Correlation-type structure activity relationships for the kinetics of gas-phase RO2 self-reactions and reaction with HO2

Structure activity relationships (SARs) are presented for the gas-phase reactions of RO2 with HO2, and the self- and cross-reactions of RO2. For RO2+HO2 the SAR is based upon a correlation between the logarithm of the measured rate coefficient and a calculated ionisation potential for the molecule R-CH=CH2, R being the same group in both the radical and molecular analogue. The correlation observed is strong and only for one RO2 species does the measured rate coefficient deviate by more than a factor of two from the linear least-squares regression line. For the self- and cross-reactions of RO2 radicals, the SAR is based upon a correlation between the logarithm of the measured rate coefficient and the calculated electrostatic potential (ESP) at the equivalent carbon atom in the RH molecule to which oxygen is attached in RO2, again R being the same group in the molecule and the radical. For cases where R is a simple alkyl-group, a strong linear correlation observed. For RO2 radicals which contain lone pair-bearing substituents and for which the calculated ESP<-0.05 self-reaction rate coefficients appear to be insensitive to the value of the ESP. For RO2 of this type with ESP>-0.05 a linear relationship between log k and the ESP is again observed. Using the relationships, 84 out of the 85 rate coefficients used to develop the SARs are predicted to within a factor of three of their measured values. A relationship is also presented that allows the prediction of the Arrhenius parameters for the self-reactions of simple alkyl RO2 radicals. On the basis of the correlations, predictions of room-temperature rate coefficients are made for a number of atmospherically important peroxyl-peroxyl radical reactions. (C) 2003 Elsevier Ltd. All rights reserved.

Synthesis of heterosulfamates. Search for structure-taste relationships

Thirty one new sodium heterosulfamates, RNHSO3Na, where the R portion contains mainly thiazole, benzothiazole, thiadiazole and pyridine ring structures, have been synthesized and their taste portfolios have been assessed. A database of 132 heterosulfamates ( both open-chain and cyclic) has been formed by combining these new compounds with an existing set of 101 heterosulfamates which were previously synthesized and for which taste data are available. Simple descriptors have been obtained using (i) measurements with Corey-Pauling-Koltun (CPK) space- filling models giving x, y and z dimensions and a volume VCPK, (ii) calculated first order molecular connectivities ((1)chi(v)) and (iii) the calculated Spartan program parameters to obtain HOMO, LUMO energies, the solvation energy E-solv and V-SPART AN. The techniques of linear (LDA) and quadratic (QDA) discriminant analysis and Tree analysis have then been employed to develop structure-taste relationships (SARs) that classify the sweet (S) and non-sweet (N) compounds into separate categories. In the LDA analysis 70% of the compounds were correctly classified ( this compares with 65% when the smaller data set of 101 compounds was used) and in the QDA analysis 68% were correctly classified ( compared to 80% previously). TheTree analysis correctly classified 81% ( compared to 86% previously). An alternative Tree analysis derived using the Cerius2 program and a set of physicochemical descriptors correctly classified only 54% of the compounds.

Age relationships beteen low level rock platforms and the high coastal slopes in Jersey and the surrounding area.

Recent research along the coastal cliffs and embayments of Jersey has revealed new aspects of the geomorphology of the rocky shore platform and its relationship with the steep slopes that link it to the island plateau above. Specifically, a rockhead platform meets a 10-30 m high, near vertical cliff at approximately 8-10 m above Jersey Datum (J.D.= ±0 m Ordnance Datum; likewise Guernsey Datum: G.D.), slopes down-towards mid-tide levels becoming ever more deeply dissected. Generalised contours of this platform show it to be distinct from a lower tidal rockhead platform which is comparatively smooth over large areas as it undergoes continuing contemporary abrasion. This lower platform is generally separated from the higher one by low cliffs, less than a metre high at mid-tidal levels, but two to three metres at the base of the backing cliffs. Both of these platforms are shown to antedate the Last Cold Stage (Devensian) head at a number of localities and this relationship is taken to represent the general situation, not only in Jersey, but throughout the other Channel Islands and adjacent coasts of Armorica. Whether either, or both, of these two platforms are older than Marine Oxygen Isotope Substage (MOIS) 5e (Ipswichian) as well is not known. However the considerable age of the numerous and wide intertidal shore platforms of the Channel Islands and adjacent coasts of Amorica makes a greater age quite possible.

Relationships between gluten rheological properties and hearth loaf characteristics

The rheological properties of fresh gluten in small amplitude oscillation in shear (SAOS) and creep recovery after short application of stress was related to the hearth breadbaking performance of wheat flours using the multivariate statistics partial least squares (PLS) regression. The picture was completed by dough mixing and extensional properties, flour protein size distribution determined by SE-HPLC, and high molecular weight glutenin subunit (HMW-GS) composition. The sample set comprised 20 wheat cultivars grown at two different levels of nitrogen fertilizer in one location. Flours yielding stiffer and more elastic glutens, with higher elastic and viscous moduli (G' and G") and lower tan 8 values in SAOS, gave doughs that were better able to retain their shape during proving and baking, resulting in breads of high form ratios. Creep recovery measurements after short application of stress showed that glutens from flours of good breadmaking quality had high relative elastic recovery. The nitrogen fertilizer level affected the protein size distribution by an increase in monomeric proteins (gliadins), which gave glutens of higher tan delta and flatter bread loaves (lower form ratio).

The physics of baking: rheological and polymer molecular structure-function relationships in breadmaking

Molecular size and structure of the gluten polymers that make up the major structural components of wheat are related to their rheological properties via modem polymer rheology concepts. Interactions between polymer chain entanglements and branching are seen to be the key mechanisms determining the rheology of HMW polymers. Recent work confirms the observation that dynamic shear plateau modulus is essentially independent of variations in MW amongst wheat varieties of varying baking performance and is not related to variations in baking performance, and that it is not the size of the soluble glutenin polymers, but the structural and rheological properties of the insoluble polymer fraction that are mainly responsible for variations in baking performance. The rheological properties of gas cell walls in bread doughs are considered to be important in relation to their stability and gas retention during proof and baking, in particular their extensional strain hardening properties. Large deformation rheological properties of gas cell walls were measured using biaxial extension for a number of doughs of varying breadmaking quality at constant strain rate and elevated temperatures in the range 25-60 degrees C. Strain hardening and failure strain of cell walls were both seen to decrease with temperature, with cell walls in good breadmaking doughs remaining stable and retaining their strain hardening properties to higher temperatures (60 degrees C), whilst the cell walls of poor breadmaking doughs became unstable at lower temperatures (45-50 degrees C) and had lower strain hardening. Strain hardening measured at 50 degrees C gave good correlations with baking volume, with the best correlations achieved between those rheological measurements and baking tests which used similar mixing conditions. As predicted by the Considere failure criterion, a strain hardening value of I defines a region below which gas cell walls become unstable, and discriminates well between the baking quality of a range of commercial flour blends of varying quality. This indicates that the stability of gas cell walls during baking is strongly related to their strain hardening properties, and that extensional rheological measurements can be used as predictors of baking quality. (C) 2004 Elsevier B.V. All rights reserved.

The physics of baking: rheological and polymer molecular structure-function relationships in breadmaking

Molecular size and structure of the gluten polymers that make up the major structural components of wheat are related to their rheological properties via modern polymer rheology concepts. Interactions between polymer chain entanglements and branching are seen to be the key mechanisms determining the rheology of HMW polymers. Recent work confirms the observation that dynamic shear plateau modulus is essentially independent of variations in MW amongst wheat varieties of varying baking performance and is not related to variations in baking performance, and that it is not the size of the soluble glutenin polymers, but the structural and rheological properties of the insoluble polymer fraction that are mainly responsible for variations in baking performance. The rheological properties of gas cell walls in bread doughs are considered to be important in relation to their stability and gas retention during proof and baking, in particular their extensional strain hardening properties. Large deformation rheological properties of gas cell walls were measured using biaxial extension for a number of doughs of varying breadmaking quality at constant strain rate and elevated temperatures in the range 25oC to 60oC. Strain hardening and failure strain of cell walls were both seen to decrease with temperature, with cell walls in good breadmaking doughs remaining stable and retaining their strain hardening properties to higher temperatures (60oC), whilst the cell walls of poor breadmaking doughs became unstable at lower temperatures (45oC to 50oC) and had lower strain hardening. Strain hardening measured at 50oC gave good correlations with baking volume, with the best correlations achieved between those rheological measurements and baking tests which used similar mixing conditions. As predicted by the Considere failure criterion, a strain hardening value of 1 defines a region below which gas cell walls become unstable, and discriminates well between the baking quality of a range of commercial flour blends of varying quality. This indicates that the stability of gas cell walls during baking is strongly related to their strain hardening properties, and that extensional rheological measurements can be used as predictors of baking quality.

Structure oil-absorption relationships during deep-fat frying

Analysis of the oil-absorption process in deep-fat fried potato cylinders (frying temperatures of 155degreesC, 170degreesC, and 185degreesC) allowed to distinguish 3 oil fractions: structural oil (absorbed during frying), penetrated surface oil (suctioned during cooling), and surface oil. Results showed that a small amount of oil penetrates during frying because most of the oil was picked up at the end of the process, suggesting that oil uptake and water removal are not synchronous phenomena. After cooling, oil was located either on the surface of the chip or suctioned into the porous crust microstructure, with an inverse relationship between them for increasing frying times.

Recalled relationships with parents and perceptions of professional support in mothers of infants treated for cleft lip

This study examined whether individual differences in perception of the quality of professional support available at a time of stress may be associated with security of attachment. We developed a new measure of parents' perceptions of emotional and practical support provided by a wide range of professionals involved in the treatment of infants with cleft lip. it showed good internal reliability and stability over 4 months. Mothers of 102 infants with cleft lip, with or without cleft palate, completed the measure at 2 and 6 months, together with the Parental Bonding Instrument and the General Health Questionnaire. Mean scores reflecting how much they could trust or talk frankly, or share their worst fears, with professionals, and the extent to which they saw them as a source of useful information or practical help, were lower among mothers with recollections of low maternal care in childhood, or high control. This was the case at 2 and 6 months, and there were some indications of an increasing contribution of low maternal care from 2 to 6 months. The associations were not explained by current depression. Further research is needed to clarify the role of attachment processes in parents' responses to serious medical conditions in their children, and into the implications for the way professionals in paediatric services provide support.

Mind-reading difficulties in the siblings of people with Asperger's syndrome: evidence for a genetic influence in the abnormal development of a specific cognitive domain

Background: Previous research suggests that the phenotype associated with Asperger's syndrome (AS) includes difficulties in understanding the mental states of others, leading to difficulties in social communication and social relationships. It has also been suggested that the first-degree relatives of those with AS can demonstrate similar difficulties, albeit to a lesser extent. This study examined 'theory of mind' (ToM) abilities in the siblings of children with AS relative to a matched control group. Method: 2 7 children who had a sibling with AS were administered the children's version of the 'Eyes Test'(Baron-Cohen, Wheelwright, Stone, & Rutherford, 1999). The control group consisted of 27 children matched for age, sex, and a measure of verbal comprehension, and who did not have a family history of AS/autism. Results: A significant difference was found between the groups on the Eyes Test, the 'siblings' group showing a poorer performance on this measure of social cognition. The difference was more pronounced among female siblings. Discussion: These results are discussed in terms of the familial distribution of a neuro-cognitive profile associated with AS, which confers varying degrees of social handicap amongst first-degree relatives. The implication of this finding with regard to the autism/AS phenotype is explored, with some discussion of why this neuro-cognitive profile (in combination with corresponding strengths) may have an evolutionary imperative.

A technique for evaluation of interactive evolutionary systems

Very large scale scheduling and planning tasks cannot be effectively addressed by fully automated schedule optimisation systems, since many key factors which govern 'fitness' in such cases are unformalisable. This raises the question of an interactive (or collaborative) approach, where fitness is assigned by the expert user. Though well-researched in the domains of interactively evolved art and music, this method is as yet rarely used in logistics. This paper concerns a difficulty shared by all interactive evolutionary systems (IESs), but especially those used for logistics or design problems. The difficulty is that objective evaluation of IESs is severely hampered by the need for expert humans in the loop. This makes it effectively impossible to, for example, determine with statistical confidence any ranking among a decent number of configurations for the parameters and strategy choices. We make headway into this difficulty with an Automated Tester (AT) for such systems. The AT replaces the human in experiments, and has parameters controlling its decision-making accuracy (modelling human error) and a built-in notion of a target solution which may typically be at odds with the solution which is optimal in terms of formalisable fitness. Using the AT, plausible evaluations of alternative designs for the IES can be done, allowing for (and examining the effects of) different levels of user error. We describe such an AT for evaluating an IES for very large scale planning.

RBF equalizer design using directional evolutionary multi-objective optimization

Whilst radial basis function (RBF) equalizers have been employed to combat the linear and nonlinear distortions in modern communication systems, most of them do not take into account the equalizer's generalization capability. In this paper, it is firstly proposed that the. model's generalization capability can be improved by treating the modelling problem as a multi-objective optimization (MOO) problem, with each objective based on one of several training sets. Then, as a modelling application, a new RBF equalizer learning scheme is introduced based on the directional evolutionary MOO (EMOO). Directional EMOO improves the computational efficiency of conventional EMOO, which has been widely applied in solving MOO problems, by explicitly making use of the directional information. Computer simulation demonstrates that the new scheme can be used to derive RBF equalizers with good performance not only on explaining the training samples but on predicting the unseen samples.

A hybridised evolutionary algorithm for multi-criterion minimum spanning tree problems

A hybridised and Knowledge-based Evolutionary Algorithm (KEA) is applied to the multi-criterion minimum spanning tree problems. Hybridisation is used across its three phases. In the first phase a deterministic single objective optimization algorithm finds the extreme points of the Pareto front. In the second phase a K-best approach finds the first neighbours of the extreme points, which serve as an elitist parent population to an evolutionary algorithm in the third phase. A knowledge-based mutation operator is applied in each generation to reproduce individuals that are at least as good as the unique parent. The advantages of KEA over previous algorithms include its speed (making it applicable to large real-world problems), its scalability to more than two criteria, and its ability to find both the supported and unsupported optimal solutions.