Molecular and electronic structures of copper-cuprizone and analogues

A paramagnetic dinuclear copper(II) complex, [CuII(L−)Cl]2 (1) while LH = (E)-1,2-diphenyl-2-(2-(pyridine-2-yl)hydrozono)ethanone, an analogue of mono-hydrazone cuprizone (LmcpzH2), was isolated and substantiated by spectra, single crystal X-ray structure determination, unrestricted density functional theory (DFT) calculations and inter alia. Magnetic susceptibility measurement and EPR spectra confirmed the triplet state of 1 above 30 K because of two paramagnetic copper(II) centers. Unrestricted DFT calculations on copper cuprizone species with doublet spin state established similar electronic features and disclosed that bis-deprotonated NN-chelation, [Cu(Lmcpz)2]2−, (cis or trans-2NN), is ∼3 × 103 kJ/mol higher in energy than the mono-deprotonated NO-chelation, Cu(LmcpzH)2, (cis or trans-2NO) precluding the existence of so far reported 2NN products. The calculations revealed that in all isomers, due to the mixing of dx2−y2 orbital with a ligand group orbital as in 1, 48–50% spin density is delocalized over the LmcpzH2 ligand. In fluid solution, 1 absorbs strongly at 527 nm due to LMCT elucidated by the time dependent (TD) DFT calculations and the excited LMCT state is fluorescent (λex = 375 nm; λem = 405, 426 nm; Φ = 0.014)

Reflecting on science fiction

Sam Maggs, Hope Nicholson, Gavin Miller, and Cecil Castellucci respond to the prompt, "What has science fiction taught you about yourself?

Privacy by typing in the π-calculus

In this paper we propose a formal framework for studying privacy in information systems. The proposal follows a two-axes schema where the first axis considers privacy as a taxonomy of rights and the second axis involves the ways an information system stores and manipulates information. We develop a correspondence between the above schema and an associated model of computation. In particular, we propose the \Pcalc, a calculus based on the π-calculus with groups extended with constructs for reasoning about private data. The privacy requirements of an information system are captured via a privacy policy language. The correspondence between the privacy model and the \Pcalc semantics is established using a type system for the calculus and a satisfiability definition between types and privacy policies. We deploy a type preservation theorem to show that a system respects a policy and it is safe if the typing of the system satisfies the policy. We illustrate our methodology via analysis of two use cases: a privacy-aware scheme for electronic traffic pricing and a privacy-preserving technique for speed-limit enforcement

Opportunities and challenges for the application of microfluidic technologies in point-of-care veterinary diagnostics

There is a growing need for low-cost, rapid and reliable diagnostic results in veterinary medicine. Point-of-care (POC) tests have tremendous advantages over existing laboratory-based tests, due to their intrinsic low-cost and rapidity. A considerable number of POC tests are presently available, mostly in dipstick or lateral flow formats, allowing cost-effective and decentralised diagnosis of a wide range of infectious diseases and public health related threats. Although, extremely useful, these tests come with some limitations. Recent advances in the field of microfluidics have brought about new and exciting opportunities for human health diagnostics, and there is now great potential for these new technologies to be applied in the field of veterinary diagnostics. This review appraises currently available POC tests in veterinary medicine, taking into consideration their usefulness and limitations, whilst exploring possible applications for new and emerging technologies, in order to widen and improve the range of POC tests available

The extended clinical phenotype of 26 patients with chronic mucocutaneous candidiasis due to gain-of-function mutations in STAT1

PURPOSE: Gain-of-function (GOF) mutations in the signal transducer and activator of transcription 1 (STAT1) result in unbalanced STAT signaling and cause immune dysregulation and immunodeficiency. The latter is often characterized by the susceptibility to recurrent Candida infections, resulting in the clinical picture of chronic mucocutaneous candidiasis (CMC). This study aims to assess the frequency of GOF STAT1 mutations in a large international cohort of CMC patients. METHODS: STAT1 was sequenced in genomic DNA from 57 CMC patients and 35 healthy family members. The functional relevance of nine different STAT1 variants was shown by flow cytometric analysis of STAT1 phosphorylation in patients' peripheral blood cells (PBMC) after stimulation with interferon (IFN)-α, IFN-γ or interleukin-27 respectively. Extended clinical data sets were collected and summarized for 26 patients. RESULTS: Heterozygous mutations within STAT1 were identified in 35 of 57 CMC patients (61 %). Out of 39 familial cases from 11 families, 26 patients (67 %) from 9 families and out of 18 sporadic cases, 9 patients (50 %) were shown to have heterozygous mutations within STAT1. Thirteen distinct STAT1 mutations are reported in this paper. Eight of these mutations are known to cause CMC (p.M202V, p.A267V, p.R274W, p.R274Q, p.T385M, p.K388E, p.N397D, and p.F404Y). However, five STAT1 variants (p.F172L, p.Y287D, p.P293S, p.T385K and p.S466R) have not been reported before in CMC patients. CONCLUSION: STAT1 mutations are frequently observed in patients suffering from CMC. Thus, sequence analysis of STAT1 in CMC patients is advised. Measurement of IFN- or IL-induced STAT1 phosphorylation in PBMC provides a fast and reliable diagnostic tool and should be carried out in addition to genetic testing

Reduced Macromolecular Carbon and Elemental Sulfur in Northwest Africa 8159: Implications for Oxygen Fugacity of the Martian Mantle

No abstract available

Similarities between explicit and implicit motor imagery in mental rotation of hands: an EEG study

Chronometric and imaging studies have shown that motor imagery is used implicitly during mental rotation tasks in which subjects for example judge the laterality of human hand pictures at various orientations. Since explicit motor imagery is known to activate the sensorimotor areas of the cortex, mental rotation is expected to do similar if it involves a form of motor imagery. So far, functional magnetic resonance imaging and positron emission tomography have been used to study mental rotation and less attention has been paid to electroencephalogram (EEG) which offers a high time-frequency resolution. The time-frequency analysis is an established method for studying explicit motor imagery. Although hand mental rotation is claimed to involve motor imagery, the time-frequency characteristics of mental rotation have never been compared with those of explicit motor imagery. In this study, time-frequency responses of EEG recorded during explicit motor imagery and during a mental rotation task, inducing implicit motor imagery, were compared. Fifteen right-handed healthy volunteers performed motor imagery of hands in one condition and hand laterality judgement tasks in another while EEG of the whole head was recorded. The hand laterality judgement was the mental rotation task used to induce implicit motor imagery. The time-frequency analysis and sLORETA localisation of the EEG showed that the activities in the sensorimotor areas had similar spatial and time-frequency characteristics in explicit motor imagery and implicit motor imagery conditions. Furthermore this sensorimotor activity was different for the left and for the right hand in both explicit and implicit motor imagery. This result supports that motor imagery is used during mental rotation and that it can be detected and studied with EEG technology. This result should encourage the use of mental rotation of body parts in rehabilitation programmes in a similar manner as motor imagery

Is the angular momentum of an electron conserved in a uniform magnetic field?

We show that an electron moving in a uniform magnetic field possesses a time-varying ``diamagnetic'' angular momentum. Surprisingly this means that the kinetic angular momentum of the electron may vary with time, despite the rotational symmetry of the system. This apparent violation of angular momentum conservation is resolved by including the angular momentum of the surrounding fields

Niche divergence facilitated by fine-scale ecological partitioning in a recent cichlid fish adaptive radiation

Ecomorphological differentiation is a key feature of adaptive radiations, with a general trend for specialisation and niche expansion following divergence. Ecological opportunity afforded by invasion of a new habitat is thought to act as an ecological release, facilitating divergence and speciation. Here, we investigate trophic adaptive morphology and ecology of an endemic clade of oreochromine cichlid fishes (Alcolapia) that radiated along a herbivorous trophic axis following colonisation of an isolated lacustrine environment, and demonstrate phenotype-environment correlation. Ecological and morphological divergence of the Alcolapia species flock are examined in a phylogenomic context, to infer ecological niche occupation within the radiation. Species divergence is observed in both ecology and morphology, supporting the importance of ecological speciation within the radiation. Comparison with an outgroup taxon reveals large-scale ecomorphological divergence but shallow genomic differentiation within the Alcolapia adaptive radiation. Ancestral morphological reconstruction suggests lake colonisation by a generalist oreochromine phenotype that diverged in Lake Natron to varied herbivorous morphologies akin to specialist herbivores in Lakes Tanganyika and Malawi

Outcome after stroke thrombolysis in patients >80 years treated within 3 hours vs >3–4.5 hours

Objective: To determine outcomes and risks of IV thrombolysis (IVT) in patients with acute ischemic stroke (AIS) >80 years of age within 3 hours compared to >3 to 4.5 hours recorded in the Safe Implementation of Treatment in Stroke (SITS) International Stroke Thrombolysis Registry. Methods: A total of 14,240 (year 2003–2015) patients >80 years of age with AIS were treated with IVT ≤4.5 hours of stroke onset (3,558 in >3–4.5 hours). Of these, 8,658 (2,157 in >3–4.5 hours) were treated otherwise according to the European Summary of Product Characteristics (EU SmPC) criteria for alteplase. Outcomes were 3-month functional independence (modified Rankin Scale score 0–2), mortality, and symptomatic intracerebral hemorrhage (SICH)/SITS. Results were compared between the groups treated in >3 to 4.5 and ≤3 hours. Results: Median age was 84 years; 61% were female in both groups. Median NIH Stroke Scale score was 12 vs 14 in the >3- to 4.5- and ≤3-hour group, respectively. Three-month functional independence was 34% vs 35% (adjusted odds ratio [aOR] 0.78, 95% confidence interval [CI] 0.69–0.89, p < 0.001); mortality was 31% vs 32% (aOR 1.10, 95% CI 0.97–1.25, p = 0.13); and SICH/SITS was 2.7% vs 1.6% (aOR 1.72, 95% CI 1.25–2.35, p = 0.001). In EU SmPC–compliant patients, 3-month functional independence was 36 vs 37% (aOR 0.79, 95% CI 0.68–0.92, p = 0.002), mortality was 29% vs 29.6% (aOR 1.10, 95% CI 0.95–1.28, p = 0.20), and SICH/SITS was 2.7% vs 1.6% (aOR 1.62, 95% CI 1.12–2.34, p = 0.01). Conclusions: In this observational study, unselected patients >80 years of age treated with IVT after 3 hours vs earlier had a slightly higher rate of SICH and similar unadjusted functional outcome but poorer adjusted outcome. The absolute difference between the treatment groups is small, and elderly patients should not be denied IVT in the later time window solely because of age without other contraindications