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 a...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.展开更多
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 ...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.展开更多
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,re...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.展开更多
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 c...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.展开更多
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/...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.展开更多
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 calcula...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).展开更多
On two dimensional maps of <sup>1</sup>H-<sup>13</sup>C correlation spectroscopy (H-C COSY) analysis for the mannan of <i>Candida tropicalis</i>, nine cross peaks of anomeric proton...On two dimensional maps of <sup>1</sup>H-<sup>13</sup>C correlation spectroscopy (H-C COSY) analysis for the mannan of <i>Candida tropicalis</i>, 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 <i>α</i>-1,6-linked polymannnosyl backbone and several oligomannnosyl side chains composed of <i>α</i>-1,2-, <i>α</i>-1,3-, and <i>β</i>-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.展开更多
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 steatosi...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.展开更多
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...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.展开更多
In this paper,Raman shifts of a-plane GaN layers grown on r-plane sapphire substrates by low-pressure metal-organic chemical vapor deposition(LPMOCVD) are investigated.We compare the crystal qualities and study the ...In this paper,Raman shifts of a-plane GaN layers grown on r-plane sapphire substrates by low-pressure metal-organic chemical vapor deposition(LPMOCVD) are investigated.We compare the crystal qualities and study the relationships between Raman shift and temperature for conventional a-plane GaN epilayer and insertion AlN/AlGaN superlattice layers for a-plane GaN epilayer using temperature-dependent Raman scattering in a temperature range from 83 K to 503 K.The temperature-dependences of GaN phonon modes(A1(TO),E2(high),and E1(TO)) and the linewidths of E2(high) phonon peak are studied.The results indicate that there exist two mechanisms between phonon peaks in the whole temperature range,and the relationship can be fitted to the pseudo-Voigt function.From analytic results we find a critical temperature existing in the relationship,which can characterize the anharmonic effects of a-plane GaN in different temperature ranges.In the range of higher temperature,the relationship exhibits an approximately linear behavior,which is consistent with the analyzed results theoretically.展开更多
Coralyne is an important alkaloid due to its anti-cancer and other medicinal properties.It targets DNA in cells and acts as human topoisomerase-I poison,telomerase inhibitor and nucleic acid intercalator.It has high t...Coralyne is an important alkaloid due to its anti-cancer and other medicinal properties.It targets DNA in cells and acts as human topoisomerase-I poison,telomerase inhibitor and nucleic acid intercalator.It has high tendency to undergo self-association,which is a matter of concern for therapeutic applications.The understanding of its interaction with DNA requires precise knowledge of chemical shifts in Nuclear Magnetic Resonance(NMR)spectra besides self-association.The present study is the first report of a complete assignment of all 1H/13C resonances in NMR spectra of coralyne in DMSO-d6 using one dimensional 1H/13C and two dimensional NMR experiments.The chemical shift of all proton and several 13C resonances have also been obtained in D2O and ethanol-d6.The same has been calculated using Density Functional Theory(DFT).NMR spectra of coralyne show upfield shift of 0.6e1.2 ppm in aromatic ring protons suggesting stacking interactions.Apart from 11 intra molecular NOE cross peaks in 2D 1H e1H ROESY spectra,3 short distance NOE correlations,H6e10OCH3,H5e10OCH3 and H12e16CH3,give direct independent evidence of the formation of a stacked dimer.The absorbance,fluorescence,circular dichroism and fluorescence lifetime experiments conducted in the present investigations corroborate results obtained by NMR.展开更多
Electron momentum spectroscopy(EMS) has been used for the first time to study core electronic structure of isoC2H2Cl2. In the present work, the pronounced difference between ionization energies of two C1 score orbital...Electron momentum spectroscopy(EMS) has been used for the first time to study core electronic structure of isoC2H2Cl2. In the present work, the pronounced difference between ionization energies of two C1 score orbitals(2A1 and 3A1) is seen as a chemical shift of 3 eV, which is due to different chemical environments of the related carbon atoms. Both the calculated spherically averaged core electron momentum distributions(MDs) and three-dimensional electron momentum density maps show that these core molecular orbitals(MOs) 2A1and 3A1 exhibit strong atomic orbital characteristics in real and momentum space. However, the core states 2B2 and 4A1, which are almost degenerate and related to two equivalent atoms, exhibit notable differences between the momentum and position depictions. In contrast to the position space, the momentum density maps of these two core MOs highlight the interference effects which are due to the nuclear positions. The 2B2 orbital of iso-C2H2Cl2 is the antisymmetric counterpart of the 4A1 core orbital in real space. However, it relates to the 4A1 orbital by an exchange of maxima and minima in momentum space. Due to interference effects between electrons scattered from different atomic centers, modulations with a periodicity of 1.12 a.u. can be seen in the computed momentum densities, which tend to decay with increasing electron momenta. Accordingly, the EMS can not only effectively image the electronic structure of compounds by studying valence orbitals, but also provides direct information on the nature of the nuclear geometry by investigating the core states.展开更多
Phthalate acid esters (PAEs) possess endocrine disruptive effects and can produce reproductive and developmental toxicities. In this paper, both experimental and theoretical studies on FT-IR, Raman and 1H NMR spectr...Phthalate acid esters (PAEs) possess endocrine disruptive effects and can produce reproductive and developmental toxicities. In this paper, both experimental and theoretical studies on FT-IR, Raman and 1H NMR spectra of diethyl phthalate (DEP) have been carried out. The geometrical structure of DEP was optimized at the HF/6-31G*, HF/6-311G**, B3LYP/6-31G*, and B3LYP/6-31 IG** levels, respectively. The harmonic vibrational frequencies, IR intensity, Raman activity and 1H NMR chemical shifts have been computed at the B3LYP/6-31G* and B3LYP/6-311G** levels. Anharmonic corrections to frequencies were obtained by means of second-order perturbation theory (PT2) at the B3LYP/6-31G* level. Based on potential energy distribution (PED), the vibrational assignments have also been performed. The theoretical calculation values were compared with the experimental observations and the results indicate they are in excellent agreement.展开更多
Three-membered BeXP (X = C, Si, Ge) and CYP (Y = O, S, Se) rings are theoretically investigated using density functional theory (DFT) methods at the B3LYP/6-311+G^* and B3PW91/6-311+G^* levels of theory. The...Three-membered BeXP (X = C, Si, Ge) and CYP (Y = O, S, Se) rings are theoretically investigated using density functional theory (DFT) methods at the B3LYP/6-311+G^* and B3PW91/6-311+G^* levels of theory. The research results show that the size of atoms has a great influence on the structural stability of these species. The wiberg bond indexs (WBIs) suggest the existence of delocalization in these structures. Negative nucleus-independent chemical shift (NICS) values for these species indicate that a strong ring current exists in these three-membered structures (Cs symmetry). A detailed molecular orbital (MO) analysis further reveals that a delocalized π MO strengthens the structural stability and makes these species show strong aromatic characters.展开更多
The equilibrium geometries, energies, harmonic vibrational frequencies, and nucleus independent chemical shifts (NICS) of the new type sandwich structures [As4MAs4]^n- (M = Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt; n ...The equilibrium geometries, energies, harmonic vibrational frequencies, and nucleus independent chemical shifts (NICS) of the new type sandwich structures [As4MAs4]^n- (M = Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt; n = 0, 1 or 2) are investigated at the B3LYP level. All the [As4MAs4]^n- species adopt staggered (D4d) conformations as their stable structures and eclipsed (D4h) conformations as their transition states, and once the sandwich complexes are formed, the As4^2- square properties remain unchanged. The NICS calculation confirms that the complexes of Fe, Co, and Ni are aromatic with negative NICS values, and those of Ru, Rh, and lx exhibit slight aromaticity, while those of Pd, Os, and Pt show slight antiaromaticity.展开更多
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, di...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.展开更多
The line positions of 19F NMR absorption of fluoranil (TFQ) or pentafluorophenylcarboxylate (PFE-16) in the presence of N-alkylphenothiazine donors have been measured. By comparing the 19F chemical shift in C6D6 of TF...The line positions of 19F NMR absorption of fluoranil (TFQ) or pentafluorophenylcarboxylate (PFE-16) in the presence of N-alkylphenothiazine donors have been measured. By comparing the 19F chemical shift in C6D6 of TFQ or PFE-16 in the absence of the donor with thosein the presence of the donor. the difference of these chemical shifts was found to be large. In thepresence of the donor. 19F upheld shifts of TFQ or PFE-16 have been observed. The experimentalresults showed that there is a charge-transfer process between TFQ or PFE-16 and the donor .When TFQ or PFE-16 accepts the charge from the donor. its 19F resonance moves upfield.展开更多
The value of the combined in-phase (IP) and opposed-phase (OP) T1-weighted (T1-W) breath-hold FLASH sequences for hepatic imaging, especially for fat content, was evaluated. Non- contrast-enhanced IP and OP T1-W GRE ...The value of the combined in-phase (IP) and opposed-phase (OP) T1-weighted (T1-W) breath-hold FLASH sequences for hepatic imaging, especially for fat content, was evaluated. Non- contrast-enhanced IP and OP T1-W GRE breath-hold images were obtained in 76 patients refereed for abdominal MRI at 1. 5T. 76 patients were divided into three groups for analysis: (1) liver with- out mass (n=8); (2) liver with hepatoma (n=34); (3) liver with haemangioma or cyst (n=34). Liver/spleen and liver/lesion signal-to-noise (SNR) and contrast-to-noise ratio (CNR) were assessed for lesion detection. Images between IP and OP sequences were compared quantitatively. The results showed that there was not statistically significant difference in liver/spleen and liver/lesion SNR be- tween IP and OP sequences. In the patients with fatty infiltration, the OP sequences yielded substan- tially lower values for liver/spleen and liver/lesion SNR than those of the IP sequences. Further- more, OP imaging showed fatty infiltration in 14 cases and demonstrated hyperintense peritumor rim in 4 cases. In 14 cases of fatty infiltration, many lesions were identified using IP images. The use of IP and OP GRE sequences provides complementary diagnostic information for hepatic lesions and fat content. Focal hepatic lesions may be obscured in the setting of fatty infiltration if only OP sequences are employed. A complete assessment of the liver with MR should include both IP and OP imaging.展开更多
The theory of chemical shift effect of substituent was applied to the assignment of the 13 C NMR spectra of the ethylene/propylene and ethylene/octene 1 copolymers. Using the parameters derived above a...The theory of chemical shift effect of substituent was applied to the assignment of the 13 C NMR spectra of the ethylene/propylene and ethylene/octene 1 copolymers. Using the parameters derived above and the DEPT technique, we then entirely assigned the 13 C NMR spectra of the ethylene/propylene/octene 1 terpolymers synthesized in the presence of the same heterogeneous supported Ziegler Natta catalyst, TiCl 4/MgCl 2/ i Bu 3Al. The present paper also covers the terpolymer composition and the monomer sequence distributions of a series of ethylene/propylene/octene 1 terpolymers.展开更多
基金Supported by the Scientific Research Foundation of Department of Education of Yunnan Province,China(No.09Y0181)
文摘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.
文摘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.
文摘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.
文摘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.
文摘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.
基金supported by the Scientific Research Foundation of Department of Education of Yunnan Province (No. 2010Z035)
文摘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).
文摘On two dimensional maps of <sup>1</sup>H-<sup>13</sup>C correlation spectroscopy (H-C COSY) analysis for the mannan of <i>Candida tropicalis</i>, 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 <i>α</i>-1,6-linked polymannnosyl backbone and several oligomannnosyl side chains composed of <i>α</i>-1,2-, <i>α</i>-1,3-, and <i>β</i>-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.
文摘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.
基金the National Natural Science Foundation of China (39770571)
文摘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.
基金Project supported by the Fundamental Research Funds for the Central Universities,China (Grant No. K50511250002)the National Key Science & Technology Special Project,China (Grant No. 2008ZX01002-002)+1 种基金the Major Program and State Key Program of the National Natural Science Foundation of China (Grant Nos. 60890191 and 60736033)the Science Fund for Youths Scholars (Grant Nos. 61204006)
文摘In this paper,Raman shifts of a-plane GaN layers grown on r-plane sapphire substrates by low-pressure metal-organic chemical vapor deposition(LPMOCVD) are investigated.We compare the crystal qualities and study the relationships between Raman shift and temperature for conventional a-plane GaN epilayer and insertion AlN/AlGaN superlattice layers for a-plane GaN epilayer using temperature-dependent Raman scattering in a temperature range from 83 K to 503 K.The temperature-dependences of GaN phonon modes(A1(TO),E2(high),and E1(TO)) and the linewidths of E2(high) phonon peak are studied.The results indicate that there exist two mechanisms between phonon peaks in the whole temperature range,and the relationship can be fitted to the pseudo-Voigt function.From analytic results we find a critical temperature existing in the relationship,which can characterize the anharmonic effects of a-plane GaN in different temperature ranges.In the range of higher temperature,the relationship exhibits an approximately linear behavior,which is consistent with the analyzed results theoretically.
基金Ministry of Human Resources and Development(MHRD),Government of India for the support for funding
文摘Coralyne is an important alkaloid due to its anti-cancer and other medicinal properties.It targets DNA in cells and acts as human topoisomerase-I poison,telomerase inhibitor and nucleic acid intercalator.It has high tendency to undergo self-association,which is a matter of concern for therapeutic applications.The understanding of its interaction with DNA requires precise knowledge of chemical shifts in Nuclear Magnetic Resonance(NMR)spectra besides self-association.The present study is the first report of a complete assignment of all 1H/13C resonances in NMR spectra of coralyne in DMSO-d6 using one dimensional 1H/13C and two dimensional NMR experiments.The chemical shift of all proton and several 13C resonances have also been obtained in D2O and ethanol-d6.The same has been calculated using Density Functional Theory(DFT).NMR spectra of coralyne show upfield shift of 0.6e1.2 ppm in aromatic ring protons suggesting stacking interactions.Apart from 11 intra molecular NOE cross peaks in 2D 1H e1H ROESY spectra,3 short distance NOE correlations,H6e10OCH3,H5e10OCH3 and H12e16CH3,give direct independent evidence of the formation of a stacked dimer.The absorbance,fluorescence,circular dichroism and fluorescence lifetime experiments conducted in the present investigations corroborate results obtained by NMR.
基金Project supported by the National Natural Science Foundation of China(Grant No.11074144)
文摘Electron momentum spectroscopy(EMS) has been used for the first time to study core electronic structure of isoC2H2Cl2. In the present work, the pronounced difference between ionization energies of two C1 score orbitals(2A1 and 3A1) is seen as a chemical shift of 3 eV, which is due to different chemical environments of the related carbon atoms. Both the calculated spherically averaged core electron momentum distributions(MDs) and three-dimensional electron momentum density maps show that these core molecular orbitals(MOs) 2A1and 3A1 exhibit strong atomic orbital characteristics in real and momentum space. However, the core states 2B2 and 4A1, which are almost degenerate and related to two equivalent atoms, exhibit notable differences between the momentum and position depictions. In contrast to the position space, the momentum density maps of these two core MOs highlight the interference effects which are due to the nuclear positions. The 2B2 orbital of iso-C2H2Cl2 is the antisymmetric counterpart of the 4A1 core orbital in real space. However, it relates to the 4A1 orbital by an exchange of maxima and minima in momentum space. Due to interference effects between electrons scattered from different atomic centers, modulations with a periodicity of 1.12 a.u. can be seen in the computed momentum densities, which tend to decay with increasing electron momenta. Accordingly, the EMS can not only effectively image the electronic structure of compounds by studying valence orbitals, but also provides direct information on the nature of the nuclear geometry by investigating the core states.
基金Financially supported by the National Natural Science Foundation of China (41071319, 20977046)the Fundamental Research Funds for the Central Universities of China (1112021101)
文摘Phthalate acid esters (PAEs) possess endocrine disruptive effects and can produce reproductive and developmental toxicities. In this paper, both experimental and theoretical studies on FT-IR, Raman and 1H NMR spectra of diethyl phthalate (DEP) have been carried out. The geometrical structure of DEP was optimized at the HF/6-31G*, HF/6-311G**, B3LYP/6-31G*, and B3LYP/6-31 IG** levels, respectively. The harmonic vibrational frequencies, IR intensity, Raman activity and 1H NMR chemical shifts have been computed at the B3LYP/6-31G* and B3LYP/6-311G** levels. Anharmonic corrections to frequencies were obtained by means of second-order perturbation theory (PT2) at the B3LYP/6-31G* level. Based on potential energy distribution (PED), the vibrational assignments have also been performed. The theoretical calculation values were compared with the experimental observations and the results indicate they are in excellent agreement.
基金supported by the 111 Project B07012 of China and the National Natural Science Foundation of China (No. 20773014)
文摘Three-membered BeXP (X = C, Si, Ge) and CYP (Y = O, S, Se) rings are theoretically investigated using density functional theory (DFT) methods at the B3LYP/6-311+G^* and B3PW91/6-311+G^* levels of theory. The research results show that the size of atoms has a great influence on the structural stability of these species. The wiberg bond indexs (WBIs) suggest the existence of delocalization in these structures. Negative nucleus-independent chemical shift (NICS) values for these species indicate that a strong ring current exists in these three-membered structures (Cs symmetry). A detailed molecular orbital (MO) analysis further reveals that a delocalized π MO strengthens the structural stability and makes these species show strong aromatic characters.
文摘The equilibrium geometries, energies, harmonic vibrational frequencies, and nucleus independent chemical shifts (NICS) of the new type sandwich structures [As4MAs4]^n- (M = Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt; n = 0, 1 or 2) are investigated at the B3LYP level. All the [As4MAs4]^n- species adopt staggered (D4d) conformations as their stable structures and eclipsed (D4h) conformations as their transition states, and once the sandwich complexes are formed, the As4^2- square properties remain unchanged. The NICS calculation confirms that the complexes of Fe, Co, and Ni are aromatic with negative NICS values, and those of Ru, Rh, and lx exhibit slight aromaticity, while those of Pd, Os, and Pt show slight antiaromaticity.
文摘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.
文摘The line positions of 19F NMR absorption of fluoranil (TFQ) or pentafluorophenylcarboxylate (PFE-16) in the presence of N-alkylphenothiazine donors have been measured. By comparing the 19F chemical shift in C6D6 of TFQ or PFE-16 in the absence of the donor with thosein the presence of the donor. the difference of these chemical shifts was found to be large. In thepresence of the donor. 19F upheld shifts of TFQ or PFE-16 have been observed. The experimentalresults showed that there is a charge-transfer process between TFQ or PFE-16 and the donor .When TFQ or PFE-16 accepts the charge from the donor. its 19F resonance moves upfield.
文摘The value of the combined in-phase (IP) and opposed-phase (OP) T1-weighted (T1-W) breath-hold FLASH sequences for hepatic imaging, especially for fat content, was evaluated. Non- contrast-enhanced IP and OP T1-W GRE breath-hold images were obtained in 76 patients refereed for abdominal MRI at 1. 5T. 76 patients were divided into three groups for analysis: (1) liver with- out mass (n=8); (2) liver with hepatoma (n=34); (3) liver with haemangioma or cyst (n=34). Liver/spleen and liver/lesion signal-to-noise (SNR) and contrast-to-noise ratio (CNR) were assessed for lesion detection. Images between IP and OP sequences were compared quantitatively. The results showed that there was not statistically significant difference in liver/spleen and liver/lesion SNR be- tween IP and OP sequences. In the patients with fatty infiltration, the OP sequences yielded substan- tially lower values for liver/spleen and liver/lesion SNR than those of the IP sequences. Further- more, OP imaging showed fatty infiltration in 14 cases and demonstrated hyperintense peritumor rim in 4 cases. In 14 cases of fatty infiltration, many lesions were identified using IP images. The use of IP and OP GRE sequences provides complementary diagnostic information for hepatic lesions and fat content. Focal hepatic lesions may be obscured in the setting of fatty infiltration if only OP sequences are employed. A complete assessment of the liver with MR should include both IP and OP imaging.
基金Supported by the Foundation of Educational Ministry of China.
文摘The theory of chemical shift effect of substituent was applied to the assignment of the 13 C NMR spectra of the ethylene/propylene and ethylene/octene 1 copolymers. Using the parameters derived above and the DEPT technique, we then entirely assigned the 13 C NMR spectra of the ethylene/propylene/octene 1 terpolymers synthesized in the presence of the same heterogeneous supported Ziegler Natta catalyst, TiCl 4/MgCl 2/ i Bu 3Al. The present paper also covers the terpolymer composition and the monomer sequence distributions of a series of ethylene/propylene/octene 1 terpolymers.