RESUMO
We describe a hybrid mass-mobility instrument in which a continuous-flow ion mobility classifier is used as a front-end separation device for mass spectrometric analysis of ions generated with an electrospray ionization source. Using nitrogen as a carrier gas, the resolving power of the nano-radial differential mobility analyzer (nRDMA) for nanometer-sized ions is 5-7 for tetraalkylammonium ions. Data are presented demonstrating the ability of the system to resolve the different aggregation and charge states of tetraalkylammonium ions and protonated peptides using a quadrupole ion trap (QIT) mass spectrometer to analyze the mobility-classified ions. Specifically, data are presented for the two charge states of the decapeptide Gramicidin S. A key feature of the new instrument is the ability to continuously transmit ions with specific mobilities to the mass spectrometer for manipulation and analysis.
Assuntos
Análise de Injeção de Fluxo , Nanoestruturas/análise , Compostos de Amônio Quaternário/análise , Análise de Injeção de Fluxo/instrumentação , Radicais Livres/análise , Nitrogênio/química , Tamanho da Partícula , Espectrometria de Massas por Ionização por Electrospray/instrumentação , Propriedades de SuperfícieRESUMO
We present a reactive empirical potential with environment-dependent bond strengths for the carbon-oxygen (CO) system. The distinct feature of the potential is the use of three adjustable parameters characterizing the bond: the strength, length, and force constant, rather than a single bond order parameter, as often employed in these types of potentials. The values of the parameters are calculated by fitting results obtained from density functional theory. The potential is tested in a simulation of oxidative unzipping of graphene sheets and carbon nanotubes. Previous higher-level theoretical predictions of graphene unzipping by adsorbed oxygen atoms are confirmed. Moreover, nanotubes with externally placed oxygen atoms are found to unzip much faster than flat graphene sheets.
RESUMO
Imaging of surfaces with carbon nanotube probes in tapping mode results frequently in complex behavior in the amplitude-distance curves monitored. Using molecular mechanics simulations, we calculate the force exerted on a nanotube pressed against a smooth surface as it undergoes deformation and buckling. This nonlinear force is then used in a macroscopic equation, describing the response of a damped harmonic oscillator, to predict the amplitude response of a nanotube AFM probe. Similarities between the prediction and experiment suggest that the complex amplitude response seen in the experiment may be explained by the nonlinearity in the force exerted on the nanotube and thus must not necessarily be related to the structure of the surface.
Assuntos
Micromanipulação/métodos , Microscopia de Força Atômica/métodos , Modelos Químicos , Modelos Moleculares , Nanotubos de Carbono/química , Nanotubos de Carbono/ultraestrutura , Simulação por Computador , Elasticidade , Teste de Materiais/métodos , Conformação Molecular , Movimento (Física) , Estresse MecânicoRESUMO
Electrowetting of carbon nanotubes by mercury was studied using classical molecular dynamics simulations in conjunction with a macroscopic electrocapillarity model. A scaled ab initio mercury dimer potential, optimized to reproduce the mercury liquid density (at 300 K), melting point, and wetting angle on graphite, was selected for the simulations. Wetting of (20,20) single-walled carbon nanotubes by mercury occurs above a threshold voltage of 2.5 V applied across the interface. Both the electrocapillary pressure and imbibition velocity increase quadratically with voltage and can acquire large values, for example, 2.4 kbar and 28 m/s at 4 V, indicating a notable driving force. The observed voltage scaling can be captured by the Lucas-Washburn equation modified to include a wetting-line friction term.
Assuntos
Eletroquímica/métodos , Mercúrio/química , Modelos Químicos , Nanotubos de Carbono/química , Ação Capilar/efeitos da radiação , Simulação por Computador , Difusão/efeitos da radiação , Campos Eletromagnéticos , Teste de Materiais/métodos , Mercúrio/efeitos da radiação , Nanotubos de Carbono/efeitos da radiação , Porosidade/efeitos da radiação , MolhabilidadeRESUMO
Pure bending of single-walled carbon nanotubes between (5,5) and (50,50) is studied using molecular dynamics based on the reactive bond order potential. Unlike smaller nanotubes, bending of (15,15) and larger ones exhibits an intermediate deformation in the transition between the buckled and fully kinked configurations. This transient bending regime is characterized by a gradual and controllable flattening of the nanotube cross section at the buckling site. Unbending of a kinked nanotube bypasses the transient bending regime, exhibiting a hysteresis due to van der Waals attraction between the tube walls at the kinked site.
RESUMO
A high-flux beam of mass-filtered F+ at low energy (100-1300 eV) was scattered off Al and Si surfaces to study core-level excitations of F0 and F+. Elastic scattering behavior for F+ was observed at energies <300 (500) eV off Al (Si) for a 90 degrees lab angle. However, above this energy threshold, orbital mixing in the hard collision step results in electronic excitation of F via molecular orbital promotion along the 4f sigma (F-2p), significantly reducing the observed ion exit energy. In addition, despite the electronegativity of F, scattering at energies >450 (700) eV off Al (Si) produces F2+-behavior which is remarkably similar to Ne+ off the same surfaces. Inelasticities measured for single collision events agree well with the energy deficits required to form (doubly excited) F** and F+** states from F0 and F+, respectively; these excited species most likely decay to inelastic F+ and F2+ via autoionization.
RESUMO
We demonstrate reversible wetting and filling of open single-wall carbon nanotubes with mercury by means of electrocapillary pressure originating from the application of a potential across an individual nanotube in contact with a mercury drop. Wetting improves the conductance in both metallic and semiconducting nanotube probes by decreasing contact resistance and forming a mercury nanowire inside the nanotube. Molecular dynamics simulations corroborate the electrocapillarity-driven filling process and provide estimates for the imbibition speed and electrocapillary pressure.