A rheological analysis of interactions in phenoxy/organoclay nanocomposites

Novel oscillatory flow results of phenoxy/organoclay nanocomposites are analysed considering the blocking effect of nanostructure on polymer chain mobility. The modification provoked by this hindering effect on loss tangent spectrum is investigated. The study of three different systems, involving a pristine montmorillonite and two montmorillonites modified with one alkyl tail and two alkyl tails, respectively, leads to conclude that polymer-alkyl repulsive interactions play the most important role in the chain mobility obstruction process. Our results suggest that polymer-alkyl interactions increase with temperature.     

Propane/propylene separation by selective olefin adsorption on Cu/SBA-15 mesoporous silica

Samples of mesoporous silica, SBA-15, were prepared under hydrothermal conditions and Cu cations were incorporated into the framework by two different impregnation techniques. The corresponding adsorption/desorption isotherms of propylene, propane, and N₂ were measured to evaluate the material's effectiveness in the separation of propane/propylene mixtures. Adsorption uptake of propylene increased and that of propane decreased in Cu containing samples as compared to the uptakes observed in undoped SBA-15 samples. It was demonstrated that the presence of Cu atoms in the adsorbent lattice led to a greater selectivity towards propylene. Furthermore, the highest level of Cu(I) were obtained in samples prepared by equilibrium impregnation, which in turn improved the olefin/paraffin uptake ratio. Under some working conditions, the amount of propylene adsorbed in selected samples is totally reversible while propane uptake was negligible.     

The Removal of S-Cysteine Protection by Means of 2-Pyridine Sulfenyl Chloride and the Subsequent Formation of Disulfide Bonds. Preliminary communication

2-Pyridine sulfenyl chloride (PS-Cl) is a useful reagent for simultaneously deprotecting and activating the mercapto-group of cysteine and of cysteine-peptides preliminary to disufide-bond formation. The S-protecting groups that are amenable to this reaction include trityl, diphenylmethyl, acetamidomethyl, t-butyl, and t-butylsulfenyl.     

Photoreactivity of tiaprofenic acid and suprofen using pig skin as an ex vivo model

The skin is repeatedly exposed to solar ultraviolet radiation. Photoreaction of drugs in the body may result in phototoxic or photoallergic side effects. Non-steroidal anti-inflammatory drugs, such as tiaprofenic acid (TPA) and the closely related isomer suprofen (SUP) are frequently associated with photosensitive disorders; they may mediate photosensitised damage to lipids, proteins and nucleic acids. Using ex vivo pig skin as a model, we investigated the photodegradation of TPA and SUP, and photobinding of these drugs to protein by means of HPLC analysis and drug-directed antibodies. Both with keratinocytes, which were first isolated from the pig skin and thereafter exposed to UVA and with keratinocytes which were isolated from pig skin after the skin was UVA exposed, time-dependent photodegradation of TPA and SUP was found, beside photoadduct formation to protein. The results of this work show that: (a) TPA and SUP were photodecomposed with similar efficiency; major photoproducts detected were decarboxytiaprofenic acid (DTPA) and decarboxysuprofen (DSUP), respectively. (b) Both drugs form photoadducts, as concluded from recognition by drug-specific antibodies. Pig skin appears to be a good model for studying the skin photosensitising potential of drugs.     

Relative stability of the 3A2, 1A2, and 1A1 states of phenylnitrene: A difference-dedicated configuration interaction calculation

The relative stability of the ³A₂, ¹A₂, and ¹A₁ states of phenylnitrene is evaluated by means of ab initio calculations followed by difference-dedicated configuration interaction (DDCI). This approach is based on effective Hamiltonian theory at a low order of perturbation to select rationally the determinants which contribute to the energy difference. The CI space built on this criterion is then treated variationally. The method allows a considerable reduction of the CI space compared with a complete CAS*SDCI calculation (where CAS stands for complete active space). Depending on the concerned energy difference, different model spaces may be chosen, as illustrated in the ³A₂ → ¹A₂ and the ³A₂ → ¹A₁ transitions in phenylnitrene. Since the CI space may reach considerable dimensions, a direct CI algorithm for selected CI spaces, the SCIEL algorithm, has been used to perform the calculations. The results are in excellent agreement with previous calculations and with available experimental data. © 1996 by John Wiley & Sons, Inc.     

Photobinding of carprofen to protein

Carprofen is a non-steroidal antiinflammatory drug with marked photosensitising properties. In order to elucidate the mechanisms underlying the phenomenon of drug-protein photobinding, mixtures of the drug and human serum albumin were irradiated under different experimental conditions. After irradiation and subsequent gel-filtration chromatography of the photomixture, the eluting protein fraction was analysed by means of fluorescence spectroscopy. The formation of drug-protein photoadducts could be evidenced by the characteristic emission properties of the carbazole chromophore. The photobinding of the drug to human serum albumin appears to involve the formation of aryl radicals resulting from carbon-halogen photocleavage. This mechanistic interpretation is supported by the observed variations in the intensity of the fluorescence spectra, which can be correlated with the lower quantum yield emission of chlorocarbazoles as compared to non-halogenated analogues. The results from laser flash photolysis studies are also in agreement with this proposal.     

Analysis of conformal-invariant scattering amplitudes for the two-dimensional world model

The explicit form of the conformal-invariant phase shift analysis in thes-channel for a scattering process involving two incoming and two outgoing particles is derived for the two-dimensional world model. The high energy behaviour of the scattering amplitudes is determined completely (up to a constant factor) by the requirement of conformal invariance. It is not possible to obtain this high energy limit by neglecting the masses right from the beginning. The main mathematical problem is the determination of the Clebsch-Gordan coefficients forSU ₀(1, 1) in the momentum basis.     

A note on random walk in random scenery

We consider a random walk in random scenery {Xn=η(S₀)+?+η(Sn),n∈N}, where a centered walk {Sn,n∈N} is independent of the scenery {η(x),x∈Zd}, consisting of symmetric i.i.d. with tail distribution P(η(x)>t)∼exp(−cαtα), with 1?α<d/2. We study the probability, when averaged over both randomness, that {Xn>ny} for y>0, and n large. In this note, we show that the large deviation estimate is of order exp(−ca(ny)), with a=α/(α+1).     

Strongly prime alternative pairs with minimal inner ideals

In this paper, we use the known classification of the finite capacity simple alternative pairs and the version of the Litoff Theorem for Jordan pairs to describe all the strongly prime alternative pairs with nonzero socle. We study the inheritance of some properties (primeness, nondegenerancy,…) when passing from the original alternative pair to the symmetrized pair. Thus, we can apply Jordan theoretical results to the alternative case. This work has been partially supported by 1) the “Plan Andaluz de Investigación y Desarrollo Tecnológico” with project no. 1027 and 2) the DGICYT with project no. PB93-0990     

Gastroesophageal reflux laryngitis resistant to omeprazole therapy

Gastroesophageal reflux disease (GERD) is known to cause a variety of symptoms that lead a patient to seek otolaryngologic care. New advances in the treatment of GERD have enabled otolaryngologists to eliminate most of the signs and symptoms caused by acid reflux. Omeprazole, the most recent pharmacologic advancement, has been reported to be universally successful in controlling acid release from the stomach of patients with GERD. This report describes a series of patients with GERD for whom high-dose omeprazole therapy was not successful in completely reducing gastric acid levels of GERD symptomatology.