Mechanical properties of surfactant bilayer membranes from atomistic and coarse-grained molecular dynamics simulations

We use simulations to predict the stability and mechanical properties of two amphiphilic bilayer membranes. We carry out atomistic MD simulations and investigate whether it is possible to use an existing coarse-grained (CG) surfactant model to map the membrane properties. We find that certain membranes can be represented well by the CG model, whereas others cannot. Atomistic MD simulations of the erucate membrane yield a headgroup area per surfactant a(0) of 0.26 nm(2), an elastic modulus K(A) of 1.7 N/m, and a bending rigidity kappa of 5 k(B)T. We find that the CG model, with the right choice for the size and potential well depth of the head, correctly reproduces a(0), kappa, as well as the fluctuation spectrum over the whole range of q values. Atomistic MD simulations of EHAC, on the other hand, suggest that this membrane is unstable. This is indicated by the fact that kappa is of the order of k(B)T, which means that the interface is extremely flexible and diffuse, and K(A) is close to zero, which means that the surface tension is zero. We argue that the CG model can be used if the headgroups are uncharged, dipolar, or effectively dipolar due to headgroup charge screening induced by counterion condensation.     

A Monte Carlo study of fluctuating polymer-grafted membranes

Using Monte Carlo simulations of an off-lattice model, we study the elastic properties of polymer-grafted membranes. Our results are found to be in good agreement with those predicted by the classical path approximation of the self-consistent field theory and scaling theory based on de Gennes' blob picture. In particular, we found that when the membrane is grafted on both sides by brushes with same molecular weight N and grafting density sigma, the excess bending modulus induced by the polymers scales as N3 sigmaalpha where alpha is consistent with 7/3, as predicted by the self-consistent field theory, and 5/2, as predicted by the scaling theory. When the polymers are grafted to one side of the membrane only, the membrane bends away from the polymers with a spontaneous curvature with a scaling that is consistent with both scaling and self-consistent field theories. When the thickness of the brush exceeds the membrane's spontaneous radius of curvature, the bending modulus approaches a constant which is of the same order as the bending modulus of the bare membrane.     

Multiscale coupling of mesoscopic- and atomistic-level lipid bilayer simulations

A multiscale method is presented to bridge between the atomistic and mesoscopic membrane systems. The atomistic model in this case is the united atom dimyristoylphosphatidylcholine membrane system, although the method is completely general. Atomistic molecular dynamics provides the expansion modulus which is used to parametrize a mesoscopic elastic membrane model. The resulting elastic membrane model, including explicit mesoscopic solvent, shows appropriate static and dynamic undulation behaviors. Large membranes of approximately 100 nm in length can then be easily simulated using the mesoscopic membrane system. The critical feedback from the mesoscopic system back down to the atomistic-scale system is accomplished by bridging the stress (or surface tension) of a small region in the mesoscopic membrane to the corresponding atomistic membrane system. Because of long length-scale modes of membranes such as undulation and buckling, the local tension responds differently from the frame tension, when subjected to external perturbations. The effect of these membrane modes is shown for the stress response of a local membrane region and therefore the atomistic membrane system. In addition, certain equilibrium static and dynamic properties of stand-alone and multiscale coupled systems are presented for several different membrane sizes. Although static properties such as two-dimensional pair-correlation function and order parameters show no noticeable discrepancy for the different systems, lipid self-diffusion and the rotational relaxation of lipid dipoles have a strong dependence on the membrane size (or long-wavelength membrane motions), which is properly modeled by the present multiscale method.     

Thermal conductivity of a polymerizing liquid

Thermal conductivity kappa of seven polymerizing liquids has been measured in real time at different temperatures, and calorimetry and dielectric spectroscopy of one liquid are performed to help interpret the results. As a covalently bonded linear chain or a network structure in the liquid grows, kappa of the Debye equation initially increases with the polymerization time t(polym) as the molecular weight, density, and sound velocity increase, as on cooling a liquid. The measured kappa reaches a maximum and then decreases, thus showing a peak at a certain t(polym) and finally becomes constant, which is not the true behavior of steady state kappa. The dielectric relaxation time of the covalently bonded structure at the t(polym) for the kappa peak is less than 5 s and the extent of polymerization is below the vitrification plateau value. The peak height increases when the pulse time for kappa measurement is increased. An increase in the liquid's temperature shifts the kappa peak to a shorter t(polym). Liquid compositions polymerizing rapidly show a similar shift, and those polymerizing slowly or whose viscosity does not reach a high enough value show a small kappa peak or none. The kappa peak may be an artifact of the time dependence of heat capacity during the pulse time used for the kappa measurement, as proposed for glasses and supercooled liquids, similar to the changes in other properties observed as an artifact of kinetic freezing/unfreezing. For a polymerizing liquid, the peak may additionally arise when the rate of increase in the elastic modulus becomes equal to the rate of decrease in equilibrium Cp. In either case, its appearance does not distinguish the Brownian motions' slowing on polymerization from that on cooling or compressing a liquid.     

Modeling a catalytic polymeric non-porous membrane reactor

A theoretical study on a catalytic polymeric non-porous membrane reactor is performed. The conversion enhancement over the thermodynamic equilibrium is studied when conducting an equilibrium gas-phase reaction of the type A+B⇔C+D. The model used considers perfectly mixed flow patterns and isothermal operation for the retentate and permeate. It is concluded that the conversion of a reversible reaction can be significantly enhanced when the reactants’ diffusion coefficients are lower and/or sorption coefficients are higher than the products’. This happens for Thiele modulus and contact time over certain threshold values. It was also observed that it is preferable to enhance conversion through an increase in the reactants’ sorption coefficients, since this leads to lower reactor dimensions. Since the performance of a non-porous membrane reactor depends on both the sorption and diffusion coefficients, a study of such system cannot be based exclusively on the permeabilities of the components. Favorable combinations of diffusion and sorption coefficients can provide a coupled effect over the reactor’s conversion.     

Effect of Bulk and Interfacial Rheological Properties on Bubble Dissolution

This paper describes theoretical calculations of the combined effect of bulk and interfacial rheological properties on dissolution behavior of a bubble in an infinite medium at saturated conditions. Either bulk or interfacial elasticity can stop the bubble dissolution process, and stability criteria are defined for the elastic cases. In the case of an elastic interface with dilation modulus E(d) and a bubble with an initial radius R(0) and initial interfacial tension sigma(0), the bubble is stabilized as it has shrunk to a relative radius of varepsilon=R/R(0)=exp(-sigma(0)/2E(d))). In case of an elastic bulk with modulus G a bubble will shrink until GR(0)=4sigma(0)varepsilon(3)/(1-5varepsilon(4)+4varepsilon(3)) is fulfilled. Bulk and interfacial viscosity can retard the dissolution process if their magnitude exceeds a certain critical value but will never completely stop bubble dissolution. Copyright 2001 Academic Press.     

Role of polydispersity in anomalous interactions in electrostatically levitated colloidal systems

In this paper, we investigate the effects of using inverse analyses developed for monodisperse particles to extract particle-particle and particle-surface potentials from simulated interfacial colloidal configurations having finite-size polydispersity. Forward Monte Carlo simulations are used to generate three-dimensional equilibrium configurations of log normal-distributed polydisperse particles confined by gravity near an underlying surface. Particles remain levitated above the substrate and stabilized against aggregation by repulsive electrostatic Derjaguin-Landau-Verwey-Overbeek pair potentials. An inverse Ornstein-Zernike analysis and an inverse Monte Carlo simulation method are used to obtain interactions from simulated distribution functions as a function of polydispersity (sigma), relative range of repulsion (kappa a), and projected interfacial concentration (rho). Both inverse analyses successfully recover input potentials for all monodisperse cases, but fail for polydispersities often encountered in experiments. For different conditions (sigma, kappa a, and rho), our results indicate softened short-range repulsion, anomalous long-range attraction, and apparent particle overlaps, which are similar to commonly reported observations in optical microscopy measurements of quasi-two-dimensional interfacial colloidal ensembles. By demonstrating signatures of, and limitations due to, polydispersity when extracting pair potentials from measured distribution functions, our specific goal is to provide a basis to objectively interpret and resolve the effects of polydispersity in optical microscopy experiments.     

A study of the elastic properties of winding composites of unidirectional structures with the use of the resonance method

Changes in the material elastic properties of winding composite rings of unidirectional structure under the influence of cyclically changing temperatures and moisture with the use of the resonance method is studied. The advantages of the resonance method over standard methods for determination of the elastic modulus are mentioned. Results of experiments for determination of the elastic modulus of winding fiberglass rings after the action of high temperature and moisture are given.     

Elastic properties of electrospun PVDF nanofibrous membranes: Experimental investigation and numerical modelling using pixel-based finite element method

In this paper, experimental investigation and numerical modelling of the mechanical properties of polyvinylidene fluoride (PVDF) nanofibrous membranes produced by electrospinning are addressed. Membranes with three different diameters are fabricated by adjusting the needle-collector distance during electrospinning. The fiber morphology and the physical properties of the resulting membranes are investigated using Scanning Electron Microscopy (SEM) while their elastic properties are probed using conventional tensile tests. It is found that the membrane with the largest nanofiber diameters are filled with large beads while the contrary is found in the membrane with the smallest nanofiber diameter. Consequently, the membrane with the smallest nanofiber diameter yielded the highest membrane Young's modulus thanks to better fiber packing and higher crystallinity in the nanofibers. Next, the experimental results serve as basis for a pixel-based finite element method (FEM) which is applied directly on the SEM images of the membranes. This technique has the advantage of providing estimations of mechanical properties from the real structure of the membranes. Two parameters are needed for this linear elastic analysis: the elastic modulus of a single fiber and the fiber percentage in the membrane. Results show that the model predictions are in good agreement with experimental data. These results suggest that the pixel-based FEM could be a promising nondestructive alternative to the conventional tensile tests.     

表面活性剂对氧化锰悬浮体系流变学振荡行为的影响

对介孔氧化锰的溶胶-凝胶法合成和用表面活性剂（脂肪醇聚氧乙烯醚, AEO_9)的模板合成过程中所得的悬浮体系的流变性质进行了对比研究。结果表明： 上述体系均具有触变性,且无论是否预剪切,其表观粘度均随时间作周期性振荡; 同时上述体系的储能模量G'和损耗模量G"亦具有周期性的振荡行为。但表面活性剂 AEO_9的引入使体系的触变性大为减弱,屈服值明显降低,凝胶结构强度减弱。同 时还发现引入AEO_9的模板合成过程中,不仅体系的表观粘度及G'大幅度下降,且 G'与G"的振荡周期显著增大,振幅亦明显减小。这说明体系中两亲分子与无机物存 在较强的相互作用,作者还对这些现象进行了讨论。     

Adsorption of DNA and electric fields decrease the rigidity of lipid vesicle membranes

The adsorption of calf-thymus DNA-fragments of 300 +/- 50 base pairs (bp) to the outer membrane monolayer of unilamellar lipid vesicles in the presence of Ca2+ ions has been quantified by the standard method of chemical relaxation spectrometry using polarized light. The vesicles of radius a = 150 +/- 45 nm are prepared from bovine brain extract type III containing 80-85% phosphatidylserine (PS) and palmitoyl-oleoyl-phosphatidylcholine (POPC) in the molar ratio PS : 2POPC; total lipid concentration [L(t)] = 1 mM in 1 mM HEPES buffer, pH 7.4 at T = 293 K (20 degrees C). The turbidity relaxations of vesicle suspensions, at the wavelength lambda = 365 nm at two characteristic electric field strengths are identified as electroelongation of the whole vesicle coupled to smoothing of thermal membrane undulations and membrane stretching, and at higher fields, to membrane electroporation (MEP). The elongation kinetics indicates that the DNA adsorption renders the membrane more flexible and prone to membrane electroporation (MEP). Remarkably, it is found that the Ca-mediated adsorption of DNA (D) decreases both, bending rigidity kappa and stretching modulus K, along an unique Langmuir adsorption isotherm for the fraction of bound DNA at the given Ca concentration [Ca(t)] = 0.25 mM. The characteristic chemo-mechanical parameter of the isotherm is the apparent dissociation equilibrium constant K(D,Ca) = 100 +/- 10 microM (bp) of the ternary complex DCaB of DNA base pairs (bp) and Ca binding to sites B on the outer vesicle surface. Whereas both kappa and K decrease in the presence of high electric fields (E), the key parameter K(D,Ca) is independent of E in the range 0 < or = E/(kV cm(-1)) < or = 40.     

Determination of the elastic moduli of polymer films by a new ultrasonic reflection method

The development and first applications of a new ultrasonic reflection method for determination of the viscoelastic properties of polymer films are reported. The complex shear modulus G* and the complex longitudinal modulus L*=K*+ 4/3 G* of the samples are derived from the measured complex reflection coefficients of an ultrasonic shear and longitudinal wave, respectively. From G and L the Young's modulus E, the compression modulus K and the Poisson ratio ν can be calculated for isotropic materials. A LiNbO₃-transducer (10° rotated Y-cut) is used for the simultaneous excitation of longitudinal and transversal ultrasonic waves, which allows to determine different elastic constants by one measurement. A measuring cell with normal incidence of the ultrasonic waves is used. The equipment has been applied to study the time dependence of the moduli during film formation from an aqueous polymer dispersion and the isothermal curing of an epoxy resin. Furthermore, the temperature dependence of the elastic constants of a carbon-black filled rubber and during non-isothermal crystallization of a semi-crystalline polymer has been studied.     

Elasticity of polymer gels: Effect of solvent quality on the shear modulus of poly(vinyl acetate) networks

The dependence of the shear modulus and of the swelling equilibrium concentration of polyvinylacetate gel homologues in equilibrium with excess isopropyl alcohol is investigated in the temperature range 30≤T≤70°C. At the theta temperature (T=52°C) the volume elastic modulus was also determined and compared with the shear modulus. The results are interpreted in terms of a free-energy function derived on the basis of the network unfolding hypothesis.     

分子动力学模拟浓度和温度对TATB/PCTFE PBX力学性能的影响

为探讨高聚物粘结炸药(Polymer Bonded Explosive, PBX)的力学性能随温度和高聚物浓度而变化的规律, 用分子动力学(MD)方法和compass力场, 对著名高能炸药1,3,5-三氨基-2,4,6-三硝基苯(TATB)与常用高聚物粘结剂聚三氟氯乙烯(PCTFE)所构成的TATB/PCTFE PBX进行模拟计算. 结果表明, 在一定范围内, 随高聚物浓度的增加, PBX的弹性系数和模量减小, 表明其刚性减小、弹性增加; 而随温度的升高, PBX的刚性减小、弹性增强. 还发现PBX的结合能随浓度增高而增大, 随温度升高而减小.     

Topology-dependent protein folding rates analyzed by a stereochemical model

It is an experimental fact that gross topological parameters of the native structure of small proteins presenting two-state kinetics, as relative contact order chi, correlate with the logarithm of their respective folding rate constant kappa(f). However, reported results show specific cases for which the (chi,log kappa(f)) dependence does not follow the overall trend of the entire collection of experimental data. Therefore, an interesting point to be clarified is to what extent the native topology alone can explain these exceptional data. In this work, the structural determinants of the folding kinetics are investigated by means of a 27-mer lattice model, in that each native is represented by a compact self-avoiding (CSA) configuration. The hydrophobic effect and steric constraints are taken as basic ingredients of the folding mechanism, and each CSA configuration is characterized according to its composition of specific patterns (resembling basic structural elements such as loops, sheets, and helices). Our results suggest that (i) folding rate constants are largely influenced by topological details of the native structure, as configurational pattern types and their combinations, and (ii) global parameters, as the relative contact order, may not be effective to detect them. Distinct pattern types and their combinations are determinants of what we call here the "content of secondary-type" structure (sigma) of the native: high sigma implies a large kappa(f). The largest part of all CSA configurations presents a mix of distinct structural patterns, which determine the chixlog kappa(f) linear dependence: Those structures not presenting a proper chi-dependent balance of patterns have their folding kinetics affected with respect to the pretense linear correlation between chi and log kappa(f). The basic physical mechanism relating sigma and kappa(f) involves the concept of cooperativity: If the native is composed of patterns producing a spatial order rich in effective short-range contacts, a properly designed sequence undertakes a fast folding process. On the other hand, the presence of some structural patterns, such as long loops, may reduce substantially the folding performance. This fact is illustrated through natives having a very similar topology but presenting a distinct folding rate kappa(f), and by analyzing structures having the same chi but different sigma.     

On the theory of permeation and thermoosmosis

It is shown that by due consideration of the mechanical equilibrium inside the membrane, formulas for membrane processes derived previously (1966) and subject to certain restrictions become perfectly general. These formulas relate membrane properties, such as mechanical and thermoosmotic permeabilities, to transport coefficients which are valid for the interior of the membrane (treated as a binary continuous system) such as diffusion coefficient and thermal diffusion factor. The method used in this general treatment is that of Thermodynamics of Irreversible Processes. As an example, the interrelation between the (mechanical) permeability and the diffusion coefficient is given explicitly.     

Using the Dugdale approximation to match a specific interaction in the adhesive contact of elastic objects

In the Maugis-Dugdale model of the adhesive contact of elastic spheres, the step cohesive stress sigma(0) is arbitrarily chosen to be the theoretical stress sigma(th) to match that of the Lennard-Jones potential. An alternative and more reasonable model is proposed in this paper. The Maugis model is first extended to that of arbitrary axisymmetric elastic objects with an arbitrary surface adhesive interaction and then applied to the case of a power-law shape function and a step cohesive stress. A continuous transition is found in the extended Maugis-Dugdale model for an arbitrary shape index n. A three-dimensional Johnson-Greenwood adhesion map is constructed. A relation of the identical pull-off force at the rigid limit is required for the approximate and exact models. With this requirement, the stress sigma(0) is found to be k(n)Deltagamma/z(0), where k(n) is a coefficient, Deltagamma the work of adhesion, and z(0) the equilibrium separation. Hence we have sigma(0) = 0.588Deltagamma/z(0), especially for n=2. The prediction of the pull-off forces using this new value shows surprisingly better agreement with the Muller-Yushchenko-Derjaguin transition than that using sigma(th) = 1.026Deltagamma/z(0), and this is true for other values of shape index n.     

Network formation in polyurethanes due to allophanate and biuret formation: Gel fraction and equilibrium modulus

Gel fraction and equilibrium elastic modulus of networks formed from α, ω-dihydroxypoly(oxypropylene) and bis(4-isocyanatophenyl)methane (MDI) as a result of side reactions were compared with theoretical predictions based on the theory of branching processes (Macromolecules, 23, 1774 (1990)). If isocyanate is in excess, trifunctional allophanate and biuret groups are formed. The experimental sol fraction can be correlated with theoretical predictions. The resulting networks are rather weak and the measured equilibrium modulus can be correlated with the theoretical values calculated from the concentration of elastically active network chains if the value of the front factor is close to that of a phantom network without a trapped entanglements contribution.     

(2n,n) potential and sticky-sphere fluids

The authors investigate the behavior of a model fluid for which the interaction energy between molecules at a separation r is of the form 4epsilon[(sigma/r)2n-(sigma/r)n], where epsilon and sigma are constants and n is a large integer. The particular properties they study are the pressure p, the mean square force F2, the elastic shear modulus at infinite frequency Ginfinity, the bulk modulus at infinite frequency Kinfinity, and the potential energy per molecule u. They show that if n is sufficiently large it is possible to derive the properties of the system in terms of two parameters, the values of the cavity function and of its derivative at the position r=sigma. As an example they examine in detail the cases with n=144 and n=72 for three different temperatures and they test the theory by comparison with a computer simulation of the system. They use the simulated pressure and the average mean square force to determine the two parameters and use these values to evaluate other properties; it is found that the theory produces results which agree with computer simulation to within approximately 3%. It is also shown that the model, when the parameter n is large, is equivalent to Baxter's sticky-sphere model with the strength of the adhesion determined by the value of n and the temperature. They use Baxter's solution of the Percus-Yevick equations for the sticky-sphere model to determine the cavity function and from that the values of the same properties. In this second approach there are no free parameters to determine from simulation; all properties are completely determined by the theory. The results obtained agree with computer simulation only to within approximately 6%. This suggests that for this model one needs a better approximation to the cavity function than that provided by the Percus-Yevick solution. Nevertheless, the model looks promising for the study of (typically small) colloidal liquids where the range of attraction is short but finite when compared to its diameter, in contrast to Baxter's sticky-sphere limit where the attractive interaction range is taken to be infinitely narrow. The continuous function approach developed here enables important physical properties such as the infinite shear modulus to be computed, which are finite in experimental systems but are undefined in the sticky-sphere model.