The distribution of PAI-1 in the plasma and platelets of normal individuals and of patients with platelet abnormalities was studied. An ELISA, capable of measuring PAI-1 in plasma at 1.5 ng/ml, and a functional assay of t-PA inhibition were used to assay platelet-free plasma (PFP), platelet-rich plasma in which the platelets were lysed (PRP) and serum. The PAI-1 concentration of normal PFP was 21.0 +/- 7.2 ng/ml (mean +/- SD) and those of PRP and serum were 282.6 +/- 68.0 and 270.3 +/- 71.9 ng/ml. The concentration of PAI-1 in PRP was proportional to the platelet count with 0.67 +/- 0.18 ng/10(6) platelets. Patients with thrombocytopenia had approximately normal PAI-1 concentrations in PFP; the extremely low concentrations in serum or PRP reflected the platelet count. A patient with grey platelet syndrome showed a comparable pattern, confirming that PAI-1 occurs in the platelet alpha-granules and indicating that the plasma concentration of PAI-1 is independent of the platelet pool of PAI-1. The median inhibitory activities towards t-PA were 1.6, 8.7 and 8.3 units/ml in normal PFP, PRP and serum respectively. PAI-1 in PFP had a median specific activity (units/mg PAI-1) about 5-fold higher than platelet PAI-1. Plasma and platelets represent two distinct pools of PAI-1, both of which should be considered in studies on the relationship between circulating PAI-1 and thrombotic disease.
The osmium(VI) nitrido complex TpOs(N)Cl(2) (1) has been prepared from K[Os(N)O(3)] and KTp in aqueous ethanolic HCl. It reacts rapidly with PhMgCl and related reagents with transfer of a phenyl group to the nitrido ligand. This forms Os(IV) metalla-analido complexes, which are readily protonated to give the analido complex TpOs(NHPh)Cl(2) (4). The nitrido-phenyl derivatives TpOs(N)PhCl and TpOs(N)Ph(2) react more slowly with PhMgCl and are not competent intermediates for the reaction of 1 with PhMgCl. Reactions of 1 with alkyl- and arylboranes similarly result in transfer of one organic group to nitrogen, leading to isolable borylamido complexes such as TpOs[N(Ph)(BPh(2))]Cl(2) (11). This is an unprecedented insertion of a nitrido ligand into a boron--carbon bond. Hydrolysis of 11 gives 4. Mechanistic studies suggest that both the Grignard and borane reactions proceed by initial weak coordination of Mg or B to the nitrido ligand, followed by migration of the carbanion to nitrogen. The hydrocarbyl group does not go to osmium and then move to nitrogen--there is no change in the atoms bound to the osmium during the reactions. It is suggested that there may be a general preference for nucleophiles to add directly to the metal--ligand multiple bond rather than binding to the metal first and migrating. Ab initio calculations show that the unusual reactivity of 1 results from its accessible LUMO and LUMO + 1, which are the Os = N pi* orbitals. The bonding in 1 and its reactivity with organoboranes are reminiscent of CO.
Pt(0)/Pd(0) metallocryptates encapsulating Tl(I) have been constructed utilizing mixed phosphine-imine ligands 2,9-bis(diphenylphosphino)-1,10-phenathroline, P2phen, and 6,6‘-bis(diphenylphosphino)-2,2‘-bipyridine, P2bpy. The red compounds [M2Tl(P2phen)3](NO3) (M = Pt, 1; M = Pd, 3) and [M2Tl(P2bpy)3](NO3) (M = Pt, 2; M = Pd, 4) have been isolated as air-stable crystalline solids. Complexes 1−4 exhibit single signals in their 205Tl NMR spectra that are well deshielded compared to the TlNO3(aq) reference signal. Additionally, 195Pt NMR spectra of complexes 1 and 2 exhibit a doublet of quartets pattern resulting from large one-bond couplings to both 31P and 205Tl. Characterization of 1−4 by single-crystal X-ray diffraction studies confirms the metallocryptand structure consisting of three phosphine-imine ligands in a D 3-symmetric cage with the Tl(I) ion in its center and the zero-valent Pt or Pd atoms on each end. Each Pd or Pt atom is coordinated to three phosphorus centers, forming approximately trigonal geometry. The Tl(I) ion is positioned away from the imine nitrogen atoms of the phosphine ligands by ∼3.5 Å. Further, the outer capping metals are distorted toward the central Tl(I) ion, indicating a strong interaction. The Pt−Tl and Pd−Tl separations are at ∼2.8 Å each, further manifesting the strength of the metallophilic attraction in these assemblies.
Background Personal construct Theory (PCP) may provide a way for people who are violent and have schizophrenia to understand and modify their behaviour. The ability to reconstrue personal relationships may lead to greater acceptance of perceived or real stresses and increased tolerance. Method A year‐long pilot study tested the feasibility of PCP‐oriented psychotherapy amongst long‐term male residents with schizophrenia in Broadmoor Hospital, all of whom had committed violent acts. A matched group completed the same instruments, but did not receive group psychotherapy. Six of the eight subjects from the index group completed the therapy, but instrument compliance varied. Results for group data cannot be presented, but an individual case report is offered, demonstrating the changes in construing that occurred over the year. These included elaboration accompanied by changes in mood, and the formation of a more appropriate construct system for managing personal relationships. Conclusions The model for therapy is feasible within a secure environment, although there are ethical issues. The evaluation of outcome requires substantial modification, and the issue of subject cooperation needs further attention. The pilot does, however, suggest that such work is then worth more substantial study, including randomization between treatment and non‐treatment groups. Copyright © 1998 Whurr Publishers Ltd.
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