Quaternization of Poly(2-diethyl aminoethyl methacrylate) Brush-Grafted Magnetic Mesoporous Nanoparticles Using 2-Iodoethanol for Removing Anionic Dyes
, Abdurrahman A. Almethen 3,*, Abeer M. Beagan 1, Hassan M. Al-Swaidan 1, Ashfaq Ahmad 1, Showkat Ahmad Bhawani 4 and Abdullah M. Alswieleh 1,†Round 1
Reviewer 1 Report
Manuscript: Quaternization of poly (2- diethyl amino ethyl methacrylate) brush grafted magnetic mesoporous nanoparticles using 2-iodoethanol for removing anionic dyes.
The manuscript presents very good work related water purification and going to be interesting for the readers.
Some minor comments are as follows.
- Authors need to include some interesting data in the abstract part of the manuscript.
- English must be improved.
- Novelty of the work be established.
- All the important results reported be compared in a tabular form to establish the superiority of the work.
- What is the significance and outcome of this study?
- Avoid the typo errors and unnecessary space in the written manuscript.
- Authors need to add future prospective of presented research in the conclusion part of the manuscript.
- Authors must need to incorporate following recent reference related to water purification the manuscript to make it more interesting for the readers.
- Environmental Science: Water Research & Technology 6 (11), 3080-3090
- Advanced Sustainable Systems, 1900114
- ACS omega 4 (26), 22008-22020
- ACS Sustainable Chemistry & Engineering 7 (6), 6140-6151
- ACS Sustainable Chemistry & Engineering 6 (3), 3279-3290
Author Response
Response to Reviews
Manuscript ID: applsci-1431361 Submitted to Applied Sciences
“Quaternization of poly (2- diethyl amino ethyl methacrylate) brush grafted magnetic mesoporous nanoparticles using 2-iodoethanol for removing anionic dyes” by K. Alotaibi et al.
Comments and Suggestions from Reviewer 1
1- Authors need to include some interesting data in the abstract part of the manuscript.
Reply: As suggested by the reviewer, more result data has been added to the abstract.
2- English must be improved.
Reply: The manuscript was carefully checked and has been edited when required.
3- Novelty of the work be established.
Reply: The novelty of this work is to synthesize new materials using quaternization process for potential applications. To the best of our knowledge, there is very little work in the literature on the use of pH-responsive polymer brushes in water remediation. In this manuscript, we developed effective materials based on silica nanoparticles and pH-sensitive poly (2-diethyl amino ethyl methacrylate) brush for removing dyes from water. This part has been added to the revised manuscript.
4- All the important results reported be compared in a tabular form to establish the superiority of the work.
Reply: We thank the reviewer, a list of maximum adsorption capacities for different types of adsorbents comparing to the synthesized nanomaterials are presented in Table 1.
5- What is the significance and outcome of this study?
Reply: We developed effective nanomaterials based on silica nanoparticles and pH-sensitive poly (2-diethyl amino ethyl methacrylate) brush for removing anionic dyes from contaminated water. Moreover, the proposed nanomaterials are capable to work effectively under a variety of environmental conditions (i.e., basic and acidic media).
6- Avoid the typo errors and unnecessary space in the written manuscript.
Reply: We accept that there were proofreading errors in the manuscript, and we have now carefully checked it in the revised manuscript.
7- Authors need to add future prospective of presented research in the conclusion part of the manuscript.
Reply: As suggested by the reviewer, the future prespective of this work has been highlighted in conclusion part in the revised manuscript.
8- Authors must need to incorporate following recent reference related to water purification the manuscript to make it more interesting for the readers.
Environmental Science: Water Research & Technology 6 (11), 3080-3090
Advanced Sustainable Systems, 1900114
ACS omega 4 (26), 22008-22020
ACS Sustainable Chemistry & Engineering 7 (6), 6140-6151
ACS Sustainable Chemistry & Engineering 6 (3), 3279-3290
Reply: We thank the reviewer for this suggestion. The suggested papers haven been added to the revised manuscript.
We hope that our revised manuscript is now considered acceptable for publication in Applied Sciences.
Author Response File: 
Author Response.docx
Reviewer 2 Report
Magnetic mesoporous silica nanoparticles were successfully synthesized and functionalized with tertiary amines. these were quatenized in order to introduce a permanent positive charge on polymeric chain. I think the paper could be published after some major revisions.
1. The introduction lacks of references to other materials used for dyes removal such as carbon nanomaterials and clays. A comparison of obtained results with ones reported in literature regarding also other common used adsorbents is necessary to be added. I suggest the authors to take into consideration the following articles and works cited inside:
Nanomaterials 2020, 10(6),1157; https://doi.org/10.3390/nano10061157
Materials 2021, 14(13), 3676; https://doi.org/10.3390/ma14133676
In particular in the second paper, a natural clay is reported for dyes removal and this is constituted by alluminosilicate layers decorated with iron oxide particles.
which are the advantages of material proposed by the author with respect to used carbon materials like graphene oxide or with respect to the possibility of using a natural clay like halloysite?
2. for the adosprtion experiments, the possibility of regenration ad reuse of powder should be investigated and reported as shown in Materials 2021, 14(13), 3676; https://doi.org/10.3390/ma14133676
3. I suggest the author to add some characterizations on the crystallinity of obtaine iron particles by XRD, Raman or by electron diffraction during TEM acquisition.
4. I do not understant why in the FTIR spectra .peaks related to amine funcitonalization never compare.
5. The removal of anionic dyes by adsorption depends on electrostatic attraction between dye molecules and asorbents. as a consequence, the charge of adsorbents is a key factor in order to have a successfull removal process. it is fundamental to know the charge of adsorbent surface according to different experimental conditions. I ask the authors to examine the surface charge of their particles by Z potentials and by the evaluation of the point of sero charge as reported in Materials 2021, 14(13), 3676; https://doi.org/10.3390/ma14133676
Author Response
Response to Reviewers
Manuscript ID: applsci-1431361 Submitted to Applied Sciences
“Quaternization of poly (2- diethyl amino ethyl methacrylate) brush grafted magnetic mesoporous nanoparticles using 2-iodoethanol for removing anionic dyes” by K. Alotaibi et al.
Comments and Suggestions from Reviewer 2
1- The introduction lacks of references to other materials used for dyes removal such as carbon nanomaterials and clays. A comparison of obtained results with ones reported in literature regarding also other common used adsorbents is necessary to be added. I suggest the authors to take into consideration the following articles and works cited inside:
Nanomaterials 2020, 10(6),1157; https://doi.org/10.3390/nano10061157
Materials 2021, 14(13), 3676; https://doi.org/10.3390/ma14133676
In particular in the second paper, a natural clay is reported for dyes removal and this is constituted by alluminosilicate layers decorated with iron oxide particles.
which are the advantages of material proposed by the author with respect to used carbon materials like graphene oxide or with respect to the possibility of using a natural clay like halloysite?
Reply: We thank the reviewer for this suggestion. A brief description of the materials used for dyes removal have been added to the revised manuscript, taking into account the suggested articles.
2- for the adsorption experiments, the possibility of regeneration and reuse of powder should be investigated and reported as shown in Materials 2021, 14(13), 3676; https://doi.org/10.3390/ma14133676
Reply: We thank the reviewer for this comment. We believe that the regeneration of adsorbents is very important, especially for high removal capacities materials. However, series of experiments have been tried to reuse the fabricated materials, such as DI-water, ethanol and mixture of both solvents to desorb the dyes from the materials surface. It was observed that such conditions were in effective. This observation might be attributed to the strong interaction between the permanent positive charge polymer brush and the permanent negatively charged dyes.
3- I suggest the author to add some characterizations on the crystallinity of obtained iron particles by XRD, Raman or by electron diffraction during TEM acquisition.
Reply: As recommended by referee, XRD pattern of magnetite iron nanoparticles was added to the revised manuscript.
4- I do not understand why in the FTIR spectra. Peaks related to amine functionalization never compare.
Reply: In this experiment, we aimed to confirm the successful CTAB removal by disappearing C-C peaks, and the successful attachment of polymer chains by appearing C=O peak. For aminated mesoporous silica, no noticeable difference in IR spectra between amine functionalized MSNs and ATRP initiated MSNs was observed, which could be related to low concentration of functional groups attached to the surface. Similar observations have been reported previously.[1.2]
5- The removal of anionic dyes by adsorption depends on electrostatic attraction between dye molecules and asorbents. as a consequence, the charge of adsorbents is a key factor in order to have a successfull removal process. it is fundamental to know the charge of adsorbent surface according to different experimental conditions. I ask the authors to examine the surface charge of their particles by Z potentials and by the evaluation of the point of sero charges reported in Materials 2021, 14(13), 3676; https://doi.org/10.3390/ma14133676
Reply: We agree with reviewer; surface charge of the materials is important parameter to understand the adsorption mechanism. Surface zeta potentials of the materials have been used to examine the surface charge of the synthesized nanomaterials. We have added the results to the revised manuscript.
We hope that our revised manuscript is now considered acceptable for publication in Applied Sciences.
References
1-Alotaibi, Khalid M., Abdurrahman A. Almethen, Abeer M. Beagan, Latifah H. Alfhaid, Maqusood Ahamed, Ahmed M. El-Toni, and Abdullah M. Alswieleh 2021. "Poly(oligo(ethylene glycol) methyl ether methacrylate) Capped pH-Responsive Poly(2-(diethylamino)ethyl methacrylate) Brushes Grafted on Mesoporous Silica Nanoparticles as Nanocarrier" Polymers 13, no. 5: 823. https://doi.org/10.3390/polym13050823
2- Alswieleh, Abdullah M., Abeer M. Beagan, Bayan M. Alsheheri, Khalid M. Alotaibi, Mansour D. Alharthi, and Mohammed S. Almeataq 2020. "Hybrid Mesoporous Silica Nanoparticles Grafted with 2-(tert-butylamino)ethyl Methacrylate-b-poly(ethylene Glycol) Methyl Ether Methacrylate Diblock Brushes as Drug Nanocarrier" Molecules 25, no. 1: 195. https://doi.org/10.3390/molecules25010195
Author Response File: Author Response.docx
Reviewer 3 Report
The manuscript presents the preparation of magnetic mesoporous silica nanoparticles for the removal of dyes, and investigates the adsorption performance towards both MO and E110. The preparation of magnetic mesoporous silica nanoparticles is novel. The reviewer suggests that the manuscript can be considered for publication in this journal after major revision. The following questions should be answered in the revised manuscript.
- The Abstract is too long, and should be refined. some introduction about common measurement methods should be cancelled.
- The adsorption of anionic dyes, cationic dyes and selective adsorption of mixed dyes for the resultant nanoparticles should be introduced.
- The XRD pattern and N2 adsorption and desorption of magnetic mesoporous silica nanoparticles should be added.
Author Response
Response to Reviews
Manuscript ID: applsci-1431361 Submitted to Applied Sciences
“Quaternization of poly (2- diethyl amino ethyl methacrylate) brush grafted magnetic mesoporous nanoparticles using 2-iodoethanol for removing anionic dyes” by K. Alotaibi et al.
Comments and Suggestions from Reviewer 3
1- The Abstract is too long, and should be refined. some introduction about common measurement methods should be cancelled.
Reply: As suggested by the reviewer, the abstract has been revised in the revised manuscript.
2- The adsorption of anionic dyes, cationic dyes and selective adsorption of mixed dyes for the resultant nanoparticles should be introduced.
Reply: We totally agree with the referee; the selectivity of the nanomaterials should be presented in this study. We expected that the removal efficiency of cationic dyes by such materials will be limited due to the repulsion force between cationic dye and positively charge polymer chains.
When MO and E110 were mixed, the absorption peaks of both dyes were overlapped, because of the wavelength of UV absorption both dyes were close.
3- The XRD pattern and N2 adsorption and desorption of magnetic mesoporous silica nanoparticles should be added.
Reply: We agree with reviewer; more techniques have been used to characterize the synthesized nanomaterials. We have added the results of XRD and N2 adsorption-desorption for the fabricated nanoparticle in the revised manuscript.
We hope that our revised manuscript is now considered acceptable for publication in Applied Sciences.
Author Response File: Author Response.docx
Round 2
Reviewer 2 Report
Dear authors,
thank you for modifications added to the manuscript according to my suggestions. I think that now the manuscript could be published in the present form
Reviewer 3 Report
The reviewer agrees with the revision of this manuscript, and suggests that the revised manuscript can be considered for publication in this journal.
