Catalytic photodegradation of organic compounds using TiO2/pillared clays synthesized using a nonconventional aluminum source

This study evaluates the photocatalytic degradation of 2,6-dichlorophenol (2,6-DCP), triclosan (TCS) and bisphenol A (BPA) by ultraviolet (UV) and visible (VIS) light in the presence of TiO2/catalysts synthesized by wet impregnation followed by calcination. The catalyst supports used were three alumina pillared clays (Al-PILC) synthesized using various aluminum sources and montmorillonite (Mt) as raw material. One of the Al-PILC was prepared following the conventional method (Al-PILCCM), using a commercial aluminum salt, and the other two were synthesized using a saline slag, with the aluminum used being extracted with the alkaline (Al-PILCBE) or the acid (Al-PILCAE) method. Mt was impregnated with various amounts of titanium (1, 5, 10, and 20 wt% Ti) and evaluated for the photodegradation of the aforementioned pollutants, comparing the results with those obtained using commercial anatase. Due to the higher conversion rates, 10 and 20 wt% Ti were chosen to impregnate the Al-PILC and to evaluate the photocatalytic performance. All materials were characterized by several techniques, which confirmed the successful formation of TiO2 in the anatase phase. In all cases, photodegradation was higher when using UV light and the most photodegraded pollutant was TCS (85.15 ± 0.49%), followed by 2,6-DCP (65.43 ± 0.79%) and, to a lesser degree, BPA (36.15 ± 0.65%). Al-PILC showed higher photodegradation percentages, with Al-PILCAE exhibiting the highest values for both types of light. An analysis of the photoproducts by HPLC-MS suggested that the preferred pathway for TCS and 2,6-DCP photodegradation depends on the type of light used.The authors are grateful for financial support from the Spanish Ministry of Science and Innovation (MCIN/AEI/10.13039/501100011033) through project PID2020-112656RB-C21. YC thanks the Universidad Pública de Navarra for a pre-doctoral grant (IberusTalent, European Union's H2020 research and innovation program under Marie Sklodowska-Curie grant agreement N° 801586). AG also thanks Banco Santander for funding via the Research Intensification Program

Neutron Monitors and Cosmogenic Isotopes as Cosmic Ray Energy-Integration Detectors : Effective Yield Functions, Effective Energy, and Its Dependence on the Local Interstellar Spectrum

The method of assessment of galactic cosmic rays (GCR) variability over different timescales, using energy-integrating ground-based detectors such as a neutron monitor and cosmogenic isotopes 10Be and 14C stored in natural archives is revisited here. The effective yield functions for cosmogenic 14C (globally mixed in the atmosphere) and 10Be (realistically deposited in the polar region) are calculated and provided, in a tabulated form, in the supporting information. The effective energy of a detector is redefined so that the variability of the flux of GCR particles at this energy is equal to that of the detector's count rate. The effective energy is found as 11–12 GeV/nucleon for the standard polar neutron monitor, and 6–7 GeV/nucleon and 5.5–6 GeV/nucleon for 14C and 10Be, respectively. New “calibration” relations between the force-field modulation potentials, based on different models of local interstellar spectra (LIS) are provided. While such relations are typically based on refitting the modeled cosmic ray spectra with a prescribed LIS model, the method introduced here straightforwardly accounts for the exact type of the detector used to assess the spectrum. The relations are given separately for ground-based neutron monitors and cosmogenic isotopes. This work allows for harmonization of different works related to variability of galactic cosmic ray flux in the vicinity of Earth, on long-term scale.Peer reviewe

Comparison of dedicated BIOSS bifurcation stents with regular drug-eluting stents for coronary artery bifurcated lesions: Pooled analysis from two randomized studies

  Background: Coronary bifurcation treatment poses a therapeutic challenge. The aim of this study was to analyze pooled data of two randomized clinical trials, POLBOS I and POLBOS II, to compare 1-year follow-up results and identify possible prognostic factors. Methods: In POLBOS trials dedicated bifurcation BiOSS® stents were compared with regular drug eluting stents (rDES) in patients with stable coronary artery disease or non ST-segment elevation acute coronary syndrome (POLBOS I: paclitaxel eluting BiOSS® Expert vs. rDES; POLBOS II: sirolimus eluting BiOSS® LIM vs. rDES). Provisional T-stenting was the default strategy. Angiographic control was performed at 12 months. The primary endpoint was major adverse cardiovascular events (MACE) rate defined as the rate of cardiac death, myocardial infarction (MI) or target lesion revascularization (TLR). Results: 445 patients, with 222 patients in the BiOSS group and 223 patients in the rDES group, were analyzed. In 26.7% cases procedures were performed within distal left main, and true bifurca­tions which accounted for 81.6% of treated lesions. At 12 months the whole population exhibited no statistical differences in terms of MACE, TLR, MI or cardiac death between rDES and BiOSS groups. In multivariate analysis odds for MACE decreased with female sex (OR 0.433, 95% CI 0.178–0.942, p = 0.047) and with proximal optimization technique use (OR 0.208, 95% CI 0.097–0.419, p < 0.001), whereas the odds for MACE increased with main vessel predilatation (OR 2.191, 95% CI 1.042–5.066, p = 0.049) and diabetes mellitus treated with insulin (OR 2.779, 95% CI 1.1–6.593, p = 0.024). Conclusions: Pooled data showed no significant difference between MACE and TLR rates for BiOSS® group vs. rDES group

Pulsar shadow as the origin of double notches in radio pulse profiles

We present the model of eclipsing a rotating, spatially extended source of directional emission by a central absorber, and apply it to the pulsar magnetosphere. The model assumes the radially extended inward radio emission along the local direction of the magnetic field, and the pulsar as the absorber. The geometry of the magnetic field lines of the rotating dipole is favourable for the double eclipse events, which we identify with the double notches observed in pulse profiles of nearby pulsars. For pulsars with large dipole inclinations 70 <~ alpha <~ 110 deg the double notches are predicted to occur within a narrow phase range of 20 to 30 deg before the main radio peak. Application of the model to PSR B0950+08 establishes it as a nearly orthogonal rotator (alpha =~ 75 deg, beta =~ -10 deg) with many pulse components naturally interpreted in terms of the inward radio emission from a large range of altitudes. The inward components include the intermittently strong, leading component of the main pulse, which would traditionally have been interpeted as a conal emission in the outward direction. The model also identifies the magnetic field lines along which the radially extended inward radio emission occurs in B0950+08. These have a narrow range of the footprint parameter s close to 1.1 (closed field line region, near the last open field lines). We describe directional characteristics of inward emission from the radially extended region and compare them with characteristics of extended outward emission. Our work shows that pulse profiles of at least some pulsars may be a superposition of both inward and outward emission.Comment: 28 pages, 13 figures, accepted by ApJ, high-quality figures are available from http://www.ncac.torun.pl/~michalf/inward1_figs

Infrared spectroscopy reveals multi-step multi-timescale photoactivation in the photoconvertible protein archetype dronpa

Photochromic fluorescent proteins play key roles in super-resolution microscopy and optogenetics. The light-driven structural changes that modulate the fluorescence involve both trans-to-cis isomerization and proton transfer. The mechanism, timescale and relative contribution of chromophore and protein dynamics are currently not well understood. Here, the mechanism of off-to-on-state switching in dronpa is studied using femtosecond-to-millisecond time-resolved infrared spectroscopy and isotope labelling. Chromophore and protein dynamics are shown to occur on multiple timescales, from picoseconds to hundreds of microseconds. Following excitation of the trans chromophore, a ground-state primary product is formed within picoseconds. Surprisingly, the characteristic vibrational spectrum of the neutral cis isomer appears only after several tens of nanoseconds. Further fluctuations in protein structure around the neutral cis chromophore are required to form a new intermediate, which promotes the final proton-transfer reaction. These data illustrate the interplay between chromophore dynamics and the protein environment underlying fluorescent protein photochromism

Ultrafast Structural Dynamics of BlsA, a Photoreceptor from the Pathogenic Bacterium Acinetobacter baumannii

Acinetobacter baumannii is an important human pathogen that can form biofilms and persist under harsh environmental conditions. Biofilm formation and virulence are modulated by blue light, which is thought to be regulated by a BLUF protein, BlsA. To understand the molecular mechanism of light sensing, we have used steady-state and ultrafast vibrational spectroscopy to compare the photoactivation mechanism of BlsA to the BLUF photosensor AppA from Rhodobacter sphaeroides. Although similar photocycles are observed, vibrational data together with homology modeling identify significant differences in the β5 strand in BlsA caused by photoactivation, which are proposed to be directly linked to downstream signaling

Femtosecond Stimulated Raman Study of the Photoactive Flavoprotein AppABLUF

Femtosecond stimulated Raman Spectroscopy (FSRS) is applied to study the photocycle of a blue light using flavin (BLUF) domain photoreceptor, AppABLUF. It is shown that FSRS spectra are sensitive to the light adapted state of the protein and probe its excited state dynamics. The dominant contribution to the most sensitive excited state Raman active modes is from flavin ring modes. However, TD-DFT calculations for excited state structures indicate that reproduction and assignment of the experimentally observed spectral shift will require high level calculations on the flavin in its specific protein environment

Photoactivation of the BLUF protein PixD Probed by the Site-Specific Incorporation of Fluorotyrosine Residues

The flavin chromophore in blue light using FAD (BLUF) photoreceptors is surrounded by a hydrogen bond network that senses and responds to changes in the electronic structure of the flavin on the ultrafast time scale. The hydrogen bond network includes a strictly conserved Tyr residue, and previously we explored the role of this residue, Y21, in the photoactivation mechanism of the BLUF protein AppA by the introduction of fluorotyrosine (F-Tyr) analogs that modulated the pKa and reduction potential of Y21 by 3.5 pH units and 200 mV, respectively. Although little impact on the forward (dark to light adapted form) photoreaction was observed, the change in Y21 pKa led to a 4,000-fold increase in the rate of dark state recovery. In the present work we have extended these studies to the BLUF protein PixD, where, in contrast to AppA, modulation in the Tyr (Y8) pKa has a profound impact on the forward photoreaction. In particular, a decrease in Y8 pKa by 2 or more pH units prevents formation of a stable light state, consistent with a photoactivation mechanism that involves proton transfer or proton coupled electron transfer from Y8 to the electronically excited FAD. Conversely, the effect of pKa on the rate of dark recovery is markedly reduced in PixD. These observations highlight very significant differences between the photocycles of PixD and AppA, despite their sharing highly conserved FAD binding architectures