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Boundaries between distinct topological phases of matter support robust, yet exotic quantum states such as spin-momentum locked transport channels or Majorana fermions1-3. The idea of using such states in spintronic devices or as qubits in quantum information technology is a strong driver of current research in condensed matter physics4-6. The topological properties of quantum states have helped to explain the conductivity of doped trans-polyacetylene in terms of dispersionless soliton states7-9. In their seminal paper, Su, Schrieffer and Heeger (SSH) described these exotic quantum states using a one-dimensional tight-binding model10,11. Because the SSH model describes chiral topological insulators, charge fractionalization and spin-charge separation in one dimension, numerous efforts have been made to realize the SSH Hamiltonian in cold-atom, photonic and acoustic experimental configurations12-14. It is, however, desirable to rationally engineer topological electronic phases into stable and processable materials to exploit the corresponding quantum states. Here we present a flexible strategy based on atomically precise graphene nanoribbons to design robust nanomaterials exhibiting the valence electronic structures described by the SSH Hamiltonian15-17. We demonstrate the controlled periodic coupling of topological boundary states18 at junctions of graphene nanoribbons with armchair edges to create quasi-one-dimensional trivial and non-trivial electronic quantum phases. This strategy has the potential to tune the bandwidth of the topological electronic bands close to the energy scale of proximity-induced spin-orbit coupling19 or superconductivity20, and may allow the realization of Kitaev-like Hamiltonians3 and Majorana-type end states21.
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The electronic, optical, and magnetic properties of graphene nanoribbons (GNRs) can be engineered by controlling their edge structure and width with atomic precision through bottom-up fabrication based on molecular precursors. This approach offers a unique platform for all-carbon electronic devices but requires careful optimization of the growth conditions to match structural requirements for successful device integration, with GNR length being the most critical parameter. In this work, the growth, characterization, and device integration of 5-atom wide armchair GNRs (5-AGNRs) are studied, which are expected to have an optimal bandgap as active material in switching devices. 5-AGNRs are obtained via on-surface synthesis under ultrahigh vacuum conditions from Br- and I-substituted precursors. It is shown that the use of I-substituted precursors and the optimization of the initial precursor coverage quintupled the average 5-AGNR length. This significant length increase allowed the integration of 5-AGNRs into devices and the realization of the first field-effect transistor based on narrow bandgap AGNRs that shows switching behavior at room temperature. The study highlights that the optimized growth protocols can successfully bridge between the sub-nanometer scale, where atomic precision is needed to control the electronic properties, and the scale of tens of nanometers relevant for successful device integration of GNRs.
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A bottom up method for the synthesis of unique tetracene-based nanoribbons, which incorporate cyclobutadiene moieties as linkers between the acene segments, is reported. These structures were achieved through the formal [2+2] cycloaddition reaction of ortho-functionalized tetracene precursor monomers. The formation mechanism and the electronic and magnetic properties of these nanoribbons were comprehensively studied by means of a multitechnique approach. Ultra-high vacuum scanning tunneling microscopy showed the occurrence of metal-coordinated nanostructures at room temperature and their evolution into nanoribbons through formal [2+2] cycloaddition at 475â K. Frequency-shift non-contact atomic force microscopy images clearly proved the presence of bridging cyclobutadiene moieties upon covalent coupling of activated tetracene molecules. Insight into the electronic and vibrational properties of the so-formed ribbons was obtained by scanning tunneling microscopy, Raman spectroscopy, and theoretical calculations. Magnetic properties were addressed from a computational point of view, allowing us to propose promising candidates to magnetic acene-based ribbons incorporating four-membered rings. The reported findings will increase the understanding and availability of new graphene-based nanoribbons with high potential in future spintronics.
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We propose an extension of the traditional valence force field model to allow for the effect of electronic polarization to be included in the inter-atomic potential. Using density functional theory as a reference, this model is parameterized for the specific case of single-layer black phosphorus by fitting the phonon dispersion relation over the entire Brillouin zone. The model is designed to account for the effect of induced dipole interaction on the long-wavelength (|q[combining right harpoon above]| â 0) modes for the case of homopolar covalent crystals. We demonstrate that the near Γ-point frequencies of the IR-active modes are substantially damped by the inclusion of the induced dipole interaction, in agreement with experiment. The fitting procedure outlined here allows for this model to be adapted to other materials, including but not limited to two-dimensional crystals.
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BACKGROUND: Excessive noradrenergic signaling contributes to aversive symptoms of alcohol withdrawal that interfere with abstinence or reductions in harmful use. METHODS: To address this aspect of alcohol use disorder, 102 active-duty soldiers participating in command-mandated Army outpatient alcohol treatment were randomized to also receive the brain-penetrant alpha-1 adrenergic receptor antagonist prazosin or placebo for 13 weeks. Primary outcomes were scores on the Penn Alcohol Craving Scale (PACS), standard drink units (SDUs) per day averaged over each week, % days of any drinking per week, and % days of heavy drinking per week. RESULTS: PACS declines did not differ significantly between the prazosin and placebo groups in the overall sample. In the subgroup with comorbid PTSD (n = 48), PACS declines were significantly greater in the prazosin than in the placebo condition (p < 0.05). Baseline alcohol consumption was markedly reduced by the pre-randomization outpatient alcohol treatment program, but the addition of prazosin treatment produced a greater slope of decline in SDUs per day compared to placebo (p = 0.01). Preplanned subgroup analyses were performed in soldiers with elevated baseline cardiovascular measures consistent with increased noradrenergic signaling. In soldiers with elevated standing heart rate (n = 15), prazosin reduced SDUs per day (p = 0.01), % days drinking (p = 0.03), and % days heavy drinking (p = 0.001) relative to placebo. In soldiers with elevated standing systolic blood pressure (n = 27), prazosin reduced SDUs per day (p = 0.04) and tended to reduce % days drinking (p = 0.056). Prazosin also reduced depressive symptoms and the incidence of emergent depressed mood more than placebo (p = 0.05 and p = 0.01, respectively). During the final 4 weeks of prazosin vs. placebo treatment that followed completion of Army outpatient AUD treatment, alcohol consumption in soldiers with elevated baseline cardiovascular measures increased in those receiving placebo but remained suppressed in those receiving prazosin. CONCLUSIONS: These results extend reports that higher pretreatment cardiovascular measures predict beneficial effects of prazosin, which may be useful for relapse prevention in patients with AUD.
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Alcoolismo , Militares , Síndrome de Abstinência a Substâncias , Humanos , Prazosina/uso terapêutico , Alcoolismo/tratamento farmacológico , Alcoolismo/epidemiologia , Síndrome de Abstinência a Substâncias/tratamento farmacológico , Consumo de Bebidas Alcoólicas/tratamento farmacológico , Etanol/uso terapêutico , Método Duplo-Cego , Resultado do TratamentoRESUMO
Graphene nanoribbons (GNRs) have attracted much interest due to their largely modifiable electronic properties. Manifestation of these properties requires atomically precise GNRs which can be achieved through a bottom-up synthesis approach. This has recently been applied to the synthesis of width-modulated GNRs hosting topological electronic quantum phases, with valence electronic properties that are well captured by the Su-Schrieffer-Heeger (SSH) model describing a 1D chain of interacting dimers. Here, ultralow bandgap GNRs with charge carriers behaving as massive Dirac fermions can be realized when their valence electrons represent an SSH chain close to the topological phase boundary, i.e., when the intra- and interdimer coupling become approximately equal. Such a system has been achieved via on-surface synthesis based on readily available pyrene-based precursors and the resulting GNRs are characterized by scanning probe methods. The pyrene-based GNRs (pGNRs) can be processed under ambient conditions and incorporated as the active material in a field effect transistor. A quasi-metallic transport behavior is observed at room temperature, whereas at low temperature, the pGNRs behave as quantum dots showing single-electron tunneling and Coulomb blockade. This study may enable the realization of devices based on carbon nanomaterials with exotic quantum properties.
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Graphene nanoribbons (GNRs) have attracted considerable interest, as their atomically tunable structure makes them promising candidates for future electronic devices. However, obtaining detailed information about the length of GNRs has been challenging and typically relies on low-temperature scanning tunneling microscopy. Such methods are ill-suited for practical device application and characterization. In contrast, Raman spectroscopy is a sensitive method for the characterization of GNRs, in particular for investigating their width and structure. Here, we report on a length-dependent, Raman-active low-energy vibrational mode that is present in atomically precise, bottom-up-synthesized armchair graphene nanoribbons (AGNRs). Our Raman study demonstrates that this mode is present in all families of AGNRs and provides information on their length. Our spectroscopic findings are corroborated by scanning tunneling microscopy images and supported by first-principles calculations that allow us to attribute this mode to a longitudinal acoustic phonon. Finally, we show that this mode is a sensitive probe for the overall structural integrity of the ribbons and their interaction with technologically relevant substrates.
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BACKGROUND: In a previously reported positive randomized controlled trial of the α1-adrenoreceptor (α1AR) antagonist prazosin for combat posttraumatic stress disorder (PTSD) in 67 active duty soldiers, baseline symptoms did not predict therapeutic response. If increased brain α1AR activation in PTSD is the target of prazosin treatment action, higher brain α1AR activation should predict greater prazosin efficacy. Although brain α1AR activation is not measurable, coregulated peripheral α1AR activation could provide an estimate of brain α1AR activation. Standing blood pressure (BP) is an accessible biological parameter regulated by norepinephrine activation of α1ARs on peripheral arterioles. METHODS: Effects of baseline standing systolic and other BP parameters on PTSD outcome measures from the previously reported randomized controlled trial were analyzed using linear mixed-effects models. Prazosin participants (n = 32) and placebo participants (n = 35) were analyzed separately. RESULTS: In prazosin participants, each 10-mm Hg higher baseline standing systolic BP increment resulted in an additional 14-point reduction (improvement) of Clinician-Administered PTSD Scale total score at end point (p = .002). All other combinations of baseline BP parameters and PTSD outcome measures were similarly significant or demonstrated trends in the predicted direction. In placebo participants, there was no signal for a baseline BP effect on PTSD outcome measures. CONCLUSIONS: These findings suggest that higher standing BP is a biomarker that helps identify persons with combat PTSD who are likely to benefit from prazosin. These results also are consistent with α1AR activation contributing to PTSD pathophysiology in a subgroup of patients.
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Antagonistas de Receptores Adrenérgicos alfa 1/farmacologia , Pressão Sanguínea/efeitos dos fármacos , Distúrbios de Guerra/tratamento farmacológico , Militares , Avaliação de Resultados em Cuidados de Saúde , Prazosina/farmacologia , Transtornos de Estresse Pós-Traumáticos/tratamento farmacológico , Antagonistas de Receptores Adrenérgicos alfa 1/administração & dosagem , Adulto , Biomarcadores , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Prazosina/administração & dosagem , Adulto JovemRESUMO
OBJECTIVE: Increased central nervous system norepinephrine outflow and alpha1-adrenergic receptor responsiveness appear to be involved in the pathophysiologic processes of trauma-related nightmares in post-traumatic stress disorder. On the basis of reports that the brain-accessible alpha1-adrenergic antagonist Prazosin substantially reduced chronic combat-related nightmares among Vietnam War veterans, we evaluated Prazosin effects on combat-related nightmares among combat soldiers returning from Operation Iraqi Freedom. METHODS: Twenty-eight soldiers who self-reported distressing combat trauma-related nightmares on a postdeployment questionnaire were prescribed low-dose Prazosin before bedtime. RESULTS: Of the 23 soldiers for whom follow-up evaluations were available, 20 experienced marked improvement (complete elimination of nightmares), 2 experienced moderate improvement (reduced nightmare frequency or intensity), and 1 experienced no change. Prazosin was well tolerated. CONCLUSIONS: Prazosin appeared highly beneficial for combat-related nightmares characteristic of post-traumatic stress disorder among troops recently returned from Operation Iraqi Freedom. These findings provide a rationale for a placebo-controlled trial to establish efficacy in this population.
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Distúrbios de Guerra/tratamento farmacológico , Sonhos/psicologia , Prazosina/uso terapêutico , Antagonistas Adrenérgicos alfa/administração & dosagem , Antagonistas Adrenérgicos alfa/uso terapêutico , Adulto , Feminino , Humanos , Iraque , Masculino , Prazosina/administração & dosagem , Resultado do Tratamento , Veteranos , GuerraRESUMO
The use of graphene and other two-dimensional materials in next-generation electronics is hampered by the significant damage caused by conventional lithographic processing techniques employed in device fabrication. To reduce the density of defects and increase mobility, Joule heating is often used since it facilitates lattice reconstruction and promotes self-repair. Despite its importance, an atomistic understanding of the structural and electronic enhancements in graphene devices enabled by current annealing is still lacking. To provide a deeper understanding of these mechanisms, atomic recrystallization and electronic transport in graphene nanoribbon (GNR) devices are investigated using a combination of experimental and theoretical methods. GNR devices with widths below 10 nm are defined and electrically measured in situ within the sample chamber of an aberration-corrected transmission electron microscope. Immediately after patterning, we observe few-layer polycrystalline GNRs with irregular sp(2)-bonded edges. Continued structural recrystallization toward a sharp, faceted edge is promoted by increasing application of Joule heat. Monte Carlo-based annealing simulations reveal that this is a result of concentrated local currents at lattice defects, which in turn promotes restructuring of unfavorable edge structures toward an atomically sharp state. We establish that intrinsic conductance doubles to 2.7 e(2)/h during the recrystallization process following an almost 3-fold reduction in device width, which is attributed to improved device crystallinity. In addition to the observation of consistent edge bonding in patterned GNRs, we further motivate the use of bonded bilayer GNRs for future nanoelectronic components by demonstrating how electronic structure can be tailored by an appropriate modification of the relative twist angle of the bonded bilayer.
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Grafite/química , Nanotubos de Carbono/química , Cristalização , Transporte de Elétrons , Modelos Moleculares , Conformação Molecular , Método de Monte CarloRESUMO
In both research and industry, materials will be exposed to stresses, be it during fabrication, normal use, or mechanical failure. The response to external stress will have an important impact on properties, especially when atomic details govern the functionalities of the materials. This review aims at summarizing current research involving the responses of graphene and graphene materials to applied stress at the nanoscale, and to categorize them by stress-strain behavior. In particular, we consider the reversible functionalization of graphene and graphene materials by way of elastic deformation and strain engineering, the plastic deformation of graphene oxide and the emergence of such in normally brittle graphene, the formation of defects as a response to stress under high temperature annealing or irradiation conditions, and the properties that affect how, and mechanisms by which, pristine, defective, and polycrystalline graphene fail catastrophically during fracture. Overall we find that there is significant potential for the use of existing knowledge, especially that of strain engineering, as well as potential for additional research into the fracture mechanics of polycrystalline graphene and device functionalization by way of controllable plastic deformation of graphene.
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Elasticidade , Grafite/química , Plásticos/química , Elétrons , Nanotecnologia , Estresse MecânicoRESUMO
OBJECTIVE: The authors conducted a 15-week randomized controlled trial of the alpha-1 adrenoreceptor antagonist prazosin for combat trauma nightmares, sleep quality, global function, and overall symptoms in active-duty soldiers with posttraumatic stress disorder (PTSD) returned from combat deployments to Iraq and Afghanistan. METHOD: Sixty-seven soldiers were randomly assigned to treatment with prazosin or placebo for 15 weeks. Drug was titrated based on nightmare response over 6 weeks to a possible maximum dose of 5 mg midmorning and 20 mg at bedtime for men and 2 mg midmorning and 10 mg at bedtime for women. Mean achieved bedtime doses were 15.6 mg of prazosin (SD=6.0) and 18.8 mg of placebo (SD=3.3) for men and 7.0 mg of prazosin (SD=3.5) and 10.0 mg of placebo (SD=0.0) for women. Mean achieved midmorning doses were 4.0 mg of prazosin (SD=1.4) and 4.8 mg of placebo (SD=0.8) for men and 1.7 mg of prazosin (SD=0.5) and 2.0 mg of placebo (SD=0.0) mg for women. Primary outcome measures were the nightmare item of the Clinician-Administered PTSD Scale (CAPS), the Pittsburgh Sleep Quality Index, and the change item of the Clinical Global Impressions Scale anchored to functioning. Secondary outcome measures were the 17-item CAPS, the Hamilton Depression Rating Scale, the Patient Health Questionnaire-9, and the Quality of Life Index. Maintenance psychotropic medications and supportive psychotherapy were held constant. RESULTS: Prazosin was effective for trauma nightmares, sleep quality, global function, CAPS score, and the CAPS hyperarousal symptom cluster. Prazosin was well tolerated, and blood pressure changes did not differ between groups. CONCLUSIONS: Prazosin is effective for combat-related PTSD with trauma nightmares in active-duty soldiers, and benefits are clinically meaningful. Substantial residual symptoms suggest that studies combining prazosin with effective psychotherapies might demonstrate further benefit.