Mood disorders are prevalent and concerning, particularly among children and adolescents. Sleep disturbances, particularly insomnia and hypersomnia (but also delayed sleep phase and sleep need), often co-occur with the mood disorders. Evidence has accrued suggesting that sleep disturbances are important pathways contributing to the mood disorders. The risk of depression is increased by preexisting insomnia, sleep problems interfere with depression treatment success, and in depressed adults treating the depression and insomnia is markedly better relative to treating depression alone. An evidence base is growing for the use of psychosocial treatments for sleep disturbance in youth. We describe the protocol we have developed for treating insomnia in depressed youth. Potential advantages for delivering psychosocial treatments for sleep disturbance, over medication treatments, are reviewed. We also discuss the importance of working with parents, the slight tip toward eveningness with the onset and progression through puberty, and the role of technology (cell phones, video games, etc.) in contributing to sleep disturbance.
Electrophilic Pt(II) complexes catalyze efficient hydroaminations of olefins by sulfonamides and weakly basic anilines. Catalysts include the structurally characterized complex (COD)Pt(OTf)2 (1) and the known dimer [PtCl2(C2H4)]2, activated by AgBF4. Experiments with substituted anilines establish an empirical pKa cutoff (conjugate acid pKa < 1) for the participation of nitrogen-containing substrates in this catalysis. Arylsulfonamides (conjugate acid pKa approximately -6) with various para substituents hydroaminate olefins such as cyclohexene in yields greater than 95% at 90 degrees C. Hydroamination of propylene by p-toluenesulfonamide proceeds with Markovnikov selectivity, suggesting a mechanism that involves olefin activation at Pt. With norbornene and p-toluenesulfonamide as the substrates and 1 as the catalyst, intermediate [(COD)Pt(norbornene)2][OTf]2 (3) was identified and characterized by 19F and 195Pt NMR spectroscopies and mass spectrometry. Kinetic studies provide the empirical rate law, rate = k(obs)[Pt][sulfonamide], and are consistent with a mechanism in which attack of a sulfonamide on the Pt-coordinated olefin is the rate-determining step.
Progressive solubilization of spinach chloroplast thylakoids by Triton X‐100 was employed to investigate the domain organization of the electron transport complexes in the thylakoid membrane. Triton/chlorophyll ratios of 1:1 were sufficient to disrupt fully the continuity of the thylakoid membrane network, but not sufficient to solubilize either photosystem I (PSI), photosystem II (PSII) or the cytochrome b 6 ‐ f (Cyt b 6 ‐ f ) complex. Progressive with the Triton concentration increase (Triton/Chl >1:1), a differential solubilization of the three electron transport complexes was observed. (a) Solubilization of the Cyt b 6 ‐ f complex from the thylakoid membrane preceded that of PSI and apparently occurred early in the solubilization of stroma‐exposed segments of the chloroplast lamellae. (b) The initial removal of chlorophyll (up to 40% of the total) occurred upon solubilization of PSI from the stroma‐exposed lamella regions in which PSI is localized. (c) The tightly appressed membrane of the grana partition regions was markedly resistant to solubilization by Triton X‐100. Thus, solubilization of PSII from this membrane region was initiated only after all Cyt b 6 ‐ f and PSI complexes were removed from the chloroplast lamellae. The results support the notion of extreme lateral heterogeneity in the organization of the electron transport complexes in higher plant chloroplasts and suggest a Cyt b 6 ‐ f localization in the membrane of the narrow fret regions which serve as a continum between the grana and stroma lamellae.
Several new poly(benzyl ether) and poly(benzyl ester) dendrimers that incorporate acid- and thermally- labile peripheral groups have been synthesized. Tertiary butyl ester terminated poly(benzyl ether) dendrimers were synthesized using (alpha) -bromo-t-butyl acetate in the preliminary protection step to afford the first generation alcohol. A standard bromination of the focal point benzylic alcohol was used for the activation step, while standard Williamson ether conditions were used for the coupling steps to afford higher generation poly(benzyl ether) dendrons. Tertiary butyl ester terminated dendrons were then coupled to a difunctional core to produce the [G-3] dendrimer. Tertiary butyl carbonate (t-Boc) terminated poly(benzyl ester) dendrimers were also synthesized. This class of dendrimers was synthesized by first protecting monomeric building block 3,5-dihydroxybenzaldehyde with di-t-butyl dicarbonate. A reductive activation step afforded the [G-1] alcohol. The growth steps were accomplished by either Mitsunobu etherification with 3,5- dihydroxybenzaldehyde or by esterification with 5- hydroxymethylisophthalic acid. Finally, coupling of the benzyl alcohol dendrons to a polyfunctional core afforded second and third generation dendrimers. Chemically amplified resists formulated from both t-butyl ester and t-Boc terminated dendrimers show high sensitivity to DUV and e-beam irradiation. Feature sizes well below 100 nm have been routinely patterned using e-beam lithography.
Identified optimal cell design and operating conditions for efficient solar-driven electrochemical reduction of CO<sub>2</sub>. Developed a method to predict polarization losses from the experimental data.
