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81.

Background  

The ability to respond to changes in the extra-intracellular environment is prerequisite for cell survival. Cellular responses to the environment include elevating defense systems, such as the antioxidant defense system. Hypoxia-evoked reactive oxygen species (ROS)-driven oxidative stress is an underlying mechanism of retinal ganglion cell (RGC) death that leads to blinding disorders. The protein peroxiredoxin 6 (PRDX6) plays a pleiotropic role in negatively regulating death signaling in response to stressors, and thereby stabilizes cellular homeostasis.  相似文献   
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Electron-transfer(ET) from organic sulfides to excited state rhenium(I)-based heteroleptic tricarbonyl complexes [Re(bpy)(CO)3(py)]+ (I) and [Re(bpy)(CO)3(ind))]+ (II) in acetonitrile solution is facile and luminescence quenching constants, kq, are in the range 105–108 M−1s−1. The detection of the sulfide radical cation in this system using time-resolved absorption spectroscopy is a direct evidence for the ET nature of the reaction. The kq values for the quenching of Re(I)-complexes with organic sulfides are analyzed with a scheme involving rate controlling electron transfer process. The measured rate constants for the electron transfer (ET) reaction are close to the values calculated from Marcus theory.  相似文献   
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We show that the complicated superpositionsV(r) of several important phenomenological forces may still lead to an elementary form of doublets of bound states under transparent algebraic constraints. Constructively, we show how (and when) the constrained couplings preserve compatibility with the physical regularity of wavefunctions.  相似文献   
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We study the static solution of the sine-Gordon wave equation in a background geometry determined by a point mass in 1+1 dimension.  相似文献   
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Triplet arylnitrenes may provide direct access to aryl azo-dimers, which have broad commercial applicability. Herein, the photolysis of p-azidostilbene ( 1 ) in argon-saturated methanol yielded stilbene azo-dimer ( 2 ) through the dimerization of triplet p-nitrenostilbene (3 1N ). The formation of 3 1N was verified by electron paramagnetic resonance spectroscopy and absorption spectroscopy (λmax ~ 375 nm) in cryogenic 2-methyltetrahydrofuran matrices. At ambient temperature, laser flash photolysis of 1 in methanol formed 3 1N (λmax ~ 370 nm, 2.85 × 107 s−1). On shorter timescales, a transient absorption (λmax ~ 390 nm) that decayed with a similar rate constant (3.11 × 107 s−1) was assigned to a triplet excited state (T) of 1 . Density functional theory calculations yielded three configurations for T of 1 , with the unpaired electrons on the azido (TA) or stilbene moiety (TTw, twisted and TFl, flat). The transient was assigned to TTw based on its calculated spectrum. CASPT2 calculations gave a singlet–triplet energy gap of 16.6 kcal mol−1 for 1 N ; thus, intersystem crossing of 1 1N to 3 1N is unlikely at ambient temperature, supporting the formation of 3 1N from T of 1 . Thus, sustainable synthetic methods for aryl azo-dimers can be developed using the visible-light irradiation of aryl azides to form triplet arylnitrenes.  相似文献   
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