TY - JOUR
T1 - Photopatterned Multidomain Gels
T2 - Multi-Component Self-Assembled Hydrogels Based on Partially Self-Sorting 1,3:2,4-Dibenzylidene-d-sorbitol Derivatives
AU - Cornwell, Daniel J.
AU - Daubney, Oliver J.
AU - Smith, David K.
N1 - © 2015, American Chemical Society. This is an author-produced version of the published paper. Uploaded in accordance with the publisher’s self-archiving policy. Further copying may not be permitted; contact the publisher for details.
PY - 2015/12/16
Y1 - 2015/12/16
N2 - We report a multicomponent self-assembling system based on 1,3:2,4-dibenzyldene-d-sorbitol (DBS) derivatives which form gels as the pH is lowered in a controlled way. The two DBS gelators are functionalized with carboxylic acids: the first in the 4-position of the aromatic rings (DBS-CO2H), the second having glycine connected through an amide bond and displaying a terminal carboxylic acid (DBS-Gly). Importantly, these two self-assembling DBS-acids have different pKa values, and as such, their self-assembly is triggered at different pHs. Slowly lowering the pH of a mixture of gelators using glucono-d-lactone (GdL) initially triggers assembly of DBS-CO2H, followed by DBS-Gly; a good degree of kinetic self-sorting is achieved. Gel formation can also be triggered in the presence of diphenyliodonium nitrate (DPIN) as a photoacid under UV irradiation. Two-step acidification of a mixture of gelators using (a) GdL and (b) DPIN assembles the two networks sequentially. By combining this approach with a mask during step b, multidomain gels are formed, in which the network based on DBS-Gly is positively patterned into a pre-existing network based on DBS-CO2H. This innovative approach yields spatially resolved multidomain multicomponent gels based on programmable low-molecular-weight gelators, with one network being positively 'written' into another.
AB - We report a multicomponent self-assembling system based on 1,3:2,4-dibenzyldene-d-sorbitol (DBS) derivatives which form gels as the pH is lowered in a controlled way. The two DBS gelators are functionalized with carboxylic acids: the first in the 4-position of the aromatic rings (DBS-CO2H), the second having glycine connected through an amide bond and displaying a terminal carboxylic acid (DBS-Gly). Importantly, these two self-assembling DBS-acids have different pKa values, and as such, their self-assembly is triggered at different pHs. Slowly lowering the pH of a mixture of gelators using glucono-d-lactone (GdL) initially triggers assembly of DBS-CO2H, followed by DBS-Gly; a good degree of kinetic self-sorting is achieved. Gel formation can also be triggered in the presence of diphenyliodonium nitrate (DPIN) as a photoacid under UV irradiation. Two-step acidification of a mixture of gelators using (a) GdL and (b) DPIN assembles the two networks sequentially. By combining this approach with a mask during step b, multidomain gels are formed, in which the network based on DBS-Gly is positively patterned into a pre-existing network based on DBS-CO2H. This innovative approach yields spatially resolved multidomain multicomponent gels based on programmable low-molecular-weight gelators, with one network being positively 'written' into another.
U2 - 10.1021/jacs.5b09691
DO - 10.1021/jacs.5b09691
M3 - Article
AN - SCOPUS:84950326895
SN - 0002-7863
VL - 137
SP - 15486
EP - 15492
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 49
ER -
