Your browser doesn't support javascript.
Mostrar: 20 | 50 | 100
Resultados 1 - 20 de 190
Filtrar
2.
J Mater Chem B ; 8(1): 155-160, 2020 Jan 07.
Artigo em Inglês | MEDLINE | ID: mdl-31782469

RESUMO

Oxytocin is a peptide hormone with high affinity to both Zn2+ and Cu2+ ions compared to other metal ions. This affinity makes oxytocin an attractive recognition layer for monitoring the levels of these essential ions in biofluids. Native oxytocin cannot differentiate between Cu2+ and Zn2+ ions and hence it is not useful for sensing Zn2+ in the presence of Cu2+. We elucidated the effect of the terminal amine group of oxytocin on the affinity toward Cu2+ using theoretical calculations. We designed a new Zn2+ selective oxytocin-based biosensor that utilizes the terminal amine for surface anchoring, also preventing the response to Cu2+. The biosensor shows exceptional selectivity and very high sensitivity to Zn2+ in impedimetric biosensing. This study shows for the first time an oxytocin derived sensor that can be used directly for sensing Zn2+ in the presence of Cu2+.

3.
Enferm. nefrol ; 22(3): 293-299, jul.-sept. 2019. tab
Artigo em Espanhol | IBECS-Express | ID: ibc-ET1-4259

RESUMO

Introducción: La Poliquistosis Renal Autosómica Dominante es una enfermedad renal crónica responsable del 10% de los casos de insuficiencia renal terminal. La participación y los grupos de apoyo entre iguales son herramientas que mejoran el bienestar, evitando complicaciones y retrasando el avance de la enfermedad. Objetivos: Detectar necesidades informativas, así como recursos de apoyo, en este grupo de pacientes mediante la puesta en marcha de una Escuela de Pacientes con poliquistosis renal autosómica dominante. Material y Método: Se utilizó un diseño mixto (cuantitativo y cualitativo). El estudio se desarrolló mediante cuatro fases: 1) Grupo focal: pacientes con poliquistosis renal y sus cuidadores; 2) Selección de los pacientes expertos; 3) Elaboración de los contenidos del programa de la Escuela de pacientes con poliquitstosis renal autosómica dominante; 4) Pilotaje del programa. Resultados: Se detectaron necesidades de información referentes al tratamiento oral y al afrontamiento de la poliquistosis renal que no están cubiertas por los equipos de nefrología. Conclusiones: La Escuela de Pacientes ha demostrado ser una herramienta útil para detectar necesidades y recursos en pacientes con poliquistosis renal autosómica dominante que han de enfrentarse a una enfermedad crónica donde se requiere la participación del paciente para garantizar la adhesión al tratamiento


Introduction: Autosomal Dominant Polycystic Kidney Disease is a chronic kidney disease responsible for 10% of cases of end-stage renal failure. Participation and peer support groups are tools that improve well-being, avoiding complications and delaying disease progression. Objectives: To detect information needs, as well as support resources, in patients with autosomal dominant polycystic kidney disease trough a Patient School. Material and Method: A mixed design (quantitative and qualitative) was used. The study was developed through four phases: 1) Focus group: patients with autosomal dominant polycystic kidney disease and their caregivers; 2) Selection of expert patients; 3) Preparation of the contents of the program of the Patient School with autosomal dominant polycystic kidney disease; 4) Piloting the program. Results: Information needs regarding oral treatment and coping with autosomal dominant polycystic kidney disease were detected, which are not covered by nephrology teams. Conclusions: Patients School has proven to be a useful tool to detect needs and resources in patients with autosomal dominant polycystic kidney disease who have to face a chronic disease where patient participation is required to ensure adherence to treatment

4.
Heliyon ; 5(7): e02078, 2019 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-31372543

RESUMO

Chrysochlamys is a genus of neotropical angiosperms distributed in wet and riparian forests from Bolivia to Mexico in altitudes from near sea-level to close to 3000 m. The wood anatomy of two species of the genus was investigated. Branches of mature stems were collected in a secondary wet forest in Colombian Northern Andes. Slides were obtained and visualized using light microscopy. Gelatinous fiber bands were found and described in C. colombiana and C. dependens. There was a higher amount of septate fibers in the latter. Average ray height and pigment deposit content in ray cells was greater in C. colombiana relative to C. dependens, but rays were commonly wider in the second one. The diversity of vessel-ray pit shapes in C. dependens is greater than in C. colombiana. In both cases rays are considered to be paedomorphic type I. Scanty to absent axial and apotracheal parenchyma was found for both species. We discuss the similarities and differences of the two species in order to establish diagnostic wood features. Also we include brief notes in comparative anatomy with other members of the Clusieaceae family, emphasizing in the incongruences found with previous reports for the genus. This is the first descriptive work in wood anatomy of C. colombiana and C. dependens.

5.
Langmuir ; 35(34): 11114-11122, 2019 Aug 27.
Artigo em Inglês | MEDLINE | ID: mdl-31361147

RESUMO

Peptides are very common recognition entities that are usually attached to surfaces using multistep processes. These processes require modification of the native peptides and of the substrates. Using functional groups in native peptides for their assembly on surfaces without affecting their biological activity can facilitate the preparation of biosensors. Herein, we present a simple single-step formation of native oxytocin monolayer on gold surface. These surfaces were characterized by atomic force spectroscopy, spectroscopic ellipsometry, and X-ray photoelectron spectroscopy. We took advantage of the native disulfide bridge of the oxytocin for anchoring the peptide to the Au surface, while preserving the metal-ion binding properties. Self-assembled oxytocin monolayer was used by electrochemical impedance spectroscopy for metal-ion sensing leading to subnanomolar sensitivities for zinc or copper ions.

6.
J Phys Condens Matter ; 31(40): 405502, 2019 Oct 09.
Artigo em Inglês | MEDLINE | ID: mdl-31195387

RESUMO

The molecular quantum cellular automata paradigm (m-QCA) offers a promising alternative framework to current CMOS implementations. A crucial aspect for implementing this technology concerns the construction of a device which effectively controls intramolecular charge-transfer processes. Tentative experimental implementations have been developed in which a voltage drop is created generating the forces that drive a molecule into a logic state. However, important factors such as the electric field profile, its possible time-dependency and the influence of temperature in the overall success of charge-transfer are relevant issues to be considered in the design of a reliable device. In this work, we theoretically study the role played by these processes in the overall intramolecular charge-transfer process. We have used a Landau-Zener (LZ) model, where different time-dependent electric field profiles have been simulated. The results have been further corroborated employing density functional tight-binding method. The role played by the nuclear motions in the electron-transfer process has been investigated beyond the Born-Oppenheimer approximation by computing the effect of the external electric field in the behavior of the potential energy surface. Hence, we demonstrate that the intramolecular charge-transfer process is a direct consequence of the coherent LZ nonadiabatic tunneling and the hybridization of the diabatic vibronic states which effectively reduces the trapping of the itinerant electron at the donor group.

7.
Langmuir ; 35(8): 2997-3004, 2019 Feb 26.
Artigo em Inglês | MEDLINE | ID: mdl-30707589

RESUMO

The ability to tune the electronic properties of oxide-bearing semiconductors such as Si/SiO2 or transparent metal oxides such as indium-tin oxide (ITO) is of great importance in both electronic and optoelectronic device applications. In this work, we describe a process that was conducted on n-type Si/SiO2 and ITO to induce changes in the substrate work function (WF). The substrates were modified by a two-step synthesis comprising a covalent attachment of coupling agents' monolayer followed by in situ anchoring reactions of polarizable chromophores. The coupling agents and chromophores were chosen with opposite dipole orientations, which enabled the tunability of the substrates' WF. In the first step, two coupling agents with opposite molecular dipole were assembled. The coupling agent with a negative dipole induced a decrease in WF of modified substrates, while the coupling agent with a positive dipole produced an increase in WFs of both ITO and Si substrates. The second modification step consisted of in situ anchoring reaction of polarizable chromophores with opposite dipoles to the coupling layer. This modification led to an additional change in the WFs of both Si/SiO2 and ITO substrates. The WF was measured by contact potential difference and modeled by density functional theory-based theoretical calculations of the WF for each of the assembly steps. A good fit was obtained between the calculated and experimental trends. This ability to design and tune the WF of ITO substrates was implemented in an organic electronic device with improved I- V characteristics in comparison to a bare ITO-based device.

8.
Phys Chem Chem Phys ; 21(4): 1904-1911, 2019 Jan 23.
Artigo em Inglês | MEDLINE | ID: mdl-30632565

RESUMO

BNC heteronanotubes are promising materials for the design of nanoscale thermoelectric devices. In particular, the structural BN doping pattern can be exploited to control the electrical and thermal transport properties of BNC nanostructures. We here address the thermoelectric transport properties of (6,6)-BNC heteronanotubes with helical and horizontal BN doping patterns. For this, we use a density functional tight-binding method combined with the Green's function technique. Our results show that the electron transmission is reduced and the electronic bandgap increased as a function of the BN concentration for different doping distribution patterns, so that (6,6)-BNC heteronanotubes become semiconducting with a tunable bandgap. The thermal conductance of helical (6,6)-BNC heteronanotubes, which is dominated by phonons, is weakly dependent on BN concentration in the range of 30-80%. Also, the Seebeck coefficient is enhanced by increasing the concentration of helical BN strips. In particular, helical (6,6)-BNC heteronanotubes with a high BN concentration (>20%) display a larger figure of merit compared to other doping distributions and, for a concentration of 50%, reach values up to 2.3 times and 3.4 times the corresponding values of a CNT at 300 K and 800 K, respectively. Our study yields new insights into the parameters tuning the thermoelectric efficiency and thus provides a starting point for designing thermoelectric devices based on BNC nanostructures.

9.
Phytother Res ; 33(3): 591-601, 2019 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-30488503

RESUMO

Osteosarcoma (OSA) is a type of bone cancer showing an aggressive biological behavior with metastatic progression. Because propolis potential for the development of new antitumoral drugs has been indicated, we evaluated the chemical composition of Colombian propolis samples and the mechanisms involved in their cytotoxic effects on OSA cells. The chemical composition was analyzed by GC-MS and the DPPH free radical scavenging activity was measured. Cluster and principal components analysis were used to establish an association with their inhibitory concentration 50% (IC50 ). Cell viability was analyzed by MTT assay; apoptosis was determined by flow cytometry; mitochondrial membrane permeability and reactive oxygen species were evaluated by rhodamine 123 and DCFH-DA. Transwell assay was used to evaluate the invasiveness of propolis-treated cells. Samples were grouped: Cluster 1 contained diterpenes and benzophenones and showed the highest antiradical activity; Cluster 2 was characterized by triterpenes, fatty acid, and diterpenes. Usm contained diterpenes and triterpenes different of the other samples and Sil contained triterpenes and flavonoids. Apoptosis, mitochondrial membrane alteration, and suppression of cell invasion were the main mechanisms involved in the inhibition of OSA cells in vitro, suggesting the potential of Colombian propolis to discover new antitumor drugs.


Assuntos
Apoptose/efeitos dos fármacos , Neoplasias Ósseas/patologia , Osteossarcoma/patologia , Própole/química , Própole/farmacologia , Animais , Antioxidantes/química , Antioxidantes/farmacologia , Neoplasias Ósseas/metabolismo , Sobrevivência Celular/efeitos dos fármacos , Colômbia , Citotoxinas/química , Citotoxinas/farmacologia , Diterpenos/química , Diterpenos/farmacologia , Doenças do Cão/metabolismo , Doenças do Cão/patologia , Cães , Flavonoides/química , Flavonoides/farmacologia , Cromatografia Gasosa-Espectrometria de Massas , Osteossarcoma/metabolismo , Espécies Reativas de Oxigênio/metabolismo , Transdução de Sinais/efeitos dos fármacos , Triterpenos/química , Triterpenos/farmacologia , Células Tumorais Cultivadas
10.
Biomolecules ; 10(1)2019 Dec 28.
Artigo em Inglês | MEDLINE | ID: mdl-31905610

RESUMO

The helical distribution of the electronic density in chiral molecules, such as DNA and bacteriorhodopsin, has been suggested to induce a spin-orbit coupling interaction that may lead to the so-called chirality-induced spin selectivity (CISS) effect. Key ingredients for the theoretical modelling are, in this context, the helically shaped potential of the molecule and, concomitantly, a Rashba-like spin-orbit coupling due to the appearance of a magnetic field in the electron reference frame. Symmetries of these models clearly play a crucial role in explaining the observed effect, but a thorough analysis has been largely ignored in the literature. In this work, we present a study of these symmetries and how they can be exploited to enhance chiral-induced spin selectivity in helical molecular systems.

11.
Rev. medica electron ; 40(6): 1750-1764, nov.-dic. 2018. tab, graf
Artigo em Espanhol | LILACS-Express | ID: biblio-978701

RESUMO

RESUMEN Introducción: estudios recientes indican que la cresta infracigomática es un sitio favorable para la colocación de mini implantes, sin embargo es importante conocer sus dimensiones anatómicas para colocarlos en una posición segura y lograr buena estabilidad. Objetivo: determinar el área, en diferentes zonas de la cresta infracigomática, que son utilizadas para la colocación de miniimplantes. Materiales y métodos: estudio descriptivo, observacional y transversal de 60 casos, con previo tratamiento de Ortodoncia y que reunieron los criterios de inclusión. Se utilizaron archivos radiográficos y de tomografías con tecnología cone-beam. Se realizó la estadística descriptiva y pruebas ANOVA, t de Student y método de comparación de Tukey para relacionar las variables. Resultados: la zona de mayor área de hueso se encontró a nivel de la cúspide mesiovestibular del segundo molar (30.2+12.1mm2). La clase esqueletal II presentó mayor área (33.6+11.2mm2). Se encontraron diferencias estadísticamente significativas al relacionar las variables área y zona, así como área y clase esqueletal, pero no hubo significancia estadística al relacionar el área con el sexo. Conclusiones. a nivel de la segunda molar superior es la referencia ideal para la colocación de mini implantes, en la cresta infracigomática, ya que esta tiene mayor área. Los casos Clase II presentan también un área mayor. El sexo no fue determinante.


ABSTRACT Introduction: recent studies indicate that the infrazygomatic crest is a favorable site for the placement of miniscrew (mini implante), however it is important to know its anatomical dimensions to place them in a secure position and to obtain good stability. Objective: to determine the area in different sites of the infrazygomatic crest that is used for the placement of mini-implants. Materials and methods: descriptive, observational and cross-sectional study of 60 cases, with previous orthodontic treatment, that fulfilled the inclusion criteria. Radiographic and tomographic files with cone-beam technology were used. Descriptive statistics, ANOVA and t-Student tests, and Tukey's comparison method were used to relate the variables. Results: The zone with the largest area was found at the level of the second molar in the mesiovestibular cusp (30.2 + 12.1 mm2). Skeletal class II showed the largest area (33.6 + 11.2mm2). Statistically significant differences were found when relating the area and site variables as well as area and skeletal class, but there was no statistical significance in relating the area to sex. Conclusions: the level of the upper second molar is the ideal reference for the placement of mini-implants in the infrazygomatic crest since it has a larger area. Class II cases also have a larger area. Sex was not determinant.

12.
Nat Commun ; 9(1): 4051, 2018 10 03.
Artigo em Inglês | MEDLINE | ID: mdl-30282989

RESUMO

Mass transport through graphene is receiving increasing attention due to the potential for molecular sieving. Experimental studies are mostly limited to the translocation of protons, ions, and water molecules, and results for larger molecules through graphene are rare. Here, we perform controlled radical polymerization with surface-anchored self-assembled initiator monolayer in a monomer solution with single-layer graphene separating the initiator from the monomer. We demonstrate that neutral monomers are able to pass through the graphene (via native defects) and increase the graphene defects ratio (Raman ID/IG) from ca. 0.09 to 0.22. The translocations of anionic and cationic monomers through graphene are significantly slower due to chemical interactions of monomers with the graphene defects. Interestingly, if micropatterned initiator-monolayers are used, the translocations of anionic monomers apparently cut the graphene sheet into congruent microscopic structures. The varied interactions between monomers and graphene defects are further investigated by quantum molecular dynamics simulations.

13.
Langmuir ; 34(47): 14103-14123, 2018 11 27.
Artigo em Inglês | MEDLINE | ID: mdl-30253096

RESUMO

Inorganic materials such as semiconductors, oxides, and metals are ubiquitous in a wide range of device technologies owing to the outstanding robustness and mature processing technologies available for such materials. However, while the important contribution of inorganic materials to the advancement of device technologies has been well established for decades, organic-inorganic hybrid device systems, which merge molecular functionalities with inorganic platforms, represent a newer domain that is rapidly evolving at an increasing pace. Such devices benefit from the great versatility and flexibility of the organic building blocks merged with the robustness of the inorganic platforms. Given the overwhelming wealth of literature covering various approaches for modifying and using inorganic devices, this feature article selectively highlights some of the advances made in the context of the diversification of devices by surface chemistry. Particular attention is given to oxide-semiconductor systems and metallic surfaces modified with organic monolayers. The inorganic device components, such as semiconductors, metals, and oxides, are modified by organic monolayers, which may serve as either active, static, or sacrificial components. We portray research directions within the broader field of organic-inorganic hybrid device systems that can be viewed as specific examples of the potential of such hybrid device systems given their comprehensive capabilities of design and diversification. Monolayer doping techniques where sacrificial organic monolayers are introduced into semiconducting elements are reviewed as a specific case, together with associated requirements for nanosystems, devices, and sensors for controlling doping levels and doping profiles on the nanometric scale. Another series of examples of the flexibility provided by the marriage of organic functional monolayers and inorganic device components are represented by a new class of biosensors, where the organic layer functionality is exploited in a functioning device for sensing. Considerations for relying on oxide-terminated semiconductors rather than the pristine semiconductor material as a platform both for processing and sensing are discussed. Finally, we cover aspects related to the use of various theoretical and computational approaches to model organic-inorganic systems. The main objectives of the topics covered here are (i) to present the advances made in each respective domain and (ii) to provide a comprehensive view of the potential uses of organic monolayers and self-assembly processes in the rapidly evolving field of molecular-inorganic hybrid device platforms and processing methodologies. The directions highlighted here provide a perspective on a future, not yet fully realized, integrated approach where organic monolayers are combined with inorganic platforms in order to obtain versatile, robust, and flexible systems with enhanced capabilities.

14.
J Phys Chem Lett ; 9(18): 5453-5459, 2018 Sep 20.
Artigo em Inglês | MEDLINE | ID: mdl-30188726

RESUMO

Chirality-induced spin selectivity (CISS) is a recently discovered effect, whose precise microscopic origin has not yet been fully elucidated; it seems, however, clear that spin-orbit interaction plays a pivotal role. Various model Hamiltonian approaches have been proposed, suggesting a close connection between spin selectivity and filtering and helical symmetry. However, first-principles studies revealing the influence of chirality on the spin polarization are missing. To clearly demonstrate the influence of the helical conformation on the spin polarization properties, we have carried out spin-dependent Density-Functional Theory (DFT) based transport calculations for a model molecular system. It consists of α-helix and ß-strand conformations of an oligo-glycine peptide, which is bonded to a nickel electrode and to a gold electrode in a two-terminal setup, similar to a molecular junction or a local probe, for example, in STM or AFM configurations. We have found that the α-helix conformation displays a spin polarization, calculated through the intrinsic magneto-resistance of the junction, about 100-1000 times larger than the linear ß-strand, clearly demonstrating the crucial role played by the molecular helical geometry on the enhancement of spin polarization associated with the CISS effect.

15.
J Phys Chem Lett ; 9(19): 5753-5758, 2018 Oct 04.
Artigo em Inglês | MEDLINE | ID: mdl-30212207

RESUMO

We use a nonlinear master equation formalism to account for thermal and disorder effects on spin-dependent electron transport in helical organic molecules coupled to two ideal leads. The inclusion of these two effects has important consequences in understanding the observed length and temperature dependence of spin polarization in experiments, which cannot be accounted for in a purely coherent tunneling model. Our approach considers a tight-binding helical Hamiltonian with disordered onsite energies to describe the resulting electronic states when low-frequency interacting modes break the electron coherence. The high-frequency fluctuating counterpart of these interactions, typical of intramolecular modes, is included by means of temperature-dependent thermally activated transfer probabilities in the master equation, which lead to hopping between localized states. We focus on the spin-dependent conductance and the spin-polarization in the linear regime (low voltage), which are analyzed as a function of the molecular length and the temperature of the system. Our results at room temperature agree well with experiments because our model predicts that the degree of spin-polarization increases for longer molecules. Also, this effect is temperature-dependent because thermal excitation competes with disorder-induced Anderson localization. We conclude that a transport mechanism based on thermally activated hopping in a disordered system can account for the unexpected behavior of the spin polarization.

16.
J Neurosci ; 38(42): 9034-9046, 2018 10 17.
Artigo em Inglês | MEDLINE | ID: mdl-30190413

RESUMO

Fast ripples (FRs; activity of >250 Hz) have been considered as a biomarker of epileptic activity in the hippocampus and entorhinal cortex; it is thought that they signal the focus of seizure generation. Similar high-frequency network activity has been produced in vitro by changing extracellular medium composition, by using pro-epileptic substances, or by electrical stimulation. Here we study the propagation of these events between different subregions of the male rat hippocampus in a recently introduced experimental model of FRs in entorhinal cortex-hippocampal slices in vitro By using a matrix of 4096 microelectrodes, the sites of initiation, propagation pathways, and spatiotemporal characteristics of activity patterns could be studied with unprecedented high resolution. To this end, we developed an analytic tool based on bidimensional current source density estimation, which delimits sinks and sources with a high precision and evaluates their trajectories using the concept of center of mass. With this methodology, we found that FRs can arise almost simultaneously at noncontiguous sites in the CA3-to-CA1 direction, underlying the spatial heterogeneity of epileptogenic foci, while continuous somatodendritic waves of activity develop. An unexpected, yet important propagation route is the propagation of activity from CA3 into the hilus and dentate gyrus. This pathway may cause reverberating activation of both regions, supporting sustained pathological network events and altered information processing in hippocampal networks.SIGNIFICANCE STATEMENT Fast ripples (FRs) have been considered as a biomarker of epileptic activity and may signal the focus of seizure generation. In a model of traumatic brain injury in the rat, FRs appear in the hippocampus within a couple of hours after an extrahippocampal, cortical lesion. We analyzed the origin and dynamics of the FRs in the hippocampus using massive electrophysiological recordings, allowing an unprecedented high spatiotemporal resolution. We show that FRs originate in distinct and noncontiguous locations within the CA3 region and uncover, with high precision, the extent and dynamics of their current density. This activity propagates toward CA1 but also backpropagates to the hilus and the dentate gyrus, suggesting activation of defined microcircuits that can sustain recurrent excitation.


Assuntos
Lesões Encefálicas Traumáticas/fisiopatologia , Ondas Encefálicas , Córtex Entorrinal/fisiopatologia , Epilepsia/fisiopatologia , Hipocampo/fisiopatologia , Neurônios/fisiologia , Animais , Lesões Encefálicas Traumáticas/complicações , Modelos Animais de Doenças , Epilepsia/etiologia , Masculino , Vias Neurais/fisiopatologia , Ratos Wistar
17.
Cell Tissue Res ; 373(3): 671-691, 2018 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-30112572

RESUMO

There is considerable experimental evidence, anatomical and physiological, that gap junctions exist in the hippocampus. Electrical coupling through these gap junctions may be divided into three types: between principal neurons, between interneurons and at mixed chemical (glutamatergic)/electrical synapses. An approach, combining in vitro experimental with modeling techniques, sheds some light on the functional consequences of electrical coupling, for network oscillations and for seizures. Additionally, in vivo experiments, using mouse connexin knockouts, suggest that the presence of electrical coupling is important for optimal performance on selected behavioral tasks; however, the interpretation of such data, in cellular terms, has so far proven difficult. Given that invertebrate central pattern generators so often depend on both chemical and electrical synapses, our hypothesis is that hippocampus-mediated and -influenced behaviors will act likewise. Experiments, likely hard ones, will be required to test this intuition.


Assuntos
Condutividade Elétrica , Junções Comunicantes/fisiologia , Hipocampo/fisiologia , Interneurônios/metabolismo , Células Piramidais/metabolismo , Animais , Axônios/metabolismo , Técnicas de Observação do Comportamento , Conexinas/genética , Dendritos/metabolismo , Estimulação Elétrica , Camundongos , Camundongos Knockout , Ratos , Sinapses/metabolismo
18.
Langmuir ; 34(26): 7698-7707, 2018 07 03.
Artigo em Inglês | MEDLINE | ID: mdl-29889539

RESUMO

We combine ambient (air) and ultrahigh vacuum (UHV) scanning tunneling microscopy (STM) and spectroscopy (STS) investigations together with density functional theory (DFT) calculations to gain a subnanometer insight into the structure and dynamic of two-dimensional (2D) surface-supported molecular networks. The planar tetraferrocene-porphyrin molecules employed in this study undergo spontaneous self-assembly via the formation of hydrogen bonded networks at the gold substrate-solution interface. To mimic liquid phase ambient deposition conditions, film formation was accomplished in UHV by electro-spraying a solution of the molecule in chloroform onto an Au(111) substrate, thereby providing access to the full spectroscopic capabilities of STM that can be hardly attained under ambient conditions. We show that molecular assembly on Au (111) is identical in films prepared under the two different conditions, and in good agreement with the theoretical predictions. However, we observe the contrast found for a given STM bias condition to be different in ambient and UHV conditions despite the similarity of the structures, and we propose possible origins of the different imaging contrast. This approach could be valuable for the thorough characterization of surface systems that involve large molecules and are prepared mainly in ambient conditions.

19.
J Phys Chem Lett ; 9(8): 2025-2030, 2018 Apr 19.
Artigo em Inglês | MEDLINE | ID: mdl-29618210

RESUMO

The interaction of low-energy photoelectrons with well-ordered monolayers of enantiopure helical heptahelicene molecules adsorbed on metal surfaces leads to a preferential transmission of one longitudinally polarized spin component, which is strongly coupled to the helical sense of the molecules. Heptahelicene, composed of only carbon and hydrogen atoms, exhibits only a single helical turn but shows excess in longitudinal spin polarization of about P Z = 6 to 8% after transmission of initially balanced left- and right-handed spin polarized electrons. Insight into the electronic structure, that is, the projected density of states, and the spin-dependent electron scattering in the helicene molecule is gained by using spin-resolved density functional theory calculations and a model Hamiltonian approach, respectively. Our results support the semiclassical picture of electronic transport along a helical pathway under the influence of spin-orbit coupling induced by the electrostatic molecular potential.

20.
Adv Sci (Weinh) ; 5(2): 1700365, 2018 02.
Artigo em Inglês | MEDLINE | ID: mdl-29619296

RESUMO

The integrity of phonon transport properties of large graphene (linear and curved) grain boundaries (GBs) is investigated under the influence of structural and dynamical disorder. To do this, density functional tight-binding (DFTB) method is combined with atomistic Green's function technique. The results show that curved GBs have lower thermal conductance than linear GBs. Its magnitude depends on the length of the curvature and out-of-plane structural distortions at the boundary, having stronger influence the latter one. Moreover, it is found that by increasing the defects at the boundary, the transport properties can strongly be reduced in comparison to the effect produced by heating up the boundary region. This is due to the large reduction of the phonon transmission for in-plane and out-of-plane vibrational modes after increasing the structural disorder in the GBs.

SELEÇÃO DE REFERÊNCIAS
DETALHE DA PESQUISA