PONE-D-22-06318Efficacy analysis of new copper complex for visible light (455, 530 nm) radical/cationic photopolymerization: the synergic effects and catalytic cyclePLOS ONE

Dear Dr. Lin,

Thank you for submitting your manuscript to PLOS ONE. After careful consideration, we feel that it has merit but does not fully meet PLOS ONE’s publication criteria as it currently stands. Therefore, we invite you to submit a revised version of the manuscript that addresses the points raised during the review process.

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Academic Editor

PLOS ONE

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3. We noticed you have some minor occurrence of overlapping text with the following previous publication(s), which needs to be addressed:

- https://pubmed.ncbi.nlm.nih.gov/34301082/

- http://turroserver.chem.columbia.edu/PDF_db/publications_901_950/NJT915.pdf

In your revision ensure you cite all your sources (including your own works), and quote or rephrase any duplicated text outside the methods section. Further consideration is dependent on these concerns being addressed.

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"JTL thanks the internal grant of Medical Photon Inc. and DCC thanks the financial support from 359 China Medical University with the grant number CMU110-ASIA-11."

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Additional Editor Comments: 

I accept the argument that the newly combined manuscript does present original research (contrary to the opinion of reviewer 1). However, based on the reviewers and my own assessment of this manuscript major revision is needed in two respects: a) the readability needs to be improved to better explain how the equations have been derived and; b) the correlation between these equations and published data needs to be better shown to demonstrate the validity of these results. Several minor comments have also been raised by the review process which should be addressed.

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Reviewers' comments:

Reviewer's Responses to Questions

Comments to the Author

1. Is the manuscript technically sound, and do the data support the conclusions?

The manuscript must describe a technically sound piece of scientific research with data that supports the conclusions. Experiments must have been conducted rigorously, with appropriate controls, replication, and sample sizes. The conclusions must be drawn appropriately based on the data presented.

Reviewer #1: Partly

Reviewer #2: Partly

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2. Has the statistical analysis been performed appropriately and rigorously?

Reviewer #1: I Don't Know

Reviewer #2: N/A

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3. Have the authors made all data underlying the findings in their manuscript fully available?

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Reviewer #1: Yes

Reviewer #2: Yes

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4. Is the manuscript presented in an intelligible fashion and written in standard English?

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Reviewer #1: No

Reviewer #2: No

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5. Review Comments to the Author

Please use the space provided to explain your answers to the questions above. You may also include additional comments for the author, including concerns about dual publication, research ethics, or publication ethics. (Please upload your review as an attachment if it exceeds 20,000 characters)

Reviewer #1: The authors aim to complement already published works from colleagues (Mokbel and al, Mau and al.) by developing analytic formulas for key parameters influencing the formation of IPNs by photopolymerization.

While the study appears to have clear objectives, the presented works lacks of novelty and originality compared to already published works (references 16, 17 and 22). In some degree, this submission seems more like a compilation of already known concepts than the presentation of original research.

Moreover, the language is unclear, making it difficult to follow (several typos and incomplete sentences). The authors should improve the readability of the text.

In my opinion, this topic has potential but this work need drastic revision:

- section 2.1 and 2.2 should be clarify for a better understanding of the developed formulas

- more correlation between the developed formulas and the published experimental data would be a great addition in section 3.1 and 3.2 in order to prove the trustworthiness of the formulas and their usefulness for simulation.

-L99, 156, 172 & 183: The authors refer to the active species for cationic polymerization (either "S" or "EDB(+)") as a radical, are you sure that it is not a cation radical?

-L205: The reaction r6 in scheme 4 seems unbalanced

-L218: What phenomenon is represented by the rate constant K12? Please add more explanation.

-L251: The authors claim the conversion of the cationic polymerization is reduced due to oxygen inhibition. However, cationic polymerization is reported in the literature, as not sensitive to oxygen. Please, justify your claim.

-L272: The authors refer to the concentration of [A] in Eq 16, please clarify.

-L374: Where does this formula come from. Please explain or add a reference.

-L505: Why have the authors consider the case of Iod/EDB without light? Please explain.

-L627: The authors have linked the difference in conversion between the free radical polymerization and the cationic polymerization to the number of species capable to initiate the reactions (2 for FRP, 1 for CP). However, the monomers used in the experimental data, TMPTA and EPOX, does not have the same functionality (TMPTA is a trifunctional monomer while EPOX is a difunctional monomer). Moreover, FRP and CP usually have not the same rate of polymerization. Please, include these facts in your explanation.

Reviewer #2: The manuscript describes kinetic schemes for two 3-initiator photochemical polymerization systems. The kinetics are complex, extending previous work of the authors and others. Some limiting cases within steady-state assumptions are examined analytically and the trends are compared with experimental results from previous work. I have no quarrel with the results or the analysis, except that it is not quantitative as claimed; however, the manuscript is difficult to read and I think it could be improved greatly, as detailed below.

1) For both G1 and G2, while the claim is made for a quantitative agreement with experiment, in fact only qualitative features are compared, increases or decreases etc. Reference is made to various figures from Refs. 16 and 17 and the reader is expected to follow the described trends mentally, imagining the figures. I would strongly suggest that pertinent figures be adapted to show both the experimental and the authors' approximate analytical solutions so that the reader can actually compare them.

2) The manuscript is the result of the fusion of two previous manuscripts and many errors have been made in the process. These must be carefully checked and corrected. Just a few examples (line 169, Scheme 3 should be Scheme 4; In Scheme 3, it should be G2, both in the scheme and in the legend; line 184, (r6) of Scheme 2 should be (r6) of Scheme 4; line 194, Scheme 1 should be Scheme 2); line 272, constant [A] in Eq. (16) should refer to Eq. (20); line 300 (12) and (13) are for G2 but this section is on G1, etc, etc).

3) Throughout the manuscript, replace oxodized by oxidized.

4) line 242, line 274, I don't think these are "comprehensive formulas". They are simplified formulas for some limiting cases.

5) line 291, S and S should be S and S'

6) lines 294 to 400, just one example of qualitative feature being misconstrued as quantitative: " faster raising rate"

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Reviewer #1: No

Reviewer #2: No

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PONE-D-22-06318R1Efficacy analysis of new copper complex for visible light (455, 530 nm) radical/cationic photopolymerization: the synergic effects and catalytic cyclePLOS ONE

Dear Dr. Lin,

Thank you for submitting your manuscript to PLOS ONE. After careful consideration, we feel that it has merit but does not fully meet PLOS ONE’s publication criteria as it currently stands. Please see my detailed comments below. Therefore, we invite you to submit a revised version of the manuscript that addresses the points raised during the review process.

Please submit your revised manuscript by Jul 24 2022 11:59PM. If you will need more time than this to complete your revisions, please reply to this message or contact the journal office at plosone@plos.org. When you're ready to submit your revision, log on to https://www.editorialmanager.com/pone/ and select the 'Submissions Needing Revision' folder to locate your manuscript file.

Please include the following items when submitting your revised manuscript:

• A rebuttal letter that responds to each point raised by the academic editor and reviewer(s). You should upload this letter as a separate file labeled 'Response to Reviewers'.
• A marked-up copy of your manuscript that highlights changes made to the original version. You should upload this as a separate file labeled 'Revised Manuscript with Track Changes'.
• An unmarked version of your revised paper without tracked changes. You should upload this as a separate file labeled 'Manuscript'.

If you would like to make changes to your financial disclosure, please include your updated statement in your cover letter. Guidelines for resubmitting your figure files are available below the reviewer comments at the end of this letter.

If applicable, we recommend that you deposit your laboratory protocols in protocols.io to enhance the reproducibility of your results. Protocols.io assigns your protocol its own identifier (DOI) so that it can be cited independently in the future. For instructions see: https://journals.plos.org/plosone/s/submission-guidelines#loc-laboratory-protocols. Additionally, PLOS ONE offers an option for publishing peer-reviewed Lab Protocol articles, which describe protocols hosted on protocols.io. Read more information on sharing protocols at https://plos.org/protocols?utm_medium=editorial-email&utm_source=authorletters&utm_campaign=protocols.

We look forward to receiving your revised manuscript.

Kind regards,

Robert Chapman, Ph.D.

Academic Editor

PLOS ONE

Journal Requirements:

Please review your reference list to ensure that it is complete and correct. If you have cited papers that have been retracted, please include the rationale for doing so in the manuscript text, or remove these references and replace them with relevant current references. Any changes to the reference list should be mentioned in the rebuttal letter that accompanies your revised manuscript. If you need to cite a retracted article, indicate the article’s retracted status in the References list and also include a citation and full reference for the retraction notice.

Additional Editor Comments (if provided):

The authors have responded to the first point (a) raised by the reviewers - the revised manuscript is more readable and the derivations better eplained. The derivations are detailed and accurate (as they were in the original submission). However, they have still not answered the main comment raised by both revieiwers - that there is no comparison of the results of the analytical solutions with experimental data.

Section 3.2 and 3.4 attempt to describe (in words) the similarities between the equations and the experimental data, which is helpful. They claim that fitting some predicted values of k, in order to plot quantitative solutions against the experimental data requires “complex numerical solutions” that are outside the scope of the present article, which focusses instead on simplified formulae.

It’s not clear why this should be the case. For example, there is only one unknown in eq. 31. The authors assert in line 416-421 that given the values of bI0 and the initial concentrations, they could calculate and compare the profiles of CP, but are hindered by lack of experimental ki and kij values. If this is true, then it should be no problem to demonstrate this by plotting the function with some fitted or assumed values of kj and kij to provide testable predictions for these and to demonstrate the validity of their equations. The same is true in points b, c, d, and e of this section and in section 3.4. Rather than just asserting the similarities between the equations and the experimental data it ought to be possible to demonstrate this by plotting the data, even without the experimentally derived values of the rate constants. Even very simple and approximate plots would permit the authors then to draw the conclusion that they have determined kinetic schemes that they have presented equations for the "kinetics and general conversion features of an IPN”.

Producing such figures (even in the absence of experimental data, to show the general trends align, or perhaps on just one set of input initiator values) should be a matter of hours and would completely put to rest this question? If this is not the case, can the authors please explain why not??

Minor typos to fix:

L133: “coupling” not “conpling”

L135: “example” not “examples"

L446: “similar to THE G1 system of 3.1”

L668: “Eqs.(“ missing text

While revising your submission, please upload your figure files to the Preflight Analysis and Conversion Engine (PACE) digital diagnostic tool, https://pacev2.apexcovantage.com/. PACE helps ensure that figures meet PLOS requirements. To use PACE, you must first register as a user. Registration is free. Then, login and navigate to the UPLOAD tab, where you will find detailed instructions on how to use the tool. If you encounter any issues or have any questions when using PACE, please email PLOS at figures@plos.org. Please note that Supporting Information files do not need this step.

Efficacy analysis of new copper complex for visible light (455, 530 nm) radical/cationic photopolymerization: the synergic effects and catalytic cycle

PONE-D-22-06318R2

Dear Dr. Lin,

We’re pleased to inform you that your manuscript has been judged scientifically suitable for publication and will be formally accepted for publication once it meets all outstanding technical requirements.

Within one week, you’ll receive an e-mail detailing the required amendments. When these have been addressed, you’ll receive a formal acceptance letter and your manuscript will be scheduled for publication.

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Kind regards,

Robert Chapman, Ph.D.

Academic Editor

PLOS ONE

Additional Editor Comments (optional):

The authors have responded to all the comments of the reviewers - the new figures help show that the equations could be used to fit the experimental data.

Reviewers' comments: