Jussi Kauppila

Electrochemical reduction of graphene oxide and its in situ spectroelectrochemical characterization

The electrochemical properties of self-assembled films of graphene oxide (GO) on mercaptoethylamine (MEA) modified rough Au-surfaces were studied. The film deposition process on MEA primed gold was followed by surface plasmon resonance measurements and the film morphology on 3-aminopropyltriethoxysilane primed Si(100)-surface was studied by atomic force microscopy. The deposited few layer thick GO films on gold were electrochemically reduced by cyclic voltammetry simultaneously as the structural changes in the film were recorded by in situ vibrational spectroscopies. In situ surface enhanced infrared spectroscopy results indicate that the effect of the applied potential on the GO structure could be divided into two parts where the changes occurring at moderate negative potentials are mainly related to changes in the double layer at the film-electrolyte interface and to hydrogen bonding of intercalated water between the GO sheets. At potentials more negative than -0.8 V vs. Ag/AgCl the reduction of GO starts to take place with concomitant conversion of the different functional groups of the film.

Confinement Effects on Drugs in Thermally Hydrocarbonized Porous Silicon

Thermally hydrocarbonized porous silicon (THCPSi) microparticles were loaded with indomethacin (IMC) and griseofulvin (GSV) using three different payloads between 6.2-19.5 and 6.2-11.4 wt %, respectively. The drug loading parameters were selected to avoid crystallization of the drug molecules on the external surface of the particles that would block the pore entrances. The successfulness of the loadings was verified with TG, DSC, and XRPD measurements. The effects of the confinement of IMC and GSV into the small mesopores of THCPSi were analyzed with helium pycnometry, FTIR, and NMR spectroscopy. The results showed the density of the THCPSi loaded drugs to be ca. 10% lower than the bulk crystalline forms, while a melt quenched amorphous drugs showed a density reduction of 3-7.5%. DSC and FTIR results confirmed that the drugs reside in an amorphous form within the THCPSi pores. Similar results were obtained with NMR, which also indicated that IMC may reside as both amorphous clusters and individual molecules within the pores. The (1)H transverse relaxation times (T2) of amorphous and THCPSi loaded drugs showed IMC relaxation times of 0.28 ms for both the cases, whereas for GSV the values were 0.32 and 0.39 ms, respectively, indicating similar limited mobility in both cases. The results indicated that strong drug-carrier interactions were not necessary for stabilizing the amorphous state of the adsorbed drug. Dissolution tests using biorelevant media, fasted state simulated intestinal fluid (FaSSIF) and simulated gastric fluid (SGF), showed that THCPSi-loaded IMC and GSV were rapidly released in FaSSIF with comparable rates to the amorphous forms, whereas in SGF the THCPSi reduced the pH dependency in the dissolution of IMC.

Effective low temperature reduction of graphene oxide with vanadium(III)

Reduction of graphene oxide (GO) with vanadium(III) trichloride under various reaction conditions has been investigated. The results show that V(III) can be used as an efficient reducing agent for GO in aqueous solutions at low concentrations and in moderate temperatures under ambient conditions. The IR spectroscopy and X-ray photoelectron spectroscopy (XPS) show that the structure of the vanadium-reduced material is similar to reduced graphene oxide prepared using TiCl3 or hydrazine as a reducing agent. The electrical conductivity of the material is also similar in all cases. However, on the basis of the XPS results, vanadium-based reduction does not leave significant reductant impurities in the product and does not lead to graphene substitution reactions. The success of vanadium(III) is somewhat surprising because the formal redox potential of the V(IV)/V(III) pair is rather anodic, but spectrophotometric studies of the reaction unambiguously showed that the process is a redox reaction. This method introduces a new facile graphene oxide reduction technique, which can be applied under ambient aqueous conditions.

Oxidative Layer-By-Layer Multilayers Based on Metal Coordination: Influence of Intervening Graphene Oxide Layers

Layer-by-layer (LbL) fabricated oxidative multilayers consisting of successive layers of inorganic polyphosphate (PP) and Ce(IV) can electrolessly form thin conducting polymer films on their surface. We describe the effect of substituting every second PP layer in the (PP/Ce) multilayers for graphene oxide (GO) as a means of modifying the structure and mechanical properties of these (GO/Ce/PP/Ce) films and enhancing their growth. Both types of LbL films are based on reversible coordinative bonding between the metal ions and the oxygen-bearing groups in PP and GO, instead of purely electrostatic interactions. The GO incorporation leads to the doubling of the areal mass density and to a dry film thickness close to 300 nm after 4 (GO/Ce/PP/Ce) tetralayers. The film roughness increases significantly with thickness. The (PP/Ce) films are soft materials with approximately equal shear storage and loss moduli, but the incorporation of GO doubles the storage modulus. PP displays a marked terminating layer effect and practically eliminates mechanical losses, making the (GO/Ce/PP/Ce) films almost pure soft elastomers. The smoothness of the (PP/Ce) films and the PP-termination effects are attributed to the reversible coordinative bonding. The (GO/Ce/PP/Ce) films oxidize pyrrole and 3,4-ethylenedioxythiophene (EDOT) and form polypyrrole and PEDOT films on their surfaces. These polymer films are considerably thicker than those formed using the (PP/Ce) multilayers with the same nominal amount of cerium layers. The GO sheets interfere with the polymerization reaction and make its kinetics biphasic. The (GO/Ce) multilayers without PP are brittle and thin.