Search results for "CLEO"

Theoretical and experimental studies of the neutron rich fission product yields at intermediate energies

2012

A new method to measure the fission product independent yields employing the ion guide technique and a Penning trap as a precision mass filter, which allows an unambiguous identification of the nuclides is presented. The method was used to determine the independent yields in the proton-induced fission of 232 Th and 238 U at 25 MeV. The data were analyzed with the consistent model for description of the fission product formation cross section at the projectile energies up to 100 MeV. Pre-compound nucleon emission is described with the two-component exciton model using Monte Carlo method. Decay of excited compound nuclei is treated within time-dependent statistical model with inclusion of the…

Two-neutron correlations at small relative momenta in ^40Ar + ^197Au collisions at 60 MeV/nucleon

2000

Two-neutron correlation functions are measured in the 40Ar + 197Au reaction at 60 MeV/nucleon to study the space-time characteristics of neutron emitting sources. The source temperatures and velocities are deduced by fitting the single-neutron energy spectra with a three-source model. A comparison of the correlation data with the predictions of the model of moving sources and with the dynamical Landau-Vlasov model suggests the relevance of a multisource description. Particular care has been paid to the influence of the relative source abundance on the shape of the correlation function.

Origin of Enzymatic Kinetic Isotope Effects in Human Purine Nucleoside Phosphorylase

2017

Here we report a study of the effect of heavy isotope labeling on the reaction catalyzed by human purine nucleoside phosphorylase (hPNP) to elucidate the origin of its catalytic effect and of the enzymatic kinetic isotope effect (EKIE). Using quantum mechanical and molecular mechanical (QM/MM) molecular dynamics (MD) simulations, we study the mechanism of the hPNP enzyme and the dynamic effects by means of the calculation of the recrossing transmission coefficient. A free energy surface (FES), as a function of both a chemical and an environmental coordinate, is obtained to show the role of the environment on the chemical reaction. Analysis of reactive and nonreactive trajectories allows us …

Dynamics of the excited-state hydrogen transfer in a (dG)·(dC) homopolymer: intrinsic photostability of DNA

2018

Multiscale molecular dynamics simulations reveal out-of-plane distortions that favour DNA photostability. A novel photostability mechanism involving four proton transfers and triggered by a nearby Na+ ion is also unveiled.

First moments of the nucleon generalized parton distributions from lattice QCD

2012

We report on our lattice calculations of the nucleon's generalized parton distributions (GPDs), concentrating on their first moments for the case of N_f=2. Due to recent progress on the numerical side we are able to present results for the generalized form factors at pion masses as low as 260 MeV. We perform a fit to one-loop covariant baryon chiral perturbation theory with encouraging results.

Sensitive Assays by Nucleophile-Induced Rearrangement of Photoactivated Diarylethenes.

2018

Upon light-induced isomerization, diarylethenes (DAEs) equipped with reactive aldehyde moieties rearrange selectively in the presence of amines, accompanied by decoloration. In a comprehensive study, the probe structure was optimized with regard to its inherent reactivity in the nucleophile-triggered rearrangement reaction. Detailed structure−reactivity relationships could be derived, in particular with regard to the type of integrated (het)aryl moieties as well as the location of the formyl residue, and the probes’ intrinsic reactivity with primary and secondary amines was optimized. Utilizing an ancillary base, the initially formed rearrangement product can engage in a subsequent catalyti…

Nucleophilic iodonium interactions (NIIs) in 2-coordinate iodine(i) and silver(i) complexes

2021

The generality of nucleophilic iodonium interactions (NIIs) has been demonstrated by preparing a range of silver(i) and iodonium (I+) complexes and studying their 15N NMR chemical shifts, with the first example of a NII-complex involving a 2-coordinate silver(i) complex being confirmed by X-ray crystallography, and its nucleophilicity studied by DFT calculations.

2020

The course of organic chemical reactions is efficiently modelled through the concepts of “electrophiles” and “nucleophiles” (meaning electron-seeking and nucleus-seeking reactive species). On the one hand, an advanced approach of the correlation of the nucleophilicity parameters N and electrophilicity E has been delivered from the linear free energy relationship log k (20 °C) = s(N + E). On the other hand, the general influence of the solvent mixtures, which are very often employed in preparative synthetic chemistry, has been poorly explored theoretically and experimentally, to date. Herein, we combined experimental and theoretical studies of the solvent influence on pyrrolidine nucleophili…

A Molecular Electron Density Theory Study of the Role of the Copper Metalation of Azomethine Ylides in [3 + 2] Cycloaddition Reactions.

2018

The copper metalation of azomethine ylides (AYs) in [3 + 2] cycloaddition (32CA) reactions with electron-deficient ethylenes has been studied within the Molecular Electron Density Theory (MEDT) at the MPWB1K/6-311G(d,p) level, in order to shed light on the electronic effect of the metalation in the course of the reaction. Analysis of the Conceptual Density Functional Theory reactivity indices indicates that the metalation of AYs markedly enhances the nucleophilicity of these species given the anionic character of the AY framework. These 32CA reactions take place through stepwise mechanisms characterized by the formation of a molecular complex. Both nonmetalated and metalated 32CA reactions …

Understanding the Participation of Fluorinated Azomethine Ylides in Carbenoid-Type [3 + 2] Cycloaddition Reactions with Ynal Systems: A Molecular Ele…

2021

The carbenoid-type (cb-type) 32CA reaction of 1,1-difluoroated azomethine ylide (DFAY) with phenylpropynal has been studied using the molecular electron density theory (MEDT). Electron localization function (ELF) characterizes DFAY as a carbenoid species participating in cb-type 32CA reactions. The supernucleophilic character of DFAY and the strong electrophilic character of the ynal cause this polar 32CA reaction to have an unappreciable barrier; the reaction, which is highly exothermic, presents total chemo- and regioselectivity. ELF topological analysis of the bonding changes along the reaction establishes its non-concerted two-stage one-step mechanism, in which the nucleophilic attack o…