Oligomer formation during gas-phase ozonolysis of small alkenes and enol ethers: new evidence for the central role of the Criegee Intermediate as oligomer chain unit

An important fraction of secondary organic aerosol (SOA) formed by atmospheric oxidation of diverse volatile organic compounds (VOC) has recently been shown to consist of high-molecular weight oligomeric species. In our previous study (Sadezky et al., 2006), we reported the identification and characterization of oligomers as main constituents of SOA from gas-phase ozonolysis of small enol ethers. These oligomers contained repeated chain units of the same chemical composition as the main Criegee Intermediates (CI) formed during the ozonolysis reaction, which were CH<sub>2</sub>O<sub>2</sub> (mass 46) for alkyl vinyl ethers (AVE) and C<sub>2</sub>H<sub>4</sub>O<sub>2</sub> (mass 60) for ethyl propenyl ether (EPE). In the present work, we extend our previous study to another enol ether (ethyl butenyl ether EBE) and a variety of structurally related small alkenes (<i>trans</i>-3-hexene, <i>trans</i>-4-octene and 2,3-dimethyl-2-butene). <br><br> Experiments have been carried out in a 570 l spherical glass reactor at atmospheric conditions in the absence of seed aerosol. SOA formation was measured by a scanning mobility particle sizer (SMPS). SOA filter samples were collected and chemically characterized off-line by ESI(+)/TOF MS and ESI(+)/TOF MS/MS, and elemental compositions were determined by ESI(+)/FTICR MS and ESI(+)/FTICR MS/MS. The results for all investigated unsaturated compounds are in excellent agreement with the observations of our previous study. Analysis of the collected SOA filter samples reveal the presence of oligomeric compounds in the mass range 200 to 800 u as major constituents. The repeated chain units of these oligomers are shown to systematically have the same chemical composition as the respective main Criegee Intermediate (CI) formed during ozonolysis of the unsaturated compounds, which is C<sub>3</sub>H<sub>6</sub>O<sub>2</sub> (mass 74) for ethyl butenyl ether (EBE), <i>trans</i>-3-hexene, and 2,3-dimethyl-2-butene, and C<sub>4</sub>H<sub>8</sub>O<sub>2</sub> (mass 88) for extit{trans}-4-octene. Analogous fragmentation pathways among the oligomers formed by gas-phase ozonolysis of the different alkenes and enol ethers in our present and previous study, characterized by successive losses of the respective CI-like chain unit as a neutral fragment, indicate a similar principal structure. In this work, we confirm the basic structure of a linear oligoperoxide – [CH(R)-O-O]<sub>n</sub> – for all detected oligomers, with the repeated chain unit CH(R)OO corresponding to the respective major CI. The elemental compositions of parent ions, fragment ions and fragmented neutrals determined by accurate mass measurements with the FTICR technique allow us to assign a complete structure to the oligomer molecules. We suggest that the formation of the oligoperoxidic chain units occurs through a new gas-phase reaction mechanism observed for the first time in our present work, which involves the addition of stabilized CI to organic peroxy radicals. Furthermore, copolymerization of CI simultaneously formed in the gas phase from two different unsaturated compounds is shown to occur during the ozonolysis of a mixture of extit{trans}-3-hexene and ethyl vinyl ether (EVE), leading to formation of oligomers with mixed chain units C<sub>3</sub>H<sub>6</sub>O<sub>2</sub> (mass 74) and CH<sub>2</sub>O<sub>2</sub> (mass 46). We therefore suggest oligoperoxide formation by repeated peroxy radical-stabilized CI addition to be a general reaction pathway of small stabilized CI in the gas phase, which represents an alternative way to high-molecular products and thus contributes to SOA formation

La différence épidémiologique des hémorragies digestives hautes entre les hommes et les femmes

Introduction: Des différences épidémiologiques, étiologique voire pronostique des hémorragies digestives hautes (HDH) entre les deux sexes opposés ont été cité par différentes études. Méthodes: Nous avons essayé de déceler ces différences à travers une analyse rétrospective nichée sur une étude prospective sur les hémorragies digestives hautes ayant inclus 945 patients.Résultats: Six cents trente-sept patients étaient des hommes (67,4% Vs 32,6%). Un antécédent d’HDH était trouvé chez 24,2% des cas sans différence significative entre les deux sexes. L’âge de survenue de l’hémorragie était plus élevé chez les femmes que chez les hommes : 51,5 ans ± 18,8 Vs 47,8 ans ± 18,3 (p : 0,003). Les étiologies de l’HDH étaient différentes entre les deux sexes. Alors que l’hémorragie liée à l’HTP était la première cause chez la femme (38 % Vs 23,5 % chezl’homme, p<0,0001), c’est la pathologie ulcéreuse qui venait en premier chez l’homme (62 % Vs 36,7 % chez la femme, p <0,0001). Un besointransfusionnel était noté chez 42,4 % des patients de sexe masculin contre 35,4 % des patientes avec un p = 0,03. Le taux de récidive et de décès global étaient de 7,5 % et de 5,7 % des cas respectivement, sans différence significative entre les deux sexes.Conclusion: L’étude trouve un profil épidémiologique, clinique et étiologique différent selon le sexe des patients.Key words: Hémorragie digestive haute, épidémiologie, sexe masculin, sexe féminin, endoscopie, ulcère gastroduodénal, hypertension portal

Reactions of OH and Cl with isopropyl formate, isobutyl formate, n-propyl isobutyrate and isopropyl isobutyrate

International audienceThe rate coefficients for the reactions of OH with isopropyl formate, isobutyl formate, n-propyl isobutyrate and isopropyl isobutyrate have been determined using both absolute and relative methods. The relative rate method has been also used to measure the room temperature rate coefficient for the reaction of Cl with the same esters. In addition, a series of runs conducted on the OH-initiated oxidation of isopropyl formate, isobutyl formate and n-propyl isobutyrate showed the formation of acetone from the three reactions. The formation of propanal was also observed for n-propyl isobutyrate

Evaluated kinetic and photochemical data for atmospheric chemistry: Volume V – heterogeneous reactions on solid substrates

This article, the fifth in the ACP journal series, presents data evaluated by the IUPAC Subcommittee on Gas Kinetic Data Evaluation for Atmospheric Chemistry. It covers the heterogeneous processes on surfaces of solid particles present in the atmosphere, for which uptake coefficients and adsorption parameters have been presented on the IUPAC website in 2010. The article consists of an introduction and guide to the evaluation, giving a unifying framework for parameterisation of atmospheric heterogeneous processes. We provide summary sheets containing the recommended uptake parameters for the evaluated processes. Four substantial appendices contain detailed data sheets for each process considered for ice, mineral dust, sulfuric acid hydrate and nitric acid hydrate surfaces, which provide information upon which the recommendations are made

Complication rare de la coloscopie chez un patient sous anticoagulant: hemopéritoine par rupture d’un hématome sous capsulaire de la rate, cas clinique

La coloscopie à visée diagnostique et/ou thérapeutique est un examen invasif fréquemment pratiquée de nos jours. La perforation colique et l'hémorragie digestive en sont les principales complications. La survenue d'un  hémopéritoine par rupture d'un hématome sous-capsulaire splénique est une complication extrêmement rare et potentiellement mortelle de la coloscopie. Un traumatisme splénique minime passé inaperçu et la prised'anticoagulant en sont des facteurs favorisants. Nous présentons le cas d'une rupture d'un hématome sous-capsulaire de la rate après une coloscopie, survenue chez un patient de 70 ans porteur d'une valve mitrale mécanique sous acénocoumarol à dose hypocaogulante. La nécessité d'obtention d'une anti coagulation rapidement efficace et l'instabilité hémodynamique avaient justifiée la réalisation d'une splénectomie. L'évolution était favorable. A travers cette observation clinique nous discutons les mécanismes et les modalités de prise en charge devant cette complication

Time trends in social contacts before and during the COVID-19 pandemic: the CONNECT study

Background Since the beginning of the COVID-19 pandemic, many countries, including Canada, have adopted unprecedented physical distancing measures such as closure of schools and non-essential businesses, and restrictions on gatherings and household visits. We described time trends in social contacts for the pre-pandemic and pandemic periods in Quebec, Canada. Methods CONNECT is a population-based study of social contacts conducted shortly before (2018/2019) and during the COVID-19 pandemic (April 2020 – February 2021), using the same methodology for both periods. We recruited participants by random digit dialing and collected data by self-administered web-based questionnaires. Questionnaires documented socio-demographic characteristics and social contacts for two assigned days. A contact was defined as a two-way conversation at a distance ≤ 2 m or as a physical contact, irrespective of masking. We used weighted generalized linear models with a Poisson distribution and robust variance (taking possible overdispersion into account) to compare the mean number of social contacts over time and by socio-demographic characteristics. Results A total of 1291 and 5516 Quebecers completed the study before and during the pandemic, respectively. Contacts significantly decreased from a mean of 8 contacts/day prior to the pandemic to 3 contacts/day during the spring 2020 lockdown. Contacts remained lower than the pre-COVID period thereafter (lowest = 3 contacts/day during the Christmas 2020/2021 holidays, highest = 5 in September 2020). Contacts at work, during leisure activities/in other locations, and at home with visitors showed the greatest decreases since the beginning of the pandemic. All sociodemographic subgroups showed significant decreases of contacts since the beginning of the pandemic. The mixing matrices illustrated the impact of public health measures (e.g. school closure, gathering restrictions) with fewer contacts between children/teenagers and fewer contacts outside of the three main diagonals of contacts between same-age partners/siblings and between children and their parents. Conclusion Physical distancing measures in Quebec significantly decreased social contacts, which most likely mitigated the spread of COVID-19