Kinetic parameters of the In(III)/In(I) electrode reaction in bromide medium

The electrode kinetic parameters of the In(III)/In(I) couple in acidic 4M bromide solution have been determined by means of the rotating disc electrode technique.

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Die elektrochemisch-kinetischen Parameter des In(III)/In(I)-Redoxsystems in Bromidlösung (Kurze Mitteilung)

Zusammenfassung Die elektrochemisch-kinetischen Parameter am In(III)/In(I)-Redoxsystem wurden in saurer 4-M-Bromidlösung mittels der rotierenden Scheibenelektrode bestimmt.

     

Standardisierung der dünnschichtchromatographischen Trennungen von Flechtensäuren zur Chemotaxonomie von Flechten

Zusammenfassung Die dünnschichtchromatographische Trennung von Flechtenextrakten zur Unterstützung der Taxonomie wurde in Bezug auf die Trennleistung und auf die Reproduzierbarkeit optimiert. Dabei wurden besonders gute Trennleistungen erhalten mit dem Flie?mittelgemisch Benzol:Dioxa:Eisessig=90∶25∶4 bei Verwendung von Kieselgel, dessen Aktivit?t durch eine Umgebung mit relativer Feuchte von 70% festgelegt wurde, und mit Methylenchlorid als Eluiermittel bei Verwendung von mit Oxals?ure impr?gniertem Kieselgel und antiparallelem Aktivit?tsgradienten. Eine hohe Reproduzierbarkeit der Trennungen wurde erreicht durch Verwendung der Vario-KS-Kammer nach Geiss, die die Einstellung einer definierten Schichtaktivit?t bzw. eines definierten Aktivit?tsgradienten und eine reproduzierbare Vorbedampfung der Schicht mit Flie?mittel erm?glicht. Es konnte gezeigt werden, da? durch unterschiedliche chromatographische Trennungen der gleichen Extrakte und durch die Verwendung verschiedener Anf?rbereagenzien die Identifizierung und damit die Aussagekraft für taxonomische Probleme steigt.

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Standardisation of the thin-layer chromatographic separation of lichen acids for the chemotaxonomy of lichens

Summary The thin-layer chromatography of lichen extracts for taxonomic studies has been optimized in relation to separation and to reproducibility. Especially good separations were found with benzene:dioxane:acetic acid (90∶25∶4) developer and silica gel thin-layer plates, whose activity was fixed by an ambient moisture content of 70%, and with methylene chloride developer and silica gel plates impregnated with oxalic acid and antiparallel activity gradient. High reproducibility of separation was obtained using the Geiss Vario-KS tank, which allows the activity of the plates or the activity gradient to be adjusted and which also allows reproducible exposure of plates to the vapour of developing solvents. By different chromatographic separations of the same extracts and by using different colour reactions the accuracy of identification for taxonomic studies has been improved.

     

Small-angle neutron scattering study of structural changes in temperature sensitive microgel colloids

The structure of temperature-sensitive poly(N-isopropylacrylamide) microgels in dilute suspension was investigated by means of small-angle neutron scattering. A direct modeling expression for the scattering intensity distribution was derived which describes very well the experimental data at all temperatures over an extensive q range. The overall particle form as well as the internal structure of the microgel network is described by the model. The influence of temperature, cross-linking density, and particle size on the structure was revealed by radial density profiles and clearly showed that the segment density in the swollen state is not homogeneous, but gradually decays at the surface. The density profile reveals a box profile only when the particles are collapsed at elevated temperatures. An increase of the cross-linking density resulted in both an increase of the polymer volume fraction in the inner region of the particle and a reduction of the smearing of the surface. The polymer volume fraction inside the colloid decreased with increasing particle size. The structural changes are in good agreement with the kinetics of the emulsion copolymerization used to prepare the microgel colloids.     

Carbocyclic analogues of nucleosides from bis-(Hydroxymethyl)-cyclopentane: synthesis,antiviral and cytostatic activities of adenosine,inosine and uridine analogues

Six new carbocyclic nucleosides were prepared by constructing a purine base (in compounds 9-11) or pyrimidine base (in 6-8) on the amino groups of (+/-)-(1 beta,2 alpha,4 beta)-4-amino-1,2-cyclopentanedimethanol (4) and (+/-)-(1 beta,3 alpha,4 beta)-4-amino-1,3-cyclopentanedimethanol (5), and their activities against a variety of viruses and tumour cell lines were determined.     

Thermal decomposition of surface compounds for the generation of small quantities of acetaldehyde: Calibration of a thermal desorption-gas chromatography-flame ionization detection

The paper presents a new method for the generation of acetaldehyde in the amounts that allow to calibrate the measuring system. The method is based on thermal decomposition of surface compounds at the range 130-190 °C, in which an acetaldehyde as the decomposition product is released. The synthetic pathway leading to the desired surface compounds is described. Investigations demonstrated that the synthesis of the compounds on the surface of the support material (silica gel) was carried out homogeneously. The technique proposed was used for the generation of gaseous standard mixtures containing acetaldehyde for the calibration of a thermal desorber-gas chromatograph-flame ionization detector system.     

Homeopathic ligand-free palladium as a catalyst in the heck reaction. A comparison with a palladacycle

[reaction: see text] Ligand-free Pd(OAc)(2) can be used as a catalyst in the Heck reaction of aryl bromides as long as the amount of catalyst is kept between 0.01 and 0.1 mol %. At higher concentrations palladium black forms and the reaction stops. The actual catalyst is monomeric. Palladacycles merely serve as a source of ligand-free palladium in Heck reactions of aryl bromides.     

UVB irradiation of normal human skin favors the development of type-2 T-cells in vivo and in primary dermal cell cultures

To determine the effect of UVB exposure on the balance of type-1 or type-2 T-cells in skin, we examined the expression of key markers interferon (IFN)-gamma and interleukin (IL)-4 in cryostat sections. IFN-gamma mRNA was clearly detectable in nonirradiated control skin, and IFN-gamma protein was found in 2% of the dermal CD3pos T-cells, whereas IL-4 mRNA was hardly detectable, and no IL-4 protein was found. In contrast, IL-4 mRNA expression increased upon irradiation, and IL-4 was found in 2% of the T-cells at day 2 after UVB-exposure. Concomitantly, IFN-gamma mRNA expression decreased, and IFN-gamma protein became absent. We also analyzed T-cells present in primary dermal cell cultures, which were used as an in vitro equivalent of the in vivo situation. As compared with T-cells from control skin, T-cells in dermal cell cultures from UVB-exposed skin displayed an increased IL-4 and decreased IFN-gamma expression. No such skewing occurred when the T-cells from irradiated skin were cloned in the absence of a dermal microenvironment. Except for an occasional positive T-cell, type-1-associated cell-surface markers (CCR5, CXCR3) or type-2 markers (CCR3, CD30, CRTH2) were undetectable in situ. But these markers were expressed on cultured dermal T-cells from UVB-exposed and control skin at a comparable level, but did not correlate with the IFN-gamma and IL-4 production. Altogether, UVB-induced changes of the dermal microenvironment favor the development of type-2 T-cells.     

Sulfonamides as ionophores for ion-selective electrodes. IV. New secondary sulfonamide podands and cryptands

New compounds — podands and cryptands with two secondary sulfonamide groups —have been synthesized and are described. They were tested as ionophores for guanidinium ions in PVC-membrane electrodes with bis (2-ethylhexyl)sebacate (DOS) as plasticizer.     

NMR chemical shifts in the low–pH form of a-chymotrypsin. A QM/MM and ONIOM–NMR study

 The relationship between hydrogen bonding and NMR chemical shifts in the catalytic triad of low-pH α-chymotrypsin is investigated by combined use of the effective fragment potential [(2001) J Phys Chem A 105:293] and ONIOM–NMR [(2000) Chem Phys Lett 317:589] methods. Our study shows that while the His57 N^δ1−H bond is stretched by a relatively modest amount (to about 1.060 ?) this lengthening, combined with the polarization due to the molecular environment, is sufficient to explain the experimentally observed chemical shifts of 18.2 ppm. Furthermore, the unusual down-field shift of H^ɛ1 (9.2 ppm) observed experimentally is reproduced and shown to be induced by interactions with the C=O group of Ser214 as previously postulated. The free-energy cost of moving H^δ1 from His57 to Asp102 is predicted to be 5.5 kcal/mol. Received: 26 September 2001 / Accepted: 6 September 2002 / Published online: 21 January 2003 Contribution to the Proceedings of the Symposium on Combined QM/MM Methods at the 222nd National Meeting of the American Chemical Society, 2001 Correspondence to: J. H. Jensen e-mail: jan-jensen@uiowa.edu Acknowledgements. This work was supported by a Research Innovation Award from the Research Corporation and a type G starter grant from the Petroleum Research Fund. The calculations were performed on IBM RS/6000 workstations obtained through a CRIF grant from the NSF (CHE-9974502) and on supercomputers at the National Center for Supercomputer Applications at Urbana-Champaign. The authors are indebted to Visvaldas Kairys for help with the CHARMM program, and to Daniel Quinn for many helpful discussions.     

Dynamic Light Scattering and NMR Studies of Napin

We analyze the structure of napin (BngNAP1), a storage protein (m.w. 14.5 kDa) from Brassica napus. On the basis of the results of ¹H NMR spectroscopy and dynamic light scattering (DLS) studies, the overall shape and secondary structure of the molecule are estimated.