Influence of vibrational energy flow on isomerization of flexible molecules: incorporating non-Rice-Ramsperger-Kassel-Marcus kinetics in the simulation of dipeptide isomerization

The conformational isomerization of a dipeptide, N-acetyl-tryptophan methyl amide (NATMA), is studied computationally by including important dynamical corrections to Rice-Ramsperger-Kassel-Marcus (RRKM) theory for the transition rate between pairs of isomers. The dynamical corrections arise from incomplete or sluggish vibrational energy flow in the dipeptide, a property suggested by the mode-selective chemistry that has been observed by Dian et al. [J. Chem. Phys. 120, 133 (2004)]. We compute the extent and rate of vibrational energy flow in NATMA quantum mechanically using local random matrix theory, which we then use to correct the RRKM theory rates. The latter rates are then introduced into a master equation to study the population dynamics of the dipeptide. Incomplete or slow vibrational energy flow is found to enhance the conformational selectivity of NATMA over RRKM estimates.     

剪切流动对聚合物共混物相行为影响的研究进展

剪切流动对聚合物共混物相行为影响的研究进展;综述     

Electroosmotic flow in a rectangular channel with variable wall zeta-potential: comparison of numerical simulation with asymptotic theory

Electroosmotic flow in a straight micro-channel of rectangular cross-section is computed numerically for several situations where the wall zeta-potential is not constant but has a specified spatial variation. The results of the computation are compared with an earlier published asymptotic theory based on the lubrication approximation: the assumption that any axial variations take place on a long length scale compared to a characteristic channel width. The computational results are found to be in excellent agreement with the theory even when the scale of axial variations is comparable to the channel width. In the opposite limit when the wavelength of fluctuations is much shorter than the channel width, the lubrication theory fails to describe the solution either qualitatively or quantitatively. In this short wave limit the solution is well described by Ajdari's theory for electroosmotic flow between infinite parallel plates (Ajdari, A., Phys. Rev. E 1996, 53, 4996-5005.) The infinitely thin electric double layer limit is assumed in the theory as well as in the simulation.     

Steady-shear viscosity of polydimethylsiloxanes over the range from the lower to the upper Newtonian region

The mechanism of non-Newtonian behavior for flow from the lower to the upper Newtonian region is explained by a modification of Graessley's theory. In the theory proposed here, a viscosity η_fric, which is based on friction between polymer segments and is almost shear-independent, is introduced in addition to Graessley's entanglement viscosity η_ent, which decreases with increasing shear rate. The theory is applied to previously obtained data on steady flow of polydimethylsiloxanes of different molecular weights. The agreement between calculated and experimental results is good. In polymers with the molecular weight above the critical molecular weight for entanglement M_c, the major contribution to viscosity near zero shear rate is η_ent. As the shear rate increases, the flow curve has an inflection where η_fric cannot be disregarded in comparison with η_ent. In the upper Newtonian region, η_fric has more influence on the viscosity than η_ent. The theory can also explain the experimental results on flow of polymers with molecular weight below M_c, which were shown to be slightly non-Newtonian in the previous paper.     

Recent advances in theoretical liquid crystal rheology

Recent significant advances in theoretical liquid crystalline rheology are presented. Dynamic simulations are performed using a complete theory which include the three major effects of liquid crystalline materials: (1) short range order elasticity, (2) long range order elasticity, and (3) viscous flow effects. The results and discussions include rectilinear simple shear flow, complex non-linear phenomena such as defect texture generation and coarsening processes under quiescent and shear conditions, and pattern formation such as banded texture during and after cessation of flow. The complete theory predicts four in-plane (1-D orientation) flow modes and five out-of-plane (2-D orientation) flow modes in one-dimensional shear flow, depending on the magnitudes of R (ratio of short to long range order elasticity) and Er (Ericksen number: ratio of viscous to elastic force). The multistability of these flow modes is clearly explained in terms of degrees of freedoms in the nematic orientation. The number of degrees of freedom increases with increasing the spatial dimension of the system, and thus more complex orientation patterns arise in the higher dimension. Well-known defect structures arise and coarsen during simulations of the isotropic to nematic phase transition. The effect of shear flow on the defect generation process is to suppress the defect nucleation, and the simulations suggest a method of how to create defect-free nematic samples. The banded textures during and after cessation of flow are also captured by the complete theory.     

Analysis of the microfluid flow in an evaporating sessile droplet

The axisymmetric time-dependent flow field in an evaporating sessile droplet whose contact line is pinned is studied numerically and using an analytical lubrication theory with a zero-shear-stress boundary condition on the free surface of the droplet at low capillary and Reynolds numbers. A finite element algorithm is developed to solve simultaneously the vapor concentration and flow field in the droplet under conditions of slow evaporation. The finite element solution confirms the accuracy of the lubrication solution, especially when terms of higher order in the droplet flatness ratio (the ratio of droplet height to radius, h/R) are included in the lubrication theory to account more accurately for the singular flow near the contact line.     

General theory for flow optimisation of split-flow thin fractionation

Recently, magnetic split-flow thin (SPLITT) fractionation has been developed to separate macromolecules, colloids, cells and particles. However, the previous theory, developed for an infinitely long channel, needs to be improved to consider the flow transit regimes at both inlet and outlet. In this paper, we describe a new approach to optimising flow-rates for particle separation which considers the effect of flow transit region. Surprisingly, the critical particle migration velocities derived by the present theory are identical to the previous simplified theory. Therefore, the previous simplified theory may have wider application than might have been expected. As a test of our theory, a numerical simulation based on solving Navier-Stokes equations has also been carried out for a magnetic SPLITT device. The trajectory of a particle with the critical migration velocity is exactly as expected by our theory. Following experimental validation, this work will facilitate the design of new SPLITT fractionation systems with smaller aspect ratio.     

Graph Methodology and Principles of Linear Nonequilibrium Thermodynamics in the Theory of Flow-Injection Analysis

It is shown that chemical, configurational, and informational properties of flow-injection systems can be interrelated with the use of the methodology of the graph theory. The main equation of the theory is derived using a mathematical expression of the transition paths from the analyte to the detection of a product of the analytical reaction. Examples of specific developments are discussed for redox reactions, ligand exchange reactions, and heterogeneous exchange reactions, with due regard to, the hidden peculiarities of their chemical mechanisms that are essential for flow analysis and also for on-line preconcentration by coprecipitation. It is also shown that the conditions obtained in a flow system correspond to the basic postulates of linear nonequilibrium thermodynamics, which provides a basis for a new approach to the theory of flow analysis. An example of a complexation reaction was used for discussing the possibility that a linear interrelation exists between flows and forces in a flow system, which corresponds to the Onsager reciprocal relation.     

Effects of flexibility on liquid crystalline polymer behavior: The nematic broken rod

A new theory for liquid crystalline polymers is developed, and its behavior in simple shear flow is analyzed. The theory accounts for molecular flexibility by employing a microstructure consisting of two rigid rods linked by a joint with a tunable stiffness. The probability distribution function equation for the orientation of the arms of the broken rod is derived. The adaptation of the smoothed particle hydrodynamics (SPH) technique for obtaining numerical solutions to this theory is detailed. The behavior of the theory at equilibrium is derived analytically and compared with numerical results; the SPH technique is then used to obtain results in flow. It is found that in the limit of a nearly stiff joint, the model gives behavior that is very similar to that of rigid rod polymers, the only difference being a lesser tendency to tumble due to greater variation in the order parameter. For nearly free joints, the shear flow induces interesting dynamics for the transition between states with the arms outstretched and those where they are folded up (so‐called “hairpins” of main‐chain LCPs). © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 281–300, 1999     

Modified graessley theory for non-newtonian viscosities of polydimethylsiloxanes and their solutions

A deviation from Graessley's theory of entanglement viscosity appears at very high shear rates when the flow of polydimethylsiloxanes of various molecular weights and their solutions with various concentrations is measured by the capillary method. In order to explain this deviation, a modified Graessley theory is proposed according to the previously reported suggestion that frictional viscosity appears not to be negligible at high shear rates. A reducing procedure taking a frictional viscosity parameter into account was performed. All of the reduced data are combined to give a master curve in spite of a wide range of molecular weight, concentration, and shear rate (from the lower Newtonian to very highest non-Newtonian flow region). The findings from the reducing procedure completely explain the mechanism of non-Newtonian flow for the bulk polymers with various molecular weights, including those below the critical molecular weight for entanglement, and for polymer solutions at any concentration. The viscosity of the linear polymer system consists of the shear-dependent entanglement term η_ent proposed by Graessley and the shear-independent frictional term η_fric. The non-Newtonian behavior depends on the ratio of η_ent/η_fric at the shear rate of measurement. The ratio of zero-shear entanglement viscosity η_ent,0 to η_fric and the critical shear rate for onset of the non-Newtonian flow may be used as a measure of the non-Newtonian behavior of the system and a measure of capability for its rising, respectively. The Graessley theory is to be included in the present modified theory and is applicable to the case of η_entη_fric ? 1.     

The determination of the viscosity coefficients of nematic liquid crystals

This paper considers the flow generated by driving a sample of nematic liquid crystal through a rectangular capillary by application of a small pressure gradient in the presence of a large aligning magnetic field. A theoretical calculation based on the continuum theory of nematics is presented which makes some allowance for non-uniform alignment induced by flow, and allows a more accurate determination of the viscosities corresponding to the three principal configurations in the plane of shear.     

A new instrument for measuring the viscoelastic properties of dilute polymer solutions

A new oscillating capillary viscometer has been developed and used for measuring viscoelastic flow properties of dilute polymer solutions. These flow properties are determined from measurements of the pressure to volume flow relationships for sinusoidal flow in cylindrical glass capillaries. The theory for this measurement procedure is based upon the known theory for oscillatory flow of a viscoelastic fluid in circular tubes and which is presented with a few supplementations in this paper.The oscillatory flow is generated by a piezoelectric driver which is dipped directly into the aqueous solution. The advantage of this driver is that the excitation voltage for the piston is a direct measure of the motion of the piston. Changes in pressure are measured with a sensitive low-pressure quartz tranducer.The viscometer was tested with aqueous glycerol solutions and a gelatin gel. The viscoelastic flow properties of dilute polymer solutions (gelatin, gelatin/color-coupler, polyacrylamide) were then investigated in the frequency range 5 Hz to 150 Hz at very small volume flow amplitudes. The results presented illustrate the suitability of the method. The results are also evaluated with regard to the stabilizing action of slightly viscoelastic gelatinous coating liquids in the high-speed coating process in the manufacture of photographic materials.     

Flow birefringence of temporary polymer networks

The statistical theory of temporary polymer networks is an effort of describing the macroscopic behavior of such networks based on molecular behavior analysis. The calculation of the stress tensor of a network and the satisfactory comparison with experimental viscosity results was shown before [Rheol. Acta 28 (1989) 193]. Here we present the foresights of the theory as regards flow birefringence. The polarizability tensor is calculated first and then the birefringence of a four-functional temporary polymer network is estimated for a stationary simple shear flow. The dependence of the calculated quantities on shear rate is in line with existing experimental evidence.     

Drag and Torque on Clusters of N Arbitrary Spheres at Low Reynolds Number

Hydrodynamics of particle clusters suspended in viscous fluids is a subject of considerable theoretical and practical importance. Using a multipole expansion of the flow velocity in a series of spherical harmonics, Lamb's fundamental solution of the Stokes flow outside a single sphere is generalized in this work to the case of N nonoverlapping spheres of arbitrary size with slip boundary conditions. The expansion coefficients are found by transforming the boundary conditions to the Lamb form and by transforming the spherical coordinates and solid spherical harmonics centered at different spheres. The problem is reduced to the solution of the linear system of equations for the expansion coefficients, which is carried out numerically. Based on the developed theory, the relation between the hydrodynamic and gyration radius of fractal-like aggregates with different structure is established. In another application, an asymptotic slip-regime dependence of the aggregate hydrodynamic radius on the Knudsen number and the number of particles is found by performing calculations of drag forces acting on the gas-borne fractal-like and straight chain aggregates. A good agreement is shown in comparing predictions of the described theory with available experimental and theoretical results on motion of various small sphere clusters in viscous fluid. Copyright 2000 Academic Press.     

Effect of surface tension and surface elasticity of a fluid-fluid interface on the motion of a particle immersed near the interface

The motion of a particle immersed in a fluid near a fluid-fluid interface is studied on the basis of the linearized Navier-Stokes equations. The motion is influenced by surface tension, dilatational surface elasticity modulus, and surface shear modulus, as well as by gravity. The backflow at the location of the particle after a sudden impulse has some universal features that are the same as for a rigid wall with stick boundary conditions. At short times the flow depends only on the mass densities of the two fluids. The nature of the short-time flow is calculated from potential flow theory. At a somewhat later time the particle shows a pronounced rebound. The maximum value of the rebound and the time at which the maximum occurs depend on the elastic properties of the interface.     

AC electrokinetics of conducting microparticles: A review

This paper reviews both theory and experimental observation of the AC electrokinetic properties of conducting microparticles suspended in an aqueous electrolyte. Applied AC electric fields interact with the induced charge in the electrical double layer at the metal particle–electrolyte interface. In general, particle motion is governed by both the electric field interacting with the induced dipole on the particle and also the induced-charge electro-osmotic (ICEO) flow around the particle. The importance of the RC time for charging the double layer is highlighted. Experimental measurements of the AC electrokinetic behaviour of conducting particles (dielectrophoresis, electro-rotation and electro-orientation) are compared with theory, providing a comprehensive review of the relative importance of particle motion due to forces on the induced dipole compared with motion arising from induced-charge electro-osmotic flow. In addition, the electric-field driven assembly of conducting particles is reviewed in relation to their AC electrokinetic properties and behaviour.     

Electrokinetic lift force for a charged particle moving near a charged wall — a modified theory and experiment

We present the refined theory of the electrokinetic lift force for a charged particle moving at a charged wall at the distance much larger than the double layer thickness. The theory is based on the lubrication approximation for the solution of the Stokes equation for the flow around a long cylinder moving near a solid wall. The “thin double layer” approximation is used to solve the ionic balance and electro-osmotic flow equations. The electrokinetic lift force is then obtained by integration of the viscous stress tensor as well as the Maxwell stress tensor over the particle surface. The resulting lift force for the cylinder translating, rotating at the wall as well as for the stationary cylinder in the wall shear flow, is considered. Following this, we apply the Derjaguin approximation to transform the obtained results to the sphere–wall geometry and we compare our theoretical predictions with the measurements of the electrokinetic lift force performed in the “colloidal particle collider” apparatus for the latex particles suspended in the glycerol–water solutions. Our theoretical results for the electrokinetic lift force exceeds by several orders of magnitude one obtained from the previously developed theory and are in a good agreement with experimental findings.     

Dependence of fragmentation behavior of colloidal aggregates on their fractal structure

The fragmentation dynamics of aggregate of non-Brownian particles in shear flow is investigated numerically. The breakup behaviors of aggregates having the same connectivity but the different space-filling properties are examined. The Lagrangian particle simulation in a linear flow field is performed. The effect of surrounding fluid on the motion of multiple particles is estimated by Stokesian dynamics approach. The inter-particle force is calculated from the retarded van der Waals potential based on the Lifshitz theory. The results obtained in this work indicate that the fragmentation behavior of colloidal aggregates depends on their fractal structure. However, if the resultant aggregate size is smaller than the critical one, the fragmentation behavior shows the universality regardless of their original structure. Furthermore, the restructuring of aggregate in shear flow and its effect on the fragmentation process are also discussed.