Published: May 25, 2011 r2011 American Chemical Society 7629 dx.doi.org/10.1021/la2007843 | Langmuir 2011, 27, 7629–7634 ARTICLE pubs.acs.org/Langmuir Site-Selective Surface Modification Using Enzymatic Soft Lithography Aur  elie Guyomard-Lack, † Nicolas Delorme, ‡ C  eline Moreau, † Jean-Franc - ois Bardeau, ‡ and Bernard Cathala* ,† † INRA, UR1268 Biopolymeres Interactions Assemblages, F-44316 Nantes, France ‡ Laboratoire de Physique de l’Etat Condens  e, UMR CNRS 6087, Universit  e du Maine b S Supporting Information ABSTRACT: Surface modification with functional polymers or molecules offers great promise for the development of smart materials and applications. Here, we describe a versatile and easy-to-use method of site-selective surface modification based on the ease of microcontact printing and the exquisite selectivity of enzymatic degradation. A micropatterned poly-L-lysine (PLL) layer on solid substrates was prepared by enzymatic degradation using trypsin enzyme immobilized on a prestructured poly(dimethlylsiloxane) (PDMS) stamp. After the enzymatic degradation of PLL and the removal of the degradation products, very well defined patterning was revealed over a large scale by fluorescence microscopy and atomic force microscopy (AFM). We investigate the advantage of our method by comparison with traditional microcontact printing and found that lateral diffusion was reduced, yielding a more accurate reproduction of the master. We also demonstrate that the stamp can be reused without reinking. The patterned surface was used for site-selective modification. The strategy was applied to two applications: the first is dedicated to the creation of amino-silane patterned surfaces, and the second illustrates the possibility of patterning polyelectrolyte multilayered thin films. ’ INTRODUCTION Surfaces patterned with micro- and nanoscale functional polymers or molecules that offer various physicochemical prop- erties have attracting considerable interest 1 for their potential applications in cell or tissue engineering, 2À4 biomimetic approaches, 5 and fundamental surface science research. 6 Soft lithography, which includes microcontact printing (μCP), has undergone a spectacular evolution since its discovery and now can achieve very fine patterning that can be applied to a wide variety of substrates. 7À10 μCP is simple enough to be used in a typical laboratory setting and does not require prohibitively expensive equipment. Moreover, μCP can also be used for the selective patterning of a surface when reactive or catalytic species are linked to the stamp. In the first case, reactive species are used as ink and transferred to the stamp. For instance, sulfonic acid- functionalized monolayer-protected gold nanoparticles were used as an ink to catalyze the hydrolysis of trimetylsilyl ether self-assembly monolayers (SAM) locally after their transfer onto the surface by microcontact printing. 11 However, despite the size of the nanoparticles that limits the diffusion, the granular nature of the nanoparticles causes an inhomogeneity in inking. To overcome this problem, the same authors report a catalytic strategy by creating functional groups on the printing stamp surface that are not transferred onto the SAM but can chemically modify the SAM surface during stamping. 12 This inkless strategy was used later by several groups to pattern surfaces by using either a chemical reaction 13À15 or a biocatalytic reaction. 16 In all cases, the catalytic microcontact improves the quality of the mold duplication by the limitation of lateral diffusion. The method reported here belongs to the catalytic strategy and is based on the deposition of a biopolymer layer on a surface and the hydrolysis of this layer by microcontact printing with an immobilized hydrolytic enzyme. Covalent attachment together with the exquisite selective degradation of enzyme provides high-quality Received: December 3, 2010 Revised: April 20, 2011