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1.
Ear Hear ; 45(4): 945-951, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-38503724

RESUMO

OBJECTIVES: Vestibular vertigo has been shown to have a high lifetime prevalence. Previous studies have described the increased morbidities associated with vestibular vertigo. DESIGN: In this cross-sectional study of the 2016 National Health Interview Study, we sought to explore whether individuals with vestibular vertigo were more likely to utilize healthcare resources compared with those without vestibular vertigo. We characterized utilization of specific healthcare resources including general doctors, specialist doctors, emergency departments, mental health professionals, and others among individuals with vestibular vertigo to better understand how individuals with vertigo interact with the US healthcare system. RESULTS: In multivariable analyses, participants with vestibular vertigo had an increased number of nights in the hospital in the last 12 months (mean difference = 0.67 days, 95% confidence interval [CI] = 0.37 to 0.97), increased odds of receiving healthcare 10 or more times in the last 12 months (odds ratio = 2.22, 95% CI = 1.99 to 2.48) and increased number of visits to a healthcare professional in the last 2 weeks (mean difference = 0.17 visits, 95% CI = 0.14 to 0.21). In addition, participants with vestibular vertigo had increased odds of visiting both general doctors, specialist doctors, and other healthcare professionals. CONCLUSIONS: These findings characterize how individuals with vestibular vertigo utilize and interact with healthcare resources compared with those without vestibular vertigo.


Assuntos
Aceitação pelo Paciente de Cuidados de Saúde , Vertigem , Humanos , Masculino , Feminino , Estados Unidos/epidemiologia , Pessoa de Meia-Idade , Vertigem/epidemiologia , Estudos Transversais , Adulto , Idoso , Aceitação pelo Paciente de Cuidados de Saúde/estatística & dados numéricos , Serviço Hospitalar de Emergência/estatística & dados numéricos , Adulto Jovem , Hospitalização/estatística & dados numéricos , Adolescente , Análise Multivariada
2.
BMJ Open ; 13(11): e072531, 2023 11 02.
Artigo em Inglês | MEDLINE | ID: mdl-37918923

RESUMO

INTRODUCTION: One-third of children in England have special educational needs (SEN) provision recorded during their school career. The proportion of children with SEN provision varies between schools and demographic groups, which may reflect variation in need, inequitable provision and/or systemic factors. There is scant evidence on whether SEN provision improves health and education outcomes. METHODS: The Health Outcomes of young People in Education (HOPE) research programme uses administrative data from the Education and Child Health Insights from Linked Data-ECHILD-which contains data from all state schools, and contacts with National Health Service hospitals in England, to explore variation in SEN provision and its impact on health and education outcomes. This umbrella protocol sets out analyses across four work packages (WP). WP1 defined a range of 'health phenotypes', that is health conditions expected to need SEN provision in primary school. Next, we describe health and education outcomes (WP1) and individual, school-level and area-level factors affecting variation in SEN provision across different phenotypes (WP2). WP3 assesses the impact of SEN provision on health and education outcomes for specific health phenotypes using a range of causal inference methods to account for confounding factors and possible selection bias. In WP4 we review local policies and synthesise findings from surveys, interviews and focus groups of service users and providers to understand factors associated with variation in and experiences of identification, assessment and provision for SEN. Triangulation of findings on outcomes, variation and impact of SEN provision for different health phenotypes in ECHILD, with experiences of SEN provision will inform interpretation of findings for policy, practice and families and methods for future evaluation. ETHICS AND DISSEMINATION: Research ethics committees have approved the use of the ECHILD database and, separately, the survey, interviews and focus groups of young people, parents and service providers. These stakeholders will contribute to the design, interpretation and communication of findings.


Assuntos
Instituições Acadêmicas , Medicina Estatal , Humanos , Adolescente , Pais , Escolaridade , Comunicação , Literatura de Revisão como Assunto
3.
BMJ Mil Health ; 2022 Jul 25.
Artigo em Inglês | MEDLINE | ID: mdl-35878969

RESUMO

Military medicine has been evolving for over 5000 years of recorded civilisation and conflict. The Army Medical Services performed poorly during the Crimean War and the British Army introduced a professional training course for medical officers in 1860. The Army Medical School and the predecessor of today's Post-Graduate Medical and Nursing Officers (PGMNO) course have had to adapt to changes in British foreign policy and military requirements. The Army Medical School instigated a rigorous scientific medical training which led to major advances in the study of tropical diseases and trauma medicine. These advances were quickly included in the training of future cohorts. Although the Army Medical School has now closed, the PGMNO course thrives at its new location at the Defence Medical Academy, Whittington. Modern general duties medical officers (GDMOs) must be able to provide medical care in a range of austere environments, including humanitarian relief and conflict zones. New clinicians complete their basic military training before completing the PGMNO course and the Diploma in the Medical Care of Catastrophes. This programme ensures that GDMOs and military nurse practitioners gain a wide knowledge of the latest military and humanitarian medicine. The current era will require clinicians who are competent generalists, who can perform in small teams in dispersed locations. This article summarises the development of the British Army's PGMNO course and the evolution of its syllabus as part of the Humanitarian and Disaster Relief Operations special issue of BMJ Military Health.

4.
Otol Neurotol ; 42(10): e1524-e1531, 2021 12 01.
Artigo em Inglês | MEDLINE | ID: mdl-34766948

RESUMO

OBJECTIVE: This study evaluated whether vestibular dysfunction is associated with reduced spatial navigation performance. STUDY DESIGN: Cross-sectional study. SETTING: Otolaryngology Clinic in the Johns Hopkins Outpatient Center and an analogous virtual reality (VR) environment. PATIENTS: Eligible patients had diagnosis of unilateral or bilateral vestibular loss. Matched healthy controls were recruited at 1:1 ratio. INTERVENTIONS: The navigation task involved a route-based or place-based strategy in both real world and VR environments. MAIN OUTCOME MEASURES: Navigation performance was measured by distance travelled relative to optimal distance (i.e., path ratio) and the Judgments of Relative Direction (JRD) task, whereby participants had to recall relative angular distances between landmarks. RESULTS: The study sample included 20 patients with vestibular loss (mean age: 61 yrs, SD: 10.2 yrs) and 20 matched controls (mean age: 60 yrs, SD: 10.4 yrs). Patients with vestibular loss travelled significantly greater distance using both route-based (path ratio 1.3 vs. 1.0, p = 0.02) and place-based (path ratio 2.6 vs. 2.0, p = 0.03) strategies in the real world. Overall, participants performed worse in virtual reality compared to real world in both path ratio (2.2 vs. 1.7; p = 0.04) and JRD error (78° vs. 67°; p < 0.01). Furthermore, while controls exhibited significant positive correlations between real world and VR performance in place-based (ß = 0.75; p < 0.001) and JRD tasks (ß = 0.70; p < 0.001), patients with vestibular loss exhibited no similar correlations. CONCLUSIONS: The vestibular system appears to play a role in navigation ability during both actual and virtual navigation, suggesting a role for static vestibular signals in navigation performance.


Assuntos
Navegação Espacial , Realidade Virtual , Estudos Transversais , Humanos , Pessoa de Meia-Idade
5.
Sci Rep ; 11(1): 18124, 2021 09 13.
Artigo em Inglês | MEDLINE | ID: mdl-34518601

RESUMO

The treatment of spinal cord injury (SCI) is a complex challenge in regenerative medicine, complicated by the low intrinsic capacity of CNS neurons to regenerate their axons and the heterogeneity in size, shape and extent of human injuries. For example, some contusion injuries do not compromise the dura mater and in such cases implantation of preformed scaffolds or drug delivery systems may cause further damage. Injectable in situ thermosensitive scaffolds are therefore a less invasive alternative. In this study, we report the development of a novel, flowable, thermosensitive, injectable drug delivery system comprising bovine collagen (BC) and fibrinogen (FB) that forms a solid BC/FB gel (Gel) immediately upon exposure to physiological conditions and can be used to deliver reparative drugs, such as the naturally occurring anti-inflammatory, anti-scarring agent Decorin, into adult rat spinal cord lesion sites. In dorsal column lesions of adult rats treated with the Gel + Decorin, cavitation was completely suppressed and instead lesion sites became filled with injury-responsive cells and extracellular matrix materials, including collagen and laminin. Decorin increased the intrinsic potential of dorsal root ganglion neurons (DRGN) by increasing their expression of regeneration associated genes (RAGs), enhanced local axon regeneration/sprouting, as evidenced both histologically and by improved electrophysiological, locomotor and sensory function recovery. These results suggest that this drug formulated, injectable hydrogel has the potential to be further studied and translated into the clinic.


Assuntos
Colágeno/química , Decorina/administração & dosagem , Fibrinogênio/química , Hidrogéis/química , Traumatismos da Medula Espinal/reabilitação , Traumatismos da Medula Espinal/terapia , Potenciais de Ação/efeitos dos fármacos , Animais , Biomarcadores , Bovinos , Sobrevivência Celular/efeitos dos fármacos , Modelos Animais de Doenças , Matriz Extracelular , Gânglios Espinais , Metaloproteinases da Matriz/metabolismo , Regeneração Nervosa/efeitos dos fármacos , Crescimento Neuronal/efeitos dos fármacos , Neurônios/fisiologia , Recuperação de Função Fisiológica , Medicina Regenerativa , Traumatismos da Medula Espinal/etiologia , Traumatismos da Medula Espinal/metabolismo , Cicatrização
6.
Psychophysiology ; 58(11): e13905, 2021 11.
Artigo em Inglês | MEDLINE | ID: mdl-34289128

RESUMO

Heart rate variability (HRV) is a well-established surrogate of cardiac and emotional health that reflects the balance between sympathetic and parasympathetic activity of the autonomic nervous system. We examined the impact of manipulating exhalation to inhalation ratio (E:I) on HRV, without altering the intrinsic breathing rate of healthy individuals. We hypothesized that a longer exhalation relative to inhalation (E:I > 1) would shift HRV metrics in a direction consistent with increased parasympathetic activity. Twenty-eight individuals (16 young [6M, age = 21-28];12 older adults [6M, age = 66-80]) completed a task during which they paced breathing according to their intrinsic respiratory rate, but altered onset of exhalation and inhalation according to 1:1 sound cue (equal exhalation and inhalation duration) or 2:1 cue (exhalation twice as long as inhalation). Paced 1:1 breathing followed these task conditions to examine residual effects. Estimates of actual E:I ratio based on thoracic movement were 1.08(0.16) for 1:1 task and 1.33(0.20) for 2:1 task, which were significantly different from one another. HRV metrics derived from electrocardiogram included root mean square of the successive differences between normal heartbeats (RMSSD) and high-frequency (HF) HRV. Analyses of HRV metrics by block showed that RMSSD and HF-HRV were higher in the 2:1 task condition compared to 1:1. Time series analysis showed that HF-HRV increased after the end of the 2:1 task block and remained elevated for four minutes. These findings suggest that longer duration of exhalation relative to inhalation, without altering breathing rate, acutely increased RMSSD and HF-HRV, consistent with enhancement of cardiac vagal tone.


Assuntos
Sistema Nervoso Autônomo/fisiologia , Expiração/fisiologia , Frequência Cardíaca/fisiologia , Inalação/fisiologia , Taxa Respiratória/fisiologia , Adulto , Idoso , Idoso de 80 Anos ou mais , Feminino , Humanos , Masculino , Adulto Jovem
8.
Hum Brain Mapp ; 41(8): 2121-2135, 2020 06 01.
Artigo em Inglês | MEDLINE | ID: mdl-32034832

RESUMO

Resting-state functional magnetic resonance imaging (rs-fMRI) is frequently used to study brain function; but, it is unclear whether BOLD-signal fluctuation amplitude and functional connectivity are associated with vascular factors, and how vascular-health factors are reflected in rs-fMRI metrics in the healthy population. As arterial stiffening is a known age-related cardiovascular risk factor, we investigated the associations between aortic stiffening (as measured using pulse-wave velocity [PWV]) and rs-fMRI metrics. We used cardiac MRI to measure aortic PWV (an established indicator of whole-body vascular stiffness), as well as dual-echo pseudo-continuous arterial-spin labeling to measure BOLD and CBF dynamics simultaneously in a group of generally healthy adults. We found that: (1) higher aortic PWV is associated with lower variance in the resting-state BOLD signal; (2) higher PWV is also associated with lower BOLD-based resting-state functional connectivity; (3) regions showing lower connectivity do not fully overlap with those showing lower BOLD variance with higher PWV; (4) CBF signal variance is a significant mediator of the above findings, only when averaged across regions-of-interest. Furthermore, we found no significant association between BOLD signal variance and systolic blood pressure, which is also a known predictor of vascular stiffness. Age-related vascular stiffness, as measured by PWV, provides a unique scenario to demonstrate the extent of vascular bias in rs-fMRI signal fluctuations and functional connectivity. These findings suggest that a substantial portion of age-related rs-fMRI differences may be driven by vascular effects rather than directly by brain function.


Assuntos
Aorta/fisiologia , Circulação Cerebrovascular/fisiologia , Conectoma , Imageamento por Ressonância Magnética , Análise de Onda de Pulso , Rigidez Vascular/fisiologia , Adolescente , Adulto , Idoso , Aorta/diagnóstico por imagem , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Marcadores de Spin , Adulto Jovem
9.
Clin Teach ; 15(2): 145-150, 2018 04.
Artigo em Inglês | MEDLINE | ID: mdl-28474405

RESUMO

BACKGROUND: All health care professionals in the UK are expected to have the medical leadership and management (MLM) skills necessary for improving patient care, as stipulated by the UK General Medical Council (GMC). CONTEXT: Newly graduated doctors reported insufficient knowledge about leadership and quality improvement skills, despite all UK medical schools reporting that MLM is taught within their curriculum. INNOVATION: A medical student society organised a series of extracurricular educational events focusing on leadership topics. The society recognised that the events needed to be useful and interesting to attract audiences. Therefore, clinical leaders in exciting fields were invited to talk about their experiences and case studies of personal leadership challenges. The emphasis on personal stories, from respected leaders, was a deliberate strategy to attract students and enhance learning. Evaluation data were collected from the audiences to improve the quality of the events and to support a business case for an intercalated degree in MLM. IMPLICATIONS: When leadership and management concepts are taught through personal stories, students find it interesting and are prepared to give up their leisure time to engage with the subject. Students appear to recognise the importance of MLM knowledge to their future careers, and are able to organise their own, and their peers', learning and development. Organising these events and collecting feedback can provide students with opportunities to practise leadership, management and quality improvement skills. These extracurricular events, delivered through a student society, allow for subjects to be discussed in more depth and can complement an already crowded undergraduate curriculum. Newly graduated doctors reported insufficient knowledge about leadership and quality improvement skills.


Assuntos
Liderança , Modelos Organizacionais , Sociedades , Estudantes de Medicina , Ensino , Educação de Graduação em Medicina , Humanos , Competência Profissional , Melhoria de Qualidade , Reino Unido
10.
BMJ Open ; 7(10): e015453, 2017 Oct 12.
Artigo em Inglês | MEDLINE | ID: mdl-29025827

RESUMO

OBJECTIVE: To investigate the effect of residential location and socioeconomic deprivation on the provision of bariatric surgery. DESIGN: Retrospective cross-sectional ecological study. SETTING: Patients resident local to one of two specialist bariatric units, in different regions of the UK, who received obesity surgery between 2003 and 2013. METHODS: Demographic data were collected from prospectively collected databases. Index of Multiple Deprivation (IMD 2010) was used as a measure of socioeconomic status. Obesity prevalences were obtained from Public Health England (2006). Patients were split into three IMD tertiles (high, median, low) and also tertiles of time. A generalised linear model was generated for each time period to investigate the effect of socioeconomic deprivation on the relationship between bariatric case count and prevalence of obesity. We used these to estimate surgical intervention provided in each population in each period at differing levels of deprivation. RESULTS: Data were included from 1163 bariatric cases (centre 1-414, centre 2-749). Incidence rate ratios (IRRs) were calculated to measure the associations between predictor and response variables. Associations were highly non-linear and changed over the 10-year study period. In general, the relationship between surgical case volume and obesity prevalence has weakened over time, with high volumes becoming less associated with prevalence of obesity. DISCUSSION: As bariatric services have matured, the associations between demand and supply factors have changed. Socioeconomic deprivation is not apparently a barrier to service provision more recently, but the positive relationships between obesity and surgical volume we would expect to find are absent. This suggests that interventions are not being taken up in the areas of need. We recommend a more detailed national analysis of the relationship between supply side and demand side factors in the provision of bariatric surgery.


Assuntos
Cirurgia Bariátrica/estatística & dados numéricos , Obesidade/epidemiologia , Obesidade/cirurgia , Áreas de Pobreza , Características de Residência , Área Programática de Saúde , Estudos Transversais , Feminino , Acessibilidade aos Serviços de Saúde , Humanos , Masculino , Pessoa de Meia-Idade , Estudos Retrospectivos , Reino Unido/epidemiologia
11.
J Health Organ Manag ; 30(7): 1081-1104, 2016 10 10.
Artigo em Inglês | MEDLINE | ID: mdl-27700475

RESUMO

Purpose Although medical leadership and management (MLM) is increasingly being recognised as important to improving healthcare outcomes, little is understood about current training of medical students in MLM skills and behaviours in the UK. The paper aims to discuss these issues. Design/methodology/approach This qualitative study used validated structured interviews with expert faculty members from medical schools across the UK to ascertain MLM framework integration, teaching methods employed, evaluation methods and barriers to improvement. Findings Data were collected from 25 of the 33 UK medical schools (76 per cent response rate), with 23/25 reporting that MLM content is included in their curriculum. More medical schools assessed MLM competencies on admission than at any other time of the curriculum. Only 12 schools had evaluated MLM teaching at the time of data collection. The majority of medical schools reported barriers, including overfilled curricula and reluctance of staff to teach. Whilst 88 per cent of schools planned to increase MLM content over the next two years, there was a lack of consensus on proposed teaching content and methods. Research limitations/implications There is widespread inclusion of MLM in UK medical schools' curricula, despite the existence of barriers. This study identified substantial heterogeneity in MLM teaching and assessment methods which does not meet students' desired modes of delivery. Examples of national undergraduate MLM teaching exist worldwide, and lessons can be taken from these. Originality/value This is the first national evaluation of MLM in undergraduate medical school curricula in the UK, highlighting continuing challenges with executing MLM content despite numerous frameworks and international examples of successful execution.


Assuntos
Currículo , Liderança , Faculdades de Medicina/organização & administração , Humanos , Entrevistas como Assunto , Pesquisa Qualitativa , Reino Unido
12.
J Chromatogr A ; 1468: 23-32, 2016 Oct 14.
Artigo em Inglês | MEDLINE | ID: mdl-27667649

RESUMO

Nonhydrolytic sol-gel (NHSG) route was used for the creation of novel zirconia-polypropylene oxide (ZrO2-PPO) sol-gel hybrid sorbents in the form of surface coatings for the extraction and preconcentration of catecholamine neurotransmitters and molecules structurally related to their deaminated metabolites. In comparison to other sorbents made of inorganic transition metal oxides, the presented hybrid organic-inorganic sorbents facilitated reversible sorption properties that allowed for efficient desorption of the extracted analytes by LC-MS compatible mobile phases. The presented sol-gel hybrid sorbents effectively overcame the major drawbacks of traditional silica- or polymer-based sorbents by providing superior pH stability (pH range: 0-14), and a variety of intermolecular interactions. Nonaqueous sol-gel treatment of PPO with ZrCl4 was employed for the derivatization of the terminal hydroxyl groups on PPO, providing zirconium trichloride-containing end groups characterized by enhanced sol-gel reactivity. NHSG ZrO2-PPO sorbent provided excellent microextraction performance for catecholamines, low detection limits (5.6-9.6pM), high run-to-run reproducibility (RSD 0.6-5.1%), high desorption efficiency (95.0-99.5%) and high enrichment factors (∼1480-2650) for dopamine and epinephrine, respectively, extracted from synthetic urine samples. The presented sol-gel sorbents provided effective alternative to conventional extraction media providing unique physicochemical characteristics and excellent extraction capability.


Assuntos
Técnicas de Química Analítica/métodos , Neurotransmissores/isolamento & purificação , Zircônio/química , Catecolaminas/isolamento & purificação , Técnicas de Química Analítica/instrumentação , Géis/química , Reprodutibilidade dos Testes , Dióxido de Silício/química
13.
Surg Endosc ; 30(12): 5419-5427, 2016 12.
Artigo em Inglês | MEDLINE | ID: mdl-27105617

RESUMO

BACKGROUND: Post-operative diaphragmatic hernias (PODHs) are serious complications following esophagectomy or total gastrectomy. The aim of this study was to describe and compare the incidence of PODHs at a high volume center over time and analyze the outcomes of patients who develop a PODH. METHODS: A prospective database of all resectional esophagogastric operations performed for cancer between January 2001 and December 2015 was analyzed. Patients diagnosed with PODH were identified and data extracted regarding demographics, details of initial resection, pathology, PODH symptoms, diagnosis and treatment. RESULTS: Out of 631 patients who had hiatal dissection for malignancy, 35 patients developed of PODH (5.5 % overall incidence). Median age was 66 (range 23-87) years. The incidence of PODH in each operation type was: 2 % (4/221) following an open 2 or 3 stage esophagectomy, 10 % (22/212) following laparoscopic hybrid esophagectomy, 7 % (5/73) following MIO, and 3 % (4/125) following total gastrectomy. The majority of patients had colon or small bowel in a left-sided hernia. Of the 35 patients who developed a PODH, 20 (57 %) patients required emergency surgery, whereas 15 (43 %) had non-urgent repair. The majority of the patients had had suture repair (n = 24) or mesh repair (n = 7) of the diaphragmatic defect. Four patients were treated non-operatively. In hospital post-operative mortality was 20 % (4/20) in the emergency group and 0 % (0/15) in the elective group. Further hernia recurrence affected seven patients (n = 7/27, 26 %) and 4 of these patients (15 %) presented with multiple recurrences. CONCLUSION: PODH is a common complication following hybrid esophagectomy and MIO. Given the high mortality from emergency repair, careful thought is needed to identify surgical techniques to prevent PODH forming when minimal access esophagectomy are performed. Upper GI surgeons need to have a low index of suspicion to investigate and treat patients for this complication.


Assuntos
Esofagectomia , Gastrectomia , Hérnia Diafragmática/etiologia , Procedimentos Cirúrgicos Minimamente Invasivos , Complicações Pós-Operatórias , Adulto , Idoso , Idoso de 80 Anos ou mais , Esofagectomia/métodos , Feminino , Gastrectomia/métodos , Hérnia Diafragmática/epidemiologia , Humanos , Incidência , Laparoscopia , Masculino , Pessoa de Meia-Idade , Complicações Pós-Operatórias/diagnóstico , Complicações Pós-Operatórias/epidemiologia , Estudos Retrospectivos
14.
Ann Surg ; 264(6): 982-986, 2016 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-26756751

RESUMO

OBJECTIVE: To determine if underreporting of secondary endpoints in randomized controlled trials occurs, using surgical site infection (SSI) as an example. BACKGROUND: SSI is a commonly measured endpoint in surgical trials and can act as a proxy marker for primary and secondary endpoint assessments across trials in a range of medical specialties. METHODS: Cross-sectional observational study of randomized trials including patients undergoing gastrointestinal surgery published in a representative selection of general medical and general surgical journals. Studies were included if SSI assessment was a prespecified endpoint. Adjusted binary logistic regression was used to identify factors associated with a high rate of SSI detection (≥10%). RESULTS: From 216 trials including 45,633 patients, the pooled SSI rate was 7.7% (3519/45,633), which was significantly higher when assessed as a primary endpoint (12.6%, 1993/15,861, 49 studies) vs as a secondary endpoint (5.1%, 1526/29,772, 167 studies, P < 0.001). When assessed as a secondary outcome, standardized definitions and formal clinical reviews were used significantly less often. When adjusted for surgical contamination and methodological confounders, secondary assessment was associated with reduced SSI detection compared with primary assessment (adjusted odds ratio 0.24, 95% confidence interval 0.08-0.69, P = 0.008). CONCLUSIONS: Secondary endpoint assessment of SSI in randomized trials was associated with significantly reduced rigor and subsequent detection rates compared with assessment as a primary endpoint. Trial investigators should ensure that primary and secondary endpoint assessments are equally robust. PRISMA guidelines should be updated to promote the conduct of meta-analysis based only on primary outcomes from randomized controlled trials.


Assuntos
Procedimentos Cirúrgicos do Sistema Digestório , Determinação de Ponto Final , Ensaios Clínicos Controlados Aleatórios como Assunto , Infecção da Ferida Cirúrgica/epidemiologia , Estudos Transversais , Humanos
15.
Dalton Trans ; 41(26): 8135-43, 2012 Jul 14.
Artigo em Inglês | MEDLINE | ID: mdl-22495289

RESUMO

The complex ((i)Pr(3)P)Ni(η(2)-Bu(3)SnCH=CH(2))(2) (1a) was characterized by NMR spectroscopy and was identified as the active species for catalytic C-H bond stannylation of partially fluorinated aromatics, for example in the reaction between pentafluorobenzene and Bu(3)SnCH=CH(2), which generates C(6)F(5)SnBu(3) and ethylene. The crystalline complex ((i)Pr(3)P)Ni(η(2)-Ph(3)SnCH=CH(2))(2) (1b) provides a more easily handled analogue, and is also capable of catalytic stannylation with added Ph(3)SnCH=CH(2) and C(6)F(5)H. Mechanistic studies on 1b show that the catalytically active species remains mononuclear. The rate of catalytic stannylation is proportional to [C(6)F(5)H] and inversely proportional to [Ph(3)SnCH=CH(2)]. This is consistent with a mechanism where reversible Ph(3)SnCH=CH(2) dissociation provides ((i)Pr(3)P)Ni(η(2)-Ph(3)SnCH=CH(2)), followed by a rate-determining reaction with C(6)F(5)H to generate the stannylation products. Kinetic competition reactions between the fluorinated aromatics pentafluorobenzene, 1,2,4,5-tetrafluorobenzene, 1,2,3,5-tetrafluorobenzene, 1,2,4-trifluorobenzene, 1,3,5-trifluorobenzene and 1,3-difluorobenzene all suggest significant Ni-aryl bond formation in the rate-determining step under catalytic conditions. Labelling studies are consistent with an insertion of the hydrogen of the arene into the vinyl group, followed by ß-elimination or ß-abstraction of the SnPh(3) moiety.

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