Title : Porous Organic Polymers: Design, Synthesis and Use in Photochemical Detoxification of a Sulfur Mustard Simulant
Date : April 20th, 2021, Tuesday
Time : 12:30
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Meeting ID: 729 064 5404
Designing new materials for the effective detoxification of chemical warfare agents1,2 is of current interest given the recent use of such
agents.3,4 Although halogenated borondipyrromethene derivatives (4,4-difluoro-4-bora-3a,4a-diaza-s-indacene or BDP or BODIPY) at the 2 and 6 positions have been extensively explored as efficient photosensitizers for generating singlet oxygen (1O2) in homogeneous media, their utilization in the design of porous organic polymers (POPs) has remained elusive due to the difficulty of controlling polymerization processes through cross-coupling synthesis pathways. Our approach to overcome these difficulties and prepare halogenated BODIPY-based porous organic polymers (X-BDP-POP where X = Br or I) represents an attractive alternative through post-synthesis modification (PSM) of the parent hydrogenated polymer. Upon synthesis of both the parent polymer, H-BDP-POP, and its post-synthetically modified derivatives, Br-BDP-POP and I-BDP-POP, the BET surface areas of all POPs have been measured and found to be 640, 430, and 400 m2·g−1, respectively. In addition, the insertion of heavy halogen atoms at the 2 and 6 positions of the BODIPY unit leads to the quenching of fluorescence and the enhancement of phosphorescence, as a result of efficient intersystem crossing. The heterogeneous photocatalytic activities of both the parent POP and its derivatives for the detoxification of the sulfur mustard simulant, 2-chloroethyl ethyl sulfide (CEES), have been examined; the results show a significant enhancement in the generation of singlet oxygen (1O2).
Both the bromination and iodination of H-BDP-POP serve to shorten by 5-fold of the time needed for the selective and catalytic photo-oxidation of CEES to 2-chloroethyl ethyl sulfoxide (CEESO).
Dr. M. Mustafa Cetin obtained his B.S. degree as a high honor student
(2005) at Karadeniz Technical University (KTU) in Trabzon, Turkey, and MSc degree as a Fulbright Scholar (2008) at State University of New York College at Buffalo (SUNY) in Buffalo, NY, USA. After working as an appointed research adjunct at SUNY between 2009 and 2011, he then moved to Lubbock, Texas for his PhD, and obtained PhD at Texas Tech University under the guidance of Professor Michael F Mayer in August 2017. His research during his PhD was mostly focused on rotaxane synthesis, polymer chemistry, catalysis, photo-redox chemistry, anti-cancer agent synthesis, and ionic liquids. Upon obtaining his PhD degree, Dr. Cetin joined the Stoddart Mechanostereochemistry Group as a Postdoctoral Fellow in September 2017, where he worked on the design, creation and characterization of chemical compounds and materials for various end uses including but not limited to molecular electronics, energy harvesting and storage, and separations technology with the 2016 Nobel Laureate Professor Sir J Fraser Stoddart at Northwestern University in Evanston, IL, USA. During his fellowship, he also worked as a Technical Specialist for Sterne, Kessler, Goldstein & Fox PLLC for nine months, where he got his training on Intellectual Property (IP) and Patents, and trained for evaluating patentability & freedom to operate analyses of innovations, preparing patent applications, patentability, infringement and validity opinions, and responding to office actions regarding patent applications. Since June 2020, Dr. Cetin is working as an Assistant Professor at Kadir Has University.