Dynamic 13C NMR spectroscopy

Dynamic ¹³C NMR spectroscopy is a recent addition to the tools available to chemists to investigate dynamic processes in molecules. The ¹³C spectra are not complicated by coupling and separation of the signals is the order of five times as large (in Hz). Consequently the temperature range over which meaningful measurements can be obtained is increased. There is therefore a marked increase in the dynamic range and accuracy of the measurements. Both very slow processes, e.g. 0.017 s^?1 for N,N-dimethylformamide and very fast processes, e.g. ΔG³ = 17.6 kJ mol^?1 for cycloocta-1,3,5-triene can be examined. In addition the technique is becoming very important in observing dynamic processes in metal carbonyls.     

金银花的13C NMR指纹图谱研究

利用PFT-NMR 核磁共振波谱仪测定了金银花特征提取物的¹³C NMR图谱,对金银花提取物的¹³C NMR指纹图谱进行了解析,与其有效成分绿原酸进行了比较,获得了金银花提取物的特征峰,并比较了不同金银花的优劣. 结果表明不同金银花提取物(M1, M2, Z1, Z2)的¹³C NMR指纹图谱都显示出绿原酸的特征共振峰,并具有很好的重现性和高度的特征性,可以成为金银花真伪鉴别的依据;优质(M1, Z1)与劣质(劣质M1,劣质Z1)金银花¹³C NMR图谱的差异进一步说明¹³C NMR指纹图谱可作为鉴别金银花质量的依据.     

13C NMR investigation of adsorbed hydrocarbons

By means of Fourier transform techniques ¹³C nmr spectra and longitudinal ¹³C magnetic relaxation times of various butene isomers sorbed on NaY and NaX zeolites have been studied. In contrast to ¹H resonance where only two broad lines can be observed, the ¹³C spectra show separated sharp lines. The shift Δσ = σ_ads-σ_free of the carbon-13 lines of adsorbed molecules with respect to the resonance positions of free molecules and the longitudinal relaxation times indicate a peculiar behaviour of the groups  CH and = C

of the adsorbed n-butene and isobutene molecules, respectively. The resonance deviations Δσ to lower fields in these groups decrease in the order isobutene (δσ = ? 10.3 ppm), but-1-ene (δσ ≈ ?5.7 ppm) and but-2-enes (Δσ ≈ ? 2.2–2.4 ppm), whereby the spectra of cis-but-2-ene and trans-but-2-ene show similar differences as found in the liquid state. When adsorbed on NaY and NaX types (silica/alumina ratios 5 and 3.5) the ¹³C nmr line positions of but-1-ene molecules are the same within the limits of experimental error, which demonstrates that electrostatic fields have no noticeable influence on the molecular parameters in these systems. Therefore one may conclude that chemical bonds to Na⁺ cations have the dominant effect on the line shift Δσ. CNDO-MO calculations based on such a model have shown that a charge transfer occurs from the π-electrons and the electrons of the methyl group hydrogen atoms to the cation.     

1H AND 13C NMR ASSIGNMENTS OF DIOSGENYL

用同核和异核二维核磁共振方法全归属了一系列合成的薯蓣皂甙元-α-L鼠李糖基-β-D葡萄糖甙的     

13C and 1H nuclear spin lattice magnetic relaxation in undoped polyacetylene

Pulsed NMR spin lattice relaxation measurements on ¹³C and ¹H nuclei in undoped trans-polyacetylene have been carried out between 6 and 295 K. The results indicate that the spin lattice relaxation is due to equilibrium fluctuations of the orientational order parameter for the protons while the carbon relaxation can be attributed to their coupling to paramagnetic impurities. In this temperature range no contribution of solitons has been detected in the relaxation mechanisms.     

Fusion cross-section measurements for the 13C+13C reaction

Absolute γ-ray yields from characteristic low-lying levels in nuclei produced in the ¹³C+ ¹³C reaction have been measured from E_c.m. = 4.0 to 15.8 MeV using an intrinsic germanium detector. Statistical-model calculations of the decay modes of the compound nucleus have been used to deduce absolute cross sections for the production of the observed residual nuclei and to determine the fusion cross section. Consistency checks on the adopted procedure lead to an estimated absolute uncertainty of ± 15 % on the deduced cross sections. Over the energy range covered, no striking evidence has been found for either broad single-particle resonances or for narrow non-statistical resonances in the cross sections for individual channels. Comparisons are made with optical-model calculations of the reaction cross section and with different expressions for the fusion cross section.     

Photodisintegration of 13C

The nucleon decay of the photoresonance in ¹³C is analyzed using bound-state shell model and R-matrix theory. Total and partial photo cross sections, branching ratios, final state population, and nucleon emission spectra are considered and compared with available data.     

Fusion cross section for 13C + 13C at low energies

The energy dependence of the fusion cross section has been measured over the range E_c.m. = 3.05–6.88 MeV by detecting the γ-rays from residual nuclei in a 4π geometry. Analyzing the 1.37 MeV photopeak, originating from ${}^{24}\text{Mg}\text{1.37}\text{MeV}\text{→}\text{g.s. transition}$, the cross sections for ²⁴Mg+2n channel were also deduced. The measured fusion cross sections have been compared with those for ¹²C + ¹²C and ¹²C + ¹³C systems and found to be significantly different. For ¹³C+¹³C the fusion cross sections agree with the standard optical-model prediction down to the lowest measured energies, while for ¹²C + ¹²C and ¹²C + ¹³C they are, at the lowest energies, too low. It is suggested that the unpaired valence nucleons facilitate fusion at energies well below the Coulomb barrier.     

Nuclear charge radii of the carbon isotopes 12C, 13C and 14C

Muonic X-ray energies of the K-series of the carbon isotopes ¹³C and ¹⁴C have been determined relative to ¹²C. For the first time, muonic atom measurements using radioactive ¹⁴C have been performed. Model-independent equivalent nuclear charge radii R_k,α and their differences have been deduced. The R_k,α radii increase by 10(14) and 32(11) am respectively with the filling of the $\text{1}\text{p}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ neutron Subshell. The results are compared with recent elastic electron scattering data. The former natural carbon data have been reanalysed using a new value for the nuclear polarization. In terms of the rms charge radius, we then obtain $\text{〈r}{}^2\text{〉}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{= 2.472(16)}\text{fm}$ for the ¹²C isotope.     

High resolution 13C NMR in undoped cis- and trans-polyacetylene

We have applied ¹³C cross-polarization (CP) powder- and MAS-NMR to cis- and trans-polyacetylene. All three elements of the chemical shift tensor (σ₁₁, σ₂₂, σ₃₃) were determined in p.p.m. with respect to TMS as: (a) Cis; σ₁₁ = ?228, σ₂₂ = ?139, σ₃₃ = ?17; (b) Trans; σ₁₁ = ?234, σ₂₂ = ?146, σ₃₃ = ?34.     

Quantum chemical interpretation of 13C NMR spectra of adsorbed molecules

In order to assist the interpretation of carbon-13 NMR spectra for molecules sorbed on solid surfaces, a theoretical analysis of resonance shifts was performed which were measured for simple alkenes and arenes in zeolites of type X and Y and on silica gel surfaces. Quantum chemical computations for simple models of adsorption complexes on the basis of CNDO and PCILO methods were combined with resonance shift calculations by means of the Ramsey theory and by employing an empirical formula to find out the most probable structures for the adsorption complexes.     

13C NMR在新型灵芝三萜类化合物的应用

高等真菌灵芝属的子实体作为著名的中药,灵芝三萜类化合物是中药灵芝主要活性化学成分,近年来灵芝三萜类化合物仍然不断被大量发现, 而且结构越来越新奇. 本文总结了10年来文献报道灵芝三萜化合物的¹³C NMR化学位移,找出了一些规律, 对进行灵芝三萜化合物类结构的研究,将提供十分便捷的途径.     

Mixed-parity neutron orbits in the scattering of 12C on 13C

In the scattering process of ¹²C on ¹³C the mixing of the p-and sd-shell orbits of the valence neutron in ¹³C has been investigated by using the coupled channel theory with the adiabatic assumption. When two nuclei approach each other an extremely anisotropic density distribution of the neutron is induced due to the mixed-parity configuration similar to the sp hybrid configurations in atomic physics. The probability of the elastic transfer of the neutron is enhanced by virtue of this deformation.     

ON VAED CHARACTERIZATION AND 13C NMR SIMULATION FOR AMINO ACIDS

提出以原子电性距离矢量(VAED)描述20种天然氨基酸中不同等价碳原子的化学环境,结合γ效应校正与碳原子类型,建立核磁共振碳谱(     

Inelastic scattering of 12C and 13C on 63Cu leading to core-excited states

The inelastic scattering of ¹²C and ¹³C projectiles has been studied on ⁶³Cu at 45 MeV incident energy. The core-excited states (based on 2⁺ in ⁶²Ni) show individual differences in the angular distributions which are due to second-order couplings (transfer and inelastic transitions). However, the sum of the core-excited states yields the same cross section as observed in the inelastic scattering of ¹²C at 48 MeV on ⁶²Ni (2⁺).