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1. Cybersecurity for Industrial Internet of Things: Architecture, Models and Lessons Learned

Author

George Bravos, Antonio J. Cabrera, Camilo Correa, Dragan Danilovic, Nikolaos Evangeliou, Gilad Ezov, Zoran Gajica, Dusan Jakovetic, Leonidas Kallipolitis, Milan Lukic, Julien Mascolo, Davide Masera, Raul Mazo, Ivan Mezei, Andreas Miaoudakis, Nemanja Milosevic, William Oliff, Jacques Robin, Michail Smyrlis, Georgia Sakellari, Giorgos Stamatis, Dusan Stamenkovic, Srdan Skrbic, Carine Souveyet, Spyridon Vantolas, Giorgos Vasiliadis, and Dejan Vukobratovic

Subjects
Anomaly detection, blockchain, cybersecurity, deep learning, Internet of Things, Electrical engineering. Electronics. Nuclear engineering, TK1-9971
Abstract

Modern industrial systems now, more than ever, require secure and efficient ways of communication. The trend of making connected, smart architectures is beginning to show in various fields of the industry such as manufacturing and logistics. The number of IoT (Internet of Things) devices used in such systems is naturally increasing and industry leaders want to define business processes which are reliable, reproducible, and can be effortlessly monitored. With the rise in number of connected industrial systems, the number of used IoT devices also grows and with that some challenges arise. Cybersecurity in these types of systems is crucial for their wide adoption. Without safety in communication and threat detection and prevention techniques, it can be very difficult to use smart, connected systems in the industry setting. In this paper we describe two real-world examples of such systems while focusing on our architectural choices and lessons learned. We demonstrate our vision for implementing a connected industrial system with secure data flow and threat detection and mitigation strategies on real-world data and IoT devices. While our system is not an off-the-shelf product, our architecture design and results show advantages of using technologies such as Deep Learning for threat detection and Blockchain enhanced communication in industrial IoT systems and how these technologies can be implemented. We demonstrate empirical results of various components of our system and also the performance of our system as-a-whole.

Published
2022
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4. Association of preoperative COVID-19 and postoperative respiratory morbidity during the Omicron epidemic wave: the DROMIS-22 multicentre prospective observational cohort studyResearch in context

Author

Marc Garnier, Jean-Michel Constantin, Raphaël Cinotti, Chafia Daoui, Dimitri Margetis, Grégory Destruhaut, Cédric Cirenei, Eric Noll, Christophe Quesnel, Agnes Lecinq, Sigismond Lasocki, Hélène Charbonneau, Stanislas Abrard, Cyril Quemeneur, Bruno Pastene, Nathanaël Lapidus, Marc Leone, El Mahdi Hafiani, Olivier Imauven, Emmanuel Rineau, Maxime Léger, Marc Danguy des Deserts, Johan Schmitt, Philippe Aries, Aurélie Gouel, Julia Voulgaropoulos, Laura Soldan, Romain Deransy, Quentin Laurent, Etienne Gayat, Franck Verdonk, Sabrina Chaouche, Amélie Cambriel, Vincent Degos, Julie Dupont, Laura Daoud, Romain Salettes, Malory Favreau, Julien Pottecher, Sophie Diemunsch, Cyril Bidon, Clémence Roy, Laëtitia Ottolenghi, Damien Edouard, Agnès Lecinq, Frédéric Mercier, Delphine Garrigue, Elsa Jozefowicz, Marie Pariès, Fabien Espitalier, Charlène Piat, Richard Descamps, Maëlle Duchesne, Stéphanie Sigaut, Laurie-Anne Thion, Julie Renard, Elsa Brocas, Besma Zbidi, Mohamed Fki, Guillaume Dufour, Mario Bucciero, Charles-Edouard Rochon, Céline Delerue, Virginie Trehel-Tursis, Julien Raft, Olivier Rangeard, Claire Thiriet, Kevin Lagarde, Angélina Pollet, Félix Pelen, Anaïs Caillard, Philippe Penven, Olivier Huet, Floriane Puel, Xavier Pichon, Laetitia Ligneres, Pauline Bleuze, Stéphanie Deryckere, Lionel Velly, Pierre Simeone, Hery Andrianjatovo, Youri Chipouline, Mouna Boolad, Denis Frasca, Quentin Plouviez, Benoit Plaud, Eric Roland, Delphine Cheron-Leroy, Samy Figueiredo, Antonia Blanié, Olivier Joannes-Boyau, Simon Monziols, Jean-Jacques Robin, Matthieu Biais, Hugues De Courson, Cécile Degryse, Marie Do-Khac, Marie-Pierre Bonnet, Aurélien Mazeraud, Jean Bardon, Eléonore Bouchereau, Karine Bezulier, Ségolène Mrozek, Nicolas Mayeur, and Sandrine Lopez

Subjects
COVID-19, Anaesthesia, Surgery, Perioperative risk, Respiratory complications, Postoperative pneumonia, Medicine (General), R5-920
Abstract

Summary: Background: Preoperative COVID-19 has been associated with excess postoperative morbi-mortality. Consequently, guidelines were developed that recommended the postponement of surgery for at least 7 weeks after the infection. We hypothesised that vaccination against the SARS-CoV-2 and the large predominance of the Omicron variant attenuated the effect of a preoperative COVID-19 on the occurrence of postoperative respiratory morbidity. Methods: We conducted a prospective cohort study in 41 French centres between 15 March and 30 May 2022 (ClinicalTrials NCT05336110), aimed at comparing the postoperative respiratory morbidity between patients with and without preoperative COVID-19 within 8 weeks prior to surgery. The primary outcome was a composite outcome combining the occurrence of pneumonia, acute respiratory failure, unexpected mechanical ventilation, and pulmonary embolism within the first 30 postoperative days. Secondary outcomes were 30-day mortality, hospital length-of-stay, readmissions, and non-respiratory infections. The sample size was determined to have 90% power to identify a doubling of the primary outcome rate. Adjusted analyses were performed using propensity score modelling and inverse probability weighting. Findings: Of the 4928 patients assessed for the primary outcome, of whom 92.4% were vaccinated against the SARS-CoV-2, 705 had preoperative COVID-19. The primary outcome was reported in 140 (2.8%) patients. An 8-week preoperative COVID-19 was not associated with increased postoperative respiratory morbidity (odds ratio 1.08 [95% CI 0.48–2.13]; p = 0.83). None of the secondary outcomes differed between the two groups. Sensitivity analyses concerning the timing between COVID-19 and surgery, and the clinical presentations of preoperative COVID-19 did not show any association with the primary outcome, except for COVID-19 patients with ongoing symptoms the day of surgery (OR 4.29 [1.02–15.8]; p = 0.04). Interpretation: In our Omicron-predominant, highly immunised population undergoing general surgery, a preoperative COVID-19 was not associated with increased postoperative respiratory morbidity. Funding: The study was fully funded by the French Society of Anaesthesiology and Intensive Care Medicine (SFAR).

Published
2023
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7. Assessment of lung ultrasound for early detection of respiratory complications in thoracic surgery

Author

Laetitia Bosch, Olivier Mathe, Jean-Jacques Robin, Isabelle Serres, François Labaste, Pierre Masquère, Maxime Grigoli, Laurent Brouchet, Jean-Marie Conil, and Vincent Minville

Subjects
Ultrasound, Thoracic surgery, Complications, Bedside, Anesthesiology, RD78.3-87.3
Abstract

Background and objectives: To assess lung ultrasound for the diagnosis and monitoring of respiratory complications in thoracic surgery. Methods: Prospective observational study in a University hospital, single institution. Adult patients scheduled for pulmonary resection surgery excluding pneumonectomy. An ultrasound follow-up was performed from the day before the surgery to the third day after surgery with calculation of B-line and lung score (reaeration and loss of aeration scores). Respiratory complications were collected throughout the hospitalization period. Results: Fifty-six patients were included. Eighteen patients presented a respiratory complication (32%), and they presented significantly higher BMI and ASA scores. Patients operated by videothoracoscopy were less at risk of complications. At day 3, a reaeration score ≤ 2 on the ventilated side or ≤ -2 on the operated side, and a B-line score > 6 on the operated side were in favor of a complication. Conclusion: Lung ultrasound can help in the diagnosis of respiratory complications following pulmonary resection surgery.

Published
2022
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13. EPIdemiology of Surgery-Associated Acute Kidney Injury (EPIS-AKI): study protocol for a multicentre, observational trial

Author

Melanie Meersch, Mira Küllmar, Carola Wempe, Alexander Zarbock, Ke Peng, Sigismond Lasocki, Thomas Rimmele, Maria Martin, Olivier Desebbe, Michele Rossi, Matthias Heringlake, Christina Massoth, Raphael Weiss, Andreas Höhn, Gael Pradel, Ana Kowark, Ahmed mohamed Ibrahim, Orestis Ioannidis, Andrea Cortegiani, Maxime Leger, Emmanuel Rineau, Pierre-Yves Egreteau, Andrea Russo, Laura Kerschke, Savino Spadaro, Carole Ichai, Vincent Cottenceau, Sebastian Ziemann, Maria Gomez, Julien Nadaud, Olivier Pérus, Philippe Magazzeni, Philippe Montravers, Deniz Karakaya, Christophe Aveline, Alexander Bentley, Tulay Ozkan Seyhan, Jean-François Pittet, Sébastien Ponsonnard, Pierre Garcon, Ana Serrano, Gulay Ok, Pierre Vautier, Jean François Gautier, Sergi Sabaté, Yusuf Tunali, Valérie Cerro, Stephanie Suria, Khaschayar Saadat-Gilani, Hichem Makhloufi, Anis Cherak, Lamine Lakhel Ghanem, Zohier Gouaglia, Dina Nasrine Guadouri, Fayrouz Naouel Hama, Mustafa Kara, Omayma Saadi, Rachida Sakhraoui, Fadila Bourou, Abdelhadi Cherifi, Rahmoune Ghania Sadaoui, Amel Ouyahia, Ilhem Ouahab, Souad Bouaoud, Meriem Abdoun, Anisse Tidjane, Benali Tabeti, Nabil Boudjenan-Serradj, Carlos Jose Pérez Rivera, Paulo Cabrer, Julián Corso, Juan Pablo García, Sharon Idarraga, Christopher Montoya, Rafael Figueroa, Eduar Aldana, María Alejandra Torrado, Zheng-min Ma, Yu-fan Yang, Ya-juan Zhu, Peter Sklienka, Michal Frelich, Vojtech Jarkulis, Pavel Sevcik, Vojtech Vodicka, Mohamed Gamal Elbahnasawy, Shady Elsalhawy, Sara Motawea, Zeinab Othman, Mohamed Sahma, Ahmed Mahmoud Nafea, Nermin Ahmed, Doaa Ali Attia, Moataz Maher Emara, Mohamed Mamdouh Bonna, Mohamed Ahmed Gabr, Amany Ismail Tarbay, Ibrahim Abdelmonaem Abdehaleem, Esraa Elsayed Mohamed, Amr Mahmoud Eldeeb, Ahmed Mohamed Abbas, John Ashraf Magdy, Zyad Hassan Hamed, Hany Mostafa Esmaeil Osman, Mostafa Samy Abbas, Oliver Joannes-Boyau, Nicolas Barraud, Corentin Berthelot, Thibault Camus, Anissa Dahmi, Mylène Defaye, Sébastien Derville, Younes El-Boustani, Elsa Deloge, Hélène Jacob, Simon Monziols, Fred Priem, Jean-Jacques Robin, Vincent Legros, Therry Floch, Salvatore Muccio, Claire Geneve, Marie Lim Legouge, Stéphanie Tao Mauny, Willy Mfam, Léa Pascot, Mireille Chartier, Benjamin Duteurtre, Aidren Le Cousin, Nathalie Begel, Claire-Annissa Chekirine, Vincent Derlon, Elodie Grein, Marie-Annick Lehair, Laurent Magazzeni, Carsten Potter, Catherine Roth, Florence Voivret, Jamil Elmawieh, Annabelle Stoclin, Cédric Cirenei, Gregoire Andrieu, Sven Couloumy, Jeremy Falcone, Marion Fajardy, Arsène Gagneuil, Emeline Girardet, Agnès Mazereeuw, Mélanie Bertel, Simon Bocher, Vanessa Carn, Lenaïg Le Guen, Guillaume Le Loup, Montaine Lefevre, Amanita Diop, Vanessa Jean-Michel, Sylvie Devlieger, Juliette Duthoit, Mohamed El Kadiri, Viviane Cassisa, Charline Masson, Pierre Verrier, Axel Coquerel, Enora Atchade, Charles-Edouard Rochon, Céline Delerue, Vidal Quentin, Vanessa Latry, Nina Queixalos, Thierry Braun, Saad Bouzoubaa, Basile Christ, Audrey Geiger, Joachim Gomille, Vianney Kieffer, Simone Mangeant, Christelle Prochilo, Christian Schmitt, Stefan Skwirba, Hubert Grand, Frédérique Boury, Nicolas Mayeur, Marie Pasquie, Vincent Bruckert, Vincent Arnould, Mona Bonciu, Thibault Chapelle, Luc Facchino, Florence Fagot-Gandet, Andrea Iachim, Elena Mannu, Rémi Plattier, Romain Rozier, Michel Boudinaud, Marie-Hélène Hausermann, My Hue Nguyen, Andersen Ramorasata, Amélie Barreau, Anne-Hélène Boivin, Céline Ravry, Nicolas Mottard, Johanne Beuvelot, Florence Prunier Bossion, Christian Dörr, Thilo Caspar von Groote, Linda Grüßer, Pia Wittig, Timo Brandenburger, Thomas Dimski, Niklas Döhmen, Laura Huthmann, Daniela Kaierle, Claude Pelletier, Manon Schleß, Sebastian Cleophas, Stephanie Haunhorst, Marina Jansen, Alexandra Schmitt, Julia Soisch, Kilian Sturm, Peter Rosenberger, Alexander Bendig, Lena Flohr, Helene Häberle, Pascal Hofmann, Jonathan Kuhle, Nora Michaela Leser, Kathrin Pfister, Stefanie Prohaska, Franziska Sennholz, Lena Stetz, Kathrin Weber, Sebastian Stehr, Stephan Klaus, Marco Sadlo, Matthias Boschin, Christian Sengelhoff, Ulrich Michael Göbel, Jan Gerrit Haaker, Carina-Kristin Göttker, Matthias Gründel, Romina Baumgärtel, Astrid Berggren, Madeleine Gülzow, Lennart Muras, Hauke Paarmann, Serge Thal, Dschamil El-Masri, Eleni Arnaoutoglou, Maria Ntalouka, Paula Stratigopoulou, Anastasia Analytis, Efthymios Mavrommatis, Petros Tzimas, Agathi Karakosta, Danai Pantazi, Antonia Dimakopoulou, Katerina Dimitropoulou, Humam Jalaawiy, Aeshah Anwar, Hashim Talib Hashim, Hogir Imad Rasheed Aldawoody, Giulia Catalisano, Gilia Ingoglia, Mariachiara Ippolito, Silvia De Rosa, Lucia Cattin, Andrea Bianchin, Marisa Barone, Gianluca Paternoster, Salvatore Lucio Cutuli, Liliana Sollazzi, Laura Cascarano, Massimo Antonelli, Paola Aceto, Bruno Romanò, Vincenzo Francesco Tripodi, Rosamaria Scappatura, Maria Cristina Vadalà, Diego Fiume, Maria Teresa Strano, Giulia Oddo, Clemente Santorsola, Bilal Abu Hussain, Adnan Raed Alnaser, Anas Hassouneh Ghassan, Khaled Hasanein, Mohammed Theab, Seokyung Shin, Seungho Jung, Kyuho Lee, Sung Mee Jung, Jongyoon Baek, Muhammed K. Elhadi, Issa Abuzeid, Mohammed Albaraesi, Sarah Aldressi, Wegdan Khalel, Eman Abdulwahed, Akram Abdulhamid Ashur Abujrad, Amer Almaghrabi, Muhand Mohammed Alteleeb, Entisar Ahmed Ali Alshareea, Marwa Isa Biala, Abdulqudus Deeknah, Dooua Ali Gheddim, Reem Ghmagh, Nawras Salih Ali AbuIkhrays, Marwa Sinan, Enas Soula, Sumayyah Ghayth Bahroun, Khawla Derwish, Aya Munir Mohamed, Eman Sayed Younes, Rayet Al Islam Benjouira, Mohamed Aliwa, Najwa Abdullah Altashani, Mohammed Omar Alteb, Ahmed Msherghi, Fatima Alagelli, Sufyan Albarouni, Ahmed Albishti, Sarah Aljamal, Mohamed Alsori, Taha Ekhuja, Suha Elzwai, Mohammed Ghula, Tahani Mustafa, Ahmed Tuwaib, Haifa Zriba, Hamza Mahmoud Agilla, Toky Andriamahefa Rafanomezantsoa, Anne Marie Camilleri Podesta, Denise Mifsud Bonnici, Tiziana Pirotta, Gilberto Adrián Gasca López, Maja Mojsova Mijovska, Tatjana Davitkovska, Aleksandra Gavrilovska, Sanja Lukikj, Marija Vesova, Dina Zafirova, Sarah Amro, Baraa N. F. Hajjaj, Muawia Alkhazendar, Yousuf Barakat, Sewar Abdulaziz Elejla, Ahmed Elhissi, Ahmed Khader, Ali Salem, Rita de Freitas Regufe, André Filipe de Oliveira Eloy, Lisbete Marisa Neto Cordeiro Perdigão, Evgeny Grigoriev, Artem Ivkin, Roman Kornelyuk, Michael Yaroustovsky, Marina Abramyan, Ekaterina Komardina, Nataliya Lesteva, Medina Aybazova, Elmira Kumykova, Svetlana Lesina, Gennady Rybakov, Alexey Shestov, Abdulnaser Ahmad Ahmad Barmou, Bushra Lotfi Altayeb Ahmed, Aisha Mohammad Eliyas, Yousra Emadeldin, Alexander Kaserer, Clara Castellucci, Julian Rössler, Samira Akbas, Andreja Möller Petrun, Irena Gregorcic, Vesna Sok, Roman Čičak, Elizabeth Bárcena, Antonio Guisado, Ismail Wi, Javier Ripollés Melchor, Ángel Becerra-Bolaños, Sergio Cabrera-Doreste, Ancor Domínguez-Arbelo, María Candelaria Delgado-Alonso, Virginia Muiño-Palomar, Aurelio Rodríguez-Pérez, Javier Mata Estévez, Maria Begona Covas Munoz, Juan Mulet Matas, Sara Perez Palao, Maria Dolores Mira Quirós, Alisia Cezara Teslev, Mercedes Garcia Alvarez, Marga Argilaga, María Campos, Albert Bainac, Astrid Batalla, Marta Giné, Gracia Herránz, Ignacio Hinojal, Margarita Logroño Ejea, Noelia de la Rosa Ruiz, María Gastaca Abasolo, Carla Rosario Houhton Acuna, Ibai Iriarte Zaranton, Ana Mendigurenmurua, María José Munoz Sanz, Erika Olea de la Fuente, María Pilar Pérez Vaquero, Ana Soto Iglesias, Ana Ugarte Mieres, Alaitz Urtiaga Urrestizala, Lourdes Ferreira, Félix Lobato, Marta Aguado Sevilla, Andres Erazo, Pere Miró, Diana Vernetta, Berta Castellano Paulis, Anabel Adell Perez, Marta Aseguinolaza Pagola, Elena delVal Peciña, Ainhoa Garmendia Odriozola, Amaia Lopetegi Aizpurua, Olatz Pavón Piquer, Pilar Plou Garcia, Paula Ortega Rezola, Antia Osorio Lopez, Isabel de la Calle Gil, Rosalía Navarro Casado, Peter Adamove, Roser Bayona Domenge, Francho Miguel Blasco Blasco, Adriana Alexandra Rueda Villamizar, Maria Antonia Perelló Llaneras, Jose Ignacio García-Sánchez, Laura Fernandez Téllez, Sara García Zamorano, Natalia Gijón Herreros, Andrea Rodriguez Esteve, Pablo Monedero Rodríguez, Isabel García Trigo, Agustín Alcaraz, Andrea Lara Jiménez, Iñigo Rubio, Nuria García, Raquel Callejas, Angel Manuel Candela Toha, Eli Claros, Pilar Cobeta, Pascual Crespo, Trini Dorado, Elena Elías, Javier Felices, Diego Gil, Nuria Mané, Adolfo Martínez, Lucía Pereira, Alberto Balvis Noemí Samaranch, Carlos Tiscar, Judith VillaHoz, Patricia Galán Menéndez, Elena Cardona, Anna Conesa, Veronica Estepa, Laura Llinares Espí, Yuri Loaiza Aldeán, Susana Manrique, Víctor Morales Ariza, Laura Villarino Villa, Elfayadh Saidahmed Mohamed Amed Suliman, Hytham Hamid, Modather Mohamed Saeed, Orhan Sungur Mukadder, Demet Altun, Nur Canbolat, Müşerref Beril Dinçer, Serap Aktaş Yıldırım, Müzeyyen İyigün, Davut Yapıcı, Levent Özdemir, Aslinur Sagun, Neval Boztug, Yesim Cetintas, Bora Dinc, Emel Gündüz, Hakkı Ünlügenç, Demet Lafli Tunay, Ozgur Komurcu, Özlem Korkmaz Dilmen, Eren Fatma Akcil, Eda Tok Alsina, Özge Hakli, Cengiz Polat, Namigar Turgut, Nurcan Kızılcık, Özge Köner, Öznur Şen, Nurdan Aydin, Burcu Basaran, Emre Sertac Bingul, Kamil Darcin, Semra Ugur, Kemal Tolga Saracoglu, Asli Demir, Özgök Aysegül, Eda Balci, Behic Girgin, Aygun Guler, Ümit Karadeniz, Nihal Özaslan, Yigit Özay Hülya, Namik Ozcan, Aysun Postaci, Mehmet Sahap, Nevriye Salman, Özlem Sağır, Bulent Atik, Murat Bicakcioglu, Hafize Fisun Demir, Ugün Fatih, Nazan Kocaoglu, Hüseyin ilksen Toprak, Duygu Demiröz Aslan, Yusuf Ziya Colak, Mustafa Soner Ozcan, Mehmet Yilmaz, Umran Karaca, Sevtap Hekimoglu Sahin, Özlem Ersoy Karka, Gizem Demir Şenoğlu, Süheyla Erkoç Karadağ, Neslihan Alkis, Volkan Baytaş, Engin Erturk, Ali Akdogan, Ahmet Besir, Dilek Kutanis, Sedat Saylan, Ersagun Tugcugil, Pinar Ayvat, Berrin Günaydın, Beyza Mehri Büyükgebiz, Omer Faruk Boran, Feyza Calisir, Yavuz Orak, Bahar Kuvaki Balkan, Sibel Büyükcoban, Erol Gökel, Sakize Ferim Günenc, Sule Özbilgin, Suna Göre, Selcan Akesen, Seda Cansabuncu, Natalia Momot, Anna Panchenko, and Kristen Rutledge

Subjects
Medicine
Abstract

Introduction More than 300 million surgical procedures are performed each year. Acute kidney injury (AKI) is a common complication after major surgery and is associated with adverse short-term and long-term outcomes. However, there is a large variation in the incidence of reported AKI rates. The establishment of an accurate epidemiology of surgery-associated AKI is important for healthcare policy, quality initiatives, clinical trials, as well as for improving guidelines. The objective of the Epidemiology of Surgery-associated Acute Kidney Injury (EPIS-AKI) trial is to prospectively evaluate the epidemiology of AKI after major surgery using the latest Kidney Disease: Improving Global Outcomes (KDIGO) consensus definition of AKI.Methods and analysis EPIS-AKI is an international prospective, observational, multicentre cohort study including 10 000 patients undergoing major surgery who are subsequently admitted to the ICU or a similar high dependency unit. The primary endpoint is the incidence of AKI within 72 hours after surgery according to the KDIGO criteria. Secondary endpoints include use of renal replacement therapy (RRT), mortality during ICU and hospital stay, length of ICU and hospital stay and major adverse kidney events (combined endpoint consisting of persistent renal dysfunction, RRT and mortality) at day 90. Further, we will evaluate preoperative and intraoperative risk factors affecting the incidence of postoperative AKI. In an add-on analysis, we will assess urinary biomarkers for early detection of AKI.Ethics and dissemination EPIS-AKI has been approved by the leading Ethics Committee of the Medical Council North Rhine-Westphalia, of the Westphalian Wilhelms-University Münster and the corresponding Ethics Committee at each participating site. Results will be disseminated widely and published in peer-reviewed journals, presented at conferences and used to design further AKI-related trials.Trial registration number NCT04165369.

Published
2021
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34. Smart functionalized phosphonic acid based copolymers: new structures for old purposes

Author

Xavier Solimando, Sophie Monge, Jean-Jacques Robin, Norbert Moszner, and Yohann Catel

Subjects
Materials science, Polymers and Plastics, Organic Chemistry, Bioengineering, Chain transfer, Methacrylate, Biochemistry, stomatognathic diseases, Polymerization, Polymer chemistry, Copolymer, Surface modification, Moiety, Reversible addition−fragmentation chain-transfer polymerization, Adhesive
Abstract

Innovative well-defined acidic photopolymerizable phosphorus-based copolymers were prepared and tested in well-known dental applications to improve the adhesion of dental self-etch adhesives (SEAs). Thus, innovative diblock copolymers of dimethyl-(methacryloyloxy)ethyl phosphonate (DMAOyEP) and 2-hydroxyethyl methacrylate (HEMA) were first synthesized by RAFT polymerization using a dithioester chain transfer agent (CTA) and then modified. First blocks were prepared with good control over the molecular weights and low dispersities. They were then used as macro-chain transfer agents (macroCTAs) to control well the polymerization of a second block. Appropriate functionalization of the diblock copolymers was performed. First, the dithiobenzoate chain-end was removed, leading to the discoloration of the copolymers. Secondly, polymerizable groups were incorporated by a partial functionalization of the hydroxyl group of the HEMA moiety with 2-isocyanatoethyl methacrylate (IEMA). Finally, the acidic copolymers were obtained via the deprotection of phosphonated ester groups. Following this strategy, a range of copolymers was developed and compared, varying the percentage of polymerizable groups, block compositions, molecular weights and architecture. Even if the adhesion of dental self-etch adhesives (SEAs) is currently adequate, improvements are still welcomed, and these new phosphonic acid-based materials are an opportunity to develop new dental formulations. So, dental adhesive properties were evaluated with shear bond strength (SBS) experiments to highlight the best developed materials. This contribution shows the interest of employing appropriate polymerization techniques, and appropriate functionalization reactions to develop new materials that could improve the specific properties of dental formulations.

Published
2020
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39. Modification of poly(styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene) via free‐radical grafting and its photo‐crosslinking

Author

Jean-Jacques Robin, Marcos Batistella, Thomas Brossier, Arnaud Regazzi, Sébastien Blanquer, Nicolas Morand, J.M. Lopez-Cuesta, Agnès Harlay, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Polymères Composites et Hybrides (PCH - IMT Mines Alès), IMT - MINES ALES (IMT - MINES ALES), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT), ARMOR, Durabilité des éco-Matériaux et Structures (DMS), Laboratoire de Mécanique et Génie Civil (LMGC), and Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-IMT - MINES ALES (IMT - MINES ALES)

Subjects
thermoplastic elastomers, Ethylene, Materials science, Polymers and Plastics, 4-vinyl-1-cyclohexene 1, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Styrene, chemistry.chemical_compound, [SPI]Engineering Sciences [physics], Polymer chemistry, Photo crosslinking, Materials Chemistry, Thermoplastic elastomer, technology, industry, and agriculture, General Chemistry, 021001 nanoscience & nanotechnology, Grafting, 0104 chemical sciences, photo-crosslinking, chemistry, 0210 nano-technology, 2-epoxide, free-radical grafting, poly(styrene-ethylene-butylene-styrene) SEBS
Abstract

International audience; Poly(styrene-b-(ethylene-co-butylene)-b-styrene) (SEBS) is functionalized via radical grafting with 4-vinyl-1-cyclohexene 1,2-epoxide (VCHO) initiated using 2,5-Bis(tert-butylperoxy)-2,5-dimethylhexane. The existence of the epoxide group on the SEBS backbone is evidenced by 1H nuclear magnetic resonance. A size exclusion chromatography (SEC) study reveals some chain coupling, and this phenomenon is limited by controlling the quantities of peroxide and monomer reagents used during the radical grafting. Photo-crosslinking of SEBS-g-VCHO under ultraviolet irradiation in the presence of a cationic initiator is then successfully performed with resultant gel contents higher than 85%. Mechanical properties of SEBS and crosslinked materials are measured by tensile tests on thin films. On the one hand, those tests reveal a significant increase of Young's modulus of the crosslinked materials. On the other hand, the diminution of elongation at break is much more limited; crosslinked materials retain their elastomeric properties with an elongation at break greater than 200%. Finally, the photosensitive SEBS-g-VCHO is used to show the adhesion performance of the photo-crosslinking coating as well as a resin for the stereolithography process.

Published
2021
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40. Photo-Cross-Linked Poly(trimethylene carbonate)/Poly(ε-caprolactone) Triblock Copolymers with Controlled Architectures: From Phase-Separated Structures to Shape-Memory Materials

Author

Michel Ramonda, Sylvain Catrouillet, Jean-Jacques Robin, Nikola Toshikj, Sébastien Blanquer, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Centrale de Technologie en Micro et Nanoélectronique CTM-­LMCP, and Université de Montpellier (UM)

Subjects
Materials science, Polymers and Plastics, Process Chemistry and Technology, Organic Chemistry, 02 engineering and technology, Shape-memory alloy, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, chemistry.chemical_compound, Chemical engineering, chemistry, Phase (matter), Copolymer, [CHIM]Chemical Sciences, Trimethylene carbonate, 0210 nano-technology, Caprolactone, ComputingMilieux_MISCELLANEOUS
Abstract

International audience

Published
2021
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41. Photo-réticulation des copolymères SEBS : De leur modification par voie radicalaire à de nouvelles applications

Author

Harlay, Agnès, Regazzi, Arnaud, Batistella, Marcos, Blanquer, Sébastien, Brossier, Thomas, Lopez-Cuesta, J., Morand, Nicolas, Jean Jacques, Robin, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Polymères Composites et Hybrides (PCH - IMT Mines Alès), IMT - MINES ALES (IMT - MINES ALES), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT), Durabilité des éco-Matériaux et Structures (DMS), Laboratoire de Mécanique et Génie Civil (LMGC), Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-IMT - MINES ALES (IMT - MINES ALES), Armor, and GFP - Groupe Français d’Études et d’Applications des Polymères

Subjects
[SPI]Engineering Sciences [physics], [SPI.MAT]Engineering Sciences [physics]/Materials
Abstract

National audience; Les élastomères thermoplastiques de la famille des copolymères poly(styrène-b-(éthylène-co-butylène)-b-styrène), dits SEBS, sont des matériaux de hautes performances en raison de leur microstructure particulière et de leur allongement à la rupture élevé. Ils sont largement utilisés comme matériaux absorbeurs de chocs, isolants de câbles ou dans des formulations d'adhésifs et de mastics. Ils présentent l’avantage de pouvoir être mis en œuvre par différents procédés (injection, extrusion, application en solution…).Bien que le SEBS soit largement utilisé aujourd'hui dans des applications de grande diffusion et des secteurs de pointe, seules quelques études se sont focalisées sur la modification du SEBS par greffage radicalaire du fait de sa sensibilité aux radicaux libres. Passaglia et Rosales ont rapporté en 2000 une dualité entre le degré de greffage d’un monomère comme l’anhydride maléïque et la β-scission, voire de réticulation des chaînes de SEBS [1,2]. Ces deux phénomènes conduisent à une dégradation très rapide des propriétés mécaniques du matériau et surtout de son allongement à la rupture. Aussi, accroître les applications potentielles du SEBS par modification de ses propriétés mécaniques reste un défi important.Dans cette étude, le SEBS a été fonctionnalisé par greffage radicalaire du 4-vinyl-1-cyclohexène 1,2-époxyde (VCHO), un monomère réactif par voie UV cationique grâce à son cycle époxyde cyclo-aliphatique. Ce greffage permet la réticulation ultérieure du SEBS sous rayonnement UV. À notre connaissance, c’est la première fois que la réactivité radicalaire du groupe vinyle du VCHO est mise en évidence, notamment par 1H-RMN, tout comme son greffage sur un polymère oléfinique. La photo-réticulation du SEBS-g-VCHO sous irradiation UV en présence d'un photoamorceur cationique a ensuite été conduite avec succès menant à des teneurs en gel supérieures à 85 %. Les propriétés mécaniques du SEBS-g-VCHO réticulé ont été caractérisées par des essais de traction sur films minces. Ces tests ont révélé une augmentation significative du module d'Young du SEBS-g-VCHO réticulé. Par ailleurs, les matériaux réticulés ont conservé leur comportement d’élastomères avec un allongement à la rupture supérieur à 200 %.Ces nouveaux matériaux pourraient donc être mis en œuvre pour la réalisation de revêtements ou de pièces obtenues en stéréolithographie 3D afin d’élargir la gamme d’élastomères réactifs actuellement utilisés dans ces applications.

Published
2021

50. Polyurethane Thermosets Using Lipidic Poly(α‐Hydroxyketone)

Author

Vincent Lapinte, Sylvain Caillol, Jean-Jacques Robin, Marc Lemaire, Benoit Briou, Pascal Etienne, Nicolas Duguet, Nam Duc Vu, Laurent Bonnet, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Catalyse Synthèse et Environnement (CASYEN), Institut de Chimie et Biochimie Moléculaires et Supramoléculaires (ICBMS), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-École Supérieure Chimie Physique Électronique de Lyon-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-École Supérieure Chimie Physique Électronique de Lyon-Centre National de la Recherche Scientifique (CNRS), Laboratoire Charles Coulomb (L2C), and Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Ketone, 030309 nutrition & dietetics, General Chemical Engineering, Alcohol, Catalysis, 03 medical and health sciences, chemistry.chemical_compound, 0404 agricultural biotechnology, medicine, Organic chemistry, Reactivity (chemistry), Thermal stability, Polyurethane, chemistry.chemical_classification, 0303 health sciences, Hydrogen bond, Organic Chemistry, 04 agricultural and veterinary sciences, 040401 food science, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, polyurethane, alpha-hydroxyketone, Castor oil, lipids (amino acids, peptides, and proteins), Vegetable oils, medicine.drug
Abstract

International audience; Lipidic polyols based on α‐hydroxyketone reactive groups were investigated for polyurethane thermosets. The reactivity of this peculiar secondary alcohol group in triacylglycerol structure was compared, without use of catalyst, to that of poly(1,2‐diol) triacylglycerol and castor oil to demonstrate the influence of ketone in the α position of the alcohol group in the presence of HDI for the urethanization rate. The kinetic effect of the ketone group was also studied on various lipidic architectures: mono(α‐hydroxyketone) ester, di(α‐hydroxyketone) diester and tri(α‐hydroxyketone) triacylglycerol. The presence of hydrogen bonds in the network coming from urethane, residual alcohol, and ketone in hard segments of PU was discussed and correlated with the thermal stability and the soft mechanical properties of the resulting polyurethane thermosets.

Published
2019
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