152 research outputs found

    3D printed catalytic reactors for aerobic selective oxidation of benzyl alcohol into benzaldehyde in continuous multiphase flow

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    In this work, novel, patterned monolithic reactors were devised to explore more efficient routes for reactant conversion in order to investigate their potential to replace the packed bed and batch reactors conventionally employed in chemical industries. Well-defined bimetallic formulations were developed to substitute platinum group metals and critical raw materials such as palladium and cobalt, at least in part, by less active, but more sustainable and cost-effective metals such as earth-abundant iron. FePd and FeCo based monoliths were 3D printed and stacked in a continuous flow tubular reactor for testing the selective oxidation of benzyl alcohol (BA) into benzaldehyde (BZ) under mild conditions (80–100 °C and atmospheric pressure). The novel monolithic reactors were evaluated against current state-of-the-art reactor technologies, conventional packed bed and batch reactors. The FeCo- and FePd-Al2O3-supported monolithic catalyst beds showed higher conversion and TOF than their packed bed counterparts under the same operating conditions, revealing the impact of the novel design on both regular geometry and composition. What is of particular interest in the catalytic measurements shown is that the combined stacking of two monoliths in a flow reactor, Al2O3-supported Fe and GO-supported FePd catalysts, can significantly improve the performance with an increase in TOF of up to 90% in comparison to their FePd analogues. Mathematical modelling was used to obtain additional insights into the physical and chemical processes governing the rate of BA conversion. It was found that due to the flow regime inside the microchannels, an axial dispersion model was appropriate, which allowed for mapping the concentration profiles of the reactants and products within the respective monolith geometries

    3D printed catalytic reactors for aerobic selective oxidation of benzyl alcohol into benzaldehyde in continuous multiphase flow

    Get PDF
    In this work, novel, patterned monolithic reactors were devised to explore more efficient routes for reactant conversion in order to investigate their potential to replace the packed bed and batch reactors conventionally employed in chemical industries. Well-defined bimetallic formulations were developed to substitute platinum group metals and critical raw materials such as palladium and cobalt, at least in part, by less active, but more sustainable and cost-effective metals such as earth-abundant iron. FePd and FeCo based monoliths were 3D printed and stacked in a continuous flow tubular reactor for testing the selective oxidation of benzyl alcohol (BA) into benzaldehyde (BZ) under mild conditions (80–100 °C and atmospheric pressure). The novel monolithic reactors were evaluated against current state-of-the-art reactor technologies, conventional packed bed and batch reactors. The FeCo- and FePd-Al2O3-supported monolithic catalyst beds showed higher conversion and TOF than their packed bed counterparts under the same operating conditions, revealing the impact of the novel design on both regular geometry and composition. What is of particular interest in the catalytic measurements shown is that the combined stacking of two monoliths in a flow reactor, Al2O3-supported Fe and GO-supported FePd catalysts, can significantly improve the performance with an increase in TOF of up to 90% in comparison to their FePd analogues. Mathematical modelling was used to obtain additional insights into the physical and chemical processes governing the rate of BA conversion. It was found that due to the flow regime inside the microchannels, an axial dispersion model was appropriate, which allowed for mapping the concentration profiles of the reactants and products within the respective monolith geometries

    A reference relative time-scale as an alternative to chronological age for cohorts with long follow-up

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    Background: Epidemiologists have debated the appropriate time-scale for cohort survival studies; chronological age or time-on-study being two such time-scales. Importantly, assessment of risk factors may depend on the choice of time-scale. Recently, chronological or attained age has gained support but a case can be made for a ‘reference relative time-scale’ as an alternative which circumvents difficulties that arise with this and other scales. The reference relative time of an individual participant is the integral of a reference population hazard function between time of entry and time of exit of the individual. The objective here is to describe the reference relative time-scale, illustrate its use, make comparison with attained age by simulation and explain its relationship to modern and traditional epidemiologic methods. Results: A comparison was made between two models; a stratified Cox model with age as the time-scale versus an un-stratified Cox model using the reference relative time-scale. The illustrative comparison used a UK cohort of cotton workers, with differing ages at entry to the study, with accrual over a time period and with long follow-up. Additionally, exponential and Weibull models were fitted since the reference relative time-scale analysis need not be restricted to the Cox model. A simulation study showed that analysis using the reference relative time-scale and analysis using chronological age had very similar power to detect a significant risk factor and both were equally unbiased. Further, the analysis using the reference relative time-scale supported fully-parametric survival modelling and allowed percentile predictions and mortality curves to be constructed. Conclusions: The reference relative time-scale was a viable alternative to chronological age, led to simplification of the modelling process and possessed the defined features of a good time-scale as defined in reliability theory. The reference relative time-scale has several interpretations and provides a unifying concept that links contemporary approaches in survival and reliability analysis to the traditional epidemiologic methods of Poisson regression and standardised mortality ratios. The community of practitioners has not previously made this connection

    Light smoking at base-line predicts a higher mortality risk to women than to men; evidence from a cohort with long follow-up

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    BACKGROUND: There is conflicting evidence as to whether smoking is more harmful to women than to men. The UK Cotton Workers’ Cohort was recruited in the 1960s and contained a high proportion of men and women smokers who were well matched in terms of age, job and length of time in job. The cohort has been followed up for 42 years. METHODS: Mortality in the cohort was analysed using an individual relative survival method and Cox regression. Whether smoking, ascertained at baseline in the 1960s, was more hazardous to women than to men was examined by estimating the relative risk ratio women to men, smokers to never smoked, for light (1–14), medium (15–24), heavy (25+ cigarettes per day) and former smoking. RESULTS: For all-cause mortality relative risk ratios were 1.35 for light smoking at baseline (95% CI 1.07-1.70), 1.15 for medium smoking (95% CI 0.89-1.49) and 1.00 for heavy smoking (95% CI 0.63-1.61). Relative risk ratios for light smoking at baseline for circulatory system disease was 1.42 (95% CI 1.01 to 1.98) and for respiratory disease was 1.89 (95% CI 0.99 to 3.63). Heights of participants provided no explanation for the gender difference. CONCLUSIONS: Light smoking at baseline was shown to be significantly more hazardous to women than to men but the effect decreased as consumption increased indicating a dose response relationship. Heavy smoking was equally hazardous to both genders. This result may help explain the conflicting evidence seen elsewhere. However gender differences in smoking cessation may provide an alternative explanation

    Deriving stage at diagnosis from multiple population-based sources: colorectal and lung cancer in England.

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    BACKGROUND: Stage at diagnosis is a strong predictor of cancer survival. Differences in stage distributions and stage-specific management help explain geographic differences in cancer outcomes. Stage information is thus essential to improve policies for cancer control. Despite recent progress, stage information is often incomplete. Data collection methods and definition of stage categories are rarely reported. These inconsistencies may result in assigning conflicting stage for single tumours and confound the interpretation of international comparisons and temporal trends of stage-specific cancer outcomes. We propose an algorithm that uses multiple routine, population-based data sources to obtain the most complete and reliable stage information possible. METHODS: Our hierarchical approach derives a single stage category per tumour prioritising information deemed of best quality from multiple data sets and various individual components of tumour stage. It incorporates rules from the Union for International Cancer Control TNM classification of malignant tumours. The algorithm is illustrated for colorectal and lung cancer in England. We linked the cancer-specific Clinical Audit data (collected from clinical multi-disciplinary teams) to national cancer registry data. We prioritise stage variables from the Clinical Audit and added information from the registry when needed. We compared stage distribution and stage-specific net survival using two sets of definitions of summary stage with contrasting levels of assumptions for dealing with missing individual TNM components. This exercise extends a previous algorithm we developed for international comparisons of stage-specific survival. RESULTS: Between 2008 and 2012, 163 915 primary colorectal cancer cases and 168 158 primary lung cancer cases were diagnosed in adults in England. Using the most restrictive definition of summary stage (valid information on all individual TNM components), colorectal cancer stage completeness was 56.6% (from 33.8% in 2008 to 85.2% in 2012). Lung cancer stage completeness was 76.6% (from 57.3% in 2008 to 91.4% in 2012). Stage distribution differed between strategies to define summary stage. Stage-specific survival was consistent with published reports. CONCLUSIONS: We offer a robust strategy to harmonise the derivation of stage that can be adapted for other cancers and data sources in different countries. The general approach of prioritising good-quality information, reporting sources of individual TNM variables, and reporting of assumptions for dealing with missing data is applicable to any population-based cancer research using stage. Moreover, our research highlights the need for further transparency in the way stage categories are defined and reported, acknowledging the limitations, and potential discrepancies of using readily available stage variables

    Inflammatory myofibroblastic tumor of epididymis: a case report and review of literature

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    Background Epididymal inflammatory myofibroblastic tumor, also known by various other synonyms is a rare benign disease. Only eight cases have been reported to date. The most common presentation is a scrotal mass of variable duration. For a scrotal mass it is difficult to distinguish a benign or malignant etiology, in addition to the origin whether from testis or epididymis. As a result the definitive diagnosis can only be established by surgical exploration. Case presentation We report the ninth case of epididymal IMT who based on clinical and radiological findings underwent radical orchidectomy, with the histology suggestive of inflammatory myofibroblastic tumor. At 4 years follow up the patient is free of disease recurrence. Conclusion IMT though rare should be considered in the differential diagnosis of epididymal mass. Clinically it is often difficult to distinguish the origin of mass and even though the disease has benign nature and course it is crucial to counsel patients for orchidectomy as definitive diagnosis is established on surgical exploration

    Are all prognostic factors in parotid gland carcinoma well recognized?

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    The aim of his study was to assess the treatment results and prognostic factors in patients with parotid gland carcinoma. The material consisted of 109 patients treated surgically, with or without complementary radiotherapy, between 1978 and 2008 (follow-up at least 5-years). 5-year overall and disease-specific survival were observed in 57.0% of the patients and 5-year disease-free survival was achieved in 50.0%. Univariate analysis including ten clinical and pathological features to assess their prognostic value was done. Parapharyngeal space invasion, facial nerve palsy, and high grade of tumor malignancy were the factors with the highest influence on the treatment results, because their presence decreased the chance for recovery 9.8, 9.7, and 8.2 times, respectively. Histologically positive cervical lymph nodes and extraparenchymal extension were the other factors connected with poor prognosis (prognosis worse 6.7 and 5.4 times, respectively). Clinically positive cervical lymph nodes, positive/uncertain microscopic margin, involvement of the deep lobe, or the whole gland increased the risk of treatment failure 3.4, 3.1, and 2.8, respectively. The age ≥60 years and male gender were statistically significant factors, correlated with poor prognosis and decreased chance for recovery 2.4 and 2.6 times. T-status and clinical stage had important influence on 5-year disease-free survival rate because there were significant differences in the treatment results between individual stages. Multivariate analysis proved that the independent prognostic value, among anatomic structures involved by the neoplasm, had mandible, facial nerve, and skin infiltration. Among tumor-related factors, T-stage and grade had the statistically significant influence on treatment results, and stage and lymph nodes metastases among clinical and pathological features. These results confirm the value of actually used TNM classification (2002). Although the parapharyngeal space invasion is a factor, which seems to have a significant, poor prognostic value, it was not included in this classification
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