The 15 symmetrically methylated derivatives of the CB11H12(-) anion (1a) have been synthesized and found to vary greatly in ease of oxidation. Cyclic voltammetry in liquid SO2 yielded fully reversible oxidation potentials for five of those that have no adjacent unsubstituted vertices in positions 7-12; three others showed some indication of reversibility. The anions 1a-16a and the Jahn-Teller distorted neutral radicals 1r-16r have been characterized by ab initio and density functional theory calculations. In the state average CASSCF(13,12)/6-31+G* approximation, the ground state potential energy surface of 1r contains five symmetry-related pairs of minima. The computational results account for the reversible redox potentials very well when the solvent is included explicitly (RI-DFT(BP)/TZVP, COSMO). For display and for a semiquantitative understanding of methyl substituent effects in terms of perturbation theory, the molecular orbitals of 1a have been expressed in the symmetry-adapted cluster basis. The results serve as an underpinning for a set of additive empirical increments for redox potential prediction. Relative to the usual hydrogen standard, a single methyl group facilitates oxidation by approximately 50, 70, 70, and 10 mV in positions 1, 2, 7, and 12, respectively. This electron donor effect on the redox potential is due to a contribution, whereas those of (inductive and direct field) type are negligible.
In a group of 60 Belgian White Blue calves less than 8 months old still housed in barns, a bovine respiratory syncytial virus (BRSV) outbreak was revealed on the basis of a direct diagnosis (immunofluorescence and virus isolation) performed on the lungs of dead animals, and the kinetics of BRSV neutralizing antibodies. Clinical signs, macroscopical and microscopical pulmonary lesions were also compatible with a BRSV infection. This outbreak is peculiar because the 35 oldest calves (204 +/- 29 days old) had been vaccinated 3-4 months before with an inactivated BRSV vaccine and 30% of these animals had died of respiratory distress. While they experienced a mild respiratory symptomatology, no death was recorded among the 25 youngest calves (69 +/- 29 days old) which had been left unvaccinated. Another peculiarity was found at the histological level where a massive infiltration of eosinophils was demonstrated in the pulmonary tissues of the dead animals. Together these data parallel the dramatic story described 30 years ago in children previously vaccinated with a formalin-inactivated human RSV (HRSV) vaccine upon a natural HRSV challenge. This illustrates that an immunopathological phenomenon also takes place after BRSV vaccination in cattle.
Canine leishmaniasis, an important zoonotic disease of dogs, is the result of an ineffective and inappropriate immune response to infection with Leishmania infantum. It is widely accepted that the appropriate immune response is characterised by a T-helper (Th)1-dominated profile in an overall mixed Th1/Th2 response. The absence of a strong Th1 response is associated with progression to the clinical disease. Thus, there is a need for an effective vaccine that could modulate the immune response to a more appropriate profile against the parasite. In this study we measured the impact of the LiESP/QA-21 canine vaccine, recently launched commercially in Europe, on selected humoral and cellular immune markers for one year after a primary vaccination course. The humoral response to vaccination was characterised by a predominantly IgG2 profile. Vaccinated dogs developed long-lasting cell-mediated immune responses against L. infantum, specifically with a stronger ability of macrophages to reduce intracellular parasite burdens in co-culture with autologous lymphocytes compared to control dogs (p=0.0002), which was correlated with induction of inducible nitric oxide synthase (iNOS) and production of nitric oxide (NO) derivatives. These results confirm that vaccination with LiESP/QA-21 is capable of inducing an appropriate Th1-dominated immune profile which persists for a full year.
The absorption structure of five light metals has been measured from the onset of Kand LII, 111-absorption up to photon energies of 140 eV (170 eV for Be). The edges a t the threshold are followed by several broad peaks which are distributed over the total energy region covered by these measurements. There is a striking similarity between the LII,III-absorption spectra of Na, Mg, and Al; a similarity can also be seen between the K-absorption spectra of Li and Be.Das optische Absorptionsverhalten yon fiinf Leichtmetallen wurde vom Einsatz der Kbzw. LII,III-Absorption bis zu Photonenenergieii von 140 eV (bei Be bis 170 eV) gemessen. Neben den Kanten beim Einsatz wurden im ganzen Spektralbereich mehrere breite Absorptionsmaxima beobachtet. Der allgemeine Verlauf der L~~,~~~-Absorptionsspektren von Na, Mg und A1 stimmt gut iiberein; Ahnlichkeiten zeigen sich auch bei den K-Absorptionsspektren von Li und Be.
A synthesis is described of the four C-halogenated 1-X-CB11H11- anions (X = I, Br, Cl, F) using N-halosuccinimides and N-fluorobis(benzenesulfonyl)amine as halogenating agents. The procedure yields only the desired product next to unreacted starting material. Regularities in the 11B and 13C NMR chemical shifts of singly halogenated icosahedral carboranes are summarized.
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