Zur Auswertung der Fließkurven konzentrierter Polymerlösungen an Hand experimenteller Messungen an Viskose

Zusammenfassung Bei formalen mathematischen Betrachtungen zur Darstellung von Fließkurven in logD-log -Darstellung undD--Darstellung wird festgestellt, daß 1. der Wendepunkt der logD-log -Darstellung stets bei kleinerenD- bzw. -Werten liegt als in derD--Darstellung, und daß 2. einer in logD—log -Darstellung gezeichneten Kurve mit Wendepunkt nicht notwendig auch eine Kurve mit Wendepunkt in normaler Auftragung entspricht. Am Beispiel des Fließverhaltens einer Viskosespinnlösung in Kapillaren bzw. Düsen mit unterschiedlichemL/R-Verhältnis wird nachgewiesen, daß ein 2.Newtonscher Bereich der Viskosität im strengen Sinne der Definition bei diesem System nicht vorliegen muß, sondern daß die scheinbare Viskosität vielmehr auch asymptotisch einem Endwert zustreben kann. Außerdem werden weitere Ergebnisse zur sog. Endkorrektur und zur Strahlaufweitung mitgeteilt.Mit 10 AbbildungenVortrag, gehalten anläßlich der Arbeitstagung Messung und Interpretation von Fließkurven der Sektion Rheologie des Vereins Österreichischer Chemiker am 17. November 1967 in Graz, Österreich.     

Crystallographic proof for an extended hydrogen-bonding network in small prolyl isomerases

Parvulins compose a family of small peptidyl-prolyl isomerases (PPIases) involved in protein folding and protein quality control. A number of amino acids in the catalytic cavity are highly conserved, but their precise role within the catalytic mechanism is unknown. The 0.8 ? crystal structure of the prolyl isomerase domain of parvulin Par14 shows the electron density of hydrogen atoms between the D74, H42, H123, and T118 side chains. This threonine residue has previously not been associated with catalysis, but a corresponding T152A mutant of Pin1 shows a dramatic reduction of catalytic activity without compromising protein stability. The observed catalytic tetrad is strikingly conserved in Pin1- and parvulin-type proteins and hence constitutes a common feature of small peptidyl prolyl isomerases.     

Cation-cation interactions between neptunyl(VI) units

The boric acid flux reaction of NpO(2)(ClO(4))(2) with NaClO(4) affords Na[(NpO(2))(4)B(15)O(24)(OH)(5)(H(2)O)](ClO(4))·0.75H(2)O (NaNpBO-1). NaNpBO-1 possesses a layered structure consisting of double neptunyl(VI) borate sheets bridged by another Np(VI) site through cation-cation interactions. The sole presence of Np(VI) in NaNpBO-1 is supported by absorption and vibrational spectroscopy.     

Systematic evolution from uranyl(VI) phosphites to uranium(IV) phosphates

Six new uranium phosphites, phosphates, and mixed phosphate-phosphite compounds were hydrothermally synthesized, with an additional uranyl phosphite synthesized at room temperature. These compounds can contain U(VI) or U(IV), and two are mixed-valent U(VI)/U(IV) compounds. There appears to be a strong correlation between the starting pH and reaction duration and the products that form. In general, phosphites are more likely to form at shorter reaction times, while phosphates form at extended reaction times. Additionally, reduction of uranium from U(VI) to U(IV) happens much more readily at lower pH and can be slowed with an increase in the initial pH of the reaction mixture. Here we explore the in situ hydrothermal redox reactions of uranyl nitrate with phosphorous acid and alkali-metal carbonates. The resulting products reveal the evolution of compounds formed as these hydrothermal redox reactions proceed forward with time.     

Simultaneous determination and validated quantification of human insulin and its synthetic analogues in human blood serum by immunoaffinity purification and liquid chromatography-mass spectrometry

Possible fatal complications of human insulin and its synthetic analogues like hypoglycemia require precise classification and quantitative determination of these drugs both for clinical purposes as well as for forensic toxicologists. A procedure was developed for the identification and quantification of human insulin and different long-acting as well as short-acting synthetic insulins in human blood serum specimens. After an immunoaffinity purification step and separation by liquid chromatography, the insulins were characterized by their five- or sixfold protonated molecule ions and diagnostic product ions. Clinical samples of 207 diabetic and 50 non-diabetic patients after the administration of human insulin or oral antidiabetics and forensic samples were analyzed for human/synthetic insulin concentrations. The method was validated according to international guidelines. Limits of detection of the insulins ranged between 1.3 and 2.8?μU/ml. Recoveries ranged between 33.2?% and 51.7?%. Precision data was in accordance with international guidelines. Clinical samples showed concentrations of human insulin lower than 301?μU/ml. Our liquid chromatography tandem mass spectrometry procedure allows unambiguous identification and quantification of the intact human insulin and its intact synthetic analogues Humalog?, Novolog?, Apidra?, Lantus?, and Levemir? in human blood serum in clinical and overdose cases. The assay could be successfully tested in patients with diabetes mellitus on therapy with insulins or oral antidiabetics.     

Differentiating between trivalent lanthanides and actinides

The reactions of LnCl(3) with molten boric acid result in the formation of Ln[B(4)O(6)(OH)(2)Cl] (Ln = La-Nd), Ln(4)[B(18)O(25)(OH)(13)Cl(3)] (Ln = Sm, Eu), or Ln[B(6)O(9)(OH)(3)] (Ln = Y, Eu-Lu). The reactions of AnCl(3) (An = Pu, Am, Cm) with molten boric acid under the same conditions yield Pu[B(4)O(6)(OH)(2)Cl] and Pu(2)[B(13)O(19)(OH)(5)Cl(2)(H(2)O)(3)], Am[B(9)O(13)(OH)(4)]·H(2)O, or Cm(2)[B(14)O(20)(OH)(7)(H(2)O)(2)Cl]. These compounds possess three-dimensional network structures where rare earth borate layers are joined together by BO(3) and/or BO(4) groups. There is a shift from 10-coordinate Ln(3+) and An(3+) cations with capped triangular cupola geometries for the early members of both series to 9-coordinate hula-hoop geometries for the later elements. Cm(3+) is anomalous in that it contains both 9- and 10-coordinate metal ions. Despite these materials being synthesized under identical conditions, the two series do not parallel one another. Electronic structure calculations with multireference, CASSCF, and density functional theory (DFT) methods reveal the An 5f orbitals to be localized and predominately uninvolved in bonding. For the Pu(III) borates, a Pu 6p orbital is observed with delocalized electron density on basal oxygen atoms contrasting the Am(III) and Cm(III) borates, where a basal O 2p orbital delocalizes to the An 6d orbital. The electronic structure of the Ce(III) borate is similar to the Pu(III) complexes in that the Ce 4f orbital is localized and noninteracting, but the Ce 5p orbital shows no interaction with the coordinating ligands. Natural bond orbital and natural population analyses at the DFT level illustrate distinctive larger Pu 5f atomic occupancy relative to Am and Cm 5f, as well as unique involvement and occupancy of the An 6d orbitals.     

Vitamin D Level in Summer and Winter Related to Measured UVR Exposure and Behavior

The influence of the summer UVR exposure on serum-25-hydroxyvitamin D (25(OH)D) in late summer and winter was investigated in an open study on 25 healthy, adult volunteers. The UVR exposure dose in standard erythema dose (SED) was monitored continuously during a summer season with personal, electronic wristwatch UVR dosimeters and sun exposure diaries. Constitutive and facultative skin pigmentation was measured in September. 25(OH)D was measured in September and February and was in mean 82 nmol/L ± 25 (mean ± SD) in September and 56 nmol/L ± 19 (mean ± SD) in February. The received cumulative UVR dose measured during a mean of 121 days was 156 SED ± 159 (mean ± SD). The following UVR exposure parameters correlated with 25(OH)D in September and February, respectively: (1) The cumulative UVR dose ( r  = 0.53; P  < 0.01) and ( r  = 0.43; P  = 0.03); (2) Mean daily hours with UVR measurements monitored by the dosimeter ( r  = 0.64, P  = 0.001) and ( r  = 0.53; P  = 0.007); (3) Days "with sun-exposed upper body" ( r  = 0.58, P  = 0.003) and ( r  = 0.50; P  = 0.01); (4) Facultative pigmentation ( r  = 0.47; P  < 0.02) and ( r  = 0.7; P  < 0.001); (5) Constitutive pigmentation ( r  = 0.06, n.s.) and ( r  = 0.43, P  = 0.03). Neither days "sunbathing" nor days with "sunscreen applied" correlated with 25(OH)D. The fall in 25(OH)D during winter was dependent on the entry value.