Local force titration of wood surfaces by chemical force microscopy

Cellulose - Chemical force microcopy, a variation of atomic force microscopy, opened the door to visualize chemical nano-properties of various materials in their natural state. The key function of...     

Alignment and resonances in 12C+12C inelastic scattering

Using the out-of-plane γ-ray particle coincidence method we have measured the spin alignment P_zz of excited ¹²C(2⁺) nuclei from ¹²C+¹²C inelastic scattering in the energy range 16 MeV ? E_cm ? 33 MeV.P_zz varies strongly as a function of energy and angle. The correlation of resonant structures in the cross section with maxima of the alignment is particularly clear in mutual inelastic scattering and in θ_cm = 90° single inelastic scattering.     

Scattering and reactions of 14C + 14C and 14C + 14C

We have studied elastic scattering, inelastic scattering and several transfer channels of the systems ¹⁴C + ¹⁴C and ¹⁴C + ¹²C over a wide range of energies up to E_c.m. = 35 eMeV and 32 MeV, respectively. The reaction channels were identified by means of kinematic coincidences between solid-state detectors, γγ coincidences were measured to determine cross sections for mutual inelastic scattering of ¹⁴C + ¹⁴C.Pronounced regular gross structures, similar to those found for ¹⁶O + ¹⁶O, are observed in the elastic excitation function of ¹⁴C + ¹⁴C at θ_c.m. = 90°, The angular distributions measured at the energies of the maxima and an optical-model analysis suggest that one or a few surface partial waves dominate the scattering behaviour. Correlated structure of narrower width is found in the inelastic channels and, to a lesser degree, in the transfer channels which appear with rather small cross sections.In ¹⁴C + ¹²C elastic scattering the gross structures are strongly fragmented, in contrast to ¹⁴C + ¹⁴C but similar to ¹²C + ¹²C. While the ¹²C(2⁺) excitation is very weak, the observed strengths of the ¹⁴C(3^?) excitation and of neutron transfer point to a substantial role of these channels as coupling partners to the elastic configuration and to their influence on the elastic scattering behaviour. A correlated intermediate structure is observed near 23.5 MeV, where a dominance of l = 18 is suggested by the elastic scattering angular distribution. This unexpectedly high l-value exceeds l_graz at this energy by at least two units of ?.     

Nanoindentation of regenerated cellulose fibres

Nanoindentation was performed on cross sections of regenerated cellulose fibres with different structure and properties. Same as in single-fibre tensile tests, the elastic modulus of lyocell was higher than the elastic modulus of viscose. However, in spite of its tensile strength being twice as high as viscose, the hardness of lyocell was 15% lower than viscose. The overall degree of orientation of cellulose chains being higher in lyocell than in viscose, it is proposed that reduced lateral bonding in lyocell is the reason for the low hardness measured by nanoindentation compared to viscose.     

Nanoindentation mapping of a wood-adhesive bond

A mapping experiment of a wood phenol–resorcinol–formaldehyde adhesive bond was performed by means of grid nanoindentation. The variability of the modulus of elasticity and the hardness was evaluated for an area of 17 μm by 90 μm. Overall, the modulus of elasticity of the adhesive was clearly lower than the modulus of wood cell walls, whereas the hardness of the adhesive was slightly higher compared to cell walls. A very slight trend of decreasing modulus of elasticity was found with increasing distance from the immediate bond line. However, the trend was superimposed by a high variability of the modulus of elasticity in dependence on the position in the wood cell wall. The unexpectedly high variation of the modulus between 12 and 24 GPa may be explained by the interaction between the helical orientation of the cellulose microfibrils in the S2 layer of the wood cell wall and the geometry of the three-sided Berkovich type indenter pyramid used. Corresponding to the very slight decrease in modulus with increasing distance from the bond line, a similar but clearer trend was found for hardness. Both trends of changing mechanical properties of wood cell walls with varying distance from the bond line are attributed to effects of adhesive penetration into the wood cell wall. PACS 81.70.-q     

Experimental and Computational Studies on the CH Amination Mechanism of Tetrahydrocarbazoles via Hydroperoxides

The acid‐catalyzed reactions of photochemically generated tetrahydrocarbazole peroxides with anilines have been studied experimentally and computationally to identify the underlying reaction mechanism. The kinetic data indicate a reaction order of one in the hydroperoxide and zero in the aniline. Computational investigations using density functional theory support the experimental findings and predict an initial tautomerization between an imine and enamine substructure of the primarily generated tetrahydrocarbazole peroxide to be the rate controlling step. The enamine tautomer then loses hydrogen peroxide upon protonation, generating a stabilized allylic carbocation that is reversibly trapped by solvent or aniline to form the isolated products.     

Synthetic Lugdunin Analogues Reveal Essential Structural Motifs for Antimicrobial Action and Proton Translocation Capability

Lugdunin, a novel thiazolidine cyclopeptide, exhibits micromolar activity against methicillin‐resistant Staphylococcus aureus (MRSA). For structure–activity relationship (SAR) studies, synthetic analogues obtained from alanine and stereo scanning as well as peptides with modified thiazolidine rings were tested for antimicrobial activity. The thiazolidine ring and the alternating d ‐ and l ‐amino acid backbone are essential. Notably, the non‐natural enantiomer displays equal activity, thus indicating the absence of a chiral target. The antibacterial activity strongly correlates with dissipation of the membrane potential in S. aureus. Lugdunin equalizes pH gradients in artificial membrane vesicles, thereby maintaining membrane integrity, which demonstrates that proton translocation is the mode of action (MoA). The incorporation of extra tryptophan or propargyl moieties further expands the diversity of this class of thiazolidine cyclopeptides.