Chemical Science symposium 2023: Chemistry of polymers 26 - 27 October 2023, London, United Kingdom
26 - 27 October 2023, London, United Kingdom Chemical Science symposium 2023: Chemistry of polymers
Book of Abstracts
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Welcome from the Royal Society of Chemistry and Chemical Science
Dear Colleagues, A warm welcome to the Chemical Science Symposium – Chemistry of Polymers.
This is the fifth in the series of Chemical Science Symposia, and like 2022 we are once again hosting this as a hybrid meeting, with the opportunity to welcome delegates to the headquarters of the Royal Society of Chemistry for face-to-face interaction, as well as looking forward to a conversation enriched by the online participation of our international community. Under the banner of our flagship journal, Chemical Science , we are shining a spotlight on cutting-edge chemistry research and giving it the sort of attention that drives scientific progress and makes a difference. Each year, we aim to keep the same format for the Symposium, with ample time available to support networking and discussion, while changing the theme to reflect the latest research developments, ensuring we bring together leading researchers from around the world. We also encourage strong participation from early career scientists and future leaders, who will be the future of this discipline. We are dedicating significant time in the programme to our poster sessions, both in person and online, and we will hear from a selection of these scientists in our flash poster presentations. We strongly encourage all delegates to actively take part in these sessions. The Chemical Science Symposium also provides a way for our wider community to regularly stay in touch with the journal editors from RSC journals in this area, and fellow researchers across a broad range of topics in the chemical sciences. This years’ Symposium is focussed on the topic of Chemistry of Polymers. We have a wide range of speakers in this Symposium who are all internationally recognised experts in aspects of polymer chemistry. Methods and topics that we will hear about will be varied such as the chemistry and synthesis of polymers, optoelectronic polymers, recyclable polymers and 3D printing, biopolymers and polymer assemblies. We hope that the lectures and poster presentations will stimulate the exchange of ideas and experiences between all participants, setting a strong platform for discussion. We’d like to thank each of the speakers, poster presenters and participants for all their contributions. Again, on behalf of the Chemical Science team, a very warm welcome to what promises to be an exciting symposium. We hope that this event will act as a springboard for future activities and that it will help in fostering new research collaborations. Luis Campos Columbia University Malika Jeffries-EL Boston University Tanja Junkers Monash University May Copsey Royal Society of Chemistry
Meeting Information
Chemical Science symposium 2023: Chemistry of polymers is organised and hosted online by the Royal Society of Chemistry. This e-book contains abstracts of the oral talks and posters presented both in-person and online at the Chemical Science Symposium 2023. All abstracts are produced directly from typescripts supplied by authors. Copyright reserved. All sessions, including the virtal posters, are available to access via the virtual lobby. Further information on how to join the meeting for those attending in person and those attending online will be detailed in the joining instructions. Networking sessions There will be regular breaks throughout the meeting for socialising, networking and continuing discussions started during the scientific sessions. During the networking time online you will be able to join existing networking rooms or initiate one-to-one chats. Existing networking rooms will be visible from the virtual lobby. To create a one-to-one chat online, simply click on the name of the person you would like to speak to and select if you would like to have a private or public conversation. For a public conversation, other delegates can join your chat room. On the web version, you can only be in one session at a time (this includes networking rooms). Posters Posters have been numbered consecutively. The posters will be available to view throughout the discussion. For those posters online they can be viewed by clicking on the link in the virtual lobby. The dedicated poster session will take place on 26 October 16:45 – 19:00 During these times, the in-person presenters will be expected to stand by their posters and the online presenters are expected be available for live chat and outside of these times, a direct message can be sent to the authors and they can respond when available.
Exhibitor
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Committee
Speakers
Luis Campos Columbia University, USA Malika Jeffries-EL Boston University, USA Tanja Junkers Monash University, Australia
Steven Armes The University of Sheffield, UK
Christopher Barner-Kowollik Queensland University of Technology, Australia
Eva Blasco Heidelberg University, Germany
Anindita Das Indian Association for the Cultivation of Science, Kolkata, India
James Hedrick IBM, USA
Brett Helms Lawrence Berkley National Laboratory, USA
Bumjoon Kim KAIST, South Korea
Christine Luscombe Okinawa Institute of Science and Technology, Japan
Krzysztof Matyjaszewski Carnegie Mellon, USA
Julien Nicolas Université Paris-Saclay, France
Javier Read de Alaniz University of California Santa Barbara, USA
Brent Sumerlin University of Florida, USA
Ben Zhong Tang The Chinese University of Hong Kong, Shenzhen, China
Helen Tran University of Toronto, Canada
Charlotte Williams University of Oxford, UK
In-person poster presenter list
P01
A game of tug-of-war: balancing enhanced activity and control in multimetallic complexes for block copolymer synthesis Maisarah Abdul Rahman University of Edinburgh, UK Thiocarbonyls: synthesis of alternative monomers for biodegradable vinyl copolymers Sade Adamolekun University of Surrey, UK Preparation of novel hyperbranched polymers for application in light emitting diodes Amal Aljohani University of Sheffield, UK Recyclable thermosets based on modified epoxy-amine network polymers Lynn Anderson Northumbria University, UK Encapsulation of magnetic nanoparticles in PEG-PL(G)A polymers of different block lengths via flash nanoprecipitation Nesrine Bali NTNU, Norway Kinetic investigation of RAFT photopolymerization in continuous flow using inline NMR analysis Magdalena Beres University of Warwick, UK RAFT polymerisation of pH-responsive monomers and the impact of polymer architecture on microalgae flocculation Valentin Beyer KU Leuven, Belgium Functional polyesters and polycarbonates preparation through catalytic ring-opening copolymerization of fatty acid epoxides Arianna Brandolese University of Birmingham, UK Are laboratory degradation proxy tests relevant to assess degradation of biodegradable polymers in the environment ? Fannie Burgevin University of Bath, UK
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Ring-opening copolymerisation with a xylose derived oxetane Ella Clark University of Bath, UK Introducing a new family of biodegradable antibacterial polymers: a structure-activity study Anna Constantinou Imperial College London, UK The synthesis and properties of poly(ester-alt-ether)-b-plla block copolymers as toughening agents for commercial polylactide Alexander Craze University of Oxford, UK Crystallisation-driven self-assembly of functionalised- poly(caprolactone) block-copolymers Ana Cubillo Alvarez University of Birmingham, UK Strands vs crosslinks: degradation and regelation of poly(butyl acrylate) networks synthesized by RAFT polymerization Frances Dawson University of Bath, UK Stereo-electronic contributions in yttrium-mediated stereoselective ring-opening polymerization of functional racemic β-lactones Ali Ahmad Dhaini Université de Rennes 1, France Visible light-mediated cis/trans isomerization of ortho-hydroxy cinnamates: from coumarins to polymers David Diaz Diaz Universidad de La Laguna, Spain Novel ‘open’ heterobimetallic catalyst for carbon dioxide and epoxide copolymerisation at low CO2 pressures Katharina Eisenhardt University of Oxford, UK Synthesis and aggregation studies of macrocycles and helices with hydrophobic inner surfaces Saquib Farooq University of Fribourg, Switzerland
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Micelle-forming graft copolymers with dual drug binding Markéta Frejková Institute of Macromolecular Chemistry AS CR, Czech Republic Radical, cationic and click-reaction photopolymerization of vegetable oil-based resin for shape memory polymers Sergejs Gaidukovs Riga Technical University, Latvia Characterisation of structural and chemical degradation of regenerated cellulose textiles degradation via accelerated aging Louise Garner UCL, UK Methods of polylactide copolymer synthesis by generating tetraphenylethane inifer groups in the PLA structure Mateusz Grabowski Centre of Molecular and Macromolecular Studies Polish Academy of Sciences, Poland Electron ptychographic imaging of polyvinyl alcohol ordering Botao Hao University of Oxford, UK Recycled polyurethane foams as new artificial soils Michael Harris University of Sheffield, UK
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The future regulation of new polymers and recycled polymers: a challenge for nomenclature and grouping
Chris Howick INOVYN, UK
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Synthesis of end-functionalized polyethylene via catalysed chain growth reaction Jiakai Huang Imperial College London, China
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Biocompatible light-responsive metamaterials via patterned electrospinning Xia Huang University College London, UK
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NacNac-Zn-pyridonate mediated ε-caprolactone ROP Jack Hughes University of Edinburgh, UK
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Synthesis and characterization of ultra-high molecular weight hydrogels via photo-initiated aqueous RAFT polymerization Gavin Irvine University of Bath, UK Exploring polymerisation chemistry for synthesising radiolabelled metal-ion polymer bioconjugates for radioimmunotherapy Samy Kichou University of Zurich, Switzerland Triblock Copoly(ester-ether)s from biobased monomers towards sustainable packaging Flore Kilens Polykey Polymers, Spain
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3D printing and upcycling of bio-based polymers Pia Klee Heidelberg University, Germany
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Two-dimensional materials as an efficient photo-initiation sources for click chemistry Azra Kocaarslan Karlsruhe Institue of Technology, Germany iBodies: a versatile tool for IVD diagnostics based on synthetic polymers Libor Kostka Institute of Macromolecular Chemistry CAS, Czech Republic HPMA-based polymers with different structures and their solution behavior Lenka Kotrchová Institute of Macromolecular Chemistry CAS, Czech Republic
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Degradable polymers via catalytic living ROMP Ankita Mandal University of Fribourg, Switzerland
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A handful of sustainable routes for catalytic ring-opening metathesis polymerization Andreas Kilbinger University of Fribourg, Switzerland The catalytic chemical recycling of waste oxygenated plastics Thom McGuire University of Oxford, UK
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Bio-sourced unsaturated polyesters for 3D-printing Claire Morand University of Birmingham / POLYKEY / UPV-EHU, UK
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Cationic ring-opening polymerisation of a thionolactone to produce recyclable materials Swarnali Neogi University of Surrey, UK A systematic study of cationic polymer brush-nucleic acid complexes Carlos Neri Queen Mary University of London, UK Studying chemical and topological rearrangements in covalent adaptive networks Henry Nguyen Northumbria University, UK Catalytic tandem dehydrochlorination–hydrogenation of PVC towards valorisation of chlorinated plastic waste Galahad O Rourke Katholieke Universiteit Leuven, Belgium Polymer additives for the enhanced photodegradation of polyethylene Molly Parry Imperial College London, UK Renewable cyclic monomers for ring-opening polymerisation and co-polymerisation with L-lactide Anita Plumley University of Bath, UK Toughening CO 2 -derived copolymer elastomers through ionomer networking Kam Poon University of Oxford, UK
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3D printable polyelectrolyte complex-integrated interpenetrating network hydrogels with customisable mechanical strength and pH-responsiveness Vaishali Pruthi Karlsruhe Institute of Technology, Germany Engineering enzymatically induced sequential mesophase transitions within polymeric formulations Parul Rathee Tel Aviv University, Israel Sugar-based polymers for renewable, degradable, and efficient battery electrolytes James Runge University of Bath, UK Synthesis of silicone resins by upcycling of silicon oil waste Shamna Salahudeen Leibniz Institute for Catalysis, Germany Innovative approach to enhance molded pulp biocomposites: unleashing the potential of silica aerogel through in-situ polymerization via vacuum Impregnation Ajit Kumar Singh Yonsei University, South Korea A green biopolymer catalyst based on natural polysaccharides for the esterification of isosorbide Katrin Staedtke Friedrich-Alexander-Universität, Germany Investigation of mass transfer limitations on heterogeneously catalyzed ring opening polymerization of propylene oxide Tabea Angela Thiel Leibniz-Institut für Katalyse e. V., Germany Volumetric 3D-Printing of thiol-ene crosslinkable poly(ε-caprolactone) Quinten Thijssen Ghent University, Belgium Photocatalytic decontamination of sulfur mustard using photo- crosslinkable hydrogel films containing a phthalocyanine derivative Gabriela Toader Military Technical Academy “Ferdinand I”, Romania
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MaDDOSY: Mass determination diffusion ordered spectroscopy on the bench top Owen Tooley University of Warwick, UK Development of novel polymers and their impact on the marine environment Eleanor Trudinger Charnley University of Bath, UK Controlled polymerization of Poly[N-[2(dimethylamino)ethyl]acrylamide (pDMAEAM) using RAFT techniques Esther Udobang University of Warwick, UK Adsorption of aldehyde-functional diblock copolymer spheres onto surface-grafted polymer brushes via dynamic covalent chemistry enables friction modification Spyridon Varlas University of Sheffield, UK 4D printing of light activated shape memory polymers with organic dyes Clara Vazquez Martel Heidelberg University, Germany Chemically recyclable fluorescent polyesters via the ring-opening copolymerization of epoxides and anhydrides Taylor Young University of Cardiff, UK Aqueous hydrophobicity-controlled self-assembly of supramolecular peptide nanotubes Min Zeng University of Warwick, UK 4D Printed multi-material soft actuators for spatiotemporal control Kun Zhou Imperial College London, UK
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Online poster presenters
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Quantification and control of the surface density of azide groups presented by coating a functional polymer Hikaru Amo Kobe University, Japan Polymer-based solid electrolyte for energy storage applications Sarah Asiri IAU, Saudi Arabia Synthesis and characterization of poly(N-isopropylmethacrylamide) microgels and their applications in nanotechnology and catalysis Robina Begum University of the Punjab, Pakistan Biopolymer-based nanodots assembly on paper for pH-dependent separation of a mixture of oppositely charged dyes Tuhin Bhattacharjee Assam Engineering College, India A comparison of thermo-responsive behavior between polyproline and periodically grafted polyproline: An explanation of its conformational origin Arjun Singh Bisht IISER, India Functionalised polyester surfaces to reduce bacterial adhesion Benedetta Brugnoli Sapienza University of Rome, Italy Charge regulation and chemical transformation of heparin-mimicking polyampholytes Katarzyna Byś Charles University, Czech Republic Electrochemically mediated atom transfer radical polymerization triggered by alternating current Francesco De Bon University of Coimbra, Portugal Poly(N-isopropylmethacrylamide) microgels for fabrication and stabilization of gold nanoparticles and their use in catalysis Zahoor Hussain Farooqi University of the Punjab, Pakistan
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Aggregation of small molecules inhibit DNase I Shunsuke Habe Kobe University, Japan
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Antimicrobial peptide functionalized novel pcl/sodium alginate fibers to combat antibiotic resistance in wound Taufiq Hasan Aneem Bangladesh University of Engineering and Technology (BUET), Bangladesh
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4D printing and recyclable polymers Hytham Hassan KU Leuven, Belgium
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Reusable surface presenting amino groups using a degradable copolymer Fuga Hoshino Kobe University, Japan Site-controlled incorporation of ATRP initiators into nucleic acids for the controlled synthesis of DNA- or RNA-polymer hybrids Jaepil Jeong Carnegie Mellon University, USA Terpene-derived bio-based elastomers and elastomeric materials via RAFT-mediated miniemulsion polymerization Uddhab Kalita Indian Institute of Technology, India Synthesis of iron-polypropylene and iron-high densıty polythylene composites Sevil Khalilova Institute of Catalysis and Inorgaic Chemistry, Azerbaijan Synthesis of a biodegradable, halochromic polymer via end- functionalization of poly(lactic acid) Vihanga Kularatne University of Colombo, Sri Lanka Architectural effect on self-assembly and biorecognition of randomly grafted linear and branched polymers at liquid crystal–water interfaces Ankita Kumari Indian Institute of Science Education and Research, India
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Studies in the field of obtaining biologically active polymer compositions from exploited low density polyethylene Rahima Mammadova Azerbaijan State Pedagogical University, Azerbaijan Isolation and characterisation of a novel biopolymer from acrocomia aculeata Farrah Mathura University of the West Indies Trinidad W.I., Trinidad and Tobago
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Visible light-assisted organocatalyzed Atom Transfer Radical Polymerization (ATRP) using BODIPY Photocatalysts
Rahul Maurya IIT Ropar, India
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Disorder outpacing order: Amyloid-inspired peptide with guanidinium motifs to dictate dynamic self-assembly vs liquid-liquid phase separation Nimisha Mavlankar Institute of Nano Science and Technology, India Inhibition of amyloid β fibrosis by stereocomplex formation with D-peptide Haruhiko Miwa Kobe University, Japan Utilising cellulose acetate derived from recycled cotton waste for efficient oil removal in water Fuad Mohamad Universiti Teknologi Malaysia, Malaysia Molecular co-assembly creates species selectivity in a conventional antifungal drug Kenta Morita Kobe University, Japan Emission tuning for thin films owing to polymer: small molecule interactions Enrique Pérez-Gutiérrez Universidad Autónoma de Puebla, Mexico
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Aromatic polyamides with tunable secondary structures and enantioseparation properties
Subhendu Samanta IISER Mohali, India
P91
Modification of Cysteine-S-sulfonated keratin properties through pH variations Diego Omar Sanchez Ramirez STIIMA-CNR, Italy A healable elastomer composites based on visible light-induced supramolecular chemistry Shrabana Sarkar Indian Institute of Technology, India Iminophenolate based Titanium and Hafnium compounds for ROCOP of epoxides with anhydrides and epoxides with CO2 Sriparna Sarkar Indian Institute of Technology, India Hydrophobic carbon quantum dots-doped 3D printed composite for antibacterial applications Mohamed Shaalan Ustav Polymerov, SAV, v.v.i., Slovakia Colloidal-based self-assembly promoted stratified multifunctional coating with self-healing ability for superior adhesion strength and hardness Diksha Sharma Indian Institute of Technology, India Preparation and investigation of polysaccharide-based highly efficient antibacterial micro-composite for efficient hemostasis Lamiya Hassan Tithy Bangladesh University of Engineering and Technology, Bangladesh Induction of apoptosis by the formation of self-assemblies of polycyclic aromatic compounds Riku Umemura Kobe University, Japan Close-loop recyclable & biodegradable covalent adaptable networks based on dynamic β-COS thiocarboxylate linkage Chandan Upadhyay Rajiv Gandhi Institute of Petroleum Technology, India Novel SynthETIC Approach For 2-oxazoline from CNSL Anjitha V V Vignan's Foundation for Science, Technology and Research, India
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Starch nanosphere-based network esterified by ferulic acid via green synthesis Siyu Yao Zhejiang University, China PMMA microspheres prepared by photopolymerization under green LED irradiation Siyuan Yu Tianjin University, China Programmable zwitterionic droplets as biomolecular sorters and model of membraneless organelles Suiying Ye ETH Zurich, Switzerland
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Polymerisation-Induced Self-Assembly (PISA): a powerful platform technology for bespoke polymer particles Prof. Steve Armes Department of Chemistry, University of Sheffield, UK Polymerisation-induced self-assembly (PISA) is a powerful and versatile technique for the rational synthesis of concentrated dispersions of block copolymer nano-objects of controllable size, shape and surface chemistry. In essence, an insoluble block is grown from one end of a soluble block in a suitable solvent. Once the growing block reaches a certain critical degree of polymerisation, micellar nucleation occurs and the soluble block then acts as a steric stabiliser. Unreacted monomer diffuses into the copolymer cores, which leads to a relatively high local concentration and hence a significant rate acceleration. Depending on the target diblock copolymer composition, the final copolymer morphology can be spheres, worms or vesicles. The design rules for PISA are generic: such syntheses may be conducted in water, polar solvents or non-polar solvents using reversible addition-fragmentation chain transfer (RAFT) polymerisation. Over the past decade, PISA has become established as a highly versatile platform technology for the rational design of bespoke polymer colloids. For example, such block copolymer nano-objects can be used as highly biocompatible worm gels for cell biology studies, as dispersants for organic agrochemical actives, as next- generation lubricant additives for ultralow viscosity automotive engine oils, or for the design of uniquely thermoresponsive amphiphilic diblock copolymers that form spheres, worms or vesicles in aqueous solution simply by adjusting the temperature from 5°C to 50°C. Various examples of PISA formulations will be discussed in this lecture.
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© The Author(s), 2023
Photochemical action plots reveal the fundamental mismatch between absorptivity and photochemical reactivity Christopher Barner-Kowollik Centre for Materials Science, Queensland University of Technology (QUT), Australia Institute of Nanotechnology (INT), Karlsruhe Institute of Technology (KIT), Germany Over the last decade, our laboratory has employed monochromatic tunable laser systems to reveal a fundamental mismatch between the absorptivity of a chromophore and its photochemical reactivity in the vast majority of covalent bond forming reaction as well as specific bond cleavage reactions. Our data overturns the long-held paradigm that effective photochemical reactions are obtained in situations where there is strong overlap between the absorption spectrum and the emission wavelength. However – as we explore herein – the absorption spectrum of a molecule provides only information about singlet excitation and remains entirely silent on the accessibility of the critical triplet states, which dictate photochemical reactivity. We propose future avenues of enquiry on how action plots can be understood and explore how they are of key importance for tailoring photochemical applications in soft matter materials design with never before seen precision. References 1. Irshadeen, I.M.; Walden, S.L.; Wegener, M.; Truong, V.X.; Frisch, H.; Blinco, J.P.; Barner-Kowollik, C. J. Am. Chem. Soc. 2021, 143, 21113. 2. Menzel, J. P.; Feist, F.; Tuten, B.; Weil, T.; Blinco, J. P.; Barner-Kowollik, C. Angew. Chem. Int. Ed. 2019, 58, 7470. 3. Nardi, M.; Blasco, E.; Barner-Kowollik, C. J. Am. Chem. Soc. 2022, 144, 1094. 4. Kalayci, K.; Frisch, H.; Truong, V. X.; Barner-Kowollik, C. Nat. Comm. 2020, 11, 4193. 5. Menzel, J.P. ; Noble, B.B. ; Blinco, J.P.; Barner-Kowollik, C. Nat. Comm. 2021, 12, 1691. 6. Rodrigues, L. L; Micallef, A. S.; Pfrunder, M.; Truong, V.X.; McMurtrie, J. C.; Dargaville, T.R.; Goldmann, A. S.; Feist, F.; Barner-Kowollik, C. J. Am. Chem. Soc. 2021, 143, 7292. 7. Houck, H. A.; Blasco, E.; Du Prez, F. E.; Barner-Kowollik, C. J. Am. Chem. Soc. 2019, 141, 12329. 8. Kodura, D.; Houck, H. A.; Bloesser, F. R.; Goldmann, A. S.; Du Prez, F. E.; Frisch, H.; Barner-Kowollik, C. Chem. Sci. 2021, 12, 1302. 9. Kodura, D.; Rodrigues, L. L.; Walden, S. L.; Goldmann, A. S.; Frisch, F.; Barner-Kowollik, C. J. Am. Chem. Soc. 2022, 144, 6343-6348 10. Walden, S. L.; Rodrigues, L. L.; Alves, J.; Blinco, J. P.; Truong, V. X.; Barner-Kowollik, C. Nat. Comm. 2022, 13, 2943. 11. Thai, D. L.; Guimarães, T. R.; Chambers, L. C.; Kammerer, J. A.; Golberg, D.; Mutlu, H.; Barner-Kowollik, C. J. Am. Chem. Soc. 2023, 145, 14748.
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© The Author(s), 2023
Shaping Functional Polymers in 3D Eva Blasco Heidelberg University, Germany
4D printing has gained much attention during the last years and become a promising tool for the fabrication of dynamic and adaptive structures with potential application in different fields ranging from biomedicine to optics to soft-robotics. The additional fourth dimension refers to the ability of a 3D printed object to change its properties over time. We can imagine it as the addition of “life-like” behavior. While great progress has been made at the macroscale, the continuous miniaturization of today´s devices has tremendously increased the demand for manufacturing at the smaller scales. Emerging technologies such as 3D laser printing (also known as two-photon lithography or direct laser writing) have enabled the precise printing of structures at the micro and nanometer scale. Our group has recently succeeded in the development of new functional materials for laser micro- and nanoprinting. In particular, we have focus on the incorporation of new features such as conductivity, subtractive manufacturing (inks allowing printing and erasing), superresolution and more recently, stimuli response for complex actuation. In this lecture, special attention will be paid to the design of inks based on functional polymers for 3D/4D microprinting. The challenges as well as the potential and perspectives of the field will be highlighted, too.
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© The Author(s), 2023
Crystallization-driven precision two-dimensional (2D) assemblies from chromophore-conjugated poly(lactide)s Anindita Das Indian Association for the Cultivation of Science, Kolkata, India Aliphatic polyesters are considered a sustainable alternative to petroleum-based polymers due to their biodegradability. Some of them, such as polylactic acids, polycaprolactone, etc., have been extensively explored in biological applications as delivery vehicles for their additional biocompatibility. Although these polymers can be easily synthesized from commercially available cyclic lactides and lactones by ring opening polymerization (ROP), they have limited properties due to the lack of tuneable side chain functionalities. Moreover, being hydrophobic, they need to be conjugated with different hydrophilic moieties for studying their self-assembly in water. Our group has established a versatile and generally applicable condensation polymerization methodology for the synthesise of functional aliphatic polyesters.1 The synthesis involves the transesterification of activated bis(pentafluorophenyl) adipate with functional diols in the presence of an organocatalyst, 4-dimethylaminopyridine (DMAP). 1 This methodology eliminates the need to remove by-products, which is still a significant challenge in the production of conventional polyesters using non-activated diesters. Following this methodology, positively charged, fluorescent aromatic pendant moieties with variation in hydrophobic chain lengths were incorporated to synthesize enzymatically degradable water-soluble polyesters, which show great potential as broad-spectrum antibacterial agents. 2 In another area, we have explored the well-known crystallization-driven self-assembly (CDSA) 3 of a biodegradable aliphatic polyester, poly-L-lactide (PLLA) to achieve structurally and functionally diverse precision two-dimensional (2D) assemblies in a crystallizable solvent (isopropanol). PLLA homopolymers, end-functionalized with different dipolar chromophores such as merocyanine (MC) or naphthalene monoimide (NMI) and nonpolar pyrene (PY) or benzene (Bn), crystallize into precise diamond-shaped 2D platelets in isopropanol. 4 This causes the terminally attached chromophores to assemble into a 2D array on the platelet surface by either dipole-dipole interactions (for NMI and MC) or aromatic stacking (PY and Bn), which leads to aggregation-induced enhanced emission (AIEE) with tuneable emission wavelengths within the 2D crystals, depending upon the nature of the end-capped chromophores.4 Further, co-assembly between NMI- and PY-functionalized PLLAs yielded similar two-component co-platelets with highly efficient Förster resonance energy transfer (FRET) from the donor (PY) to the acceptor (NMI) dye with remarkable efficiency (~80%) on the 2D surface. Further, by incorporating the same donor and acceptor dyes at the chain ends of the two enantiomers (PLLA and PDLA), we were able to monitor the stereo- complex co-crystallization in the solution phase by FRET studies, whose similar diamond-shaped 2D structure showed enhanced stability as compared to the individual homo-platelets.5 Furthermore, we studied the scope of these SC co-crystals for surface decoration with external fluorescent dyes for cascade energy transfer and white light emission. 5 Various aspects of these two topics will be covered in the talk. References 1. Biswas, S.; Das, A.* Chem. Eur. J. 2023. 29, e202203849. 2. Biswas, S.; Barman, R.; Das, A.* manuscript under preparation 3. MacFarlane, L.; Zhao, C.; Cai, J.; Qiu, H.*; Manners, I.* Chem. Sci. 2021, 12, 4661-4682. 4. Rajak, A.; Das, A.* Angew. Chem. Int. Ed. 2022, 61, e202116572. (Selected as a Hot Paper and Cover Picture). 5. Rajak, A.; Das, A.* Angew. Chem. Int. Ed. 2023 (doi.org/10.1002/anie.202314290).
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© The Author(s), 2023
Application of organic catalysis and sustainable chemistry towards AI-assisted materials discovery James Hedrick IBM, USA The discovery, development and deployment of new materials provides business opportunities as well as drives advances in high value applications ranging from microelectronics to medicine. As progress in computational chemistry and AI systems continue, there influence on materials discovery including the creation of new polymer-forming reactions and catalysts discovery will become more pervasive. We have developed a broad class of highly active organic catalysts that span many orders of magnitude over a large palette of monomers. Fundamental mechanistic and theoretical investigations together with AI-assisted insights have created new pathways to well-defined macromolecular architectures. To overcome the time to market challenge, the merging of automated synthesis, high-throughput characterization, and predictive AI into a single pipeline offers the opportunity to dramatically accelerate materials development at a fraction of the traditional
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© The Author(s), 2023
Design of electroactive polymers for intrinsically-stretchable polymer solar cells Bumjoon J. Kim Department of Chemical and Biomolecular Engineering, Korea Advanced Institute of Science and Technology (KAIST), Republic of Korea Considering the technical standards required for wearable electronics, such as mechanical robustness, the development of fully stretchable OSCs (f-SOSCs) should be accelerated. Concurrently, f-SOSCs offer an intriguing platform for testing the mechanical and electrical properties of new polymeric materials. This presentation will discuss key studies aimed at making each layer of f-SOSCs both stretchable and efficient, with an emphasis on strategies to simultaneously enhance the photovoltaic and mechanical properties of the active layer. I will outline material design strategies to enhance the mechanical robustness of the PSCs as well as their power conversion efficiencies (PCEs). These strategies include; i) incorporating a high-molecular weight polymer acceptor as a tie molecule into active layers, ii) developing new electroactive polymers consisting of hard and soft segments and iii) developing new materials that improve molecular miscibility in the donor-acceptor blends. With these contributions, the f-SOSCs achieving over 14% PCE and excellent stretchability have been developed. References 1. Park, J. S. et al. Adv. Mater. 2022, 34, 2201623
2. Lee, J. W. et al. Energy Environ. Sci. 2021, 14, 4067 3. Lee, J. W. et al. Energy Environ. Sci. 2022, 15, 4672 4. Lee, J. W. et al. Adv. Mater. 2022, 34, 2207544 5. Seo, S. et al. Adv. Mater. 2023, 35, 2300230
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© The Author(s), 2023
The unexpected kinetics in the synthesis of polythiophene derivatives
Christine Luscombe Okinawa Institute of Science and Technology, Japan
Conjugated polymers with ethylene glycol side chains are emerging as ideal materials for bioelectronics, particularly for application in organic electrochemical transistors (OECTs). To improve the OECT device performance, developing an efficient synthetic strategy that will provide access to novel high-performing materials besides focusing on molecular design is important. While much effort is being devoted to designing new polymers by modifying the glycol side chains, understanding how their nature affects the polymerization kinetics and, eventually the polymer structure and properties is unknown. In this work, we have studied the influence of the content of the ethylene glycol side chain and its linkage to the formation of the active Grignard monomer species upon Grignard metathesis in three thiophene derivatives. A strong dependence of the monomer’s concentration on polymerization was noted in our study, indicating that for synthesizing a glyocolated polythiophene, P3MEEMT- a high-performing OECT material, a minimum of 0.15 M monomer is needed. Furthermore, kinetic studies by GPC show uncontrolled polymerization behavior contrary to the controlled chain growth characteristics of the KCTP.
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© The Author(s), 2023
Nanostructured functional materials enabled by atom transfer radical polymerization Krzysztof Matyjaszewski Carnegie Mellon University, Center for Macromolecular Engineering, USA Many advanced nanostructured functional materials were recently designed and prepared by reversible deactivation radical polymerization. Copper-based ATRP (atom transfer radical polymerization) catalytic systems with polydentate nitrogen ligands are among the most efficient reversible deactivation radical polymerization systems. ATRP enables rational design of (co)polymers with specific architecture and functionality, followed by precise and efficient polymer synthesis and characterization to prepare advanced materials with target properties. Various copolymers, molecular brushes, hybrid materials, and bioconjugates were prepared with high precision. Examples of nanostructured multifunctional hybrid materials for applications related to biology, environment, and energy will be presented. 1-7 References 1. Matyjaszewski, K.; Gnanou, Y.; Hadjichristidis, N.; Muthukumar, M., Eds. Macromolecular Engineering, 2nd Ed.; 2nd ed.; Wiley VCH: Weinheim, 2022. http://dx.doi.org/10.1002/9783527815562.mme0036 ISBn: 978-3-527-34455-0 2. Wang, C.; Zhao, R.; Fan, W.; Li, L.; Feng, H.; Li, Z.; Yan, C.; Shao, X.; Matyjaszewski, K.; Wang, Z., Tribochemically Controlled Atom Transfer Radical Polymerization Enabled by Contact Electrification, Angewandte Chemie International Edition 2023, 62, e202309440. http://dx.doi.org/https://doi.org/10.1002/anie.202309440. 3. Jeong, J.; Szczepaniak, G.; Das, S. R.; Matyjaszewski, K., Expanding the architectural horizon of nucleic-acid-polymer biohybrids by site-controlled incorporation of ATRP initiators in DNA and RNA, Chem 2023, 9, 2023.2007.2013. http:// dx.doi.org/https://doi.org/10.1016/j.chempr.2023.07.013. 4. De Luca Bossa, F.; Yilmaz, G.; Matyjaszewski, K., Fast Bulk Depolymerization of Polymethacrylates by ATRP, ACS Macro Letters 2023, 12, 1173-1178. http://dx.doi.org/10.1021/acsmacrolett.3c00389. 5. Jeong, J.; Hu, X.; Murata, H.; Szczepaniak, G.; Rachwalak, M.; Kietrys, A.; Das, S. R.; Matyjaszewski, K., RNA-Polymer Hybrids via Direct and Site-Selective Acylation with the ATRP Initiator and Photoinduced Polymerization, Journal of the American Chemical Society 2023, 145, 14435-14445. http://dx.doi.org/10.1021/jacs.3c03757. 6. Kapil, K.; Szczepaniak, G.; Martinez, M. R.; Murata, H.; Jazani, A. M.; Jeong, J.; Das, S. R.; Matyjaszewski, K., Visible- Light-Mediated Controlled Radical Branching Polymerization in Water, Angewandte Chemie International Edition 2023, 62, e202217658. http://dx.doi.org/https://doi.org/10.1002/anie.202217658. 7. Kapil, K.; Jazani, A. M.; Szczepaniak, G.; Murata, H.; Olszewski, M.; Matyjaszewski, K., Fully Oxygen-Tolerant Visible-Light- Induced ATRP of Acrylates in Water: Toward Synthesis of Protein-Polymer Hybrids, Macromolecules 2023, 56, 2017-2026. http://dx.doi.org/10.1021/acs.macromol.2c02537.
P09
© The Author(s), 2023
Vinyl polymer engineering for the development of new materials for biomedical applications Julien Nicolas Université Paris-Saclay, CNRS, France Synthetic polyesters and polypeptides are regarded as gold standards for the development of polymer-based nanoscale systems (e.g., polymer nanoparticles, polymer prodrugs) for biomedical applications. However, despite their non-degradability, vinyl polymers offer many advantages in terms of macromolecular engineering. For instance, owing to their great versatility and ease of functionalization, vinyl polymers can be advantageously used for the design of polymer prodrugs for drug delivery purposes. Our group has recently reported on the design of a new class of polymer prodrug nanocarriers by using the “drug-initiated” method, which consists in the controlled growth of vinyl polymers from anticancer drug-bearing controlling agents for reversible deactivation radical polymerization to prepare well-defined and high drug content polymer prodrug nanoparticles with in vitro and in vivo anticancer activity.1,2,3 This approach has also been applied to the synthesis of water-soluble polymer prodrugs for subcutaneous administration of irritant/vesicant anticancer drugs as an alternative to traditional intravenous chemotherapy.4 To challenge traditional polyesters, a lot of effort is also currently focused on the design of degradable vinyl polymers to make them suitable for biomedical applications.5 One of the most potent approaches relies on the introduction of labile groups in the carbon polymer backbone by radical ring-opening polymerization (rROP) of cyclic monomers (e.g., cyclic ketene acetals) with traditional vinyl monomers.6 Yet, despite promising achievements, important limitations still stand, such as the poor hydrolytic degradation of rROP copolymers in physiological conditions, which still cannot compete that of aliphatic polyesters. In this context, we have recently reported the development of: (i) new copolymerization systems that enable the synthesis of well-defined, thermosensitive vinyl copolymers with enhanced hydrolytic degradation in water and PBS (Figure 1)7 and (ii) new polymerization processes to generate aqueous suspensions of degradable vinyl copolymer nanoparticles for biomedical applications.8
Figure 1. Synthesis of thermosensitive vinyl copolymers obtained by copolymerization of acrylamide (AAm) and cyclic ketene acetals (CKA) that can form nanoparticles and degrade faster than PLA and PLGA. References: 1. 1. Nicolas, J. Chem. Mater. 2016, 28, 1591 2. 2. Guégain, E.; Tran, J.; Deguettes, Q.; Nicolas, J. Chem. Sci. 2018, 9, 8291 3. 3. Lages, M.; Pesenti, T.; Zhu, C.; Le, D.; Mougin, J.; Guillaneuf, Y.; Nicolas, J. Chem. Sci. 2023, 14, 3311 4. 4. Bordat, A.; Boissenot, T.; Ibrahim, N.; Ferrere, M.; Levêque, M.; Potiron, L.; Denis, S.; Garcia-Argote, S.; Carvalho, O.; Abadie, J.; Cailleau, C.; Pieters, G.; Tsapis, N.; Nicolas, J. J. Am. Chem. Soc. 2022, 144, 18844
5. 5. Delplace, V.; Nicolas, J. Nature Chem. 2015, 7, 771 6. 6. Pesenti, T.; Nicolas, J. ACS Macro Letters 2020, 9, 1812 7. 7. Bossion, A.; Zhu, C.; Guerassimoff, L.; Mougin, J.; Nicolas, J. Nature Commun. 2022, 13, 2873 8. 8. Zhu, C.; Denis, S.; Nicolas, J. Chem. Mater. 2022, 34, 1875
P10
© The Author(s), 2023
Exploration of light responsive materials Javier Read de Alaniz University of California, Santa Barbara, USA
Photons have multiple enabling advantages to control chemical reactions, processes and stimuli-responsive materials. In this seminar, I will discuss our groups effort to design and develop a new class of negative photochromic molecules termed donor-acceptor Stenhouse adducts (DASA), their incorporation into polymers and subsequent effort to unlock their potential to create photoresponsive materials.
P11
© The Author(s), 2023
Photocatalysis to synthesize, derivatize, depolymerize and degrade polymers Brent Sumerlin University of Florida, USA Post-polymerization modification strategies have advanced considerably in recent decades due to the discovery and development of highly efficient chemoselective reactions. These methods facilitate the synthesis of complex macromolecules by providing methods to transform pendent or terminal reactive groups of polymers into the desired functionality after polymerization. Post-polymerization modification often enables polymers with diverse properties to be generated from the starting material merely by using different reagents for functionalization. Ideal modifications to polymer structures are rapid, specific, efficient, and able to be performed catalytically to lead to functional polymers or copolymers inaccessible by direct polymerization. Relying solely on mild ultraviolet or visible light irradiation of thiocarbonylthio compounds, we have developed a new avenue to polymer-protein conjugates, semi-telechelic polymers, and well-defined ultrahigh molecular weight (UHMW) block polymers. Using either a photocatalyst or relying on the direct activation of photoactive functional groups, we devised a strategy to functional polymers with unprecedented molecular weights, complex architectures, and controlled microstructures. Photochemistry applied to commodity poly(meth)acrylates allowed us to (i) synthesize polymers by photoiniferter polymerization and (ii) install new functionality to these polymers to prepare copolymers of (meth)acrylates and olefins that are inaccessible by direct copolymerization. Extending these approaches to the rapidly growing field of photocatalytic decarboxylation, we were also able to prepare photodegradable polymers that have all-carbon backbones. Finally, we have demonstrated that by employing the traditional conditions of photopolymerization at elevated temperatures, we can achieve dramatically accelerated depolymerization to regenerate monomer, suggesting low-energy photochemistry can be leveraged to approach life-cycle circularity. We have also demonstrated that the end groups that result from reversible-deactivation radical polymerization allow depolymerization of polymethacrylates in the bulk at temperatures up to 250°C lower than traditional processes. We demonstrated that decarboxylation of copolymers possessing activated esters or carboxylic acids is a versatile method for the derivatization or degradation of polymer backbones. The process is attractive for polymer modification because it is rapid, involves mild conditions, and, in some cases, bypasses the need for preactivation, granting high atom economy. We established that the backbone radicals generated by direct decarboxylation can be converted into multiple functional groups or lead to chain cleavage, depending on the structure of the copolymer and the presence of other reagents. Extending these approaches to the rapidly growing field of photocatalytic decarboxylation, we can also exploit photochemistry for degrading polymers despite their all-carbon backbones. We have also demonstrated that by exploiting the end groups that result from controlled radical polymerization, we are able to achieve dramatically accelerated depolymerization to regenerate monomer, suggesting low-energy photochemistry or thermal treatment can be leveraged to approach life-cycle circularity
P12
© The Author(s), 2023
Advanced functional polymers with aggregation-induced emission Ben Zhong Tang School of Science and Engineering, Shenzhen Institute of Aggregate Science and Technology, The Chinese University of Hong Kong, China Polymers with aggregation-induced emission (AIE) characteristics are a class of materials that show weak light emission in dilute solutions but become intensively emissive in the aggregated state. They have attracted tremendous attention in the past decades due to their excellent processability, efficient solid-state emission, high sensitivity in fluorescence sensing, unique mechanical properties, diverse topological and morphological structures, etc. In this talk, the recent research progress on the synthesis, structures, and functionalities of AIE- active polymers will be introduced. Moreover, new AIE-active systems (clusteroluminescent polymers) without conventional chromophores will also be discussed. A general method for synthesizing AIE-active polymers is to incorporate AIE-active luminogens (AIEgens) into the side chain, main chain, or center/terminal of a polymer structure. By using different polymerization or post-modification strategies, a large variety of AIE-active polymers with linear, star-shaped, dendritic, hyperbranched, cross-linked, or three-dimensionally ordered structures have been constructed. The combination of AIE effect and the polymer characteristics enable AIE-active polymers to find a wide range of practical applications, including fluorescence chemosensing, bioprobing, bioimaging, as well as light emitting device fabrication. We hope this talk could provide some insight into the design strategy and the structure-property relationship of functional polymers from AIEgens to benefit the further advancement of this area and to show a picture of the bright future of AIE-active polymers. References 1. J. Mei, N.L.C. Leung, R.T.K. Kwok, J.W.Y. Lam, B.Z. Tang. Chem. Rev. 2015, 115, 11718.
2. A.J. Qin, J.W.Y. Lam, B.Z. Tang. Prog. Polym. Sci. 2012, 37, 182. 3. Hu, R.; Qin, A.; Tang, B. Z. Prog. Polym. Sci. 2020, 100, 101176. 4. He, B.; Huang, J.; Liu, X.; Zhang, J.; J.W.Y. Lam, B.Z. Tang. Prog. Polym. Sci. 2022, 126, 101503. 5. Yan, H.; He, Y.; Wang, D.; Han, T.; B.Z. Tang. Aggregate 2023, e331. 6. Fu, X.; Qin, A.; B.Z. Tang. Aggregate 2023, e350.
P13
© The Author(s), 2023
Sequence-controlled peptoid polymers Helen Tran Department of Chemistry, University of Toronto
The presentation of bioactive moieties in terms of multivalency, ligand density, and architecture plays a central role in biological recognition processes, including cellular adhesion and pathogen binding. Polypeptoids that self-assemble into two-dimensional (2D) nanosheets have potential to recapitulate these precise molecular recognition motifs onto a flexible platform for biosensing. The traditional solid-phase method for the synthesis of peptoids allows for precise control over the placement of potential recognition sites in the sequence, yet generates molecules on a small scale (~100 mg). Recent solution-phase synthetic methods have enabled gram- scale synthesis but lack sequence-specificity needed for self-assembly and precise incorporation of molecular recognition motifs. Herein, we present our motivations and efforts in bridging this divide. Moreover, we share our progress in replacing solvents traditionally used in the synthesis of peptoids with greener alternatives.
P14
© The Author(s), 2023
Oxygenated polymers for solid-state batteries Charlotte K. Williams Department of Chemistry, University of Oxford, UK
Polymers showing the right combination of electrochemical, mechanical and chemical properties could help deliver practical all-solid-state batteries for high-performance next-generation energy storage devices. These batteries require better polymers as both electrolytes and binders to better manage the active particle volume changes upon charge/discharge cycles and improve interfacial contact within composite cathodes. Further, currently used binders, e.g. polyvinylidene fluoride (PVDF), may be challenged by the proposed European Chemicals Agency bans on per- and poly fluoroalkyl substances (PFAS) – our research focusses on the discovery of alternative oxygenated polymers.1 This lecture will present the production, properties and performances of various new polycarbonates, -ethers and -esters within copolymers, for use in solid state batteries.2 Controlled polymerizations are used to produce well defined copolymers with the ability to moderate compositions, structures and resulting properties. These polymerizations exploit recent discoveries of highly active and selective polymerization catalysts.3, 4 These syntheses apply monomers including carbon dioxide, epoxides, cyclic esters and carbonates to deliver ABA block polymer structures (where A = polymer featuring a Tg> room temperature and B = block polymer featuring Tg < room temperature).2 Polymer thermal and mechanical properties will be outlined, together with data on phase separated nanostructures. Polymer properties relevant to batteries will include lithium-ion conductivity, transference numbers, electrochemical/chemical stability be presented, including lithium-ion conductivity and transference number, electrochemical/chemical stabilities and interfacial adhesion. The highest performing block polymers are used in composite cathodes using NMC (LiNi0.8Mn0.1Co0.1O2) as the active cathode with lithium Agyrodite (Li6PS5Cl) as the solid electrolyte– the resulting solid-state batteries demonstrate high capacities and excellent capacity retention. Performances are benchmarked against currently used binders and electrolytes.2 The potential to ‘recycle’ these polymers is outlined as a future option which may help improve sustainability and battery recycling.5 References 1. X. Lim, Nature, 2023, 620, 24-27. 2. G. L. Gregory, H. Gao, B. Liu, X. Gao, G. J. Rees, M. Pasta, P. G. Bruce and C. K. Williams, J. Am. Chem. Soc., 2022, 144, 17477-17486. 3. A. C. Deacy, G. L. Gregory, G. S. Sulley, T. T. D. Chen and C. K. Williams, J. Am. Chem. Soc., 2021, 143, 10021-10040. 4. W. T. Diment, W. Lindeboom, F. Fiorentini, A. C. Deacy and C. K. Williams, Acc. Chem. Res., 2022, 55, 1997-2010. 5. T. M. McGuire, A. C. Deacy, A. Buchard and C. K. Williams, J. Am. Chem. Soc., 2022, 144, 18444-18449.
P15
© The Author(s), 2023
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