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The uranyl complexes UO2(OAc)(L) and UO2Cl(L) of the redox-active, acyclic diamido–dipyrrin anion L– are reported and their redox properties explored. Because of the inert nature of the complexes toward hydrolysis and oxidation, synthesis of both the ligands and complexes was conducted under ambient conditions. Voltammetric, electron paramagnetic resonance spectroscopy, and density functional theory studies show that one-electron chemical reduction by the reagent CoCp2 leads to the formation of a dipyrrin radical for both complexes [Cp2Co][UO2(OAc)(L•)] and [Cp2Co][UO2Cl(L•)].

Background Antimicrobial use in Irish older persons residential care facilities (OP RCFs) is higher than in other European countries. In 2020/21, for the first time, an antimicrobial pharmacist (AMP) was appointed to each community healthcare organization (CHO) to monitor, develop and promote antimicrobial stewardship in community settings. Objectives To establish baseline antibiotic use, develop antimicrobial stewardship tools for OP RCFs, promote best practice in relation to antimicrobial stewardship (AMS) and monitor trends in antimicrobial use in HSE (state-run) OP RCFs. Methods A baseline point prevalence survey (PPS) of antimicrobial use was conducted across all HSE OP RCFs between October 2020 and August 2021. Following the survey, key national recommendations and AMS resources were developed in collaboration with the national Antimicrobial Resistance and Infection Control Programme. Feedback was provided to participating facilities by CHO AMPs with antimicrobial stewardship support and education for nursing and medical staff. In September 2021, monthly monitoring of antibiotic use was established in HSE OP RCFs in collaboration with local managers, to capture the proportion of antibiotics used for prophylaxis or treatment each month. Results A baseline PPS of antimicrobial use in 2020/21 showed that 11.9% (528/4446) of residents were on a systemic antibiotic, with 6.3% on antibiotic prophylaxis. Urinary tract infection accounted for 51% of antibiotic prescriptions. Following the baseline PPS, CHO AMPs developed an AMS toolkit for OP RCFs, engaged with nursing and medical staff to communicate PPS results, AMS resources and support implementation of AMS recommendations. Subsequently, monthly self-reporting of antimicrobial use in HSE OP RCFs was commenced in September 2021 and showed a sustained decrease in antimicrobial use with 7.9% residents on an antibiotic in Quarter 2 2022, with 2.7% on antibiotic prophylaxis. Conclusions Newly appointed CHO AMPs have successfully promoted AMS across HSE OP RCFs. Following audit, feedback, education, development and promotion of antimicrobial stewardship resources, there was a sustained decrease in the proportion of residents on antibiotics used for treatment and prophylaxis of infection.

Background Antimicrobial use in mental health inpatient settings has not been extensively examined in Ireland. The Healthcare-Associated Infection and Antimicrobial Use in Long-Term Care Facilities (HALT) study 2016 found that Irish long-term care facilities caring for residents with psychiatric conditions had an antimicrobial prevalence rate of 7.7%, higher than the European average of 4.9%. National community antimicrobial prescribing guidelines are available at www.antibioticprescribing.ie. In addition, a preferred antibiotic initiative for community settings advocates prescribers to choose ‘Green’ (preferred) antibiotics over ‘Red’ (reserved) agents. Reserved agents are considered to have more adverse effects, drug interactions and potential for development of antimicrobial resistance. The patient safety implications of antimicrobial stewardship along with an ageing population, and potential drug–drug interactions between many antimicrobials and psychotropic medications prompted a review of antimicrobial use practices in mental health services. Methods A sample of adult inpatient mental health facilities (MHF) operated by the state's Health Service Executive (HSE) were surveyed by community antimicrobial pharmacists (AMPs) between November 2021 and January 2022. AMPs reviewed patients’ medication charts for systemic antimicrobial prescriptions in the previous 30 days in addition to medical notes and laboratory results (where available). Adherence to HSE National community antimicrobial guidelines and the systems and structures in place to support antimicrobial stewardship were assessed. Results In total, 1003 patients in 51 MHFs were surveyed. At the time of survey, 6.3% (n=66) patients were on a systemic antimicrobial and 15% (n=153) had received a systemic antimicrobial within the previous 30 days. Prophylaxis accounted for 50% of antibiotic use (3.3% of all patients), with the most common indication being the prevention of urinary tract infection (UTI) (58%). Prophylaxis duration exceeded six months in 61% of prescriptions. The median duration of treatment courses was seven days. The proportion of ‘Green’ (preferred) antimicrobials versus ‘Red’ (reserved) antimicrobials was 58% versus 38%. Co-amoxiclav, a ‘Red’ agent was the most commonly prescribed antibiotic for treatment of infection (31%). Adherence with choice of antimicrobial agent as per national antimicrobial guidelines was 76%; adherence of dosing regimen was 75% and adherence with recommended duration was 46%. The main themes for non-adherence with choice of agent were use of unnecessarily broad spectrum agents, nitrofurantoin prescribed in renal impairment and inappropriate formulation of nitrofurantoin chosen. Dipstick urinalysis was performed routinely (on admission and/or at designated intervals) for persons asymptomatic of UTI in 53% (n=27) of MHFs. Conclusions This PPS established antimicrobial use practices in HSE MHFs and identified opportunities for improvement relating to the safe and optimal use of antimicrobials. Key national recommendations from this survey were

Transplantation of any organ into a recipient requires a donor. Lung transplant has a long history of an inadequate number of suitable donors to meet demand, leading to deaths on the waiting list annually since national data was collected, and strict listing criteria. Before the Uniform Determination of Death Act (UDDA), passed in 1980, legally defined brain death in the U.S., all donors for lung transplant came from sudden death victims [uncontrolled Donation after Circulatory Death donors (uDCDs)] in the recipient's hospital emergency department. After passage of the UDDA, uDCDs were abandoned to Donation after Brain Death donors (DBDs)-perhaps prematurely. Compared to livers and kidneys, many DBDs have lungs that are unsuitable for transplant, due to aspiration pneumonia, neurogenic pulmonary edema, trauma, and the effects of brain death on lung function. Another group of donors has become available-patients with a devastating irrecoverable brain injury that do not meet criteria for brain death. If a decision is made by next-of-kin (NOK) to withdraw life support and allow death to occur by asphyxiation, with NOK consent, these individuals can have organs recovered if death occurs relatively quickly after cessation of mechanical ventilation and maintenance of their airway. These are known as controlled Donation after Circulatory Death donors (cDCDs). For a variety of reasons, in the U.S., lungs are recovered from cDCDs at a much lower rate than kidneys and livers. Ex-vivo lung perfusion (EVLP) in the last decade has had a modest impact on increasing the number of lungs for transplant from DBDs, but may have had a larger impact on lungs from cDCDs, and may be indispensable for safe transplantation of lungs from uDCDs. In the next decade, DCDs may have a substantial impact on the number of lung transplants performed in the U.S. and around the world.

Background The HALT study in 2016 found that residents in Irish OPS RCFs were twice as likely to be on systemic antimicrobial compared with European average (10% v 5%). National antibiotic prescribing guidelines are available at www.antibioticprescribing.ie and prescribers are encouraged to choose ‘green’ (preferred) over ‘red’ (reserved) agents. HSE Community Antimicrobial Pharmacists (AMPs) have been employed since 2020. We aimed to establish the quality and quantity of antimicrobial prescribing in OPS-RCFs to inform antimicrobial stewardship activities. Methods All residents in HSE OPS-RCFs were surveyed between October 2020 and August 2021. AMPs reviewed all medication charts for systemic antimicrobials prescribed within previous 30 days. Medical notes +/- laboratory results were reviewed for persons on antimicrobials. Adherence to guidelines was assessed and information obtained on practices related to antimicrobial use. Results The survey included 4,448 individuals in 121 OPS RCFs. 12% were on systemic antimicrobial at time of survey. 27% received an antimicrobial in the previous 30 days. 50% of antibiotic use on survey day was for prophylaxis (6.3% of all residents). Prophylaxis exceeded 6 months in 66% persons, and 12 months in 57%. There was high usage of green versus red agents (65% vs 30%). Co-amoxiclav (red) was most commonly prescribed antimicrobial to treat infection (19%). 42% of sites reported routine use of dipstick urinalysis to support diagnosis of UTI in asymptomatic residents. 36% of sites did not have onsite electronic laboratory access. 61% of facilities did not record residents’ pneumococcal vaccination status. Conclusion Key national recommendations: Review all UTI prophylaxis within 6 months of initiation with view to de-prescribing.Cease routine use of dipstick urinalysis to support diagnosis of UTI for asymptomatic persons.Electronic access to laboratory results on-site required to support timely decision-making.All staff should be aware of the national antimicrobial guidelines.Pneumococcal vaccine status should be determined, and provided as necessary.

Multiple studies from the literature suggest that a high proportion of women on scientific teams contributes to successful team collaboration, but how the proportion of women impacts team success and why this is the case, is not well understood. One perspective suggests that having a high proportion of women matters because women tend to have greater social sensitivity and promote even turn-taking in meetings. Other studies have found women are more likely to collaborate and are more democratic. Both explanations suggest that women team members fundamentally change team functioning through the way they interact. Yet, most previous studies of gender on scientific teams have relied heavily on bibliometric data, which focuses on the prevalence of women team members rather than how they act and interact throughout the scientific process. In this study, we explore gender diversity in scientific teams using various types of relational data to investigate how women impact team interactions. This study focuses on 12 interdisciplinary university scientific teams that were part of an institutional team science program from 2015 to 2020 aimed at cultivating, integrating, and translating scientific expertise. The program included multiple forms of evaluation, including participant observation, focus groups, interviews, and surveys at multiple time points. Using social network analysis, this article tested five hypotheses about the role of women on university-based scientific teams. The hypotheses were based on three premises previously established in the literature. Our analyses revealed that only one of the five hypotheses regarding gender roles on teams was supported by our data. These findings suggest that scientific teams may create ingroups, when an underrepresented identity is included instead of excluded in the outgroup, for women in academia. This finding does not align with the current paradigm and the research on the impact of gender diversity on teams. Future research to determine if high-functioning scientific teams disrupt rather than reproduce existing hierarchies and gendered patterns of interactions could create an opportunity to accelerate the advancement of knowledge while promoting a just and equitable culture and profession.

The dissolution of elemental noble metals (NMs) such as gold, platinum, palladium, and copper in organic solutions is necessary for their recycling but carries a high environmental burden due to the use of strong acids and toxic reagents. Herein, a new approach is presented for the rapid dissolution of elemental NMs in organic solvents using mixtures of triphenylphosphine dichloride or oxalyl chloride and hydrogen peroxide, forming metal chloride salts directly. Almost quantitative dissolution of metallic Au, Pd, and Cu was observed within minutes at room temperature. For Pt, dissolution by hydrogen peroxide was inhibited but achieved, albeit more slowly, using the chlorinating oxidant alone. After leaching, transfer of Pt(IV) and Pd(II) chloride salts from the organic phase into a 6 M HCl aqueous phase facilitated the separation of Pt(IV) by precipitation using a simple diamide ligand. In contrast, the retention of Au(III) chloridometalate in the organic phase allowed its selective separation from Ni and Cu from a leachate solution obtained from electronic CPUs. This new approach has potential application in the hydrometallurgical leaching and purification of NMs from ores, spent catalysts, and electronic- and nano-wastes.

Undergraduate capstone courses in sociology are designed to integrate students’ knowledge in the discipline and to culminate the classroom experience with field application. Are capstones achieving these goals in a durable way? Although the short-term outcomes of capstone courses have been researched, fewer studies have documented the long-term outcomes of capstone courses. We conducted a survey of sociology capstone alumni to understand the long-term outcomes of the sociology capstone by asking sociology alumni about their capstone experience. Our research revealed that all capstones produced long-term outcomes as measured in the alumni survey. Second, alumni of the community-based research capstone experienced a more profound and longer reaching effect than those who participated in the internship or traditional capstone seminar format. Alumni reported the development of professional skills, application of sociological concepts and research skills, and a sense of being part of a community.

Transition metal complexes bearing metal–boron bonds are of particular relevance to catalytic C–H borylation reactions, with iridium polyboryl and polyhydrido-boryl complexes the current benchmark catalysts for these transformations. Herein, we demonstrate that polyhydride boryl phosphine rhenium complexes are accessible and catalyze the C–H borylation of heteroaromatic substrates. Reaction of [K(DME)(18-c-6)][ReH4(Bpin)(η2-HBpin)(κ2-H2Bpin)] 1 with 1,3-bis(diphenylphosphino)propane (dppp) produced [K(18-c-6)][ReH4(η2-HBpin)(dppp)] 2 through substitution of two equivalents of HBpin, and protonation of 2 formed the neutral complex [ReH6(Bpin)(dppp)] 3. Combined X-ray crystallographic and DFT studies show that 2 is best described as a σ-borane complex, whereas 3 is a boryl complex. Significantly, the boryl complex 3 acted as a catalyst for the C(sp2)–H borylation of a variety of heteroarenes (14 examples including furan, thiophene, pyrrole and indole derivatives) and displayed similar reactivity to the iridium analogues.

Today’s societal challenges, such as climate change and global pandemics, are increasingly complex and require collaboration across scientific disciplines to address. Scientific teams bring together individuals of varying backgrounds and expertise to work collaboratively on creating new knowledge to address these challenges. Within a scientific team, there is inherent diversity in disciplinary cultures and preferences for interpersonal collaboration. Such diversity contributes to the potential strength of the created knowledge but can also impede progress when teams struggle to collaborate productively. Facilitation is a professional practice-based form of interpersonal expertise that supports group members to do their best thinking. Although facilitation has been demonstrated to support group functioning in a wide range of contexts, its role in supporting scientific teams has been largely overlooked. This essay defines scientific facilitation as a form of interactional expertise and explains how facilitating scientific teams requires skills in managing interpersonal interactions as well as understanding how different types of disciplinary knowledge integrate in the creation of new knowledge. Next, it explains how this science facilitation expertise may be developed through metacognition. Finally, it provides examples of how scientific facilitation could be more widely incorporated into research by describing three pathways to expand the use of facilitation theory and techniques in collaborative scientific research: developing facilitation skills among scientists leading teams, using broadly trained facilitators, and using specialised science facilitators. The strengths and risks of each path are discussed, and criteria are suggested for selecting the right approach for a given team science project.

Supramolecular chemical strategies for Rare Earth (RE) element separations are emerging which amplify the small changes in properties across the series to bias selectivity in extraction or precipitation. These advances are important as the REs are crucial to modern technologies yet their extraction, separation, and recycling using conventional techniques remain challenging. We report here a pre-organised triamidoarene platform which, under acidic, biphasic conditions, uniquely and selectively precipitates light RE nitratometalates as supramolecular capsules. The capsules exhibit both intra- and intermolecular hydrogen bonds that dictate selectivity, promote precipitation, and facilitate the straightforward release of the RE and recycling of the receptor. This work provides a self-assembly route to metal separations that exploits size and shape complementarity and has the potential to integrate into conventional processes due to its compatibility with acidic metal feed streams.

While pure chemistry aims to enhance knowledge within the chemical sciences, applied chemistry exploits the principles and theories of chemistry to answer specific questions or solve real-world challenges [...]

The oxo- and catecholate-bridged UIV/UIV Pacman complex [{(py)UIVOUIV(μ-O2C6H4)(py)}(LA)] A (LA = a macrocyclic "Pacman" ligand; anthracenylene hinge between N4-donor pockets, ethyl substituents on meso-carbon atom of each N4-donor pocket) featuring a bent UIV-O-UIV oxo bridge readily reacts with small molecule substrates to undergo either oxo-atom functionalisation or substitution. Complex A reacts with H2O or MeOH to afford [{(py)UIV(μ-OH)2UIV(μ-O2C6H4)(py)}(LA)] (1) and [{(py)UIV(μ-OH)(μ-OMe)UIV(μ-O2C6H4)(py)}(LA)] (2), respectively, in which the bridging oxo ligand in A is substituted for two bridging hydroxo ligands or one bridging hydroxo and one bridging methoxy ligand, respectively. Alternatively, A reacts with either 0.5 equiv. of S8 or 4 equiv. of Se to provide [{(py)UIV(μ-η2:η2-E2)UIV(μ-O2C6H4)(py)}(LA)] (E = S (3), Se (4)) respectively, in which the [E2]2- ion bridges the two UIV centres. To the best of our knowledge, complex A is the first example of either a d- or f-block bimetallic μ-oxo complex that activates elemental chalcogens. Complex A also reacts with XeF2 or 2 equiv. of Me3SiCl to provide [{(py)UIV(μ-X)2UIV(μ-O2C6H4)(py)}(LA)] (X = F (5), Cl (6)), in which the oxo ligand has been substituted for two bridging halido ligands. Reacting A with either XeF2 or Me3SiCl in the presence of O(Bcat)2 at room temperature forms [{(py)UIV(μ-X)(μ-OBcat)UIV(μ-O2C6H4)(py)}(LA)] (X = F (5A), Cl (6A)), which upon heating to 80 °C is converted to 5 and 6, respectively. In order to probe the importance of the bent UIV-O-UIV motif in A on the observed reactivity, the bis(boroxido)-UIV/UIV complex, [{(py)(pinBO)UIVOUIV(OBpin)(py)}(LA)] (B), featuring a linear UIV-O-UIV bond angle was treated with H2O and Me3SiCl. Complex B reacts with two equiv. of either H2O or Me3SiCl to provide [{(py)HOUIVOUIVOH(py)}(LA)] (7) and [{(py)ClUIVOUIVCl(py)}(LA)] (8), respectively, in which reactions occur preferentially at the boroxido ligands, with the μ-oxo ligand unchanged. The formal UIV oxidation state is retained in all of the products 1-8, and selective reactions at the bridging oxo ligand in A is facilitated by: (1) its highly nucleophilic character which is a result of a non-linear UIV-O-UIV bond angle causing an increase in U-O bond covalency and localisation of the lone pairs of electrons on the μ-oxo group, and (2) the presence of the bridging catecholate ligand, which destabilises a linear oxo-bridging geometry and stabilises the resulting products.

BACKGROUND: Trial monitoring is an important component of good clinical practice to ensure the safety and rights of study participants, confidentiality of personal information, and quality of data. However, the effectiveness of various existing monitoring approaches is unclear. Information to guide the choice of monitoring methods in clinical intervention studies may help trialists, support units, and monitors to effectively adjust their approaches to current knowledge and evidence. OBJECTIVES: To evaluate the advantages and disadvantages of different monitoring strategies (including risk‐based strategies and others) for clinical intervention studies examined in prospective comparative studies of monitoring interventions. SEARCH METHODS: We systematically searched CENTRAL, PubMed, and Embase via Elsevier for relevant published literature up to March 2021. We searched the online 'Studies within A Trial' (SWAT) repository, grey literature, and trial registries for ongoing or unpublished studies. SELECTION CRITERIA: We included randomized or non‐randomized prospective, empirical evaluation studies of different monitoring strategies in one or more clinical intervention studies. We applied no restrictions for language or date of publication. DATA COLLECTION AND ANALYSIS: We extracted data on the evaluated monitoring methods, countries involved, study population, study setting, randomization method, and numbers and proportions in each intervention group. Our primary outcome was critical and major monitoring findings in prospective intervention studies. Monitoring findings were classified according to different error domains (e.g. major eligibility violations) and the primary outcome measure was a composite of these domains. Secondary outcomes were individual error domains, participant recruitment and follow‐up, and resource use. If we identified more than one study for a comparison and outcome definitions were similar across identified studies, we quantitatively summarized effects in a meta‐analysis using a random‐effects model. Otherwise, we qualitatively summarized the results of eligible studies stratified by different comparisons of monitoring strategies. We used the GRADE approach to assess the certainty of the evidence for different groups of comparisons. MAIN RESULTS: We identified eight eligible studies, which we grouped into five comparisons. 1. Risk‐based versus extensive on‐site monitoring: based on two large studies, we found moderate certainty of evidence for the combined primary outcome of major or critical findings that risk‐based monitoring is not inferior to extensive on‐site monitoring. Although the risk ratio was close to 'no difference' (1.03 with a 95% confidence interval [CI] of 0.81 to 1.33, below 1.0 in favor of the risk‐based strategy), the high imprecision in one study and the small number of eligible studies resulted in a wide CI of the summary estimate. Low certainty of evidence suggested that monitoring strategies with extensive on‐site monitoring were associated with considerably higher resource use and costs (up to a factor of 3.4). Data on recruitment or retention of trial participants were not available. 2. Central monitoring with triggered on‐site visits versus regular on‐site visits: combining the results of two eligible studies yielded low certainty of evidence with a risk ratio of 1.83 (95% CI 0.51 to 6.55) in favor of triggered monitoring intervention. Data on recruitment, retention, and resource use were not available. 3. Central statistical monitoring and local monitoring performed by site staff with annual on‐site visits versus central statistical monitoring and local monitoring only: based on one study, there was moderate certainty of evidence that a small number of major and critical findings were missed with the central monitoring approach without on‐site visits: 3.8% of participants in the group without on‐site visits and 6.4% in the group with on‐site visits had a major or critical monitoring finding (odds ratio 1.7, 95% CI 1.1 to 2.7; P = 0.03). The absolute number of monitoring findings was very low, probably because defined major and critical findings were very study specific and central monitoring was present in both intervention groups. Very low certainty of evidence did not suggest a relevant effect on participant retention, and very low‐quality evidence indicated an extra cost for on‐site visits of USD 2,035,392. There were no data on recruitment. 4. Traditional 100% source data verification (SDV) versus targeted or remote SDV: the two studies assessing targeted and remote SDV reported findings only related to source documents. Compared to the final database obtained using the full SDV monitoring process, only a small proportion of remaining errors on overall data were identified using the targeted SDV process in the MONITORING study (absolute difference 1.47%, 95% CI 1.41% to 1.53%). Targeted SDV was effective in the verification of source documents but increased the workload on data management. The other included study was a pilot study which compared traditional on‐site SDV versus remote SDV and found little difference in monitoring findings and the ability to locate data values despite marked differences in remote access in two clinical trial networks. There were no data on recruitment or retention. 5. Systematic on‐site initiation visit versus on‐site initiation visit upon request: very low certainty of evidence suggested no difference in retention and recruitment between the two approaches. There were no data on critical and major findings or on resource use. AUTHORS' CONCLUSIONS: The evidence base is limited in terms of quantity and quality. Ideally, for each of the five identified comparisons, more prospective, comparative monitoring studies nested in clinical trials and measuring effects on all outcomes specified in this review are necessary to draw more reliable conclusions. However, the results suggesting risk‐based, targeted, and mainly central monitoring as an efficient strategy are promising. The development of reliable triggers for on‐site visits is ongoing; different triggers might be used in different settings. More evidence on risk indicators that identify sites with problems or the prognostic value of triggers is needed to further optimize central monitoring strategies. In particular, approaches with an initial assessment of trial‐specific risks that need to be closely monitored centrally during trial conduct with triggered on‐site visits should be evaluated in future research.

Preparing Construction Management (CM) students for their professional lives must include not only training on technical skills, but also a variety of personal interaction skills, from working with...

The recycling of metals from end-of-life secondary sources such as electronic waste remains a significant environmental and technological challenge currently detrimental to the development of circular economies. The complex nature of electronic waste, containing a myriad of different elemental metals, means that sophisticated yet simple separation methods need to be developed in order to recycle these valuable and often critical metal resources. In this work simple primary, secondary, and tertiary amides are appraised as reagents that selectively transport gold from aqueous to organic phases in a solvent extraction experiment. While the strength of extraction of gold from single metal solutions is ordered 3o>2o>1o, the 3o and 2o amides are ineffective at gold transport from mixed-metal solutions of concentrations representative of smartphones due to the formation of a third, dense phase. Increasing the polarity of the organic phase can negate third phase formation but at the expense of selectivity. The identities of the species that reside in the organic and third phases have been studied by a combination of slope analysis, mass spectrometry, NMR spectroscopy, and computational methods. These techniques show that protonation of the amide L occurs at the oxygen atom, resulting in the protonated dimer HL2+ which acts as a receptor for AuCl4− to form dynamic supramolecular aggregates in the organic phase. The characterization of a tin complex in the third phase by X-ray crystallography supports these conclusions and furthermore, suggests the preference for the chelation of the proton by two amide molecules instead of the transport of hydronium into the organic phase and its subsequent use as structural template.

Scientists are increasingly charged with solving complex societal, health, and environmental problems. These systemic problems require teams of expert scientists to tackle research questions through collaboration, coordination, creation of shared terminology, and complex social and intellectual processes. Despite the essential need for such interdisciplinary interactions, little research has examined the impact of scientific team support measures like training, facilitation, team building, and expertise. The literature is clear that solving complex problems requires more than contributory expertise, expertise required to contribute to a field or discipline. It also requires interactional expertise, socialised knowledge that includes socialisation into the practices of an expert group. These forms of expertise are often tacit and therefore difficult to access, and studies about how they are intertwined are nearly non-existent. Most of the published work in this area utilises archival data analysis, not individual team behaviour and assessment. This study addresses the call of numerous studies to use mixed-methods and social network analysis to investigate scientific team formation and success. This longitudinal case-based study evaluates the following question: How are scientific productivity, advice, and mentoring networks intertwined on a successful interdisciplinary scientific team? This study used applied social network surveys, participant observation, focus groups, interviews, and historical social network data to assess this specific team and assessed processes and practices to train new scientists over a 15-year period. Four major implications arose from our analysis: (1) interactional expertise and contributory expertise are intertwined in the process of scientific discovery; (2) team size and interdisciplinary knowledge effectively and efficiently train early career scientists; (3) integration of teaching/training, research/discovery, and extension/engagement enhances outcomes; and, (4) interdisciplinary scientific progress benefits significantly when interpersonal relationships among scientists from diverse disciplines are formed. This case-based study increases understanding of the development and processes of an exemplary team and provides valuable insights about interactions that enhance scientific expertise to train interdisciplinary scientists.

A new constrained-cavity [1 + 1] Schiff-base dipyrrin macrocycle comprising an N4donor-pocket has been synthesised by spontaneous oxidation andin situcrystallisation. Access to Fe(ii) and Zn(ii) complexes is achieved by salt elimination reactions of the lithium salt. All compounds have been characterised by NMR and UV-vis spectroscopy, X-ray crystallography, and DFT analysis.

Photocatalysis has proved its potential in cleaving the Cβ-O linkages between the natural aromatic units in lignin biomass and converting abundant lignin biomass to valuable aromatic monomer products. However, the slow reaction rate and low selectivity for aromatic monomers still hinder its future industrial implementation. To address these challenges in photocatalytic Cβ-O bond fragmentation, a Zn/S rich phase zinc indium sulfide photocatalyst was developed to promote hydrogenolysis of Cβ-O linkages in lignin. In this work, water is for the first time, used as the hydrogen donor and can significantly promote the photocatalytic process by eliminating the limitation of protons supply. The reaction selectivity for aromatic monomers increased by 170% and PP-ol conversion rate raised by 58% comparing to the reaction condition without water. Notably, complete conversion of lignin model compounds with an expectational improved reaction rate and over 90% selectivity for aromatic monomers have been achieved in this study. The isotopic labeling experiments and kinetic isotope effects (KIE) measurements also indicate that the dissociation of the O–H bond in water which provides protons to the Cβ-O bond hydrogenolysis process is a critical step to this reaction. Mechanistic studies reveal that the dehydrogenated radical intermediates are initially generated by the oxidation of photogenerated holes, and the protons generated from photocatalytic water splitting are superior in facilitating the subsequently hydrogenolysis process of Cβ-O bonds. This study provides a new and effective strategy to promote the cleavage of Cβ-O linkages and is helpful for the future development of photocatalytic lignin valorization.

BackgroundFor medical conditions with numerous interventions worthy of investigation, there are many advantages of a multi-arm multi-stage (MAMS) platform trial approach. However, there is currently limited knowledge on uptake of the MAMS design, especially in the late-phase setting. We sought to examine uptake and characteristics of late-phase MAMS platform trials, to enable better planning for teams considering future use of this approach.DesignWe examined uptake of registered, late-phase MAMS platforms in the EU clinical trials register, Australian New Zealand Clinical Trials Registry, International Standard Randomised Controlled Trial Number registry, Pan African Clinical Trials Registry, WHO International Clinical Trial Registry Platform and databases: PubMed, Medline, Cochrane Library, Global Health Library and EMBASE. Searching was performed and review data frozen on 1 April 2021. MAMS platforms were defined as requiring two or more comparison arms, with two or more trial stages, with an interim analysis allowing for stopping of recruitment to arms and typically the ability to add new intervention arms.Results62 late-phase clinical trials using an MAMS approach were included. Overall, the number of late-phase trials using the MAMS design has been increasing since 2001 and been accelerated by COVID-19. The majority of current MAMS platforms were either targeting infectious diseases (52%) or cancers (29%) and all identified trials were for treatment interventions. 89% (55/62) of MAMS platforms were evaluating medications, with 45% (28/62) of the MAMS platforms having at least one or more repurposed medication as a comparison arm.ConclusionsHistorically, late-phase trials have adhered to long-established standard (two-arm) designs. However, the number of late-phase MAMS platform trials is increasing, across a range of different disease areas. This study highlights the potential scope of MAMS platform trials and may assist research teams considering use of this approach in the late-phase randomised clinical trial setting.PROSPERO registration numberCRD42019153910.

We present direct photon-hadron correlations in 200 GeV/A Au+Au, d+Au, and p+p collisions, for direct photon pT from 5–12 GeV/c, collected by the PHENIX Collaboration in the years from 2006 to 2011. We observe no significant modification of jet fragmentation in d+Au collisions, indicating that cold nuclear matter effects are small or absent. Hadrons carrying a large fraction of the quark's momentum are suppressed in Au+Au compared to p+p and d+Au. As the momentum fraction decreases, the yield of hadrons in Au+Au increases to an excess over the yield in p+p collisions. The excess is at large angles and at low hadron pT and is most pronounced for hadrons associated with lower momentum direct photons. Comparison to theoretical calculations suggests that the hadron excess arises from medium response to energy deposited by jets.

A UIV/UIV “Pacman” complex exhibits facile oxo-ligand functionalisation and substitution reactivity, owing to a bridging catecholate ligand that enhances the μ-oxo nucleophilicity and stabilises the resulting products., The oxo- and catecholate-bridged UIV/UIV Pacman complex [{(py)UIVOUIV(μ-O2C6H4)(py)}(LA)] A (LA = a macrocyclic “Pacman” ligand; anthracenylene hinge between N4-donor pockets, ethyl substituents on meso-carbon atom of each N4-donor pocket) featuring a bent UIV–O–UIV oxo bridge readily reacts with small molecule substrates to undergo either oxo-atom functionalisation or substitution. Complex A reacts with H2O or MeOH to afford [{(py)UIV(μ-OH)2UIV(μ-O2C6H4)(py)}(LA)] (1) and [{(py)UIV(μ-OH)(μ-OMe)UIV(μ-O2C6H4)(py)}(LA)] (2), respectively, in which the bridging oxo ligand in A is substituted for two bridging hydroxo ligands or one bridging hydroxo and one bridging methoxy ligand, respectively. Alternatively, A reacts with either 0.5 equiv. of S8 or 4 equiv. of Se to provide [{(py)UIV(μ-η2:η2-E2)UIV(μ-O2C6H4)(py)}(LA)] (E = S (3), Se (4)) respectively, in which the [E2]2– ion bridges the two UIV centres. To the best of our knowledge, complex A is the first example of either a d- or f-block bimetallic μ-oxo complex that activates elemental chalcogens. Complex A also reacts with XeF2 or 2 equiv. of Me3SiCl to provide [{(py)UIV(μ-X)2UIV(μ-O2C6H4)(py)}(LA)] (X = F (5), Cl (6)), in which the oxo ligand has been substituted for two bridging halido ligands. Reacting A with either XeF2 or Me3SiCl in the presence of O(Bcat)2 at room temperature forms [{(py)UIV(μ-X)(μ-OBcat)UIV(μ-O2C6H4)(py)}(LA)] (X = F (5A), Cl (6A)), which upon heating to 80 °C is converted to 5 and 6, respectively. In order to probe the importance of the bent UIV–O–UIV motif in A on the observed reactivity, the bis(boroxido)-UIV/UIV complex, [{(py)(pinBO)UIVOUIV(OBpin)(py)}(LA)] (B), featuring a linear UIV–O–UIV bond angle was treated with H2O and Me3SiCl. Complex B reacts with two equiv. of either H2O or Me3SiCl to provide [{(py)HOUIVOUIVOH(py)}(LA)] (7) and [{(py)ClUIVOUIVCl(py)}(LA)] (8), respectively, in which reactions occur preferentially at the boroxido ligands, with the μ-oxo ligand unchanged. The formal UIV oxidation state is retained in all of the products 1–8, and selective reactions at the bridging oxo ligand in A is facilitated by: (1) its highly nucleophilic character which is a result of a non-linear UIV–O–UIV bond angle causing an increase in U–O bond covalency and localisation of the lone pairs of electrons on the μ-oxo group, and (2) the presence of the bridging catecholate ligand, which destabilises a linear oxo-bridging geometry and stabilises the resulting products.

Background and importance Intensive clinical pharmacy input from admission to discharge has been shown to improve patient outcomes. The clinical pharmacy service in our institution has historically been under-resourced. Aim and objectives The study aim was to develop a ward based clinical pharmacy service and to evaluate its impact using a number of clinical, safety and financial metrics. Material and methods A clinical pharmacist was assigned to provide pharmaceutical care to patients on a medicine for the older person ward. Over an 8 week period, the pharmacist prospectively recorded her interventions/activities. To assess impact on patient care, interventions were graded according to the Eadon criteria. The potential cost avoidance associated with interventions was estimated using two methods identified in the literature. Both define costs related to medication errors and calculate cost avoidance associated with clinical interventions based on prevention of harm. Medication incident reporting was analysed to assess the impact on patient safety. Results Eighty–four patients received a pharmacist review. Across a spectrum of activities, a total of 267 pharmacist interventions were recorded: 87% of patients had at least one pharmacist intervention. A total of 90% of interventions requiring follow–up with the medical team were accepted and resulted in a change to patient care. Eadon grading of interventions deemed that 81% of interventions improved the standard of patient care. Two different methods were used to estimate potential cost avoidance: one estimated annual savings of €154 103–€344 926; the other estimated these at €174 373. Given current pharmacist salary costs, this equates to a cost–benefit ratio of 2.8:1 to 6.3:1. (This does not include the 27% reduction in drug spend observed during the study period. However, more longitudinal data are required to confirm and characterise this phenomenon.) In the third quarter of 2018, 21 medication incidents were reported from the study ward compared with an average of 4 incident reports from the first and second quarters of 2018. This represents a fivefold increase in medication incident reporting, suggestive of an enhanced culture of patient safety. Conclusion and relevance This study assessed and quantified a wide spectrum of pharmacist contributions to medication management and safety. Costing of these contributions estimated the cost–benefit ratio of the clinical pharmacy service, providing compelling support for the extension of this service throughout the hospital. References and/or acknowledgements No conflict of interest.

Background and importance Biosimilars offer substantial savings to healthcare systems. In Ireland, however, prescriber hesitance remains an obstacle to their introduction. In June 2013, biosimilar infliximab was licensed by the EMA. Despite being one of the first European countries with commercial availability, penetration of the Irish market was only 25% in April 2018. In a Dublin acute hospital, a novel system for infliximab reimbursement exists across the primary and secondary care interface. This presented further challenges to implementing a biosimilar switch programme due to the lack of perceivable incentives for key stakeholders. Aim and objectives This descriptive review outlines the development of a trans-interface gain sharing (TIGS) programme catalysing the introduction of biosimilar infliximab in an Irish acute hospital. Material and methods Trans-interface engagement with key stakeholders began in 2017. Within the acute hospital, multiple impediments to biosimilar adoption were identified. In September 2018, the parameters of the TIGS programme were finalised, projecting cost saving for primary care and creating an income stream for secondary care, to be used for service development and enhancement. Achievement of procurement savings was the primary outcome of this study, with the impact of income generation within the acute hospital as secondary outcomes. Results Within 12 months of commencing the TIGS programme, the percentage of patients on biosimilar infliximab increased from 25% to 95%. Despite a 3.5% increase in infliximab usage, the procurement cost decreased by 45.4% (projected full year saving for 2019 of €859 372). To stimulate rapid uptake, the TIGS programme apportioned 80% of the savings to the acute hospital for at least the first 2 years. These savings were invested in pharmacy and rheumatology frontline services and provided the budgetary headroom to support increased access to alternative biologic therapies in gastroenterology (51.6% growth in access to vedolizumab). Conclusion and relevance In its first year, the TIGS programme stimulated successful introduction of biosimilar infliximab with projected procurement savings of almost €1m. The front loading of savings to frontline services will continue for a further 12–18 months, with recalibration of the gain share arrangement in 2021. References and/or acknowledgements No conflict of interest.

Crystals of a Cu complex of the macrocyclic Schiff-base calixpyrrole or 'Pacman' ligand, Cu2(L), do not contain any solvent-accessible void space at ambient pressure, but adsorb neon at 4.67 GPa, forming Cu2(L)·3.5Ne.

Crystals of a Cu complex of the macrocyclic Schiff-base calixpyrrole or 'Pacman' ligand, Cu

A combination of mass spectrometry, DFT calculations and 31P{1H} NMR spectroscopy has been used to define the mode of action of the commercial cobalt extractant, bis(2,4,4-trimethylpentyl)phosphinic acid (CYANEX®272, L1H) in Co recovery. The nature of the Co(II)-complexes formed in the water-immiscible phase is determined largely by the propensity of phosphinates to form strong interligand H-bonds in the outer coordination sphere and also to form stable µ2-Co-O-P-O-Co bridges. At low Co loading levels, the predominant species is the 4:1 complex, [Co(L1.L1H)2], in which coordinated neutral phosphinic acid ligands form strong H-bonds to adjacent anionic phosphinates. At higher Co loading, oligomers such as [(L1.L1H)Co(L12Co)n(L1.L1H)] are formed with µ2-phosphinate bridging, resulting in a substantial increase in the viscosity of the water-immiscible phase. The presence of tris(2,4,4-trimethylpentyl)phosphine oxide (L2) in the commercial formulation reduces the viscosity because its incorporation into oligomeric complexes such as [(L2)Co{L13CoL1CoL13Co}mL1] can terminate chains, resulting in a lower average molecular weight. The uptake of Zn by L1H shows a very similar dependence of viscosity on loading, and DOSY spectra and mass spectrometry demonstrate that higher molecular weight species are present at high Zn loading.

The use of amidoxime-functionalized polymer fibers as a sorbent for uranium has attracted recent interest for the extraction of uranium from seawater. Vanadium is one of the main competing ions for uranium sorption as V(v) species, however, vanadium is also present as V(iv) in seawater. In the present study, the interactions of V(iv) with amidoxime and similar ligands were explored. Attempts were made to synthesize V(iv) complexes of glutaroimide-dioxime, a molecular analogue of polymer sorbents. However, V(iv) was found to react irreversibly with glutaroimide-dioxime and other oxime groups, oxidizing to the V(v) oxidation state. We have explored the reactions and propose mechanisms, as well as characterized the redox behavior of the vanadium-glutaroimide-dioxime complex.

Combining computational modeling with experimental measurements has revealed the self-assembly of nano-aggregate structures in the transfer of HCl and PtCl62– from an aqueous phase into toluene by the common industrial extractant tributyl phosphate (TBP). Molecular dynamics simulations have been coupled to analytical measurements to provide an atomistic interpretation of the mode of action of TBP under 6 M and 10 M HCl conditions. The structures conform to reverse micelles, where the Cl– or PtCl62– core is encapsulated by a hydration shell that acts as a mediating bridge to the electronegative oxygen atom in the TBP phosphate groups. For the 6 M HCl extraction model, the data support stable aggregates forming from 2–3 TBP molecules around one chloride anion if the number of water molecules encapsulating the chloride anion is no more than five; increasing the water content to 10 molecules allows a fourth TBP molecule to coordinate. For the 10 M HCl extraction model, stable structures are obtained that conform to the empirical formula (TBP.HCl.H2O)3–5. At 6 M HCl, extraction of PtCl62– is achieved by encapsulation by four TBP molecules; the data for extraction at 10 M HCl indicate larger aggregates containing multiple PtCl62– anions are likely to be forming. In all cases, the hydrated core regions of the reverse micelles are considerably exposed. The diameters of the self-assembled structures around chloride ions agree well with available literature data from small-angle neutron-scattering experiments.

In this article we present the rational synthesis and full characterization of molecular Pd3 clusters sandwiched by imidazolium- and pyridinium-functionalized cycloheptatrienide ligands, of general formula [Pd3Br3(C7H6R)2]+. From functionalized η3-cycloheptatrienide Pd complexes as starting materials, PdBr2(η3-C7H6R), a number of synthetic routes were tested and a generally applicable strategy was developed on the basis of the formation of dimeric “preclusters”, [{PdBr(η3-C7H6R)}2(μ-Br)]+, which exhibit a Pd–Pd interaction. Spectroscopic and electrochemical results indicate a noninteger, common oxidation state of Pd in the trinuclear clusters, and crystallographic analysis reveals distinct differences in the binding properties of the Pd atoms in the solid state, suggesting that in certain environments there are even two discernible oxidation states, which is supported by computational analysis of the charge distribution.

The synthesis, metalation, and redox properties of an acyclic bis(iminothienyl)methene L− are presented. This π-conjugated anion displays pronounced redox activity, undergoing facile one-electron oxidation to the acyclic, metal-free, neutral radical L* on reaction with FeBr2. In contrast, reaction of L− with CuI forms the unique, neutral Cu2I2(L*) complex of a ligand-centered radical, whereas reaction with the stronger oxidant AgBF4 forms the metal-free radical dication L*2+.

An analysis of 552 structures of metal complexes of alkyl and arylphosphinates in the Cambridge Crystallographic Database shows that the phosphinate ligating group is remarkably versatile and is able to adopt ten different binding motifs in both mono- and polynuclear complexes in which an individual phosphinate group can bind to up to five metal atoms. The majority of both homo- and heteroleptic complexes contain Msingle bondOsingle bondPR2double bond; length as m-dashOsingle bondM units in oligomeric and polymeric structures. In many heteroleptic complexes ligands containing hydrogen bond donors form strong bonding interactions with the phosphinate, generating pseudochelated structures. Similar pseudochelates, −Osingle bondPR2double bond; length as m-dashO⋯Hsingle bondOsingle bondPR2double bond; length as m-dashO, are formed when both a phosphinate and its parent phosphinic acid are coordinated to a single metal atom. Such structures feature also in the solution chemistry involved in metal extraction processes using phosphinate ligands. As might be expected, many of the binding motifs found in phosphinate complexes are similar to those in carboxylate complexes but there are fewer examples of phosphinates being used to form metal organic frameworks.

Pinpointing disulfide linkage pattern is critical in the characterization of proteins and peptides consisting of multiple disulfide bonds. Herein, we report a method based on coupling online disulfide modification and tandem mass spectrometry (MS/MS) to distinguish peptide disulfide regio-isomers. Such a method relies on a new disulfide bond cleavage reaction in solution, involving methanol as a reactant and 254 nm ultraviolet (UV) irradiation. This reaction leads to selective cleavage of a disulfide bond and formation of sulfenic methyl ester (–SOCH3) at one cysteine residue and a thiol (–SH) at the other. Under low energy collision-induced dissociation (CID), cysteine sulfenic methyl ester motif produces a signature methanol loss (–32 Da), allowing its identification from other possible isomeric structures such as S-hydroxylmethyl (–SCH2OH) and methyl sulfoxide (–S(O)-CH3). Since disulfide bond can be selectively cleaved and modified upon methoxy addition, subsequent MS2 CID of the methoxy addition product provides enhanced sequence coverage as demonstrated by the analysis of bovine insulin. More importantly, this reaction does not induce disulfide scrambling, likely due to the fact that radical intermediates are not involved in the process. An approach based on methoxy addition followed by MS3 CID has been developed for assigning disulfide linkage patterns in peptide disulfide regio-isomers. This methodology was successfully applied to characterizing peptide systems having two disulfide bonds and three disulfide linkage isomers: side-by-side, overlapped, and looped-within-a-loop configurations.

Deoxydehydration (DODH) is one of the most promising tools to reduce the oxygen content of biomass (sugars and polyols) and provide analogues of platform chemicals that are derived from fossil resources. This reaction converts a vicinal diol into an alkene and is typically catalyzed by high-oxidation-state metal-oxo compounds in the presence of a stoichiometric reductant, with examples of both homogeneous and heterogeneous systems. This mini-review will highlight the developments in this field over the past 5 years and focus on efforts to solve the problems that currently prevent DODH being performed on a commercial scale, including the nature of the reductant, substrate scope and selectivity, and catalyst recovery and expense.

The uranyl ion, [U

Current methods for the extraction of rhodium carry the highest carbon footprint and worst pollution metrics of all of the elements used in modern technological applications. Improving upon existing methods is made difficult by the limited understanding of the molecular-level chemistry occurring in these processes, particularly in the hydrometallurgical separation step. While many of the precious metals can be separated by solvent extraction, there currently exist no commercial extraction reagents for Rh. This is due to its complicated mixed speciation upon leaching into hydrochloric acid, which gives rise to difficulties in designing effective reagents for solvent extraction. Herein we show that the diamidoamine reagent N-n-hexyl-bis(N-methyl-N-n-octyl-ethylamide)amine transports Rh(III) from aqueous HCl into an organic phase as the mono-aquated dianion [RhCl5(H2O)]2– through the formation of an outer-sphere assembly; this assembly has been characterized by experimentation (slope analysis, FT-IR and NMR spectroscopy, EXAFS, SANS, ESI-MS) and computational modeling. The paper demonstrates the importance of applying a broad range of techniques to obtain a convincing mode of action view for the complex processes involved in anion recognition in the solution phase. A consistent and comprehensive understanding of how the ligand operates to achieve Rh(III) selectivity over the competitor anion Cl− has emerged. This knowledge will guide the rational design of the next generation of extractants and thus offers promise for improving the sustainability of metal extraction from both traditional mining sources and the recycling of secondary source materials.

The reactions between alcohols and the tetranuclear ethyl-Zn complexes of an ortho-phenylene-bridged polypyrrole macrocycle, Zn4Et4(L1) 1 and the related anthracenyl-bridged macrocyclic complex, Zn4Et4(THF)4(L2) 2 have been studied. With long-chain alcohols such as n-hexanol, the clean formation of the tetranuclear hexoxide complex Zn4(OC6H13)4(L1) 3 occurs. In contrast, the use of shorter-chain alcohols such as i-propanol results in the trinuclear complex Zn3(μ2-OiPr)2(μ3-OiPr)(HL1) 4 that arises from demetalation; this complex was characterised by X-ray crystallography. The clean formation of these polynuclear zinc clusters allowed a study of their use as catalysts in the ring-opening copolymerisation (ROCOP) reaction between cyclohexene oxide and CO2. In situ reactions involving the pre-catalyst 1 and n-hexanol formed the desired polymer with the best selectivity for polycarbonate (90%) at 30 atm CO2, whilst the activity and performance of pre-catalyst 2 was poor in comparison.

The recycling of metals such as gold and copper from discarded end-of-life electronic waste (e-waste or WEEE) is an important aspect to the development of environmentally benign manufacturing processes that exhibit circularity in materials flow. Global e-waste production is increasing at a 3–5% rate, so it is concerning that only 30% is recycled using regulated processes. We present here a new hydrometallurgical route for the technically feasible recycling of copper and gold from waste printed circuit boards (WPCBs) of mobile phones. This process comprises the liberation of the metallic fractions from downsized WPCBs, a two-stage acid leaching process to provide a bulk separation of copper and gold from the other metals present, and subsequent purification of the copper and gold-containing solutions by solvent extraction using highly selective phenolic oxime and amide extractants, respectively. Complete dissolution of the base metals was seen using 3 M nitric acid at 30 °C and the selective separation of copper from this leach liquor was achieved by solvent extraction using ACORGA M5640 dissolved in kerosene. The residues from base-metal leaching were treated with a mixture of 3 M sulfuric acid and 3 M sodium bromide at 70 °C, resulting in greater than 95% gold dissolution. The selective separation of gold from this precious metal leachate was achieved by solvent extraction using 0.1 M tertiary amide extractant dissolved in toluene. This process delivers complete copper and gold recycling from WPCBs under relatively benign laboratory conditions and represents a proof of concept for liberating valuable and critical metals back into active service from end-of-life electronic devices.

The possibility of recovering rare earth elements from solutions containing their chloridometalate anions [LnClx](x−3)− via the process: LnClx(x−3)− + (x − 3)Lorg + (x–3)H+ ⇌ [(LH)x−3LnClx]org has been tested using 2-(1,3-bis(hexylamino)-1,3-dioxopropan-2-yl)-4,6-di-tert-butylpyridine (PMA), tri-n-butylphosphate (TBP), and tri-n-octylamine (TOA), which are known to be strong extractants for transition metal chloridometalates. While DFT calculations indicate that the formation of the neutral assembly [(PMAH)3LaCl6] in the gas phase is favorable, no uptake of La(III) from 6 M HCl by toluene solutions of PMA (or of TBP or TOA) was observed in solvent extraction experiments. Successful uptake of the [PtCl6]2− dianion by PMA and the failure to extract the [IrCl6]3− trianion under the same conditions indicate that the higher hydration energy of the latter makes transfer to the toluene solution less favorable and that this militates against extraction of La(III) chlorido complexes carrying charges of −3 or larger in which all the inner-sphere water molecules have been replaced. Computational results confirm literature observations that, in contrast to transition metal trications, formation of REE metalate anions such as [LnClx](x−3)− is not very favorable, particularly so for chloride, compared with nitrato or sulfato systems. Also, they indicate that the formation of outer-sphere assemblies such as {[La(H2O)9]·xCl} in which water ligands are retained in the inner sphere, H-bonded to anions, is more stable than inner-sphere complexes containing an equivalent number of anions. The high level of hydration of such species disfavors their transfer into nonpolar water-immiscible solvents. It is unlikely that recovery of [LnClx](x−3)− from acidic solutions can be achieved efficiently using currently available anion exchange extractants operating in a “pH-swing” process. Receptors giving very high binding energies to chloridolanthanates will be needed to offset the high dehydration energies required.