Destruction of perfluoroalkyl surfactant aggregates by beta-cyclodextrin

A water 1H NMRD and 19F NMR spectroscopy study has proved, for the first time, that perfluoroalkyl surfactant micelles can be completely destroyed upon addition of beta-cyclodextrin to form successively 1:1 and 2:1 (beta-CD:R(F)) inclusion complexes.     

Complete Carbonylation of fac-

The rate constant of ligand exchange on the complex fac-[(99)Tc(H(2)O)(3)(CO)(3)](+) was determined by means of (13)C, (17)O, and (99)Tc NMR spectroscopy under pressurized conditions in aqueous media. After keeping the sample under CO pressure for an extended period, the formation of [(99)Tc(CO)(6)](+) could unambiguously be detected in the (13)C and (99)Tc NMR spectra.     

High pressure cyanide exchange study on a square-planar tetracyanometalate complex of Pt(II)

Abstract

Previous studies of cyanide exchange on square planar tetracyanoplatinate complex [Pt(CN)₄]^2- have been undertaken only at a high pH. For a more complete fundamental understanding of this system we extended the investigations of these exchanges over a large pH range. NMR kinetics methods (magnetisation transfer, isotopic exchange) proved to be very useful for obtaining quantitative rate data of the cyanide exchange on this complex. In fact it is quite significant that the reactivity of this metal center spans a ca. 9-order of magnitude range as a function of pH.

Variable temperature and variable pressure studies were undertaken in aqueous solutions and the following activation parameters obtained: ΔH? = (25.1 ± 0.4) kJmol^?1 and activation entropy ΔS? = -(142±2)JK^?1mol^?1 and activation volume ΔV? = -(27±2)cm³mol^?1.     

The first high-pressure high-resolution NMR probe for a normal bore cryomagnet1

Abstract

We describe a high-pressure high-resolution NMR probe fitting into a 4.7 Tesla normal bore (50 mm Ø) cryomagnet used with a Bruker AC-200 spectrometer. The probe is designed for a pressure range from 0.1 to 200 MPa and can be used in a temperature domain from -50 to + 120°C. Eguipped with a double tuned frequeney adapter circuit the probe is used for ¹H (200 MHz) observation and ²H (30.7 MHz) field locking for easy homogeneity adjustment. The resolution obtained routinely is better than 1 Hz (< 5′10^?9). Other frequencies, e.g. 27.1 MHz for ¹⁷O observation, can easily be obtained by changing and according the frequency adapter box.     

Dinitrogen Fixation of Microbe-Plant Associations as Affected by Nitrate and Ammonium Supply

Abstract

The dinitrogen fixation activity of Azospirillum sp., and Pantoea agglomerans strains was determined by ¹⁵N₂ incorporation after incubation with ¹⁵N₂ labeled air or/and by acetylene reduction. These bacterial strains were able to fix N₂ both in pure culture and in association with wheat plants in hydroponics. Nitrogenase activity of Azospirillum sp., in pure culture was more rapidly inhibited by the addition of NH₄ ⁺ than NO₃ ^?. The N₂ fixation of P. agglomerans decreased only by NH₄ ⁺ -addition, but was stimulated by NO₃ ^?. Nitrogen fixation in association with wheat plants remained unaffected by both N compounds. However, nitrogen derived from the atmosphere (N_dfa) contributed only very little to the overall nitrogen nutrition of the plants.     

Bestimmung der 63Ni-Aktivität in Pflanzenmaterial

A sensitive and simple method for the ⁶³Ni determination in plant material is needed to investigate the Ni uptake by plants and legume nodules, respectively. It could be shown that the liquid scintillation counting after a wet oxidation of the dry matter and resolving the residue in diluted HCl is suitable for this purpose. The method developed is demonstrated using two different ⁶³Ni labelled plant materials. The detection limit amounts to 80 Bq. g^?1 dry matter assuming a counting time of 10 min and a standard deviation of ±3% (95 confidence level).     

Distribution of Externally Applied 15NH4 + or 15NO3 − in White Lupins at Different Developmental Stages

White lupins (Lupinus albus L., var. Kievsky mutant) were grown in Mitscherlich pots. ¹⁵NH₄NO₃ or NH₄ ¹⁵NO₃ (10 or 95 at% ¹⁵N exc.) was applied at the late vegetative stage (14–16 leaves) or at the generative stage (end of bloom), respectively. Dry weight increase (ΔDW) of the plants as well as the ¹⁵N distribution in different organs and N fractions (NO_{3 ?}-N, NH₂-N, protein N) were investigated after 5 days and 50 days (maturity). The following results were obtained:

1. In comparison with the ¹⁵N derived from NO₃ ^?, the ¹⁵N derived from NH₄ ⁺ was more strongly retained in the roots. When transported into the shoot, it was more strongly translocated into the tip.

2. More ¹⁵N derived from NH⁴ ₊ was incorporated into proteins and reduced soluble N compounds than ¹⁵N derived from NO₄ ^?. Even in the above-ground plant tissues, a considerable proportion of the latter was found as NO₃ ^?.

3. In the long-term experiment (harvest at maturity 50 days after application), no difference in translocation and incorporation could be found between the two offered ¹⁵N sources.     

Investigations into beam monitors at the AEg ̄ IS experiment

Detailed diagnostic of antiproton beams at low energies is required for essentially all experiments at the Antiproton Decelerator (AD), but will be particularly important for the future Extra Low ENergy Antiproton ring (ELENA) and its keV beam lines to the different experiments. Many monitors have been successfully developed and operated at the AD, but in particular beam profile monitoring remains a challenge. A dedicated beam instrumentation and detector test stand has recently been setup at the AE \(\bar {g}\) IS experiment (Antimatter Experiment: Gravity, Interferometry, Spectroscopy). Located behind the actual experiment, it allows for parasitic use of the antiproton beam at different energies for testing and calibration. With the aim to explore and validate different candidate technologies for future low energy beam lines, as well as the downstream antihydrogen detector in AE \(\bar {g}\) IS, measurements have been carried out using Silicon strip and pixel detectors, a purpose-built secondary emission monitor and emulsions. Here, results from measurements and characterization of the different detector types with regard to their future use at the AD complex are presented.     

19F NMR study of mixed pentafluorochlorotantalum-trimethylphosphate adducts in solution

All twelve adducts comprising to the series TaF_5-iCl_i·(MeO)₃PO (O ≤ i ≤ 5) have been prepared in CH₂Cl₂ solution and characterised by ¹⁹F NMR Fourier Transform spectroscopy. The measured ΔG's of formation show that the mixed adducts are in slightly lower concentration than expected from a statistical distribution. The compounds are found to be more stable when fluorine rather than chlorine occupies an axial position; in addition, adducts with the same halide trans to each other are more stable than other isomers.     

Phosphinic derivative of DTPA conjugated to a G5 PAMAM dendrimer: an 17O and 1H relaxation study of its Gd(III) complex

A DTPA-based chelate containing one phosphinate group was conjugated to a generation 5 polyamidoamine (PAMAM) dendrimer via a benzylthiourea linkage. The Gd(III) complex of this novel conjugate has potential as a contrast agent for magnetic resonance imaging (MRI). The chelates bind Gd3+via three nitrogen atoms, four carboxylates and one phosphinate oxygen, and one water molecule completes the inner coordination sphere. The monomer Gd(III) chelates bearing nitrobenzyl and aminobenzyl groups ([Gd(DTTAP-bz-NO2)(H2O)]2- and [Gd(DTTAP-bz-NH2)(H2O)]2-) as well as the dendrimeric Gd(III) complex G5-(Gd(DTTAP))63) were studied by multiple-field, variable temperature 17O and 1H NMR. The rate of water exchange is faster than that of [Gd(DTPA)(H2O)]2- and very similar on the two monomeric complexes (8.9 and 8.3 x 10(6) s-1 for [Gd(DTTAP-bz-NO2)(H2O)]2- and [Gd(DTTAP-bz-NH2)(H2O)]2-, respectively), while it is decreased on the dendrimeric conjugate (5.0 x 10(6) s-1). The Gd(III) complex of the dendrimer conjugate has a relaxivity of 26.8 mM-1 s-1 at 37 degrees C and 0.47 T (corresponding to 1H Larmor frequency of 20 MHz). Given the contribution of the second sphere water molecules to the overall relaxivity, this value is slightly higher than those reported for similar size dendrimers. The experimental 17O and 1H NMR data were fitted to the Solomon-Bloembergen-Morgan equations extended with a contribution from second coordination sphere water molecules. The rotational dynamics of the dendrimeric conjugate was described in terms of global and local motions with the Lipari-Szabo approach.