Infrared spectroscopy of phytochrome and model pigments

Fourier-transform infrared difference spectra between the red-absorbing and far-red-absorbing forms of oat phytochrome have been measured in H2O and 2H2O. The difference spectra are compared with infrared spectra of model compounds, i.e. the (5Z,10Z,15Z)- and (5Z,10Z,15E)-isomers of 2,3,7,8,12,13,17,18-octaethyl-bilindion (Et8-bilindion), 2,3-dihydro-2,3,7,8,12,13,17,18-octaethyl-bilindion (H2Et8-bilindion), and protonated H2Et8-bilindion in various solvents. The spectra of the model compounds show that only for the protonated forms can clear differences between the two isomers be detected. Since considerable differences are present between the spectra of Et8-bilindion and H2Et8-bilindion, it is concluded that only the latter compound can serve as a model system of phytochrome. The 2H2O effect on the difference spectrum of phytochrome supports the view that the chromophore in red-absorbing phytochrome is protonated and suggests, in addition, that it is also protonated in far-red-absorbing phytochrome. The spectra show that protonated carboxyl groups are influenced. The small amplitudes in the difference spectra exclude major changes of protein secondary structure

Extended Thromboprophylaxis with Betrixaban in Acutely Ill Medical Patients

Background Patients with acute medical illnesses are at prolonged risk for venous thrombosis. However, the appropriate duration of thromboprophylaxis remains unknown. Methods Patients who were hospitalized for acute medical illnesses were randomly assigned to receive subcutaneous enoxaparin (at a dose of 40 mg once daily) for 10±4 days plus oral betrixaban placebo for 35 to 42 days or subcutaneous enoxaparin placebo for 10±4 days plus oral betrixaban (at a dose of 80 mg once daily) for 35 to 42 days. We performed sequential analyses in three prespecified, progressively inclusive cohorts: patients with an elevated d-dimer level (cohort 1), patients with an elevated d-dimer level or an age of at least 75 years (cohort 2), and all the enrolled patients (overall population cohort). The statistical analysis plan specified that if the between-group difference in any analysis in this sequence was not significant, the other analyses would be considered exploratory. The primary efficacy outcome was a composite of asymptomatic proximal deep-vein thrombosis and symptomatic venous thromboembolism. The principal safety outcome was major bleeding. Results A total of 7513 patients underwent randomization. In cohort 1, the primary efficacy outcome occurred in 6.9% of patients receiving betrixaban and 8.5% receiving enoxaparin (relative risk in the betrixaban group, 0.81; 95% confidence interval [CI], 0.65 to 1.00; P=0.054). The rates were 5.6% and 7.1%, respectively (relative risk, 0.80; 95% CI, 0.66 to 0.98; P=0.03) in cohort 2 and 5.3% and 7.0% (relative risk, 0.76; 95% CI, 0.63 to 0.92; P=0.006) in the overall population. (The last two analyses were considered to be exploratory owing to the result in cohort 1.) In the overall population, major bleeding occurred in 0.7% of the betrixaban group and 0.6% of the enoxaparin group (relative risk, 1.19; 95% CI, 0.67 to 2.12; P=0.55). Conclusions Among acutely ill medical patients with an elevated d-dimer level, there was no significant difference between extended-duration betrixaban and a standard regimen of enoxaparin in the prespecified primary efficacy outcome. However, prespecified exploratory analyses provided evidence suggesting a benefit for betrixaban in the two larger cohorts. (Funded by Portola Pharmaceuticals; APEX ClinicalTrials.gov number, NCT01583218. opens in new tab.

Characterizing organic particle impacts on inert metal surfaces: Foundations for capturing organic molecules during hypervelocity transits of Enceladus plumes

The presence and accessibility of a sub‐ice‐surface saline ocean at Enceladus, together with geothermal activity and a rocky core, make it a compelling location to conduct further, in‐depth, astrobiological investigations to probe for organic molecules indicative of extraterrestrial life. Cryovolcanic plumes in the south polar region of Enceladus enable the use of remote in situ sampling and analysis techniques. However, efficient plume sampling and the transportation of captured organic materials to an organic analyzer present unique challenges for an Enceladus mission. A systematic study, accelerating organic ice‐particle simulants into soft inert metal targets at velocities ranging 0.5–3.0 km s−1, was carried out using a light gas gun to explore the efficacy of a plume capture instrument. Capture efficiency varied for different metal targets as a function of impact velocity and particle size. Importantly, organic chemical compounds remained chemically intact in particles captured at speeds up to ~2 km s−1. Calibration plots relating the velocity, crater, and particle diameter were established to facilitate future ice‐particle impact experiments where the size of individual ice particles is unknown

Probing structural evolution along multidimensional reaction coordinates with femtosecond stimulated Raman spectroscopy

Mapping out multidimensional potential energy surfaces has been a goal of physical chemistry for decades in the quest to both predict and control chemical reactivity. Recently a new spectroscopic approach called Femtosecond Stimulated Raman Spectroscopy or FSRS was introduced that can structurally interrogate multiple dimensions of a reactive potential energy surface. FSRS is an ultrafast laser technique which provides complete time-resolved, background-free Raman spectra in a few laser shots. The FSRS technique provides simultaneous ultrafast time (~50 fs) and spectral (~8 cm⁻¹) resolution, thus enabling one to follow reactive structural evolutions as they occur. In this perspective we summarize how FSRS has been used to follow structural dynamics and provide mechanistic detail on three classical chemical reactions: a structural isomerization, an electron transfer reaction, and a proton transfer reaction.This is the author's peer-reviewed final manuscript, as accepted by the publisher. The published article is copyrighted by the Royal Society of Chemistry and can be found at: http://pubs.rsc.org/en/journals/journalissues/cp

Anle138b interaction in alpha-synuclein aggregates by dynamic nuclear polarization NMR

Small molecules that bind to oligomeric protein species such as membrane proteins and fibrils are of clinical interest for development of therapeutics and diagnostics. Definition of the binding site at atomic resolution via NMR is often challenging due to low binding stoichiometry of the small molecule. For fibrils and aggregation intermediates grown in the presence of lipids, we report atomic-resolution contacts to the small molecule at sub nm distance via solid-state NMR using dynamic nuclear polarization (DNP) and orthogonally labelled samples of the protein and the small molecule. We apply this approach to α-synuclein (αS) aggregates in complex with the small molecule anle138b, which is a clinical drug candidate for disease modifying therapy. The small central pyrazole moiety of anle138b is detected in close proximity to the protein backbone and differences in the contacts between fibrils and early intermediates are observed. For intermediate species, the 100 K condition for DNP helps to preserve the aggregation state, while for both fibrils and oligomers, the DNP enhancement is essential to obtain sufficient sensitivity

Perovskite Silicon Tandem Solar Cells Above 30 Conversion Efficiency on Submicron Sized Textured Czochralski Silicon Bottom Cells with Improved Hole Transport Layers

In perovskite silicon tandem solar cells, the utilization of silicon heterojunction SHJ solar cells as bottom cells is one of the most promising concepts. Here, we present optimization strategies for the top cell processing and their integration into SHJ bottom cells based on industrial Czochralski Cz Si wafers of 140 amp; 956;m thickness. We show that combining the self assembled monolayer [4 3,6 dimethyl 9H carbazol 9 yl butyl]phosphonic acid Me 4PACz with an additional phosphonic acid PA with different functional groups, can improve film formation when used as a hole transport layer improving wettability, minimizing shunt fraction and reducing nonradiative losses at the buried interface. Transient surface photovoltage and transient photoluminescence measurements confirm that the combined Me 4PACz PA layer has similar charge transport properties to Me 4PACz alone. Moreover, this work demonstrates the potential for thin, double side submicron sized textured industry relevant silicon bottom cells yielding a high accumulated short circuit current density of 40.2 mA cm2 and reaching a stabilized power conversion efficiency of gt;30 . This work paves the way toward industry compatible, highly efficient tandem cells based on a production compatible SHJ bottom cel

pH and rate of ‘dark’ events in toad retinal rods : test of a hypothesis on the molecular origin of photoreceptor noise

Thermal activation of the visual pigment constitutes a fundamental constraint on visual sensitivity. Its electrical correlate in the membrane current of dark-adapted rods are randomly occurring discrete ‘dark events’ indistinguishable from responses to single photons. It has been proposed that thermal activation occurs in a small subpopulation of rhodopsin molecules where the Schiff base linking the chromophore to the protein part is unprotonated. On this hypothesis, rates of thermal activation should increase strongly with rising pH. The hypothesis has been tested by measuring the effect of pH changes on the frequency of discrete dark events in red rods of the common toad Bufo bufo. Dark noise was recorded from isolated rods using the suction pipette technique. Changes in cytoplasmic pH upon manipulations of extracellular pH were quantified by measuring, using fast single-cell microspectrophotometry, the pH-dependent metarhodopsin I–metarhodopsin II equilibrium and subsequent metarhodopsin III formation. These measurements show that, in the conditions of the electrophysiological experiments, changing perfusion pH from 6.5 to 9.3 resulted in a cytoplasmic pH shift from 7.6 to 8.5 that was readily sensed by the rhodopsin. This shift, which implies an 8-fold decrease in cytoplasmic [H+], did not increase the rate of dark events. The results contradict the hypothesis that thermal pigment activation depends on prior deprotonation of the Schiff base

Inkjet Printed FASn1 xPbxI3 Based Perovskite Solar Cells

Metal halide perovskite solar cells PSCs have gained significant attention in thin film photovoltaic research for their high power conversion efficiency PCE and facile fabrication processes. This study presents the use of inkjet printing to fabricate thin films of combinatorial mixed formamidinium tin lead perovskites and evaluates their layer quality and device performance. Our findings demonstrate that incorporating Pb up to 50 into FASnI3 films enhances lattice stability. The investigation focused on optimizing the composition ratio for improved photovoltaic performance with FASn0.5Pb0.5I3 based PSCs achieving the highest PCE of 10.26 . Additionally, these cells exhibited an absorption spectrum extending beyond 1000 nm, corresponding to a 1.25 eV bandgap. The results suggest that inkjet printing can effectively enhance the efficiency of tin lead based PSCs, supporting scalability in device manufacturin