374 research outputs found

    Temperature Dependence Study of the Kinetics and Product Yields of the HO_2 + CH_3C(O)O_2 Reaction by Direct Detection of OH and HO_2 Radicals Using 2f-IR Wavelength Modulation Spectroscopy

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    The HO_2 + CH_3C(O)O_2 reaction consists of three product channels: CH_3C(O)OOH + O_2 (R1a), CH_3C(O)OH + O_3 (R1b), and OH + CH_3C(O)O + O_2 (R1c). The overall rate constant (k_1) and product yields (α_(1a), α_(1b), and α_(1c)) were determined over the atmospherically-relevant temperature range of 230 - 294 K at 100 Torr in N_2. Time resolved kinetics measurements were performed in a pulsed laser photolysis experiment in a slow flow cell employing simultaneous infrared (IR) and ultraviolet (UV) absorption spectroscopy. HO_2 and CH_3C(O)O_2 were formed by Cl-atom reactions with CH_3OH and CH_3CHO, respectively. Heterodyne near- and mid-infrared (NIR and MIR) wavelength modulation spectroscopy (WMS) was employed to selectively detect HO_2 and OH radicals. Ultraviolet absorption at 225 nm and 250 nm was used to detect various peroxy radicals as well as ozone (O_3). These experimental techniques enabled direct measurements of α_(1c) and α_(1b) via time-resolved spectroscopic detection in the MIR and the UV, respectively. At each temperature, experiments were performed at various ratios of initial HO_2 and CH_3C(O)O_2 concentrations to quantify the secondary chemistry. The Arrhenius expression was found to be k1(T) = 1.38^(+1.17)_(-0.63)×10^(-12)exp[(730±170)/T] cm^(-3) molecule^(-1) s^(-1). Α_(1a) was temperature-independent while α_(1b) and α_(1c) increased and decreased, respectively, with increasing temperatures. These trends are consistent with the current recommendation by the IUPAC data evaluation. Hydrogen-bonded adducts of HO_2 with the precursors, HO_2.CH_3OH and HO_2.CH_3CHO, played a role at lower temperatures; as part of this work, kinetics of the adducts were also measured

    Temperature Dependence Study of the Kinetics and Product Yields of the HO_2 + CH_3C(O)O_2 Reaction by Direct Detection of OH and HO_2 Radicals Using 2f-IR Wavelength Modulation Spectroscopy

    Get PDF
    The HO_2 + CH_3C(O)O_2 reaction consists of three product channels: CH_3C(O)OOH + O_2 (R1a), CH_3C(O)OH + O_3 (R1b), and OH + CH_3C(O)O + O_2 (R1c). The overall rate constant (k_1) and product yields (α_(1a), α_(1b), and α_(1c)) were determined over the atmospherically-relevant temperature range of 230 - 294 K at 100 Torr in N_2. Time resolved kinetics measurements were performed in a pulsed laser photolysis experiment in a slow flow cell employing simultaneous infrared (IR) and ultraviolet (UV) absorption spectroscopy. HO_2 and CH_3C(O)O_2 were formed by Cl-atom reactions with CH_3OH and CH_3CHO, respectively. Heterodyne near- and mid-infrared (NIR and MIR) wavelength modulation spectroscopy (WMS) was employed to selectively detect HO_2 and OH radicals. Ultraviolet absorption at 225 nm and 250 nm was used to detect various peroxy radicals as well as ozone (O_3). These experimental techniques enabled direct measurements of α_(1c) and α_(1b) via time-resolved spectroscopic detection in the MIR and the UV, respectively. At each temperature, experiments were performed at various ratios of initial HO_2 and CH_3C(O)O_2 concentrations to quantify the secondary chemistry. The Arrhenius expression was found to be k1(T) = 1.38^(+1.17)_(-0.63)×10^(-12)exp[(730±170)/T] cm^(-3) molecule^(-1) s^(-1). Α_(1a) was temperature-independent while α_(1b) and α_(1c) increased and decreased, respectively, with increasing temperatures. These trends are consistent with the current recommendation by the IUPAC data evaluation. Hydrogen-bonded adducts of HO_2 with the precursors, HO_2.CH_3OH and HO_2.CH_3CHO, played a role at lower temperatures; as part of this work, kinetics of the adducts were also measured

    Hierarchical Graph Transformation

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    If systems are specified by graph transformation, large graphs should be structured in order to be comprehensible. In this paper, we present an approach for the rule-based transformation of hierarchically structured (hyper)graphs. In these graphs, distinguished hyperedges contain graphs that can be hierarchical again. Our framework extends the well-known double-pushout approach from at to hierarchical graphs. In particular, we show how pushouts and pushout complements of hierarchical graphs and graph morphisms can be constructed recursively. Moreover, we make rules more expressive by introducing variables which allow to copy and to remove hierarchical subgraphs in a single rule application

    Concomitant Carcinoma in situ in Cystectomy Specimens Is Not Associated with Clinical Outcomes after Surgery

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    Objective: The aim of this study was to externally validate the prognostic value of concomitant urothelial carcinoma in situ (CIS) in radical cystectomy (RC) specimens using a large international cohort of bladder cancer patients. Methods: The records of 3,973 patients treated with RC and bilateral lymphadenectomy for urothelial carcinoma of the bladder (UCB) at nine centers worldwide were reviewed. Surgical specimens were evaluated by a genitourinary pathologist at each center. Uni- and multivariable Cox regression models addressed time to recurrence and cancer-specific mortality after RC. Results: 1,741 (43.8%) patients had concomitant CIS in their RC specimens. Concomitant CIS was more common in organ-confined UCB and was associated with lymphovascular invasion (p < 0.001). Concomitant CIS was not associated with either disease recurrence or cancer-specific death regardless of pathologic stage. The presence of concomitant CIS did not improve the predictive accuracy of standard predictors for either disease recurrence or cancer-specific death in any of the subgroups. Conclusions: We could not confirm the prognostic value of concomitant CIS in RC specimens. This, together with the discrepancy between pathologists in determining the presence of concomitant CIS at the morphologic level, limits the clinical utility of concomitant CIS in RC specimens for clinical decision-making. Copyright (C) 2011 S. Karger AG, Base

    School Absenteeism As an Adjunct Surveillance Indicator: Experience during the Second Wave of the 2009 H1N1 Pandemic in Quebec, Canada

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    A school absenteeism surveillance system was implemented in the province of Quebec, Canada during the second wave of the 2009 H1N1 pandemic. This paper compares this surveillance approach with other available indicators.All (3432) elementary and high schools from Quebec were included. Each school was required to report through a web-based system any day where the proportion of students absent for influenza-like illness (ILI) exceeded 10% of current school enrolment.Between October 18 and December 12 2009, 35.6% of all schools met the 10% absenteeism threshold. This proportion was greater in elementary compared to high schools (40% vs 19%) and in smaller compared to larger schools (44% vs 22%). The maximum absenteeism rate was reached the first day of reporting or within the next two days in 55% and 31% of schools respectively. The first reports and subsequent peak in school absenteeism provincially preceded the peak in paediatric hospitalization by two and one weeks, respectively. Trends in school surveillance otherwise mirrored other indicators.During a pandemic, school outbreak surveillance based on a 10% threshold appears insufficient to trigger timely intervention within a given affected school. However, school surveillance appears well-correlated and slightly anticipatory compared to other population indicators. As such, school absenteeism warrants further evaluation as an adjunct surveillance indicator whose overall utility will depend upon specified objectives, and other existing capacity for monitoring and response

    Tumour-derived alkaline phosphatase regulates tumour growth, epithelial plasticity and disease-free survival in metastatic prostate cancer

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    BACKGROUND: Recent evidence suggests that bone-related parameters are the main prognostic factors for overall survival in advanced prostate cancer (PCa), with elevated circulating levels of alkaline phosphatase (ALP) thought to reflect the dysregulated bone formation accompanying distant metastases. We have identified that PCa cells express ALPL, the gene that encodes for tissue nonspecific ALP, and hypothesised that tumour-derived ALPL may contribute to disease progression. METHODS: Functional effects of ALPL inhibition were investigated in metastatic PCa cell lines. ALPL gene expression was analysed from published PCa data sets, and correlated with disease-free survival and metastasis. RESULTS: ALPL expression was increased in PCa cells from metastatic sites. A reduction in tumour-derived ALPL expression or ALP activity increased cell death, mesenchymal-to-epithelial transition and reduced migration. Alkaline phosphatase activity was decreased by the EMT repressor Snail. In men with PCa, tumour-derived ALPL correlated with EMT markers, and high ALPL expression was associated with a significant reduction in disease-free survival. CONCLUSIONS: Our studies reveal the function of tumour-derived ALPL in regulating cell death and epithelial plasticity, and demonstrate a strong association between ALPL expression in PCa cells and metastasis or disease-free survival, thus identifying tumour-derived ALPL as a major contributor to the pathogenesis of PCa progression.British Journal of Cancer advance online publication, 22 December 2016; doi:10.1038/bjc.2016.402 www.bjcancer.com

    MaDe4IC: an abstract method for managing model dependencies in inter-organizational cooperations

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    Inter-organizational cooperations are complex in terms of coordination, agreements, and value creation for involved partners. When managing complex cooperations, it is vital to maintain models describing them. Changing one model to regain consistency with the running system might result in new inconsistencies. As a consequence, this maintenance phase grows in complexity with increasing number of models. In this context, challenges are to ensure consistency at design time and to monitor the system at runtime, i.e., at design time, consistency between different models describing the cooperation needs to be ensured. At runtime, behavior of the software system needs to be compared with its underlying models. In this paper, we propose a structured and model-independent method that supports ensuring and maintaining consistency between running system and underlying models for inter-organizational cooperations

    Canonical Graph Shapes

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    Abstract. Graphs are an intuitive model for states of a (software) system that include pointer structures — for instance, object-oriented programs. However, a naive encoding results in large individual states and large, or even unbounded, state spaces. As usual, some form of abstraction is necessary in order to arrive at a tractable model. In this paper we propose a decidable fragment of first-order graph logic that we call local shape logic (LSL) as a possible abstraction mechanism, inspired by previous work of Sagiv, Reps and Wilhelm. An LSL formula constrains the multiplicities of nodes and edges in state graphs; abstraction is achieved by reasoning not about individual, concrete state graphs but about their characteristic shape properties. We go on to define the concept of the canonical shape of a state graph, which is expressed in a monomorphic sub-fragment of LSL, for which we define a graphical representation. We show that the canonical shapes give rise to an automatic finite abstraction of the state space of a software system, and we give an upper bound to the size of this abstract state space

    Coordination and resource-related difficulties encountered by Quebec's public health specialists and infectious diseases/medical microbiologists in the management of A (H1N1) - a mixed-method, exploratory survey

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    <p>Abstract</p> <p>Background</p> <p>In Quebec, the influenza A (H1N1) pandemic was managed using a top-down style that left many involved players with critical views and frustrations. We aimed to describe physicians' perceptions - infectious diseases specialists/medical microbiologists (IDMM) and public health/preventive medicine specialists (PHPMS) - in regards to issues encountered with the pandemics management at the physician level and highlight suggested improvements for future healthcare emergencies.</p> <p>Methods</p> <p>In April 2010, Quebec IDMM and PHPMS physicians were invited to anonymously complete a web-based learning needs assessment. The survey included both open-ended and multiple-choice questions. Descriptive statistics were used to report on the frequency distribution of multiple choice responses whereas thematic content analysis was used to analyse qualitative data generated from the survey and help understand respondents' experience and perceptions with the pandemics.</p> <p>Results</p> <p>Of the 102 respondents, 85.3% reported difficulties or frustrations in their practice during the pandemic. The thematic analysis revealed two core themes describing the problems experienced in the pandemic management: coordination and resource-related difficulties. Coordination issues included communication, clinical practice guidelines, decision-making, roles and responsibilities, epidemiological investigation, and public health expert advisory committees. Resources issues included laboratory resources, patient management, and vaccination process.</p> <p>Conclusion</p> <p>Together, the quantitative and qualitative data suggest a need for improved coordination, a better definition of roles and responsibilities, increased use of information technologies, merged communications, and transparency in the decisional process. Increased flexibility and less contradiction in clinical practice guidelines from different sources and increased laboratory/clinical capacity were felt critical to the proper management of infectious disease emergencies.</p
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