How to cite:Balme, M.R.; Rocchi, V.; Jones, C.; Sammonds, P.R.; Meredith, P.G. and Boon, S. (2004). Fracture toughness measurements on igneous rocks using a high-pressure, high-temperature rock fracture mechanics cell. Journal of Volcanology and Geothermal Research, ABSTRACTA sound knowledge of mechanical properties of rocks at high temperatures and pressures is essential for modelling volcanological problems such as fracture of lava flows and dike emplacement. In particular, fracture toughness is a scale invariant material property of a rock that describes its resistance to tensile failure. A new fracture mechanics apparatus has been constructed enabling fracture toughness measurements on large (60mm diameter) rock core samples at temperatures up to 750°C and pressures up to 50 MPa. We present a full description of this apparatus and, by plotting fracture resistance as a function of crack length, show that the size of the samples is sufficient for reliable fracture toughness measurements. A series of tests on Icelandic, Vesuvian and Etnean basalts at temperatures from 30-600 o C and confining pressures up to 30 MPa gave fracture toughness values between 1.4 and 3.8 MPam 1/2 . The Icelandic basalt is the strongest material and the Etnean material sampled from the surface crust of a lava flow the weakest. Increasing temperature does not greatly affect the fracture toughness of the Etnean or Vesuvian material but the Icelandic samples showed a marked increase in toughness at around 150 o C, followed by a return to ambient toughness levels. This material also became tougher under moderate confining pressure but the other two materials showed little change in toughness. We describe in terms of fracture mechanics probable causes for the changes in fracture toughness and compare our experimental results with values obtained from dike propagation modelling found in the literature.

Optical probes operating in the second near-infrared window (NIR-II, 1,000-1,700 nm), where tissues are highly transparent, have expanded the applicability of fluorescence in the biomedical field. NIR-II fluorescence enables deep-tissue imaging with micrometric resolution in animal models, but is limited by the low brightness of NIR-II probes, which prevents imaging at low excitation intensities and fluorophore concentrations. Here, we present a new generation of probes (Ag 2 S superdots) derived from chemically synthesized Ag 2 S dots, on which a protective shell is grown by femtosecond laser irradiation. This shell reduces the structural defects, causing an 80-fold enhancement of the quantum yield. PEGylated Ag 2 S superdots enable deep-tissue in vivo imaging at low excitation intensities (<10 mW cm −2) and doses (<0.5 mg kg −1), emerging as unrivaled contrast agents for NIR-II preclinical bioimaging. These results establish an approach for developing superbright NIR-II contrast agents based on the synergy between chemical synthesis and ultrafast laser processing.

Commercial polystyrene Merrifield-type resins have been post-synthetically functionalised with BODIPY photosensitisers via a novel aryl ester linking strategy in continuous-flow. A unique synthetic advantage of post-synthetically modifying heterogeneous materials in flow was identified. The homogeneous analogues of the polymer-supported BODIPYs were synthesised and used as reference to assess photophysical properties altered by the polymer-support and linker. The homogeneous and polymer-supported BODIPYs were applied in visible-light photosensitisation of singlet oxygen for the conversion of α-terpinene to ascaridole. Materials produced in flow were superior to batch in terms of functional loading and photosensitisation efficiency. Flow photochemical reactions generally outperformed batch by a factor of 4 with respect to rate of reaction. The polymer-supported BODIPY resins could be irradiated for 96 h without loss of photosensitising ability. Additional material synthetic modification and conditions optimisation using an in-line NMR spectrometer resulted in a 24-fold rate enhancement from the initial material and conditions.

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Ag 2 S semiconductor nanoparticles (NPs) are near-infrared luminescent probes with outstanding properties (good biocompatibility, optimum spectral operation range, and easy biofunctionalization) that make them ideal probes for in vivo imaging. Ag 2 S NPs have, indeed, made possible amazing challenges including in vivo brain imaging and advanced diagnosis of the cardiovascular system. Despite the continuous redesign of synthesis routes, the emission quantum yield (QY) of Ag 2 S NPs is typically below 0.2%. This leads to a low luminescent brightness that avoids their translation into the clinics. In this work, an innovative synthetic methodology that permits a 10-fold increment in the absolute QY from 0.2 up to 2.3% is presented. Such an increment in the QY is accompanied by an enlargement of photoluminescence lifetimes from 184 to 1200 ns. The optimized synthetic route presented here is based on a fine control over both the Ag core and the Ag/S ratio within the NPs. Such control reduces the density of structural defects and decreases the nonradiative pathways. In addition, we demonstrate that the superior performance of the Ag 2 S NPs allows for high-contrast in vivo bioimaging.