Earthworms produce granules of intricately zoned calcite

Earthworms of the family Lumbricidae, which includes many common species, produce and secrete up to millimeter-sized calcite granules, and the intricate fine-scale zoning of their constituent crystals is unique for a biomineral. Granule calcite is produced by crystallization of amorphous calcium carbonate (ACC) that initially precipitates within the earthworm calciferous glands, then forms protogranules by accretion on quartz grain cores. Crystallization of ACC is mediated by migrating fluid films and is largely complete within 24 11 of ACC production and before granules leave the earthworm. Variations in the density of defects formed as a byproduct of trace element incorporation during calcite crystall growth have generated zoning that can be resolved by cathodoluminescence imaging at ultraviolet to blue wavelengths and using the novel technique of scanning electron microscope charge contrast imaging. Mapping of calcite crystal orientations by electron backscatter diffraction reveals an approximate radial fabric to the granules that reflects crystal growth from internal nucleation sites toward their margins. The survival within granules of ACC inclusions for months after they enter soils indicates that they crystallize only within the earthworm and in the presence of fluids containing biochemical catalysts. The earthworm probably promotes crystallization of ACC in order to prevent remobilization of the calcium carbonate by dissolution. Calcite granules vividly illustrate the role of transient precursors in biomineralization, but the underlying question of why earth-worms produce granules in volumes sufficient to have a measurable impact on soil carbon cycling remains to be answered.

Alkene-arene meta photocycloadditions with a four-carbon-atom tether: efficient approach toward the polycyclic ring systems of aphidicolin and stemodinone

At the end of its tether! The fusion of a six-membered ring onto the four-carbon-atom tether of substrate 1 provides an efficient approach toward the polycyclic ring systems of the natural products aphidicolin and stemodinone. The reaction represents a unique example of a preference for product formation from an endo exciplex in an intramolecular system (exo:endo 2:3=1.0:1.2).

Autistic symptomatology and language ability in autism spectrum disorder and specific language impairment

Background: Autism spectrum disorders (ASD) and specific language impairment (SLI) are common developmental disorders characterised by deficits in language and communication. The nature of the relationship between them continues to be a matter of debate. This study investigates whether the co-occurrence of ASD and language impairment is associated with differences in severity or pattern of autistic symptomatology or language profile. Methods: Participants (N = 97) were drawn from a total population cohort of 56,946 screened as part of study to ascertain the prevalence of ASD, aged 9 to 14 years. All children received an ICD-10 clinical diagnosis of ASD or No ASD. Children with nonverbal IQ 80 were divided into those with a language impairment (language score of 77 or less) and those without, creating three groups: children with ASD and a language impairment (ALI; N = 41), those with ASD and but no language impairment (ANL; N = 31) and those with language impairment but no ASD (SLI; N = 25). Results: Children with ALI did not show more current autistic symptoms than those with ANL. Children with SLI were well below the threshold for ASD. Their social adaptation was higher than the ASD groups, but still nearly 2 SD below average. In ALI the combination of ASD and language impairment was associated with weaker functional communication and more severe receptive language difficulties than those found in SLI. Receptive and expressive language were equally impaired in ALI, whereas in SLI receptive language was stronger than expressive. Conclusions: Co-occurrence of ASD and language impairment is not associated with increased current autistic symptomatology but appears to be associated with greater impairment in receptive language and functional communication.

Regression, developmental trajectory and associated problems in disorders in the autism spectrum: the SNAP study

We report rates of regression and associated findings in a population derived group of 255 children aged 9-14 years, participating in a prevalence study of autism spectrum disorders (ASD); 53 with narrowly defined autism, 105 with broader ASD and 97 with non-ASD neurodevelopmental problems, drawn from those with special educational needs within a population of 56,946 children. Language regression was reported in 30% with narrowly defined autism, 8% with broader ASD and less than 3% with developmental problems without ASD. A smaller group of children were identified who underwent a less clear setback. Regression was associated with higher rates of autistic symptoms and a deviation in developmental trajectory. Regression was not associated with epilepsy or gastrointestinal problems.

Model selection approaches for non-linear system identification: a review

The identification of non-linear systems using only observed finite datasets has become a mature research area over the last two decades. A class of linear-in-the-parameter models with universal approximation capabilities have been intensively studied and widely used due to the availability of many linear-learning algorithms and their inherent convergence conditions. This article presents a systematic overview of basic research on model selection approaches for linear-in-the-parameter models. One of the fundamental problems in non-linear system identification is to find the minimal model with the best model generalisation performance from observational data only. The important concepts in achieving good model generalisation used in various non-linear system-identification algorithms are first reviewed, including Bayesian parameter regularisation and models selective criteria based on the cross validation and experimental design. A significant advance in machine learning has been the development of the support vector machine as a means for identifying kernel models based on the structural risk minimisation principle. The developments on the convex optimisation-based model construction algorithms including the support vector regression algorithms are outlined. Input selection algorithms and on-line system identification algorithms are also included in this review. Finally, some industrial applications of non-linear models are discussed.

The synthesis, structure, reactivity and electrochemical properties of ruthenium complexes featuring cyanoacetylide ligands

The complex [Ru(C&3bond; CC&3bond; N)(dppe)Cp*] (1) is readily obtained (ca. 70%) from the sequential reaction of [Ru(C=CH2)(dppe)Cp*]PF6 with (BuLi)-Bu-n and phenyl cyanate. The complex behaves as a typical transition metal acetylide upon reaction with tetracyanoethene, affording a metallated pentacyanobutadiene. Complex I is a useful metalloligand, and its reactions with [W(thf)(CO)5], [RuCl(PPh3)(2)Cp], [RuCl(dppe)Cp*] or cis-[RuCl2(dppe)(2)] all afforded products featuring the M-C&3bond; CC&3bond; N-M' motif, for which ground state structures indicate a degree of polarisation. Electrochemical and spectroelectrochemical studies reveal moderate interactions between the metal centres in the 35-electron dications [{Cp*(dppe)Ru}(mu-C&3bond; CC&3bond; N){RuL2Cp'}](2+) Ru(PPh3)(2)CP, Ru(dppe)Cp*).

Molybdate and tungstate transfer by rat ileum competitive inhibition by sulphate

For both MoO42− and WO42− the maximum rate of uptake by the small intestine of the rat (studied in vitro using the everted sac technique) occurs in the lower ileum. Kinetic constants, derived by a least squares procedure, are compared with those previously obtained for SO42− transport. For both and , , with only small differences between sacs IV and V. Mutual inhibition of MoO42− and WO42− transport and inhibition of both by SO42− are competitive processes. This is shown by the generally good agreement between values and derived values and by V values in the presence and absence of the inhibiting species. The three ions SO42−, MoO42− and WO42− are probably transferred across the intestine by a common carrier system. Implications for the sulphate-molybdenum interaction in molybdosis are discussed.

In-situ spatio-temporal measurements of the detailed azimuthal substructure of the substorm current wedge

The substorm current wedge (SCW) is a fundamental component of geomagnetic substorms. Models tend to describe the SCW as a simple line current flowing into the ionosphere towards dawn and out of the ionosphere towards dusk, linked by a westward electrojet. We use multi-spacecraft observations from perigee passes of the Cluster 1 and 4 spacecraft during a substorm on 15 Jan 2010, in conjunction with ground-based observations, to examine the spatial structuring and temporal variability of the SCW. At this time, the spacecraft travelled east-west azimuthally above the auroral region. We show that the SCW has significant azimuthal sub-structure on scales of 100~km at altitudes of 4,000-7,000~km. We identify 26 individual current sheets in the Cluster 4 data and 34 individual current sheets in the Cluster 1 data, with Cluster 1 passing through the SCW 120-240~s after Cluster 4 at 1,300-2,000~km higher altitude. Both spacecraft observed large-scale regions of net upward and downward field-aligned current, consistent with the large-scale characteristics of the SCW, although sheets of oppositely directed currents were observed within both regions. We show that the majority of these current sheets were closely aligned to a north-south direction, in contrast to the expected east-west orientation of the pre-onset aurora. Comparing our results with observations of the field-aligned current associated with bursty bulk flows (BBFs) we conclude that significant questions remain for the explanation of SCW structuring by BBF driven ``wedgelets". Our results therefore represent constraints on future modelling and theoretical frameworks on the generation of the SCW.