Alessandro Kovtun

Electrochemical Functionalization of Graphene at the Nanoscale with Self-Assembling Diazonium Salts

We describe a fast and versatile method to functionalize high-quality graphene with organic molecules by exploiting the synergistic effect of supramolecular and covalent chemistry. With this goal, we designed and synthesized molecules comprising a long aliphatic chain and an aryl diazonium salt. Thanks to the long chain, these molecules physisorb from solution onto CVD graphene or bulk graphite, self-assembling in an ordered monolayer. The sample is successively transferred into an aqueous electrolyte, to block any reorganization or desorption of the monolayer. An electrochemical impulse is used to transform the diazonium group into a radical capable of grafting covalently to the substrate and transforming the physisorption into a covalent chemisorption. During covalent grafting in water, the molecules retain the ordered packing formed upon self-assembly. Our two-step approach is characterized by the independent control over the processes of immobilization of molecules on the substrate and their covalent tethering, enabling fast (t < 10 s) covalent functionalization of graphene. This strategy is highly versatile and works with many carbon-based materials including graphene deposited on silicon, plastic, and quartz as well as highly oriented pyrolytic graphite.

Poly(3-hexylthiophene) Nanoparticles Containing Thiophene-S,S-dioxide: Tuning of Dimensions, Optical and Redox Properties, and Charge Separation under Illumination

We describe the preparation of poly(3-hexylthiophene-S,S-dioxide) nanoparticles using Rozens reagent, HOF·CH3CN, either on poly(3-hexylthiophene) (P3HT) or on preformed P3HT nanoparticles (P3HT-NPs). In the latter case, core-shell nanoparticles (P3HT@PTDO-NPs) are formed, as confirmed by X-ray photoelectron spectroscopy measurements, indicating the presence of oxygen on the outer shell. The different preparation modalities lead to a fine-tuning of the chemical-physical properties of the nanoparticles. We show that absorption and photoluminescence features, electrochemical properties, size, and stability of colloidal solutions can be finely modulated by controlling the amount of oxygen present. Atomic force microscopy measurements on the nanoparticles obtained by a nanoprecipitation method from preoxidized P3HT (PTDO-NPs) display spherical morphology and dimensions down to 5 nm. Finally, Kelvin probe measurements show that the coexistence of p- and n-type charge carriers in all types of oxygenated nanoparticles makes them capable of generating and separating charge under illumination. Furthermore, in core-shell nanoparticles, the nanosegregation of the two materials, in different regions of the nanoparticles, allows a more efficient charge separation.

Electrical release of dopamine and levodopa mediated by amphiphilic β-cyclodextrins immobilized on polycrystalline gold

Vesicles of cationic amphiphilic β-cyclodextrins have been immobilized on polycrystalline gold by exploiting the chemical affinity between their amino groups and Au atoms. The presence of cyclodextrins has been widely investigated by means of AFM, XPS, kelvin probe and electrochemical measurements. This multi-functional coating confers distinct electrochemical features such as pH-dependent behavior and partial/total blocking properties towards electro-active species. The host-guest properties of β-cyclodextrins have been successfully exploited in order to trap drugs, like dopamine and levodopa. The further release of these drugs was successfully achieved by providing specific electrical stimuli. This proof-of-concept led us to fabricate an electronic device (i.e. an organic transistor) capable of dispensing both dopamine and levodopa in aqueous solution.

Charge-Injection Organic Gauges to Detect Dopamine Down to the Nanomolar Scale

A multilayer self-assembled monolayer (MuL-SAM) composed by i) cysteamine, ii) 4-formilphenyl boronic acid and iii) dopamine has been used to functionalize polycrystalline Au. Its electrochemical characterization shows how this surface engineering makes Au reactive toward dopamine. Kelvin probe measurements have shown how MuL-SAM tunes the surface potential of the bare Au. Such measurements are correlated with the electrical performances of organic field-effect transistors (OFETs), whose source/drain electrodes have been functionalized by MuL-SAM. Such devices, operated as charge-injection organic gauges (CIOGs), have shown sensitivity to the concentration of dopamine in the range of [1, 50] nM.

Graphene Oxide Promotes Site-Selective Allylic Alkylation of Thiophenes with Alcohols

The graphene oxide (GO) assisted allylic alkylation of thiophenes with alcohols is presented. Mild reaction conditions and a low GO loading enabled the isolation of a range of densely functionalized thienyl and bithienyl compounds in moderate to high yields (up to 90%). The cooperative action of the Brønsted acidity, epoxide moieties, and π-surface of the 2D-promoter is highlighted as crucial in the reaction course of the present Friedel-Crafts-type protocol.

Graphene-Pyrene Nanocomposites Obtained Using Azide Chemistry

In this study we describe a simple and fast procedure for the covalent functionalization of pristine graphene with a pyrene-terminated alkylazide, transformed in a highly reactive radical by thermal activation. The functionalized graphene sheets showed enhanced dispersibility in organic solvents compared to the pristine ones, thus enhancing their solution processability and compatibility with solvents or polymers. The relative improvement of solubility estimated form the absorption spectra was ≈60% in CHCl3 and ≈1200% in THF. The obtained materials were characterized by optical absorption spectroscopy, photoemission spectroscopy, infrared spectroscopy and X-rays photoelectron spectroscopy. The presence of the pyrene photoemitting chromophore in the grafting unit allowed to monitor the successful grafting and to confirm the effectiveness of the alkylazide to improve graphene solubility even when present in small amounts on the graphene surface.