Diffusion of linear polyisoprene molecules into polyisoprene networks

Diffusion and equilibrium absorption of polyisoprene liquids into crosslinked samples of cis-polyisoprene (natural rubber) have been studied by direct observation of volume swelling. Natural rubber was crosslinked in the form of fine threads, about 40 ± 20 μm in diameter, using a gaseous reaction with SO₂ and H₂S (the Peachey process). An optical microscope was used to observe the relatively rapid absorption of linear high-molecular-weight polyisoprene liquids by these fine threads. From the kinetics of absorption, values of the self-diffusion coefficient D_s of polyisoprene were estimated. They ranged from 10^?16 m²/s to 10^?12 m²/s, depending upon molecular weight, and varied with molecular weight approximately as M^?2 over the entire range employed, from 1,000 to 60,000 g/mol, i.e., both above and below the entanglement molecular weight. Amounts of polymer absorbed at equilibrium varied widely, depending upon the degree of crosslinking of the host material and the molecular weight of the absorbing liquid. They were in reasonable agreement in all cases with simple swelling theory, with the heat of mixing equated to zero.     

Wafer-scale thin encapsulated two-dimensional nanochannels and its application toward visualization of single molecules

We present a new and simple approach to fabricate wafer-scale, thin encapsulated, two-dimensional nanochannels by using conventional surface-micromachining technology and thin-film evaporation. The key steps to the realization of two-dimensional nanochannels are a fine etching of a sacrificial layer to create underetching spaces at the nanometer regime, and an accurate thin-film evaporation for encapsulation. Well-defined cross-sectional, encapsulated nanochannel arrays with dimensions as small as 20 nm in both width and height have been realized at the wafer-scale. The fabricated nanochannels with a channel length of 10mm have been used as a suitable fluidic platform for confining a solution containing nanomolar concentrations of Alexa fluorescent molecules. Initial results toward visualization of single Alexa molecules in the confined solution are reported.     

Diffusion properties of dye molecules in nanoporous TiO2 networks

The adsorption of ruthenium-dye molecules out of ethanol solution onto TiO2 particles of nanoporous TiO2 films was used to study the molecules' diffusion through these layers by means of optical absorption spectrometry. Dependent on pore size, porosity, and particle size, effective diffusion constants as low as D(eff) = 4 x 10(-9) cm2/s were deduced from the uptake curves by applying a simple model for combined diffusion and adsorption. These diffusion constants for diffusion through the nanoporous network are up to 3 orders of magnitude lower than in bulk ethanol and are discussed with respect to the properties of the nanoporous material.     

Enantioselective recognition in biomimetic single artificial nanochannels

Efficient enantiomer discrimination with a convenient system remains a challenge in the fields of biochemistry, medical science, and pharmaceutics. Here we report a simple enantioselective sensing device based on a single artificial β-cyclodextrin-modified nanochannel system. This nanodevice shows highly selective recognition of histidine enantiomers through monitoring of ionic current signatures.     

Diffusion of long molecules through solid polyethylene. I. Topological constraints

It is proposed that the mobility of sufficiently long molecules undergoing translational diffusion through solid polyethylene is significantly reduced by tie molecules and fixed entanglements within the interlamellar regions of the matrix. The effect on the diffusion coefficient both of diffusant molecular length and of the host matrix morphology is considered, and a semiquantitative relation between them obtained. This indicates that the mobility of long diffusants is higher in polyethylene which has been cooled slowly from the melt than it is in quenched polyethylene, in marked contrast to the behavior of gaseous and other small diffusants.     

Design of optimally switchable molecules by genetic algorithms

We demonstrate the possibility to design molecules for specific tasks, using a fully automatic global optimization setup employing genetic algorithms. As an example, we tune the two excitation wavelengths of a molecular switch backbone to arbitrarily pre-set values, by an automatic optimization of the substituent pattern.     

Photoionization of oriented molecules

A general expression for the angular distribution of photoelectrons with defined spin polarization ejected from oriented molecules is derived in the electric-dipole approximation in the limit of a weak radiation field. An analysis of its geometrical part permits to draw definite conclusions without calculating matrix elements. For linear molecules it is shown that in Hund's cases (a) and (b) photoelectrons may be polarized only parallel to the molecular axis, while in Hund's case (c) they may be polarized in any direction. Appearance of a circular dichroism for nonchiral oriented molecules of relatively low symmetry is predicted. Dependence of a circular dichroism in the angular distribution of photoelectrons on the symmetry of molecules is demonstrated. The results may serve as the framework for studying molecules oriented on surfaces, in liquid crystals, or by molecular beam techniques.     

Motion of single long DNA molecules through arrays of magnetic columns

We present a videomicroscopy study of T4 DNA (169 kbp) in microfluidic arrays of posts formed by the self-assembly of magnetic beads. We observe DNA moving through an area of 10 000 microm(2), typically containing 100-600 posts. We determine the distribution of the contact times with the posts and the distribution of passage times across the field of view for hundreds of DNA per experiment. The contact time is well approximated by a Poisson process, scaling like the inverse of the field strength, independent of the density of the array. The distribution of passage times allows us to estimate the mean velocity and dispersivity of the DNA during its motion over distances long compared to our field of view. We compare these values with those computed from a lattice Monte Carlo model and geometration theory. We find reasonable quantitative agreement between the lattice Monte Carlo model and experiment, with the error increasing with increasing post density. The deviation between theory and experiment is attributed to the high mobility of DNA after disengaging from the posts, which leads to a difference between the contact time and the total time lost by colliding. Classical geometration theory furnishes surprisingly good agreement for the dispersivity, while geometration theory with a mean free path significantly overestimates the dispersivity.     

Diffusion of long molecules through solid polyethylene. II. Measurements and results

The diffusion coefficient for two diffusants of the type n-(CH₂)NX is measured, where N ? 25, 45 and X is a suitable label; the matrix is linear polyethylene cooled at two widely differing rates from the melt. The measuring technique used is a recently developed one based on infrared microdensitometry. The results indicate that these diffusants diffuse faster in the slowly cooled matrix, in marked contrast to the behavior of gaseous diffusants. They are in agreement with the predictions of the model developed in a previous paper (part I), in which the constraints imposed by interlamellar tie molecules on long diffusants were shown to be important.     

Diffusion of polymer molecules into polymer networks: Effect of stresses and contraints

Fine threads of cis-1, 4-polyisoprene, diameter ca. 50 μm, were prepared by drawing from solution and drying. They were crosslinked by reaction with H₂S and SO₂ and then swollen with linear cis-polyisoprene liquids of varied molecular weight M_s, from 1,000 to 24,000 g/mol. Diffusion coefficients were determined from the initial rate of uptake, for both unrestrained and stretched threads. They were found to be in good agreement for stretches of up to about 300%. On the other hand, the equilibrium uptake increased markedly (> 100%) over this range of strain, similar to the increase in swelling observed with low-molecular-weight liquids. Values of diffusion coefficient were also obtained from the rate of deswelling upon release of swollen threads from tension, and from the rate of uptake of polymer liquids by a thin coating of crosslinked polymer, bonded onto glass fibers. Satisfactory agreement was obtained in all cases. A number of simple experiments thus give similar values for the diffusion coefficient of polymer liquids in lightly crosslinked polymer networks, in the range 10^?13?10^?16 m²/s, depending upon the molecular weight M_s of the polymer liquid approximately weight as M^?2_s. The amount of liquid absorbed was strongly dependent on its molecular weight, M_s, the degree of crosslinking of the host material, and applied stresses or constraints.     

Diffusion in a unidimensional zeolite pore system: Propane in AlPO4-5

Self-diffusion and diffusive transport of propane in large (≈ 180 μm) crystals of AlPO₄-5 have been studied by ZLC and tracer ZLC methods. In contrast to the results of recent studies of the self-diffusion of CH₄ and CF₄ in the same zeolite by the PFG NMR method the results of the present study show a rather fast one-dimensional Fickian diffusion process (D ≈ 10⁻⁵–10⁻⁶ cm² s⁻¹ at 300 K) with no evidence of single-file behavior. A possible explanation for this apparent discrepancy is suggested.     

Mechanical properties and molecular mobility in oriented polyolefines

The static modulus of elasticity (E) and the correlation time of rotation ( _c ) of 2,-2,6,6-tetramethylpiperidine-1-oxyl are studied as a function of the temperature (210<T <350°K) for oriented films of isotactic polypropylene and polyethylene of high and low density.E and _c change both upon heating and polymer orientation; this result indicates that sample properties are influenced by the microstructure of the amorphous phase where probes are localized.     

Diffusion of vibrationally excited molecules

A treatment is presented for the effect of intermolecular vibrational energy transfer on the diffusion coefficient of vibrationally excited molecules. An analytic treatment based on random walk statistics and a Monte Carlo type calculation have been performed. Both methods yield very similar results which correlate well with existing experimental studies. A hard sphere collision model is treated extensively with comparisons made to other internmolecular potentials. The results support the involvement of long range energy transfer in V → V interactions. The effect of temeprature on the diffusion coefficient of vibrationally excited molecules is calculated, with applications to the CO^*₂CO₂ system.     

Electronic structure of long molecules with conjugated bonds

The -electron system in a long molecule of the polyene type was calculated according to the Hartree-Fock self-consistent field method in which electrons with different spins are located on different molecular orbitals. The ground state of the -electron system in a long molecule is found to be antiferromagnetic and possesses a gap in the one-particle excitation spectrum. The calculated value of the first -electron transition as a function of the number of atoms in the polyene chain is in good agreement with experiment.     

Photoionization of oriented molecules in a gas phase

Use of a coincidence technique for registration of fragment ions and photoelectroms from dissociative ionization of molecules opens the possibility of studying the photoionization of oriented molecules in a gas phase. The first results obtained by this technique for O₂ molecules are presented. The angular distribution of photoelectrons as a function of an angle between molecular axis and a photoelectron momentum is measured for theB ² _g ^– final ionic state using the HeI resonance radiation. From measured data it follows that the ratio of channel cross sections is /=0.67±0.08.     

New method to evaluate the mobility of ions in the nanochannels of polymer electrolyte membranes

The behavior of excited PyS⁻ with the quencher NO₂⁻ in an ionomer solution of anion-conductive resin and in the nanochannels of an anion-conductive membrane was investigated by luminescence quenching measurements. Compared with the behavior of an excited Ru(bpy)₃²⁺-MV²⁺ system in the presence of Nafion, the mobility of ions in the nanochannels of an ion-conductive resin is proved to depend on ion size, structure of nanochannel and channel medium.     

Deceptive simplicity in NMR spectra of oriented molecules

The theory for deceptive simplicity in the NMR spectra of oriented molecules is discussed in terms of degeneracy of subspectra. The conditions for the degeneracy of AB, AB₂ and AA′BB′ spectra leading to deceptive simplicity in the spectra of the type ABX, AB₂X, AA′BB′X and AA′XX′ are reported. It is shown that the conditions for deceptive simplicity are easily fulfilled for ABX, AA′BB′X and AA′XX′ cases. It is further demonstrated that deceptive simplicity is not so common in AB₂X spectra. The proton spectra of partially oriented 2,4,5-trichloronitrobenzene (AB) and 2,6-dibromo-pyridine (AB₂) are use to illustrate degeneracy and those of p-chloro- and p-bromo-fluorobenzenes are reported to demonstrate deceptive simplicity.