| Texto completo | |
| Autor(es): Mostrar menos - |
Soares, Bruna M.
[1]
;
Sodre, Pedro T.
[1]
;
Aguilar, Andrea M.
[2]
;
Gerbelli, Barbara B.
[1]
;
Pelin, Juliane N. B. D.
[1]
;
Arguello, Karina B.
[1]
;
Silva, Emerson R.
[3]
;
de Farias, Marcelo A.
[4]
;
Portugal, Rodrigo V.
[4]
;
Schmuck, Carsten
[5]
;
Coutinho-Neto, Mauricio D.
[1]
;
Alves, Wendel A.
[1]
Número total de Autores: 12
|
| Afiliação do(s) autor(es): | [1] Univ Fed ABC, Ctr Ciencias Nat & Humanas, BR-09210580 Santo Andre, SP - Brazil
[2] Univ Fed Sao Paulo, Inst Ciencias Ambientais Quim & Farmaceut, BR-09972270 Diadema - Brazil
[3] Univ Fed Sao Paulo, Dept Biofis, BR-04023062 Sao Paulo - Brazil
[4] CNPEM, Brazilian Nanotechnol Natl Lab, BR-13083970 Campinas, SP - Brazil
[5] Univ Duisburg Essen, Inst Organ Chem, D-45117 Essen - Germany
Número total de Afiliações: 5
|
| Tipo de documento: | Artigo Científico |
| Fonte: | Physical Chemistry Chemical Physics; v. 23, n. 18, p. 10953-10963, MAY 14 2021. |
| Citações Web of Science: | 0 |
| Resumo | |
Four amphiphilic peptides were synthesized, characterized, and evaluated regarding their efficiency in the catalysis of direct aldol reactions in water. The lipopeptides differ by having a double lipid chain and a guanidinium pyrrole group functionalizing one Lys side chain. All the samples are composed of the amino acids l-proline (P), l-arginine (R), or l-lysine (K) functionalized with the cationic guanidiniocarbonyl pyrrole unit (GCP), l-tryptophan (W), and l-glycine (G), covalently linked to one or two long aliphatic chains, leading to surfactant-like designs with controlled proline protonation state and different stereoselectivity. Critical aggregation concentrations (cac) were higher in the presence of the GCP group, suggesting that self-assembly depends on charge distribution along the peptide backbone. Cryogenic Transmission Electron Microscopy (Cryo-TEM) and Small Angle X-ray Scattering (SAXS) showed a rich polymorphism including spherical, cylindrical, and bilayer structures. Molecular dynamics simulations performed to assess the lipopeptide polymorphs revealed an excellent agreement with core-shell arrangements derived from SAXS data and provided an atomistic view of the changes incurred by modifying head groups and lipid chains. The resulting nanostructures behaved as excellent catalysts for aldol condensation reactions, in which superior conversions (>99%), high diastereoselectivities (ds = 94 : 6), and enantioselectivities (ee = 92%) were obtained. Our findings contribute to elucidate the effect of nanoscale organization of lipopeptide assemblies in the catalysis of aldol reactions in an aqueous environment. (AU) | |
| Processo FAPESP: | 17/02317-2 - Interfaces em materiais: propriedades eletrônicas, magnéticas, estruturais e de transporte |
| Beneficiário: | Adalberto Fazzio |
| Modalidade de apoio: | Auxílio à Pesquisa - Temático |
| Processo FAPESP: | 18/05888-3 - Biossensores baseados em peptídeos anfifílicos para detecção e diagnóstico de doenças |
| Beneficiário: | Barbara Bianca Gerbelli |
| Modalidade de apoio: | Bolsas no Brasil - Pós-Doutorado |
| Processo FAPESP: | 15/20446-9 - Estudo da auto-organização de estruturas hierárquicas de peptídeos em solução em presença de nanopartículas metálicas |
| Beneficiário: | Juliane Nogueira Batista Dias Pelin |
| Modalidade de apoio: | Bolsas no Brasil - Doutorado Direto |
| Processo FAPESP: | 14/50867-3 - INCT 2014: Instituto Nacional de Ciência e Tecnologia de Bioanalítica |
| Beneficiário: | Marco Aurelio Zezzi Arruda |
| Modalidade de apoio: | Auxílio à Pesquisa - Temático |