Summary
Brewer’s spent grain (BSG) was evaluated for its potential as a functional baking ingredient. Scanning electron microscopy (SEM) was used to examine the microstructure of BSG and wheat flours. Baked snacks (breadsticks) were prepared using 15%, 25% and 35% BSG and evaluated for their baking quality and fibre and protein content (over a period of 3 months). The addition of BSG altered the baking characteristics of the breadsticks by affecting their structure and texture. The snacks appeared to lack in cellular structure and crispiness. However, they had quite a stable shelf‐life, as changes in texture, moisture and aw progressed at a low rate. Addition of 25% and 35% BSG significantly increased the protein content of the snacks, and addition of 15% BSG more than doubled the content of dietary fibre in the samples.
The structures and properties of the homoleptic copper(I) complexes [Cu(1)(2)][PF(6)] and [Cu(2)(2)][PF(6)] (1 = 6,6'-dimethyl-2,2'-bipyridine, 2 = 6,6'-bis{2-[4-(N,N'-diphenylamino)phenyl]ethenyl}-2,2'-bipyridine) are compared, and a strategy of ligand exchange in solution has been used to prepare eight TiO(2) surface-bound heteroleptic complexes incorporating ligands with bpy metal-binding domains and carboxylate or phosphonate anchoring groups. The presence of the extended π-system in 2 significantly improves dye performance, and the most efficient sensitizers are those with phosphonate or phenyl-4-carboxylate anchoring units; a combination of [Cu(2)(2)](+) with the phosphonate anchoring ligand gives a very promising performance (η = 2.35% compared to 7.29% for standard dye N719 under the same conditions). The high-energy bands in the electronic absorption spectrum of [Cu(2)(2)](+) which arise from ligand-based transitions dominate the spectrum, whereas that of [Cu(1)(2)](+) exhibits both MLCT and ligand π* ← π bands. Both [Cu(1)(2)][PF(6)] and [Cu(2)(2)][PF(6)] are redox active; while the former exhibits both copper-centred and ligand-based processes, [Cu(2)(2)][PF(6)] shows only ligand-based reductions. Results of TD-DFT calculations support these experimental data. They predict an electronic absorption spectrum for [Cu(1)(2)](+) with an MLCT band and high-energy ligand-based transitions, and a spectrum for [Cu(2)(2)](+) comprising transitions involving mainly contributions from orbitals with ligand 2 character. We have assessed the effects of the atomic orbital basis set on the calculated absorption spectrum of [Cu(1)(2)](+) and show that a realistic spectrum is obtained by using a 6-311++G** basis set on all atoms, or 6-311++G** on copper and 6-31G* basis set on all other atoms; a smaller basis set on copper leads to unsatisfactory results. Electronic absorption spectra of six heteroleptic complexes have been predicted using TD-DFT calculations, and the transitions making up the dominant bands analysed in terms of the character of the HOMO-LUMO manifold. The calculational data reveal dominant phosphonate ligand character in the LUMO for the dye found to function most efficiently in practice, and also reveal that the orbital character in the HOMOs of the two most efficient dyes is dominated by the non-anchoring ligand 2, suggesting that ligand 2 enhances the performance of the sensitizer by minimizing back-migration of an electron from the semiconductor to the dye.
A complex of α‐lactalbumin and oleic acid has previously been shown to induce apoptosis in cancer cells in a number of in vitro and in vivo trials. This complex is called HAMLET or BAMLET, depending on the origin of α‐la (human/bovine alpha‐lactalbumin made lethal to tumour cells). In the current study, it was shown that bovine β‐lactoglobulin (β‐lg), upon binding sodium oleate (NaOle), the salt of oleic acid, also acquires cytotoxicity towards tumour cells (human monocytic cells U937), analogously to HAMLET/BAMLET complexes. The properties of the complex were characterized using FIR spectroscopy, HPLC and SDS‐PAGE. It was shown that the level of covalent oligomerization (dimers and trimers) of β‐lg increased with increasing the molar ratio of sodium oleate NaOle:β‐lg in the preparation procedure. At the same time, increasing the molar ratio of NaOle:β‐lg increased the cytotoxicity of the complex. The increase in cytotoxicity appeared to be dependent on the amount of bound NaOle in the complex, but not on the content of multimeric forms of β‐lg. The NaOle/β‐lg complex also showed similarity with BAMLET in penetrating the cell membrane and co‐localizing with the cell nucleus. Furthermore, DNA fragmentation studies suggested that tumour cells (U937) treated with the complex died by apoptosis, as in the case of BAMLET, and healthy cells appeared to be less affected by treatment, as shown with model rat adrenal pheochromocytoma cells PC12. In conclusion, β‐lg and NaOle can form complexes with apoptosis‐inducing qualities comparable to those of BAMLET.
Practical applications: Globular proteins such as the milk proteins α‐lactalbumin and β‐lactoglobulin can bind oleic acid, thereby converting into a complex with high biological activity against tumour cells. Its cytotoxicity is strongly dependent on the binding stoichiometry, indicating the importance of oleic acid in the cell death.
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