scholarly journals Application of Lanthanide Shift Reagent to the 1H-NMR Assignments of Acridone Alkaloids

Molecules ◽  
2020 ◽  
Vol 25 (22) ◽  
pp. 5383
Author(s):  
Sio-Hong Lam ◽  
Hsin-Yi Hung ◽  
Ping-Chung Kuo ◽  
Daih-Huang Kuo ◽  
Fu-An Chen ◽  
...  
Keyword(s):  
Least Squares ◽  
Nmr Assignments ◽  
Least Squares Method ◽  
Chemical Shifts ◽  
Shift Reagent ◽  
Spectral Studies ◽  
Lanthanide Shift Reagent ◽  
Planar Structures ◽  
Acridone Alkaloids ◽  
The Eu

This study investigates the application of the paramagnetic shift reagent tris(dipivaloylmethanato)-europium(III) in NMR spectral studies of permethoxyacridone alkaloids (1–3) and pyranoacridone alkaloids (4–6). The induced chemical shifts (∆δ) of all protons were observed for the same molecule, and were compared to deduce the positions resulting from the distance nearby the Eu(dpm)3. Assignment of the H-2, H-4 and H-8 of polysubstituted acridones could be distinguished based on the least-squares method of lanthanide-induced shifts plotted against the mole ratios of Eu(dpm)3 to the substrate. The developed method is not only potentially useful for determining the planar structures of polysubstituted compounds, such as acridones, anthraquinones, xanthones, flavonoids, and phenanthrenes, but also applicable for their stereochemistry.

The 1H NMR spectra and the conformation of 1,6-anhydro-β-D-hexopyranoses and their triacetates

1979 ◽  
Vol 44 (6) ◽  
pp. 1949-1964 ◽  
Author(s):  
Miloš Buděšínský ◽  
Tomáš Trnka ◽  
Miloslav Černý
Keyword(s):  
Nmr Spectra ◽  
Chemical Shifts ◽  
Shift Reagent ◽  
Point Of View ◽  
Coupling Constants ◽  
Lanthanide Shift Reagent ◽  
Pyranose Ring ◽  
H Nmr ◽  
Vicinal Coupling Constants

The 1H NMR spectra of 1,6-anhydro-β-D-hexopyranoses and their triacetates, measured in hexadeuteriodimethyl sulfoxide or deuteriochloroform, confirmed the existence of these compounds in 1C4(D) conformations, with the pyranose ring partly planarized in dependence on the configuration of the substituents in positions C(2), C(3) and C(4). The effects of the substituents on the chemical shifts and the adjusted relationship for the dependence of vicinal coupling constants on the torsion angle are discussed in detail from the point of view of the determination of the configuration and the conformation of 1,6-anhydro-β-D-hexopyranoses and their derivatives. The 1H NMR spectra of triacetates were also measured in the presence of the lanthanide shift reagent, tris(1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl-4,6-octanedione) europium (III) [Eu.(FOD)3].

Association of a Europium Shift Reagent with Dialkylnitrosamines

1974 ◽  
Vol 52 (2) ◽  
pp. 315-324 ◽  
Author(s):  
Richard A. Perry ◽  
Yuan L. Chow
Keyword(s):  
Chemical Shifts ◽  
Equilibrium Constants ◽  
Molecular Geometry ◽  
Shift Reagent ◽  
Nitroso Group ◽  
Contact Shift ◽  
Substrate Ratio ◽  
The Eu

The Eu(fod)3 induced shifts of the n.m.r. signals of various nitrosamines were studied at a constant lanthanide concentration and also at constant nitrosamine concentration. The bound chemical shifts (ΔB) and binding equilibrium constants (K) were determined. The stoichiometry of the complexes appears to be 1:1 in CDCl3 in agreement with the criteria of two types of existing tests designed to determine Eu–substrate ratio. On the basis of the experimental ΔB values, the molecular geometry of Eu–nitrosamine complexes were computed according to the principle of pseudo-contact shift. It was concluded that the Eu atom complexed at the oxygen of the nitroso group and that the conformations of nitrosamines in the complexes were basically the same as those of uncomplexed nitrosamines.

Evaluation of the Binding Constants, Bound Chemical Shifts, and Stoichiometry of Lanthanide–Substrate Complexes

1972 ◽  
Vol 50 (13) ◽  
pp. 2119-2129 ◽  
Author(s):  
Ian Armitage ◽  
G. Dunsmore ◽  
L. D. Hall ◽  
A. G. Marshall
Keyword(s):  
Chemical Shift ◽  
Chemical Shifts ◽  
Binding Constants ◽  
Shift Reagent ◽  
Accurate Solution ◽  
Conventional Procedure ◽  
Equilibrium Binding ◽  
Straight Line ◽  
Equilibrium Binding Constant ◽  
The Eu

A theoretical analysis of the equilibrium between a lanthanide shift reagent, L, and a substrate, S, is presented. When [Formula: see text] then a plot of [S]0vs. (1/δ) at constant [L]0 gives a straight line whose slope is [L]0ΔB and whose y-intercept is −{(1/KB) + [L]0}, where KB is the equilibrium binding constant, δ is the induced chemical shift, and ΔB is the bound chemical shift. A more general and accurate solution using a computer programme is applicable for all ratios of [L]0/[S]0. It is also shown that the conventional procedure for evaluating ΔB leads to varying values for ΔB that are generally too small, even under the most optimal conditions. Eu(DPM)34 has a KB of ca. 34.21 mol−1 with n-propylamine and KB of ca. 9.71 mol−1 with neo-pentanol. These values increase by at least 10-fold (to ≥ 1001 mol−1) for the corresponding complexes with Eu(FOD)34 shift reagent. However, the bound chemical shifts for the Eu(FOD)3 complexes are nearly the same as for the Eu(DPM)3 complexes. Finally, it is shown definitively that the association between Eu(DPM)3 and either n-propylamine or neo-pentanol has 1:1 stoichiometry; with Eu(FOD)3 a tentative assignment of 1:1 stoichiometry can be made.

‘Least squares’ method—theorem or law?

1980 ◽  
Vol 59 (9) ◽  
pp. 8
Author(s):  
D.E. Turnbull
Keyword(s):  
Least Squares ◽  
Least Squares Method

An Augmented Iteratively Re-weighted and Refined Least Squares Method for lp Minimization Problem in Inverse Modeling of Potential Field Magnetic Data

2020 ◽  
Vol 1 (3) ◽  
Author(s):  
Maysam Abedi
Keyword(s):  
Magnetic Field ◽  
Magnetic Susceptibility ◽  
Least Squares ◽  
Minimization Problem ◽  
Potential Field ◽  
Field Data ◽  
Least Squares Method ◽  
Porphyry Copper ◽  
Magnetic Data ◽  
Magnetic Field Data

The presented work examines application of an Augmented Iteratively Re-weighted and Refined Least Squares method (AIRRLS) to construct a 3D magnetic susceptibility property from potential field magnetic anomalies. This algorithm replaces an lp minimization problem by a sequence of weighted linear systems in which the retrieved magnetic susceptibility model is successively converged to an optimum solution, while the regularization parameter is the stopping iteration numbers. To avoid the natural tendency of causative magnetic sources to concentrate at shallow depth, a prior depth weighting function is incorporated in the original formulation of the objective function. The speed of lp minimization problem is increased by inserting a pre-conditioner conjugate gradient method (PCCG) to solve the central system of equation in cases of large scale magnetic field data. It is assumed that there is no remanent magnetization since this study focuses on inversion of a geological structure with low magnetic susceptibility property. The method is applied on a multi-source noise-corrupted synthetic magnetic field data to demonstrate its suitability for 3D inversion, and then is applied to a real data pertaining to a geologically plausible porphyry copper unit.  The real case study located in  Semnan province of  Iran  consists  of  an arc-shaped  porphyry  andesite  covered  by  sedimentary  units  which  may  have  potential  of  mineral  occurrences, especially  porphyry copper. It is demonstrated that such structure extends down at depth, and consequently exploratory drilling is highly recommended for acquiring more pieces of information about its potential for ore-bearing mineralization.

Theoretical accuracy of the last squares method in the isotope dilution analysis

1984 ◽  
Vol 49 (4) ◽  
pp. 805-820
Author(s):  
Ján Klas
Keyword(s):  
Least Squares ◽  
Isotope Dilution ◽  
Least Squares Method ◽  
Isotope Dilution Analysis ◽  
Straight Line ◽  
The One ◽  
Two Parameter ◽  
Theoretical Accuracy

The accuracy of the least squares method in the isotope dilution analysis is studied using two models, viz a model of a two-parameter straight line and a model of a one-parameter straight line.The equations for the direct and the inverse isotope dilution methods are transformed into linear coordinates, and the intercept and slope of the two-parameter straight line and the slope of the one-parameter straight line are evaluated and treated.

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