Complete Analysis of the 1H and 13C NMR Spectra of 5-Isopropylsulfonyl-2-Norbornenes Through the Application of Two-Dimensional NMR Techniques

Total assignment of ¹³C and ¹H NMR spectra of the 5-isopropylsulfonyl-2-norbornenes 2 was achieved using the concerted application of two-dimensional homonuclear and heteronuclear chemical shift correlations. The stereochemistry of both the diastereoisomers endo 2a and exo 2b have been established using the magnitude of the proton coupling constants.     

Selective dephasing of OH and NH proton magnetization based on (1)H chemical-shift anisotropy recoupling

A method for selectively suppressing the signals of OH and NH protons in (1)H combined rotation and multiple-pulse spectroscopy (CRAMPS) and in (1)H-(13)C heteronuclear correlation (HETCOR) solid-state NMR spectra is presented. It permits distinction of overlapping CH and OH/NH proton signals, based on the selective dephasing of the magnetization of OH and NH protons by their relatively large (1)H chemical-shift anisotropies. For NH protons, the (14)N-(1)H dipolar coupling also contributes significantly to this dephasing. The dephasing is achieved by a new combination of heteronuclear recoupling of these anisotropies with (1)H homonuclear dipolar decoupling. Since the 180 degrees pulses traditionally used for heteronuclear dipolar and chemical-shift anisotropy recoupling would result in undesirable homonuclear dephasing of proton magnetization, instead the necessary inversion of the chemical-shift Hamiltonian every half rotation period is achieved by inverting the phases of all the pulses in the HW8 multiple-pulse sequence. In the HETCOR experiments, carefully timed (13)C 180 degrees pulses remove the strong dipolar coupling to the nearby (13)C spin. The suppression of NH and OH peaks is demonstrated on crystalline model compounds. The technique in combination with HETCOR NMR is applied to identify the CONH and NH-CH groups in chitin and to distinguish NH and aromatic proton peaks in a peat humin.     

取代基效应对二芳基硝酮CH=N(O)桥基1H NMR化学位移的影响

合成一系列取代二芳基硝酮XArCH=N（O）ArY化合物,测定其核磁共振氢谱（¹H NMR）,指认出桥基CH=N（O）上质子的化学位移δH[CH=N（O）],定量研究取代基效应对δH[CH=N（O）]的影响.得到一个4参数定量方程,标准偏差（S）为0.020,较好地表达了δH[CH=N（O）]的变化规律.结果表明,该类化合物的δH[CH=N（O）]主要受4个因素影响：X基团的场/诱导效应[σ_F（X）];Y基团的共轭效应[σ_R（X）];基团X和Y之间的特殊交叉作用（Δσ²）;以及基团X和O^-之间的特殊交叉作用[Δσ²_（X-O^-）].其中,Δσ²_（X-O^-）对δ_{H[CH=N（O）]}变化的贡献超过70%.通过δH[CH=N（O）]与二芳基希夫碱XArCH=NArY桥基CH=N上质子化学位移的δH（CH=N）比较发现,这两类化合物桥基上质子的化学位移之间没有良好的线性关系.因而,在应用NMR谱图解析有机化合物分子结构时,不能简单地用δH（CH=N）的变化去类比δ_{H[CH=N（O）]}的变化.     

14N chemical shifts and quadrupole coupling constants of inorganic nitrates

The isotropic chemical shift and the nuclear quadrupole coupling constant for (14)N were obtained for 14 inorganic nitrates by solid-state MAS NMR measurements at two different field strengths, 9.4 and 11.7 T. The compounds studied were polycrystalline powders of AgNO(3), Al(NO(3))(3), Ba(NO(3))(2), Ca(NO(3))(2), CsNO(3), KNO(3), LiNO(3), Mg(NO(3))(2), NaNO(3), Pb(NO(3))(2), RbNO(3), Sr(NO(3))(2), Th(NO(3))(4)center dot4H(2)O, and UO(2)(NO(3))(2)center dot3H(2)O. Even though the spectra show broadening due to (14)N quadrupole interactions, linewidths of a few hundred hertz and a good signal-to-noise ratio were achieved. From the position of the central peaks at the two fields, the chemical shifts and the nuclear quadrupole coupling constants were calculated. The chemical shifts for all compounds studied range from 282 to 342 ppm with respect to NH(4)Cl. The nuclear quadrupole coupling constants range from 429 kHz for AgNO(3) to 993 kHz for LiNO(3). These data are compared with those available in the literature.     

Recoupled polarization-transfer methods for solid-state (1)H--(13)C heteronuclear correlation in the limit of fast MAS

An in-depth account of the effects of homonuclear couplings and multiple heteronuclear couplings is given for a recently published technique for (1)H--(13)C dipolar correlation in solids under very fast MAS, where the heteronuclear dipolar coupling is recoupled by means of REDOR pi-pulse trains. The method bears similarities to well-known solution-state NMR techniques, which form the framework of a heteronuclear multiple-quantum experiment. The so-called recoupled polarization-transfer (REPT) technique is versatile in that rotor-synchronized (1)H--(13)C shift correlation spectra can be recorded. In addition, weak heteronuclear dipolar coupling constants can be extracted by means of spinning sideband analysis in the indirect dimension of the experiment. These sidebands are generated by rotor encoding of the reconversion Hamiltonian. We present generalized variants of the initially described heteronuclear multiple-quantum correlation (HMQC) experiment, which are better suited for certain applications. Using these techniques, measurements on model compounds with (13)C in natural abundance, as well as simulations, confirm the very weak effect of (1)H--(1)H homonuclear couplings on the spectra recorded with spinning frequencies of 25--30 kHz. The effect of remote heteronuclear couplings on the spinning-sideband patterns of CH(n) groups is discussed, and (13)C spectral editing of rigid organic solids is shown to be practicable with these techniques.     

Multi-dimensional 1H-13C HETCOR and FSLG-HETCOR NMR study of sphingomyelin bilayers containing cholesterol in the gel and liquid crystalline states

(13)C cross polarization magic angle spinning (CP-MAS) and (1)H MAS NMR spectra were collected on egg sphingomyelin (SM) bilayers containing cholesterol above and below the liquid crystalline phase transition temperature (T(m)). Two-dimensional (2D) dipolar heteronuclear correlation (HETCOR) spectra were obtained on SM bilayers in the liquid crystalline (L(alpha)) state for the first time and display improved resolution and chemical shift dispersion compared to the individual (1)H and (13)C spectra and significantly aid in spectral assignment. In the gel (L(beta)) state, the (1)H dimension suffers from line broadening due to the (1)H-(1)H homonuclear dipolar coupling that is not completely averaged by the combination of lipid mobility and MAS. This line broadening is significantly suppressed by implementing frequency switched Lee-Goldburg (FSLG) homonuclear (1)H decoupling during the evolution period. In the liquid crystalline (L(alpha)) phase, no improvement in line width is observed when FSLG is employed. All of the observed resonances are assignable to cholesterol and SM environments. This study demonstrates the ability to obtain 2D heteronuclear correlation experiments in the gel state for biomembranes, expands on previous SM assignments, and presents a comprehensive (1)H/(13)C NMR assignment of SM bilayers containing cholesterol. Comparisons are made to a previous report on cholesterol chemical shifts in dimyristoylphosphatidylcholine (DMPC) bilayers. A number of similarities and some differences are observed and discussed.     

REDOR-determined distances from heterospins to clusters of 13C labels

The use of rotational-echo double resonance NMR to measure distances from an observed tightly coupled cluster of 13C spins to a distant 15N, 31P, or 19F is practical if all homonuclear 13C-13C dipolar interactions are suppressed by multiple-pulse decoupling during heteronuclear dipolar evolution. This scheme is first calibrated by experiments performed on multiply labeled alanines and then applied in the measurement of 19F-13C distances in p-trifluoromethylphenyl [1,2-13C2]acetate.     

NMR Studies of Hindered Rotation. The Diels-Alder Adduct of Phencyclone with N-n-Propylmaleimide: Restricted Motion of Bridgehead Phenyls

The Diels-Alder adduct of phencyclone and N-n-propylmaleimide has been studied in CDCl₃ solution at ambient temperatures by one-and two-dimensional ¹H NMR (300 MHz) and ¹³C NMR (75 MHz) techniques. Clear evidence is presented from slow exchange limit (SEL) spectra for hindered rotation of the bridgehead phenyls in the adduct. Full ¹H spectral assignments have been made via selective homonuclear decoupling and high resolution COSY experiments. The number of signals in the aryl region of ¹³C NMR spectra also indicated slow rotation about the C(sp²)-C(sp³) bond to the unsubstantiated bridgehead phenyls. Striking evidence of magnetic anisotropic effects, seen from ¹H NMR, permits stereochemical assignment of the adduct as endo.     

Three-dimensional through-bond homonuclear-heteronuclear correlation experiments for quadrupolar nuclei in solid-state NMR applied to (27)Al-O-(31)P-O-(27)Al networks

We present here the first 3D homonuclear/heteronuclear correlation experiment applied to quadrupolar nuclei and making use of the sole scalar J-coupling. This experiment, based on the 2D-Homonuclear-Heteronuclear Single Quantum Correlation (H-HSQC) experiment, uses a relayed transfer from the (27)Al central transition to neighbouring (31)P spins and to the central transition of a second (27)Al. It confirms the correlation map characterizing the two (27)Al and the (31)P NMR signatures of (27)Al-O-(31)P-O-(27)Al chemically bonded molecular motifs.     

Determination of J coupling constants between spin-1/2 and quadrupolar nuclei in inorganic solids from spin echo and refocused INEPT experiments: a case study on AlPO₄ berlinite

A systematic study utilizing rotor-synchronized homonuclear ((31)P, (27)Al) and heteronuclear ({(31)P}(27)Al and {(27)Al}(31)P) spin echo, and {(27)Al}(31)P refocused INEPT experiments (employing soft pulses for selective excitation of the central transition for the quadrupolar (27)Al (I=5/2)) have been performed on AlPO(4) berlinite at 30 kHz MAS to better understand the J modulation behavior involving half-integer quadrupolar nuclei in solid materials with framework structure. Analyses of the J modulation on either the (27)Al or (31)P coherence in both the {(31)P}(27)Al and {(27)Al}(31)P spin echo experiments, and both periods of the refocused INEPT experiment yield consistent results for the (2)J(AlP) (Al-O-P) coupling constant (ca. 25 Hz). It is noted that the coupling of each (27)Al to four (31)P spins during the first ((27)Al) evolution period of the refocused INEPT, and the populations of (31)P coupled to different numbers (0-4) of (27)Al in the ± 1/2 Zeeman states during (31)P coherence evolution, which have been neglected in previous studies, must be taken into account for proper treatment. Analysis of J modulation on the spin ((27)Al) coupled to spin-1/2 nuclei in general gives more accurate results. Weak long-range homonuclear (4)J(PP) (P-O-Al-O-P) coupling was also observed from the (31)P spin echo and INADEQUATE experiments.     

Inhomogeneity-free heteronuclear iMQC

Intermolecular dipolar interactions between proton and carbon spins can be used to indirectly detect carbon spectra with high sensitivity. In this communication, we present a modified sequence that, in addition to the high sensitivity of heteronuclear intermolecular multiple quantum coherence (iMQC) experiments, retains the line narrowing capability characteristic of homonuclear zero-quantum coherences. We demonstrate that this sequence can be used to obtain high resolution (13)C spectra in the presence of magnetic field inhomogeneities, both for thermal and hyperpolarized samples, and discuss applications to water-hyperpolarized carbon imaging.     

TOTAL ASSIGNMENT OF 1H AND 13C NMR SPECTRA OF A BRIDGED TRIRUTHENIUM CLUSTER-POLYPYRIDINE DIMER BASED ON 2D (COSY,HMQC, AND HMBC) TECHNIQUES

The bridged ruthenium cluster-polypyridine dimer [Ru₃O(CH₃COO)₆(py)₂(tmbpy)Ru(bpy)₂(Cl)](PF₆)₂ (py = pyridine, = 2, 2′-bipyridine and tmbpy = 4, 4′-trimethylenedipyridine) has been synthesized and structurally characterized based on ¹H and ¹³C NMR spectroscopy. This species exhibits a complex pattern of NMR signals due to the presence of a paramagnetic [Ru₃O] core and seven non-equivalent aromatic rings. 2D NMR (COSY, HMQC and HMBC) correlation techniques have been required for the total assignment of the ¹H and ¹³C NMR spectra.     

Structural Assignment of Isomeric S‐ and S,N‐1‐Alkoxycarbonylalkylated 6‐Amino‐2‐thiouracil Derivatives by Means of 1H and 13C NMR Spectroscopy

Abstract

The structures of new isomeric 2‐alkoxycarbonylalkylthio‐ and 2‐alkoxy‐ carbonylalkylthio‐1‐alkoxycarbonylalkyl‐6‐aminouracils (1–21) have been established on the basis of the ¹H NMR and ¹³C NMR spectroscopic data. The ¹H NMR and ¹³C NMR spectra of 1–21 have been fully assigned by a combination of two‐dimensional experiments [heteronuclear multiple quantum coherence (HMQC) and heteronuclear multiple bond correlation (HMBC)]. The ¹³C NMR spectra have been shown to be able to differentiate between isomers.     

Sensitivity enhancement, assignment, and distance measurement in 13C solid-state NMR spectroscopy for paramagnetic systems under fast magic angle spinning

Despite success of previous studies, high-resolution solid-state NMR (SSNMR) of paramagnetic systems has been still largely unexplored because of limited sensitivity/resolution and difficulty in assignment due to large paramagnetic shifts. Recently, we demonstrated that an approach using very-fast magic angle spinning (VFMAS; spinning speed 20kHz) enhances resolution/sensitivity in (13)C SSNMR for paramagnetic complexes [Y. Ishii, S. Chimon, N.P. Wickramasinghe, A new approach in 1D and 2D (13)C high resolution solid-state NMR spectroscopy of paramagnetic organometallic complexes by very fast magic-angle spinning, J. Am. Chem. Soc. 125 (2003) 3438-3439]. In this study, we present a new strategy for sensitivity enhancement, signal assignment, and distance measurement in (13)C SSNMR under VFMAS for unlabeled paramagnetic complexes using recoupling-based polarization transfer. As a robust alternative of cross-polarization (CP), rapid application of recoupling-based polarization transfer under VFMAS is proposed. In the present approach, a dipolar-based analog of INEPT (dipolar INEPT) methods is used for polarization transfer and a (13)C signal is observed under VFMAS without (1)H decoupling. The resulting low duty factor permits rapid signal accumulation without probe arcing at recycle times ( approximately 3 ms/scan) matched to short (1)H T(1) values of small paramagnetic systems ( approximately 1 ms). Experiments on Cu(dl-Ala)(2) showed that the fast repetition approach under VFMAS provided sensitivity enhancement by a factor of 8-66 for a given sample, compared with the (13)C MAS spectrum under moderate MAS at 5kHz. The applicability of this approach was also demonstrated for a more challenging system, Mn(acac)(3), for which (13)C and (1)H paramagnetic shift dispersions reach 1500 and 700 ppm, respectively. It was shown that effective-evolution-time dependence of transferred signals in dipolar INEPT permitted one to distinguish (13)CH, (13)CH(2), (13)CH(3), (13)CO2- groups in 1D experiments for Cu(DL-Ala)(2) and Cu(Gly)(2). Applications of this technique to 2D (13)C/(1)H correlation NMR under VFMAS yielded reliable assignments of (1)H resonances as well as (13)C resonances for Cu(DL-Ala)(2) and Mn(acac)(3). Quantitative analysis of cross-peak intensities in 2D (13)C/(1)H correlation NMR spectra of Cu(DL-Ala)(2) provided distance information between non-bonded (13)C-(1)H pairs in the paramagnetic system.     

1,2-二氢-4-苯基(2H)二氮杂萘酮的NMR谱研究

报道了1,2-二氢-2-(4-氨基苯基)-4-[4-(4-氨基苯氧基)苯基](2H)二氮杂萘-1-酮的合成,并用2D同核化学位移相关谱(¹H,¹H-COSY),2DROESY谱,2D异核¹³C-¹H相关谱和2D异核¹³C-¹H多键相关谱(HMBC)对该化合物的¹H和¹³C NMR谱进行了完整归属,证明了此化合物是含二氮杂萘酮结构,而不是二氮杂萘醚结构.     

Three-dimensional 13C shift/1H-15N coupling/15N shift solid-state NMR correlation spectroscopy.

Triple-resonance experiments capable of correlating directly bonded and proximate carbon and nitrogen backbone sites of uniformly 13C- and 15N-labeled peptides in stationary oriented samples are described. The pulse sequences integrate cross-polarization from 1H to 13C and from 13C to 15N with flip-flop (phase and frequency switched) Lee-Goldburg irradiation for both 13C homonuclear decoupling and 1H-15N spin exchange at the magic angle. Because heteronuclear decoupling is applied throughout, the three-dimensional pulse sequence yields 13C shift/1H-15N coupling/15N shift correlation spectra with single-line resonances in all three frequency dimensions. Not only do the three-dimensional spectra correlate 13C and 15N resonances, they are well resolved due to the three independent frequency dimensions, and they can provide up to four orientationally dependent frequencies as input for structure determination. These experiments have the potential to make sequential backbone resonance assignments in uniformly 13C- and 15N-labeled proteins.     

Dipolar coupling information in multispin systems: application of a compensated REDOR NMR approach to inorganic phosphates. Rotational echo double resonance

An experimental strategy has been developed for measuring multiple dipole-dipole interactions in inorganic compounds using the technique of rotational echo double resonance (REDOR) NMR. Geometry-independent information about the dipole couplings between the observe nuclear species S (arbitrary quantum number) and the heteronuclear species I (spin-12) can be conveniently obtained from the experimental curve of DeltaS/S(0) versus dipolar evolution time by limiting the analysis to the initial data range 0 < delta S/S(0) < 0.30. Numerical simulations have been carried out on a three-spin system of type SI(2) in order to assess the effect of the I-I homonuclear dipole-dipole coupling and the influence of experimental imperfections such as finite pulse length and misadjustments of the 180 degrees pulses applied to the I-spin species. The simulations show further that within the initial data range the effects of such misadjustments can be internally compensated by a modified sequence having an additional 180 degrees pulse on the I channel in the middle of the dipolar evolution periods. Experimental (27)Al?(31)P? REDOR results on the multispin systems Al(PO(3))(3), AlPO(4), [AlPO(4)](12)(C(3)H(7))(4)NF, and Na(3)PO(4) confirm the general utility of this approach. Thus, for applications to unknown systems the compensation strategy obviates calibration procedures with model compounds.     

三种不同的钒氧簇合物的合成和光谱研究

利用水热法合成了三种钒氧簇合物：[{Ni(phen)₂}₂V₄O₁₂]H₂O (Ⅰ),[N(CH₂CH₂)₃NH]Na(H₂O)₆{K₄(H₂O)₄ [V₁₀O₂₈]}(H₂O)₄ (Ⅱ)和[(CH₃)₄N]₆[V₁₅O₃₆Cl] (Ⅲ)。通过用FTIR, UV-Vis DRS和荧光光谱研究了它们的结构和性能的关系。FTIR研究表明,化合物的相关基团的特征振动吸收峰和其结构相关。化合物Ⅰ的固体紫外漫反射光谱在200, 230, 260和350 nm出现四个宽峰,分别对应O_t→V, O_μ→Ni,O_μ→V荷移和phen的π-π*跃迁。文章还对这三个钒氧簇合物的荧光光谱进行了研究。最后,应用Gaussian98的量子化学计算,说明化合物Ⅰ的结构特点。     

Spin-edited 2D HSQC-TOCSY experiments for the measurement of homonuclear and heteronuclear coupling constants: application to carbohydrates and peptides

Simple modifications of the sensitivity-improved HSQC-TOCSY pulse sequence are proposed for the easy determination of the sign and the magnitude of homonuclear and heteronuclear coupling constants. Whereas in well-resolved regions, a clean two-component E.COSY-like pattern allows a direct measurement from a single 2D spectrum, separate acquisition of equivalent single-component TROSY/anti-TROSY spectra becomes highly interesting when spectral crowding complicates the spectral analysis. It is also demonstrated that an additional restricted planar mixing element after the isotropic TOCSY process completely retains all spin-editing features and permits the accurate measurement of the sign and the size of the corresponding homonuclear proton-proton coupling constants. Among others, the proposed techniques are particularly suited for molecules presenting a great number of CH and NH spin systems. Examples and practical details of the implementation of these techniques on standard carbohydrates and peptides at 13C and 15N natural abundance are provided.     

2D separated-local-field spectra from projections of 1D experiments

A novel procedure for reconstruction of 2D separated-local-field (SLF) NMR spectra from projections of 1D NMR data is presented. The technique, dubbed SLF projection reconstruction from one-dimensional spectra (SLF-PRODI), is particularly useful for uniaxially oriented membrane protein samples and represents a fast and robust alternative to the popular PISEMA experiment which correlates (1)H-(15)N dipole-dipole couplings with (15)N chemical shifts. The different 1D projections in the SLF-PRODI experiment are obtained from 1D spectra recorded under influence of homonuclear decoupling sequences with different scaling factors for the heteronuclear dipolar couplings. We demonstrate experimentally and numerically that as few as 2-4 1D projections will normally be sufficient to reconstruct a 2D SLF-PRODI spectrum with a quality resembling typical PISEMA spectra, leading to significant reduction of the acquisition time.