Schiff Base Complexes of Copper(II)

The crystal structures of four Schiff base molecules are presented, one of which is a re-appraisal of a previously reported structure. Crystals of N,N\u27-1,2-phenylene-bis(salicylideneiminato)copper(II) have been grown from both chloroform and pyridine. The structure from chloroform shows two crystallographically distinct squareplanar molecules per asymmetric unit in an orthorhombic cell, a = 20.159(2), b = 14.918(1), c = 13.329(1) Å; space group Pna21. Two different stereochemistries are observed when pyridine is the solvent. One has square planar geometry and the other square pyramidal with a pyridine molecule bound in the fifth co-ordination site. The space group is P1 with a = 8.748(4), b = 14.499(4), c = 18.725(5) Å, α = 109.93(3), β = 91.99(2), γ = 101.64(3)°. Bis(N-phenyl pyridoxylideneiminato)copper(II) crystallises in a monoclinic cell, space group P21/c, a = 5.7037(6), b = 20.394(1), c = 10.6321(6) Å, β = 101.443(6)° with the trans square planar co-ordination geometry. In the re-appraised structure of aqua(5-phosphopyridoxylidene-DLphenylalanineato) copper(II) the complex is square pyramidal with two oxygen and one nitrogen donor from the ligand. The fourth site is occupied by a water molecule and the fifth, apical donor is a phosphate oxygen from an adjacent molecule. The space group is triclinic P1 with a = 8.697(2), b = 13.039(3), c = 12.418(3) Å, α = 110.49(2), β = 108.61(2), γ = 63.65(10)°

(2,2′-Bipyridine-κ2 N,N′)[2-tert-butyl­anilinato(2−)]dichloridooxido­molybdenum(VI) dichloro­methane hemisolvate

The MoVI atom in the title structure, [Mo(C10H13N)Cl2O(C10H8N2)]·0.5CH2Cl2, has a distorted octa­hedral coord­ination sphere with cis-orientated oxide and imide ligands, trans-chloride ligands and the 2,2′-bipyridine (bipy) ligand N atoms lying trans to the oxide and imide ligands. An imide-ligand tert-butyl-methyl-group H atom makes a close approach with the oxide ligand (distance = 2.53 Å) and the imide-ligand N atom (distance = 2.41 Å). Another imide-ligand tert-butyl-methyl-group H atom makes a close approach to a chloride ligand (distance = 2.82 Å). One bipy-ligand α-H atom makes a close approach to the oxide ligand (distance = 2.4 Å) and the other α-H atom makes a close approach to the imide-ligand phenyl-ring ortho-H atom (distance = 2.52 Å). These close approaches suggest the presence of weak intra­molecular hydrogen bonds. The solvent molecule has been modelled under consideration of half-occupancy

Phenylcyanamidocopper(I) and Silver(I) Complexes: Synthetic and Structural Studies

Phenylcyanamidocopper(I) and silver(I) complexes of the type, [{M(PPh3)2L}2] (M = Cu, L = 4-NO2pcyd or 4-Me2Npcyd; M = Ag, L = 4-Me2Npcyd), [Cu(PPh3)3L] (L = pcyd or 4-NO2-pcyd), [Ag-(PPh3)3L] (L = pcyd, 2-Clpcyd, 4-Clpcyd, 4-Brpcyd, 4-MeOpcyd, 4-NO2pcyd or 4-Me2Npcyd), [Ag(Me2phen)(2-Clpcyd)] (Me2phen = 2,9-dimethyl-1,10-phenanthroline) and [Ag(dppm)(4-Brpcyd)] (dppm = bis(diphenylphosphino)methane) have been synthesised and characterised and the crystal structures of four of the complexes determined. For both [{Cu(PPh3)2(4-Me2Npcyd)}2] ⋅ CH2Cl2 and [{Ag(PPh3)2(4-Me2Npcyd)}2], the cyanamide ligands bridge the metal atoms in a μ-1,3-fashion through the cyano and amido nitrogens. Each metal atom has a distorted tetrahedral geometry, being bound to two triphenylphosphine phosphorus atoms and two nitro-gen atoms from 4-Me2Npcyd ligands to give a \u27P2N2\u27 coordination sphere. In the case of the Cu complex the dimer is centrosymmetric but for the Ag complex the metal atoms are not equivalent. The complexes, [Ag(PPh3)3(4-Brpcyd)] and [Ag(PPh3)3(4-Me-Opcyd)], are discrete monomers, in which each of the Ag atoms adopts a distorted tetrahedral geometry, being bound to three triphenylphosphine phosphorus atoms and one phenylcyanamide ligand binding in a terminal fashion through the cyano nitrogen

Space Environment Effects on Silicone Seal Materials

A docking system is being developed by the NASA to support future space missions. It is expected to use redundant elastomer seals to help contain cabin air during dockings between two spacecraft. The sealing surfaces are exposed to the space environment when vehicles are not docked. In space, the seals will be exposed to temperatures between 125 to -75 C, vacuum, atomic oxygen, particle and ultraviolet radiation, and micrometeoroid and orbital debris (MMOD). Silicone rubber is the only class of space flight-qualified elastomeric seal material that functions across the expected temperature range. NASA Glenn has tested three silicone elastomers for such seal applications: two provided by Parker (S0899-50 and S0383-70) and one from Esterline (ELA-SA-401). The effects of atomic oxygen (AO), UV and electron particle radiation, and vacuum on the properties of these three elastomers were examined. Critical seal properties such as leakage, adhesion, and compression set were measured before and after simulated space exposures. The S0899-50 silicone was determined to be inadequate for extended space seal applications due to high adhesion and intolerance to UV, but both S0383-70 and ELA-SA-401 seals were adequate

Space Environment's Effects on Seal Materials

A Low Impact Docking System (LIDS) is being developed by the NASA Johnson Space Center to support future missions of the Crew Exploration Vehicle (CEV). The LIDS is androgynous, such that each system half is identical, thus any two vehicles or modules with LIDS can be coupled. Since each system half is a replica, the main interface seals must seal against each other instead of a conventional flat metal surface. These sealing surfaces are also expected to be exposed to the space environment when vehicles are not docked. The NASA Glenn Research Center (NASA GRC) is supporting this project by developing the main interface seals for the LIDS and determining the durability of candidate seal materials in the space environment. In space, the seals will be exposed to temperatures of between 50 to 50 C, vacuum, atomic oxygen, particle and ultraviolet radiation, and micrometeoroid and orbital debris (MMOD). NASA GRC is presently engaged in determining the effects of these environments on our candidate elastomers. Since silicone rubber is the only class of seal elastomer that functions across the expected temperature range, NASA GRC is focusing on three silicone elastomers: two provided by Parker Hannifin (S0-899-50 and S0-383-70) and one from Esterline Kirkhill (ELA-SA-401). Our results from compression set, elastomer to elastomer adhesion, and seal leakage tests before and after various simulated space exposures will be presented

Characteristics of Elastomer Seals Exposed to Space Environments

A universal docking and berthing system is being developed by the National Aeronautics and Space Administration (NASA) to support all future space exploration missions to low-Earth orbit (LEO), to the Moon, and to Mars. The Low Impact Docking System (LIDS) is being designed to operate using a seal-on-seal configuration in numerous space environments, each having unique exposures to temperature, solar radiation, reactive elements, debris, and mission duration. As the LIDS seal is likely to be manufactured from an elastomeric material, performance evaluation of elastomers after exposure to atomic oxygen (AO) and ultraviolet radiation (UV) was conducted, of which the work presented herein was a part. Each of the three candidate silicone elastomer compounds investigated, including Esterline ELA-SA-401, and Parker Hannifin S0383-70 and S0899-50, was characterized as a low outgassing compound, per ASTM E595, having percent total mass loss (TML) less than 1.0 percent and collected volatile condensable materials (CVCM) less than 0.1 percent. Each compound was compatible with the LIDS operating environment of -50 to 50 C. The seal characteristics presented include compression set, elastomer-to-elastomer adhesion, and o-ring leakage rate. The ELA-SA-401 compound had the lowest variation in compression set with temperature. The S0383-70 compound exhibited the lowest compression set after exposure to AO and UV. The adhesion for all of the compounds was significantly reduced after exposure to AO and was further decreased after exposure to AO and UV. The leakage rates of o-ring specimens showed modest increases after exposure to AO. The leakage rates after exposure to AO and UV were increased by factors of up to 600 when compared to specimens in the as-received condition

Associations of occupational standing with musculoskeletal symptoms: A systematic review with meta-analysis

Objective Given the high exposure to occupational standing in specific occupations, and recent initiatives to encourage intermittent standing among white-collar workers, a better understanding of the potential health consequences of occupational standing is required. We aimed to review and quantify the epidemiological evidence on associations of occupational standing with musculoskeletal symptoms. Design A systematic review was performed. Data from included articles were extracted and described, and meta-analyses conducted when data were sufficiently homogeneous. Data sources Electronic databases were systematically searched. Eligibility criteria Peer-reviewed articles on occupational standing and musculoskeletal symptoms from epidemiological studies were identified. Results Of the 11 750 articles screened, 50 articles reporting 49 studies were included (45 cross-sectional and 5 longitudinal; n=88 158 participants) describing the associations of occupational standing with musculoskeletal symptoms, including low-back (39 articles), lower extremity (14 articles) and upper extremity (18 articles) symptoms. In the meta-analysis, 'substantial' (>4 hours/workday) occupational standing was associated with the occurrence of low-back symptoms (pooled OR (95% CI) 1.31 (1.10 to 1.56)). Evidence on lower and upper extremity symptoms was too heterogeneous for meta-analyses. The majority of included studies reported statistically significant detrimental associations of occupational standing with lower extremity, but not with upper extremity symptoms. Conclusions The evidence suggests that substantial occupational standing is associated with the occurrence of low-back and (inconclusively) lower extremity symptoms, but there may not be such an association with upper extremity symptoms. However, these conclusions are tentative as only limited evidence was found from high-quality, longitudinal studies with fully adjusted models using objective measures of standing

A Three-Stage Colonization Model for the Peopling of the Americas

Background: We evaluate the process by which the Americas were originally colonized and propose a three-stage model that integrates current genetic, archaeological, geological, and paleoecological data. Specifically, we analyze mitochondrial and nuclear genetic data by using complementary coalescent models of demographic history and incorporating nongenetic data to enhance the anthropological relevance of the analysis. Methodology/Findings: Bayesian skyline plots, which provide dynamic representations of population size changes over time, indicate that Amerinds went through two stages of growth <40,000 and <15,000 years ago separated by a long period of population stability. Isolation-with-migration coalescent analyses, which utilize data from sister populations to estimate a divergence date and founder population sizes, suggest an Amerind population expansion starting <15,000 years ago. Conclusions/Significance: These results support a model for the peopling of the New World in which Amerind ancestors diverged from the Asian gene pool prior to 40,000 years ago and experienced a gradual population expansion as they moved into Beringia. After a long period of little change in population size in greater Beringia, Amerinds rapidly expanded into the Americas <15,000 years ago either through an interior ice-free corridor or along the coast. This rapid colonization of the New World was achieved by a founder group with an effective population size of <1,000–5,400 individuals. Our model presents a detailed scenario for the timing and scale of the initial migration to the Americas, substantially refines th

Attention bias to emotional faces varies by IQ and anxiety in Williams syndrome

Individuals with Williams syndrome (WS) often experience significant anxiety. A promising approach to anxiety intervention has emerged from cognitive studies of attention bias to threat. To investigate the utility of this intervention in WS, this study examined attention bias to happy and angry faces in individuals with WS (N=46). Results showed a significant difference in attention bias patterns as a function of IQ and anxiety. Individuals with higher IQ or higher anxiety showed a significant bias toward angry, but not happy faces, whereas individuals with lower IQ or lower anxiety showed the opposite pattern. These results suggest that attention bias interventions to modify a threat bias may be most effectively targeted to anxious individuals with WS with relatively high IQ

CATMoS: Collaborative Acute Toxicity Modeling Suite.

BACKGROUND: Humans are exposed to tens of thousands of chemical substances that need to be assessed for their potential toxicity. Acute systemic toxicity testing serves as the basis for regulatory hazard classification, labeling, and risk management. However, it is cost- and time-prohibitive to evaluate all new and existing chemicals using traditional rodent acute toxicity tests. In silico models built using existing data facilitate rapid acute toxicity predictions without using animals. OBJECTIVES: The U.S. Interagency Coordinating Committee on the Validation of Alternative Methods (ICCVAM) Acute Toxicity Workgroup organized an international collaboration to develop in silico models for predicting acute oral toxicity based on five different end points: Lethal Dose 50 (LD50 value, U.S. Environmental Protection Agency hazard (four) categories, Globally Harmonized System for Classification and Labeling hazard (five) categories, very toxic chemicals [LD50 (LD50≤50mg/kg)], and nontoxic chemicals (LD50>2,000mg/kg). METHODS: An acute oral toxicity data inventory for 11,992 chemicals was compiled, split into training and evaluation sets, and made available to 35 participating international research groups that submitted a total of 139 predictive models. Predictions that fell within the applicability domains of the submitted models were evaluated using external validation sets. These were then combined into consensus models to leverage strengths of individual approaches. RESULTS: The resulting consensus predictions, which leverage the collective strengths of each individual model, form the Collaborative Acute Toxicity Modeling Suite (CATMoS). CATMoS demonstrated high performance in terms of accuracy and robustness when compared with in vivo results. DISCUSSION: CATMoS is being evaluated by regulatory agencies for its utility and applicability as a potential replacement for in vivo rat acute oral toxicity studies. CATMoS predictions for more than 800,000 chemicals have been made available via the National Toxicology Program's Integrated Chemical Environment tools and data sets (ice.ntp.niehs.nih.gov). The models are also implemented in a free, standalone, open-source tool, OPERA, which allows predictions of new and untested chemicals to be made. https://doi.org/10.1289/EHP8495