A new class of dyes, platinum(II) and palladium(II) complexes of the porphyrin ketones (or "oxochlorins"), exhibiting strong phosphorescence at room temperature is described. Several representative compounds were prepared and studied by spectral luminescence methods in solution. Compared to the related porphyrin and chlorin complexes, the new dyes display high photochemical stability, long wave spectral characteristics, and good compatibility with semiconductor optoelectronics (e.g., excitation by light-emitting diodes). These properties make the new dyes promising for a number of relevant applications, such as quenched phosphorescence sensing and phosphorescence probing (e.g., in binding assays). Analytical application of the porphyrin ketone complexes to phosphorescence lifetime-based sensing of molecular oxygen is described. Platinum(II) octaethylporphine ketone was dissolved in a polystyrene layer to give an oxygen-sensitive film. Oxygen measurements were performed with a prototype fiber-optic instrument based on solid-state components, such as light-emitting diodes and photodiodes. The instrument measured phosphorescence lifetime via changes in phase shift The phosphorescence lifetime was determined to change from about 61.4 ps at zero oxygen to 16.3 ps in air (210 hPa of oxygen) at 22 °C. The analytically useful range of the sensor was 0-210 hPa of oxygen partial pressure, with a detection limit of 1.5 hPa. The precision of the device was 1.0 hPa at 210 hPa of oxygen and 0.5 hPa at zero oxygen.Platinum (II) and palladium (II) complexes of porphyrins are known to exhibit strong phosphorescence at room temperatures,1-4 with quantum yields of > 10%. Compared to most other types of phosphorescent organic dyes, porphyrin complexes have long (1) Eastwood, D.; Gouterman, M.
From June 1998 to July 1999, 370 lots of oysters in the shell were sampled at 275 different establishments (71%, restaurants or oyster bars; 27%, retail seafood markets: and 2%, wholesale seafood markets) in coastal and inland markets throughout the United States. The oysters were harvested from the Gulf (49%). Pacific (14%), Mid-Atlantic (18%), and North Atlantic (11%) Coasts of the United States and from Canada (8%). Densities of Vibrio vulnificus and Vibrio parahaemolyticus were determined using a modification of the most probable number (MPN) techniques described in the Food and Drug Administration's Bacteriological Analytical Manual. DNA probes and enzyme immunoassay were used to identify suspect isolates and to determine the presence of the thermostable direct hemolysin gene associated with pathogenicity of V. parahaemolyticus. Densities of both V. vulnifcus and V. parahaemolyticus in market oysters from all harvest regions followed a seasonal distribution, with highest densities in the summer. Highest densities of both organisms were observed in oysters harvested from the Gulf Coast, where densities often exceeded 10,000 MPN/g. The majority (78%) of lots harvested in the North Atlantic, Pacific, and Canadian Coasts had V. vulnificus densities below the detectable level of 0.2 MPN/g; none exceeded 100 MPN/g. V. parahaemolyticus densities were greater than those of V. vulnificus in lots from these same areas, with some lots exceeding 1,000 MPN/g for V. parahaemolyticus. Some lots from the Mid-Atlantic states exceeded 10,000 MPN/g for both V. vulnificus and V. parahaemolyicus. Overall, there was a significant correlation between V. vulificus and V. parahaemolyticus densities (r = 0.72, n = 202, P < 0.0001), but neither density correlated with salinity. Storage time significantly affected the V. vulnificus (10% decrease per day) and V. parahaemolyticus (7% decrease per day) densities in market oysters. The thermostable direct hemolysin gene associated with V parahaemolyticus virulence was detected in 9 of 3,429 (0.3%) V. parahaemolyticus cultures and in 8 of 198 (4.0%) lots of oysters. These data can be used to estimate the exposure of raw oyster consumers to V. vulnificus and V. parahaemolyticus.
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