The photochemistry of α‐terthienyl (αT) and its mono‐ and dodo derivatives has been examined using nanosecond laser Hash photolysis techniques. The triplet states of these intermediates have been characterized, and show strong triplet‐triplet absorptions with maxima in the 450 to 490 nm region. The triplet lifetimes are normally reduced by efficient triplet‐triplet annihilation and self‐quenching both of which approach diffusion control. Triplet lifetimes in methanol obtained by extrapolation to zero laser dose and zero concentration are 30, 12.5 and 9.4 μs for αT and its mono‐ and dodo derivatives, respectively; the effect of iodo substitution on the lifetimes is attributed to heavy atom effects. The triplet states are efficiently quenched by oxygen and the electron acceptor methyl viologen, while amines tire very poor triplet quenchers. The iodo derivatives are photolabile. undergoing C‐I bond cleavage from the singlet state, a process that was studied in benzene solvent, where the complex between iodine atoms and benzene can be readily characterized.
Modification of αT by replacement of the central thiophene ring by an aromatic ring (i.e. DTB) causes drastic changes in the triplet and singlet state kinetic and spectroscopic characteristics.
Very little is known about the infl uence of the mechanical environment on the healing of large segmental defects. This partly refl ects the lack of standardised, well characterised technologies to enable such studies. Here we report the design, construction and characterisation of a novel external fi xator for use in conjunction with rat femoral defects. This device not only imposes a predetermined axial stiffness on the lesion, but also enables the stiffness to be changed during the healing process. The main frame of the fi xator consists of polyethylethylketone with titanium alloy mounting pins. The stiffness of the fi xator is determined by interchangeable connection elements of different thicknesses. Fixators were shown to stabilise 5 mm femoral defects in rats in vivo for at least 8 weeks during unrestricted cage activity. No distortion or infections, including pin infections, were noted. The healing process was simulated in vitro by inserting into a 5 mm femoral defect, materials whose Young's moduli approximated those of the different tissues present in regenerating bone. These studies confi rmed that, although the external fixator is the major determinant of axial stiffness during the early phase of healing, the regenerate within the lesion subsequently dominates this property. There is much clinical interest in altering the mechanics of the defect to enhance bone healing. Our data suggest that, if alteration of the mechanical environment is to be used to modulate the healing of large segmental defects, this needs to be performed before the tissue properties become dominant.
Lanthanide ions (Ln3+) inhibited the proliferative response of human lymphocytes to various polyclonal mitogens and the 'purified protein derivative' (PPD) of the tuberculin antigen. Of the four Ln3+ ions tested lanthanum (La3+) was the strongest inhibitor; erbium (Er3+) and lutetium (Lu3+) were only weakly active, while samarium (Sm3+) had intermediate potency. At a concentration of 1 mM, La3+ almost completely inhibited the uptake of [3H]-thymidine by lymphocytes exposed to mitogenic agents. Trypan blue exclusion tests confirmed that the La3+ ions were not toxic. These findings may bear upon the reported anti-inflammatory properties of the lanthanides.
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