A mechanistically-distinct approach to fluorescence visualization of singlet oxygen.

We describe fluorescence detection of 1O2 by a new strategy. Oxidation of a non-fluorescent sulfoxide by 1O2 occurs via intramolecular oxygen atom transfer in a reactive persulfoxide intermediate. The resulting sulfone shows significantly enhanced (>50-fold) emission. This approach complements known methods, and is being extended to biological 1O2 imaging.

Modulating the efficiency of Ru(II) luminescence via ion binding-induced conformational restriction of bipyridyl ligands.

Conformational restriction imposed upon Ru(bpy)32+ crown ether complexes by metal ion binding leads to enhanced luminescence.

New molybdenum catalysts for alkyl olefin epoxidation. Their implications for the mechanism of oxygen atom transfer.

We report here the design, synthesis, and characterization of new (dioxo)Mo(VI) epoxidation catalysts based on monoanionic tridentate ligands. Two important features distinguish these catalysts from those previously reported. First, their coordination environment remains well-defined during the epoxidation reaction. Second, the ligand design does not permit simultaneous coordination of olefin and alkyl hydroperoxide. Based on the study of these new catalysts, we conclude that direct oxygen atom transfer from coordinated alkyl peroxide to olefin remains the simplest mechanism consistent with the available data. We discuss literature discrepancies in this regard.

Impairment in cognitive and exercise performance during prolonged antarctic residence: effect of thyroxine supplementation in the polar triiodothyronine syndrome.

Humans who work in Antarctica display deficits in cognition, disturbances in mood, increased energy requirements, a decline of thyroid hormone products, and an increase of serum TSH. We compared measurements in 12 subjects, before deployment (baseline), with 11 monthly studies during Antarctic residence (AR). After 4 months of AR (period 1), half of the subjects (T(4) group) received L-thyroxine [64 nmol.day(-)(1) (0.05 mg.day(-)(1))]; and the other half, a placebo (placebo group) for the next 7 months of AR (period 2). During period 1, there was a 12.3 +/- 5.1% (P < 0.03) decline on the matching-to-sample (M-t-S) cognitive task and an increase in depressive symptoms, compared with baseline. During the intervention in period 2, M-t-S scores for the T(4)-treated group returned to baseline values; whereas the placebo group, in contrast, showed a reduced M-t-S score (11.2 +/- 1.3%; P < 0.0003) and serum free T(4) (5.9 +/- 2.4%; P < 0.02), compared with baseline. The change in M-t-S score was correlated with the change in free T(4) (P < 0.0003) during both periods, and increases in serum TSH preceded worsening scores in depression, tension, anger, lack of vigor, and total mood disturbance (P < 0.001) during period 2. Additionally, the submaximal work rate for a fixed O(2) use decreased 22.5 +/- 4.9% in period 1 and remained below baseline in period 2 (25.2 +/- 2.3%; P < 0.005) for both groups. After 4 months of AR, the L-thyroxine supplement was associated with improved cognition, which seems related to circulating T(4). Submaximal exercise performance decrements, observed during AR, were not changed with this L-thyroxine dose.

Circannual pattern of hypothalamic-pituitary-thyroid (HPT) function and mood during extended antarctic residence.

The seasonal variation in thyroid function and mood was examined in 10 men and two women who spent the 1997 or 1998 austral winter at McMurdo Station, Antarctica. Serum samples of TSH, free T3 and free T4 were collected each month over a 10-month period (October-August), along with responses to the Profile of Mood States (POMS) and the Center for Epidemiologic Studies - Depression (CES-D) Scale. Both TSH and mood (a summary score created from the POMS depression, anger, fatigue and confusion subscales) exhibited a circannual pattern with peaks during the months of November and July and a trough during the months of March and April. High levels of tension-anxiety and confusion were preceded by declines in free T3 and T4. However, increases in tension-anxiety and total mood disturbance also preceded a decline in free T3 levels, suggesting a feedback of mood on T3 levels. Levels of free T4 were independently associated with preceding increases in anger scores. These results support the hypothesis that the symptoms characteristic of the winter-over syndrome is a state of relative CNS hypothyroidism. This model of seasonal variation in thyroid function and mood also has implications for an understanding of potential mechanisms underlying the association between latitude and SAD or S-SAD.

Convenient synthesis and transformation of 2,6-dichloro-4-iodopyridine.

We describe a convenient scalable synthesis of 2,6-dichloro-4-iodopyridine and demonstrate its utility by stepwise elaboration to a number of 2,4,6-trisubstituted pyridines. [reaction: see text]

Enantioselective epoxide hydrolysis: catalysis involving microbes, mammals and metals.

Although alkyl epoxides are difficult to synthesize in enantiomerically pure form they can often be prepared by the enantioselective hydrolysis of racemic epoxide. The best methods for this transformation are all catalytic and they illustrate the complementary role that biological and synthetic catalysts can play in organic chemistry.

Fluorescence assays for screening combinatorial libraries of drug candidates.

The following subjects will be addressed sequentially: recent advances in the application of the green fluorescent protein (GFP) to monitoring biological processes; a new fluorescent reporter for monitoring b-lactamase expression; a new fluorescent reporter for monitoring membrane potential; and, some wild speculation about the future.

Synthetic and biological catalysts in chemical synthesis: how to assess practical utility.

Enzymes, synthetic catalysts, and catalytic antibodies can all be used to perform asymmetric reactions, but their practical utility is not always easy to evaluate. Criteria with which to compare such catalysts are proposed and illustrated for asymmetric epoxidation, a reaction to which all three approaches have been applied.