An Application of the Polarizable Continnum Model for Obtaining Chalcones Magnetic Properties

2020 ◽  
Vol 12 (7) ◽  
pp. 939-950
Author(s):  
Agnes Jalowitzki Silva ◽  
Thaís F. Giacomello ◽  
Gunar V. da S. Mota ◽  
Antônio M. de J. Chaves ◽  
Fabio L. P. Costa
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Chemical Shift ◽  
Population Distribution ◽  
Chemical Shifts ◽  
Biological Activities ◽  
Geometry Optimization ◽  
Analytical Techniques ◽  
Spectroscopic Techniques ◽  
Nuclear Magnetic

Chalcones exhibit a wide variety of beneficial biological activities. In addition, these compounds include the prevention of diseases related to oxidative stress. The structural characterization of these molecules by means of analytical techniques can become a difficult task due to the complexity of some structures. However, cases of erroneously established natural product structure review are still found in the literature despite recent advances in spectroscopic techniques. Therefore, it is necessary to develop quantum calculation protocols that can aid in the correct structural ascertainment of these compounds. Thus, in this work, we tried to develop a parameterized protocol for calculations of chemical shift of carbon-13 nuclear magnetic resonance, in order to ensure a correct structural determination of polyphenols, with a focus on chalcones. For this, a series of molecules belonging to this class, with complex and varied structural skeletons, reliably elucidated in the literature, was selected and subjected to stochastic conformational searches using the Monte Carlo method and the Merk molecular force filed. The lower energy conformations of each molecule were selected for the geometry optimization step, performed at the mPW1PW91/6-31G(d) level. The chemical shifts of carbon-13 were calculated at the same level of theory, taking into account the population distribution of Boltzmann. The calculations were affected in both liquid phases, using the Polarizable Continuous Model as an implicit solvation model. The results show that the level of theory applied in the liquid phase allows a good reproduction of the experimental data. The application of the scaling factor allows the cancellation of systematic errors, which means that the values of scaled chemical shift are closer to the experimental ones. Thus, the parameterized protocol proved to be an important tool for the structural elucidation of polyphenols by calculations of carbon-13 nuclear magnetic resonance chemical shifts.

Carbon-13 Nuclear Magnetic Resonance Studies of Some Methyl Substituted Diphenylmethanes

1974 ◽  
Vol 52 (18) ◽  
pp. 3196-3200 ◽  
Author(s):  
Gerald W. Buchanan ◽  
Giorgio Montaudo ◽  
Paolo Finocchiaro
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Chemical Shift ◽  
Ring Current ◽  
Chemical Shifts ◽  
Magnetic Resonance Studies ◽  
Nuclear Magnetic

Carbon-13 n.m.r. chemical shifts are reported for diphenylmethane and nine methylated derivatives. Results are compared with those for related methylbenzenes. In the case of tri-ortho-substituted materials the predominance of a perpendicular conformation is suggested. Ring current calculations show that in contrast to the 1H chemical shift interpretations, the 13C shielding trends cannot originate primarily from anisotropic effects.

Use of Replaced Chalcones to Generate a 13C Chemical Shift Staging Factor for Chalcone and Its Derivate

2020 ◽  
Vol 12 (4) ◽  
pp. 464-472
Author(s):  
Thaís F. Giacomello ◽  
Gunar V. da S. Mota ◽  
Antônio M. de J. C. Neto ◽  
Fabio L. P. Costa
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Chemical Shift ◽  
Density Functional ◽  
Chemical Shifts ◽  
Atomic Orbital ◽  
Scaling Factor ◽  
Orbital Method ◽  
Beneficial Effects ◽  
Nuclear Magnetic

Chalcones have attracted the attention of researchers for decades, they are biologically classified as secondary metabolites of low molecular weight. These are considered as the precursors of flavonoids and they are widely distributed in plants such as vegetables, fruits, teas and spices. It has been demonstrating that chalcones possess many important bioactivities including properties of antioxidants and other evidence of its potential beneficial effects on health. Chalcone compounds and its derivatives have been showing a growing interest in the therapeutic properties. Nuclear magnetic resonance (NMR) spectroscopy is one of the most important tools for determining the structures of organic molecules. In the work present a 13C Nuclear magnetic resonance chemical shift protocol of chalcones and derivative based on the application of scaling factor with chalcone molecules. This protocol consists of using density functional theory with gauge-including atomic orbital method to calculating 13C chemical shifts and the application of a parameterized scaling factor in order to ensure accurate structural determination of chalcones and derivative.

Nuclear Magnetic Resonance Study of Caesium-133 in Binary Molten Trifluoroacetate Salt Mixtures

2001 ◽  
Vol 56 (3-4) ◽  
pp. 288-290 ◽  
Author(s):  
V. N. Mirny ◽  
V. V. Trachevski ◽  
T. A. Mimaya
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Chemical Shift ◽  
Chemical Shifts ◽  
Nuclear Magnetic Resonance Study ◽  
Magnetic Resonance Study ◽  
Sodium Potassium ◽  
Salt Mixtures ◽  
Nuclear Magnetic

Abstract The chemical shifts of Cs+ in binary melts of caesium trifluoroacetate with lithium, sodium, potassium or thallium trifluoroacetates have been studied as a function of composition. An influence of added foreign cations on chemical shift of caesium nuclei has been found. The nature of the intra-and intermolecular paramagnetic contributions into the shifts of 133Cs is discussed.

13C Nuclear Magnetic Resonance of Oximes. I. Solvent and Isotope Effects on the 13C Chemical Shifts of Acetoxime

1972 ◽  
Vol 50 (12) ◽  
pp. 1956-1958 ◽  
Author(s):  
N. Gurudata
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Chemical Shift ◽  
Solvent Effects ◽  
Chemical Shifts ◽  
Isotope Effects ◽  
Solvent Interactions ◽  
13C Chemical Shifts ◽  
13C Nuclear Magnetic Resonance ◽  
Nuclear Magnetic

The 13C n.m.r. spectrum of acetoxime has been obtained in five representative solvents and the chemical shifts of the three carbon atoms measured. The solvent effects on the chemical shifts are found to reflect specific solute–solvent interactions. The effect of deuteration of the α-protons on the chemical shift of the oximino carbon is also discussed.

Selenium-77 nuclear magnetic resonance studies of selenols, diselenides, and selenenyl sulfides

1988 ◽  
Vol 66 (1) ◽  
pp. 54-60 ◽  
Author(s):  
Khoon-Sin Tan ◽  
Alan P. Arnold ◽  
Dallas L. Rabenstein
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Chemical Shift ◽  
Chemical Shifts ◽  
Proton Exchange ◽  
Exchange Reactions ◽  
Nuclear Magnetic Resonance Spectra ◽  
Ph Range ◽  
Magnetic Resonance Spectra ◽  
Nuclear Magnetic

77Se and 1H nuclear magnetic resonance spectra have been measured for selenols (RSeH), diselenides (RSeSeR), and selenenyl sulfides (RSeSR′), including selenenyl sulfides formed by reaction of glutathione and penicillamine with selenocystine and related diselenides. Exchange processes strongly affect the 77Se and 1H nuclear magnetic resonance spectra of all three classes of compounds. Sharp, exchange-averaged resonances are observed in the 1H nuclear magnetic resonance spectra of selenols; however, selenol proton exchange causes the 77Se resonances to be extremely broad over the pH range where the selenol group is titrated. Selenol/diselenide exchange [Formula: see text] also results in exchange-averaged 1H resonances for solutions containing RSeH and RSeSeR; however, the 77Se resonances were too broad to detect. Exchange reactions have similar effects on nuclear magnetic resonance spectra of solutions containing selenols and selenenyl sulfides. The results indicate selenol/diselenide exchange is much faster than thiol/disulfide exchange. The 77Se chemical shift depends on the chemical state of the selenium, e.g., titration of the selenol group of selenocysteamine causes the 77Se resonance to be shielded by 164 ppm, oxidation of the selenol to form the diselenide selenocystamine causes a deshielding of 333 ppm, and oxidation to form the selenenyl sulfide [Formula: see text] results in a deshielding of 404 ppm. 77Se chemical shifts were found to be in the range −240 to −270 ppm (relative to (CH3)2Se) for selenolates, approximately −80 ppm for selenols, 230–360 ppm for diselenides, and 250–340 ppm for selenenyl sulfides. The 77Se chemical shift is also affected by titration of neighboring carboxylic acid and ammonium groups, and their pkA values can be calculated from 77Se chemical shift data.

The characterization of primary, secondary, and tertiary vanadate alkyl esters by 51V nuclear magnetic resonance spectroscopy

1988 ◽  
Vol 66 (10) ◽  
pp. 2570-2574 ◽  
Author(s):  
Alan S. Tracey ◽  
Michael J. Gresser
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Chemical Shift ◽  
Magnetic Resonance Spectroscopy ◽  
Nuclear Magnetic Resonance Spectroscopy ◽  
Chemical Shifts ◽  
Hydroxyl Group ◽  
Resonance Spectroscopy ◽  
Low Field ◽  
Nuclear Magnetic

A variety of alkyl vanadates has been studied by 51V nuclear magnetic resonance spectroscopy. It was found that the equilibrium constant for condensation of vanadate with alcohols is insensitive to whether the hydroxyl group is primary, secondary, or tertiary. These products, however, have characteristic vanadium chemical shifts that allow assignment of nmr signals to the appropriate ester. It was also found that chemical shifts are additive in the sense that the chemical shifts of the esters ROVO3H− are one half the chemical shift of the diesters (RO)2VO2− when those shifts are given relative to −559 ppm. This effect is independent of whether the signals are to high or low field of −559 ppm and the additivity extends to mixed ligand systems. This value of −559 ppm is close but not equal to the chemical shift of the vanadate monoanion, H2VO41−, which is at −561 ppm. These results are at variance with arguments concerning the effects of ligand bulkiness on chemical shifts of vanadium(V) complexes.

Nuclear Magnetic Resonance of Compounds Related to DDT: Part II. Aromatic Protons

1968 ◽  
Vol 22 (5) ◽  
pp. 506-512 ◽  
Author(s):  
Norman E. Sharpless ◽  
Robert B. Bradley
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Chemical Shift ◽  
Electron Density ◽  
Chemical Shifts ◽  
Molecular Orbital Calculations ◽  
Aromatic Rings ◽  
Butyl Group ◽  
Nuclear Magnetic Resonance Spectra ◽  
Nuclear Magnetic

The nuclear magnetic resonance spectra of the aromatic protons of DDT and 31 of its analogs and derivatives have been analyzed. Chemical shifts of these molecules are functions of the electronegativities of the substituents on the ring, as well as those in the aliphatic portion, although substitution of the ring chlorine in DDT by either a nitro or a t-butyl group leads to anomalous values. Molecular orbital calculations show that the chemical shift of the proton ortho to the ring substituent depends upon the π electron density at the corresponding carbon, but the chemical shift of the proton meta to this substituent is independent of the π electron density at the corresponding carbon. The data also indicate that the two aromatic rings in DDT are independent of each other.

scholarly journals Determining isoleucine side-chain rotamer-sampling in proteins from 13C chemical shift

2019 ◽  
Vol 55 (94) ◽  
pp. 14107-14110
Author(s):  
Lucas Siemons ◽  
Boran Uluca-Yazgi ◽  
Ruth B. Pritchard ◽  
Stephen McCarthy ◽  
Henrike Heise ◽  
...  
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Chemical Shift ◽  
Chemical Shifts ◽  
Side Chain ◽  
Conformational Sampling ◽  
Side Chains ◽  
13C Chemical Shift ◽  
Nuclear Magnetic

A framework is presented to derive the conformational sampling of isoleucine side chains from nuclear magnetic resonance 13C chemical shifts.

Relationship between oxygen-17 nuclear magnetic resonance chemical shifts and Π-bonding to oxygen in the dichromate ion

1967 ◽  
Vol 45 (6) ◽  
pp. 605-608 ◽  
Author(s):  
R. G. Kidd
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Chemical Shift ◽  
Linear Relationship ◽  
Chemical Shifts ◽  
Chromium Vi ◽  
Nuclear Magnetic

A linear relationship between 17O chemical shift and degree of π-bonding from oxygen to chromium in a number of chromium(VI) compounds is reported. The basis for this relationship is presented in terms of chemical shift theory. The 17O chemical shift values for the two types of oxygen in the Cr2O72− ion are shown to be consistent with an angular rather than a linear Cr—O—Cr arrangement.

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