Knotting matters: orderly molecular entanglements
Entangling strands in a well-ordered manner can produce useful effects, from shoelaces and fishing nets to brown paper packages tied up with strings. At the nanoscale, non-crystalline polymer chains of sufficient length and flexibility randomly form tangled mixtures containing open knots of differen...
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| Published in | Chemical Society reviews Vol. 51; no. 18; pp. 7779 - 789 |
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| Main Authors | , , , , , |
| Format | Journal Article |
| Language | English |
| Published |
London
Royal Society of Chemistry
20.09.2022
The Royal Society of Chemistry |
| Subjects | |
| Online Access | Get full text |
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| Summary: | Entangling strands in a well-ordered manner can produce useful effects, from shoelaces and fishing nets to brown paper packages tied up with strings. At the nanoscale, non-crystalline polymer chains of sufficient length and flexibility randomly form tangled mixtures containing open knots of different sizes, shapes and complexity. However, discrete molecular knots of precise topology can also be obtained by controlling the number, sequence and stereochemistry of strand crossings: orderly molecular entanglements. During the last decade, substantial progress in the nascent field of molecular nanotopology has been made, with general synthetic strategies and new knotting motifs introduced, along with insights into the properties and functions of ordered tangle sequences. Conformational restrictions imparted by knotting can induce allostery, strong and selective anion binding, catalytic activity, lead to effective chiral expression across length scales, binding modes in conformations efficacious for drug delivery, and facilitate mechanical function at the molecular level. As complex molecular topologies become increasingly synthetically accessible they have the potential to play a significant role in molecular and materials design strategies. We highlight particular examples of molecular knots to illustrate why these are a few of our favourite things.
We review recent progress in molecular knotting, the chemistry of orderly molecular entanglements. As complex nanotopologies become increasingly accessible they may play significant roles in molecular design. |
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| Bibliography: | Lucian Pirvu was born in Romania. He obtained his MChem degree from the University of Manchester in 2015, and then joined Prof. David A. Leigh's group at the same institution for a PhD studying the synthesis of lanthanide template molecular knots. He is currently a postdoctoral research associate in the group of Prof. Nicholas J. Turner at the University of Manchester working on the application of enzymatic cascades to the synthesis of pharmaceutically relevant molecules. Zoe Ashbridge is from Cornwall (UK). She completed her undergraduate MSci degree at the University of Nottingham. During this time, she undertook a research project on the synthesis of pillararene rotaxanes under the supervision of Prof. Neil R. Champness. She joined the group of Prof. David A. Leigh as a PhD student at the University of Manchester in 2018. Her research interests include the synthesis and applications of complex molecular topology. Stephen Fielden was born in Bury, Greater Manchester (UK). He obtained an MChem from the University of Oxford and then undertook his PhD in Prof. David A. Leigh's group at the University of Manchester. Stephen moved to work with Prof. Rachel O'Reilly at the University of Birmingham, where he currently holds a Leverhulme Early Career Fellowship. His research interests include molecular machines, out-of-equilibrium chemical systems and polymer nanotechnology. Liang Zhang was born in Lanzhou (China) and got his BSc and MSc from Fudan University (China). He then moved to UK and obtained his PhD from the University of Manchester under the supervision of Prof. David A. Leigh. Currently, he is a Zijiang Outstanding Young Professor at East China Normal University in Shanghai, China. His research focuses on molecular nanotopology and molecular electronics. Fredrik Schaufelberger is from Gothenburg, Sweden, and received his PhD from KTH Royal Institute of Technology in Stockholm. In 2017, he moved to the group of Prof. David A. Leigh at the University of Manchester with a Marie Sk odowska-Curie Individual Fellowship. After a research stay with Prof. Molly M. Stevens at Imperial College London, he took up a position as assistant professor at KTH Royal Institute of Technology. His group studies topologically complex molecules for applications in biomedicine and biomaterials. David A. Leigh was born in Birmingham (UK) and obtained his BSc and PhD from the University of Sheffield. He holds the Sir Samuel Hall Chair of Chemistry at the University of Manchester and is a Royal Society Research Professor. His research interests include molecular nanotopology and molecular nanotechnology. ObjectType-Article-2 SourceType-Scholarly Journals-1 ObjectType-Feature-3 content type line 23 ObjectType-Review-1 |
| ISSN: | 0306-0012 1460-4744 |
| DOI: | 10.1039/d2cs00323f |