Substituent Effects on 13C NMR and 1H NMR Chemical Shifts of CH=N in Multi-substituted Benzylideneanilines

Fifty-three samples of multi-substituted benzylideneanilines XArCH=NArYs （abbreviated XBAYs） were synthesized and their NMR spectra were determined. An extensional study of substituent effects on the 1H NMR chemical shifts （δH（CH=N）） and 13C NMR chemical shifts （δc（CH=N）） of the CH=N bridging group from di-substituted to multi-substituted XBAYs was made based on a total of 182 samples of XBAYs, together with the NMR data of other 129 samples of di-substituted XBAYs quoted from literatures. The results show thatthe substituent specific cross-interaction effect parameter （△（∑σ）2） plays an important role in quantifying the δc（CH=N） values of XBAYs, but it is negligible for quantifying the δH （CH=N） values; the other substituent parameters also present different influences on the δc （CH=N） and （δH （CH=N）. On the whole, the contributions of X and Y to the δc （CH=N） of XBAYs are balanced, but the δH（CH=N） values of XBAYs mainly rely on the contributions of X.

Relative Chemical Shifts for Obtaining Accurate Chemical Shifts of Hydrogen Atoms in CH Groups

Accurate chemical shifts of hydrogen atoms in CH groups are difficult to obtain. To solve this problem, relative chemical shifts are introduced. Internal and external standard methods were used to measure the chemical shifts in a whole-concentration of N-methylacetamide- water system. Determination of the chemical shifts of hydrogen atoms, especially those of CH groups, according to the two methods yielded significant differences. Relative chemical shifts were proven to be independent of the reference and may be applied to other systems.

Correlation of ^1H NMR Chemical Shift for Aqueous Solutions by Statistical Associating Fluid Theory Association Model

1H NMR chemical shifts of binary aqueous mixtures of acylamide, alcohol, dimethyl sulphoxide (DMSO), and acetone are correlated by statistical associating fluid theory (SAFT) association model. The comparison between SAPT association model and Wilson equation shows that the former is better for dealing with aqueous solutions. Finally, the specialties of both models are discussed.

Simulation of ^(13)C NMR chemical shifts of carbinol carbon atoms using quantitative structure-spectrum relationships

A quantitative structure-spectrum relationship (QSSR) model was developed to simulate 13C nuclear magnetic resonance (NMR) spectra of carbinol carbon atoms for 55 alcohols. The proposed model,using multiple linear regression,contained four descriptors solely extracted from the molecular structure of compounds. The statistical results of the final model show that R2= 0.982 4 and S=0.869 8 (where R is the correlation coefficient and S is the standard deviation). To test its predictive ability,the model was further used to predict the 13C NMR spectra of the carbinol carbon atoms of other nine compounds which were not included in the developed model. The average relative errors are 0.94% and 1.70%,respectively,for the training set and the predictive set. The model is statistically significant and shows good stability for data variation as tested by the leave-one-out (LOO) cross-validation. The comparison with other approaches also reveals good performance of this method.

Prediction of the ^(13)C NMR Chemical Shifts of Stilbene Analogues by GIAO Method

After the geometry optimization at B3LYP/6-31＋G（d,p） level,the calculations of the NMR chemical shifts of a series of stilbene analogues were carried out by means of Gauge Including Atomic Orbitals（GIAO） method at HF/6-31＋G（d） level and B3LYP/6-311G＋（2d,p） level,respectively.The 13C NMR chemical shifts calculated at both HF/6-31＋G（d） and B3LYP/6-31＋G（d,p） levels are in agreement with the observed values.By virtue of a series of linear correction equations（δpred.=a＋bδcalcd.） of the 13C chemical shifts,accurate prediction of 13C chemical shifts was achieved for the new stilbene compounds.For the 13C NMR chemical shifts calculated at HF/6-31＋G（d） level,the linear correlation of δpred.with δexptl.is excellent,and the square of correlation coefficient,r2,is 0.9985.The maximum absolute difference between δpred.and δexptl.,Δδ,is 2.3,and the root-mean-square error between δpred.and δexptl.is 0.98.In the meantime,for those obtained at B3LYP/6-31＋G（d,p） level,the linear correlation of δpred.with δexptl.is also excellent,and the square of correlation coefficient,r2,is up to 0.9987.The maximum absolute difference between δpred.and δexptl.,Δδ,is 2.2,and the root-mean-square error between δpred.and δexptl.is only 0.88.

DFT Studies on Thermal Stabilities,Electronic Structures,and ^(13)C Chemical Shifts of C_(24)O_2 Based on Fullerene C_(24)(D_6)

Quantum chemical calculations on some possible equilibrium geometries of C24O2 isomers derived from C24 （D6） and C24O have been performed using density functional theory （DFT） method. The geometric and electronic structures as well as the relative energies and thermal stabilities of various C24O2 isomers at the ground state have been calculated at the B3LYP/6-31G（d） level of theory. And the 1,4,2,5-C24O2 isomer was found to be the most stable geometry where two oxygen atoms were added to the longest carbon-carbon bonds in the same pentagon from a thermodynamic point of view. Based on the optimized neutral geometries, the vertical ionization potential and vertical electron affinity have been obtained. Meanwhile, the vibrational frequencies, IR spectrum, and 13C chemical shifts of various C24O2 isomers have been calculated and analyzed.

Prediction of the ^(13)C NMR Chemical Shifts of Fluorenone Analogues by the GIAO Method

After the geometry optimization at B3LYP/6-31＋G（d,p） level,the NMR calcula-tions of a series of fluorenone analogues have been carried out by GIAO method at HF/6-31＋G（d） level and B3LYP/6-311G＋（2d,p） level,respectively.The 13C NMR chemical shifts calculated at HF/6-31＋G（d） level show better agreement with the observed values.By a series of linear correction equations （δpred=a ＋ bδcalc）,accurate prediction of 13C chemical shifts was achieved for the new fluorenone compound.The linear correlation of δpred with δexptl is excellent,and the square of correlation coefficient,r2,is up to 0.994.The maximum absolute difference between δpred and δexptl,Δδ,is 4.6 ppm,and the root-mean-square error between δpred and δexptl is only 2.6 ppm.

Structures and Hydrogen Bonding Interactions in Urea-water System Studied by All-atom MD Simulation and Chemical Shifts in NMR Spectrum

The interactions and structures of the urea-water system are studied by an all-atom molecular dynamics （MD） simulation. The hydrogen-bonding network and the radial distribution functions are adopted in MD simulations. The structures of urea-water mixtures can be classified into different regions from the analysis of the hydrogen-bonding network. The urea molecule shows the certain tendency to the self-aggregate with the mole fraction of urea increasing. Moreover, the results of the MD simulations are also compare with the chemical shifts and viscosities of the urea aqueous solutions, and the statistical results of the average number hydrogen bonds in the MD simulations are in agreement with the experiment data such as chemical shifts of the hydrogen atom and viscosity.

Substituent Effect on Mercury-199 Chemical Shifts in Some Bisarylmercurials and Aryl(2-benzothiazolylthio) mercurials

The present paper covers the 199 Hg NMR chemical shifts of 24 substituted diphenylmercurials and phenyl(2-benzothiazolylthio)mercurials. There is a good linear relationship between the chemical shift and the Hammett constant of the substituents for both series of compounds, and electron donating substituents cause the chemical shift towards downfield.

SUBSTITUENT CHEMICAL SHIFT (SCS) AND THE SEQUENCE STRUCTURE OF ETHYLENE-VINYL ALCOHOL COPOLYMERS

Three ethylene-vinyl alcohol copolymers were studied by means of the substituent chemical shift (SCS) method. The SCS parameters of hydroxy (-OH) in two different solvents were obtained: in deuterium oxide/phenol (20/80 W/W ) the parameters are S_1 = 42.77±0.08ppm, S_2 = 7.15±0.06 ppm, S_3 (s)= -4.08±0.02ppm, S_3 (t) =-3.09±0.20ppm,S_4 = 0.48±0.03ppm, S_5 = 0.26±0.05ppm. In o-dichloro-benzen-d_4 S_1(s)=44.79±0.61ppm, S_2=7.40±0.00ppm, S_3(s)=-4.51±0.17ppm, S_3(t)=-3.13 ±0.00 ppm, S_4 =0.63±0.04ppm, S_5=0.36±0.00ppm.Simultaneously the ^(13)CNMR spectra of EVA copolymers were assigned by using the SCS parameters obtained.

Ab Initio Prediction of ^(29)Si-NMR Chemical Shifts

The ability of several ab initio models to predict experimental 29Si-NMR chemical shift is examined. The shielding values of trimethylsilyl chloride (A), t-butyldimethylsilyl chloride (B) and allyltrimethylsilane (C) are calculated by GIAO , CSGT and IGAIM methods, using HF/6-31G*, B3LYP/6-31G*, HF/6-311+G **, B3LYP/6-311+G ** and MPW1PW91/6-311+G ** models respectively. The 29Si chemical shifts calculated by GIAO method using HF/6-311+G ** model are highly in agreement with those obtained experimentally. All of the models above reproduce the trends of chemical shifts in all cases studied, suggesting that the models are of practical value.

Prediction of the ^(13)C NMR Chemical Shifts of 9,10-Dihydrophenanthrene Analogues by the GIAO Method

After the geometry optimizations at the B3LYP/6-31＋G（d,p） level, the NMR calculations of a series of 9,10-dihydrophenanthrene analogues have been carried out by GIAO method at the HF/6-31＋G（d） level. The calculated ^13C NMR chemical shifts are in agreement with the observed values. By a series of linear correlation equations （δpred = a ＋ bδcal.c） of the ^13C chemical shifts, accurate prediction of ^13C chemical shifts was achieved for the new 9,10- dihydrophenanthrene compound, for which the predicted ^13C NMR chemical shifts are in quite good agreement with the experimental values. The linear correlation between δpred and δexptl is excellent, and the square of correlation coefficient, r^2, is up to 0.9973. The maximum absolute difference between δpred and δexptl, △δ, is 4.5 ppm, and the rms error between δpred and δexpt is 2.55 ppm. In the meantime, according to the theoretical predicted result, we could confirm that the new 9,10-dihydrophenanthrene analogue is erianthridin （2,7-dihydroxy-3,4-dimethoxy-9,10-dihydro- phenanthrene）.

Anomeric Proton and Carbon (H1-C1) NMR Chemical Shifts of Antigenic Mannans Obtained from Pathogenic Yeast <i>Candida tropicalis</i>

On two dimensional maps of 1H-13C correlation spectroscopy (H-C COSY) analysis for the mannan of Candida tropicalis, nine cross peaks of anomeric proton and carbon were useful for the purpose of obtaining information on the chemical structure of this molecule. Namely, the mannans was comb-like structure constructed with the linear α-1,6-linked polymannnosyl backbone and several oligomannnosyl side chains composed of α-1,2-, α-1,3-, and β-1,2-linkages. Therefore, in the structural investigation of comb-like mannan, two-dimensional H-C COSY analysis is as useful as two-dimensional nuclear Hartmann-Hahn (HOHAHA) analysis.

Two-point Dixon and six-point Dixon magnetic resonance techniques in the detection,quantification and grading of hepatic steatosis

BACKGROUND Hepatic steatosis is a very common problem worldwide.AIM To assess the performance of two-and six-point Dixon magnetic resonance(MR)techniques in the detection,quantification and grading of hepatic steatosis.METHODS A single-center retrospective study was performed in 62 patients with suspected parenchymal liver disease.MR sequences included two-point Dixon,six-point Dixon,MR spectroscopy(MRS)and MR elastography.Fat fraction(FF)estimates on the Dixon techniques were compared to the MRS-proton density FF(PDFF).Statistical tests used included Pearson’s correlation and receiver operating characteristic.RESULTS FF estimates on the Dixon techniques showed excellent correlation(≥0.95)with MRS-PDFF,and excellent accuracy[area under the receiver operating characteristic(AUROC)≥0.95]in:(1)Detecting steatosis;and(2)Grading severe steatosis,(P<0.001).In iron overload,two-point Dixon was not evaluable due to confounding T2*effects.FF estimates on six-point Dixon vs MRS-PDFF showed a moderate correlation(0.82)in iron overload vs an excellent correlation(0.97)without iron overload,(P<0.03).The accuracy of six-point Dixon in grading mild steatosis improved(AUROC:0.59 to 0.99)when iron overload cases were excluded.The excellent correlation(>0.9)between the Dixon techniques vs MRSPDFF did not change in the presence of liver fibrosis(P<0.01).CONCLUSION Dixon techniques performed satisfactorily for the evaluation of hepatic steatosis but with exceptions.

DFT Study on Electronic Structures and Spectroscopic Properties of Oligo（silanylenediethynylanthracene）

Poly（silanylenediethynylanthracene） （PSDEA） exhibits a hole-transporting ability experimentally. In order to simulate the property of PSDEA, a series of silanylenediethynylanthracene oligomers were designed. The structures of these oligomers were optimized by using density function theory at B3LYP/6-31G（d） level. The energy gaps of the oligomers decrease with the increase in the chain length. The energy gaps of the oligomers also decrease in the presence of the electron-withdrawing group on the anthracene ring. The 13C chemical shifts and nucleus independent chemical shifts （NICS） at the anthracene ring center in the oligomers were calculated at B3LYP/6-31G level. The chemical shifts of the carbon atoms connected with the nitryl group changed upfield, compared with those of the carbon atoms without the nitryl group. The aromaticity at the anthracene ring center decreases in the presence of the electron-withdrawing group, whereas increases with the increase in the number of the silanylene units. The most sensitive location for calculating the NICS values is 0.1 nm above the anthracene plane.

Structures and Intermolecular Interactions in Dimethyl Sulfoxide-Water System Studied by All-atom Molecular Simulations

An all-atom dimethyl sulfoxide （DMSO） and water model have been used for molecular dynamics simulation. The NMR and IR spectra are also performed to study the structures and interactions in the DMSO-water system. And there are traditional strong hydrogen bonds and weak C-H- ~ ~ O contacts existing in the mixtures according to the analysis of the radial distribution functions. The insight structures in the DMSO-water mixtures can be classified into different regions by the analysis of the hydrogen-bonding network. Interestingly, the molar fraction of DMSO 0.35 is found to be a special concentration by the network. It is the transitional region which is from the water rich region to the DMSO rich region. The stable aggregates of （DMSO）m＇S=O…… HW-OW-（H20）n might play a key role in this region. Moreover, the simulation is compared with the chemical shifts in NMR and wavenumbers in IR with concentration dependence. And the statistical results of the average number hydrogen bonds in the MD simulations are in agreement with the experiment data in NMR and IR spectra.

Isolation and NMR Study on Swainsonine from Locoweed,Astragalus strictus

Locoweed is a poisonous plant wildly distributed in most area of the world and can cause livestock poisoning or death with significant economic loss. The principal responsible for its toxicity is indolizidine alkaloid swainsonine, a new potential anticancer and antiviral drug. Astragalus strictus is mainly distributed in Tibet of China and is a serious hazard to the local livestock industry. To analyze its main toxic ingredients and supply more structural information and more accurate data, swainsonine has been isolated from this plant by D101 macroporous resin and the ^1H and ^13C chemical shifts of the compound has been assigned by 1D-NMR and 2D-NMR techniques. At the same time, complete assignments of swainsonine＇s ^13C spectral signals are reported.

Interactions of 1-hexyl-3-methylimidazolium Bromide with Acetone

^1H and ^13C NMR chemical shifts were determined to investigate the interactions of acetone with a room temperature ionic liquid 1-hexyl-3- methylimidazolium bromide [C6mim]Br at various mole fractions. Changes in chemical shifts of hydrogen nuclei and of carbon nuclei with the acetone concentration indicated the formation of hydrogen bond between anion of the ionic liquid and methyl protons of acetone. The NMR results were in good agreement with the ab initio computational results.

Studies on NaXe Clusters

The chemical shift of Na-23 in excimer NaXe was measured by using nuclear magnetic resonance (NMR) spectra, which is in good agreement with the theoretical value obtained by ab initio calculations. The bond length, dissociation energy, dipole of NaXe and Mulliken charges at Na and Xe in NaXe were calculated, respectively. The spectra of ultraviolet (UV) fluorescence and surface-enhanced Raman scattering of NaXe were also measured.