The reduction of protons into dihydrogen is important because of its potential use in a wide range of energy applications. The preparation of efficient and cheap catalysts for this reaction is one of ...the issues that need to be tackled to allow the widespread use of hydrogen as an energy carrier. In this paper, we report the study of an amorphous molybdenum sulfide (MoS x ) proton reducing electrocatalyst under functional conditions, using in situ X-ray absorption spectroscopy. We probed the local and electronic structures of both the molybdenum and sulfur elements for the as prepared material as well as the precatalytic and catalytic states. The as prepared material is very similar to MoS3 and remains unmodified under functional conditions (pH = 2 aqueous HNO3) in the precatalytic state (+0.3 V vs RHE). In its catalytic state (−0.3 V vs RHE), the film is reduced to an amorphous form of MoS2 and shows spectroscopic features that indicate the presence of terminal disulfide units. These units are formed concomitantly with the release of hydrogen, and we suggest that the rate-limiting step of the HER is the reduction and protonation of these disulfide units. These results show the implication of terminal disulfide chemical motifs into HER driven by transition-metal sulfides and provide insight into their reaction mechanism.
Quantitative energy-resolved collision-induced dissociation cross-sections by tandem ESI-MS provide absolute thermochemical data for phosphine binding energies in first- and second-generation ...ruthenium metathesis catalysts of 33.4 and 36.9 kcal/mol, respectively. Furthermore a study of the ring-closing metathesis in the second-generation system to liberate norbornene by forming the 14-electron reactive intermediate from the intramolecular π-complex gives an estimate of the olefin binding energy to the 14-electron complex of around 18 kcal/mol, assuming a loose transition state. The results reported here are in remarkably good agreement with the latest DFT calculations using the M06-L functional.
Amorphous molybdenum sulfide films are efficient hydrogen evolution catalysts in water. The films are prepared via simple electro-polymerization procedures and are characterized by XPS, electron ...microscopy and electronic absorption spectroscopy. Whereas the precatalysts could be MoS3 or MoS2, the active form of the catalysts is identified as amorphous MoS2. Significant geometric current densities are achieved at low overpotentials (e.g., 15 mA cm-2 at small eta = 200 mV) using these catalysts. The catalysis is compatible with a wide range of pHs (e.g., 0 to 13). The current efficiency for hydrogen production is quantitative. A 40 mV Tafel slope is observed, suggesting a rate-determining ion+atom step. The turnover frequency per active site is calculated. The amorphous molybdenum sulfide films are among the most active non-precious hydrogen evolution catalysts.
BACKGROUND
Universal pathogen inactivation of platelet concentrates (PCs) using amotosalen/ultraviolet A with 7‐day storage was implemented in Switzerland in 2011. Routine‐use data were analyzed at ...the University Hospital Basel, Switzerland.
STUDY DESIGN
A retrospective two‐cohort study of patient and PC characteristics, component usage, patient outcomes, count increments (CIs), and adverse events were analyzed for two consecutive 5‐year periods with either 0‐ to 5‐day‐old conventional PC (C‐PC) (n = 14,181) or 0‐ to 7‐day‐old pathogen‐inactivated PC (PI‐PC) (n = 22,579).
RESULTS
In both periods, PCs were issued for transfusion on a “first in, first out” basis. With 7‐day PI‐PC, wastage was reduced from 8.7% to 1.5%; 16.6% of transfused PI‐PCs were more than 5 days old. Transfusion of PI‐PC more than 5 days old compared with 5 days old or less did not increase platelet and RBC use on the same or next day as an indirect measure of hemostasis and did not increase transfusion reactions. Mean corrected count increments (CCIs) for PI‐PC stored for 5 days or less were 22.6% lower than for C‐PC (p < 0.001), and declined with increasing storage duration for both, although the correlation was weak (r2 = 0.005‐0.014). Mean number of PCs used per patient and duration of PC support were not different for hematology/oncology, allogeneic and autologous hematopoietic stem cell transplant (HSCT), and general medical/surgical patients, who used the majority (~92.0%) of PI‐PCs. Five‐year treatment‐related mortality in allogeneic HSCT was unchanged in the PI‐PC period.
CONCLUSIONS
PI‐PCs with 7‐day storage reduced wastage and did not increase PC or red blood cell utilization or adverse reactions compared with fresh PI‐PC or a historical control group, demonstrating preserved efficacy and safety.
BACKGROUNDUniversal pathogen inactivation of platelet concentrates (PCs) using amotosalen/ultraviolet A with 7‐day storage was implemented in Switzerland in 2011. Routine‐use data were analyzed at ...the University Hospital Basel, Switzerland.STUDY DESIGNA retrospective two‐cohort study of patient and PC characteristics, component usage, patient outcomes, count increments (CIs), and adverse events were analyzed for two consecutive 5‐year periods with either 0‐ to 5‐day‐old conventional PC (C‐PC) (n = 14,181) or 0‐ to 7‐day‐old pathogen‐inactivated PC (PI‐PC) (n = 22,579).RESULTSIn both periods, PCs were issued for transfusion on a “first in, first out” basis. With 7‐day PI‐PC, wastage was reduced from 8.7% to 1.5%; 16.6% of transfused PI‐PCs were more than 5 days old. Transfusion of PI‐PC more than 5 days old compared with 5 days old or less did not increase platelet and RBC use on the same or next day as an indirect measure of hemostasis and did not increase transfusion reactions. Mean corrected count increments (CCIs) for PI‐PC stored for 5 days or less were 22.6% lower than for C‐PC (p < 0.001), and declined with increasing storage duration for both, although the correlation was weak (r2 = 0.005‐0.014). Mean number of PCs used per patient and duration of PC support were not different for hematology/oncology, allogeneic and autologous hematopoietic stem cell transplant (HSCT), and general medical/surgical patients, who used the majority (~92.0%) of PI‐PCs. Five‐year treatment‐related mortality in allogeneic HSCT was unchanged in the PI‐PC period.CONCLUSIONSPI‐PCs with 7‐day storage reduced wastage and did not increase PC or red blood cell utilization or adverse reactions compared with fresh PI‐PC or a historical control group, demonstrating preserved efficacy and safety.
Introduction: Faith and systems of beliefs are known to impact not only the emotional, but also the immunological state of believers in ways that we are just starting to understand. Moreover, ...clinical implications of previous studies are limited.
The aim of the "HEALING" (Hospital-based Ecumenical and Linguistic Immuno-NeuroloGic) Study was to examine immunological and neurological changes in hospitalized patients after meeting a chaplain coupled with biblical readings.
Methods: Hospitalized patients were pre-screened to find those who were the most in need of an intervention. A passage from the Bible was read to them during a meeting with the chaplain at the bedside (n= 20) or in the chapel (n= 18). No meeting occurred in the randomized control group (n=19). Blood samples were taken 30 minutes prior, and 60 minutes after the meeting to measure white blood cells (WBC), interferon gamma (IFN-γ), immunoglobulin M (IgM), IgA, IgG, and complement 3 (C3). A subgroup of the visited patients was subjected to functional magnetic resonance imaging (fMRI), where they were played an audiotape of readings of the same passage from the Bible (n=21).
Results: Lymphocyte counts increased more often after the more successful visits, but the immunological changes were not significant. Conversely, a significant (p
fwe=0.003) correlation was revealed between changes in lymphocytes and activation of the angular gyrus (left BA39) during fMRI, a brain area involved in word recognition.
Conclusions: Although limited by the sample size and cohort study design, the findings suggest the depth of psycho-immunological changes could depend on the degree to which the chaplains' main message is understood.
Background: High-frequency blood group antigens (HFA) are present in >90% of the human population, according to some reports even in >99% of individuals. Therefore, patients lacking HFA may become ...challenging for transfusion support because compatible blood is hardly found, and if the patient carries alloantibodies, the cross-match will be positive with virtual every red cell unit tested. Methods: In this study, we applied high-throughput blood group SNP genotyping on >37,000 Swiss blood donors, intending to identify homozygous carriers of low-frequency blood group antigens (LFA). Results: 326 such individuals were identified and made available to transfusion specialists for future support of patients in need of rare blood products. Conclusion: Thorough comparison of minor allele frequencies using population genetics revealed heterogeneity of allele distributions among Swiss blood donors which may be explained by the topographical and cultural peculiarities of Switzerland. Moreover, geographically localized donor subpopulations are described which contain above-average numbers of individuals carrying rare blood group genotypes.
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