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Article
Peer-Review Record

Metal Ion-Induced Formation of Metallogels by Visible-Light-Responsive Phenylalanine-Functionalized Arylazopyrazole Ligands

Photochem 2023, 3(4), 427-441; https://doi.org/10.3390/photochem3040026
by Mikayla Browning, Alexandra Jefferson, Jazz Geter and Kesete Ghebreyessus *
Reviewer 1: Anonymous
Reviewer 2: Anonymous
Photochem 2023, 3(4), 427-441; https://doi.org/10.3390/photochem3040026
Submission received: 1 September 2023 / Revised: 6 October 2023 / Accepted: 17 October 2023 / Published: 24 October 2023

Round 1

Reviewer 1 Report

In this manuscript, a visible-light responsive arylazopyrazole-functionalized phenylalanine (4-MeS-AAP-NF) derived ligand has been designed and synthesized. It was found to form metallogels with reversible photoresponsive properties in a mixed methanol/water (MeOH/H2O)) solvents. The morphology and viscoelastic properties of the yellow-orange opaque metallogels have been characterized by scanning electron microscopy (SEM) and rheological measurement, respectively. Moreover, the gels showed a slow reversible visible-light-induced gel-to-sol phase transition under blue and then sol-to-gel transition by green light irradiation resulting in re-formation of the original gel state. This work is suitable for publication in Photochem after a minor revision. However, there are some questions remain to be addressed to make the manuscript more suitable.

 

1.     Please delete all the synthetic steps in Experimental Procedure.

2.     In Scheme 1, the synthetic route for 4-MeS-AAP-CH2CO2H should be redrawn with the same size and standard.

3.     The pictures for Figure 2, Figure 5 and Figure 6 are very messy, please redraw it.

The English expression is generally good!

Author Response

Dear Ms. Yang,

We thank the reviewers’ for their constructive comments.

Since most of the comments of the reviewers focused on figures and schemes no highlights are made. However, the requested changes to the figures and schemes have been applied.

Re: photochem-2616647

Answers to reviewer’s comments are given below.

Reviewer 1 Comments and Suggestions for Authors

In this manuscript, a visible-light responsive arylazopyrazole-functionalized phenylalanine (4-MeS-AAP-NF) derived ligand has been designed and synthesized. It was found to form metallogels with reversible photoresponsive properties in a mixed methanol/water (MeOH/H2O)) solvents. The morphology and viscoelastic properties of the yellow-orange opaque metallogels have been characterized by scanning electron microscopy (SEM) and rheological measurement, respectively. Moreover, the gels showed a slow reversible visible-light-induced gel-to-sol phase transition under blue and then sol-to-gel transition by green light irradiation resulting in re-formation of the original gel state. This work is suitable for publication in Photochem after a minor revision. However, there are some questions remain to be addressed to make the manuscript more suitable. 

  1. Please delete all the synthetic steps in Experimental Procedure.

The synthetic procedures are removed

  1. In Scheme 1, the synthetic route for 4-MeS-AAP-CH2CO2H should be redrawn with the same size and standard.

Scheme 1, the synthetic route for 4-MeS-AAP-CH2CO2H is redrawn to address reviewers’ concerns.

  1. The pictures for Figure 2, Figure 5 and Figure 6 are very messy, please redraw it.

The pictures in Figure 2, and Figure 5 are redrawn. But we are not sure what the issue is with figure 6.

 

Comments on the Quality of English Language

The English expression is generally good!

Submission Date

01 September 2023

Date of this review

20 Sep 2023 18:54:40

 

Reviewer 2 Report


Comments for author File: Comments.pdf

Author Response

Dear Ms. Yang,

We thank the reviewers’ for their constructive comments.

Since most of the comments of the reviewers focused on figures and schemes no highlights are made. However, the requested changes to the figures and schemes have been applied.

Answers to reviewer’s comments are given below.

Reviewer 2 comments

Re: photochem-2616647

 Metal Ion-Induced formation of Metallogels by Visible-Light Responsive PhenylalanineFunctionalized Arylazopyrazole Ligands Mikayla Browning , Alexandra Jefferson , Jazz Geter , Kese Ghebereyesssus Reviewer General Comments:

The authors prepared a publication in which they designed the metallogels photo switches based on arylazopyrazole derivatives. It was shown that gelation occurred in the presence of divalent metal cations at basic conditions. The manuscript is wellwritten, and the experimental work and discussions are well-presented. The conclusions are agreeable, and the authors did a great job utilizing different experimental techniques to support their conclusions.

Specific Minor Comments:

  1. Do authors have expanded or planned to expand their study to monovalent and trivalent metal cations? Does the gelation depend on the nature of the cation or its charge?

 

Yes, currently we are working on to trivalent ions based transition and main group metals

  1. Did the authors observe any gelation in the presence of bivalent metal cations in neutral or acidic conditions? If not, what are the reasons?

 

No gelation was observed at pH 7 or less.

 

  1. Page 9 of 17: Figure 2 needs minor improvements as the series of arrows on the right side of the figure are not straight.

Figure 2 is adjusted to address reviewer’s concerns.

  1. General questions: How stable are the metallogels under room temperature?

 

The metallogels are very stable under normal conditions. They stay for months without breaking apart

 

Thank you for the opportunity to review the manuscript.

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