Improving the hydrolytic stability of aryl cyanate esters by examining the effects of extreme environments on polycyanurate copolymers

Three cyanate ester monomer or oligomer species: 2,2-bis(4-cyanatophenyl)propane 1, 1-1-bis(4-dicyanatophenyl)ethane 2, and the oligomeric phenolic cyanate 3, are blended in various ratios to form binary mixtures (18 in total), formulated with copper(II) acetylacetonate (200 ppm) in dodecylphenol (1 % w/v active copper suspension) and cured (3 Kmin-1 to 150 °C + 1 hour; 3 Kmin-1 to 200 °C + 3 hours) followed by a post cure (3 Kmin-1 to 260 °C + 1 hour). Cured copolymers were exposed to environments of elevated relative humidity (75 % RH) and parallel immersion testing in H2O, H2SO4 (10 %) and NaOH (10 %) at 25 °C for a period of up to 2 years and accelerated ageing in boiling water (14 days). Periodic measurements are made of moisture gain along with infrared spectra and compared with cured homopolymers. Changes in mass are recorded periodically throughout exposure, prior to destructive thermo-mechanical analyses. Dynamic mechanical thermal analysis data comparing neat and exposed blends demonstrate the detrimental effect of moisture ingress whilst data from thermogravimetric analysis demonstrate no change in degradation onset between neat and exposed materials. An optimised blend of 1:1 of monomer units 1 and 2 was found to absorb less moisture than blends of different stoichiometry or between other respective monomeric units, consequently limiting the deleterious effect of moisture ingress

Investigation of structure property relationships in liquid processible, solvent free, thermally stable bismaleimide-triazine (BT) resins

Three cyanate ester monomer or oligomer species: 2,2-bis(4-cyanatophenyl)propane 1, 1-1-bis(4-cyanatophenyl)ethane (2), and the oligomeric phenolic cyanate (PrimasetTM PT30) (3), are blended in various ratios with bis(4-maleimidophenyl)methane, (4), to form binary and ternary mixtures (11 in total) and cured, in the absence of catalysts (3 K/min to 150 °C + 1 hour; 3 K/min to 200 °C + 3 hours), followed by a post cure (3 K/min to 260 °C + 1 hour). The use of liquid monomer, (2), offers the possibility of liquid processing in blends containing minority compositions of bismaleimide. Glycidylmethacrylate is explored as a reactive diluent (2.5-10 wt %) to linked interpenetrating network polymer structures comprising cyanate ester and bismaleimide components with glass transition temperatures of 267-275 ºC, depending on composition; the onset of thermo-oxidative degradation ranges from 386-397 ºC. When a binary blend of (2) and (3) (with the former in the minority) is co-cured with (4), an excellent balance of properties is achieved with liquid processing, a Tg greater than 400 C and onset of degradation of 425 ºC in static air. Kinetic analysis of DSC data using Ozawa and Kissinger methods yield activation energies of between 107- 112 kJ/mole for a binary blend of (1)90-(4)10, which is in good agreement with literature. Molecular dynamics simulation of the same blend in cured form gave a simulated glass transition temperature of 250 C that is in very close agreement with empirical DMTA data

Surveying drifting icebergs and ice islands: Deterioration detection and mass estimation with aerial photogrammetry and laser scanning

Icebergs and ice islands (large, tabular icebergs) are challenging targets to survey due to their size, mobility, remote locations, and potentially difficult environmental conditions. Here, we assess the precision and utility of aerial photography surveying with structure-from-motion multi-view stereo photogrammetry processing (SfM) and vessel-based terrestrial laser scanning (TLS) for iceberg deterioration detection and mass estimation. For both techniques, we determine the minimum amount of change required to reliably resolve iceberg deterioration, the deterioration detection threshold (DDT), using triplicate surveys of two iceberg survey targets. We also calculate their relative uncertainties for iceberg mass estimation. The quality of deployed Global Positioning System (GPS) units that were used for drift correction and scale assignment was a major determinant of point cloud precision. When dual-frequency GPS receivers were deployed, DDT values of 2.5 and 0.40 m were calculated for the TLS and SfM point clouds, respectively. In contrast, values of 6.6 and 3.4 m were calculated when tracking beacons with lower-quality GPS were used. The SfM dataset was also more precise when used for iceberg mass estimation, and we recommend further development of this technique for iceberg-related end-uses

Pure Stationary States of Open Quantum Systems

Using Liouville space and superoperator formalism we consider pure stationary states of open and dissipative quantum systems. We discuss stationary states of open quantum systems, which coincide with stationary states of closed quantum systems. Open quantum systems with pure stationary states of linear oscillator are suggested. We consider stationary states for the Lindblad equation. We discuss bifurcations of pure stationary states for open quantum systems which are quantum analogs of classical dynamical bifurcations.Comment: 7p., REVTeX

The major brain cholesterol metabolite 24(s)-hydroxycholesterol is a potent allosteric modulator of N-methyl-d-aspartate receptors

N-methyl-d-aspartate receptors (NMDARs) are glutamate-gated ion channels that are critical to the regulation of excitatory synaptic function in the CNS. NMDARs govern experience-dependent synaptic plasticity and have been implicated in the pathophysiology of various neuropsychiatric disorders including the cognitive deficits of schizophrenia and certain forms of autism. Certain neurosteroids modulate NMDARs experimentally but their low potency, poor selectivity, and very low brain concentrations make them poor candidates as endogenous ligands or therapeutic agents. Here we show that the major brain-derived cholesterol metabolite 24(S)-hydroxycholesterol (24(S)-HC) is a very potent, direct, and selective positive allosteric modulator of NMDARs with a mechanism that does not overlap that of other allosteric modulators. At submicromolar concentrations 24(S)-HC potentiates NMDAR-mediated EPSCs in rat hippocampal neurons but fails to affect AMPAR or GABA(A) receptors (GABA(A)Rs)-mediated responses. Cholesterol itself and other naturally occurring oxysterols present in brain do not modulate NMDARs at concentrations ≤10 μm. In hippocampal slices, 24(S)-HC enhances the ability of subthreshold stimuli to induce long-term potentiation (LTP). 24(S)-HC also reverses hippocampal LTP deficits induced by the NMDAR channel blocker ketamine. Finally, we show that synthetic drug-like derivatives of 24(S)-HC, which potently enhance NMDAR-mediated EPSCs and LTP, restore behavioral and cognitive deficits in rodents treated with NMDAR channel blockers. Thus, 24(S)-HC may function as an endogenous modulator of NMDARs acting at a novel oxysterol modulatory site that also represents a target for therapeutic drug development

Epigenomic Comparison Reveals Activation of “Seed” Enhancers during Transition from Naive to Primed Pluripotency

SummaryNaive mouse embryonic stem cells (mESCs) and primed epiblast stem cells (mEpiSCs) represent successive snapshots of pluripotency during embryogenesis. Using transcriptomic and epigenomic mapping we show that a small fraction of transcripts are differentially expressed between mESCs and mEpiSCs and that these genes show expected changes in chromatin at their promoters and enhancers. Unexpectedly, the cis-regulatory circuitry of genes that are expressed at identical levels between these cell states also differs dramatically. In mESCs, these genes are associated with dominant proximal enhancers and dormant distal enhancers, which we term seed enhancers. In mEpiSCs, the naive-dominant enhancers are lost, and the seed enhancers take up primary transcriptional control. Seed enhancers have increased sequence conservation and show preferential usage in downstream somatic tissues, often expanding into super enhancers. We propose that seed enhancers ensure proper enhancer utilization and transcriptional fidelity as mammalian cells transition from naive pluripotency to a somatic regulatory program

The relative and absolute timing accuracy of the EPIC-pn camera on XMM-Newton, from X-ray pulsations of the Crab and other pulsars

Reliable timing calibration is essential for the accurate comparison of XMM-Newton light curves with those from other observatories, to ultimately use them to derive precise physical quantities. The XMM-Newton timing calibration is based on pulsar analysis. However, as pulsars show both timing noise and glitches, it is essential to monitor these calibration sources regularly. To this end, the XMM-Newton observatory performs observations twice a year of the Crab pulsar to monitor the absolute timing accuracy of the EPIC-pn camera in the fast Timing and Burst modes. We present the results of this monitoring campaign, comparing XMM-Newton data from the Crab pulsar (PSR B0531+21) with radio measurements. In addition, we use five pulsars (PSR J0537-69, PSR B0540-69, PSR B0833-45, PSR B1509-58 and PSR B1055-52) with periods ranging from 16 ms to 197 ms to verify the relative timing accuracy. We analysed 38 XMM-Newton observations (0.2-12.0 keV) of the Crab taken over the first ten years of the mission and 13 observations from the five complementary pulsars. All the data were processed with the SAS, the XMM-Newton Scientific Analysis Software, version 9.0. Epoch folding techniques coupled with \chi^{2} tests were used to derive relative timing accuracies. The absolute timing accuracy was determined using the Crab data and comparing the time shift between the main X-ray and radio peaks in the phase folded light curves. The relative timing accuracy of XMM-Newton is found to be better than 10^{-8}. The strongest X-ray pulse peak precedes the corresponding radio peak by 306\pm9 \mus, which is in agreement with other high energy observatories such as Chandra, INTEGRAL and RXTE. The derived absolute timing accuracy from our analysis is \pm48 \mus.Comment: 16 pages, 9 figures. Accepted for publication on A&