UV-ozone patterning of micro-nano fibrillated cellulose (MNFC) with alkylsilane self-assembled monolayers
- 423 Downloads
- 4 Citations
Abstract
We report on a facile photolithography-based procedure for surface energy patterning of novel micro-nano fibrillated cellulose (MNFC) films and demonstrate spatial control of protein adsorption. The kinetics of oxidative degradation of chemisorbed hydrophobic alkylsilane monolayers on MNFC upon exposure to UV/ozone and the effect on the adsorption of bovine serum albumin (BSA) as a function of pH were studied using surface sensitive techniques. Wetting properties, surface morphology and surface chemical composition of the MNFC films were investigated by using water contact angle goniometry, atomic force microscopy and X-ray photoelectron spectroscopy, respectively. Optical microscopy was used to give a spatial-specific visualization of adsorbed dye-tagged BSA. UV/ozone exposure turned the initially hydrophobic alkylsilane covered MNFC substrate into a hydrophilic surface. As a result, significant changes in local wetting characteristics were observed leading to a quantitative change in BSA adsorption. Moreover, by using a UV mask, it was possible to create a hydrophobic-hydrophilic pattern on the MNFC film, and thus spatially-resolved adsorption of protein patterns were achieved. These results extend the understanding and further the applicability of MNFC films towards microfluidic-based (bio)diagnostics.
Keywords
Nanocellulose (MNFC) Photolithography Silane Self-assembled monolayer (SAM) Protein patterningNotes
Acknowledgments
This work was funded by the Academy of Finland (264743). Dr. Ville Jokinen is thanked for providing the patterned steel masks used in the UV/O3 patterning. Dr. Juan Delgado, Maija Vuoriluoto, Ritva Kivelä, Marja Kärkkäinen, Rita Hatakka and Anu Anttila are acknowledged for their valued guidance.
Author contributions
The manuscript was written through contributions of all authors. All authors have given approval of the final version of the manuscript.
Supplementary material
References
- Abdelmouleh M, Boufi S, Ben Salah A, Belgacem MN, Gandini A (2002) Interaction of silane coupling agents with cellulose. Langmuir 18:3203–3208. doi: 10.1021/la011657g CrossRefGoogle Scholar
- Arkles B (1977) Tailoring surfaces with silanes. ChemTech 7:766–778Google Scholar
- Beamson G, Briggs D (1992) High resolution XPS of organic polymers: the scienta ESCA300 database. Wiley, ChichesterGoogle Scholar
- Bračič M, Mohan T, Kargl R, Griesser T, Hribernik S, Köstler S, Stana-Kleinschek K, Fras-Zemljič L (2014) Preparation of PDMS ultrathin films and patterned surface modification with cellulose. RSC Adv 4:11955–11961. doi: 10.1039/c3ra47380e CrossRefGoogle Scholar
- Charreau H, Foresti ML, Vázquez A (2013) Nanocellulose patents trends: a comprehensive review on patents on cellulose nanocrystals, microfibrillated and bacterial cellulose. Recent Pat Nanotechnol 7:56–80. doi: 10.2174/187221013804484854 CrossRefGoogle Scholar
- Cunha AG, Freire C, Silvestre A, Neto CP, Gandini A, Belgacem MN, Chaussy D, Beneventi D (2010) Preparation of highly hydrophobic and lipophobic cellulose fibers by a straightforward gas-solid reaction. J Colloid Interface Sci 344:588–595. doi: 10.1016/S1359-8368(98)00055-9 CrossRefGoogle Scholar
- DeMore WB, Sander SP, Golden DM, Hampson RF, Kurylo MJ, Howard CJ, Ravishankara AR, Kolb CE, Molina MJ (1997) Chemical kinetics and photochemical data for use in stratospheric modeling, evaluation number 12. JPL Publication 97-4. NASA Jet Propulsion Laboratory, California Institute of Technology, Pasadena, USA, pp 149–219Google Scholar
- Dulcey CS, Georger JH Jr, Krauthamer V, Stenger DA, Fare TL, Calvert JM (1991) Deep UV photochemistry of chemisorbed monolayers: patterned coplanar molecular assemblies. Science 252:551–554. doi: 10.1126/science.2020853 CrossRefGoogle Scholar
- Fadeev AY, McCarthy TJ (2000) Self-assembly is not the only reaction possible between alkyltrichlorosilanes and surfaces: monomolecular and oligomeric covalently attached layers of dichloro- and trichloroalkylsilanes on silicon. Langmuir 16:7268–7274. doi: 10.1021/la000471z CrossRefGoogle Scholar
- Fukuzumi H, Saito T, Iwata T, Kumamoto Y, Isogai A (2009) Transparent and high gas barrier films of cellulose nanofibers prepared by TEMPO-mediated oxidation. Biomacromolecules 10:162–165. doi: 10.1021/bm801065u CrossRefGoogle Scholar
- He Q, Ma C, Hu X, Chen H (2013) Method for fabrication of paper-based microfluidic devices by alkylsilane self-assembling and UV/O3-patterning. Anal Chem 85:1327–1331. doi: 10.1021/ac303138x CrossRefGoogle Scholar
- Henriksson M, Berglund LA, Isaksson P, Lindström T, Nishino T (2008) Cellulose nanopaper structures of high toughness. Biomacromolecules 9:1579–1585. doi: 10.1002/adma.200803174 CrossRefGoogle Scholar
- Jin M, Wang J, Hao Y, Liao M, Zhao Y (2011) Tunable geometry and wettability of organosilane nanostructured surfaces by water content. Polym Chem 2:1658–1660. doi: 10.1039/c1py00246e CrossRefGoogle Scholar
- Johansson L-S (2002) Monitoring fibre surfaces with XPS in papermaking processes. Microchim Acta 138:217–223. doi: 10.1007/s006040200025 CrossRefGoogle Scholar
- Kargl R, Mohan T, Köstler S, Spirk S, Doliška A, Stana-Kleinschek K, Ribitsch V (2013) Functional patterning of biopolymer thin films using enzymes and lithographic methods. Adv Funct Mater 23:308–315. doi: 10.1002/adfm.201200607 CrossRefGoogle Scholar
- Korhonen JT, Huhtamäki T, Verho T, Ras RHA (2014) Hollow polysiloxane nanostructures based on pressure-induced film expansion. Surf Innov 2:116–126. doi: 10.1680/si.13.00047 CrossRefGoogle Scholar
- Li S, Zhang S, Wang X (2008) Fabrication of superhydrophobic cellulose-based materials through a solution-immersion process. Langmuir 24:5585–5590. doi: 10.1021/la800157t CrossRefGoogle Scholar
- Malamud D, Drysdale JW (1978) Isoelectric points of proteins: a table. Anal Biochem 86:620–647. doi: 10.1016/0003-2697(78)90790-x CrossRefGoogle Scholar
- McGovern ME, Kallury KMR, Thompson M (1994) Role of solvent on the silanization of glass with octadecyltrichlorosilane. Langmuir 10:3607–3614. doi: 10.1021/la00022a038 CrossRefGoogle Scholar
- Milanez DH, Amaral RM, Faria LIL, Gregolin JAR (2013) Assessing nanocellulose developments using science and technology indicators. Mat Res 16:635–641. doi: 10.1590/S1516-14392013005000033 CrossRefGoogle Scholar
- Nogi M, Iwamoto S, Nakagaito AN, Yano H (2009) Optically transparent nanofiber paper. Adv Mater 21:1595–1598. doi: 10.1002/adma.200803174 CrossRefGoogle Scholar
- Österberg M, Peresin MS, Johansson L-S, Tammelin T (2013) Clean and reactive nanostructured cellulose surface. Cellulose 20:983–990. doi: 10.1007/s10570-013-9920-8 CrossRefGoogle Scholar
- Ostuni E, Chapman RG, Holmlin RE, Takayama S, Whitesides GW (2001) A survey of structure-property relationships of surfaces that resist the adsorption of protein. Langmuir 17:5605–5620. doi: 10.1021/la010384m CrossRefGoogle Scholar
- Peresin MS, Vartiainen J, Kunnari V, Kaljunen T, Tammelin T, Qvintus P (2012) Large-scale nanofibrillated cellulose film: an overview on its production, properties, and potential applications. In: Proceeding of the 4th International Conference on Pulping, Papermaking and Biotechnology (ICPPB’12), Nanjing, China, pp 891–895Google Scholar
- Rollings DAE, Veinot JGC (2008) Polysiloxane nanofibers via surface initiated polymerization of vapor phase reagents: a mechanism of formation and variable wettability of fiber-bearing substrates. Langmuir 24:13653–13662. doi: 10.1021/la801595m CrossRefGoogle Scholar
- Silva RA, Urzúa MD, Petri DFS, Dubin PL (2010) Protein adsorption onto polyelectrolyte layers: effects of protein hydrophobicity and charge anisotropy. Langmuir 26:14032–14038. doi: 10.1021/la102254g CrossRefGoogle Scholar
- Song J, Rojas OJ (2013) Approaching super-hydrophobicity from cellulosic materials: a review. Nord Pulp Pap Res J 28:216–238. doi: 10.3183/NPPRJ-2013-28-02-p216-238 CrossRefGoogle Scholar
- Stevens MJ (1999) Thoughts on the structure of alkylsilane monolayers. Langmuir 15:2773–2778. doi: 10.1021/la981064e CrossRefGoogle Scholar
- Swerin A, Ödberg L, Lindström T (1990) Deswelling of hardwood kraft pulp fibers by cationic polymers: the effect on wet pressing and sheet properties. Nord Pulp Pap Res J 5:188–196. doi: 10.3183/NPPRJ-1990-05-04-p188-196 CrossRefGoogle Scholar
- Tammelin T, Hippi U, Salminen A (2013) Method for the preparation of NFC films on supports. PCT Int Appl, WO 2013060934, PCT/FI2012/051015Google Scholar
- Tanford C, Buzzell JG (1956) The viscosity of aqueous solutions of bovine serum albumin between pH 4.3 and 10.5. J Phys Chem 60:225–231. doi: 10.1021/j150536a020 CrossRefGoogle Scholar
- Ulman A (1996) Formation and structure of self-assembled monolayers. Chem Rev 96:1533–1554. doi: 10.1021/cr9502357 CrossRefGoogle Scholar
- Valadez-Gonzalez A, Cervantes-Uc JM, Olayo R, Herrera-Franco PJ (1999) Chemical modification of henequén fibers with an organosilane coupling agent. Compos Part B Eng 30:321–331. doi: 10.1016/S1359-8368(98)00055-9 CrossRefGoogle Scholar
- Wang X, Liu G, Zhang G (2012) Effect of surface wettability on ion-specific protein adsorption. Langmuir 28:14642–14653. doi: 10.1021/la303001j CrossRefGoogle Scholar
- Wolfberger A, Kargl R, Griesser T, Spirk S (2014) Photoregeneration of trimethylsilyl cellulose as a tool for microstructuring ultrathin cellulose supports. Molecules 19:16266–16273. doi: 10.3390/molecules191016266 CrossRefGoogle Scholar
- Ye T, McArthur EA, Borguet E (2005) Mechanism of UV photoreactivity of alkylsiloxane self-assembled monolayers. J Phys Chem B 109:9927–9938. doi: 10.1021/jp0474273 CrossRefGoogle Scholar
- Yetisen AK, Akram MS, Lowe CR (2013) Paper-based microfluidic point-of-care diagnostic devices. Lab Chip 13:2210–2251. doi: 10.1039/c3lc50169h CrossRefGoogle Scholar