Nickel(II) complexes of whole set of the simple ethylenediaminetetracarboxylate ligands:DFT study of complexes invoking molecular orbital and configurational analysis

The whole set of the nickel(II) complexes with no derivatized edta-type hexadentate ligands has been investigated from their structural and electronic properties. Two more complexes have been prepared in order to complete the whole set: trans(O5)-[Ni(ED3AP)]2- and trans(O5O6)-[Ni(EDA3P)]2- complexes. trans(O5) geometry has been verified crystallographically and trans(O5O6) geometry of the second complex has been predicted by the DFT theory and spectral analysis. Mutual dependance has been established between: the number of the five-membered carboxylate rings, octahedral/tetrahedral deviation of metal-ligand/nitrogen-neighbour-atom angles and charge-transfer energies (CTE) calculated by the Morokuma’s energetic decomposition analysis; energy of the absorption bands and HOMO–LUMO gap.

Atomic Charge Transfer-counter Polarization Effects Determine Infrared Ch Intensities Of Hydrocarbons: A Quantum Theory Of Atoms In Molecules Model.

Atomic charge transfer-counter polarization effects determine most of the infrared fundamental CH intensities of simple hydrocarbons, methane, ethylene, ethane, propyne, cyclopropane and allene. The quantum theory of atoms in molecules/charge-charge flux-dipole flux model predicted the values of 30 CH intensities ranging from 0 to 123 km mol(-1) with a root mean square (rms) error of only 4.2 km mol(-1) without including a specific equilibrium atomic charge term. Sums of the contributions from terms involving charge flux and/or dipole flux averaged 20.3 km mol(-1), about ten times larger than the average charge contribution of 2.0 km mol(-1). The only notable exceptions are the CH stretching and bending intensities of acetylene and two of the propyne vibrations for hydrogens bound to sp hybridized carbon atoms. Calculations were carried out at four quantum levels, MP2/6-311++G(3d,3p), MP2/cc-pVTZ, QCISD/6-311++G(3d,3p) and QCISD/cc-pVTZ. The results calculated at the QCISD level are the most accurate among the four with root mean square errors of 4.7 and 5.0 km mol(-1) for the 6-311++G(3d,3p) and cc-pVTZ basis sets. These values are close to the estimated aggregate experimental error of the hydrocarbon intensities, 4.0 km mol(-1). The atomic charge transfer-counter polarization effect is much larger than the charge effect for the results of all four quantum levels. Charge transfer-counter polarization effects are expected to also be important in vibrations of more polar molecules for which equilibrium charge contributions can be large.

Site Specific Spin Dynamics In Bafe2as2: Tuning The Ground State By Orbital Differentiation.

The role of orbital differentiation on the emergence of superconductivity in the Fe-based superconductors remains an open question to the scientific community. In this investigation, we employ a suitable microscopic spin probe technique, namely Electron Spin Resonance (ESR), to investigate this issue on selected chemically substituted BaFe2As2 single crystals. As the spin-density wave (SDW) phase is suppressed, we observe a clear increase of the Fe 3d bands anisotropy along with their localization at the FeAs plane. Such an increase of the planar orbital content is interestingly independent of the chemical substitution responsible for suppressing the SDW phase. As a consequence, the magnetic fluctuations in combination with this particular symmetry of the Fe 3d bands are propitious ingredients for the emergence of superconductivity in this class of materials.

Comparison Of Different Transfer Impression Techniques Accuracy For Osseointegrated Implants.

Abstract The aim of this study was to evaluate three transfer techniques used to obtain working casts of implant-supported prostheses through the marginal misfit and strain induced to metallic framework. Thirty working casts were obtained from a metallic master cast, each one containing two implant analogues simulating a clinical situation of three-unit implant-supported fixed prostheses, according to the following transfer impression techniques: Group A, squared transfers splinted with dental floss and acrylic resin, sectioned and re-splinted; Group B, squared transfers splinted with dental floss and bis-acrylic resin; and Group N, squared transfers not splinted. A metallic framework was made for marginal misfit and strain measurements from the metallic master cast. The misfit between metallic framework and the working casts was evaluated with an optical microscope following the single-screw test protocol. In the same conditions, the strain was evaluated using strain gauges placed on the metallic framework. The data was submitted to one-way ANOVA followed by the Tukey's test (α=5%). For both marginal misfit and strain, there were statistically significant differences between Groups A and N (p<0.01) and Groups B and N (p<0.01), with greater values for the Group N. According to the Pearson's test, there was a positive correlation between the variables misfit and strain (r=0.5642). The results of this study showed that the impression techniques with splinted transfers promoted better accuracy than non-splinted one, regardless of the splinting material utilized.

Orbital apex syndrome due to aspergillosis: case report

We report the case of a 73-year-old female who presented facial numbness and pain in the first division of the trigeminal nerve, ptosis, diplopia and visual loss on the right side for the previous four months. The neurological, radiological and histological examination demonstrated a rare case of invasive fungal aspergillosis of the central nervous system, causing orbital apex syndrome, later transformed in temporal brain abscess. She died ten months later due to respiratory and renal failure in spite of specific antimycotic therapy.

Orbital abscess after facial trauma

This paper reports a rare case of acute severe orbital abscess manifested 2 days after a facial trauma without bone fracture in a 20-year-old Afro-American female. The symptoms worsened within the 24 h prior to hospital admission resulting in visual disturbances such as diplopia and photophobia. The clinical findings at the first consultation included fever, periorbital swelling and redness, ptosis, proptosis and limitation of ocular movements upwards, downwards, to the right and to the left. Computed tomography scan showed proptosis with considerable soft tissue swelling on the left side and no fracture was evidenced in the facial skeleton, including the zygomatic-orbital complex. After hospital admission and antibiotic therapy intravenously the patient was conducted to the operation room and submitted to incision and drainage under general anesthesia. The orbit was approached thorough both eyelids and the maxillary sinus was reached only through the Caldwell-Luc approach. The postoperative period was uneventful and the rapid improvement of symptoms was remarkable. Visual acuity and ocular motility returned to the normal ranges within 2 days after the surgical intervention. After 12 postoperative days, the patient presented with significative improvement in the ptosis and proptosis, and acceptable scars.

Electrocatalytic oxidation of methanol by the [Ru3O(OAc)6(py)2(CH3OH)]3+cluster: improving the metal-ligand electron transfer by accessing the higher oxidation states of a multicentered system

The [Ru3O(Ac)6(py)2(CH3OH)]+ cluster provides an effective electrocatalytic species for the oxidation of methanol under mild conditions. This complex exhibits characteristic electrochemical waves at -1.02, 0.15 and 1.18 V, associated with the Ru3III,II,II/Ru3III,III,II/Ru 3III,III,III /Ru3IV,III,III successive redox couples, respectively. Above 1.7 V, formation of two RuIV centers enhances the 2-electron oxidation of the methanol ligand yielding formaldehyde, in agreement with the theoretical evolution of the HOMO levels as a function of the oxidation states. This work illustrates an important strategy to improve the efficiency of the oxidation catalysis, by using a multicentered redox catalyst and accessing its multiple higher oxidation states.

Spin alignment measurements of the K*(0)(892) and phi(1020) vector mesons in heavy ion collisions at root S(NN)=200 GeV

We present the first spin alignment measurements for the K*(0)(892) and phi(1020) vector mesons produced at midrapidity with transverse momenta up to 5 GeV/c at root s(NN) = 200 GeV at RHIC. The diagonal spin-density matrix elements with respect to the reaction plane in Au+Au collisions are rho(00) = 0.32 +/- 0.04 (stat) +/- 0.09 (syst) for the K*(0) (0.8 < p(T) < 5.0 GeV/c) and rho(00) = 0.34 +/- 0.02 (stat) +/- 0.03 (syst) for the phi (0.4 < p(T) < 5.0 GeV/c) and are constant with transverse momentum and collision centrality. The data are consistent with the unpolarized expectation of 1/3 and thus no evidence is found for the transfer of the orbital angular momentum of the colliding system to the vector-meson spins. Spin alignments for K(*0) and phi in Au+Au collisions were also measured with respect to the particle's production plane. The phi result, rho(00) = 0.41 +/- 0.02 (stat) +/- 0.04 (syst), is consistent with that in p+p collisions, rho(00) = 0.39 +/- 0.03 (stat) +/- 0.06 (syst), also measured in this work. The measurements thus constrain the possible size of polarization phenomena in the production dynamics of vector mesons.

Sensitization Prevalence, Antibody Cross-Reactivity and Immunogenic Peptide Profile of Api g 2, the Non-Specific Lipid Transfer Protein 1 of Celery

Background: Celery (Apium graveolens) represents a relevant allergen source that can elicit severe reactions in the adult population. To investigate the sensitization prevalence and cross-reactivity of Api g 2 from celery stalks in a Mediterranean population and in a mouse model. Methodology: 786 non-randomized subjects from Italy were screened for IgE reactivity to rApi g 2, rArt v 3 (mugwort pollen LTP) and nPru p 3 (peach LTP) using an allergen microarray. Clinical data of 32 selected patients with reactivity to LTP under investigation were evaluated. Specific IgE titers and cross-inhibitions were performed in ELISA and allergen microarray. Balb/c mice were immunized with purified LTPs; IgG titers were determined in ELISA and mediator release was examined using RBL-2H3 cells. Simulated endolysosomal digestion was performed using microsomes obtained from human DCs. Results: IgE testing showed a sensitization prevalence of 25.6% to Api g 2, 18.6% to Art v 3, and 28.6% to Pru p 3 and frequent co-sensitization and correlating IgE-reactivity was observed. 10/32 patients suffering from LTP-related allergy reported symptoms upon consumption of celery stalks which mainly presented as OAS. Considerable IgE cross-reactivity was observed between Api g 2, Art v 3, and Pru p 3 with varying inhibition degrees of individual patients' sera. Simulating LTP mono-sensitization in a mouse model showed development of more congruent antibody specificities between Api g 2 and Art v 3. Notably, biologically relevant murine IgE cross-reactivity was restricted to the latter and diverse from Pru p 3 epitopes. Endolysosomal processing of LTP showed generation of similar clusters, which presumably represent T-cell peptides. Conclusions: Api g 2 represents a relevant celery stalk allergen in the LTP-sensitized population. The molecule displays common B cell epitopes and endolysosomal peptides that encompass T cell epitopes with pollen and plant-food derived LTP.

MULTILINE DOPPLER IMAGING OF MR SER IN HIGH STATE

Doppler images in Balmer, He I, He II and C II lines, and simultaneous I-band photometry of the polar MR Ser are presented and analyzed. The Balmer and Helium Doppler tomograms, of this bright polar at high mass transfer state show the emission from the accretion flow and the heated surface of the companion star. As a result of a comparison between the Doppler tomograms, the ionization structure of the flow could be constrained. The highest ionization region was found in the vicinity of the magnetospheric radius. Photoionization modeling of the accretion column indicates that the Balmer and Helium emission line production in this system can be explained only by the central soft X-ray illumination. The orbital ephemeris of MR Ser has been revised.

The qWR star HD 45166 - II. Fundamental stellar parameters and evidence of a latitude-dependent wind

Context. The enigmatic object HD 45166 is a qWR star in a binary system with an orbital period of 1.596 day, and presents a rich emission-line spectrum in addition to absorption lines from the companion star (B7 V). As the system inclination is very small (i = 0.77 degrees +/- 0.09 degrees), HD 45166 is an ideal laboratory for wind-structure studies. Aims. The goal of the present paper is to determine the fundamental stellar and wind parameters of the qWR star. Methods. A radiative transfer model for the wind and photosphere of the qWR star was calculated using the non-LTE code CMFGEN. The wind asymmetry was also analyzed using a recently-developed version of CMFGEN to compute the emerging spectrum in two-dimensional geometry. The temporal-variance spectrum (TVS) was calculated to study the line-profile variations. Results. Abundances and stellar and wind parameters of the qWR star were obtained. The qWR star has an effective temperature of T(eff) = 50 000 +/- 2000 K, a luminosity of log(L/L(circle dot)) = 3.75 +/- 0.08, and a corresponding photospheric radius of R(phot) = 1.00 R(circle dot). The star is helium-rich (N(H)/N(He) = 2.0), while the CNO abundances are anomalous when compared either to solar values, to planetary nebulae, or to WR stars. The mass-loss rate is. M = 2.2 x 10(-7) M(circle dot) yr(-1), and the wind terminal velocity is v(infinity) = 425 km s(-1). The comparison between the observed line profiles and models computed under different latitude-dependent wind densities strongly suggests the presence of an oblate wind density enhancement, with a density contrast of at least 8: 1 from equator to pole. If a high velocity polar wind is present (similar to 1200 km s(-1)), the minimum density contrast is reduced to 4:1. Conclusions. The wind parameters determined are unusual when compared to O-type stars or to typical WR stars. While for WR stars v(infinity)/v(esc) > 1.5, in the case of HD 45166 it is much smaller (v(infinity)/v(esc) = 0.32). In addition, the efficiency of momentum transfer is eta = 0.74, which is at least 4 times smaller than in a typical WR. We find evidence for the presence of a wind compression zone, since the equatorial wind density is significantly higher than the polar wind. The TVS supports the presence of such a latitude-dependent wind and a variable absorption/scattering gas near the equator.

A VLT/FLAMES survey for massive binaries in Westerlund 1 III. The WC9d binary W239 and implications for massive stellar evolution

Context. There is growing evidence that a treatment of binarity amongst OB stars is essential for a full theory of stellar evolution. However the binary properties of massive stars - frequency, mass ratio & orbital separation - are still poorly constrained. Aims. In order to address this shortcoming we have undertaken a multiepoch spectroscopic study of the stellar population of the young massive cluster Westerlund 1. In this paper we present an investigation into the nature of the dusty Wolf-Rayet star and candidate binary W239. Methods. To accomplish this we have utilised our spectroscopic data in conjunction with multi-year optical and near-IR photometric observations in order to search for binary signatures. Comparison of these data to synthetic non-LTE model atmosphere spectra were used to derive the fundamental properties of the WC9 primary. Results. We found W239 to have an orbital period of only similar to 5.05 days, making it one of the most compact WC binaries yet identified. Analysis of the long term near-IR lightcurve reveals a significant flare between 2004-6. We interpret this as evidence for a third massive stellar component in the system in a long period (> 6 yr), eccentric orbit, with dust production occuring at periastron leading to the flare. The presence of a near-IR excess characteristic of hot (similar to 1300 K) dust at every epoch is consistent with the expectation that the subset of persistent dust forming WC stars are short (< 1 yr) period binaries, although confirmation will require further observations. Non-LTE model atmosphere analysis of the spectrum reveals the physical properties of the WC9 component to be fully consistent with other Galactic examples. Conclusions. The simultaneous presence of both short period Wolf-Rayet binaries and cool hypergiants within Wd 1 provides compelling evidence for a bifurcation in the post-Main Sequence evolution of massive stars due to binarity. Short period O+OB binaries will evolve directly to the Wolf-Rayet phase, either due to an episode of binary mediated mass loss - likely via case A mass transfer or a contact configuration - or via chemically homogenous evolution. Conversely, long period binaries and single stars will instead undergo a red loop across the HR diagram via a cool hypergiant phase. Future analysis of the full spectroscopic dataset for Wd 1 will constrain the proportion of massive stars experiencing each pathway; hence quantifying the importance of binarity in massive stellar evolution up to and beyond supernova and the resultant production of relativistic remnants.

Cyclic variability of the circumstellar disk of the Be star zeta Tauri I. Long-term monitoring observations

Context. Emission lines formed in decretion disks of Be stars often undergo long-term cyclic variations, especially in the violet-to-red (V/R) ratio of their primary components. The underlying structural and dynamical variations of the disks are only partly understood. From observations of the bright Be-shell star. Tau, the possibly broadest and longest data set illustrating the prototype of this behaviour was compiled from our own and archival observations. It comprises optical and infrared spectra, broad-band polarimetry, and interferometric observations. Aims. The dense, long-time monitoring permits a better separation of repetitive and ephemeral variations. The broad wavelength coverage includes lines formed under different physical conditions, i.e. different locations in the disk, so that the dynamics can be probed throughout much of the disk. Polarimetry and interferometry constrain the spatial structure. All together, the objective is a better understand the dynamics and life cycle of decretion disks. Methods. Standard methods of data acquisition, reduction, and analysis were applied. Results. From 3 V/R cycles between 1997 and 2008, a mean cycle length in Ha of 1400-1430 days was derived. After each minimum in V/R, the shell absorption weakens and splits into two components, leading to 3 emission peaks. This phase may make the strongest contribution to the variability in cycle length. There is no obvious connection between the V/R cycle and the 133-day orbital period of the not otherwise detected companion. V/R curves of different lines are shifted in phase. Lines formed on average closer to the central star are ahead of the others. The shell absorption lines fall into 2 categories differing in line width, ionization/excitation potential, and variability of the equivalent width. They seem to form in separate regions of the disk, probably crossing the line of sight at different times. The interferometry has resolved the continuum and the line emission in Br gamma and HeI 2.06. The phasing of the Br gamma emission shows that the photocenter of the line-emitting region lies within the plane of the disk but is offset from the continuum source. The plane of the disk is constant throughout the observed V/R cycles. The observations lay the foundation for the fully self-consistent, one-armed, disk-oscillation model developed in Paper II.

Activation of endogenous p53 by combined p19Arf gene transfer and nutlin-3 drug treatment modalities in the murine cell lines B16 and C6

Background: Reactivation of p53 by either gene transfer or pharmacologic approaches may compensate for loss of p19Arf or excess mdm2 expression, common events in melanoma and glioma. In our previous work, we constructed the pCLPG retroviral vector where transgene expression is controlled by p53 through a p53-responsive promoter. The use of this vector to introduce p19Arf into tumor cells that harbor p53wt should yield viral expression of p19Arf which, in turn, would activate the endogenous p53 and result in enhanced vector expression and tumor suppression. Since nutlin-3 can activate p53 by blocking its interaction with mdm2, we explored the possibility that the combination of p19Arf gene transfer and nutlin-3 drug treatment may provide an additive benefit in stimulating p53 function. Methods: B16 (mouse melanoma) and C6 (rat glioma) cell lines, which harbor p53wt, were transduced with pCLPGp19 and these were additionally treated with nutlin-3 or the DNA damaging agent, doxorubicin. Viral expression was confirmed by Western, Northern and immunofluorescence assays. p53 function was assessed by reporter gene activity provided by a p53-responsive construct. Alterations in proliferation and viability were measured by colony formation, growth curve, cell cycle and MTT assays. In an animal model, B16 cells were treated with the pCLPGp19 virus and/or drugs before subcutaneous injection in C57BL/6 mice, observation of tumor progression and histopathologic analyses. Results: Here we show that the functional activation of endogenous p53wt in B16 was particularly challenging, but accomplished when combined gene transfer and drug treatments were applied, resulting in increased transactivation by p53, marked cell cycle alteration and reduced viability in culture. In an animal model, B16 cells treated with both p19Arf and nutlin-3 yielded increased necrosis and decreased BrdU marking. In comparison, C6 cells were quite susceptible to either treatment, yet p53 was further activated by the combination of p19Arf and nutlin-3. Conclusions: To the best of our knowledge, this is the first study to apply both p19Arf and nutlin-3 for the stimulation of p53 activity. These results support the notion that a p53 responsive vector may prove to be an interesting gene transfer tool, especially when combined with p53- activating agents, for the treatment of tumors that retain wild-type p53.

Longitudinal spin transfer to Lambda and Lambda hyperons in polarized proton-proton collisions at s=200 GeV

The longitudinal spin transfer, D(LL), from high energy polarized protons to Lambda and Lambda hyperons has been measured for the first time in proton-proton collisions at s=200 GeV with the STAR detector at the Relativistic Heavy Ion Collider. The measurements cover pseudorapidity, eta, in the range |eta|< 1.2 and transverse momenta, p(T), up to 4 GeV/c. The longitudinal spin transfer is found to be D(LL)=-0.03 +/- 0.13(stat)+/- 0.04(syst) for inclusive Lambda and D(LL)=-0.12 +/- 0.08(stat)+/- 0.03(syst) for inclusive Lambda hyperons with <>=0.5 and << p(T)>>=3.7 GeV/c. The dependence on eta and p(T) is presented.