No abstract

The photophysical properties of fac-[Re(CO)3(dppz)(py)]+ (1, where dppz = dipyrido[3,2-a: 2',3'-c]phenazine) in CH3CN have been investigated using a series of complementary techniques including visible and infrared transient absorption and resonance Raman spectroscopy on the picosecond and nanosecond timescales. The results confirm previous reports that the lowest-lying emissive state in 1 is a triplet intra-ligand (3IL) state localised on the dppz ligand and have provided detailed information on the dynamics of 1 upon photoexcitation, including the relative energies of the excited state species encountered and the electronic distribution within these. If the dppz ligand is viewed in terms of phenanthroline (phen) and phenazine (phz) moieties, the emissive state is probably more accurately described as a 3 pi-->pi *(phz) IL state. The picosecond studies have shown that this emissive state is formed, at least in part, within 30 ps of excitation from a precursor, which is possibly a 3 pi-->pi *(phen) IL state. On the nanosecond timescale, TRIR has been employed to elucidate further dynamics and reveal the presence of an energetically close-lying state in equilibrium with the emissive state. This has tentatively been assigned as being 3d pi(Re)-->pi *(phz) metal-to-ligand charge transfer (MLCT) in nature. A summary of the photophysics is proposed in the form of a Jablonski scheme. Time dependent density functional theory (TD-DFT) calculations support the relative ordering and suggested electronic character of the excited state species involved.

The photophysical properties of [Re(CO)(3)(dppz)(py)](+) (dppz = dipyrido-[3,2-a:2',3'-c] phenazine) and its 11,12 substituted derivatives [Re(CO)(3)(dppzMe(2))(py)](+) and [Re(CO)(3)(dppzF(2))(py)](+) have been examined in organic and aqueous environments using phosphorescence and picosecond transient visible and infrared absorption spectroscopic methods. The roles of the intraligand IL(pi-pi*) and metal-to-ligand charge transfer MLCT(phz) excited states are evaluated and used to explain the major effect of difluoro-substitution, which is particularly remarkable in water, where the excited state of [Re(CO)(3)(dppzF(2))(py)](+) is strongly quenched.

A family of mesomorphic bis(alkoxystilbazole) silver(I) dodecylsulphate and octylsulphate complexes has been studied by X-ray scattering in their various mesophases. In particular, many of the complexes exhibit a thermotropic cubic mesophase and, for one example, a monodomain was obtained allowing the space group to be unequivocally identified. A model for the formation of these cubic phases is proposed

Object Bone morphogenetic proteins (BMPs) are involved in the growth and development of many tissues, but it is their role in skeletal development and their unique ability to induce ectopic and orthotopic osteogenesis that has attracted the greatest interest. Expression of the BMP-13 gene has been shown to be predominantly localized to hypertrophic chondrocytes in regions of endochondral bone formation during development, as well as in mature articular cartilage in the adult. In addition, the application of BMP-13 on a collagen carrier induces neotendon/ligament formation when delivered subcutaneously or intramuscularly in rodents. The aim of the present study was to determine the histological and ultrastructural changes that occur after the intramuscular injection of a first-generation BMP-13 adenoviral vector. Methods Athymic nude rats were injected with 3.75 × 1010 plaque-forming unit adenovirus (Ad)-BMP-13 or Ad-β-galactosidase in the thigh musculature, and the regions examined using light and electron microscopy at various time points between 2 and 100 days postinjection. As early as 2 days after injection of Ad-BMP-13, progenitor cells were observed infiltrating between the transduced muscle fibers. These cells subsequently proliferated, differentiated, and secreted large amounts of collagenous extracellular matrix. By 100 days postinjection, the induced tissue had the histological and ultrastructural appearance of neotendon/ligament, which was clearly demarcated from the surrounding muscle. Small foci of bone and fibrocartilage were also seen within the induced tissue. A short-term bromodeoxyuri-dine study also demonstrated rapid mesenchymal cell proliferation at the Ad-BMP-13 injection site as early as 48 hours postinjection. Conclusions The results of this study suggest that in the future the use of the BMP-13 gene may have therapeutic utility for the healing of tendon and ligament tears and avulsion injuries.