182297-45-6Relevant articles and documents
Enzymatic- and light-degradable hybrid nanogels: Crosslinking of polyacrylamide with acrylate-functionalized Dextrans containing photocleavable linkers
Klinger, Daniel,Landfester, Katharina
scheme or table, p. 1062 - 1075 (2012/06/01)
Enzymatically cleavable and light-degradable hybrid nanogels were prepared by free radical inverse miniemulsion copolymerization of acrylamide (AAm) with a newly synthesized functional dextran crosslinker containing acrylate moieties attached to the backbone via a photolabile linker, that is, dextran-photolabile linker-acrylate (Dex-PL-A). The Dex-PL-A/AAm feed ratio was systematically varied to investigate the influence of the particle composition on the gel properties. The resulting hydrogel nanoparticles were examined with regard to their degradation behavior upon the appliance of the two orthogonal stimuli by turbidity measurements in combination with dynamic light scattering. Although continuous photolytic cleavage of the photolabile linkers between polyacrylamide chains and dextran molecules was found to proceed fast and quantitatively yielding completely disintegrated networks, stepwise irradiation resulted in partial degradation of crosslinking points. Thus, nanogels of a desired specific degree of swelling (DGS) can be obtained by adjusting the irradiation time accordingly. Partial enzymatic cleavage of the dextran backbones of the Dex-PL-A crosslinking molecules resulted in an increase in the DGS of the nanogels up to a constant value. Subsequent irradiation of those swollen hydrogel particles was used to fully degrade the network structure in a second step. Hence, a two-step degradation profile was realized by the combination of the two orthogonal stimuli.
Photo-sensitive PMMA microgels: Light-triggered swelling and degradation
Klinger, Daniel,Landfester, Katharina
experimental part, p. 1426 - 1440 (2012/04/23)
Two classes (type A and type B) of novel photolabile divinyl functionalized crosslinkers based on o-nitrobenzyl derivatives were synthesized and investigated with regard to their photolytic performance upon UV irradiation. The systematic variation of the molecular structure resulted in different degradation rates depending on the irradiation conditions. Thus, the successive and independent cleavage is enabled by either adjusting the applied wavelengths or irradiation times. The respective molecules were used to build up photodegradable PMMA microgels by free radical copolymerization with MMA in a miniemulsion polymerization process. UV light-induced degradation of the swollen microgels was monitored by time dependent turbidity measurements and the resulting kinetics were found to correlate with the photolysis rates of the respective crosslinkers in solution. The irradiation wavelength-controlled selective partial cleavage of type B crosslinking points was achieved by UV irradiation with λ > 315 nm and resulted in particles with extensively increased volumes consisting of highly swollen networks. In addition, the irradiation time-controlled selective complete degradation of particles containing type B crosslinkers was accomplished. By using broadband UV light containing wavelengths of λ 315 nm, the successive complete particle disintegration of type B and type A microgels was observed. Hence, the specific performance of the synthesized microgels can be precisely triggered by means of the used UV light wavelengths, doses and intensities, thus representing a great potential as new light-responsive nanoscaled materials.
Model Studies for New o-Nitrobenzyl Photolabile Linkers: Substituent Effects on the Rates of Photochemical Cleavage
Holmes, Christopher P.
, p. 2370 - 2380 (2007/10/03)
Both a model phenacyl and o-nitrobenzyl photolabile linker from the literature along with four new o-nitrobenzyl linkers were prepared and the kinetics of their photolytic cleavage examined in solution. The linkers were prepared by amidation of the carboxylic acid anchoring tether with benzylamine, and the cleavable benzylic substituent was chosen to be either acetic acid or acetamide. Irradiation of the linkers in four solvents (methanol, p-dioxane, and aqueous buffer ± dithiothreitol) at 365 nm and analysis via HPLC afforded kinetic rates of cleavage suitable for comparative purposes. The phenacyl linker was found to cleave slowly under aqueous conditions with no detectable cleavage being observed in the organic solvents. Known o-nitrobenzyl linker 4 showed modest rates of cleavage in aqueous and organic solvents. Incorporation of two alkoxy groups in the benzene ring to generate the veratryl-based linker 13a increased the rate of cleavage dramatically, and introduction of an additional benzylic methyl group (13b) increased the rate of cleavage by an additional 5 fold. Increasing the length of the anchoring carboxylic acid tether from acetic to butyric acid (19) improved the cleavage kinetics modestly in organic media and slightly diminished the rates in water. The amide model linker 21 cleaved from 3 to 7 times faster than the corresponding ester linkage 19. An amide-generating linker 26 was prepared, and its performance to generate photolabile solid supports was briefly examined. The stability of the linker and subsequent cleavage upon photolysis from the support of an isotopically enriched 4-thiazolidinone was demonstrated by gel phase 13C NMR.
