Luminosity-dependent changes of the cyclotron line energy and spectral hardness in Cepheus X-4

Context. X-ray spectra of accreting pulsars are generally observed to vary with their X-ray luminosity. In particular, the hardness of the X-ray continuum is found to depend on luminosity. In a few sources, the correlation between the energy of the cyclotron resonance scattering feature (CRSF) and the luminosity is clear. Different types (signs) of the correlation are believed to reflect different accretion modes. Aims. We analyse two NuSTAR observations of the transient accreting pulsar Cep X-4 during its 2014 outburst. Our analysis is focused on a detailed investigation of the dependence of the CRSF energy and of the spectral hardness on X-ray luminosity, especially on short timescales. Methods. To investigate the spectral changes as a function of luminosity within each of the two observations, we used the intrinsic variability of the source on the timescale of individual pulse cycles (tens of seconds), the so-called pulse-to-pulse variability. Results. We find that the NuSTAR spectrum of Cep X-4 contains two CRSFs: the fundamental line at ~30 keV and its harmonic at ~55 keV. We find for the first time that the energy of the fundamental CRSF increases and the continuum becomes harder with increasing X-ray luminosity not only between the two observations, that is, on the long timescale, but also within an individual observation, on the timescale of a few tens of seconds. We investigate these dependencies in detail including their non-linearity. We discuss a possible physical interpretation of the observed behaviour in the frame of a simple one-dimensional model of the polar emitting region with a collisionless shock formed in the infalling plasma near the neutron star surface. With this model, we are able to reproduce the observed variations of the continuum hardness ratio and of the CRSF energy with luminosity

Spectroscopic behavior of pyrrolanthrone and its derivative in aprotic and protic solvents

Recently synthesized pyrrolanthrone, naphtho[1,2,3-cd]indole-6(2H)-one (PyAn), and its water-soluble derivative, 3(naphtho[1,2,3-cd]indole-6(2H)-one-2-yl) sodium propylsulfonate, are very promising for anticancer therapy due to both the fluorescent and cytotoxic properties. The present study is focused on the spectroscopic analysis of solvent effects in PyAn and its derivative. An increase of the solvent polarity results in the bathochromic shift in emission and absorption spectra that indicates the involvement of ππ∗-type transition. The double linear correlation of Stokes shift with bulk solvent polarity functions (in terms of Lippert's, Bakhshiev's and Chamma-Viallet's models) and microscopic solvent polarity parameter E(30)T for aprotic and protic solvents is observed. Both general and specific solvent effects are revealed for the solute-solvent systems. Fluorescence quantum yield, fluorescence lifetime and excited-state dipole moment were defined for PyAn and its derivative in different solvents for the first time. The obtained information is of a great importance for the characterization of intermolecular interactions of drugs with biomolecules for the development of new drug delivery systems

Spectroscopic behavior of pyrrolanthrone and its derivative in aprotic and protic solvents

Recently synthesized pyrrolanthrone, naphtho[1,2,3-cd]indole-6(2H)-one (PyAn), and its water-soluble derivative, 3(naphtho[1,2,3-cd]indole-6(2H)-one-2-yl) sodium propylsulfonate, are very promising for anticancer therapy due to both the fluorescent and cytotoxic properties. The present study is focused on the spectroscopic analysis of solvent effects in PyAn and its derivative. An increase of the solvent polarity results in the bathochromic shift in emission and absorption spectra that indicates the involvement of ππ∗-type transition. The double linear correlation of Stokes shift with bulk solvent polarity functions (in terms of Lippert's, Bakhshiev's and Chamma-Viallet's models) and microscopic solvent polarity parameter () 30 N ET for aprotic and protic solvents is observed. Both general and specific solvent effects are revealed for the solute-solvent systems. Fluorescence quantum yield, fluorescence lifetime and excited-state dipole moment were defined for PyAn and its derivative in different solvents for the first time. The obtained information is of a great importance for the characterization of intermolecular interactions of drugs with biomolecules for the development of new drug delivery systems

Luminosity-dependent changes of the cyclotron line energy and spectral hardness in Cepheus X-4

Context. X-ray spectra of accreting pulsars are generally observed to vary with their X-ray luminosity. In particular, the hardness of the X-ray continuum is found to depend on luminosity. In a few sources, the correlation between the energy of the cyclotron resonance scattering feature (CRSF) and the luminosity is clear. Different types (signs) of the correlation are believed to reflect different accretion modes. Aims. We analyse two NuSTAR observations of the transient accreting pulsar Cep X-4 during its 2014 outburst. Our analysis is focused on a detailed investigation of the dependence of the CRSF energy and of the spectral hardness on X-ray luminosity, especially on short timescales. Methods. To investigate the spectral changes as a function of luminosity within each of the two observations, we used the intrinsic variability of the source on the timescale of individual pulse cycles (tens of seconds), the so-called pulse-to-pulse variability. Results. We find that the NuSTAR spectrum of Cep X-4 contains two CRSFs: the fundamental line at ~30 keV and its harmonic at ~55 keV. We find for the first time that the energy of the fundamental CRSF increases and the continuum becomes harder with increasing X-ray luminosity not only between the two observations, that is, on the long timescale, but also within an individual observation, on the timescale of a few tens of seconds. We investigate these dependencies in detail including their non-linearity. We discuss a possible physical interpretation of the observed behaviour in the frame of a simple one-dimensional model of the polar emitting region with a collisionless shock formed in the infalling plasma near the neutron star surface. With this model, we are able to reproduce the observed variations of the continuum hardness ratio and of the CRSF energy with luminosity

Luminosity-dependent Changes of the Cyclotron Line Energy and Spectral Hardness in Cepheus X-4

Context. X-ray spectra of accreting pulsars are generally observed to vary with their X-ray luminosity. In particular, the hardness of the X-ray continuum is found to depend on luminosity. In a few sources, the correlation between the energy of the cyclotron resonance scattering feature (CRSF) and the luminosity is clear. Different types (signs) of the correlation are believed to reflect different accretion modes. Aims. We analyse two NuSTAR observations of the transient accreting pulsar Cep X-4 during its 2014 outburst. Our analysis is focused on a detailed investigation of the dependence of the CRSF energy and of the spectral hardness on X-ray luminosity, especially on short timescales. Methods. To investigate the spectral changes as a function of luminosity within each of the two observations, we used the intrinsic variability of the source on the timescale of individual pulse cycles (tens of seconds), the so-called pulse-to-pulse variability. Results. We find that the NuSTAR spectrum of Cep X-4 contains two CRSFs: the fundamental line at ~30 keV and its harmonic at ~55 keV. We find for the first time that the energy of the fundamental CRSF increases and the continuum becomes harder with increasing X-ray luminosity not only between the two observations, that is, on the long timescale, but also within an individual observation, on the timescale of a few tens of seconds. We investigate these dependencies in detail including their non-linearity. We discuss a possible physical interpretation of the observed behaviour in the frame of a simple one-dimensional model of the polar emitting region with a collisionless shock formed in the infalling plasma near the neutron star surface. With this model, we are able to reproduce the observed variations of the continuum hardness ratio and of the CRSF energy with luminosity

Iron metabolic pathways in the processes of sponge plasticity.

The ability to regulate oxygen consumption evolved in ancestral animals and is intrinsically linked to iron metabolism. The iron pathways have been intensively studied in mammals, whereas data on distant invertebrates are limited. Sea sponges represent the oldest animal phylum and have unique structural plasticity and capacity to reaggregate after complete dissociation. We studied iron metabolic factors and their expression during reaggregation in the White Sea cold-water sponges Halichondria panicea and Halisarca dujardini. De novo transcriptomes were assembled using RNA-Seq data, and evolutionary trends were analyzed with bioinformatic tools. Differential expression during reaggregation was studied for H. dujardini. Enzymes of the heme biosynthesis pathway and transport globins, neuroglobin (NGB) and androglobin (ADGB), were identified in sponges. The globins mutate at higher evolutionary rates than the heme synthesis enzymes. Highly conserved iron-regulatory protein 1 (IRP1) presumably interacts with the iron-responsive elements (IREs) found in mRNAs of ferritin (FTH1) and a putative transferrin receptor NAALAD2. The reaggregation process is accompanied by increased expression of IRP1, the antiapoptotic factor BCL2, the inflammation factor NFκB (p65), FTH1 and NGB, as well as by an increase in mitochondrial density. Our data indicate a complex mechanism of iron regulation in sponge structural plasticity and help to better understand general mechanisms of morphogenetic processes in multicellular species

Chameleonic Reactivity of Vicinal Diazonium Salt of Acetylenyl-9,10-anthraquinones: Synthetic Application toward Two Heterocyclic Targets

The nature of products in the diazotization of 1-amino-2-acetylenyl-9,10-anthraquinones strongly depends on the nature of substituents at both the alkyne and at the anthraquinone core. Donor substitution (NHAr, OH) at the fourth position stabilizes the diazonium salt at C1, decelerating electrophilic cyclization at the arylethynyl substituent at C2. This effect allows the replacement of the diazonium with azide group and subsequent closure into isoxazole ring with preservation of the alkyne. In contrast, electrophilic 5-<i>exo</i>-<i>dig</i> cyclizations to condensed pyrazoles is observed for the combination of donor substituents at the aryl alkyne moiety and an OAc substituent at C4. The latter process provides a new synthetic route to 3-ethynyl-[1,9-<i>cd</i>]isoxazol-6-ones that are difficult to access otherwise. DFT calculations suggest that donor substituents have only a minor effect on alkyne and diazonium polarization in the reactant but provide specific transition state stabilization by stabilizing the incipient vinyl cation. This analysis provides the first computational data on electrophilic 5-<i>exo</i>-<i>dig</i> cyclization in its parent form and the nucleophile-promoted version. This cyclization is a relatively fast but endothermic process that is rendered thermodynamically feasible by the enol-keto tautomerization with concomitant aromatization in the five-membered heteroaromatic ring. Computations suggest that the importance of nucleophilic assistance in the transition state for a relatively weak nucleophile such as water is minor because the energy gain due to the Lewis base coordination to the carbocationic center is more than compensated for by the unfavorable entropic term for the bimolecular proces