The direct scission of the triple bond of dinitrogen (N2) by a metal complex is an alluring entry point into the transformation of N2 to ammonia (NH3) in molecular catalysis. Reported herein is a ...pincer-ligated rhenium system that reduces N2 to NH3 via a well-defined reaction sequence involving reductive formation of a bridging N2 complex, photolytic N2 splitting, and proton-coupled electron transfer (PCET) reduction of the metal–nitride bond. The new complex (PONOP)ReCl3 (PONOP = 2,6-bis(diisopropylphosphinito)pyridine) is reduced under N2 to afford the trans,trans-isomer of the bimetallic complex (PONOP)ReCl22(μ-N2) as an isolable kinetic product that isomerizes sequentially upon heating into the trans,cis and cis,cis isomers. All isomers are inert to thermal N2 scission, and the trans,trans-isomer is also inert to photolytic N2 cleavage. In striking contrast, illumination of the trans,cis and cis,cis-isomers with blue light (405 nm) affords the octahedral nitride complex cis-(PONOP)Re(N)Cl2 in 47% spectroscopic yield and 11% quantum yield. The photon energy drives an N2 splitting reaction that is thermodynamically unfavorable under standard conditions, producing a nitrido complex that reacts with SmI2/H2O to produce a rhenium tetrahydride complex (38% yield) and furnish ammonia in 74% yield.
The pulsar/massive star binary system PSR B1259−63/LS 2883 is one of the best-studied gamma-ray binaries, a class of systems whose bright gamma-ray flaring can provide important insights into ...high-energy physics. Using the Australian Long Baseline Array, we have conducted very long baseline interferometric observations of PSR B1259−63 over 4.4 years, fully sampling the 3.4-year orbital period. From our measured parallax of 0.38 ± 0.05 mas- we use a Bayesian approach to infer a distance of |$2.6^{+0.4}_{-0.3}$| kpc. We find that the binary orbit is viewed at an angle of 154 ± 3° to the line of sight, implying that the pulsar moves clockwise around its orbit as viewed on the sky. Taking our findings together with previous results from pulsar timing observations, all seven orbital elements for the system are now fully determined. We use our measurement of the inclination angle to constrain the mass of the stellar companion to lie in the range 15–31 M_⊙. Our measured distance and proper motion are consistent with the system having originated in the Cen OB1 association and receiving a modest natal kick, causing it to have moved ∼8 pc from its birthplace over the past ∼3 × 10^5 years. The orientation of the orbit on the plane of the sky matches the direction of motion of the X-ray synchrotron-emitting knot observed by the Chandra X-ray Observatory to be moving away from the system.
The role of vibrational coherence-concerted vibrational motion on the excited-state potential energy surface-in the isomerization of retinal in the protein rhodopsin remains elusive, despite ...considerable experimental and theoretical efforts. We revisited this problem with resonant ultrafast heterodyne-detected transient-grating spectroscopy. The enhanced sensitivity that this technique provides allows us to probe directly the primary photochemical reaction of vision with sufficient temporal and spectral resolution to resolve all the relevant nuclear dynamics of the retinal chromophore during isomerization. We observed coherent photoproduct formation on a sub-50 fs timescale, and recovered a host of vibrational modes of the retinal chromophore that modulate the transient-grating signal during the isomerization reaction. Through Fourier filtering and subsequent time-domain analysis of the transient vibrational dynamics, the excited-state nuclear motions that drive the isomerization reaction were identified, and comprise stretching, torsional and out-of-plane wagging motions about the local C11=C12 isomerization coordinate.
Background
The present interdisciplinary consensus review proposes clinical considerations and recommendations for anaesthetic practice in patients undergoing gastrointestinal surgery with an ...Enhanced Recovery after Surgery (ERAS) programme.
Methods
Studies were selected with particular attention being paid to meta‐analyses, randomized controlled trials and large prospective cohort studies. For each item of the perioperative treatment pathway, available English‐language literature was examined and reviewed. The group reached a consensus recommendation after critical appraisal of the literature.
Results
This consensus statement demonstrates that anaesthesiologists control several preoperative, intraoperative and postoperative ERAS elements. Further research is needed to verify the strength of these recommendations.
Conclusions
Based on the evidence available for each element of perioperative care pathways, the Enhanced Recovery After Surgery (ERAS ®) Society presents a comprehensive consensus review, clinical considerations and recommendations for anaesthesia care in patients undergoing gastrointestinal surgery within an ERAS programme. This unified protocol facilitates involvement of anaesthesiologists in the implementation of the ERAS programmes and allows for comparison between centres and it eventually might facilitate the design of multi‐institutional prospective and adequately powered randomized trials.
Quantum entanglement between distant qubits is an important feature of quantum networks. Distribution of entanglement over long distances can be enabled through coherently interfacing qubit pairs via ...photonic channels. Here, we report the realization of optically generated quantum entanglement between electron spin qubits confined in two distant semiconductor quantum dots. The protocol relies on spin-photon entanglement in the trionic Λ system and quantum erasure of the Raman-photon path information. The measurement of a single Raman photon is used to project the spin qubits into a joint quantum state with an interferometrically stabilized and tunable relative phase. We report an average Bell-state fidelity for |ψ^{(+)}⟩ and |ψ^{(-)}⟩ states of 61.6±2.3% and a record-high entanglement generation rate of 7.3 kHz between distant qubits.
Context. LOFAR offers the unique capability of observing pulsars across the 10−240 MHz frequency range with a fractional bandwidth of roughly 50%. This spectral range is well suited for studying the ...frequency evolution of pulse profile morphology caused by both intrinsic and extrinsic effects such as changing emission altitude in the pulsar magnetosphere or scatter broadening by the interstellar medium, respectively. Aims. The magnitude of most of these effects increases rapidly towards low frequencies. LOFAR can thus address a number of open questions about the nature of radio pulsar emission and its propagation through the interstellar medium. Methods. We present the average pulse profiles of 100 pulsars observed in the two LOFAR frequency bands: high band (120–167 MHz, 100 profiles) and low band (15–62 MHz, 26 profiles). We compare them with Westerbork Synthesis Radio Telescope (WSRT) and Lovell Telescope observations at higher frequencies (350 and 1400 MHz) to study the profile evolution. The profiles were aligned in absolute phase by folding with a new set of timing solutions from the Lovell Telescope, which we present along with precise dispersion measures obtained with LOFAR. Results. We find that the profile evolution with decreasing radio frequency does not follow a specific trend; depending on the geometry of the pulsar, new components can enter into or be hidden from view. Nonetheless, in general our observations confirm the widening of pulsar profiles at low frequencies, as expected from radius-to-frequency mapping or birefringence theories.
Pre-term or full-term childbirth can be experienced as physically or psychologically traumatic. Cumulative and trans-generational effects of traumatic stress on both psychological and physical health ...indicate the ethical requirement to investigate appropriate preventative treatment for stress symptoms in women following a routine traumatic experience such as childbirth.
The objective of this review was to investigate the effectiveness of early psychological interventions in reducing or preventing post-traumatic stress symptoms and post-traumatic stress disorder in post-partum women within twelve weeks of a traumatic birth.
Randomised controlled trials and pilot studies of psychological interventions preventing or reducing post-traumatic stress symptoms or PTSD, that included women who had experienced a traumatic birth, were identified in a search of Cochrane Central Register of Randomised Controlled Trials, MEDLINE, Embase, Psychinfo, PILOTS, CINAHL and Proquest Dissertations databases. One author performed database searches, verified results with a subject librarian, extracted study details and data. Five authors appraised extracted data and agreed upon risk of bias. Analysis was completed with Rev Man 5 software and quality of findings were rated according to Grading of Recommendation, Assessment, Development, and Evaluation.
Eleven studies were identified that evaluated the effectiveness of a range of early psychological interventions. There was firm evidence to suggest that midwifery or clinician led early psychological interventions administered within 72 hours following traumatic childbirth are more effective than usual care in reducing traumatic stress symptoms in women at 4-6 weeks. Further studies of high methodological quality that include longer follow up of 6-12 months are required in order to substantiate the evidence of the effectiveness of specific face to face and online early psychological intervention modalities in preventing the effects of stress symptoms and PTSD in women following a traumatic birth before introduction to routine care and practice.
CRD42020202576, https://www.crd.york.ac.uk/prospero/display_record.php?RecordID=202576.
Celotno besedilo
Dostopno za:
DOBA, IZUM, KILJ, NUK, PILJ, PNG, SAZU, SIK, UILJ, UKNU, UL, UM, UPUK
The efficacy of reduced intensity conditioning (RIC) allogeneic hematopoietic cell transplantation (HCT) for Philadelphia chromosome positive (Ph+) acute lymphoblastic leukemia (ALL) is uncertain. We ...analyzed 197 adults with Ph+ ALL in first complete remission; 67 patients receiving RIC were matched with 130 receiving myeloablative conditioning (MAC) for age, donor type and HCT year. Over 75% received pre-HCT tyrosine kinase inhibitors (TKIs), mostly imatinib; 39% (RIC) and 49% (MAC) were minimal residual disease (MRD)(neg) pre-HCT. At a median 4.5 years follow-up, 1-year transplant-related mortality (TRM) was lower in RIC (13%) than MAC (36%; P=0.001) while the 3-year relapse rate was 49% in RIC and 28% in MAC (P=0.058). Overall survival (OS) was similar (RIC 39% (95% confidence interval (CI) 27-52) vs 35% (95% CI 27-44); P=0.62). Patients MRD(pos) pre-HCT had higher risk of relapse with RIC vs MAC (hazard ratio (HR) 1.97; P=0.026). However, patients receiving pre-HCT TKI in combination with MRD negativity pre-RIC HCT had superior OS (55%) compared with a similar MRD population after MAC (33%; P=0.0042). In multivariate analysis, RIC lowered TRM (HR 0.6; P=0.057), but absence of pre-HCT TKI (HR 1.88; P=0.018), RIC (HR 1.891; P=0.054) and pre-HCT MRD(pos) (HR 1.6; P=0.070) increased relapse risk. RIC is a valid alternative strategy for Ph+ ALL patients ineligible for MAC and MRD(neg) status is preferred pre-HCT.
This Letter reports the first scientific results from the observation of antineutrinos emitted by fission products of ^{235}U at the High Flux Isotope Reactor. PROSPECT, the Precision Reactor ...Oscillation and Spectrum Experiment, consists of a segmented 4 ton ^{6}Li-doped liquid scintillator detector covering a baseline range of 7-9 m from the reactor and operating under less than 1 m water equivalent overburden. Data collected during 33 live days of reactor operation at a nominal power of 85 MW yield a detection of 25 461±283 (stat) inverse beta decays. Observation of reactor antineutrinos can be achieved in PROSPECT at 5σ statistical significance within 2 h of on-surface reactor-on data taking. A reactor model independent analysis of the inverse beta decay prompt energy spectrum as a function of baseline constrains significant portions of the previously allowed sterile neutrino oscillation parameter space at 95% confidence level and disfavors the best fit of the reactor antineutrino anomaly at 2.2σ confidence level.
Aqueous hydride transfer is a fundamental step in emerging alternative energy transformations such as H2 evolution and CO2 reduction. “Hydricity,” the hydride donor ability of a species, is a key ...metric for understanding transition metal hydride reactivity, but comprehensive studies of aqueous hydricity are scarce. An extensive and self-consistent aqueous hydricity scale is constructed for a family of Ru and Ir hydrides that are key intermediates in aqueous catalysis. A reference hydricity is determined using redox potentiometry and spectrophotometric titration for a particularly water-soluble species. Then, relative hydricity values for a range of species are measured using hydride transfer equilibria, taking advantage of expedient new synthetic procedures for Ru and Ir hydrides. This large collection of hydricity values provides the most comprehensive picture so far of how ligands impact hydricity in water. Strikingly, we also find that hydricity can be viewed as a continuum in water: the free energy of hydride transfer changes with pH, buffer composition, and salts present in solution.
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