Possibility of Helical Interlayer Coupling in the Magnetic Superlattices and Overlayers

We consider interlayer magnetic coupling in a superlattice and/or overlayer in the case when spacer layer has the tendency towards formation of the helical spin density wave. Within phenomenological Landau-Ginzburg approach we show that the mutual interplay of the SDW and interlayer coupling spin polarization can lead to the helical interlayer coupling. When surface anisotropy is accounted for the effective interaction mimics interlayer biquadratic coupling.     

Time-resolved fluorescence studies of ribonuclease T1 in reversed micelles

Time-resolved fluorescence intensity and anisotropy decay data were obtained for ribonuclease T₁ entrapped in bis(2-ethylhexyl) sodium sulfosuccinate/heptane reverse micelles, as a function of the size of the inner water pool at neutral pH. Data have been presented previously to show that this protein retains its native structure and undergoes reversible thermal unfolding in these reverse micelles (Shastry and Eftink,Biochemistry 36, in press). The fluorescence decay of entrapped protein is similar to that for the protein in buffer. The rotational correlation time of entrapped ribonuclease T₁ is found to be longer than that in buffer; this rotational correlation time decreases with increasing size of the water pool but is still over twice the value for the protein in buffer for the largest size of water pool investigated, indicating an increased microviscosity within the reverse micelle. Thermal unfolding of the protein results in a significant decrease in the rotational correlation time of the entrapped proteins, consistent with the protein being unfolded but not interacting with the inner surfactant wall of the reverse micelle.Nomenclature _i Amplitude of component i associated with fluorescence decay _i - _i Fractional intensity associated with fluorescence decay time _i - Rotational correlation time g_i Amplitude of component i associated with anisotropy decay _i - _max Fluorescence emission maximum - r_o Fundamental anisotropy of an immobilized fluorophore - _i Fluorescence lifetime of component i - W_o Ratio of water molecules per detergent molecules in a reverse micelle     

LINEAR DICHROISM STUDY OF METALLOPORPHYRIN TRANSITION MOMENTS IN VIEW OF RADIATIONLESS INTERACTIONS WITH TRYPTOPHAN IN HEMOPROTEINS

We measured the linear dichroism of several metalloporphyrins embedded in stretched polyvinyl alcohol (PVA) films to estimate the orientation of the absorption transition moments, which in hemoproteins are relevant to the radiationless energy transfer between tryptophan and heme. The metalloporphyrins were derivatives of protoporphyrin IX (PPIX), namely Fe³⁺-PPIX (ferric-heme) and Fe²⁺CO-PPIX (CO-heme), Mg-PPIX (Mg-heme) and Zn-PPIX (Zn-heme). Measurements were conducted between 300 and 700 nm. In all cases the linear dichroism was wavelength dependent, indicating the presence of several transition moments with different orientations. We focused our attention on the near-UV (300–380 nm) and Soret (380450 nm) absorption bands. Deconvolution in terms of Gaussian components gave three components between 380 and 450 nm and only one in the 300–380 nm region. Deconvolution of the near-UV and Soret spectra of oxy-, deoxy- and carbonmonoxyhemoglobin gave very similar results, suggesting a very similar orientation of the various transition moments in the free and protein-embedded hemes. It should be stressed that the single 300–380 nm band is the only one responsible for the overlap integral that regulates the energy transfer from tryptophan to heme in hemoproteins (Gryczynski et al., Biophys. J . 63, 648–653, 1992). The dichroism of this single band indicated that its transition moment is oriented at about 60 from the α-γ meso-axis of the heme moiety. We conclude that the heme should be considered a linear oscillator when it acts as acceptor of energy transfer from tryptophans.     

Surface plasmon-coupled polarized emission of N-acetyl-l-tryptophanamide

We report an observation of ultraviolet (UV) surface plasmon-coupled emission (SPCE) of N-acetyl-l-tryptophanamide (NATA). The sample was spin coated from poly(vinyl alcohol) (PVA) solution on 20 nm aluminum film deposited on a quartz substrate. The directional UV SPCE occurs within a well-defined narrow angle at 52 degrees from the normal to the coupling hemicylinder quartz prism. The NATA directional emission is highly p polarized as expected for surface plasmon-coupled radiation. The 10 nm protective SiO2 layer deposited on top of the aluminum film significantly neutralized the fluorophore quenching by the metal surface. SPCE of NATA demonstrates a remarkable intrinsic dispersive property-the maximum of the emission spectrum depends on the observation angle. The efficient spectral resolution of SPCE can be used in the construction of miniaturized spectrofluorometers. The observation of SPCE of tryptophan opens a new possibility for the study of many unlabeled proteins with the technique complementary to surface plasmon resonance analysis.     

Interaction of isomeric forms of xanthophyll pigment zeaxanthin with dipalmitoylphosphatidylcholine studied in monomolecular layers

Two-component monomolecular layers were formed with DPPC and two stereoisomers of zeaxanthin 9-cis and 13-cis at the argon-water interface. Very distinct over-additivity which represents affection of a lipid arrangement in the membrane has been observed in the case of zeaxanthin 9-cis (maximum at 20 mol%) but not in the case of zeaxanthin 13-cis. The differences in the organization of the isomers of zeaxanthin-DPPC monolayers are interpreted in terms of the different orientation of both xanthophylls at the interface observed at relatively high surface pressures (>25 mN/m) comparable to the surface pressures of biomembranes. The results are consistent with the model according to which zeaxanthin 9-cis adopts a vertical orientation at the polar-nonpolar interface in contrast to zeaxanthin 13-cis, which is oriented horizontally owing to the fact that it interacts by two hydroxyl groups with the same hydrophobic-hydrophilic interface in the monolayer. The findings are discussed in comparison with the behavior of zeaxanthin in the conformation all-trans in the same system. Zeaxanthin all-trans forms efficiently molecular aggregates in the mixed monolayers in contrast to cis isomers. Circular dichroism measurements show the formation of molecular structures by zeaxanthin 13-cis that are interpreted as dimers. FTIR measurements show that these dimers are stabilized by van der Waals interactions unlike aggregated structures formed by all-trans zeaxanthin that are stabilized by hydrogen bonding. Physiological importance of the differences in aggregation and orientation of stereoisomers of zeaxanthin in lipid environment is discussed.     

A systematic SAR study of C10 modified paclitaxel analogues using a combinatorial approach

A library with 63 paclitaxel analogues modified at the C10 position of paclitaxel has been prepared using parallel solution phase synthesis. Most of the C10 analogues were slightly less active than paclitaxel in the tubulin assembly assay and had reduced potency in the B16 melanoma and MCF-7 cell line cytotoxicity assays. These modifications at C10, however, did not lead to the total loss of activity, indicating that the C10 moiety of paclitaxel may not be directly involved in the drug-microtubule interactions, but could influence its binding affinity to P-glycoprotein. Approximately 50% of the analogues demonstrated better activity against the drug resistant cell line MCF7-ADR. However, the increase in activity was 10-fold at most. This result demonstrates that the cytotoxicity against this drug resistant cancer cell line is sensitive to structural changes at the C10 position of paclitaxel. It was also found that the presence of a nitrogen atom in the C10 substituent might play a role in the interaction of analogues with microtubules.     

Flotation-spectrophotometric determination of rhodium using stannous chloride and Rhodamine 6G

Summary The conditions for the formation of a rhodium compound with tin(II) and Rhodamine 6G, in HCl medium, and their flotation with organic solvents of low polarity have been examined. The effect of the organic solvent on the flotation has been observed. The compound with Rhodamine 6G, separated and washed, is dissolved in acetone. The acetone solution is a basis of the developed sensitive and precise flotation-spectrophotometric method. The molar absorptivity in this method is 4.0×10⁵ at 530 nm. Beer's law is obeyed in the concentration range 0.04–0.5g Rh/ml. The components molar ratios in the isolated compound were determined, and the formula [(R6G⁺)₃Rh(SnCl₃ ^–)₄]·[(R6G⁺)(SnCl₃ ^–)] was proposed. The effect of the other platinum metals on the determination of rhodium with Rhodamine 6G was examined.

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Flotation und spektrophotometrische Bestimmung von Rhodium mit Zinn(II)cblorid und Rhodamin 6G

Zusammenfassung Die Bildung einer Rhodiumverbindung mit Sn(II) und Rhodamin 6G in salzsaurem Medium und deren Flotation mit organischen Lösungsmitteln geringer Polarität wurden untersucht. Der Einfluß des organischen Lösungsmittels auf die Flotation ist sicher. Die Verbindung mit Rhodamin 6G wurde abgetrennt, gewaschen und in Aceton gelöst. Diese Lösung bietet die Grundlage für die ausgearbeitete genaue spektrophotometrische Methode. Die molare Absorptivität beträgt 4,0×10⁵ bei 530 nm. Im Konzentrationsbereich 0,04–0,5g Rh/ml wird das Beersche Gesetz befolgt. Die Bestimmung des Verhältnisses der Komponenten ergab als Formel [(R6G⁺)₃Rh(SnCl₃ ^–)₄]·[(R6G⁺)(SnCl₃ ^–)]. Der Einfluß anderer Platinmetalle auf die vorgeschlagene Bestimmungsmethode wurde untersucht.

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This work was supported by Research Program MR-I-32.     

Orbit algebras that are invariant under stable equivalences of Morita type

In this note we show that there are a lot of orbit algebras that are invariant under stable equivalences of Morita type between self-injective algebras. There are also indicated some links between Auslander-Reiten periodicity of bimodules and noetherianity of their orbit algebras.