Estimation and predictors of the Omega-3 Index in the UK Biobank

Information on the Omega-3 Index (O3I) in the United Kingdom (UK) are scarce. The UK-Biobank (UKBB) contains data on total plasma omega-3 polyunsaturated fatty acids (n3-PUFA%) and DHA% measured by NMR. The aim of our study was to create an equation to estimate the O3I (eO3I) from these data. We first performed an interlaboratory experiment with 250 random blood samples in which the O3I was measured in erythrocytes by gas chromatography, and total n3% and DHA% were measured in plasma by NMR. The best predictor of eO3I included both DHA% and a derived metric, the total n3%-DHA%. Together these explained 65% of the variability (r=0.832, p<0.0001). We then estimated the O3I in 117, 108 UKBB subjects and correlated it with demographic and lifestyle variables in multivariable adjusted models. The mean (SD) eO3I was 5.58% (2.35%) this UKBB cohort. Several predictors were significantly correlated with eO3I (all p<0.0001). In general order of impact and with directionality (- = inverse, + = direct): oily-fish consumption (+), fish oil supplement use (+), female sex (+), older age (+), alcohol use (+), smoking (-), higher waist circumference and BMI (-), lower socioeconomic status and less education (-). Only 20.5% of eO3I variability could be explained by predictors investigated, and oily-fish consumption accounted for 7.0% of that. With the availability of the eO3I in the UKBB cohort we will be in a position to link risk for a variety of diseases with this commonly-used and well-documented marker of n3-PUFA biostatus

Copper Containing Silicates as Catalysts for Liquid Phase Cyclohexane Oxidation

Copper containing silicates have been prepared by an acid-catalyzed sol-gel process. The materials were characterized by X-ray diffraction and fluorescence, EPR spectroscopy, elemental analysis, N2-physisorption, thermogravimetry, differential scanning calorimetry, temperature-programmed reduction, FTIR and UV/VIS spectroscopy. The silicates were shown to be efficient catalysts for the oxidation of cyclohexane with tert-butyl hydroperoxide as oxidant. Cyclohexanol and cyclohexanone were obtained as the main products. The metal was shown to be weakly bound to the silicate matrix and metal leaching was observed. Leaching was quantified by X-ray fluorescence and leaching tests showed that the catalytic activity is due to supported copper species. Leached copper showed no activity in the homogeneous phase.Silicatos contendo cobre foram preparados pelo processo sol-gel catalisado por ácido. Os materiais foram caracterizados por difração e fluorescência de raios X, espectroscopia EPR, análise elementar, fisissorção de N2, termogravimetria, calorimetria diferencial de varredura, redução à temperatura programada, espectroscopia FTIR e UV/VIS. Os silicatos mostram-se catalisadores eficientes para a oxidação do cicloexano com hidroperóxido de tert-butila como oxidante e obtiveram-se cicloexanona e cicloexanol como produtos principais da reação. O metal mostrou-se fracamente ligado à matriz de sílica e foi observada lixiviação do metal para a fase líquida. A lixiviação foi quantificada por fluorescência de raios X. Testes de lixiviação mostraram que a atividade catalítica é devida às espécies de cobre suportadas. O cobre lixiviado não mostrou nenhuma atividade catalítica em fase homogênea.170176Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq

Porous Ultra-Thin Films from Photocleavable Block Copolymers: In-Situ Degradation Kinetics Study of Pore Material

On the basis of the major application for block copolymers to use them as separation membranes, lithographic mask, and as templates, the preparation of highly oriented nanoporous thin films requires the selective removal of the minor phase from the pores. In the scope of this study, thin film of polystyrene-block-poly(ethylene oxide) block copolymer with a photocleavable junction groups based on ortho-nitrobenzylester (ONB) (PS-hν-PEO) was papered via the spin coating technique followed by solvent annealing to obtain highly-ordered cylindrical domains. The polymer blocks are cleaved by means of a mild UV exposure and then the pore material is washed out of the polymer film by ultra-pure water resulting in arrays of nanoporous thin films to remove one block. The removal of the PEO materials from the pores was proven using the grazing-incidence small-angle X-ray scattering (GISAXS) technique. The treatment of the polymer film during the washing process was observed in real time after two different UV exposure time (1 and 4 h) in order to draw conclusions regarding the dynamics of the removal process. In-situ X-ray reflectivity measurements provide statistically significant information about the change in the layer thickness as well as the roughness and electron density of the polymer film during pore formation. 4 H UV exposure was found to be more efficient for PEO cleavage. By in-situ SFM measurements, the structure of the ultra-thin block copolymer films was also analysed and, thus, the kinetics of the washing process was elaborated. The results from both measurements confirmed that the washing procedure induces irreversible change in morphology to the surface of the thin film

Derivation of the Supermolecular Interaction Energy from the Monomer Densities in the Density Functional Theory

The density functional theory (DFT) interaction energy of a dimer is rigorously derived from the monomer densities. To this end, the supermolecular energy bifunctional is formulated in terms of mutually orthogonal sets of orbitals of the constituent monomers. The orthogonality condition is preserved in the solution of the Kohn-Sham equations through the Pauli blockade method. Numerical implementation of the method provides interaction energies which agree with those obtained from standard supermolecular calculations within less than 0.1% error for three example functionals: Slater-Dirac, PBE0 and B3LYP, and for two model van der Waals dimers: Ne2 and (C2H4)2, and two model H-bond complexes: (HF)2 and (NH3)2.Comment: 6 pages, 1 figure, REVTeX

Pulmonary artery interventions after Norwood procedure: Does type or position of shunt predict need for intervention?

ObjectivesPulmonary artery stenosis is a potential complication after Norwood palliation for hypoplastic left heart syndrome. It is unclear whether the shunt type or position in the Norwood procedure is associated with the risk of the development of pulmonary artery stenosis. We examined the risk of pulmonary artery stenosis and the need for pulmonary artery intervention in children undergoing the Norwood procedure with either the right ventricle to pulmonary artery conduit or modified Blalock-Taussig shunt.MethodsA retrospective review was performed of all patients who underwent the Norwood procedure from January 1, 2003, to September 1, 2011. The data from 100 patients were reviewed, including catheterization and echocardiographic data, right ventricle to pulmonary artery conduit (n = 67, right shunt position in 17 and left in 50), and right ventricle to pulmonary artery (n = 33). The primary outcome measure was the need for operative or catheter-based pulmonary artery intervention.ResultsNo patients in the right ventricle to pulmonary artery group required catheterization-based pulmonary artery interventions. Surgical pulmonary arterioplasty was performed frequently and equally in both the right ventricle to pulmonary artery and right ventricle to pulmonary artery groups at the bidirectional Glenn procedure. Catheter-based pulmonary arterioplasty was performed more frequently in the right ventricle to pulmonary artery conduit group, especially when the conduit was positioned to the right side of the neoaorta. These patients had a 12.73 increased odds of a pulmonary artery intervention compared with the left to right ventricle to pulmonary artery conduit (P = .04).ConclusionsConsistent with a previous multicenter randomized trial, patients who received a right ventricle to pulmonary artery conduit versus a right ventricle to pulmonary artery have a greater risk of requiring pulmonary artery interventions. Patients with right ventricle to pulmonary artery conduit placement to the right underwent a greater number of pulmonary artery interventions but demonstrated overall improved growth of the branch pulmonary arteries compared with the patients receiving a left-sided right ventricle to pulmonary artery conduit

Strategic verbal rehearsal in adolescents with mild intellectual disabilities: A multi-centre European study

Background: There is a long-held view that verbal short-term memory problems of individuals with intellectual disabilities (ID) might be due to a deficit in verbal rehearsal. However, the evidence is inconclusive and word length effects as indicator of rehearsal have been criticised. Aim & Method: The aim of this multi-site European study was to investigate verbal rehearsal in adolescents with mild ID (n=90) and a comparison group of typically developing children matched individually for mental age (MA, n=90). The investigation involved: (1) a word length experiment with non-verbal recall using pointing and (2) ‘self-paced’ inspection times to infer whether verbal strategies were utilised when memorising a set of pictorial items. Results: The word length effect on recall did not interact with group, suggesting that adolescents with ID and MA comparisons used similar verbal strategies, possibly phonological recoding of picture names. The inspection time data suggested that high span individuals in both groups used verbal labelling or single item rehearsal on more demanding lists, as long named items had longer inspection times. Conclusions: The findings suggest that verbal strategy use is not specifically impaired in adolescents with mild ID and is mental age appropriate, supporting a developmental perspective

Nematic suspension of a microporous layered silicate obtained by forceless spontaneous delamination via repulsive osmotic swelling for casting high-barrier all-inorganic films

Exploiting the full potential of layered materials for a broad range of applications requires delamination into functional nanosheets. Delamination via repulsive osmotic swelling is driven by thermodynamics and represents the most gentle route to obtain nematic liquid crystals consisting exclusively of single-layer nanosheets. This mechanism was, however, long limited to very few compounds, including 2:1-type clay minerals, layered titanates, or niobates. Despite the great potential of zeolites and their microporous layered counterparts, nanosheet production is challenging and troublesome, and published procedures implied the use of some shearing forces. Here, we present a scalable, eco-friendly, and utter delamination of the microporous layered silicate ilerite into single-layer nanosheets that extends repulsive delamination to the class of layered zeolites. As the sheet diameter is preserved, nematic suspensions with cofacial nanosheets of ≈9000 aspect ratio are obtained that can be cast into oriented films, e.g., for barrier applications

Engineering Art Galleries

The Art Gallery Problem is one of the most well-known problems in Computational Geometry, with a rich history in the study of algorithms, complexity, and variants. Recently there has been a surge in experimental work on the problem. In this survey, we describe this work, show the chronology of developments, and compare current algorithms, including two unpublished versions, in an exhaustive experiment. Furthermore, we show what core algorithmic ingredients have led to recent successes

Congenital deficiency reveals critical role of ISG15 in skin homeostasis

Ulcerating skin lesions are manifestations of human ISG15 deficiency, a type I interferonopathy. However, chronic inflammation may not be their exclusive cause. We describe two siblings with recurrent skin ulcers that healed with scar formation upon corticosteroid treatment. Both had a homozygous nonsense mutation in the ISG15 gene, leading to unstable ISG15 protein lacking the functional domain. We characterized ISG15(-/-) dermal fibroblasts, HaCaT keratinocytes, and human induced pluripotent stem cell-derived vascular endothelial cells. ISG15-deficient cells exhibited the expected hyperinflammatory phenotype, but also dysregulated expression of molecules critical for connective tissue and epidermis integrity, including reduced collagens and adhesion molecules, but increased matrix metalloproteinases. ISG15(-/-) fibroblasts exhibited elevated ROS levels and reduced ROS scavenger expression. As opposed to hyperinflammation, defective collagen and integrin synthesis was not rescued by conjugation-deficient ISG15. Cell migration was retarded in ISG15(-/-) fibroblasts and HaCaT keratinocytes, but normalized under ruxolitinib treatment. Desmosome density was reduced in an ISG15(-/-) 3D epidermis model. Additionally, there were loose architecture and reduced collagen and desmoglein expression, which could be reversed by treatment with ruxolitinib/doxycycline/TGF-beta 1. These results reveal critical roles of ISG15 in maintaining cell migration and epidermis and connective tissue homeostasis, whereby the latter likely requires its conjugation to yet unidentified targets