Tribochemical nanolithography: selective mechanochemical removal of photocleavable nitrophenyl protecting groups with 23 nm resolution at speeds of up to 1 mm s−1

We describe the mechanochemical regulation of a reaction that would otherwise be considered to be photochemical, via a simple process that yields nm spatial resolution. An atomic force microscope (AFM) probe is used to remove photocleavable nitrophenyl protecting groups from alkylsilane films at loads too small for mechanical wear, thus enabling nanoscale differentiation of chemical reactivity. Feature sizes of 20–50 nm are achieved repeatably and controllably at writing rates up to 1 mm s−1. Line widths vary monotonically with the load up to 2000 nN. To demonstrate the capacity for sophisticated surface functionalisation provided by this strategy, we show that functionalization of nanolines with nitrilo triacetic acid enables site-specific immobilization of histidine-tagged green fluorescent protein. Density functional theory (DFT) calculations reveal that the key energetic barrier in the photo-deprotection reaction of the nitrophenyl protecting group is excitation of a π–π* transition (3.1 eV) via an intramolecular charge-transfer mechanism. Under modest loading, compression of the adsorbate layer causes a decrease in the N–N separation, with the effect that this energy barrier can be reduced to as little as 1.2 eV. Thus, deprotection becomes possible via either absorption of visible photons or phononic excitation transfer, facilitating fast nanolithography with a very small feature size

From Monochrome to Technicolor: Simple Generic Approaches to Multicomponent Protein Nanopatterning Using Siloxanes with Photoremovable Protein-Resistant Protecting Groups.

We show that sequential protein deposition is possible by photodeprotection of films formed from a tetraethylene-glycol functionalized nitrophenylethoxycarbonyl-protected aminopropyltriethoxysilane (NPEOC-APTES). Exposure to near-UV irradiation removes the protein-resistant protecting group, and allows protein adsorption onto the resulting aminated surface. The protein resistance was tested using proteins with fluorescent labels and microspectroscopy of two-component structures formed by micro- and nanopatterning and deposition of yellow and green fluorescent proteins (YFP/GFP). Nonspecific adsorption onto regions where the protecting group remained intact was negligible. Multiple component patterns were also formed by near-field methods. Because reading and writing can be decoupled in a near-field microscope, it is possible to carry out sequential patterning steps at a single location involving different proteins. Up to four different proteins were formed into geometric patterns using near-field lithography. Interferometric lithography facilitates the organization of proteins over square cm areas. Two-component patterns consisting of 150 nm streptavidin dots formed within an orthogonal grid of bars of GFP at a period of ca. 500 nm could just be resolved by fluorescence microscopy

Zwitterionic Poly(amino acid methacrylate) Brushes

A new cysteine-based methacrylic monomer (CysMA) was conveniently synthesized via selective thia-Michael addition of a commercially available methacrylate-acrylate precursor in aqueous solution without recourse to protecting group chemistry. Poly(cysteine methacrylate) (PCysMA) brushes were grown from the surface of silicon wafers by atom-transfer radical polymerization. Brush thicknesses of ca. 27 nm were achieved within 270 min at 20 °C. Each CysMA residue comprises a primary amine and a carboxylic acid. Surface zeta potential and atomic force microscopy (AFM) studies of the pH-responsive PCysMA brushes confirm that they are highly extended either below pH 2 or above pH 9.5, since they possess either cationic or anionic character, respectively. At intermediate pH, PCysMA brushes are zwitterionic. At physiological pH, they exhibit excellent resistance to biofouling and negligible cytotoxicity. PCysMA brushes undergo photodegradation: AFM topographical imaging indicates significant mass loss from the brush layer, while XPS studies confirm that exposure to UV radiation produces surface aldehyde sites that can be subsequently derivatized with amines. UV exposure using a photomask yielded sharp, well-defined micropatterned PCysMA brushes functionalized with aldehyde groups that enable conjugation to green fluorescent protein (GFP). Nanopatterned PCysMA brushes were obtained using interference lithography, and confocal microscopy again confirmed the selective conjugation of GFP. Finally, PCysMA undergoes complex base-catalyzed degradation in alkaline solution, leading to the elimination of several small molecules. However, good long-term chemical stability was observed when PCysMA brushes were immersed in aqueous solution at physiological pH