27 research outputs found

    Cryogenic Ion Spectroscopy of the Green Fluorescent Protein Chromophore in Vacuo

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    We present the spectrum of the S1 ← S0 transition of an anionic model for the chromophore of the green fluorescent protein in vacuo at cryogenic temperatures, showing previously unresolved vibrational features, and resolving the band origin at 20850 cm-1 (479.6 nm) with unprecedented accuracy. The vibrational spectrum establishes that the molecule is in the Z isomer at low temperature. At increased temperature, theS1 ← S0 band shifts to the red, which we tentatively attribute to emergent population of the E isomer

    Probing the Microsolvation Environment of the Green Fluorescent Protein Chromophore In Vacuo

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    We present vibrational and electronic photodissociation spectra of a model chromophore of the green fluorescent protein in complexes with up to two water molecules, prepared in a cryogenic ion trap at 160–180 K. We find the band origin of the singly hydrated chromophore at 20 985 cm–1 (476.5 nm) and observe partially resolved vibrational signatures. While a single water molecule induces only a small shift of the S1 electronic band of the chromophore, without significant change of the Franck–Condon envelope, the spectrum of the dihydrate shows significant broadening and a greater blue shift of the band edge. Comparison of the vibrational spectra with predicted infrared spectra from density functional theory indicates that water molecules can interact with the oxygen atom on the phenolate group or on the imidazole moiety, respectively

    A randomized, triple-masked, active-controlled investigation of the relative effects of dose, concentration, and infusion rate for continuous popliteal-sciatic nerve blocks in volunteers

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    BackgroundIt remains unknown whether local anaesthetic dose is the only factor influencing continuous popliteal-sciatic nerve block effects, or whether concentration, volume, or both exert an influence as well.MethodsBilateral sciatic catheters were inserted in volunteers (n=24). Catheters were randomly assigned to ropivacaine of either 0.1% (8 ml h(-1)) or 0.4% (2 ml h(-1)) for 6 h. The primary endpoint was the tolerance to transcutaneous electrical stimulation within the tibial nerve distribution at hour 6. Secondary endpoints included current tolerance at other time points and plantar flexion maximum voluntary isometric contraction (22 h total).ResultsAt hour 6, tolerance to cutaneous stimulation for limbs receiving 0.1% ropivacaine was [mean (standard deviation)] 27.0 (20.2) vs26.9 (20.4) mA for limbs receiving 0.4% [estimated mean difference 0.2 mA; 90% confidence interval (CI) -8.2 to 8.5; P=0.02 and 0.03 for lower and upper boundaries, respectively]. Because the 90% CI fell within the prespecified tolerance ±10 mA, we conclude that the effect of the two concentration/volume combinations were equivalent. Similar negative findings were found for the secondary outcomes.ConclusionsFor continuous popliteal-sciatic nerve blocks, we found no evidence that local anaesthetic concentration and volume influence block characteristics, suggesting that local anaesthetic dose (mass) is the primary determinant of perineural infusion effects in this anatomic location. These findings suggest that for ambulatory perineural local anaesthetic infusion-for which there is usually a finite local anaesthetic reservoir-decreasing the basal rate while increasing the local anaesthetic concentration may allow for increased infusion duration without compromising postoperative analgesia.Clinical trial registrationNCT01898689
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