Effect of Oxygen Concentration on Photo-oxidation and Photosensitizer Bleaching in Butter

The effect of headspace oxygen concentration and color of light on photo-oxidation and degradation of photosensitizers in butter was studied. Butter samples were stored under 0%, 0.4%, 0.8%, 1.6%, 3.0%, 5.0%, 21% oxygen, and exposed to violet, green or red light. Storage time was 36 h. Degree of photo-oxidation was measured by a trained sensory panel. Photobleaching of six different photosensitizers was estimated based on front face fluorescence excitation and emission landscapes and spectral curve resolution (parallel factor analysis). The higher oxygen concentration, the more sensory degraded were the samples. Violet light resulted in slightly higher degrees of photo-oxidation than green and red light for low oxygen concentrations. Bleaching rate and course as function of O₂ concentration differed between the photosensitizers. It is suggested that the rate of photobleaching is a balance between type I and type II photoreactions.     

Lysine-specific molecular tweezers are broad-spectrum inhibitors of assembly and toxicity of amyloid proteins

Amyloidoses are diseases characterized by abnormal protein folding and self-assembly, for which no cure is available. Inhibition or modulation of abnormal protein self-assembly, therefore, is an attractive strategy for prevention and treatment of amyloidoses. We examined Lys-specific molecular tweezers and discovered a lead compound termed CLR01, which is capable of inhibiting the aggregation and toxicity of multiple amyloidogenic proteins by binding to Lys residues and disrupting hydrophobic and electrostatic interactions important for nucleation, oligomerization, and fibril elongation. Importantly, CLR01 shows no toxicity at concentrations substantially higher than those needed for inhibition. We used amyloid β-protein (Aβ) to further explore the binding site(s) of CLR01 and the impact of its binding on the assembly process. Mass spectrometry and solution-state NMR demonstrated binding of CLR01 to the Lys residues in Aβ at the earliest stages of assembly. The resulting complexes were indistinguishable in size and morphology from Aβ oligomers but were nontoxic and were not recognized by the oligomer-specific antibody A11. Thus, CLR01 binds already at the monomer stage and modulates the assembly reaction into formation of nontoxic structures. The data suggest that molecular tweezers are unique, process-specific inhibitors of aberrant protein aggregation and toxicity, which hold promise for developing disease-modifying therapy for amyloidoses.     

A new way of probing reaction networks: analyzing multidimensional parameter space

Technically relevant partial oxidation reactions represent complex reaction networks. Establishing a kinetic model for a system of multiple consecutive and parallel reaction steps is a challenging goal. The synthesis of acrylic acid by oxidation of propane using MoVTeNb mixed oxide as catalyst is such a reaction network. In an on-going study, a 10- fold parallel reactor set-up is used to vary systematically reaction conditions in a broad range over a single, well-defined MoVTeNb oxide. Selectivity and product yield in a multidimensional parameter space can give insight into the reaction network. Apparent activation energies and reaction orders of propane are derived for several conditions. Optimum reaction conditions within the investigated parameter space are specified. The results presented within this contribution contain about 200 data points measured in steady states each corresponding to reaction conditions that differ in temperature, contact time, and propane feed concentration. The fact that this data was collected in less than two months shows clearly the advantage of parallel screening of reaction conditions for mechanistic studies.     

Aiding the self-assembly of supramolecular polyoxometalates under hydrothermal conditions to give precursors of complex functional oxides

In?situ Raman spectroscopy allows insight into molecular processes under hydrothermal conditions during synthesis of complex nanostructured MoVTeNb oxides (see picture: Nb?yellow, Mo?blue, V/Mo?pale blue, Te?red). Based on the knowledge acquired, the synthesis can be more efficiently directed towards the desired product with improved functionality.