Measuring stress changes within seismically active fault zones has been a longsought goal of seismology. Here we show that such stress changes are measurable by exploiting the stress dependence of seismic wave speed from an active source cross-well experiment conducted at the SAFOD drill site. Over a two-month period we observed an excellent anti-correlation between changes in the time required for an S wave to travel through the rock along a fixed pathway -a few microseconds--and variations in barometric pressure. We also observed two large excursions in the traveltime data that are coincident with two earthquakes that are among those predicted to produce the largest coseismic stress changes at SAFOD. Interestingly, the two excursions started approximately 10 and 2 hours before the events, respectively, suggesting that they may be related to pre-rupture stress induced changes in crack properties, as observed in early laboratory studies [1][2] .It is well known from laboratory experiments that seismic velocities vary with the level of applied stress [3][4][5] . Such dependence is attributed to the opening/closing of microcracks due to changes in the stress normal to the crack surface [6][7][8] . In principle, this dependence constitutes a stress meter, provided the induced velocity changes can be 2 measured precisely and continuously. Indeed, there were several attempts in the 1970s to accomplish this goal using either explosive or non explosive surface sources 9-11 . The source repeatability and the precision in traveltime measurement appeared to be the main challenges in making conclusive observations.With the availability of highly repeatable sources, modern data acquisition systems, and advanced computational capability, Yamamura et al. 12 showed compelling evidence that seismic velocity along a baseline in a vault near the coast of Miura Bay, Japan, responds regularly to tidal stress changes. Silver et al. 13 found an unambiguous dependence of seismic velocity on barometric pressure from a series of cross-well experiments at two test sites in California. The stress sensitivity depends primarily on crack density and has a strong nonlinear dependence on confining pressure.Consequently, crack density is expected to decrease rapidly with depth as should stress sensitivity. It is thus unclear whether the stress-induced velocity variations observed at shallow depths [12][13] are still detectable at seismogenic depth.To explore stress sensitivity at seismogenic depth, we have conducted an experiment at Parkfield where adjacent deep wells, the SAFOD (San Andreas Fault Observatory at Depth) pilot and main holes (Figure 1), are available. Accurately located seismicity together with the availability of high-quality geophysical data in the Parkfield region make it one of the best areas to detect temporal changes related to the earthquake cycle.A specially-designed 18-element piezoelectric source and a three-component accelerometer were deployed inside the pilot and main holes, respectively, at ~1 km depth (see methods)...

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Porphodilactones represent the porphyrin analogues, in which the peripheral bonds of two pyrrole rings are replaced by lactone moieties. They provide an opportunity to investigate how β-substituent orientation of porphyrinoids modulates the electronic structures and optical properties, in a manner similar to what is observed with naturally occurring chlorophylls. In this work, a comprehensive description of the synthesis, characterization, and optical properties of meso-tetrakispentafluorophenylporphodilactone isomers is first reported. The β-dilactone moieties are found to lie at opposite pyrrole positions (trans- and cis-configurations are defined by the relative orientations of the carbonyl group when one lactone moiety is fixed), in accordance with earlier computational predictions (Gouterman, M. J. Am. Chem. Soc. 1989, 111, 3702). The relative orientation of the β-dilactone moieties has a significant influence on the electronic structures and photophysical properties. For example, the Qy band of trans-porphodilactone is red-shifted by 19 nm relative to that of the cis-isomer, and there is a 2-fold increase in the absorption intensity, which resembles the similar trends that have been reported for natural chlorophyll f and d. An in depth analysis of magnetic circular dichroism spectral data and TD-DFT calculations at the B3LYP/6-31G(d) level of theory demonstrates that the trans- and cis-orientations of the dilactone moieties have a significant effect on the relative energies of the frontier π-molecular orbitals. Importantly, the biological behaviors of the isomers reveal their different photocytotoxicity in NIR region (>650 nm). The influence of the relative orientation of the β-substituents on the optical properties in this context provides new insights into the electronic structures of porphyrinoids which could prove useful during the development of near-infrared absorbing photosensitizers.

We report the extraordinary result of rapid fibre Bragg grating inscription in doped polymer optical fibres based on polymethyl methacrylate in only 7 ms, which is two orders of magnitude faster than the inscription times previously reported. This was achieved using a new dopant material, diphenyl disulphide, which was found to enable a fast, positive refractive index change using a low ultraviolet dose. These changes were investigated and found to arise from photodissociation of the diphenyl disulphide molecule and subsequent molecular reorganization. We demonstrate that gratings inscribed in these fibres can exhibit at least a 15 times higher sensitivity than silica glass fibre, despite their quick inscription times. As a demonstration of the sensitivity, we selected a highly stringent situation, namely, the monitoring of a human heartbeat and respiratory functions. These findings could permit the inscription of fibre Bragg gratings during the fibre drawing process for mass production, allowing cost-effective, single-use, in vivo sensors among other potential uses.

Learning nature's approach to modulate photophysical properties of NIR porphyrinoids by fine-tuning β-substituents including the number and position, in a manner similar to naturally occurring chlorophylls, has the potential to circumvent the disadvantages of traditional "extended π-conjugation" strategy such as stability, molecular size, solubility, and undesirable π-π stacking. Here we show that such subtle structural changes in Pt(II) or Pd(II) cis/trans-porphodilactones (termed by cis/trans-Pt/Pd) influence photophysical properties of the lowest triplet excited states including phosphorescence, Stokes shifts, and even photosensitization ability in triplet-triplet annihilation reactions with rubrene. Prominently, the overall upconversion capability (η, η = ε·Φ(UC)) of Pd or Pt trans-complex is 10(4) times higher than that of cis-analogue. Nanosecond time-resolved infrared (TR-IR) spectroscopy experiments showed larger frequency shift of ν(C═O) bands (ca. 10 cm(-1)) of cis-complexes than those of trans-complexes in the triplet excited states. These spectral features, combining with TD-DFT calculations, suggest the strong electronic coupling between the lactone moieties and the main porphyrin chromophores and thus the importance of precisely positioning β-substituents by mimicking chlorophylls, as an alternative to "extended π-conjugation", in designing NIR active porphyrinoids.

The near-infrared (NIR) luminescence efficiency of lanthanide complexes is largely dependent on the electronic and photophysical properties of antenna ligands. Although porphyrin ligands are efficient sensitizers of lanthanide NIR luminescence, non-pyrrolic porphyrin analogues, which have unusual symmetry and electronic states, have been much less studied. In this work, we used porpholactones, a class of β-pyrrolic-modified porphyrins, as ligands and investigated the photophysical properties of lanthanide porpholactones Yb-1 a-5 a. Compared with Yb porphyrin complexes, the porpholactone complexes displayed remarkable enhancement of NIR emission (50-120 %). Estimating the triplet-state levels of porphyrin and porpholactone in Gd complexes revealed that β-lactonization of porphyrinic ligands lowers the ligand T1 state and results in a narrow energy gap between this state and the lowest excited state of Yb(3+) . Transient absorption spectra showed that Yb(III) porpholactone has a longer transient decay lifetime at the Soret band than the porphyrin analogue (30.8 versus 17.0 μs). Thus, the narrower energy gap and longer lifetime arising from β-lactonization are assumed to enhance NIR emission of Yb porpholactones. To demonstrate the potential applications of Yb porpholactone, a water-soluble Yb bioprobe was constructed by conjugating glucose to Yb-1 a. Interestingly, the NIR emission of this Yb porpholactone could be specifically switched on in the presence of glucose oxidase and then switched off by addition of glucose. This is the first demonstration that non-pyrrolic porphyrin ligands enhance the sensitization efficiency of lanthanide luminescence and also display switchable NIR emission in the region of biological analytes (800-1400 nm).

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A novel all-polymer fiber-optic pH sensor using a UV-cured pH-sensitive hydrogel, poly(ethylene glycol) diacrylate (PEGDA), coated on a polymer fiber Bragg grating was developed. The PEGDA increased in volume according to the pH value of the surrounding fluid, which subsequently induced a lateral stress in the polymer fiber Bragg grating. The proposed pH sensor exhibits a pH sensitivity of up to -0.41 nm/pH and a fast response time of 30 s.