Solvent‐ and interface‐induced surface segregation in blends of isotactic polypropylene with poly(ethylene‐co‐propylene) rubber

The surface compositions and morphologies of melt‐quenched blends of isotactic polypropylene (iPP) with aspecific poly(ethylene‐co‐propylene) rubber (aEPR) were characterized by atomic force microscopy, optical microscopy, and X‐ray photoelectron spectroscopy. The surface morphologies and compositions formed in the melt are frozen‐in by crystallization of the iPP component and, depending on the processing conditions, are enriched in iPP or aEPR or contain a phase‐separated mix of iPP and aEPR. Enrichment of iPP is observed for blends melted in open air, in agreement with earlier work showing the high surface activity of atactic polypropylene at open interfaces. Surface segregation of iPP is suppressed at confined interfaces. Blends melt‐pressed between hydrophilic and hydrophobic substrates have phase‐separated iPP and aEPR domains present at the surface, which grow in size as the melt time increases. Surface enrichment of aEPR is observed after exposing melt‐pressed blends to n‐hexane vapor, which preferentially solvates aEPR and draws it to the surface. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 421–432, 2004     

Two Stage Solid Phase Extraction with Subsequent HPLC Isolation for Structure Elucidation of Major Metabolites of (+)-(R)-2-{3-(benzo[1,4]dioxan-2-yl-methylamino)-1-propyl}-3(2H)-pyridazinone (GYKI-16084)

GYKI-16084 – (+)-(R)-2-{3-(benzo[1,4]dioxan-2-yl-methylamino)-1-propyl}-3(2H)-pyridazinone hydrochloride – is a new drug candidate for the treatment of benign prostatic hyperplasia. In our study the major metabolites formed in the rat and dog were isolated from dog and rat urine, then their structures were elucidated by means of MS and NMR. A two stage solid phase extraction (SPE) procedure and a semi-preparative HPLC method were developed utilizing various mechanisms of separation. The major metabolites proved to be isomeric glucuronides of the benzodioxane moiety hydroxylated at positions 6 or 7 and {2-(2-carboxyethyl)-3(2H)-pyridazinone}.     

The photodissociation of water by doped iron oxides: The unblased p/n assembly

Mott-Schottky capacitance measurements are used to locate semiconductor band edges for a short-circuited p-type/n-type α-Fe₂O₃ assembly in aqueous solution. The thermodynamic feasibility of the catalytic photodiscussion of water without external bias is verified for this assembly from an energy level diagram obtained for the electrode/electrolyte interfaces. Photocurrent stability and Auger analysis of the electrode show no evidence of electrode dissolution. Oxygen evolution is monitored from an assembly using mass spectrometry and H₂¹⁸O enriched water.     

Classification of signatures of Bovine Spongiform Encephalopathy in serum using infrared spectroscopy

Signatures of Bovine Spongiform Encephalopathy (BSE) have been identified in serum by means of "Diagnostic Pattern Recognition (DPR)". For DPR-analysis, mid-infrared spectroscopy of dried films of 641 serum samples was performed using disposable silicon sample carriers and a semi-automated DPR research system operating at room temperature. The combination of four mathematical classification approaches (principal component analysis plus linear discriminant analysis, robust linear discriminant analysis, artificial neural network, support vector machine) allowed for a reliable assignment of spectra to the class "BSE-positive" or "BSE-negative". An independent, blinded validation study was carried out on a second DPR research system at the Veterinary Laboratory Agency, Weybridge, UK. Out of 84 serum samples originating from terminally-ill, BSE-positive cattle, 78 were classified correctly. Similarly, 73 out of 76 BSE-negative samples were correctly identified by DPR such that, numerically, an accuracy of 94.4 % can be calculated. At a confidence level of 0.95 (alpha = 0.05) these results correspond to a sensitivity > 85% and a specificity > 90%. Identical class assignment by all four classifiers occurred in 75% of the cases while ambiguous results were obtained in only 8 of the 160 cases. With an area under the ROC (receiver operating charateristics) curve of 0.991, DPR may potentially supply a valuable surrogate marker for BSE even in cases in which a deliberate bias towards improved sensitivity or specificity is desired. To the best of our knowledge, DPR is the first and--up to now--only method which has demonstrated its capability of detecting BSE-related signatures in serum.     

Entropically mediated polyolefin blend segregation at buried sapphire and air interfaces investigated by infrared-visible sum frequency generation vibrational spectroscopy

The segregation behavior of binary polymer blends at hydrophilic solid sapphire and air interfaces was investigated by infrared-visible sum frequency generation (SFG) vibrational spectroscopy. SFG spectra were collected from a bulk miscible blend consisting of identical molecular weight (approximately 54,000) and similar surface free energy (29-35 dyn/cm) components of atactic polypropylene (aPP) and aspecific poly(ethylene-co-propylene) rubber (aEPR). Characteristic CH resonances of the blend were contrasted with those of the individual components at both buried (sapphire/polymer) and free (air/polymer) interfaces. Preferential segregation of the aPP component was observed after annealing at both air/polymer and sapphire/polymer interfaces. SFG spectra revealed ordering of the polymer backbone segments with the methylene (CH2) groups perpendicular to the surface at the sapphire interface and the methyl (CH3) groups upright at the air interface. The SFG results indicate that the surface composition can be determined from the peak intensities that are characteristic of each component and that conformational entropy played a likely role in surface segregation. aPP occupied a smaller free volume at the surface because of a statistically smaller segment length (aPP is more flexible and has a shorter length). In addition, the high density of the ordered CH3 side branches enhanced the surface activity by allowing the long-chain backbone segments of aPP to order at the surface.     

The coadsorption of potassium and co on the pt(111) crystal surface: A TDS,HREELS and UPS study

The interaction of CO with a potassium covered Pt(111) surface is investigated using thermal desorption (TDS), high resolution electron energy loss (HREELS) and ultraviolet photoelectron (UPS) spectroscopies. When submonolayer amounts of potassium are preadsorbed, the adsorption energy of CO increases from 25 to 36 kcal/mole, while substantial shifts in the site occupancy from the linear to the bridged site are observed. The CO stretching vibrational frequencies are shown to decrease continuously with either increasing potassium coverage or decreasing CO coverage. A minimum CO stretching frequency of 1400 cm^?1 is observed, indicative of a CO bond order of 1.5. The work function decreases by up to 4.5 eV at submonolayer potassium coverages, but then increases by 1.5 eV upon CO co-adsorption. The results indicate that the large adsorption energy, vibrational frequency and work function changes are due to molecular CO adsorption with a substantial charge donation from potassium through the platinum substrate and into the 2π¹_CO orbital.     

Absolute resonance strengths in the $^{6,7}Li(\alpha, \gamma)^{10,11}B$ reactions

The absolute strengths of the keV resonance in the reaction and of the keV resonance in the reaction have been measured to meV and meV, respectively, in good agreement with previous values. These resonances can be used to measure the absolute acceptance of the recoil separator ERNA to a precision of about 10%.Received: 12 December 2003, Revised: 10 February 2004, Published online: 3 August 2004PACS: 24.30.-v Resonance reactions - 25.40.Lw Radiative capture - 26.20. + f Hydrostatic stellar nucleosynthesis