Pub Date : 2024-04-04DOI: 10.1016/j.giant.2024.100262
Weifeng Peng , Huanyu Lei , Bingyu Zou , Luhao Qiu , Yaohao Song , Xiang Huang , Fan Ye , Feng Bao , Mingjun Huang
Low-dielectric polymers face prominent development challenges at high frequency. Particularly, the relationship between the high-frequency dielectric loss and polymer structures remains not clear enough. Besides, the strategies for achieving low dielectric loss usually have to scarify other important materials properties, e.g., heat resistance or dimensional stability. Herein, fluorine-containing aromatic polyimides were systematically investigated. Among them, simple fluorine atom (-F) substituted polyimides exhibit remarkable low dielectric loss at high frequency (10 GHz) as well as comprehensive advantages, including near-zero thermal expansion coefficient, extremely high thermal decomposition stability, high optical transmittance and excellent mechanical properties. The fundamental mechanisms of low dielectric loss are fully discussed. Benefiting from the unique electric effect and compact size of -F group, -F substituted polyimides display low dipolar density and strongly restricted dipolar motion, contributing to a reduced permanent dipolar polarization loss. Moreover, the concept of induced dipolar polarization was introduced to illustrate the nontrivial impact of F-substituted effect on conjugated electron cloud polarization loss in aromatic polymer system. This work not only provides valuable insights for understanding the mechanism of dielectric loss at high frequency for aromatic polymers, but also opens up broader application possibilities of polyimides in microelectronic and wireless communications industries.
低介电聚合物在高频领域面临着突出的开发挑战。特别是,高频介电损耗与聚合物结构之间的关系仍然不够清晰。此外,实现低介电损耗的策略通常需要牺牲材料的其他重要特性,如耐热性或尺寸稳定性。在此,我们对含氟芳香族聚酰亚胺进行了系统研究。其中,简单氟原子(-F)取代的聚酰亚胺在高频率(10 GHz)下具有显著的低介电损耗,同时还具有综合优势,包括近乎零的热膨胀系数、极高的热分解稳定性、高透光率和优异的机械性能。本文充分讨论了低介电损耗的基本机制。得益于 -F 基团独特的电效应和紧凑的尺寸,-F 取代的聚酰亚胺显示出较低的偶极密度和较强的偶极运动限制,从而降低了永久偶极极化损耗。此外,还引入了诱导偶极极化的概念,以说明 F 取代效应对芳香族聚合物体系中共轭电子云极化损耗的非同一般的影响。这项研究不仅为理解芳香族聚合物高频介电损耗的机理提供了宝贵的见解,还为聚酰亚胺在微电子和无线通信行业的应用提供了更广阔的可能性。
{"title":"Fluorine atom substituted aromatic polyimides: Unlocking extraordinary dielectric performance and comprehensive advantages","authors":"Weifeng Peng , Huanyu Lei , Bingyu Zou , Luhao Qiu , Yaohao Song , Xiang Huang , Fan Ye , Feng Bao , Mingjun Huang","doi":"10.1016/j.giant.2024.100262","DOIUrl":"https://doi.org/10.1016/j.giant.2024.100262","url":null,"abstract":"<div><p>Low-dielectric polymers face prominent development challenges at high frequency. Particularly, the relationship between the high-frequency dielectric loss and polymer structures remains not clear enough. Besides, the strategies for achieving low dielectric loss usually have to scarify other important materials properties, e.g., heat resistance or dimensional stability. Herein, fluorine-containing aromatic polyimides were systematically investigated. Among them, simple fluorine atom (-F) substituted polyimides exhibit remarkable low dielectric loss at high frequency (10 GHz) as well as comprehensive advantages, including near-zero thermal expansion coefficient, extremely high thermal decomposition stability, high optical transmittance and excellent mechanical properties. The fundamental mechanisms of low dielectric loss are fully discussed. Benefiting from the unique electric effect and compact size of -F group, -F substituted polyimides display low dipolar density and strongly restricted dipolar motion, contributing to a reduced permanent dipolar polarization loss. Moreover, the concept of induced dipolar polarization was introduced to illustrate the nontrivial impact of F-substituted effect on conjugated electron cloud polarization loss in aromatic polymer system. This work not only provides valuable insights for understanding the mechanism of dielectric loss at high frequency for aromatic polymers, but also opens up broader application possibilities of polyimides in microelectronic and wireless communications industries.</p></div>","PeriodicalId":34151,"journal":{"name":"GIANT","volume":null,"pages":null},"PeriodicalIF":7.0,"publicationDate":"2024-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S2666542524000274/pdfft?md5=f12fe99a2912ae3460cda2bd3c93df18&pid=1-s2.0-S2666542524000274-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140542799","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-04-04DOI: 10.1016/j.giant.2024.100258
Sandro Dattilo , Chiara Zagni , Tommaso Mecca , Vincenzo Patamia , Giuseppe Floresta , Pietro Nicotra , Sabrina C. Carroccio , Antonio Rescifina
The novelty of this work consists of synthesizing and exploiting a heterogeneous catalyst containing ammonium chloride as part of the polymeric sponge sites for CO2 capture. To this aim, the polymerization of 2-acryloyl(oxyethyl)trimethylammonium chloride was performed in cryo-condition, in the presence of a crosslinking agent, obtaining a lightweight macroporous freestanding material. Its efficiency in converting aromatic and aliphatic epoxides to the corresponding carbonates was successfully proved by using proton Nuclear Magnetic Resonance (1H NMR). Remarkably, the conversion of styrene oxide (SO) to styrene carbonate (SC) reached a yield of 99 % after 24 h of reaction. The calculated yield versus the aliphatic cyclohexene oxide is 71 %. Similar results were obtained by substituting the resin counter anion with Br−, although the conversion kinetic was slower than the chloride. It is worth noticing that reactions took place in the mixture without adding the tetrabutylammonium bromide (TBAB), typically used as a co-catalyst to convert epoxides into carbonates. The recyclability of the as-prepared catalyst was evaluated for four reaction cycles, evidencing stable properties without significant depletion of CO2 capture efficiency. Most importantly, the post-cleaning of the catalytic sponge is not required to be reused. Finally, the green chemistry metrics applied to the process demonstrated that our approach significantly mitigates risks and reduces environmental impact, thus elevating the overall cleanliness of our proof of concept.
{"title":"Solvent-free conversion of CO2 in carbonates through a sustainable macroporous catalyst","authors":"Sandro Dattilo , Chiara Zagni , Tommaso Mecca , Vincenzo Patamia , Giuseppe Floresta , Pietro Nicotra , Sabrina C. Carroccio , Antonio Rescifina","doi":"10.1016/j.giant.2024.100258","DOIUrl":"https://doi.org/10.1016/j.giant.2024.100258","url":null,"abstract":"<div><p>The novelty of this work consists of synthesizing and exploiting a heterogeneous catalyst containing ammonium chloride as part of the polymeric sponge sites for CO<sub>2</sub> capture. To this aim, the polymerization of 2-acryloyl(oxyethyl)trimethylammonium chloride was performed in cryo-condition, in the presence of a crosslinking agent, obtaining a lightweight macroporous freestanding material. Its efficiency in converting aromatic and aliphatic epoxides to the corresponding carbonates was successfully proved by using proton Nuclear Magnetic Resonance (<sup>1</sup>H NMR). Remarkably, the conversion of styrene oxide (SO) to styrene carbonate (SC) reached a yield of 99 % after 24 h of reaction. The calculated yield versus the aliphatic cyclohexene oxide is 71 %. Similar results were obtained by substituting the resin counter anion with Br<sup>−</sup>, although the conversion kinetic was slower than the chloride. It is worth noticing that reactions took place in the mixture without adding the tetrabutylammonium bromide (TBAB), typically used as a co-catalyst to convert epoxides into carbonates. The recyclability of the as-prepared catalyst was evaluated for four reaction cycles, evidencing stable properties without significant depletion of CO<sub>2</sub> capture efficiency. Most importantly, the post-cleaning of the catalytic sponge is not required to be reused. Finally, the green chemistry metrics applied to the process demonstrated that our approach significantly mitigates risks and reduces environmental impact, thus elevating the overall cleanliness of our proof of concept.</p></div>","PeriodicalId":34151,"journal":{"name":"GIANT","volume":null,"pages":null},"PeriodicalIF":7.0,"publicationDate":"2024-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S2666542524000237/pdfft?md5=30a42f121cc921ad375eece1b4b67236&pid=1-s2.0-S2666542524000237-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140545777","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-04-01DOI: 10.1016/j.giant.2024.100254
Silvio Poppe , Anne Lehmann , Matthias Steimecke , Marko Prehm , Yangyang Zhao , Changlong Chen , Yu Cao , Feng Liu , Carsten Tschierske
A series of K-shaped bolapolyphiles, consisting of a p-terphenyl core, two polar glycerol end-groups and a swallow-tailed alkyl side-chain were synthesized and investigated. By increasing the side-chain volume an astonishing variety of very different liquid crystalline (LC) phases was observed, ranging from a rectangular (Colrec/c2mm) and a square honeycomb (Colsqu/p4mm) via a highly complex zeolite-like octagon/pentagon honeycomb filled with additional strings of rod-bundles (ColrecZ/c2mm), a new 3D-hexagonal (Rc) double network phase, a double and even a single network cubic phase (double gyroid Cub/Iad and single diamond Cub/Fdm, respectively) to a correlated lamellar phase (LamSm/c2mm). Though these LC structures are highly complex and there is a delicate balance of steric and geometric frustration determining the phase formation, there is only a small effect of permanent molecular chirality in the glycerol groups ((R,R)-configuration) on them, which is attributed to a slightly different packing density of uniformly chiral and racemic glycerols, but not to an effect of induced helicity. Compared to related T-shaped bolapolyphiles with a single linear n-alkyl side-chain, which form exclusively honeycomb phases, the complexity of self-assembly is enhanced for the K-shaped compounds due to a competition between the requirements of space filling, chain stretching and geometric frustration, and affected by the shape of the polar glycerol domains at the junctions.
我们合成并研究了一系列由对三联苯核心、两个极性甘油端基和一个燕尾烷基侧链组成的 K 型硼烷多聚物。通过增加侧链的体积,观察到了多种不同的液晶(LC)相,从矩形(Colrec/c2mm)和方形蜂窝(Colsqu/p4mm)到高度复杂的沸石状八角形/五角形蜂窝,其中还填充了额外的杆束串(ColrecZ/c2mm)、新的三维六边形(R3‾c)双网络相、双网络立方相甚至单网络立方相(分别为双陀螺 Cub/Ia3‾d 和单金刚石 Cub/Fd3‾m)到相关片状相(LamSm/c2mm)。虽然这些 LC 结构非常复杂,而且决定相形成的立体和几何挫折之间存在微妙的平衡,但甘油基团中的永久分子手性((R,R)-构型)对它们的影响很小,这归因于均匀手性甘油和外消旋甘油的堆积密度略有不同,而不是诱导螺旋的影响。与具有单一线性正烷基侧链的 T 型波拉苯并酞化合物相比,K 型化合物的自组装复杂性更高,这是由于空间填充、链伸展和几何挫折等要求之间的竞争造成的,并受到交界处极性甘油域形状的影响。
{"title":"Reticular liquid crystal design: Controlling complex self-assembly of p-terphenyl rods by side-chain engineering and chirality","authors":"Silvio Poppe , Anne Lehmann , Matthias Steimecke , Marko Prehm , Yangyang Zhao , Changlong Chen , Yu Cao , Feng Liu , Carsten Tschierske","doi":"10.1016/j.giant.2024.100254","DOIUrl":"https://doi.org/10.1016/j.giant.2024.100254","url":null,"abstract":"<div><p>A series of K-shaped bolapolyphiles, consisting of a <em>p</em>-terphenyl core, two polar glycerol end-groups and a swallow-tailed alkyl side-chain were synthesized and investigated. By increasing the side-chain volume an astonishing variety of very different liquid crystalline (LC) phases was observed, ranging from a rectangular (Col<sub>rec</sub>/<em>c</em>2<em>mm</em>) and a square honeycomb (Col<sub>squ</sub>/<em>p</em>4<em>mm</em>) via a highly complex zeolite-like octagon/pentagon honeycomb filled with additional strings of rod-bundles (Col<sub>rec</sub><sup>Z</sup>/<em>c</em>2<em>mm</em>), a new 3D-hexagonal (<em>R</em><span><math><mover><mrow><mn>3</mn></mrow><mo>‾</mo></mover></math></span><em>c</em>) double network phase, a double and even a single network cubic phase (double gyroid Cub/<em>Ia</em><span><math><mover><mrow><mn>3</mn></mrow><mo>‾</mo></mover></math></span><em>d</em> and single diamond Cub/<em>Fd</em><span><math><mover><mrow><mn>3</mn></mrow><mo>‾</mo></mover></math></span><em>m</em>, respectively) to a correlated lamellar phase (Lam<sub>Sm</sub>/<em>c</em>2<em>mm</em>). Though these LC structures are highly complex and there is a delicate balance of steric and geometric frustration determining the phase formation, there is only a small effect of permanent molecular chirality in the glycerol groups ((<em>R,R</em>)-configuration) on them, which is attributed to a slightly different packing density of uniformly chiral and racemic glycerols, but not to an effect of induced helicity. Compared to related T-shaped bolapolyphiles with a single linear <em>n</em>-alkyl side-chain, which form exclusively honeycomb phases, the complexity of self-assembly is enhanced for the K-shaped compounds due to a competition between the requirements of space filling, chain stretching and geometric frustration, and affected by the shape of the polar glycerol domains at the junctions.</p></div>","PeriodicalId":34151,"journal":{"name":"GIANT","volume":null,"pages":null},"PeriodicalIF":7.0,"publicationDate":"2024-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S2666542524000195/pdfft?md5=ac442a6a9533db3122bfd99fc86aa7cc&pid=1-s2.0-S2666542524000195-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140559146","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-04-01DOI: 10.1016/j.giant.2024.100260
Xinhong Xiong , Songzi Xu , Li Yang , Hong Wang , Guifeng Xia , Qiucheng Yang , Qian Wu , Jiaxi Cui
Passive icephobic coatings attract increasing attention due to their harmless strategy for preventing undesirable ice accumulation. Slippery liquid-infused surfaces display extremely low ice adhesion (τice) but are argued for their poor stabilities and longevities due to inevitable liquid consumption. Herein we reported a class of lubricated polysiloxane coatings that can maintain low τice (∼2.2 kPa) for a long time (>800 icing/deicing cycle). The coatings have slippery lubricated surfaces and switchable porous matrices loading a large amount of liquid in isolated porevoids. Such droplet-embedded structure allows the surfaces to continuously maintain highly swelling states in a self-adaptive manner, i.e., only in the conditions icing or oil consumption occur dose oil is released, and thus show excellent long-term icephobicity. Besides, these materials exhibit good mechanical properties, antifatigue, and substrate adhesion. Because the coatings can be prepared via facile and green method from cheap starting materials, we foresee their broad application prospect in many fields.
{"title":"Self-regulated secretory materials for long-term icephobicity","authors":"Xinhong Xiong , Songzi Xu , Li Yang , Hong Wang , Guifeng Xia , Qiucheng Yang , Qian Wu , Jiaxi Cui","doi":"10.1016/j.giant.2024.100260","DOIUrl":"https://doi.org/10.1016/j.giant.2024.100260","url":null,"abstract":"<div><p>Passive icephobic coatings attract increasing attention due to their harmless strategy for preventing undesirable ice accumulation. Slippery liquid-infused surfaces display extremely low ice adhesion (τ<sub>ice</sub>) but are argued for their poor stabilities and longevities due to inevitable liquid consumption. Herein we reported a class of lubricated polysiloxane coatings that can maintain low τice (∼2.2 kPa) for a long time (>800 icing/deicing cycle). The coatings have slippery lubricated surfaces and switchable porous matrices loading a large amount of liquid in isolated porevoids. Such droplet-embedded structure allows the surfaces to continuously maintain highly swelling states in a self-adaptive manner, i.e., only in the conditions icing or oil consumption occur dose oil is released, and thus show excellent long-term icephobicity. Besides, these materials exhibit good mechanical properties, antifatigue, and substrate adhesion. Because the coatings can be prepared via facile and green method from cheap starting materials, we foresee their broad application prospect in many fields.</p></div>","PeriodicalId":34151,"journal":{"name":"GIANT","volume":null,"pages":null},"PeriodicalIF":7.0,"publicationDate":"2024-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S2666542524000250/pdfft?md5=4ae31894cafaa4b0ab94c482c01113ae&pid=1-s2.0-S2666542524000250-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140351175","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-03-31DOI: 10.1016/j.giant.2024.100257
Jiahao Huang , Man-Hin Kwok , Bin Zhao , Lei Zhu
For liquid crystals (LCs) and liquid crystalline polymers (LCPs), a chiral smectic C (SmC*) phase has been mandatory for breaking the symmetry and achieving ferroelectricity. However, this SmC* phase leads to rather low spontaneous polarization (Ps, 0.1–5 mC/m2), which has limited their usage in various electronic and electro-optical applications. In this mini-review, we highlight three new types of ferroelectric LCPs with high Ps values reported in the last decade. The first system refers to the ferroelectric nematic LCs and LCPs. The large dipole moment (>9 Debye or D) and oblique molecular shape induce a polar packing of calamitic nematics. The Ps can reach as high as 40 mC/m2. The second example is a ferroelectric supramolecular LCP, in which the highly polar cyano groups in the core lead to a polar structure of the hexagonal columnar phase after electric poling. The Ps can reach ∼ 20 mC/m2. The third system utilizes highly dipolar sulfonyl groups (dipole moment ∼4.5 D) in the side chains of mesogen-free comb-shaped LCPs. By combining finely tuned dipolar interactions and mobile LC order, these mesogen-free comb-like LCPs have shown good potential for ferroelectricity with high Ps. These ferroelectric LCPs with high Ps will enable new electronic and electro-optical applications in the future.
{"title":"Emerging polymer ferroelectrics with liquid crystalline order","authors":"Jiahao Huang , Man-Hin Kwok , Bin Zhao , Lei Zhu","doi":"10.1016/j.giant.2024.100257","DOIUrl":"10.1016/j.giant.2024.100257","url":null,"abstract":"<div><p>For liquid crystals (LCs) and liquid crystalline polymers (LCPs), a chiral smectic C (SmC*) phase has been mandatory for breaking the symmetry and achieving ferroelectricity. However, this SmC* phase leads to rather low spontaneous polarization (<em>P</em><sub>s</sub>, 0.1–5 mC/m<sup>2</sup>), which has limited their usage in various electronic and electro-optical applications. In this mini-review, we highlight three new types of ferroelectric LCPs with high <em>P<sub>s</sub></em> values reported in the last decade. The first system refers to the ferroelectric nematic LCs and LCPs. The large dipole moment (>9 Debye or D) and oblique molecular shape induce a polar packing of calamitic nematics. The <em>P<sub>s</sub></em> can reach as high as 40 mC/m<sup>2</sup>. The second example is a ferroelectric supramolecular LCP, in which the highly polar cyano groups in the core lead to a polar structure of the hexagonal columnar phase after electric poling. The <em>P<sub>s</sub></em> can reach ∼ 20 mC/m<sup>2</sup>. The third system utilizes highly dipolar sulfonyl groups (dipole moment ∼4.5 D) in the side chains of mesogen-free comb-shaped LCPs. By combining finely tuned dipolar interactions and mobile LC order, these mesogen-free comb-like LCPs have shown good potential for ferroelectricity with high <em>P<sub>s</sub></em>. These ferroelectric LCPs with high <em>P<sub>s</sub></em> will enable new electronic and electro-optical applications in the future.</p></div>","PeriodicalId":34151,"journal":{"name":"GIANT","volume":null,"pages":null},"PeriodicalIF":7.0,"publicationDate":"2024-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S2666542524000225/pdfft?md5=f893e876c0ee292018325f531a83476e&pid=1-s2.0-S2666542524000225-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140402314","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-03-30DOI: 10.1016/j.giant.2024.100259
Congyi Yang , Yifan Jia , Weiwen Yuan , Guoxing Liao , Qianqian Yu , Zhe Tang , Yuan Ji , Guanghui Liu , Fangrong Tan , Paul D. Topham , LinGe Wang
Nanofibers serve as widely employed tissue engineering scaffolds in diverse biomedical applications. When implanted in vivo, it is crucial for tissue engineering scaffolds to be visualizable, enabling the monitoring of their shape, position, and performance. This capability facilitates the effective assessment of implant deformations, displacements, degradations, and functionalities. However, in many biomedical imaging techniques such as magnetic resonance imaging (MRI), the contrast of tissue engineering scaffolds is often inadequate. MRI is particularly notable for its effectiveness in imaging soft tissues. Previous endeavors to enhance the contrast of tissue engineering scaffolds in MRI have involved the use of negative contrast agents (CAs). Nonetheless, negative CAs can result in artifacts, thus favoring the preference for positive CAs due to their ability to generate clearer boundaries. In this study, we successfully prepared composite polyamide 6 nanofibrous scaffolds with ultrafine dispersion Fe(OH)3 nanoparticles using electrospinning and in-situ growth techniques. The relaxation properties of the magnetic nanofibrous scaffolds confirmed the successful production of scaffolds suitable for positive imaging. In vitro cell seeding experiments demonstrated the efficient proliferation and adhesion of endothelial cells and fibroblasts. In vivo studies further revealed the biocompatibility and functionality of the scaffolds. These findings indicate that the prepared PA6/Fe(OH)3 composite nanofibrous scaffolds can enable straightforward, safe, and efficient in vivo positive contrast MRI monitoring, thereby playing a pivotal role in the integration of diagnosis and treatment within tissue engineering scaffolds.
{"title":"Enhanced contrast imaging with polyamide 6/Fe(OH)3 nanofibrous scaffolds: A focus on high T1 relaxivity","authors":"Congyi Yang , Yifan Jia , Weiwen Yuan , Guoxing Liao , Qianqian Yu , Zhe Tang , Yuan Ji , Guanghui Liu , Fangrong Tan , Paul D. Topham , LinGe Wang","doi":"10.1016/j.giant.2024.100259","DOIUrl":"https://doi.org/10.1016/j.giant.2024.100259","url":null,"abstract":"<div><p>Nanofibers serve as widely employed tissue engineering scaffolds in diverse biomedical applications. When implanted <em>in vivo</em>, it is crucial for tissue engineering scaffolds to be visualizable, enabling the monitoring of their shape, position, and performance. This capability facilitates the effective assessment of implant deformations, displacements, degradations, and functionalities. However, in many biomedical imaging techniques such as magnetic resonance imaging (MRI), the contrast of tissue engineering scaffolds is often inadequate. MRI is particularly notable for its effectiveness in imaging soft tissues. Previous endeavors to enhance the contrast of tissue engineering scaffolds in MRI have involved the use of negative contrast agents (CAs). Nonetheless, negative CAs can result in artifacts, thus favoring the preference for positive CAs due to their ability to generate clearer boundaries. In this study, we successfully prepared composite polyamide 6 nanofibrous scaffolds with ultrafine dispersion Fe(OH)<sub>3</sub> nanoparticles using electrospinning and <em>in-situ</em> growth techniques. The relaxation properties of the magnetic nanofibrous scaffolds confirmed the successful production of scaffolds suitable for positive imaging. <em>In vitro</em> cell seeding experiments demonstrated the efficient proliferation and adhesion of endothelial cells and fibroblasts. <em>In vivo</em> studies further revealed the biocompatibility and functionality of the scaffolds. These findings indicate that the prepared PA6/Fe(OH)<sub>3</sub> composite nanofibrous scaffolds can enable straightforward, safe, and efficient <em>in vivo</em> positive contrast MRI monitoring, thereby playing a pivotal role in the integration of diagnosis and treatment within tissue engineering scaffolds.</p></div>","PeriodicalId":34151,"journal":{"name":"GIANT","volume":null,"pages":null},"PeriodicalIF":7.0,"publicationDate":"2024-03-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S2666542524000249/pdfft?md5=7b4f97a2bbd01d00ff50de3dfe931ee4&pid=1-s2.0-S2666542524000249-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140345441","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A metal-free and solvent-free method for the synthesis of quinazolin-4(3H)-ones is proposed by condensation cyclization of 2-aminobenzamides and aldehydes using 1-butyl-3-methylimida-zolium tetrafluoride ([Bmim]BF4) as ionic liquid catalyst. In this reaction, [Bmim]BF4 acts as both a catalyst and a solvent without need for additional catalysts and solvents. This method exhibits favorable functional group tolerance in substrates and affords a series of desired products in moderate to excellent yields. In addition, it is noteworthy that the reaction yield is still as high as 87% after [Bmim]BF4 is recycled at least four times.
{"title":"Recyclable ionic liquid-mediated synthesis of quinazolin-4(3H)-ones under metal-free and solvent-free conditions","authors":"Xue Ma, Peng Li, Xuerou Chen, Siqi Li, Wuji Sun, Qidi Zhong","doi":"10.1016/j.giant.2024.100255","DOIUrl":"https://doi.org/10.1016/j.giant.2024.100255","url":null,"abstract":"<div><p>A metal-free and solvent-free method for the synthesis of quinazolin-4(3<em>H</em>)-ones is proposed by condensation cyclization of 2-aminobenzamides and aldehydes using 1-butyl-3-methylimida-zolium tetrafluoride ([Bmim]BF<sub>4</sub>) as ionic liquid catalyst. In this reaction, [Bmim]BF<sub>4</sub> acts as both a catalyst and a solvent without need for additional catalysts and solvents. This method exhibits favorable functional group tolerance in substrates and affords a series of desired products in moderate to excellent yields. In addition, it is noteworthy that the reaction yield is still as high as 87% after [Bmim]BF<sub>4</sub> is recycled at least four times.</p></div>","PeriodicalId":34151,"journal":{"name":"GIANT","volume":null,"pages":null},"PeriodicalIF":7.0,"publicationDate":"2024-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S2666542524000201/pdfft?md5=cb66995979f1c6c7d115a4402a2e6423&pid=1-s2.0-S2666542524000201-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140342493","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-03-26DOI: 10.1016/j.giant.2024.100256
Xinrui Dong , Hu Liu , Haibao Liu , Xiaoqin Zhang , Xiaoran Deng
In recent years, significant advancements in nanotechnology have yielded remarkable improvements in biomedical applications. Nanocarriers, harnessed from the principles of nanotechnology, have garnered widespread utilization in medicine delivery and diagnostics. However, the progression of nanocarriers has been hindered by two key challenges: low drug loading capacity and the potential for carrier-induced toxicity. To surmount these obstacles, the rapid development and expansion of carrier-free drug delivery systems (CFDDSs) composed of pure drugs and prodrugs have emerged as a promising solution. Extensive endeavors have been undertaken to explore novel excipients, therapeutic agents, self-assembly processes, and therapeutic mechanisms, aimed at expanding the horizons of CFDDSs and enhancing their therapeutic efficacy. This comprehensive review provides an overview of CFDDSs, elucidating their self-assembly mechanisms. Additionally, we examine their diverse biomedical applications while shedding light on the challenges ahead for the future development and clinical implementation of CFDDSs. This review serves to enhance our understanding of the intricate mechanisms governing drug nanoassembly formation and fosters the advancement of CFDDSs in the expansive realm of biomedical research.
{"title":"Carrier-free nanomedicines: Mechanisms of formation and biomedical applications","authors":"Xinrui Dong , Hu Liu , Haibao Liu , Xiaoqin Zhang , Xiaoran Deng","doi":"10.1016/j.giant.2024.100256","DOIUrl":"https://doi.org/10.1016/j.giant.2024.100256","url":null,"abstract":"<div><p>In recent years, significant advancements in nanotechnology have yielded remarkable improvements in biomedical applications. Nanocarriers, harnessed from the principles of nanotechnology, have garnered widespread utilization in medicine delivery and diagnostics. However, the progression of nanocarriers has been hindered by two key challenges: low drug loading capacity and the potential for carrier-induced toxicity. To surmount these obstacles, the rapid development and expansion of carrier-free drug delivery systems (CFDDSs) composed of pure drugs and prodrugs have emerged as a promising solution. Extensive endeavors have been undertaken to explore novel excipients, therapeutic agents, self-assembly processes, and therapeutic mechanisms, aimed at expanding the horizons of CFDDSs and enhancing their therapeutic efficacy. This comprehensive review provides an overview of CFDDSs, elucidating their self-assembly mechanisms. Additionally, we examine their diverse biomedical applications while shedding light on the challenges ahead for the future development and clinical implementation of CFDDSs. This review serves to enhance our understanding of the intricate mechanisms governing drug nanoassembly formation and fosters the advancement of CFDDSs in the expansive realm of biomedical research.</p></div>","PeriodicalId":34151,"journal":{"name":"GIANT","volume":null,"pages":null},"PeriodicalIF":7.0,"publicationDate":"2024-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S2666542524000213/pdfft?md5=b9e4ba90f3133f3bf0ca392b0b3cc3de&pid=1-s2.0-S2666542524000213-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140339044","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-03-19DOI: 10.1016/j.giant.2024.100253
Shengbo Ge , Guiyang Zheng , Yang Shi , Zhongfeng Zhang , Abdullatif Jazzar , Ximin He , Saddick Donkor , Zhanhu Guo , Ding Wang , Ben Bin Xu
The emerging interests in high-performance biocomposites grows significantly driven by their superior environmental sustainability. This study proposes a unique biocomposite strategy by implementing an acetic and ball-milled treatment to disrupt the bamboo cell wall structure, thereby facilitating further processing by effectively increasing the active sites and specific surface area in the bamboo fiber. The fibers are subsequently carboxymethylated to introduce carboxyl groups which facilitate physical bonding between the fibers and Mg2+ ions that are added to the system. These ions form metal-coordination bonds with the carboxyl groups, acting as ion bridges that significantly strengthen the inter-fiber bonding. The resulted biocomposite exhibits impressive mechanical properties, including a high tensile strength (94.24 MPa) and flexural strength (104.14 MPa), not only that, changes in elastic modulus also highlight changes in fiber bonding, the flexural modulus is 21.29 GPa and the tensile modulus is 7.01 GPa. Moreover, it maintains a low water uptake capacity of only 6.8 % despite being submerged for 12 h. The thermal conductivity and fire retardancy have also been improved. The synergic bonding ability between the cellulose and lignin in the fibers, coupled with the glue-free thermoforming process, enhances the material performance and renders it fully recyclable, thus reducing environmental pollution and providing cost-effective engineering materials to society.
{"title":"Facile fabrication of high-strength biocomposite through Mg2+-enhanced bonding in bamboo fiber","authors":"Shengbo Ge , Guiyang Zheng , Yang Shi , Zhongfeng Zhang , Abdullatif Jazzar , Ximin He , Saddick Donkor , Zhanhu Guo , Ding Wang , Ben Bin Xu","doi":"10.1016/j.giant.2024.100253","DOIUrl":"10.1016/j.giant.2024.100253","url":null,"abstract":"<div><p>The emerging interests in high-performance biocomposites grows significantly driven by their superior environmental sustainability. This study proposes a unique biocomposite strategy by implementing an acetic and ball-milled treatment to disrupt the bamboo cell wall structure, thereby facilitating further processing by effectively increasing the active sites and specific surface area in the bamboo fiber. The fibers are subsequently carboxymethylated to introduce carboxyl groups which facilitate physical bonding between the fibers and Mg<sup>2+</sup> ions that are added to the system. These ions form metal-coordination bonds with the carboxyl groups, acting as ion bridges that significantly strengthen the inter-fiber bonding. The resulted biocomposite exhibits impressive mechanical properties, including a high tensile strength (94.24 MPa) and flexural strength (104.14 MPa), not only that, changes in elastic modulus also highlight changes in fiber bonding, the flexural modulus is 21.29 GPa and the tensile modulus is 7.01 GPa. Moreover, it maintains a low water uptake capacity of only 6.8 % despite being submerged for 12 h. The thermal conductivity and fire retardancy have also been improved. The synergic bonding ability between the cellulose and lignin in the fibers, coupled with the glue-free thermoforming process, enhances the material performance and renders it fully recyclable, thus reducing environmental pollution and providing cost-effective engineering materials to society.</p></div>","PeriodicalId":34151,"journal":{"name":"GIANT","volume":null,"pages":null},"PeriodicalIF":7.0,"publicationDate":"2024-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S2666542524000183/pdfft?md5=b14ce1af812666a7cbb5cbf4d664d0e3&pid=1-s2.0-S2666542524000183-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140268892","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-03-15DOI: 10.1016/j.giant.2024.100252
Li Yu , Baiyang Chen , Ziying Li , Yue Su , Xuesong Jiang , Zeguang Han , Yongfeng Zhou , Deyue Yan , Xinyuan Zhu , Ruijiao Dong
Synthetic chemistry has played a vital role in miscellaneous fields of human civilization over the past century. The synthetic stage yet remains time-consuming and labor-intensive. To overcome these limitations, automation has been introduced to transform synthetic chemistry, leading to the development of high-throughput methods for molecular discovery. Automated flow chemical synthesis (AFCS) has recently emerged as a promising candidate, offering improved efficiency, scalability, and sustainability over the well-known automated solid-phase peptide synthesis. To further advance AFCS, elements like artificial intelligence-based computer-aided structure design and synthesis planning, autonomously assembled compatible synthesis with enhanced automated process control, and autonomous optimization can be considered. This review focuses on recent advances in computer-aided automated flow chemical synthesis (CAAFCS) of polymers in living polymerization and iterative synthesis strategy. The current challenges and outlook are finally discussed for developing more powerful CAAFCS systems and expanding their applicability across numerous fields, potentially providing brand-new perspectives and guidelines for future developments in this field.
{"title":"Computer-aided automated flow chemical synthesis of polymers","authors":"Li Yu , Baiyang Chen , Ziying Li , Yue Su , Xuesong Jiang , Zeguang Han , Yongfeng Zhou , Deyue Yan , Xinyuan Zhu , Ruijiao Dong","doi":"10.1016/j.giant.2024.100252","DOIUrl":"10.1016/j.giant.2024.100252","url":null,"abstract":"<div><p>Synthetic chemistry has played a vital role in miscellaneous fields of human civilization over the past century. The synthetic stage yet remains time-consuming and labor-intensive. To overcome these limitations, automation has been introduced to transform synthetic chemistry, leading to the development of high-throughput methods for molecular discovery. Automated flow chemical synthesis (AFCS) has recently emerged as a promising candidate, offering improved efficiency, scalability, and sustainability over the well-known automated solid-phase peptide synthesis. To further advance AFCS, elements like artificial intelligence-based computer-aided structure design and synthesis planning, autonomously assembled compatible synthesis with enhanced automated process control, and autonomous optimization can be considered. This review focuses on recent advances in computer-aided automated flow chemical synthesis (CAAFCS) of polymers in living polymerization and iterative synthesis strategy. The current challenges and outlook are finally discussed for developing more powerful CAAFCS systems and expanding their applicability across numerous fields, potentially providing brand-new perspectives and guidelines for future developments in this field.</p></div>","PeriodicalId":34151,"journal":{"name":"GIANT","volume":null,"pages":null},"PeriodicalIF":7.0,"publicationDate":"2024-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S2666542524000171/pdfft?md5=587ecd8af97aad0e89d35b6f2c949f02&pid=1-s2.0-S2666542524000171-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140150355","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}