Force-extension curve of a polymer in a high-frequency electric field

We study theoretically the conformation and force-extension curve of a semiflexible polymer in a spatially uniform ac electric field. The polymer backbone minimizes its energy by aligning along one of two orientations parallel to the field. In a strong ac field, hairpin kinks develop between regions of opposite alignment. These kinks are mathematically described as sine-Gordon solitons. We calculate the equation of state of the one-dimensional kink gas, which yields the force-extension curve of the polymer. A sufficiently strong ac field causes the polymer to extend spontaneously to almost its full contour length. The theory is applied to recent experiments on dielectrophoretic stretching of DNA.     

Probability distribution of internal distances of a single polymer in good solvent

IfP _ij(x) is the probability distribution function of the scaled distancex between two elementsi andj of a long polymer in a good solvent, it is shown by Monte Carlo calculations that is in good agreement with out data for allx (B is a normalization constant). As a model we consider the freely jointed chain consisting ofN=160 rigid links. We estimate the exponents to ₀=0.27±0.01, ₀=2.44±0.02 (fori=1,j=N); ₁=0.55±0.06, ₁=2.60±0.15 (fori=1,j=N/2); ₂=0.9±0.1, ₂=2.48±0.06 (fori=N/4,j=3N/4). ₀ and ₀ are in agreement with ₀=1/(1-v) and ₀=(-1)/v proposed by Fisher and des Cloiseaux respectively, but we find concerning ₁ and ₂ that our estimates differ from recent -expansion calculations, by an amount of 20–30%. We analyse the crossover between the various exponents.     

Emission of a single conjugated polymer chain isolated in its single crystal monomer matrix

The excitonic luminescence of a highly ordered single conjugated polymer chain is studied by microphotoluminescence. At T< or =10 K it consists of a single Lorentzian line. The linewidth increases linearly with T between 6 and 60 K, from 350 microeV at 6 K, indicating a pure dephasing time of approximately 2 ps. Above 10 K, other neighboring regions along the chain direction start to emit at a slightly higher (by approximately 1 meV) energy. This indicates very small inhomogeneous broadening, very long chains ( > or =10 microm), and a long range and very rapid exciton energy transfer ( >10 microm in <100 ps).     

Molecular dynamics simulation of AFM studies of a single polymer chain

Single polymer chain force-extension behavior measured by Atomic Force Microscopy (AFM) was interpreted by molecular dynamics (MD) simulation performed by applying a bead-spring (coarse-graining) model in which the bond potential function between adjacent beads is described by a worm-like chain (WLC) model. Simulation results indicate that caution should be applied when interpreting experimental AFM data, because the data vary depending on the point of AFM tip-polymer chain attachment. This approach offers an effective way for eventual analysis of the mechanical behavior of complex polymer networks.     

Surface diffusion dynamics of a single polymer chain in dilute solution

Comprehensive three-dimensional dissipative particle dynamics simulations are carried out to elucidate the diffusion mechanism of a strongly adsorbed polymer chain on a solid surface in dilute solutions. We find Rouse and reptation dynamics for polymer chain diffusing on smooth and rough surfaces (with obstacles or sticking points), respectively. Combining with scaling analysis, we find that the interactions between the surface and the fluid screen the hydrodynamic interaction. The different scaling as found for a polymer chain diffusing on a fluid membrane [Phys. Rev. Lett. 82, 1911 (1999)] and on a solid surface [Nature (London) 406, 146 (2000)] may be explained by the solid surface inhomogeneity that induces reptation.     

A comprehensive molecular dynamics study of a single polystyrene chain in a good solvent

In this study, molecular characteristics of polystyrene (PS) was calculated measuring its dilute-solution properties in toluene at 288.15 K via molecular dynamics (MD) simulations. The solution models consisted of PS chains with different number of repeating units all of which were in a dilute regime. In order to investigate the compatibility between the polymer and the solvent molecules, interaction energy and Flory-Huggins (FH) interaction parameter were estimated. The simulation results indicate that increasing the chain repeating units enhanced the interaction between the solute and the solvent. Additionally, the chain dimensions were evaluated calculating the radius of gyration (R_g) and end-to-end distance, r0. To determine the dynamic behavior of the chains in the solutions, mean square displacement (MSD) and diffusivity coefficient were calculated. The simulation results indicated that the chain rigidity at low molecular weight and chain flexibility with increasing the molecular weight influenced chains dynamic behavior and diffusivity. Moreover, radial distribution function (RDF) illustrated the effect of steric hindrance of the chains in dilute solution on capturing the solvent molecules. In addition, solution viscosity was calculated by performing non-equilibrium molecular dynamics simulation (NEMD). The obtained results of chain characteristics and viscosity showed a good agreement with experimental results published previously. This agreement confirms the accuracy of the applied simulation method to characterize the dilute solutions and the chains characteristics.     

First observation of two-stage collapsing kinetics of a single synthetic polymer chain

Using a narrowly distributed poly(N-isoporpylacrylamide) (PNIPAM) chain with a degree of polymerization (N) of 3100, randomly labeled with pyrene, we have, for the first time, observed the two-stage kinetics of the coil-to-globule transition. Two characteristic relaxation times, tau(fast) for the crumpling of a random coil (approximately 12 ms) and tau(slow) for the collapsing of the crumpled chain to a compact globule (approximately 270 ms), were measured. To our knowledge, this is the first experimental evidence supporting the two-stage collapsing kinetics of single synthetic polymer chain previously proposed by de Gennes, Dawson, and Grosberg.     

Equal autophonic level curves under different room acoustics conditions

The indirect auditory feedback from one's own voice arises from sound reflections at the room boundaries or from sound reinforcement systems. The relative variations of indirect auditory feedback are quantified through room acoustic parameters such as the room gain and the voice support, rather than the reverberation time. Fourteen subjects matched the loudness level of their own voice (the autophonic level) to that of a constant and external reference sound, under different synthesized room acoustics conditions. The matching voice levels are used to build a set of equal autophonic level curves. These curves give an indication of the amount of variation in voice level induced by the acoustic environment as a consequence of the sidetone compensation or Lombard effect. In the range of typical rooms for speech, the variations in overall voice level that result in a constant autophonic level are on the order of 2 dB, and more than 3 dB in the 4 kHz octave band. By comparison of these curves with previous studies, it is shown that talkers use acoustic cues other than loudness to adjust their voices when speaking in different rooms.     

Variational theory for a single polyelectrolyte chain

Variational methods are applied to a single polyelectrolyte chain. The polymer is modeled as a Gaussian chain with screened electrostatic repulsion between all monomers. As a variational Hamiltonian, the most general Gaussian kernel, including the possibility of a classical or mean polymer path, is employed. The resulting self-consistent equations are systematically solved both for large and small monomer-monomer separations along the chain. In the absence of screening, the polymer is stretched on average. It is described by a straight classical path with Gaussian fluctuations around it. If the electrostatic repulsion is screened, the polymer is isotropically swollen for large separations, and for small separations the polymer correlation function is calculated as an analytic expansion in terms of the monomer-monomer separation along the chain. The electrostatic persistence length and the electrostatic blobsize are inferred from the crossover between distinct scaling ranges. We perform a global analysis of the scaling behavior as a function of the screening length and electrostatic interaction strength , where is the Bjerrum length and A is the distance of charges along the polymer chain. We find three different scaling regimes. i) A Gaussian-persistent regime with Gaussian behavior at small, persistent behavior at intermediate, and isotropically swollen behavior at large length scales. This regime occurs for weakly charged polymers and only for intermediate values of the screening length. The electrostatic persistence length is defined as the crossover length between the persistent and the asymptotically swollen behavior and is given by and thus disagrees with previous (restricted) variational treatments which predict a linear dependence on the screening length .ii) A Gaussian regime with Gaussian behavior at small and isotropically swollen behavior at large length scales. This regime occurs for weakly charged polymers and/or strong screening, and the electrostatic repulsion between monomers only leads to subfluent corrections to Gaussian scaling at small separations. The concept of a persistence length is without meaning in this regime. iii) A persistent regime , where the chain resembles a stretched rod on intermediate and small scales. Here the persistence length is given by the original Odijk prediction, , if the overstretching of the chain is avoided. We also investigate the effects of a finite polymer length and of an additional excluded-volume interaction, which modify the resultant scaling behavior. Applications to experiments and computer simulations are discussed. Received 24 December 1997     

A wavelet approach to fault diagnosis of a gearbox under varying load conditions

Varying load can cause changes in a measured gearbox vibration signal. However, conventional techniques for fault diagnosis are based on the assumption that changes in vibration signal are only caused by deterioration of the gearbox. There is a need to develop a technique to provide accurate state indicator of gearbox under fluctuating load conditions. This paper presents an approach to gear fault diagnosis based on complex Morlet continuous wavelet transform under this condition. Gear motion residual signal, which represents the departure of time synchronously averaged signal from the average tooth-meshing vibration, is analyzed as source data due to its lower sensitiveness to the alternating load condition. A fault growth parameter based on the amplitude of wavelet transform is proposed to evaluate gear fault advancement quantitatively. We found that this parameter is insensitive to varying load and can correctly indicate early gear fault. For a comparison, the advantages and disadvantages of other measures such as kurtosis, mean, variance, form factor and crest factor, both of residual signal and mean amplitude of continuous wavelet transform waveform, are also discussed. The effectiveness of the proposed fault indicator is demonstrated using a full lifetime vibration data history obtained under sinusoidal varying load.     

Collapse of a polymer chain

The behavior of a polymer chain near the Flory temperature is determined. The discussion is based on the analogy proposed by de Gennes between a polymer chain near the Flory temperature and a magnetic system near the tricritical point.     

Structure of bottle-brush brushes under good solvent conditions: a molecular dynamics study

We report a simulation study for bottle-brush polymers grafted on a rigid backbone. Using a standard coarse-grained bead-spring model extensive molecular dynamics simulations for such macromolecules under good solvent conditions are performed. We consider a broad range of parameters and present numerical results for the monomer density profile, density of the untethered ends of the grafted flexible backbones and the correlation function describing the range that neighboring grafted bottle-brushes are affected by the presence of the others due to the excluded-volume interactions. The end beads of the flexible backbones of the grafted bottle-brushes do not access the region close to the rigid backbone due to the presence of the side chains of the grafted bottle-brush polymers, which stretch the chains further in the radial directions. Although a number of different correlation lengths exist as a result of the complex structure of these macromolecules, their properties can be tuned with high accuracy in good solvents. Moreover, qualitative differences with 'typical' bottle-brushes are discussed. Our results provide a first approach to characterizing such complex macromolecules with a standard bead-spring model.     

The effect of solvent quality on thickening of single chain single crystal studied by Monte Carlo simulations

We reported dynamical Monte Carlo simulations to study the effect of solvent quality on crystallization and the subsequent isothermal thickening of a single homopolymer chain. The results showed that prior coil-globule transition could enhance nucleation and crystallization of the single chain. The solvent quality decided by the contacts between solvents and chain monomers resulted in different crystallizing and thickening behaviors. Typically further fold-length of an isolated chain extended easily in good solution. Otherwise the thickening mechanism was hard to develop in poor solution due to the confinement of liquid-solid interfaces.     

Variational theory for a single polyelectrolyte chain revisited

We reconsider the electrostatic contribution to the persistence length, , of a single, infinitely long-charged polymer in the presence of screening. A Gaussian variational method is employed, taking as the only variational parameter. For weakly charged and flexible chains, crumpling occurs at small length scales because conformational fluctuations overcome electrostatic repulsion. The electrostatic persistence length depends on the square of the screening length, , as first argued by Khokhlov and Khachaturian by applying the Odijk-Skolnick-Fixman (OSF) theory to a string of crumpled blobs. We compare our approach to previous theoretical works (including variational formulations) and show that the result found by several authors comes from the improper use of a cutoff at small length scales. For highly charged and stiff chains, crumpling does not occur; here we recover the OSF result and validate the perturbative calculation for slightly bent rods.PACS: 36.20.-r Macromolecules and polymer molecules - 82.70.-y Disperse systems; complex fluids - 87.15.-v Biomolecules: structure and physical properties     

Solid-like friction of a polymer chain

We propose a simple friction model for isolated polymer chains on a solid substrate. The chains are pulled at constant velocity by one end, the other end can be trapped on the solid substrate on localised sites. We focus on the energy dissipation due to the traps. This simple model leads to nontrivial friction laws, depending on the velocity and the distance between traps. Some refinements of the model such as the effect of thermal fluctuations are also reported. Received 20 March 2000     

Condensation of a chain polymer molecule

A new expression for the expansion coefficient of a flexible chain polymer molecule can be given in such a way that its first term corresponds to the case with only a hard-sphere repulsion and the other terms represent the effects of attraction between the segments. For low and high temperatures, more convenient expressions are used to find a possible condensation into a liquid-like condensed state from a gas-like state. It is found that in the condensed state, the square average end-to-end distance varies as N^?, where N is the number of segments and the exponent ? is around 0.6 in contrast to 1.2 for the high temperature case.     

Self-sustained oscillations in systems with delay under irregularly varying excitation conditions

A mathematical model of a system consisting of two coupled chaotic delay subsystems is presented. Instead of constant initial conditions in the form of a single impetus to excite the subsystems, continuous irregular oscillations are used that simulate intrinsic noise and continue acting on self-sustained oscillations after their excitation. An equation of an autonomous subsystem with regard to feedback variation is derived. It is shown that, when an autonomous subsystem is excited by irregular oscillations, chaotic motions become stochastic. In this case, the intensity of oscillations simulating intrinsic noise increases, suppressing self-sustained oscillations and providing the regenerative amplification of irregular oscillations. Interaction of coupled oscillations for identical and nonidentical subsystems is considered for the case of different noiselike initial conditions. It is found that interacting oscillations are not completely identical even if the parameters of the subsystems are the same.