NMR investigations on alanyl‐[15% 13C, 95% 15N]‐proline: 15N chemical shifts and 13C15N coupling constants

Blomberg, F.; Rüterjans, Heinz; Lintner, Karl; Toma, Flavio; Fermandjian, Serge

doi:10.1002/mrc.1270111204

Cited by 15 publications

(5 citation statements)

References 14 publications

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“…The dipeptide alanylproline, which from studies of both 13C (Evans & Rabenstein, 1974;Gierasch et al, 1982) and 15N (Blomberg et al, 1978) spectra, has been reported to undergo slow cis-trans isomerism, being approximately 35% as the cis isomer. 15N NMR spectra of the zwitterion of Ala-[15N]Pro showed two lines separated by 0.8 ppm (32 Hz at 9.4 T) at 30 °C, a similar result to that obtained for iV-formyl-and jV-acetylproline (Hawkes et al, 1975).…”

Section: Resultsmentioning

confidence: 99%

.lambda. cro Repressor complex with OR3 DNA: nitrogen-15 NMR observations

Leighton¹,

Lu²

1987

Biochemistry

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15N NMR studies of the coliphage lambda cro repressor are presented. The protein has been uniformally labeled with 15N, and individual amino acids have been incorporated. Although the four C-terminal residues (63-66) were not located in the original crystallographic studies of the protein [Anderson, W.F., Ohlendorf, D.H., Takeda, Y., & Matthews, B.W. (1981) Nature (London) 290, 754], it has been proposed that the C-terminus is involved in DNA binding [Ohlendorf, D.H., Anderson, W.F., Fisher, R.G., Takeda, Y., & Matthews, B.W. (1982) Nature (London) 298, 718]. These experiments give direct verification of that proposal. [15N]Amide resonances are assigned for residues 56, 62, 63, and 66 in the C-terminus by enzymatic digestion and by 13C-15N double-labeling experiments. 15N[1H] nuclear Overhauser effects show that the C-terminus is mobile on a nanosecond time scale. Exchange experiments using distortionless enhancement via polarization transfer, which is sensitive to proton exchange on the 1/JNH (10 ms) time scale, indicate that the amide protons in the C-terminus are freely accessible to solvent. It is thus a flexible arm in solution. The binding of both specific operator and nonspecific DNA is shown to reduce both the mobility and the degree of solvent exposure of this arm. Two-dimensional 15N-1H correlation experiments using 15N-labeled cro reveal inconsistencies with previously reported 1H NMR assignments for the lysine amides [Weber, P.L., Wemmer, D.E., & Reid, B.R. (1985) Biochemistry 24, 4553]. This result suggests that those assignments require reexamination, illustrating the utility of 15N labeling for obtaining 1H resonance assignments of biomolecules. Furthermore, isomerization of the peptide bond of Pro-59, which has been previously suggested (Weber et al., 1985) and which would significantly affect the properties of the C-terminal arm, is shown to not occur.

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Section: Resultsmentioning

confidence: 99%

.lambda. cro Repressor complex with OR3 DNA: nitrogen-15 NMR observations

Leighton¹,

Lu²

1987

Biochemistry

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“…This is the case, for instance, of prolines [28], substituted benzaldoximes [29], and cyclic model peptides [30]. Besides, it is hoped that a detailed knowledge of the solvent effects on each separate component may clarify the points discussed by Kricheldorf [9].…”

Section: F One-and Two-bond C-n Couplingsmentioning

confidence: 97%

A theoretical study of medium effects on the transmission mechanisms of the fermi contact term of spin–spin coupling constants in the acetamide molecule

Facelli

Giribet

Contreras

1984

Int J of Quantum Chemistry

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Solvent effects on different transmission mechanisms of spin-spin coupling constants are analyzed from a theoretical viewpoint. Medium effects are introduced using the solvaton model, and 'the decomposition of coupling constants in u-and n-electron transmitted components is accomplished with the PRMO method. Trends thus obtained are in fairly good agreement with experimental findings reported in the literature. In all types of couplings studied in this work, cr and T components show opposite behavior when increasing the polarity of the solvent.

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“…In the times when robust water suppression techniques were still absent, 21 the pK a values for the rotameric states were determined by means of 13 C, 15 N and 17 O NMR, delivering results with a certain degree of discrepancy. 19,22,23 Fig. 1 The np* interaction in a polypeptide chain.…”

Section: Introductionmentioning

confidence: 99%

Energetic contribution to both acidity and conformational stability in peptide models

2016

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The acidity of N-acyl amino acids is dependent upon the rotameric state of the amide bond. In this work we systematically investigated the acidity difference of the rotamers (Delta pK(a)) in the frames of various acetylated amino acids. Our results indicated a mutual interaction of two carbonyl groups of an attractive type. We observed conservative Delta pK(a)s for acyclic amino acids (2.2-3.0 kJ mol(-1)), whereas in the case of alicyclic amino acids, the experimental values revealed a strong dependency on the structural context (1.5-4.4 kJ mol(-1)). In homologous amino acids (alpha-, beta-, gamma-, etc.), the strength of the attraction decays in an exponential fashion. Furthermore, the interaction can accumulate through a chain of amide bonds in a cascade fashion, as demonstrated by an Ac-Pro-Pro dipeptide. As a result, we demonstrate that Delta pK(a) is an experimental parameter to estimate increments in the carbonyl-carbonyl alignment, as determined by the amino acid or peptidyl context. This parameter is also important in understanding the roles of amino acids in both protein folding and translation in biological systems as well as their evolutionary appearance in the genetic code.DFG, EXC 314, Unifying Concepts in Catalysi

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NMR investigations on alanyl‐[15% ¹³C, 95% ¹⁵N]‐proline: ¹⁵N chemical shifts and ¹³C¹⁵N coupling constants

Cited by 15 publications

References 14 publications

.lambda. cro Repressor complex with OR3 DNA: nitrogen-15 NMR observations

.lambda. cro Repressor complex with OR3 DNA: nitrogen-15 NMR observations

A theoretical study of medium effects on the transmission mechanisms of the fermi contact term of spin–spin coupling constants in the acetamide molecule

Energetic contribution to both acidity and conformational stability in peptide models

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