Crystallographic structure and morphology of bithiophene-fluorene polymer nanocrystals

Nanocrystals of the polymer poly(9,9-dioctylfluorenyl-co-bithiophene) (F8T2) with a molecular weight of 3.2 kg/mol are grown in a para-xylene solution. The typical morphology of the crystals is needle like with typical widths of 50 nm and lengths of about 200 nm. The crystal structure and morphology are stable up to a temperature of 353 K. The structure solution is obtained by x-ray powder diffraction (XRD) pattern with data modelling by a stochastic global optimization procedure which allows simultaneous indexing and molecular packing determination. Final Rietveld refinement was applied on the most promising crystal structure with a = 1.376 nm, b = 3.105 nm, c = 2.690 nm and ß = 109.5° within the space group C2/c choosing the polymer backbone parallel to the b-axis. The structural motifs of the molecular packing could be identified: aromatic units within a single polymer chain are slightly bent relative to the chain axis, octyl side chains are aligned along the polymer backbone and aromatic units of neighbouring molecules display a strong tendency to stack parallel to each other. XRD results of F8T2 with a molecular weight of 19 kg/mol reveal the same peak positions compared to the 3.2 kg/mol material, showing that both materials crystallise similarly and can be described by the same crystallographic unit cell. The smaller peak intensities together with the broader peak widths, however, show that the ability of crystal formation for the 19 kg/mol material is reduced

Adsorption Studies of Organophosphonic Acids on Differently Activated Gold Surfaces

In this study, the formation of self-assembled monolayers consisting of three organophosphonic acids (vinyl-, octyl-, and tetradecylphosphonic acid) from isopropanol solutions onto differently activated gold surfaces is studied in situ and in real time using multiparameter surface plasmon resonance (MP-SPR). Data retrieved from MP-SPR measurements revealed similar adsorption kinetics for all investigated organophosphonic acids (PA). The layer thickness of the immobilized PA is in the range of 0.6–1.8 nm corresponding to monolayer-like coverage and correlates with the length of the hydrocarbon chain of the PA molecules. After sintering the surfaces, the PA are irreversibly attached onto the surfaces as proven by X-ray photoelectron spectroscopy and attenuated total reflection infrared and grazing incidence infrared spectroscopy. Potential adsorption modes and interaction mechanisms are proposed

Tunable Semicrystalline Thin Film Cellulose Substrate for High-Resolution, <i>In-Situ</i> AFM Characterization of Enzymatic Cellulose Degradation

In the field of enzymatic cellulose degradation, fundamental interactions between different enzymes and polymorphic cellulose materials are of essential importance but still not understood in full detail. One technology with the potential of direct visualization of such bioprocesses is atomic force microscopy (AFM) due to its capability of real-time <i>in situ</i> investigations with spatial resolutions down to the molecular scale. To exploit the full capabilities of this technology and unravel fundamental enzyme–cellulose bioprocesses, appropriate cellulose substrates are decisive. In this study, we introduce a semicrystalline-thin-film-cellulose (SCFTC) substrate which fulfills the strong demands on such ideal cellulose substrates by means of (1) tunable polymorphism via variable contents of homogeneously sized cellulose nanocrystals embedded in an amorphous cellulose matrix; (2) nanoflat surface topology for high-resolution and high-speed AFM; and (3) fast, simple, and reproducible fabrication. The study starts with a detailed description of SCTFC preparation protocols including an in-depth material characterization. In the second part, we demonstrate the suitability of SCTFC substrates for enzymatic degradation studies by combined, individual, and sequential exposure to TrCel6A/TrCel7A cellulases (<i>Trichoderma reesei</i>) to visualize synergistic effects down to the nanoscale

Tunable Semicrystalline Thin Film Cellulose Substrate for High-Resolution, <i>In-Situ</i> AFM Characterization of Enzymatic Cellulose Degradation

In the field of enzymatic cellulose degradation, fundamental interactions between different enzymes and polymorphic cellulose materials are of essential importance but still not understood in full detail. One technology with the potential of direct visualization of such bioprocesses is atomic force microscopy (AFM) due to its capability of real-time <i>in situ</i> investigations with spatial resolutions down to the molecular scale. To exploit the full capabilities of this technology and unravel fundamental enzyme–cellulose bioprocesses, appropriate cellulose substrates are decisive. In this study, we introduce a semicrystalline-thin-film-cellulose (SCFTC) substrate which fulfills the strong demands on such ideal cellulose substrates by means of (1) tunable polymorphism via variable contents of homogeneously sized cellulose nanocrystals embedded in an amorphous cellulose matrix; (2) nanoflat surface topology for high-resolution and high-speed AFM; and (3) fast, simple, and reproducible fabrication. The study starts with a detailed description of SCTFC preparation protocols including an in-depth material characterization. In the second part, we demonstrate the suitability of SCTFC substrates for enzymatic degradation studies by combined, individual, and sequential exposure to TrCel6A/TrCel7A cellulases (<i>Trichoderma reesei</i>) to visualize synergistic effects down to the nanoscale