The extended TORO technique was applied to the structural analysis of endo-D-Tyr-gramicidin S, cyclo(-Val-Orn-Leu-D-Phe-D-Tyr-Pro-Val-Orn-Leu-D-Phe-Pro-), which has a slightly distorted symmetry from C2, by the insertion of D-Tyr and equivalent alpha-proton chemical shifts in the 1H NMR spectrum. All NMR signals of the two dominant isomers of this antibiotic with trans-trans prolines were determined by using the extended TORO technique with TOCSY and ROESY spectra. This technique is generally applicable for distinguishing overlapped signals of alpha- and amide protons from the main chains of peptides. 相似文献
Two-dimensional 1H NMR experiments that achieve band-selective, homonuclear decoupling in both the indirectly detected F1 and directly detected F2 dimensions were used to assign the highly overlapped 1H NMR spectrum of the peptide Ac-SRGKARVRAKVKDQTK-NH2, both free in solution and bound to heparin. Band-selective, homonuclear decoupling during the evolution period was achieved using a double pulsed field gradient spin-echo (DPFGSE) with semi-selective shaped pulses; band-selective, homonuclear decoupling during the acquisition period was achieved by time-shared semi-selective shaped pulse decoupling. Regular TOCSY, ROESY and NOESY spectra and TOCSY, ROESY and NOESY spectra measured with band-selective, homonuclear decoupling in the evolution (F1) dimension (BASHD-TOCSY, ROESY and NOESY spectra) and with band-selective, homonuclear decoupling in both the F1 and F2 dimensions (D-(or Double)-BASHD-TOCSY, ROESY and NOESY spectra) are reported and compared for the peptide and its heparin complex. Complete assignment of the 1H-NMR spectra of the free and heparin-complexed peptide was achieved with the high resolution of the D-BASHD-TOCSY, ROESY and NOESY spectra. Characterization of the heparin-complexed peptide is of interest because of the ability of the peptide to neutralize the anticoagulant activity of heparin. 相似文献
A methodology for preparing supramolecular hydrogels from guest‐modified cyclodextrins (CDs) based on the host–guest and hydrogen‐bonding interactions of CDs is presented. Four types of modified CDs were synthesized to understand better the gelation mechanism. The 2D ROESY NMR spectrum of β‐CD‐AmTNB (Am=amino, TNB=trinitrobenzene) reveals that the TNB group was included in the β‐CD cavity. Pulsed field gradient NMR (PFG NMR) spectroscopy and AFM show that β‐CD‐AmTNB formed a supramolecular polymer in aqueous solution through head‐to‐tail stacking. Although β‐CD‐AmTNB did not produce a hydrogel due to insufficient growth of supramolecular polymers, β‐CD‐CiAmTNB (Ci=cinnamoyl) formed supramolecular fibrils through host–guest interactions. Hydrogen bonds between the cross‐linked fibrils resulted in the hydrogel, which displayed excellent chemical‐responsive properties. Gel‐to‐sol transitions occurred by adding 1‐adamantane carboxylic acid (AdCA) or urea. 1H NMR and induced circular dichroism (ICD) spectra reveal that AdCA released the guest parts from the CD cavity and that urea acts as a denaturing agent to break the hydrogen bonds between CDs. The hydrogel was also destroyed by adding β‐CD, which acts as the competitive host to reduce the fibrils. Furthermore, the gel changed to a sol by adding methyl orange (MO) as a guest compound, but the gel reappeared upon addition of α‐CD, which is a stronger host for MO. 相似文献
The assignment of the NMR spectra of the polynuclear heteroaromatic naphtho[2′,1′:5,6]naphtho‐[2′,1′:4,5]thieno[2,3‐c]quinoline is reported. The analysis was based on the homonuclear ROESY, heteronuclear direct GHSQC, IDR‐GHSQC‐TOCSY, and long‐range GHMBC experiments. The complete 1H and 13C shift assignments are reported. 相似文献
This paper reports the use of natural amino acids, the tripeptide β-strand mimic Hao, and the β-turn mimic δ-linked ornithine to generate water-soluble 54-, 78-, and 102-membered-ring macrolactams. These giant macrocycles were efficiently prepared by synthesis of the corresponding protected linear peptides, followed by solution-phase cyclization and deprotection. The protected linear peptide precursors were synthesized on 2-chlorotrityl chloride resin by conventional Fmoc-based solid-phase peptide synthesis. Macrocyclization was typically performed using HCTU and N,N-diisopropylethylamine in DMF at ca. 0.5 mM concentration. The macrocycles were isolated in 13-45% overall yield after HPLC purification and lyophilization. 1D, 2D TOCSY, and 2D ROESY (1)H NMR studies of the 54- and 78-membered-ring macrolactams establish that these compounds fold to form β-sheet structures in aqueous solutions. 相似文献
Three new pregnane glycosides, tinctorosides A–C ( 1 – 3 , resp.), together with one known pregnane glycoside, stephanoside B ( 4 ), were isolated from the stems of Marsdenia tinctoria R. Br . (Asclepiadaceae). Their structures were elucidated by extensive spectral methods, especially 2D‐NMR experiments (1H,1H‐COSY, HSQC, HMBC, TOCSY, HSQC‐TOCSY, and ROESY), and chemical evidence. 相似文献
In this paper, we describe an improved 2D selective‐TOCSY‐COSY experiment for the unambiguous assignment of an individual sugar component in oligosaccharides. We used a DQFCOSY with a pulsed‐field gradient instead of a conventional COSY in this improved experiment. The network of proton signals for a selected sugar in an oligosaccharide is observed as the diagonal peaks in the 2D spectrum by use of the first TOCSY period, and the correlation signals between J‐coupled neighboring protons are clearly observed as the cross peak, including the signals observed close to the diagonal peaks by the second DQFCOSY development. Even when the signals do not appear in a well‐separated form of a 1D spectrum, unambiguous sequential assignment of the proton signals of individual sugar components in an oligosaccharide is achieved by this method. 相似文献
The self‐diffusion (Dc) coefficients of various lanthanum(III) diamagnetic analogues of open‐chain and macrocyclic complexes of gadolinium used as MRI contrast agents were determined in dilute aqueous solutions (3–31 mM ) by pulsed‐field‐gradient (PFG) high‐resolution 1H‐NMR spectroscopy. The self‐diffusion coefficient of H2O (Dw) was obtained for the same samples to derive the relative diffusion constant, a parameter involved in the outersphere paramagnetic‐relaxation mechanism. The results agree with an averaged relative diffusion constant of 2.5 (±0.1)×10?9 and of 3.3 (±0.1)×10?9 m2 s?1 at 25 and 37°, respectively, for 'small' contrast agents (Mr 500–750 g/mol), and with the value of bulk H2O (2.2×10?9 and 2.9×10?9 m2 s?1 at 25° and at 37°, respectively) for larger complexes. The use of the measured values of Dc for the theoretical fitting of proton NMRD curves of gadolinium complexes shows that the rotational correlation times (τR) are very close to those already reported. However, differences in the electronic relaxation time (τSO) at very low field and in the correlation time (τV) related to electronic relaxation were found. 相似文献
Summary: Pulse field gradient‐NMR (PFG‐NMR) spectroscopy is determined to be a more suitable method for the investigation of self‐association processes in multi‐component (co)polymer systems than light scattering methods. Here the co‐micellization of mixtures of the diblock copolymer polystyrene‐block‐(hydrogenated polyisoprene) (PS‐HPI) and the triblock copolymer polystyrene‐block‐(hydrogenated polybutadiene)‐block‐polystyrene (PS‐HPB‐PS) in decane is investigated by PFG‐NMR spectroscopy and the results compared to those experimentally determined by static (SLS) and dynamic (DLS) light scattering. As expected, diffusion coefficients determined by PFG‐NMR spectroscopy are systematically lower than those from DLS. The PFG‐NMR measurements provided higher values of cequation/tex2gif-stack-1.gif(X)/ctot than the model calculations, illustrating that the basic assumption used in the calculations, i.e., that the number concentration of co‐micelles in mixed solutions follows the dilution with a triblock copolymer solution, 1 − X, is not fully valid at high X (weight fraction of PS‐HPB) values.
Comparison of PFG‐NMR spectroscopy and SLS (cequation/tex2gif-stack-2.gif/ctot = equilibrium concentration of free PS‐HPB‐PS over the total concentration of copolymers in solution, X = weight fraction of PS‐HPB). 相似文献
Four novel γ‐pyrone (=4H‐pyran‐4‐one) metabolites, petrorhagiosides A–D, along with four known analogs, have been isolated from the MeOH extract of Petrorhagia saxifraga, a perennial herbaceous plant typical of Mediterranean vegetation. The structures of the new compounds were established on the basis of extensive spectroscopic analyses including 1D‐ an 2D‐NMR (1H,1H‐DQ‐COSY, TOCSY, HSQC, CIGAR‐HMBC, and HSQC‐TOCSY) experiments. 相似文献