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31.
Dr. Timothy A. Hill Dr. Nicholas E. Shepherd Dr. Frederik Diness Prof. Dr. David P. Fairlie 《Angewandte Chemie (International ed. in English)》2014,53(48):13020-13041
Many proteins exert their biological activities through small exposed surface regions called epitopes that are folded peptides of well‐defined three‐dimensional structures. Short synthetic peptide sequences corresponding to these bioactive protein surfaces do not form thermodynamically stable protein‐like structures in water. However, short peptides can be induced to fold into protein‐like bioactive conformations (strands, helices, turns) by cyclization, in conjunction with the use of other molecular constraints, that helps to fine‐tune three‐dimensional structure. Such constrained cyclic peptides can have protein‐like biological activities and potencies, enabling their uses as biological probes and leads to therapeutics, diagnostics and vaccines. This Review highlights examples of cyclic peptides that mimic three‐dimensional structures of strand, turn or helical segments of peptides and proteins, and identifies some additional restraints incorporated into natural product cyclic peptides and synthetic macrocyclic peptidomimetics that refine peptide structure and confer biological properties. 相似文献
32.
Reaction of Amino Acids,Di‐ and Tripeptides with the Environmental Oxidant NO3.: A Laser Flash Photolysis and Computational Study 下载免费PDF全文
Absolute rate coefficients for the reaction between the important environmental free radical oxidant NO3. and a series of N‐ and C‐protected amino acids, di‐ and tripeptides were determined using 355 nm laser flash photolysis of cerium(IV) ammonium nitrate in the presence of the respective substrates in acetonitrile at 298±1 K. Through combination with computational studies it was revealed that the reaction with acyclic aliphatic amino acids proceeds through hydrogen abstraction from the α‐carbon, which is associated with a rate coefficient of about 1.8×106 m ?1 s?1 per abstractable hydrogen atom. The considerably faster reaction with phenylalanine [k=(1.1±0.1)×107 m ?1 s?1] is indicative for a mechanism involving electron transfer. An unprecedented amplification of the rate coefficient by a factor of 7–20 was found with di‐ and tripeptides that contain more than one phenylalanine residue. This suggests a synergistic effect between two aromatic rings in close vicinity, which makes such peptide sequences highly vulnerable to oxidative damage by this major environmental pollutant. 相似文献
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Animal venoms and toxins are now recognized as major sources of bioactive molecules that may be tomorrow's new drug leads. Their complexity and their potential as drug sources have been demonstrated by application of modern analytical technologies, which have revealed venoms to be vast peptide combinatorial libraries. Structural as well as pharmacological diversity is immense, and mass spectrometry is now one of the major investigative tools for the structural investigation of venom components. Recent advances in its use in the study of venom and toxins are reviewed. The application of mass spectrometry techniques to peptide toxin sequence determination by de novo sequencing is discussed in detail, in the light of the search for novel analgesic drugs. We also present the combined application of LC-MALDI separation with mass fingerprinting and ISD fragmentation for the determination of structural and pharmacological classes of peptides in complex spider venoms. This approach now serves as the basis for the full investigation of complex spider venom proteomes, in combination with cDNA analysis. 相似文献
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This study describes the use of peptide vesicular platforms for the templated growth of fibrillar structures to craft hybrids that retain the gross morphological features of two discreet self-assembled peptides. A synthetic triskelion peptide, which results in the rapid emergence of self-assembled spherical structures, was employed as a template. Addition of either one of two different peptides, both of which form long filamentous structures when co-incubated with the triskelion solution, affords hybrids that retain the gross morphology of both the spherical and filamentous structures. It is surmised that this process is aided by hydrogen bonding and the interdigitation of aromatic residues, which leads to the growth of hybrid structures. We believe that observations concerning the surface-assisted growth of peptide fibrils and tubular structures from vesicular platforms may have ramifications for the design and development of peptide-based hybrid materials with controlled hierarchical structures. 相似文献
36.
Engineering Homochiral Metal–Organic Frameworks by Spatially Separating 1D Chiral Metal–Peptide Ladders: Tuning the Pore Size for Enantioselective Adsorption 下载免费PDF全文
Dr. Kyriakos C. Stylianou Dr. Laura Gómez Dr. Inhar Imaz Dr. Cristóbal Verdugo‐Escamilla Dr. Xavi Ribas Prof. Daniel Maspoch 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(28):9964-9969
The reaction of the chiral dipeptide glycyl‐L(S)‐glutamate with CoII ions produces chiral ladders that can be used as rigid 1D building units. Spatial separation of these building units with linkers of different lengths allows the engineering of homochiral porous MOFs with enhanced pore sizes, pore volumes, and surface areas. This strategy enables the synthesis of a family of isoreticular MOFs, in which the pore size dictates the enantioselective adsorption of chiral molecules (in terms of their size and enantiomeric excess). 相似文献
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Synthetic oligopeptides with a tryptophan residue at the C-terminus have been used for the synthesis of gold and silver nanoparticles at pH 11. The tryptophan residue in the peptides is responsible for the reduction of metal ions to the respective metals, possibly through electron transfer. A mechanistic pathway has been proposed to explain the reductive properties of the tryptophan moiety of the peptide based on some spectroscopic techniques, such as UV-visible and fluorescence spectroscopy. This study reveals that some of the peptide molecules are converted to its corresponding ditryptophan, kynurenine form and some cross-linked products, all of which are highly fluorescent species. The resultant peptide-functionalized metal nanoparticles have also been characterized by UV-visible spectroscopy, transmission electron microscopy, and Fourier transform IR spectroscopy and thermogravimatric analysis. 相似文献
39.
Yang J Alemany LB Driver J Hartgerink JD Barron AR 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(9):2530-2545
A series of [60]fullerene-substituted phenylalanine (Baa) and lysine derivatives have been prepared by the condensation of 1,2-(4'-oxocyclohexano)fullerene with the appropriately protected (4-amino)phenylalanine and lysine, respectively. Conversion of the imine to the corresponding amine is achieved by di-acid catalyzed hydroboration. The reduction of the imine is not accompanied by hydroboration of the fullerene cage. The [70]fullerene phenylalanine derivative has also been prepared as have the di-amino acid derivatives. The compounds were characterized by MALDI-TOF mass spectrometry, UV/Vis spectroscopy, and cyclic voltammetry. 1H and 13C NMR spectroscopy allowed the observation of diastereomers. Fullerene-substituted peptides may be synthesized on relatively large scale by solid-phase peptide synthesis. The presence of the C60-substituted amino acid in a peptide has a significant effect on the secondary structures and self-assembly properties of peptides as compared to the native peptide. The antioxidant assay of Baa and a Baa-derived anionic peptide was determined to be significantly more potent than Trolox. 相似文献
40.
John M. Beierle W. Seth Horne Dr. Jan H. van Maarseveen Prof. Dr. Beatrice Waser Jean Claude Reubi Prof. Dr. M. Reza Ghadiri Prof. Dr. 《Angewandte Chemie (International ed. in English)》2009,48(26):4725-4729
A would‐be amide : A 1,4‐disubstituted 1,2,3‐triazole was used as a surrogate for a trans amide bond to create a library of 16 diastereomeric pseudotetrapeptides as β‐turn mimetics. High‐resolution structural analysis indicated that these scaffolds adopt distinct, rigid, conformationally homogeneous β‐turn‐like structures (see example), some of which bind somatostatin receptor subtypes selectively, and some of which show broad‐spectrum activity.