Search results for " Functional"
showing 10 items of 1811 documents
NMR Spectroscopic Evidence for the Intermediacy of XeF3− in XeF2/F− Exchange, Attempted Syntheses and Thermochemistry of XeF3− Salts, and Theoretical…
2010
The existence of the trifluoroxenate(II) anion, XeF(3)(-), had been postulated in a prior NMR study of the exchange between fluoride ion and XeF(2) in CH(3)CN solution. The enthalpy of activation for this exchange, ΔH(⧧), has now been determined by use of single selective inversion (19)F NMR spectroscopy to be 74.1 ± 5.0 kJ mol(-1) (0.18 M) and 56.9 ± 6.7 kJ mol(-1) (0.36 M) for equimolar amounts of [N(CH(3))(4)][F] and XeF(2) in CH(3)CN solvent. Although the XeF(3)(-) anion has been observed in the gas phase, attempts to prepare the Cs(+) and N(CH(3))(4)(+) salts of XeF(3)(-) have been unsuccessful, and are attributed to the low fluoride ion affinity of XeF(2) and fluoride ion solvation in…
Theoretical Study on the Photo-Oxidation and Photoreduction of an Azetidine Derivative as a Model of DNA Repair
2021
Photocycloreversion plays a central role in the study of the repair of DNA lesions, reverting them into the original pyrimidine nucleobases. Particularly, among the proposed mechanisms for the repair of DNA (6-4) photoproducts by photolyases, it has been suggested that it takes place through an intermediate characterized by a four-membered heterocyclic oxetane or azetidine ring, whose opening requires the reduction of the fused nucleobases. The specific role of this electron transfer step and its impact on the ring opening energetics remain to be understood. These processes are studied herein by means of quantum-chemical calculations on the two azetidine stereoisomers obtained from photocyc…
Island Homoaromaticity in the W-Shaped 2,4-Diphospha-3-arsapentadienide Anion and Related Compounds - Theoretical and Experimental Investigations
2012
A series of anions with general formula (R2C=P)2Pn– (Pn = N, P, As, Sb; R = H, Me, CF3, SiH3, SiMe3, SiF3) was investigated theoretically at the DFT (RI-BP86/TZVP) and RI-MP2/TZVP levels of approximation. Significantly sharpened central PPnP bond angles were predicted for the species with π-acceptor R substituents. The corresponding bond angle values decrease in the order Pn = N >> P > As > Sb. This finding is in agreement with the previously published structural data for [(Me3Si)2C=P]2P–. An island homoaromaticity was proposed as a suitable explanation for the observed effect. In more detail, it consists of shifting negative charge to the electron-withdrawing terminal groups with formation…
Attachment of chloride anion to sugars: mechanistic investigation and discovery of a new dopant for efficient sugar ionization/detection in mass spec…
2012
International audience; A new method for efficient ionization of sugars in the negative-ion mode of electrospray mass spectrometry is presented. Instead of using strongly hydrophobic dopants such as dichloromethane or chloroform, efficient ionization of sugars has been achieved by using aqueous HCl solution for the first time. This methodology makes it possible to use hydrophilic dopants, which are more appropriate for chromatographic separation techniques with efficient sugar ionization and detection in mass spectrometry. The interaction between chloride anions and monosaccharides (glucose and galactose) was studied by DFT in the gas phase and by implementing the polarizable continuum mode…
Density functional theory studies of OH-modified open-ended single-wall zigzag carbon nanotubes (SWCNTs)
2010
Abstract Functionalized carbon nanotubes (CNTs) are often formed as result of oxidation and cleaning of raw product grown on metal catalyst. Structure and energy of ideal and OH-modified single-wall nanotubes (SWCNTs) of different length (2.8, 7.0 and 13.5 A) were obtained at the DFT-B3LYP level. From one to nine OH groups were added at the end of the nanotube and a nonadditive dependence of attachment energy on the number of substituents was observed. The energetics of SWCNT end substitution with OH groups was supported by high level MP2 and CCSD(T) determination of reaction energy: R – H + 1 / 2 O 2 → R – OH + Δ E for methane, benzene and anthracene. In addition, a vibrational analysis of…
Serum antioxidant capacity and peroxide level of seven healthy subjects after consumption of different foods
2016
This article reports experimental data related to the research article entitled “Different effectiveness of two pastas supplemented with either lipophilic or hydrophilic/phenolic antioxidants in affecting serum as evaluated by the novel Antioxidant/Oxidant Balance approach” (M.N. Laus, M. Soccio, M. Alfarano, A. Pasqualone, M.S. Lenucci, G. Di Miceli, D. Pastore, 2016) [1]. Antioxidant status of blood serum of seven healthy subjects was evaluated during four hours after consumption of two functional pastas, supplemented with either bran oleoresin or bran water extract obtained from durum wheat. For comparison, the effect of a non-supplemented reference pasta was also evaluated, as well as t…
Multiple normalized solutions for a Sobolev critical Schrödinger-Poisson-Slater equation
2021
We look for solutions to the Schr\"{o}dinger-Poisson-Slater equation $$- \Delta u + \lambda u - \gamma (|x|^{-1} * |u|^2) u - a |u|^{p-2}u = 0 \quad \text{in} \quad \mathbb{R}^3, $$ which satisfy \begin{equation*} \int_{\mathbb{R}^3}|u|^2 \, dx = c \end{equation*} for some prescribed $c>0$. Here $ u \in H^1(\mathbb{R}^3)$, $\gamma \in \mathbb{R},$ $ a \in \mathbb{R}$ and $p \in (\frac{10}{3}, 6]$. When $\gamma >0$ and $a > 0$, both in the Sobolev subcritical case $p \in (\frac{10}{3}, 6)$ and in the Sobolev critical case $p=6$, we show that there exists a $c_1>0$ such that, for any $c \in (0,c_1)$, the equation admits two solutions $u_c^+$ and $u_c^-$ which can be characterized respectively…
Energy dissipative solutions to the Kobayashi-Warren-Carter system
2017
In this paper we study a variational system of two parabolic PDEs, called the Kobayashi-Warren-Carter system, which models the grain boundary motion in a polycrystal. The focus of the study is the existence of solutions to this system which dissipate the associated energy functional. We obtain existence of this type of solutions via a suitable approximation of the energy functional with Laplacians and an extra regularization of the weighted total variation term of the energy. As a byproduct of this result, we also prove some $\Gamma$-convergence results concerning weighted total variations and the corresponding time-dependent cases. Finally, the regularity obtained for the solutions togethe…
Singular integrals on regular curves in the Heisenberg group
2019
Let $\mathbb{H}$ be the first Heisenberg group, and let $k \in C^{\infty}(\mathbb{H} \, \setminus \, \{0\})$ be a kernel which is either odd or horizontally odd, and satisfies $$|\nabla_{\mathbb{H}}^{n}k(p)| \leq C_{n}\|p\|^{-1 - n}, \qquad p \in \mathbb{H} \, \setminus \, \{0\}, \, n \geq 0.$$ The simplest examples include certain Riesz-type kernels first considered by Chousionis and Mattila, and the horizontally odd kernel $k(p) = \nabla_{\mathbb{H}} \log \|p\|$. We prove that convolution with $k$, as above, yields an $L^{2}$-bounded operator on regular curves in $\mathbb{H}$. This extends a theorem of G. David to the Heisenberg group. As a corollary of our main result, we infer that all …
Dimension estimates for the boundary of planar Sobolev extension domains
2020
We prove an asymptotically sharp dimension upper-bound for the boundary of bounded simply-connected planar Sobolev $W^{1,p}$-extension domains via the weak mean porosity of the boundary. The sharpness of our estimate is shown by examples.