Organic monolayer derivatization

In order to construct an ordered monolayer on a carbon surface, a premodified smooth and functionalized film is needed. Electrochemical reduction of diazonium salts or oxidation of amine-containing compounds and arylacetate produces free radicals, resulting in covalent derivatization of the carbon surface in nonaqueous solutions (Figure 3). The premodification by free radical grafting methods is quite mild, simple, and rapid experimentally. The monolayers prepared as a precursor film for subsequent assembly are stable to harsh environments and can endure elevated temperatures, and especially are organized in order, compact, and charge-rich. 

During the last decade the field of electrochemistry has witnessed a very fast progress on the modification of electrode surfaces. From the predominant use of random polymeric structures, prevalent in the electrode modification efforts of the late 70s and early 80s, electrochemists have learnt to control the molecular architecture of the electrode-solution interface to a degree that was clearly out of reach a decade ago. Many electrode modification methods developed recently rely on the use of thiolate self-assembled monolayers (SAMs) [1-3]. These systems offer unparalleled ease of preparation and levels of molecular organization close to those that can be reached with Langmuir-Blodgett film methods. Therefore, electrodes derivatized with unfunctionalized or functionalized alkanethiolate monolayers have been the subject of extensive research work during the last few years [4, 5]. 

Although silicon nanocrystals are now more commonly prepared by a variety of means which are easier to scale up, e.g., pyrolysis of silanes (Xuegeng et al. 2004), thermal treatment of silsesquioxanes (Hessel et al. 2006, 2010), and from reactions of molecular silicon compounds (Wilcoxon et al. 1999 Bley and Kauzlarich 1996), this review will concentrate on routes which proceed via the formation of porous silicon. More general reviews of silicon nanocrystals Irom physics and chemistry perspectives are available (Shirahata 2011 Kang et al. 2011 Heitmann et al. 2005). Derivatization of porous silicon and SiNCs usually relies on the chemistry of the hydrogen-terminated silicon surface, which shares some of the organic reactivity of hydrosilanes (Buriak 2002). Reaction with alcohols results in Si-O-C bonded monolayers (Sweryda-Krawiec et al. 1999), but these are suseeptible to hydrolysis under ambient conditions. Alternately, addition of surface Si-H aeross a C = C double bond produces Si-C bonded monolayers, which are very stable. 

ORIENTATION STUDIES OF LB FILMS FABRICATED WITH SURFACE ACTIVE PYRROLES AND POLYPYRROLE. The molecular organizations of multilayer thin films of the surface active pyrrole derivatives used to formed mixed monolayers with electrically conductive polypyrrole chains and ferrocene derivatized pyrroles have also been examined by FTIR reflection/absorption techniques. The materials investigated in... 

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