Abstract
The development of simple strategies capable of simultaneously producing hydrophilic surfaces and controlled surface topography is rare in spite of their huge potential for a wide myriad of applications. Herein, we first summarize the different strategies to fabricate microstructured hydrogel surfaces and the different biological applications described in the literature. Then, we describe a procedure used to fabricate wrinkled structures in thermoplastics. We present a straightforward approach to form microwrinkled surfaces on polycarbonate (PC) film after a process that involves three different steps: first, the contact between a photosensitive monomer mixture based on vinylpyrrolidone (VP) and the PC substrate; second, a UV-curing step of this solution; and third, the hydrogel detachment as a result of the swelling in ethanol. Several parameters allow us to vary the wrinkle characteristics including the contact time between the PC surface and the photopolymerizable solution prior to the UV-vis irradiation, the type of solvent, as well as the cross-linking degree. By contact angle measurements and by confocal Raman microscopy, we were able to demonstrate that the PC wrinkled surface produced after hydrogel detachment has a thin hydrogel layer. Thus the hydrogel presented an internal rupture close to the PC substrate. Finally, we evaluated biocompatibility analyzing cell proliferation, cell morphology, and cell detachment on the substrates with both variable chemical composition and wrinkle size and period.
This is a preview of subscription content, log in via an institution.
Buying options
Tax calculation will be finalised at checkout
Purchases are for personal use only
Learn about institutional subscriptionsReferences
C.-M. Chen, S. Yang, Wrinkling instabilities in polymer films and their applications. Polym. Int. 61(7), 1041–1047 (2012)
A. Schweikart, A. Fery, Controlled wrinkling as a novel method for the fabrication of patterned surfaces. Microchim. Acta 165(3–4), 249–263 (2009)
J. Genzer, J. Groenewold, Soft matter with hard skin: From skin wrinkles to templating and material characterization. Soft Matter 2(4), 310–323 (2006)
S. McCormick, Materials science – Exploiting wrinkle formation. Science 317(5838), 605–606 (2007)
F. Weiss, S. Cai, Y. Hu, M.K. Kang, R. Huang, Z. Suo, Creases and wrinkles on the surface of a swollen gel. J. Appl. Phys. 114(7), 073507 (2013)
S. Cai, D. Chen, Z. Suo, R.C. Hayward, Creasing instability of elastomer films. Soft Matter 8(5), 1301–1304 (2012)
S.S. Velankar, V. Lai, R.A. Vaia, Swelling-induced delamination causes folding of surface-tethered polymer gels. ACS Appl. Mater. Interfaces 4(1), 24–29 (2012)
T. Bahners, L. Prager, S. Kriehn, J.S. Gutmann, Super-hydrophilic surfaces by photo-induced micro-folding. Appl. Surf. Sci. 259, 847–852 (2012)
Y.-P. Cao, B. Li, X.-Q. Feng, Surface wrinkling and folding of core-shell soft cylinders. Soft Matter 8(2), 556–562 (2012)
R. Schubert, T. Scherzer, M. Hinkefuss, B. Marquardt, J. Vogel, M.R. Buchmeiser, VUV-induced micro-folding of acrylate-based coatings. 1. Real-time methods for the determination of the micro-folding kinetics. Surf. Coat. Technol. 203(13), 1844–1849 (2009)
D.P. Holmes, A.J. Crosby, Draping films: A wrinkle to fold transition. Phys. Rev. Lett. 105(3), 038303 (2010)
J. Rodríguez-Hernández, Wrinkled interfaces: Taking advantage of surface instabilities to pattern polymer surfaces. Prog. Polym. Sci. 42, 1–41 (2015)
K. Efimenko, M. Rackaitis, E. Manias, A. Vaziri, L. Mahadevan, J. Genzer, Nested self-similar wrinkling patterns in skins. Nat. Mater. 4(4), 293 (2005)
T. Ohzono, M. Shimomura, Ordering of microwrinkle patterns by compressive strain. Phys. Rev. B 69(13), 132202 (2004)
T. Ohzono, M. Shimomura, Geometry-dependent stripe rearrangement processes induced by strain on preordered microwrinkle patterns. Langmuir 21(16), 7230–7237 (2005)
W.M. Choi, J. Song, D.-Y. Khang, H. Jiang, Y.Y. Huang, J.A. Rogers, Biaxially stretchable “wavy” silicon nanomembranes. Nano Lett. 7(6), 1655–1663 (2007)
H. Jiang, D.-Y. Khang, J. Song, Y. Sun, Y. Huang, J.A. Rogers, Finite deformation mechanics in buckled thin films on compliant supports. Proc. Natl. Acad. Sci. 104(40), 15607–15612 (2007)
N. Uchida, T. Ohzono, Orientational ordering of buckling-induced microwrinkles on soft substrates. Soft Matter 6(22), 5729–5735 (2010)
P.J. Yoo, Fabrication of complexly patterned wavy structures using self-organized anisotropic wrinkling. Electron. Mater. Lett. 7(1), 17–23 (2011)
N. Bowden, S. Brittain, A.G. Evans, J.W. Hutchinson, G.M. Whitesides, Spontaneous formation of ordered structures in thin films of metals supported on an elastomeric polymer. Nature 393(6681), 146 (1998)
J. Kim, H.H. Lee, Wave formation by heating in thin metal film on an elastomer. J. Polym. Sci. B Polym. Phys. 39(11), 1122–1128 (2001)
P.J. Yoo, H.H. Lee, Complex pattern formation by adhesion-controlled anisotropic wrinkling. Langmuir 24(13), 6897–6902 (2008)
T. Okayasu, H.L. Zhang, D.G. Bucknall, G.A.D. Briggs, Spontaneous formation of ordered lateral patterns in polymer thin-film structures. Adv. Funct. Mater. 14(11), 1081–1088 (2004)
J.Y. Chung, A.J. Nolte, C.M. Stafford, Diffusion-controlled, self-organized growth of symmetric wrinkling patterns. Adv. Mater. 21(13), 1358–1362 (2009)
H. Vandeparre, S. Gabriele, F. Brau, C. Gay, K.K. Parker, P. Damman, Hierarchical wrinkling patterns. Soft Matter 6(22), 5751–5756 (2010)
S.K. Basu, A.V. McCormick, L. Scriven, Stress generation by solvent absorption and wrinkling of a cross-linked coating atop a viscous or elastic base. Langmuir 22(13), 5916–5924 (2006)
D. Breid, A.J. Crosby, Surface wrinkling behavior of finite circular plates. Soft Matter 5(2), 425–431 (2009)
M. Guvendiren, J.A. Burdick, S. Yang, Kinetic study of swelling-induced surface pattern formation and ordering in hydrogel films with depth-wise crosslinking gradient. Soft Matter 6(9), 2044–2049 (2010)
J. Huang, M. Juszkiewicz, W.H. De Jeu, E. Cerda, T. Emrick, N. Menon, T.P. Russell, Capillary wrinkling of floating thin polymer films. Science 317(5838), 650–653 (2007)
D. Vella, M. Adda-Bedia, E. Cerda, Capillary wrinkling of elastic membranes. Soft Matter 6(22), 5778–5782 (2010)
O. Wichterle, D. Lim, Hydrophilic gels for biological use. Nature 185(4706), 117 (1960)
F. Ullah, M.B.H. Othman, F. Javed, Z. Ahmad, H.M. Akil, Classification, processing and application of hydrogels: A review. Mater. Sci. Eng. C 57, 414–433 (2015)
K. Varaprasad, G.M. Raghavendra, T. Jayaramudu, M.M. Yallapu, R. Sadiku, A mini review on hydrogels classification and recent developments in miscellaneous applications. Mater. Sci. Eng. C 79, 958–971 (2017)
W. Roorda, H. Bodde, A. De Boer, H. Junginger, Synthetic hydrogels as drug delivery systems. Pharm. Weekbl. 8(3), 165–189 (1986)
S.J. Buwalda, K.W. Boere, P.J. Dijkstra, J. Feijen, T. Vermonden, W.E. Hennink, Hydrogels in a historical perspective: From simple networks to smart materials. J. Control. Release 190, 254–273 (2014)
E.M. Ahmed, Hydrogel: Preparation, characterization, and applications: A review. J. Adv. Res. 6(2), 105–121 (2015)
W.A. Laftah, S. Hashim, A.N. Ibrahim, Polymer hydrogels: A review. Polym.-Plast. Technol. Eng. 50(14), 1475–1486 (2011)
G.M. Raghavendra, K.Varaprasad, T. Jayaramudu, Biomaterials: Design, Development and Biomedical Applications, Nanotechnology Applications for Tissue Engineering. (Elsevier, Oxford, 2015), pp. 21–44
K. Sharma, B. Kaith, V. Kumar, S. Kalia, V. Kumar, H. Swart, Water retention and dye adsorption behavior of Gg-cl-poly (acrylic acid-aniline) based conductive hydrogels. Geoderma 232, 45–55 (2014)
S. Ma, B. Yu, X. Pei, F. Zhou, Structural hydrogels. Polymer 98, 516–535 (2016)
B.R. Saunders, B. Vincent, Microgel particles as model colloids: Theory, properties and applications. Adv. Colloid Interf. Sci. 80(1), 1–25 (1999)
P. Bradna, P. Stern, O. Quadrat, J. Snuparek, Thickening effect of dispersions of ethyl acrylate-methacrylic acid copolymer prepared by different polymerization routes. Colloid Polym. Sci. 273(4), 324–330 (1995)
L.A. Lyon, Z. Meng, N. Singh, C.D. Sorrell, A.S. John, Thermoresponsive microgel-based materials. Chem. Soc. Rev. 38(4), 865–874 (2009)
C.M. Nolan, M.J. Serpe, L.A. Lyon, Thermally modulated insulin release from microgel thin films. Biomacromolecules 5(5), 1940–1946 (2004)
J. Kim, M.J. Serpe, L.A. Lyon, Hydrogel microparticles as dynamically tunable microlenses. J. Am. Chem. Soc. 126(31), 9512–9513 (2004)
K. Ishii, Synthesis of microgels and their application to coatings. Colloids Surf. A Physicochem. Eng. Asp. 153(1–3), 591–595 (1999)
L. Ionov, Biomimetic hydrogel-based actuating systems. Adv. Funct. Mater. 23(36), 4555–4570 (2013)
S. Ma, M. Scaraggi, D. Wang, X. Wang, Y. Liang, W. Liu, D. Dini, F. Zhou, Nanoporous substrate-infiltrated hydrogels: A bioinspired regenerable surface for high load bearing and tunable friction. Adv. Funct. Mater. 25(47), 7366–7374 (2015)
L. Binan, A. Ajji, G. De Crescenzo, M. Jolicoeur, Approaches for neural tissue regeneration. Stem Cell Rev. Rep. 10(1), 44–59 (2014)
A.E. Haggerty, M. Oudega, Biomaterials for spinal cord repair. Neurosci. Bull. 29(4), 445–459 (2013)
N. Bassik, B.T. Abebe, K.E. Laflin, D.H. Gracias, Photolithographically patterned smart hydrogel based bilayer actuators. Polymer 51(26), 6093–6098 (2010)
P. Gruner, M. Arlt, T. Fuhrmann-Lieker, Surface wrinkling induced by photofluidization of low molecular azo glasses. ChemPhysChem 14(2), 424–430 (2013)
N. Lambricht, T. Pardoen, S. Yunus, Giant stretchability of thin gold films on rough elastomeric substrates. Acta Mater. 61(2), 540–547 (2013)
M. Ramanathan, B.S. Lokitz, J.M. Messman, C.M. Stafford, S.M. Kilbey II, Spontaneous wrinkling in azlactone-based functional polymer thin films in 2D and 3D geometries for guided nanopatterning. J. Mater. Chem. C 1(11), 2097–2101 (2013)
Z. Wu, N. Bouklas, R. Huang, Swell-induced surface instability of hydrogel layers with material properties varying in thickness direction. Int. J. Solids Struct. 50(3–4), 578–587 (2013)
Z. Chen, Y.Y. Kim, S. Krishnaswamy, Anisotropic wrinkle formation on shape memory polymer substrates. J. Appl. Phys. 112(12), 124319 (2012)
Y.-C. Chen, A.J. Crosby, Wrinkling of inhomogeneously strained thin polymer films. Soft Matter 9(1), 43–47 (2013)
J. Dervaux, M.B. Amar, Mechanical instabilities of gels. Annu. Rev. Condens. Matter Phys. 3(1), 311–332 (2012)
C.M. Chen, S. Yang, Wrinkling instabilities in polymer films and their applications. Polym. Int. 61(7), 1041–1047 (2012)
B. Li, Y.-P. Cao, X.-Q. Feng, H. Gao, Mechanics of morphological instabilities and surface wrinkling in soft materials: A review. Soft Matter 8(21), 5728–5745 (2012)
J. Gu, X. Li, H. Ma, Y. Guan, Y. Zhang, One-step synthesis of PHEMA hydrogel films capable of generating highly ordered wrinkling patterns. Polymer 110, 114–123 (2017)
M. Guvendiren, S. Yang, J.A. Burdick, Swelling-induced surface patterns in hydrogels with gradient crosslinking density. Adv. Funct. Mater. 19(19), 3038–3045 (2009)
C.M. González-Henríquez, D.H. Sagredo-Oyarce, M.A. Sarabia-Vallejos, J. Rodríguez-Hernández, Fabrication of micro and sub-micrometer wrinkled hydrogel surfaces through thermal and photocrosslinking processes. Polymer 101, 24–33 (2016)
M. Guvendiren, J.A. Burdick, The control of stem cell morphology and differentiation by hydrogel surface wrinkles. Biomaterials 31(25), 6511–6518 (2010)
M. Guvendiren, S. Yang, J.A. Burdick, Swelling-induced surface patterns in hydrogels with gradient crosslinking density. Adv. Funct. Mater. 19(19), 3038–3045 (2009)
C. Tang, B. Li, C. Zou, L. Liu, H. Chen, Voltage-induced wrinkle performance in a hydrogel by dielectric elastomer actuation. Polymer 10(7), 697 (2018)
A. Parfitt, Age-related structural changes in trabecular and cortical bone: Cellular mechanisms and biomechanical consequences. Calcif. Tissue Int. 36(1), S123–S128 (1984)
V.I. Sikavitsas, J.S. Temenoff, A.G. Mikos, Biomaterials and bone mechanotransduction. Biomaterials 22(19), 2581–2593 (2001)
F. Greqoir, C. Smas, H. Sul, Understanding adipocyte differentiation. Physiol. Rev. 78, 783–809 (1998)
A.E. Grigoriadis, J. Heersche, J.E. Aubin, Differentiation of muscle, fat, cartilage, and bone from progenitor cells present in a bone-derived clonal cell population: Effect of dexamethasone. J. Cell Biol. 106(6), 2139–2151 (1988)
J. Fukuda, Y. Sakai, K. Nakazawa, Novel hepatocyte culture system developed using microfabrication and collagen/polyethylene glycol microcontact printing. Biomaterials 27(7), 1061–1070 (2006)
S.F. Wong, D.Y. No, Y.Y. Choi, D.S. Kim, B.G. Chung, S.-H. Lee, Concave microwell based size-controllable hepatosphere as a three-dimensional liver tissue model. Biomaterials 32(32), 8087–8096 (2011)
J.C. Mohr, J.J. de Pablo, S.P. Palecek, 3-D microwell culture of human embryonic stem cells. Biomaterials 27(36), 6032–6042 (2006)
J. Fukuda, A. Khademhosseini, Y. Yeo, X. Yang, J. Yeh, G. Eng, J. Blumling, C.-F. Wang, D.S. Kohane, R. Langer, Micromolding of photocrosslinkable chitosan hydrogel for spheroid microarray and co-cultures. Biomaterials 27(30), 5259–5267 (2006)
H. Tekin, M. Anaya, M.D. Brigham, C. Nauman, R. Langer, A. Khademhosseini, Stimuli-responsive microwells for formation and retrieval of cell aggregates. Lab Chip 10(18), 2411–2418 (2010)
K.H. Lee, D.Y. No, S.-H. Kim, J.H. Ryoo, S.F. Wong, S.-H. Lee, Diffusion-mediated in situalginate encapsulation of cell spheroids using microscale concave well and nanoporous membrane. Lab Chip 11(6), 1168–1173 (2011)
Y.-S. Hwang, B.G. Chung, D. Ortmann, N. Hattori, H.-C. Moeller, A. Khademhosseini, Microwell-mediated control of embryoid body size regulates embryonic stem cell fate via differential expression of WNT5a and WNT11. Proc. Natl. Acad. Sci. 106(40), 16978–16983 (2009)
J.M. Karp, J. Yeh, G. Eng, J. Fukuda, J. Blumling, K.-Y. Suh, J. Cheng, A. Mahdavi, J. Borenstein, R. Langer, A. Khademhosseini, Controlling size, shape and homogeneity of embryoid bodies using poly(ethylene glycol) microwells. Lab Chip 7(6), 786–794 (2007)
J. Park, C.H. Cho, N. Parashurama, Y. Li, F. Berthiaume, M. Toner, A.W. Tilles, M.L. Yarmush, Microfabrication-based modulation of embryonic stem cell differentiation. Lab Chip 7(8), 1018–1028 (2007)
M.D. Ungrin, C. Joshi, A. Nica, C. Bauwens, P.W. Zandstra, Reproducible, ultra high-throughput formation of multicellular organization from single cell suspension-derived human embryonic stem cell aggregates. PLoS One 3(2), e1565 (2008)
H.-C. Moeller, M.K. Mian, S. Shrivastava, B.G. Chung, A. Khademhosseini, A microwell array system for stem cell culture. Biomaterials 29(6), 752–763 (2008)
A.P. Napolitano, P. Chai, D.M. Dean, J.R. Morgan, Dynamics of the self-assembly of complex cellular aggregates on micromolded nonadhesive hydrogels. Tissue Eng. 13(8), 2087–2094 (2007)
A.B. Bernard, C.-C. Lin, K.S. Anseth, A microwell cell culture platform for the aggregation of pancreatic β-cells. Tissue Eng. Part C Methods 18(8), 583–592 (2012)
B.R. Lee, J.W. Hwang, Y.Y. Choi, S.F. Wong, Y.H. Hwang, D.Y. Lee, S.-H. Lee, In situ formation and collagen-alginate composite encapsulation of pancreatic islet spheroids. Biomaterials 33(3), 837–845 (2012)
J. Dahlmann, G. Kensah, H. Kempf, D. Skvorc, A. Gawol, D.A. Elliott, G. Dräger, R. Zweigerdt, U. Martin, I. Gruh, The use of agarose microwells for scalable embryoid body formation and cardiac differentiation of human and murine pluripotent stem cells. Biomaterials 34(10), 2463–2471 (2013)
Z. Zhao, J. Gu, Y. Zhao, Y. Guan, X. Zhu, Y. Zhang, Hydrogel thin film with swelling-induced wrinkling patterns for high-throughput generation of multicellular spheroids. Biomacromolecules 15(9), 3306–3312 (2014)
A. Ivascu, M. Kubbies, Rapid generation of single-tumor spheroids for high-throughput cell function and toxicity analysis. J. Biomol. Screen. 11(8), 922–932 (2006)
I. Aranaz, E. Martinez-Campos, M.E. Nash, M.G. Tardajos, H. Reinecke, C. Elvira, V. Ramos, J.L. Lopez-Lacomba, A. Gallardo, Pseudo-double network hydrogels with unique properties as supports for cell manipulation. J. Mater. Chem. B 2(24), 3839–3848 (2014)
A. Gallardo, N. Lujan, H. Reinecke, C. García, A.D. Campo, J. Rodriguez-Hernandez, Chemical and topographical modification of polycarbonate surfaces through diffusion/photocuring processes of hydrogel precursors based on vinylpyrrolidone. Langmuir 33(7), 1614–1622 (2017)
H. Yuk, T. Zhang, S. Lin, G.A. Parada, X. Zhao, Tough bonding of hydrogels to diverse non-porous surfaces. Nat. Mater. 15(2), 190–196 (2016)
X. Zhu, P. Lu, W. Chen, J. Dong, Studies of UV crosslinked poly(N-vinylpyrrolidone) hydrogels by FTIR, Raman and solid-state NMR spectroscopies. Polymer 51(14), 3054–3063 (2010)
M. Luo, Y. Hong, W. Yao, C. Huang, Q. Xu, Q. Wu, Facile removal of polyvinylpyrrolidone (PVP) adsorbates from Pt alloy nanoparticles. J. Mater. Chem. A 3(6), 2770–2775 (2015)
K. Bruckmoser, K. Resch, T. Kisslinger, T. Lucyshyn, Measurement of interdiffusion in polymeric materials by applying Raman spectroscopy. Polym. Test. 46, 122–133 (2015)
E. Martinez-Campos, A. Gallardo, N. Lujan, A. Santos-Coquillat, H. Reinecke, A.D. Campo, J. Rodriguez-Hernandez, Wrinkled hydrogel surfaces with modulated surface chemistry and topography: Evaluation as supports for cell growth and transplant. Submitted to ACS Appl. Biomater. (2018)
A. Gallardo, E. Martínez-Campos, C. García, A.L. Cortajarena, J. Rodríguez-Hernández, Hydrogels with modulated ionic load for mammalian cell harvesting with reduced bacterial adhesion. Biomacromolecules 18(5), 1521–1531 (2017)
K. Nagase, M. Yamato, H. Kanazawa, T. Okano, Poly (N-isopropylacrylamide)-based thermoresponsive surfaces provide new types of biomedical applications. Biomaterials 153, 27–48 (2018)
Acknowledgments
The authors gratefully acknowledge support from the Consejo Superior de Investigaciones Científicas (CSIC). Equally, this work was financially supported by the Ministerio de Economía y Competitividad (MINECO) through MAT2013-47902-C2-1-R, MAT2013-42957-R, and MAT2016-78437-R, FEDER-EU.
Author information
Authors and Affiliations
Corresponding authors
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2019 Springer Nature Switzerland AG
About this chapter
Cite this chapter
Martinez, E. et al. (2019). Wrinkled Hydrogel Formation by Interfacial Swelling on Thermoplastic Surfaces. In: González-Henríquez, C., Rodríguez-Hernández, J. (eds) Wrinkled Polymer Surfaces. Springer, Cham. https://doi.org/10.1007/978-3-030-05123-5_5
Download citation
DOI: https://doi.org/10.1007/978-3-030-05123-5_5
Published:
Publisher Name: Springer, Cham
Print ISBN: 978-3-030-05122-8
Online ISBN: 978-3-030-05123-5
eBook Packages: Chemistry and Materials ScienceChemistry and Material Science (R0)