Spectroscopic Study of the Interaction of Reactive Dyes with Polymeric Cationic Modifiers of Cotton Fabrics
, Labrini Sygellou 1, Charalampos Anastasopoulos 3, Konstantinos S. Andrikopoulos 1,4,*, Georgios Bokias 3,* and George A. Voyiatzis 1
Round 1
Reviewer 1 Report
This work described the spectroscopic study of the in-termolecular interactions. Water-soluble copolymers of vinyl benzyl chloride and vinyl benzyl triethylammo-nium chloride (VBCTEAM) have been used as cellulose cationic modifiers. Several spectro-scopic techniques were applied, and detailed information related to the interaction of the reactive dye molecules with the cationic polymer modifiers at molecular level was acquired The results revealed that the sulfonate/sulfate anions of the dyes interact with the cationic VBCTEAM units of the polymer via electrostatic interactions.
I recommend that this paper can be further consideration for publication in this journal, after authors consider the following minor corrections:
1. The abstract section is too long, please cutoff irrelevant description, even duplicated section, and prepare a shorter and more concise one. So does the introduction and conclusions section.
2 A lot of the references used in text are out of data , even Spectrochim. Acta. 1960, please consider updating them.
Author Response
We would like to thank all reviewers for spending their time for evaluating our MS. In the next pages we perform a step-to-step answer to all of their comments/questions.
We do hope that after the revision our MS is appropriate for publication in Applied Sciences.
Reviewer 1
Open Review
( ) I would not like to sign my review report
(x) I would like to sign my review report
Quality of English Language
( ) English very difficult to understand/incomprehensible
( ) Extensive editing of English language and style required
( ) Moderate English changes required
(x) English language and style are fine/minor spell check required
( ) I am not qualified to assess the quality of English in this paper
Comments and Suggestions for Authors
This work described the spectroscopic study of the in-termolecular interactions. Water-soluble copolymers of vinyl benzyl chloride and vinyl benzyl triethylammo-nium chloride (VBCTEAM) have been used as cellulose cationic modifiers. Several spectro-scopic techniques were applied, and detailed information related to the interaction of the reactive dye molecules with the cationic polymer modifiers at molecular level was acquired The results revealed that the sulfonate/sulfate anions of the dyes interact with the cationic VBCTEAM units of the polymer via electrostatic interactions.
I recommend that this paper can be further consideration for publication in this journal, after authors consider the following minor corrections:
Reviewer’s comment: 1. The abstract section is too long, please cutoff irrelevant description, even duplicated section, and prepare a shorter and more concise one. So does the introduction and conclusions section.
Our answer: We have performed revisions in the abstract, introduction and conclusions sections. We hope that the revised sections are in accordance with the reviewer’s suggestions.
Reviewer’s comment: 2 A lot of the references used in text are out of data, even Spectrochim. Acta. 1960, please consider updating them.
Our answer: We have performed changes (additions/deletions) in the references according to the reviewer’ s suggestion. More precisely:
Ref 48 was replaced by “Lo, M; Diaw, A.K.D; Gningue-Sall, D; Oturan, M.A; Chehimi, M.M; Aaron, J-J. A novel fluorescent sensor based on electrosynthesized benzene sulfonic acid-doped polypyrrole for determination of Pb(II)and Cu(II). Luminescence. 2019, 34, 489– 499. https://doi.org/10.1002/bio.3626”
Ref 50 was replaced by: Jevavijayan, S. Spectroscopic (FTIR, FT-Raman), molecular electrostatic potential, NBO and HOMO-LUMO analysis of sulfonyl chloride based on DFT calculations. Spectrochim. Acta A Mol. Biomol. Spectrosc. 2015, 136, part B, 890-899. https://doi.org/10.1016/j.saa.2014.09.110.
Ref 52 was deleted.
Author Response File: 
Author Response.pdf
Reviewer 2 Report
Dear authors,
Concerning the manuscript “Spectroscopic study of the interaction of reactive dyes with polymeric cationic modifiers of cotton”
There is no doubt that it summarizes valuable information concerning using cationic polymers for treated cotton fabrics to upgrading coloring properties under environmentally-friendly conditions.
The work seems quite well organized, however, I find that there are some aspects that the authors could consider, in order to facilitate the reading and understanding of the article, such as:
1. In title, term “fabric” or “fabrics” must be added to the end of title.
2. In abstract, the last paragraph needs to be clear and significantly of application and more scientific.
3. In introduction, the background is little, the authors should enrich this part and emphasize the necessity of "application of different polymers" for dyeing cotton with reactive dyes and give some examples.
- This manuscript is organized but lacks specific comparative analysis. What are the advantages of " cationic modifiers" compared with traditional technology for dyeing cotton fabrics with reactive dyes?
5. This manuscript needs to explain how to vs the significant drawbacks, such as uneven dyeing and poor thermal stability, in addition to toxicity or unpleasant odour.
6. Scheme 1., transfer it to material section, (a b c in same line), (Novacron Ruby NRS-3B) quality is poor and missing structure of VBCTEAM
7. The methodology must be clearer for experimental, because in material some important details missing such as design of fabric (weaving or knitted), weight, thickness and raw or bleaching...etc and what of other chemicals used ?
8. In sample preparation authors need to be clear and significantly for the difference between binary and ternary systems.
9. Please add C.I. for two dyes (one bifunctional reactive dye (MCT/V. S) and the other is monofunctional V.S).
10. This manuscript needs some tests method add such as K/S for liquid and fabrics, fastness properties, N%- content, EDX and dye bath absorption.
11. This manuscript is need to improve organized and comparative analysis.
12. In supplementary file, need to be clearer for these methods was mention S2.1 Dyeing protocol at high and low temperatures without salt and S2.2 Dyeing protocol at high and low temperatures with salt, Fig. S1(Remazol Brilliant Blue R reactive dye only) and what is (RT) refer to?
13. Please revisit the entire manuscript for minor grammar issues.
14. Recheck figures titles, details and font size. For example, figure 2 the Remazol Brilliant Blue R correction to font size, please recheck font of P(VBC-co-VBCTEAM53 in fig 5 (a) and figure 6 please add (a) and (b) in figure.
15. In image 1., missing another dye and another cationic polymer and full details.
16. In discussion and perspectives, the author should consider giving some methodological design about how to improve the performance of using this process more specifically.
Author Response
Reviewer 2
Open Review
(x) I would not like to sign my review report
( ) I would like to sign my review report
Quality of English Language
( ) English very difficult to understand/incomprehensible
( ) Extensive editing of English language and style required
(x) Moderate English changes required
( ) English language and style are fine/minor spell check required
( ) I am not qualified to assess the quality of English in this paper
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Can be improved |
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Does the introduction provide sufficient background and include all relevant references? |
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Are all the cited references relevant to the research? |
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Is the research design appropriate? |
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Are the methods adequately described? |
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Are the results clearly presented? |
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Are the conclusions supported by the results? |
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Comments and Suggestions for Authors
Dear authors,
Concerning the manuscript “Spectroscopic study of the interaction of reactive dyes with polymeric cationic modifiers of cotton”
There is no doubt that it summarizes valuable information concerning using cationic polymers for treated cotton fabrics to upgrading coloring properties under environmentally-friendly conditions.
The work seems quite well organized, however, I find that there are some aspects that the authors could consider, in order to facilitate the reading and understanding of the article, such as:
- Reviewer’s comment: In title, term “fabric” or “fabrics” must be added to the end of title.
Our answer: According to the reviewer’s suggestion the title has been altered: “Spectroscopic study of the interaction of reactive dyes with polymeric cationic modifiers of cotton fabrics”
- Reviewer’s comment: In abstract, the last paragraph needs to be clear and significantly of application and more scientific.
Our answer: We have altered the last part of the abstract in accordance to the reviewer’s suggestion: “Moreover, the comparative study of dye application on modified and unmodified fabrics suggests that, unlike the latter where dyes are chemically bound to cellulose, electrostatic forces dominate the interaction of modified fabrics with dye molecules.”
- Reviewer’s comment:In introduction, the background is little, the authors should enrich this part and emphasize the necessity of "application of different polymers" for dyeing cotton with reactive dyes and give some examples.
Our answer: The use of different polymers as modifiers refers to one of our previous works. The reviewer is correct: the necessity to try various polymers is not straightforward in our MS. We have thus added the following phase (line 69): “Hence, the molar ratio between VBCTEAM and VBC segments designates dye update of the modified fabric and modifier grafting on cellulose accordingly.”
- Reviewer’s comment:This manuscript is organized but lacks specific comparative analysis. What are the advantages of " cationic modifiers" compared with traditional technology for dyeing cotton fabrics with reactive dyes?
Our answer: As far as the low molecular weight cationic modifiers are concerned, there is already a short discussion in the introduction (lines 51-55). Regarding the cationic polymer modifiers we have enriched our discussion and added the following phrase in line 71 of the revised MS: “Polymers offer additional properties with respect to other low molecular weight cationic modifiers not only by assuring more uniform dyeing, lower processing costs and stability but because their structure may be manipulated in order to accomplish grafting/dye uptake/other e.g. antimicrobial properties with optimal performance.”
- Reviewer’s comment:This manuscript needs to explain how to vs the significant drawbacks, such as uneven dyeing and poor thermal stability, in addition to toxicity or unpleasant odour.
Our answer: Part of this study has been recently published by our group and is given as reference [53]. The related discussion has been added in line 408.
- Reviewer’s comment:Scheme 1., transfer it to material section, (a b c in same line), (Novacron Ruby NRS-3B) quality is poor and missing structure of VBCTEAM
Our answer: Because of the fact that the synthesis of the polymers has been a subject of an additional work (already cited in the introduction) we believe that the reference to Scheme 1 in the introduction where the description of the polymers’ structure appears for the first time in the MS is required. We did correct the alignment of a, b, c, letters. As for the structure of VBCTEAM it is included in (c) for x=100.
- Reviewer’s comment: The methodology must be clearer for experimental, because in material some important details missing such as design of fabric (weaving or knitted), weight, thickness and raw or bleaching...etc and what of other chemicals used ?
Our answer: in the materials section, line 98 a sentence for the fabric design has been added “Double jersey knitted (Rib 1x1 alignment, knot length 4.4mm) pure cotton fabrics have been used, avoiding the application of alkali bleaching.” More details about the materials used in every part of the process, is referred in Sections S.1 and S.2 and also in a previous work of our team (reference 32).
- Reviewer’s comment: In sample preparation authors need to be clear and significantly for the difference between binary and ternary systems.
Our answer: We thank the reviewer for his/her comment. In the beginning of section 2.2.1 we have added the phrase: “Prototype binary systems of cationic polymers and dyes in the same aqueous solution were studied in order to observe any interactions without the presence of the cellulose substrate.” This phrase explains the purpose of the extensive study of the binary system. In addition, we have added the phrase: “The study of the ternary system dye-modifier-cellulose is considered as the most significant at least from the applications point of view. After application of a modification procedure on cotton substrates using cationic polymers (section S1) and subsequently following a dyeing procedure (section S2) several ternary systems were produced. Details concerning this process has been already mentioned elsewhere [32].” at the beginning of section 2.2.2. We do hope that the binary/ternary definition is more clear.
- Reviewer’s comment: Please add C.I. for two dyes (one bifunctional reactive dye (MCT/V. S) and the other is monofunctional V.S).
Our answer: In accordance with the reviewer’s suggestion, we have added the following phrase in section 2.1: “The reactive dyes: Remazol Brilliant Blue R (C.I 61200/ CAS 2580-78-1) and Novacron Ruby NRS-3B (C.I reactive red mixture-89157-03-9; 718619-88-6) were purchased from Huntsman International LLC. The composition of the second dye mixture is not exactly known, however, our XPS data indicate major contribution of the 718619-88-6 component.”
- Reviewer’s comment: This manuscript needs some tests method add such as K/S for liquid and fabrics,fastness properties, N%- content, EDX and dye bath absorption.
Our answer:These (K/S for liquids and fabrics and fastness properties) factors have been extensively studied by our team and been published at the journal “Sustainability”, MDPI . This article focuses on the environmental impact of the new dyeing process. (https://doi.org/10.3390/su15043144). We have added it as reference 53 along with a short discussion in line 407 of the revised MS. Stoichiometric measurements and detailed absorption studies have been mentioned in ref. 32.
- Reviewer’s comment: This manuscript is need to improve organized and comparative analysis.
Our answer: We thank the reviewer for his/her recommendation. We have added a paragraph (lines 404-410 in the revised MS) and also altered the caption in Image 1 so that the comparative analysis is better presented.
- Reviewer’s comment: In supplementary file, need to be clearer for these methods was mention S2.1 Dyeing protocol at high and low temperatures without salt and S2.2 Dyeing protocol at high and low temperatures with salt, Fig. S1(Remazol Brilliant Blue R reactive dye only) and what is (RT) refer to?
Our answer: in Supplementary file, Fig.S1 (c) an image of Novacron Ruby/PVBCTEAM binary mixture has been added. R.T abbreviation has been replaced by “Room Temperature”.
- Reviewer’s comment: Please revisit the entire manuscript for minor grammar issues.
Our answer: We went throughout the MS and altered the grammatical issues that were revealed.
- Reviewer’s comment: Recheck figures titles, details and font size. For example, figure 2 the Remazol Brilliant Blue R correction to font size, please recheck font of P(VBC-co-VBCTEAM53 in fig 5 (a) and figure 6 please add (a) and (b) in figure.
Our answer: All figure font size has been set to 11. In figure 5 and 6 (a) and (b) has been added in each graph.
- Reviewer’s comment: In image 1., missing another dye and another cationic polymer and full details.
Our answer: In image 1, part (b) has been added which refers to the Remazol Brilliant Blue dyed fabrics before and after modification with PVBCTEAM. Also, a sentence has been added in line 391 “while similar color intensity is observed in the modified fabrics with the copolymer.”
- Reviewer’s comment: In discussion and perspectives, the author should consider giving some methodological design about how to improve the performance of using this process more specifically.
Our answer: We added a phrase at the end of our conclusions. We hope that this clarifies the reviewer’s comment.
Author Response File: Author Response.pdf
Reviewer 3 Report
This manuscript reported that cotton cationization with low molecular-weight/polymeric cationic modifiers allows the effective dyeing of fabrics with reactive dyes under salt-free and more environmentally-friendly conditions. Water-soluble copolymers of vinyl benzyl chloride and vinyl benzyl triethylammonium chloride (VBCTEAM) have been used as cellulose cationic modifiers. This manuscript can meet the scope of the journal of “Applied Sciences”. However, there are still some problems in this manuscript. It needs a minor revision before becomes acceptable for publication in this journal. In this manuscript, there are several language mistakes. For example：
(1) Page 6, “XPS spectra of Remazol Brilliant Blue R in the spectral region of”
(2) Page 7, “depending on the transition, this red-shift varies in the range of 2-15 nm, being more significant for the n-π* type of transition(s) observed at ~500-550 nm.”
(3) Page 13, “A side effect of these dyes is the increased re-quirement of alkaline (sodium carbonate) and temperature (80oC) in the dye bath [33-35].”
(4) Page 13, “where the morphology of untreated, dyed untreated and dyed treated fibers remains similar indicating that both modifier and dye are covering just a few nm of the fibers’ surface, the order of XPS penetration depth.”
Author Response
Reviewer 3
Open Review
(x) I would not like to sign my review report
( ) I would like to sign my review report
Quality of English Language
( ) English very difficult to understand/incomprehensible
( ) Extensive editing of English language and style required
( ) Moderate English changes required
(x) English language and style are fine/minor spell check required
( ) I am not qualified to assess the quality of English in this paper
|
Yes |
Can be improved |
Must be improved |
Not applicable |
|
|
Does the introduction provide sufficient background and include all relevant references? |
(x) |
( ) |
( ) |
( ) |
|
Are all the cited references relevant to the research? |
(x) |
( ) |
( ) |
( ) |
|
Is the research design appropriate? |
(x) |
( ) |
( ) |
( ) |
|
Are the methods adequately described? |
( ) |
(x) |
( ) |
( ) |
|
Are the results clearly presented? |
( ) |
(x) |
( ) |
( ) |
|
Are the conclusions supported by the results? |
(x) |
( ) |
( ) |
( ) |
Comments and Suggestions for Authors
This manuscript reported that cotton cationization with low molecular-weight/polymeric cationic modifiers allows the effective dyeing of fabrics with reactive dyes under salt-free and more environmentally-friendly conditions. Water-soluble copolymers of vinyl benzyl chloride and vinyl benzyl triethylammonium chloride (VBCTEAM) have been used as cellulose cationic modifiers. This manuscript can meet the scope of the journal of “Applied Sciences”. However, there are still some problems in this manuscript. It needs a minor revision before becomes acceptable for publication in this journal. In this manuscript, there are several language mistakes. For example：
- Reviewer’s comment: Page 6, “XPS spectra of Remazol Brilliant Blue R in the spectral region of”
Our answer: this sentence (line 187) has been replaced by “XPS spectra of Remazol Brilliant Blue R reactive dye of C1s, S2p, N1s, Na1s, and O1s orbitals’ characteristic spectral regions are shown in Fig. 2”
(2) Reviewer’s comment: Page 7, “depending on the transition, this red-shift varies in the range of 2-15 nm, being more significant for the n-π* type of transition(s) observed at ~500-550 nm.”
Our answer: We have rephrased the sentence in line 231 of the revised MS. “depending on the transition, this red-shift varies (2-15 nm), having a greater value for the n-π* type of transition(s) observed at ~500-550 nm.”
(3) Reviewer’s comment: Page 13, “A side effect of these dyes is the increased re-quirement of alkaline (sodium carbonate) and temperature (80oC) in the dye bath [33-35].”
Our answer:: this sentence (line 364) has been replaced by “The most important disadvantage of this dye category, is the increased requirement of alkaline concentration (sodium carbonate) and temperature (80oC) in the dye bath [33-35]”
(4) Reviewer’s comment: Page 13, “where the morphology of untreated, dyed untreated and dyed treated fibers remains similar indicating that both modifier and dye are covering just a few nm of the fibers’ surface, the order of XPS penetration depth.”
Our answer:: this sentence (line 377) has been replaced by “where the morphology of untreated, dyed untreated and dyed treated fibers remains similar in the scale of hundreds of nm. This observation indicates that both modifier and dye are covering just a few nm of the fibers’ surface, which is similar to the order of XPS penetration depth.”
Author Response File: Author Response.pdf
Round 2
Reviewer 2 Report
Authors have carefully responded the previous comments to despite improved quality of the manuscript after revision, I still have eight minor comments that should be properly addressed:
1. Line 19. Add VBC as abbreviation of vinyl benzyl chloride
2. Line 21. Add full name of dyes
3. Line 87. Please change name of dye from Novacron Ruby NRS-3B to Novacron Ruby S-3B according in line 50 (for all manuscript) also change chemical structure to chemical structure what you mention in your pervious article (https://doi.org/10.3390/su15043144).
4. Figure 5 and 9. Recheck P(VBC-co- VBCTEAM53) and correct it to P(VBC-co- VBCTEAM53)
5. Figure 9. Concert it to XPS spectra of Sulfur orbital 1s (a) and Sodium 2p (b) for Novacron Ruby S-3B dye and the binary system
6. In material section. Please add chemicals used like (NaOH…etc)
7. In Image 1. Please add picture of dye Novacron Ruby NRS-3B without salt
8. In Supplementary material. Add full details of Image S3 (name of cationic and name of dye)
9. please change dichloro-triazine to monochloro-triazine
finally, the fastness properties I mean is light fastness and rubbing fastness according to test methods from AATCC or ISO for textile you didn't mention in your previous article
Author Response
We would like to thank the reviewer for his/her meticulous revision. We attempt to respond to his/her comments in our answers below:
Comments and Suggestions for Authors
Authors have carefully responded the previous comments to despite improved quality of the manuscript after revision, I still have eight minor comments that should be properly addressed:
- Reviewer’s comment: Line 19. Add VBC as abbreviation of vinyl benzyl chloride
Our answer: In accordance with the reviewer’s suggestion, we have added the abbreviation of VBC in line 19.
- Reviewer’s comment: Line 21. Add full name of dyes
Our answer: We have added the full names of both dyes in line 21.
- Reviewer’s comment: Line 87. Please change name of dye from Novacron Ruby NRS-3Bto Novacron Ruby S-3B according in line 50 (for all manuscript) also change chemical structure to chemical structure what you mention in your pervious article (https://doi.org/10.3390/su15043144).
Our answer: The name of Novacron Ruby dye has been replaced in the whole manuscript after the correct reviewer’s comment. We kept the same chemical structure with our previous work for Novacron Ruby dye in the revised-2 MS.
- Reviewer’s comment: Figure 5 and 9. Recheck P(VBC-co- VBCTEAM53) and correct it to P(VBC-co- VBCTEAM53)
Our answer: We have performed the appropriate corrections in both Figures.
- Reviewer’s comment: Figure 9. Concert it to XPS spectra of Sulfur orbital 1s (a) and Sodium 2p (b) for Novacron Ruby S-3B dye and the binary system
Our answer: We thank the reviewer for his comment. The caption has been replaced by: “XPS spectra of Sulfur orbital 2p (a) and Sodium 1s (b) for Novacron Ruby S-3B dye and the binary system.”
- Reviewer’s comment: In material section. Please add chemicals used like (NaOH…etc)
Our answer: In the material section (line 92.) we have added a sentence “The NaCl and NaOH were both purchased from Sigma-Aldrich (Steinheim, Germany).”
- Reviewer’s comment: In Image 1. Please add picture of dye Novacron Ruby NRS-3B without salt
Our answer: Image 1. a) has been altered, after adding the dyed without modification and salt fabric.
- Reviewer’s comment: In Supplementary material. Add full details of Image S3 (name of cationic and name of dye)
Our answer: In supplementary material we have altered the caption of Image S3. after the review’s suggestion: “SEM images of untreated cotton fibers (left), treated cotton fibers with P(VBC-co-VBCTEAM53) (middle), treated and dyed cotton fibers with Remazol Brilliant Blue R (right).”
- Reviewer’s comment: please change dichloro-triazine to monochloro-triazine
Our answer: We thank the reviewer for his comment, in line 358 it is stated that. “Novacron Ruby S-3B is bifunctional, since it contains also one chloro-triazine reactive site…”
Reviewer’s comment: finally, the fastness properties I mean is light fastness and rubbing fastness according to test methods from AATCC or ISO for textile you didn't mention in your previous article
Our answer: We wish to thank the reviewer for his/her suggestion. We have already performed the ISO 105-C06 Fastness to Washing test using the Ahiba Polymat microwasher, which we have access to. Fabric color fastness to rubbing tests (dry or wet) using the AATCC-08 or ISO-105-X12 protocols are very important (probably overlapping the washing fastness tests), however require specific instrumentation, which we do not have access to. It is true that our detailed study on the interactions dictating the ternary system under investigation at molecular level may be corelated to such measurements as well, but since the rubbing fastness depends among other things to the nature of the color and the depth of shade this could be an additional work involving a laboratory dedicated to the specific measurements.
Author Response File: 
Author Response.docx
