Towards the chemical control of molecular packing: syntheses and crystal structures of three trans-[NiL4(NCS)2] complexes

Three nickel(II) isothiocyanato complexes of the formula trans-[NiL4(NCS)2] (L = ethylisonicotinate, methylisonicotinate and 4-benzoylpyridine) have been prepared: [Ni(ethylisonicotinate) 4(NCS)2] (I), [Ni(methylisonicotinate)4(NCS)2] (II) and [Ni(4-benzoylpyridine)4(NCS)2] (III). All three complexes are monomeric and have a distorted octahedral geometry around NiII. Despite their apparent molecular similarity, the crystal density of (III) (1.454 g cm 3) is significantly higher than that of (I) and (II) (both 1.408 g cm 3), suggesting that the molecular packing is most efficient in (III). A study of the molecular Hirshfeld surfaces, together with density functional theory (DFT) calculations, provide insights into the origin of the molecular packing features, and it is suggested that the greater crystal density of (III) results from smaller intermolecular electrostatic repulsions

Electron Exchange Coupling for Single Donor Solid-State Qubits

Inter-valley interference between degenerate conduction band minima has been shown to lead to oscillations in the exchange energy between neighbouring phosphorus donor electron states in silicon \cite{Koiller02,Koiller02A}. These same effects lead to an extreme sensitivity of the exchange energy on the relative orientation of the donor atoms, an issue of crucial importance in the construction silicon-based spin quantum computers. In this article we calculate the donor electron exchange coupling as a function of donor position incorporating the full Bloch structure of the Kohn-Luttinger electron wavefunctions. It is found that due to the rapidly oscillating nature of the terms they produce, the periodic part of the Bloch functions can be safely ignored in the Heitler-London integrals as was done by Koiller et. al. [Phys. Rev. Lett. 88,027903(2002),Phys. Rev. B. 66,115201(2002)], significantly reducing the complexity of calculations. We address issues of fabrication and calculate the expected exchange coupling between neighbouring donors that have been implanted into the silicon substrate using an 15keV ion beam in the so-called 'top down' fabrication scheme for a Kane solid-state quantum computer. In addition we calculate the exchange coupling as a function of the voltage bias on control gates used to manipulate the electron wavefunctions and implement quantum logic operations in the Kane proposal, and find that these gate biases can be used to both increase and decrease the magnitude of the exchange coupling between neighbouring donor electrons. The zero-bias results reconfirm those previously obtained by Koiller.Comment: 10 Pages, 8 Figures. To appear in Physical Review

Myeloperoxidase and oxidation of uric acid in gout: implications for the clinical consequences of hyperuricaemia

Objectives. The aims of this study were to establish whether, in patients with gout, MPO is released from neutrophils and urate is oxidized to allantoin and if these effects are attenuated by allopurinol. Methods. MPO, urate, allantoin and oxypurinol were measured in plasma from 54 patients with gout and 27 healthy controls. Twenty-three patients had acute gout, 13 of whom were receiving allopurinol, and 31 had intercritical gout, 20 of whom were receiving allopurinol. Ten additional gout patients had samples collected before and after 4 weeks of allopurinol. Results. Plasma MPO and its specific activity were higher (P < 0.05) in patients with acute gout not receiving allopurinol compared with controls. MPO protein in patients’ plasma was related to urate concentration (r = 0.5, P < 0.001). Plasma allantoin was higher (P < 0.001) in all patient groups compared with controls. In controls and patients not receiving allopurinol, allantoin was associated with plasma urate (r = 0.62, P < 0.001) and MPO activity (r = 0.45, P < 0.002). When 10 patients were treated with allopurinol, it lowered their plasma urate and allantoin (P = 0.002). In all patients receiving allopurinol, plasma allantoin was related to oxypurinol (r = 0.65, P < 0.0001). Oxypurinol was a substrate for purified MPO that enhanced the oxidation of urate. Conclusion. Increased concentrations of urate in gout lead to the release of MPO from neutrophils and the oxidation of urate. Products of MPO and reactive metabolites of urate may contribute to the pathology of gout and hyperuricaemia. At low concentrations, oxypurinol should reduce inflammation, but high concentrations may contribute to oxidative stress

Perineal Assessment and Repair Longitudinal Study (PEARLS): a matched-pair cluster randomized trial.

Perineal trauma during childbirth affects millions of women worldwide every year. The aim of the Perineal Assessment and Repair Longitudinal Study (PEARLS) was to improve maternal clinical outcomes following childbirth through an enhanced cascaded multiprofessional training program to support implementation of evidence-based perineal management

An obstetric sphincter injury risk identification system (OSIRIS): is this a clinically useful tool?

INTRODUCTION AND HYPOTHESIS: To establish the contribution of maternal, fetal and intrapartum factors to the risk of incidence of obstetric anal sphincter injuries (OASIS) and assess the feasibility of an OASIS risk prediction model based on variables available to clinicians prior to birth. METHODS: This was a population-based, retrospective cohort study using single-site data from the birth database of Aarhus University Hospital, Denmark. The participants were all women who had a singleton vaginal birth during the period 1989 to 2006. Univariate and multivariate logistic regression analyses were performed using multiple imputations for missing data and internally validated using bootstrap methods. The main outcome measures were the contributions of maternal, fetal and intrapartum events to the incidence of OASIS. RESULTS: A total of 71,469 women met the inclusion criteria, of whom 1,754 (2.45 %) sustained OASIS. In the multivariate analysis of variables known prior to birth, maternal age 20 – 30 years (OR 1.65, 95 % CI 1.44 – 1.89) and ≥30 years (OR 1.60, 95 % CI 1.39 – 1.85), occipitoposterior fetal position (OR 1.34, 95 % CI 1.06 – 1.70), induction/augmentation of labour (OR 1.46, 95 % CI 1.32 – 1.62), and suspected macrosomia (OR 2.20, 95 % CI 1.97 – 2.45) were independent significant predictors of OASIS, with increasing parity conferring a significant protective effect. The ‘prebirth variable’ model showed a 95 % sensitivity and a 24 % specificity in predicting OASIS with 1 % probability, and a 3 % sensitivity and a 99 % specificity in predicting OASIS with a 10 % probability. CONCLUSIONS: Our model identified several significant OASIS risk factors that are known prior to actual birth. The prognostic model shows potential for ruling out OASIS (high sensitivity with a low risk cut-off value), but is not useful for ruling in the event. ELECTRONIC SUPPLEMENTARY MATERIAL: The online version of this article (doi:10.1007/s00192-016-3125-2) contains supplementary material, which is available to authorized users

Myeloperoxidase and oxidative stress in rheumatoid arthritis

Objective. To determine whether MPO contributes to oxidative stress and disease activity in RA and whether it produces hypochlorous acid in SF. Methods. Plasma and where possible SF were collected from 77 RA patients while 120 healthy controls supplied plasma only. MPO and protein carbonyls were measured by ELISAs. 3-Chlorotyrosine in proteins and allantoin in plasma were measured by mass spectrometry. Results. Plasma MPO concentrations were significantly higher in patients with RA compared with healthy controls [10.8 ng/ml, inter-quartile range (IQR): 7.214.2; P < 0.05], but there was no significant difference in plasma MPO protein concentrations between RA patients with high disease activity (HDA; DAS-28 >3.2) and those with low disease activity (LDA; DAS-28 43.2) (HDA 27.9 ng/ml, 20.234.1 vs LDA 22.1 ng/ml, 16.934.9; P > 0.05). There was a significant relationship between plasma MPO and DAS-28 (r = 0.35; P = 0.005). Plasma protein carbonyls and allantoin were significantly higher in patients with RA compared with the healthy controls. MPO protein was significantly higher in SF compared with plasma (median 624.0 ng/ml, IQR 258.42433.0 vs 30.2 ng/ml, IQR 25.150.9; P < 0.0001). The MPO present in SF was mostly active. 3-Chlorotyrosine, a specific biomarker of hypochlorous acid, was present in proteins from SF and related to the concentration of MPO (r = 0.69; P = 0.001). Protein carbonyls in SF were associated with MPO protein concentration (r = 0.40; P = 0.019) and 3-chlorotyrosine (r = 0.66; P = 0.003). Conclusion. MPO is elevated in patients with RA and promotes oxidative stress through the production of hypochlorous acid

Perineal resuturing versus expectant management following vaginal delivery complicated by a dehisced wound (PREVIEW): a nested qualitative study

Objective: To explore women's lived experiences of a dehisced perineal wound following childbirth and how they felt participating in a pilot and feasibility randomised controlled trial (RCT). Design: A nested qualitative study using semistructured interviews, underpinned by descriptive phenomenology. Participants and setting: A purposive sample of six women at 6-9 months postnatal who participated in the RCT were interviewed in their own homes. Results: Following Giorgi's analytical framework the verbatim transcripts were analysed for key themes. Women's lived experiences revealed 4 emerging themes: (1) Physical impact, with sub-themes focusing upon avoiding infection, perineal pain and the impact of the wound dehiscence upon daily activities; (2) Psychosocial impact, with sub-themes of denial, sense of failure or self-blame, fear, isolation and altered body image; (3) Sexual impact; and (4) Satisfaction with wound healing. A fifth theme 'participating in the RCT' was 'a priori' with sub-themes centred upon understanding the randomisation process, completing the trial questionnaires, attending for hospital appointments and acceptability of the treatment options. Conclusions: To the best of our knowledge, this is the first qualitative study to grant women the opportunity to voice their personal experiences of a dehisced perineal wound and their views on the management offered. The powerful testimonies presented disclose the extent of morbidity experienced while also revealing a strong preference for a treatment option.sch_die7pub5266pub

Ecological implications of a flower size/number trade-off in tropical forest trees

Peer reviewedPublisher PD

Industrial work placement in higher education: a study of civil engineering student engagement

For civil engineering undergraduates, the opportunity to spend a period of time in formal industrial work placement provides an invaluable learning experience. This paper reviews student engagement with short-term industrial placement and provides analysis of questionnaires (n=174) returned by undergraduates studying civil engineering at four Higher Education Institutes (HEI’s) in the West of Scotland. The data captures industrial placement statistics, employability skill-sets and presents brief testimonies from students. Whilst the journey to becoming a professional civil engineer is undoubtedly enhanced by short-term placement clear opportunities exist for HEI’s to affect and change existing pedagogical discourse. Commentary is likely to resonate beyond civil engineering and serve as a timely reminder of the need to re-invigorate academia / industry curriculum partnerships

Evaluation of accuracy of mediolateral episiotomy incisions using a training model

Background: Episiotomy is one of the most commonly performed surgical procedures worldwide. In the UK the use of episiotomy is selective, rather than routine, and a right mediolateral episiotomy (RMLE) is considered standard practice. According to The National Institute of Health and Care Excellence (NICE, 2007) guideline for intrapartum care such an episiotomy should be cut at an angle between 45° and 60° to the vertical axis. Recent evidence suggests that the angle of incision of mediolateral episiotomy (MLE) is associated with risk of obstetric anal sphincter injury (OASIS).Objective: to assess the accuracy of individual practitioner's techniques when performing a RMLE.Design: an audit of practice against nationally set standards.Setting: at a national midwifery conference and prior to three multiprofessional perineal repair training workshops in the West Midlands region of the UK.Participants: 144 midwives and 53 obstetric trainees.Measurements: practitioners were asked to perform a RMLE incision on a bespoke training model, which is designed to give a realistic representation of a stretched perineum at crowning of the baby's head. Four parameters were measured: (1) distance of the starting point from the midline; (2) angle subtended to the perpendicular; (3) length and (4) shape of the incision (curved, straight or J-shaped).Findings: of the 197 incisions performed only 12.7% (14.6%, n=21/144 of midwives and 7.5%, n=4/53 of obstetricians) complied with the defined technique of a RMLE for correctness of angle and placement. A 2-sided Fisher's exact test showed no significant difference between previous attendance at perineal management training and incision accuracy