42 research outputs found

    Transforming PPh3 into Bidentate Phosphine Ligands at Ru-Zn Heterobimetallic Complexes

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    The reaction of [Ru(PPh 3) 3Cl 2] with excess ZnMe 2 led to P-C/C-H bond activation and P-C/C-C bond formation to generate a chelating diphenylphosphinobenzene ligand as well as a cyclometallated (diphenylphosphino)biphenyl group in the final product of the reaction, [Ru(dppbz)(PPh 2(biphenyl)′)(ZnMe)] (1; dppbz = 1,2-bis(diphenylphosphino)benzene); PPh 2(biphenyl)′ = cyclometallated PPh 2(biphenyl). The mechanism of reaction was studied and C-C coupling to give a bidentate 2,2′-bis(diphenylphosphino)biphenyl (BIPHEP) ligand was suggested to be one of the key steps of the process. This was confirmed by the reaction of [Ru(BIPHEP)(PPh 3)HCl] with ZnMe 2, which also gave 1. An analogous set of steps took place upon addition of ZnMe 2 to [Ru(rac-BINAP)(PPh 3)HCl] (rac-BINAP = racemic(2,2′-bis(diphenylphosphino)-1,1′-binaphthyl) to give [Ru(dppbz)(PPh 2(binaphthyl)′)ZnMe] (3). H 2 and the C-H bond of PhCCH added across the Ru-Zn bond of 1, and also reversed the phosphine cyclometallation, to give [Ru(dppbz)(Ph 2P(biphenyl))(H) 2(H)(ZnMe)] (4) and [Ru(dppbz)(Ph 2P(biphenyl))(CCPh) 2(H)(ZnMe)] (5) respectively. </p

    Draft genome sequence of Pseudomonas putida CA-3, a bacterium capable of styrene degradation and medium-chain-length polyhydroxyalkanoate synthesis

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    Pseudomonas putida strain CA-3 is an industrial bioreactor isolate capable of synthesizing biodegradable polyhydroxyalkanoate polymers via the metabolism of styrene and other unrelated carbon sources. The pathways involved are subject to regulation by global cellular processes. The draft genome sequence is 6,177,154 bp long and contains 5,608 predicted coding sequences

    Induction and repression of the sty operon in Pseudomonas putida CA-3 during growth on phenylacetic acid under organic and inorganic nutrient-limiting continuous culture conditions

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    The effects of various nutrient-limiting conditions on expression of the sty operon in Pseudomonas putida CA-3 were investigated. It was observed that limiting concentrations of the carbon source phenylacetic acid, resulted in high levels of phenylacetyl coenzyme A (CoA) ligase activity, this was accompanied also by upper pathway styrene monooxygenase enzyme activity. The introduction of inorganic nutrient limitations, (nitrate, sulfate and phosphate), caused a dramatic reduction in detectable levels of phenylacetyl CoA ligase activity, particularly in the presence of the primary carbon source, succinate. Under these conditions it was no longer possible to detect styrene monooxygenase activity. Reverse transcription PCR analysis of total RNA, isolated under each of the continuous culture conditions examined, revealed that variations in the levels of enzyme activity coincided with altered patterns of corresponding paaK (phenylacetyl CoA ligase) and styA (styrene monooxygenase) gene expression. Transcription of the upper pathway regulatory sensor kinase gene styS was also observed to be growth condition-dependent. These observations suggest that induction/repression of the sty operon in P. putida CA-3, during growth on phenylacetic acid under continuous culture conditions, involves regulatory mechanisms coordinately affecting both the upper and lower pathways and acting at the level of gene transcriptio

    A between sex analysis of self and proxy efficacy and its relationship with attendance at a community based chronic illness rehabilitation programme.

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    Background: Physical activity is a principal intervention in primary and secondary prevention of chronic illness. While the benefits of community based rehabilitation is acknowledged,the rate of attendance and adherence remains sub optimal. Self-efficacy is acknowledged to be a key factor relating to adherence in rehabilitation but the construct of proxy efficacy, defined as one’s confidence in the skills and abilities of a third party to function effectively on another’s behalf, is less often studied. This paper examines the relationship between gender and ‘self’ and ‘proxy-efficacy’ and their potential role in attendance to a community based chronic illness rehabiliation (CBCIR) programme. Methods: Participants attending induction at the programme completed a questionnaire assessing demographics and both self (9 items) and proxy efficacy for exercise (9 items) which was assessed on a Likert scale from 0 (not confident at all) to 10 (very confident), with a higher score indicating greater efficacy. Subsequently, attendance was objectively monitored by researchers at exercise sessions for 24 weeks. Results: 69 participants (M age=65.5 +9.8 years, 56% Male) completed all measures. Mean proxy-efficacy and mean self-efficacy is significantly greater in women compared to men (p<0.05). Mean proxy-efficacy was found to be higher than mean self-efficacy in both males (proxy-efficacy=8.7+1.2, self efficacy=8.3+1.8) and females (proxyefficacy= 7.7+2.2, self-efficacy=6.5+2.0) with no correlation between the variables. Correlational analyses found a moderate significant positive correlation between proxy efficacy and number of weeks attended in the 24 weeks (r=.440,p<.05) in women with no correlation observed between self-efficacy and weeks attended. No correlations are observed between either form of efficacy and attendance in men. Discussion: Participants report greater confidence in the proxy agent than themselves as the agent. This was furthered in women with an association identified between proxy efficacy and 24-week attendance. These results suggest the importance of the proxy for women in a CBCIR setting but further longitudinal research should be carried out in the area of proxy efficacy and attendance at community based chronic illness rehabilitation programmes. Implications: An understanding of these variables help CBCIR programme facilitators intervene to ensure greater attendance

    DairyWater: striving for sustainability within the dairy processing industry in the Republic of Ireland

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    peer-reviewedThis Review describes the objectives and methodology of the DairyWater project as it aims to aid the Irish dairy processing industry in achieving sustainability as it expands. With the abolition of European milk quotas in March 2015, the Republic of Ireland saw a surge in milk production. The DairyWater project was established in anticipation of this expansion of the Irish dairy sector in order to develop innovative solutions for the efficient management of water consumption, wastewater treatment and the resulting energy use within the country's dairy processing industry. Therefore, the project can be divided into three main thematic areas: dairy wastewater treatment technologies and microbial analysis, water re-use and rainwater harvesting and environmental assessment. In order to ensure the project remains as relevant as possible to the industry, a project advisory board containing key industry stakeholders has been established. To date, a number of large scale studies, using data obtained directly from the Irish dairy industry, have been performed. Additionally, pilot-scale wastewater treatment (intermittently aerated sequencing batch reactor) and tertiary treatment (flow-through pulsed ultraviolet system) technologies have been demonstrated within the project. Further details on selected aspects of the project are discussed in greater detail in the subsequent cluster of research communications

    Determinants of Depressive Symptoms at 1 Year Following ICU Discharge in Survivors of $ 7 Days of Mechanical Ventilation : Results From the RECOVER Program, a Secondary Analysis of a Prospective Multicenter Cohort Study

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    Abstract : Background: Moderate to severe depressive symptoms occur in up to one-third of patients at 1 year following ICU discharge, negatively affecting patient outcomes. This study evaluated patient and caregiver factors associated with the development of these symptoms. Methods: This study used the Rehabilitation and Recovery in Patients after Critical Illness and Their Family Caregivers (RECOVER) Program (Phase 1) cohort of 391 patients from 10 medical/surgical university-affiliated ICUs across Canada. We determined the association between patient depressive symptoms (captured by using the Beck Depression Inventory II [BDI-II]), patient characteristics (age, sex, socioeconomic status, Charlson score, and ICU length of stay [LOS]), functional independence measure (FIM) motor subscale score, and caregiver characteristics (Caregiver Assistance Scale and Center for Epidemiologic Studies-Depression Scale) by using linear mixed models at time points 3, 6, and 12 months. Results: BDI-II data were available for 246 patients. Median age at ICU admission was 56 years (interquartile range, 45-65 years), 143 (58%) were male, and median ICU LOS was 19 days (interquartile range, 13-32 days). During the 12-month follow-up, 67 of 246 (27.2%) patients had a BDI-II score ≥ 20, indicating moderate to severe depressive symptoms. Mixed models showed worse depressive symptoms in patients with lower FIM motor subscale scores (1.1 BDI-II points per 10 FIM points), lower income status (by 3.7 BDI-II points; P = .007), and incomplete secondary education (by 3.8 BDI-II points; P = .009); a curvilinear relation with age (P = .001) was also reported, with highest BDI-II at ages 45 to 50 years. No associations were found between patient BDI-II and comorbidities (P = .92), sex (P = .25), ICU LOS (P = .51), or caregiver variables (Caregiver Assistance Scale [P = .28] and Center for Epidemiologic Studies Depression Scale [P = .74]). Conclusions: Increased functional dependence, lower income, and lower education are associated with increased severity of post-ICU depressive symptoms, whereas age has a curvilinear relation with symptom severity. Knowledge of risk factors may inform surveillance and targeted mental health follow-up. Early mobilization and rehabilitation aiming to improve function may serve to modify mood disorders

    Review and analysis of fire and explosion accidents in maritime transportation

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    The globally expanding shipping industry has several hazards such as collision, capsizing, foundering, grounding, stranding, fire, and explosion. Accidents are often caused by more than one contributing factor through complex interaction. It is crucial to identify root causes and their interactions to prevent and understand such accidents. This study presents a detailed review and analysis of fire and explosion accidents that occurred in the maritimetransportation industry during 1990–2015. The underlying causes of fire and explosion accidents are identified and analysed. This study also reviewed potential preventative measures to prevent such accidents. Additionally, this study compares properties of alternative fuels and analyses their effectiveness in mitigating fire and explosionhazards. It is observed that Cryogenic Natural Gas (CrNG), Liquefied Natural Gas (LNG) and methanol have properties more suitable than traditional fuels in mitigating fire risk and appropriate management of their hazards could make them a safer option to traditional fuels. However, for commercial use at this stage, there exist several uncertainties due to inadequate studies, and technological immaturity. This study provides an insight into fire and explosion accident causation and prevention, including the prospect of using alternative fuels for mitigating fire and explosion risks in maritime transportation

    Rehabilitation versus surgical reconstruction for non-acute anterior cruciate ligament injury (ACL SNNAP): a pragmatic randomised controlled trial

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    BackgroundAnterior cruciate ligament (ACL) rupture is a common debilitating injury that can cause instability of the knee. We aimed to investigate the best management strategy between reconstructive surgery and non-surgical treatment for patients with a non-acute ACL injury and persistent symptoms of instability.MethodsWe did a pragmatic, multicentre, superiority, randomised controlled trial in 29 secondary care National Health Service orthopaedic units in the UK. Patients with symptomatic knee problems (instability) consistent with an ACL injury were eligible. We excluded patients with meniscal pathology with characteristics that indicate immediate surgery. Patients were randomly assigned (1:1) by computer to either surgery (reconstruction) or rehabilitation (physiotherapy but with subsequent reconstruction permitted if instability persisted after treatment), stratified by site and baseline Knee Injury and Osteoarthritis Outcome Score—4 domain version (KOOS4). This management design represented normal practice. The primary outcome was KOOS4 at 18 months after randomisation. The principal analyses were intention-to-treat based, with KOOS4 results analysed using linear regression. This trial is registered with ISRCTN, ISRCTN10110685, and ClinicalTrials.gov, NCT02980367.FindingsBetween Feb 1, 2017, and April 12, 2020, we recruited 316 patients. 156 (49%) participants were randomly assigned to the surgical reconstruction group and 160 (51%) to the rehabilitation group. Mean KOOS4 at 18 months was 73·0 (SD 18·3) in the surgical group and 64·6 (21·6) in the rehabilitation group. The adjusted mean difference was 7·9 (95% CI 2·5–13·2; p=0·0053) in favour of surgical management. 65 (41%) of 160 patients allocated to rehabilitation underwent subsequent surgery according to protocol within 18 months. 43 (28%) of 156 patients allocated to surgery did not receive their allocated treatment. We found no differences between groups in the proportion of intervention-related complications.InterpretationSurgical reconstruction as a management strategy for patients with non-acute ACL injury with persistent symptoms of instability was clinically superior and more cost-effective in comparison with rehabilitation management

    Microbiota Around Dental Implants in Partially Edentulous Patients: A Prospective Analysis

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    Master of ScienceProsthodonticshttps://deepblue.lib.umich.edu/bitstream/2027.42/147935/1/ot_114.pd
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