Rotational band crossings in the actinides

In the actinides bothi _13/2 protons andj _15/2 neutrons are close to the Fermi surface. At rapid rotation these high-j particles will unpair and align their orbital angular momentum along the axis of rotation giving rise tos-bands that cross the ground-state band. Coulomb excitation of the odd nuclei ₂₃₇ ⁹³ Np (established up to the 45/2⁺ state) and ₂₃₅ ⁹² U (established up to the 51/2^? state) provides specific information about these band crossings: From the saturating alignment of the odd high-j particle in both nuclei at intermediate rotational frequencies we find the aligned angular momentum of thei _13/2 protons-band to be 6.6? while the corresponding value for thej _15/2 neutrons-band is 5.5?. At more rapid rotation above ?ω=0.18 MeV we observe additional alignment in²³⁵U. This is ascribed to the interaction of the protons-band. From the gradual onset of the additional alignment we deduce that forZ=92 the protons-band interacts strongly with the ground-state band and from a comparison of the actual amount of alignment with the full value of 6.6? we estimate the crossing to occur around ?gw _c ^p =0.25 MeV.     

Superconductivity and resistance behaviour of σ-phase alloys: Nb−Rh and Ta−Rh

Superconductivity, structure and electrical resistance behaviour of -phase alloys of Nb–Rh and Ta–Rh are investigated. The Ta–Rh alloys do not become superconducting above 1.2 K. The andH _c2 (0) values of a homogeneous alloy with the composition Nb_65.2Rh_34.8 are 2.95 K, 13.9 kG/K and 23 kG, respectively, whereas for an inhomogeneous alloy with the composition Nb_63.7Rh_36.3 these values are 4.24 K, 5.5 kG/K and 14 kG, respectively. Splat quenching results in a substantial increase in the andH _c2 (0) values of the Rh-rich sample. Annealing (900°C, 100 h) of the Rh-rich sample leads only to small changes in the superconducting properties but a small amount of Nb–Rh solid solution has been formed. The electrical resistance of Nb_65.2Rh_34.8 decreases with decreasing temperature and varies asT ^0.5 between 150 and 240 K and asT between 60 and 140 K. For Ta_70.0Rh_30.0 the temperature coefficient changes to negative values below 170K. values are calculated for Nb–Rh using McMillan's formula. An estimatedT _c value of Ta–Rh is 0.2 K. TheH _c2 (0) values of Nb–Rh are in good agreement with the theoreticalH _c ^2** (0) values.Dedicated to Prof. Dr. W. Buckel on the occasion of his 60th birthday     

Instrumental neutron activation analysis of spruce needles and trees

Tree rings and needles of young spruce clones from the immission area of the Al-refinery Ranshofen (Upper Austria), which had ceased production in 1992, were investigated by INAA. Short time irradiation was performed for determining, Al, Mn, Ca and Cl, while the elements Na, K, Rb, Ba, Zn, Fe, Sc, Cr, Co, Br and in some samples also Ca were determined via middle- and long-lived radioisotopes. Irradiation and counting conditions are given. Accuracy and sensitivity are sufficient to describe the trends of the element concentrations in needles and with the exception of Cr, Sc and Br, in tree rings. Ca-concentrations derived from⁴⁹Ca (short-time irradiation) and⁴⁷Ca (long-time irradiation) are compared and show good agreement Additionally Mg was determined in some samples by ICP-AES and if possble, by INAA. The results are compared.     

Syntheses and Structure of Gd<Subscript>3</Subscript>Rh<Subscript>1.940(7)</Subscript>In<Subscript>4</Subscript>

Summary. The gadolinium–rhodium–indide Gd₃Rh_1.940(7)In₄ was prepared by arc-melting of the elements and subsequent annealing in a corundum crucible in a sealed silica tube. Gd₃Rh_1.940(7)In₄ adopts the hexagonal Lu₃Co_1.87In₄ type, space group , a = 781.4(5), c = 383.8(3) pm, wR2 = 0.0285, BASF = 0.375(1) (merohedric twinning via a twofold axis (xx0)), 648 F² values, 22 variables. The structure is derived from the well known ZrNiAl type through an ordering of rhodium and indium atoms on the Ni2 sites. The Rh/In ordering forces a reduction of the space group symmetry from to , leading to merohedric twinning for the investigated crystal. The Rh1 site has an occupancy of only 94.0(7)%. The investigated crystal had a composition Gd₃Rh_1.940(7)In₄. The main geometrical motif are three types of centered, tricapped trigonal prisms, i.e., [Rh1In2₆Gd₃], [Rh2Gd₆In2₃], and [In1Gd₆In2₃]. The shortest interatomic distances occur for Rh–In (276–296 pm) followed by In–In (297 pm). Together, the rhodium and indium atoms build up a three-dimensional [Rh_1.940(7)In₄] network, in which the gadolinium atoms fill slightly distorted pentagonal channels. The crystal chemistry of Gd₃Rh_1.940(7)In₄ is discussed on the basis of a group-subgroup scheme.     

pH-induced destabilization of lipid bilayers by a peptide from the VP3 protein of the capsid of hepatitis A virus.

The membrane destabilizing and fusogenic properties of the synthetic peptide VP3(110-121), corresponding to an immunogenic sequence of the hepatitis A virus (HAV) VP3 capsid protein, were studied. By tryptophan fluorescence and acryalmide quenching it was demonstrated that the peptide binds liposomes of POPC-SM-DPPE (47 + 39 + 14) and POPC-SM-DPPE-DOTAP (40 + 33 + 12 + 15) and penetrates the membrane, at both neutral and acidic pH (POPC = 1-palmitoyl-2-oleoylglycero-sn-3-phosphocholine; SM = sphingomyelin; DPPE = 1,2-dipalmitoylphosphatidylethanolamine; DOTAP = 1,2-dioleoyl-3-trimethylammoniumpropane). VP3(110-121) did not have membrane-destabilizing properties at neutral pH. Acid-induced destabilization of the vesicles was demonstrated by fluorescence techniques and dynamic light scattering. VP3(110-121) induced aggregation of POPC-SM-DPPE-DOTAP (40 + 33 + 12 + 15) vesicles, lipid mixing and leakage of vesicle contents, all consistent with fusion of vesicles. In POPC-SM-DPPE (47 + 39 + 14) vesicles, at acidic pH, VP3(110-121) induced membrane destabilization with leakage of contents but without aggregation of vesicles or lipid mixing. The peptide only showed fusogenic properties when bound to the vesicles at neutral pH before acidification to pH below 6.0, and no effect was seen if the peptide was added to vesicles already set at acidic pH. These results may have physiological significance in the mechanism of infection of host hepatic cells by HAV.     

1.5-Diaza-3.7-diphospha-cyclooctane

The alkyl (aryl)-bishydroxymethylphosphines react with primary amines to give the title compounds. With optically active amines optically active phosphines are formed.     

Tautomerism and stereochemistry of dihydroxyperylenequinones: Force field investigations

Summary Stereochemistry and tautomerism of cercosporin and several of its partial structure models were investigated using an MM2 derived force field method. Besides the propeller type conformer, which was found before by X-ray crystallography, the complicated energy hypersurface was shown to contain a novel double-butterfly conformer of similar stability. The interconversion barrier between these conformers and their enantiomers was found to be unusually high due to buttressing effects of neighbor substituents. Judged from the calculations, the 4,9-tautomer of cercosporin could also be present in favoring instances besides the 3,10-tautomer, whereas the 3,9-tautomer is strongly destabilized.

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Tautomerie und Stereochemie von Dihydroxyperylenchinonen: Untersuchungen mit Hilfe der Kraftfeld-Methodik

Zusammenfassung Die Stereochemie von Cercosporin und einigen seiner Partialstrukturmodelle wurde Hilfe einer von MM2 abgeleiteten Kraftfeldmethodik untersucht. In der komplizierten Energiehyperfläche wurde neben dem aus der Röntgenstrukturanalyse bekannten Propeller-Konformeren auch ein neues Doppelschmetterling-Konformer ähnlicher Stabilität aufgefunden. Die Interkonversionsbarrieren zwischen diesen Konformeren und ihren Enantiomeren sind außergewöhnlich hoch, was auf einen Buttressing-Effekt der benachbarten Substituenten zurückgeführt wurde. Aus den Rechnungen folgte auch, daß neben dem 3,10-Tautomeren in günstigen Fällen auch das 4,9-Tautomere des Cercosporins vorliegen kann, wogegen das 3,9-Tautomere stark destabilisiert ist.

     

Regio- and stereoselective transfer of p-toluenesulfonamido group from sulfur to carbon: preparation of aminoalcohol derivatives from allylalcohols

A novel methodology for the regio- and stereoselective synthesis of amino alcohol derivatives from allylalcohols/ethers via intramolecular nucleophilic participation by the sulfilimine moiety is disclosed. The sulfilimine moiety is stereospecifically transformed to a sulfinyl moiety with an inverted configuration. The reaction is general and affords highly functionalised products.     

Sorption of Co(II) ong-alumina in the presence and absence of fulvic acid</p> </p>

Summary The removal of heavy metal ion Co(II) from aqueous solution was studied usingg-Al₂O₃ by batch technique. The experiments were performed at T=20±2 °C, in 0.01M NaNO₃ solutions and under aerobic conditions. The effect of pH, ionic strength, fulvic acid (FA) and alumina amount on the sorption of Co(II) on alumina were also investigated. The pH affected the sorption of Co(II) significantly as compared with the effect of FA and ionic strength. The results indicated that strong chemical bonds are formed between Co(II) and functional groups of the bare or FA coated alumina, and a precipitation of Co(II) takes place on the alumina surface, induced by a transition from the adsorption to surface. The addition sequences of Co/FA on Co(II) sorption were also studied: the sorption of Co(II) in the ternary system was found independent of addition sequences.</p> </p>     

MONITORING LIGHT-INDUCED CHANGES IN ISOLATED, INTACT EYE LENSES

Fluorescence spectral changes occurring upon irradiation with 300 nm light have been monitored in situ in isolated, intact, whole lenses from the eyes of several species. The findings corroborate observations on other individual constituent protein molecules in the solution state, and also reveal features attributable to the supramolecular protein assembly that exists in the whole lens. Irradiation of the lens with 300 nm light causes red shifts in the tryptophan emission spectrum, suggesting alterations in the protein packing in the lens. Intermolecular energy transfer from tryptophan to one of the photoproducts, presumably N-formylkynurenine (N-FK), occurs in the condensed-phase sample. The N-FK formed is photodegraded efficiently in the lens, indicating that the photodynamic effects of endogenous N-FK might not be as severe as has been thought. Species variation in the photoevents are evident, particularly in avian lenses that contain the variant δ-crystallin as the core protein. The photoinduced changes in the near-UV circular dichroism of δ-crystallin (which is α-helical, as opposed to the β-sheet structure of α-, β-, and -γ-crystallins), isolated from chicken lenses, are remarkably different from other crystallins. Irradiation of δ-crystallin leads to a drastic reduction of circular dichroism intensity in the 250–300 nm region, whereas no changes are seen in the peptide absorption band.