Amorphous carbon materials find numerous applications in diverse areas ranging from implantable biodevices to electronics and catalysis. The spontaneous grafting of aryldiazonium salts is an important strategy for the modification of these materials and it is widely used in order to display a range of functionalities or to provide anchoring groups for further functionalization. We have investigated the spontaneous attachment of 4-nitrobenzenediazonium salts from aqueous solutions onto amorphous carbon materials that differ in their sp 2 content with the aim of understanding to what extent bulk composition affects rates and yields of aryldiazonium adsorption at the carbon/solution interface. Amorphous carbons were deposited in the form of thin films via reactive magnetron sputtering, and were characterized using a combination of Raman, infrared, UV-Vis and X-ray Photoelectron Spectroscopy in order to determine their sp 2 content. Attenuated Total Internal Reflection Fourier Transform Infrared spectroscopy (ATR-FTIR) was used to monitor in situ and in real time the aryldiazonium adsorption process at the carbon/solution interface. These measurements demonstrate that rates and yields of adsorption for the same aryldiazonium salt increase non-linearly vs. sp 2 concentration. Studies of aryldiazonium salt grafting as a function of time carried out ex situ via cyclic voltammetry showed that the amorphous carbon film with highest sp 2 content displays significantly lower grafting yields than glassy carbon, a material with 100% sp 2 content. Intercalation experiments using 4-nitrobenzylamine suggest that the difference in relative density of graphitic edge planes exposed at the carbon surface is in excellent agreement with the observed relative grafting yields. We discuss the implications of these results for the development of structure/reactivity relationships that can be leveraged for understanding the surface chemistry of disordered carbon materials.

Please cite this article as: Natali M, Soldi L, Giordani S. A photoswitchable Zn (II) selective spiropyranbased sensor, Tetrahedron (2010Tetrahedron ( ), doi: 10.1016Tetrahedron ( /j.tet.2010 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

Self-assembled organic layers are an important tool for modifying surfaces in a range of applications in materials science. Covalent modification of metal surfaces with aryldiazonium cations has attracted much attention primarily because this reaction offers a route for spontaneously grafting a variety of aromatic moieties from solution with high yield. We have investigated the kinetics of this process by performing real-time, in situ nanogravimetric measurements. The spontaneous grafting of 4-nitrobenzene diazonium salts onto gold electrodes was studied via quartz crystal microbalance (QCM) from aqueous solutions of the salt at varying concentrations. The concentration dependence of the grafting rate within the first 10 min is best modeled by assuming a reversible adsorption process with free energy comparable to that reported for arylthiols self-assembled on gold. Multilayer formation was observed after extended grafting times and was found to be favored by increasing bulk concentrations of the diazonium salt. Modified gold surfaces were characterized ex situ with cyclic voltammetry, infrared reflection absorbance spectroscopy, and X-ray photoemission spectroscopy. Based on the experimentally determined free energy of adsorption and on the observed grafting rates, we discuss a proposed mechanism for aryldiazonium chemisorption.

This paper provides a synthetic and comprehensive overview on environmentally friendly anticorrosive polymeric coatings. Firstly, the economic and environmental impact of corrosion is presented to highlight the need of anticorrosive polymeric coatings as a flexible and effective solution to protect a metal. Secondly, the implementation of regulations together with the consumer awareness for environmental considerations and protection of health are the driving force for a progressive but significant change in the sector. Therefore, within the protective organic coatings market, this article provides a review of the most recent developments in environmentally friendly solutions, including bio-based and water-borne epoxy, hyperbranched polyester for low- volatile organic compounds (VOC) coatings, waterborne polyurethane and non-isocyanate polyurethanes (NIPUs), and graphene or bio-based fillers for acrylics. Moreover, this paper outlines new trends such as smart additives, bio-based corrosion inhibitors, and functional antibiocorrosive coatings as superhydrophobics. Finally, industrially relevant applications of environmentally friendly anticorrosive polymeric coatings including solutions for marine and off-shore industries are summarized.

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