We report the synthesis of layered [Zn(2)(bdc)(2)(H(2)O)(2)] and [Cu(2)(bdc)(2)(H(2)O)(2)] (bdc = benzdicarboxylate) metal-organic frameworks (MOF) carried out using the liquid-phase epitaxy approach employing self-assembled monolayer (SAM) modified Au-substrates. We obtain Cu and Zn MOF-2 structures, which have not yet been obtained using conventional, solvothermal synthesis methods. The 2D Cu(2+) dimer paddle wheel planes characteristic for the MOF are found to be strictly planar, with the planes oriented perpendicular to the substrate. Intercalation of an organic dye, DXP, leads to a reversible tilting of the planes, demonstrating the huge potential of these surface-anchored MOFs for the intercalation of large, planar molecules.
The influence of pressure on the structure and protein-protein interaction potential of dense protein solutions was studied and analyzed using small-angle x-ray scattering in combination with a liquid state theoretical approach. The structural as well as the interaction parameters of dense lysozyme solutions are affected by pressure in a nonlinear way. The structural properties of water lead to a modification of the protein-protein interactions below 4 kbar, which might have significant consequences for the stability of proteins in extreme natural environments.
The pillared-layered metal−organic framework compounds M 2 (BME-bdc) 2 (dabco) (M 2+ = Zn 2+ , Co 2+ , Ni 2+ , Cu 2+ ; BME-bdc 2− = 2,5-bis(2-methoxyethoxy)-1,4-benzenedicarboxylate; dabco = diazabicyclo[2.2.2]octane) exhibit structural flexibility and undergo guest and temperature-induced reversible phase transitions between a narrow pore (np) and a large pore (lp) form. These transitions were analyzed in detail by powder X-ray diffraction ex and in situ, isothermal gas adsorption measurements and differential scanning calorimetry. The threshold parameters (gas pressure or temperature), the magnitude of the phase transitions (volume change) as well as their transition enthalpies are strikingly dependent on the chosen metal cation M 2+ . This observation is assigned to the different electronic structures and ligand field effects on the coordination bonds. Accordingly, in situ powder X-ray diffraction measurements as a function of CO 2 pressure reveal different mechanisms for the np to lp phase transition during CO 2 adsorption.
Marine organisms have evolved a surprising mechanism to counteract the deleterious effects of urea by trimethylammonium N‐oxide (TMAO). The effect of pressure on the structure and intermolecular interactions of lysozyme in urea and TMAO solutions was studied (see picture). These findings help to understand the compensatory effect of urea–TMAO mixtures in deep‐sea organisms.
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