Open nanoshells such as nanobowls or nanocups collectively described as ‘semi shells’ have unique plasmonic properties due to their lack of symmetry. So far, their fabrication was based on multistep and laborious methods such as solid state sputter coating or selective deposition/etching using sacrificial templates. In this work, we report a rapid one step colloidal synthetic protocol for PEGylated semi-shell (SS) fabrication by simultaneous facet specific anisotropic chemical etching of rhombic dodecahedral ZIF-8 and heterogenous nucleation & growth of gold. The SS possesses a strong localized surface plasmon resonance in the near-infrared region, which is retained after surface passivation with polyethylene glycol and subsequent cryopreservation for extended shelf-life. Freshly reconstituted PEGylated SS was found to be safe & non-toxic in healthy C57BL/6 mice post intravenous administration. The PEGylated SS displayed significant photothermal efficiency of ~37% with 808 nm laser irradiation. Preclinical assessment of intra-tumoral photothermal efficacy indicated complete remission of primary breast tumor mass with insignificant metastasis to vital organs in 4T1 FL2 tumor bearing CD1 nude mice. Further, PEGylated SS mediated photothermal therapy also yielded morbidity free survivael of 75% for up to 90 days, indicating their potential to significantly improve outcomes in advanced breast tumors. Anisotropic gold-based colloidal nanoparticles such as semi shells have unique optical properties and widespread applications such as in bioimaging, biosensing and therapy, however, the fabrication process of semi shells remains a challenge due to laborious multistep solid state and colloidal procedures. In this study, the authors develop a rapid one-pot colloidal synthetic route for the fabrication of semi shells using ZIF-8 as a sacrificial template, and demonstrate their promise for photothermal therapy.
开放式纳米壳，如纳米碗或纳米杯，统称为 "半壳"，因其缺乏对称性而具有独特的等离子特性。迄今为止，它们的制造基于多步骤的费力方法，如固态溅射镀膜或使用牺牲模板的选择性沉积/蚀刻。在这项工作中，我们报告了通过同时对菱形十二面体 ZIF-8 进行切面特异性各向异性化学蚀刻和金的异质成核与生长，一步快速合成 PEG 化半壳（SS）的胶体合成方案。这种 SS 在近红外区域具有很强的局部表面等离子体共振，经聚乙二醇表面钝化和低温保存后，其保质期得以延长。新鲜重组的聚乙二醇化 SS 经静脉注射后，在健康的 C57BL/6 小鼠体内安全无毒。在 808 纳米激光照射下，PEG 化 SS 的光热效率高达 37%。瘤内光热疗效的临床前评估表明，在4T1 FL2肿瘤的CD1裸鼠体内，原发性乳腺肿瘤肿块完全消退，重要器官的转移不明显。此外，聚乙二醇化 SS 介导的光热疗法在长达 90 天的时间里无发病率的存活率也高达 75%，这表明它们具有显著改善晚期乳腺肿瘤治疗效果的潜力。
{"title":"Plasmonic semi shells derived from simultaneous in situ gold growth and anisotropic acid etching of ZIF-8 for photothermal ablation of metastatic breast tumor","authors":"Kritika Sood, Purvi Mathur, Sulagna Rath, Pranjali Yadav, Navneet Kaur, Priyanka Sharma, Mimansa, Deepak Singh Chauhan, Sonalika Vaidya, Rohit Srivastava, Abhijit De, Asifkhan Shanavas","doi":"10.1038/s42004-024-01317-w","DOIUrl":"10.1038/s42004-024-01317-w","url":null,"abstract":"Open nanoshells such as nanobowls or nanocups collectively described as ‘semi shells’ have unique plasmonic properties due to their lack of symmetry. So far, their fabrication was based on multistep and laborious methods such as solid state sputter coating or selective deposition/etching using sacrificial templates. In this work, we report a rapid one step colloidal synthetic protocol for PEGylated semi-shell (SS) fabrication by simultaneous facet specific anisotropic chemical etching of rhombic dodecahedral ZIF-8 and heterogenous nucleation & growth of gold. The SS possesses a strong localized surface plasmon resonance in the near-infrared region, which is retained after surface passivation with polyethylene glycol and subsequent cryopreservation for extended shelf-life. Freshly reconstituted PEGylated SS was found to be safe & non-toxic in healthy C57BL/6 mice post intravenous administration. The PEGylated SS displayed significant photothermal efficiency of ~37% with 808 nm laser irradiation. Preclinical assessment of intra-tumoral photothermal efficacy indicated complete remission of primary breast tumor mass with insignificant metastasis to vital organs in 4T1 FL2 tumor bearing CD1 nude mice. Further, PEGylated SS mediated photothermal therapy also yielded morbidity free survivael of 75% for up to 90 days, indicating their potential to significantly improve outcomes in advanced breast tumors. Anisotropic gold-based colloidal nanoparticles such as semi shells have unique optical properties and widespread applications such as in bioimaging, biosensing and therapy, however, the fabrication process of semi shells remains a challenge due to laborious multistep solid state and colloidal procedures. In this study, the authors develop a rapid one-pot colloidal synthetic route for the fabrication of semi shells using ZIF-8 as a sacrificial template, and demonstrate their promise for photothermal therapy.","PeriodicalId":10529,"journal":{"name":"Communications Chemistry","volume":" ","pages":"1-13"},"PeriodicalIF":5.9,"publicationDate":"2024-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11464763/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142388669","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-07DOI: 10.1038/s42004-024-01315-y
Roland Pollak, Leon Koch, Benedikt König, Sara S. Ribeiro, Nirnay Samanta, Klaus Huber, Simon Ebbinghaus
Cellular stress and ageing involve an increase in crowding and aggregation of amylogenic proteins. We here investigate if crowding is the intrinsic cause of aggregation and utilise a previously established non-protein aggregation sensor, namely pseudoisocyanine chloride (PIC). PIC shows fibrillization in cells into a highly fluorescent J-aggregated state and is sensitive to crowding. Surprisingly, cell stress conditions stabilise the monomeric rather than the aggregated state of PIC both in the cytoplasm and in stress granules. Regarding the different physiochemical changes of the cytoplasm occurring upon cell stress, involving volume reduction, phase separation and solidification, the intrinsic crowding effect is not the key factor to drive associated self-assembly processes. Cellular stress and ageing involve an increase in crowding and aggregation of amylogenic proteins, but the connection between protein destabilisation and the onset of aggregation is poorly understood. Here, the authors utilize a non-protein aggregation sensor based on pseudoisocyanine chloride to analyse the effect of macromolecular crowding in the cytoplasm on the self-assembly process, and find that the high crowding densities observed in the cytoplasm and stress granules upon stress are not an intrinsic cause for aggregation of amylogenic proteins.
{"title":"Cell stress and phase separation stabilize the monomeric state of pseudoisocyanine chloride employed as a self-assembly crowding sensor","authors":"Roland Pollak, Leon Koch, Benedikt König, Sara S. Ribeiro, Nirnay Samanta, Klaus Huber, Simon Ebbinghaus","doi":"10.1038/s42004-024-01315-y","DOIUrl":"10.1038/s42004-024-01315-y","url":null,"abstract":"Cellular stress and ageing involve an increase in crowding and aggregation of amylogenic proteins. We here investigate if crowding is the intrinsic cause of aggregation and utilise a previously established non-protein aggregation sensor, namely pseudoisocyanine chloride (PIC). PIC shows fibrillization in cells into a highly fluorescent J-aggregated state and is sensitive to crowding. Surprisingly, cell stress conditions stabilise the monomeric rather than the aggregated state of PIC both in the cytoplasm and in stress granules. Regarding the different physiochemical changes of the cytoplasm occurring upon cell stress, involving volume reduction, phase separation and solidification, the intrinsic crowding effect is not the key factor to drive associated self-assembly processes. Cellular stress and ageing involve an increase in crowding and aggregation of amylogenic proteins, but the connection between protein destabilisation and the onset of aggregation is poorly understood. Here, the authors utilize a non-protein aggregation sensor based on pseudoisocyanine chloride to analyse the effect of macromolecular crowding in the cytoplasm on the self-assembly process, and find that the high crowding densities observed in the cytoplasm and stress granules upon stress are not an intrinsic cause for aggregation of amylogenic proteins.","PeriodicalId":10529,"journal":{"name":"Communications Chemistry","volume":" ","pages":"1-8"},"PeriodicalIF":5.9,"publicationDate":"2024-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11458801/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142388668","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-04DOI: 10.1038/s42004-024-01312-1
Janos Wasternack, Hendrik V. Schröder, J. Felix Witte, Mihkel Ilisson, Henrik Hupatz, Julian F. Hille, Marius Gaedke, Arto M. Valkonen, Sebastian Sobottka, Alexander Krappe, Mario Schubert, Beate Paulus, Kari Rissanen, Biprajit Sarkar, Siegfried Eigler, Ute Resch-Genger, Christoph A. Schalley
In nature, molecular environments in proteins can sterically protect and stabilize reactive species such as organic radicals through non-covalent interactions. Here, we report a near-infrared fluorescent rotaxane in which the stabilization of a chemically labile squaraine fluorophore by the coordination of a tetralactam macrocycle can be controlled chemically and electrochemically. The rotaxane can be switched between two co-conformations in which the wheel either stabilizes or exposes the fluorophore. Coordination by the wheel affects the squaraine’s stability across four redox states and renders the radical anion significantly more stable—by a factor of 6.7—than without protection by a mechanically bonded wheel. Furthermore, the fluorescence properties can be tuned by the redox reactions in a stepwise manner. Mechanically interlocked molecules provide an excellent scaffold to stabilize and selectively expose reactive species in a co-conformational switching process controlled by external stimuli. Incorporating sensitive chromophores into interlocked systems that are mechanically responsive to external stimuli is attractive for tuning of the dye’s optical properties and stability. Here, the authors report the mechanically controlled protection and deprotection of a squaraine dye within a [2]rotaxane, governed by macrocycle shielding/de-shielding upon chloride addition or oxidation.
{"title":"Switchable protection and exposure of a sensitive squaraine dye within a redox active rotaxane","authors":"Janos Wasternack, Hendrik V. Schröder, J. Felix Witte, Mihkel Ilisson, Henrik Hupatz, Julian F. Hille, Marius Gaedke, Arto M. Valkonen, Sebastian Sobottka, Alexander Krappe, Mario Schubert, Beate Paulus, Kari Rissanen, Biprajit Sarkar, Siegfried Eigler, Ute Resch-Genger, Christoph A. Schalley","doi":"10.1038/s42004-024-01312-1","DOIUrl":"10.1038/s42004-024-01312-1","url":null,"abstract":"In nature, molecular environments in proteins can sterically protect and stabilize reactive species such as organic radicals through non-covalent interactions. Here, we report a near-infrared fluorescent rotaxane in which the stabilization of a chemically labile squaraine fluorophore by the coordination of a tetralactam macrocycle can be controlled chemically and electrochemically. The rotaxane can be switched between two co-conformations in which the wheel either stabilizes or exposes the fluorophore. Coordination by the wheel affects the squaraine’s stability across four redox states and renders the radical anion significantly more stable—by a factor of 6.7—than without protection by a mechanically bonded wheel. Furthermore, the fluorescence properties can be tuned by the redox reactions in a stepwise manner. Mechanically interlocked molecules provide an excellent scaffold to stabilize and selectively expose reactive species in a co-conformational switching process controlled by external stimuli. Incorporating sensitive chromophores into interlocked systems that are mechanically responsive to external stimuli is attractive for tuning of the dye’s optical properties and stability. Here, the authors report the mechanically controlled protection and deprotection of a squaraine dye within a [2]rotaxane, governed by macrocycle shielding/de-shielding upon chloride addition or oxidation.","PeriodicalId":10529,"journal":{"name":"Communications Chemistry","volume":" ","pages":"1-11"},"PeriodicalIF":5.9,"publicationDate":"2024-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11452610/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142375235","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-04DOI: 10.1038/s42004-024-01303-2
Dr Shira Joudan is an Assistant Professor in the Department of Chemistry at the University of Alberta in Edmonton, Canada. Her environmental analytical chemistry research group studies the environmental fate of organic contaminants, including halogenated chemicals like per- and polyfluoroalkyl substances (PFAS).
{"title":"Women in Chemistry: Q&A with Dr Shira Joudan","authors":"","doi":"10.1038/s42004-024-01303-2","DOIUrl":"10.1038/s42004-024-01303-2","url":null,"abstract":"Dr Shira Joudan is an Assistant Professor in the Department of Chemistry at the University of Alberta in Edmonton, Canada. Her environmental analytical chemistry research group studies the environmental fate of organic contaminants, including halogenated chemicals like per- and polyfluoroalkyl substances (PFAS).","PeriodicalId":10529,"journal":{"name":"Communications Chemistry","volume":" ","pages":"1-2"},"PeriodicalIF":5.9,"publicationDate":"2024-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11452680/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142375236","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-02DOI: 10.1038/s42004-024-01286-0
Nimrod Moiseyev
The ability to slow down or enhance chemical reactions, by a seemingly simple setup of reactions inside a cavity made of two parallel mirrors is fascinating. Unfortunately, currently, theory and experiment have not yet fully converged. Since theory and experiment perfectly match for atom/molecular collisions in gas phase the enhancing chemical reactions in gas phase through its coupling to quantized electromagnetic modes in a dark cavity is investigated. Here the conditions and guidelines for selecting the proper type of reactions that can be enhanced by a dark cavity are provided. Showing that the asymmetric reaction rates of O + D2 → [ODD]# → OD + D and H + ArCl → [ArHCl]# → H + Ar + Cl can be enhanced by a dark cavity. On the other hand, an effect of the dark cavity on the symmetric reaction of hydrogen exchange in methane is predicted to be negligible. Notice that the theory is not limited to microwave cavities only. The ability to slow down or enhance chemical reactions inside a cavity made of two parallel mirrors is fascinating but remains somewhat enigmatic. Here, the author presents a theoretical concept aimed at helping experimentalists select chemical reactions whose rates can be enhanced inside a dark microwave cavity.
通过在两个平行镜面组成的空腔内进行看似简单的反应设置，减缓或增强化学反应的能力令人着迷。遗憾的是，目前理论与实验尚未完全融合。由于气相中原子/分子碰撞的理论和实验完全吻合，因此我们研究了通过与暗腔中的量子化电磁模式耦合来增强气相中的化学反应。这里提供了选择暗腔可增强的适当反应类型的条件和指南。结果表明，暗腔可以提高 O + D2 → [ODD]# → OD + D 和 H + ArCl → [ArHCl]# → H + Ar + Cl 的不对称反应速率。另一方面，暗腔对甲烷中氢交换对称反应的影响预计可以忽略不计。请注意，该理论并不仅限于微波空穴。
{"title":"Conditions for enhancement of gas phase chemical reactions inside a dark microwave cavity","authors":"Nimrod Moiseyev","doi":"10.1038/s42004-024-01286-0","DOIUrl":"10.1038/s42004-024-01286-0","url":null,"abstract":"The ability to slow down or enhance chemical reactions, by a seemingly simple setup of reactions inside a cavity made of two parallel mirrors is fascinating. Unfortunately, currently, theory and experiment have not yet fully converged. Since theory and experiment perfectly match for atom/molecular collisions in gas phase the enhancing chemical reactions in gas phase through its coupling to quantized electromagnetic modes in a dark cavity is investigated. Here the conditions and guidelines for selecting the proper type of reactions that can be enhanced by a dark cavity are provided. Showing that the asymmetric reaction rates of O + D2 → [ODD]# → OD + D and H + ArCl → [ArHCl]# → H + Ar + Cl can be enhanced by a dark cavity. On the other hand, an effect of the dark cavity on the symmetric reaction of hydrogen exchange in methane is predicted to be negligible. Notice that the theory is not limited to microwave cavities only. The ability to slow down or enhance chemical reactions inside a cavity made of two parallel mirrors is fascinating but remains somewhat enigmatic. Here, the author presents a theoretical concept aimed at helping experimentalists select chemical reactions whose rates can be enhanced inside a dark microwave cavity.","PeriodicalId":10529,"journal":{"name":"Communications Chemistry","volume":" ","pages":"1-10"},"PeriodicalIF":5.9,"publicationDate":"2024-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s42004-024-01286-0.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142364715","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-02DOI: 10.1038/s42004-024-01305-0
Gerardo M. Casanola-Martin, Anas Karuth, Hai Pham-The, Humbert González-Díaz, Dean C. Webster, Bakhtiyor Rasulev
Glass transition temperature of polymers, Tg, is an important thermophysical property, which sometimes can be difficult to measure experimentally. In this regard, data-driven machine learning approaches are important alternatives to assess Tg values, in a high-throughput way. In this study, a large dataset of more than 900 polymers with reported glass transition temperature (Tg) was assembled from various public sources in order to develop a predictive model depicting the structure-property relationships. The collected dataset was curated, explored via cluster analysis, and then split into training and test sets for validation purposes and then polymer structures characterized by molecular descriptors. To find the models, several machine learning techniques, including multiple linear regression (MLR), k-nearest neighbor (k-NN), support vector machine (SVM), random forest (RF), gaussian processes for regression (GPR), and multi-layer perceptron (MLP) were explored. As result, a model with the subset of 15 descriptors accurately predicting the glass transition temperatures was developed. The electronic effect indices were determined to be important properties that positively contribute to the Tg values. The SVM-based model showed the best performance with determination coefficients (R2) of 0.813 and 0.770, for training and test sets, respectively. Also, the SVM model showed the lowest estimation error, RMSE = 0.062. In addition, the developed structure-property model was implemented as a web app to be used as an online computational tool to design and evaluate new homopolymers with desired glass transition profiles. Glass transition temperatures (Tg) of polymers are important thermophysical descriptors, but they can be difficult to determine experimentally. Here, the authors develop a data-driven support vector machine structure-property model to assess Tg values in a high-throughput manner, and implement the model into a web app.
{"title":"Machine learning analysis of a large set of homopolymers to predict glass transition temperatures","authors":"Gerardo M. Casanola-Martin, Anas Karuth, Hai Pham-The, Humbert González-Díaz, Dean C. Webster, Bakhtiyor Rasulev","doi":"10.1038/s42004-024-01305-0","DOIUrl":"10.1038/s42004-024-01305-0","url":null,"abstract":"Glass transition temperature of polymers, Tg, is an important thermophysical property, which sometimes can be difficult to measure experimentally. In this regard, data-driven machine learning approaches are important alternatives to assess Tg values, in a high-throughput way. In this study, a large dataset of more than 900 polymers with reported glass transition temperature (Tg) was assembled from various public sources in order to develop a predictive model depicting the structure-property relationships. The collected dataset was curated, explored via cluster analysis, and then split into training and test sets for validation purposes and then polymer structures characterized by molecular descriptors. To find the models, several machine learning techniques, including multiple linear regression (MLR), k-nearest neighbor (k-NN), support vector machine (SVM), random forest (RF), gaussian processes for regression (GPR), and multi-layer perceptron (MLP) were explored. As result, a model with the subset of 15 descriptors accurately predicting the glass transition temperatures was developed. The electronic effect indices were determined to be important properties that positively contribute to the Tg values. The SVM-based model showed the best performance with determination coefficients (R2) of 0.813 and 0.770, for training and test sets, respectively. Also, the SVM model showed the lowest estimation error, RMSE = 0.062. In addition, the developed structure-property model was implemented as a web app to be used as an online computational tool to design and evaluate new homopolymers with desired glass transition profiles. Glass transition temperatures (Tg) of polymers are important thermophysical descriptors, but they can be difficult to determine experimentally. Here, the authors develop a data-driven support vector machine structure-property model to assess Tg values in a high-throughput manner, and implement the model into a web app.","PeriodicalId":10529,"journal":{"name":"Communications Chemistry","volume":" ","pages":"1-9"},"PeriodicalIF":5.9,"publicationDate":"2024-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s42004-024-01305-0.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142364716","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-01DOI: 10.1038/s42004-024-01287-z
Tricia Breen Carmichael (she/her) is a Professor in the Department of Chemistry and Biochemistry at the University of Windsor.
特里西娅-布林-卡迈克尔（她/她）是温莎大学化学与生物化学系教授。
{"title":"Women in chemistry: Q&A with Professor Tricia Breen Carmichael","authors":"","doi":"10.1038/s42004-024-01287-z","DOIUrl":"10.1038/s42004-024-01287-z","url":null,"abstract":"Tricia Breen Carmichael (she/her) is a Professor in the Department of Chemistry and Biochemistry at the University of Windsor.","PeriodicalId":10529,"journal":{"name":"Communications Chemistry","volume":" ","pages":"1-2"},"PeriodicalIF":5.9,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s42004-024-01287-z.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142360087","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-09-30DOI: 10.1038/s42004-024-01308-x
Adrian Sanchez-Fernandez, Ignacio Insua, Javier Montenegro
As in natural cytoskeletons, the cooperative assembly of fibrillar networks can be hosted inside compartments to engineer biomimetic functions, such as mechanical actuation, transport, and reaction templating. Coacervates impose an optimal liquid-liquid phase separation within the aqueous continuum, functioning as membrane-less compartments that can organise such self-assembling processes as well as the exchange of information with their environment. Furthermore, biological fibrillation can often be controlled or assisted by intracellular compartments. Thus, the reconstitution of analogues of natural filaments in simplified artificial compartments, such as coacervates, offer a suitable model to unravel, mimic, and potentially exploit cellular functions. This perspective summarises the latest developments towards assembling fibrillar networks under confinement inside coacervates and related compartments, including a selection of examples ranging from biological to fully synthetic monomers. Comparative analysis between coacervates, lipid vesicles, and droplet emulsions showcases the interplay between supramolecular fibres and the boundaries of the corresponding compartment. Combining inspiration from natural systems and the custom properties of tailored synthetic fibrillators, rational monomer and compartment design will contribute towards engineering increasingly complex and more realistic artificial protocells. The bottom-up reconstitution of natural filaments within simplified artificial cellular compartments, such as coacervates, offer a model to study, mimic, and potentially exploit cellular functions. Here, the authors summarize the latest developments towards assembling confined fibrillar networks inside coacervates and related compartments, including a selection of examples ranging from biological to fully synthetic building blocks.
{"title":"Supramolecular fibrillation in coacervates and other confined systems towards biomimetic function","authors":"Adrian Sanchez-Fernandez, Ignacio Insua, Javier Montenegro","doi":"10.1038/s42004-024-01308-x","DOIUrl":"10.1038/s42004-024-01308-x","url":null,"abstract":"As in natural cytoskeletons, the cooperative assembly of fibrillar networks can be hosted inside compartments to engineer biomimetic functions, such as mechanical actuation, transport, and reaction templating. Coacervates impose an optimal liquid-liquid phase separation within the aqueous continuum, functioning as membrane-less compartments that can organise such self-assembling processes as well as the exchange of information with their environment. Furthermore, biological fibrillation can often be controlled or assisted by intracellular compartments. Thus, the reconstitution of analogues of natural filaments in simplified artificial compartments, such as coacervates, offer a suitable model to unravel, mimic, and potentially exploit cellular functions. This perspective summarises the latest developments towards assembling fibrillar networks under confinement inside coacervates and related compartments, including a selection of examples ranging from biological to fully synthetic monomers. Comparative analysis between coacervates, lipid vesicles, and droplet emulsions showcases the interplay between supramolecular fibres and the boundaries of the corresponding compartment. Combining inspiration from natural systems and the custom properties of tailored synthetic fibrillators, rational monomer and compartment design will contribute towards engineering increasingly complex and more realistic artificial protocells. The bottom-up reconstitution of natural filaments within simplified artificial cellular compartments, such as coacervates, offer a model to study, mimic, and potentially exploit cellular functions. Here, the authors summarize the latest developments towards assembling confined fibrillar networks inside coacervates and related compartments, including a selection of examples ranging from biological to fully synthetic building blocks.","PeriodicalId":10529,"journal":{"name":"Communications Chemistry","volume":" ","pages":"1-11"},"PeriodicalIF":5.9,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s42004-024-01308-x.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142329477","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-09-30DOI: 10.1038/s42004-024-01309-w
Umbertoluca Ranieri, Christophe Bellin, Lewis J. Conway, Richard Gaal, John S. Loveday, Andreas Hermann, Abhay Shukla, Livia E. Bove
Ammonium fluoride (NH₄F) exhibits a variety of crystalline phases depending on temperature and pressure. By employing Raman spectroscopy and synchrotron X-ray diffraction beyond megabar pressures (up to 140 GPa), we have here observed a novel dense solid phase of NH₄F, characterised by the tetragonal P4/nmm structure also observed in other ammonium halides under less extreme pressure conditions, typically a few GPa. Using detailed ab-initio calculations and reevaluating earlier theoretical models pertaining to other ammonium halides, we examine the microscopic mechanisms underlying the transition from the low-pressure cubic phase (P-43m) to the newly identified high-pressure tetragonal phase (P4/nmm). Notably, NH₄F exhibits distinctive properties compared to its counterparts, resulting in a significantly broader pressure range over which this transition unfolds, facilitating the identification of its various stages. Our analysis points to a synergistic interplay driving the transition to the P4/nmm phase, which we name phase VIII. At intermediate pressures (around 40 GPa), a displacive transition of fluorine ions initiates a tetragonal distortion of the cubic phase. Subsequently, at higher pressures (around 115 GPa), every second ammonium ion undergoes a rotational shift, adopting an anti-tetrahedral arrangement. This coupled effect orchestrates the transition process, leading to the formation of the tetragonal phase. Solid ammonium fluoride has fascinating structural similarities with water ice, despite its ionic character. Here, the authors investigate NH4F at room temperature and high pressure, and report a new tetragonal phase formed through displacive transition of fluorine ions and subsequent rotation of ammonium ions in ‘antiferromagnetic’ units at ~115 GPa, which is unlike any form of ice.
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Pub Date : 2024-09-30DOI: 10.1038/s42004-024-01307-y
Professor Hongjing Dou is a full Professor at the Institute of Composite Materials, School of Materials Science and Engineering at Shanghai Jiao Tong University, China, where she leads a research group focused on bionanomaterials and their biomedical applications.
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