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1.
Phys Rev Lett ; 130(21): 216703, 2023 May 26.
Artigo em Inglês | MEDLINE | ID: mdl-37295087

RESUMO

The precession of magnon pseudospin about the equilibrium pseudofield, the latter capturing the nature of magnonic eigenexcitations in an antiferromagnet, gives rise to the magnon Hanle effect. Its realization via electrically injected and detected spin transport in an antiferromagnetic insulator demonstrates its high potential for devices and as a convenient probe for magnon eigenmodes and the underlying spin interactions in the antiferromagnet. Here, we observe a nonreciprocity in the Hanle signal measured in hematite using two spatially separated platinum electrodes as spin injector or detector. Interchanging their roles was found to alter the detected magnon spin signal. The recorded difference depends on the applied magnetic field and reverses sign when the signal passes its nominal maximum at the so-called compensation field. We explain these observations in terms of a spin transport direction-dependent pseudofield. The latter leads to a nonreciprocity, which is found to be controllable via the applied magnetic field. The observed nonreciprocal response in the readily available hematite films opens interesting opportunities for realizing exotic physics predicted so far only for antiferromagnets with special crystal structures.


Assuntos
Eletricidade , Campos Magnéticos , Física
2.
Nature ; 528(7582): 387-91, 2015 Dec 17.
Artigo em Inglês | MEDLINE | ID: mdl-26641312

RESUMO

Radiative transfer of energy at the nanometre length scale is of great importance to a variety of technologies including heat-assisted magnetic recording, near-field thermophotovoltaics and lithography. Although experimental advances have enabled elucidation of near-field radiative heat transfer in gaps as small as 20-30 nanometres (refs 4-6), quantitative analysis in the extreme near field (less than 10 nanometres) has been greatly limited by experimental challenges. Moreover, the results of pioneering measurements differed from theoretical predictions by orders of magnitude. Here we use custom-fabricated scanning probes with embedded thermocouples, in conjunction with new microdevices capable of periodic temperature modulation, to measure radiative heat transfer down to gaps as small as two nanometres. For our experiments we deposited suitably chosen metal or dielectric layers on the scanning probes and microdevices, enabling direct study of extreme near-field radiation between silica-silica, silicon nitride-silicon nitride and gold-gold surfaces to reveal marked, gap-size-dependent enhancements of radiative heat transfer. Furthermore, our state-of-the-art calculations of radiative heat transfer, performed within the theoretical framework of fluctuational electrodynamics, are in excellent agreement with our experimental results, providing unambiguous evidence that confirms the validity of this theory for modelling radiative heat transfer in gaps as small as a few nanometres. This work lays the foundations required for the rational design of novel technologies that leverage nanoscale radiative heat transfer.

3.
Proc Natl Acad Sci U S A ; 115(20): E4577-E4583, 2018 05 15.
Artigo em Inglês | MEDLINE | ID: mdl-29712853

RESUMO

Metalloproteins, proteins containing a transition metal ion cofactor, are electron transfer agents that perform key functions in cells. Inspired by this fact, electron transport across these proteins has been widely studied in solid-state settings, triggering the interest in examining potential use of proteins as building blocks in bioelectronic devices. Here, we report results of low-temperature (10 K) electron transport measurements via monolayer junctions based on the blue copper protein azurin (Az), which strongly suggest quantum tunneling of electrons as the dominant charge transport mechanism. Specifically, we show that, weakening the protein-electrode coupling by introducing a spacer, one can switch the electron transport from off-resonant to resonant tunneling. This is a consequence of reducing the electrode's perturbation of the Cu(II)-localized electronic state, a pattern that has not been observed before in protein-based junctions. Moreover, we identify vibronic features of the Cu(II) coordination sphere in transport characteristics that show directly the active role of the metal ion in resonance tunneling. Our results illustrate how quantum mechanical effects may dominate electron transport via protein-based junctions.


Assuntos
Cobre/química , Elétrons , Metaloproteínas/química , Modelos Teóricos , Transporte de Elétrons , Humanos , Temperatura
4.
Phys Rev Lett ; 124(15): 156803, 2020 Apr 17.
Artigo em Inglês | MEDLINE | ID: mdl-32357030

RESUMO

Quantum fluctuations are imprinted with valuable information about transport processes. Experimental access to this information is possible, but challenging. We introduce the dynamical Coulomb blockade (DCB) as a local probe for fluctuations in a scanning tunneling microscope (STM) and show that it provides information about the conduction channels. In agreement with theoretical predictions, we find that the DCB disappears in a single-channel junction with increasing transmission following the Fano factor, analogous to what happens with shot noise. Furthermore we demonstrate local differences in the DCB expected from changes in the conduction channel configuration. Our experimental results are complemented by ab initio transport calculations that elucidate the microscopic nature of the conduction channels in our atomic-scale contacts. We conclude that probing the DCB by STM provides a technique complementary to shot noise measurements for locally resolving quantum transport characteristics.

5.
Nature ; 498(7453): 209-12, 2013 Jun 13.
Artigo em Inglês | MEDLINE | ID: mdl-23765496

RESUMO

Atomic and single-molecule junctions represent the ultimate limit to the miniaturization of electrical circuits. They are also ideal platforms for testing quantum transport theories that are required to describe charge and energy transfer in novel functional nanometre-scale devices. Recent work has successfully probed electric and thermoelectric phenomena in atomic-scale junctions. However, heat dissipation and transport in atomic-scale devices remain poorly characterized owing to experimental challenges. Here we use custom-fabricated scanning probes with integrated nanoscale thermocouples to investigate heat dissipation in the electrodes of single-molecule ('molecular') junctions. We find that if the junctions have transmission characteristics that are strongly energy dependent, this heat dissipation is asymmetric--that is, unequal between the electrodes--and also dependent on both the bias polarity and the identity of the majority charge carriers (electrons versus holes). In contrast, junctions consisting of only a few gold atoms ('atomic junctions') whose transmission characteristics show weak energy dependence do not exhibit appreciable asymmetry. Our results unambiguously relate the electronic transmission characteristics of atomic-scale junctions to their heat dissipation properties, establishing a framework for understanding heat dissipation in a range of mesoscopic systems where transport is elastic--that is, without exchange of energy in the contact region. We anticipate that the techniques established here will enable the study of Peltier effects at the atomic scale, a field that has been barely explored experimentally despite interesting theoretical predictions. Furthermore, the experimental advances described here are also expected to enable the study of heat transport in atomic and molecular junctions--an important and challenging scientific and technological goal that has remained elusive.

6.
J Chem Phys ; 150(17): 174705, 2019 May 07.
Artigo em Inglês | MEDLINE | ID: mdl-31067872

RESUMO

Motivated by a recent experiment [C. Guo et al., Proc. Natl. Acad. Sci. U. S. A. 113, 10785 (2016)], we carry out a theoretical study of electron transport through peptide-based single-molecule junctions. We analyze the pristine hepta-alanine and its functionalizations with a single tryptophan unit, which is placed in three different locations along the backbone. Contrary to expectations from the experiment on self-assembled monolayers, we find that insertion of tryptophan does not raise the electrical conductance and that the resulting peptides instead remain insulating in the framework of a coherent transport picture. The poor performance of these molecules as conductors can be ascribed to the strongly off-resonant transport and low electrode-molecule coupling of the frontier orbitals. Although the introduction of tryptophan increases the energy of the highest occupied molecular orbital (HOMO) of the peptides in the gas phase, the new HOMO states are localized on the tryptophan unit and therefore essentially do not contribute to coherent charge transport.


Assuntos
Oligopeptídeos/química , Triptofano/química , Teoria da Densidade Funcional , Condutividade Elétrica , Modelos Químicos , Estrutura Molecular
7.
Angew Chem Int Ed Engl ; 58(34): 11852-11859, 2019 08 19.
Artigo em Inglês | MEDLINE | ID: mdl-31246354

RESUMO

A sample-type protein monolayer, that can be a stepping stone to practical devices, can behave as an electrically driven switch. This feat is achieved using a redox protein, cytochrome C (CytC), with its heme shielded from direct contact with the solid-state electrodes. Ab initio DFT calculations, carried out on the CytC-Au structure, show that the coupling of the heme, the origin of the protein frontier orbitals, to the electrodes is sufficiently weak to prevent Fermi level pinning. Thus, external bias can bring these orbitals in and out of resonance with the electrode. Using a cytochrome C mutant for direct S-Au bonding, approximately 80 % of the Au-CytC-Au junctions show at greater than 0.5 V bias a clear conductance peak, consistent with resonant tunneling. The on-off change persists up to room temperature, demonstrating reversible, bias-controlled switching of a protein ensemble, which, with its built-in redundancy, provides a realistic path to protein-based bioelectronics.


Assuntos
Citocromos c/química , Citocromos c/metabolismo , Condutividade Elétrica , Eletrodos , Heme/química , Ferro/química , Eletroquímica , Transporte de Elétrons , Humanos , Oxirredução , Conformação Proteica
8.
Phys Chem Chem Phys ; 20(48): 30392-30402, 2018 Dec 12.
Artigo em Inglês | MEDLINE | ID: mdl-30489582

RESUMO

We present a theoretical study of the blue-copper azurin extracted from Pseudomonas aeruginosa and several of its single amino acid mutants. For the first time, we consider the whole structure of this kind of protein rather than limiting our analysis to the copper complex only. This is accomplished by combining fully ab initio calculations based on density functional theory with atomic-scale molecular dynamics simulations. Beyond the main features arising from the copper complex, our study reveals the role played by the peripheral parts of the proteins. In particular, we find that oxygen atoms belonging to carboxyl groups which are distributed all over the protein contribute to electronic states near the HOMO. The contribution of the outer regions to the electronic structure of azurins had so far been overlooked. Our results highlight the need to investigate them thoroughly; this is especially important in prospect of understanding complex processes such as the electronic transport through metal-metalloprotein-metal junctions.

9.
J Am Chem Soc ; 139(43): 15337-15346, 2017 11 01.
Artigo em Inglês | MEDLINE | ID: mdl-28981262

RESUMO

Bioelectronics moves toward designing nanoscale electronic platforms that allow in vivo determinations. Such devices require interfacing complex biomolecular moieties as the sensing units to an electronic platform for signal transduction. Inevitably, a systematic design goes through a bottom-up understanding of the structurally related electrical signatures of the biomolecular circuit, which will ultimately lead us to tailor its electrical properties. Toward this aim, we show here the first example of bioengineered charge transport in a single-protein electrical contact. The results reveal that a single point-site mutation at the docking hydrophobic patch of a Cu-azurin causes minor structural distortion of the protein blue Cu site and a dramatic change in the charge transport regime of the single-protein contact, which goes from the classical Cu-mediated two-step transport in this system to a direct coherent tunneling. Our extensive spectroscopic studies and molecular-dynamics simulations show that the proteins' folding structures are preserved in the single-protein junction. The DFT-computed frontier orbital of the relevant protein segments suggests that the Cu center participation in each protein variant accounts for the different observed charge transport behavior. This work is a direct evidence of charge transport control in a protein backbone through external mutagenesis and a unique nanoscale platform to study structurally related biological electron transfer.


Assuntos
Azurina/química , Engenharia de Proteínas , Azurina/síntese química , Azurina/genética , Cobre/química , Transporte de Elétrons , Eletrônica , Simulação de Dinâmica Molecular , Mutagênese , Mutação Puntual , Dobramento de Proteína , Teoria Quântica , Análise Espectral
10.
Nano Lett ; 15(2): 1006-11, 2015 Feb 11.
Artigo em Inglês | MEDLINE | ID: mdl-25607343

RESUMO

We report conductance and thermopower measurements of metallic atomic-size contacts, namely gold and platinum, using a scanning tunneling microscope (STM) at room temperature. We find that few-atom gold contacts have an average negative thermopower, whereas platinum contacts present a positive thermopower, showing that for both metals, the sign of the thermopower in the nanoscale differs from that of bulk wires. We also find that the magnitude of the thermopower exhibits minima at the maxima of the conductance histogram in the case of gold nanocontacts while for platinum it presents large fluctuations. Tight-binding calculations and Green's function techniques, together with molecular dynamics simulations, show that these observations can be understood in the context of the Landauer-Büttiker picture of coherent transport in atomic-scale wires. In particular, we show that the differences in the thermopower between these two metals are due to the fact that the elastic transport is dominated by the 6s orbitals in the case of gold and by the 5d orbitals in the case of platinum.


Assuntos
Ouro/química , Platina/química , Teoria Quântica , Temperatura , Microscopia de Tunelamento , Simulação de Dinâmica Molecular
11.
Nanotechnology ; 26(29): 291001, 2015 Jul 24.
Artigo em Inglês | MEDLINE | ID: mdl-26133791

RESUMO

We demonstrate large rectification ratios (> 100) in single-molecule junctions based on a metal-oxide cluster (polyoxometalate), using a scanning tunneling microscope (STM) both at ambient conditions and at low temperature. These rectification ratios are the largest ever observed in a single-molecule junction, and in addition these junctions sustain current densities larger than 10(5) A cm(-2). By following the variation of the I-V characteristics with tip-molecule separation we demonstrate unambiguously that rectification is due to asymmetric coupling to the electrodes of a molecule with an asymmetric level structure. This mechanism can be implemented in other type of molecular junctions using both organic and inorganic molecules and provides a simple strategy for the rational design of molecular diodes.

12.
Beilstein J Org Chem ; 11: 1068-78, 2015.
Artigo em Inglês | MEDLINE | ID: mdl-26199662

RESUMO

We describe the synthesis and single-molecule electrical transport properties of a molecular wire containing a π-extended tetrathiafulvalene (exTTF) group and its charge-transfer complex with F4TCNQ. We form single-molecule junctions using the in situ break junction technique using a homebuilt scanning tunneling microscope with a range of conductance between 10 G0 down to 10(-7) G0. Within this range we do not observe a clear conductance signature of the neutral parent molecule, suggesting either that its conductance is too low or that it does not form a stable junction. Conversely, we do find a clear conductance signature in the experiments carried out on the charge-transfer complex. Due to the fact we expected this species to have a higher conductance than the neutral molecule, we believe this supports the idea that the conductance of the neutral molecule is very low, below our measurement sensitivity. This idea is further supported by theoretical calculations. To the best of our knowledge, these are the first reported single-molecule conductance measurements on a molecular charge-transfer species.

13.
ACS Nano ; 18(12): 9221-9231, 2024 Mar 26.
Artigo em Inglês | MEDLINE | ID: mdl-38488287

RESUMO

We investigate the direction-dependent switching current in a flux-tunable four-terminal Josephson junction defined in an InAs/Al two-dimensional heterostructure. The device exhibits the Josephson diode effect with switching currents that depend on the sign of the bias current. The superconducting diode efficiency, reaching a maximum of |η| ≈ 34%, is widely tunable─both in amplitude and sign─as a function of magnetic fluxes and gate voltages. Our observations are supported by a circuit model of three parallel Josephson junctions with nonsinusoidal current-phase relation. With respect to conventional Josephson interferometers, phase-tunable multiterminal Josephson junctions enable large diode efficiencies in structurally symmetric devices, where local magnetic fluxes generated on the chip break both time-reversal and spatial symmetries. Our work presents an approach for developing Josephson diodes with wide-range tunability that do not rely on exotic materials.

14.
J Am Chem Soc ; 135(6): 2052-5, 2013 Feb 13.
Artigo em Inglês | MEDLINE | ID: mdl-23330549

RESUMO

We present a theoretical study of electron transport through single-molecule junctions incorporating a Pt(6) metal cluster bound within an organic framework. The insertion of this molecule between a pair of electrodes leads to a fully atomically engineered nanometallic device with high conductance at the Fermi level and two sequential high on/off switching states. The origin of this property can be traced back to the existence of a degenerate HOMO consisting of two asymmetric orbitals with energies close to the Fermi level of the metal leads. The degeneracy is broken when the molecule is contacted to the leads, giving rise to two resonances that become pinned to the Fermi level and display destructive interference.

15.
J Adv Nurs ; 69(12): 2759-71, 2013 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-23517542

RESUMO

AIM: To report the adaptation into Spanish and psychometric testing of the Position on Nursing Diagnosis scale. BACKGROUND: The Position on Nursing Diagnosis is a scale that uses the semantic differential technique to measure nurses' attitudes towards the nursing diagnosis concept. DESIGN: Methodological design. METHOD: The scale was cross-culturally adapted through a process including translation, comparison with versions in other languages, back-translation, review, and pre-testing. An opportunistic sample of 621 Spanish registered nurses was recruited from August-December 2011. Reliability was evaluated through internal consistency and test-retest reliability. Construct validity, using both exploratory factor analysis and the known-group technique, and concurrent validity were assessed. FINDINGS: The Position on Nursing Diagnosis-Spanish Version was obtained from the cross-cultural adaptation process. High internal consistency and satisfactory test-retest reliability over a two week period (n = 240) were found. In the principal component analysis, all items loaded strongly on a single-factor which accounted for adequate variance, supporting the unidimensionality of the scale. A statistically significant difference was found comparing the scores of nurses who were members of the Spanish Association of Nomenclature, Taxonomy and Nursing Diagnosis and those who were not. Concurrent validity was supported by the significant correlation found between the scores and the degree of nursing diagnosis utilization and attendance to training sessions. CONCLUSION: The findings support the validity and reliability of the Position on Nursing Diagnosis-Spanish Version for its use among Spanish registered nurses as a measurement of their attitude towards the nursing diagnosis concept.


Assuntos
Comparação Transcultural , Diagnóstico de Enfermagem , Psicometria , Tradução , Adulto , Estudos Transversais , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Reprodutibilidade dos Testes , Espanha
16.
Rev Esc Enferm USP ; 47(3): 591-9, 2013 Jun.
Artigo em Português | MEDLINE | ID: mdl-24601134

RESUMO

The Positions on Nursing Diagnosis (PND) is a scale that uses the semantic differential technique to measure nurses' attitudes towards the nursing diagnosis concept. The aim of this study was to develop a shortened form of the Spanish version of this scale and evaluate its psychometric properties and efficiency. A double theoretical-empirical approach was used to obtain a short form of the PND, the PND-7-SV, which would be equivalent to the original. Using a cross-sectional survey design, the reliability (internal consistency and test-retest reliability), construct (exploratory factor analysis, known-groups technique and discriminant validity) and criterion-related validity (concurrent validity), sensitivity to change and efficiency of the PND-7-SV were assessed in a sample of 476 Spanish nursing students. The results endorsed the utility of the PND-7-SV to measure attitudes toward nursing diagnosis in an equivalent manner to the complete form of the scale and in a shorter time.


Assuntos
Atitude do Pessoal de Saúde , Diagnóstico de Enfermagem/estatística & dados numéricos , Enfermagem , Inquéritos e Questionários , Estudos Transversais , Feminino , Humanos , Masculino , Psicometria , Reprodutibilidade dos Testes , Espanha , Estudantes de Enfermagem , Adulto Jovem
17.
Rev Enferm ; 36(4): 8-12, 2013 Apr.
Artigo em Espanhol | MEDLINE | ID: mdl-23745485

RESUMO

BACKGROUND/AIMS: In recent decades the fight against breast cancer has focused primarily on the treatment and secondary prevention (early detection mainly). In the case of breast self-examination, althought it has not been prove to reduce mortality, it is important in cases detected by women themselves (it is estimated 90% of total), mainly in the interval cancers. OBJECTIVES: To identify within women with breast cancer, how many do self-examination and identify associated factors. Describe the clinical and pathological features of cancers in women who do perform self-examination. METHODOLOGY: In women diagnosed with breast cancer during 2007 in a hospital in the province of Cadiz, Spain, is reconstructed in retrospect the story related the cancer process: symptoms, psychosocial factors that determine the contact with the health system, preventive practices (self-examination, mammography screening). A description of the pathological tumor: presenting symptom, tumor size, node negative, grade of differentiation. RESULTS: We studied 149 women with breast cancer, from whom 52% did self-exploration. Women who performed self-examination were younger (54.78 years) against the women who did not (65.63 years), married (66.2%), active workers and have a higher educational level. The assessment of the first symptoms in these women as "important" is positively correlated with those women who practice self-examination. For other preventive practices, women who does self-examination are also the most actives in early detection programs (74.4% against 29.5% which didn't do self-examination). For the pathologic characteristics of tumor in women who did self-examination: the tumor size was 2.5 cm, 50.7/are well differentiated, and 59.1% of cases the nodes are negative. CONCLUSIONS: Women who does self-examination are younger, have higher educational level, are married, are active workers and are often involved in other preventive practices. On them, the tumors diagnosed have a smaller size, are diagnosed at earlier stages and usually present better degree of differentiation.


Assuntos
Neoplasias da Mama/diagnóstico , Neoplasias da Mama/prevenção & controle , Autoexame de Mama , Autoexame de Mama/estatística & dados numéricos , Feminino , Humanos , Pessoa de Meia-Idade
18.
J Phys Chem Lett ; 14(49): 11242-11249, 2023 Dec 14.
Artigo em Inglês | MEDLINE | ID: mdl-38059566

RESUMO

We conducted a theoretical study of electron transport through junctions of the blue-copper azurin from Pseudomonas aeruginosa. We found that single-site hopping can lead to either higher or lower current values compared to fully coherent transport. This depends on the structural details of the junctions as well as the alignment of the protein orbitals. Moreover, we show how the asymmetry of the IV curves can be affected by the position of the tip in the junction and that, under specific conditions, such a hopping mechanism is consistent with a fairly low temperature dependence of the current. Finally, we show that increasing the number of hopping sites leads to higher hopping currents. Our findings, from fully quantum calculations, provide deep insight to help guide the interpretation of experimental IV curves on highly complex systems.

19.
Nat Commun ; 14(1): 6794, 2023 Oct 25.
Artigo em Inglês | MEDLINE | ID: mdl-37880208

RESUMO

Magnetic impurities on superconductors lead to bound states within the superconducting gap, so called Yu-Shiba-Rusinov (YSR) states. They are parity protected, which enhances their lifetime, but makes it more difficult to excite them. Here, we realize the excitation of YSR states by microwaves facilitated by the tunnel coupling to another superconducting electrode in a scanning tunneling microscope (STM). We identify the excitation process through a family of anomalous microwave-assisted tunneling peaks originating from a second-order resonant Andreev process, in which the microwave excites the YSR state triggering a tunneling event transferring a total of two charges. We vary the amplitude and the frequency of the microwave to identify the energy threshold and the evolution of this excitation process. Our work sets an experimental basis and proof-of-principle for the manipulation of YSR states using microwaves with an outlook towards YSR qubits.

20.
Nat Commun ; 14(1): 6798, 2023 Oct 26.
Artigo em Inglês | MEDLINE | ID: mdl-37884490

RESUMO

Light-matter coupling allows control and engineering of complex quantum states. Here we investigate a hybrid superconducting-semiconducting Josephson junction subject to microwave irradiation by means of tunnelling spectroscopy of the Andreev bound state spectrum and measurements of the current-phase relation. For increasing microwave power, discrete levels in the tunnelling conductance develop into a series of equally spaced replicas, while the current-phase relation changes amplitude and skewness, and develops dips. Quantitative analysis of our results indicates that conductance replicas originate from photon assisted tunnelling of quasiparticles into Andreev bound states through the tunnelling barrier. Despite strong qualitative similarities with proposed signatures of Floquet-Andreev states, our study rules out this scenario. The distortion of the current-phase relation is explained by the interaction of Andreev bound states with microwave photons, including a non-equilibrium Andreev bound state occupation. The techniques outlined here establish a baseline to study light-matter coupling in hybrid nanostructures and distinguish photon assisted tunnelling from Floquet-Andreev states in mesoscopic devices.

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