Complex Formation of Alkyl-N-iminodiacetic Acids and Hard Metal Ions in Aqueous Solution and Solid State

The calcium(II), iron(III) and chromium(III) alkyl-N-iminodiacetate systems have been studied in aqueous solution with respect to stability, acid-base properties and structure. The calcium(II) ion forms only one weak complex with methyl-N-iminodiacetic acid in water,K-1 = 12.9 (2) mol(-1).dm(3), while iron(III) and chromium(III) form very stable complexes with alkyl-N-iminodiacetic acids. The calcium(II)-methyl-N-iminodiacetate complex is octahedral in the solid state with most probably water in the remaining positions giving a mean Ca-O bond distance of ca. 2.36 angstrom. The iron(III) alkyl-N-iminodiacetate complexes have low solubility due to a strong tendency to form polymeric structures. Depending on pH in the solution at their preparation, the degree of hydrolysis in the resulting compound(s) may differ. In the solid state, the polymeric iron(III) alkyl-N-iminodiacetate compounds seem to have the mean composition Fe2O(C-x-IDA)(5); the mean Fe-O bond distances to the oxo group and the alkyl-N-iminodiacetate ligands are 1.92 and 2.02 angstrom, respectively. In these complexes the nitrogen atoms are bound at much longer bond distances, 0.1-0.2 angstrom, than the carboxylate oxygens. This distribution with short strong Fe-O bonds and much longer and weaker Fe-N bonds is also found in most other structurally characterized iron(III) carboxylated amine/polyamine complexes. The chromium(III) alkyl-N-iminodiacetate complexes are octahedral in both solution and solid state, and the low solubility of the solid compounds indicates a polymeric structure with the ligands bridging chromium(III) ions. Also, chromium(III) binds oxygen atoms in carboxylated amines at significantly shorter distance than the nitrogen stoms. The chromium(III) alkyl-N-iminodiacetate complexes display such slow kinetics at titration with strong base that the back-titration with strong acid shows completely different acid-base properties, thus the acid-base reactions are irreversible

Complex Formation Between Zinc(II) and Alkyl-N-iminodiacetic Acids in Aqueous Solution and Solid State

Removal of metal compounds from wastewater using processes where metals can be removed and valuable chemicals recycled is of significant industrial importance. Chelating surfactants are an interesting group of chemicals to be used in such applications. Carboxylated polyamines are a promising group to be used in such processes. To apply carboxylated polyamines as chelating surfactants, detailed knowledge of the solution chemistry, including complex formation, kinetics and structures of pure fundamental systems, is required. In this study zinc(II) alkyl-N-iminodiacetate systems with varying length of the alkyl chain have been studied. Acidic and stability constants have been studied by potentiometry, and the structures of both solids and aqueous solutions have been determined by EXAFS. Zinc(II) forms two strong complexes with alkyl-N-iminodiacetates in aqueous solution. In an attempt to determine the acidic constants of these complexes, the deprotonation of the nitrogen atom in the complex bound ligands, it was observed that this reaction is very slow and no accurate values could be obtained. The bis(alkyl-N-iminodiacetato)zincate(II) complexes take, however, up two protons in the pH region 3-7, which means that this complex is approximately singly protonated in the pH region 3-7 and doubly protonated at pH < 3. The bis(n-hexyl-N-iminodiacetato)zincate(II) complex at pH = 13 has a distorted octahedral configuration with four short strong Zn-O bonds at 2.08(1) angstrom, while the Zn-N bonds are weaker at much longer distance, 2.28(2) angstrom. Similar configurations are also found in most reported structures of zinc(II) complexes with carboxylated amines/polyamines. The singly protonated complex seems to be five-coordinate, with four Zn-O bond distances at ca. 2.03 angstrom, and a single Zn-N bond distance in the range 2.15-2.25 angstrom. The relationship between the structure of the protonated bis(n-hexyl-N-iminodiacetato)zincate(II) complex and the slow kinetics in the region pH = 3-7 are discussed

Multiple Genetic Loci Associated with Pug Dog Thoracolumbar Myelopathy

Pug dogs with thoracolumbar myelopathy (PDM) present with a specific clinical phenotype that includes progressive pelvic limb ataxia and paresis, commonly accompanied by incontinence. Vertebral column malformations and lesions, excessive scar tissue of the meninges, and central nervous system inflammation have been described. PDM has a late onset and affects more male than female dogs. The breed-specific presentation of the disorder suggests that genetic risk factors are involved in the disease development. To perform a genome-wide search for PDM-associated loci, we applied a Bayesian model adapted for mapping complex traits (BayesR) and a cross-population extended haplotype homozygosity test (XP-EHH) in 51 affected and 38 control pugs. Nineteen associated loci (harboring 67 genes in total, including 34 potential candidate genes) and three candidate regions under selection (with four genes within or next to the signal) were identified. The multiple candidate genes identified have implicated functions in bone homeostasis, fibrotic scar tissue, inflammatory responses, or the formation, regulation, and differentiation of cartilage, suggesting the potential relevance of these processes to the pathogenesis of PDM

Mutations in the CYP27B1 gene cause vitamin D dependent rickets in pugs

Rickets is a disorder of bone development and can be the result of either dietary or genetic causes. Here, related pugs from 2 litters were included. Three pugs had clinical signs including, lameness, bone deformities, and dyspnea. One other pug was found dead. Radiographs of 2 affected pugs, 5 and 6 months old, showed generalized widening, and irregular margination of the physes of both the appendicular and the axial skeleton with generalized decrease in bone opacity and bulbous swelling of the costochondral junctions. Two pugs had low serum calcium and 1,25 (OH)(2)D-3 concentrations. Test results further indicated secondary hyperparathyroidism with adequate concentrations of 25-hydroxyvitamin D. Necropsy revealed tongue-like projections of cartilage extending into the metaphysis consistent with rickets, loss of metaphyseal mineralization and lung pathology. Vitamin D-dependent rickets was diagnosed. A truncating mutation in the 1 alpha-hydroxylase gene (CYP27B1) was identified by genome sequence analysis of the pugs with VDDR type 1A. Vitamin D-dependent rickets type 1A can occur in young pugs, and if left untreated is a life-threatening condition. Early medical intervention can reverse clinical signs and should be instituted as soon as possible

A combined photobiological-photochemical route to C-10 cycloalkane jet fuels from carbon dioxide via isoprene

The hemiterpene isoprene is a volatile C-5 hydrocarbon with industrial applications. It is generated today from fossil resources, but can also be made in biological processes. We have utilized engineered photosynthetic cyanobacteria for direct, light-driven production of bio-isoprene from carbon dioxide, and show that isoprene in a subsequent photochemical step, using either near-UV or simulated or natural solar light, can be dimerized into limonene, paradiprene, and isomeric C10H16 hydrocarbons (monoterpenes) in high yields under photosensitized conditions (above 90% after 44 hours with near-UV and 61% with simulated solar light). The optimal sensitizer in our experiments is di(naphth-1-yl)methanone which we use with a loading of 0.1 mol%. It can also easily be recycled for subsequent photodimerization cycles. The isoprene dimers generated are a mixture of [2 + 2], [4 + 2] and [4 + 4] cycloadducts, and after hydrogenation this mixture is nearly ideal as a drop-in jet fuel. Importantly the photodimerization can be carried out at ambient conditions. However, the high content of hydrogenated [2 + 2] dimers in our isoprene dimer mix lowers the flash point below the threshold (38 degrees C); yet, these dimers can be converted thermally into [4 + 2] and [4 + 4] dimers. When hydrogenated these monoterpenoids fully satisfy the criteria for drop-in jet fuels with regard to energy density, flashpoint, kinematic viscosity, density, and freezing point. Life-cycle assessment results show a potential to produce the fuel in an environmentally sustainable way

Long-term treatment with egg oral immunotherapy enhances sustained unresponsiveness that persists after cessation of therapy

We previously reported results of a randomized, placebo-controlled study of egg oral immunotherapy (eOIT), in which 27.5% of subjects achieved sustained unresponsiveness (SU) after 2 years. Here we report results of treatment through 4 years and long-term follow-up

FEELnc : a tool for long non-coding RNA annotation and its application to the dog transcriptome

Whole transcriptome sequencing (RNA-seq) has become a standard for cataloguing and monitoring RNA populations. One of the main bottlenecks, however, is to correctly identify the different classes of RNAs among the plethora of reconstructed transcripts, particularly those that will be translated (mRNAs) from the class of long non-coding RNAs (lncRNAs). Here, we present FEELnc (FlExible Extraction of LncRNAs), an alignment-free program that accurately annotates lncRNAs based on a Random Forest model trained with general features such as multi k-mer frequencies and relaxed open reading frames. Benchmarking versus five state-of-the-art tools shows that FEELnc achieves similar or better classification performance on GENCODE and NONCODE data sets. The program also provides specific modules that enable the user to fine-tune classification accuracy, to formalize the annotation of lncRNA classes and to identify lncRNAs even in the absence of a training set of non-coding RNAs. We used FEELnc on a real data set comprising 20 canine RNA-seq samples produced by the European LUPA consortium to substantially expand the canine genome annotation to include 10 374 novel lncRNAs and 58 640 mRNA transcripts. FEELnc moves beyond conventional coding potential classifiers by providing a standardized and complete solution for annotating lncRNAs and is freely available at https://github.com/tderrien/FEELnc.Peer reviewe

A High Density SNP Array for the Domestic Horse and Extant Perissodactyla: Utility for Association Mapping, Genetic Diversity, and Phylogeny Studies

An equine SNP genotyping array was developed and evaluated on a panel of samples representing 14 domestic horse breeds and 18 evolutionarily related species. More than 54,000 polymorphic SNPs provided an average inter-SNP spacing of ∼43 kb. The mean minor allele frequency across domestic horse breeds was 0.23, and the number of polymorphic SNPs within breeds ranged from 43,287 to 52,085. Genome-wide linkage disequilibrium (LD) in most breeds declined rapidly over the first 50–100 kb and reached background levels within 1–2 Mb. The extent of LD and the level of inbreeding were highest in the Thoroughbred and lowest in the Mongolian and Quarter Horse. Multidimensional scaling (MDS) analyses demonstrated the tight grouping of individuals within most breeds, close proximity of related breeds, and less tight grouping in admixed breeds. The close relationship between the Przewalski's Horse and the domestic horse was demonstrated by pair-wise genetic distance and MDS. Genotyping of other Perissodactyla (zebras, asses, tapirs, and rhinoceros) was variably successful, with call rates and the number of polymorphic loci varying across taxa. Parsimony analysis placed the modern horse as sister taxa to Equus przewalski. The utility of the SNP array in genome-wide association was confirmed by mapping the known recessive chestnut coat color locus (MC1R) and defining a conserved haplotype of ∼750 kb across all breeds. These results demonstrate the high quality of this SNP genotyping resource, its usefulness in diverse genome analyses of the horse, and potential use in related species

Identification of Genomic Regions Associated with Phenotypic Variation between Dog Breeds using Selection Mapping

Peer reviewe