductive. Even so, the nanosheets act as light-harvesting structures in an artificial photosynthesis system capable of reducing water to hydrogen but not as efficiently as the Zn/Sn clovers. Electronic supplementary information (ESI) available: Details of the crystallographic refinement, tables of refinement parameters and bond distances and NSD analysis, and figures showing SEM images of Zn/Sn nanosheets and clovers, the solid grown at different porphyrin concentrations, SEM images of nanosheets at high and low magnification, an ORTEP image showing the five crystallographically distinct porphyrin molecules and the water molecules, and a view of the crystal structure down the b axis are given in the ESI. CCDC reference number 833006. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c2nr11826b

Electronic Structure and Bonding in Complex Biomolecule

NASA Astrophysics Data System (ADS)

Ouyang, Lizhi

2005-03-01

For over a century vitamin B12 and its enzyme cofactor derivates have persistently attracted research efforts for their vital biological role, unique Co-C bonding, rich red-ox chemistry, and recently their candidacies as drug delivery vehicles etc. However, our understanding of this complex metalorganic molecule's efficient enzyme activated catalytic power is still controversial. We have for the first time calculated the electronic structure, Mulliken effective charge and bonding of a whole Vitamin B12 molecule without any structural simplification by first- principles approaches based on density functional theory using structures determined by high resolution X-ray diffraction. A partial density of states analysis shows excellent agreement with X-ray absorption data and has been used successfully to interpret measured optical absorption spectra. Mulliken bonding analysis of B12 and its derivatives reveal noticeable correlations between the two axial ligands which could be exploited by the enzyme to control the catalytic process. Our calculated X-ray near edge structure of B12 and its derivates using Slater's transition state theory are also in good agreement with experiments. The same approach has been applied to other B12 derivatives, ferrocene peptides, and recently DNA molecules.

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

Ioannidou, Chrysoula; Lioutas, Christos B.; Frangis, Nikolaos

The high-performance PbTe-SnTe-PbS-thermoelectric system forms a completely new composite PbTe PbSnS2 with high n-type figure of merit. Electron diffraction and high-resolution electron microscopy characterization of the thermoelectric composite PbTe + 25% PbSnS2 reveals that the system is nanostructured, with PbSnS(2)nanocrystals in the range Of 80 to 500 nm in size. In most of the cases, they are endotaxially grown within the PbTe matrix. Three independent crystal superstructures were observed for the PbSnS2 inclusions, originating from the same parent SnS-type structure. The presence of the parent structure is not excluded. Modified structural models for two of the superstructures observed in themore » PbSnS2 precipitates are proposed: Often, more than one of the structural phases am observed In the same nanocrystal, providing one extra phonon scattering factor in the system. Evidence was also found for the growth process of the nanocrystals, starting from PbS and followed by gradual dissolving of SnS. Our findings suggest that this nanostructured thermoelectric composite exhibits unique structural complexity, which Contributes to the low lattice thermal :conductivity reported for these nanocomposite materials.« less

45 CFR 164.312 - Technical safeguards.

Code of Federal Regulations, 2012 CFR

2012-10-01

... REQUIREMENTS SECURITY AND PRIVACY Security Standards for the Protection of Electronic Protected Health... that maintain electronic protected health information to allow access only to those persons or software... specifications: (i) Unique user identification (Required). Assign a unique name and/or number for identifying and...

Structural and optical studies of hydrothermally synthesized MoS{sub 2} nanostructures

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

Chacko, Levna; Swetha, A. K.; Aneesh, P. M., E-mail: aneeshpm@cukerala.ac.in

2016-05-06

Transition-metal dichalcogenides like molybdenum disulphide have intrigued intensive interest as two-dimensional (2D) materials beyond extensively studied graphene due to their unique electronic and optical properties. Here we report the hydrothermal synthesis of MoS{sub 2} nanostructures without the addition of any surfactants. The structural and optical properties of the synthesized samples were characterized by various techniques, including X-ray diffraction (XRD), UV-Vis absorption, photoluminescence (PL), and Raman analysis. XRD and Raman spectroscopic studies confirm the formation of hexagonal phase and well ordered stacking of S-Mo-S layers. The increased lattice parameters of MoS{sub 2} samples are due to the stress or strain inducedmore » bending and folding of the layers. The synthesized MoS{sub 2} nanostructures shows a large optical absorption in 300-700 nm region and strong luminescence at 640 nm. In addition, the optical results demonstrates the quantum confinement in layered d-electron material MoS{sub 2} that can lead to engineer its various properties for electronic and optoelectronic applications.« less

Recent Advances in Micro-/Nanostructured Metal-Organic Frameworks towards Photonic and Electronic Applications.

PubMed

Yang, Xiaogang; Lin, Xianqing; Zhao, Yong Sheng; Yan, Dongpeng

2018-05-02

Micro- and nanometer-sized metal-organic frameworks (MOFs) materials have attracted great attention due to their unique properties and various potential applications in photonics, electronics, high-density storage, chemo-, and biosensors. The study of these materials supplies insight into how the crystal structure, molecular components, and micro-/nanoscale effects can influence the performance of inorganic-organic hybrid materials. In this Minireview article, we introduce recent breakthroughs in the controlled synthesis of MOF micro-/nanomaterials with specific structures and compositions, the tunable photonic and electronic properties of which would provide a novel platform for multifunctional applications. Firstly, the design strategies for MOFs based on self-assembly and crystal engineering principles are introduced. Attention is then focused on the methods of fabrication of low-dimensional MOF micro-/nanostructures. Their new applications including two-photon excited fluorescence, multi-photon pumped lasing, optical waveguides, nonlinear optical (NLO), and field-effect transistors are also outlined. Finally, we briefly discuss perspectives on the further development of these hybrid crystalline micro-/nanomaterials. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The physics of solid-state neutron detector materials and geometries.

PubMed

Caruso, A N

2010-11-10

Detection of neutrons, at high total efficiency, with greater resolution in kinetic energy, time and/or real-space position, is fundamental to the advance of subfields within nuclear medicine, high-energy physics, non-proliferation of special nuclear materials, astrophysics, structural biology and chemistry, magnetism and nuclear energy. Clever indirect-conversion geometries, interaction/transport calculations and modern processing methods for silicon and gallium arsenide allow for the realization of moderate- to high-efficiency neutron detectors as a result of low defect concentrations, tuned reaction product ranges, enhanced effective omnidirectional cross sections and reduced electron-hole pair recombination from more physically abrupt and electronically engineered interfaces. Conversely, semiconductors with high neutron cross sections and unique transduction mechanisms capable of achieving very high total efficiency are gaining greater recognition despite the relative immaturity of their growth, lithographic processing and electronic structure understanding. This review focuses on advances and challenges in charged-particle-based device geometries, materials and associated mechanisms for direct and indirect transduction of thermal to fast neutrons within the context of application. Calorimetry- and radioluminescence-based intermediate processes in the solid state are not included.

Cotton-based Cellulose Nanomaterials for Applications in Composites and Electronics

NASA Astrophysics Data System (ADS)

Farahbakhsh, Nasim

A modern society demands development of highly valued and sustainable products via innovative process technologies and utilizing bio-based alternatives for petroleum based materials. Systematic comparative study of nanocellulose particles as a biodegradable and renewable reinforcing agent can help to develop criteria for selecting an appropriate candidate to be incorporated in polymer nanocomposites. Of particular interest has been nanocellulosic materials including cellulose nanocrystal (CNC) and micro/nanofibrilated cellulose (MFC/NFC) which possess a hierarchical structure that permits an ordered structure with unique properties that has served as building blocks for the design of green and novel materials composites for applications in flexible electronics, medicine and composites. Key differences exist in nanocellulosic materials as a result the process by which the material is produced. This research demonstrates the applicability for the use of recycled cotton as promising sustainable material to be utilized as a substrate for electronic application and a reinforcing agent choice that can be produced without any intensive purification process and be applied to synthetic-based polymer nanocomposites in melt-processing. (Abstract shortened by ProQuest.).

229Thorium-doped calcium fluoride for nuclear laser spectroscopy.

PubMed

Dessovic, P; Mohn, P; Jackson, R A; Winkler, G; Schreitl, M; Kazakov, G; Schumm, T

2014-03-12

The (229)thorium isotope presents an extremely low-energy isomer state of the nucleus which is expected around 7.8 eV, in the vacuum ultraviolet (VUV) regime. This unique system may bridge between atomic and nuclear physics, enabling coherent manipulation and precision spectroscopy of nuclear quantum states using laser light. It has been proposed to implant (229)thorium into VUV transparent crystal matrices to facilitate laser spectroscopy and possibly realize a solid-state nuclear clock. In this work, we validate the feasibility of this approach by computer modelling of thorium doping into calcium fluoride single crystals. Using atomistic modelling and full electronic structure calculations, we find a persistent large band gap and no additional electronic levels emerging in the middle of the gap due to the presence of the dopant, which should allow direct optical interrogation of the nuclear transition.Based on the electronic structure, we estimate the thorium nuclear quantum levels within the solid-state environment. Precision laser spectroscopy of these levels will allow the study of a broad range of crystal field effects, transferring Mössbauer spectroscopy into the optical regime.

Extraordinary epitaxial alignment of graphene islands on Au(111)

NASA Astrophysics Data System (ADS)

Wofford, Joseph M.; Starodub, Elena; Walter, Andrew L.; Nie, Shu; Bostwick, Aaron; Bartelt, Norman C.; Thürmer, Konrad; Rotenberg, Eli; McCarty, Kevin F.; Dubon, Oscar D.

2012-05-01

Pristine, single-crystalline graphene displays a unique collection of remarkable electronic properties that arise from its two-dimensional, honeycomb structure. Using in situ low-energy electron microscopy, we show that when deposited on the (111) surface of Au carbon forms such a structure. The resulting monolayer, epitaxial film is formed by the coalescence of dendritic graphene islands that nucleate at a high density. Over 95% of these islands can be identically aligned with respect to each other and to the Au substrate. Remarkably, the dominant island orientation is not the better lattice-matched 30° rotated orientation but instead one in which the graphene [01] and Au [011] in-plane directions are parallel. The epitaxial graphene film is only weakly coupled to the Au surface, which maintains its reconstruction under the slightly p-type doped graphene. The linear electronic dispersion characteristic of free-standing graphene is retained regardless of orientation. That a weakly interacting, non-lattice matched substrate is able to lock graphene into a particular orientation is surprising. This ability, however, makes Au(111) a promising substrate for the growth of single crystalline graphene films.

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

Liu, Jing; Hosseinpour, Pegah M.; Lewis, Laura H., E-mail: lhlewis@neu.edu

To furnish insight into correlations of electronic and local structure and photoactivity, arrays of short and long TiO{sub 2} nanotubes were synthesized by electrochemical anodization of Ti foil, followed by thermal treatment in O{sub 2} (oxidizing), Ar (inert), and H{sub 2} (reducing) environments. The physical and electronic structures of these nanotubes were probed with x-ray diffraction, scanning electron microscopy, and synchrotron-based x-ray absorption spectroscopy, and correlated with their photocatalytic properties. The photocatalytic activity of the nanotubes was evaluated by monitoring the degradation of methyl orange under UV-VIS light irradiation. Results show that upon annealing at 350 °C all as-anodized amorphous TiO{submore » 2} nanotube samples partially transform to the anatase structure, with variations in the degree of crystallinity and in the concentration of local defects near the nanotubes' surface (∼5 nm) depending on the annealing conditions. Degradation of methyl orange was not detectable for the as-anodized TiO{sub 2} nanotubes regardless of their length. However, the annealed long nanotubes demonstrated detectable catalytic activity, which was more significant with the H{sub 2}-annealed nanotubes than with the Ar- and O{sub 2}-annealed nanotube samples. This enhanced photocatalytic response of the H{sub 2}-annealed long nanotubes relative to the other samples is positively correlated with the presence of a larger concentration of lattice defects (such as Ti{sup 3+} and anticipated oxygen vacancies) and a slightly lower degree of crystallinity near the nanotube surface. These physical and electronic structural attributes impact the efficacy of visible light absorption; moreover, the increased concentration of surface defects is postulated to promote the generation of hydroxyl radicals and thus accelerate the photodegradation of the methyl orange. The information obtained from this study provides unique insight into the role of the near-surface electronic and defect structure, crystal structure, and the local chemical environment on the photocatalytic activity and may be employed for tailoring the materials' properties for photocatalysis and other energy-related applications.« less

Hierarchical architecture of ReS2/rGO composites with enhanced electrochemical properties for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Qi, Fei; Chen, Yuanfu; Zheng, Binjie; He, Jiarui; Li, Qian; Wang, Xinqiang; Lin, Jie; Zhou, Jinhao; Yu, Bo; Li, Pingjian; Zhang, Wanli

2017-08-01

Rhenium disulfide (ReS2), a two-dimensional (2D) semiconductor, has attracted more and more attention due to its unique anisotropic electronic, optical, mechanical properties. However, the facile synthesis and electrochemical property of ReS2 and its composite are still necessary to be researched. In this study, for the first time, the ReS2/reduced graphene oxide (rGO) composites have been synthesized through a facile and one-pot hydrothermal method. The ReS2/rGO composites exhibit a hierarchical, interconnected, and porous architecture constructed by nanosheets. As anode for lithium-ion batteries, the as-synthesized ReS2/rGO composites deliver a large initial capacity of 918 mAh g-1 at 0.2 C. In addition, the ReS2/rGO composites exhibit much better electrochemical cycling stability and rate capability than that of bare ReS2. The significant enhancement in electrochemical property can be attributed to its unique architecture constructed by nanosheets and porous structure, which can allow for easy electrolyte infiltration, efficient electron transfer, and ionic diffusion. Furthermore, the graphene with high electronic conductivity can provide good conductive passageways. The facile synthesis approach can be extended to prepare other 2D transition metal dichalcogenides semiconductors for energy storage and catalytic application.

Electron Microscopy and Analytical X-ray Characterization of Compositional and Nanoscale Structural Changes in Fossil Bone

NASA Astrophysics Data System (ADS)

Boatman, Elizabeth Marie

The nanoscale structure of compact bone contains several features that are direct indicators of bulk tissue mechanical properties. Fossil bone tissues represent unique opportunities to understand the compact bone structure/property relationships from a deep time perspective, offering a possible array of new insights into bone diseases, biomimicry of composite materials, and basic knowledge of bioapatite composition and nanoscale bone structure. To date, most work with fossil bone has employed microscale techniques and has counter-indicated the survival of bioapatite and other nanoscale structural features. The obvious disconnect between the use of microscale techniques and the discernment of nanoscale structure has prompted this work. The goal of this study was to characterize the nanoscale constituents of fossil compact bone by applying a suite of diffraction, microscopy, and spectrometry techniques, representing the highest levels of spatial and energy resolution available today, and capable of complementary structural and compositional characterization from the micro- to the nanoscale. Fossil dinosaur and crocodile long bone specimens, as well as modern ratite and crocodile femurs, were acquired from the UC Museum of Paleontology. Preserved physiological features of significance were documented with scanning electron microscopy back-scattered imaging. Electron microprobe wavelength-dispersive X-ray spectroscopy (WDS) revealed fossil bone compositions enriched in fluorine with a complementary loss of oxygen. X-ray diffraction analyses demonstrated that all specimens were composed of apatite. Transmission electron microscopy (TEM) imaging revealed preserved nanocrystallinity in the fossil bones and electron diffraction studies further identified these nanocrystallites as apatite. Tomographic analyses of nanoscale elements imaged by TEM and small angle X-ray scattering were performed, with the results of each analysis further indicating that nanoscale structure is highly conserved in these four fossil specimens. Finally, the results of this study indicate that bioapatite can be preserved in even the most ancient vertebrate specimens, further supporting the idea that fossilization is a preservational process. This work also underlines the importance of using appropriately selected characterization and analytical techniques for the study of fossil bone, especially from the perspective of spatial resolution and the scale of the bone structural features in question.

The low energy plasma in the Uranian magnetosphere

NASA Technical Reports Server (NTRS)

Mcnutt, R. L., Jr.; Belcher, J.; Bridge, H.; Lazarus, A. J.; Richardson, J.; Sands, M.; Bagenal, F.; Eviatar, A.; Goertz, C.; Ogilvie, K.

1987-01-01

The Plasma Science experiment on Voyager 2 detected a magnetosphere filled with a tenuous plasma, rotating with the planet. Temperatures of the plasma, composed of protons and electrons, ranged from 10 eV to about 1 keV. The sources of these protons and electrons are probably the ionosphere of Uranus or the extended neutral hydrogen cloud surrounding the planet. As at earth, Jupiter, and Saturn, there is an extended magnetotail with a central plasma sheet. Although similar in global structure to the magnetospheres of these planets, the large angle between the rotation and magnetic axes of the planet and the orientation of the rotation axis with respect to the solar wind flow make the Uranian magnetosphere unique.

Photon Science for Renewable Energy

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

Hussain, Zahid; Tamura, Lori; Padmore, Howard

2010-03-31

Our current fossil-fuel-based system is causing potentially catastrophic changes to our planet. The quest for renewable, nonpolluting sources of energy requires us to understand, predict, and ultimately control matter and energy at the electronic, atomic, and molecular levels. Light-source facilities - the synchrotrons of today and the next-generation light sources of tomorrow - are the scientific tools of choice for exploring the electronic and atomic structure of matter. As such, these photon-science facilities are uniquely positioned to jump-start a global revolution in renewable and carbonneutral energy technologies. In these pages, we outline and illustrate through examples from our nation's lightmore » sources possible scientific directions for addressing these profound yet urgent challenges.« less

Two worlds collide: Image analysis methods for quantifying structural variation in cluster molecular dynamics

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

Steenbergen, K. G., E-mail: kgsteen@gmail.com; Gaston, N.

2014-02-14

Inspired by methods of remote sensing image analysis, we analyze structural variation in cluster molecular dynamics (MD) simulations through a unique application of the principal component analysis (PCA) and Pearson Correlation Coefficient (PCC). The PCA analysis characterizes the geometric shape of the cluster structure at each time step, yielding a detailed and quantitative measure of structural stability and variation at finite temperature. Our PCC analysis captures bond structure variation in MD, which can be used to both supplement the PCA analysis as well as compare bond patterns between different cluster sizes. Relying only on atomic position data, without requirement formore » a priori structural input, PCA and PCC can be used to analyze both classical and ab initio MD simulations for any cluster composition or electronic configuration. Taken together, these statistical tools represent powerful new techniques for quantitative structural characterization and isomer identification in cluster MD.« less

Inherent structure length in metallic glasses: Simplicity behind complexity

DOE PAGES

Wu, Yuan; Wang, Hui; Cheng, Yongqiang; ...

2015-08-06

One of the central themes in materials science is the structure-property relationship. In conventional crystalline metals, their mechanical behaviour is often dictated by well-defined structural defects such as dislocations, impurities, and twins. However, the structure-property relationship in amorphous alloys is far from being understood, due to great difficulties in characterizing and describing the disordered atomic-level structure. Here, we report a universal, yet simple, correlation between the macroscopic mechanical properties (i.e., yield strength and shear modulus) and a unique characteristic structural length in metallic glasses (MGs). Lastly, our analysis indicates that this characteristic length can incorporate effects of both the inter-atomicmore » distance and valence electron density in MGs, and result in the observed universal correlation. The current findings shed lights on the basic understanding of mechanical properties of MGs from their disordered atomic structures.« less

Two worlds collide: image analysis methods for quantifying structural variation in cluster molecular dynamics.

PubMed

Steenbergen, K G; Gaston, N

2014-02-14

Inspired by methods of remote sensing image analysis, we analyze structural variation in cluster molecular dynamics (MD) simulations through a unique application of the principal component analysis (PCA) and Pearson Correlation Coefficient (PCC). The PCA analysis characterizes the geometric shape of the cluster structure at each time step, yielding a detailed and quantitative measure of structural stability and variation at finite temperature. Our PCC analysis captures bond structure variation in MD, which can be used to both supplement the PCA analysis as well as compare bond patterns between different cluster sizes. Relying only on atomic position data, without requirement for a priori structural input, PCA and PCC can be used to analyze both classical and ab initio MD simulations for any cluster composition or electronic configuration. Taken together, these statistical tools represent powerful new techniques for quantitative structural characterization and isomer identification in cluster MD.

The structure and organization of lanceolate mechanosensory complexes at mouse hair follicles

PubMed Central

Li, Lishi; Ginty, David D

2014-01-01

In mouse hairy skin, lanceolate complexes associated with three types of hair follicles, guard, awl/auchene and zigzag, serve as mechanosensory end organs. These structures are formed by unique combinations of low-threshold mechanoreceptors (LTMRs), Aβ RA-LTMRs, Aδ-LTMRs, and C-LTMRs, and their associated terminal Schwann cells (TSCs). In this study, we investigated the organization, ultrastructure, and maintenance of longitudinal lanceolate complexes at each hair follicle subtype. We found that TSC processes at hair follicles are tiled and that individual TSCs host axonal endings of more than one LTMR subtype. Electron microscopic analyses revealed unique ultrastructural features of lanceolate complexes that are proposed to underlie mechanotransduction. Moreover, Schwann cell ablation leads to loss of LTMR terminals at hair follicles while, in contrast, TSCs remain associated with hair follicles following skin denervation in adult mice and, remarkably, become re-associated with newly formed axons, indicating a TSC-dependence of lanceolate complex maintenance and regeneration in adults. DOI: http://dx.doi.org/10.7554/eLife.01901.001 PMID:24569481

The structure and organization of lanceolate mechanosensory complexes at mouse hair follicles.

PubMed

Li, Lishi; Ginty, David D

2014-02-25

In mouse hairy skin, lanceolate complexes associated with three types of hair follicles, guard, awl/auchene and zigzag, serve as mechanosensory end organs. These structures are formed by unique combinations of low-threshold mechanoreceptors (LTMRs), Aβ RA-LTMRs, Aδ-LTMRs, and C-LTMRs, and their associated terminal Schwann cells (TSCs). In this study, we investigated the organization, ultrastructure, and maintenance of longitudinal lanceolate complexes at each hair follicle subtype. We found that TSC processes at hair follicles are tiled and that individual TSCs host axonal endings of more than one LTMR subtype. Electron microscopic analyses revealed unique ultrastructural features of lanceolate complexes that are proposed to underlie mechanotransduction. Moreover, Schwann cell ablation leads to loss of LTMR terminals at hair follicles while, in contrast, TSCs remain associated with hair follicles following skin denervation in adult mice and, remarkably, become re-associated with newly formed axons, indicating a TSC-dependence of lanceolate complex maintenance and regeneration in adults. DOI: http://dx.doi.org/10.7554/eLife.01901.001.

Unique Fe2P Nanoparticles Enveloped in Sandwichlike Graphited Carbon Sheets as Excellent Hydrogen Evolution Reaction Catalyst and Lithium-Ion Battery Anode.

PubMed

Zhang, Yan; Zhang, Huijuan; Feng, Yangyang; Liu, Li; Wang, Yu

2015-12-09

The novel Fe2P nanoparticles encapsulated in sandwichlike graphited carbon envelope nanocomposite (Fe2P/GCS) that can be first applied in hydrogen evolution reaction (HER) as well as lithium-ion batteries (LIBs) has been designed and fabricated. The unique sandwiched Fe2P/GCS is characterized with several prominent merits, including large specific surface area, nanoporous structure, excellent electronic conductivity, enhanced structural integrity and so on. All of these endow the Fe2P/GCS with brilliant electrochemical performance. When used as a HER electrocatalyst in acidic media, the harvested Fe2P/GCS demonstrates low onset overpotential and Tafel slope as well as particularly outstanding durability. Moreover, as an anode material for LIBs, the sandwiched Fe2P/GCS presents high specific capacity and excellent cyclability and rate capability. As a consequence, the acquired Fe2P/GCS is a promising material for energy applications, especially HER and LIBs.

Strong competition between orbital ordering and itinerancy in a frustrated spinel vanadate

DOE PAGES

Ma, Jie; Lee, Jun Hee; Hahn, Steven E.; ...

2015-01-26

In this study, the crossover from localized to itinerant electron regimes in the geometrically frustrated spinel system Mn 1-xCo xV 2O 4 is explored by neutron-scattering measurements, first-principles calculations, and spin models. At low Co doping, the orbital ordering (OO) of the localized V 3+ spins suppresses magnetic frustration by triggering a tetragonal distortion. At high Co doping levels, however, electronic itinerancy melts the OO and lessens the structural and magnetic anisotropies, thus increasing the amount of geometric frustration for the V-site pyrochlore lattice. Contrary to the predicted paramagentism induced by chemical pressure, the measured noncollinear spin states in themore » Co-rich region of the phase diagram provide a unique platform where localized spins and electronic itinerancy compete in a geometrically frustrated spinel.« less

Stable and metastable nanowires displaying locally controllable properties

DOEpatents

Sutter, Eli Anguelova; Sutter, Peter Werner

2014-11-18

Vapor-liquid-solid growth of nanowires is tailored to achieve complex one-dimensional material geometries using phase diagrams determined for nanoscale materials. Segmented one-dimensional nanowires having constant composition display locally variable electronic band structures that are determined by the diameter of the nanowires. The unique electrical and optical properties of the segmented nanowires are exploited to form electronic and optoelectronic devices. Using gold-germanium as a model system, in situ transmission electron microscopy establishes, for nanometer-sized Au--Ge alloy drops at the tips of Ge nanowires (NWs), the parts of the phase diagram that determine their temperature-dependent equilibrium composition. The nanoscale phase diagram is then used to determine the exchange of material between the NW and the drop. The phase diagram for the nanoscale drop deviates significantly from that of the bulk alloy.

Hybrid membrane-microfluidic components using a novel ceramic MEMS technology

NASA Astrophysics Data System (ADS)

Lutz, Brent J.; Polyakov, Oleg; Rinaldo, Chris

2012-03-01

A novel hybrid nano/microfabrication technology has been employed to produce unique MEMS and microfluidic components that integrate nanoporous membranes. The components are made by micromachining a self-organized nanostructured ceramic material that is biocompatible and amenable to surface chemistry modification. Microfluidic structures, such as channels and wells, can be made with a precision of <2 microns. Thin-film membranes can be integrated into the bottom of these structures, featuring a wide range of possible thicknesses, from 100 micron to <50 nm. Additionally, these membranes may be non-porous or porous (with controllable pore sizes from 200 nm to <5 nm), for sophisticated size-based separations. With previous and current support from the NIH SBIR program, we have built several unique devices, and demonstrated improved separations, cell culturing, and imaging (optical and electron microscopy) versus standard products. Being ceramic, the material is much more robust to demanding environments (e.g. high and low temperatures and organic solvents), compared to polymer-based devices. Additionally, we have applied multiple surface modification techniques, including atomic layer deposition, to manipulate properties such as electrical conductivity. This microfabrication technology is highly scaleable, and thus can yield low-cost, reliable, disposable microcomponents and devices. Specific applications that can benefit from this technology includes cell culturing and assays, imaging by cryo-electron tomography, environmental sample processing, as well as many others.

Fundamental Studies and Development of III-N Visible LEDs for High-Power Solid-State Lighting Applications

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

Dupuis, Russell

The goal of this program is to understand in a fundamental way the impact of strain, defects, polarization, and Stokes loss in relation to unique device structures upon the internal quantum efficiency (IQE) and efficiency droop (ED) of III-nitride (III-N) light-emitting diodes (LEDs) and to employ this understanding in the design and growth of high-efficiency LEDs capable of highly-reliable, high-current, high-power operation. This knowledge will be the basis for our advanced device epitaxial designs that lead to improved device performance. The primary approach we will employ is to exploit new scientific and engineering knowledge generated through the application of amore » set of unique advanced growth and characterization tools to develop new concepts in strain-, polarization-, and carrier dynamics-engineered and low-defect materials and device designs having reduced dislocations and improved carrier collection followed by efficient photon generation. We studied the effects of crystalline defect, polarizations, hole transport, electron-spillover, electron blocking layer, underlying layer below the multiplequantum- well active region, and developed high-efficiency and efficiency-droop-mitigated blue LEDs with a new LED epitaxial structures. We believe new LEDs developed in this program will make a breakthrough in the development of high-efficiency high-power visible III-N LEDs from violet to green spectral region.« less

Creation of artificial skyrmions and antiskyrmions by anisotropy engineering

NASA Astrophysics Data System (ADS)

Zhang, S.; Petford-Long, A. K.; Phatak, C.

2016-08-01

Topologically non-trivial spin textures form a fundamental paradigm in solid-state physics and present unique opportunities to explore exciting phenomena such as the topological Hall effect. One such texture is a skyrmion, in which the spins can be mapped to point in all directions wrapping around a sphere. Understanding the formation of these spin textures, and their energetic stability, is crucial in order to control their behavior. In this work, we report on controlling the perpendicular anisotropy of continuous Co/Pt multilayer films with ion irradiation to form unique spin configurations of artificial skyrmions and antiskyrmions that are stabilized by their demagnetization energy. We elucidate their behavior using aberration-corrected Lorentz transmission electron microscopy. We also discuss the energetic stability of these structures studied through in-situ magnetizing experiments performed at room temperature, combined with micromagnetic simulations that successfully reproduce the spin textures and behavior. This research offers new opportunities towards creation of artificial skyrmion or antiskyrmion lattices that can be used to investigate not only fundamental properties of their interaction with electron currents but also technological applications such as artificial magnonic crystals.

Quantum dot-decorated semiconductor micro- and nanoparticles: A review of their synthesis, characterization and application in photocatalysis.

PubMed

Bajorowicz, Beata; Kobylański, Marek P; Gołąbiewska, Anna; Nadolna, Joanna; Zaleska-Medynska, Adriana; Malankowska, Anna

2018-06-01

Quantum dot (QD)-decorated semiconductor micro- and nanoparticles are a new class of functional nanomaterials that have attracted considerable interest for their unique structural, optical and electronic properties that result from the large surface-to-volume ratio and the quantum confinement effect. In addition, because of QDs' excellent light-harvesting capacity, unique photoinduced electron transfer, and up-conversion behaviour, semiconductor nanoparticles decorated with quantum dots have been used widely in photocatalytic applications for the degradation of organic pollutants in both the gas and aqueous phases. This review is a comprehensive overview of the recent progress in synthesis methods for quantum dots and quantum dot-decorated semiconductor composites with an emphasis on their composition, morphology and optical behaviour. Furthermore, various approaches used for the preparation of QD-based composites are discussed in detail with respect to visible and UV light-induced photoactivity. Finally, an outlook on future development is proposed with the goal of overcoming challenges and stimulating further research into this promising field. Copyright © 2018 Elsevier B.V. All rights reserved.

Creation of artificial skyrmions and antiskyrmions by anisotropy engineering

DOE PAGES

Zhang, S.; Petford-Long, A. K.; Phatak, C.

2016-08-10

Topological spin textures form a fundamental paradigm in solid state physics and present unique opportunities to explore exciting phenomena such as the quantum Hall effect. One such non-trivial spin texture is a skyrmion, in which the spins can be mapped to point in all directions wrapping around a sphere. Understanding the formation of these spin textures, and their topological and energetic stability, is crucial in order to control their behavior. In this work, we report on controlling the anisotropy of continuous Co/Pt multilayer films with ion irradiation to form unique domain configurations of artificial skyrmions and antiskyrmions. We elucidate theirmore » behavior using aberration-corrected Lorentz transmission electron microscopy. We also discuss the energetic stability of these structures studied through in-situ magnetizing experiments performed at room temperature, combined with micromagnetic simulations that successfully reproduce the spin textures and behavior. As a result, this research offers new opportunities towards creation of artificial skyrmion or antiskyrmion lattices that can be used to investigate not only fundamental properties of their interaction with electron currents but also technological applications such as artificial magnonic crystals.« less

A new look at lunar soil collected from the sea of tranquility during the Apollo 11 mission.

PubMed

Kiely, Carol; Greenberg, Gary; Kiely, Christopher J

2011-02-01

Complementary state-of-the-art optical, scanning electron, and X-ray microscopy techniques have been used to study the morphology of Apollo 11 lunar soil particles (10084-47). The combination of innovative lighting geometries with image processing of a through focal series of images has allowed us to obtain a unique collection of high-resolution light micrographs of these fascinating particles. Scanning electron microscopy (SEM) stereo-pair imaging has been exploited to illustrate some of the unique morphological properties of lunar regolith. In addition, for the first time, X-ray micrographs with submicron resolution have been taken of individual particles using X-ray ultramicroscopy (XuM). This SEM-based technique lends itself readily to the imaging of pores, cracks, and inclusions and allows the internal structure of an entire particle to be viewed. Rotational SEM and XuM movies have also been constructed from a series of images collected at sequential angles through 360°. These offer a new and insightful view of these complex particles providing size, shape, and spatial information on many of their internal features.

Creation of artificial skyrmions and antiskyrmions by anisotropy engineering

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

Zhang, S.; Petford-Long, A. K.; Phatak, C.

Topological spin textures form a fundamental paradigm in solid state physics and present unique opportunities to explore exciting phenomena such as the quantum Hall effect. One such non-trivial spin texture is a skyrmion, in which the spins can be mapped to point in all directions wrapping around a sphere. Understanding the formation of these spin textures, and their topological and energetic stability, is crucial in order to control their behavior. In this work, we report on controlling the anisotropy of continuous Co/Pt multilayer films with ion irradiation to form unique domain configurations of artificial skyrmions and antiskyrmions. We elucidate theirmore » behavior using aberration-corrected Lorentz transmission electron microscopy. We also discuss the energetic stability of these structures studied through in-situ magnetizing experiments performed at room temperature, combined with micromagnetic simulations that successfully reproduce the spin textures and behavior. As a result, this research offers new opportunities towards creation of artificial skyrmion or antiskyrmion lattices that can be used to investigate not only fundamental properties of their interaction with electron currents but also technological applications such as artificial magnonic crystals.« less

Integrated digital inverters based on two-dimensional anisotropic ReS2 field-effect transistors

PubMed Central

Liu, Erfu; Fu, Yajun; Wang, Yaojia; Feng, Yanqing; Liu, Huimei; Wan, Xiangang; Zhou, Wei; Wang, Baigeng; Shao, Lubin; Ho, Ching-Hwa; Huang, Ying-Sheng; Cao, Zhengyi; Wang, Laiguo; Li, Aidong; Zeng, Junwen; Song, Fengqi; Wang, Xinran; Shi, Yi; Yuan, Hongtao; Hwang, Harold Y.; Cui, Yi; Miao, Feng; Xing, Dingyu

2015-01-01

Semiconducting two-dimensional transition metal dichalcogenides are emerging as top candidates for post-silicon electronics. While most of them exhibit isotropic behaviour, lowering the lattice symmetry could induce anisotropic properties, which are both scientifically interesting and potentially useful. Here we present atomically thin rhenium disulfide (ReS2) flakes with unique distorted 1T structure, which exhibit in-plane anisotropic properties. We fabricated monolayer and few-layer ReS2 field-effect transistors, which exhibit competitive performance with large current on/off ratios (∼107) and low subthreshold swings (100 mV per decade). The observed anisotropic ratio along two principle axes reaches 3.1, which is the highest among all known two-dimensional semiconducting materials. Furthermore, we successfully demonstrated an integrated digital inverter with good performance by utilizing two ReS2 anisotropic field-effect transistors, suggesting the promising implementation of large-scale two-dimensional logic circuits. Our results underscore the unique properties of two-dimensional semiconducting materials with low crystal symmetry for future electronic applications. PMID:25947630

Electron crystallography of ultrathin 3D protein crystals: Atomic model with charges

PubMed Central

Yonekura, Koji; Kato, Kazuyuki; Ogasawara, Mitsuo; Tomita, Masahiro; Toyoshima, Chikashi

2015-01-01

Membrane proteins and macromolecular complexes often yield crystals too small or too thin for even the modern synchrotron X-ray beam. Electron crystallography could provide a powerful means for structure determination with such undersized crystals, as protein atoms diffract electrons four to five orders of magnitude more strongly than they do X-rays. Furthermore, as electron crystallography yields Coulomb potential maps rather than electron density maps, it could provide a unique method to visualize the charged states of amino acid residues and metals. Here we describe an attempt to develop a methodology for electron crystallography of ultrathin (only a few layers thick) 3D protein crystals and present the Coulomb potential maps at 3.4-Å and 3.2-Å resolution, respectively, obtained from Ca2+-ATPase and catalase crystals. These maps demonstrate that it is indeed possible to build atomic models from such crystals and even to determine the charged states of amino acid residues in the Ca2+-binding sites of Ca2+-ATPase and that of the iron atom in the heme in catalase. PMID:25730881

Electron crystallography of ultrathin 3D protein crystals: atomic model with charges.

PubMed

Yonekura, Koji; Kato, Kazuyuki; Ogasawara, Mitsuo; Tomita, Masahiro; Toyoshima, Chikashi

2015-03-17

Membrane proteins and macromolecular complexes often yield crystals too small or too thin for even the modern synchrotron X-ray beam. Electron crystallography could provide a powerful means for structure determination with such undersized crystals, as protein atoms diffract electrons four to five orders of magnitude more strongly than they do X-rays. Furthermore, as electron crystallography yields Coulomb potential maps rather than electron density maps, it could provide a unique method to visualize the charged states of amino acid residues and metals. Here we describe an attempt to develop a methodology for electron crystallography of ultrathin (only a few layers thick) 3D protein crystals and present the Coulomb potential maps at 3.4-Å and 3.2-Å resolution, respectively, obtained from Ca(2+)-ATPase and catalase crystals. These maps demonstrate that it is indeed possible to build atomic models from such crystals and even to determine the charged states of amino acid residues in the Ca(2+)-binding sites of Ca(2+)-ATPase and that of the iron atom in the heme in catalase.

Structural and phylogenetic analysis of Rhodobacter capsulatus NifF: uncovering general features of nitrogen-fixation (nif)-flavodoxins.

PubMed

Pérez-Dorado, Inmaculada; Bortolotti, Ana; Cortez, Néstor; Hermoso, Juan A

2013-01-09

Analysis of the crystal structure of NifF from Rhodobacter capsulatus and its homologues reported so far reflects the existence of unique structural features in nif flavodoxins: a leucine at the re face of the isoalloxazine, an eight-residue insertion at the C-terminus of the 50's loop and a remarkable difference in the electrostatic potential surface with respect to non-nif flavodoxins. A phylogenetic study on 64 sequences from 52 bacterial species revealed four clusters, including different functional prototypes, correlating the previously defined as "short-chain" with the firmicutes flavodoxins and the "long-chain" with gram-negative species. The comparison of Rhodobacter NifF structure with other bacterial flavodoxin prototypes discloses the concurrence of specific features of these functional electron donors to nitrogenase.

Monoclinic Tungsten Oxide with {100} Facet Orientation and Tuned Electronic Band Structure for Enhanced Photocatalytic Oxidations.

PubMed

Zhang, Ning; Chen, Chen; Mei, Zongwei; Liu, Xiaohe; Qu, Xiaolei; Li, Yunxiang; Li, Siqi; Qi, Weihong; Zhang, Yuanjian; Ye, Jinhua; Roy, Vellaisamy A L; Ma, Renzhi

2016-04-27

Exploring surface-exposed highly active crystal facets for photocatalytic oxidations is promising in utilizing monoclinic WO3 semiconductor. However, the previously reported highly active facets for monoclinic WO3 were mainly toward enhancing photocatalytic reductions. Here we report that the WO3 with {100} facet orientation and tuned surface electronic band structure can effectively enhance photocatalytic oxidation properties. The {100} faceted WO3 single crystals are synthesized via a facile hydrothermal method. The UV-visible diffuse reflectance, X-ray photoelectron spectroscopy valence band spectra, and photoelectrochemical measurements suggest that the {100} faceted WO3 has a much higher energy level of valence band maximum compared with the normal WO3 crystals without preferred orientation of the crystal face. The density functional theory calculations reveal that the shift of O 2p and W 5d states in {100} face induce a unique band structure. In comparison with the normal WO3, the {100} faceted WO3 exhibits an O2 evolution rate about 5.1 times in water splitting, and also shows an acetone evolution rate of 4.2 times as well as CO2 evolution rate of 3.8 times in gaseous degradation of 2-propanol. This study demonstrates an efficient crystal face engineering route to tune the surface electronic band structure for enhanced photocatalytic oxidations.

Advances in 2D boron nitride nanostructures: nanosheets, nanoribbons, nanomeshes, and hybrids with graphene.

PubMed

Lin, Yi; Connell, John W

2012-11-21

The recent surge in graphene research has stimulated interest in the investigation of various 2-dimensional (2D) nanomaterials. Among these materials, the 2D boron nitride (BN) nanostructures are in a unique position. This is because they are the isoelectric analogs to graphene structures and share very similar structural characteristics and many physical properties except for the large band gap. The main forms of the 2D BN nanostructures include nanosheets (BNNSs), nanoribbons (BNNRs), and nanomeshes (BNNMs). BNNRs are essentially BNNSs with narrow widths in which the edge effects become significant; BNNMs are also variations of BNNSs, which are supported on certain metal substrates where strong interactions and the lattice mismatch between the substrate and the nanosheet result in periodic shallow regions on the nanosheet surface. Recently, the hybrids of 2D BN nanostructures with graphene, in the form of either in-plane hybrids or inter-plane heterolayers, have also drawn much attention. In particular, the BNNS-graphene heterolayer architectures are finding important electronic applications as BNNSs may serve as excellent dielectric substrates or separation layers for graphene electronic devices. In this article, we first discuss the structural basics, spectroscopic signatures, and physical properties of the 2D BN nanostructures. Then, various top-down and bottom-up preparation methodologies are reviewed in detail. Several sections are dedicated to the preparation of BNNRs, BNNMs, and BNNS-graphene hybrids, respectively. Following some more discussions on the applications of these unique materials, the article is concluded with a summary and perspectives of this exciting new field.

Final Technical Report

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

Dr. Asok K. Ray

2012-05-22

During the past decades, considerable theoretical efforts have been devoted to studying the electronic and geometric structures and related properties of surfaces. Such efforts are particularly important for systems like the actinides for which experimental work is relatively difficult to perform due to material problems and toxicity. The actinides are characterized by a gradual filling of the 5f-electron shell with the degree of localization increasing with the atomic number Z along the last series of the periodic table. The open shell of the 5f electrons determines the atomic, molecular, and solid state properties of the actinide elements and their compoundsmore » and understanding the quantum mechanics of the 5f electrons is the defining issue in the chemistry and physics of actinide elements. These elements are also characterized by the increasing prominence of relativistic effects and their studies can, in fact, help us understand the role of relativity throughout the periodic table. However, the electronic and geometric structures of the actinides, specifically the trans-uranium actinides and the roles of the 5f electrons in chemical bonding are still not well understood. This is crucial not only for our understanding of the actinides but also for the fact that the actinides constitute 'the missing link' between the d transition elements and the lanthanides. The 5f orbitals have properties intermediate between those of localized 4f and delocalized 3d orbitals. Thus, a proper understanding of the actinides will help us understand the behavior of the lanthanides and transition metals as well. In fact, there is an urgent need for continued extensive and detailed theoretical research in this area to provide significant and deep understandings of the electronic and geometric structures of the actinides. In this work, we have performed electronic structure studies for plutonium (Pu), americium (Am), and curium (Cm) surfaces, and molecular adsorptions on Pu and Am surfaces. In particular, the region at the boundary of Pu and Am, is widely believed to be the crossover region between d-like itinerant and f-like localized behavior The eventual goal is a complete understanding of the surface chemistry and physics processes of all actinide surfaces, defining the chemistry and physics of such heavy elements. Among the actinides, plutonium, with five 5f electrons in the solid state, is arguably the most complex, fascinating, and enigmatic element known to mankind and has attracted extraordinary scientific and technological interests because of its unique properties, generating a significant body of research in diverse areas, including superconductivity. Pu has, at least, six stable allotropes between room temperature and melting at atmospheric pressure, indicating that the valence electrons can hybridize into a number of complex bonding arrangements. Central and critical questions relate to the electronic structure, localization of the 5f electrons and the magnetism of Pu. For the light-actinides, from Th to Pu, the 5f electrons are believed to be delocalized, hybridizing with the 6d and 7s electrons. For the heavier actinides, Am and beyond, the 5f electrons are localized with the 5f orbitals progressively lower in energy relative to the 6d configuration. Hence, Pu is in a position where the 5f electronic behavior changes from itinerant to localized. As far as magnetism is concerned, a majority of the theoretical calculations continues to claim the existence of magnetism while almost all the experimental results do not find any support for such claims. The second element of interest to us, namely americium, occupies a central position in the actinide series with respect to the involvement of 5f electrons in metallic bonding. It is widely believed that the 5f electrons in Am are localized and that Am undergoes a series of crystallographic phase changes with pressure. Fully-relativistic all electron surface studies of the different phases of Am, initially for the dhcp and the fcc surfaces, can and have provided us with valuable information about chemical bonding in Am and the transitions from f-electron delocalization to f-electron localization in trans-uranium compounds. In particular, a comparative study of the electronic structures of the Pu and Am surfaces using the techniques of all-electron modern density functional theory and beyond can provide significant information about the role of 5f electrons in bond formation as also the localization of the 5f electrons, matters of considerable controversies. The change from metallic 5f bonding into local-moment nonbonding configurations that takes place between Pu and Am is rather unique in the periodic table and is at the very heart of our understanding of electronic structure. We believe that, considering the narrow bandwidth of surface states, any transition from itinerant to localized behavior first takes place at the actinide surfaces with possible reconstructions.« less

Aerogel materials with periodic structures imprinted with cellulose nanocrystals.

PubMed

Xu, Yi-Tao; Dai, Yiling; Nguyen, Thanh-Dinh; Hamad, Wadood Y; MacLachlan, Mark J

2018-02-22

Novel aerogel materials with periodic structures derived from chiral nematic liquid crystalline cellulose nanocrystals (CNCs) are reported. The liquid crystalline structure of phase-separated CNCs is locked by a simple solvent exchange method or silica condensation. Both cellulose and silica/cellulose aerogel materials were obtained after critical point drying, and subsequent calcination of the silica/cellulose composite afforded a silica aerogel with periodic order. Gas adsorption and electron microscopy studies revealed that these materials have high surface areas and a unique chiral nematic structure imparted from the helicoidal CNC template. This is a new, scalable approach to aerogel materials with highly anisotropic structures. The high porosity and periodic, chiral features of these new materials may make them suitable for applications that require anisotropic properties or as hard templates for the construction of other ordered aerogels.

A Census of Plasma Waves and Structures Associated With an Injection Front in the Inner Magnetosphere

NASA Astrophysics Data System (ADS)

Malaspina, David M.; Ukhorskiy, Aleksandr; Chu, Xiangning; Wygant, John

2018-04-01

Now that observations have conclusively established that the inner magnetosphere is abundantly populated with kinetic electric field structures and nonlinear waves, attention has turned to quantifying the ability of these structures and waves to scatter and accelerate inner magnetospheric plasma populations. A necessary step in that quantification is determining the distribution of observed structure and wave properties (e.g., occurrence rates, amplitudes, and spatial scales). Kinetic structures and nonlinear waves have broadband signatures in frequency space, and consequently, high-resolution time domain electric and magnetic field data are required to uniquely identify such structures and waves as well as determine their properties. However, most high-resolution fields data are collected with a strong bias toward high-amplitude signals in a preselected frequency range, strongly biasing observations of structure and wave properties. In this study, an ˜45 min unbroken interval of 16,384 samples/s field burst data, encompassing an electron injection event, is examined. This data set enables an unbiased census of the kinetic structures and nonlinear waves driven by this electron injection, as well as determination of their "typical" properties. It is found that the properties determined using this unbiased burst data are considerably different than those inferred from amplitude-biased burst data, with significant implications for wave-particle interactions due to kinetic structures and nonlinear waves in the inner magnetosphere.

Comparison of intrinsic dynamics of cytochrome p450 proteins using normal mode analysis

PubMed Central

Dorner, Mariah E; McMunn, Ryan D; Bartholow, Thomas G; Calhoon, Brecken E; Conlon, Michelle R; Dulli, Jessica M; Fehling, Samuel C; Fisher, Cody R; Hodgson, Shane W; Keenan, Shawn W; Kruger, Alyssa N; Mabin, Justin W; Mazula, Daniel L; Monte, Christopher A; Olthafer, Augustus; Sexton, Ashley E; Soderholm, Beatrice R; Strom, Alexander M; Hati, Sanchita

2015-01-01

Cytochrome P450 enzymes are hemeproteins that catalyze the monooxygenation of a wide-range of structurally diverse substrates of endogenous and exogenous origin. These heme monooxygenases receive electrons from NADH/NADPH via electron transfer proteins. The cytochrome P450 enzymes, which constitute a diverse superfamily of more than 8,700 proteins, share a common tertiary fold but < 25% sequence identity. Based on their electron transfer protein partner, cytochrome P450 proteins are classified into six broad classes. Traditional methods of pro are based on the canonical paradigm that attributes proteins' function to their three-dimensional structure, which is determined by their primary structure that is the amino acid sequence. It is increasingly recognized that protein dynamics play an important role in molecular recognition and catalytic activity. As the mobility of a protein is an intrinsic property that is encrypted in its primary structure, we examined if different classes of cytochrome P450 enzymes display any unique patterns of intrinsic mobility. Normal mode analysis was performed to characterize the intrinsic dynamics of five classes of cytochrome P450 proteins. The present study revealed that cytochrome P450 enzymes share a strong dynamic similarity (root mean squared inner product > 55% and Bhattacharyya coefficient > 80%), despite the low sequence identity (< 25%) and sequence similarity (< 50%) across the cytochrome P450 superfamily. Noticeable differences in Cα atom fluctuations of structural elements responsible for substrate binding were noticed. These differences in residue fluctuations might be crucial for substrate selectivity in these enzymes. PMID:26130403

Substrate-Induced Allosteric Change in the Quaternary Structure of the Spermidine N-Acetyltransferase SpeG.

PubMed

Filippova, Ekaterina V; Weigand, Steven; Osipiuk, Jerzy; Kiryukhina, Olga; Joachimiak, Andrzej; Anderson, Wayne F

2015-11-06

The spermidine N-acetyltransferase SpeG is a dodecameric enzyme that catalyzes the transfer of an acetyl group from acetyl coenzyme A to polyamines such as spermidine and spermine. SpeG has an allosteric polyamine-binding site and acetylating polyamines regulate their intracellular concentrations. The structures of SpeG from Vibrio cholerae in complexes with polyamines and cofactor have been characterized earlier. Here, we present the dodecameric structure of SpeG from V. cholerae in a ligand-free form in three different conformational states: open, intermediate and closed. All structures were crystallized in C2 space group symmetry and contain six monomers in the asymmetric unit cell. Two hexamers related by crystallographic 2-fold symmetry form the SpeG dodecamer. The open and intermediate states have a unique open dodecameric ring. This SpeG dodecamer is asymmetric except for the one 2-fold axis and is unlike any known dodecameric structure. Using a fluorescence thermal shift assay, size-exclusion chromatography with multi-angle light scattering, small-angle X-ray scattering analysis, negative-stain electron microscopy and structural analysis, we demonstrate that this unique open dodecameric state exists in solution. Our combined results indicate that polyamines trigger conformational changes and induce the symmetric closed dodecameric state of the protein when they bind to their allosteric sites. Copyright © 2015. Published by Elsevier Ltd.

Substrate-induced allosteric change in the quaternary structure of the spermidine N-acetyltransferase SpeG

DOE PAGES

Filippova, Ekaterina V.; Weigand, Steven J.; Osipiuk, Jerzy; ...

2015-09-26

The spermidine N-acetyltransferase SpeG is a dodecameric enzyme that catalyzes the transfer of an acetyl group from acetyl coenzyme A to polyamines such as spermidine and spermine. SpeG has an allosteric polyamine-binding site and acetylating polyamines regulate their intracellular concentrations. The structures of SpeG from Vibrio cholerae in complexes with polyamines and cofactor have been characterized earlier. Here, we present the dodecameric structure of SpeG from V. cholerae in a ligand-free form in three different conformational states: open, intermediate and closed. All structures were crystallized in C2 space group symmetry and contain six monomers in the asymmetric unit cell. Twomore » hexamers related by crystallographic 2-fold symmetry form the SpeG dodecamer. The open and intermediate states have a unique open dodecameric ring. This SpeG dodecamer is asymmetric except for the one 2-fold axis and is unlike any known dodecameric structure. Using a fluorescence thermal shift assay, size-exclusion chromatography with multi-angle light scattering, small-angle X-ray scattering analysis, negative-stain electron microscopy and structural analysis, we demonstrate that this unique open dodecameric state exists in solution. As a result, our combined results indicate that polyamines trigger conformational changes and induce the symmetric closed dodecameric state of the protein when they bind to their allosteric sites.« less

14 CFR 221.203 - Unique rule numbers required.

Code of Federal Regulations, 2014 CFR

2014-01-01

... 14 Aeronautics and Space 4 2014-01-01 2014-01-01 false Unique rule numbers required. 221.203... PROCEEDINGS) ECONOMIC REGULATIONS TARIFFS Electronically Filed Tariffs § 221.203 Unique rule numbers required... bear a unique rule number. (b) The unique rule numbers for the fares specified in this section shall be...

Atomic Layer Deposition of Nickel on ZnO Nanowire Arrays for High-Performance Supercapacitors.

PubMed

Ren, Qing-Hua; Zhang, Yan; Lu, Hong-Liang; Wang, Yong-Ping; Liu, Wen-Jun; Ji, Xin-Ming; Devi, Anjana; Jiang, An-Quan; Zhang, David Wei

2018-01-10

A novel hybrid core-shell structure of ZnO nanowires (NWs)/Ni as a pseudocapacitor electrode was successfully fabricated by atomic layer deposition of a nickel shell, and its capacitive performance was systemically investigated. Transmission electron microscopy and X-ray photoelectron spectroscopy results indicated that the NiO was formed at the interface between ZnO and Ni where the Ni was oxidized by ZnO during the ALD of the Ni layer. Electrochemical measurement results revealed that the Ti/ZnO NWs/Ni (1500 cycles) electrode with a 30 nm thick Ni-NiO shell layer had the best supercapacitor properties including ultrahigh specific capacitance (∼2440 F g -1 ), good rate capability (80.5%) under high current charge-discharge conditions, and a relatively better cycling stability (86.7% of the initial value remained after 750 cycles at 10 A g -1 ). These attractive capacitive behaviors are mainly attributed to the unique core-shell structure and the combined effect of ZnO NW arrays as short charge transfer pathways for ion diffusion and electron transfer as well as conductive Ni serving as channel for the fast electron transport to Ti substrate. This high-performance Ti/ZnO NWs/Ni hybrid structure is expected to be one of a promising electrodes for high-performance supercapacitor applications.

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

Li, Hao; Malliakas, Christos D.; Han, Fei

The quaternary compound TlHgInS3 crystallizes in a new structure type of space group, C2/c, with cell parameters a = 13.916(3) angstrom, b = 3.9132(8) angstrom, c = 21.403(4) angstrom, beta = 104.16(3)degrees, V = 1130.1(8) angstrom(3), and rho = 7.241 g/cm(3). The structure is a unique three-dimensional framework with parallel tunnels, which is formed by (1)(infinity)[InS33-] infinite chains bridged by linearly coordinated Hg2+ ions. TlHgInS3 is a semiconductor with a band gap of 1.74 eV and a resistivity of similar to 4.32 G Omega cm. TlHgInS3 single crystals exhibit photocurrent response when exposed to Ag X-rays. The mobility-lifetime product (mumore » tau) of the electrons and holes estimated from the photocurrent measurements are (mu tau)(e) approximate to 3.6 x 10(-4) cm(2)/V and (mu tau)(h) approximate to 2.0 x 10(-4) cm(2)/V. Electronic structure calculations at the density functional theory level indicate an indirect band gap and a relatively small effective mass for both electrons and holes. Based on the photoconductivity data, TlHgInS3 is a potential material for radiation detection applications.« less

Discrete Electronic Bands in Semiconductors and Insulators: Potential High-Light-Yield Scintillators

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

Shi, Hongliang; Du, Mao-Hua

Bulk semiconductors and insulators typically have continuous valence and conduction bands. In this paper, we show that valence and conduction bands of a multinary semiconductor or insulator can be split to narrow discrete bands separated by large energy gaps. This unique electronic structure is demonstrated by first-principles calculations in several quaternary elpasolite compounds, i.e., Cs 2NaInBr 6, Cs 2NaBiCl 6, and Tl 2NaBiCl 6. The narrow discrete band structure in these quaternary elpasolites is due to the large electronegativity difference among cations and the large nearest-neighbor distances in cation sublattices. We further use Cs 2NaInBr 6 as an example tomore » show that the narrow bands can stabilize self-trapped and dopant-bound excitons (in which both the electron and the hole are strongly localized in static positions on adjacent sites) and promote strong exciton emission at room temperature. The discrete band structure should further suppress thermalization of hot carriers and may lead to enhanced impact ionization, which is usually considered inefficient in bulk semiconductors and insulators. Finally, these characteristics can enable efficient room-temperature light emission in low-gap scintillators and may overcome the light-yield bottleneck in current scintillator research.« less

Discrete Electronic Bands in Semiconductors and Insulators: Potential High-Light-Yield Scintillators

DOE PAGES

Shi, Hongliang; Du, Mao-Hua

2015-05-12

Bulk semiconductors and insulators typically have continuous valence and conduction bands. In this paper, we show that valence and conduction bands of a multinary semiconductor or insulator can be split to narrow discrete bands separated by large energy gaps. This unique electronic structure is demonstrated by first-principles calculations in several quaternary elpasolite compounds, i.e., Cs 2NaInBr 6, Cs 2NaBiCl 6, and Tl 2NaBiCl 6. The narrow discrete band structure in these quaternary elpasolites is due to the large electronegativity difference among cations and the large nearest-neighbor distances in cation sublattices. We further use Cs 2NaInBr 6 as an example tomore » show that the narrow bands can stabilize self-trapped and dopant-bound excitons (in which both the electron and the hole are strongly localized in static positions on adjacent sites) and promote strong exciton emission at room temperature. The discrete band structure should further suppress thermalization of hot carriers and may lead to enhanced impact ionization, which is usually considered inefficient in bulk semiconductors and insulators. Finally, these characteristics can enable efficient room-temperature light emission in low-gap scintillators and may overcome the light-yield bottleneck in current scintillator research.« less

The Hydric Effect in Inorganic Nanomaterials for Nanoelectronics and Energy Applications.

PubMed

Sun, Xu; Guo, Yuqiao; Wu, Changzheng; Xie, Yi

2015-07-08

Protons, as one of the world's smallest ions, are able to trigger the charge effect without obvious lattice expansion inside inorganic materials, offering a unique and important test-bed for controlling their diverse functionalities. Arising from the high chemical reactivity of hydrogen (easily losing an electron) with various main group anions (easily accepting a proton), the hydric effect provides a convenient and environmentally benign route to bring about fascinating new physicochemical properties, as well as to create new inorganic structures based on the "old lattice" without dramatically destroying the pristine structure, covering most inorganic materials. Moreover, hydrogen atoms tend to bond with anions or to produce intrinsic defects, both of which are expected to inject extra electrons into lattice framework, promising advances in control of bandgap, spin behavior, and carrier concentration, which determine functionality for wide applications. In this review article, recently developed effective hydric strategies are highlighted, which include the conventional hydric reaction under high temperature or room temperature, proton irradiation or hydrogen plasma treatment, and gate-electrolyte-driven adsorption or doping. The diverse physicochemical properties brought by the hydric effect via modulation of the intrinsic electronic structure are also summarized, finding wide applications in nanoelectronics, energy applications, and catalysis. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Retention of Electronic Conductivity in LaAlO3/SrTiO3 Nanostructures Using a SrCuO2 Capping Layer

NASA Astrophysics Data System (ADS)

Aurino, P. P.; Kalabukhov, A.; Borgani, R.; Haviland, D. B.; Bauch, T.; Lombardi, F.; Claeson, T.; Winkler, D.

2016-08-01

The interface between two wide band-gap insulators, LaAlO3 and SrTiO3 (LAO/STO) offers a unique playground to study the interplay and competitions between different ordering phenomena in a strongly correlated two-dimensional electron gas. Recent studies of the LAO/STO interface reveal the inhomogeneous nature of the 2DEG that strongly influences electrical-transport properties. Nanowires needed in future applications may be adversely affected, and our aim is, thus, to produce a more homogeneous electron gas. In this work, we demonstrate that nanostructures fabricated in the quasi-2DEG at the LaAlO3/SrTiO3 interface, capped with a SrCuO2 layer, retain their electrical resistivity and mobility independent of the structure size, ranging from 100 nm to 30 μ m . This is in contrast to noncapped LAO/STO structures, where the room-temperature electrical resistivity significantly increases when the structure size becomes smaller than 1 μ m . High-resolution intermodulation electrostatic force microscopy reveals an inhomogeneous surface potential with "puddles" of a characteristic size of 130 nm in the noncapped samples and a more uniform surface potential with a larger characteristic size of the puddles in the capped samples. In addition, capped structures show superconductivity below 200 mK and nonlinear current-voltage characteristics with a clear critical current observed up to 700 mK. Our findings shed light on the complicated nature of the 2DEG at the LAO/STO interface and may also be used for the design of electronic devices.

First-principles study of crystal and electronic structure of rare-earth cobaltites

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

Topsakal, M.; Leighton, C.; Wentzcovitch, R. M.

Using density functional theory plus self-consistent Hubbard U (DFT + U{sub sc}) calculations, we have investigated the structural and electronic properties of the rare-earth cobaltites RCoO{sub 3} (R = Pr – Lu). Our calculations show the evolution of crystal and electronic structure of the insulating low-spin RCoO{sub 3} with increasing rare-earth atomic number (decreasing ionic radius), including the invariance of the Co-O bond distance (d{sub Co–O}), the decrease of the Co-O-Co bond angle (Θ), and the increase of the crystal field splitting (Δ{sub CF}) and band gap energy (E{sub g}). Agreement with experiment for the latter improves considerably with the use of DFT + U{sub sc}more » and all trends are in good agreement with the experimental data. These trends enable a direct test of prior rationalizations of the trend in spin-gap associated with the spin crossover in this series, which is found to expose significant issues with simple band based arguments. We also examine the effect of placing the rare-earth f-electrons in the core region of the pseudopotential. The effect on lattice parameters and band structure is found to be small, but distinct for the special case of PrCoO{sub 3} where some f-states populate the middle of the gap, consistent with the recent reports of unique behavior in Pr-containing cobaltites. Overall, this study establishes a foundation for future predictive studies of thermally induced spin excitations in rare-earth cobaltites and similar systems.« less

Electron Flow in Multiheme Bacterial Cytochromes is a Balancing Act Between Heme Electronic Interaction and Redox Potentials

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

Breuer, Marian; Rosso, Kevin M.; Blumberger, Jochen

The naturally widespread process of electron transfer from metal reducing bacteria to extracellular solid metal oxides entails unique biomolecular machinery optimized for long-range electron transport. To perform this function efficiently microorganisms have adapted multi-heme c-type cytochromes to arrange heme cofactors into wires that cooperatively span the cellular envelope, transmitting electrons along distances greater than 100 Angstroms. Implications and opportunities for bionanotechnological device design are self-evident. However, at the molecular level how these proteins shuttle electrons along their heme wires, navigating intraprotein intersections and interprotein interfaces effciently, remains a mystery so far inaccessible to experiment. To shed light on this criticalmore » topic, we carried out extensive computer simulations to calculate Marcus theory quantities for electron transfer along the ten heme cofactors in the recently crystallized outer membrane cytochrome MtrF. The combination of electronic coupling matrix elements with free energy calculations of heme redox potentials and reorganization energies for heme-to-heme electron transfer allows the step-wise and overall electron transfer rate to be estimated and understood in terms of structural and dynamical characteristics of the protein. By solving a master equation for electron hopping, we estimate an intrinsic, maximum possible electron flux through solvated MtrF of 104-105 s-1, consistent with recently measured rates for the related MtrCAB protein complex. Intriguingly, this flux must navigate thermodynamically uphill steps past low potential hemes. Our calculations show that the rapid electron transport through MtrF is the result of a clear correlation between heme redox potential and the strength of electronic coupling along the wire: Thermodynamically uphill steps occur only between electronically well connected stacked heme pairs. This suggests that the protein evolved to harbor low potential hemes, presumably necessary for reduction of certain soluble substrates, without slowing down electron ow. These findings are particularly profound in light of the apparently well conserved staggered cross heme wire structural motif in functionally related outer-membrane proteins.« less

Magnetism on a Boron-doped Si(111)-√ 3 × √ 3 Surface

NASA Astrophysics Data System (ADS)

Moon, Chang-Youn; Eom, Daejin; Koo, Ja-Yong

2018-03-01

We perform first-principles calculation to investigate the possible magnetism on the Si(111)-√ 3 × √ 3 surface, which is stabilized for highly boron-doped samples. When the silicon adatom on top of a boron atom is removed to form a defect structure, three silicon dangling bonds are exposed, generating half-filled doubly degenerate energy levels in the band gap, which stabilizes a local magnetic moment of 2 μ B . When many such defect structures are adjacent to one another, they are found to align antiferromagnetically. However, we demonstrate that the ferromagnetism can be stabilized by adjusting the number of electrons in the defects, suggesting a possibility towards spintronic applications for this unique silicon surface structure.

Investigations of glass structure using fluorescence line narrowing and moleuclar dynamics simulations

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

Weber, M.J.; Brawer, S.A.

1982-07-02

The local structure at individual ion sites in simple and multicomponent glasses is simulated using methods of molecular dynamics. Computer simulations of fluoroberyllate glasses predict a range of ion separations and coordination numbers that increases with increasing complexity of the glass composition. This occurs at both glass forming and glass modifying cation sites. Laser-induced fluorescence line-narrowing techniques provide a unique probe of the local environments of selected subsets of ions and are used to measure site to site variations in the electronic energy levels and transition probabilities of rare earth ions. These and additional results from EXAFS, neutron and x-raymore » diffraction, and NMR experiments are compared with simulated glass structures.« less

Liquid crystals from mesogens containing gold nanoparticles

NASA Astrophysics Data System (ADS)

Lewandowski, Wiktor; Gorecka, Ewa

Long-range ordered structures made of nanoparticles are perspective materials for future optical, electronic and sensing technologies. Conspicuous physicochemical features of nanoparticle aggregates originate from distant-dependent collective interactions, therefore lately a lot of attention was put to the development of assembly strategies allowing control over nanoparticle spatial distribution. In this chapter we will focus on the assembly process based on using thermotropic liquid-crystalline molecules as surface nanoparticle ligands. First, we discuss architectural parameters that inuence structure and thermal properties of the aggregates. Then, we show that this approach enables formation of assemblies with metamaterial characteristic, gives access to dynamic materials with light-, magneto- and thermo-responsive behavior and allows formation of aggregates with unique structures, which all make this strategy an attractive object of research.

Assemble: an interactive graphical tool to analyze and build RNA architectures at the 2D and 3D levels.

PubMed

Jossinet, Fabrice; Ludwig, Thomas E; Westhof, Eric

2010-08-15

Assemble is an intuitive graphical interface to analyze, manipulate and build complex 3D RNA architectures. It provides several advanced and unique features within the framework of a semi-automated modeling process that can be performed by homology and ab initio with or without electron density maps. Those include the interactive editing of a secondary structure and a searchable, embedded library of annotated tertiary structures. Assemble helps users with performing recurrent and otherwise tedious tasks in structural RNA research. Assemble is released under an open-source license (MIT license) and is freely available at http://bioinformatics.org/assemble. It is implemented in the Java language and runs on MacOSX, Linux and Windows operating systems.

Self-assembled phase-change nanowire for nonvolatile electronic memory

NASA Astrophysics Data System (ADS)

Jung, Yeonwoong

One of the most important subjects in nanosciences is to identify and exploit the relationship between size and structural/physical properties of materials and to explore novel material properties at a small-length scale. Scale-down of materials is not only advantageous in realizing miniaturized devices but nanometer-sized materials often exhibit intriguing physical/chemical properties that greatly differ from their bulk counterparts. This dissertation studies self-assembled phase-change nanowires for future nonvolatile electronic memories, mainly focusing on their size-dependent memory switching properties. Owing to the one-dimensional, unique geometry coupled with the small and tunable sizes, bottom-designed nanowires offer great opportunities in terms for both fundamental science and practical engineering perspectives, which would be difficult to realize in conventional top-down based approaches. We synthesized chalcogenide phase-change nanowires of different compositions and sizes, and studied their electronic memory switching owing to the structural change between crystalline and amorphous phases. In particular, we investigated nanowire size-dependent memory switching parameters, including writing current, power consumption, and data retention times, as well as studying composition-dependent electronic properties. The observed size and composition-dependent switching and recrystallization kinetics are explained based on the heat transport model and heterogeneous nucleation theories, which help to design phase-change materials with better properties. Moreover, we configured unconventional heterostructured phase-change nanowire memories and studied their multiple memory states in single nanowire devices. Finally, by combining in-situ/ex-situ electron microscopy techniques and electrical measurements, we characterized the structural states involved in electrically-driven phase-change in order to understand the atomistic mechanism that governs the electronic memory switching through phase-change.

Impact of speciation on the electron charge transfer properties of nanodiamond drug carriers

NASA Astrophysics Data System (ADS)

Sun, Baichuan; Barnard, Amanda S.

2016-07-01

Unpassivated diamond nanoparticles (bucky-diamonds) exhibit a unique surface reconstruction involving graphitization of certain crystal facets, giving rise to hybrid core-shell particles containing both aromatic and aliphatic carbon. Considerable effort is directed toward eliminating the aromatic shell, but persistent graphitization of subsequent subsurface-layers makes perdurable purification a challenge. In this study we use some simple statistical methods, in combination with electronic structure simulations, to predict the impact of different fractions of aromatic and aliphatic carbon on the charge transfer properties of the ensembles of bucky-diamonds. By predicting quality factors for a variety of cases, we find that perfect purification is not necessary to preserve selectivity, and there is a clear motivation for purifying samples to improve the sensitivity of charge transfer reactions. This may prove useful in designing drug delivery systems where the release of (selected) drugs needs to be sensitive to specific conditions at the point of delivery.Unpassivated diamond nanoparticles (bucky-diamonds) exhibit a unique surface reconstruction involving graphitization of certain crystal facets, giving rise to hybrid core-shell particles containing both aromatic and aliphatic carbon. Considerable effort is directed toward eliminating the aromatic shell, but persistent graphitization of subsequent subsurface-layers makes perdurable purification a challenge. In this study we use some simple statistical methods, in combination with electronic structure simulations, to predict the impact of different fractions of aromatic and aliphatic carbon on the charge transfer properties of the ensembles of bucky-diamonds. By predicting quality factors for a variety of cases, we find that perfect purification is not necessary to preserve selectivity, and there is a clear motivation for purifying samples to improve the sensitivity of charge transfer reactions. This may prove useful in designing drug delivery systems where the release of (selected) drugs needs to be sensitive to specific conditions at the point of delivery. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr03068h

Electrochemically induced actuation of liquid metal marbles

NASA Astrophysics Data System (ADS)

Tang, Shi-Yang; Sivan, Vijay; Khoshmanesh, Khashayar; O'Mullane, Anthony P.; Tang, Xinke; Gol, Berrak; Eshtiaghi, Nicky; Lieder, Felix; Petersen, Phred; Mitchell, Arnan; Kalantar-Zadeh, Kourosh

2013-06-01

Controlled actuation of soft objects with functional surfaces in aqueous environments presents opportunities for liquid phase electronics, novel assembled super-structures and unusual mechanical properties. We show the extraordinary electrochemically induced actuation of liquid metal droplets coated with nanoparticles, so-called ``liquid metal marbles''. We demonstrate that nanoparticle coatings of these marbles offer an extra dimension for affecting the bipolar electrochemically induced actuation. The nanoparticles can readily migrate along the surface of liquid metals, upon the application of electric fields, altering the capacitive behaviour and surface tension in a highly asymmetric fashion. Surprising actuation behaviours are observed illustrating that nanoparticle coatings can have a strong effect on the movement of these marbles. This significant novel phenomenon, combined with unique properties of liquid metal marbles, represents an exciting platform for enabling diverse applications that cannot be achieved using rigid metal beads.Controlled actuation of soft objects with functional surfaces in aqueous environments presents opportunities for liquid phase electronics, novel assembled super-structures and unusual mechanical properties. We show the extraordinary electrochemically induced actuation of liquid metal droplets coated with nanoparticles, so-called ``liquid metal marbles''. We demonstrate that nanoparticle coatings of these marbles offer an extra dimension for affecting the bipolar electrochemically induced actuation. The nanoparticles can readily migrate along the surface of liquid metals, upon the application of electric fields, altering the capacitive behaviour and surface tension in a highly asymmetric fashion. Surprising actuation behaviours are observed illustrating that nanoparticle coatings can have a strong effect on the movement of these marbles. This significant novel phenomenon, combined with unique properties of liquid metal marbles, represents an exciting platform for enabling diverse applications that cannot be achieved using rigid metal beads. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr00185g

Electronic and School-Based Victimization: Unique Contexts for Adjustment Difficulties during Adolescence

ERIC Educational Resources Information Center

Fredstrom, Bridget K.; Adams, Ryan E.; Gilman, Rich

2011-01-01

Previous research suggests that school-based and electronic victimization have similar negative consequences, yet it is unclear whether these two contexts offer overlapping or unique associations with adolescents' adjustment. 802 ninth-graders (43% male, mean age = 15.84 years), majority being Caucasian (82%), completed measures assessing the…

Enhanced Raman Scattering on In-plane Anisotropic Layered Materials

DOE PAGES

Liang, Liangbo; Meunier, Vincent; Sumpter, Bobby G.; ...

2015-11-19

Surface-enhanced Raman scattering (SERS) on two-dimensional (2D) layered materials has provided a unique platform to study the chemical mechanism (CM) of the enhancement due to its natural separation from electromagnetic enhancement. The CM stems from the basic charge interactions between the substrate and molecules. Despite the extensive studies of the energy alignment between 2D materials and molecules, an understanding of how the electronic properties of the substrate are explicitly involved in the charge interaction is still unclear. Lately, a new group of 2D layered materials with anisotropic structure, including orthorhombic black phosphorus (BP) and triclinic rhenium disulphide (ReS2), has attractedmore » great interest due to their unique anisotropic electrical and optical properties. Herein, we report a unique anisotropic Raman enhancement on few-layered BP and ReS2 using copper phthalocyanine (CuPc) molecules as a Raman probe, which is absent on isotropic graphene and h-BN. According to detailed Raman tensor analysis and density functional theory calculations, anisotropic charge interactions due to the anisotropic carrier mobilities of the 2D materials are responsible for the angular dependence of the Raman enhancement. Our findings not only provide new insights into the CM process in SERS, but also open up new avenues for the exploration and application of the electronic properties of anisotropic 2D layered materials.« less

Photon gating in four-dimensional ultrafast electron microscopy.

PubMed

Hassan, Mohammed T; Liu, Haihua; Baskin, John Spencer; Zewail, Ahmed H

2015-10-20

Ultrafast electron microscopy (UEM) is a pivotal tool for imaging of nanoscale structural dynamics with subparticle resolution on the time scale of atomic motion. Photon-induced near-field electron microscopy (PINEM), a key UEM technique, involves the detection of electrons that have gained energy from a femtosecond optical pulse via photon-electron coupling on nanostructures. PINEM has been applied in various fields of study, from materials science to biological imaging, exploiting the unique spatial, energy, and temporal characteristics of the PINEM electrons gained by interaction with a "single" light pulse. The further potential of photon-gated PINEM electrons in probing ultrafast dynamics of matter and the optical gating of electrons by invoking a "second" optical pulse has previously been proposed and examined theoretically in our group. Here, we experimentally demonstrate this photon-gating technique, and, through diffraction, visualize the phase transition dynamics in vanadium dioxide nanoparticles. With optical gating of PINEM electrons, imaging temporal resolution was improved by a factor of 3 or better, being limited only by the optical pulse widths. This work enables the combination of the high spatial resolution of electron microscopy and the ultrafast temporal response of the optical pulses, which provides a promising approach to attain the resolution of few femtoseconds and attoseconds in UEM.

Photon gating in four-dimensional ultrafast electron microscopy

PubMed Central

Hassan, Mohammed T.; Liu, Haihua; Baskin, John Spencer; Zewail, Ahmed H.

2015-01-01

Ultrafast electron microscopy (UEM) is a pivotal tool for imaging of nanoscale structural dynamics with subparticle resolution on the time scale of atomic motion. Photon-induced near-field electron microscopy (PINEM), a key UEM technique, involves the detection of electrons that have gained energy from a femtosecond optical pulse via photon–electron coupling on nanostructures. PINEM has been applied in various fields of study, from materials science to biological imaging, exploiting the unique spatial, energy, and temporal characteristics of the PINEM electrons gained by interaction with a “single” light pulse. The further potential of photon-gated PINEM electrons in probing ultrafast dynamics of matter and the optical gating of electrons by invoking a “second” optical pulse has previously been proposed and examined theoretically in our group. Here, we experimentally demonstrate this photon-gating technique, and, through diffraction, visualize the phase transition dynamics in vanadium dioxide nanoparticles. With optical gating of PINEM electrons, imaging temporal resolution was improved by a factor of 3 or better, being limited only by the optical pulse widths. This work enables the combination of the high spatial resolution of electron microscopy and the ultrafast temporal response of the optical pulses, which provides a promising approach to attain the resolution of few femtoseconds and attoseconds in UEM. PMID:26438835

Growth and characterization of n-AlGaN 1-D structures with varying Al composition using u-GaN seeds

NASA Astrophysics Data System (ADS)

Kang, San; Chatterjee, Uddipta; Um, Dae-Young; Seo, In Seok; Lee, Cheul-Ro

2017-12-01

Like all the ternary alloys in III-nitride materials family, aluminum gallium nitride (AlGaN) has unique band gap tuning property which enables the alloy to be suitable for many opto-electronic applications. The direct band gap of AlGaN can be tuned from 3.4 to 6.2 eV by changing the composition. In this article, the growth of ternary n-AlGaN micro and nano structures on Si (1 1 1) substrate is demonstrated via 2-step growth method employing metal organic chemical vapor deposition. During the growth flow of Trimethygallium is varied to modulate the final Al/Ga ratio. After the growth, various morphological, crystalline and optical characterizations are carried out to probe in the properties of the grown structures. Recorded X-ray diffraction patterns reveal that the realized structures are wurtzite single crystalline n-AlGaN having a near homogeneous Al distribution and validated by energy dispersive X-ray spectroscopy. Low temperature cathodoluminescence spectra show band edge emission in deep UV region which enables the grown n-AlGaN structures to efficiently find opto-electronic applications in the aforementioned region. Finally, planar photoconductive devices are fabricated using the grown 1-D structures and photocurrent evolution is measured. Structure bearing highest Al content shows a manifold enhancement in photo activity compared to other grown samples. Absolute photoresponsivities of the grown samples are calculated to be 301.47, 116 and 38.13 mA/W which is in accord with the findings of low temperature cathodoluminescence investigation. Therefore, it can be concluded that the successful realization of n-AlGaN 1-D structures varying Al content facilitates the further developments of the field concerning nano- and opto-electronic devices.

Sequence and structural characterization of great salt lake bacteriophage CW02, a member of the T7-like supergroup.

PubMed

Shen, Peter S; Domek, Matthew J; Sanz-García, Eduardo; Makaju, Aman; Taylor, Ryan M; Hoggan, Ryan; Culumber, Michele D; Oberg, Craig J; Breakwell, Donald P; Prince, John T; Belnap, David M

2012-08-01

Halophage CW02 infects a Salinivibrio costicola-like bacterium, SA50, isolated from the Great Salt Lake. Following isolation, cultivation, and purification, CW02 was characterized by DNA sequencing, mass spectrometry, and electron microscopy. A conserved module of structural genes places CW02 in the T7 supergroup, members of which are found in diverse aquatic environments, including marine and freshwater ecosystems. CW02 has morphological similarities to viruses of the Podoviridae family. The structure of CW02, solved by cryogenic electron microscopy and three-dimensional reconstruction, enabled the fitting of a portion of the bacteriophage HK97 capsid protein into CW02 capsid density, thereby providing additional evidence that capsid proteins of tailed double-stranded DNA phages have a conserved fold. The CW02 capsid consists of bacteriophage lambda gpD-like densities that likely contribute to particle stability. Turret-like densities were found on icosahedral vertices and may represent a unique adaptation similar to what has been seen in other extremophilic viruses that infect archaea, such as Sulfolobus turreted icosahedral virus and halophage SH1.

Molecular dynamics-based refinement and validation for sub-5 Å cryo-electron microscopy maps

PubMed Central

Singharoy, Abhishek; Teo, Ivan; McGreevy, Ryan; Stone, John E; Zhao, Jianhua; Schulten, Klaus

2016-01-01

Two structure determination methods, based on the molecular dynamics flexible fitting (MDFF) paradigm, are presented that resolve sub-5 Å cryo-electron microscopy (EM) maps with either single structures or ensembles of such structures. The methods, denoted cascade MDFF and resolution exchange MDFF, sequentially re-refine a search model against a series of maps of progressively higher resolutions, which ends with the original experimental resolution. Application of sequential re-refinement enables MDFF to achieve a radius of convergence of ~25 Å demonstrated with the accurate modeling of β-galactosidase and TRPV1 proteins at 3.2 Å and 3.4 Å resolution, respectively. The MDFF refinements uniquely offer map-model validation and B-factor determination criteria based on the inherent dynamics of the macromolecules studied, captured by means of local root mean square fluctuations. The MDFF tools described are available to researchers through an easy-to-use and cost-effective cloud computing resource on Amazon Web Services. DOI: http://dx.doi.org/10.7554/eLife.16105.001 PMID:27383269

Atom Probe Tomography Analysis of Gallium-Nitride-Based Light-Emitting Diodes

NASA Astrophysics Data System (ADS)

Prosa, Ty J.; Olson, David; Giddings, A. Devin; Clifton, Peter H.; Larson, David J.; Lefebvre, Williams

2014-03-01

Thin-film light-emitting diodes (LEDs) composed of GaN/InxGa1-xN/GaN quantum well (QW) structures are integrated into modern optoelectronic devices because of the tunable InGaN band-gap enabling emission of the full visible spectrum. Atom probe tomography (APT) offers unique capabilities for 3D device characterization including compositional mapping of nano-volumes (>106 nm3) , high detection efficiency (>50%), and good sensitivity. In this study, APT is used to understand the distribution of dopants as well as Al and In alloying agents in a GaN device. Measurements using transmission electron microscopy (TEM) and secondary ion mass spectrometry (SIMS) have also been made to improve the accuracy of the APT analysis by correlating the information content of these complimentary techniques. APT analysis reveals various QW and other optoelectronic structures including a Mg p-GaN layer, an Al-rich electron blocking layer, an In-rich multi-QW region, and an In-based super-lattice structure. The multi-QW composition shows good quantitative agreement with layer thickness and spacing extracted from a high resolution TEM image intensity analysis.

Zernike phase contrast cryo-electron tomography of sodium-driven flagellar hook-basal bodies from Vibrio alginolyticus.

PubMed

Hosogi, Naoki; Shigematsu, Hideki; Terashima, Hiroyuki; Homma, Michio; Nagayama, Kuniaki

2011-01-01

Vibrio alginolyticus use flagella to swim. A flagellum consists of a filament, hook and basal body. The basal body is made up of a rod and several ring structures. This study investigates the structure of the T ring which is a unique component of the V. alginolyticus sodium ion-driven flagellar basal body. Using Zernike phase contrast (ZPC) cryo-electron tomography, we compared the 3D structures of purified hook-basal bodies (HBB) from a wild-type strain (KK148) and a deletion mutant lacking MotX and MotY (TH3), which are thought to form the T ring. ZPC images of HBBs had highly improved signal-to-noise ratio compared to conventional phase contrast images. We observed the outline of the HBBs from strains KK148 and TH3, and the TH3 mutant was missing its T ring. In the wild-type strain, the T ring was beneath the LP ring and seemed to form a ring shape with diameter of 32 nm. Copyright © 2010 Elsevier Inc. All rights reserved.

Recent Applications of 2D Inorganic Nanosheets for Emerging Energy Storage System.

PubMed

Oh, Seung Mi; Patil, Sharad B; Jin, Xiaoyan; Hwang, Seong-Ju

2018-04-03

Among many types of nanostructured inorganic materials, highly anisotropic 2D nanosheets provide unique advantages in designing and synthesizing efficient electrode and electrocatalyst materials for novel energy storage technologies. 2D inorganic nanosheets boast lots of unique characteristics such as high surface area, short ion diffusion path, tailorable compositions, and tunable electronic structures. These merits of 2D inorganic nanosheets render them promising candidate materials as electrodes for diverse secondary batteries and supercapacitors, and electrocatalysts. A wide spectrum of examples is presented for inorganic nanosheet-based electrodes and electrocatalysts. Future perspectives in research about 2D nanosheet-based functional materials are discussed to provide insight for the development of next-generation energy storage systems using 2D nanostructured materials. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Missert, Nancy; Kotula, Paul G.; Rye, Michael

We used a focused ion beam to obtain cross-sectional specimens from both magnetic multilayer and Nb/Al-AlOx/Nb Josephson junction devices for characterization by scanning transmission electron microscopy (STEM) and energy dispersive X-ray spectroscopy (EDX). An automated multivariate statistical analysis of the EDX spectral images produced chemically unique component images of individual layers within the multilayer structures. STEM imaging elucidated distinct variations in film morphology, interface quality, and/or etch artifacts that could be correlated to magnetic and/or electrical properties measured on the same devices.

Unique magnetic and thermoelectric properties of chemically functionalized narrow carbon polymers.

PubMed

Zberecki, K; Wierzbicki, M; Swirkowicz, R; Barnaś, J

2017-02-01

We analyze magnetic, transport and thermoelectric properties of narrow carbon polymers, which are chemically functionalized with nitroxide groups. Numerical calculations of the electronic band structure and the corresponding transmission function are based on density functional theory. Transport and thermoelectric parameters are calculated in the linear response regime, with particular interest in charge and spin thermopowers (charge and spin Seebeck effects). Such nanoribbons are shown to have thermoelectric properties described by large thermoelectric efficiency, which makes these materials promising from the application point of view.

Synthesis of polyoxometalate-loaded epoxy composites

DOEpatents

Anderson, Benjamin J

2014-10-07

The synthesis of a polyoxometalate-loaded epoxy uses a one-step cure by applying an external stimulus to release the acid from the polyoxometalate and thereby catalyze the cure reaction of the epoxy resin. Such polyoxometalate-loaded epoxy composites afford the cured epoxy unique properties imparted by the intrinsic properties of the polyoxometalate. For example, polyoxometalate-loaded epoxy composites can be used as corrosion resistant epoxy coatings, for encapsulation of electronics with improved dielectric properties, and for structural applications with improved mechanical properties.

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

Bartels, Ludwig; Ernst, Karl-Heinz; Gao, Hong-Jun

Supramolecular self-assembly at surfaces is one of the most exciting and active fields in Surface Science today. Applications can take advantage of two key properties: (i) versatile pattern formation over a broad length scale and (ii) tunability of electronic structure and transport properties, as well as frontier orbital alignment. It provides a new frontier for Chemical Physics as it uniquely combines the versatility of Organic Synthesis and the Physics of Interfaces. The Journal of Chemical Physics is pleased to publish this Special Topic Issue, showcasing recent advances and new directions.

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

Verzhbitskiy, Ivan A.; Corato, Marzio De; Ruini, Alice

Bottom-up approaches allow the production of ultranarrow and atomically precise graphene nanoribbons (GNRs) with electronic and optical properties controlled by the specific atomic structure. Combining Raman spectroscopy and ab initio simulations, we show that GNR width, edge geometry, and functional groups all influence their Raman spectra. As a result, the low-energy spectral region below 1000 cm –1 is particularly sensitive to edge morphology and functionalization, while the D peak dispersion can be used to uniquely fingerprint the presence of GNRs and differentiates them from other sp 2 carbon nanostructures.

Layered Chalcogenides beyond Graphene: from Electronic Structure Evolution to the Spin Transport

NASA Astrophysics Data System (ADS)

Yuan, Hongtao

2014-03-01

Recent efforts on graphene-like atomic layer materials, aiming at novel electronic properties and quantum phenomena beyond graphene, have attracted much attention for potential electronics/spintronics applications. Compared to the weak spin-orbit-interaction (SOI) in graphene, metal chalcogenides MX2 have heavy 4d/5d elements with strong atomic SOI, providing a unique way for generating spin polarization based on valleytronics physics. Indeed, such a spin-polarized band structure has been demonstrated theoretically and supported by optical investigations. However, despite these exciting progresses, following two important issues in MX2 community remain elusive: 1. the quantitative band structure of MX2 compounds (where are the valleys -band maxima/minima- locating in the BZ) have not been experimentally confirmed. Especially for those cleaved ultrathin mono- and bi-layer flakes hosting most of recently-reported exotic phenomena at the 2D limit, the direct detection for band dispersion becomes of great importance for valleytronics. 2. Spin transports have seldom been reported even though such a strong SOI system can serve as an ideal platform for the spin polarization and spin transport. In this work, we started from the basic electronic structures of representative MX2, obtained by ARPES, and investigated both the band variation between these compounds and their band evolution from bulk to the monolayer limit. After having a systematic understanding on band structures, we reported a giant Zeeman-type spin-polarization generated and modulated by an external electric field in WSe2 electric-double-layer transistors. The non-magnetic approach for realizing such an intriguing spin splitting not only keeps the system time-reversally invariant but also suggests a new paradigm for manipulating the spin-degrees of freedom of electrons. Acknowledge the support from DoE, BES, Division of MSE under contract DE-AC02-76SF00515.

Structural Analysis of MoS2 and other 2D layered materials using LEEM/LEED-I(V) and STM

NASA Astrophysics Data System (ADS)

Grady, Maxwell; Dai, Zhongwei; Jin, Wencan; Dadap, Jerry; Osgood, Richard; Sadowski, Jerzy; Pohl, Karsten

Layered two-dimensional materials, such as molybdenum disulfide, MoS2, are of interest for the development of many types of novel electronic devices. To fully understand the interfaces between these new materials, the atomic reconstructions at their surfaces must be understood. Low Energy Electron Microscopy and Diffraction, LEEM/ μLEED, present a unique method for rapid material characterization in real space and reciprocal space with high resolution. Here we present a study of the surface structure of 2H-MoS2 using μLEED intensity-voltage analysis. To aid this analysis, software is under development to automate the procedure of extracting I(V) curves from LEEM and LEED data. When matched with computational modeling, this data provides information with angstrom level resolution concerning the three dimensional atomic positions. We demonstrate that the surface structure of bulk MoS2 is distinct from the bulk crystal structure and exhibits a smaller surface relaxation at 320K compared to previous results at 95K. Furthermore, suspended monolayer samples exhibit large interlayer relaxations compared to the bulk surface termination. Further techniques for refining layer thickness determination are under development.

Origin of spin gapless semiconductor behavior in CoFeCrGa: Theory and Experiment

DOE PAGES

Bainsla, Lakhan; Mallick, A. I.; Raja, M. Manivel; ...

2015-07-08

Despite a plethora of materials suggested for spintronic applications, a new class of materials has emerged, namely spin gapless semiconductors (SGS), which offers potentially more advantageous properties than existing ones. These magnetic semiconductors exhibit a finite band gap for one spin channel and a closed gap for the other. Supported by electronic-structure calculations, we report evidence of SGS behavior in equiatomic quaternary CoFeCrGa, having a cubic Heusler (prototype LiMgPdSn) structure but exhibiting chemical disorder (DO 3 structure). CoFeCrGa is found to transform from SGS to half-metallic phase under pressure, which is attributed to unique electronic-structure features. The saturation magnetization (Mmore » S) was obtained at 8K agrees with the Slater-Pauling rule and the Curie temperature (T C) is found to exceed 400K. Carrier concentration (up to 250K) and electrical conductivity are observed to be nearly temperature independent, prerequisites for SGS. The anomalous Hall coefficient is estimated to be 185S/cm at 5K. Considering the SGS properties and high T C, this material appears to be promising for spintronic applications.« less

CIT-7, a crystalline, molecular sieve with pores bounded by 8 and 10-membered rings† †Electronic supplementary information (ESI) available: Details of the synthesis and characterization of all materials as well as details on the synchrotron and RED data collection and structure determination, including the cif file. See DOI: 10.1039/c4sc03935a Click here for additional data file.

PubMed Central

Schmidt, Joel E.; Xie, Dan; Rea, Thomas

2015-01-01

A new crystalline molecular sieve, denoted CIT-7, is synthesized using an imidazolium-based diquaternary organic structure directing agent (OSDA). The framework structure is determined from a combination of rotation electron diffraction and synchrotron X-ray powder diffraction data. The structure has 10 crystallographically unique tetrahedral atoms (T-atoms) in the unit cell, and can be described as an ordered arrangement of the [425462] mtw building unit and a previously unreported [4452] building unit. The framework contains a 2-dimensional pore system that is bounded by 10 T-atom rings (10-ring, 5.1 Å × 6.2 Å opening) that are connected with oval 8-rings (2.9 Å × 5.5 Å opening) through medium-sized cavities (∼7.9 Å) at the channel intersections. CIT-7 can be synthesized over a broad range of compositions including pure-silica and heteroatom, e.g., aluminosilicate and titanosilicate, containing variants. PMID:29163872

X-ray Diffraction from Membrane Protein Nanocrystals

PubMed Central

Hunter, M.S.; DePonte, D.P.; Shapiro, D.A.; Kirian, R.A.; Wang, X.; Starodub, D.; Marchesini, S.; Weierstall, U.; Doak, R.B.; Spence, J.C.H.; Fromme, P.

2011-01-01

Membrane proteins constitute >30% of the proteins in an average cell, and yet the number of currently known structures of unique membrane proteins is <300. To develop new concepts for membrane protein structure determination, we have explored the serial nanocrystallography method, in which fully hydrated protein nanocrystals are delivered to an x-ray beam within a liquid jet at room temperature. As a model system, we have collected x-ray powder diffraction data from the integral membrane protein Photosystem I, which consists of 36 subunits and 381 cofactors. Data were collected from crystals ranging in size from 100 nm to 2 μm. The results demonstrate that there are membrane protein crystals that contain <100 unit cells (200 total molecules) and that 3D crystals of membrane proteins, which contain <200 molecules, may be suitable for structural investigation. Serial nanocrystallography overcomes the problem of x-ray damage, which is currently one of the major limitations for x-ray structure determination of small crystals. By combining serial nanocrystallography with x-ray free-electron laser sources in the future, it may be possible to produce molecular-resolution electron-density maps using membrane protein crystals that contain only a few hundred or thousand unit cells. PMID:21190672

PbSe-Based Colloidal Core/Shell Heterostructures for Optoelectronic Applications

PubMed Central

Zaiats, Gary; Yanover, Diana; Vaxenburg, Roman; Tilchin, Jenya; Sashchiuk, Aldona; Lifshitz, Efrat

2014-01-01

Lead-based (IV–VI) colloidal quantum dots (QDs) are of widespread scientific and technological interest owing to their size-tunable band-gap energy in the near-infrared optical region. This article reviews the synthesis of PbSe-based heterostructures and their structural and optical investigations at various temperatures. The review focuses on the structures consisting of a PbSe core coated with a PbSexS1–x (0 ≤ x ≤ 1) or CdSe shell. The former-type shells were epitaxially grown on the PbSe core, while the latter-type shells were synthesized using partial cation-exchange. The influence of the QD composition and the ambient conditions, i.e., exposure to oxygen, on the QD optical properties, such as radiative lifetime, Stokes shift, and other temperature-dependent characteristics, was investigated. The study revealed unique properties of core/shell heterostructures of various compositions, which offer the opportunity of fine-tuning the QD electronic structure by changing their architecture. A theoretical model of the QD electronic band structure was developed and correlated with the results of the optical studies. The review also outlines the challenges related to potential applications of colloidal PbSe-based heterostructures. PMID:28788244

Transition metal oxides for organic electronics: energetics, device physics and applications.

PubMed

Meyer, Jens; Hamwi, Sami; Kröger, Michael; Kowalsky, Wolfgang; Riedl, Thomas; Kahn, Antoine

2012-10-23

During the last few years, transition metal oxides (TMO) such as molybdenum tri-oxide (MoO(3) ), vanadium pent-oxide (V(2) O(5) ) or tungsten tri-oxide (WO(3) ) have been extensively studied because of their exceptional electronic properties for charge injection and extraction in organic electronic devices. These unique properties have led to the performance enhancement of several types of devices and to a variety of novel applications. TMOs have been used to realize efficient and long-term stable p-type doping of wide band gap organic materials, charge-generation junctions for stacked organic light emitting diodes (OLED), sputtering buffer layers for semi-transparent devices, and organic photovoltaic (OPV) cells with improved charge extraction, enhanced power conversion efficiency and substantially improved long term stability. Energetics in general play a key role in advancing device structure and performance in organic electronics; however, the literature provides a very inconsistent picture of the electronic structure of TMOs and the resulting interpretation of their role as functional constituents in organic electronics. With this review we intend to clarify some of the existing misconceptions. An overview of TMO-based device architectures ranging from transparent OLEDs to tandem OPV cells is also given. Various TMO film deposition methods are reviewed, addressing vacuum evaporation and recent approaches for solution-based processing. The specific properties of the resulting materials and their role as functional layers in organic devices are discussed. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A three-dimensional metal grid mesh as a practical alternative to ITO

NASA Astrophysics Data System (ADS)

Jang, Sungwoo; Jung, Woo-Bin; Kim, Choelgyu; Won, Phillip; Lee, Sang-Gil; Cho, Kyeong Min; Jin, Ming Liang; An, Cheng Jin; Jeon, Hwan-Jin; Ko, Seung Hwan; Kim, Taek-Soo; Jung, Hee-Tae

2016-07-01

The development of a practical alternative to indium tin oxide (ITO) is one of the most important issues in flexible optoelectronics. In spite of recent progress in this field, existing approaches to prepare transparent electrodes do not satisfy all of their essential requirements. Here, we present a new substrate-embedded tall (~350 nm) and thin (~30 nm) three-dimensional (3D) metal grid mesh structure with a large area, which is prepared via secondary sputtering. This structure satisfies most of the essential requirements of transparent electrodes for practical applications in future opto-electronics: excellent optoelectronic performance (a sheet resistance of 9.8 Ω □-1 with a transmittance of 85.2%), high stretchability (no significant change in resistance for applied strains <15%), a sub-micrometer mesh period, a flat surface (a root mean square roughness of approximately 5 nm), no haze (approximately 0.5%), and strong adhesion to polymer substrates (it survives attempted detachment with 3M Scotch tape). Such outstanding properties are attributed to the unique substrate-embedded 3D structure of the electrode, which can be obtained with a high aspect ratio and in high resolution over large areas with a simple process. As a demonstration of its suitability for practical applications, our transparent electrode was successfully tested in a flexible touch screen panel. We believe that our approach opens up new practical applications in wearable electronics.The development of a practical alternative to indium tin oxide (ITO) is one of the most important issues in flexible optoelectronics. In spite of recent progress in this field, existing approaches to prepare transparent electrodes do not satisfy all of their essential requirements. Here, we present a new substrate-embedded tall (~350 nm) and thin (~30 nm) three-dimensional (3D) metal grid mesh structure with a large area, which is prepared via secondary sputtering. This structure satisfies most of the essential requirements of transparent electrodes for practical applications in future opto-electronics: excellent optoelectronic performance (a sheet resistance of 9.8 Ω □-1 with a transmittance of 85.2%), high stretchability (no significant change in resistance for applied strains <15%), a sub-micrometer mesh period, a flat surface (a root mean square roughness of approximately 5 nm), no haze (approximately 0.5%), and strong adhesion to polymer substrates (it survives attempted detachment with 3M Scotch tape). Such outstanding properties are attributed to the unique substrate-embedded 3D structure of the electrode, which can be obtained with a high aspect ratio and in high resolution over large areas with a simple process. As a demonstration of its suitability for practical applications, our transparent electrode was successfully tested in a flexible touch screen panel. We believe that our approach opens up new practical applications in wearable electronics. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr03060b

Electronic, Vibrational and Thermoelectric Properties of Two-Dimensional Materials

NASA Astrophysics Data System (ADS)

Wickramaratne, Darshana

The discovery of graphene's unique electronic and thermal properties has motivated the search for new two-dimensional materials. Examples of these materials include the layered two-dimensional transition metal dichalcogenides (TMDC) and metal mono-chalcogenides. The properties of the TMDCs (eg. MoS 2, WS2, TaS2, TaSe2) and the metal mono-chalcogenides (eg. GaSe, InSe, SnS) are diverse - ranging from semiconducting, semi-metallic and metallic. Many of these materials exhibit strongly correlated phenomena and exotic collective states such as exciton condensates, charge density waves, Lifshitz transitions and superconductivity. These properties change as the film thickness is reduced down to a few monolayers. We use first-principles simulations to discuss changes in the electronic and the vibrational properties of these materials as the film thickness evolves from a single atomic monolayer to the bulk limit. In the semiconducting TMDCs (MoS2, MoSe2, WS2 and WSe2) and monochalcogenides (GaS, GaSe, InS and InSe) we show confining these materials to their monolayer limit introduces large band degeneracies or non-parabolic features in the electronic structure. These changes in the electronic structure results in increases in the density of states and the number of conducting modes. Our first-principles simulations combined with a Landauer approach show these changes can lead to large enhancements up to an order of magnitude in the thermoelectric performance of these materials when compared to their bulk structure. Few monolayers of the TMDCs can be misoriented with respect to each other due to the weak van-der-Waals (vdW) force at the interface of two monolayers. Misorientation of the bilayer semiconducting TMDCs increases the interlayer van-der-Waals gap distance, reduces the interlayer coupling and leads to an increase in the magnitude of the indirect bandgap by up to 100 meV compared to the registered bilayer. In the semi-metallic and metallic TMDC compounds (TiSe2, TaS 2, TaSe2) a phase transition to a charge density wave (CDW) ground state occurs at a temperature that is unique to each material. Confining these materials to a single monolayer or few-monolayers can increase or decrease their CDW transition temperature and change the magnitude of the CDW energy gap. We show the low energy Raman modes observed in 1T-TaSe2 and 1T-TaS2 in their CDW ground state can emerge from zone folded phonons due to the reconstruction of the lattice in the bulk and monolayer structures. In 1T-TiSe2 the driving mechanism of the CDW is excitonic condensation. We show the excitonic gap of the monolayer and bilayer structures can increase by up to a factor of 3 compared to the excitonic gap of the bulk structure.

Geometric, electronic, and bonding properties of AuNM (N = 1-7, M = Ni, Pd, Pt) clusters.

PubMed

Yuan, D W; Wang, Yang; Zeng, Zhi

2005-03-15

Employing first-principles methods, based on density functional theory, we report the ground state geometric and electronic structures of gold clusters doped with platinum group atoms, Au(N)M (N = 1-7, M = Ni, Pd, Pt). The stability and electronic properties of Ni-doped gold clusters are similar to that of pure gold clusters with an enhancement of bond strength. Due to the strong d-d or s-d interplay between impurities and gold atoms originating in the relativistic effects and unique properties of dopant delocalized s-electrons in Pd- and Pt-doped gold clusters, the dopant atoms markedly change the geometric and electronic properties of gold clusters, and stronger bond energies are found in Pt-doped clusters. The Mulliken populations analysis of impurities and detailed decompositions of bond energies as well as a variety of density of states of the most stable dopant gold clusters are given to understand the different effects of individual dopant atom on bonding and electronic properties of dopant gold clusters. From the electronic properties of dopant gold clusters, the different chemical reactivity toward O(2), CO, or NO molecule is predicted in transition metal-doped gold clusters compared to pure gold clusters.

Typomorphic Characteristics of Molybdenite from the Bystrinsky Cu-Au Porphyry-Skarn Deposit, Eastern Transbaikal Region, Russia

NASA Astrophysics Data System (ADS)

Kovalenker, V. A.; Trubkin, N. V.; Abramova, V. D.; Plotinskaya, O. Yu.; Kiseleva, G. D.; Borisovskii, S. E.; Yazykova, Yu. I.

2018-01-01

The paper presents pioneering data on the composition, texture, and crystal structure of molybdenite from various types of molybdenum mineralization at the Bystrinsky Cu-Au-Fe porphyry-skarn deposit in the eastern Transbaikal region, Russia. The data were obtained using electron microprobe analysis (EMPA), laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS), and high-resolution transmission electron microscopy (HRTEM). Molybdenite found at the deposit in skarn, sulfide-poor quartz veins, and quartz-feldspar alteration markedly differs in the concentrations of trace elements determined by their species in the mineral, as well as in its structural features. Molybdenite-2H from skarn associated with phyllosilicates occurs as ultrafine crystals with uniform shape and texture; no dislocations or inclusions were found but amorphous silica was. The molybdenite composition is highly contrasting in the content and distribution of both structure-related (Re, W, and Se) and other (Mn, Co, Ni, Cu, Zn, As, Ag, Cd, Sb, Te, Ag, Pd, Au, Hg, Pb, and Bi) metals. In the sulfide-poor quartz veins, highly structurally heterogeneous (2H + 3R) molybdenite microcrystals with abundant defects (dislocations and volumetrically distributed inclusions) are associated with illite, goethite, and barite. Some single crystals are unique three-phase (2H + 3R polytypes + amorphous MoS2). The mineral has a low concentration of all trace elements, which are uniformly distributed. However, individual domains with uniquely high Pd, Te, Ni, Hg, and W concentrations caused by mineral inclusions are found in some grains. Molybdenite from quartz-feldspar alteration is characterized by low concentrations of all trace elements except for Re and Se, which enrich some domains of the grains. Our data indicate that the compositional and structural heterogeneity of molybdenite from the Bystrinsky deposit are its crucial features, which obviously correlate with the types of Mo mineralization.

Topological Electride Y2C.

PubMed

Huang, Huaqing; Jin, Kyung-Hwan; Zhang, Shunhong; Liu, Feng

2018-03-14

Two-dimensional (2D) electrides are layered ionic crystals in which anionic electrons are confined in the interlayer space. Here, we report a discovery of nontrivial [Formula: see text] topology in the electronic structures of 2D electride Y 2 C. Based on first-principles calculations, we found a topological [Formula: see text] invariant of (1; 111) for the bulk band and topologically protected surface states in the surfaces of Y 2 C, signifying its nontrivial electronic topology. We suggest a spin-resolved angle-resolved photoemission spectroscopy (ARPES) measurement to detect the unique helical spin texture of the spin-polarized topological surface state, which will provide characteristic evidence for the nontrivial electronic topology of Y 2 C. Furthermore, the coexistence of 2D surface electride states and topological surface state enables us to explain the outstanding discrepancy between the recent ARPES experiments and theoretical calculations. Our findings establish a preliminary link between the electride in chemistry and the band topology in condensed-matter physics, which are expected to inspire further interdisciplinary research between these fields.

Electron capture activation of the disulfide bond. The role of the asymmetry and electronegativity.

PubMed

Gámez, José A; Serrano-Andrés, Luis; Yáñez, Manuel

2010-02-07

The effects of electron capture on the structure of XSSX' disulfide derivatives in which the substituents attached to the sulfur atoms have different electronegativites have been investigated at different levels of theory, namely DFT, MP2, QCISD and CASSCF/CASPT2. Although it has been generally assumed that electron attachment to disulfide derivatives leads to a systematic and significant activation of the S-S bond, our results show that this is the case only when the substituents X or X' have low electronegativity. Otherwise, the S-S bond in the anion remains practically unperturbed and only the S-X bond is largely activated or even broken, because the extra electron occupies the sigma*(S-X) rather than the sigma*(S-S) antibonding orbital. Our results also show that S-S activation yields a system with a unique anion, whereas when the S-X activation is significant, two stable anionic species, stretched and bent, are formed.

Comparative morphology of zebra (Dreissena polymorpha) and quagga (Dreissena bugensis) mussel sperm: Light and electron microscopy

USGS Publications Warehouse

Walker, G.K.; Black, M.G.; Edwards, C.A.

1996-01-01

Adult zebra (Dreissena polymorpha) and quagga (Dreissena bugensis) mussels were induced to release large quantities of live spermatozoa by the administration of 5-hydroxytryptamine (serotonin). Sperm were photographed alive using phase-contrast microscopy and were fixed subsequently with glutaraldehyde followed by osmium tetroxide for eventual examination by transmission or scanning electron microscopy. The sperm of both genera are of the ect-aquasperm type. Their overall dimensions and shape allow for easy discrimination at the light and scanning electron microscopy level. Transmission electron microscopy of the cells reveals a barrel-shaped nucleus in zebra mussel sperm and an elongated nucleus in quagga mussel sperm. In both species, an acrosome is cradled in a nuclear fossa. The ultrastructure of the acrosome and axial body, however, is distinctive for each species. The structures of the midpiece are shown, including a unique mitochondrial "skirt" that includes densely packed parallel cristae and extends in a narrow sheet from the mitochondria.