Networks of micronized fat crystals grown under static conditions.

Dispersing micronized fat crystals (MFCs) in oil is a novel route to largely decouple fat crystallisation and network formation and thus to simplify the manufacture of fat-continuous food products. MFCs dispersed in oil form a weak-interaction network organized by crystal aggregates in a continuous net of crystalline nanoplatelets. The rough surface of MFC nanoplatelets hampers stacking into one-dimensional aggregates, which explains the high mass fractal dimensions of the networks formed in MFC dispersions. Applying shear does not have a significant effect on the fractal dimensions of MFC networks, and MFC aggregates in the range of 5-10 µm remain intact. However, shear leads to a significant loss of storage modulus and yield stress over a time frame of an hour. This can be attributed to irreversible disruption of the continuous net of nanoplatelets. Rheo-SAXS revealed that shear releases nanoplatelets from the continuous net, which subsequently align in the shear field and undergo rapid recrystallisation. The release of thin and metastable nanoplatelets from the weak-link network bears relevance for simplified and more effective manufacturing of emulsified food products by effectively decoupling crystallisation, network formation and emulsification.

Self-Assembly and Anti-Amyloid Cytotoxicity Activity of Amyloid beta Peptide Derivatives.

The self-assembly of two derivatives of KLVFF, a fragment Aß(16-20) of the amyloid beta (Aß) peptide, is investigated and recovery of viability of neuroblastoma cells exposed to Aß (1-42) is observed at sub-stoichiometric peptide concentrations. Fluorescence assays show that NH2-KLVFF-CONH2 undergoes hydrophobic collapse and amyloid formation at the same critical aggregation concentration (cac). In contrast, NH2-K(Boc)LVFF-CONH2 undergoes hydrophobic collapse at a low concentration, followed by amyloid formation at a higher cac. These findings are supported by the ß-sheet features observed by FTIR. Electrospray ionization mass spectrometry indicates that NH2-K(Boc)LVFF-CONH2 forms a significant population of oligomeric species above the cac. Cryo-TEM, used together with SAXS to determine fibril dimensions, shows that the length and degree of twisting of peptide fibrils seem to be influenced by the net peptide charge. Grazing incidence X-ray scattering from thin peptide films shows features of ß-sheet ordering for both peptides, along with evidence for lamellar ordering of NH2-KLVFF-CONH2. This work provides a comprehensive picture of the aggregation properties of these two KLVFF derivatives and shows their utility, in unaggregated form, in restoring the viability of neuroblastoma cells against Aß-induced toxicity.

The evolution of bicontinuous polymeric nanospheres in aqueous solution.

Complex polymeric nanospheres in aqueous solution are desirable for their promising potential in encapsulation and templating applications. Understanding how they evolve in solution enables better control of the final structures. By unifying insights from cryoTEM and small angle X-ray scattering (SAXS), we present a mechanism for the development of bicontinuous polymeric nanospheres (BPNs) in aqueous solution from a semi-crystalline comb-like block copolymer that possesses temperature-responsive functionality. During the initial stages of water addition to THF solutions of the copolymer the aggregates are predominantly vesicles; but above a water content of 53% irregular aggregates of phase separated material appear, often microns in diameter and of indeterminate shape. We also observe a cononsolvency regime for the copolymer in THF-water mixtures from 22 to 36%. The structured large aggregates gradually decrease in size throughout dialysis, and the BPNs only appear upon cooling the fully aqueous dispersions from 35 °C to 5 °C. Thus, the final BPNs are ultimately the result of a reversible temperature-induced morphological transition.