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Chiral hexa- and nona-methylene bridged bis(L-Leu-oxalamide) gelators. First oxalamide gels containing aggregates with chiral morphology


Šijaković Vujičić, Nataša; Glasovac, Zoran; Zweep, Niek; van Esch, Jan H.; Vinković, Marijana; Popović, Jasminka; Žinić, Mladen
Chiral hexa- and nona-methylene bridged bis(L-Leu-oxalamide) gelators. First oxalamide gels containing aggregates with chiral morphology // Chemistry : a European journal, 19 (2013), 26; 8558-8572 doi:10.1002/chem.201300642 (međunarodna recenzija, članak, znanstveni)


Naslov
Chiral hexa- and nona-methylene bridged bis(L-Leu-oxalamide) gelators. First oxalamide gels containing aggregates with chiral morphology

Autori
Šijaković Vujičić, Nataša ; Glasovac, Zoran ; Zweep, Niek ; van Esch, Jan H. ; Vinković, Marijana ; Popović, Jasminka ; Žinić, Mladen

Izvornik
Chemistry : a European journal (0947-6539) 19 (2013), 26; 8558-8572

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni

Ključne riječi
Oxalamide gelators; chiral; self-assembly; gelation; chiral morphology

Sažetak
Chiral amino acid- and amino alcohol-oxalamides are well known as versatile and efficient gelators of various lipophilic and polar organic solvents and water. To further explore the capacity of the amino acid-oxalamide structural fragment as gelation generating motif the dioxalamide dimethyl ester 16Me, 19Me and dicarboxylic acid 26OH, 29OH derivatives containing flexible methylene bridges with odd (9 ; n = 7) and even (6 ; n = 4) number of methylene groups were prepared. Their self-assembly motifs and gelation properties were studied by a number of methods (FTIR, 1H-NMR, CD, TEM, DSC, XRPD, molecular modelling, MMFF94 and DFT). In contrast to the previously studied chiral bis(amino acid, or amino alcohol) oxalamide gelators where no chiral morphology was ever observed in the gels, the conformationally more flexible 16Me, 19Me, 26OH and 29OH endow gelators capable of forming diverse aggregates of achiral and chiral morphologies such as helical fibers, twisted tapes, nano-tubules, straight fibers and tapes in some cases coexisting in the same gel sample. It is shown that DSC determined gelation enthalpies could not be correlated with gelator and solvent clogP values. Spectroscopic results show that intermolecular hydrogen bonding between oxalamide units provides the major and self-assembly directing intermolecular interaction in the aggregates. Molecular modelling studies reveal that molecular flexibility of gelators due to the presence of the polymethylene bridges gives three conformations (zz, p1 and p2) close in energy which could form oxalamide hydrogen bonded layers. The aggregates of p1 and p2 conformations tend to twist due to steric repulsion between neighbouring iBu groups at chiral centres. XRPD results on 16Me and 19Me xerogels prove formation of p1 and p2 gel aggregates, respectively. The latter results explain the formation of gel aggregates with chiral morphology and also the simultaneous presence of aggregates of diverse morphology in the same gel system.

Izvorni jezik
Engleski

Znanstvena područja
Kemija



POVEZANOST RADA


Projekt / tema
098-0982904-2912 - Samo-udruživanje u gelovima i sinteza funkcionalnih hibridnih materijala (Leo Frkanec, )
098-0982929-2917 - Spektroskopija NMR i modeliranje bioaktivnih molekula (Dejan Plavšić, )

Ustanove
Institut "Ruđer Bošković", Zagreb

Časopis indeksira:


  • Current Contents Connect (CCC)
  • Web of Science Core Collection (WoSCC)
    • Science Citation Index Expanded (SCI-EXP)
    • SCI-EXP, SSCI i/ili A&HCI
  • Scopus
  • MEDLINE


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