Thermoresponsive Chemical Connectors Based on Hybrid Nanowire Forests**

Microand nanostructured surfaces found in biological systems have inspired the fabrication of functional materials with unique optical, chemical, and mechanical properties. Inspired by the nanofibrillar structures of gecko adhesives, we recently reported self-selective, chemical connectors (i.e., fasteners) based on interpenetrating nanowire (NW) forests, which primarily use the highly tunable van der Waals (vdW) interactions to enable efficient binding of components at both macroand microscales. Of particular interest to certain practical applications are programmable fasteners that can change their adhesion properties on command, for example, in response to external stimuli. In this regard, herein, we report programmable NW fasteners that reversibly change their wet adhesion strength in response to a thermal change of the environment. The thermoresponsive NW fasteners are based on core/multishell hybrid NW forests with an outer shell of poly(N-isopropylacrylamide) (PNIPAM). PNIPAM is a thermoresponsive hydrogel with a lower critical solution temperature (LCST) of approximately 32 8C in water. Specifically, at room temperature, PNIPAM absorbs water, resulting in the swelling of the polymer and hydrophilic surface properties. However, PNIPAM shrinks at temperatures higher than the LCSTand transforms to a hydrophobic state. We utilized this well known property of PNIPAM in conjunction with high aspect ratio nanofibrillar structures to enable programmable fasteners with tunable properties. The fabrication procedure for the thermoresponsive NW fasteners is outlined in Figure 1a. First, Ge/parylene core/ shell NW forests were prepared by growing Ge NW forests

[1]  Metin Sitti,et al.  Adhesion and anisotropic friction enhancements of angled heterogeneous micro-fiber arrays with spherical and spatula tips , 2007 .

[2]  Ronald S. Fearing,et al.  Wet and Dry Adhesion Properties of Self‐Selective Nanowire Connectors , 2009 .

[3]  Liangti Qu,et al.  Carbon Nanotube Arrays with Strong Shear Binding-On and Easy Normal Lifting-Off , 2008, Science.

[4]  T. Okano,et al.  Comb-type grafted hydrogels with rapid deswelling response to temperature changes , 1995, Nature.

[5]  R. Rosenfeld Nature , 2009, Otolaryngology--head and neck surgery : official journal of American Academy of Otolaryngology-Head and Neck Surgery.

[6]  K. Iwai,et al.  Fluorescence label studies of thermo-responsive poly(N-isopropylacrylamide) hydrogels , 2000 .

[7]  Jianzhong Wu,et al.  Phase behavior of thermally responsive microgel colloids. , 2003, Physical review letters.

[8]  Hyunhyub Ko,et al.  Hybrid core-multishell nanowire forests for electrical connector applications , 2009 .

[9]  M. Shibayama,et al.  Shrinking Kinetics of Poly(N-isopropylacrylamide) Gels T-Jumped across Their Volume Phase Transition Temperatures , 1999 .

[10]  Pulickel M. Ajayan,et al.  Carbon nanotube-based synthetic gecko tapes , 2007, Proceedings of the National Academy of Sciences.

[11]  Ralph Spolenak,et al.  Evidence for capillarity contributions to gecko adhesion from single spatula nanomechanical measurements. , 2005, Proceedings of the National Academy of Sciences of the United States of America.

[12]  Ronald P. Manginell,et al.  Programmed Adsorption and Release of Proteins in a Microfluidic Device , 2003, Science.

[13]  R. Full,et al.  Adhesive force of a single gecko foot-hair , 2000, Nature.

[14]  H. G. Schild Poly(N-isopropylacrylamide): experiment, theory and application , 1992 .

[15]  P. C. Rieke,et al.  Reversible Surface Properties of Glass Plate and Capillary Tube Grafted by Photopolymerization of N-Isopropylacrylamide , 1998 .

[16]  Y. Nakayama,et al.  Thermoresponsive artificial extracellular matrix for tissue engineering: hyaluronic acid bioconjugated with poly(N-isopropylacrylamide) grafts. , 2001, Biomacromolecules.

[17]  A. Geim,et al.  Microfabricated adhesive mimicking gecko foot-hair , 2003, Nature materials.

[18]  George M. Whitesides,et al.  Beyond molecules: Self-assembly of mesoscopic and macroscopic components , 2002, Proceedings of the National Academy of Sciences of the United States of America.

[19]  C. Tanford Macromolecules , 1994, Nature.

[20]  A. Scherz,et al.  Stimuli responsive materials: new avenues toward smart organic devices , 2005 .

[21]  Clément Sanchez,et al.  Biomimetism and bioinspiration as tools for the design of innovative materials and systems , 2005, Nature materials.

[22]  Hyunhyub Ko,et al.  Hybrid core-shell nanowire forests as self-selective chemical connectors. , 2009, Nano letters.

[23]  A. Fujishima,et al.  Effects of the Surface Roughness on Sliding Angles of Water Droplets on Superhydrophobic Surfaces , 2000 .