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1.
Nano Lett ; 24(23): 6889-6896, 2024 Jun 12.
Artículo en Inglés | MEDLINE | ID: mdl-38739156

RESUMEN

Thermal conductivity is a critical material property in numerous applications, such as those related to thermoelectric devices and heat dissipation. Effectively modulating thermal conductivity has become a great concern in the field of heat conduction. Here, a quantum modulation strategy is proposed to modulate the thermal conductivity/heat flux by exciting targeted phonons. It shows that the thermal conductivity of graphene can be tailored in the range of 1559 W m-1 K-1 (decreased to 49%) to 4093 W m-1 K-1 (increased to 128%), compared with the intrinsic value of 3189 W m-1 K-1. The effects are also observed for graphene nanoribbons and bulk silicon. The results are obtained through both density functional theory calculations and molecular dynamics simulations. This novel modulation strategy may pave the way for quantum heat conduction.

2.
J Am Chem Soc ; 146(26): 17765-17772, 2024 Jul 03.
Artículo en Inglés | MEDLINE | ID: mdl-38902874

RESUMEN

Chirality, a fundamental attribute of nature, significantly influences a wide range of phenomena related to physical properties, chemical reactions, biological pharmacology, and so on. As a pivotal aspect of chirality research, chirality recognition contributes to the synthesis of complex chiral products from simple chiral compounds and exhibits intricate interplay between chiral materials. However, macroscopic detection technologies cannot unveil the dynamic process and intrinsic mechanisms of single-molecule chirality recognition. Herein, we present a single-molecule detection platform based on graphene-molecule-graphene single-molecule junctions to measure the chirality recognition involving interactions between amines and chiral alcohols. This approach leads to the realization of in situ and real-time direct observation of chirality recognition at the single-molecule level, demonstrating that chiral alcohols exhibit compelling potential to induce the formation of the corresponding chiral configuration of molecules. The amalgamation of theoretical analyses with experimental findings reveals a synergistic action between electrostatic interactions and steric hindrance effects in the chirality recognition process, thus substantiating the microscopic mechanism governing the chiral structure-activity relationship. These studies open up a pathway for exploring novel chiral phenomena from the fundamental limits of chemistry, such as chiral origin and chiral amplification, and offer important insights into the precise synthesis of chiral materials.

3.
Nano Lett ; 22(23): 9418-9423, 2022 Dec 14.
Artículo en Inglés | MEDLINE | ID: mdl-36449564

RESUMEN

Scanning tunneling microscope (STM)-induced luminescence provides an ideal platform for electrical generation and the atomic-scale manipulation of nonclassical states of light. However, despite its extreme importance in quantum technologies, squeezed light emission with reduced quantum fluctuations has hitherto not been demonstrated in such a platform. Here, we theoretically predict that the emitted light from the plasmon mode can be squeezed in an STM single molecular junction subject to an external laser drive. Going beyond the traditional paradigm that generates squeezing with the quadratic interaction of photons, our prediction explores the molecular coherence involved in an anharmonic energy spectrum of a coupled plasmon-molecule-exciton system. Furthermore, we show that, by selectively exciting the energy ladder, the squeezed plasmon can show either sub- or super-Poissonian statistical properties. We also demonstrate that, following the same principle, the molecular excitonic mode can be squeezed simultaneously.

4.
Phys Rev Lett ; 128(23): 236401, 2022 Jun 10.
Artículo en Inglés | MEDLINE | ID: mdl-35749188

RESUMEN

Investigation of intermolecular electron spin interaction is of fundamental importance in both science and technology. Here, radical pairs of all-trans retinoic acid molecules on Au(111) are created using an ultralow temperature scanning tunneling microscope. Antiferromagnetic coupling between two radicals is identified by magnetic-field-dependent spectroscopy. The measured exchange energies are from 0.1 to 1.0 meV. The biradical spin coupling is mediated through O─H⋯O hydrogen bonds, as elucidated from analysis combining density functional theory calculation and a modern version of valence bond theory.


Asunto(s)
Electrones , Enlace de Hidrógeno
5.
Acta Haematol ; 145(2): 144-151, 2022.
Artículo en Inglés | MEDLINE | ID: mdl-34551411

RESUMEN

Mixed lineage leukemia (MLL) T10 is a relatively rare partner for the KMT2A lysine (K)-specific methyltransferase 2A gene. The common features and coexisting mutations of acute myeloid leukemia (AML) patients with KMT2A-MLLT10 remain unknown. In this study, 10 adult AML patients with KMT2A-MLLT10 fusions were picked up from 496 AML patients by using RT-polymerase chain reaction (PCR) and/or fluorescence in situ hybridization, and then screened for mutations in the 49 genes panel with next-generation sequencing and PCR, followed by direct Sanger sequencing. Of the 10 unique individuals identified, 6 were male and 4 were female (M:F ratio, 1.5:1) with ages ranging from 19 to 52 years (median 39.5 years). Most (90%, 9/10) patients with KMT2A-MLLT10 were accompanied by additional mutations. Twelve mutated genes were detected, averaging 2.1 mutations per patient (range, 0-4). The most frequently mutated gene was NRAS (n = 5). Clinical and laboratory data pointed to common features: French American British-M5 subtype (n = 7), a high rate of relapse, and biomarkers CD33 (n = 10), CD117 (n = 9), CD13 (n = 8), and CD64 (n = 8). Overall, most patients harbored at least one mutation. A high incidence of mutations affecting the RAS signaling pathway or RAS regulating components was found in 50% (5/10) patients. The overall survival is about 12.0 months. Allogeneic-hematopoietic stem cell transplantation trends to improve survival in selected patients.


Asunto(s)
Leucemia Mieloide Aguda , Proteína de la Leucemia Mieloide-Linfoide , Adulto , Femenino , Secuenciación de Nucleótidos de Alto Rendimiento , Humanos , Hibridación Fluorescente in Situ , Leucemia Mieloide Aguda/genética , Leucemia Mieloide Aguda/terapia , Masculino , Persona de Mediana Edad , Mutación , Proteína de la Leucemia Mieloide-Linfoide/genética , Transducción de Señal , Adulto Joven
6.
J Chem Phys ; 157(17): 174303, 2022 Nov 07.
Artículo en Inglés | MEDLINE | ID: mdl-36347693

RESUMEN

Maintaining stability of single-molecular junctions (SMJs) in the presence of current flow is a prerequisite for their potential device applications. However, theoretical understanding of nonequilibrium heat transport in current-carrying SMJs is a challenging problem due to the different kinds of nonlinear interactions involved, including electron-vibration and anharmonic vibrational coupling. Here, we overcome this challenge by accelerating Langevin-type current-induced molecular dynamics using machine-learning potential derived from density functional theory. We show that SMJs with graphene electrodes generate an order of magnitude less heating than those with gold electrodes. This is rooted in the better phonon spectral overlap of graphene with molecular vibrations, rendering harmonic phonon heat transport being dominant. In contrast, in a spectrally mismatched junction with gold electrodes, anharmonic coupling becomes important to transport heat away from the molecule to surrounding electrodes. Our work paves the way for studying current-induced heat transport and energy redistribution in realistic SMJs.

7.
Nano Lett ; 21(16): 7005-7011, 2021 Aug 25.
Artículo en Inglés | MEDLINE | ID: mdl-34350759

RESUMEN

The Mott state in 1T-TaS2 is predicted to host quantum spin liquids (QSLs). However, its insulating mechanism is controversial due to complications from interlayer coupling. Here, we study the charge transfer state in monolayer 1T-NbSe2, an electronic analogue to TaS2 exempt from interlayer coupling, using spectroscopic imaging scanning tunneling microscopy and first-principles calculations. Monolayer NbSe2 surprisingly displays two types of star of David (SD) motifs with different charge transfer gap sizes, which are interconvertible via temperature variation. In addition, bilayer 1T-NbSe2 shows a Mott collapse by interlayer coupling. Our calculation unveils that the two types of SDs possess distinct structural distortions, altering the effective Coulomb energies of the central Nb orbital. Our calculation suggests that the charge transfer gap, the same parameter for determining the QSL regime, is tunable with strain. This finding offers a general strategy for manipulating the charge transfer state in related systems, which may be tuned into the potential QSL regime.

8.
Angew Chem Int Ed Engl ; 61(45): e202210939, 2022 11 07.
Artículo en Inglés | MEDLINE | ID: mdl-36098651

RESUMEN

Intermolecular charge transport plays a vital role in the fields of electronics, as well as biochemical systems. Here, we design supramolecular dimer junctions and investigate the effects of charge state and energy level alignment on charge transport under nanoconfinement. Incoherent tunneling caused by thermally-induced vibrations is enhanced in positively charged systems. The transition between coherent and incoherent tunneling is associated with specific molecular vibration modes. Positively charged systems with smaller torsional barriers and vibrational frequencies result in lower transition temperatures. Multiple thermal effects have a great impact on the conductance in the off-resonant tunneling, while thermally-induced vibron-assisted tunneling contributes more to the transport in the resonant tunneling. These investigations offer a deep mechanism understanding of intermolecular charge transport and facilitate the development of practical functional molecular devices.


Asunto(s)
Electrónica , Vibración , Transporte de Electrón
9.
J Cell Mol Med ; 24(23): 14110-14120, 2020 12.
Artículo en Inglés | MEDLINE | ID: mdl-33118329

RESUMEN

Androgen receptor (AR) can suppress hepatocellular carcinoma (HCC) invasion and metastasis at an advanced stage. Vasculogenic mimicry (VM), a new vascularization pattern by which tumour tissues nourish themselves, is correlated with tumour progression and metastasis. Here, we investigated the effect of AR on the formation of VM and its mechanism in HCC. The results suggested that AR could down-regulate circular RNA (circRNA) 7, up-regulate micro RNA (miRNA) 7-5p, and suppress the formation of VM in HCC Small hairpin circR7 (ShcircR7) could reverse the impact on VM and expression of VE-cadherin and Notch4 increased by small interfering AR (shAR) in HCC, while inhibition of miR-7-5p blocked the formation of VM and expression of VE-cadherin and Notch4 decreased by AR overexpression (oeAR) in HCC. Mechanism dissection demonstrated that AR could directly target the circR7 host gene promoter to suppress circR7, and miR-7-5p might directly target the VE-cadherin and Notch4 3'UTR to suppress their expression in HCC. In addition, knockdown of Notch4 and/or VE-cadherin revealed that shVE-cadherin or shNotch4 alone could partially reverse the formation of HCC VM, while shVE-cadherin and shNotch4 together could completely suppress the formation of HCC VM. Those results indicate that AR could suppress the formation of HCC VM by down-regulating circRNA7/miRNA7-5p/VE-Cadherin/Notch4 signals in HCC, which will help in the design of novel therapies against HCC.


Asunto(s)
Carcinoma Hepatocelular/etiología , Carcinoma Hepatocelular/metabolismo , Neoplasias Hepáticas/etiología , Neoplasias Hepáticas/metabolismo , Neovascularización Patológica/genética , Neovascularización Patológica/metabolismo , Receptores Androgénicos/metabolismo , Antígenos CD/metabolismo , Biomarcadores , Cadherinas/metabolismo , Carcinoma Hepatocelular/patología , Línea Celular Tumoral , Regulación Neoplásica de la Expresión Génica , Humanos , Neoplasias Hepáticas/patología , MicroARNs/genética , Interferencia de ARN , ARN Circular/genética , Receptor Notch4/metabolismo , Transducción de Señal
10.
Nano Lett ; 19(8): 5133-5139, 2019 Aug 14.
Artículo en Inglés | MEDLINE | ID: mdl-31276417

RESUMEN

van der Waals (vdW) heterostructures, stacking different two-dimensional materials, have opened up unprecedented opportunities to explore new physics and device concepts. Especially interesting are recently discovered two-dimensional magnetic vdW materials, providing new paradigms for spintronic applications. Here, using density functional theory (DFT) calculations, we investigate the spin-dependent electronic transport across vdW magnetic tunnel junctions (MTJs) composed of Fe3GeTe2 ferromagnetic electrodes and a graphene or hexagonal boron nitride (h-BN) spacer layer. For both types of junctions, we find that the junction resistance changes by thousands of percent when the magnetization of the electrodes is switched from parallel to antiparallel. Such a giant tunneling magnetoresistance (TMR) effect is driven by dissimilar electronic structure of the two spin-conducting channels in Fe3GeTe2, resulting in a mismatch between the incoming and outgoing Bloch states in the electrodes and thus suppressed transmission for an antiparallel-aligned MTJ. The vdW bonding between electrodes and a spacer layer makes this result virtually independent of the type of the spacer layer, making the predicted giant TMR effect robust with respect to strain, interface distance, and other parameters, which may vary in the experiment. We hope that our results will further stimulate experimental studies of vdW MTJs and pave the way for their applications in spintronics.

11.
Phys Chem Chem Phys ; 21(33): 18259-18264, 2019 Aug 21.
Artículo en Inglés | MEDLINE | ID: mdl-31393476

RESUMEN

The anharmonicity of phonons in a solid is ultimately rooted in the chemical bonding. However, the direct connection between phonon anharmoncity and chemical bonding is difficult to make experimentally or theoretically, mainly due to their complicated lattice structures. Here, with the help of first-principles calculations, we show that the intrinsically low lattice thermal conductivity (κ) of Bi2O2X (X = S, Se, Te) shows a strong connection to the electrostatic inter-layer coupling. We explain our results by the strong anharmonic chemical bonding between Bi and chalcogen atoms. Additionally, due to the strong anharmonicity, a large portion of phonon modes has a mean free path shorter than the average atomic distance. We employ a recently proposed two-channel model to take into account their contribution to κ.

12.
Nano Lett ; 18(11): 6826-6831, 2018 11 14.
Artículo en Inglés | MEDLINE | ID: mdl-30335393

RESUMEN

The coupling between molecular exciton and gap plasmons plays a key role in single molecular electroluminescence induced by a scanning tunneling microscope (STM). But it has been difficult to clarify the complex experimental phenomena. By employing the nonequilibrium Green's function method, we propose a general theoretical model to understand the light emission spectrum of single molecule and gap plasmons from an energy transport point of view. The coherent interaction between gap plasmons and molecular exciton leads to a prominent Fano resonance in the emission spectrum. We analyze the dependence of the Fano line shape on the system parameters, based on which we provide a unified account of several recent experimental observations. Moreover, we highlight the effect of the tip-molecule electronic coupling on the spectrum.

13.
Small ; 14(7)2018 02.
Artículo en Inglés | MEDLINE | ID: mdl-29319224

RESUMEN

The important role of p-n junction in modulation of the optoelectronic properties of semiconductors is widely cognized. In this work, for the first time the synthesis of p-GaSe/n-MoS2 heterostructures via van der Waals expitaxial growth is reported, although a considerable lattice mismatching of ≈18% exists. According to the simulation, a significant type II p-n junction barrier located at the interface is expected to be formed, which can modulate optoelectronic properties of MoS2 effectively. It is intriguing to reveal that the presence of GaSe can result in obvious Raman and photoluminescence (PL) shift of MoS2 compared to that of pristine one, more interestingly, for PL peak shift, the effect of GaSe-induced tensile strain on MoS2 has overcome the p-doping effect of GaSe, evidencing the strong interlayer coupling between GaSe and MoS2 . As a result, the photoresponse rate of heterostructures is improved by almost three orders of magnitude compared with that of pristine MoS2 .


Asunto(s)
Molibdeno/química , Semiconductores , Espectrometría Raman
14.
Opt Express ; 26(23): 30444-30455, 2018 Nov 12.
Artículo en Inglés | MEDLINE | ID: mdl-30469918

RESUMEN

We study the decay of gap plasmons localized between a scanning tunneling microscope tip and metal substrate, excited by inelastic tunneling electrons. The overall excited energy from the tunneling electrons is divided into two categories in the form of resistive dissipation and electromagnetic radiation, which together can further be separated into four diffierent channels, including SPP channel on the tip, SPP channel on the substrate, air mode channel and direct quenching channel. In this work, we study the enhancement factor, i.e. Purcell factor, of the STM tunnel junctions, which are mediated by the nearby metallic structures. We find that the gap plasmon mode is most likely to couple to the SPP channel on the tip, rather than the SPP channel on the substrate or the air mode. The direct quenching in the apex of tip also takes a considerable portion especially in high frequency region, the enhancement factor of direct quenching in the tip is much higher than the direct quenching in the substrate. We adopt four tips with diffierent apex radii, i.e., 1 nm, 5 nm, 10 nm, 20 nm. When the apex size is small, the frequency dependent enhancement factor from the SPPs contribution has a pronounced peak at 1.55 eV, however, as the radius increases, the peak of enhancement factor in the high frequency region appears, the 1.55 eV peak becomes less dominated. This phenomenon can be attributed to the change of tip shape, in the form of mode coupling. Our results also show a relationship between the direct quenching in the substrate and in the tip. With the larger radius of apex, the ratio of these two part of energy approaches 1, which indicate that the energy distribution of direct quenching is sensitive to the shape of the tip-substrate gap.

15.
J Pharmacokinet Pharmacodyn ; 45(3): 469-482, 2018 06.
Artículo en Inglés | MEDLINE | ID: mdl-29556866

RESUMEN

Modeling the relationship between drug concentrations and heart rate corrected QT interval (QTc) change from baseline (C-∆QTc), based on Phase I single ascending dose (SAD) or multiple ascending dose (MAD) studies, has been proposed as an alternative to thorough QT studies (TQT), in assessing drug-induced QT prolongation risk. The present analysis used clinical SAD, MAD and TQT study data of an experimental compound, AZD5672, to evaluate the performance of: (i) three computational platforms (linear mixed-effects modeling implemented via PROC MIXED in SAS, as well as in R using LME4 package and linear quantile mixed models (LQMM) implemented via LQMM package; (ii) different model structures with and without treatment- or time-specific intercepts; and (iii) three methods for calculating the confidence interval (CI) of QTc prolongation (analytical and bootstrap methods with fixed or varied geometric mean concentrations). We show that treatment- and time-specific intercepts may need to be included into C-∆QTc modeling through PROC MIXED or LME4, regardless of their statistical significance. With the intersection union test (IUT) in the TQT study as a reference for comparison, inclusion of these intercepts increased the feasibility for C-∆QTc modelling of SAD or MAD to reach the same conclusion as the IUT analysis based on TQT study. Compared to PROC MIXED or LME4, the LQMM method is less dependent on inclusion of treatment- or time-specific intercepts, and the bootstrap CI calculation methods provided higher likelihood for C-∆QTc modeling of SAD and MAD studies to reach the same conclusion as the IUT based on the TQT study.


Asunto(s)
Bencenoacetamidas/farmacología , Frecuencia Cardíaca/efectos de los fármacos , Sulfonamidas/farmacología , Intervalos de Confianza , Relación Dosis-Respuesta a Droga , Método Doble Ciego , Electrocardiografía/métodos , Femenino , Voluntarios Sanos , Humanos , Modelos Lineales , Masculino
16.
PLoS Comput Biol ; 12(2): e1004495, 2016 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-26871706

RESUMEN

Developing physiologically-based pharmacokinetic (PBPK) models for chemicals can be resource-intensive, as neither chemical-specific parameters nor in vivo pharmacokinetic data are easily available for model construction. Previously developed, well-parameterized, and thoroughly-vetted models can be a great resource for the construction of models pertaining to new chemicals. A PBPK knowledgebase was compiled and developed from existing PBPK-related articles and used to develop new models. From 2,039 PBPK-related articles published between 1977 and 2013, 307 unique chemicals were identified for use as the basis of our knowledgebase. Keywords related to species, gender, developmental stages, and organs were analyzed from the articles within the PBPK knowledgebase. A correlation matrix of the 307 chemicals in the PBPK knowledgebase was calculated based on pharmacokinetic-relevant molecular descriptors. Chemicals in the PBPK knowledgebase were ranked based on their correlation toward ethylbenzene and gefitinib. Next, multiple chemicals were selected to represent exact matches, close analogues, or non-analogues of the target case study chemicals. Parameters, equations, or experimental data relevant to existing models for these chemicals and their analogues were used to construct new models, and model predictions were compared to observed values. This compiled knowledgebase provides a chemical structure-based approach for identifying PBPK models relevant to other chemical entities. Using suitable correlation metrics, we demonstrated that models of chemical analogues in the PBPK knowledgebase can guide the construction of PBPK models for other chemicals.


Asunto(s)
Modelos Biológicos , Preparaciones Farmacéuticas/metabolismo , Farmacocinética , Animales , Biología Computacional , Humanos , Bases del Conocimiento , Ratones , Ratas , Porcinos
17.
Angew Chem Int Ed Engl ; 56(39): 11769-11773, 2017 09 18.
Artículo en Inglés | MEDLINE | ID: mdl-28727903

RESUMEN

Atomic-scale mechanochemistry is realized from force exerted by a C60 -functionalized scanning tunneling microscope tip. Two conformers of tin phthalocyanine can be prepared on coinage-metal surfaces. A transition between these conformers is induced on Cu(111) and Ag(100). Density-functional calculations reveal details of this reaction. Because of the large energy barrier of the reaction and the strong interaction of SnPc with Cu(111), the process cannot be achieved by electrical means.

18.
Phys Rev Lett ; 116(2): 027201, 2016 Jan 15.
Artículo en Inglés | MEDLINE | ID: mdl-26824562

RESUMEN

All-trans-retinoic acid (ReA), a closed-shell organic molecule comprising only C, H, and O atoms, is investigated on a Au(111) substrate using scanning tunneling microscopy and spectroscopy. In dense arrays single ReA molecules are switched to a number of states, three of which carry a localized spin as evidenced by conductance spectroscopy in high magnetic fields. The spin of a single molecule may be reversibly switched on and off without affecting its neighbors. We suggest that ReA on Au is readily converted to a radical by the abstraction of an electron.

19.
Environ Sci Technol ; 50(11): 5961-71, 2016 06 07.
Artículo en Inglés | MEDLINE | ID: mdl-27124219

RESUMEN

The toxicity-testing paradigm has evolved to include high-throughput (HT) methods for addressing the increasing need to screen hundreds to thousands of chemicals rapidly. Approaches that involve in vitro screening assays, in silico predictions of exposure concentrations, and pharmacokinetic (PK) characteristics provide the foundation for HT risk prioritization. Underlying uncertainties in predicted exposure concentrations or PK behaviors can significantly influence the prioritization of chemicals, though the impact of such influences is unclear. In the current study, a framework was developed to incorporate absorbed doses, PK properties, and in vitro dose-response data into a PK/pharmacodynamic (PD) model to allow for placement of chemicals into discrete priority bins. Literature-reported or predicted values for clearance rates and absorbed doses were used in the PK/PD model to evaluate the impact of their uncertainties on chemical prioritization. Scenarios using predicted absorbed doses resulted in a larger number of bin misassignments than those scenarios using predicted clearance rates, when comparing to bin placement using literature-reported values. Sensitivity of parameters on the model output of toxicological activity was examined across possible ranges for those parameters to provide insight into how uncertainty in their predicted values might impact uncertainty in activity.


Asunto(s)
Simulación por Computador , Pruebas de Toxicidad , Humanos , Cinética , Modelos Teóricos , Incertidumbre
20.
Nano Lett ; 15(8): 5229-34, 2015 Aug 12.
Artículo en Inglés | MEDLINE | ID: mdl-26151091

RESUMEN

Low-dimensional electronic and glassy phononic transport are two important ingredients of highly efficient thermoelectric materials, from which two branches of thermoelectric research have emerged. One focuses on controlling electronic transport in the low dimension, while the other focuses on multiscale phonon engineering in the bulk. Recent work has benefited much from combining these two approaches, e.g., phonon engineering in low-dimensional materials. Here we propose to employ the low-dimensional electronic structure in bulk phonon-glass crystals as an alternative way to increase the thermoelectric efficiency. Through first-principles electronic structure calculations and classical molecular dynamics simulations, we show that the π-π-stacking bis(dithienothiophene) molecular crystal is a natural candidate for such an approach. This is determined by the nature of its chemical bonding. Without any optimization of the material parameters, we obtained a maximum room-temperature figure of merit, ZT, of 1.48 at optimal doping, thus validating our idea.

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