Advanced Electrochemical Detection of Tetrabromobisphenol A and Hexabromocyclododecane via Modified Carbon Electrodes with Inorganic Nanoparticles: A Short Review

Round 1

Reviewer 1 Report

Comments and Suggestions for Authors

In the paper, the author provide the short review for electrochemical detection of Tetrabromobisphenol A and Hexabromocyclododecane. While the topic of environmental pollutants and the detection of brominated flame retardants (BFRs) is highly relevant and significant, the manuscript is not suitable for publication under current status.

 

1. The whole review lacks innovation, some of the reviews already include this information. The abstract suggests that the study primarily reviews existing advancements in electrochemical detection methods for BFRs using inorganic modifiers. However, it does not clearly present any novel findings, methodologies, or significant improvements over the existing body of knowledge. To be considered for publication, the manuscript should provide a clear indication of original contributions to the field.

 

2. The review is only targeted at the carbon electrodes, which is too limited. I recommend the author expand all kinds of electrochemical sensors.

 

3. The title mentioned inorganic nanoparticles, however, there no special information in the review, which should be added.

 

4. Some of electrochemical detection methods are missing, like SWV in voltammetric method, and potentiometric and amperometric sensing reports.

 

 

 

Comments on the Quality of English Language

English still need to be polished 

Author Response

Response to Reviewer 1 Comments

Thank you very much for taking the time to review this manuscript. Please find the detailed responses below and the corresponding revisions/corrections highlighted/in track changes in the re-submitted files.

A point-by-point response to Comments and Suggestions for Authors                     

Comments 1: [The whole review lacks innovation, and some reviews already include this information. The abstract suggests that the study primarily reviews advancements in electrochemical detection methods for BFRs using inorganic modifiers. However, it does not present any novel findings, methodologies, or significant improvements over the existing body of knowledge. To be considered for publication, the manuscript should clearly indicate original contributions to the field.]

Response:

Dear reviewer, we have done our best to find the literature that has used carbon electrodes for the detection of Tetrabromobisphenol A (TBPA) and Hexabromocyclododecane (HBCD). To the best of our knowledge, we have discussed each relevant article (note we are not discussing Bisphenol A (BPA) which has been widely studied). We feel the detection of TBPA and HBCD is very important, and unfortunately, there are significantly fewer articles available on these chemicals compared to other molecules like BPA. Therefore, we are highlighting articles that have used carbon electrodes for these two compounds. We have further expanded the article by discussing the importance of carbon electrodes and how inorganic nanoparticles can improve electrode performance. If the reviewer suggests any articles that have used carbon electrodes for TBPA and HBCD we are happy to include them in the review.

Comments 2: [The review is only targeted at the carbon electrodes, which is too limited. I recommend the author expand all kinds of electrochemical sensors.]

Response:

Thank you for your valuable feedback. We acknowledge your concern regarding the scope of our review. However, our focus on carbon electrodes is intentional due to their significant advantages and promising future in the field of electrochemical detection. Below, we elaborate on the rationale for concentrating on carbon-based materials and discuss their unique benefits and potential for future advancements. We have added section 4 to discuss the advantages of carbon electrodes over other electrodes.

Advantages of Carbon Electrodes:

• Wide Potential Window: Carbon electrodes possess a wide potential window in aqueous solutions, allowing for the detection of various analytes without interference from solvent decomposition.
• Low Background Currents: The low background current of carbon electrodes enhances the signal-to-noise ratio, improving the sensitivity and reliability of electrochemical measurements.
• Chemical Stability: Carbon materials are chemically stable in various environments, making them suitable for a wide range of applications, including harsh conditions.
• Ease of Modification: Carbon electrodes can be easily modified with various functional groups, nanoparticles, and other materials to enhance their selectivity and sensitivity for specific analytes.
• Cost-Effectiveness: Carbon-based materials are generally more cost-effective compared to other electrode materials, facilitating widespread use and accessibility.
• Biocompatibility: The biocompatibility of carbon electrodes makes them suitable for biosensing applications, including the detection of biological molecules and pathogens.

Future Potential of Carbon Electrodes:

The future of carbon electrodes in electrochemical sensing is highly promising. Advances in nanotechnology and materials science continue to enhance the properties of carbon-based materials, leading to the development of novel electrode architectures such as graphene, carbon nanotubes, and carbon quantum dots. These innovations offer improved surface area, electrical conductivity, and functionalization capabilities, which are expected to significantly advance the field of electrochemical detection.

However, as per the reviewer's suggestion, we tried to find out other than carbon electrodes to sense TBPA and HBCD we found an article which has used the platinum electrode and we have discussed that article (section 6).

Comments 3: [The title mentioned inorganic nanoparticles, however, there no special information in the review, which should be added.]

Response:

In response to the reviewer's feedback regarding the inclusion of information on inorganic nanoparticles in the review manuscript, we have carefully revisited the content and aim to enhance the discussion by incorporating relevant details on this crucial aspect of electrochemical sensing. We have added section 5 relating to this issue.

Inorganic nanoparticles play a pivotal role in advancing electrochemical sensing methodologies due to their unique properties such as high surface area, excellent conductivity, and tunable surface chemistry. These nanoparticles are often integrated into electrode surfaces to enhance sensitivity, selectivity, and stability in detecting analytes like brominated flame retardants (BFRs) such as Tetrabromobisphenol A (TBBPA) and Hexabromocyclododecane (HBCD). By modifying electrode surfaces with inorganic nanoparticles, researchers have achieved improved electrochemical performance, enabling lower detection limits and enhanced robustness against interferences commonly encountered in environmental samples.

Specifically, inorganic nanoparticles such as gold nanoparticles (AuNPs), silver nanoparticles (AgNPs), and metal oxides (e.g., titanium dioxide (TiO2), iron oxide (Fe3O4)) have been extensively studied and applied in electrochemical sensors for BFR detection. These nanoparticles not only facilitate electron transfer kinetics but also provide active sites for specific molecular interactions, thereby amplifying the sensor's analytical capabilities.

Moreover, the integration of inorganic nanoparticles in sensor designs allows for the development of multifunctional platforms capable of simultaneous detection of multiple analytes, which is critical in environmental monitoring applications. Furthermore, advancements in nanotechnology have enabled the fabrication of nanostructured electrodes with tailored properties, offering new avenues for enhancing sensor performance in terms of stability and reproducibility.

In summary, we acknowledge the importance of including comprehensive information on inorganic nanoparticles in the review manuscript. By integrating these insights, we aim to provide a more holistic view of electrochemical sensing strategies for BFR detection, emphasizing the pivotal role of nanomaterials in advancing the field toward more sensitive and selective analytical methods.

Comments 4: [Some of electrochemical detection methods are missing, like SWV in voltammetric method, and potentiometric and amperometric sensing reports]

Response:

We agree that developing sensors based on amperometry, potentiometry, and SWV are equally advantageous to CV and DPV. Unfortunately, no literature used SWV to detect TBPA and HBCD. However, we found an article that explored the utility of amperometry to sense TBPA and we have discussed that article in brief [Ref 32].

 

Reviewer 2 Report

Comments and Suggestions for Authors

In this manuscript, the authors reviewed the voltammetric detection of Tetrabromobisphenol (not Hexabromocyclododecane) via modified carbon electrodes with inorganic particles. Overall, the manuscript is poorly written in terms of scientific content and the use of the English is poor and informal. Due to the critical lacks in the manuscript, in my opinion, significant improvements are necessary for it to be considered a worthy and helpful paper for the scientific community. After these improvements, I would be happy to reconsider the submission of the paper to Electrochem MDPI.

 

The authors reviewed the detection of tetrabromobisphenol A and hexabromocyclododecane (at all) by voltammetric sensors using carbon-based electrodes modified with inorganic (nano)particles.

The manuscript focuses only on one compound and one technique, and it is clear that there is not enough information to write a review.

The manuscript is only a compilation of some articles on the subject, in a very limited field because they only considered one electrochemical detection technique. As for hexabromocyclododecane detection, as the authors said, “there aren't specific papers available under the title of HBCD detection by electrochemical methods,” so my question here is: How can you review something if it does not exist? It doesn't make sense.
In my opinion, the authors are reviewing TBBPA detection.

There are many things to improve in this manuscript. The most important one, the critical discussion of the revised results. But also, other things like using the same nomenclature for the two unique compounds they mentioned in the manuscript, Part 2 which states the detection methods can be expanded by including more details, a table that compiles the reviewed articles and shows more examples found in the literature (including captions), etc.

The conclusions are acceptable.

More references need to be included throughout the manuscript.

The figures need to be improved in number and also in quality. At least a table needs to be included.

Author Response

Response to Reviewer 2 Comments

Thank you very much for taking the time to review this manuscript. Please find the detailed responses below and the corresponding revisions/corrections highlighted/in track changes in the re-submitted files.

A point-by-point response to Comments and Suggestions for Authors                     

Comments 1: [The manuscript focuses only on one compound and one technique, and it is clear that there is not enough information to write a review.]

Response:

Thank you for your valuable feedback. We acknowledge your concern regarding the scope of our review. However, our focus on carbon electrodes is intentional due to their significant advantages and promising future in the field of electrochemical detection. Below, we elaborate on the rationale for concentrating on carbon-based materials and discuss their unique benefits and potential for future advancements. We have added section 4 to discuss the advantages of carbon electrodes over other electrodes.

Advantages of Carbon Electrodes:

• Wide Potential Window: Carbon electrodes possess a wide potential window in aqueous solutions, allowing for the detection of various analytes without interference from solvent decomposition.
• Low Background Currents: The low background current of carbon electrodes enhances the signal-to-noise ratio, improving the sensitivity and reliability of electrochemical measurements.
• Chemical Stability: Carbon materials are chemically stable in various environments, making them suitable for a wide range of applications, including harsh conditions.
• Ease of Modification: Carbon electrodes can be easily modified with various functional groups, nanoparticles, and other materials to enhance their selectivity and sensitivity for specific analytes.
• Cost-Effectiveness: Carbon-based materials are generally more cost-effective compared to other electrode materials, facilitating widespread use and accessibility.
• Biocompatibility: The biocompatibility of carbon electrodes makes them suitable for biosensing applications, including the detection of biological molecules and pathogens.

Future Potential of Carbon Electrodes:

The future of carbon electrodes in electrochemical sensing is highly promising. Advances in nanotechnology and materials science continue to enhance the properties of carbon-based materials, leading to the development of novel electrode architectures such as graphene, carbon nanotubes, and carbon quantum dots. These innovations offer improved surface area, electrical conductivity, and functionalization capabilities, which are expected to significantly advance the field of electrochemical detection.

However, as per the reviewer's suggestion, we tried to find out other than carbon electrodes to sense TBPA and HBCD we found an article which has used the platinum electrode and we have discussed that article (section 6).

Comments 2: [Hexabromocyclododecane (HBCD) Detection.]

Response:

We appreciate your observation. Given the lack of specific studies on HBCD detection by electrochemical methods, we have refocused the review solely on TBBPA detection. We clarified this in the introduction and scope sections, ensuring the manuscript accurately reflects the current state of research on TBBPA detection using modified carbon electrodes.

Comments 3: [The most important one, the critical discussion of the revised results. But also, other things like using the same nomenclature for the two unique compounds they mentioned in the manuscript.]

Response:

We have enhanced the critical discussion of the reviewed results, providing deeper insights into the advantages, limitations, and future directions of TBBPA detection methods. We ensured consistent nomenclature throughout the manuscript for all mentioned compounds, specifically focusing on TBBPA.

Comments 4: [Expansion of Detection Methods Section]

Response:

We have added amperometry detection.

Comments 5: [Inclusion of Tables and Figures]

Response:

Included

 

Reviewer 3 Report

Comments and Suggestions for Authors

1. A promising but unevenly explored field is revealed by the thorough investigation of electrochemical techniques for the detection of brominated flame retardants (BFRs), specifically Tetrabromobisphenol A (TBA) and Hexabromocyclododecane (HBCD). The research findings highlight notable advancements in improving detection sensitivity with carbon-based electrodes, but they also highlight areas that require more work.

2. The topic is original and relevant in this area. This eliminates some gaps in this area.

3. The most promising results come from research using graphene or CeO2 nanocubes modified GCEs for TBA detection; these studies show remarkable sensitivity and low detection limits. These adjustments greatly enhance electrode performance, making it possible to identify TBA in various environmental sample types. Future research should focus on improving and developing electrochemical methods for HBCD detection.

4. Questions: What is the mechanism of influence of CeO2 nanocubes, graphene and polymers with a molecular structure on the results obtained? What is the accuracy of determining TBA and HBCD?

5. The conclusions are consistent with the evidence presented.

6. Links are appropriate.

7. Additional comments to tables and figures are not required.

The work has theoretical and practical significance.

Comments on the Quality of English Language

1. A promising but unevenly explored field is revealed by the thorough investigation of electrochemical techniques for the detection of brominated flame retardants (BFRs), specifically Tetrabromobisphenol A (TBA) and Hexabromocyclododecane (HBCD). The research findings highlight notable advancements in improving detection sensitivity with carbon-based electrodes, but they also highlight areas that require more work.

2. The topic is original and relevant in this area. This eliminates some gaps in this area.

3. The most promising results come from research using graphene or CeO2 nanocubes modified GCEs for TBA detection; these studies show remarkable sensitivity and low detection limits. These adjustments greatly enhance electrode performance, making it possible to identify TBA in various environmental sample types. Future research should focus on improving and developing electrochemical methods for HBCD detection.

4. Questions: What is the mechanism of influence of CeO2 nanocubes, graphene and polymers with a molecular structure on the results obtained? What is the accuracy of determining TBA and HBCD?

5. The conclusions are consistent with the evidence presented.

6. Links are appropriate.

7. Additional comments to tables and figures are not required.

The work has theoretical and practical significance.

Author Response

Response to Reviewer 3 Comments

Thank you very much for taking the time to review this manuscript. Please find the detailed responses below and the corresponding revisions/corrections highlighted/in track changes in the re-submitted files.

A point-by-point response to Comments and Suggestions for Authors                     

Comments 1: [A promising but unevenly explored field is revealed by the thorough investigation of electrochemical techniques for the detection of brominated flame retardants (BFRs), specifically Tetrabromobisphenol A (TBA) and Hexabromocyclododecane (HBCD). The research findings highlight notable advancements in improving detection sensitivity with carbon-based electrodes, but they also highlight areas that require more work]

Response: We appreciate the reviewer’s acknowledgment of the promise and relevance of our study in the field of electrochemical detection of BFRs. We are very thankful to the reviewers for their kind encouragement. We have now emphasized both the advancements and the areas needing further exploration in the revised manuscript. Specifically, we have expanded the discussion on current gaps in the research and proposed future directions, particularly focusing on the detection methods for HBCD, where the literature is sparse.

Comments 2: [The topic is original and relevant in this area. This eliminates some gaps in this area.]

Response: Thank you for recognizing the originality and relevance of our topic. We have strengthened our manuscript by highlighting the unique contributions and how our review addresses existing gaps in the detection of BFRs, particularly TBBPA and HBCD.

Comments 3: [The most promising results come from research using graphene or CeO2 nanocubes modified GCEs for TBA detection; these studies show remarkable sensitivity and low detection limits. These adjustments greatly enhance electrode performance, making it possible to identify TBA in various environmental sample types. Future research should focus on improving and developing electrochemical methods for HBCD detection.]

Response: We agree with the reviewer on the promising nature of graphene and CeO2 nanocubes-modified GCEs. In the revised manuscript, we have included a more detailed discussion on the mechanisms by which these materials enhance detection sensitivity and performance. We have also proposed future research directions aimed at developing effective electrochemical methods for HBCD detection.

 

Comments 4: [What is the mechanism of influence of CeO2 nanocubes, graphene and polymers with a molecular structure on the results obtained? What is the accuracy of determining TBA and HBCD?]

Response: We have added section 5 to highlight inorganic NP advantages

Mechanism of Influence:

CeO2 Nanocubes: CeO2 nanocubes enhance the electrochemical properties of electrodes through their high surface area and excellent catalytic activity. They facilitate the adsorption and electron transfer processes, thereby improving the sensitivity and lowering the detection limits for TBBPA.

Graphene: Graphene offers a large surface area, high electrical conductivity, and strong mechanical strength. These properties enhance electron transfer rates and provide more active sites for the adsorption of TBBPA, leading to improved sensitivity and lower detection limits.

Polymers with Molecular Structure: Polymers, particularly those with tailored molecular structures, can provide specific binding sites for TBBPA, enhancing selectivity. They can also improve the stability and reproducibility of the electrode response.

 

Comments 5: [The conclusions are consistent with the evidence presented.]

Response: Thank you for your positive feedback on our conclusions. We have ensured that the conclusions remain aligned with the expanded discussions and additional details provided in the revised manuscript.

Comments 6: [Links are appropriate]

Response: Thank you. We have reviewed and confirmed the appropriateness of all references and links cited in the manuscript.

Comments 7: [Additional comments to tables and figures are not required.]

Response: Thank you for your feedback. We have ensured that the tables and figures included in the manuscript are clear, informative, and of high quality.

 

Round 2

Reviewer 1 Report

Comments and Suggestions for Authors

The authors made good revision, no comment anymore