Self-bonding in an amorphous polymer below the glass transition: A T-peel test investigation

Films of amorphous polystyrene (PS) with a weight-average molecular weight (M_w) of 225 × 10³ g/mol were bonded in a T-peel test geometry, and the fracture energy (G) of a PS/PS interface was measured at the ambient temperature as a function of the healing time (t_h) and healing temperature (T_h). G was found to develop with (t_h)^1/2 at T_h = T_g-bulk − 33 °C (where T_g-bulk is the glass-transition temperature of the bulk sample), and log G was found to develop with 1/T_h at T_g-bulk − 43 °C ≤ T_h ≤ T_g-bulk − 23 °C. The smallest measured value of G = 1.4 J/m² was at least one order of magnitude larger than the work of adhesion required to reversibly separate the PS surfaces. These three observations indicated that the development of G at the PS/PS interface in the temperature range investigated (<T_g-bulk) was controlled by the diffusion of chain segments feasible above the glass-transition temperature of the interfacial layer, in agreement with our previous findings for fracture stress development at several polymer/polymer interfaces well below T_g-bulk. Close values of G = 8–9 J/m² were measured for the symmetric interfaces of polydisperse PS [M_w = 225 × 10³, weight-average molecular weight/number-average molecular weight (M_w/M_n) = 3] and monodisperse PS (M_w = 200 × 10³, M_w/M_n = 1.04) after healing at T_h = T_g-bulk − 33 °C for 24 h. This implies that the self-bonding of high-molecular-weight PS at such relatively low temperatures is not governed by polydispersity. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1861–1867, 2004     

Structure of norbornene-fused 3,1-oxazine double cycloadducts

Pentacyclic isoxazolines were obtained by the cycloaddition of benzonitrile oxide to norbornene-azetidinone-fused 3,1-oxazines. The constitutions of two of the isomers obtained, and the configurations and conformations of all products, were determined by means of ¹H and ¹³C NMR spectroscopy and DNOE experiments.     

Interpretation of the polyelectrolyte and antipolyelectrolyte effects of poly(N‐vinylimidazole‐co‐sodium styrenesulfonate) hydrogels

Hydrogels of N‐vinylimidazole (VI) and sodium styrenesulfonate (SSS) were synthesized in aqueous solution by radical crosslinking copolymerization with N,N′‐methylene‐bis(acrylamide) as crosslinker. Swelling in several saline solutions was measured for hydrogel samples synthesized with different comonomer concentrations (C_T = 10, 25, or 40%) and with SSS mole fractions covering a broad range (f_SSS = 0–0.7), while the crosslinker ratio was 2 wt % in all cases. The degree of swelling in aqueous solution with a specific ionic strength (μ), plotted versus the SSS composition of the feed, shows a minimum for any set of samples synthesized with a fixed C_T. The dependence of swelling on μ shows both polyelectrolyte (f_SSS beyond the minimum) and antipolyelectrolyte behaviors (in the low f_SSS limit). It was found that the nonGaussian factor of the crosslinking density and the polymer‐solvent interaction parameter increase with f_SSS for any C_T. Moreover, in the low f_SSS limit, the osmotic swelling pressure is governed not only by the ionic contribution, but also by the polymer‐solvent mixing and, the concentration of mobile counterions inside the gel is not proportional to the net fixed charge but to the addition of cationic and anionic side groups, what discards the formation of ionic pairs. The antipolyelectrolyte effect is interpreted as due to the increasing protonation of VI as μ goes up. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1683–1693, 2007     

Count(q) versus the pigeon-hole principle

For each there exists a model of which satisfies the Count() principle. Furthermore, if contains all prime factors of there exist and a bijective map mapping onto . A corollary is a complete classification of the Count() versus Count() problem. Another corollary shows that the pigeon-hole principle for injective maps does not follow from any of the Count() principles. This solves an open question [Ajtai 94]. Received August 16, 1994 / Revised version received April 29, 1996     

Recycling in telomerization of butadiene with D‐xylose: Pd(TPPTS)n‐KF/Al2O3 as an active catalyst

A palladium‐TPPTS catalyst heterogenized on KF/alumina has been shown to be effective and recyclable for the selective formation of monooctadienylxylopyranosides via the telomerization of butadiene with D ‐xylose. Copyright © 2007 John Wiley & Sons, Ltd.     

Specific high performance liquid chromatographic determination of the molecular weight and concentration of hyaluronic acid in complex mixtures by labelled hyaluronate binding proteins.

A simple High performance liquid chromatographic (HPLC) method for the specific determination of the molecular weight and concentration of hyaluronic acid (HA) in complex mixtures has been developed. Hyaluronate-binding proteins isolated from bovine cartilage labelled by 125I or fluoresceinisothiocyanate were used as specific markers. The specific binding affinities of the markers were compared and were found to have association constants of 1.6 x 10(7) M-1 and 1.2 x 10(7) M-1 respectively. The HA levels and molecular weight distributions can be easily determined in the range 10-500 ng/mL in complex mixtures by the use of markers, molecular sieving HPLC columns and appropriate detectors. It has been demonstrated clearly that the method is useful for the highly specific determination of the parameters in complex biological samples such as serum and synovial fluids and is recommended for clinical applications.     

LIDAR mapping of ozone-episode dynamics in Paris and intercomparison with spot analyzers Supplementary material available at http://link.springer.de/journals/apb

Continuous mapping of an ozone episode in Paris in June 1999 has been performed using a differential absorption lidar system. The 2D ozone concentration vertical maps recorded over 33 h at the Champ de Mars are compiled in a video clip that gives access to local photochemical dynamics with unprecedented precision. The lidar data are compared over the whole period with point monitors located at 0-, 50-, and 300-m altitudes on the Eiffel Tower. Very good agreement is found when spatial resolution, acquisition time, and required concentration accuracy are optimized. Sensitivity to these parameters for successful intercomparison in urban areas is discussed. Received: 11 February 2002 / Published online: 14 March 2002     

Enhanced selectivity of the isolation of basic drugs from body fluids by means of extraction minicolumns and sophisticated elution schemes.

The paper presents results and experience obtained in the isolation of a number of basic polar/non-polar solutes (drugs, their metabolites and structural derivatives) from biological samples by using the separation minicolumns Separcol SI and Separcol SI C18 L/T. The aim was to provide insight into some simple procedures yielding optimal selectivity/specificity of the isolation of the studied solutes either by proper selection of the sorbent or by applying sophisticated elution schemes which use to advantage different properties of the eluents/solvents.     

Thickness dependence of free‐standing thin films

Below a critical thickness, of about 60 nm, the glass transition temperature of polystyrene (PS) films decreases with film thickness, as demonstrated using free‐standing films. A geometrical model is developed here describing this phenomenon in the case of ideal (Gaussian) chains. This model, which can be considered as an application of the free volume model, assumes that the decrease of the glass transition temperature from thick to ultrathin films is due to the modification of the interpenetration between neighboring chains. The theoretical curve deduced from the model is in excellent agreement with the PS experimental results, without using any adjustable parameters. From these results, it can be concluded that new chain motions, usually buried in bulk samples, are expressed by the presence of the surface. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 10–17, 2007