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5.
Inorg Chem ; 57(6): 3387-3398, 2018 Mar 19.
Artigo em Inglês | MEDLINE | ID: mdl-29517228

RESUMO

A series of representative late d-block metal complexes bearing a rigid bis(phosphine) ligand, iPr2P-Ace-PPh2 (L, Ace = acenaphthene-5,6-diyl), was prepared and fully characterized by various techniques, including multinuclear NMR and single-crystal X-ray diffraction. The heteroleptic nature of the peri-substituted ligand L allows for the direct observation of the JPP couplings in the 31P{1H} NMR spectra. Magnitudes of JPP are correlated with the identity and geometry of the metal and the distortions of the ligand L. The forced overlap of the phosphine lone pairs due to the constraints imposed by the rigid acenaphthene skeleton in L results in a large 4 JPP of 180 Hz. Sequestration of the lone pairs, either via oxidation of the phosphine or via metal chelation, results in distinct changes in the magnitude of JPP. For tetrahedral d10 complexes ([LMCl2], M = Zn, Cd, Hg), the JPP is comparable to or larger than (193-309 Hz) that in free ligand L, although the P···P separation in these complexes is increased by ca. 0.4 Å (compare to free ligand L). The magnitude of JPP diminishes to 26-117 Hz in square planar d8 complexes ([LMX2], M = Ni, Pd, Pt; X = Cl, Br) and the octahedral Mo0 complex ([LMo(CO)4], 33 Hz). Coupling deformation density calculations indicate the through-space interaction dominates in free L, while in metal complexes the main coupling pathway is via the metal atom.

6.
BMJ Open ; 8(2): e018618, 2018 02 22.
Artigo em Inglês | MEDLINE | ID: mdl-29472259

RESUMO

INTRODUCTION: Acute colorectal surgery forms a significant proportion of emergency admissions within the National Health Service. There is limited evidence to suggest minimally invasive surgery may be associated with improved clinical outcomes in this cohort of patients. Consequently, there is a need to assess the clinical effectiveness and cost-effectiveness of laparoscopic surgery in the acute colorectal setting. However,emergency colorectal surgical trials have previously been difficult to conduct due to issues surrounding recruitment and equipoise. The LaCeS (randomised controlled trial of Laparoscopic versus open Colorectal Surgery in the acute setting) feasibility trial will determine the feasibility of conducting a definitive, phase III trial of laparoscopic versus open acute colorectal resection. METHODS AND ANALYSIS: The LaCeS feasibility trial is a prospective, multicentre, single-blinded, parallel group, pragmatic randomised controlled feasibility trial. Patients will be randomised on a 1:1 basis to receive eitherlaparoscopic or open surgery. The trial aims to recruit at least 66 patients from five acute general surgical units across the UK. Patients over the age of 18 with a diagnosis of acute colorectal pathology requiring resection on clinical and radiological/endoscopic investigations, with a National Confidential Enquiry into Patient Outcome and Death classification of urgent will be considered eligible for participation. The primary outcome is recruitment. Secondary outcomes include assessing the safety profile of laparoscopic surgery using intraoperative and postoperative complication rates, conversion rates and patient-safety indicators as surrogate markers. Clinical and patient-reported outcomes will also be reported. The trial will contain an embedded qualitative study to assess clinician and patient acceptability of trial processes. ETHICS AND DISSEMINATION: The LaCeS feasibility trial is approved by the Yorkshire and The Humber, Bradford Leeds Research Ethics Committee (REC reference: 15/ YH/0542). The results from the trial will be presented at national and international colorectal conferences and will be submitted for publication to peer-reviewed journals. TRIAL REGISTRATION NUMBER: ISRCTN15681041; Pre-results.


Assuntos
Cirurgia Colorretal/efeitos adversos , Cirurgia Colorretal/economia , Laparoscopia/efeitos adversos , Laparoscopia/economia , Complicações Pós-Operatórias/epidemiologia , Análise Custo-Benefício , Estudos de Viabilidade , Humanos , Complicações Pós-Operatórias/etiologia , Estudos Prospectivos , Qualidade de Vida , Projetos de Pesquisa , Método Simples-Cego , Resultado do Tratamento , Reino Unido
7.
Surg Endosc ; 31(7): 2959-2967, 2017 07.
Artigo em Inglês | MEDLINE | ID: mdl-27826775

RESUMO

BACKGROUND: Colonoscopy is currently the gold standard for detection of colorectal lesions, but may be limited in anatomically localising lesions. This audit aimed to determine the accuracy of colonoscopy lesion localisation, any subsequent changes in surgical management and any potentially influencing factors. METHODS: Patients undergoing colonoscopy prior to elective curative surgery for colorectal lesion/s were included from 8 registered U.K. sites (2012-2014). Three sets of data were recorded: patient factors (age, sex, BMI, screener vs. symptomatic, previous abdominal surgery); colonoscopy factors (caecal intubation, scope guide used, colonoscopist accreditation) and imaging modality. Lesion localisation was standardised with intra-operative location taken as the gold standard. Changes to surgical management were recorded. RESULTS: 364 cases were included; majority of lesions were colonic, solitary, malignant and in symptomatic referrals. 82% patients had their lesion/s correctly located at colonoscopy. Pre-operative CT visualised lesion/s in only 73% of cases with a reduction in screening patients (64 vs. 77%; p = 0.008). 5.2% incorrectly located cases at colonoscopy underwent altered surgical management, including conversion to open. Univariate analysis found colonoscopy accreditation, scope guide use, incomplete colonoscopy and previous abdominal surgery significantly influenced lesion localisation. On multi-variate analysis, caecal intubation and scope guide use remained significant (HR 0.35, 0.20-0.60 95% CI and 0.47; 0.25-0.88, respectively). CONCLUSION: Lesion localisation at colonoscopy is incorrect in 18% of cases leading to potentially significant surgical management alterations. As part of accreditation, colonoscopists need lesion localisation training and awareness of when inaccuracies can occur.


Assuntos
Benchmarking , Colonoscopia/normas , Neoplasias Colorretais/diagnóstico , Adulto , Idoso , Idoso de 80 Anos ou mais , Neoplasias Colorretais/diagnóstico por imagem , Neoplasias Colorretais/patologia , Feminino , Humanos , Masculino , Auditoria Médica , Pessoa de Meia-Idade , Medicina Estatal , Reino Unido/epidemiologia
8.
BMJ Open ; 6(9): e008810, 2016 09 06.
Artigo em Inglês | MEDLINE | ID: mdl-27601484

RESUMO

INTRODUCTION: Laparoscopic surgery combined with enhanced recovery programmes has become the gold standard in the elective management of colorectal disease. However, there is no consensus with regard to the optimal perioperative analgesic regime in this cohort of patients, with a number of options available, including thoracic epidural spinal analgesia, patient-controlled analgesia, subcutaneous and/or intraperitoneal local anaesthetics, local anaesthetic wound infiltration catheters and transversus abdominis plane blocks. This study aims to explore any differences in analgesic strategies employed across the North East of England and to assess whether any variation in practice has an impact on clinical outcomes. METHODS AND ANALYSIS: All North East Colorectal units will be recruited for participation by the Northern Surgical Trainees Research Association (NoSTRA). Data will be collected over a consecutive 2-month period. Outcome measures will include postoperative pain score, postoperative opioid analgesic use and side effects, length of stay, 30-day complication rates, 30-day reoperative rates and 30-day readmission rates. ETHICS AND DISSEMINATION: Ethical approval for this study has been granted by the National Research Ethics Service. The protocol will be disseminated through NoSTRA. Individual unit data will be presented at local meetings. Overall collective data will be published in peer-reviewed journals and presented at relevant surgical meetings.


Assuntos
Anestesia por Condução/métodos , Laparoscopia/efeitos adversos , Manejo da Dor/métodos , Assistência Perioperatória/métodos , Reoperação/estatística & dados numéricos , Adolescente , Adulto , Idoso , Analgésicos Opioides/uso terapêutico , Colo/cirurgia , Procedimentos Cirúrgicos Eletivos/efeitos adversos , Inglaterra , Feminino , Humanos , Laparoscopia/métodos , Tempo de Internação/estatística & dados numéricos , Masculino , Pessoa de Meia-Idade , Medição da Dor , Dor Pós-Operatória/etiologia , Readmissão do Paciente/estatística & dados numéricos , Estudos Prospectivos , Reto/cirurgia , Projetos de Pesquisa , Resultado do Tratamento , Adulto Jovem
9.
J Surg Oncol ; 111(4): 431-8, 2015 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-25557554

RESUMO

The standardization of surgical techniques supplemented with appropriate neoadjuvant chemoradiation has led to the decline in local recurrence rates of rectal cancer (LRRC) from 25-50% to 5-10%. The outcomes reported for surgical intervention in LRRC is encouraging, however, a number of controversies exist especially in the ultra-advanced and palliative setting. Incorporating health-related quality of life (HRQoL) outcomes in this field could supplement traditional clinical endpoints in assessing the effectiveness of surgical intervention in this cohort. This review aimed to identify the HRQOL themes that might be relevant to patients with LRRC. A systematic review was undertaken to identify all studies reporting HRQoL in LRRC. Each study was evaluated with regards to its design and statistical methodology. A meta-synthesis of qualitative and quantitative studies was undertaken to identify relevant HRQoL themes. A total of 14 studies were identified, with 501 patients, with 80% of patients undergoing surgery. HRQoL was the primary endpoint in eight studies. Eight themes were identified: physical, psychological and social impact, symptoms, financial and occupational impact, relationships with others, communication with healthcare professionals and sexual function. The impact on HRQoL is multifactorial and wide ranging, with a number of issues identified that are not included in current measures. These issues must be incorporated into the assessment of HRQoL in LRRC through the development of a validated, disease-specific tool.


Assuntos
Recidiva Local de Neoplasia/fisiopatologia , Recidiva Local de Neoplasia/psicologia , Qualidade de Vida , Neoplasias Retais/fisiopatologia , Neoplasias Retais/psicologia , Comunicação , Humanos , Relações Interpessoais , Debilidade Muscular/fisiopatologia , Dor/fisiopatologia , Relações Profissional-Paciente , Retorno ao Trabalho , Disfunções Sexuais Psicogênicas , Comportamento Social
10.
J Surg Case Rep ; 2012(1): 2, 2012 Jan 01.
Artigo em Inglês | MEDLINE | ID: mdl-24960717

RESUMO

Colorectal cancer is a common type of cancer in developed countries and is an important public health problem. Patients with colorectal cancer presents in a variety of ways in different settings. Most commonly, they present in the outpatient settings with changes in bowel habits, rectal bleeding and iron deficiency anaemia. This case reports an atypical presentation of colorectal cancer and how the cancer was diagnosed and treated.

12.
Appl Opt ; 42(30): 6006-15, 2003 Oct 20.
Artigo em Inglês | MEDLINE | ID: mdl-14594058

RESUMO

Novel implementations of single-fiber laser-induced breakdown spectroscopy and laser-induced fluorescence spectroscopy systems that gated light switches based on frustrated total internal reflection are described. The switching devices are largely wavelength independent, with full temporal and spatial separation of laser and fluorescence light. Wavelength-independent beam separation or beam combination schemes can be implemented for coaxial optical setups, e.g., in single-fiber or telescopic experimental arrangements. Selected practical examples of schemes for qualitative and quantitative analytical spectroscopy are discussed.

13.
Appl Opt ; 42(30): 6119-32, 2003 Oct 20.
Artigo em Inglês | MEDLINE | ID: mdl-14594074

RESUMO

The application of laser-induced breakdown spectroscopy to the analysis of single biological microparticles (bioaerosols) is described, exemplified here for a range of pollens. Spectra were recorded by exposure of the pollen to a single laser pulse from a Nd:YAG laser (lambda = 1064 nm, Ep approximately 30 mJ). The intensities of the single-pulse laser-induced breakdown spectra fluctuated dramatically, but an internal signal calibration procedure was applied that referenced elemental line intensities to the carbon matrix of the sample (represented by molecular bands of CN and C2). This procedure allowed us to determine relative element concentration distributions for the different types of pollen. These pollens exhibited some distinct concentration variations, for both major and minor (trace) elements in the biomatrix, through which ultimately individual pollens might be identified and classified. The same pollen samples were also analyzed by Raman microscopy, which provided molecular compositional data (even with spatial resolution). These data allowed us to distinguish between biological and nonbiological specimens and to obtain additional classification information for the various pollen families, complementing the laser-induced breakdown spectroscopy measurement data.


Assuntos
Aerossóis/análise , Aerossóis/química , Temperatura Alta , Lasers , Pólen/química , Pólen/classificação , Análise Espectral/métodos , Poluentes Atmosféricos/análise , Poluentes Atmosféricos/química , Monitoramento Ambiental/métodos , Estudos de Viabilidade , Helianthus/química , Lilium/química , Lilium/classificação , Microesferas , Tamanho da Partícula , Poaceae/química , Análise Espectral Raman/métodos
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