Multicatalytic Hybrid Materials for Biocatalytic and Chemoenzymatic Cascades—Strategies for Multicatalyst (Enzyme) Co-Immobilization

Round 1

Reviewer 1 Report

The manuscript entitled “Multi-catalytic materials for biocatalytic and chemoenzymatic cascades – strategies for catalysts co-immobilization” presents co-immobilization of catalyst technique and their usability in various transformation processes in particular for multi-cascade reactions. Especially valuable are the reaction cascades presented to complement the text, however authors should emphasize more the materials used for co-immobilization, as the title indicates. For each type of co-immobilization technique (enzymes or enzyme/non-enzyme catalyst) tables summarizing the materials used for immobilization and the enzymes immobilized on them and application would be very helpful to readers.

In my opinion the manuscript is publishable after some revisions suggested below.

Specific comments:

• tables summarizing the materials used for differents co-immobilization/the enzymes and other catalyst/application should be inculded to the manuscript
  
• too low resolution of Figures 1, 6 and 8, visible especially on printed version, suggested resolution improvement,
• Table 1 should be on one page
• inconsistency of figure and diagram captions, some are bolded and some are not,
• caption of figure 8 goes to the next page.

Author Response

Answers to Referee 1

 

The manuscript entitled “Multi-catalytic materials for biocatalytic and chemoenzymatic cascades – strategies for catalysts co-immobilization” presents co-immobilization of catalyst technique and their usability in various transformation processes in particular for multi-cascade reactions. Especially valuable are the reaction cascades presented to complement the text, however authors should emphasize more the materials used for co-immobilization, as the title indicates. For each type of co-immobilization technique (enzymes or enzyme/non-enzyme catalyst) tables summarizing the materials used for immobilization and the enzymes immobilized on them and application would be very helpful to readers.

Dear referee, thank you for your kind comments and suggestions. All of them were marked in yellow in the body of manuscript.

In my opinion the manuscript is publishable after some revisions suggested below.

Specific comments:

• tables summarizing the materials used for differents co-immobilization/the enzymes and other catalyst/application should be inculded to the manuscript

Dear referee, thank you for your consideration. In the text, a concise table summarizing different matrices used for co-immobilization of enzymes for synthetic purposes was added (table 1)

• Too low resolution of Figures 1, 6 and 8, visible especially on printed version, suggested resolution improvement

Thank you for your advise. We have changed.

• Table 1 should be on one page

Thank you for your suggestion. Table 1 is now table 2, and we adjusted to one page.

• Inconsistency of figure and diagram captions, some are bolded and some are not.

Thank you dear referee, we have analized and corrected them.

• Caption of figure 8 goes to the next page.

Thank you, dear referee, we have corrected.

Author Response File: Author Response.pdf

Reviewer 2 Report

The review from Dr Amanda Silva de Miranda and co-workers focus on the Multi-catalytic materials for biocatalytic and chemoenzymatic cascades – strategies for catalysts co-immobilization. I should note that this review was appropriately written and will be interesting to readers in the field. Therefore, I recommend acceptance of the manuscript after minor revision based on the following comments:

1. Title: ‘Multi-catalytic materials’ is not a common term, suggest ‘multi-catalytic hybrid materials’ (MCHMs). MCHMs are feature as chemical and biological catalysts co-immobilized on the same support.
2. Title: Should emphasis on ‘multi-catalyst (enzyme) co-immobilization’
3. Line 34: should include ‘regio-‘
4. Line 71: suggest using ‘multi-(bio)catalysts’ to avoid confusion with single enzyme.
5. Line 84: not very clear for ‘co-immobilization of enzymes solely’ (see line 71)
6. Line 92: unique selectivity
7. Line 96: add a reference for biocatalytic process (Catalysts 2020, 10, 1303; doi:10.3390/catal10111303)
8. Table 1: ‘amide bond formation’ is not a correct term. (imidamide)
9. Table 1: ‘Carrier binding with bifunctional reagents’ is not a reaction (Schiff’s base formation)
10. Table 1: It is a mercury-sulfide formation reaction.
11. Table 1: The drawing for formation of the M-E bond is not correct. A half arrow is needed to draw start from M radical to meet another half arrow’s head to indicate the bond formation.
12. Line 288: 72% to replace 71.86%
13. Line 367: 1:05 (not sure is correct?)
14. Lines 413, 588, 623, 630 and. 688: et al. should be in italic.
15. Line 425: can indicate the red line representing the cross-linker.
16. Line 529: need to define ‘Km’
17. Line 587, Figure 3: ‘racemization’ is not a good term. Racemization is a conversion of an optically active compound into a racemic mixture (results in an optically inactive mixture). Here, is a kinetic resolution with epimerizing the chiral center.
18. Line 618, Figure 4: Re-draw the chemical structures as the bond lines are not straight.
19. Line 619: Figure 4 (a) should further explain in the caption for ‘HMF to FDCA’.
20. Line 632: should explain ZIF-8 (a kind of MOF).
21. Line 642: need to explain ‘NMOF’ as nanocrystalline MOF.
22. Line 702: the ‘2’ of CO₂ need to use subscript.
23. Lines 708-710, 1000, 1045, 1082, 1083, 1088 and 1089: the % number can be reported as integer.
24. Lines 775, 897 and 972: a space is needed between number and ‘h’.
25. Line 791: Scheme 1 missing 16 ’h’
26. Line 799: the % number can be reported as integer. Replaces 99.89% with ‘>99 %’
27. Line 833: typo mistake ‘usefulness’
28. Line 997: Typo with '(Pt@UiO-66@LAAO)'
29. Line 1057: add an abbreviation for (NaDC) and (Mi)

 

 

 

 

Author Response

Answers to the Referee 2

 

      Dear Referee, thank you for your kind and detailed revision. All points were analyzed and changed according your suggestions.

1. Title: ‘Multi-catalytic materials’ is not a common term, suggest ‘multi-catalytic hybrid materials’ (MCHMs). MCHMs are feature as chemical and biological catalysts co-immobilized on the same support.

Changed

1. Title: Should emphasis on ‘multi-catalyst (enzyme) co-immobilization’

Changed

1. Line 34: should include ‘regio-‘

Done

1. Line 71: suggest using ‘multi-(bio)catalysts’ to avoid confusion with single enzyme.

Done

1. Line 84: not very clear for ‘co-immobilization of enzymes solely’ (see line 71)

The sentence was rewriten

1. Line 92: unique selectivity

Done

1. Line 96: add a reference for biocatalytic process (Catalysts 2020, 10, 1303; doi:10.3390/catal10111303)

The reference was added

1. Table 1: ‘amide bond formation’ is not a correct term. (imidamide)

Done

1. Table 1: ‘Carrier binding with bifunctional reagents’ is not a reaction (Schiff’s base formation)

Ok, Thank you, it was changed. And now it is table 2.

1. Table 1: It is a mercury-sulfide formation reaction.

Ok. Thank you. Now it is table 2.

1. Table 1: The drawing for formation of the M-E bond is not correct. A half arrow is needed to draw start from M radical to meet another half arrow’s head to indicate the bond formation.

Ok. The drawing was changed, thank you.

1. Line 288: 72% to replace 71.86%

Ok, replaced, thank you

1. Line 367: 1:05 (not sure is correct?)

The ratio was really 1:0.5.

1. Lines 413, 588, 623, 630 and. 688: et al. should be in italic.

Ok, it was changed. Thank you

1. Line 425: can indicate the red line representing the cross-linker.

It was indicated.

1. Line 529: need to define ‘Km’

It was better defined. Thank you

1. Line 587, Figure 3: ‘racemization’ is not a good term. Racemization is a conversion of an optically active compound into a racemic mixture (results in an optically inactive mixture). Here, is a kinetic resolution with epimerizing the chiral center.

The figure was changed.

1. Line 618, Figure 4: Re-draw the chemical structures as the bond lines are not straight.

It was redrawed.

1. Line 619: Figure 4 (a) should further explain in the caption for ‘HMF to FDCA’.

It was explained. Thank you

1. Line 632: should explain ZIF-8 (a kind of MOF).

It was explained in the sentence. Thank you.

1. Line 642: need to explain ‘NMOF’ as nanocrystalline MOF.

It was explained better in the sentence. Thank you

1. Line 702: the ‘2’ of CO₂ need to use subscript.

Changed

1. Lines 708-710, 1000, 1045, 1082, 1083, 1088 and 1089: the % number can be reported as integer.

Ok, thank you. The numbers were changed

1. Lines 775, 897 and 972: a space is needed between number and ‘h’.

Added

1. Line 791: Scheme 1 missing 16 ’h’

Added

1. Line 799: the % number can be reported as integer. Replaces 99.89% with ‘>99 %’

Replaced

1. Line 833: typo mistake ‘usefulness’

Corrected

1. Line 997: Typo with '(Pt@UiO-66@LAAO)'

Corrected

1. Line 1057: add an abbreviation for (NaDC) and (Mi)

Added

 

Author Response File: Author Response.pdf