Search results for "isomeria"
showing 10 items of 20 documents
High vibrational overtone excitation‐induced conformational isomerization of glycolic acid in solid argon matrix
2018
First observation of high-K isomeric states in $$^{249}$$Md and $$^{251}$$Md
2021
Decay spectroscopy of the odd-proton nuclei $^{249}$Md and $^{251}$Md has been performed. High-K isomeric states were identified for the first time in these two nuclei through the measurement of their electromagnetic decay. An isomeric state with a half-life of 2.8(5) ms and an excitation energy $\ge 910$ keV was found in $^{249}$Md. In $^{251}$Md, an isomeric state with a half-life of 1.4(3) s and an excitation energy $\ge 844$ keV was found. Similarly to the neighbouring $^{255}$Lr, these two isomeric states are interpreted as 3 quasi-particle high-K states and compared to new theoretical calculations. Excited nuclear configurations were calculated within two scenarios: via blocking nucle…
Measurement of fission yields and isomeric yield ratios at IGISOL
2018
Data on fission yields and isomeric yield ratios (IYR) are tools to study the fission process, in particular the generation of angular momentum. We use the IGISOL facility with the Penning trap JYFLTRAP in Jyväskylä, Finland, for such measurements on 232Th and natU targets. Previously published fission yield data from IGISOL concern the 232Th(p,f) and 238U(p,f) reactions at 25 and 50 MeV. Recently, a neutron source, using the Be(p,n) reaction, has been developed, installed and tested. We summarize the results for (p,f) focusing on the first measurement of IYR by direct ion counting. We also present first results for IYR and relative yields for Sn and Sb isotopes in the 128-133 mass range fr…
Conformationally Locked Pyramidality Explains the Diastereoselectivity in the Methylation of trans-Fused Butyrolactones
2020
A stereoselectivity model inspired by the total synthesis of stemona alkaloids is developed to explain why enolate-derived 3,4-fused butyrolactones are methylated with a preference for syn alkylation. The model shows how conformational locking present in nonplanar enolate structures favors syn over anti methylation, due to less significant structural distortions in the syn pathway. The developed model was also successfully used to rationalize selectivities of previously documented methylation reactions. peerReviewed
Steric vs. electronic stereocontrol in syndio- or iso-selective ROP of functional chiral β-lactones mediated by achiral yttrium-bisphenolate complexes
2018
International audience; Origins of stereoselectivity in ROP of racemic chiral cyclic esters promoted by achiral yttrium complexes, resulting in the formation of highly heterotactic polylactide, and highly syndiotactic or, more uniquely, highly isotactic poly(3-hydroxybutyrate)s, are discussed. A close interplay between the nature of the cyclic ester, most particularly of the exocyclic functional chain installed on the chiral center of β-lactones, and the ortho-substituents installed on the phenolate rings of the ligand, results in various determining secondary interactions of steric and also electronic nature.
Computational investigations of 18-electron triatomic sulfur–nitrogen anions
2018
MRCI-SD/def2-QZVP and PBE0/def2-QZVP calculations have been employed for the analysis of geometries, stabilities, and bonding of isomers of the 18-electron anions N2S2−, NS2−, and NSO−. Isomers of the isoelectronic neutral molecules SO2, S2O, S3, and O3 are included for comparison. The sulfur-centered acyclic NSN2−, NSS−, and NSO− anions are the most stable isomers of their respective molecular compositions. However, the nitrogen-centered isomers SNS− and SNO− lie close enough in energy to their more stable counterparts to allow their occurrence. The experimental structural information, where available, is in good agreement with the optimized bond parameters. The bonding in all investigate…
Design, Construction, and Characterization of a New Regioisomer and Diastereomer Material Based on the Spirooxindole Scaffold Incorporating a Sulphon…
2020
The 1,3-dipolar cycloaddition reaction is one of the most rapid, and efficient protocols to access, and construct highly divergent heterocycle chiral auxiliaries. Free catalyst synthesis of spirooxindole scaffold incorporating sulphone moiety via one pot&ndash
Photoactive Yellow Protein Chromophore Photoisomerizes around a Single Bond if the Double Bond Is Locked
2020
Photoactivation in the Photoactive Yellow Protein, a bacterial blue light photoreceptor, proceeds via photo-isomerization of the double C=C bond in the covalently attached chromophore. Quantum chemistry calculations, however, have suggested that in addition to double bond photo-isomerization, the isolated chromophore and many of its analogues, can isomerize around a single C-C bond as well. Whereas double bond photo-isomerization has been observed with x-ray crystallography, experimental evidence for single bond photo-isomerization is currently lacking. Therefore, we have synthesized a chromophore analogue, in which the formal double bond is covalently locked in a cyclopentenone ring and ca…
The Photocycle of Bacteriophytochrome Is Initiated by Counterclockwise Chromophore Isomerization.
2022
Photoactivation of bacteriophytochrome involves a cis–trans photoisomerization of a biliverdin chromophore, but neither the precise sequence of events nor the direction of the isomerization is known. Here, we used nonadiabatic molecular dynamics simulations on the photosensory protein dimer to resolve the isomerization mechanism in atomic detail. In our simulations the photoisomerization of the D ring occurs in the counterclockwise direction. On a subpicosecond time scale, the photoexcited chromophore adopts a short-lived intermediate with a highly twisted configuration stabilized by an extended hydrogen-bonding network. Within tens of picoseconds, these hydrogen bonds break, allowing the c…
Fluorination of some highly functionalized cycloalkanes: chemoselectivity and substrate dependence.
2017
A study exploring the chemical behavior of some dihydroxylated β-amino ester stereo- and regioisomers, derived from unsaturated cyclic β-amino acids is described. The nucleophilic fluorinations involving hydroxy–fluorine exchange of some highly functionalized alicyclic diol derivatives have been carried out in view of selective fluorination, investigating substrate dependence, neighboring group assistance and chemodifferentiation.