首页 > 最新文献

Molecular Systems Design & Engineering最新文献

英文 中文
Development of a light-responsive fluorinated poly(arylene ether) copolymer containing azobenzene groups in the main polymer chain† 开发聚合物主链中含有偶氮苯基团的光响应型含氟聚(芳基醚)共聚物†。
IF 3.6 3区 工程技术 Q2 CHEMISTRY, PHYSICAL Pub Date : 2023-11-07 DOI: 10.1039/D3ME00150D
Ihor M. Tkachenko, Yuriy I. Kurioz, Ruslan M. Kravchuk, Alexander L. Tolstov, Anatoliy V. Glushchenko, Vassili G. Nazarenko and Valery V. Shevchenko

A novel light-responsive poly(arylene ether) copolymer with both azobenzene and perfluorinated biphenylene units as well as meta-linked fragments in the main polymer chain is synthesized. The copolymer is synthesized using aromatic nucleophilic substitution reaction from decafluorobiphenyl and two dihydroxyl-substituted monomers, fluorinated bis-azobenzene-based phenol derivative, and resorcinol. The chemical structure of the copolymer is characterized using 1H, 19F NMR, FTIR, Raman and UV/vis spectroscopy techniques. The polymer shows remarkable solubility in organic solvents resulting in the formation of robust, self-supporting films. It displays impressive mechanical characteristics as well as remarkable resistance to thermo-oxidative degradation. Under UV light irradiation, photoisomerization occurs both in solution and in the solid copolymer film. The solid polymer films exhibit intense and stable birefringence changes upon the irradiation, enabling the fabrication of diffraction gratings. The study indicates that this synthetic approach is a simple and effective method for designing light-responsive materials.

我们合成了一种新型光响应聚(芳基醚)共聚物,这种共聚物的聚合物主链中同时含有偶氮苯和全氟联苯单元以及元连接片段。这种共聚物是由十氟联苯和两种二羟基取代单体、氟化双偶氮苯基苯酚衍生物以及间苯二酚通过芳香族亲核取代反应合成的。共聚物的化学结构采用 1H、19F NMR、FTIR、拉曼和 UV/vis 光谱技术进行表征。该聚合物在有机溶剂中的溶解度极高,可形成坚固的自支撑薄膜。它具有令人印象深刻的机械特性和出色的抗热氧化降解能力。在紫外线照射下,溶液和固体共聚物薄膜都会发生光异构化。固态聚合物薄膜在辐照后会出现强烈而稳定的双折射变化,从而可以制作衍射光栅。研究表明,这种合成方法是设计光响应材料的一种简单而有效的方法。
{"title":"Development of a light-responsive fluorinated poly(arylene ether) copolymer containing azobenzene groups in the main polymer chain†","authors":"Ihor M. Tkachenko, Yuriy I. Kurioz, Ruslan M. Kravchuk, Alexander L. Tolstov, Anatoliy V. Glushchenko, Vassili G. Nazarenko and Valery V. Shevchenko","doi":"10.1039/D3ME00150D","DOIUrl":"10.1039/D3ME00150D","url":null,"abstract":"<p >A novel light-responsive poly(arylene ether) copolymer with both azobenzene and perfluorinated biphenylene units as well as <em>meta</em>-linked fragments in the main polymer chain is synthesized. The copolymer is synthesized using aromatic nucleophilic substitution reaction from decafluorobiphenyl and two dihydroxyl-substituted monomers, fluorinated bis-azobenzene-based phenol derivative, and resorcinol. The chemical structure of the copolymer is characterized using <small><sup>1</sup></small>H, <small><sup>19</sup></small>F NMR, FTIR, Raman and UV/vis spectroscopy techniques. The polymer shows remarkable solubility in organic solvents resulting in the formation of robust, self-supporting films. It displays impressive mechanical characteristics as well as remarkable resistance to thermo-oxidative degradation. Under UV light irradiation, photoisomerization occurs both in solution and in the solid copolymer film. The solid polymer films exhibit intense and stable birefringence changes upon the irradiation, enabling the fabrication of diffraction gratings. The study indicates that this synthetic approach is a simple and effective method for designing light-responsive materials.</p>","PeriodicalId":91,"journal":{"name":"Molecular Systems Design & Engineering","volume":" 2","pages":" 149-157"},"PeriodicalIF":3.6,"publicationDate":"2023-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135504576","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Cation/anion-exchange mode switching chromatography utilizing pH-responsive mixed charge polymer-modified silica beads† 利用 pH 值响应型混合电荷聚合物改性硅胶珠的阳离子/阴离子交换模式转换色谱法†...
IF 3.6 3区 工程技术 Q2 CHEMISTRY, PHYSICAL Pub Date : 2023-11-03 DOI: 10.1039/D3ME00100H
Taisei Kaku, Koichi Deura, Tomoka Yoshii, Daniel Citterio and Yuki Hiruta

The separation capacity of a column typically remains constant. By applying stimuli-responsive materials to the stationary phase, the separation capacity in a single column can be tuned; however, the separation mode is not completely switched. In this study, we aimed to develop a cation/anion-exchange mode switching chromatography approach, in which the monomer ratio is adjusted, enabling the surface charge to become either negative or positive in response to mobile phase pH. Three types of beads were prepared, each modified with a pH-responsive mixed-charge polymer combining a cationic monomer, a pH-responsive carboxylic acid monomer, a neutral monomer, and a cross-linking monomer. The composition ratio of the cationic monomer to the pH-responsive carboxylic acid monomer was set at 1 : 2 so that the cation-exchange mode occurs at a pH above the pKa and the anion-exchange mode occurs below the pKa. At a pH below the pKa, the retention factor of the negatively charged compound increased. In contrast, at a pH above the pKa, the retention factor of the positively charged compound increased, confirming the charge switching on the bead surface. Switching to the cation- and anion-exchange mode enabled the separation of five basic antidepressants and acidic non-steroidal anti-inflammatory drugs, respectively. Utilizing a pH-responsive mixed-charge polymer, we attributed a cation/anion-exchange mode to a single column.

色谱柱的分离能力通常保持不变。通过在固定相中使用刺激响应材料,可以调整单个色谱柱的分离能力;但分离模式并不能完全切换。在本研究中,我们旨在开发一种阳离子/阴离子交换模式切换色谱方法,通过调节单体比例,使表面电荷随流动相 pH 值的变化而变成负电荷或正电荷。我们制备了三种珠子,每种珠子都用 pH 响应型混合电荷聚合物修饰,该聚合物由阳离子单体、pH 响应型羧酸单体、中性单体和交联单体组成。阳离子单体与 pH 响应型羧酸单体的组成比例设定为 1:2,这样阳离子交换模式在 pH 值高于 pKa 时发生,阴离子交换模式在 pH 值低于 pKa 时发生。当 pH 值低于 pKa 时,带负电荷化合物的保留因子增加。相反,当 pH 值高于 pKa 时,带正电荷的化合物的保留因子增加,这证实了珠子表面的电荷转换。切换到阳离子和阴离子交换模式后,五种碱性抗抑郁药和酸性非甾体抗炎药分别得以分离。利用 pH 响应型混合电荷聚合物,我们在单个色谱柱上实现了阳离子/阴离子交换模式。
{"title":"Cation/anion-exchange mode switching chromatography utilizing pH-responsive mixed charge polymer-modified silica beads†","authors":"Taisei Kaku, Koichi Deura, Tomoka Yoshii, Daniel Citterio and Yuki Hiruta","doi":"10.1039/D3ME00100H","DOIUrl":"10.1039/D3ME00100H","url":null,"abstract":"<p >The separation capacity of a column typically remains constant. By applying stimuli-responsive materials to the stationary phase, the separation capacity in a single column can be tuned; however, the separation mode is not completely switched. In this study, we aimed to develop a cation/anion-exchange mode switching chromatography approach, in which the monomer ratio is adjusted, enabling the surface charge to become either negative or positive in response to mobile phase pH. Three types of beads were prepared, each modified with a pH-responsive mixed-charge polymer combining a cationic monomer, a pH-responsive carboxylic acid monomer, a neutral monomer, and a cross-linking monomer. The composition ratio of the cationic monomer to the pH-responsive carboxylic acid monomer was set at 1 : 2 so that the cation-exchange mode occurs at a pH above the p<em>K</em><small><sub>a</sub></small> and the anion-exchange mode occurs below the p<em>K</em><small><sub>a</sub></small>. At a pH below the p<em>K</em><small><sub>a</sub></small>, the retention factor of the negatively charged compound increased. In contrast, at a pH above the p<em>K</em><small><sub>a</sub></small>, the retention factor of the positively charged compound increased, confirming the charge switching on the bead surface. Switching to the cation- and anion-exchange mode enabled the separation of five basic antidepressants and acidic non-steroidal anti-inflammatory drugs, respectively. Utilizing a pH-responsive mixed-charge polymer, we attributed a cation/anion-exchange mode to a single column.</p>","PeriodicalId":91,"journal":{"name":"Molecular Systems Design & Engineering","volume":" 1","pages":" 56-62"},"PeriodicalIF":3.6,"publicationDate":"2023-11-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/me/d3me00100h?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135446903","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Designing polyurethane-based microcapsules with tailored swelling behaviours for enhanced oil recovery† 设计具有定制溶胀行为的聚氨酯基微胶囊,用于提高石油采收率†。
IF 3.6 3区 工程技术 Q2 CHEMISTRY, PHYSICAL Pub Date : 2023-11-02 DOI: 10.1039/D3ME00137G
Tongyi Wang, Yongsheng Liu, Jiawei Li, Jun Zhang, Jian Hou, Youguo Yan and Xiao Wang

Polyurethane (PU) materials have been widely used for developing microcapsules due to their excellent polymerization, encapsulation, and controlled release properties. These unique properties endow PU-based microcapsules with desired functions for enhanced oil recovery (EOR). However, there are some special requirements for PU-based microcapsules in their application of the EOR process, such as they are expected to exhibit good stability at room temperature but thermo-responsive swelling-release properties in the oil reservoir. To enhance the functionality of PU-based microcapsules for EOR, after validating the swelling-release behaviors of PU-based microcapsules, we employed all-atom molecular dynamics (MD) simulations to study the effects of molecular structure of PU-based polymers on thermo-responsivity of microcapsules. The simulation results demonstrate that the diisocyanate segments have significant influence on swelling behaviors of PUs. The different diisocyanate segments, including isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI), and hexamethylene diisocyanate (HDI), have different impacts on the flexibility of the polymer, which further influence the network structure of the polymer matrix. The different swelling behaviors of PU-based polymers were further analyzed from energetic and kinetic perspectives, and it is demonstrated that TDI–PU can combine stability and thermo-responsivity together. In addition, the introduction of anionic functional groups can further facilitate the swelling process. The findings in this study serve as a foundation for future studies toward the development of polymer flooding technology and provide valuable molecular insights into the swelling mechanism of PU-based polymers.

聚氨酯(PU)材料具有出色的聚合、封装和控释性能,因此被广泛用于开发微胶囊。这些独特的性能赋予了聚氨酯基微胶囊在提高石油采收率(EOR)方面所需的功能。然而,聚氨酯基微胶囊在 EOR 过程中的应用有一些特殊要求,例如它们在室温下应表现出良好的稳定性,但在油藏中应具有热响应膨胀释放特性。为了增强聚氨酯基微胶囊在 EOR 中的功能,在验证了聚氨酯基微胶囊的膨胀释放行为后,我们采用全原子分子动力学(MD)模拟研究了聚氨酯基聚合物的分子结构对微胶囊热响应性的影响。模拟结果表明,二异氰酸酯段对聚氨酯的溶胀行为有显著影响。不同的二异氰酸酯段(包括异佛尔酮二异氰酸酯(IPDI)、甲苯二异氰酸酯(TDI)、4,4′-二苯基甲烷二异氰酸酯(MDI)和六亚甲基二异氰酸酯(HDI))对聚合物的柔韧性有不同的影响,从而进一步影响聚合物基体的网络结构。从能量和动力学角度进一步分析了聚氨酯基聚合物的不同溶胀行为,结果表明 TDI-PU 可以将稳定性和热响应性结合在一起。此外,阴离子官能团的引入可进一步促进溶胀过程。本研究的发现为今后开发聚合物淹没技术的研究奠定了基础,并为聚氨酯基聚合物的溶胀机理提供了宝贵的分子见解。
{"title":"Designing polyurethane-based microcapsules with tailored swelling behaviours for enhanced oil recovery†","authors":"Tongyi Wang, Yongsheng Liu, Jiawei Li, Jun Zhang, Jian Hou, Youguo Yan and Xiao Wang","doi":"10.1039/D3ME00137G","DOIUrl":"10.1039/D3ME00137G","url":null,"abstract":"<p >Polyurethane (PU) materials have been widely used for developing microcapsules due to their excellent polymerization, encapsulation, and controlled release properties. These unique properties endow PU-based microcapsules with desired functions for enhanced oil recovery (EOR). However, there are some special requirements for PU-based microcapsules in their application of the EOR process, such as they are expected to exhibit good stability at room temperature but thermo-responsive swelling-release properties in the oil reservoir. To enhance the functionality of PU-based microcapsules for EOR, after validating the swelling-release behaviors of PU-based microcapsules, we employed all-atom molecular dynamics (MD) simulations to study the effects of molecular structure of PU-based polymers on thermo-responsivity of microcapsules. The simulation results demonstrate that the diisocyanate segments have significant influence on swelling behaviors of PUs. The different diisocyanate segments, including isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI), and hexamethylene diisocyanate (HDI), have different impacts on the flexibility of the polymer, which further influence the network structure of the polymer matrix. The different swelling behaviors of PU-based polymers were further analyzed from energetic and kinetic perspectives, and it is demonstrated that TDI–PU can combine stability and thermo-responsivity together. In addition, the introduction of anionic functional groups can further facilitate the swelling process. The findings in this study serve as a foundation for future studies toward the development of polymer flooding technology and provide valuable molecular insights into the swelling mechanism of PU-based polymers.</p>","PeriodicalId":91,"journal":{"name":"Molecular Systems Design & Engineering","volume":" 1","pages":" 46-55"},"PeriodicalIF":3.6,"publicationDate":"2023-11-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"134888591","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Self-assembled monolayers as hole-transporting materials for inverted perovskite solar cells 自组装单层膜作为倒钙钛矿太阳能电池的空穴传输材料
IF 3.6 3区 工程技术 Q2 CHEMISTRY, PHYSICAL Pub Date : 2023-11-01 DOI: 10.1039/D3ME00144J
Zhong-Rui Lan, Jiang-Yang Shao and Yu-Wu Zhong

The emerging perovskite solar cells (PSCs) have been explored as the most promising photovoltaic technology in the past decade, with the sharp increase of the power conversion efficiency (PCE) from 3.8% to certified 26.1%, comparable to that of crystalline silicon solar cells. Compared to conventional PSCs, inverted PSCs show attractive advantages, such as high device stability, negligible hysteresis and excellent compatibility with flexible and tandem devices. Self-assembled monolayers (SAMs) have been considered as one of the most promising hole-transporting materials (HTMs) for inverted PSCs owing to their low costs and material consumption and simple device fabrication with high PCEs. This review summarizes the recent developments in highly efficient SAMs as HTMs for inverted PSCs. On the basis of the anchoring group, three categories of SAMs are identified and discussed: SAMs with phosphonic acid, SAMs with carboxylic acid, and SAMs based on other anchoring groups. Finally, a future outlook of SAMs for high-performance inverted PSCs is provided. We hope that this review will be useful for the further design of SAMs toward the eventual commercialization of PSCs.

在锚定基团的基础上,讨论了高性能倒钙钛矿太阳能电池中三种自组装单层空穴传输材料。
{"title":"Self-assembled monolayers as hole-transporting materials for inverted perovskite solar cells","authors":"Zhong-Rui Lan, Jiang-Yang Shao and Yu-Wu Zhong","doi":"10.1039/D3ME00144J","DOIUrl":"10.1039/D3ME00144J","url":null,"abstract":"<p >The emerging perovskite solar cells (PSCs) have been explored as the most promising photovoltaic technology in the past decade, with the sharp increase of the power conversion efficiency (PCE) from 3.8% to certified 26.1%, comparable to that of crystalline silicon solar cells. Compared to conventional PSCs, inverted PSCs show attractive advantages, such as high device stability, negligible hysteresis and excellent compatibility with flexible and tandem devices. Self-assembled monolayers (SAMs) have been considered as one of the most promising hole-transporting materials (HTMs) for inverted PSCs owing to their low costs and material consumption and simple device fabrication with high PCEs. This review summarizes the recent developments in highly efficient SAMs as HTMs for inverted PSCs. On the basis of the anchoring group, three categories of SAMs are identified and discussed: SAMs with phosphonic acid, SAMs with carboxylic acid, and SAMs based on other anchoring groups. Finally, a future outlook of SAMs for high-performance inverted PSCs is provided. We hope that this review will be useful for the further design of SAMs toward the eventual commercialization of PSCs.</p>","PeriodicalId":91,"journal":{"name":"Molecular Systems Design & Engineering","volume":" 12","pages":" 1440-1455"},"PeriodicalIF":3.6,"publicationDate":"2023-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2023/me/d3me00144j?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135319612","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Inhibitory behaviour and adsorption stability of benzothiazole derivatives as corrosion inhibitors towards galvanised steel† 苯并噻唑衍生物作为镀锌钢腐蚀抑制剂的抑制行为和吸附稳定性†。
IF 3.6 3区 工程技术 Q2 CHEMISTRY, PHYSICAL Pub Date : 2023-10-30 DOI: 10.1039/D3ME00153A
Qiushi Deng, José María Castillo-Robles, Ernane de Freitas Martins, Pablo Ordejón, Jan-Niclas Gorges, Philipp Eiden, Xiao-Bo Chen, Patrick Keil and Ivan Cole

An in-depth understanding of corrosion inhibitor behaviour(s) at the metal–solution interface governed by unique molecular features is the key premise to realising molecular tailoring for pronounced metal protection. This study investigated the distinct adsorption behaviours induced by merely replacing the chemical functionality upon benzothiazole, i.e., 2-mercaptobenzothiazole (2-MBT) and 2-aminobenzothiazole (2-ABT), towards electro-galvanised steel (ZE) corrosion using both experimental and theoretical approaches. Electrochemical results confirm that both inhibitor candidates act as corrosion inhibitors for ZE in NaCl solution. The underlying interactions of the inhibitor molecule with the targeting metal, dissolved metal ions and corrosion products were explored by means of X-ray photoelectron spectroscopy, focused ion beam scanning electron microscopy and Raman spectroscopy. It is suggested that 2-MBT facilitates the precipitation upon the ZE by complexing with the released Zn2+ in solution, while 2-ABT promotes preferentially thin inhibitor film formation initiated by chemisorption. Density functional theory (DFT) reveals that at high concentrations the molecules tend to adsorb vertically (slightly tilted) at the surface, where the presented heteroatoms enhance surface–molecule interaction. In addition, DFT suggests that the strong binding strength of 2-MBT could facilitate the formation of complexes with displaced Zn. Based on the proposed mechanisms, the adsorption stability upon polarised ZE surfaces was determined, which reveals that 2-MBT forms a thick inhibitor layer at a relatively high polarisation state, whereas 2-ABT dissociates from the surface with the increasing value of surface overpotential. The findings of this study provide structural understanding that underpins inhibitor tailoring and molecular design to achieve the desired inhibition properties.

深入了解腐蚀抑制剂在金属-溶液界面上受独特分子特征支配的行为,是实现分子定制以提供明显金属保护的关键前提。本研究采用实验和理论方法,研究了仅通过更换苯并噻唑(即 2-巯基苯并噻唑 (2-MBT) 和 2-氨基苯并噻唑 (2-ABT))的化学官能团而引起的电镀锌钢 (ZE) 腐蚀的不同吸附行为。电化学结果证实,这两种候选抑制剂都是 NaCl 溶液中 ZE 的腐蚀抑制剂。通过 X 射线光电子能谱、聚焦离子束扫描电子显微镜和拉曼光谱,研究了抑制剂分子与目标金属、溶解金属离子和腐蚀产物之间的潜在相互作用。结果表明,2-MBT 通过与溶液中释放的 Zn2+ 复配,促进了 ZE 上的沉淀,而 2-ABT 则通过化学吸附作用优先促进了抑制剂薄膜的形成。密度泛函理论(DFT)显示,在高浓度下,分子倾向于垂直(略微倾斜)吸附在表面上,在这种情况下,所呈现的杂原子会增强表面与分子之间的相互作用。此外,DFT 还表明,2-MBT 的强结合力可促进与移位的 Zn 形成复合物。根据所提出的机制,测定了极化 ZE 表面的吸附稳定性,结果表明 2-MBT 在相对较高的极化状态下会形成较厚的抑制剂层,而 2-ABT 则会随着表面过电势值的增加而从表面解离。本研究的发现为抑制剂的定制和分子设计提供了结构上的理解,从而实现理想的抑制特性。
{"title":"Inhibitory behaviour and adsorption stability of benzothiazole derivatives as corrosion inhibitors towards galvanised steel†","authors":"Qiushi Deng, José María Castillo-Robles, Ernane de Freitas Martins, Pablo Ordejón, Jan-Niclas Gorges, Philipp Eiden, Xiao-Bo Chen, Patrick Keil and Ivan Cole","doi":"10.1039/D3ME00153A","DOIUrl":"10.1039/D3ME00153A","url":null,"abstract":"<p >An in-depth understanding of corrosion inhibitor behaviour(s) at the metal–solution interface governed by unique molecular features is the key premise to realising molecular tailoring for pronounced metal protection. This study investigated the distinct adsorption behaviours induced by merely replacing the chemical functionality upon benzothiazole, <em>i.e.</em>, 2-mercaptobenzothiazole (2-MBT) and 2-aminobenzothiazole (2-ABT), towards electro-galvanised steel (ZE) corrosion using both experimental and theoretical approaches. Electrochemical results confirm that both inhibitor candidates act as corrosion inhibitors for ZE in NaCl solution. The underlying interactions of the inhibitor molecule with the targeting metal, dissolved metal ions and corrosion products were explored by means of X-ray photoelectron spectroscopy, focused ion beam scanning electron microscopy and Raman spectroscopy. It is suggested that 2-MBT facilitates the precipitation upon the ZE by complexing with the released Zn<small><sup>2+</sup></small> in solution, while 2-ABT promotes preferentially thin inhibitor film formation initiated by chemisorption. Density functional theory (DFT) reveals that at high concentrations the molecules tend to adsorb vertically (slightly tilted) at the surface, where the presented heteroatoms enhance surface–molecule interaction. In addition, DFT suggests that the strong binding strength of 2-MBT could facilitate the formation of complexes with displaced Zn. Based on the proposed mechanisms, the adsorption stability upon polarised ZE surfaces was determined, which reveals that 2-MBT forms a thick inhibitor layer at a relatively high polarisation state, whereas 2-ABT dissociates from the surface with the increasing value of surface overpotential. The findings of this study provide structural understanding that underpins inhibitor tailoring and molecular design to achieve the desired inhibition properties.</p>","PeriodicalId":91,"journal":{"name":"Molecular Systems Design & Engineering","volume":" 1","pages":" 29-45"},"PeriodicalIF":3.6,"publicationDate":"2023-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135261206","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Bis-ferrocenyl-hydrazide metal complexes: studying electronic functional groups as newly potent homogeneous photocatalysts for C(sp3)–H and C(sp2)–H bond oxidation utilizing visible light condition† 双二茂铁酰肼金属配合物:研究电子官能团,作为利用可见光条件氧化 C(sp3)-H 和 C(sp2)-H 键的新型强效均相光催化剂†。
IF 3.6 3区 工程技术 Q2 CHEMISTRY, PHYSICAL Pub Date : 2023-10-30 DOI: 10.1039/D3ME00133D
Mohammad Bashiri, Mona Hosseini-Sarvari and Sara Fakhraee

A crucial challenge in using organo-metal complexes for photocatalytic organic reactions is the need to develop applications of homogeneous photocatalysts that can effectively function under visible light conditions. For the first time, the use of binuclear complexes containing ferrocenyl-hydrazides as a ligand and nickel or copper as central metals as homogeneous photocatalysts in the oxidation of organic compounds is presented. The new organometal photocatalysts were prepared and identified using techniques, such as FT-IR spectroscopy, NMR spectroscopy, XRD, XRF, XPS, SEM, TGA, EDX, UV-visible, and photocurrent measurements. The oxidation of benzylic C(sp3)–H bonds to produce oxygenated molecules and the selective conversion of C–C double bonds to benzaldehyde can be achieved using bis-ferrocenyl hydrazide complexes with electron-withdrawing or electron-donating groups on the hydrazide moiety under visible-light irradiation in an air atmosphere, at ambient temperature and without the need for external oxidants. The synthesized complexes also can be used to oxygenate 1H-indole to 1H-indole-2,3-dione. The investigation of the role of donating and withdrawing functional groups in the synthesized complexes for selected oxidation reactions is a significant benefit of this report. It was found that only the [(FcHz)2Ni] and [(FcHz)2Cu] complexes without functional groups were able to provide a suitable response in the oxidation of the compounds. Additionally, the theoretical DFT and TD-DFT methodologies enabled us to describe the photocatalytic oxidation behavior of these metal complexes. The calculations showed conformational changes in the structure of metal complexes after oxidation. The molecular orbital and natural transition orbital analyses revealed the nature of electronic transitions in the UV-visible absorption bands.

将有机金属配合物用于光催化有机反应的一个关键挑战是,需要开发可在可见光条件下有效发挥作用的均相光催化剂。本文首次介绍了以二茂铁酰肼为配体、镍或铜为中心金属的双核配合物在有机化合物氧化过程中作为均相光催化剂的应用。利用傅立叶变换红外光谱、核磁共振光谱、XRD、XRF、XPS、扫描电镜、TGA、EDX、紫外可见光和光电流测量等技术制备并鉴定了新型有机金属光催化剂。在空气环境、环境温度和无需外部氧化剂的情况下,使用酰肼分子上带有电子吸收基团或电子捐赠基团的双二茂铁酰肼复合物,在可见光照射下可实现苄基 C(sp3)-H 键的氧化,生成含氧分子,并将 C-C 双键选择性地转化为苯甲醛。合成的配合物还可用于将 1H -吲哚氧合为 1H -吲哚-2,3-二酮。本报告的一大亮点是研究了合成复合物中的捐赠和撤回官能团在特定氧化反应中的作用。研究发现,只有不含官能团的[(FcHz)2Ni]和[(FcHz)2Cu]配合物才能在化合物的氧化反应中提供合适的反应。此外,我们还利用 DFT 和 TD-DFT 理论方法描述了这些金属复合物的光催化氧化行为。计算结果表明,氧化后金属复合物的结构发生了构象变化。分子轨道和自然过渡轨道分析揭示了紫外-可见吸收带中电子跃迁的性质。
{"title":"Bis-ferrocenyl-hydrazide metal complexes: studying electronic functional groups as newly potent homogeneous photocatalysts for C(sp3)–H and C(sp2)–H bond oxidation utilizing visible light condition†","authors":"Mohammad Bashiri, Mona Hosseini-Sarvari and Sara Fakhraee","doi":"10.1039/D3ME00133D","DOIUrl":"10.1039/D3ME00133D","url":null,"abstract":"<p >A crucial challenge in using organo-metal complexes for photocatalytic organic reactions is the need to develop applications of homogeneous photocatalysts that can effectively function under visible light conditions. For the first time, the use of binuclear complexes containing ferrocenyl-hydrazides as a ligand and nickel or copper as central metals as homogeneous photocatalysts in the oxidation of organic compounds is presented. The new organometal photocatalysts were prepared and identified using techniques, such as FT-IR spectroscopy, NMR spectroscopy, XRD, XRF, XPS, SEM, TGA, EDX, UV-visible, and photocurrent measurements. The oxidation of benzylic C(sp<small><sup>3</sup></small>)–H bonds to produce oxygenated molecules and the selective conversion of C–C double bonds to benzaldehyde can be achieved using bis-ferrocenyl hydrazide complexes with electron-withdrawing or electron-donating groups on the hydrazide moiety under visible-light irradiation in an air atmosphere, at ambient temperature and without the need for external oxidants. The synthesized complexes also can be used to oxygenate 1<em>H</em>-indole to 1<em>H</em>-indole-2,3-dione. The investigation of the role of donating and withdrawing functional groups in the synthesized complexes for selected oxidation reactions is a significant benefit of this report. It was found that only the [(FcHz)<small><sub>2</sub></small>Ni] and [(FcHz)<small><sub>2</sub></small>Cu] complexes without functional groups were able to provide a suitable response in the oxidation of the compounds. Additionally, the theoretical DFT and TD-DFT methodologies enabled us to describe the photocatalytic oxidation behavior of these metal complexes. The calculations showed conformational changes in the structure of metal complexes after oxidation. The molecular orbital and natural transition orbital analyses revealed the nature of electronic transitions in the UV-visible absorption bands.</p>","PeriodicalId":91,"journal":{"name":"Molecular Systems Design & Engineering","volume":" 1","pages":" 112-139"},"PeriodicalIF":3.6,"publicationDate":"2023-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135261209","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Theoretical insights into the compatibility of template-monomer-crosslinker-solvent for cortisol molecularly imprinted polymer pre-polymerization† 皮质醇分子印迹聚合物预聚合模板-单体-交联剂-溶剂相容性的理论研究
IF 3.6 3区 工程技术 Q2 CHEMISTRY, PHYSICAL Pub Date : 2023-10-25 DOI: 10.1039/D3ME00077J
Victoria T. Adeleke, Oluwakemi Ebenezer, Madison Lasich and Samuel M. Mugo

Detection of cortisol (Cort), a stress hormone, is essential in monitoring chronic and mental health stress. As such, there is growing interest in the development of cortisol molecularly imprinted polymers (MIPs) as molecular receptors for sensor development. Of the cortisol MIPs described in the literature, the optimization of the functional monomers has been through trial-and-error experimentation. Through a computational approach, the number of optimization experiments can be reduced, which is time efficient and cost effective, while reducing chemical wastage. In addition to density functional theory (DFT) calculations, this study used an atomistic molecular dynamics simulation approach that resembles that of the real-life experimental methods to elucidate the compatibility of template-monomer-crosslinkers-solvent for cortisol MIP receptors that can efficiently recognize and capture cortisol from biological fluids. The functional monomer investigated were 4-vinylpyridine (4VP), acrylic acid (AA), acrylamide (AM), glycidyl methacrylate (GMA), 2-hydroxyethyl methacrylate (HEMA) and methylacrylic acid (MAA) with ethylene glycol dimethacrylate (EGDMA) as the crosslinker. The intermolecular hydrogen bonds and the template-monomer binding energies obtained through DFT suggested Cort-MAA as the most stable complex both in the gas phase and solution. Considering the calculated solvent energies, acetonitrile was recommended as a porogenic solvent. Through molecular dynamics simulation, various parameters were analyzed to explain the compatibility of the functional monomer with the cortisol template in the MIP development. From blend analysis of template-monomer, Cort-4VP was found to be the most miscible complex. For template-monomer-crosslinker (EGDMA), the mean square displacement (MSD) and diffusion coefficient analyses indicated 1 : 2 (cortisol/monomer) as the ratio in which the complexes are most stable. The highest peaks observed from the Radial distribution function were for Cort-MAA and Cort-AA at 1 : 4 indicating better interactions of the functional monomers with the Cort. Investigating the effect of solvents for template-monomer-crosslinker-solvent, the lowest MSD was at 1 : 4 with three complexes having the lowest values for solubility parameters at 1 : 4 confirming this ratio to be generally suitable for the composition of cortisol MIPs pre-polymerization.

皮质醇(Cort)是一种压力荷尔蒙,其检测对于监测慢性和心理健康压力至关重要。因此,人们对开发皮质醇分子印迹聚合物(MIPs)作为传感器开发的分子受体越来越感兴趣。在文献中描述的皮质醇分子印迹聚合物中,功能单体的优化一直是通过试错实验进行的。通过计算方法,可以减少优化实验的次数,既省时又省钱,同时还能减少化学品的浪费。除密度泛函理论(DFT)计算外,本研究还采用了与实际实验方法类似的原子分子动力学模拟方法,以阐明模板-单体-交联剂-溶剂对皮质醇 MIP 受体的兼容性,从而有效识别和捕获生物液体中的皮质醇。研究的功能单体包括 4-乙烯基吡啶(4VP)、丙烯酸(AA)、丙烯酰胺(AM)、甲基丙烯酸缩水甘油酯(GMA)、甲基丙烯酸 2-羟乙基酯(HEMA)和丙烯酸甲酯(MAA),交联剂为乙二醇二甲基丙烯酸酯(EGDMA)。通过 DFT 得到的分子间氢键和模板-单体结合能表明,Cort-MAA 在气相和溶液中都是最稳定的复合物。考虑到计算得出的溶剂能,推荐使用乙腈作为成孔溶剂。通过分子动力学模拟,分析了各种参数,以解释在 MIP 开发过程中功能单体与可的松模板的相容性。从模板-单体的混合分析中发现,Cort-4VP 是混溶性最好的复合物。模板-单体-交联剂(EGDMA)的均方位移(MSD)和扩散系数分析表明,1:2(可的松/单体)的比例是复合物最稳定的比例。从径向分布函数中观察到的最高峰是 Cort-MAA 和 Cort-AA 在 1 :4 时,Cort-MAA 和 Cort-AA 的峰值最高,表明功能单体与 Cort 的相互作用更好。在研究溶剂对模板-单体-交联剂-溶剂的影响时,MSD 在 1 :4 时,三种复合物的溶解度参数值最低:4 时,三种复合物的溶解度参数值最低,这表明该比例基本适合可的松 MIP 的预聚合成分。
{"title":"Theoretical insights into the compatibility of template-monomer-crosslinker-solvent for cortisol molecularly imprinted polymer pre-polymerization†","authors":"Victoria T. Adeleke, Oluwakemi Ebenezer, Madison Lasich and Samuel M. Mugo","doi":"10.1039/D3ME00077J","DOIUrl":"10.1039/D3ME00077J","url":null,"abstract":"<p >Detection of cortisol (Cort), a stress hormone, is essential in monitoring chronic and mental health stress. As such, there is growing interest in the development of cortisol molecularly imprinted polymers (MIPs) as molecular receptors for sensor development. Of the cortisol MIPs described in the literature, the optimization of the functional monomers has been through trial-and-error experimentation. Through a computational approach, the number of optimization experiments can be reduced, which is time efficient and cost effective, while reducing chemical wastage. In addition to density functional theory (DFT) calculations, this study used an atomistic molecular dynamics simulation approach that resembles that of the real-life experimental methods to elucidate the compatibility of template-monomer-crosslinkers-solvent for cortisol MIP receptors that can efficiently recognize and capture cortisol from biological fluids. The functional monomer investigated were 4-vinylpyridine (4VP), acrylic acid (AA), acrylamide (AM), glycidyl methacrylate (GMA), 2-hydroxyethyl methacrylate (HEMA) and methylacrylic acid (MAA) with ethylene glycol dimethacrylate (EGDMA) as the crosslinker. The intermolecular hydrogen bonds and the template-monomer binding energies obtained through DFT suggested Cort-MAA as the most stable complex both in the gas phase and solution. Considering the calculated solvent energies, acetonitrile was recommended as a porogenic solvent. Through molecular dynamics simulation, various parameters were analyzed to explain the compatibility of the functional monomer with the cortisol template in the MIP development. From blend analysis of template-monomer, Cort-4VP was found to be the most miscible complex. For template-monomer-crosslinker (EGDMA), the mean square displacement (MSD) and diffusion coefficient analyses indicated 1 : 2 (cortisol/monomer) as the ratio in which the complexes are most stable. The highest peaks observed from the Radial distribution function were for Cort-MAA and Cort-AA at 1 : 4 indicating better interactions of the functional monomers with the Cort. Investigating the effect of solvents for template-monomer-crosslinker-solvent, the lowest MSD was at 1 : 4 with three complexes having the lowest values for solubility parameters at 1 : 4 confirming this ratio to be generally suitable for the composition of cortisol MIPs pre-polymerization.</p>","PeriodicalId":91,"journal":{"name":"Molecular Systems Design & Engineering","volume":" 1","pages":" 99-111"},"PeriodicalIF":3.6,"publicationDate":"2023-10-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"134980425","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Machine learning prediction of self-assembly and analysis of molecular structure dependence on the critical packing parameter 机器学习预测自组装并分析分子结构对临界堆积参数的依赖性
IF 3.6 3区 工程技术 Q2 CHEMISTRY, PHYSICAL Pub Date : 2023-10-20 DOI: 10.1039/D3ME00151B
Yuuki Ishiwatari, Takahiro Yokoyama, Tomoya Kojima, Taisuke Banno and Noriyoshi Arai

Amphiphilic molecules spontaneously form self-assembly structures depending on physical conditions such as the molecular structure, concentration, and temperature. These structures exhibit various functionalities according to their morphology. The critical packing parameter (CPP) is used to correlate self-organized structures with the chemical composition. However, accurately calculating it requires information about both the molecular shape and molecular aggregates, making it challenging to apply directly in molecular design. We aimed to predict the self-assembled structure of a molecule directly from its chemical structure and to analyze the factors influencing it using machine learning. Dissipative particle dynamics simulations were used to reproduce many self-assembly structures comprising various chemical structures, and their CPPs were calculated. Machine learning models were built using the chemical structures as input data and the CPPs as output data. As a result, both random forest and the gated recurrent unit showed high prediction accuracy. Feature importance analysis and sample size dependence revealed that the amphiphilic nature of molecules significantly influences the self-assembly structures. Additionally, selecting an appropriate molecular structure representation for each algorithm is crucial. The study results should contribute to product development in the fields of materials science, materials chemistry, and medical materials.

两亲性分子会根据分子结构、浓度和温度等物理条件自发形成自组装结构。这些结构根据其形态表现出不同的功能。临界堆积参数(CPP)用于将自组织结构与化学成分联系起来。然而,准确计算临界堆积参数需要同时获得分子形状和分子聚集的信息,因此将其直接应用于分子设计具有挑战性。我们的目标是直接从化学结构预测分子的自组装结构,并利用机器学习分析其影响因素。我们利用耗散粒子动力学模拟重现了许多由不同化学结构组成的自组装结构,并计算了它们的CPP。以化学结构作为输入数据,以 CPPs 作为输出数据,建立了机器学习模型。结果,随机森林和门控递归单元都显示出很高的预测准确性。特征重要性分析和样本大小依赖性揭示了分子的两亲性对自组装结构的重要影响。此外,为每种算法选择合适的分子结构表示方法也至关重要。研究结果将有助于材料科学、材料化学和医用材料领域的产品开发。
{"title":"Machine learning prediction of self-assembly and analysis of molecular structure dependence on the critical packing parameter","authors":"Yuuki Ishiwatari, Takahiro Yokoyama, Tomoya Kojima, Taisuke Banno and Noriyoshi Arai","doi":"10.1039/D3ME00151B","DOIUrl":"10.1039/D3ME00151B","url":null,"abstract":"<p >Amphiphilic molecules spontaneously form self-assembly structures depending on physical conditions such as the molecular structure, concentration, and temperature. These structures exhibit various functionalities according to their morphology. The critical packing parameter (CPP) is used to correlate self-organized structures with the chemical composition. However, accurately calculating it requires information about both the molecular shape and molecular aggregates, making it challenging to apply directly in molecular design. We aimed to predict the self-assembled structure of a molecule directly from its chemical structure and to analyze the factors influencing it using machine learning. Dissipative particle dynamics simulations were used to reproduce many self-assembly structures comprising various chemical structures, and their CPPs were calculated. Machine learning models were built using the chemical structures as input data and the CPPs as output data. As a result, both random forest and the gated recurrent unit showed high prediction accuracy. Feature importance analysis and sample size dependence revealed that the amphiphilic nature of molecules significantly influences the self-assembly structures. Additionally, selecting an appropriate molecular structure representation for each algorithm is crucial. The study results should contribute to product development in the fields of materials science, materials chemistry, and medical materials.</p>","PeriodicalId":91,"journal":{"name":"Molecular Systems Design & Engineering","volume":" 1","pages":" 20-28"},"PeriodicalIF":3.6,"publicationDate":"2023-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/me/d3me00151b?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135102806","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Rational design of water-harvesting hydrogels† 合理设计集水性水凝胶†。
IF 3.6 3区 工程技术 Q2 CHEMISTRY, PHYSICAL Pub Date : 2023-10-20 DOI: 10.1039/D3ME00132F
Moki K. Thanusing, Peidong Shen, Brett L. Pollard and Luke A. Connal

Water-harvesting polymer materials have the potential to create new sources of potable water. However, a holistic understanding of the relationship between polymer structure and water-harvesting properties is lacking compared to studies on specific materials. In this work, we synthesised a library of methacrylic acid-co-poly(ethylene glycol) methyl ether methacrylate)-based hydrogels (poly(MAA-co-PEGMA)) with directed modifications, including composition, crosslinker lengths, crosslinking density and preparation of the hydrogels. MAA serves as a hygroscopic monomer while PEGMA provides hydrophilicity and thermoresponsive properties. The water uptake and release capabilities of all materials was also assessed. The optimised composition of the copolymer (75 : 5 : 20 MAA : EGDMA : PEGMA, mole%) has a water uptake of 98 mg g−1 polymer at 60% RH after 24 hours. The poly(MAA-co-PEGMA) materials also show a capability for water release, showing no significant decrease in water uptake capacity after repeated uptake-release cycles. Minimum temperatures for water release could easily be adjusted with polymer composition, ranging from 50–70 °C. The data presented in this body of work serves as a foundation for future efforts in creating thermoresponsive, water-harvesting polymers with real-world applications.

集水聚合物材料具有创造新饮用水源的潜力。然而,与对特定材料的研究相比,我们还缺乏对聚合物结构与集水性能之间关系的全面了解。在这项工作中,我们合成了一个甲基丙烯酸-聚(乙二醇)甲基醚甲基丙烯酸酯水凝胶(poly(MAA-co-PEGMA))库,并对其进行了定向改性,包括成分、交联剂长度、交联密度和水凝胶的制备。MAA 具有吸湿性单体的作用,而 PEGMA 则具有亲水性和热致伸缩性。此外,还对所有材料的吸水和释放能力进行了评估。经过优化的共聚物成分(75 : 5 : 20 MAA : EGDMA : PEGMA,摩尔%)在 60% 相对湿度条件下,24 小时后的吸水率为 98 mg g-1 聚合物。聚(MAA-co-PEGMA)材料还显示出了释放水的能力,在重复吸水-释放循环后,吸水能力没有明显下降。根据聚合物成分的不同,可以很容易地调节释水的最低温度,范围在 50-70 °C 之间。这些数据为今后开发具有实际应用价值的热致伸缩性吸水聚合物奠定了基础。
{"title":"Rational design of water-harvesting hydrogels†","authors":"Moki K. Thanusing, Peidong Shen, Brett L. Pollard and Luke A. Connal","doi":"10.1039/D3ME00132F","DOIUrl":"10.1039/D3ME00132F","url":null,"abstract":"<p >Water-harvesting polymer materials have the potential to create new sources of potable water. However, a holistic understanding of the relationship between polymer structure and water-harvesting properties is lacking compared to studies on specific materials. In this work, we synthesised a library of methacrylic acid-<em>co</em>-poly(ethylene glycol) methyl ether methacrylate)-based hydrogels (poly(MAA-<em>co</em>-PEGMA)) with directed modifications, including composition, crosslinker lengths, crosslinking density and preparation of the hydrogels. MAA serves as a hygroscopic monomer while PEGMA provides hydrophilicity and thermoresponsive properties. The water uptake and release capabilities of all materials was also assessed. The optimised composition of the copolymer (75 : 5 : 20 MAA : EGDMA : PEGMA, mole%) has a water uptake of 98 mg g<small><sup>−1</sup></small> polymer at 60% RH after 24 hours. The poly(MAA-<em>co</em>-PEGMA) materials also show a capability for water release, showing no significant decrease in water uptake capacity after repeated uptake-release cycles. Minimum temperatures for water release could easily be adjusted with polymer composition, ranging from 50–70 °C. The data presented in this body of work serves as a foundation for future efforts in creating thermoresponsive, water-harvesting polymers with real-world applications.</p>","PeriodicalId":91,"journal":{"name":"Molecular Systems Design & Engineering","volume":" 1","pages":" 63-72"},"PeriodicalIF":3.6,"publicationDate":"2023-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135102818","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Facile and eco-friendly synthesis of hydrogen bonding-rich bio-based bisbenzoxazine resins with low surface free energy, strong adhesion strength and high thermal stability† 低表面自由能、强附着力和高热稳定性的富氢键生物基双苯并恶嗪树脂的简便和环保合成†.
IF 3.6 3区 工程技术 Q2 CHEMISTRY, PHYSICAL Pub Date : 2023-10-17 DOI: 10.1039/D3ME00066D
Yin Lu, Nan Li, Yaliang Peng, Mohamed Gamal Mohamed, Shiao-Wei Kuo and Kan Zhang

A facile and eco-friendly synthetic strategy has been developed to achieve a series of hydrogen bonding-rich bio-based thermosetting resins in this study. Using both safe and green solvents, we successfully synthesized target bio-based bisbenzoxazines (DcTa-fa, DcTa-sa, and DcTa-da) with high purity from five different naturally resourced raw materials. The chemical structures of the obtained bisbenzoxazine monomers were verified by nuclear magnetic resonance technology (including 1H and 13C NMR, two-dimensional 1H–1H nuclear Overhauser effect spectroscopy (NOESY), and 1H–13C heteronuclear multiple quantum coherence (HMQC)) and Fourier transform infrared spectroscopy (FT-IR). The polymerization processes were systematically investigated by differential scanning calorimetry (DSC) and in situ FT-IR analysis. Contact angle measurements were conducted and the corresponding results revealed tunable surface properties during the polymerization process of each bio-based bisbenzoxazine resin. In order to understand the relationship between the chemical structure and surface properties, more detailed FT-IR analyses were carried out to investigate the hydrogen bonding networks in the resulting polybenzoxazines. Notably, poly(DcTa-fa) presented excellent thermal stability (Td10 of 377 °C, Yc of 53.7 wt%) and strong adhesion strength (5.232 ± 0.26 MPa), while poly(DcTa-sa) and poly(DcTa-da) showed outstanding surface properties with very low surface free energy values (22.91 and 22.84 mJ m−2). These results highlight the utility of smart and sustainable benzoxazine chemistry and offer a facile and green synthetic approach to access hydrogen bonding-rich bio-based benzoxazine resins with many attractive properties.

本研究开发了一种简便、环保的合成策略,以获得一系列富含氢键的生物基热固性树脂。我们使用安全和绿色溶剂,从五种不同的天然原料中成功合成了高纯度的目标生物基双苯并恶嗪(DcTa-fa、DcTa-sa 和 DcTa-da)。通过核磁共振技术(包括 1H 和 13C NMR、二维 1H-1H 核奥弗霍塞尔效应光谱(NOESY)和 1H-13C 异核多重量子相干(HMQC))和傅立叶变换红外光谱(FT-IR)验证了所获得的双苯并恶嗪单体的化学结构。通过差示扫描量热法(DSC)和原位傅立叶变换红外分析系统地研究了聚合过程。接触角测量结果表明,每种生物基双苯并恶嗪树脂在聚合过程中都具有可调的表面特性。为了了解化学结构与表面特性之间的关系,还进行了更详细的傅立叶变换红外分析,以研究生成的聚苯并恶嗪中的氢键网络。值得注意的是,聚(DcTa-fa)具有出色的热稳定性(Td10 为 377 ℃,Yc 为 53.7 wt%)和较强的粘附强度(5.232 ± 0.26 MPa),而聚(DcTa-sa)和聚(DcTa-da)则表现出出色的表面特性,其表面自由能值非常低(22.91 和 22.84 mJ m-2)。这些结果凸显了智能和可持续苯并恶嗪化学的实用性,并提供了一种简便、绿色的合成方法来获得富含氢键的生物基苯并恶嗪树脂,这种树脂具有许多吸引人的特性。
{"title":"Facile and eco-friendly synthesis of hydrogen bonding-rich bio-based bisbenzoxazine resins with low surface free energy, strong adhesion strength and high thermal stability†","authors":"Yin Lu, Nan Li, Yaliang Peng, Mohamed Gamal Mohamed, Shiao-Wei Kuo and Kan Zhang","doi":"10.1039/D3ME00066D","DOIUrl":"10.1039/D3ME00066D","url":null,"abstract":"<p >A facile and eco-friendly synthetic strategy has been developed to achieve a series of hydrogen bonding-rich bio-based thermosetting resins in this study. Using both safe and green solvents, we successfully synthesized target bio-based bisbenzoxazines (<strong>DcTa-fa</strong>, <strong>DcTa-sa</strong>, and <strong>DcTa-da</strong>) with high purity from five different naturally resourced raw materials. The chemical structures of the obtained bisbenzoxazine monomers were verified by nuclear magnetic resonance technology (including <small><sup>1</sup></small>H and <small><sup>13</sup></small>C NMR, two-dimensional <small><sup>1</sup></small>H–<small><sup>1</sup></small>H nuclear Overhauser effect spectroscopy (NOESY), and <small><sup>1</sup></small>H–<small><sup>13</sup></small>C heteronuclear multiple quantum coherence (HMQC)) and Fourier transform infrared spectroscopy (FT-IR). The polymerization processes were systematically investigated by differential scanning calorimetry (DSC) and <em>in situ</em> FT-IR analysis. Contact angle measurements were conducted and the corresponding results revealed tunable surface properties during the polymerization process of each bio-based bisbenzoxazine resin. In order to understand the relationship between the chemical structure and surface properties, more detailed FT-IR analyses were carried out to investigate the hydrogen bonding networks in the resulting polybenzoxazines. Notably, <strong>poly(DcTa-fa)</strong> presented excellent thermal stability (<em>T</em><small><sub>d10</sub></small> of 377 °C, <em>Y</em><small><sub>c</sub></small> of 53.7 wt%) and strong adhesion strength (5.232 ± 0.26 MPa), while <strong>poly(DcTa-sa)</strong> and <strong>poly(DcTa-da)</strong> showed outstanding surface properties with very low surface free energy values (22.91 and 22.84 mJ m<small><sup>−2</sup></small>). These results highlight the utility of smart and sustainable benzoxazine chemistry and offer a facile and green synthetic approach to access hydrogen bonding-rich bio-based benzoxazine resins with many attractive properties.</p>","PeriodicalId":91,"journal":{"name":"Molecular Systems Design & Engineering","volume":" 1","pages":" 86-98"},"PeriodicalIF":3.6,"publicationDate":"2023-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"136373933","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
期刊
Molecular Systems Design & Engineering
全部 Acc. Chem. Res. ACS Applied Bio Materials ACS Appl. Electron. Mater. ACS Appl. Energy Mater. ACS Appl. Mater. Interfaces ACS Appl. Nano Mater. ACS Appl. Polym. Mater. ACS BIOMATER-SCI ENG ACS Catal. ACS Cent. Sci. ACS Chem. Biol. ACS Chemical Health & Safety ACS Chem. Neurosci. ACS Comb. Sci. ACS Earth Space Chem. ACS Energy Lett. ACS Infect. Dis. ACS Macro Lett. ACS Mater. Lett. ACS Med. Chem. Lett. ACS Nano ACS Omega ACS Photonics ACS Sens. ACS Sustainable Chem. Eng. ACS Synth. Biol. Anal. Chem. BIOCHEMISTRY-US Bioconjugate Chem. BIOMACROMOLECULES Chem. Res. Toxicol. Chem. Rev. Chem. Mater. CRYST GROWTH DES ENERG FUEL Environ. Sci. Technol. Environ. Sci. Technol. Lett. Eur. J. Inorg. Chem. IND ENG CHEM RES Inorg. Chem. J. Agric. Food. Chem. J. Chem. Eng. Data J. Chem. Educ. J. Chem. Inf. Model. J. Chem. Theory Comput. J. Med. Chem. J. Nat. Prod. J PROTEOME RES J. Am. Chem. Soc. LANGMUIR MACROMOLECULES Mol. Pharmaceutics Nano Lett. Org. Lett. ORG PROCESS RES DEV ORGANOMETALLICS J. Org. Chem. J. Phys. Chem. J. Phys. Chem. A J. Phys. Chem. B J. Phys. Chem. C J. Phys. Chem. Lett. Analyst Anal. Methods Biomater. Sci. Catal. Sci. Technol. Chem. Commun. Chem. Soc. Rev. CHEM EDUC RES PRACT CRYSTENGCOMM Dalton Trans. Energy Environ. Sci. ENVIRON SCI-NANO ENVIRON SCI-PROC IMP ENVIRON SCI-WAT RES Faraday Discuss. Food Funct. Green Chem. Inorg. Chem. Front. Integr. Biol. J. Anal. At. Spectrom. J. Mater. Chem. A J. Mater. Chem. B J. Mater. Chem. C Lab Chip Mater. Chem. Front. Mater. Horiz. MEDCHEMCOMM Metallomics Mol. Biosyst. Mol. Syst. Des. Eng. Nanoscale Nanoscale Horiz. Nat. Prod. Rep. New J. Chem. Org. Biomol. Chem. Org. Chem. Front. PHOTOCH PHOTOBIO SCI PCCP Polym. Chem.
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
0
微信
客服QQ
Book学术公众号 扫码关注我们
反馈
×
意见反馈
请填写您的意见或建议
请填写您的手机或邮箱
×
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
现在去查看 取消
×
提示
确定
Book学术官方微信
Book学术文献互助
Book学术文献互助群
群 号:481959085
Book学术
文献互助 智能选刊 最新文献 互助须知 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 Book学术 All rights reserved.
ghs 京公网安备 11010802042870号 京ICP备2023020795号-1