Shaping graphene with optical forging: from a single blister to complex 3D structures.

Properties of graphene, such as electrical conduction and rigidity can be tuned by introducing local strain or defects into its lattice. We used optical forging, a direct laser writing method, under an inert gas atmosphere, to produce complex 3D patterns of single layer graphene. We observed bulging of graphene out of the plane due to defect induced lattice expansion. By applying low peak fluences, we obtained a 3D-shaped graphene surface without either ablating it or deforming the underlying Si/SiO2 substrate. We used micromachining theory to estimate the single-pulse modification threshold fluence of graphene, which was 8.3 mJ cm-2, being an order of magnitude lower than the threshold for ablation. The control of exposure parameters allowed the preparation of blisters with various topographies. The optically forged structures were studied with atomic force microscopy and Raman spectroscopy. Optically forged blisters act as building blocks in the formation of more complex structures. We found a simple geometric rule that helps to predict the shape of complex patterns which are created by the overlapping multiple exposures. Optical forging enables writing of extended patterns with diffraction unlimited features, which makes this method promising in the production of nanodevices with locally induced surface modifications.

Tuning protein adsorption on graphene surfaces via laser-induced oxidation.

An approach for controlled protein immobilization on laser-induced two-photon (2P) oxidation patterned graphene oxide (GO) surfaces is described. Selected proteins, horseradish peroxidase (HRP) and biotinylated bovine serum albumin (b-BSA) were successfully immobilized on oxidized graphene surfaces, via non-covalent interactions, by immersion of graphene-coated microchips in the protein solution. The effects of laser pulse energy, irradiation time, protein concentration and duration of incubation on the topography of immobilized proteins and consequent defects upon the lattice of graphene were systemically studied by atomic force microscopy (AFM) and Raman spectroscopy. AFM and fluorescence microscopy confirmed the selective aggregation of protein molecules towards the irradiated areas. In addition, the attachment of b-BSA was detected by a reaction with fluorescently labelled avidin-fluorescein isothiocyanate (Av-FITC). In contrast to chemically oxidized graphene, laser-induced oxidation introduces the capability for localization on oxidized areas and tunability of the levels of oxidation, resulting in controlled guidance of proteins by light over graphene surfaces and progressing towards graphene microchips suitable for biomedical applications.

Higher activation barriers can lift exothermic rate restrictions in electron transfer and enable faster reactions.

Electron transfer reactions are arguably the simplest chemical reactions but they have not yet ceased to intrigue chemists. Charge-separation and charge-recombination reactions are at the core of life-sustaining processes, molecular electronics and solar cells. Intramolecular electron donor-acceptor systems capture the essential features of these reactions and enable their fundamental understanding. Here, we report intramolecular electron transfers covering a range of 100 kcal mol-1 in exothermicities that show an increase, then a decrease, and finally an increase in rates with the driving force of the reactions. Concomitantly, apparent activation energies change from positive, to negative and finally to positive. Reactions with positive activation energies are found to be faster than analogous reactions with negative effective activation energies. The increase of the reorganization energy with the driving force of the reactions can explain the peculiar free-energy relationship observed in this work.

Dynamics of Radical Ion Pairs following Photoinduced Electron Transfer in Solvents with Low and Intermediate Polarities.

Fluorescence quenching of p-xylene, naphthalene, or pyrene by fumaronitrile in apolar solvents and in solvents of intermediate polarities leads to weakly fluorescent radical ion pairs. This emission is assigned to ion pairs in close contact on the basis of their solvent polarity dependence, kinetics, and thermodynamics. The temperature-dependence of the intensity and fluorescence emission maxima of ion pairs in methyl acetate reveals that they have decay channels competitive with their thermal equilibration. The results presented in this work are consistent with the direct formation of contact ion pairs in weakly polar solvents and in solvents of intermediate polarities as the result of bimolecular photoinduced electron transfer reactions between aromatic hydrocarbons and nitriles. The implications of these findings in free-energy relationships of electron transfer reactions are discussed.