分子动力学模拟证明了PNIPAM和PDEA在甘油溶液中的热响应行为

IF 4.1 Q2 MATERIALS SCIENCE, MULTIDISCIPLINARY
Scott D. Hopkins, Estela Blaisten-Barojas
{"title":"分子动力学模拟证明了PNIPAM和PDEA在甘油溶液中的热响应行为","authors":"Scott D. Hopkins, Estela Blaisten-Barojas","doi":"10.3389/fnano.2023.1292259","DOIUrl":null,"url":null,"abstract":"Polymers exhibiting thermoresponsive behavior above a lower critical solution temperature (LCST) undergo a coil-to-globule phase transition that has many biomedical applications, including biosensing, the control of release devices, and gene or drug delivery systems. In addition, there has been sustained scientific interest in these polymers for their use in industrial applications, including water treatment and desalination. Since the coil-to-globule phase transition is greatly affected by the hydrophilic/hydrophobic balance of the polymer-solvent interactions, the LCST of a particular thermoresponsive polymer depends on the solvent environment and can be tuned through the modification of solution parameters such as co-solvent molar concentrations. While there have been numerous experimental and computational studies focused on the properties of these polymers in aqueous solutions, study of their behavior in more viscous solvents has been limited. In this article, the thermoresponsive behavior of poly (N-isopropylacrylamide) (PNIPAM) and poly (N,N-diethylacrylamide) (PDEA) has been evaluated when in solution with water, the highly viscous liquid glycerol, and both 50:50 and 90:10 glycerol:water mixtures. The adopted methodology includes molecular dynamics techniques and a modified OPLS all-atom force field, which is particularly challenging when the monomers of the targeted polymers have side-chains consisting of a hydrophobic isopropyl group and a hydrophilic amide group along the carbon backbone chain. Hence, our approach entailed simulations at the microsecond scale. The structural and energetic properties of the polymers were characterized, including radius of gyration, solvent accessible surface area, polymer-solvent hydrogen bonding, and interaction energies. Our predictions indicate that these polymers sustain a coil-to-globule phase transition in glycerol solvents at significantly higher LCSTs when compared to the LCST in less viscous aqueous solutions. These predictions highlight valuable insights that will prove advantageous for industrial and nano-scale applications requiring polymer phase behavior with elevated LCST well above ambient temperature.","PeriodicalId":34432,"journal":{"name":"Frontiers in Nanotechnology","volume":"3 1","pages":"0"},"PeriodicalIF":4.1000,"publicationDate":"2023-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Molecular dynamics simulations evidence the thermoresponsive behavior of PNIPAM and PDEA in glycerol solutions\",\"authors\":\"Scott D. Hopkins, Estela Blaisten-Barojas\",\"doi\":\"10.3389/fnano.2023.1292259\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Polymers exhibiting thermoresponsive behavior above a lower critical solution temperature (LCST) undergo a coil-to-globule phase transition that has many biomedical applications, including biosensing, the control of release devices, and gene or drug delivery systems. In addition, there has been sustained scientific interest in these polymers for their use in industrial applications, including water treatment and desalination. Since the coil-to-globule phase transition is greatly affected by the hydrophilic/hydrophobic balance of the polymer-solvent interactions, the LCST of a particular thermoresponsive polymer depends on the solvent environment and can be tuned through the modification of solution parameters such as co-solvent molar concentrations. While there have been numerous experimental and computational studies focused on the properties of these polymers in aqueous solutions, study of their behavior in more viscous solvents has been limited. In this article, the thermoresponsive behavior of poly (N-isopropylacrylamide) (PNIPAM) and poly (N,N-diethylacrylamide) (PDEA) has been evaluated when in solution with water, the highly viscous liquid glycerol, and both 50:50 and 90:10 glycerol:water mixtures. The adopted methodology includes molecular dynamics techniques and a modified OPLS all-atom force field, which is particularly challenging when the monomers of the targeted polymers have side-chains consisting of a hydrophobic isopropyl group and a hydrophilic amide group along the carbon backbone chain. Hence, our approach entailed simulations at the microsecond scale. The structural and energetic properties of the polymers were characterized, including radius of gyration, solvent accessible surface area, polymer-solvent hydrogen bonding, and interaction energies. Our predictions indicate that these polymers sustain a coil-to-globule phase transition in glycerol solvents at significantly higher LCSTs when compared to the LCST in less viscous aqueous solutions. These predictions highlight valuable insights that will prove advantageous for industrial and nano-scale applications requiring polymer phase behavior with elevated LCST well above ambient temperature.\",\"PeriodicalId\":34432,\"journal\":{\"name\":\"Frontiers in Nanotechnology\",\"volume\":\"3 1\",\"pages\":\"0\"},\"PeriodicalIF\":4.1000,\"publicationDate\":\"2023-10-16\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Frontiers in Nanotechnology\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://doi.org/10.3389/fnano.2023.1292259\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"MATERIALS SCIENCE, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Frontiers in Nanotechnology","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.3389/fnano.2023.1292259","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"MATERIALS SCIENCE, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0

摘要

聚合物在较低的临界溶液温度(LCST)以上表现出热响应行为,经历线圈到球体的相变,具有许多生物医学应用,包括生物传感、释放装置控制、基因或药物输送系统。此外,科学界一直对这些聚合物在工业应用中的应用感兴趣,包括水处理和海水淡化。由于线圈到球的相变很大程度上受到聚合物-溶剂相互作用的亲疏水平衡的影响,因此特定热敏聚合物的LCST取决于溶剂环境,并且可以通过修改溶液参数(如共溶剂摩尔浓度)来调节。虽然已经有大量的实验和计算研究集中在这些聚合物在水溶液中的性质上,但对它们在粘性溶剂中的行为的研究却很有限。本文研究了聚N-异丙基丙烯酰胺(PNIPAM)和聚N,N-二乙基丙烯酰胺(PDEA)在水、高粘性液体甘油、50:50和90:10甘油:水混合物溶液中的热响应行为。采用的方法包括分子动力学技术和改进的ops全原子力场,当目标聚合物的单体沿碳主链具有由疏水异丙基和亲水酰胺基组成的侧链时,这尤其具有挑战性。因此,我们的方法需要在微秒尺度上进行模拟。表征了聚合物的结构和能量性质,包括旋转半径、溶剂可达表面积、聚合物-溶剂氢键和相互作用能。我们的预测表明,与低粘性水溶液中的LCST相比,这些聚合物在高LCST的甘油溶剂中保持线圈到球体的相变。这些预测突出了有价值的见解,将证明有利于工业和纳米级应用,这些应用需要在高于环境温度的高LCST下聚合物相行为。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Molecular dynamics simulations evidence the thermoresponsive behavior of PNIPAM and PDEA in glycerol solutions
Polymers exhibiting thermoresponsive behavior above a lower critical solution temperature (LCST) undergo a coil-to-globule phase transition that has many biomedical applications, including biosensing, the control of release devices, and gene or drug delivery systems. In addition, there has been sustained scientific interest in these polymers for their use in industrial applications, including water treatment and desalination. Since the coil-to-globule phase transition is greatly affected by the hydrophilic/hydrophobic balance of the polymer-solvent interactions, the LCST of a particular thermoresponsive polymer depends on the solvent environment and can be tuned through the modification of solution parameters such as co-solvent molar concentrations. While there have been numerous experimental and computational studies focused on the properties of these polymers in aqueous solutions, study of their behavior in more viscous solvents has been limited. In this article, the thermoresponsive behavior of poly (N-isopropylacrylamide) (PNIPAM) and poly (N,N-diethylacrylamide) (PDEA) has been evaluated when in solution with water, the highly viscous liquid glycerol, and both 50:50 and 90:10 glycerol:water mixtures. The adopted methodology includes molecular dynamics techniques and a modified OPLS all-atom force field, which is particularly challenging when the monomers of the targeted polymers have side-chains consisting of a hydrophobic isopropyl group and a hydrophilic amide group along the carbon backbone chain. Hence, our approach entailed simulations at the microsecond scale. The structural and energetic properties of the polymers were characterized, including radius of gyration, solvent accessible surface area, polymer-solvent hydrogen bonding, and interaction energies. Our predictions indicate that these polymers sustain a coil-to-globule phase transition in glycerol solvents at significantly higher LCSTs when compared to the LCST in less viscous aqueous solutions. These predictions highlight valuable insights that will prove advantageous for industrial and nano-scale applications requiring polymer phase behavior with elevated LCST well above ambient temperature.
求助全文
通过发布文献求助,成功后即可免费获取论文全文。 去求助
来源期刊
Frontiers in Nanotechnology
Frontiers in Nanotechnology Engineering-Electrical and Electronic Engineering
CiteScore
7.10
自引率
0.00%
发文量
96
审稿时长
13 weeks
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
确定
请完成安全验证×
copy
已复制链接
快去分享给好友吧!
我知道了
右上角分享
点击右上角分享
0
联系我们:info@booksci.cn Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。 Copyright © 2023 布克学术 All rights reserved.
京ICP备2023020795号-1
ghs 京公网安备 11010802042870号
Book学术文献互助
Book学术文献互助群
群 号:481959085
Book学术官方微信