Beta-peptide explained

Beta-peptides (β-peptides) are peptides derived from β-amino acids, in which the amino group is attached to the β-carbon (i.e. the carbon two atoms away from the carboxylate group). The parent β-amino acid is β-alanine (H2NCH2CH2CO2H), a common natural substance, but most examples feature substituents in place of one or more C-H bonds. β-peptides usually do not occur in nature. β-peptide-based antibiotics are being explored as ways of evading antibiotic resistance.[1] Early studies in this field were published in 1996 by the group of Dieter Seebach[1] and that of Samuel Gellman.[2]

Structure

As there are two carbons available for substitution, β-amino acids have four sites (chirality included; as opposed to two in α-amino acids) for attaching the organic residue group. Accordingly, two main types β-amino acids exist differing by which carbon the residue is attached to: ones with the organic residue (R) next to the amine are called β3 and those with position next to the carbonyl group are called β2. A β-peptide can consist of only one kind of these amino acids (β2-peptides and β3-peptides), or have a combination of the two. Furthermore, a β-amino acid can form a ring using both of its sites and also be incorporated into a peptide.[3]

Synthesis

β-Amino acids have been prepared by many routes,[4] [5] including some based on the Arndt-Eistert synthesis.

Secondary structure

Because their backbones are longer than those of normal peptides, β-peptides form disparate secondary structures. The alkyl substituents at both the α and β positions in a β-amino acid favor a gauche conformation about the bond between the α-carbon and β-carbon. This also affects the thermodynamic stability of the structure.

Many types of helix structures consisting of β-peptides have been reported. These conformation types are distinguished by the number of atoms in the hydrogen-bonded ring that is formed in solution; 8-helix, 10-helix, 12-helix, 14-helix,[6] and 10/12-helix have been reported. Generally speaking, β-peptides form a more stable helix than α-peptides.[7]

Clinical potential

β-peptides are stable against proteolytic degradation in vitro and in vivo, a potential advantage over natural peptides.[8] β-Peptides have been used to mimic natural peptide-based antibiotics such as magainins, which are highly potent but difficult to use as drugs because they are degraded by proteolytic enzymes.[9]

Examples

β-amino acids with a wide variety of substituents exist. Named by analogy to the biological α-amino acids, the following have been found naturally: β-alanine, β-leucine, β-lysine, β-arginine, β-glutamate, β-glutamine, β-phenylalanine and β-tyrosine.[10] Of these, β-alanine is found in mammals and incorporated in pantothenic acid, an essential nutrient.[10] Two α-amino acids are also structurally β-amino acids: aspartic acid and asparagine.[10] Microcystins are a class of compounds containing a β-isoaspartyl (i.e. aspartic acid linked with its beta-carboxyl) residue.[10]

See also

Notes and References

  1. Seebach D, Overhand M, ((Kühnle FNM)), Martinoni B, Oberer L, Hommel U, Widmer H . June 1996 . β-Peptides: Synthesis by Arndt-Eistert homologation with concomitant peptide coupling. Structure determination by NMR and CD spectroscopy and by X-ray crystallography. Helical secondary structure of a -hexapeptide in solution and its stability towards pepsin . . 79 . 4 . 913–941 . 10.1002/hlca.19960790402.
  2. Appella DH, Christianson LA, Karle IL, Powell DR, Gellman SH. 1996. β-Peptide Foldamers: Robust Helix Formation in a New Family of -Amino Acid Oligomers. J. Am. Chem. Soc.. 118. 51. 13071–2. 10.1021/ja963290l.
  3. Seebach D, Matthews JL . β-Peptides: a surprise at every turn . . 21 . 2015–22 . 1997 . 10.1039/a704933a .
  4. Basler B, Schuster O, Bach T . Conformationally constrained β-amino acid derivatives by intramolecular [2 + 2]-photocycloaddition of a tetronic acid amide and subsequent lactone ring opening . J. Org. Chem. . 70 . 24 . 9798–808 . November 2005 . 16292808 . 10.1021/jo0515226.
  5. Murray JK, Farooqi B, Sadowsky JD . Efficient synthesis of a β-peptide combinatorial library with microwave irradiation . J. Am. Chem. Soc. . 127 . 38 . 13271–80 . September 2005 . 16173757 . 10.1021/ja052733v . etal.
  6. Vasantha. Basavalingappa. George. Gijo. Raghothama. Srinivasarao. Balaram. Padmanabhan. January 2017. Homooligomeric β3 (R)-valine peptides: Transformation between C14 and C12 helical structures induced by a guest Aib residue. Biopolymers. 108. 1. e22935. 10.1002/bip.22935. 1097-0282. 27539268. 205497333 . 2022-05-07. 2022-02-13. https://web.archive.org/web/20220213154445/https://pubmed.ncbi.nlm.nih.gov/27539268/. live.
  7. Gademann K, Hintermann T, Schreiber JV . Beta-peptides: twisting and turning . Curr. Med. Chem. . 6 . 10 . 905–25 . October 1999 . 10.2174/092986730610220401154606 . 10519905 . 247917035 .
  8. Beke T, Somlai C, Perczel A . Toward a rational design of β-peptide structures . J Comput Chem . 27 . 1 . 20–38 . January 2006 . 16247761 . 10.1002/jcc.20299. 35579693 .
  9. Porter EA, Weisblum B, Gellman SH . Mimicry of host-defense peptides by unnatural oligomers: antimicrobial β-peptides . . 124 . 25 . 7324–30 . 2002 . 10.1021/ja0260871 . 12071741.
  10. Book: Juaristi . E. . Soloshonok . Vadim A. . Enantioselective Synthesis of Beta-Amino Acids . 6 May 2005 . Wiley Inc. . 9780471698470 . Hoboken, New Jersey (NJ) . 559972352 . 7 May 2022 . 7 May 2022 . https://web.archive.org/web/20220507184706/https://www.google.co.in/books/edition/Enantioselective_Synthesis_of_Beta_Amino/WpgRvHGa0zIC?hl=en&gbpv=1&dq=8+beta+forms&pg=PA23 . live .