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Article: Experimental and theoretical comparison of actinide and lanthanide bonding in M[N(EPR(2))(2)](3) complexes (M = U, Pu, La, Ce; E = S, Se, Te; R = Ph, iPr, H).

Gaunt, Andrew J / Reilly, Sean D / Enriquez, Alejandro E / Scott, Brian L / Ibers, James A / Sekar, Perumal / Ingram, Kieran I M / Kaltsoyannis, Nikolas / Neu, Mary P

Inorganic chemistry

2008 Volume 47, Issue 1, Page(s) 29–41

Abstract: Treatment of M[N(SiMe3)2]3 (M = U, Pu (An); La, Ce (Ln)) with NH(EPPh2)2 and NH(EPiPr2)2 (E = S, Se ... that the enhanced covalency in the M-E bond as group 16 is descended arises mostly from increased metal d-orbital ... afforded the neutral complexes M[N(EPR2)2]3 (R = Ph, iPr). Tellurium donor complexes were synthesized ...

Abstract	Treatment of M[N(SiMe3)2]3 (M = U, Pu (An); La, Ce (Ln)) with NH(EPPh2)2 and NH(EPiPr2)2 (E = S, Se), afforded the neutral complexes M[N(EPR2)2]3 (R = Ph, iPr). Tellurium donor complexes were synthesized by treatment of MI3(sol)4 (M = U, Pu; sol = py and M = La, Ce; sol = thf) with Na(tmeda)[N(TePiPr2)2]. The complexes have been structurally and spectroscopically characterized with concomitant computational modeling through density functional theory (DFT) calculations. The An-E bond lengths are shorter than the Ln-E bond lengths for metal ions of similar ionic radii, consistent with an increase in covalent interactions in the actinide bonding relative to the lanthanide bonding. In addition, the magnitude of the differences in the bonding is slightly greater with increasing softness of the chalcogen donor atom. The DFT calculations for the model systems correlate well with experimentally determined metrical parameters. They indicate that the enhanced covalency in the M-E bond as group 16 is descended arises mostly from increased metal d-orbital participation. Conversely, an increase in f-orbital participation is responsible for the enhancement of covalency in An-E bonds compared to Ln-E bonds. The fundamental and practical importance of such studies of the role of the valence d and f orbitals in the bonding of the f elements is emphasized.
MeSH term(s)	Actinoid Series Elements/chemistry ; Binding Sites ; Computer Simulation ; Crystallography, X-Ray ; Lanthanoid Series Elements/chemistry ; Ligands ; Models, Chemical ; Models, Molecular ; Organometallic Compounds/chemical synthesis ; Organometallic Compounds/chemistry ; Quantum Theory
Chemical Substances	Actinoid Series Elements ; Lanthanoid Series Elements ; Ligands ; Organometallic Compounds
Language	English
Publishing date	2008-01-07
Publishing country	United States
Document type	Comparative Study ; Journal Article ; Research Support, Non-U.S. Gov't ; Research Support, U.S. Gov't, Non-P.H.S.
ZDB-ID	1484438-2
ISSN	1520-510X ; 0020-1669
ISSN (online)	1520-510X
ISSN	0020-1669
DOI	10.1021/ic701618a
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Article ; Online: Covalency in the f element-chalcogen bond. computational studies of M[N(EPR2)2]3 (M = La, Ce, Pr, Pm, Eu, U, Np, Pu, Am, Cm; E = O, S, Se, Te; R = H, (i)Pr, Ph).

Ingram, Kieran I M / Tassell, Matthew J / Gaunt, Andrew J / Kaltsoyannis, Nikolas

Inorganic chemistry

2008 Volume 47, Issue 17, Page(s) 7824–7833

Abstract: ... N(EPH 2) 2] 3 (M = La, Ce, U, Pu; E = O, S, Se, Te), models for the experimentally characterized M[N ... obtained only for E = S and Se. Comparison of the electronic structures of six- and nine-coordinate M[N(EPH ... M and E down group 16, and larger f populations. The latter are interpreted not as evidence of f ...

Abstract	The geometric and electronic structures of the title complexes have been studied using scalar relativistic, gradient-corrected density functional theory. Extension of our previous work on six-coordinate M[N(EPH 2) 2] 3 (M = La, Ce, U, Pu; E = O, S, Se, Te), models for the experimentally characterized M[N(EP (i)Pr 2) 2] 3, yields converged geometries for all of the other 4f and 5f metals studied and for all four group 16 elements. By contrast, converged geometries for nine-coordinate M[N(EPPh 2) 2] 3 are obtained only for E = S and Se. Comparison of the electronic structures of six- and nine-coordinate M[N(EPH 2) 2] 3 suggests that coordination of the N atoms produces only minor changes in the metal-chalcogen interactions. Six-coordinate Eu[N(EPH 2) 2] 3 and Am[N(EPH 2) 2] 3 with the heavier group 16 donors display geometric and electronic properties rather different from those of the other members of the 4f and 5f series, in particular, longer than expected Eu-E and Am-E bond lengths, smaller reductions in charge difference between M and E down group 16, and larger f populations. The latter are interpreted not as evidence of f-based metal-ligand covalency but rather as being indicative of ionic metal centers closer to M (II) than M (III). The Cm complexes are found to be very ionic, with very metal-localized f orbitals and Cm (III) centers. The implications of the results for the separation of the minor actinides from nuclear wastes are discussed, as is the validity of using La (III)/U (III) comparisons as models for minor actinide/Eu systems.
Language	English
Publishing date	2008-09-01
Publishing country	United States
Document type	Journal Article
ZDB-ID	1484438-2
ISSN	1520-510X ; 0020-1669
ISSN (online)	1520-510X
ISSN	0020-1669
DOI	10.1021/ic800835k
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Article ; Online: Time for reassessment of remote ischaemic preconditioning.

Gaunt, M E

The British journal of surgery

2016 Volume 103, Issue 4, Page(s) 319–321

MeSH term(s)	Animals ; Humans ; Ischemic Preconditioning/methods ; Reperfusion Injury/prevention & control ; Telemedicine/methods
Language	English
Publishing date	2016-03
Publishing country	England
Document type	Journal Article ; Review
ZDB-ID	2985-3
ISSN	1365-2168 ; 0263-1202 ; 0007-1323 ; 1355-7688
ISSN (online)	1365-2168
ISSN	0263-1202 ; 0007-1323 ; 1355-7688
DOI	10.1002/bjs.10132
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Article ; Online: Investigating the factors associated with meaningful improvement on the SF-36-PFS and exploring the appropriateness of this measure for young people with ME/CFS accessing an NHS specialist service: a prospective cohort study.

Gaunt, Daisy / Brigden, Amberly / Metcalfe, Chris / Loades, Maria / Crawley, Esther

BMJ open

2023 Volume 13, Issue 8, Page(s) e069110

Abstract: Objectives: Paediatric myalgic encephalomyelitis/chronic fatigue syndrome (ME/CFS) is relatively common and disabling, but little is known about the factors associated with outcome. We aimed to describe the number and characteristics of young people ... ...

Abstract	Objectives: Paediatric myalgic encephalomyelitis/chronic fatigue syndrome (ME/CFS) is relatively common and disabling, but little is known about the factors associated with outcome. We aimed to describe the number and characteristics of young people reaching the 10-point minimal clinically important difference (MCID) of SF-36-Physical Function Subscale (SF-36-PFS) and to investigate factors associated with reaching the MCID. Design: Prospective observational cohort study. Setting: A specialist UK National Health Service ME/CFS service, Southwest England; recruitment between March 2014 and August 2015. Participants: 193 eligible patients with ME/CFS aged 8-17 years reported baseline data. 124 (65%) and 121 (63%) with outcome data at 6 and 12 months, respectively. Outcome measures: SF-36-PFS (primary outcome). Chalder Fatigue Questionnaire, school attendance, visual analogue pain scale, Hospital Anxiety and Depression Scale, Spence Young People Anxiety Scale, Clinical Global Impression scale and EQ-5D-Y (secondary). Results: At 6 months 48/120 (40%) had reached the MCID for SF-36-PFS. This had increased to 63/117 (54%) at 12 months. On the Clinical Global Impressions, 77% and 79% reported feeling either a little better, much better or very much better. Those with worse SF-36-PFS at baseline assessment were more likely to achieve the MCID for SF-36-PFS at 6 months (odds ratio 0.97, 95% confidence interval 0.96 to 0.99, p value 0.003), but there was weaker evidence of effect at 12 months (OR 0.98, 95% CI 0.97 to 1.00, p value 0.038). No other factors at baseline were associated with the odds of reaching the MCID at 6 months. However, at 12 months, there was strong evidence of an effect of pain on MCID (OR 0.97, 95% CI 0.95 to 0.99, p value 0.001) and SF-36-PFS on MCID (OR 0.96, 95% CI 0.94 to 0.98, p value 0.001). Conclusions: 40% and 54% of young people reached the MCID at 6 and 12 months, respectively. No factors at assessment (other than SF-36-PFS at 6 months, and pain and SF-36-PFS at 12 months) are associated with MCID of SF-36-PFS at either 6 or 12 months. Further work is needed to explore the most appropriate outcome measure for capturing clinical meaningful improvement for young people with ME/CFS.
MeSH term(s)	Humans ; Child ; Adolescent ; Fatigue Syndrome, Chronic ; Prospective Studies ; State Medicine ; Emotions ; Pain
Language	English
Publishing date	2023-08-24
Publishing country	England
Document type	Observational Study ; Journal Article ; Research Support, Non-U.S. Gov't
ZDB-ID	2599832-8
ISSN	2044-6055 ; 2044-6055
ISSN (online)	2044-6055
ISSN	2044-6055
DOI	10.1136/bmjopen-2022-069110
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Article ; Online: Participant retention in paediatric randomised controlled trials published in six major journals 2015-2019: systematic review and meta-analysis.

Gaunt, Daisy M / Papastavrou Brooks, Cat / Pedder, Hugo / Crawley, Esther / Horwood, Jeremy / Metcalfe, Chris

Trials

2023 Volume 24, Issue 1, Page(s) 403

Abstract: ... for each reviewed trial's primary outcome. Context (e.g. population, disease) and design (e.g. length of trial ...

Abstract	Background: The factors which influence participant retention in paediatric randomised controlled trials are under-researched. Retention may be more challenging due to child developmental stages, involving additional participants, and proxy-reporting of outcomes. This systematic review and meta-analysis explores the factors which may influence retention in paediatric trials. Methods: Using the MEDLINE database, paediatric randomised controlled trials published between 2015 and 2019 were identified from six general and specialist high-impact factor medical journals. The review outcome was participant retention for each reviewed trial's primary outcome. Context (e.g. population, disease) and design (e.g. length of trial) factors were extracted. Retention was examined for each context and design factor in turn, with evidence for an association being determined by a univariate random-effects meta-regression analysis. Results: Ninety-four trials were included, and the median total retention was 0.92 (inter-quartile range 0.83 to 0.98). Higher estimates of retention were seen for trials with five or more follow-up assessments before the primary outcome, those less than 6 months between randomisation and primary outcome, and those that used an inactive data collection method. Trials involving children aged 11 and over had the higher estimated retention compared with those involving younger children. Those trials which did not involve other participants also had higher retention, than those where they were involved. There was also evidence that a trial which used an active or placebo control treatment had higher estimated retention, than treatment-as-usual. Retention increased if at least one engagement method was used. Unlike reviews of trials including all ages of participants, we did not find any association between retention and the number of treatment groups, size of trial, or type of treatment. Conclusions: Published paediatric RCTs rarely report the use of specific modifiable factors that improve retention. Including multiple, regular follow-ups with participants before the primary outcome may reduce attrition. Retention may be highest when the primary outcome is collected up to 6 months after a participant is recruited. Our findings suggest that qualitative research into improving retention when trials involve multiple participants such as young people, and their caregivers or teachers would be worthwhile. Those designing paediatric trials also need to consider the use of appropriate engagement methods. RESEARCH ON RESEARCH (ROR) REGISTRY: https://ror-hub.org/study/2561.
MeSH term(s)	Humans ; Child ; Adolescent ; Periodicals as Topic ; Databases, Factual ; Publications ; Qualitative Research ; Registries ; Randomized Controlled Trials as Topic
Language	English
Publishing date	2023-06-14
Publishing country	England
Document type	Meta-Analysis ; Systematic Review ; Journal Article ; Review
ZDB-ID	2040523-6
ISSN	1745-6215 ; 1468-6694 ; 1745-6215
ISSN (online)	1745-6215
ISSN	1468-6694 ; 1745-6215
DOI	10.1186/s13063-023-07333-w
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Article ; Online: Correction: Defining the minimally clinically important difference of the SF-36 physical function subscale for paediatric CFS/ME: triangulation using three different methods.

Brigden, Amberly / Parslow, Roxanne M / Gaunt, Daisy / Collin, Simon M / Jones, Andy / Crawley, Esther

Health and quality of life outcomes

2023 Volume 21, Issue 1, Page(s) 16

Language	English
Publishing date	2023-02-18
Publishing country	England
Document type	Published Erratum
ZDB-ID	2098765-1
ISSN	1477-7525 ; 1477-7525
ISSN (online)	1477-7525
ISSN	1477-7525
DOI	10.1186/s12955-022-02078-7
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Article ; Online: Who should we ask about mental health symptoms in adolescents with CFS/ME? Parent-child agreement on the revised children's anxiety and depression scale.

Serafimova, Teona / Loades, Maria / Gaunt, Daisy / Crawley, Esther

Clinical child psychology and psychiatry

2021 Volume 26, Issue 2, Page(s) 367–380

Abstract: Background: One in three adolescents with chronic fatigue syndrome/myalgic encephalomyelitis (CFS/ME) have mental health problems. Multi-informant perspectives are key to psychological assessment. Understanding parent-child agreement is crucial to ... ...

Abstract	Background: One in three adolescents with chronic fatigue syndrome/myalgic encephalomyelitis (CFS/ME) have mental health problems. Multi-informant perspectives are key to psychological assessment. Understanding parent-child agreement is crucial to accurate diagnosis, particularly where severe fatigue limits self-report. Methods: Agreement on the revised children's anxiety and depression scale (RCADs) was assessed between parents and children with CFS/ME ( Results: Diagnostic thresholds were met more frequently based on child-report. Parent- and child-report had similar sensitivity and specificity on RCADS compared to gold-standard diagnostic interviews. Regression analysis found similar accuracy between both reports. For anxiety diagnoses, odds ratio (OR) for child-report was 1.10 (CI = 1.06-1.14), and 1.10 (CI = 1.05-1.14) for parent-report. For depression, OR for child report was 1.26 (CI = 1.11-1.43), while for parent-report is was 1.25 (CI = 1.10-1.41). For total score, OR for child-report was 1.10 (CI = 1.05-1.13) while OR for parent-report was 1.09 (CI = 1.05-1.13). Conclusions: Reasonable agreement was observed between parent- and child-report of mental health symptoms in paediatric CFS/ME. While parent-report can facilitate psychological evaluation in CFS/ME, this is not a substitute for a child's own report.
MeSH term(s)	Adolescent ; Anxiety/diagnosis ; Child ; Depression/diagnosis ; Fatigue Syndrome, Chronic/diagnosis ; Humans ; Mental Health ; Parent-Child Relations
Language	English
Publishing date	2021-02-15
Publishing country	England
Document type	Journal Article
ZDB-ID	1324235-0
ISSN	1461-7021 ; 1359-1045
ISSN (online)	1461-7021
ISSN	1359-1045
DOI	10.1177/1359104521994880
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Article ; Online: Informed consent in randomised controlled trials: further development and evaluation of the participatory and informed consent (PIC) measure.

Wade, Julia / Humphrys, Elka / Realpe, Alba X / Gaunt, Daisy M / Burt, Jenni

Trials

2023 Volume 24, Issue 1, Page(s) 305

Abstract: Background: Informed consent is an accepted ethical and legal prerequisite for trial participation, yet there is no standardised method of assessing patient understanding for informed consent. The participatory and informed consent (PIC) measure was ... ...

Abstract	Background: Informed consent is an accepted ethical and legal prerequisite for trial participation, yet there is no standardised method of assessing patient understanding for informed consent. The participatory and informed consent (PIC) measure was developed for application to recruitment discussions to evaluate recruiter information provision and evidence of patient understanding. Preliminary evaluation of the PIC indicated the need to improve inter-rater and intra-rater reliability ratings and conduct further psychometric evaluation. This paper describes the assessment, revision and evaluation of the PIC within the context of OPTiMISE, a pragmatic primary care-based trial. Methods: This study used multiple methods across two phases. In phase one, one researcher applied the existing PIC measure to 18 audio-recorded recruitment discussions from the OPTiMISE study and made detailed observational notes about any uncertainties in application. Appointments were sampled to be maximally diverse for patient gender, study centre, recruiter and before and after an intervention to optimise information provision. Application uncertainties were reviewed by the study team, revisions made and a coding manual developed and agreed. In phase two, the coding manual was used to develop tailored guidelines for applying the PIC to appointments within the OPTiMISE trial. Two researchers then assessed 27 further appointments, purposively sampled as above, to evaluate inter-rater and intra-rater reliability, content validity and feasibility. Results: Application of the PIC to 18 audio-recorded OPTiMISE recruitment discussions resulted in harmonisation of the scales rating recruiter information provision and evidence of patient understanding, minor amendments to clarify wording and the development of detailed generic coding guidelines for applying the measure within any trial. Application of the revised measure using these guidelines to 27 further recruitment discussions showed good feasibility (time to complete), content validity (completion rate) and reliability (inter- and intra-rater) of the measure. Conclusion: The PIC provides a means to evaluate the content of information provided by recruiters, patient participation in recruitment discussions and, to some extent, evidence of patient understanding. Future work will use the measure to evaluate recruiter information provision and evidence of patient understanding both across and within trials.
MeSH term(s)	Humans ; Patient Selection ; Reproducibility of Results ; Patient Participation ; Informed Consent ; Research Personnel ; Randomized Controlled Trials as Topic
Language	English
Publishing date	2023-05-02
Publishing country	England
Document type	Journal Article
ZDB-ID	2040523-6
ISSN	1745-6215 ; 1468-6694 ; 1745-6215
ISSN (online)	1745-6215
ISSN	1468-6694 ; 1745-6215
DOI	10.1186/s13063-023-07296-y
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Article: Using a checklist within simulation improves trainees' confidence on ward rounds.

Pearson, Grace Me / Wege, Sally E / Rosen, Sarah A / Gaunt, Daisy M / Henderson, Emily J

Future healthcare journal

2022 Volume 9, Issue 2, Page(s) 171–173

Abstract: Ward rounds are integral to maintaining patient safety in everyday clinical care. Junior doctors are often expected to conduct independent rounds on graduation, but many feel ill-equipped to do so. We developed a safety checklist and simulation sessions ... ...

Abstract	Ward rounds are integral to maintaining patient safety in everyday clinical care. Junior doctors are often expected to conduct independent rounds on graduation, but many feel ill-equipped to do so. We developed a safety checklist and simulation sessions to improve junior-led ward round practice at one district general hospital. We found that embedding a checklist within simulation is an effective way to teach ward round skills and increase confidence among undergraduate and postgraduate medical trainees.
Language	English
Publishing date	2022-08-04
Publishing country	England
Document type	Journal Article
ZDB-ID	3016427-8
ISSN	2514-6653 ; 2514-6645
ISSN (online)	2514-6653
ISSN	2514-6645
DOI	10.7861/fhj.2021-0195
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Article ; Online: Chlorination of Pu and U Metal Using GaCl

Carpenter, Stephanie H / Klamm, Bonnie E / Fetrow, Taylor V / Scott, Brian L / Gaunt, Andrew J / Anderson, Nickolas H / Tondreau, Aaron M

Inorganic chemistry

2023 Volume 62, Issue 22, Page(s) 8462–8466

Abstract: The oxidative chlorination of the plutonium metal was achieved through a reaction with gallium(III) chloride ( ... ...

Abstract	The oxidative chlorination of the plutonium metal was achieved through a reaction with gallium(III) chloride (GaCl
Language	English
Publishing date	2023-05-23
Publishing country	United States
Document type	Journal Article
ZDB-ID	1484438-2
ISSN	1520-510X ; 0020-1669
ISSN (online)	1520-510X
ISSN	0020-1669
DOI	10.1021/acs.inorgchem.3c00522
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