Apparatus for infrared measurement of sorption/desorption in strained polymeric films

A new apparatus has been developed for optical measurement of sorption/desorption in transparent polymer films at a given strain or stress. The technique utilizes a chosen infrared absorption frequency of the diffusing vapor in a spectral region where the film has negligible absorption. From the time dependence of the IR absorption at this frequency the sorption/desorption behavior of the film may be determined at any strain or stress. The simultaneous measurement of mechanical relaxation as a function of the amount of sorbed vapor is also possible. The results presented here show the applicability of the apparatus for determining the transport and mechanical properties of a low-density polyethylene film in ethyl acetate vapor at 30°C.     

Electroformation in a flow chamber with solution exchange as a means of preparation of flaccid giant vesicles

A recently described technique [Estes and Mayer, Biochim. Biophys. Acta 1712 (2005) 152-160] for the preparation of giant unilamellar vesicles (GUVs) in solutions with high ionic strength is examined. By observing a series of osmotic swellings followed by vesicle bursts upon a micropipette transfer of a single POPC GUV from a sucrose solution into an iso-osmolar glycerol solution, a value for the permeability of POPC membrane for glycerol, P=(2.09+/-0.82) x 10(-8)m/s, has been obtained. Based on this result, an alternative mechanism is proposed for the observed exchange of vesicle interior. With modifications, the method of Estes and Mayer is then applied to preparation of flaccid GUVs.     

Determination of caffeine and associated compounds in food, beverages, natural products, pharmaceuticals, and cosmetics by micellar electrokinetic capillary chromatography

A method is described for quantitating caffeine, theobromine, theophylline, paracetamol, propyphenazone, acetylsalicylic acid, salicylic acid, and codeine phosphate in corresponding real samples of food, beverages, natural products, pharmaceuticals, and cosmetic preparations by micellar electrokinetic capillary chromatography. The separation is carried out at 25 degrees C and 25 kV, using a 20mM phosphate buffer (pH 9.0), 80mM sodium dodecyl sulfate, and 7.5% (v/v) acetonitrile. UV detection is at 210 nm. The method is shown to be specific, accurate (recoveries over the range 98.9-101.2%), linear over the tested range (correlation coefficients >/= 0.9993), and precise (relative standard deviation below 2.1%). The method is applied for the quantitative analysis of these compounds in different foods, beverages, natural products, pharmaceuticals, and cosmetic products.     

Morphology and fracture of drawn crystalline polymers

Drawn crystalline polymers, fibers and films, exhibit a characteristic fibrous structure with the long and narrow microfibril as the basic element. The highly oriented microfibrils originating from the same stack of parallel lamellae of the starting material form the fibril which, as a rule, differs a little in drawing ratio from adjacent fibrils. As a consequence of this variation and the location of the ends of microfibrils on the outer boundary of the fibril, this is the area of reduced strength where the fracture phenomena start. The free ends of microfibrils are point vacancy defects of the microfibrillar superlattice which, under applied stress, open and form microcracks long before the sample fails. The radial crack propagation first breaks the microfibrils adjacent to the microcrack at the point vacancy and produces a great many radicals as a consequence of the rupture of tie molecules in at least one amorphous layer of each broken microfibril. Longitudinal crack propagation proceeds along the boundary between adjacent microfibrils and creates very few radicals because there are very few interfibrillar tie molecules which can be ruptured during this process. The coalescence of microcracks by radial and axial growth finally leads to a crack of critical size which by catastrophical growth leads to sample failure. If the longitudinal growth is sufficiently enhanced, the fracture surface is fibrous with individually broken fibrils which are separated from each other by longitudinal voids. Such an effect occurs in a torsional test, at the end of cold drawing, and very often in cyclic loading tests.     

The amount and location of amorphous component in polyethylene single crystals

Polyethylene single crystals from dilute solutions usually have a density ρ which is less than that of the ideal crystal lattice (ρ_c = 1.000 g/cm³). This density defect can be formally assigned to an “amorphous” component (1-α) = (ρ_c-ρ)/(ρ_c-ρa) and may be caused by vacancies in the crystal lattice and/or by the surface disorder connected with chain folds. The two-phase concept of single crystal structure assumes a very nearly ideal lattice core and two amorphous layers on the fold-containing surfaces. It is supported by density and heat content data of annealed samples, by small-angle X-ray scattering, by wide-line NMR investigations, and by the results of fuming nitric acid treatment.

The maximum thickness of the amorphous surface layer as a function of temperature may be estimated from the free energy requirement of such a layer. With regular chain folds one has a high concentration of gauche conformations yielding a high surface energy. The need for such a concentration disappears in the amorphous layer with loose loops. This gain in energy may be spent for surface melting. Still more important is the gain in entropy caused by the random distribution of loop lengths.     

A Planar linear arboricity conjecture

The linear arboricity la(G) of a graph G is the minimum number of linear forests (graphs where every connected component is a path) that partition the edges of G. In 1984, Akiyama et al. [Math Slovaca 30 (1980), 405–417] stated the Linear Arboricity Conjecture (LAC) that the linear arboricity of any simple graph of maximum degree Δ is either ?Δ/2? or ?(Δ + 1)/2?. In [J. L. Wu, J Graph Theory 31 (1999), 129–134; J. L. Wu and Y. W. Wu, J Graph Theory 58(3) (2008), 210–220], it was proven that LAC holds for all planar graphs. LAC implies that for Δ odd, la(G) = ?Δ/2?. We conjecture that for planar graphs, this equality is true also for any even Δ?6. In this article we show that it is true for any even Δ?10, leaving open only the cases Δ = 6, 8. We present also an O(n logn) algorithm for partitioning a planar graph into max{la(G), 5} linear forests, which is optimal when Δ?9. © 2010 Wiley Periodicals, Inc. J Graph Theory     

Analysis of Atorvastatin and Related Substances by MEKC

A new micellar electrokinetic capillary chromatographic (MEKC) method has been developed for simultaneous quantitation of atorvastatin (AT) and its related substances. The separation was carried out in an extended light path capillary at applied voltage of 30 kV using a background electrolyte consisting of 10 mM sodium tetraborate buffer pH 9.5, 50 mM sodium dodecyl sulphate and 20% (v/v) methanol. The addition of methanol to the running buffer resulted in a very effective choice to achieve resolution between the peaks of charged substances adjacent to AT as well as the peaks of neutral drug-related substances. Linear calibration curves were established over the concentration range 100–1,200 μg mL^?1 for AT and 1.0–12.5 μg mL^?1 for related substances. The proposed MEKC procedure has been validated with respect to selectivity, precision, linearity, limits of detection, and quantitation, accuracy and robustness. The method has been successfully applied to the determination of AT and purity evaluation of bulk drug and formulated products.     

Dynamic viscosity of polymer solutions

The dynamic viscosity of different long chain polymers in Aroclor permits an easy extrapolation to zero concentration only in the limiting cases of Newtonian, i. e., constant viscosity at low and high frequency, respectively. The first intrinsic viscosity []₀ is independent of any concept of the internal viscosity. In the case of polystyrene it is proportional toM ^0,65 which shows that Aroclor is a good solvent for this polymer. The second intrinsic viscosity [] turns out to be independent ofM. It is best reproduced by the model where the internal viscosity resists only the deformation rate of the single link. The displacement rate of more distant beads is affected by the internal viscosity only in the case that it involves the deformation rate of the links. The angles between successive links may be changed at any rate.In the intermediate range of frequencies the extrapolation of the observed dynamic viscosity to the intrinsic value was never made. The experimental data are so much affected by the concentration, i. e., by the interaction of adjacent molecules, that no conclusion may be derived from them about the properties of the isolated macromolecule. A master curve independent ofM andc is obtained by plotting of (G- )K/c over ₁. This means that the deformation mode in the whole molecular weight and concentration range investigated is the same. But this mode is different from that of the independent macromolecule in infinite dilution. The master curve may be described by the excess intrinsic viscosity of the Rouse model with the internal viscosity acting either between the beads on the same link only or between any distinct beads. As a consequence of the concentration effects, however, no conclusions about the properties of the single molecule can be derived from such an agreement.Dedicated to Prof. Dr. F. H. Müller.     

Electron microscopy of drawn polypropylene

Extremely thin polypropylene films formed by evaporation of dilute solutions floating on water, thin films deposited on Mylar or on carbon-coated Mylar, and bulk samples were deformed; after etching with aqua regia or chromic acid, the surfaces were studied by electron microscopy of surface replicas. At small draw ratio, microfibrils with lateral dimensions of about 200 Å, originating in micronecks at crack boundaries of the original crystal lamellae, were obtained in isolated areas exhibiting maximum local strain separated by large regions of much less deformed material. With increasing draw ratio the necked regions grow, the old structure gradually being reduced to smaller and smaller islands until it disappears completely. The inhomogeneity of strain in adjacent bundles of microfibrils creates a great many longitudinal voids with more or less disoriented microfibrils bridging the gaps. The regular arrangement of crystalline blocks of rather uniform length and width can be occasionally seen on surface replicas of drawn samples, and much better on dark-field electron micrographs of drawn and annealed thin membranes. In the latter case the blocks are very uniform and have similar dimensions along and perpendicular to the axis of the microfibril. The evidence from the electron micrographs, together with previous small-angle x-ray scattering data, supports Peterlin's molecular model for plastic deformation of crystalline polymers.