High H2 Sorption Energetics in Zeolitic Imidazolate Frameworks

A combined experimental and theoretical study of H2 sorption was carried out on two isostructural zeolitic imidazolate frameworks ZIFs , namely ZIF 68 and ZIF 69. The former consists of Zn2 ions that are coordinated to two 2 nitroimidazolate and two benzimidazolate linkers in a tetrahedral fashion, while 5 chlorobenzimidazolate is used in place of benzimidazolate in the latter compound. H2 sorption measurements showed that the two ZIFs display similar isotherms and isosteric heats of adsorption Qst . The experimental initial H2 Qst value for both ZIFs was determined to be 8.1 kJ mol 1, which is quite high for materials that do not contain exposed metal centers. Molecular simulations of H2 sorption in ZIF 68 and ZIF 69 confirmed the similar H2 sorption properties between the two ZIFs, but also suggest that H2 sorption is slightly favored in ZIF 68 with regards to uptake at 77 K 1.0 atm. This work also presents inelastic neutron scattering INS spectra for H2 sorbed in ZIFs for the first time. The spectra for ZIF 68 and ZIF 69 show a broad range of intensities starting from about 4 meV. The most favorable H2 sorption site in both ZIFs corresponds to a confined region between two adjacent 2 nitroimidazolate linkers. Two dimensional quantum rotation calculations for H2 sorbed at this site in ZIF 68 and ZIF 69 produced rotational transitions that are in accord with the lowest energy peak observed in the INS spectrum for the respective ZIFs. We found that the primary binding site for H2 in the two ZIFs generates high barriers to rotation for the adsorbed H2, which are greater than those in several metal organic frameworks MOFs which possess open metal sites. H2 sorption was also observed for both ZIFs in the vicinity of the nitro groups of the 2 nitroimidazolate linkers. This study highlights the constructive interplay of experiment and theory to elucidate critical details of the H2 sorption mechanism in these two isostructural ZIF

Attachment Styles Within the Coach-Athlete Dyad: Preliminary Investigation and Assessment Development

The present preliminary study aimed to develop and examine the psychometric properties of a new sport-specific self-report instrument designed to assess athletes’ and coaches’ attachment styles. The development and initial validation comprised three main phases. In Phase 1, a pool of items was generated based on pre-existing self-report attachment instruments, modified to reflect a coach and an athlete’s style of attachment. In Phase 2, the content validity of the items was assessed by a panel of experts. A final scale was developed and administered to 405 coaches and 298 athletes (N = 703 participants). In Phase 3, confirmatory factor analysis of the obtained data was conducted to determine the final items of the Coach-Athlete Attachment Scale (CAAS). Confirmatory factor analysis revealed acceptable goodness of fit indexes for a 3-first order factor model as well as a 2-first order factor model for both the athlete and the coach data, respectively. A secure attachment style positively predicted relationship satisfaction, while an insecure attachment style was a negative predictor of relationship satisfaction. The CAAS revealed initial psychometric properties of content, factorial, and predictive validity, as well as reliability

Regulating C₂H₂/CO₂ adsorption selectivity by electronic-state manipulation of iron in metal-organic frameworks

The separation of C2H2 from C2H2/CO2 mixture is of great importance, yet highly challenging in the petrochemical industry due to their similar physicochemical properties. While open-metal sites (OMSs) in metal-organic frameworks (MOFs) are known to possess high affinity toward C2H2, its selective adsorption performance regulated by the electronic state of the same OMSs remains unexplored. Here, we report a metal electronic-state manipulation approach to construct a pair of isostructural Fe-MOFs, namely LIFM-26(Fe[II]/Fe[III]) and LIFM-27(Fe[III]) with different Fe[II] or Fe[III] oxidation states on the Fe centers, which display mixed-valent Fe[II]/Fe[III] centers in the former and sole Fe[III] centers in the latter. Remarkably, LIFM-26(Fe[II]/Fe[III]) shows significantly enhanced C2H2 uptake capacity than LIFM-27(Fe[III]), attested by adsorption isotherms and IAST calculations, as well as simulated and experimental breakthrough experiments. Furthermore, in situ infrared (IR) and molecular calculations unveil that the presence of Fe[II] in LIFM-26(Fe[II]/Fe[III]) results in stronger Fe[II]–C2H2 interactions than Fe[III]–C2H2, which plays a key role in the C2H2/CO2 separation

Geographical and temporal distribution of SARS-CoV-2 clades in the WHO European Region, January to June 2020

We show the distribution of SARS-CoV-2 genetic clades over time and between countries and outline potential genomic surveillance objectives. We applied three available genomic nomenclature systems for SARS-CoV-2 to all sequence data from the WHO European Region available during the COVID-19 pandemic until 10 July 2020. We highlight the importance of real-time sequencing and data dissemination in a pandemic situation. We provide a comparison of the nomenclatures and lay a foundation for future European genomic surveillance of SARS-CoV-2.Peer reviewe

Response of a Lake Michigan coastal lake to anthropogenic catchment disturbance

A paleolimnological investigation of post-European sediments in a Lake Michigan coastal lake was used to examine the response of Lower Herring Lake to anthropogenic impacts and its role as a processor of watershed inputs. We also compare the timing of this response with that of Lake Michigan to examine the role of marginal lakes as ‘early warning’ indicators of potential changes in the larger connected system and their role in buffering Lake Michigan against anthropogenic changes through biotic interactions and material trapping. Sediment geochemistry, siliceous microfossils and nutrient-related morphological changes in diatoms, identified three major trophic periods in the recent history of the lake. During deforestation and early settlement (pre-1845–1920), lake response to catchment disturbances results in localized increases in diatom abundances with minor changes in existing communities. In this early phase of disturbance, Lower Herring Lake acts as a sediment sink and a biological processor of nutrient inputs. During low-lake levels of the 1930s, the lake goes through a transitional period characterized by increased primary productivity and a major shift in diatom communities. Post-World War II (late 1940s–1989) anthropogenic disturbances push Lower Herring Lake to a new state and a permanent change in diatom community structure dominated by Cyclotella comensis . The dominance of planktonic summer diatom species associated with the deep chlorophyll maximum (DCM) is attributed to epilimnetic nutrient depletion. Declining Si:P ratios are inferred from increased sediment storage of biogenic silica and morphological changes in the silica content of Aulacoseira ambigua and Stephanodiscus niagarae . Beginning in the late 1940s, Lower Herring Lake functions as a biogeochemical processor of catchment inputs and a carbon, nutrient and silica sink. Microfossil response to increased nutrients and increased storage of biogenic silica in Lower Herring Lake and other regional embayments occur approximately 20–25 years earlier than in a nearby Lake Michigan site. Results from this study provide evidence for the role of marginal lakes and bays as nutrient buffering systems, delaying the impact of anthropogenic activities on the larger Lake Michigan system.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/43091/1/10933_2004_Article_1688.pd

The Cholecystectomy As A Day Case (CAAD) Score: A Validated Score of Preoperative Predictors of Successful Day-Case Cholecystectomy Using the CholeS Data Set

Background Day-case surgery is associated with significant patient and cost benefits. However, only 43% of cholecystectomy patients are discharged home the same day. One hypothesis is day-case cholecystectomy rates, defined as patients discharged the same day as their operation, may be improved by better assessment of patients using standard preoperative variables. Methods Data were extracted from a prospectively collected data set of cholecystectomy patients from 166 UK and Irish hospitals (CholeS). Cholecystectomies performed as elective procedures were divided into main (75%) and validation (25%) data sets. Preoperative predictors were identified, and a risk score of failed day case was devised using multivariate logistic regression. Receiver operating curve analysis was used to validate the score in the validation data set. Results Of the 7426 elective cholecystectomies performed, 49% of these were discharged home the same day. Same-day discharge following cholecystectomy was less likely with older patients (OR 0.18, 95% CI 0.15–0.23), higher ASA scores (OR 0.19, 95% CI 0.15–0.23), complicated cholelithiasis (OR 0.38, 95% CI 0.31 to 0.48), male gender (OR 0.66, 95% CI 0.58–0.74), previous acute gallstone-related admissions (OR 0.54, 95% CI 0.48–0.60) and preoperative endoscopic intervention (OR 0.40, 95% CI 0.34–0.47). The CAAD score was developed using these variables. When applied to the validation subgroup, a CAAD score of ≤5 was associated with 80.8% successful day-case cholecystectomy compared with 19.2% associated with a CAAD score >5 (p < 0.001). Conclusions The CAAD score which utilises data readily available from clinic letters and electronic sources can predict same-day discharges following cholecystectomy

Improvement of parenteral nutrition-associated cholestasis in an adult using fish oil-based parenteral nutrition

Parenteral nutrition-associated cholestasis (PNAC) is a severe complication of parenteral nutrition. Standard feed preparations contain soybean and olive oil that are rich in ω-6 polyunsaturated fats, and which studies suggest can be hepatotoxic. Preparations containing fish oil, rich in ω-3 polyunsaturated fats, may be hepatoprotective and have been used in the critical care setting as immunotherapy. A case demonstrating dramatic improvement in liver function and overall clinical condition in an adult with PNAC and intestinal failure within 8 weeks of changing to a fish oil-based parenteral feed is reported. As far as is known, this is the first report of an adult patient whose parenteral nutrition-associated liver disease resolved after a parenteral nutrition lipid emulsion was changed to the fish oil-containing emulsion, SMOFlipid