Polymer translocation through a nanopore induced by adsorption: Monte Carlo simulation of a coarse-grained model

Dynamic Monte Carlo simulation of a bead-spring model of flexible macromolecules threading through a very narrow pore in a very thin rigid membrane are presented, assuming at the cis side of the membrane a purely repulsive monomer-wall interaction, while the trans side is attractive. Two choices of monomer-wall attraction epsilon are considered, one choice is slightly below and the other slightly above the "mushroom to pancake" adsorption threshold epsilon(c) for an infinitely long chain. Studying chain lengths N=32, 64, 128, and 256 and varying the number of monomers N(trans) (time t=0) that have already passed the pore when the simulation started, over a wide range, we find for epsilonepsilon(c) a finite number N(trans)(t=0) suffices that the translocation probability is close to unity. In the case epsilonepsilon(c), we find that the translocation time scales as tau proportional, variant N(1.65+/-0.08). We suggest a tentative scaling explanation for this result. Also the distribution of translocation times is obtained and discussed.     

Optical absorption of semiconducting and metallic nanospheres with the confined electron-phonon coupling

We study the optical absorption, especially the (far-) infrared absorption by phonons, of semiconducting and metallic nanospheres. In the nanoscopic sphere, phonons as well as states of electronic excitations are quantized by confinement. It is also known that in the nanoscopic geometry, the confined electron-phonon interaction has a different form from the usual one in the bulk. First, we analyze the phonon and electron contributions to the dielectric response of nanospheres like epsilon(q,omega)=epsilon(ph)(q,omega)+epsilon(el)(q,omega) or 1epsilon(q,omega)=1epsilon(sc-ph)(q,omega)+1epsilon(el)(q,omega) from the confined electron-phonon interaction for three cases: the intrinsic semiconductor, the doped semiconductor, and the metal. From the dielectric response, the optical absorption spectra are calculated within the semiclassical framework concentrating on the (far-) infrared region and compared to the spectra without imposing confinement. Nontrivial differences of the spectra with confined phonons stem from two features: the electron-phonon coupling matrix has a different form and the phase space q of the confined phonon is reduced because of its quantization to q(n). Finally, size distribution effects in an ensemble of isolated nanospheres are briefly discussed. Those effects are found to be important in metallic spheres with rapid sweepings of resonances by a small change of the sphere size.     

Influence of steric factors on exciplex energy and magnetic field effect

With the advent of spin chemistry, magnetic field effect (MFE) on exciplex luminescence has emerged as an important domain of research. MFE is a diffusion controlled phenomenon and hence is solvent dielectric (epsilon) dependent. It maximizes at a particular epsilon (epsilon(max)) for a specific exciplex system. Various attempts have been made to explain the variation of this epsilon(max) from one exciplex to another. In our present work we have succeeded for the first time to enmark the energy of exciplex (E(ex)) as the prime factor in determining the epsilon(max). We have indicated a definite inverse correlation (1:1) between epsilon(max) and E(ex). We have also tried to correlate some parameters that are important in exciplex formation, e.g. Charton's steric constant (nu(c)), repulsive energy (R(e)) and E(ex).     

Universal growth of microdomains and gelation transition in agar hydrogels

Investigations were carried out on aqueous sols and gels of agar (extracted from red seaweed Gelidiella acerosa) to explore the growth of microdomains en route to gelation. Isothermal frequency sweep studies on gel samples revealed master plots showing power-law dependence of gel elastic modulus, |G*|, on oscillation frequency, omega as |G*| approximately omegan, independent of temperature, with 0.5Tg). The S(q,t) behavior close to the gel transition point (Tg approximately (38+/-3 degrees C determined from rheology) followed a stretched exponential function: S(t)=A exp(-t/ts)beta. The beta factor increased from 0.25 to 1 as the gel temperature approached 25 degrees C from Tg, and relaxation time, ts, showed a peak at T approximately 30 degrees C. The SLS data (in the sol state) suggested the scaling of scattered intensity, Is(q) approximately epsilon(-gamma) (epsilon=(T/Tg-1), T>Tg) with gamma=0.13+/-0.03, and the presence of two distinct domains characterized by a Guinier regime (low q) and a power-law regime (high q). Close to and above Tg (+2 degrees C), IS(q) scaled with q as Is(q) approximately q(-alpha) with alpha=2.2+/-0.2, which decreased to 1.4+/-1 just below Tg (-2 degrees C), implying a coil-helix transition for 0.2% (w/v) and 0.3% (w/v) samples. For a 0.01% sample, alpha=3.5+/-0.5 which indicated the presence of spherical microgels.     

The critical adsorption point of self-avoiding walks: a finite-size scaling approach

The critical adsorption of self-avoiding polymer chain in a simple cubic lattice onto a flat surface is studied with Monte Carlo simulations. The dependence of number of surface contacts M on chain length N and polymer-surface interaction epsilon is investigated by a finite-size scaling approach. We estimate the critical adsorption point epsilon(c)=0.291+/-0.002 and the exponent phi=0.54+/-0.01. The asymptotic behaviors M proportional variant N for epsilon>epsilon(c) and M proportional variant N(0) for epsilon相似文献   

Packing density of slurry-packed capillaries at low aspect ratios

The average interparticle voidage or porosity (epsilon(inter)) in cylindrical capillaries is studied in dependence on the column diameter (d(c)) to particle diameter (d(p)) ratio for 5 < d(c)/d(p) < 50. Using optimized slurry and packing solvents, high pressure and ultrasonication, 5 mum-sized porous C18-silica particles were slurry-packed into fused-silica capillaries having ids from 30 to 250 mum. Packing densities are assessed by a polystyrene standard which is size-excluded from the intraparticle pore space of the packings. For d(c)/d(p) > 35 densely packed beds are realized (epsilon(inter) = 0.36-0.37), while for decreasing aspect ratios an exponential increase in epsilon(inter )is observed reaching epsilon(inter ) approximately 0.47 at d(c)/d(p) = 5. This behaviour is ascribed to a combination of the geometrical wall effect operating in the direct vicinity of the column wall, caused by the inability of the particles to form a dense packing against the hard surface of the column wall, and particle characteristics like the size distribution, shape and surface roughness. Results are compared with the literature data to address also the importance of absolute particle size in studying structure-transport relations in packed beds in dependence on the aspect ratio d(c)/d(p).     

Study on threshold behavior of operation voltage in metal filament-based polymer memory

In the metal filament formation-based organic memory, the positive voltage application over the threshold electric field strength (170 MV/m) is necessary for the filament formation in Cu/P3HT/Al device. By the positive voltage application, the copper ions are generated and drifted into polymer layer, which is clearly confirmed by the secondary ion mass spectroscopy. Also, the field strength (100 MV/m) required for the drift process could be independently determined with a new pulse operation method. We could conclude that the threshold field strength of 170 MV/m was determined by the ionization process of copper. Furthermore, the dependence of the positive field strength and the temperature on the memory behavior was studied.     

Simple determination of relative hydrogen atom affinities by supercritical fluid chromatography/atmospheric pressure chemical ionization mass spectrometry

Coupled supercritical fluid chromatography and atmospheric pressure chemical ionization mass spectrometry was applied to estimate hydrogen atom affinities. The intensities of the M⁺ and MH⁺ peaks in the mass spectra were measured at various drift voltages (collision energies). The ratios of the two peaks were plotted against the drift voltages to obtain threshold drift voltages. The threshold drift voltages of polycyclic aromatic hydrocarbons were plotted and found to be proportional to the values of reported hydrogen atom affinities. The value for acenaphthylene was estimated to be 292.9 kJ mol^?1 from this relationship.     

Collective membrane motions of high and low amplitude, studied by dynamic light scattering and micro-interferometry

Undulations of lipid bilayers were experimentally studied for the two limiting cases of high and weak lateral tension using two well established model systems: freely suspended planar lipid bilayers, so-called black lipid membranes (BLM) for high-tension studies and large unilamellar vesicles (LUV) for measurements at weak tension. This variation in tension results in changes of undulation amplitudes from several hundred nm (LUV) down to 1 nm (BLM), thus requiring different physical methods for their detection. We have employed microinterferometric techniques (RICM) for studying the regime of weak tension and dynamic light scattering (DLS) for that of high tension. The dedicated DLS set-up allowed the measurements of undulations over a wide wave vector range of 250 < q/cm-1 < 35,000 cm-1. This enabled the observation of collective membrane modes in two regimes, the oscillating one at low q and the overdamped regime at high q. The transition between both regimes at the bifurcation point is rather abrupt and depends on the lateral tension of the bilayer, as is demonstrated by comparing the dispersion curves of pure lipid and of lipid-cholestrol BLMs over the same q-range. The DLS measurements allowed a critical test of a hydrodynamic theory of the dispersion behaviour of membrane collective modes under tension. The DLS measurements are compared with RICM results of undulatory excitations of giant vesicles weakly adhering to substrates in the 10(-6)-2.5 x 10(-7) m wavelength regime and at low frequencies (0.1-25 Hz). Experimental evidence for the strong decrease in the relaxation rate by the hydrodynamic coupling of the membrane with the wall is established.     

A new type of layer structure defects in chiral smectics

Under a low frequency AC electric field applied to the S_A phase an apparently homogeneous planar structure is obtained which is in fact composed of a system of parallel stripes perpendicular to the smectic layers. This texture persists even in the S*_C phase. The stripes are explained as a contrast on elongated focal conics originating from undulations of smectic layers. Such undulations are formed as a consequence of a reduction in the smectic layer thickness due to the electroclinic effect. The deformation of smectic layers has been calculated on the basis of the elastic free energy associated with their deformation.     

Novel design for drift tubes in ion mobility spectrometry for optimised resolution of peak clusters

In the past decade, Ion Mobility Spectrometry has established a very strong foot hold in medical and biological applications due to its numerous advantages including sensitivity, ruggedness and reproducibility. During the analysis of complex samples such as human breath, it is very probable that two or more analytes form peak clusters due to similar drift times and pre-separation times, thus hindering the identification of the analytes. Furthermore, such overlapping of signal makes quantification very difficult or even impossible. Resolving these peak clusters is important to enable proper identification and quantification of analytes detected for diagnosis. Hence, we designed a drift tube with variable length for investigating the influence of varying drift lengths and electric field on resolution. Peak cluster formations usually seen between acetone and the reactant ion peak, between the dimer peaks of 2-Heptanone and 4-Heptanone have been resolved with the new drift tube after optimisation. These novel drift tubes could easily negate the peak clusters often encountered when complex medical and biological samples are measured with the ion mobility spectrometer. Furthermore, the fact that these drift tubes can be altered in length thereby providing a wide range of electric fields (from 50 to 3300 V.cm⁻¹), opens up new research options in ion motions in an electric field.     

Structure-drift time relationships in ion mobility mass spectrometry

Ion mobility spectrometry (IMS) separates ions while they travel through a buffer gas under the influence of an electrical field. The separation is affected by mass and charge but most particularly by shape (collision cross section). When coupled to MS, IMS-MS offers therefore a powerful tool for structural elucidation and isomer separation. Systematic studies aimed to compare and quantitate the effects of structural changes on drift time such as length and ramification of carbon chain, unsaturation, geometrical isomerism (cis/trans isomers for instance), cyclization and ring size are, however, scarce. Herein we used traveling wave ion mobility mass spectrometry (TWIM-MS) to systematically evaluate the relationship between structure and drift time. For that, a series of deprotonated carboxylic acids were used as model ions with a carboxylate “charge tag” for gas phase MS manipulation. Carboxylic acids showed a near linear correlation between the increase of carbon number and the increase of collision cross section (CCS). The number of double bonds changes slightly the CCS of unsaturated acids. No differences in drift time and no significant differences in CCS of cis- and trans-double bond of oleic and elaidic acids were observed. Cyclization considerably reduces the CCS. In cyclic carboxylic acids, the increase of double bonds and aromatization significantly reduces the CCS and the drift times. The use of a more polarizable drift gas, CO_2, improved in some cases the separation, as for biomarker isomers of steranoic acids. The β-isomer (cis-decaline) has smaller CCS and therefore displayed lower drift time compared to the α-isomer (trans-decaline). Structural changes revealed by calculations were correlated with trends in drift times.     

Theory of operation for differential ion mobility spectrometry without alpha

Using the Langevin equation for ion motion in the presence of a variable electric field, and expressing the collision frequency in a manner that conforms to scattering a polyatomic ion with an equivalent hard-sphere core, a relationship is derived for the compensation and dispersion fields in a differential ion mobility spectrometer (DIMS). For a conservative collision (no clustering or ion-neutral dissociation or rearrangement interactions), the compensation field depends on both even and odd powers of the dispersion field, and the relationship between both fields is independent of pressure when the fields are divided by the drift gas density. Because the first and most important approximation for the compensation field is proportional to the square of ion mobility under zero field conditions, the compensation field increases with the temperature of the drift gas, but the functional form for the temperature dependence involves higher order terms and requires additional knowledge of the temperature dependence for the collision cross section. Duty cycle curves for long-chain secondary ketones compare favorably to experiments using an asymmetric rectangular waveform for excitation.     

Drift of spiral waves controlled by a polarized electric field

The drift behavior of spiral waves under the influence of a polarized electric field is investigated in the light that both the polarized electric field and the spiral waves possess rotation symmetry. Numerical simulations of a reaction-diffusion model show that the drift velocity of the spiral tip can be controlled by changing the polarization mode of the polarized electric field and some interesting drift phenomena are observed. When the electric field is circularly polarized and its rotation follows that of the spiral, the drift speed of the spiral tip reaches its maximal value. On the contrary, opposite rotation between the spiral and electric field locks the drift of the spiral tip. Analytical results based on the weak deformation approximation are consistent with the numerical results. We hope that our theoretical results will be observed in experiments, such as the Belousov-Zhabotinsky reaction.     

Static and dynamic properties of tethered chains at adsorbing surfaces: a Monte Carlo study

We present extensive Monte Carlo simulations of tethered chains of length N on adsorbing surfaces, considering the dilute case in good solvents, and analyze our results using scaling arguments. We focus on the mean number M of chain contacts with the adsorbing wall, on the chain's extension (the radius of gyration) perpendicular and parallel to the adsorbing surface, on the probability distribution of the free end and on the density profile for all monomers. At the critical adsorption strength epsilon(c) one has M(c) approximately N(phi), and we find (using the above results) as best candidate phi to equal 0.59. However, slight changes in the estimation of epsilon(c) lead to large deviations in the resulting phi; this might be a possible reason for the difference in the phi values reported in the literature. We also investigate the dynamical scaling behavior at epsilon(c), by focusing on the end-to-end correlation function and on the correlation function of monomers adsorbed at the wall. We find that at epsilon(c) the dynamic scaling exponent a (which describes the relaxation time of the chain as a function of N) is the same as that of free chains. Furthermore, we find that for tethered chains the modes perpendicular to the surface relax quicker than those parallel to it, which may be seen as a splitting in the relaxation spectrum.     

Droplet-based microfluidics with nonaqueous solvents and solutions

In droplet-based ("digital") microfluidics, liquid droplets in contact with dielectric surfaces are created, moved, merged and mixed by applying AC or DC potentials across electrodes patterned beneath the dielectric. We show for the first time that it is possible to manipulate droplets of organic solvents, ionic liquids, and aqueous surfactant solutions in air by these mechanisms using only modest voltages (<100 V) and frequencies (<10 kHz). The feasibility of moving any liquid can be predicted empirically from its frequency-dependent complex permittivity, epsilon*. The threshold for droplet actuation in air with our two-plate device configuration is /epsilon*/>8x10(-11). The mechanistic implications of these results are discussed, along with the greatly expanded range of applications for digital microfluidics that these results suggest are now feasible.     

Stability and magnetic characterization of oleate-covered magnetite ferrofluids in different nonpolar carriers

This work describes the preparation and stability evaluation of suspensions consisting of hydrophobic magnetite nanoparticles dispersed in different organic solvents. The ferrite particles are covered by a shell of chemisorbed oleate ions following a procedure that is described in detail. The oleate-covered particles were dispersed in different organic solvents with dielectric constants, epsilon(r), ranging between 1.8 and 9, and the centrifugal field strength needed to remove particle aggregates formed during the synthesis was determined for the different liquid carriers used. A thermodynamic analysis demonstrated that the observed stability of the suspensions in liquids with epsilon(r) < 5 is well correlated with the very low lyophobic attraction between the particles. This can easily be surmounted by thermal agitation, since the van der Waals attraction is negligible. In contrast, for liquids with epsilon(r) > 9, the suspensions become unstable because of the combined action of the van der Waals and lyophobic attractions, the latter being dominant for very polar solvents. Finally, a complete magnetic characterization of the oleate-magnetite powder, as well as of several stable ferrofluids prepared with it, was carried out. From this characterization, the magnetic diameters and magnetic moments of the particles immersed in the different liquid carriers were estimated and compared to those corresponding to the dry magnetic particles. This made it possible to estimate the thickness of the nonmagnetic layer on the particles.     

Bradbury-Nielsen vs. Field switching shutters for high resolution drift tube ion mobility spectrometers

A key component in the design of every drift tube ion mobility spectrometer (IMS) is the ion shutter which controls the injection of ions into the drift tube. Especially, compact drift tube IMS require very short injection pulses to achieve high resolution and therefore require fast ion shutters. Thus, it is important to find an ion shutter principle that can be readily scaled towards these short injection widths without causing major non-idealities in the injection process, such as drift field inhomogeneities, ion loss and ion discrimination by mobility. In this paper, we compare different ion shutter principles, foremost the Bradbury-Nielsen gate and a field switching design. It is shown through theoretical considerations and field simulations that the Bradbury-Nielsen shutter is more universally applicable and typically less complex for long injections widths but field inhomogeneities associated with its operating principle impede the scaling process. Thus, the currently less used field switching shutters will become the superior principle when very short injection widths are required, as this shutter principle allows for single digit microsecond widths.