Size Dependence of Nanoscale Confinement on Chiral Transformation

Molecular dynamic simulations of the chiral transition of a difluorobenzo[c]phenanthrene molecule (C₁₈H₁₂F₂, D molecule) in single‐walled boron‐nitride nanotubes (SWBNNTs) revealed remarkable effects of the nanoscale confinement. The critical temperature, above which the chiral transition occurs, increases considerably with the nanotube diameter, and the chiral transition frequency decreases almost exponentially with respect to the reciprocal of temperature. The chiral transitions correlate closely with the orientational transformations of the D molecule. Furthermore, the interaction energy barriers between the D molecule and the nanotube for different orientational states can characterize the chiral transition. This implies that the temperature threshold of a chiral transition can be controlled by a suitable nanotube. These findings provide new insights to the effect of nanoscale confinement on molecular chirality.     

Threshold voltage for purely flexoelectric deformations of conducting homeotropic nematic layers

Elastic deformations induced by an electric field in homeotropic nematic layers with finite anchoring energy were studied numerically. A nematic material possessing flexoelectric properties and characterized by a positive dielectric anisotropy was considered. The ionic space charge and the ion transport across the layer were taken into account. The director orientation, the electric field strength and the ion concentrations were calculated as functions of the coordinate normal to the layer. The calculations show that the electric field distribution, which determines the form of the deformations, is influenced by the ionic current and therefore depends on the ionic content and on the properties of the electrodes. Several types of deformations were distinguished. When the electrode contacts are well conducting or when the ionic content is low, the threshold voltage is very close to the value U _f valid for an insulating nematic. When the electrodes are poorly conducting or blocking at high ion concentration, the threshold voltage decreases much below U _f. At moderate ion concentrations, i.e. between 10¹⁹ and 10²⁰ m^?3, two different behaviours were found depending on the sign of the sum of flexoelectric coefficients e ₁₁+e ₃₃. In the case of e ₁₁+e ₃₃<0, the threshold voltage decreases with the ionic content; in the case of e ₁₁+e ₃₃>0, the deformations occur in two separate voltage regimes. They arise above a certain threshold voltage, disappear at some higher voltage and reappear at an even higher threshold.     

The optical response of liquid crystal cells to a low frequency driving voltage

This study investigates the optical response of liquid crystal cells to a low frequency square wave voltage of 0.1 Hz. It is found that there are three physical phenomena that dominate the overall properties of the device. The first is the discharging effect whereby the effective voltage over the liquid crystal layer decreases as a function of time; this occurs due to mobile ions being present within the liquid crystal material. The second is the charging-up of the cell where the effective voltage increases with time; this is attributed to charge separation taking place within the polyimide layer upon application of the d.c. voltage component. The third effect is cell asymmetry whereby the effective voltage depends upon the polarity of the externally applied field; this is the result of a locked-in d.c. holding voltage being present within the cell layers. These three effects are analysed in some detail with the view of developing a liquid crystal cell capable of being driven with a low frequency square wave voltage. A model of a liquid crystal cell in which the liquid crystal material can dissolve impurity ions from the alignment layers and in which the ions can then become re-adsorbed into the polyimide layer is deduced.     

Threshold flexoelectric deformations in homeotropic nematic layers

Elastic deformations of nematic liquid crystal layers subjected to a d.c. electric field were studied numerically. The flexoelectric properties of the nematic material and the presence of ionic space charge were taken into account. Homeotropic alignment with finite surface anchoring strength was assumed. The director orientation and the electric potential distribution were calculated; the space charge density was also determined. It was found that the threshold voltage strongly depended on the parameters of the system. In particular, a threshold as low as a few tenths of a volt occurred under suitable circumstances. In the case of a negative dielectric anisotropy, Δ ε, such low values of the threshold voltage existed when the ion concentration was sufficiently high, and given sufficiently large magnitudes of the flexoelectric coefficients and a sufficiently small anchoring energy. If the ion concentration was low or if the flexoelectric coefficients were small or if the surface anchoring was strong, the threshold was equal to several volts. In the case of positive dielectric anisotropy, the threshold amounted to several tenths of a volt for a weakly anisotropic and highly conductive material. If the dielectric anisotropy was sufficiently high or if the ion concentration was sufficiently low, the threshold voltage increased with Δ ε and reached tens of volts. These results can be explained as the effect of the inhomogeneous electric field arising in the vicinity of the surfaces, due to the ionic space charge redistributed by the external voltage. They are qualitatively consistent with earlier experiments which show the effect of the ion concentration on the elastic deformations in flexoelectric nematics. They correspond also with theoretical results concerning the effect of the electric field produced by the surface polarization or by the adsorption of ions.     

Drifting undulations in an achiral smectic C liquid crystal driven by a static electric field

We report a novel dc field-driven propagative instability associated with the thermally induced layer undulations of the smectic C phase in a phenyl benzoate. While the undulations are two-dimensional, the drift is observed only along the wave vector q parallel to the c director; undulations with orthogonal q and c remain stable. The drift, which is nonhysteretic, takes place in a hopping way between equilibrium positions; it has a well-defined threshold in a given region, but the threshold varies rather widely for different regions. The average propagation velocity increases linearly from zero with the control parameter epsilon until epsilon approximately 2 but tends to saturate thereafter. Significantly, the drift direction reverses on switching the field polarity. The mechanism responsible for the drift appears to involve a coupling between the transverse field gradients due to the conductivity anisotropy and the transverse component of the flexoelectric polarization.     

The influence of the flexoelectric effect on the electrohydrodynamic instability in nematics

A rigorous three-dimensional linear analysis of the electrohydrodynamic instability in nematic liquid crystals including the flexoelectric effect is presented for the case of an applied d.c. voltage. The flexoelectric effect leads to an appreciable reduction of the threshold and to the appearance of oblique rolls at threshold for the standard material MBBA. We discuss the influence of a magnetic field and test several approximations against the rigorous results     

Stiffness measurement of nanosized liposomes using solid‐state nanopore sensor with automated recapturing platform

This paper describes a method to gauge the stiffness of nanosized liposomes – a nanoscale vesicle – using a custom‐made recapture platform coupled to a solid‐state nanopore sensor. The recapture platform electrically profiles a given liposome vesicle multiple times through automated reversal of the voltage polarity immediately following a translocation instance to re‐translocate the same analyte through the nanopore – provides better statistical insight at the molecular level by analyzing the same particle multiple times compared to conventional nanopore platforms. The capture frequency depends on the applied voltage with lower voltages (i.e., 100 mV) permitting higher recapture instances than at higher voltages (>200 mV) since the probability of particles exiting the nanopore capture radius increases with voltage. The shape deformation was inferred by comparing the normalized relative current blockade ( at the two voltage polarities to that of a rigid particle, i.e., polystyrene beads. We found that liposomes deform to adopt a prolate shape at higher voltages. This platform can be further applied to investigate the stiffness of other types of soft matters, e.g., virus, exosomes, endosomes, and accelerate the potential studies in pharmaceutics for increasing the drug packing and unpacking mechanism by controlling the stiffness of the drug vesicles.     

Trapping mode dipolar DC collisional activation in the RF‐only ion guide of a linear ion trap/time‐of‐flight instrument for gaseous bio‐ion declustering

The application of dipolar direct current (DDC) to the radio frequency‐only ion guide (Q0) of a hybrid quadrupole/time‐of‐flight mass spectrometer for collision‐induced declustering of large bio‐ions is described. As a broadband technique, ion trap DDC collisional activation (CA) is employed to decluster ions simultaneously over a relatively broad mass‐to‐charge (m/z) range. Declustering DDC CA can yield significantly narrower peaks relative to those observed in the absence of declustering methods, depending upon the extent of noncovalent adduction associated with the ions, and can also be used in conjunction with other methods, such as nozzle–skimmer CA. The key experimental variables in the DDC experiment are the DDC voltage (V_DDC), V_RF, and the time over which V_DDC is applied. The V_DDC/V_RF ratio is key to the extent to which ion temperatures are elevated and also influences the upper m/z limit for ion storage. The V_DDC/V_RF ratio affects ion temperatures and the upper m/z limit in opposing directions. That is, as the ratio increases, the ion temperature also increases, whereas the upper m/z storage limit decreases. However, for a given V_DDC/V_RF ratio, the upper m/z storage limit can be increased by increasing V_RF, at the expense of the lower m/z limit for ion storage. The key value of the approach is that it affords a relatively precise degree of control over ion temperatures as well as the time over which they are elevated to a higher temperature. The utility of the method is illustrated by the application of ion trap DDC CA in Q0 to oligonucleotide, protein, and multimeric protein complex analyte ions. Copyright © 2013 John Wiley & Sons, Ltd.     

Kinetics of the droplet formation at the early and intermediate stages of the spinodal decomposition in homopolymer blends

The kinetics of the droplet formation during the spinodal decomposition (SD) of the homopolymer blends has been studied by numerical integration of the Cahn‐Hilliard‐Cook equation. We have found that the droplet formation and growth occurs when the minority phase volume fraction, f_m , approaches the percolation threshold value, f_thr = 0.3 ± 0.01. The time for the formation of the disperse droplet morphology (coarsening time) depends only on the equilibrium minority phase volume fraction, f_m . f_m approaches its equilibrium value logarithmically at the late SD stages, and, therefore, the coarsening time decreases exponentially as the average volume fraction or the quench depth decrease. Since the temporal evolution of the total interfacial area does not depend on the quench conditions and blend morphology, the average droplet size and the droplet number density is determined by the coarsening time. Within the time scale studied, the droplet number density decreases with time as t ^{–0.63±0.03}; the average mean curvature decreases as t ^{–0.35±0.05}; the average Gaussian curvature decreases as t ^{–0.42±0.03}, and the average droplet compactness ˜V/S^3/2 where S is the surface area and V is the volume) approaches a spherical limit logarithmically with time. The droplets with larger area have lower compactness and in the low compactness limit their area is a parabolic function of compactness. The size and shape distribution functions have been also investigated.     

A blue-green-emitting 3D supramolecular compound: synthesis,crystal structure and effect of solvents and temperature on the luminescent properties

A blue-green-emitting three-dimensional supramolecular compound (C₁₀O₂N₂H₈)(C₉O₇H₆) (1) was synthesised under hydrothermal conditions and structurally characterised by elemental analysis, IR spectrum, ¹H NMR and single-crystal X-ray diffraction. The crystal belongs to triclinic system with P 1¯ space group. The crystal structure is stabilised by O–H…O, O–H…N hydrogen bonds and π–π interactions (π–π stacking distance is 3.282 Å). Compound 1 exhibits intense green luminescence in solid state at 298 K (λ_em = 546 nm). In addition, absorption and fluorescence characteristics of compound 1 have been investigated in different solvents (DMSO, CH₃CN and CH₃OH). The results show that compound 1 exhibits a large red shift in both absorption and emission spectra as solvent polarity increases (polarity: DMSO>CH₃CN>CH₃OH), indicating a change in dipole moment of compound 1 upon excitation. Although the emission spectra of compound 1 in CH₃OH are close to it in dimethyl sulfoxide (DMSO), it is revealed that the luminescence behaviour of compound 1 depends not only on the polarity of environment but also on the hydrogen bonding properties of the solvent. Meanwhile, temperature strongly affects the emission spectra of compound 1. Emission peaks of compound 1 were blue shift at 77 K than those at 298 K in both solid state (ca. 142 nm) and solution (ca. 6–23 nm), which was due to the non-radiative transition decreases at low temperature. Moreover, the quantum yield and fluorescence lifetime of compound 1 were also measured, which increased with increasing polarity of solvent, lifetime in DMSO at 298 K (τ₁ = 0.92 μs, τ₂ = 8.71 μs) was the longest one in solvents (298 K: τ₁ = 0.87–0.92 μs, τ₂ = 7.50–8.71 μs; 77 K: τ₁ = 0.72–0.90 μs, τ₂ = 6.88–7.45 μs), which was also shorter than that in solid state (298 K: τ₁ = 1.13 μs, τ₂ = 7.50 μs; 77 K: τ₁ = 0.97 μs, τ₂ = 8.97 μs). This was probably because of the weak polarity environment of compound 1 in solid state.     

锂离子电池正极材料LiFePO4的结构与电化学性能的研究

利用固相法和球化工艺合成了橄榄石型LiFePO4粉体.该粉体由直径为10-15μm的团簇体组成.以合成材料为正极的锂离子电池的循环伏安特性表明,在循环过程中,锂离子插入和脱出具有单一的可逆机制.在不同温度下,材料的交流复阻抗谱表明,随着温度的升高,电池电化学阻抗明显减小.充放电测试结果表明,在17mA/cm2的电流密度下,材料工作电压平稳,电极极化效应较小,容量接近其理论值.在170mA/cm2的电流密度下,电池容量没有明显的减小趋势,而在170mA/cm2电流密度以上时,电池容量迅速降低,且电极极化效应比较显著.经过较大的电流密度测试后,材料在小电流密度下仍然保持着接近理论容量的循环容量.     

Electrical properties of polypyrrole/p‐InP structure

The polypyrrole/p‐InP structure has been fabricated by the electrochemical polymerization of the organic polypyrrole onto the p‐InP substrate. The current–voltage (I–V), capacitance–voltage (C–V), and capacitance–frequency (C–f) characteristics of the PPy/p‐InP structure have been determined at room temperature. The structure showed nonideal I–V behavior with the ideality factor and the barrier height 1.48 and 0.69 eV respectively. C–f measurements of the structure have been carried out using the Schottky capacitance spectroscopy technique and it has been seen that there is a good agreement between the experimental and theoretical values. Also, it has been seen that capacitance almost show a plateau up to a certain value of frequency, after which, the capacitance decreases. The higher values of capacitance at low frequencies were attributed to the excess capacitance resulting from the interface states in equilibrium with the p‐InP that can follow the a.c. signal. The interface state density N_ss and relaxation time τ of the structure were determined from C–f characteristics. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1572–1579, 2006     

Flexoelectric deformations of homeotropic nematic layers in the presence of ionic conductivity

Elastic deformations of homeotropic nematic liquid crystal layers subjected to a d.c. electric field were studied numerically in order to find the dependence of threshold voltage on the properties of such a system. A nematic material characterized by a negative sum of flexoelectric coefficients and by a small negative dielectric anisotropy was considered. The flow of ionic current was taken into account. The electric properties are described in terms of a weak electrolyte model. Finite surface anchoring strength was assumed. The director orientation, the electric potential and the ion concentrations were calculated as functions of the coordinate normal to the layer. It was found that the threshold for the deformation depends on the distributions of the ions, governed by the generation constant and by the properties of the electrodes. The effects observed may be interpreted as a consequence of the separation of the ions. When the electrodes have pronounced blocking character, a high and non-uniform electric field, created by the subelectrode ion space charges, causes drastic decrease of the threshold voltage, much below the value U _f valid for the insulating nematic. On the other hand, the electric field gradient arising in the bulk at moderate concentrations has a stabilizing effect and remarkably enhances the threshold above U _f. When the electrodes are conducting there are no significant space charges and the threshold voltage remains close to U _f. These results indicate that phenomena related to the charge transport should be taken into account in the analysis of the elastic deformations of ion-containing flexoelectric nematics.     

Dynamics of unfolded protein transport through an aerolysin pore

Protein export is an essential mechanism in living cells and exported proteins are usually translocated through a protein-conducting channel in an unfolded state. Here we analyze, by electrical detection, the entry and transport of unfolded proteins, at the single molecule level, with different stabilities through an aerolysin pore, as a function of the applied voltage and protein concentration. The frequency of ionic current blockades varies exponentially as a function of the applied voltage and linearly as a function of protein concentration. The transport time of unfolded proteins decreases exponentially when the applied voltage increases. We prove that the ionic current blockade duration of a double-sized protein is longer than that assessed for a single protein supporting the transport phenomenon. Our results fit with the theory of confined polyelectrolyte and with some experimental results about DNA or synthetic polyelectrolyte translocation through protein channels as a function of applied voltage. We discuss the potential of the aerolysin nanopore as a tool for protein folding studies as it has already been done for α-hemolysin.     

Behaviour of polymer dispersed cholesteric droplets with negative dielectric anisotropy in electric fields

The behaviour of chiral, polymer dispersed cholesteric liquid crystals with negative dielectric anisotropy in electric fields has been studied for a system with large cholesteric pitch (several μm) using polarizing microscopy. A uniformly oriented region appears in the centre of the droplets for voltages above a threshold voltage. We find that the radius of this region increases exponentially with increasing field strength, while the threshold voltage decreases with increasing drop diameter and with increasing pitch. Investigation of the dynamics reveals a single step mechanism with a time constant of a few seconds when a field is suddenly switched on. The switch-off process is more complex and much slower.     

A study on free volume of acrylonitrile‐styrene copolymer and methyl methacrylate‐styrene copolymer by using positron annihilation

The o‐Ps lifetime τ₃ and the intensity I₃ of ST‐AN copolymers and ST‐MMA copolymers have been determined by using the positron annihilation technique. The average free volume hole radius R is estimated according to Tao's and Eldrup's model. The result shows that the average free volume hole size mainly attributes to lateral group volume and polarity of macromolecular chain as well as polymerizing temperature, and the o‐Ps intensity I₃ to the effect of the lateral group volume and the polarity. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 465–472, 1999     

DC conduction in chloroprene rubber (CR)

The time and temperature dependence of DC and electrical conductivity of vulcanized and fresh samples of crystalline CR have been investigated. The conduction has been found to occur by an ionic mechanism. The existence of ionic conduction is supported by the appearance of a peak in the current-time curves after the reversal of the polarity of the applied voltage. An anomalous behaviour was observed in the temperature dependence of the electrical conductivity and was attributed to the phase transition of CR from the crystalline to the amorphous state. It was also found that vulcanization increases the mobility of the current carriers and hence the electrical conductivity. On the contrary the milling process decreased both mobility and conductivity.     

Kinetics of Coil-to-Globule Transition of Dansyl-Labeled Poly(N-isopropyl-acrylamide) Chains in Aqueous Solution

The coil-to-globule transition of thermally sensitive linear poly(N-isopropylacrylamide) (PNIPAM) labeled with dansyl group is induced by 1.54 μm laser pulses (width≈10 ns). The dansyl group is used to follow the transition kinetics because its fluorescence intensity is very sensitive to its micro-environment. As the molar ratio of NIPAM monomer to dansyl group increases from 110 to 300, the effect of covalently attached dansyl fluorophores on the transition decreases. In agreement with our previous study in which we used 8-anilino-1-naphthalensulfonic acid ammonium salt free in water as a fluorescent probe, the current study reveals that the transition has two distinct stages with two characteristic times, namely, τ_fast≈0.1 ms, which can be attributed to the nucleation and formation of some "pearls" (lo-cally contracting segments) on the chain, and τ_slow≈0.5 ms, which is related to the merging and coarsening of the "pearls". τ_fast is independent of the PNIPAM chain length over a wide range (M_w=2.8×10⁶-4.2×10⁷ g/mol). On the other hand, τ_slow only slightly increases with the chain length.     

Polyelectrolyte entry and transport through an asymmetric alpha-hemolysin channel

We study the entry and transport of a polyelectrolyte, dextran sulfate (DS), through an asymmetric alpha-hemolysin protein channel inserted into a planar lipid bilayer. We compare the dynamics of the DS chains as they enter the channel at the opposite stem or vestibule sides. Experiments are performed at the single-molecule level by using an electrical method. The frequency of current blockades varies exponentially as a function of applied voltage. This frequency is smaller for the stem entrance than for the vestibule one, due to a smaller coupling with the electric field and a larger activation energy for entry. The value of the activation energy is quantitatively interpreted as an entropic effect of chain confinement. The translocation time decreases when the applied voltage increases and displays an exponential variation which is independent of the stem or vestibule sides.     

Relationship between spontaneous generation of voltage and structural features in a single crystal of Pr0.6Ca0.4MnO3

Spontaneous generation of electrical voltage U was found for the perovskite-like single crystal of Pr_0.6Ca_0.4MnO₃, wherein the charge and orbital orderings occur at T _CO = 240 K and the antiferromagnetic one occurs at the Neel point T _N = 174 K. With decreasing the temperature, the U value increases first slowly (in the temperature range of 300 K-T _CO) and then more rapidly (T _CO-T _N). Starting from T _N, U increases exponentially and, at 85 K, reaches the value of 115 mV (in the ab plane) and 6.5 mV (along the c axis). The magnetic field has a different effect on the U value in different temperature ranges: in the temperature range of 85–130 K, it decreases U and, in the range of 130–240 K, increases U. The spontaneous voltage is thought to be caused by the existence of ferromagnetic and charge-orbital-ordered clusters of different topology in the sample. The latter clusters have own features and their structure are described by the non-centrosymmetric space group P2₁ nm.