Density functional theory study on ion adsorption and electroosmotic flow in a membrane with charged cylindrical pores†

ABSTRACT

Ion adsorption and electroosmotic flow induced by an external electric field have a variety of practical applications, especially for membrane technology. In this work, a partially perturbative density functional theory (DFT) based on the modified fundamental measure theory was applied to investigate the ion density distributions and partitions in a charged cylindrical pore. Different types of electrolyte solutions, including both charge symmetric and asymmetric, were examined using the proposed theory with various pore diameters, bulk densities, ion valencies and surface charge densities. The ion concentration profiles calculated with the theory exhibit good agreements with the results of the Monte Carlo simulations, while the results of the Poisson–Boltzmann equation deviate greatly especially for the high valence electrolytes in narrow cylindrical pores. Some interesting phenomena discovered in both experiments and simulations, such as the reverse distribution of the ions and charge inversion, can be well reproduced with the DFT. Based on the ion concentration distributions obtained from the DFT, the transient velocity profiles of the electroosmotic flow in the charged cylindrical nanopores were calculated with the Navier–Stokes (NS) equation. The characteristics of the electroosmotic flow were discussed under the different bulk electrolyte concentrations and thickness of the electric double layer inside the nanopore. The enhancement of the velocity near the pore wall, which cannot be described by the traditional theory, was well characterised by the DFT combined with the NS equation.     

Neutral beam sputtering of positive ion clusters from alkali halides

Neutral argon atom beams of 15 keV energy have been used to sputter alkali halides and the ejected positive ions have been analysed in energy, mass and angular distribution.

The use of a neutral beam, rather than an ion beam, minimizes surface charge and the deflection of ejected ions by electrostatic interaction with a charged incident beam.

A cluster component of the form K₂Cl⁺, K₃Cl⁺ ₂ and higher members of the series is found for all alkali halides studied.     

Water Transport through Multinanopores Membranes

We investigate the influence of correlation between water molecules transport through the neighbouring nanopores, whose centres are at a distance of only 6.2A, using the molecular dynamics simulations. Water molecule distribution in nanopore and average water flow are obtained. It is found that the average water molecule number and water flow are slightly different between a system made of the neighbouring nanopores and a system of a single pore. This indicates that transport of water chains in neighbouring pores do no show significant influence each other. These findings should be helpful in designing efficient artificial membrane made of nanopores and providing an insight into effects of the biological channel structure on the water permeation.     

Size and stability of liposomes: A possible role of hydration and osmotic forces

Dynamic light scattering and electrophoretic mobility measurements have been used to characterize the size, size distribution and zeta potentials (ζ-potentials) of egg yolk phosphatidylcholine (EYPC) liposomes in the presence of monovalent ions ( Na⁺ and K⁺). To study the stability of liposomes the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory has been extended by introducing the hydrated radius of the adsorbed ions onto the liposome surfaces. The decrease of liposome size is explained on the basis of the membrane impermeability to some ions which generate osmotic forces, which leads to evacuate water from liposome inside.     

Artificial Modulation of Ferroelectric Thin Films into Antiferroelectric through H+ Implantation for High-Density Charge Storage

Hydrogen ions are implanted into Pb（Zro.3Tio.7）03 1014 ions/cm^2. Pseudo-antiferroelectric behaviour in thin films at the energy of 40keV with a flux of 5 x the implanted thin films is observed, as confirmed by the measurements of polarization versus electric hysteresis loops and capacitance versus voltage curves. X-ray diffrac- tion patterns show the film structures before and after H＋ implantation both to be perovskite of a tetragonal symmetry. These findings indicate that hydrogen ions exist as stable dopants within the films. It is believed that the dopants change domain-switching behaviour via the boundary charge compensation. Meanwhile, time dependence of leakage current density after time longer than lOs indicates the enhancement of the leakage cur- rent nearly in one order for the implanted film, but the current at time shorter than i s is mostly the same as that of the original film without the ionic implantation. The artificial tailoring of the antiferroelectric behaviour through H＋ implantation in ferroelectric thin films is finally proven to be achievable for the device application of high-density charge storage.     

Infrared intensities of ion-water interactions in aqueous electrolyte solutions

The i.r. absorption intensities have been measured of the fundamental vibrations of water molecules in metal halide aqueous solutions. Pseudo-isosbestic points were observed in the regions of both the stretching and bending vibrations and interpreted in terms of two states of water molecules in the solutions. The intensities of the stretching vibrations of water molecules coordinated to the dissolved ions have been estimated. The intensities become stronger in the order, Li⁺ > Na⁺ > K⁺ for the cations and F^- > Cl^- > Br^- > I^- for the anions. These orders are consistent with the strengths of the ion-water interactions, which are related to the dynamical behavior of the water molecules in the primary hydration shell.     

Structural Deformation of CO22+ in Intense Femtosecond Laser Fields

The angular distributions of CO^＋ from the dissociation of CO2^2＋ and CO2^＋ in intense femtosecond laser fields （45 fs, about 5 × 10^15 W/cm^2） are studied at a laser wavelength of 800nm based on the time-of-flight mass spectra of CO^＋ fragment ions. The experimental results show that structural deformation occurs in the charge state of CO2^2＋ and the CO^＋ maintains linear geometrical structure.     

Ionizing Dose Effect of Thermal Oxides Implanted with Si^＋ Ions

Total ionizing dose effects of Si^＋ ion implanted thermal oxides are studied by 10keV x-ray irradiation. Photoluminescence （PL） method is engaged to investigate nanostructures of samples. Ar^＋ implanted samples are also studied by the same way to provide a comparison. The results show that Si^＋ implantation following with high temperature annealing can significantly reduce the radiation induced flatband shift, which is caused by net posi- tive charge accumulation in oxides. This reduction is attributed to the formation of Si nanoscale structures. Ar^＋ implantation is also found to reduce the radiation induced flatband shift, while it is different that the reduction with Si^＋ implantation shows little dependence on implant dose of Ar^＋ ions. This is explained by possible increase of recombination centres.     

Observation of Nano-Dots on HOPG Surface Induced by Highly Charged Arq+ Impact

Highly charged ions （HCIs） have huge potential energy due to their high charge state. When a HCI reaches a solid surface, its potential energy is released immediately on the surface to cause a nano-scale defect. Thus, HCIs are expected to be useful for solid-surface modifications on the nano-scale. We investigate the defects on a highly oriented pyrolytic graphite （HOPG） surface induced by slow highly charged Ar^q＋ ions with impact energy of 20-2000qeV with scanning probe microscopy （SPM）. In order to clarify the role of kinetic and potential energies in surface modification, the nano-defects are characterized in lateral size and height corresponding to the kinetic energy and charge state of the HCIs. Both the potential energy and kinetic energy of the ions may influence the size of nano-defect. Since potential energy increases dramatically with increasing charge state, the potential energy effect is expected to be much larger than the kinetic energy effect in the case of extremely high charge states. This implies that pure surface modification on the nano-scale could be carried out by slow highly charged ions. The mean size of nano-defect region could also be controlled by selecting the charge state and kinetic energy of HCI.     

Secondary Collision and the Enhancement of the K+π+ Ratio in the High Energy Heavy-ion Collision

The enhancement of K⁺/π⁺ ratio in the high energy heavy-ion collision is believed to be a possible signature of the quark gluon plasma.Based on the Participant Nucleon Model and the concept of the formation time of secondary particles,the K⁺/π⁺ ratio in the central collision of Si(14.5GeV/c) and Au are calculated by Monte Carlo simulation.The following secondary collisions are considered.πN→K⁺Y、ππ→KK and the single charge exchange reaction between pions and nucleons.The calculation results show that the increased K⁺/π⁺ ratio caused by these secondary collisions is not enough to explain the experimental data observed by the E802 group at BNL.     

Diffusion of ions in supercritical water: Dependence on ion size and solvent density and roles of voids and necks

We have performed molecular dynamics simulations of alkali metal (Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺) and halide (F⁻, Cl⁻, Br⁻, I⁻) ions in supercritical water at 673 K. The calculations were done for water at three different densities of 1.0, 0.7 and 0.35 g cm⁻³ to investigate the effects of solute size on the diffusion of ions in supercritical water. On increase of ion size, we observe a maximum for diffusion of ions in supercritical water of higher densities (1.0 and 0.7 g cm⁻³). However, no such maximum is found for ion diffusion in the supercritical water of low density (0.35 g cm⁻³) or for diffusion of neutral solutes at all densities. These results are analyzed in terms of passage through voids and necks present in supercritical water. Correlations of the observed diffusion behavior with the sizes of ions and voids present in the systems are discussed.     

The study of B→K(*)l+l- decays in family non-universal Z' models

In a combined investigation of B→K^(*)l⁺l^- decays, constraints on the related couplings in family non-universal Z' models are derived. We find that within the allowed parameter space, the recently observed forward-backward asymmetry in the B→K^(*)l⁺l^- decay can be explained by flipping the signs of the Wilson coefficients C₉^eff and C₁₀. With the obtained constraints, we also calculate the branching ratio of the B_s→μ⁺μ^- decay. The upper bound of our prediction is nearly an order of magnitude smaller than the upper bound given by the CDF Collaboration recently.     

D0-MESON DECAYS Γ（D0→K+K-）/Γ（D0→π+π-）

In this paper the nonleptonic D⁰-decays are discussed. Using Gilman and Wise's methods, we derived the effective Hamiltonian for Cabibbo-suppressed nonleptonic D^0*-decays. The rate F(D⁰→K⁺K^-)/Γ(D⁰→π⁺π^-)～1.26 is obtained. Some problems in this method of the calculations are discussed roughly.     

Molecular understanding of osmosis in semipermeable membranes

We investigate single-file osmosis of water through a semipermeable membrane with an uncharged, a positively and a negatively charged nanopore. Molecular dynamics simulations indicate that the osmotic flux through a negatively charged pore (J_) is higher compared to the osmotic flux in a positively charged pore (J+) followed by the osmotic flux in the uncharged pore (J(0)), i.e., J_ > J+ > J(0). The molecular mechanisms governing osmosis, steady state osmosis, and the observed osmotic flux dependence on the nanopore charge are explained by computing all the molecular interactions involved and identifying the molecular interactions that play an important role during and after osmosis. This study helps in a fundamental understanding of osmosis and in the design of advanced nanoporous membranes for various applications of osmosis.     

Analysis of Bs→φμ+μ- decay within supersymmetry

Motivated by the rst measurement on B(B_s→φμ⁺μ^-) by the CDF Collaboration, we study the supersymmetric e ects in semi-leptonic B_s→φμ⁺μ^- decay. In our evaluations, we analyze the dependences of the dimuon invariant mass spectrum and the forward-backward asymmetry on relevant supersymmetric couplings in the MSSM with and without R-parity. The analyses show that the new experimental upper limits of B(B_s→φμ⁺μ^-)from the LHCb Collaboration could further improve the bounds on sneutrino exchange couplings and (δ_LL^u)₂₃ as well as (δ_LL,RR^u)₂₃ mass insertion couplings. In addition, within the allowed ranges of relevant couplings under the constraints from B(B_s→φμ⁺μ^-), B(B→K^(*)μ⁺μ^-) and (B_s→φμ⁺μ^-), the dimuon forward-backward asymmetry and the di erential dimuon forward-backward asymmetry of B_s→φμ⁺μ^-are highly sensitive to the squark exchange contribution and the (δ_LL^u)₂₃ mass insertion contribution. The results obtained in this work will be very useful in searching for supersymmetric signals at the LHC.     

Luminescent Characteristics of LiSrBO3：Eu3＋ Phosphor for White Light Emitting Diode

LiSrBO3 ：Eu3＋ phosphor is synthesized by a high solid-state reaction method, and its luminescent characteristics are investigated. The emission and excitation spectra of LiSrBO3：Eu3＋ phosphors exhibit that the phosphors can be effectively excited by near ultraviolet （401 nm） and blue （471 nm） light, and emit 615nm red light. The effect of Eua＋ concentration on the emission spectrum of LiSrBO3：Eu3＋ phosphor is studied; the results show that the emission intensity increases with increasing Eu3＋ concentration, and then decreases because of concentration quenching. It reaches the maximum at 3mol%, and the concentration self-quenching mechanism is the dipoledipole interaction according to the Dexter theory. Under the conditions of charge compensation Li＋, Na＋ or K＋ incorporated in LiSrBO3, the luminescent intensities of LiSrBO3 ：Eua＋ phosphor are enhanced.     

Single-Walled Carbon Nanotubes Acting as Controllable Transport Channels

The motion and equilibrium distribution of water molecules adsorbed inside neutral and negatively charged singlewalled carbon nanotubes (SWNTs) have been studied using molecular dynamics simulations (MDSs) at room temperature based on CHARMM (Chemistry at HARvard Molecular Mechanics) potential parameters. We find that water molecules have a conspicuous electropism phenomenon and regular tubule patterns inside and outside the charged tube wall. The analyses of the motion behaviour of water molecules in the radial and axial directions show that by charging the SWNT, the adsorption efficiency is greatly enhanced, and the electric field produced by the charged SWNTs prevents water molecules from flowing out of the nanotube. However, water molecules can travel through the neutral SWNT in a fluctuating manner. This indicates that by electrically charging and uncharging the SWNTs, one can control the adsorption and transport behaviour of polar molecules in SWNTs for using as a stable storage medium or long transport channels. The transport velocity can be tailored by changing the charge on the SWNTs, which may have a further application as modulatable transport channels.     

Search for the Decays D+→φe+ν,D+→φK－π+e+ν,D0→φK－e+νand D0→φK－μ+ν

We report the results of a search for the semileptonic decays D⁺→e⁺ν,D⁺→K^－π⁺e⁺ν,D⁰→K^－e⁺ν and D⁰→K^－μ⁺ν using the BES detector at the BEPC e⁺e^－ Collider. Using a data sample of 22.3pb^－1 collected at the center of mass energy s=4.03GeV, we select 2472±87D 0 tag DX and 7628±149D 0 tag DX singly tagged D events, where the X could be γ, π 0 and/or π^±. Based on the method of "combined D⁺and D⁰ single and double tags", we determine that 2471±218 D⁺X and 7629±251 D⁰ X are contained in the recoil side of the singly tagged neutral and charged D mesons, respectively. No events for the 4 semileptonic decay modes are observed in the recoil side of the tagged D mesons. The 90% confidence level upper limits of B(D⁺→e⁺ν)<1.38%,B(D⁺→K^－π⁺e⁺ν)<2.01%,B(D⁰→K^－e⁺ν)<0.53% and B(D⁰→K^－μ⁺ν)<0.53% are determined from the search for the semileptonic decays of D⁺ and D⁰.     

Hofmeister series and ionic effects of alkali metal ions on DNA conformation transition in normal and less polarised water solvent

Normal and less polarised water models are used as the solvent to investigate Hofmeister effects and alkali metal ionic effects on dodecamer d(CGCGAATTCGCG) B-DNA with atomic dynamics simulations. As normal water solvent is replaced by less polarised water, the Hofmeister series of alkali metal ions is changed from Li⁺ > Na⁺ ? K⁺ ? Cs⁺ ? Rb⁺ to Li⁺ > Na⁺ > K⁺ > Rb⁺ > Cs⁺. In less polarised water, DNA experiences the B→A conformational transition for the lighter alkali metal counterions (Li⁺, Na⁺ and K⁺). However, it keeps B form for the heavier ions (Rb⁺ and Cs⁺). We find that the underlying cause of the conformation transition for these alkali metal ions except K⁺ is the competition between water molecules and counterions coupling to the free oxygen atoms of the phosphate groups. For K⁺ ions, the ‘economics’ of phosphate hydration and ‘spine of hydration’ are both concerned with the DNA helixes changing.