Synthesis and conformation of the cyclic octapeptides cyclo(Phe‐Pro)4, cyclo(Leu‐Pro)4, and cyclo[Lys(Z)‐Pro]4

Kimura, Shunsaku; Imanishi, Yukio

doi:10.1002/bip.360221006

Cited by 15 publications

(10 citation statements)

References 17 publications

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“…Therefore, the mobility of a helix segment in the wheel can be discussed on the basis of T 1 . 13 T 1 values of C of Ala and Lys, which are involved in the backbone of the helix, were compared. In mono9, which is a linear nonapeptide, T 1 values of C showed a tendency to increase from the central residue of the helical segment, Lys, to the terminal residue, Ala.…”

Section: Resultsmentioning

confidence: 99%

Unique Helical Triangle Molecular Geometry Induced by Dipole–Dipole Interactions

Ishikawa¹,

Morita²,

Kimura³

2007

Bulletin of the Chemical Society of Japan

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Novel helix-peptide wheels, in which three helices were connected by using a template, were prepared, and the dipole-dipole interactions among the helices were studied in relation to the formation of a planar triangle structure containing three helices. The helical segments had a 3 10 -helix structure.13 C spin-lattice relaxation time (T 1 ) measurements showed that the helical segments had restricted mobility. Deuterium exchange rates of amide protons were accelerated in the helix-peptide wheels compared to the respective linear helix peptides, suggesting that there is torsion on the cylindrical shape. Therefore, the predominant structure of the helix-peptide wheels is a planar triangle in solution. Further, the triangle structure was successfully transferred onto a gold substrate.Nano-science using organic molecules has attracted much attention in various fields. One key factor for the development of nano-science is to prepare organic molecules with well-determined geometry in terms of regio-and stereo-specificity, configuration, and conformation. Recently, a trend to use larger molecules has become prominent in the field of materials science with the aim to produce high-performance and highly functional materials. However, it becomes difficult to control the structure of larger molecules. Advancements in covalent chemistry contribute greatly to the preparation of well-specified large molecules, but secondary interactions, such as hydrogen bonds, 1 electrostatic interaction, 2 and CH-interaction, 3 etc., are also helpful to regulate the molecular shape. In the present study, another secondary interaction, dipole-dipole interaction, was examined for geometry regulation of three helices in one molecule.Proteins are typical examples for molecular architecture with a highly regulated structure. In nature, helix bundles are a common motif in proteins, and exhibit a variety of physiological activities, such as acting as ion channels. On the other hand, a helix triangle, in which three peptide helices were connected in a cyclic way by covalent bonds to generate a planar structure, was prepared as an unprecedented helix assembly. 4 Interestingly, the cyclization yield of the linear three peptide helices connected in a series was relatively high, suggesting that the dipole-dipole interaction may promote the cyclization probability via an attractive electrostatic force between the Nterminal with a partial positive charge and the C-terminal with a partial negative charge of the linear precursor peptide. We, therefore, designed a new helix triangle without covalent bonds between the N-terminal and the C-terminal but with dipole-dipole interaction acting between them.The molecular structures of the helix-peptide wheel, in which three helical peptides were connected by using the template molecule 1,3,5-benzenetricarboxylic acid through amidebond formation with the side chains of the Lys residues located in the middle of the helical peptide chains, are shown in Fig. 1. The three helices either nonapeptide or hexapeptide can ...

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Section: Resultsmentioning

confidence: 99%

Unique Helical Triangle Molecular Geometry Induced by Dipole–Dipole Interactions

Ishikawa¹,

Morita²,

Kimura³

2007

Bulletin of the Chemical Society of Japan

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“…Assuming re = 'R and proportionality between a 3 and the molecular weight, NT 1 is inversely proportional to the molecular weight. 22 as that of I, respectively. That is to say, the contribution of 'g to re can almost be neglected, though the small difference of NT 1 between 2 and 3 having the same molecular weight is considered due to difference in steric hindrance between iso-and sec-butyl groups.…”

Section: Smentioning

confidence: 99%

“…In these cases, macrocycle concentrations are disregarded, though NT 1 increases slightly with decrease of peptide concentration. 22 …”

Section: Smentioning

confidence: 99%

Conformations of 24-Membered Ring Pseudopeptides Containing N,N′-Ethylene-Bridged Dipeptides Constructed from (S)-Alanine, -Leucine, -Isoleucine, and -Phenylalanine

Kojima

Goto

Yamashita

1994

Polym J

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ABSTRACT:24-Membered ring pseudopeptides, cyclo[Gly-eXX-Gly] 2 { eXX; N,N'-ethylenebridged dipeptide, X=(S)-alanine(A), -leucine(L), -isoleucine(I), and -phenylalanine(F)} and cyclo[Sar-eXX-GlyJi {X = (S)-A and -F} were prepared and their conformations were investigated by 1 H and 13 C NMR spectroscopy in dimethylsulfoxide-d6• It was found from NMR measurements that the major conformers (~90% abundance) of the four cyclo[Gly-eXX-Gly] 2 and major ones ("' 70%) of the two cyclo[Sar-eXX-Gly ] 2 have C2-symmetric structures, in which all peptide bonds of cyclo[Gly-eXX-Gly] 2 (X=A, L, and I) and cyclo[Sar-eAA-Gly] 2 are trans, while two Gly-eFF peptide bonds of cyclo[Gly-eFF-Gly] 2 and two Sar-eFF ones of cyclo[SareFF-Gly]2 are cis though the other peptide bonds are trans. 13 C spin-lattice relaxation times (T1) of all macrocycles showed small contribution of segmental mobility to T1 . The structures of cyclo[Gly-eAA-GlyJi and cyclo[Sar-eAA-Gly] 2 were optimized by molecular mechanics on the basis of NMR data.

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“…A limited number of crystallographic data of cyclooctapeptides are reported in the literature, and in all cases they concern chemically and structurally symmetrical compounds 4–17. In addition to these, only few asymmetric cyclic octapeptides have been characterized in solution 18–21.…”

Section: Introductionmentioning

confidence: 99%

Solid state structural analysis of the cyclooctapeptide cyclo- (Pro1-Pro-Phe-Phe-Ac6c-Ile-D-Ala-Val8)

et al. 2000

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Synthesis and conformation of the cyclic octapeptides cyclo(Phe‐Pro)₄, cyclo(Leu‐Pro)₄, and cyclo[Lys(Z)‐Pro]₄

Cited by 15 publications

References 17 publications

Unique Helical Triangle Molecular Geometry Induced by Dipole–Dipole Interactions

Unique Helical Triangle Molecular Geometry Induced by Dipole–Dipole Interactions

Conformations of 24-Membered Ring Pseudopeptides Containing N,N′-Ethylene-Bridged Dipeptides Constructed from (S)-Alanine, -Leucine, -Isoleucine, and -Phenylalanine

Solid state structural analysis of the cyclooctapeptide cyclo- (Pro1-Pro-Phe-Phe-Ac6c-Ile-D-Ala-Val8)

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