Modified infiltration of solvated ions and ionic liquid in a nanoporous carbon

Infiltration of ions in a nanoporous carbon is responsive to the external electric field. If the liquid phase is an aqueous solution of electrolyte, the effective solid-liquid interfacial tension decreases as the voltage rises, similar to the electrowetting phenomenon at a large graphite surface. If the liquid phase is an ionic liquid, however, the effective interfacial tension increases with the voltage. The accessible nanopore volume is not dependent on the electric field. The unique phenomena should be related to the confinement effects of the nanopore inner surfaces.     

Probing nanotube-nanopore interactions

We demonstrate a new nanoscale system consisting of a nanotube threaded through a nanopore in aqueous solution. Its electrical and mechanical properties are sensitive to experimentally controllable conformational changes on sub-Angstrom length scales. Ionic current transport through a nanopore is significantly suppressed by the threading nanotube and the mechanical interactions between the nanotube and pore are accounted for by a folding geometry. The experiments provide first measurements of the longitudinal resolution and metrology of a solid-state nanopore "microscope." This new nanostructure provides a means to study molecule-nanotube interactions in conducting ionic solutions as well as geometrical and surface properties of nanopores and nanotubes.     

MD模拟方法研究圆柱形纳米微孔的吸附平衡

本文用MD（分子动力学）模拟方法对圆柱形纳米微孔中的Lennard-Jones流体的物理吸附平衡及界面现象进行了研究。模拟中引入新型势模型,采用了计数法计算平衡压力,预测了在不同孔径下（直径为 3～5nm）的吸附等温线,分析了毛细凝聚理论用于纳米微孔吸附的局限性。并比较了同一纳米尺度的窄缝形微孔和圆柱形微孔吸附的差异。     

Controlling ionic current through a nanopore by tuning pH: a local equilibrium Monte Carlo study

ABSTRACT

The purpose of this work is to create a model of a nanofluidic transistor which is able to mimic the effects of pH on nanopore conductance. The pH of the electrolyte is an experimentally controllable parameter through which the charge pattern can be tuned: pH affects the ratio of the protonated/deprotonated forms of the functional groups anchored to the surface of the nanopore (for example, amino and carboxyl groups). Thus, the behaviour of the bipolar transistor changes as it becomes ion selective in acidic/basic environments. We relate the surface charge to pH and perform particle simulations (Local Equilibrium Monte Carlo) with different nanopore geometries (cylindrical and double conical). The simulations form a self consistent system with the Nernst–Planck equation with which we compute ionic flux. We discuss the mechanism behind pH-control of ionic current: formation of depletion zones.     

Nanobubbles in solid-state nanopores

From conductance and noise studies, we infer that nanometer-sized gaseous bubbles (nanobubbles) are the dominant noise source in solid-state nanopores. We study the ionic conductance through solid-state nanopores as they are moved through the focus of an infrared laser beam. The resulting conductance profiles show strong variations in both the magnitude of the conductance and in the low-frequency noise when a single nanopore is measured multiple times. Differences up to 5 orders of magnitude are found in the current power spectral density. In addition, we measure an unexpected double-peak ionic conductance profile. A simple model of a cylindrical nanopore that contains a nanobubble explains the measured profile and accounts for the observed variations in the magnitude of the conductance.     

Magnetoelectric effect in multiferroic NdMn_2O_5

We have measured the dielectric constant for NdMn_2O_5 in an external magnetic field to map out the magnetoelectric phase diagram. The phase diagram corresponds well with the previously reported data of neutron diffraction and magnetic susceptibility. Our main finding is the observation of a dielectric anomaly in the low temperature phase with a strong magnetoelectric effect, which is attributed to the independent Nd~(3+) ordering. Moreover, the absence of the dielectric anomaly in the paramagnetic phase is discussed, keeping in view the exchange interaction and its dependence on the rareearth R~(3+) ionic radius.     

Response of disordered matter to electromagnetic fields

We have studied a variety of different disordered materials, including molecular and ionic liquids, supercooled liquids, glasses, ionic conductors, and doped semiconductors, in ac electromagnetic fields over an exceptional broad dynamic range, including the rarely investigated GHz to THz region. All classes of disordered matter exhibit an astonishingly similar response: In addition to Jonscher's time-honored "universal dielectric response," a superlinear power-law increase of the frequency-dependent conductivity shows up bridging the gap between the classical dielectric and the infrared region. Thus the universal dielectric behavior of disordered matter extends up to much higher frequencies than thought until now.     

Concentration polarization in translocation of DNA through nanopores and nanochannels

In this Letter we provide a theory to show that high-field electrokinetic translocation of DNA through nanopores or nanochannels causes large transient variations of the ionic concentrations in front and at the back of the DNA due to concentration polarization (CP). The CP causes strong local conductivity variations, which can successfully explain the nontrivial current transients and ionic distributions observed in molecular dynamics simulations of nanopore DNA translocations as well as the transient current dips and spikes measured for translocating hairpin DNA. Most importantly, as the future of sequencing of DNA by nanopore translocation will be based on time-varying electrical conductance, CP, must be considered in experimental design and interpretation--currently these studies are mostly based on the incomplete pore conductance models that ignore CP and transients in the electrical conductance.     

Study on ionic conductivity and dielectric properties of PEO-based solid nanocomposite polymer electrolytes

The ionic conductivity and dielectric properties of the solid nanocomposite polymer electrolytes formed by dispersing a low particle-sized TiO₂ ceramic filler in a poly (ethylene oxide) (PEO)-AgNO₃ matrix are presented and discussed. The solid nanocomposite polymer electrolytes are prepared by hot press method. The optimum conducting solid polymer electrolyte of polymer PEO and salt AgNO₃ is used as host matrix and TiO₂ as filler. From the filler concentration-dependent conductivity study, the maximum ionic conductivity at room temperature is obtained for 10 wt% of TiO₂. The real part of impedance (Z′) and imaginary part of impedance (Z″) are analyzed using an LCR meter. The dielectric properties of the highest conducting solid polymer electrolyte are analyzed using dielectric permittivity (ε′), dielectric loss (ε″), loss tangent (tan δ), real part of the electric modulus (M′), and imaginary part of the electric modulus (M″). It is observed that the dielectric constant (ε′) increases sharply towards the lower frequencies due to the electrode polarization effect. The maxima of the loss tangent (tan δ) shift towards higher frequencies with increasing temperature. The peaks observed in the imaginary part of the electric modulus (M″) due to conductivity relaxation shows that the material is ionic conductor. The enhancement in ionic conductivity is observed when nanosized TiO₂ is added into the solid polymer electrolyte.     

Low frequency dielectric spectroscopy of two room temperature chiral liquid crystal mixtures

Dielectric spectroscopy of two room temperature chiral liquid crystal mixtures (W-96 and W-97) have been carried out in the frequency range of 100?mHz–10?MHz. Low frequency dielectric relaxation modes corresponding to collective behavior of molecules (Goldstone- and soft-modes) in the SmC* phase have been found to be masked by the ionic conductance. Two slow modes of dielectric relaxation due to the ionic conductance have been detected (below 15?Hz) in planar-aligned samples. It has been observed that the effect of ionic conductance decreases with the number of thermal annealing cycles on the materials. With large number of thermal annealing cycles it has been possible to wipe out the effects of ionic conductance and then to detect other weak modes of dielectric relaxation which are otherwise masked.     

First principles study of the vibrational,dielectric and thermal properties of SrClF

SrClF is an important optical crystal and has many technological applications. In this work, vibrational, dielectric and thermal properties of SrClF were investigated by density functional perturbation calculation. The calculated Born effective charges are close to their nominal ionic charges, revealing the ionic characteristic of SrClF. Group theory analysis indicates that there are two E _u and A _2u infrared modes at the Brillouin zone center of SrClF. The LO-TO splitting of these infrared modes were calculated and discussed and their vibrational modes were sketched. Static dielectric constants were studied, which show that SrClF has a larger ionic dielectric contribution than its electrons. Its birefringence was calculated and the infrared reflectance spectra were simulated, which can be used to explain the experimental findings. Based on the computed phonon dispersion curves, the lattice heat capacity, the Grüneisen parameter and the thermal expansion coefficient as functions of temperature were predicted.     

Copolymer-homopolymer mixtures in a nanopore

We have performed the cell dynamics simulation with the time-dependent Ginzburg-Landau theory to study the selfassembled morphology of A-B diblock copolymers and C homopolymers in a neutral nanopore. The nanopore diameter and length are systematically varied to examine their effects on the structures of various morphologies and their phase transition. From the simulation, it is observed that the equilibrium morphology of the confined system is sensitive to pore diameter D and pore length Lpore , the phase behavior in neutral nanopores is due to an interplay of two factors: the surface effect and the extension effect. When the nanopore length and the lamellae spacing are not commensurate, the surface effect prevails at small nanopores (small diameters or short lengths), the extension effect takes over at larger nanopores (large diameters or long lengths). When the nanopore length and the lamellae spacing are commensurate, the surface effect dominates. Furthermore, the interactions between different monomers are also discussed and we obtain a transition from a tilted pancakes/cylinder structure (L⊥tilted ) to a concentric cylindrical structure with defects and to a concentric cylindrical structure (L|| ). We also investigate the effect of the relative concentrations of diblock copolymer-homopolymer and obtain a transition in which the position of the C blocks changes from the outer of the cylinder to the middle of the cylinder and then to the inner of the cylinder with the concentration of the C blocks decreasing.     

Conductivity and dielectric relaxation of gelatin films with glycerol as plasticizer

Gelatin films complexed with ionic salts are of current interest as potential solid polymer electrolytes. However, even without salt, gelatin films are found to have quite high ionic conductivity at room temperature (around 30 °C), when plasticized with an adequate fraction of glycerol. In the present work, the admittance and dielectric properties of gelatin are studied as a function of glycerol content and temperature. An enhancement in the ionic conductivity by four orders of magnitude to ～9.13?×?10^?3 S/m at room temperature is obtained by adding 35.71 wt% of glycerol. This enhancement appears to be correlated with the changes in the local microstructure on plasticizer addition. Admittance and dielectric relaxation have been studied to understand the dynamics of the charge carriers. Differential scanning calorimetry, X-ray diffraction and scanning electron microscopy are also done.     

Asymmetrical guided magnetic polaritons in a ferromagnetic slab

The dispersion relations for guided magnetic polaritons are obtained in an ordered ferromagnetic slab. For this anisotropic system, the guided modes do not have the reflection symmetry with respect to the median plane of the slab which is known to exist for the dielectric polaritons in an ionic crystal slab. The dispersion relations and the phase angles are given for typical values of the parameters.     

Computer analysis of the AFM images of the nanopore system on the SiO2/Si structure surface,obtained by Zn ion implantation

A computer study of morphological characteristics using AFM images of a self-organized surface nanopore system in the structure of SiO₂/Si(100) is performed. The nanopore system is obtained via Zn ion doping with subsequent thermal annealing. AFM images of the nanopore system are studied using the STIMAN 3D software. A correct quantitative estimate is made of the morphology of this nanopore system using a number of parameters (equivalent diameter, area, total area, and shape coefficient). Estimating the morphology of the self-organized surface nanopore system in the structure of SiO₂/Si(100) allows us to narrow the possible practical applications of the resulting system in opto- and nanoelectronics.     

On gas phase transitions in a 2D nanopore

A gas distribution function for a 2D nanopore was derived, making possible calculations of thermodynamic characteristics such as pressure and heat capacity. The dependence of pressure and heat capacity on the least nanopore size was considered suggesting the presence of specific phase transitions in the gas in a certain temperature range. The phase transitions are associated with size quantization which results in “effective” interaction (attraction) between gas molecules.     

Polarity-dependent dielectric torque in nematic liquid crystals

The dielectric dispersion in the uniaxial nematic liquid crystals affects the switching dynamics of the director, as the dielectric torque is determined by not only the present values of the electric field and director but also by their past values. We demonstrate that this "dielectric memory" leads to an unusual contribution to the dielectric torque that is linear in the present field and thus polarity sensitive. This torque can be used to accelerate the "switch-off" phase of director dynamics.     

Poisson-Fokker-Planck model for biomolecules translocation through nanopore driven by electroosmotic flow

A non-continuous electroosmotic flow model (PFP model) is built based on Poisson equation, Fokker-Planck equation and Navier-Stokse equation, and used to predict the DNA molecule translocation through nanopore. PFP model discards the continuum assumption of ion translocation and considers ions as discrete particles. In addition, this model includes the contributions of Coulomb electrostatic potential between ions, Brownian motion of ions and viscous friction to ion transportation. No ionic diffusion coefficient and other phenomenological parameters are needed in the PFP model. It is worth noting that the PFP model can describe non-equilibrium electroosmotic transportation of ions in a channel of a size comparable with the mean free path of ion. A modified clustering method is proposed for the numerical solution of PFP model, and ion current translocation through nanopore with a radius of 1 nm is simulated using the modified clustering method. The external electric field, wall charge density of nanopore, surface charge density of DNA, as well as ion average number density, influence the electroosmotic velocity profile of electrolyte solution, the velocity of DNA translocation through nanopore and ion current blockade. Results show that the ion average number density of electrolyte and surface charge density of nanopore have a significant effect on the translocation velocity of DNA and the ion current blockade. The translocation velocity of DNA is proportional to the surface charge density of nanopore, and is inversely proportional to ion average number density of electrolyte solution. Thus, the translocation velocity of DNAs can be controlled to improve the accuracy of sequencing by adjusting the external electric field, ion average number density of electrolyte and surface charge density of nanopore. Ion current decreases when the ion average number density is larger than the critical value and increases when the ion average number density is lower than the critical value. Our numerical simulation shows that the translocation velocity of DNA given by the PFP model agrees with the experimental, results better than that given by PNP model or PB model.     

Ferroelectricity associated with the metastable phase “III” of AgNO3

The dielectric constant, dc resistance, D-E ferroelectric hysteresis loop and dilatometric analysis of the three phases I, II, and III of AgNO₃ single crystals has been studied over the temperature range 100–200° C. A ferroelectric behaviour of the metastable phase III was detected here for the first time similar to what happened in KNO₃. The ferroelectric is attributed here to Ag⁺-ion vacancy formation in the unit cell of AgNO₃. The energy activating the process of vacancy formation was found to beE _v=2.6 eV. It was found that an ionic shift from one lattice point to another requires an amount of energy to overcome a potential barrierE _m=0.1 eV. A model is suggested to explain such behaviour. Dilatometric analysis indicated that this metastable phase transition III is accompanied by an expansion of the unit cell.     

Relationship between oxide-ion conductivity and dielectric relaxation in the Ln2Zr2O7 system having pyrochore-type compositions (Ln=Yb, Y, Gd, Eu, Sm, Nd, La)

Ln₂Zr₂O₇ (Ln=Yb, Y, Gd, Eu, Sm, Nd, La) system changed from fluorite (F)-type to pyrochlore (P)-type phases when the ionic radius ratios, r(Ln³⁺)/r(Zr⁴⁺), were larger than 1.26. The oxide-ion conductivity showed sharp maximum at the vicinity of the phase boundary between the F- and P-type phases. The frequency dependence of dielectric constant () and dielectric loss factor () were successfully explained by the superimposition of Debye-type polarization due to dopant-vacancy associate and electrode-electrolyte interfacial polarization by the numerical calculation. The peak of dielectric loss tangent (tan δ) was ascribed to the dopant-vacancy associate. The ε_r(0) and dielectric constant of the associate (ε_r0) showed also the maximum values at the vicinity of the phase boundary between the F- and P-type phases.