Documente Academic
Documente Profesional
Documente Cultură
Thermoresponsive polymers
4.1 Conformational transition 4.2 Co-nonsolvency 4.3 Switchable networks 4.4 Micro- and nanogels
aqueous solutions of poly(N-isopropyl acrylamide) (PNIPAM) become abruptly turbid at the cloud point (32C) thermoresponsive (switchable) behavior
chain conformation: swollen collapsed sharp transition at the cloud point collapsed chains form large aggregates turbid solution
cloud point
H. G. Schild, Prog. Polym. Sci. 1992. S.-Y. Lin et al., Polymer 1999. Y. Katsumoto et al., J. Phys. Chem. A32002
NIPAM / 5 H2O
NIPAM / NIPAM
LCST behavior
LCST behavior: behavior opposite of UCST reason: specific interaction of the polymer with the solvent, e.g. H-bonding
4.2 Cononsolvency
Mw= 160 000 g/mol polymer concentration: 0.4 mg/mL
PNIPAM in organic solvents: e.g. dioxane, tetrahydrofurane (THF) or methanol: good solvent at all temperatures PNIPAM in solvent mixtures H2O/dioxane, H2O/THF, H2O methanol: cloud point goes down miscibility gap
THF
methanol
(iii) xMeOH > 0.45: swollen chains chain conformation depends strongly on fraction of cononsolvent
PNIPAM, 26 x 106 g/mol dilute solution, T = 20 C cononsolvent: methanol
PNIPAM in H2O: H2O molecules bind to PNIPAM in long sequences hydration is cooperative phenomenon
steric reason: if one H2O binds to the polar part of the side group, space is created for next H2O molecule, it is favorable to bind to the PNIPAM monomer which is next to the first H2O
F. Tanaka et al., J. Phys.: Cond. Matter 23, 284105 (2011). 8
cooperative binding for both solvents competition between H-bonds PNIPAM/H2O and PNIPAM/methanol: competitive adsorption sequences of H2O/methanol along chain
F. Tanaka et al., Phys. Rev. Lett. 101, 028302 (2008). F. Winnik et al., Macromolecules 23, 2415 (1990). H. Kojima, F. Tanaka, Soft Matter 8, 3010 (2012).
Switchable valves
test molecule: tryptophan (TRY)
Absorbance open
20C:
40C:
closed
Time (h)
Application in microfluidics
Applications in ophthalmology
ocular diseases: age-related macular degeneration, diabetic retinopathy use anti-VEGF therapy major drawback: treatment must be repeated every 4 to 6 weeks desire: develop a relatively noninvasive delivery method which is more effective and longer lasting idea: use PNIPAM hydrogels with poly(ethylene glycol) diacrylate (PEGDA) better thermoresponsive characteristics homogeneous pores encapsulate and release protein homogeneous pore size
13
RT
37C
J.J. Kang Derwent, W.F. Mieler, Trans. Am. Ophthalmol. Soc. 106, 206 (2008)
protein release rate is governed by compression of hydrogel in response to temperature pore size: the finer, the longer the release time but also stiffer (difficult to inject through needle)
protein molar mass ~ 100 kg/mol
initially fast release, then leveling off still a lot of protein in hydrogel use degradable hydrogel
time course of swelling of PNIPAM gel bead in water during a temperature jump
T. Tanaka et al., Phys. Rev. Lett. 55, 2455 (1985)
15
swollen
microgels (R = 100 nm to ~5 m) more difficult preparation faster switching crystallization, glass formation,
Y. Hirokawa et al., J. Chem. Phys. 1984 M. Shibayama et al., J. Chem. Phys. 1992
T. Hellweg et al., Coll. Surf. A 2002 M. Stieger et al., Langmuir 2004, S. Hfl et al., Polymer 2007
16
Collapse of nanogels
micelle with polystyrene core and PNIPAM shell R = 16 nm t = 12 nm
20 Kernradius Mizellradius halber Abstand
15
Radien (nm)
10
0.1
10
100
1000
Zeit (s)
J. Adelsberger, C.M.P. et al., Macromol. Rapid Commun. 33, 254 (2012) 17
18
UV-Vis spectra full lines: 15C, swollen state dotted lines: 50C: collapsed state shift of absorption maximum change of color
19