Investigating the influence of the sulfur oxidation state on solid state conformation

Design, synthesis and structural characterization of a series of diphenylacetylene derivatives bearing organosulfur, amide and amine moieties has been achieved in which the molecular conformation is controlled through variation of the hydrogen bond properties on alteration of the oxidisation level of sulfur.

Physico-chemical properties and component interactions in high solids food systems

The present study aimed to investigate interactions of components in the high solids systems during storage. The systems included (i) lactose–maltodextrin (MD) with various dextrose equivalents at different mixing ratios, (ii) whey protein isolate (WPI)–oil [olive oil (OO) or sunflower oil (SO)] at 75:25 ratio, and (iii) WPI–oil– {glucose (G)–fructose (F) 1:1 syrup [70% (w/w) total solids]} at a component ratio of 45:15:40. Crystallization of lactose was delayed and increasingly inhibited with increasing MD contents and higher DE values (small molecular size or low molecular weight), although all systems showed similar glass transition temperatures at each aw. The water sorption isotherms of non-crystalline lactose and lactose–MD (0.11 to 0.76 aw) could be derived from the sum of sorbed water contents of individual amorphous components. The GAB equation was fitted to data of all non-crystalline systems. The protein–oil and protein–oil–sugar materials showed maximum protein oxidation and disulfide bonding at 2 weeks of storage at 20 and 40°C. The WPI–OO showed denaturation and preaggregation of proteins during storage at both temperatures. The presence of G–F in WPI–oil increased Tonset and Tpeak of protein aggregation, and oxidative damage of the protein during storage, especially in systems with a higher level of unsaturated fatty acids. Lipid oxidation and glycation products in the systems containing sugar promoted oxidation of proteins, increased changes in protein conformation and aggregation of proteins, and resulted in insolubility of solids or increased hydrophobicity concomitantly with hardening of structure, covalent crosslinking of proteins, and formation of stable polymerized solids, especially after storage at 40°C. We found protein hydration transitions preceding denaturation transitions in all high protein systems and also the glass transition of confined water in protein systems using dynamic mechanical analysis.

Transitions: From novice participation to expertise, pre-school 'matters' in an Irish pre-school community

This in depth, qualitative, participant observer study tracks children's transition experiences from novice to experienced membership of their pre-school community. It also considers adult roles in mediating this process in the context of the recent introduction of a universal free-pre-school year for children growing up in Ireland. Participation and the space to negotiate a participatory identity is understood in this study as a key element of positive experiences of early years transitions, within pre-school and beyond. The underlying theoretical framework is socio-cultural. This approach shifts from a scientific positivist view of thinking and learning as an individual inside the head process and asserts the historical, social, cultural as well as the situated context of learning and meaning making All participants, including myself as researcher, are recognised, explored and valued as embedded in the cultural context studied. In a sense, this approach tilts the worlds being observed through participation in them and reflects them in new light. The aim is to interpret and reflect the multiple realities constructed in this context rather than seek a truth out there waiting to be found. Special efforts are made to be invited in to and acknowledge children's expertise in the cultural worlds they negotiate with peers and adults in pre-school. The aim is to better understand what children may find motivating, interesting or problematic as they interpret reproduce and transform meaning within their play and learning worlds. My aim is for an honest rendering of the voices of stakeholders in pre-school communities from teachers, parents, and policy makers to children themselves. It makes visible constraints; potentials and possibilities within everyday Irish pre-school practices in the situated context studied as well as the broader societal, legislative and macro policy influences it reflects. Casting light on the taken for granted opens the possibility of adaptation or transformation. Transition itself can act as a tool to meet the changing needs of children on their developmental pathways across the life cycle