Early social experience and individual differences in infants' joint attention

Fifty-nine healthy infants were filmed with their mothers and with a researcher at two, four, six and nine months in face-to-face play, and in toy-play at six and nine months. During toy-play at both ages, two indices of joint attention (JA)—infant bids for attention, and percent of time in shared attention—were assessed, along with other behavioural measures. Global ratings were made at all four ages of infants’ and mothers’ interactive style. The mothers varied in psychiatric history (e.g., half had experienced postpartum depression) and socioeconomic status, so their interactive styles were diverse. Variation in nine-month infant JA — with mother and with researcher — was predicted by variation in maternal behaviour and global ratings at six months, but not at two or four months. Concurrent adult behaviour also influenced nine-month JA, independent of infant ratings. Six-month maternal behaviours that positively predicted later JA (some of which remained important at nine months) included teaching, conjoint action on a toy, and global sensitivity. Other behaviours (e.g., entertaining) negatively predicted later JA. Findings are discussed in terms of social-learning and neurobiological accounts of JA emergence.

X-ray scattering study of the effect of hydration on the cross-beta structure of amyloid fibrils

We have investigated the effect of sample hydration on the wide-angle X-ray scattering patterns of amyloid fibrils from two different sources, hen egg white lysozyme (HEWL) and an 11-residue peptide taken from the sequence of transthyretin (TTR105-115). Both samples show an inter-strand reflection at 4.7 Å and an inter-sheet reflection which occurs at 8.8 and 10 Å for TTR105-115 and HEWL fibrils, respectively. The positions, widths, and relative intensities of these reflections are conserved in patterns obtained from dried stalks and hydrated samples over a range of fibril concentrations. In 2D scattering patterns obtained from flow-aligned hydrated samples, the inter-strand and inter-sheet reflections showed, respectively, axial and equatorial alignment relative to the fibril axis, characteristic of the cross-β structure. Our results show that the cross-β structure of the fibrils is not a product of the dehydrating conditions typically employed to produce aligned samples, but is conserved in individual fibrils in hydrated samples under dilute conditions comparable to those associated with other biophysical and spectroscopic techniques. This suggests a structure consisting of a stack of two or more sheets whose interfaces are inaccessible to bulk water.

Rapid, uncatalyzed ring-opening polymerization of individual macrocyclic poly(arylene thioether ketone)s under dynamic heating conditions

Uncatalyzed, ring-opening polymerization of individual macrocyclic poly(arylene thioether ketone)s (1-4) and mixtures (5) under dynamic heating conditions has been demonstrated for the first time. High-molecular-weight, film-forming products were obtained after heating of the macrocycles up to 480 degreesC, with a heating rate of 10-20 degreesC /min. Depending on the macrocyclic structure and heat treatment conditions, the polymers obtained were amorphous or semicrystalline, soluble or slightly crosslinked. NMR analyses of the soluble polymers revealed their linear, highly regular structure. According to NMR, DSC, and TGA studies, the polymers obtained do not contain any residual macrocycles. The polymers with thio-p-arylene moieties in the main chain were thermally stabile. The catalyzed ring opening polymerization of 5 carried out in diphenyl sulfone solution is also reported for comparison. Using quantum mechanical calculations of the ring opening of macrocycles, a reaction mechanism is suggested. Preparation of nanosized poly(thioether ketone) fibrils by a replication method is described.

Synthesis and properties of tetra-μ-acetatodiruthenium(II,III) phenylphosphinate and phenylphosphonate complexes: X-ray crystal structures of [Ru2(μ-O2CCH3)4(HPhPO2)2]H and [Ru2(μ-O2CCH3)4(PhPO3H)2]H·H2O

Phenylphosphinic acid (HPhPO2H) and phenylphosphonic acid (PhPO3H2) react with a methanolic solution of [Ru2(μ-O2CCH3)4(O2CCH3)2]H·0.7H2O at room temperature to give [Ru2(μ-O2CCH3)4(HPhPO2)2H (1) and [Ru2(μ-O2CCH3)4 (PhPO3H)2]H·H2O (2), respectively. The X-ray crystal structures of 1 and 2 each show the RuRu core to be ligated by four bridging bidentate acetate ligands [RuRu distances: 1 = 2.272(1) Å; 2 = 2.267(2) Å] and two axial phenylphosphinate and phenylphosphonate ligands, respectively. In each complex the individual bimetallic molecules are linked together by a hydrogen ion which bridges the oxygen atoms of neighbouring axial ligands. In 2 the water molecule is also hydrogen-bonded to one of the axial phenylphosphonate groups. Spectroscopic, magnetic and cyclic voltammetric data for the complexes are given.

Frying of potato chips in a blend of canola oil and palm olein: changes in levels of individual fatty acids and tocols

The changes occurring in the levels of nutritionally relevant oil components were assessed during repeated frying of potato chips in a blend of palm olein and canola oil (1:1 w/w). The blend suffered minimal reductions in omega-3 and omega-6 polyunsaturated fatty acids. There was no significant difference between the fatty acid composition of the oil extracted from the product and that of the frying medium, in all three cases. The blend also contained a significant amount of tocols which add a nutritional value to the oil. The concentration of the tocols was satisfactorily retained over the period of oil usage, in contrast to the significant loses observed in the case of the individual oils. The blend also performed well when assessed by changes in total polar compounds, free fatty acids, p-anisidine value. When fried in used oil, the product oil content increased progressively with oil usage time. This study shows that blended frying oils can combine good stability and nutritional quality

Perceived helplessness is associated with individual differences in the central motor output system

Learned helplessness is a maladaptive response to uncontrollable stress characterized by impaired motor escape responses, reduced motivation and learning deficits. There are important individual differences in the likelihood of becoming helpless following exposure to uncontrollable stress but little is known about the neural mechanisms underlying these individual differences. Here we used structural MRI to measure gray and white matter in individuals with chronic pain, a population at high risk for helplessness due to prolonged exposure to a poorly controlled stressor (pain). Given that self-reported helplessness is predictive of treatment outcomes in chronic pain, understanding such differences might provide valuable clinical insight. We found that the magnitude of self-reported helplessness correlated with cortical thickness in the supplementary motor area (SMA) and midcingulate cortex, regions implicated in cognitive aspects of motor behavior. We then examined the white matter connectivity of these regions and found that fractional anisotropy of connected white matter tracts along the corticospinal tract was associated with helplessness and mediated the relationship between SMA cortical thickness and helplessness. These data provide novel evidence that links individual differences in the motor output pathway with perceived helplessness over a chronic and poorly controlled stressor.

Redox behavior of the model catalyst Pd/CeO2-x/Pt(111)

Photoelectron spectroscopy and scanning tunneling microscopy have been used to investigate how the oxidation state of Ce in CeO2-x(111) ultrathin films is influenced by the presence of Pd nanoparticles. Pd induces an increase in the concentration of Ce3+ cations, which is interpreted as charge transfer from Pd to CeO2-x(111) on the basis of DFT+U calculations. Charge transfer from Pd to Ce4+ is found to be energetically favorable even for individual Pd adatoms. These results have implications for our understanding of the redox behavior of ceria-based model catalyst systems.

Observing the in situ chiral modification of Ni nanoparticles using scanning transmission X-ray microspectroscopy

Enantioselective heterogeneous hydrogenation of Cdouble bond; length as m-dashO bonds is of great potential importance in the synthesis of chirally pure products for the pharmaceutical and fine chemical industries. One of the most widely studied examples of such a reaction is the hydrogenation of β-ketoesters and β-diketoesters over Ni-based catalysts in the presence of a chiral modifier. Here we use scanning transmission X-ray microscopy combined with near-edge X-ray absorption fine structure spectroscopy (STXM/NEXAFS) to investigate the adsorption of the chiral modifier, namely (R,R)-tartaric acid, onto individual nickel nanoparticles. The C K-edge spectra strongly suggest that tartaric acid deposited onto the nanoparticle surfaces from aqueous solutions undergoes a keto-enol tautomerisation. Furthermore, we are able to interrogate the Ni L2,3-edge resonances of individual metal nanoparticles which, combined with X-ray diffraction (XRD) patterns showed them to consist of a pure nickel phase rather than the more thermodynamically stable bulk nickel oxide. Importantly, there appears to be no “particle size effect” on the adsorption mode of the tartaric acid in the particle size range ~ 90–~ 300 nm.