A Short-Cut Data Mining Method for the Mass Spectrometric Characterization of Block Copolymers

Round 1

Reviewer 1 Report

The manuscript is concerned with a short-cut data mining method to estimate block copolymer compositions from mass spectra. The work showed simple and direct, and do not need more corrections about the theory and the experiments. Therefore, I recommend this article for publication.

Author Response

The manuscript is concerned with a short-cut data mining method to estimate block copolymer compositions from mass spectra. The work showed simple and direct, and do not need more corrections about the theory and the experiments. Therefore, I recommend this article for publication.

 

Reply: Thank you for the review.

Author Response File: Author Response.pdf

Reviewer 2 Report

The article “A Short-Cut Data Mining Method for the Mass Spectrometric Characterization of Block Copolymers” by Ákos Kuki, Gergő Róth, Anna Nagy, Miklós Zsuga, Sándor Kéki and Tibor Nagy describes the method to process the mass-spectroscopic data for polymeric block-copolymers and derive structural and compositional information.

As a test system, the authors selected ethylene oxide – propylene oxide copolymers. The data presented in the article unambiguously shows that the novel method simplifies the processing of the MS spectra of the copolymers and provides molecular properties characteristics with high accuracy. The strong point of the article is the comparison of the results obtained by the novel method and traditionally from NMR data. Additionally, authors provide xls. sheets with the demonstration of the data processing.

In my opinion, this paper can be published after minor revision.

Below the authors can find some points to address prior to publication.

For me the only research question remains: will the method work as good if the other classes of copolymers selected? I believe that this question will be answered by the authors in their later research. They can provide some discussion on this topic. Additionally, it is important to specify the criteria of applicability of the method for a particular class of copolymers. Furthermore, if the method was tested only on PEO-PPO block-copolymers, it is better to write so in the title not to mislead the readers.

Additional question that the authors are encouraged to discuss is how the presence of random copolymers affects the results.

 

Minor comments:

1. In the introduction part the authors can write a paragraph on the existing methods for the processing of MS spectra.
2. Table 1. Column two with the origin of the samples is not needed as all the samples were obtained from BASF.
3. “The instrument is assembled with a solid phase laser (355 nm).” Better to write “The instrument is equipped with a solid phase laser (355 nm).”
4. Results and discussion section starts with the justification of PEO-PPO copolymers selection. For me this belongs to the introduction part.
5. Table 2. Authors can add the specification of the copolymers stated by the supplier.
6. Authors use the word “drastic” several times in the paper. In my opinion it is better to substitute it with “significant”, “sufficient” which will make the text neat and easily-readable.
7. For the dispersity of the polymers authors are encouraged to use the symbol Đ.

 

Author Response

Reviewer 2:

The article “A Short-Cut Data Mining Method for the Mass Spectrometric Characterization of Block Copolymers” by Ákos Kuki, Gergő Róth, Anna Nagy, Miklós Zsuga, Sándor Kéki and Tibor Nagy describes the method to process the mass-spectroscopic data for polymeric block-copolymers and derive structural and compositional information.

As a test system, the authors selected ethylene oxide – propylene oxide copolymers. The data presented in the article unambiguously shows that the novel method simplifies the processing of the MS spectra of the copolymers and provides molecular properties characteristics with high accuracy. The strong point of the article is the comparison of the results obtained by the novel method and traditionally from NMR data. Additionally, authors provide xls. sheets with the demonstration of the data processing.

In my opinion, this paper can be published after minor revision.

Below the authors can find some points to address prior to publication.

1. For me the only research question remains: will the method work as good if the other classes of copolymers selected? I believe that this question will be answered by the authors in their later research. They can provide some discussion on this topic. Additionally, it is important to specify the criteria of applicability of the method for a particular class of copolymers. Furthermore, if the method was tested only on PEO-PPO block-copolymers, it is better to write so in the title not to mislead the readers.

Reply: In our ion the data mining method is universal, however, the application of the method is limited by the instrumentation of mass spectrometric analysis. The applicability of the MS for polymer and copolymer analysis is well discussed in the literature.

 

The following sentence was added to the conclusion part:

"The proposed Short-cut method can be applied for the analysis of other copolymers, too."

 

2. Additional question that the authors are encouraged to discuss is how the presence of random copolymers affects the results.

Reply: Random copolymers can be measured with similar efficiency, thus the results would also be reliable in these cases. The polydispersity ratio of the two monomers is the same for random copolymers, thus the composition drift would result a horizontal line.

Minor comments:

1. In the introduction part the authors can write a paragraph on the existing methods for the processing of MS spectra.

Reply: In the introduction the existing data handling methods are listed. The data processing strategies were discussed in previous articles where the aim was the method development. Herein only the simplification of evaluation was shown.

1. Table 1. Column two with the origin of the samples is not needed as all the samples were obtained from BASF.

Reply: Column was removed.

1. “The instrument is assembled with a solid phase laser (355 nm).” Better to write “The instrument is equipped with a solid phase laser (355 nm).”

Reply: It was changed as requested.

1. Results and discussion section starts with the justification of PEO-PPO copolymers selection. For me this belongs to the introduction part.

Reply: It was placed at the end of introduction.

We demonstrate our new short-cut data mining method for copolymer mass spectra through the characterization of ethylene oxide (EO) – propylene oxide (PO) copolymers. The amphiphilic block copolymers consisting of polyethylene oxide (PEO) and polypropylene oxide (PPO) blocks arranged in a triblock PEO−PPO−PEO or the reversed PPO–PEO–PPO structure are widely used as nonionic surfactant in industrial and domestic applications, pharmaceuticals, cosmetics, and so on [20-22]

The following sentence was given at the beginning of the Results and Discussion:

"The ethylene oxide (EO) – propylene oxide (PO) based amphiphilic block copolymers are widely used in the chemical industry."

 

1. Table 2. Authors can add the specification of the copolymers stated by the supplier.

Reply: The copolymers were a generous gift from BASF, however the specifications were not given. The compositions of the copolymers from the general description of the Pluronics by BASF were used.

1. Authors use the word “drastic” several times in the paper. In my opinion it is better to substitute it with “significant”, “sufficient” which will make the text neat and easily-readable.

Reply: It was modified, accordingly.

1. For the dispersity of the polymers authors are encouraged to use the symbol Đ.

Reply: It was modified as suggested.

Author Response File: Author Response.pdf

Reviewer 3 Report

Title: A Short-Cut Data Mining Method for the Mass Spectrometric Characterization of Block Copolymers

Reviewer comments: (Express Comments to the Author):

The manuscript discussed by Kuki et al. proposed a new data mining approach as a short cut method to measure the copolymer composition from mass spectra. The characteristic copolymer parameters was tested by processing of the MALDI-TOF MS spectra, which indicated that this method could exhibit very well the compositional properties of the Pluronic-type triblock copolymers. Through reducing the mass spectra information, this method could be performed with the common spreadsheet software, and easy to implement.

The paper is written well except few problems. Only if these problems can well be done, it will be recommended to publish.

Remarks to the Author:

1. In this manuscript, the Table 3 could not be clearly assigned.
2. The deviance of EO molar fraction located at 30-35 polymerization degrees was very apparent. The short-cut method was not simulated the abnormal phenomena that obtained by the referenced MALDI-TOF MS approach. This reason must be carefully explained from the perspective of theoretical
3. In introduction, if possible, some important and relative reports about spectral study (e.g., Optics & Laser Technology 148 (2022) 107765, Journal of Luminescence 243 (2022) 118684, Opt. Express, 2021, 29(4): 5152-5165, and so on) should be added to show clear background.
4. The authors have put forward a new method, but the number of samples was still too thin to prove the universality of this method.

This research is great meaningful and valuable, as a reviewer, I think this manuscript should be worthy to publish if above some errors can be properly resolved.

Author Response

Reviewer 3

The manuscript discussed by Kuki et al. proposed a new data mining approach as a short cut method to measure the copolymer composition from mass spectra. The characteristic copolymer parameters was tested by processing of the MALDI-TOF MS spectra, which indicated that this method could exhibit very well the compositional properties of the Pluronic-type triblock copolymers. Through reducing the mass spectra information, this method could be performed with the common spreadsheet software, and easy to implement.

The paper is written well except few problems. Only if these problems can well be done, it will be recommended to publish.

Remarks to the Author:

1. In this manuscript, the Table 3 could not be clearly assigned.

Reply: "Table 3" is a typo, we mean Table 2.

1. The deviance of EO molar fraction located at 30-35 polymerization degrees was very apparent. The short-cut method was not simulated the abnormal phenomena that obtained by the referenced MALDI-TOF MS approach. This reason must be carefully explained from the perspective of theoretical

Reply: The deviance in the mentioned region is the result of the low intensities. Since the copolymer sample has bimodal distribution, in addition to the copolymer, homopolymer is also present. In this region, the intensity of the peaks is close to the detection limit, thus the acceptance or the decline of even one peak during the peak-picking has a high effect on the resulting EO molar fraction. The application of intensity threshold would result distorted distribution. However, that region has low impact on the copolymer quantities.

The following sentences were added.

"In this region the intensity of the peaks is close to the detection limit, thus, the acceptance or the decline of even one peak during the peak-picking has a high effect on the resulting EO molar fraction."

 

1. In introduction, if possible, some important and relative reports about spectral study (e.g., Optics & Laser Technology 148 (2022) 107765, Journal of Luminescence 243 (2022) 118684, Opt. Express, 2021, 29(4): 5152-5165, and so on) should be added to show clear background.

Reply: We focused on the mass spectrometric experiment of polymers.

 

1. The authors have put forward a new method, but the number of samples was still too thin to prove the universality of this method.

Reply: Samples were investigated in a wide range of composition and molecular weight. The aim of our article is to suggest simple and efficient datamining method. The analysis of additional copolymers goes beyond the purpose of this article.

The following sentence was added to the conclusion part.

"The proposed Short-cut method can be applied for the analysis of other copolymers, too."

Author Response File: Author Response.pdf