Metallocene‐based functionalized polyolefins as compatibilizers in polyolefin nanocomposites

This article reports a study of some functionalized polyolefins evaluated as compatibilizers in polyethylene nanocomposites. The functionalized polymers were prepared by direct metallocene‐mediated copolymerizations of ethylene and a functional comonomer. The prepared nanocomposites were evaluated for mechanical and barrier property enhancement. A good combination of mechanical and barrier properties was obtained with the metallocene‐based functionalized polyethylene. The toughness–stiffness balance was better than or comparable to that achieved with conventional functionalized polymers such as maleic anhydride grafted polyethylene. The results also indicated that these metallocene‐based functionalized polyolefins, when used as compatibilizers, could have relatively higher molar masses and lower functionality than those of conventional post‐reactor‐modified compatibilizers, and so the drawbacks associated with the latter could be avoided. Their inherent properties could also further improve the final nanocomposite properties. This was attributed to the more homogeneous nature of metallocene‐catalyzed polymers in comparison with post‐reactor‐modified products. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1094–1100, 2004     

Thermal cure monitoring of phenolic resole resins based on in situ fluorescence technique

The thermal curing reaction of two phenolic resole resins is monitored using the fluorescence technique. The intrinsic fluorescence can be used as an indicator for cure monitoring for the first resole. As the thermal curing proceeds, the intrinsic fluorescence intensity of the resole resin decreases and exhibits a few nanometers of redshift. The fluorescence intensity of the emission maxima is correlated with the conversion measured by differential scanning spectroscopy. A linear correlation is found at three different temperatures. The intrinsic fluorescence cannot always be used for monitoring the curing process of phenolic resole resins. Thus, three intramolecular charge transfer compounds and two organic donor–π‐acceptor salts are selected and applied for the cure monitoring of the second phenolic resole resin. As the curing reaction proceeds, the fluorescence emission spectra of the probes exhibit a blue spectral shift and the intensity changes because of environmental changes. An intensity ratio method is applied in which the ratios of the low‐ to high‐intensity changes in the emission bands are used to determine the degree of the curing process. There is a smooth correlation between the intensity ratio method and the degree of cure. The method enables one to follow the changes in the polymer structure at low and intermediate degrees of the curing process (below 70%) and obtain comparable results from different types of probes during the same curing process. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1773–1780, 2002     

Electrostatic image theory for two anisotropic half-spaces

An image solution for the canonical electrostatic problem of a point charge in an anisotropic half-space bounded by another anisotropic half-space is presented. The image source is obtained in operator form by using Fourier-transformed Maxwell equations and transmission line theory. After applying Heaviside operator calculus the image operator can be interpreted as a combination of a point charge and a sector of planar charge. The new theory is shown to coincide with the previously known image solutions of less general anisotropic media. In addition to being applicable to any physically feasible anisotropic medium of electrostatics, the method can be used for steady-current conductivity problems via a duality transformation.     

On the system of word equations x i 1 x i 2…x i m=y i 1 y i 2…y i n (i=1, 2, …) in a free monoid

 It is proved that the system of word equations x ⁱ ₁=y ⁱ ₁ y ⁱ ₂…y ⁱ _n , i=1, 2,…, ⌈n/2⌉ +1, has only cyclic solutions. Some sharpenings concerning the cases n=5, 7 and n≥9 are derived as well as results concerning the general system of equations x ⁱ ₁ x ⁱ ₂…x ⁱ _m =y ⁱ ₁ y ⁱ ₂…y ⁱ _n , i=1, 2,… . Applications to test sets of certain bounded languages are considered. Received: 18 May 1995/2 January 1996     

Development of LC/MS/MS methods for cocktail dosed Caco-2 samples using atmospheric pressure photoionization and electrospray ionization

Good reliability of Caco-2 permeability studies requires competent sampling and analytical methods to ensure the comparability of day-to-day experiments. In this work, two n-in-one LC/MS/MS methods based on two different ionization techniques were developed and validated for a group of reference compounds; eight of them are recommended by the Food and Drug Administration (FDA) for the evaluation of oral drug permeability. The performance of a new ionization technique, atmospheric pressure photoionization (APPI), as an interface for quantitative LC/MS analysis was evaluated in comparison to the electrospray ionization (ESI). Generally, the validation parameters, including sensitivity, accuracy, and repeatability, were comparable for the APPI and ESI methods. The main difference was that the linear quantitative range of APPI was 3-4 orders of magnitude (r(2) >/= 0.998) whereas in ESI it was typically 2-3 orders of magnitude (r(2) >/= 0.990). By the APPI and ESI methods, the simultaneous analysis of nine highly heterogeneous compounds was achieved within 5.5-7 min, which leads to significant savings in time and cost of the analyses. The successful validation data indicate the usefulness of both the methods for the rapid and sensitive (LOD values typically 相似文献   

Complex stability of sugars and sugar alcohols with NA + , CA 2+ , and LA 3+ in chromatographic separations using poly(styrene- CO -divinylbenzene) resins and aqueous organic eluents

The complex formation between metal ions and carbohydrates in solvent mixtures has been studied by chromatographic measurements. The effect of noncomplexing partition was decreased by attaching the active groups only on the shell of the stationary phase particles. Poly(styrene- co -divinylbenzene) resin beads were surface-sulfonated for that purpose. Thus the inner part of the sulfonated bead remained inactive and nonswellable. The counter-ions examined were Na + , Ca 2+ , and La 3+ , and the organic cosolvents were ethanol and acetonitrile. The stability constants of the very weakly complexing D -glucose, D -xylose, and L -rhamnose, the weakly complexing D -fructose and L -arabinose, and the strongly complexing xylitol and D -sorbitol were determined. The increasing organic cosolvent content increased the retention times, which is explained by the increased complex stability between the complexing solute and the counter-ion. The effect was greatest for the complex-forming sugars in the Ca 2+ form and for the sugar alcohols in the La 3+ form. The organic cosolvent had only a minor effect on the weakly complexing components, whereas the complex stability of the strongly complexing xylitol and sorbitol in 50 wt% ethanol solution in the La 3+ resin was more than five times higher compared to the stability measured in pure water.     

High prevalence of rheumatoid factor in community-based series of patients with rheumatoid arthritis meeting the new (1987) ARA criteria: RF-negative non-erosive rheumatoid arthritis is very rare

The possible relation of acquired cystic kidney disease to renal cell carcinoma resulted in an interdisciplinary concern about this disease. Kidneys from 125 autopsies of dialysis patients were studied. Twenty-four of the patients had tumors. Beside four renal adenocarcinomas and two urothelial carcinomas, incidental small tumor nodules were described in 15.1%. Men had more nodules than women. Patients with nodules had a higher average cyst count, often with multi-layered epithelium. There was no difference in age or time of dialysis. This suggests a factor which mediates cyst and tumor proliferation, independent from the time of dialysis. With the improvement in imaging techniques, an increasing number of small renal tumors will be found. Further studies are necessary to evaluate the risk of small kidney cell tumors and their association with acquired cystic kidney disease.     

Increased incidence of alcohol-related deaths from accidents and violence in subjects with ankylosing spondylitis

Subjects with ankylosing spondylitis (AS) have an increased incidence of deaths from accidents and violence, which is due in part, but perhaps not entirely, to the vulnerability of the affected spine to fractures. The present study covered all the 71 subjects (58 men and 13 women) who had died in Finland in 1989 and who were entitled under the nationwide sickness insurance scheme to receive specially reimbursed medication for AS. The death certificates of an earlier cohort study dealing with mortality in AS were also re-examined. Sixteen subjects (14 men and two women) in the 1989 mortality series had died of accidents and violence. Nine of the deaths (three accidents, two suicides and four alcohol poisonings) were alcohol related. The relative risk of such deaths in subjects with AS compared to the Finnish population as a whole was 2.64 (95% confidence interval 1.44-4.84). In the cohort study, 16 deaths had been due to accidents and violence, the expected number being 11.4. Eight of the 16 deaths had been alcohol related. Uncontrolled use of alcohol is an important determinant in the surplus of deaths from accidents and violence in Finnish patients with AS.     

Alteration in adrenocortical function in horses with recurrent airway obstruction after aerosol and parenteral administration of beclomethasone dipropionate and dexamethasone, respectively

OBJECTIVE: To determine alteration in adrenocortical function in horses with recurrent airway obstruction (heaves) after aerosol and parenteral administration of beclomethasone dipropionate and dexamethasone, respectively. ANIMALS: 6 horses with inducible and reversible heaves. PROCEDURE: Episodes of heaves were induced by exposure to moldy hay and straw for 7 days (natural challenge). Horses then underwent treatment (aerosolized beclomethasone, parenterally administered dexamethasone, and aerosolized propellant) for 7 days. Horses remained in the mold-contaminated environment for 7 days after discontinuation of drugs. Adrenocortical function was determine by serial evaluation of cortisol concentration in serum obtained on days 0, 7, 9, 12, 14, 16, 19, and 21. Adrenocorticotropic hormone stimulation testing was performed in 4 horses/treatment group on days 0, 7, 14, and 21. RESULTS: Endogenous cortisol production was suppressed in beclomethasone- and dexamethasone-treated horses within 2 days of treatment but recovered to values similar to those in propellant-treated horses approximately 2 and 4 days after discontinuation of drugs. Serum cortisol concentration in propellant-treated horses gradually decreased during the study and was significantly lower than baseline on days 14, 16, 19, and 21. Mean increase in serum cortisol concentration in response to ACTH stimulation testing after beclomethasone and dexamethasone administration did not differ significantly from the response observed in propellant-treated horses. CONCLUSIONS: Aerosol and parenteral administration of beclomethasone and dexamethasone, respectively, suppressed adrenocortical function; however, endogenous cortisol production resumed approximately 2 and 4 days after discontinuation of drugs. Responsiveness to ACTH stimulation testing was not affected by the 7-day treatment period.