Advanced optical applications of fluorescent carbon dots (C-dots) require highly integrated host-guest solid-state materials with a careful design of C-dots – matrix interface to control the optical response. We have developed a new synthesis based on the grafting of an organo-functional silane (3-glycidyloxypropyltrimethoxysilane, GPTMS) on amino-functionalized C-dots, which enables the fabrication of highly fluorescent organosilica-based hybrid organic-inorganic films through sol-gel process. The GPTMS grafting onto C-dots has been achieved via an epoxy–amine reaction under controlled conditions. Besides providing an efficient strategy to embed C-dots into a hybrid solid-state material, the modification of C-dots surface by GPTMS allows tuning their photoluminescence properties and gives rise to an additional, intense emission around 490 nm. Photoluminescence spectra reveal an interaction between C-dots surface and the polymeric chains which are locally formed by GPTMS polymerization. The present method is a step forward to the development of a surface modification technology aimed at controlling C-dots host-guest systems at the nanoscale.
The molecular-imprinting approach was used to obtain a nanogel preparation capable of catalysing the cross-aldol reaction between 4-nitrobenzaldehyde and acetone. A polymerisable proline derivative was used as the functional monomer to mimic the enamine-based mechanism of aldolase type I enzymes. The diketone template used to create the cavity was designed to imitate the intermediate of the aldol reaction and was bound to the functional monomer using a reversible covalent interaction prior to polymerisation. By using a high-dilution polymerisation method, soluble imprinted nanogels were prepared with dimensions similar to those of an enzyme and with the advantage of solubility and flexibility previously unattainable with monolithic polymers. Following template removal and estimation of active-site concentrations, the kinetic characterisation of both imprinted and non-imprinted nanogels was carried out with catalyst concentrations between 0.7 and 3.5 mol %. Imprinted nanogel AS147 was found to have a k(cat) value of 0.25 x 10(-2) min(-1), the highest value ever achieved with imprinted polymers catalysing C--C bond formation. Comparison of the catalytic constants for both imprinted nanogel AS147 and non-imprinted nanogel AS133 gave a ratio of k(cat 147)/k(cat 133)=18.8, which is indicative of good imprinting efficiency and highlights the significance of the template during the imprinting process. This work represents a significant demonstration of the superiority of nanogels, when the molecular-imprinting approach is used, over "bulk" polymers for the generation of catalysts.
The present review is focused on a specific class of nanocomposites obtained through integration of graphene or carbon-based nanomaterials (such as carbon nanodots) with mesoporous inorganic or hybrid materials, obtained via template assisted self-assembly. The task of integrating graphene and carbon nanodots with a self-assembly process is still very challenging and this review shows some of the solutions which have been envisaged so far. These nanocomposite materials are an ideal interactive platform for developing innovative functional applications; they have a high capability of undergoing integration into advanced devices, which well exploits the advantage of tuning the wide properties and flexibility of the soft-chemistry route. A wide range of applications have been developed so far which span from sensing to electronics up to optics and biomedicine. Even though a large number of proof-of-concepts have been reported to date, an even greater expansion of applications in the field is expected to happen in the near future.
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