Impact of the dicyanomethylene substitution position on the cyclophane macrocycle formation in carbazole-based biradicals

π-Conjugated biradical compounds, featuring unique unsaturated valences and radical centers in the ground state, are fundamentally important for understanding the nature of chemical bonds and have potential applications in material science. [1] Recently, it has been demonstrated that several -conjugated mono- and biradicals systems form long strain -bonds between two unpaired electrons resulting in macrocyclic or staircase oligomers or polymers by self-assembly processes. [2] Therefore, these materials are potential building blocks for dynamic covalent chemistry (DCC) since the aggregates can be formed or broken upon soft external stimuli. For instance, 2,7-dicyanomethylene-9-(2-ethylhexyl)carbazole biradical (p-Cz-alkyl in Figure 1) reversibly converts upon soft stimuli (temperature, pressure, light) to a cyclophane tetramer as a result from the formation (or bond cleavage) of long C-C single bonds.[3] Here, we present an experimental and theoretical study in order to investigate how the N-substitution and the change from para- to meta-dicyanomethylene substitution on carbazole-based biradicals affects their biradical character and thus, their tendency to act as useful motifs for DCC (see Figure 1).Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tec

An infrared integrated optic astronomical beam combiner for stellar interferometry at 3-4 microns

Integrated-optic, astronomical, two-beam and three-beam, interferometric combiners have been designed and fabricated for operation in the L band (3 - 4 microns) for the first time. The devices have been realized in titanium-indiffused, x-cut lithium niobate substrates, and on-chip electro-optic fringe scanning has been demonstrated. White light fringes were produced in the laboratory using the two-beam combiner integrated with an on-chip Y-splitter.Comment: This paper was published in Optics Express and is made available as an electronic reprint with the permission of OSA. The paper can be found at the following URL on the OSA website: http://www.opticsinfobase.org/oe. Systematic or multiple reproduction or distribution to multiple locations via electronic or other means is prohibited and is subject to penalties under la

Singular del Pezzo surfaces that are equivariant compactifications

We determine which singular del Pezzo surfaces are equivariant compactifications of G_a^2, to assist with proofs of Manin's conjecture for such surfaces. Additionally, we give an example of a singular quartic del Pezzo surface that is an equivariant compactification of a semidirect product of G_a and G_m.Comment: 14 pages, main result extended to non-closed ground field

Analyzing Interactions of Calmodulin with HIV-1 Matrix Protein

Human immunodeficiency virus (HIV) attacks the immune system and if left untreated, could cause acquired immunodeficiency syndrome (AIDS). The HIV matrix protein (HIV-MA) is involved in replication and regulation of the HIV virus. Calmodulin (CaM), a calcium-binding protein found in all eukaryotes, has a potential role in the viral replication of HIV-MA which plays a key role in the replication of HIV. In order to investigate the interactions between calmodulin and the HIV-MA, a series of titrations with CaM are performed using circular dichroism. Circular dichroism (CD) uses circularly polarized light to observe the secondary structure of a molecule. The circularly polarized light is broken up into left and right components. When the molecule contains a chiral center, the left and right components are absorbed to different extents, and the differential absorption is measured with CD. Through a series of titrations, the chemical environment is changed in small increments so the molecule will experience conformational changes. As the conformation changes, CD is used to measure the ellipticity which provides a better understanding of the secondary structure that is a result of these chemical interactions. Since CaM plays a potential role in the viral replication of HIV-MA, CD is used to investigate the protein-protein interactions and conformational changes

Epigenetics and the estrogen receptor

The position effect variegation in Drosophila and Schizosaccharomyces pombe, and higher-order chromatin structure regulation in yeast, is orchestrated by modifier genes of the Su(var) group, (e.g., histone deacetylases ([HDACs]), protein phosphatases) and enhancer E(Var) group (e.g., ATP [adenosine 5\u27-triphosphate]-dependent nucleosome remodeling proteins). Higher-order chromatin structure is regulated in part by covalent modification of the N-terminal histone tails of chromatin, and histone tails in turn serve as platforms for recruitment of signaling modules that include nonhistone proteins such as heterochromatin protein (HP1) and NuRD. Because the enzymes governing chromatin structure through covalent modifications of histones (acetylation, methylation, phosphorylation, ubiquitination) can also target nonhistone substrates, a mechanism is in place by which epigenetic regulatory processes can affect the function of these alternate substrates. The posttranslational modification of histones, through phosphorylation and acetylation at specific residues, alters chromatin structure in an orchestrated manner in response to specific signals and is considered the basis of a histone code. In an analogous manner, specific residues within transcription factors form a signaling module within the transcription factor to determine genetic target specificity and cellular fate. The architecture of these signaling cascades in transcription factors (SCITs) are poorly understood. The regulation of estrogen receptor (ERalpha) by enzymes that convey epigenetic signals is carefully orchestrated and is reviewed here

Electrical conductivity during incipient melting in the oceanic low-velocity zone

International audienceThe low-viscosity layer in the upper mantle, the asthenosphere, is a requirement for plate tectonics1. The seismic low velocities and the high electrical conductivities of the asthenosphere are attributed either to subsolidus, water-related defects in olivine minerals2, 3, 4 or to a few volume per cent of partial melt5, 6, 7, 8, but these two interpretations have two shortcomings. First, the amount of water stored in olivine is not expected to be higher than 50 parts per million owing to partitioning with other mantle phases9 (including pargasite amphibole at moderate temperatures10) and partial melting at high temperatures9. Second, elevated melt volume fractions are impeded by the temperatures prevailing in the asthenosphere, which are too low, and by the melt mobility, which is high and can lead to gravitational segregation11, 12. Here we determine the electrical conductivity of carbon-dioxide-rich and water-rich melts, typically produced at the onset of mantle melting. Electrical conductivity increases modestly with moderate amounts of water and carbon dioxide, but it increases drastically once the carbon dioxide content exceeds six weight per cent in the melt. Incipient melts, long-expected to prevail in the asthenosphere10, 13, 14, 15, can therefore produce high electrical conductivities there. Taking into account variable degrees of depletion of the mantle in water and carbon dioxide, and their effect on the petrology of incipient melting, we calculated conductivity profiles across the asthenosphere for various tectonic plate ages. Several electrical discontinuities are predicted and match geophysical observations in a consistent petrological and geochemical framework. In moderately aged plates (more than five million years old), incipient melts probably trigger both the seismic low velocities and the high electrical conductivities in the upper part of the asthenosphere, whereas in young plates4, where seamount volcanism occurs6, a higher degree of melting is expected

Oxidative stress in pregnancy and fertility pathologies

Oxidative stress designates the state of imbalance between reactive oxygen species (ROS) production and antioxidant levels. In a healthy placenta, there is an increase in ROS production, due to formation of new tissues and inherent metabolism, but this is balanced by higher levels of antioxidants. However, this balance is lost in some situations, with a consequent increase in oxidative stress levels. Oxidative stress has been implicated in several placental disorders and pregnancy pathologies. The present review intends to summarize what is known about the relationship between oxidative stress and well-known pregnancy disorders

The Mantle Transition Zone Beneath West Antarctica: Seismic Evidence for Hydration and Thermal Upwellings

Although prior work suggests that a mantle plume is associated with Cenozoic rifting and volcanism in West Antarctica, the existence of a plume remains conjectural. Here we use P wave receiver functions (PRFs) from the Antarctic POLENET array to estimate mantle transition zone thickness, which is sensitive to temperature perturbations, throughout previously unstudied parts of West Antarctica. We obtain over 8000 high-quality PRFs using an iterative, time domain deconvolution method filtered with a Gaussian width of 0.5 and 1.0, corresponding to frequencies less than ∼0.24 and ∼0.48 Hz, respectively. Single-station and common conversion point stacks, migrated to depth using the AK135 velocity model, indicate that mantle transition zone thickness throughout most of West Antarctica does not differ significantly from the global average, except in two locations; one small region exhibits a vertically thinned (210 ± 15 km) transition zone beneath the Ruppert Coast of Marie Byrd Land and another laterally broader region shows slight, vertical thinning (225 ± 25 km) beneath the Bentley Subglacial Trench. We also observe the 520 discontinuity and a prominent negative peak above the mantle transition zone throughout much of West Antarctica. These results suggest that the mantle transition zone may be hotter than average in two places, possibly due to upwelling from the lower mantle, but not broadly across West Antarctica. Furthermore, we propose that the transition zone may be hydrated due to \u3e100 million years of subduction beneath the region during the early Mesozoic

Multi-messenger observations of a binary neutron star merger

On 2017 August 17 a binary neutron star coalescence candidate (later designated GW170817) with merger time 12:41:04 UTC was observed through gravitational waves by the Advanced LIGO and Advanced Virgo detectors. The Fermi Gamma-ray Burst Monitor independently detected a gamma-ray burst (GRB 170817A) with a time delay of ~1.7 s with respect to the merger time. From the gravitational-wave signal, the source was initially localized to a sky region of 31 deg2 at a luminosity distance of 40+8-8 Mpc and with component masses consistent with neutron stars. The component masses were later measured to be in the range 0.86 to 2.26 Mo. An extensive observing campaign was launched across the electromagnetic spectrum leading to the discovery of a bright optical transient (SSS17a, now with the IAU identification of AT 2017gfo) in NGC 4993 (at ~40 Mpc) less than 11 hours after the merger by the One- Meter, Two Hemisphere (1M2H) team using the 1 m Swope Telescope. The optical transient was independently detected by multiple teams within an hour. Subsequent observations targeted the object and its environment. Early ultraviolet observations revealed a blue transient that faded within 48 hours. Optical and infrared observations showed a redward evolution over ~10 days. Following early non-detections, X-ray and radio emission were discovered at the transient’s position ~9 and ~16 days, respectively, after the merger. Both the X-ray and radio emission likely arise from a physical process that is distinct from the one that generates the UV/optical/near-infrared emission. No ultra-high-energy gamma-rays and no neutrino candidates consistent with the source were found in follow-up searches. These observations support the hypothesis that GW170817 was produced by the merger of two neutron stars in NGC4993 followed by a short gamma-ray burst (GRB 170817A) and a kilonova/macronova powered by the radioactive decay of r-process nuclei synthesized in the ejecta