Search results for "NMR"
showing 10 items of 1575 documents
Dimerization control in the self-assembly behavior of copillar[5]arenes bearing ω-hydroxyalkoxy groups.
2012
Two novel copillar[5]arenes bearing ω-hydroxyalkoxy groups are synthesized and their self-assembly properties are studied by (1)H NMR spectroscopy, specific viscosity, and X-ray measurements. The copillar[5]arene 2b bearing a 6-hydroxyhexyloxy group exhibits a reversible self-assembly behavior, leading to the formation of the self-inclusion monomer and hugging dimers. The reversible self-assembly behavior can be controlled by tuning solvent, temperature, guest, and H-bond interaction. However, the copillar[5]arene 2a bearing a short 4-hydroxybutyloxy group does not show such a self-assembly behavior to the formation of the self-inclusion monomer and hugging dimers.
Emerging dynamics in surfactant-based liquid mixtures: octanoic acid/bis(2-ethylhexyl) amine systems.
2012
This work focuses on the dynamic phenomena emerging in self-assembled transient intermolecular networks formed when two different surfactants are mixed. In particular, the relaxation processes in liquid mixtures composed by bis(2-ethylhexyl)amine (BEEA) and octanoic acid (OA) in the whole composition range has been investigated by dielectric spectroscopy and Brillouin spectroscopy. A thorough analysis of all the experimental data consistently suggests that, mainly driven by acid-base interactions arising when the two surfactants are mixed, supra-molecular aggregates formation causes the slowing down of molecular dynamics. This, in turn, reflects to longer-range relaxations. These changes ha…
Drug Screening Boosted by Hyperpolarized Long-Lived States in NMR
2014
International audience; : Transverse and longitudinal relaxation times (T1ρ and T1 ) have been widely exploited in NMR to probe the binding of ligands and putative drugs to target proteins. We have shown recently that long-lived states (LLS) can be more sensitive to ligand binding. LLS can be excited if the ligand comprises at least two coupled spins. Herein we broaden the scope of ligand screening by LLS to arbitrary ligands by covalent attachment of a functional group, which comprises a pair of coupled protons that are isolated from neighboring magnetic nuclei. The resulting functionalized ligands have longitudinal relaxation times T1 ((1) H) that are sufficiently long to allow the powerf…
Über zinn-haltige heterocyclen
1981
Abstract A complete series of diphenyl and mixed methyl/chlorine/bromine/iodinephenyl substituted oxadithia- and trithiastannocanes has been prepared by reactions between the respective disodium dithiolates and tin dihalides. The 13C NMR chemical shifts of these compounds and the coupling constants J(119Sn13C) are dependent upon the magnetic anisotropy of the substituents and the bond angles at the tin atom. The crystal structure of 2,2-diphenyl-1,3,6-trithia-2-stannocane has been determined and refined to R = 0.039. The environment of Sn is a monocapped tetrahedron (transannular distance Sn⋯S 324.6(1) pm). This type of coordination, intermediate between a tetrahedron and a trigonal bipyra…
Orbital Decomposition of the Carbon Chemical Shielding Tensor in Gold(I) N-Heterocyclic Carbene Complexes.
2020
The good performance of N‐heterocyclic carbenes (NHCs), in terms of versatility and selectivity, has called the attention of experimentalists and theoreticians attempting to understand their electronic properties. Analyses of the Au(I)–C bond in [(NHC)AuL]+/0 (L stands for a neutral or negatively charged ligand), through the Dewar–Chatt–Duncanson model and the charge displacement function, have revealed that NHC is not purely a σ‐donor but may have a significant π‐acceptor character. It turns out, however, that only the σ‐donation bonding component strongly correlates with one specific component of the chemical shielding tensor. Here, in extension to earlier works, a current density analysi…
A CNDO/2 study on the additivity and the nature of the non-additivity of the substituent effects on13C NMR shifts in chlorobenzenes and chlorophenols
1980
The general correlation between the electron densities and the 13C NMR chemical shifts is found to be quite poor in the cases discussed. The non-additivities of the substituent effects on the chemical shifts and the CNDO/2 electron densities correlate only weakly. However, when the electron densities are made specific to different types of atomic orbitals, the s electrons have a pronounced effect in all the models tested. This is explained by an indirect effect on the 〈1/r3〉 term of the p electrons. Good correlations are found between the sums of the chemical shifts and the corresponding sums of the substituent charge excesses. The different behaviour of OH and Cl substituents in the additi…
The Acqualadrone Rostrum: a physical-chemical investigation to understand the Material History
2013
The aim of this work is to define the conservation state and to ascertain the provenance of raw materials used in the construction of the Acqualadrone Rostrum. In 2008 the rostrum (an offensive naval weapon mounted on the prow at the waterline), from an ancient warship was recovered from the Mediterranean near Acqualadrone, Messina, Sicily. The archaeological discovery has led to the need for scientific research in order to plan the conservation treatment of this artefact. The discovery is exceptional because of the presence of a wooden section from the original ship. The physical-chemical investigation, by using some complementary spectroscopic techniques, was focused on the characterizati…
Solid state nmr characterization of the waterlogged wooden part of Acqualadrone roman rostrum
2014
The roman rostrum found in the sea of Acqualadrone (ME) was characterized in our previous papers. In the present work solid state NMR spectroscopy was applied on a wooden sample of the same artefact collected by coring and divided in four parts in order to correlate the conservation state to the depth. Results were compared with those obtained for a modern wood of the same species. A structural study was performed by the acquisition of 13C Cross Polarization Magic Angle Spinning (13C CP MAS NMR) spectra. These spectra were acquired to assign the chemical shifts of the species that are present in the wooden matrix. In addition the spectra analysis allowed us to determine the cellulose crysta…
Physicochemical Characterization Of Ancient Paper And Parchment With Solid State Nuclear Magnetic Resonance
2014
Historical paper and parchment are widely investigated in order to comprehend mechanisms of degradation and to plan proper conservation interventions. NMR spectroscopy is a powerful tool that allows to the changes occurring during the degradation process and to get information on the state of conservation. In this work a Cross Polarization Magic Angle Spinning Nuclear Magnetic Resonance (13C{1H} CP MAS NMR) study of a 16th century book is reported. The physicochemical characterization of paper samples collected from the book was performed through the evaluation of intensity and the changes in line width of signals in the spectra. 13C{1H} CP MAS NMR spectra of paper samples collected from th…
Chemometrics as a Tool of Origin Determination of Polish Monofloral and Multifloral Honeys
2014
The aim of this study was to evaluate the application of chemometrics studies to determine the botanical origin of Polish monofloral honeys using NMR spectroscopy. Aqueous extracts of six kinds of honeys, namely, heather (Calluna vulgaris L.), buckwheat (Fagopyrum esculentum L), lime (Tilia L), rape (Brassica napus L. var. napus), acacia (Acacia Mill.), and multifloral ones, were analyzed. Multivariate chemometric data analysis was performed using principal component analysis (PCA) and orthogonal partial least-squares discriminant analysis (OPLS-DA). Chemometric analysis supported by pollen analysis revealed the incorrect classification of acacia honeys by the producers. Characteristic moti…