Content of review 1, reviewed on November 17, 2023
The Chem Sci manuscript from the Sardon group presents a new type of covalent adaptable networks (CANs) based on the dynamic covalent oxime bond. The authors convincingly show how the oxime bond is the hydrolytically more stable counterpart of the more widely used (in CANs) dynamic covalent imine bond. By combination of detailed small molecule studies, supported by computations, and material synthesis and characterisation the authors nicely show the potential of oxime bonds in dynamic polymers. Provided that the authors can address my remaining points (which I will outline below), I recommend to accept this Chem Sci manuscript.
My first point is related to the computational studies. While they clearly show that the (acid-catalysed) metathesis reaction is feasible, it is not clear whether similar computations would also reveal the transimination pathway to be equally feasible too. Did the authors consider (and perhaps also compute) this transimination pathway? As they are most likely aware of themselves, the transimination pathway can be favoured (at least in case of conventional imines) by having an (slight) excess of amine. Such conditions might have been explored by the authors here too!?
Related to the computational studies, I would suggest to use more contrasting colours in Figure 3. The current use of orange and brown is not ideal. Similarly the use of colours is in Figure 4 is somewhat confusing. In panel B the blue data are for both the orange monomer (TPTM) and blue monomer (HDT); in fact, the blue data are for 80% related to the orange monomer. At least, I would suggest to add labels to panel B, and/or use different colours altogether.
Regarding the recycling studies: have the authors looked at what happens after multiple recycling steps? In particular, given the fact that the catalyst is inside the material? Will it remain active over multiple recycling steps?
Finally some very minor points that I picked up and wanted to share with the authors:
- Page 2, left column, line 9: to what SI section is being referred?
- Page 2, right column, fourth line from the bottom: ‘hydrolysis or excess of oxime’ seems to be weirdly phrased.
- Page 4, right column, line 10: replace KJ/mol by kJ/mol.
Source
© 2023 the Reviewer.
Content of review 2, reviewed on December 18, 2023
The authors have satisfactorily addressed the comments by both reviewers. As a result, I suggest to accept the manuscript.
I do want to suggest to include two of the authors' answers to the reviewer comments (as given in their rebuttal) into the main text too:
1) the discussion about the choice of metathesis over transimination in their computational studies (i.e. their answer to comment 1 of reviewer 1);
2) the motivation for the choice of acids/bases (i.e. their answer to comment 3 of reviewer 2).
I believe that also the reader of the paper would benefit from learning about these considerations.
Source
© 2023 the Reviewer.
References
Luca, P., Marta, X., Francesca, L., Giulia, V., Enrico, B., Fermin, E., Haritz, S. 2024. Oxime metathesis: tuneable and versatile chemistry for dynamic networks. Chemical Science.
