Dataset Information

Investigating the role of chain and linker length on the catalytic activity of an H₂ production catalyst containing a ?-hairpin peptide.

ABSTRACT: Building on our recent report of an active H₂ production catalyst [Ni(P^Ph ₂N^Prop-peptide)₂]²⁺ (Prop = para-phenylpropionic acid, peptide (R10) = WIpPRWTGPR-NH₂, p = D-proline and P₂N = 1-aza-3,6-diphosphacycloheptane) that contains structured ?-hairpin peptides, here we investigate how H₂ production is effected by: (1) the length of the hairpin (eight or ten residues) and (2) limiting the flexibility between the peptide and the core complex by altering the length of the linker: para-phenylpropionic acid (three carbons) or para-benzoic acid (one carbon). Reduction of the peptide chain length from ten to eight residues increases or maintains the catalytic current for H₂ production for all complexes, suggesting a non-productive steric interaction at longer peptide lengths. While the structure of the hairpin appears largely intact for the complexes, NMR data are consistent with differences in dynamic behavior which may contribute to the observed differences in catalytic activity. Molecular dynamics simulations demonstrate that complexes with a one-carbon linker have the desired effect of restricting the motion of the hairpin relative to the complex; however, the catalytic currents are significantly reduced compared to complexes containing a three-carbon linker as a result of the electron withdrawing nature of the -COOH group. These results demonstrate the complexity and interrelated nature of the outer coordination sphere on catalysis.

SUBMITTER: Reback ML

PROVIDER: S-EPMC7577397 | biostudies-literature | 2016

REPOSITORIES: biostudies-literature

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Investigating the role of chain and linker length on the catalytic activity of an H2 production catalyst containing a β-hairpin peptide.

Reback Matthew L ML Ginovska Bojana B Buchko Garry W GW Dutta Arnab A Priyadarshani Nilusha N Kier Brandon L BL Helm Monte L ML Raugei Simone S Shaw Wendy J WJ

Journal of coordination chemistry 20160602 11-13

Building on our recent report of an active H2 production catalyst [Ni(PPh 2NProp-peptide)2]2+ (Prop = para-phenylpropionic acid, peptide (R10) = WIpPRWTGPR-NH2, p = D-proline and P2N = 1-aza-3,6-diphosphacycloheptane) that contains structured β-hairpin peptides, here we investigate how H2 production is effected by: (1) the length of the hairpin (eight or ten residues) and (2) limiting the fl ...[more]

PMID: 33093711

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Project description:Multiple studies have been published emphasizing the significant role of nanoparticle (NP) carriers in antigenic peptide-based subunit vaccines for the induction of potent humoral and cellular responses. Various design parameters of nanoparticle subunit vaccines such as linker chemistry, the proximity of antigenic peptide to NPs, and the density of antigenic peptides on the surface of NPs play an important role in antigen presentation to dendritic cells (DCs) and in subsequent induction of CD8+ T cell response. In this current study, we evaluated the role of peptide antigen proximity and density on DC uptake, antigen cross-presentation, in vitro T cell proliferation, and in vivo induction of CD8+ T cells. To evaluate the role of antigen proximity, CSIINFEKL peptides were systematically conjugated to poly(ethylene glycol) (PEG) hydrogels through N-hydroxysuccinimide-PEG-maleimide linkers of varying molecular weights: 2k, 5k, and 10k. We observed that the peptides conjugated to NPs via the 2k and 5k PEG linkers resulted in higher uptake in bone marrow-derived DCs (BMDCs) and increased p-MHC-I formation on the surface of bone marrow-derived DCs (BMDCs) as compared to the 10k PEG linker formulation. However, no significant differences in vitro T cell proliferation and induction of in vivo CD8+ T cells were found among linker lengths. To study the effect of antigen density, CSIINFEKL peptides were conjugated to PEG hydrogels via 5k PEG linkers at various densities. We found that high antigen density NPs presented the highest p-MHC-I on the surface of BMDCs and induced higher proliferation of T cells, whereas NPs with low peptide density resulted in higher DC cell uptake and elevated frequency of IFN-γ producing CD8+ T cells in mice as compared to the medium- and high-density formulations. Altogether, findings for these experiments highlighted the importance of linker length and peptide antigen density on DC cell uptake, antigen presentation, and induction of in vivo CD8+ T cell response.

Dataset Information

Investigating the role of chain and linker length on the catalytic activity of an H₂ production catalyst containing a ?-hairpin peptide.

Publications

Investigating the role of chain and linker length on the catalytic activity of an H<sub>2</sub> production catalyst containing a β-hairpin peptide.

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Dataset Information

Investigating the role of chain and linker length on the catalytic activity of an H2 production catalyst containing a ?-hairpin peptide.

Publications

Investigating the role of chain and linker length on the catalytic activity of an H<sub>2</sub> production catalyst containing a β-hairpin peptide.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Investigating the role of chain and linker length on the catalytic activity of an H₂ production catalyst containing a ?-hairpin peptide.