Synthetic methodologies in organic chemistry involving incorporation of [<sup>17</sup>O] and [<sup>18</sup>O] isotopes

Théodorou, Vassiliki; Skobridis, Konstantinos; Alivertis, Dimitrios; Gerothanassis, Ioannis P.

doi:10.1002/jlcr.3212

Cited by 25 publications

(15 citation statements)

References 225 publications

(278 reference statements)

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“…[62][63] These conditions prohibit acidcatalyzed exchange to be used for 17 O enrichment in protected amino acids or proteins, and therefore we have turned to an alternative procedure utilizing mild conditions and yielding 17 O/ 18 O isotopic enrichment efficiencies of >95%. 46,59,[62][63][64] Utilizing this approach, illustrated in The following reagents were purchased from Sigma Aldrich (St. Louis, MO), 1-ethyl-3-(3-dimethylaminopropyl)carboiimide hydrochloride (EDC • HCl), dimethylformamide (kept in a septum container), and 3,5-dimethylpyridine, which was then reacted with HBr (33% in acetic acid) to form 3,5-dimethylpyridine • HBr that was lyophilized to remove residual water. All Peptide, N-Ac-VL).…”

Section: Materials and Synthesismentioning

confidence: 99%

¹⁷O MAS NMR Correlation Spectroscopy at High Magnetic Fields

et al. 2017

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The structure of two protected amino acids, FMOC-l-leucine and FMOC-l-valine, and a dipeptide, N-acetyl-l-valyl-l-leucine (N-Ac-VL), were studied via one- and two-dimensional solid-state nuclear magnetic resonance (NMR) spectroscopy. Utilizing O magic-angle spinning (MAS) NMR at multiple magnetic fields (17.6-35.2 T/750-1500 MHz forH) the O quadrupolar and chemical shift parameters were determined for the two oxygen sites of each FMOC-protected amino acids and the three distinct oxygen environments of the dipeptide. The one- and two-dimensional,O, N-O, C-O, and H-O double-resonance correlation experiments performed on the uniformly C,N and 70% O-labeled dipeptide prove the attainability ofO as a probe for structure studies of biological systems. N-O and C-O distances were measured via one-dimensional REAPDOR and ZF-TEDOR experimental buildup curves and determined to be within 15% of previously reported distances, thus demonstrating the use of O NMR to quantitate interatomic distances in a fully labeled dipeptide. Through-space hydrogen bonding of N-Ac-VL was investigated by a two-dimensionalH-detected O R-R-INEPT experiment, furthering the importance of O for studies of structure in biomolecular solids.

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Section: Materials and Synthesismentioning

confidence: 99%

¹⁷O MAS NMR Correlation Spectroscopy at High Magnetic Fields

et al. 2017

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“…The most common approach to improving the sensitivity of 17 O NMR experiments is isotopic enrichment of oxygen-17, for which a variety of methods have been successfully demonstrated. 3,[27][28][29][30][31] More recently, it has been demonstrated that with the large NMR sensitivity enhancements provided by high-field dynamic nuclear polarization (DNP), [32][33][34] natural isotopic abundance 17 O NMR experiments can be performed on inorganic materials. 19, 23-24, 26, 35-36 The resolution of 17 O SSNMR spectra is most often improved either by utilizing selective 17 O labeling schemes, 37 working at the highest possible magnetic field strengths, 12,25,[38][39] or using multiple quantum magic angle spinning (MQMAS).…”

Section: Introductionmentioning

confidence: 99%

Probing O–H Bonding through Proton Detected¹H–¹⁷O Double Resonance Solid-State NMR Spectroscopy

et al. 2018

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The ubiquity of oxygen in organic, inorganic, and biological systems has stimulated the application and development of 17O solid-state NMR spectroscopy as a probe of molecular structure and dynamics. Unfortunately, 17O solid-state NMR experiments are often hindered by the combination of broad NMR signals and low sensitivity. Here, it is demonstrated that fast MAS and proton detection with the D-RINEPT pulse sequence can be generally applied to enhance the sensitivity and resolution of 17O solid-state NMR experiments. Complete 2D 17O→1H D-RINEPT correlation NMR spectra were typically obtained in fewer than 10 hours from less than 10 milligrams of material, with low to moderate 17O enrichment (less than 20%). 2D 1H-17O correlation solid-state NMR spectra allow overlapping oxygen sites to be resolved on the basis of proton chemical shifts or by varying the mixing time used for 1H-17O magnetization transfer. In addition, J-resolved or separated local field (SLF) blocks can be incorporated into the D-RINEPT pulse sequence to allow direct measurement of one-bond 1H-17O scalar coupling constants (1JOH) or 1H-17O dipolar couplings (DOH), respectively; the latter of which can be used to infer 1H-17O bond lengths. 1JOH and DOH calculated from planewave density functional theory (DFT) show very good agreement with experimental values. Therefore, the 2D 1H-17O correlation experiments, 1H-17O scalar and dipolar couplings, and planewave DFT calculations provide a method to precisely determine proton positions relative to oxygen atoms. This capability opens new opportunities to probe interactions between oxygen and hydrogen in a variety of chemical systems. Disciplines

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“…al. [19]. (TBDMS-Cl = tert -butyldimethylsilyl chloride; TMEDA = tetramethylethylenediamine, DMF = dimethylformamide)…”

Section: Highlightsmentioning

confidence: 99%

“…Moreover, we highlight only state-of-the-art syntheses for these substrates with an emphasis on methodologies that generate substrates isotopically enriched at a single atomic position. Interested readers should also consult excellent reviews by Theodorou et al [19] and Milecki [20], which contain a more complete account of isotopically labeled nucleotides.…”

Section: Introductionmentioning

confidence: 99%

Heavy atom labeled nucleotides for measurement of kinetic isotope effects

Weissman

York

et al. 2015

Biochimica et Biophysica Acta (BBA) - Proteins and Proteomics

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Experimental analysis of kinetic isotope effects represents an extremely powerful approach for gaining information about the transition state structure of complex reactions not available through other methodologies. Implementation of this approach to the study of nucleic acid chemistry requires the synthesis of nucleobases and nucleotides enriched for heavy isotopes at specific positions. In this review we highlight current approaches to the synthesis of nucleic acids site-specifically enriched for heavy oxygen and nitrogen and their application in heavy atom isotope effect studies.

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Synthetic methodologies in organic chemistry involving incorporation of [¹⁷O] and [¹⁸O] isotopes

Cited by 25 publications

References 225 publications

¹⁷O MAS NMR Correlation Spectroscopy at High Magnetic Fields

¹⁷O MAS NMR Correlation Spectroscopy at High Magnetic Fields

Probing O–H Bonding through Proton Detected¹H–¹⁷O Double Resonance Solid-State NMR Spectroscopy

Heavy atom labeled nucleotides for measurement of kinetic isotope effects

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Synthetic methodologies in organic chemistry involving incorporation of [17O] and [18O] isotopes

Cited by 25 publications

References 225 publications

17O MAS NMR Correlation Spectroscopy at High Magnetic Fields

17O MAS NMR Correlation Spectroscopy at High Magnetic Fields

Probing O–H Bonding through Proton Detected1H–17O Double Resonance Solid-State NMR Spectroscopy

Heavy atom labeled nucleotides for measurement of kinetic isotope effects

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Synthetic methodologies in organic chemistry involving incorporation of [¹⁷O] and [¹⁸O] isotopes

¹⁷O MAS NMR Correlation Spectroscopy at High Magnetic Fields

¹⁷O MAS NMR Correlation Spectroscopy at High Magnetic Fields

Probing O–H Bonding through Proton Detected¹H–¹⁷O Double Resonance Solid-State NMR Spectroscopy