Publications by authors named "McKiernan G"

The advent of high-intensity lasers enables us to recreate and study the behaviour of matter under the extreme densities and pressures that exist in many astrophysical objects. It may also enable us to develop a power source based on laser-driven nuclear fusion. Achieving such conditions usually requires a target that is highly uniform and spherically symmetric.

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A fluorous-tagged linker for the parallel synthesis of small- and medium-ring and macrocyclic nitrogen heterocycles using ring-closing metathesis is described. The linker was designed such that "cyclization-release" of the cyclic heterocyclic products was coupled with liberation of the active catalyst. The design of the linker was validated using a non-fluorous-tagged model.

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[reaction: see text] Novel titanium benzylidenes (Schrock carbenes) bearing an arylboronate group are generated from thioacetals with low valent titanium species, Cp(2)Ti[P(OEt)(3)](2), and alkylidenate Merrifield resin-bound esters to give enol ethers. Treatment with 1% TFA gives 2-substituted (benzo[b]furan-5-yl)boronates, and solid-phase Suzuki cross-coupling gives 2,5-disubstituted benzofurans. Steps in the syntheses of thioacetal substrates include selective lithiation-boronation, hydrolysis of a MOM group without affecting a boronate ester, and cross-coupling with bis(pinacolato)diboron.

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Titanium(IV) benzylidenes bearing a masked oxygen or nitrogen nucleophile in the ortho position were generated from thioacetals, using low-valent titanocene complex, Cp2Ti[P(OEt)3]2. Methylene acetal, alkyl ether, silyl ether, fluoro, tertiary amino, and N-alkyl, N-benzyl, N-prenyl, and N-silyl tert-butyl carbamate groups were tolerated in the titanium alkylidene reagents (Schrock carbenes). Aryl-chlorine bonds were stable to the titanium benzylidene functionality, but there was poor chemoselectivity for the reduction of the thioacetal in the presence of an aryl chloride.

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Over the past two years, the photopheresis treatment program at Yale-New Haven Hospital has treated 32 patients with cutaneous T-cell lymphoma. There were 19 erythrodermic patients who had photopheresis as their first systemic therapy. Five of these cleared 75 percent of their skin and the majority of erythrodermics achieved an improved quality of life.

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A woman who emigrated to the United States from the Dominican Republic developed the first signs of cutaneous T cell lymphoma during the last trimester of her pregnancy. This patient, found to have a positive reaction against human T-lymphotropic (leukemia-lymphoma) virus type I (HTLV-I), was followed up prospectively from the appearance of the initial skin lesion to the development of high-count helper T cell leukemia. Antibodies reactive with the core protein of HTLV-I were also identified in her husband and mother but not in her 2-year-old daughter.

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Plasma exchange was used to treat 10 patients with polyneuropathy and a monoclonal antibody (plasma cell dyscrasia). Six patients had improvement of the neuropathy, while three patients had stabilisation of the neuropathy during plasma exchange. The patients who improved maintained a 64% or greater decrease in the monoclonal antibody between exchanges.

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