Chromophores from hexeneuronic acids: identification of HexA-derived chromophores

© 2017, The Author(s). Hexeneuronic acids (HexA) have long been known as triggers for discoloration processes in glucuronoxylan-containing cellulosic pulps. They are formed under the conditions of pulping from 4-O-methylglucuronic acid residues, and are removed in an “A stage” along the bleaching sequences, which mainly comprises acidic washing treatments. The chemical structures of HexA-derived chromophoric compounds 4–8, which make up 90% of the HexA-derived chromophores, are reported here for the first time. The compounds are ladder-type, mixed quinoid-aromatic oligomers of the bis(furano)-[1,4]benzoquinone and bis(benzofurano)-[1,4] benzoquinone type. The same chromophoric compounds are generated independently of the starting material, which can be either a) HexA in pulp, b) the HexA model compound methyl 1- 13 C-4-deoxy-β-L-threo-hex-4-enopyranosiduronic acid (1) or c) a mixture of the primary degradation intermediates of 1, namely 5-formyl-furancarboxylic acid (2) and 2-furancarboxylic acid (3). Isotopic labeling ( 13 C) in combination with NMR spectroscopy and mass spectrometry served for structure elucidation, and final confirmation was provided by X-ray structure analysis. 13 C-Isotopic labeling was also used to establish the formation mechanisms, showing all the compounds to be composed of condensed, but otherwise largely intact, 2-carbonylfuran and 2-carbonylfuran-5-carboxylic acid moieties. These results disprove the frequent assumption that HexA-derived or furfural-derived chromophores are linear furanoid polymers, and might have a direct bearing on structure elucidation studies of “humins”, which are formed as dark-colored byproducts in depolymerization of pentosans and hexosans in different biorefinery scenarios

Inter-rater reliability and stability of diagnoses of autism spectrum disorder in children identified through screening at a very young age

To examine the inter-rater reliability and stability of autism spectrum disorder (ASD) diagnoses made at a very early age in children identified through a screening procedure around 14 months of age. In a prospective design, preschoolers were recruited from a screening study for ASD. The inter-rater reliability of the diagnosis of ASD was measured through an independent assessment of a randomly selected subsample of 38 patients by two other psychiatrists. The diagnoses at 23 months and 42 months of 131 patients, based on the clinical assessment and the diagnostic classifications of standardised instruments, were compared to evaluate stability of the diagnosis of ASD. Inter-rater reliability on a diagnosis of ASD versus non-ASD at 23 months was 87% with a weighted κ of 0.74 (SE 0.11). The stability of the different diagnoses in the autism spectrum was 63% for autistic disorder, 54% for pervasive developmental disorder, not otherwise specified (PDD-NOS), and 91% for the whole category of ASD. Most diagnostic changes at 42 months were within the autism spectrum from autistic disorder to PDD-NOS and were mainly due to diminished symptom severity. Children who moved outside the ASD category at 42 months made significantly larger gains in cognitive and language skills than children with a stable ASD diagnosis. In conclusion, the inter-rater reliability and stability of the diagnoses of ASD established at 23 months in this population-based sample of very young children are good

Chromophores from hexeneuronic acids (HexA): synthesis of model compounds and primary degradation intermediates

Hexeneuronic acid (HexA) is formed under pulping conditions from 4-O-methyl-glucuronic acid residues in xylans by methanol elimination. It is usually removed by an acidic washing treatment (A-stage) within the pulp bleaching sequence. Hexeneuronic acid has long been recognized as a source of color generation in pulps, but the chemical structure of the actual chromophoric compounds remained elusive. We report the synthesis of isotopically (13C) labeled HexA model units carrying a label at any of the six carbon atoms. Confirming pertinent literature accounts, it is shown that HexA forms three primary degradation intermediates, 2-furancarboxylic acid, 5-formyl-2-furancarboxylic acid, and formic acid, under mildly acidic conditions, and their formation mechanism is discussed. 2-Furancarboxylic acid is demonstrated to be deformylation product of 5-formyl-2-furancarboxylic acid. The three primary intermediates are colorless and do not represent chromophores themselves. Their mixture, upon thermal or acidic treatment, gives rise to the same chromophores that are also directly formed from HexA.(VLID)221167

Equine Amplification and Virulence of Subtype IE Venezuelan Equine Encephalitis Viruses Isolated during the 1993 and 1996 Mexican Epizootics

To assess the role of horses as amplification hosts during the 1993 and 1996 Mexican Venezuelan equine encephalitis (VEE) epizootics, we subcutaneously infected 10 horses by using four different equine isolates. Most horses showed little or no disease and low or nonexistent viremia. Neurologic disease developed in only 1 horse, and brain histopathologic examination showed meningeal lymphocytic infiltration, perivascular cuffing, and focalencephalitis. Three animals showed mild meningoencephalitis without clinical disease. Viral RNA was detected in the brain of several animals 12-14 days after infection. These data suggest that the duration and scope of the recent Mexican epizootics were limited by lack of equine amplification characteristic of previous, more extensive VEE outbreaks. The Mexican epizootics may have resulted from the circulation of a more equine-neurotropic, subtype IE virus strain or from increased transmission to horses due to amplification by other vertebrate hosts or transmission by more competent mosquito vectors

Predictive value of subclinical autistic traits at age 14–15 months for behavioural and cognitive problems at age 3–5 years

It is unclear whether subclinical autistic traits at very young age are transient or stable, and have clinical relevance. This study investigated the relationship between early subclinical autistic traits and the occurrence of later developmental and behavioural problems as well as problems in cognitive and language functioning. Parents of infants aged 14–15 months from the general population completed the Early Screening of Autistic Traits Questionnaire (ESAT). Three groups of children with high, moderate, and low ESAT-scores (total n = 103) were selected. Follow-up assessments included the CBCL 1½–5 at age 3 years, and the SCQ, the ADI-R, the ADOS-G, a non-verbal intelligence test, and language tests for comprehension and production at age 4–5 years. None of the children met criteria for autism spectrum disorder at follow-up. Children with high ESAT-scores at 14–15 months showed significantly more internalizing and externalizing problems at age 3 years and scored significantly lower on language tests at age 4–5 years than children with moderate or low ESAT-scores. Further, significantly more children with high ESAT-scores (14/26, 53.8%) than with moderate and low ESAT-scores (5/36, 13.9% and 1/41, 2.4%, respectively) were in the high-risk/clinical range on one or more outcome domains (autistic symptoms, behavioural problems, cognitive and language abilities). Subclinical autistic traits at 14–15 months predict later behavioural problems and delays in cognitive and language functioning rather than later ASD-diagnoses. The theoretical implications of the findings lie in the pivotal role of early social and communication skills for the development of self-regulation of emotions and impulses. The practical implications bear on the early recognition of children at risk for behavioural problems and for language and cognitive problems

Play Behavior and Attachment in Toddlers with Autism

Play helps to develop social skills. Children with autism show deviances in their play behavior that may be associated with delays in their social development. In this study, we investigated manipulative, functional and symbolic play behavior of toddlers with and without autism (mean age: 26.45, SD 5.63). The results showed that the quality of interaction between the child and the caregiver was related to the development of play behavior. In particular, security of attachment was related to better play behavior. When the developmental level of the child is taken into account, the attachment relationship of the child with the caregiver at this young age is a better predictor of the level of play behavior than the child's disorder

Stern Review: The Economics of Climate Change

The Review's executive summary states that "the Review first examines the evidence on the economic impacts of climate change itself, and explores the economics of stabilizing greenhouse gases in the atmosphere. The second half of the Review considers the complex policy challenges involved in managing the transition to a low-carbon economy and in ensuring that societies can adapt to the consequences of climate change that can no longer be avoided". The report's main conclusion is that the benefits of strong, early action on climate change considerably outweigh the costs