80-73-9Relevant articles and documents
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Yoder,Zuckerman
, p. 694 (1966)
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A DIPOLE MOMENT STUDY OF N-METHYL AND N,N'-DIMETHYL-IMIDAZOLIDIN-2-ONES, IMIDAZOLIDINE-2-THIONES AND -2-SELENONES
Lumbroso, H.,Liegeois, Ch.,Devillanova, F. A.,Verani, G.
, p. 239 - 252 (1981)
The electric dipole moments in benzene and dioxan of potentially tautomerizable N-methylimidazolidin-2-one, N-methylimidazolidine-2-thione and -2-selenone clearly support the lactam structure for these compounds.The fact that their dipole moments in dioxan are markedly greater than those in benzene is explained by a higher (HN-C=Y) mesomeric moment in the hydrogen-bonded solute...dioxan complexes.Analysis of the dipole moments in benzene of N,N'-dimethylimidazolidin-2-one, N,N'dimethylimidazolidine-2-thione and -2-selenone shows that the mesomeric moment (due to contribution of +N=C-Y- zwitterionic valence structures) gradually increases on going from Y=O to Y=S, and Y=Se.Finally, preferred conformations, from their dipole moments in benzene, are suggested for tetramethylurea and tetramethylthiourea.
Optochemical Control of Bacterial Gene Expression: Novel Photocaged Compounds for Different Promoter Systems
Bier, Claus,Binder, Dennis,Bitzenhofer, Nora Lisa,Drepper, Thomas,Haase, Mona,Hilgers, Fabienne,Hogenkamp, Fabian,Jaeger, Karl-Erich,Ophoven, Vera,Pietruszka, J?rg
, (2021/12/06)
Photocaged compounds are applied for implementing precise, optochemical control of gene expression in bacteria. To broaden the scope of UV-light-responsive inducer molecules, six photocaged carbohydrates were synthesized and photochemically characterized, with the absorption exhibiting a red-shift. Their differing linkage through ether, carbonate, and carbamate bonds revealed that carbonate and carbamate bonds are convenient. Subsequently, those compounds were successfully applied in vivo for controlling gene expression in E. coli via blue light illumination. Furthermore, benzoate-based expression systems were subjected to light control by establishing a novel photocaged salicylic acid derivative. Besides its synthesis and in vitro characterization, we demonstrate the challenging choice of a suitable promoter system for light-controlled gene expression in E. coli. We illustrate various bottlenecks during both photocaged inducer synthesis and in vivo application and possibilities to overcome them. These findings pave the way towards novel caged inducer-dependent systems for wavelength-selective gene expression.
Reaction of Nitroxyl (HNO) with Hydrogen Sulfide and Hydropersulfides
Zarenkiewicz, Jessica,Khodade, Vinayak S.,Toscano, John P.
, p. 868 - 877 (2021/01/14)
Nitroxyl (HNO) has gained a considerable amount of attention because of its promising pharmacological effects. The biochemical mechanisms of HNO activity are associated with the modification of regulatory thiol proteins. Recently, several studies have suggested that hydropersulfides (RSSH), presumed signaling products of hydrogen sulfide (H2S)-mediated thiol (RSH) modification, are additional potential targets of HNO. However, the interaction of HNO with reactive sulfur species beyond thiols remains relatively unexplored. Herein, we present characterization of HNO reactivity with H2S and RSSH. The reaction of H2S with HNO leads to the formation of hydrogen polysulfides and sulfur (S8), suggesting a potential role in sulfane sulfur homeostasis. Furthermore, we show that hydropersulfides are more efficient traps for HNO than their thiol counterparts. The reaction of HNO with RSSH at varied stoichiometries has been examined with the observed production of various dialkylpolysulfides (RSSnSR) and other nitrogen-containing dialkylpolysulfide species (RSS-NH-SnR). We do not observe evidence of sulfenylsulfinamide (RS-S(O)-NH2) formation, a pathway expected by analogy with the known reactivity of HNO with thiol.
Fast Cyclization of a Proline-Derived Self-Immolative Spacer Improves the Efficacy of Carbamate Prodrugs
Belvisi, Laura,Borlandelli, Valentina,Corno, Cristina,Dal Corso, Alberto,Gennari, Cesare,Perego, Paola,Pignataro, Luca
, p. 4176 - 4181 (2020/02/05)
Self-immolative (SI) spacers are sophisticated chemical constructs designed for molecular delivery or material degradation. We describe herein a (S)-2-(aminomethyl)pyrrolidine SI spacer that is able to release different types of anticancer drugs (possessing either a phenolic or secondary and tertiary hydroxyl groups) through a fast cyclization mechanism involving carbamate cleavage. The high efficiency of drug release obtained with this spacer was found to be beneficial for the in vitro cytotoxic activity of protease-sensitive prodrugs, compared with a commonly used spacer of the same class. These findings expand the repertoire of degradation machineries and are instrumental for the future development of highly efficient delivery platforms.