Correction: The role of ion solvation in lithium mediated nitrogen reduction.

[This corrects the article DOI: 10.1039/D2TA07686A.].

The role of ion solvation in lithium mediated nitrogen reduction.

Since its verification in 2019, there have been numerous high-profile papers reporting improved efficiency of lithium-mediated electrochemical nitrogen reduction to make ammonia. However, the literature lacks any coherent investigation systematically linking bulk electrolyte properties to electrochemical performance and Solid Electrolyte Interphase (SEI) properties. In this study, we discover that the salt concentration has a remarkable effect on electrolyte stability: at concentrations of 0.6 M LiClO4 and above the electrode potential is stable for at least 12 hours at an applied current density of -2 mA cm-2 at ambient temperature and pressure. Conversely, at the lower concentrations explored in prior studies, the potential required to maintain a given N2 reduction current increased by 8 V within a period of 1 hour under the same conditions. The behaviour is linked more coordination of the salt anion and cation with increasing salt concentration in the electrolyte observed via Raman spectroscopy. Time of flight secondary ion mass spectrometry and X-ray photoelectron spectroscopy reveal a more inorganic, and therefore more stable, SEI layer is formed with increasing salt concentration. A drop in faradaic efficiency for nitrogen reduction is seen at concentrations higher than 0.6 M LiClO4, which is attributed to a combination of a decrease in nitrogen solubility and diffusivity as well as increased SEI conductivity as measured by electrochemical impedance spectroscopy.

The origin of overpotential in lithium-mediated nitrogen reduction.

The verification of the lithium-mediated nitrogen reduction system in 2019 has led to an explosion in the literature focussing on improving the metrics of faradaic efficiency, stability, and activity. However, while the literature acknowledges the vast intrinsic overpotential for nitrogen reduction due to the reliance on in situ lithium plating, it has thus far been difficult to accurately quantify this overpotential and effectively analyse further voltage losses. In this work, we present a simple method for determining the Reversible Hydrogen Electrode (RHE) potential in the lithium-mediated nitrogen reduction system. This method allows for an investigation of the Nernst equation and reveals sources of potential losses. These are namely the solvation of the lithium ion in the electrolyte and resistive losses due to the formation of the solid electrolyte interphase. The minimum observed overpotential was achieved in a 0.6 M LiClO4, 0.5 vol% ethanol in tetrahydrofuran electrolyte. This was -3.59 ± 0.07 V vs. RHE, with a measured faradaic efficiency of 6.5 ± 0.2%. Our method allows for easy comparison between the lithium-mediated system and other nitrogen reduction paradigms, including biological and homogeneous mechanisms.

Towards the elucidation of the high oxygen electroreduction activity of PtxY: surface science and electrochemical studies of Y/Pt(111).

We have prepared an yttrium modified Pt(111) single crystal under ultra-high vacuum conditions, simulating a bulk alloy. A Pt overlayer is formed upon annealing the crystal above 800 K. The annealed structure binds CO weaker than Pt(111), with a pronounced peak at 295 K in the temperature programmed desorption of CO. When depositing a large amount of yttrium at 1173 K, a (1.88 × 1.88)R30° structure relative to Pt(111) was observed by low energy electron diffraction. Such an electron diffraction pattern could correspond to a (2 × 2)R30° structure under 6% compressive strain. This structure is in agreement with the structure of the vacancies in a Pt Kagomé layer in Pt5Y rotated 30° with respect to the bulk of the Pt(111). The Pt overlayer is relatively stable in air; however, after performing oxygen reduction activity measurements in an electrochemical cell, a thick Pt overlayer was measured by the angle resolved X-ray photoelectron spectroscopy depth profile. The activity of the annealed Y/Pt(111) for the oxygen reduction reaction was similar to that of polycrystalline Pt3Y.

Weekend hospitalization and additional risk of death: an analysis of inpatient data.

OBJECTIVE: To assess whether weekend admissions to hospital and/or already being an inpatient on weekend days were associated with any additional mortality risk. DESIGN: Retrospective observational survivorship study. We analysed all admissions to the English National Health Service (NHS) during the financial year 2009/10, following up all patients for 30 days after admission and accounting for risk of death associated with diagnosis, co-morbidities, admission history, age, sex, ethnicity, deprivation, seasonality, day of admission and hospital trust, including day of death as a time dependent covariate. The principal analysis was based on time to in-hospital death. PARTICIPANTS: National Health Service Hospitals in England. MAIN OUTCOME MEASURES: 30 day mortality (in or out of hospital). RESULTS: There were 14,217,640 admissions included in the principal analysis, with 187,337 in-hospital deaths reported within 30 days of admission. Admission on weekend days was associated with a considerable increase in risk of subsequent death compared with admission on weekdays, hazard ratio for Sunday versus Wednesday 1.16 (95% CI 1.14 to 1.18; P < .0001), and for Saturday versus Wednesday 1.11 (95% CI 1.09 to 1.13; P < .0001). Hospital stays on weekend days were associated with a lower risk of death than midweek days, hazard ratio for being in hospital on Sunday versus Wednesday 0.92 (95% CI 0.91 to 0.94; P < .0001), and for Saturday versus Wednesday 0.95 (95% CI 0.93 to 0.96; P < .0001). Similar findings were observed on a smaller US data set. CONCLUSIONS: Admission at the weekend is associated with increased risk of subsequent death within 30 days of admission. The likelihood of death actually occurring is less on a weekend day than on a mid-week day.

Survivorship of the bio-action metatarsophalangeal joint arthroplasty for hallux rigidus: 5-year follow-up.

BACKGROUND: Metatarsophalangeal joint arthroplasty is an accepted treatment for hallux rigidus. There are few reports of the long-term results of this procedure. METHODS: A series of 15 consecutive bio-action first metatarsophalangeal total joint replacements were retrospectively reviewed after a minimum follow-up of 5 years. The patients were assessed using the American Orthopaedic Foot and Ankle Society Score. Patient satisfaction and standard radiographs were also examined. RESULTS: Subjectively, just over half the patients were satisfied with the results of the surgery. Objectively, however mechanical failure of the implant was universal, as determined radiographically. DISCUSSION: Despite some success in relieving symptoms in patients, we have abandoned this procedure because of the high and increasing rate of failure, as demonstrated both clinically and radiologically.

Alloys of platinum and early transition metals as oxygen reduction electrocatalysts.

The widespread use of low-temperature polymer electrolyte membrane fuel cells for mobile applications will require significant reductions in the amount of expensive Pt contained within their cathodes, which drive the oxygen reduction reaction (ORR). Although progress has been made in this respect, further reductions through the development of more active and stable electrocatalysts are still necessary. Here we describe a new set of ORR electrocatalysts consisting of Pd or Pt alloyed with early transition metals such as Sc or Y. They were identified using density functional theory calculations as being the most stable Pt- and Pd-based binary alloys with ORR activity likely to be better than Pt. Electrochemical measurements show that the activity of polycrystalline Pt(3)Sc and Pt(3)Y electrodes is enhanced relative to pure Pt by a factor of 1.5-1.8 and 6-10, respectively, in the range 0.9-0.87 V.

Safety and immunogenicity of live attenuated quadrivalent human-bovine (UK) reassortant rotavirus vaccine administered with childhood vaccines to infants.

The safety and immunogenicity of an orally administered, live rotavirus vaccine comprised of four strains, each with a titer of 10(5.3) or 10(5.8) pfu, and each having 10 genes from the UK bovine strain and the VP7 gene from human rotavirus serotype 1, 2, 3, or 4, were evaluated in adults, young children and infants in randomized, double-blind phase 1 trials. Three doses of rotavirus vaccine or placebo given with childhood immunizations to infants at 2, 4, and 6 months of age were well tolerated and did not inhibit antibody responses to childhood vaccines which included DTP, Hib, hepatitis B and OPV. Serum rotavirus antibody responses were detected in 12 of 20 infants after 1 dose, and in 19/19 of the vaccinees after three doses. Neutralizing antibody responses were detected more often against the bovine rotavirus UK strain (95%) than to human rotavirus VP7 serotypes 1 (37%), 2 (32%), 3 (32%) or 4 (32%). The efficacy of this quadrivalent rotavirus vaccine needs to be evaluated further.

Erythrocyte Fy antigen phenotyping helps differentiate so-called benign tertian malarias.

Isolated cases of malaria are increasing in frequency in nonendemic countries. Blood film examination remains a mainstay of diagnosis of these sporadic cases because immunologic and molecular methods are unavailable, expensive, and problematic. Two tertian malarial species, Plasmodium vivax and Plasmodium ovale, may appear to be similar morphologically. Plasmodium ovale infection is infrequent, and misdiagnosis of this species is common. Plasmodium vivax infection can be ruled out, however, if a patient's erythrocytes phenotype as Fy(a-b-), because these cells completely resist entry by the latter species.

Community case management for mental illness.

These case vignettes clearly illustrate the complexity which is modern psychiatric case management. In the case of Mr D, one of the salient facets of case management was medication monitoring in the context of the introduction of a new depot injection. This was a function in which nursing knowledge of medications and their side effects was undoubtedly advantageous. Any adverse experience with medication is likely to have negative ramifications regarding future compliance. Therefore, a nurse case manager is ideally suited to provide the appropriate information on psychotropic medications and to confidently answer most questions about these medications, and promptly identify any possible emerging side effects. In the case of Mr X, the management began with a practical and crisis focus involving suicide prevention. This developed into supportive psychotherapy, which required sensitive but proactive intervention and, ultimately, significant counselling skills. Mr L's case management had a different focus again, characterised by the development of a new and comprehensive case formulation and a creative nurturing of an individual's identified strength in music. The vignettes not only serve to highlight the well-established heterogeneity of mental illness, but they also importantly illuminate the heterogeneity of case management, a reality obscured in the descriptions of case management models which perhaps misleadingly have given the impression of the process as being merely a number of clearly defined tasks or functions. In actual fact, though the coordination of care appears to represent a common feature, the case management relationship remains an ever changing one, with adaptability, refined clinical skills and practical problem solving skills being the essential requisites of an effective case manager. Therefore, attempts to present this important activity in terms of any one model seem to miss the point. For the consumers of psychiatric services, the experience of case management is unique, and for case managers too the experience with each 'case managed' individual is unique. This uniqueness, together with the diverse skills involved in case management needs to be acknowledged. One way of acknowledging this is, as demonstrated, in the presentation of case vignettes and comprehensive case studies. As psychiatric nursing moves toward the new millennium, case management offers psychiatric nurses (as the clinician most often cast in the role of case manager), the exciting opportunity to extend their role and responsibilities. More importantly, it offers mental health care workers the opportunity to be more actively involved in the liberation of psychiatric patients from a situation of custodial care to a new life in the community.

Hepatitis B vaccination of premature infants: a reassessment of current recommendations for delayed immunization.

OBJECTIVE: Current American Academy of Pediatrics and United States Public Health Service Immunization Practices Advisory Committee recommendations for hepatitis B immunization in premature infants weighing <2 kg at birth born to hepatitis B surface antigen (HBSAg)-negative mothers are to delay the initiation of vaccination until such infants reach 2 kg or until 2 months of age. This proposal to delay vaccination at birth in these low-risk infants was based on limited studies not conducted in the United States. We sought to reassess current recommendations to delay administration of hepatitis B vaccine in low-risk premature infants by determining the immunogenicity of early hepatitis B vaccination in a US population and identifying variables associated with poor immunogenicity. METHODS: A total of 148 infants <37 weeks' gestation born to mothers negative for HBSAg were recruited at birth and stratified to three birth weight groups: <1000 g, 1000 to 1500 g, and >1500 g. Recombinant hepatitis B vaccine was administered within the first week of life, at 1 to 2 months of age, and at 6 to 7 months of age. Serum obtained at birth and after the second and third doses of vaccine was tested for antibody to HBSAg. Variables associated with poor response were sought prospectively by collecting demographic and clinical data. RESULTS: A total of 118 subjects (83%) completed the study. Postsecond dose sera were available for 117 infants and postthird dose sera were available for 112 infants. The seroprotection rate (attaining >/=10 mIU/mL HBS antibody) after two doses was low (25%) regardless of birth weight; infants weighing <1000 g at birth had the poorest response (11%). The seroprotection response rate after three doses of vaccine increased with birth weight; infants weighing 1500 g at birth (group 3; 84% response rate). The seroprotection response rate of group 3 infants after three doses of vaccine, although low, could not be differentiated from the response rates reported for full-term infants using 95% confidence intervals. Of all infants who did not achieve protective levels of antibody after three doses of vaccine, 96% (26/27) weighed <1700 g at birth. The geometric mean HBS antibody levels in responders were 88 and 386 mIU/mL after two and three doses, respectively. Of 36 children with a birth weight >1500 g, 33 (91%) achieved levels of HBS antibody >100 mIU/mL after three doses of vaccine, compared with 25/35 (71%) of infants with birth weight <1500 g. Using logistic regression analysis, nonresponders were more likely than were responders to have been treated with steroids (26% vs 9%) and to have had a low birth weight (1037 g vs 1455 g). In addition, the seroresponse rate of black infants was more likely than that of white infants to be associated with poor weight gain (falling off 2 percentile ranks in weight) in the first 6 months of life: 22% of black and 60% of white children who failed to gain weight adequately responded to vaccination, compared with 92% of black and 70% of white children who were growing adequately. Of interest, the only infant with a birth weight of >1700 g who did not make protective levels of specific antibody after three doses of vaccine was 2300 g at birth, but had inadequate weight gain in the first 6 months of life. CONCLUSIONS: This study supports current recommendations of the American Academy of Pediatrics and the Centers for Disease Control and Prevention for delaying the initiation of hepatitis B immunization beyond the first week of life for premature infants at low risk for hepatitis B infection, particularly in newborns weighing <1700 g at birth. In addition, we have identified variables other than birth weight that were associated with an inadequate immune response to early hepatitis B vaccination in premature infants, such as poor weight gain in the first 6 months of life

Dentists, pills and pregnancies.

Unplanned pregnancies may occur if antibiotics are prescribed to women using the combined oral contraceptive pill. To investigate awareness of the potential for this interaction among general dental practitioners, the authors designed a cross-sectional questionnaire based study and sent it out to a random sample of GDPs in Scotland.

Food safety and residues in Australian agricultural produce.

A brief history of food safety in Australia in the context of the development of scientific knowledge is presented. Australia's food and food commodity residue and contamination surveillance and monitoring programs are outlined. Although chemical residues are perceived as a major health risk by the general community, the risk of food causing illness or death because of chemical residues is low. The major threat to human health from food is microbiological contamination, in terms of deaths, sickness and economic loss. The emerging influences in food safety are scientific and technical developments, deregulation, social and demographic factors, and the media. The risk of disruption of domestic and export markets by food safety issues is considerable. The emergence of international standards for food production and processing will enable commercial contractual arrangements to minimise the frequency of disruptive food safety incidents.

Programs for surveillance and monitoring of antibacterial residues in Australia, 1989 to 1993.

The development of a State-based confirmatory testing capability for antibiotic residues in meat in Australia has allowed the rapid feedback to producers failing to comply with antibiotic maximum residue limits. The identification of problem areas in various categories of livestock, and subsequent focused surveillance programs, has reduced the prevalence of antibacterial residues in both domestic and export meat products. Failure to observe withholding periods of antibacterial drugs after treatment is the most significant cause of non-compliance. In the period July 1991 to June 1993 the compliance rate for antibacterial residues for all species was 99.9%.

Monitoring and surveillance in abattoirs of residues of antibacterial substances--a description of programs in Australia and the USA.

Australia and the USA are major international meat exporting countries. Both countries conduct programs to monitor and survey for antibacterial residues. Australian programs use a urine screening test, whereas the US programs use tissue fluids as the test medium. The development of surveillance programs to provide rapid feedback to producers is a feature of the Australian programs. The programs in each country compare favourably with regard to numbers of animals tested, results and action taken to prevent residues. The results of the Australian programs justify the promotion of a 'clean food' image for Australian meat products with respect to antibacterial drugs.

The isolation and identification of cis-diamminedichloroplatinum (ii)-DNA adducts by anion-exchange HPLC and inductively coupled plasma mass-spectrometry.

The adducts produced by the reaction of cis-diamminedichloroplatinum(II) with DNA have previously been isolated and characterised. These adducts may be measured at the cellular level by immunochemical detection but the accuracy of this assay is dependent on the number of adducts per nucleotide. We have developed a novel assay for cisplatin-DNA adducts, utilising an established method in which platinated DNA is digested to form a mixture of nucleotides and adducts; these are then separated by anion exchange HPLC. The number of cisplatin-DNA adducts is determined by measurement of the platinum content of the HPLC fractions by inductively coupled plasma mass spectrometry. The assay has been validated by cochromatography of purified drug-DNA adducts whose identity has been confirmed by NMR. We describe an application of the assay, namely the measurement of in vitro removal of cisplatin-DNA adducts from calf thymus DNA by cell free extracts derived from tumour cell lines. Adduct removal is dependent on both the amount of extract protein and the duration of the reaction. Almost 70% of adducts are removed from 5mug of DNA (drug:nucleotide ratio 0.08) by 80mug of extract. Other potential applications of the assay are discussed.

ICU admissions from an obstetrical hospital.

To ascertain the anaesthetic complications requiring post-anaesthetic respiratory support in a large obstetrical hospital, the hospital records of obstetrical patients admitted to an adjacent general intensive care unit (ICU) were studied. Obstetrical patients who required mechanical ventilation following anaesthetic complications were identified and their hospital records reviewed. In a ten-year period there were 61,435 women delivered at the Mater Mothers Hospital (MMH) in Brisbane, Queensland, Australia. Of these 24,161 had an anaesthetic associated with delivery including 7,452 general anaesthetics (GAs) and 16,709 regional anaesthetics (RAs). There were also 3,708 GAs and 17 RAs for procedures other than delivery. During this period there were 126 obstetrical admissions to the ICU. Sixteen were due to anaesthetic complications, twelve followed GA and four followed RA. Complications included anaphylaxis, high block and failure of tracheal intubation. The incidence of a major complication of a GA causing admission to the ICU was 1 in 932 and for RA was 1 in 4177 when these were given for delivery (P less than 0.01). If a complication requiring ICU admission and mechanical ventilation is used as the criterion of safety it appears that RA is safer than a GA for delivery.