Sensitivity- and Gradient-Enhanced Hetero (ω1) Half-Filtered TOCSY Experiment for Measuring Long-Range Heteronuclear Coupling Constants

An enhanced version of the X(ω₁) half-filtered TOCSY experiment for measurement of long-range heteronuclear coupling constants is proposed which yields high-quality spectra with substantially increased sensitivity and resolution. The modified method features gradient-enhanced X filtering sequences, broadband homonuclear decoupling duringt₁, optional¹J_XHscaling in theF₁domain, and gradient coherence selection in combination with the sensitivity-enhanced protocol for the TOCSY transfer. These modifications extend the applicability of the method—coupling constants can be measured accurately for natural abundance samples at low concentrations and for compounds yielding complex spectra. Computer-aided analysis of E.COSY-type multiplets is applied for the determination of heteronuclear long-range coupling constants.     

Sensitivity- and Gradient-Enhanced Hetero (ω1) Half-Filtered TOCSY Experiment for Measuring Long-Range Heteronuclear Coupling Constants

An enhanced version of the X(ω₁) half-filtered TOCSY experiment for measurement of long-range heteronuclear coupling constants is proposed which yields high-quality spectra with substantially increased sensitivity and resolution. The modified method features gradient-enhanced X filtering sequences, broadband homonuclear decoupling duringt₁, optional¹J_XHscaling in theF₁domain, and gradient coherence selection in combination with the sensitivity-enhanced protocol for the TOCSY transfer. These modifications extend the applicability of the method—coupling constants can be measured accurately for natural abundance samples at low concentrations and for compounds yielding complex spectra. Computer-aided analysis of E.COSY-type multiplets is applied for the determination of heteronuclear long-range coupling constants.     

Sensitivity- and Gradient-Enhanced Heteronuclear Coupled/Decoupled HSQC–TOCSY Experiments for Measuring Long-Range Heteronuclear Coupling Constants

A pulsed field gradient version of the sensitivity-enhanced 2D HSQC–TOCSY experiment is proposed for measurement of long-range heteronuclear coupling constants. The coupling constants are obtained by computer-aided analysis of mixed-phase multiplets with and without the heteronuclear splitting. Generation of pure phase data is not required. Since large¹J_XHandJ_HHcouplings are used for coherence transfer, smallⁿJ_XHcan be measured accurately, which could be difficult to obtain from purely heteronuclear polarization transfer experiments.     

盐酸非索非那定的NMR归属和立体化学研究

盐酸非索非那定(1),是第2代抗组胺药,其完整的NMR信号归属及其立体化学研究未见到报道. 由于大部分信号出现重叠,该化合物 ¹H NMR谱图解析比较困难,采用常规方法研究不易得到比较完整的NMR结构信息. 本文采用1D TOCSY、1D ROESY和2D NMR相结合的方法进行研究,得到了盐酸非索非那定完整的NMR信号归属. 此外,根据1D ROESY实验结果以及得到的有关偶合常数,推得该化合物的的立体结构,如（1）所示.     

2D NMR Study on 4-O-Tetrahydropyranylepiisopicropodophyllin

A complete assignment of the two dimensional ¹H and ¹³C NMR spectra of the title compound, which is a key intermediate for preparation of podophyllotoxin derivatives, is presented The proton signals have been assigned from DQF-COSY, TOCSY, ¹H-¹H coupling patterns, and by the comparisons of chemical shifs with those of similar podophyllum lignans. Complete ¹³C NMR assignments have been made from HMQC.HMBC and DEPT spectra. Further information on the stereochemistry of the molecule was obtained from 2D NOESY and NOE-difference techniques.

     

一种薯蓣皂苷的NMR研究

从七叶一枝花中分离得到一种薯蓣皂苷薯蓣皂苷元3-O-α-L-阿拉伯呋喃糖基- (1→4)-α-L-鼠李吡喃糖基(1→2)-β-D-葡萄吡喃糖苷. 应用1D和2D NMR 实验技术（包括¹H-¹H COSY, HSQC和HMBC）对化合物结构进行研究,对其¹H和¹³C化学位移进行了完全归属. 实验中运用了选择性1D TOCSY技术对糖环的质子峰进行了归属.     

Accurate Measurements of Multiple-Bond C–H Coupling Constants from Phase-Sensitive 2D INEPT Spectra

Measurements of multiple-bond ¹³C–¹H coupling constants are of great interest for the assignment of nonprotonated ¹³C resonances and the elucidation of molecular conformation in solution. Usually, the heteronuclear multiple-bond coupling constants were measured either by the J_CH splittings mostly in selective 2D spectra or in 3D spectra, which are time consuming, or by the cross peak intensity analysis in 2D quantitative heteronuclear J correlation spectra (1994, G. Zhu, A. Renwick, and A. Bax, J. Magn. Reson. A 110, 257; 1994, A. Bax, G. W. Vuister, S. Grzesiek, F. Delaglio, A. C. Wang, R. Tschudin, and G. Zhu, Methods Enzymol. 239, 79.), which suffer from the accuracy problem caused by the signal-to-noise ratio and the nonpure absorptive peak patterns. Concerted incrementation of the duration for developing proton antiphase magnetization with respect to carbon-13 and the evolution time for proton chemical shift in different steps in a modified INEPT pulse sequence provides a new method for accurate measurements of heteronuclear multiple-bond coupling constants in a single 2D experiment.     

黄花远志黄花皂甙D的二维核磁共振谱研究

用一维、二维波谱技术研究了从中药黄花远志根中分离出一种含六个糖的三萜皂甙,黄花皂甙D,确定了皂甙的双糖链结构以及甙元与糖基、糖基与糖基间的连接位置,并对其一维谱进行了归属.     

Multiple resonance heteronuclear decoupling under MAS: dramatic increase of spectral resolution at moderate magnetic field and MAS frequencies

The effects of multiple-resonance heteronuclear decoupling under magic angle spinning (MAS) on the resolution of one-dimensional ¹⁹F and ³¹P and various two-dimensional MAS NMR spectra and on the residual non-refocusable coherence lifetimes in fluorinated aluminophosphate AlPO₄-CJ2, i.e. a compound that contains numerous highly abundant nuclei but no homonuclear spin bath, has been investigated. The design of the four-channel (¹H, ¹⁹F, ²⁷Al, ³¹P) MAS probe used for this study is first described. ¹H and ¹H–²⁷Al double-resonance decouplings allows lengthening the optimized transverse relaxation and increasing the resolution in the ¹⁹F and ³¹P dimensions. Under the application of multi-nuclear decoupling, a two-dimensional ¹⁹F–³¹P CP-HETCOR correlation spectrum for AlPO₄-CJ2 is recorded with unprecedented high-resolution in the two dimensions. Moreover, because ¹H-decoupling increases the ¹⁹F , it has been applied during the entire duration of the 2D NMR experiments, allowing the direct use of residual small interactions to generate ¹⁹F–¹⁹F and ¹⁹F–²⁷Al 2D NMR correlation spectra in AlPO₄-CJ2.     

Relaxation times and line widths of isotopically-substituted nitroxides in aqueous solution at X-band

Optimization of nitroxides as probes for EPR imaging requires detailed understanding of spectral properties. Spin lattice relaxation times, spin packet line widths, nuclear hyperfine splitting, and overall lineshapes were characterized for six low molecular weight nitroxides in dilute deoxygenated aqueous solution at X-band. The nitroxides included 6-member, unsaturated 5-member, or saturated 5-member rings, most of which were isotopically labeled. The spectra are near the fast tumbling limit with T₁∼T₂ in the range of 0.50–1.1 μs at ambient temperature. Both spin–lattice relaxation T₁ and spin–spin relaxation T₂ are longer for ¹⁵N- than for ¹⁴N-nitroxides. The dominant contributions to T₁ are modulation of nitrogen hyperfine anisotropy and spin rotation. Dependence of T₁ on nitrogen nuclear spin state m_I was observed for both ¹⁴N and ¹⁵N. Unresolved hydrogen/deuterium hyperfine couplings dominate overall line widths. Lineshapes were simulated by including all nuclear hyperfine couplings and spin packet line widths that agreed with values obtained by electron spin echo. Line widths and relaxation times are predicted to be about the same at 250 MHz as at X-band.     

Infrared spectra of acetylene dimers and acetylene–nitrogen: (DCCD)2, H-bonded DCCD–HCCH, and DCCD–NN in the 4.1 μm region

Infrared spectra of the weakly-bound T-shaped acetylene dimers DCCD–DCCD and DCCD–HCCH are studied in the region of the DCCD ν₃ fundamental (∼2440 cm⁻¹) using a pulsed supersonic slit-jet expansion and a tunable diode laser probe. The K_a = 0 ← 1 and 1 ← 0 subbands, corresponding to the vibration of the DCCD monomer at the “top” of the T, are analyzed. Compared to the analogous spectrum of HCCH–HCCH, the present results are much less perturbed. The tunneling splitting for (DCCD)₂ in the excited state is determined to be 141 MHz, a big reduction from the previously determined ground state value of 424 MHz. The dimer A rotational constants show a large apparent increase upon vibrational excitation, and we discuss whether this increase is real. The linear DCCD–NN complex is also observed as an impurity in the spectrum, and it too is found to be unperturbed, in contrast with HCCH–NN.     

二蕊荷莲豆环肽B的NMR应用研究

植物环肽的¹H 和¹³C NMR图谱, 由于各种氨基酸自旋系统质子和碳的化学位移非常接近，谱峰高度重叠，结构解析比较困难. 文中以二蕊荷莲豆环肽B为例讨论了
现代2D NMR新技术，在植物环肽结构解析中的应用. HMQC-TOCSY图谱在氢谱方向和碳谱方向分别提供每一个氨基酸自旋系统内的氢和除季碳外碳的全相关信息，从而将每个氨基酸残基的NMR信号相互区分开来；结合¹H-¹H COSY 和 HMQC或HSQC图谱，就可以准确归属每个氨基酸的氢和碳的化学位移. 氨基酸残基之间的连接顺序可用HMBC、NOESY或ROESY图谱获得.     

用新近发展的1H NMR技术研究腐殖酸

将一些新近发展起来的¹H NMR技术用于溶在不同溶剂(D₂O,NaOH/D₂O及DMSO-d₆)中的腐殖酸样品的研究,这包括全相关谱方法(TOCSY),扩散谱方法和最大量子谱方法(MAXY).DMSO溶液的TOCSY谱中4与8之间的相关峰表明在腐殖酸中可能包含有不溶于水的多肽,扩散谱指出在碱性条件下,一些小分子脱离了腐殖酸聚合体,而MAXY谱编辑方法则使得一些细致的归属成为可能.     

Adiabatic Mixing in the Liquid State

Adiabatic spin inversion has been used in the liquid state very efficiently for decoupling purposes. Here we show that it can also be adapted for spin mixing experiments, such as the TOCSY and clean TOCSY experiment, and is superior to previously employed mixing sequences. The main advantage of adiabatic mixing sequences over the conventional mixing schemes used in liquid state experiments is an extremely low sensitivity to RF field inhomogeneity and miscalibration of theB₁field strength. The method is evaluated experimentally by comparing results obtained with different mixing schemes in the basic 2D TOCSY experiment. In addition to higher reliability, adiabatic mixing provides a sensitivity improvement of ca. 20% as compared to conventional mixing schemes. This is explained by higher signal losses due to RF inhomogeneity in the experiments employing traditional mixing schemes. More significant sensitivity improvements can be expected in situations where RF homogeneity is traditionally poor, for example, in large volume probes and magnetic resonance imaging experiments.     

Randomized Acquisition for the Suppression of Systematic F1 Artifacts in Two-Dimensional NMR Spectroscopy

2D spectra, particularly for homonuclear correlation, can show a variety of artifactual signals in the F₁ domain. Common sources include carry-over of signal modulation from one transient to the next (“rapid pulsing artifacts”) and systematic variations in room temperature (“parallel diagonals”). In both cases there is one very simple expedient which can greatly reduce the impact of these sources of error. Multidimensional data sets are almost invariably recorded by simply incrementing or decrementing evolution periods, largely for reasons of convenience and historical precedent. If instead the sampling of the evolution periods is carried out in random order, the perturbations responsible for the sharp F₁ signals in the conventional experiment manifest themselves as t₁ noise. Since the randomized acquisition redistributes coherent artifactual signals randomly in F₁, the maximum artifactual signal is substantially reduced in the randomized experiment and no longer appears in the form of misleading distinct peaks.     

MRICOM–MRI COntrast Modelling using 2D T1–T2 correlation spectra and relaxation signatures

Image contrast is calculated by inputting experimental 2D T₁–T₂ relaxation spectra into the ODIN software interface. The method involves characterising a magnetic resonance imaging pulse sequence with a “relaxation signature” which describes the sensitivity of the sequence to relaxation and is independent of sample parameters. Maximising (or minimising) the overlap between the experimental 2D T₁–T₂ relaxation spectra and the relaxation signature can then be used to maximise image contrast. The concept is illustrated using relaxation signatures for the echo planar imaging and Turbo spin-echo imaging sequences, together with in-vitro 2D T₁–T₂ spectra for liver and cartilage.     

Gradient-Enhanced One-Dimensional Proton Chemical-Shift Correlation with Full Sensitivity

High-quality spectra were obtained by implementing pulsed field gradients (PFGs) as part of 1D selective experiments. The use of PFGs for coherence rejection rather than coherence selection ensures that there is no loss of signal and the sensitivity of these experiments is the same as that of their phase-cycled predecessors. The excitation scheme chosen ensures that these experiments are highly resistant to spin–spin relaxation. The following techniques are described: 1D ge-TOCSY, 1D ge-NOESY, 1D ge-TOCSY–TOCSY, 1D ge-NOESY–NOESY, 1D ge-TOCSY–NOESY, and 1D ge-NOESY–TOCSY. Their applications, for the separation of overlapping spin systems, tracing spin-diffusion signals, and extending the transfer of magnetization beyond an individual spin system, are illustrated using oligo- and polysaccharide samples.     

Unravelling the visible spectrum of strontium monomethoxide

The bands of the A²E–X²A₁ and B²A₁–X²A₁ electronic transitions of SrO¹²CH₃ and the B²A₁–X²A₁ transition of SrO¹³CH₃ have been recorded at high resolution using a laser ablation jet source. The optical–optical double resonance population depletion technique was used to facilitate the assignment of the spectra. Rotational levels with K = 0, ±1 in the X²A₁ and B²A₁ states and K = 0, 1 and 2 in the A²E state have all been characterised. A perturbation affecting the B²A₁ state caused a reversal of the ordering of the spin-rotation components, F₁ and F₂, in the SrO¹²CH₃ isotopologue. This required the introduction of a modified rotational constant B_mod, affecting only the K = 1, F₂ component of the B²A₁ state, in order to model the SrO¹²CH₃ data in a global fit of the A²E–X²A₁ and B²A₁–X²A₁ transitions.     

A High-Resolution C 3D CSA-CSA-CSA Correlation Experiment by Means of Magic Angle Turning

It is shown in this paper that a previously reported 90° sample flipping ¹³C 2D CSA-CSA correlation experiment may be carried out alternatively by employing constant slow sample rotation about the magic angle axis and by synchronizing the read pulse to of the rotor cycle. A high-resolution 3D CSA-CSA-CSA correlation experiment based on the magic angle turning technique is reported in which the conventional 90° 2D CSA-CSA powder pattern for each carbon in a system containing a number of inequivalent carbons may be separated according to the isotropic chemical shift value. The technique is demonstrated on 1,2,3-trimethoxybenzene in which all of the overlapping powder patterns that cannot be segregated by the 2D CSA-CSA experiment are resolved successfully by the 3D CSA-CSA-CSA experiment, including even the two methoxy groups (M₁ and M₃) whose isotropic shifts, confirmed by high-speed MAS, are separated by only 1 ppm. A difference of 4 ppm in the principal value component (δ₃₃) between M₁ and M₃ is readily obtained.     

Empirical revision of noise mapping

Following the Directive 2002/49/EC the European States shall apply the day–evening–night level, L_den, among others, for revision of the strategic noise mapping. Definition of L_den is based on A-weighted long term average sound levels, L_d, L_e, and L_n, which represent 365 days, evenings, and nights of a typical year. L_den approximation can be found from a few measurements of the A-weighted short term average sound levels, during the day-, evening-, and nights, L_di, L_ei, and L_ni, where i = 1, 2, … , m ? 365. The uncertainty of L_den approximation is calculated.