412 research outputs found
Are C14-C15 single bond isomerizations of the retinal chromophore involved in the proton-pumping mechanism of bacteriorhodopsin?
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 subâiceâsurface saline ocean at Enceladus, together with geothermal activity and a rocky core, make it a compelling location to conduct further, inâdepth, 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 iceâparticle simulants into soft inert metal targets at velocities ranging 0.5â3.0 km sâ1, 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 sâ1. Calibration plots relating the velocity, crater, and particle diameter were established to facilitate future iceâparticle impact experiments where the size of individual ice particles is unknown
Dark-adapted bacteriorhodopsin contains 13-cis, 15-syn and all-trans, 15-anti retinal Schiff bases.
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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
cmâ»Âč) 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
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
pH and rate of âdarkâ 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 âdark eventsâ 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 Iâmetarhodopsin 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
An open-access database and analysis tool for perovskite solar cells based on the FAIR data principles
Large datasets are now ubiquitous as technology enables higher-throughput experiments, but rarely can a research field truly benefit from the research data generated due to inconsistent formatting, undocumented storage or improper dissemination. Here we extract all the meaningful device data from peer-reviewed papers on metal-halide perovskite solar cells published so far and make them available in a database. We collect data from over 42,400 photovoltaic devices with up to 100 parameters per device. We then develop open-source and accessible procedures to analyse the data, providing examples of insights that can be gleaned from the analysis of a large dataset. The database, graphics and analysis tools are made available to the community and will continue to evolve as an open-source initiative. This approach of extensively capturing the progress of an entire field, including sorting, interactive exploration and graphical representation of the data, will be applicable to many fields in materials science, engineering and biosciences
An open-access database and analysis tool for perovskite solar cells based on the FAIR data principles
Large datasets are now ubiquitous as technology enables higher-throughput experiments, but rarely can a research field truly benefit from the research data generated due to inconsistent formatting, undocumented storage or improper dissemination. Here we extract all the meaningful device data from peer-reviewed papers on metal-halide perovskite solar cells published so far and make them available in a database. We collect data from over 42, 400 photovoltaic devices with up to 100 parameters per device. We then develop open-source and accessible procedures to analyse the data, providing examples of insights that can be gleaned from the analysis of a large dataset. The database, graphics and analysis tools are made available to the community and will continue to evolve as an open-source initiative. This approach of extensively capturing the progress of an entire field, including sorting, interactive exploration and graphical representation of the data, will be applicable to many fields in materials science, engineering and biosciences. © 2021, The Author(s)
Reproductive biology of Thamnodynastes hypoconia (Serpentes: Dipsadidae) in Brazilian subtemperate wetlands
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.
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