Search results for "Nuclear magnetic resonance spectroscopy"
showing 10 items of 843 documents
NMR Spectroscopic and quantum chemical characterization of the (E)- and (Z)- isomers of the penta-1,3-dienyl-2-cation
2003
Dilute solutions of the (E )− and (Z )− isomers of pent-1,3-dienyl-2-cations (1) were obtained from reaction of 4-chloro-1,2-pentadiene (2) with SbF5 in SO2ClF/SO2F2 at −135 °C using high-vacuum co-condensation techniques. The experimental NMR spectra of the mixture of the two isomers were compared with quantum chemical 13C NMR chemical shift calculations at HF-SCF, MP2, CCSD and CCSD(T) levels using MP2/tzp geometries. Quantum chemical shift calculations were performed with a tzp basis (9s5p1d/5s3p1d) for carbon and a dz basis (4s/2s) for hydrogen using gauge-including atomic orbitals (GIAOs). The HF-SCF calculations deviate significantly for the positively charged carbon atoms of the ally…
Induction of ambuic acid derivatives by the endophytic fungus Pestalotiopsis lespedezae through an OSMAC approach
2021
Abstract Ten new ambuic acid derivatives, pestallic acids H–Q including one new iodinated natural product along with two known compounds, ambuic acid and ambuic acid 18-acetate, were obtained through fermentation of the endophytic fungus Pestalotiopsis lespedezae on solid rice medium with 3.5% NaI. Pestallic acids H–Q were undetectable in cultures of the fungus grown on solid rice medium lacking NaI or in those where NaI had been replaced by NaCl or NaBr. The structures of the new metabolites were established on basis of 1D/2D NMR and HRESIMS data. Their absolute configurations were determined by Mosher’s method and TDDFT-ECD calculations. The compounds failed to show antibacterial activity…
Diterpenoids from Tetraclinis articulata that Inhibit Various Human Leukocyte Functions
2003
Ten new compounds, eight of them pimarane derivatives (1-8), together with a menthane dimer (9) and a totarane diterpenoid (10), were isolated from the leaves and wood of Tetraclinis articulata. The structures of 1-10 were established by using spectroscopic techniques, including 2D NMR spectra. Pimaranes 1-5 were found to possess an unusual cis interannular union of the B and C rings, which, from a biogenetic perspective, could be derived from the hydration of a carbocation at C-8. Compounds 4-6 and a mixture of 7 and 11 modulated different human leukocyte functions at a concentration of 10 microM, mainly the degranulation process measured as myeloperoxidase release and, to a lesser extent,…
NMR spectroscopy evaluation of direct relationship between soils and molecular composition of red wines from Aglanico grapes
2010
1H NMR spectroscopy was employed to investigate the molecular quality of Aglianico red wines from the Campania region of Italy. The wines were obtained from three different Aglianico vineyards characterized by different microclimatic and pedological properties. In order to reach an objective evaluation of “terroir” influence on wine quality, grapes were subjected to the same winemaking procedures. The careful subtraction of water and ethanol signals from NMR spectra allowed to statistically recognize the metabolites to be employed in multivariate statistical methods: Principal Component Analysis (PCA), Discriminant Analysis (DA) and Hierarchical Clustering Analysis (HCA). The three wines we…
2H NMR Time Domain Analysis of Ultraslow Reorientations in Supercooled Liquids
1998
A method for evaluating 2H NMR stimulated echo experiments in the time domain is presented. It exhibits a high sensitivity to molecular reorientation mechanisms for small angles. Reorientations with jump angles below 25degrees can be resolved with a precision of approximately 1degrees so that, e.g., rotational diffusion and finite jump angle mechanisms become distinguishable. The method, applicable to isotropic reorientation models, is thought to extend the domain of 2D exchange spectroscopy where the best resolution is obtained in the large angle range of anisotropic reorientational mechanisms. Application to reorientation in the supercooled melt of ortho-terphenyl is presented. These data…
Stimulated-echo NMR spectroscopy of 9Be and 7Li in solids: method and application to ion conductors.
2002
The generation of pure quadrupolar stimulated-echo spectra is successfully demonstrated for the spin-3/2 probe 9Be in a single crystal of triglycine fluoberyllate. This solid exhibits a paraelectric-to-ferroelectric phase transition. From experiments carried out for various mixing times no indications for a slow soft mode could be detected in this crystal. Then ion conducting lithium metal phosphates were studied using 7Li, another spin-3/2 probe which allows for a non-selective excitation of the entire NMR spectrum. In the indium and the scandium phosphates ultra-slow Li hopping processes could be detected directly via the stimulated-echo technique in a time range of up to four orders of m…
Magnetic resonance imaging of (1)H long lived states derived from parahydrogen induced polarization in a clinical system.
2015
Hyperpolarization is a powerful tool to overcome the low sensitivity of nuclear magnetic resonance (NMR). However, applications are limited due to the short lifetime of this non equilibrium spin state caused by relaxation processes. This issue can be addressed by storing hyperpolarization in slowly decaying singlet spin states which was so far mostly demonstrated for non-proton spin pairs, e.g. 13C-13C. Protons hyperpolarized by parahydrogen induced polarization (PHIP) in symmetrical molecules, are very well suited for this strategy because they naturally exhibit a long-lived singlet state. The conversion of the NMR silent singlet spin state to observable magnetization can be achieved by ma…
Laser spectroscopy and the properties of light nuclei near the neutron drip line
1993
The interesting nuclear structure phenomena observed in some light nuclei at the neutron drip line suggest the measurement of basic ground state properties such as spins, magnetic moments and electric quadrupole moments. Here it will be discussed what experiments are presently feasable using laser spectroscopy. For the outstanding example of a “halo” nucleus,11Li, the development of a technique combining β-asymmetry detected optical pumping in a fast beam with NMR spectroscopy has yielded pertinent results, the most recent of which is an experimental value of the nuclear quadrupole moment.
Two-dimensional single- and multiple-quantum correlation spectroscopy in zero-field nuclear magnetic resonance.
2020
We present single- and multiple-quantum correlation $J$-spectroscopy detected in zero ($<\!\!1$~$\mu$G) magnetic field using a \Rb vapor-cell magnetometer. At zero field the spectrum of ethanol appears as a mixture of \carbon isotopomers, and correlation spectroscopy is useful in separating the two composite spectra. We also identify and observe the zero-field equivalent of a double-quantum transition in ${}^{13}$C$_2$-acetic acid, and show that such transitions are of use in spectral assignment. Two-dimensional spectroscopy further improves the high resolution attained in zero-field NMR since selection rules on the coherence-transfer pathways allow for the separation of otherwise overlappi…
Zero-field nuclear magnetic resonance spectroscopy of viscous liquids
2014
Abstract We report zero-field NMR measurements of a viscous organic liquid, ethylene glycol. Zero-field spectra were taken showing resolved scalar spin–spin coupling (J-coupling) for ethylene glycol at different temperatures and water contents. Molecular dynamics strongly affects the resonance linewidth, which closely follows viscosity. Quantum chemical calculations have been used to obtain the relative stability and coupling constants of all ethylene glycol conformers. The results show the potential of zero-field NMR as a probe of molecular structure and dynamics in a wide range of environments, including viscous fluids.