Phosphonic systems. Part 12. Fragmentation-rearrangement of dialkyl 2-acyloxyalkylphosphonates

Dialkyl esters of 2-acyloxyalkylphosphonic acids, RCH(OAc)CH₂PO₃R′₂, undergo thermolytic fragmentation to an alkene RCHCH₂, a new ester AcOR′, and an alkyl metaphosphate R′OPO₂. The reaction represents a new type of a process in which a metaphosphate species is generated from a neutral precursor and involves alkyl group (R′) migration as a prerequisite for the reaction. Mechanistic studies indicate that the reaction involves interaction between the phosphoryl group and the electrophilic center of the Ac group, followed by the intramolecular dealkylation of the P O R′ function and the subsequent fragmentation of the intermediate.     

Molecular details of ovalbumin-pectin complexes at the air/water interface: a spectroscopic study

To stabilize air-water interfaces, as in foams, the adsorption of surface-active components is a prerequisite. An approach to controlling the surface activity of proteins is noncovalent complex formation with a polyelectrolyte in the bulk phase. The molecular properties of egg white ovalbumin in a complex with pectin in the bulk solution and at air/water interfaces were studied using drop tensiometry (ADT) and time-resolved fluorescence anisotropy techniques. The complex formation of ovalbumin with pectin in the bulk resulted in the formation of a compact structure with a different spatial arrangement depending on the protein/pectin ratio. Complex formation did not provide an altered protein structure, whereas the conformational stability was slightly increased in the complex. In excess pectin, an overall condensed complex structure is formed, whereas at limited pectin concentrations the structure of the complex is more "segmental". The characteristics of these structures did not depend on pH in the 7.0 to 4.5 regime. Interaction with pectin in the bulk solution resulted in a significantly slower adsorption of the protein to the air/water interface. The limited mobility of the protein at the interface was found for both ovalbumin and ovalbumin-pectin complexes. From both the rotational dynamics and total fluorescence properties of the protein in the absence and presence of pectin, it was suggested that the complex does not dissociate at the interface. Ovalbumin in the complex retains its initial "aqueous" microenvironment at the interface, whereas in the absence of pectin the microenvironment of the protein changed to a more nonpolar one. This work illustrates a more general property of polyelectrolytes, namely, the ability to retain a protein in its microenvironment. Insight into this property provides a new tool for better control of the surface activity of complex biopolymer systems.     

Colloidal aspects of texture perception

Recently, considerable attention has been given to the understanding of texture attributes that cannot directly be related to physical properties of food, such as creamy, crumbly and watery. The perception of these attributes is strongly related to the way the food is processed during food intake, mastication, swallowing of it and during the cleaning of the mouth after swallowing. Moreover, their perception is modulated by the interaction with other basic attributes, such as taste and aroma attributes (e.g. sourness and vanilla). To be able to link the composition and structure of food products to more complicated texture attributes, their initial physical/colloid chemical properties and the oral processing of these products must be well understood. Understanding of the processes in the mouth at colloidal length scales turned out to be essential to grasp the interplay between perception, oral physiology and food properties. In view of the huge differences in physical chemical properties between food products, it is practical to make a distinction between solid, semi-solid, and liquid food products. The latter ones are often liquid dispersions of emulsion droplets or particles in general. For liquid food products for instance flow behaviour and colloidal stability of dispersed particles play a main role in determining their textural properties. For most solid products stiffness and fracture behaviour in relation to water content are essential while for semi-solids a much larger range of mechanical properties will play a role. Examples of colloidal aspects of texture perception will be discussed for these three categories of products based on selected sensory attributes and/or relevant colloidal processes. For solid products some main factors determining crispness will be discussed. For crispiness of dry cellular solid products these are water content and the architecture of the product at mesoscopic length scales (20-1000 µm). In addition the distribution of water at mesoscopic length scales was found to be important. For semi-solid foods, sensory characteristics as spreadability, watery and crumbliness are primarily determined by food properties at mesoscopic length scales. Crumbliness is directly related to the formation of free running cracks that occur during eating of the product. Exudation of the continuous liquid phase of gels during compression gives rise to watery/juicy sensory attributes. For liquid food products, colloidal interactions of emulsion droplets, particles, proteins, and polysaccharides with saliva and oral surfaces were found to affect texture characteristics as creaminess, fattiness, roughness and astringency.     

Parameter sensitivity of the ‘Limits to Growth’ world model

The mathematical model basic to the results of ‘The Limits to Growth’ is found to be very sensitive to small parameter variations. By changing three parameters by 10% each in 1975 the world population collapse predicted by the model is averted.     

Decoupled magnetic subsystems in the random mixture FepCo1-p(C5H5NO)6(ClO4)2

Specific heat data on the random mixtures Fe_pCo_1-pL₆(ClO₄)₂, where L = C₅H₅NO, are presented. The Fe and Co magnetic atoms have competing anisotropies since the pure Fe and Co compounds are known to be good examples of the simple cubic, $\text{S =}\text{1}\text{2}$, Ising and XY magnet, respectively. The experimental data show the two magnetic subsystems in the mixtures to be almost completely decoupled, which is a consequence of the fact that the crystal field anisotropies of the Fe²⁺ and Co²⁺ ions, yielding g_∥ ? g_⊥ and g_⊥ ? g_∥, respectively, are very strong compared to the magnetic exchange interactions. Consequently the two magnetic subsystems experience one another as nonmagnetic impurities. A model is presented which explains these results, as well as those previously found for related random mixtures, in terms of two interpenetrating percolation clusters.