Interactions of fluorophores with complex surfaces and spectroscopic examinations of ancient manuscripts

In the first part of this thesis, it was found by fibre-optic fluorescence spectroscopy, that the greening of fabrics washed in optical brighteners is due to a reabsorption effect. The quantum yield of fluorescence of the optical brighteners OB15, OB36 and OB49 in water are $0.11$, $0.08$ and $0.71$ respectively. Their respective fluorescence natural lifetimes are $6700\pm109$, $5971\pm712$ and $1685\pm22$ ps. In solution, the excited state of OB15 experiences more competing relaxation processes as the solvatochromic shift increases. OB49 displays the opposite trend. A literature cellulose model surface is employed as a cotton mimic for evanescent wave fluorescence studies. Two model greases are similarly developed and used, and a third is presented for future work. These are based on surface-specific reactions with glass substrates, and the doping of a regenerated cellulose film with long chain alcohols. On doped cellulose surfaces, some low quantum yields occur compared to clean cellulose and bulk solution. Photobleaching behaviours are also observed. Both dyes physisorb rigidly to cellulose and grease models. The second part of this thesis identifies the pigment palette of the earliest Northumbrian manuscripts pre- and post-1066, by Raman and diffuse reflectance spectroscopy. It develops a suite of multispectral imaging programs in MATLAB for facile classification of pigments across a page ab initio, using data reduction and colour spaces. Raman and reflectance data are meta-analysed using symmetric permutation to split manuscripts and pigments into groups ab initio. It was also generalised, that the palette of the pre-Hastings selected manuscripts contained vergaut, indigo, orpiment, impure red lead, and copper green pigments, as well as orcein purples. Immediately post-1066 white lead, red ochre, vermilion and lapis lazuli appear in the palette in England, though vergaut and indigo disappear and the red lead used is essentially pure

Proximal forearm fractures: epidemiology, functional results and predictors of outcome

Proximal forearm fractures account for over 10% of all upper limb fractures. There is limited epidemiological data available and much of the literature focuses on the more complex fracture patterns, with the role of non-operative management for the isolated proximal forearm fracture still to be defined. Prospective short and long-term patient reported outcome data for simple isolated fractures of the radial head and olecranon would help define the indications for the non-operative management of these injuries. This thesis aims to test the hypothesis that non-operative management provides a comparable outcome to operative intervention for defined fractures of the proximal forearm. A large prospective database of 6872 fractures collected over a one-year period was used to define the epidemiology of proximal forearm fractures. A separate large prospective study carried out over an eighteen-month period using a pre-defined management protocol for all isolated radial head and neck fractures was analysed to determine the short and long-term outcome. Additional retrospective databases were collected and analysed to determine the short and long-term outcome for the non-operative and operative management of olecranon fractures, as well as the operative management of complex radial head fractures. Finally, two prospective randomised controlled trials (PRCTs) of isolated displaced fractures of the olecranon were carried out to compare 1) tension band wire (TBW) versus plate fixation in younger patients (<75 years) and 2) operative versus non-operative management in elderly patients (≥75 years). The primary outcome measure for these studies was the upper limb specific patient reported Disabilities of the Arm, Shoulder and Hand (DASH) score. Secondary outcome measures included surgeon reported outcome scores, complication rates and cost. The incidence of proximal forearm fractures was 68 per 100,000. Radial head fractures fit a type D distribution curve (unimodal young man, bimodal woman) and radial neck type A (unimodal young man, unimodal older woman). Proximal ulna and olecranon fractures were both a type F (unimodal older man, unimodal older woman), with an increasing incidence after the 6th decade. Over 90% of proximal radial fractures were isolated stable fractures. Prospective analysis of 201 isolated proximal radius fractures found that the patient and surgeon reported outcome following primary non-operative management for Mason type 1 and type 2 (n=185) fractures was excellent in the short and long-term, with <2% of patients undergoing secondary surgical intervention. At a mean of 10 years post injury (n=100), the mean DASH score was 5.8 and 92% of patients were satisfied. Factors associated with a poorer short and long-term patient reported outcome included increasing fracture displacement (≥5mm) and socio-economic deprivation. Retrospective analysis of 105 acute unstable complex radial head fractures found that the mean short-term functional outcome was good (mean Broberg and Morrey Score 80) following radial head replacement. In the long-term (mean 7 years), 28% of patients required removal or revision of the prosthesis, with younger patients and silastic implants independent risk factors (both p<0.05). Retrospective analysis of 36 operatively managed isolated displaced olecranon fractures found satisfactory short and long-term outcomes, with the symptomatic metalwork removal rate 47% and the mean DASH 2.5 at a mean of seven years post injury. In the PRCT of plate (n=34) versus TBW (n=33) fixation, comparable functional and patient reported outcomes (DASH 8.5 vs 13.5; p=0.252) were found at one year following injury. Complication rates were significantly higher in the TBW group (63.3% vs 37.5%; p=0.042), predominantly due to a significantly higher rate of symptomatic metalwork removal (50.0% vs 21.9%; p=0.021), resulting in equivocal costs for both techniques (p=0.131). In older lower-demand patients, short and long-term retrospective analysis found very satisfactory outcomes following non-operative management of isolated displaced fractures of the olecranon, with patient satisfaction 91% and no patients requiring surgery for a symptomatic non-union. The preliminary results of the PRCT of non-operative (n=8) versus operative (n=11) management demonstrated comparable functional and patient reported outcomes at all points over the one-year following injury (all p≥0.05), with a higher rate of complications (81.8% vs 14.3%; p=0.013) and cost (p=0.01) following surgical intervention. The association found between fragility and the epidemiology of proximal forearm fractures highlighted the importance of considering non-operative management for these injuries. These findings support non-operative management for isolated stable radial head and neck fractures. For more complex injuries when radial head replacement is indicated, there is a high rate of removal or revision, with younger patients most at risk. In younger active patients with an isolated displaced fracture of the olecranon, TBW and plate fixation provide comparable short-term results, with TBW fixation as cost effective despite an increased rate of metalwork removal. In older lower demand patients, this data provides strong evidence for the non-operative management of isolated displaced olecranon fractures

The gatekeeper: individual differences are key in the chain from perception to behaviour

A basic assumption in mainstream social cognition is that the path from perception to behaviour is often automatic and direct, as supported for example by several experimental studies showing that priming can lead directly to a congruent behaviour without any need of conscious awareness of the process. However, we argue that the priming of a goal or an object activates individual differences in automatic evaluations at the associative level that in turn are the key predictors of action (gatekeeper model). A study (n = 90) on the American stereotype is presented to support the model. The results show that individual differences of the American stereotype as assessed with the IAT predicts a relevant action (essay evaluation) but only under condition of priming. Broader implications for predictive validity of implicit measures are also discussed

The Clinical Frailty Scale can be used retrospectively to assess the frailty of patients with hip fracture:a validation study

PURPOSE: Frailty is a common clinical syndrome affecting hip fracture patients. Recognising and accurately assessing frailty status is important in clinical and research settings. The Rockwood Clinical Frailty Scale (CFS) is a commonly used instrument and demonstrates a strong correlation with mortality and length of hospital admission following hip fracture. What is not understood, however, is the validity of retrospectively assigned CFS scores in hip fracture patients. The aim of this study was to assess the validity of retrospective non-orthogeriatrician assigned CFS scores in hip fracture patients. METHODS: Hip fracture patients from a single major trauma centre were assessed and CFS scores were assigned prospectively by non-orthogeriatric clinicians (n = 57). A subset of these patients were also assigned a prospective CFS score by a specialist orthogeriatrician (n = 27). Two separate blinded observers (non-orthogeriatric clinicians) assigned CFS scores retrospectively using electronic patient records alone. Agreement and precision was examined using the Bland–Altman plot, accuracy was assessed using R(2) statistic and inter-rater reliability was assessed using quadratic weighted Cohen’s kappa. RESULTS: Seventy percent of the cohort were female with an average age of 83. Agreement was high between prospective non-orthogeriatrician assigned CFS scores and retrospective non-orthogeriatrician assigned CFS scores, with a low bias (0.046) and good accuracy (R(2) = 73%). Good agreement was also seen in comparisons between prospective orthogeriatrician assigned CFS scores versus retrospective non-orthogeriatrician assigned scores, with a low bias (0.23) and good accuracy (R(2) = 78%). Good inter-rater reliability was seen between blinded observers with a quadratic weighted Cohen’s kappa of 0.76. CONCLUSIONS: Retrospective CFS scores assigned by non-orthogeriatricians are a valid means of assessing frailty status in hip fracture patients. However, our results suggest a tendency for non-orthogeriatricians to marginally overestimate frailty status when assigning CFS scores retrospectively. LEVEL OF EVIDENCE: 3