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Gareth AD Hardy Nesrina Imami Mark R Nelson Ann K Sullivan Ron Moss Marlén MI Aasa-Chapman Brian Gazzard Frances M Gotch 《Journal of immune based therapies and vaccines》2007,5(1):6-12
Background
Fully functional HIV-1-specific CD8 and CD4 effector T-cell responses are vital to the containment of viral activity and disease progression. These responses are lacking in HIV-1-infected patients with progressive disease. We attempted to augment fully functional HIV-1-specific CD8 and CD4 effector T-cell responses in patients with advanced chronic HIV-1 infection. 相似文献2.
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Sankaranarayanan J Bort LN Mandel SM Chen P Krause JA Brooks EE Tsang P Gudmundsdottir AD 《Organic letters》2008,10(5):937-940
Solid-state photolysis of 1a,b yields selectively cis-3a,b. X-ray analysis of 1a,b reveals the molecules adopt an extended structure and as such the crystal packing arrangement consists of planar, pi-stacked molecules. The shortest intermolecular distance between adjacent N-atoms is approximately 3.76 A and would lead to formation of trans-3a,b, whereas cis-3a,b is formed by dimerization between N-atoms that are approximately 3.9 A apart. We propose that the molecular orbital alignment of the adjacent nitrenes controls the solid-state reactivity. 相似文献
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Anushree Das Emily A. Lao Anna D. Gudmundsdottir 《Photochemistry and photobiology》2016,92(3):388-398
Photolysis of ester 1 in argon‐saturated methanol and acetonitrile does not produce any product, whereas irradiation of 1 in oxygen‐saturated methanol yields peroxide 2 . Laser flash photolysis studies demonstrate that 1 undergoes intramolecular H atom abstraction to form biradical 3 (λ max ~ 340 nm), which intersystem crosses to form photoenols Z ‐ 4 and E ‐ 4 (λ max ~ 380 nm). Photoenols 4 decay by regenerating ester 1 . With the aid of density functional theory calculations, it was concluded the photoenol E ‐ 4 does not undergo spontaneous lactonization or electrocyclic ring closure because the transition state barriers for these reactions are too large to compete with reketonization of E ‐ 4 to form 1 . 相似文献
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Rajesh S. Murthy Sivaramakrishnan Muthukrishnan Sridhar Rajam Sarah M. Mandel Bruce S. Ault Anna D. Gudmundsdottir 《Journal of photochemistry and photobiology. A, Chemistry》2009,201(2-3):157-167
Photolysis of azides 1–4 in methanol, which have a built-in intramolecular triplet sensitizer, yields mainly carbamates 5–8. Laser flash photolysis of 1–4 shows formation of their triplet-excited ketone, which decays by intramolecular energy transfer to form triplet nitrenes 1n–4n. Irradiating 1–3 in matrices yields isocyanic acid, whereas photolysis of 4 forms isocyanate 4i. The depletion rate of the azide bands between 2100 and 2200 cm?1 is different than the rate of formation for the isocyanic acid bands at ~2265 cm?1; thus, the formation of isocyanic acid is a stepwise process. Irradiating 1 in matrices produces an absorption band due to nitrene 1n (λmax ~ 343 nm), which is depleted upon further irradiation, whereas the absorption due to 4-acetyl benzaldehyde (λmax ~ 280 nm) increases with prolonged irradiation. We propose that formation of isocyanic acid in matrices must come from secondary photolysis of nitrenes 1n–3n. This mechanism is further supported by calculation, which show that the estimated transition state for 1n–4n to fall apart to yield alkoxy and cyanato radicals is only ~34 kcal/mol above the ground state of the triplet nitrenes and thus the cleavage can take place photochemically. Thus, nitrenes 1n–4n can be formed selectively, but these intermediates are highly photosensitive and undergo secondary photolysis in matrices. 相似文献
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We have directly time resolved the lattice motions associated with the formation of the self-trapped exciton in the quasi-one-dimensional system [Pt(en)(2)] [Pt(en)2Br2];(PF6)(4) ( en = ethylene-diamine, C2H8N2), using femtosecond impulsive excitation techniques. A strongly damped, low-frequency wave packet modulation at approximately 110 cm(-1) accompanies the formation of the self-trapped exciton on a approximately 200 fs time scale following excitation of the intervalence charge-transfer transition. Coherent oscillations at the ground state vibrational frequency and its harmonics are also detected. 相似文献
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This paper gives one-term componentwise asymptotics for theM and spectral matrices of a self-adjoint realisation of aneven-order ordinary differential expression. The underlyinginterval is assumed to have at least one regular endpoint, andthe boundary conditions are supposed to be separated. Furthermore,the weight function and the reciprocal of the highest-ordercoefficient are supposed to be of regular variation at the regularendpoint, in the sense of Bingham, Goldie and Teugels. 1991Mathematics Subject Classification: 34B24, 34E05. 相似文献