Abstract:The reaction of the tetravalent uranium [U(IV)] with dimethyldioxirane (DMD) in strongly acidic water-acetone solutions is accompanied by chemiluminescence (CL) in the visible (Vis) and infra-red (IR) regions. At least three independent reaction pathways are involved in the U(IV)-DMD oxidation: the first entails the non-chemiluminescent oxidation of U(IV) to the uranyl ion (UO(2) (2+)); the second involves the catalytic decomposition of DMD by U(IV) to afford singlet oxygen, as manifested by its characteristic… Show more
“…Dioxiranes, three-membered-ring peroxides, are known as highly efficient and selective oxidants capable of performing a variety of oxidative transformations valuable for synthetic purposes. − It was recently shown that some of these chemical transformations are accompanied by CL due to the release of singlet oxygen. In particular, the CL of singlet oxygen at 1270 nm was observed in the N -oxide-catalyzed decomposition ,, (Scheme , pathway 1) of dimethyldioxirane (DMD) and methyl(trifluoromethyl)dioxirane (TFD), in the metal-induced reaction − of DMD (Scheme , pathway 2), and in the catalyzed ,, decomposition of DMD and TFD by anionic nucleophiles (Scheme , pathway 3). 18 …”
Section: 4 Dioxiranesmentioning
confidence: 99%
“…[199][200][201][202][203][204][205] It was recently shown that some of these chemical transformations are accompanied by CL due to the release of singlet oxygen. In particular, the CL of singlet oxygen at 1270 nm was observed in the N-oxide-catalyzed decomposition 117,206,207 (Scheme 18, pathway 1) of dimethyldioxirane (DMD) and methyl-(trifluoromethyl)dioxirane (TFD), in the metal-induced reaction [208][209][210] of DMD (Scheme 18, pathway 2), and in the catalyzed 133,207,211 decomposition of DMD and TFD by anionic nucleophiles (Scheme 18, pathway 3).…”
“…Dioxiranes, three-membered-ring peroxides, are known as highly efficient and selective oxidants capable of performing a variety of oxidative transformations valuable for synthetic purposes. − It was recently shown that some of these chemical transformations are accompanied by CL due to the release of singlet oxygen. In particular, the CL of singlet oxygen at 1270 nm was observed in the N -oxide-catalyzed decomposition ,, (Scheme , pathway 1) of dimethyldioxirane (DMD) and methyl(trifluoromethyl)dioxirane (TFD), in the metal-induced reaction − of DMD (Scheme , pathway 2), and in the catalyzed ,, decomposition of DMD and TFD by anionic nucleophiles (Scheme , pathway 3). 18 …”
Section: 4 Dioxiranesmentioning
confidence: 99%
“…[199][200][201][202][203][204][205] It was recently shown that some of these chemical transformations are accompanied by CL due to the release of singlet oxygen. In particular, the CL of singlet oxygen at 1270 nm was observed in the N-oxide-catalyzed decomposition 117,206,207 (Scheme 18, pathway 1) of dimethyldioxirane (DMD) and methyl-(trifluoromethyl)dioxirane (TFD), in the metal-induced reaction [208][209][210] of DMD (Scheme 18, pathway 2), and in the catalyzed 133,207,211 decomposition of DMD and TFD by anionic nucleophiles (Scheme 18, pathway 3).…”
“…The oxidation of tetravalent uranium [U(IV)] to the uranyl ion (UO 2 2+ ) has been a topic of research because of the high intensity of CL observed due to the high yield of excited uranyl ion, which in some cases is close to unity (57). CL was verified during the oxidation of U(IV) by the inorganic oxidants KHSO 5 , XeF 2 , O 3 , Na 2 S 2 O 8 , O 2 and XeO 3 , in which [Ox] represents the oxidant: …”
From an expression screen in a fish model, the medaka, we have isolated Ol-KIP (Oryzias latipes-kinase inhibitor protein), a new member of the KIP subfamily of cyclin-dependent kinase (Cdk) inhibitors. We have analysed its expression in the developing and adult brain by in situ hybridization and by double labeling with Ol-KIP mRNA and proliferating cell nuclear antigen (PCNA) antibodies. Ol-KIP presents a complex expression pattern in several areas of the embryonic central nervous system, most often in close vicinity to proliferative neuroepithelia. We studied in great detail its expression in the optic tectum: Ol-KIP is expressed in a ringshaped domain lying exactly between the proliferative and the postmitotic zones of this structure and is, therefore, potentially involved in cell cycle exit. In the adult CNS, Ol-KIP expression persists in numerous nuclei, both close and distant from proliferative ventricular areas. So, Ol-KIP expression is in part compatible with a sustained "stop signal" role for proliferation, but its expression in postmitotic zones suggests that KIP proteins may have late neuronal function(s), in addition to inhibiting Cdks. This first detailed study of the expression profile of a KIP gene in a nonmammalian vertebrate, thus, opens perspectives for analysing the role of these regulators in brain development and function.
Nucleophilic anions such as Cl(-), I(-), Br(-), t-BuO(-), O(2)(-) and OH(-) efficiently catalyze the decomposition of dimethyldioxirane (DMD) and methyl(trifluoromethyl)dioxirane (TFD). Singlet oxygen ((1)O(2)) is formed in these catalytic reactions, as demonstrated by the characteristic infrared chemiluminescence (IR-CL) at 1268 nm. The yield of (1)O(2) generation, measured by the IR-CL method, lies in the range between 2 and 98%, which depends on the particular anion employed. For the bromide ion, the catalytic decomposition of the dioxirane is in competition with the oxidation of Br(-) to elemental bromine.
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