Understanding the Two-Dimensional Mixing Behavior of 1-Naphthalenethiol and Octanethiol.

A two-dimensional (2D) mixture in the form of a self-assembled monolayer composed of two distinct organothiol compounds was created by sequentially depositing 1-naphthalenethiol (1NT) and octanethiol (OT) on a gold surface. By varying the sequence of deposition, two mixed surface systems were created. The surface structure of the resulting mixed monolayer was characterized with Scanning Tunneling Microscopy (STM) and showed surface disorder across all investigated domains.

Electrochemical Attachment of Diazonium-Generated Films on Nanoporous Gold.

Nanoporous gold provides a high surface area platform for further chemistry, but the stability of the molecular linkages to the surface will limit applications. We attached aryl molecular layers to nanoporous gold electrodes through electrochemical reduction of the corresponding aryl-diazonium salt and studied the properties and stability of the resulting films in varied attachment conditions. Infrared reflection absorption spectroscopy and X-ray photoelectron spectroscopy were used to confirm the presence of the molecular layers.

Norrish Type I surface photochemistry for butyrophenone on TiO2(110).

The photofragmentation of butyrophenone yields benzoate and a propyl radical on oxidized TiO2(110). Oxygen dissociates in native oxygen vacancies to produce reactive oxygen adatoms which react with butyrophenone to create photoactive butyrophenone-O complexes that are sensitive to hole oxidation created upon UV illumination. The same O adatoms also trap one of the primary photoproducts, phenyl-CO, to produce benzoate.

Highly stable redox-active molecular layers by covalent grafting to conductive diamond.

We demonstrate a modular "click"-based functionalization scheme that allows inexpensive conductive diamond samples to serve as an ultrastable platform for surface-tethered electrochemically active molecules stable out to ∼1.3 V vs Ag/AgCl. We have cycled surface-tethered Ru(tpy)(2) to this potential more than 1 million times with little or no degradation in propylene carbonate and only slightly reduced stability in water and acetonitrile.

Surface chemistry for stable and smart molecular and biomolecular interfaces via photochemical grafting of alkenes.

Many emerging fields such as biotechnology and renewable energy require functionalized surfaces that are "smart" and highly stable. Surface modification schemes developed previously have often been limited to simple molecules or have been based on weakly bound layers that have limited stability. In this Account, we report on recent developments enabling the preparation of molecular and biomolecular interfaces that exhibit high selectivity and unprecedented stability on a range of covalent materials including diamond, vertically aligned carbon nanofibers, silicon, and metal oxides.

Photochemical grafting and patterning of biomolecular layers onto TiO2 thin films.

TiO2 thin films are highly stable and can be deposited onto a wide variety of substrate materials under moderate conditions. We demonstrate that organic alkenes will graft to the surface of TiO2 when illuminated with UV light at 254 nm and that the resulting layers provide a starting point for the preparation of DNA-modified TiO2 thin films exhibiting excellent stability and biomolecular selectivity. By using alkenes with a protected amino group at the distal end, the grafted layers can be deprotected to yield molecular layers with exposed primary amino groups that can then be used to covalently link DNA oligonucleotides to the TiO2 surface.

Highly stable molecular layers on nanocrystalline anatase TiO2 through photochemical grafting.

Well-defined molecular layers can be formed on the surface of nanocrystalline anatase TiO2 by photochemically grafting organic molecules bearing a terminal vinyl group. The molecular layers produced are shown to have minimal oxidation and are able to be patterned and uniformly grafted through optically thick nanocrystalline films. Stability tests show that the layers have excellent stability in deionized water at 80 degrees C, aqueous solutions at pH=1.