Numerical simulation of Monte Carlo ion transport at atmospheric pressure within improved air amplifier geometry

A computational fluid dynamics (CFD) software package ANSYS Fluent was employed for simulation of ion transport at atmospheric pressure between a nano-electrospray ionization (nano-ESI) emitter and the mass spectrometer (MS) sampling inlet tube inside an improved air amplifier device incorporating a radiofrequency ion funnel. The flow field, electric field and the ion trajectory calculations were carried out in separate steps. Parallelized user-defined functions were written to accommodate the additional static and transient electric fields and the elastic ion-gas collisions with the Monte Carlo hard-sphere simulation abilities within Fluent’s environment. The ion transmission efficiency from a nano-ESI emitter to the MS sampling inlet was evaluated for different air amplifier and ion funnel operating conditions by tracking 250 sample reserpine ions. Results show that the high velocity gas stream and the external electric field cause a rapid acceleration of the ion beam and its dispersion along the centreline of the air amplifier which leads to reduction of the space-charge effect and the beam divergence. The radiofrequency potential applied to the ion funnel contributed to additional ion focusing.     

Experimental and simulation investigation of ion transfer in different sampling capillaries

Atmospheric pressure interfaces were a fundamental structure for transferring air generated ions into the vacuum manifold of a mass spectrometer. This work is devoted to the characterization of ion transfer in metal capillaries through both experimental and simulated investigations. The impact of capillary configurations on ion transmission efficiency was evaluated using an electrospray mass spectrometer with various bent capillaries as the transfer devices. In addition, a numerical model has been set up by coupling the SIMION 8.0 and the computational flow dynamics for simulation study of ion migration in the complex atmospheric system. The transfer efficiency was found to be highly affected by the variation in electric field and the capillary geometry, revealing that the hydrodynamic and electric force were both dominant and interactional during the transmission process. The consistency of the results from the experimental analysis and simulation modeling proved the validity of the model, which was helpful for understanding ion activity in transfer capillaries. Copyright © 2015 John Wiley & Sons, Ltd.     

Electric field-controlled water permeation coupled to ion transport through a nanopore

We report molecular dynamics simulations of a generic hydrophobic nanopore connecting two reservoirs which are initially at different Na(+) concentrations, as in a biological cell. The nanopore is impermeable to water under equilibrium conditions, but the strong electric field caused by the ionic concentration gradient drives water molecules in. The density and structure of water in the pore are highly field dependent. In a typical simulation run, we observe a succession of cation passages through the pore, characterized by approximately bulk mobility. These ion passages reduce the electric field, until the pore empties of water and closes to further ion transport, thus providing a possible mechanism for biological ion channel gating.     

Magnetic relaxation dispersion of lithium ion in solutions of DNA

The magnetic field dependence of the nuclear spin-lattice relaxation rate constant defines the magnetic relaxation dispersion (MRD) and provides a direct characterization of the molecular dynamics that cause fluctuations in the magnetic couplings in the system and may also indicate the dimensional constraints on the motion. The counterion cloud surrounding a linear polyelectrolyte ion, such as DNA in solution, provides an interesting opportunity for ion confinement that helps in understanding the thermodynamics and the dynamics of the interactions between the polyion and other solutes. The MRD profiles of lithium ion and tetramethylammonium ion were recorded in dilute aqueous solutions of native calf thymus DNA, which provides a long, charged rod that reorients slowly. The 7Li ion relaxes through the nuclear electric quadrupole coupling and the proton-lithium dipole-dipole coupling; the protons of the tetramethylammonium ion relax by dipole-dipole coupling. MRD profiles of the 7Li+ ion are dominated by transient interactions with the DNA that yield a linear dependence of the spin-lattice relaxation rate constant on the logarithm of the Larmor frequency. This magnetic field dependence is consistent with diffusive ion motions that modulate two spatial coordinates that characterize the relaxation couplings in the vicinity of the polyion. Motions around the rod and fluctuations in the ion distance from the rod are consistent with these constraints for lithium. The magnetic field dependence of the tetramethylammonium ion proton relaxation rate constant is weak, but also approximately a linear function of the logarithm of the Larmor frequency, which implies that the field dependence is caused in part by local order in the DNA solution.     

Mechanical actuation of ion channels using a piezoelectric planar patch clamp system

High-throughput screening of ion channels is now possible with the advent of the planar patch clamp system. This system drastically increases the number of ion channels that can be studied, as multiple ion channel experiments can now be conducted in parallel. However, due to tedious, usually pressure-driven mechanotransduction techniques, there has been a slow integration of this technology into the field of mechanosensitive ion channels. By implementing a piezoelectric quartz substrate into a planar patch clamp system, we show that the patch clamp substrate itself can be used to mechanically actuate ion channels. The piezoelectric substrate transduces an external, applied electric field into a mechanical tension, so precise actuation of the membrane can be accomplished. By applying this electric field only to the outer edges of the substrate, no ulterior electric field is created in the vicinity of the membrane during actuation. Further, with resonant frequencies ranging from 1 kHz to 200 MHz, quartz substrates can be used to apply a wide range of time-varying tensions to cell membranes. This will allow for new and instructive investigations into the dynamic mechanotransductive properties of ion channels.     

Monte Carlo simulation of ion transport in non-linear ion mobility spectrometry

A program for Monte Carlo simulation of ion transport in non-linear ion mobility spectrometry, also known as field asymmetric ion mobility spectrometry (FAIMS) or differential mobility spectrometry (DMS), has been developed. Simulations are based on elastic collisions between the ions and the gas particles, and take into account the effects of flow dynamics and asymmetric electric fields. Using this program, the separation and diffusion of the ions moving in a planar DMS filtration gap are demonstrated. Ion focusing in a cylindrical filtration gap is also confirmed. A characteristic compensation voltage is found to provide insight for understanding separation in non-linear ion mobility spectrometry. The simulation program is used to study the characteristics of non-linear ion mobility spectrometry, the effect of the carrier gas flow, and the dependence of the compensation voltage and nonlinear mobility coefficient (α) on the applied asymmetric electric field.     

Effects of disordered interchain interactions on polaron dynamics in semiconducting polymers

Polaron dynamics in a system of two randomly coupled polymer chains is simulated using a nonadiabatic evolution method. The simulations are performed within the framework of the Su-Schrieffer-Heeger model modified to include disordered interchain interactions and an external electric field. By analysing the polaron velocity statistically, we find that the polaron motion is determined by the competition between the electric field and the disordered interchain interactions. Polaron dynamics are classified into two types, weak-coupling dynamics and strong-coupling dynamics. It is found that the strength of interchain interactions is the dominant factor controlling charge propagation in weak-coupling dynamics, whereas the effects of disorder are dominant in strong-coupling dynamics. The charge carriers tend to have higher mobility for stronger interchain coupling, and interchain coupling disorder can be favorable for charge transport depending on the coupling strength and the electric field.     

迁移管的电场强度对真空紫外电离-离子迁移谱仪性能的影响

离子迁移管是离子迁移谱仪的核心部分,它用来产生均匀的电场,以使不同迁移率的离子进行分离。本研究以丙酮为例,详细研究了本课题组所研制的真空紫外电离源-离子迁移谱仪中迁移管的电场参数对离子的灵敏度和分辨率的影响,发现电压的增大灵敏度增大,但是分辨率存在一个最佳的电压,这些结果可用于迁移谱的优化设计。     

The role of external electric fields in enhancing ion mobility, drift velocity, and drift-diffusion rates in aqueous electrolyte solutions

Molecular simulations have been carried out using the method of molecular dynamics to investigate the role of external electric fields on the ion mobility, drift velocity, and drift-diffusion rate of ions in aqueous electrolyte solutions. These properties are critical for a range of processes including electrodialysis, electro-deionization, electrophoresis, and electroosmosis. Our results show that external electric fields relax the hydrated ion structure at significantly larger time scales (between 300 and 800 ps), than most other relaxation processes in solutions (generally of the order of 1 ps). Previous studies that did not account for the much longer relaxation times did not observe this behavior for ions even with very high electric fields. External electric fields must also overcome several (at least two or more) activation energy barriers to significantly change the structure of hydrated ions. As a result, the dynamic behavior changes almost in bands as a function of electric field strengths, rather than linearly. Finally, the effect of the field is much less dramatic on water than the ions. Thus electric fields will be of more significance in processes that involve the transport of ions (such as electro-deionization) than the transport of water (electroosmosis).     

Electroconvective dendrites in nematic phases having short range smectic order exhibited by the 4,n-alkoxybenzoic acids

Electroconvective (EC) dendrites (parabolic type) in nematic (N) liquid crystals with short range smectic order shown by 4,n-octyloxybenzoic acid (8-OBA) were observed. The driving of the dendrites by lateral d.c. and a.c. electric field parameters in the nematic temperature range was carried out. The dynamics of dendrite growth were studied and analysed by the Ivantsov two-dimensional solution for the diffusion equation. Using various combinations of blocked and unblocked electrodes, we studied dependences between the dimensionless electric field parameter and product of the dendrite parabolic radius and the velocity of the dendrite growth and found that the type of electrode significantly modifies these basic dependences. We attribute this effect possibly to the opposing ion propagation, i.e. gradient of electric field in direction opposite to that of the charge injection. A possible mechanism of EC dendrite growth is suggested. A comparison with thermal dendrites in liquid crystals is presented.     

Experimental study of electric effects in multispecies ion-exchange kinetics

The model of internal diffusion kinetics developed previously that takes into account the macroscopic nature of the electric field occurring in the transient processes of multispecies ion exchange (MIE) was applied to carrying out experiments on the detection of this field. The electric effects of MIE are detected by weak electric fields amplified through a reversible avalanche breakthrough of coions into the ion exchanger. This breakthrough occurs when the Donnan potential at the interface is neutralized for a short time. A setup is designed for experimental studies of the electric effects of multispecies ion exchange. The setup consists of an ion-exchange membrane separating three flow chambers and the measuring circuit of a differential potentiometer. The conditions under which some effects are observed were analyzed. The following effects were observed experimentally: a breakdown of the ground state of the system when a trace component is added, autooscillations of the membrane potential, a sensitive and selective response of the system to the added trace component, and a series of potential peaks as a response to a mixture of ions added     

Ion mobility spectrometer—field asymmetric ion mobility spectrometer-mass spectrometry

Since the development of electrospray ionization (ESI) for ion mobility spectrometry mass spectrometry (IMMS), IMMS have been extensively applied for characterization of gas-phase bio-molecules. Conventional ion mobility spectrometry (IMS), defined as drift tube IMS (DT-IMS), is typically a stacked ring design that utilizes a low electric field gradient. Field asymmetric ion mobility spectrometry (FAIMS) is a newer version of IMS, however, the geometry of the system is significantly different than DT-IMS and data are collected using a much higher electric field. Here we report construction of a novel ambient pressure dual gate DT-IMS coupled with a FAIMS system and then coupled to a quadrupole ion trap mass spectrometer (QITMS) to form a hybrid three-dimensional separation instrument, DT-IMS-FAIMS-QITMS. The DT-IMS was operated at ~3 Townsend (electric field/number density (E/N) or (Td)) and was coupled in series with a FAIMS, operated at ~80 Td. Ions were mobility-selected by the dual gate DT-IMS into the FAIMS and from the FAIMS the ions were detected by the QITMS for as either MS or MSⁿ. The system was evaluated using cocaine as an analytical standard and tested for the application of separating three isomeric tri-peptides: tyrosine-glycine-tryptophan (YGW), tryptophan-glycine-tyrosine (WGY) and tyrosine-tryptophan-glycine (YWG). All three tri-peptides were separated in the DT-IMS dimension and each had one mobility peak. The samples were partially separated in the FAIMS dimension but two conformation peaks were detected for the YWG sample while YGW and WGY produced only one peak. Ion validation was achieved for all three samples using QITMS.     

周期性变电场下熔体静电纺丝射流的介观模拟

利用介观模拟的耗散粒子动力学法, 对纺丝射流稳定直线段区域进行变电场模拟, 并以三维的射流路径呈现出来. 研究了不同控制频率下的变电场对聚合物分子链的运动情况、 射流直径及下落行为的影响. 结果表明, 与稳定电场相比, 周期性改变电场能够有效提高分子链的拉伸, 使射流直径减小, 较低的控制频率能够加速射流的下落, 从而获得较细的纤维.     

分子动力学模拟研究纳米碳管中甲醇-水混合溶液的结构与输运性质

利用分子动力学模拟方法,对比考察了平衡条件、外压作用、梯度电场作用下,摩尔比为1:1的甲醇-水混合溶液在纳米碳管(CNT)中的静态结构以及输运行为.研究发现:在平衡体系与外压作用下,纳米碳管内甲醇与水呈现出明显的不混溶现象,甲醇主要分布于管壁附近,水分子主要分布于纳米碳管轴心附近;而在梯度电场作用下,纳米碳管由疏水性向亲水性转变,更多的水分子分布于管壁,导致纳米碳管内甲醇-水的不混溶现象消失.另一方面,在外压作用下,纳米碳管内甲醇与水呈现单向移动;而在梯度电场下,甲醇与水呈现快速的双向移动,其流通量较相应外压作用体系高出近一个数量级,但由于双向的流通量大小相近,导致净流通量与外压作用下的净流通量差异不大.     

Solvent reorganization in electron and ion transfer reactions near a smooth electrified surface: a molecular dynamics study

Molecular dynamics simulations of electron and ion transfer reactions near a smooth surface are presented, analyzing the effect of the geometrical constraint of the surface and the interfacial electric field on the relevant solvation properties of both a monovalent negative ion and a neutral atom. The simulations show that, from the solvation point of view, ion adsorption is an uphill process due to the need to shed off the ion's solvation shell and displace water from the surface. Atom adsorption, on the other hand, has only a small barrier, related to the molecularity of the solvent. Both the electrostatic interaction of the ion with the solvent and the ion's solvent reorganization energy (the relevant parameter in the Marcus electron transfer theory) decrease as the surface is approached, whereas these parameters are not sensitive to the distance from the surface for the atom. This is a consequence of the importance of long-range electrostatic interactions for ion solvation and the importance of short-range interactions for atom solvation. The electric field either attracts or repels an ion to or from the surface, but the field has no influence on the solvent reorganization energy. By including the quantum-mechanical electron transfer between the metal surface and the ion/atom in solution in the MD simulation by using a model Hamiltonian, we calculated two-dimensional free energy surfaces for ion adsorption allowing for partial charge transfer, based on a fully molecular picture of ion solvation near the surface.     

Ionic Polymerization under an Electric Field as a Relaxational Method for the Investigation of Kinetics. I. On Results of the Change in Space Distribution of Ions

Abstract

Investigations were made which show that the change in the dynamics of polymerization and in molecular weight of the polymer under an electric field is connected with the redistribution of the ions growing macromolecules and counterions. Analysis of the equations obtained showed that the field can either increase or decrease the rate of the process. The effect's trend and magnitude depend on the ratio of the mobilities of macroions and counterions, degree of dissociation of active centers, and the ratio of rate constants of free ions and ion pairs. An analysis of literature data relevant to polymerization under an electric field was made.     

分子动力学模拟研究纳米碳管中甲醇-水混合溶液的结构与输运性质

利用分子动力学模拟方法,对比考察了平衡条件、外压作用、梯度电场作用下,摩尔比为1：1 的甲醇-水混合溶液在纳米碳管（CNT）中的静态结构以及输运行为. 研究发现：在平衡体系与外压作用下,纳米碳管内甲醇与水呈现出明显的不混溶现象,甲醇主要分布于管壁附近,水分子主要分布于纳米碳管轴心附近;而在梯度电场作用下,纳米碳管由疏水性向亲水性转变,更多的水分子分布于管壁,导致纳米碳管内甲醇-水的不混溶现象消失. 另一方面,在外压作用下,纳米碳管内甲醇与水呈现单向移动;而在梯度电场下,甲醇与水呈现快速的双向移动,其流通量较相应外压作用体系高出近一个数量级,但由于双向的流通量大小相近,导致净流通量与外压作用下的净流通量差异不大.     

Direct measurement of ion accumulation at the electrode electrolyte interface under an oscillatory electric field

The ionic charge accumulation at the metal-electrolyte interface is directly measured by using differential interferometry as a function of magnitude and frequency (2-50 kHz) of external electric field. The technique developed probes the ion dynamics confined to the electrical double layer. The amplitude of modulation of the ions is linearly proportional to the amplitude of applied potential. The linearity is observed up to high electrode potentials and salt concentrations. The frequency response of the ion dynamics at the interface is interpreted in terms of the classical RC model.     

Predicting ion concentration polarization and analyte stacking/focusing at nanofluidic interfaces

We report on the investigation of electropreconcentration phenomena in micro-/nanofluidic devices integrating 100 μm long nanochannels using 2D COMSOL simulations based on the coupled Poisson–Nernst–Planck and Navier–Stokes system of equations. Our numerical model is used to demonstrate the influence of key governing parameters such as electrolyte concentration, surface charge density, and applied axial electric field on ion concentration polarization (ICP) dynamics in our system. Under sufficiently extreme surface-charge-governed transport conditions, ICP propagation is shown to enable various transient and stationary stacking and counter-flow gradient focusing mechanisms of anionic analytes. We resolve these spatiotemporal dynamics of analytes and electrolyte ICP over disparate time and length scales, and confirm previous findings that the greatest enhancement is observed when a system is tuned for analyte focusing at the charge, excluding microchannel, nanochannel electrical double layer (EDL) interface. Moreover, we demonstrate that such tuning can readily be achieved by including additional nanochannels oriented parallel to the electric field between two microchannels, effectively increasing the overall perm-selectivity and leading to enhanced focusing at the EDL interfaces. This approach shows promise in providing added control over the extent of ICP in electrokinetic systems, particularly under circumstances in which relatively weak ICP effects are observed using only a single channel.