We report on an easy-to-use, successful, and reproducible route to synthesize functionalized graphite oxide (GO) and its conversion to graphene-like materials through chemical or thermal reduction of GO. Graphite oxide containing hydroxyl, epoxy, carbonyl, and carboxyl groups loses mainly hydroxyl and epoxy groups during reduction, whereas carboxyl species remain untouched. The interaction of functionalized graphene with fluorescent methylene blue (MB) is investigated and compared to graphite, fully oxidized GO, as well as thermally and chemically reduced GO. Optical absorption and emission spectra of the composites indicate a clear preference for MB interaction with the GO derivatives containing a large number of functional groups (GO and chemically reduced GO), whereas graphite and thermally reduced GO only incorporate a few MB molecules. These findings are consistent with thermogravimetric, X-ray photoelectron spectroscopic, and Raman data recorded at every stage of preparation. The optical data also indicate concentration-dependent aggregation of MB on the GO surface leading to stable MB dimers and trimers. The MB dimers are responsible for fluorescence quenching, which can be controlled by varying the pH value.

The adsorption and self‐organisation process of alkyl‐phosphonic acids and phosphoric acid monoalkyl esters on technical aluminium surfaces have been investigated by different surface sensible techniques: Grazing angle FT‐IR‐ spectroscopy, angle dependent XPS and Auger‐ spectroscopy. The aim of these studies was to replace the present technical procedure for pretreatment of aluminum surfaces with Chromate acid in order to improve the corrosion inhibition and the coating adhesion. The ability for self‐assembly is given by substances which have a surface reactive group and a long‐aliphatic or aromatic spacer and a supramolecular order is built‐up between these spacers. The results show that these molecules are able to adsorb spontaneously onto the aluminum surface and subsequently a structured molecular order is formed. These effects were confirmed by industrial linked adhesion and corrosion tests.

Summary: The infrared absorption (IR) spectrum of alkyl phosphonic acid adsorbed on the α‐Al2O3 (0001) surface has been calculated by means of a density‐functional based tight‐binding method. Thereby mono‐dentate, bi‐dentate and tri‐dentate bonding of the acid to the surface have been considered. In addition, experimentally obtained Fourier Transform Infrared Spectra (FTIR) of octadecylphosphonic acid (ODPA) on the natural surface of aluminium have been included. The absence of the PO band in the experimental surface spectrum and in the calculated spectrum of the tridentate adsorption complexes showed that adsorption of (alkyl)phosphonic acids on aluminium favours tridentate bonding, where the acid is bound to the surface via three symmetric POAl bonds.

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The surface immobilization of oligo- and poly(ethylene glycol) on solids is a widely used approach to prevent the nonspecific adsorption of proteins, bacteria, and cells. A novel tri(ethylene glycol) derivative, phosphoric acid-mono(22-carboxy-12,15,18,21-tetraoxadocosyl) ester, was synthesized with the aim to produce self-assembled monolayers (SAMs) on metal/metal oxide surfaces. This compound contains two reactive, terminal moieties: the phosphoric acid group as anchor to the surface, and the carboxylic group as linker for further attachment of molecules such as peptides and proteins to be present at the surface. The adsorption on titanium-dioxide-coated substrates was studied quantitatively and the resulting SAMs were characterized by angle-dependent X-ray photoelectron spectroscopy (XPS) and spectroscopic ellipsometry. XPS data showed that the monomolecular layer is attached with the phosphate group to the substrate, but not fully ordered. The dry adlayer thickness was determined to be 13.4 A, which is less than expected for a densely packed monolayer. Surface concentration calculated from ellipsometry data resulted in a grafting density of 2.03 molecules/nm2.

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We report on the improved assembly and characterization of a small molecule organic field‐effect transistor (OFET). Novel α,ω‐dicyano substituted β,β′‐dibutylquaterthiophene molecules (DCNDBQT) were synthesized and characterized by UV–Vis spectroscopy, differential scanning calorimetry, thermal gravimetric analysis and cyclic voltammetry. The ultra‐thin organic film formation on TiO2 templates was effectively promoted through the specifically designed bifunctional self assembly molecules (SAM) 5‐cyano‐2‐(butyl‐4‐phosphonic acid)‐3‐butylthiophene (CNBTPA). Excellent structural properties were found for up to 9 DCNDBQT molecule thick films prepared through UHV vacuum sublimation as investigated with UHV non‐contact atomic force microscopy (nc‐AFM) and X‐ray diffraction. Both X‐ray and nc‐AFM data indicate that the DCNDBQT molecules form a well‐ordered terraced structure exhibiting step heights of 1.5 nm to 2.0 nm layers. Hence, the DCNDBQTmolecules are linked to the functional SAM interface layer by H‐bond interactions (see structure model) standing quasi perpendicular to the TiO2 template, and thus providing optimal orbital overlap neigh‐bouring thiophene rings. The vacuum sublimated DCNDBQT molecules form a closed packed and dense molecular layer that was used to construct and operate a nanoscopic OFET‐structure. The resulting field mobilities of 10–5 cm2 V–1 s–1 reflect a high current density in our ultrathin but highly ordered structure. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)

The influence of the molecular structure on the stabilization of charged states was studied in detail by in situ ESR UV-vis NIR spectroelectrochemistry at a novel α,ω-dicyano substituted β,β'-dibutylquaterthiophene (DCNDBQT) and the electrochemically generated cation and anion radicals have been proved for the first time. The voltammetry of DCNDBQT results in two separate oxidation steps with the reversible first one. The experimental absorption maxima at 646 and 1052 nm together with the calculated ones (by DFT method) as well as an ESR signal at the first anodic step prove the presence of a radical cation. Three additional optical bands (554, 906, and 1294 nm for CT-transition) can be attributed to the formation of cation radical dimer. The dicationic structure formed in the second oxidation step is not stable. The stabilization proceeds via a dimer formation in two chemical follow-up reactions. The existence of the dimeric structures was proved by ex situ MALDI TOF mass spectrometry. As the substitution by cyano groups opens the route to cathodic reductions, DCNDBQT shows a single quasi-reversible reduction step. Here, the in situ ESR UV-vis NIR spectroelectrochemical measurements and theoretical calculations let us confirm the electrochemical generation of an anion radical. As we found a low number of anion radicals by quantitative ESR spectroelectrochemistry and an appearance of additional bands in the UV-vis NIR absorption spectra, the formation of dimeric structures must be considered and was corroborated by mass spectrometry. The role of dimerization in the reaction mechanism of the DCNDBQT oxidation and reduction are discussed in general. The experimental results were interpreted using the quantum chemical calculations based on density functional theory.