Influence of low-barrier hydrogen bonds on solid state 17O NMR spectra of labelled phthalate species

Howes, A. P.; Jenkins, R.M.; Smith, Mark E.; Crout, David H. G.; Dupree, Ray

doi:10.1039/b104308k

Cited by 19 publications

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“…The sensitivity of the 17 O NMR parameters is well illustrated by a sample of valine that was initially 17 O-enriched and then subsequently reacted with 9-fluorenylmethoxycarbonyl (fmoc) to protect the oxygen-labeled sites during further synthesis. The 17 O MAS NMR spectrum again shows two clearly separated second-order quadrupolar line shapes, from the carbonyl and hydroxyl oxygens, but their parameters are significantly different from those of pure valine (Table 1). Figure 2a shows the spectrum of L-alanine hydrochloride, together with a simulation, which is similar to those of the other acid hydrochlorides with clearly resolved CdO and OH lines.…”

Section: Resultsmentioning

confidence: 88%

“…In a fashion similar to that of fmoc-protected valine the NMR parameters of fmoc-protected alanine are significantly different from those of the unprotected acid (Table 1); in particular for both protected acids the carbonyl shift is ∼25 ppm smaller than for the unprotected form. The 17 O MAS (Figure 7a) NMR spectrum from D-glutamic acid is more complex since the molecule has two inequivalent COOH groups so that there are two inequivalent carbonyl and hydroxyl groups in each unit cell. Hence, there are two resonances in both the carbonyl and hydroxyl regions.…”

Section: Resultsmentioning

confidence: 99%

“…It is entirely feasible that biomolecules comprising 50-100 amino acid residues enriched at one position could be observed by a combination of MAS and DOR. This capability would bring 17 O NMR data can be readily collected at reasonably high fields (14.1 T) from amino acids with good signal-to-noise ratios from samples where only 10-20 atom % 17 O enriched water was used in the sample preparation. Typical 17 O MAS NMR spectra consist of well-separated second-order quadrupole line shapes from the carbonyl and hydroxyl oxygens.…”

Section: Discussionmentioning

confidence: 99%

“…(a)17 O MAS NMR spectrum of l-alanine hydrochloride together with simulation, (b) MAS NMR spectrum of L-alanine together with simulation, and (c) DOR spectrum of L-alanine, outer rotor speed 1800 Hz.…”

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Solid-State ¹⁷O NMR of Amino Acids

et al. 2004

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17 O solid-state NMR from 14 amino acids is reported here, greatly increasing the number investigated. In most cases well-separated resonances from carbonyl and hydroxyl oxygens with distinct second-order quadrupolar line shapes are observed using a 600 MHz spectrometer with fast magic angle spinning (MAS). This is in contrast to the motionally averaged resonances usually seen from amino acids in solution. For amino acids double-angle rotation (DOR) produces a decrease in the line width by more than a factor of 40, providing very high resolution, ∼1 ppm, spectra. The oxygen lines in alanine and the carbonyl oxygens in L-glutamic acid hydrochloride are assigned using 1 H-decoupled DOR. The NMR interaction parameters for amino acids show a wide variation of Q , from 6.4 to 8.6 MHz, η, from 0.0 to 0.9, and δ iso , from 83 to 353 ppm. The high quality of the MAS NMR line shapes obtained at 14.1 T means that even small changes in parameters can be very accurately deduced, offering the possibility of 17 O NMR as a sensitive probe of structural changes in these and related compounds. The D-and L-forms of glutamic acid hydrochloride are shown to have the same NMR parameters to within error, which are very different from those reported in the literature for the D,L-form. A strong correlation (∼-1200 ppm/Å) is found between δ iso and the C-O bond length of the carbonyl oxygens. On the basis of these data, enriching specific amino acids in more complex polypeptides and proteins could provide site-selective information about the bonding and functionality of different sites in biomolecules. An estimate is made of the possible detection limit for such species.

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confidence: 99%

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Solid-State ¹⁷O NMR of Amino Acids

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“…The first two-dimensional (2D) 17 O MQMAS and DAS for organic materials were reported by Wu et al and Gann et al, respectively. Recently, 17 O DOR has been reported on amino acids and glutamic acid and 17 O MAS on phthalate compounds …”

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confidence: 99%

Experimental and Theoretical ¹⁷O NMR Study of the Influence of Hydrogen-Bonding on CO and O−H Oxygens in Carboxylic Solids

et al. 2006

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A systematic solid-state 17O NMR study of a series of carboxylic compounds, maleic acid, chloromaleic acid, KH maleate, KH chloromaleate, K2 chloromaleate, and LiH phthalate.MeOH, is reported. Magic-angle spinning (MAS), triple-quantum (3Q) MAS, and double angle rotation (DOR) 17O NMR spectra were recorded at high magnetic fields (14.1 and 18.8 T). 17O MAS NMR for metal-free carboxylic acids and metal-containing carboxylic salts show featured spectra and demonstrate that this combined, where necessary, with DOR and 3QMAS, can yield site-specific information for samples containing multiple oxygen sites. In addition to 17O NMR spectroscopy, extensive quantum mechanical calculations were carried out to explore the influence of hydrogen bonding at these oxygen sites. B3LYP/6-311G++(d,p) calculations of 17O NMR parameters yielded good agreement with the experimental values. Linear correlations are observed between the calculated 17O NMR parameters and the hydrogen bond strengths, suggesting the possibility of estimating H-bonding information from 17O NMR data. The calculations also revealed intermolecular H-bond effects on the 17O NMR shielding tensors. It is found that the delta11 and delta22 components of the chemical shift tensor at O-H and C=O, respectively, are aligned nearly parallel with the strong H-bond and shift away from this direction as the H-bond interaction weakens.

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NQRS Data for C8H5Li2O4.5 [C8H4Li2O4·1/2(H2O)] (Subst. No. 1059)

Chihara¹,

Nakamura²

2010

Landolt-Börnstein - Group III Condensed Matter

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Influence of low-barrier hydrogen bonds on solid state 17O NMR spectra of labelled phthalate species

Cited by 19 publications

References 20 publications

Solid-State ¹⁷O NMR of Amino Acids

Solid-State ¹⁷O NMR of Amino Acids

Experimental and Theoretical ¹⁷O NMR Study of the Influence of Hydrogen-Bonding on CO and O−H Oxygens in Carboxylic Solids

NQRS Data for C8H5Li2O4.5 [C8H4Li2O4·1/2(H2O)] (Subst. No. 1059)

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Influence of low-barrier hydrogen bonds on solid state 17O NMR spectra of labelled phthalate species

Cited by 19 publications

References 20 publications

Solid-State 17O NMR of Amino Acids

Solid-State 17O NMR of Amino Acids

Experimental and Theoretical 17O NMR Study of the Influence of Hydrogen-Bonding on CO and O−H Oxygens in Carboxylic Solids

NQRS Data for C8H5Li2O4.5 [C8H4Li2O4·1/2(H2O)] (Subst. No. 1059)

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Solid-State ¹⁷O NMR of Amino Acids

Solid-State ¹⁷O NMR of Amino Acids

Experimental and Theoretical ¹⁷O NMR Study of the Influence of Hydrogen-Bonding on CO and O−H Oxygens in Carboxylic Solids