Green Composites from Thiophene Chalcones and Rice Husk Lignin: An Alternative of Powder for Latent Fingermark

Round 1

Reviewer 1 Report

MS No.: surfaces-1951574-peer-review-v1

Title: Green composites from thiophene chalcones and rice husk lignin: An alternative of powder for latent fingermark on glass surfaces

This manuscript describes the synthesis of effective and inexpensive rice husk derived lignin/thiophene chalcone composite for application in  forensic  science  as  a  fingermark developer. The new material was properly characterized, resulting in clear and sharp images of latent fingermark with minimal background staining, I have some questions that should be addressed in the Manuscript before acceptance, which I include here below.

1)      In section 2.1/ Preparation of rice husk, what is the meaning of ethanol solution?

2)      In section 2.2: The authors claimed that “All samples were analyzed by  infrared  spectroscopy  and  a spectrophotometer” It should be “Characterized” instead of “analyzed”.

3)      In Fig. 1(a) the authors represent the absorbance as "arbitrary units" for the Y axis. However, the absorbance intensity depends on the solution concentration and therefore, it is confusing the reader.

4)      The fluorescence spectroscopic data is important characteristics for latent fingermarks and should be reported.

5)      The resolution of Figures is not good

6)    The manuscript has deficiency citation to similar works published before like

https://doi.org/10.1007/s00449-021-02639-y

https://doi.org/10.1016/j.molstruc.2020.127840

https://doi.org/10.1016/j.jiec.2021.11.026

Author Response

Submission of revised manuscript entitled:

“Green composites from thiophene chalcones and rice husk lignin: An alternative of powder for latent fingermark”

Thank you for the opportunity to resubmit a revised version of the manuscript. We really appreciate your interest in the manuscript, and we are grateful for Reviewer’s comments. We addressed all comments, and we believe it has improved the clarity and quality of the manuscript. Thereby, the changes have been highlighted in the revised manuscript. We hope that this version of the manuscript is now suitable for publication in Surfaces. We are available for any other suggestions.

Best regards,

The authors

Reviewer 1

This manuscript describes the synthesis of effective and inexpensive rice husk derived lignin/thiophene chalcone composite for application in  forensic  science  as  a  fingermark developer. The new material was properly characterized, resulting in clear and sharp images of latent fingermark with minimal background staining, I have some questions that should be addressed in the Manuscript before acceptance, which I include here below.

• In section 2.1/ Preparation of rice husk, what is the meaning of ethanol solution?

Thank you for the comment. Actually, there was a misspelling where the solution had already been described previously. In this procedure, a sodium hydroxide dissolved in ethanol was used. A new sentence was added to the text at section 2.1.

• In section 2.2: The authors claimed that “All samples were analyzed by  infrared  spectroscopy  and  a spectrophotometer” It should be “Characterized” instead of “analyzed”.

Thank you for the comment. We have replaced 'analyzed' for 'characterized' in section 2.2 as suggested.

• In Fig. 1(a) the authors represent the absorbance as "arbitrary units" for the Y axis. However, the absorbance intensity depends on the solution concentration and therefore, it is confusing the reader.

We agree with the reviewer, the absorbance intensity depends on the concentration of the solution. In this study, the same concentration was used for all samples. Thus, differences in the bands were observed for chalcone and lignin in the final product due to the mixing of the compounds in m/m ratio. Furthermore, the bands related to the chromophore groups present in each compound were identified. For better understanding, we added new sentences into the text.

• The fluorescence spectroscopic data is important characteristics for latent fingermarks and should be reported.

Agreed and thankful to the reviewer's comment. Fluorescence is indeed an important tool for fingerprint evaluation. Fluorescence analysis was added to the manuscript, but the results were promising only for pure chalcones. When chalcones are mixed with rice husk lignin, they lose the fluorescence characteristic. Thus, this is a future perspective to improve this composite in order for it to demonstrate its fluorescent potential.

5)      The resolution of Figures is not good

All the figures have had an improvement in quality.

6)    The manuscript has deficiency citation to similar works published before like

https://doi.org/10.1007/s00449-021-02639-y

https://doi.org/10.1016/j.molstruc.2020.127840

https://doi.org/10.1016/j.jiec.2021.11.026

Thank you for the suggestion and for the key references sent. All indicated references have been added to the text. In addition, other references have also been inserted.

Author Response File: Author Response.docx

Reviewer 2 Report

It is interesting to report an effective and inexpensive rice husk derived lignin/thiophene chalcone composite for application in forensic science as a fingermark developer, which is an interesting alternative to be applied as a technological, reproducible and renewable product. However, some issues need to be resolved prior to publication.

1. The paper only showed the latent fingermark imaging on the glass surfaces using rice husk derived lignin/thiophene chalcone composite. As is well-known, the smooth glass surface is not the typical surface in forensic science application, some other rough surfaces are suggested to be used in the latent fingermark developing.

Author Response

Submission of revised manuscript entitled:

“Green composites from thiophene chalcones and rice husk lignin: An alternative of powder for latent fingermark”

Thank you for the opportunity to resubmit a revised version of the manuscript. We really appreciate your interest in the manuscript, and we are grateful for Reviewer’s comments. We addressed all comments, and we believe it has improved the clarity and quality of the manuscript. Thereby, the changes have been highlighted in the revised manuscript. We hope that this version of the manuscript is now suitable for publication in Surfaces. We are available for any other suggestions.

Best regards,

The authors

Reviewer 2

It is interesting to report an effective and inexpensive rice husk derived lignin/thiophene chalcone composite for application in forensic science as a fingermark developer, which is an interesting alternative to be applied as a technological, reproducible and renewable product. However, some issues need to be resolved prior to publication.

The paper only showed the latent fingermark imaging on the glass surfaces using rice husk derived lignin/thiophene chalcone composite. As is well-known, the smooth glass surface is not the typical surface in forensic science application, some other rough surfaces are suggested to be used in the latent fingermark developing.

We thank the reviewer for the comment. Fingermarks developed on other surfaces such as ceramic and cardboard were added to the manuscript. The new images are shown in Figure 3 of the manuscript.

2. Some articles on fluorescence fingerprint development may be useful for literature review in the Introduction part, such as ACS Applied Materials & Interfaces, 2019, 11(38), 35294-35304; ACS Applied Nano Materials, 2022, 5(7) 9929–9939;Advanced functional materials 27.14 (2017): 1606243.3. Please check the scale bar of Figure 3a, it is 1 mm or 1 μm.

Thank you for the comment. and for the key references sent. All indicated references have been added to the text. Moreover, the scale bar of the Figure 3a was corrected to 1 mm.

4. The sentence “10-91-1095 cm-1 C-O stretching in secondary alcohols or aliphatic ethers should be revised in page 3.

There was a typo, the correct band is 1091-1095 cm-1 and a correction has been made in the manuscript.

Author Response File: Author Response.docx

Reviewer 3 Report

This manuscript describes the development of a novel hybrid composite of RHL and thiophene chalcone for application as a latent fingermark development technique.

After a careful peer-reviewing process, I must inform you that, the subject of this paper is interesting and can be considered for publication in Surfaces after a MAJOR REVISION. I believe that the paper contains relevant information for the scientific community focused on recent advances in human identification techniques. I believe that the results are informative but must be well organized and improved in the next revision(s). Therefore, there are some questions about this submission and some revisions are necessary for this work. The major/minor issues are indicated as follows:

1.    Typos and minor grammar errors (including punctuation) and formatting mistakes (font change, etc) are common in the manuscript. A considerable number of sentences are not comprehensible, some of which can be due to typos or grammar errors. Careful proofreading is mandatory for this case.

2.    The abstract is not well written. Some details of the experimental processes were missed in the abstract. Please revise this section. 

3.    The state-of-the-art needs to be described more in the “Introduction”. Please revise the last paragraph of this section.

4.    The new findings related to this work should be stated in the introduction clearly.

5.    Please provide the manufacturer/model/code and also the manufacturer country of the raw materials as well as all testing equipment used for evaluations.

6.    Authors must show which questions/problems have been answered in this work. In this case, the correct and detailed information about this study focused on green composites used for fingermark identification must be provided in this manuscript.

7.    In this manuscript, results are well presented, but discussion on the obtained results must be completely provided in this manuscript. As can be seen, a “comprehensive” and “comparative” discussion is missed in this work. This should be provided as well.

8.    Please provide major findings in the “Conclusions” section with a bullet-point style.

9.    There is no description of the future plans for research in the first part of the “Conclusions” section. This should be completed in this section.

10. Recently published references are beneficial for this work. Please check and use new references focused on your work.

11.  Also, please double-check and revise the reference list according to the MDPI / Surfaces journal requirements.

Author Response

Submission of revised manuscript entitled:

“Green composites from thiophene chalcones and rice husk lignin: An alternative of powder for latent fingermark”

Thank you for the opportunity to resubmit a revised version of the manuscript. We really appreciate your interest in the manuscript, and we are grateful for Reviewer’s comments. We addressed all comments, and we believe it has improved the clarity and quality of the manuscript. Thereby, the changes have been highlighted in the revised manuscript. We hope that this version of the manuscript is now suitable for publication in Surfaces. We are available for any other suggestions.

Best regards,

The authors

Reviewer 3

This manuscript describes the development of a novel hybrid composite of RHL and thiophene chalcone for application as a latent fingermark development technique.

After a careful peer-reviewing process, I must inform you that, the subject of this paper is interesting and can be considered for publication in Surfaces after a MAJOR REVISION. I believe that the paper contains relevant information for the scientific community focused on recent advances in human identification techniques. I believe that the results are informative but must be well organized and improved in the next revision(s). Therefore, there are some questions about this submission and some revisions are necessary for this work. The major/minor issues are indicated as follows:

1. Typos and minor grammar errors (including punctuation) and formatting mistakes (font change, etc) are common in the manuscript. A considerable number of sentences are not comprehensible, some of which can be due to typos or grammar errors. Careful proofreading is mandatory for this case.

Thank you for the suggestion. The manuscript was entirely revised and the grammar errors were corrected.

2. The abstract is not well written. Some details of the experimental processes were missed in the abstract. Please revise this section. 

We appreciate the comment. The abstract was revised according to the suggestion. The new abstract is shown below:

“This study reports a route to obtain a novel and cost-effective rice husk derived lignin/thiophene chalcone green composite for application in forensic science as a fingermark developer trough high energy milling.  The material was properly characterized by UV-Vis, IR, fluorescence, X-ray diffraction and scanning electron microscopy. The product provided clear and sharp images of latent fingermark with minimal background staining, revealing all ridge details. Thus, the composite presented good performance as a fingermark developer, becoming an interesting alternative to be applied as a technological, reproducible and renewable product.”

3. The state-of-the-art needs to be described more in the “Introduction”. Please revise the last paragraph of this section.

Agreed. The introduction section was revised and the changes made to the text are shown below:

“The development of hybrid materials containing two or more phases to generate increased physical and chemical properties is an approach that has been continuously applied in different fields of science [4]. Accordingly, there has been an increasing search for this class of material for fingermark development [5]. As an example, it can be cited the use of lanthanide doping to obtain core-shell nanoarchitectures [6] and Europium ions doped with calcium hydroxy stannate [7], both studied as fingermarks revealing materials in different surfaces. Other hybrid materials such as red fluorescent carbon dot powder [8] and doping of Li⁺ to improve the luminescence permittivity of green nano-phosphor CaWO₄:Tb₃⁺ are also reported [9]. In this scenario, rice husk is an interesting waste material that can be used for biosynthesis of gold nanoparticles [10] or for lignin extraction [11]. Moreover, organic molecules such as curcumins [12] and chalcones [13] have also been efficiently applied in LFM development.”

“The application of powders to latent fingermarks has been long established as an effective and reliable method for developing latent fingermarks both in crime scenes and in a laboratory scale. Most studies have focused on the development – or optimization – of conventional detection techniques [17]. Nevertheless, fundamental issues still need improvement and the actual efficiency of detection sequences remain hard to assess when considering non-supervised items (approximately 50% of fingermarks escape detection) [18,19]. The development of new materials to detect LFM through clean chemistry, with low cost of production, high sensibility and low toxicity, seems to be an interesting alternative.”

4. 4.    The new findings related to this work should be stated in the introduction clearly.

Agreed and thankful for the suggestion. The introduction section was revised and the changes made to the text are highlighted in yellow.

5. Please provide the manufacturer/model/code and also the manufacturer country of the raw materials as well as all testing equipment used for evaluations.

The manufacturer/model/code and also the country of manufacture have been added to the text for all the equipment used.

6. Authors must show which questions/problems have been answered in this work. In this case, the correct and detailed information about this study focused on green composites used for fingermark identification must be provided in this manuscript.

We appreciate the suggestion. The introduction, results and conclusions of the article were revised and all modifications are highlighted in yellow throughout the text. 

7. In this manuscript, results are well presented, but discussion on the obtained results must be completely provided in this manuscript. As can be seen, a “comprehensive” and “comparative” discussion is missed in this work. This should be provided as well.

A new paragraph correlating the results has been inserted at the end of the discussion and is highlighted. The new paragraph is shown below:

‘Thus, a new composite was obtained from a fluorescent chalcone and rice husk lignin. This material was characterized by UV-Vis, IR, fluorescence, X-ray diffraction and scanning electron microscopy. The chalcone used presents fluorescence, but the final product with the presence of lignin does not. However, the compost was applied efficiently to develop fingermarks, that could be used for human identification. The material also showed adherence to fingermark and different surfaces. Scanning electron microscopy confirms that the material shows affinity for fingermarks and not with the surface. Thus, the proposed material is an interesting alternative for the area of papiloscopy, which can be obtained in large scale and also presents a certain sustainability due to the use of lignin from rice husk, which would be a waste.’

8. Please provide major findings in the “Conclusions” section with a bullet-point style.

Thanks for the comment. The conclusion section was revised and changes made to the text are highlighted in yellow.

9. There is no description of the future plans for research in the first part of the “Conclusions” section. This should be completed in this section.

Thank you for the comment. A new sentence describing the future perspective for this research was added to the conclusion section as suggested.  

10. Recently published references are beneficial for this work. Please check and use new references focused on your work.

Thank you. A series of new references were added to the manuscript to contextualize the problem and what has been published recently.

11. Also, please double-check and revise the reference list according to the MDPI / Surfaces journal requirements.

All references have been checked and fixed.

Author Response File: Author Response.docx

Round 2

Reviewer 1 Report

Dear Editor

The authors have satisfactorily addressed most of my concerns. This revised manuscript can be accepted for publication.

Reviewer 2 Report

The authors addressed most of my issues, but the advance of latent fingermark detection using persistent luminescence materials should be contrastively introduced in introduction part, some references should be cited, such as ACS Appl. Nano Mater. 2022, 5, 7, 9929–9939.

Reviewer 3 Report

No more comments.