Pub Date : 2024-08-08DOI: 10.1021/acsnanoscienceau.4c0003010.1021/acsnanoscienceau.4c00030
Dan Luo, Zhiheng Xie, Shuangqun Chen, Tianyi Yang, Yalin Guo*, Ying Liu, Zhouhao Zhu, Liyong Gan*, Lingmei Liu and Jianfeng Huang*,
Electrochemical semihydrogenation (ESH) of alkynes to alkenes is an appealing technique for producing pharmaceutical precursors and polymer monomers, while also preventing catalyst poisoning by alkyne impurities. Cu is recognized as a cost-effective and highly selective catalyst for ESH, whereas its activity is somewhat limited. Here, from a mechanistic standpoint, we hypothesize that electron-deficient Cu can enhance ESH activity by promoting the rate-determining step of alkene desorption. We test this hypothesis by utilizing Cu–Ag hybrids as electrocatalysts, developed through a welding process of Ag nanoparticles with Cu nanowires. Our findings reveal that these rationally engineered Cu–Ag hybrids exhibit a notable enhancement (2–4 times greater) in alkyne conversion rates compared to isolated Ag NPs or Cu NWs, while maintaining over 99% selectivity for alkene products. Through a combination of operando and computational studies, we verify that the electron-depleted Cu sites, resulting from electron transfer between Ag nanoparticles and Cu nanowires, effectively weaken the adsorption of alkenes, thereby substantially boosting ESH activity. This work not only provides mechanistic insights into ESH but also stimulates compelling strategies involving hybridizing distinct metals to optimize ESH activity.
{"title":"Enhancing Electrocatalytic Semihydrogenation of Alkynes via Weakening Alkene Adsorption over Electron-Depleted Cu Nanowires","authors":"Dan Luo, Zhiheng Xie, Shuangqun Chen, Tianyi Yang, Yalin Guo*, Ying Liu, Zhouhao Zhu, Liyong Gan*, Lingmei Liu and Jianfeng Huang*, ","doi":"10.1021/acsnanoscienceau.4c0003010.1021/acsnanoscienceau.4c00030","DOIUrl":"https://doi.org/10.1021/acsnanoscienceau.4c00030https://doi.org/10.1021/acsnanoscienceau.4c00030","url":null,"abstract":"<p >Electrochemical semihydrogenation (ESH) of alkynes to alkenes is an appealing technique for producing pharmaceutical precursors and polymer monomers, while also preventing catalyst poisoning by alkyne impurities. Cu is recognized as a cost-effective and highly selective catalyst for ESH, whereas its activity is somewhat limited. Here, from a mechanistic standpoint, we hypothesize that electron-deficient Cu can enhance ESH activity by promoting the rate-determining step of alkene desorption. We test this hypothesis by utilizing Cu–Ag hybrids as electrocatalysts, developed through a welding process of Ag nanoparticles with Cu nanowires. Our findings reveal that these rationally engineered Cu–Ag hybrids exhibit a notable enhancement (2–4 times greater) in alkyne conversion rates compared to isolated Ag NPs or Cu NWs, while maintaining over 99% selectivity for alkene products. Through a combination of operando and computational studies, we verify that the electron-depleted Cu sites, resulting from electron transfer between Ag nanoparticles and Cu nanowires, effectively weaken the adsorption of alkenes, thereby substantially boosting ESH activity. This work not only provides mechanistic insights into ESH but also stimulates compelling strategies involving hybridizing distinct metals to optimize ESH activity.</p>","PeriodicalId":29799,"journal":{"name":"ACS Nanoscience Au","volume":null,"pages":null},"PeriodicalIF":4.8,"publicationDate":"2024-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsnanoscienceau.4c00030","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142436719","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-07-18DOI: 10.1021/acsnanoscienceau.4c00016
Luiz H. Vieira, Marco A. Rossi, Letícia F. Rasteiro, José M. Assaf, Elisabete M. Assaf
Although chemical promotion led to essential improvements in Cu-based catalysts for CO2 hydrogenation to methanol, surpassing structural limitations such as active phase aggregation under reaction conditions remains challenging. In this report, we improved the textural properties of Cu/In2O3/CeO2 and Cu/In2O3/ZrO2 catalysts by coating the nanoparticles with a mesoporous SiO2 shell. This strategy limited particle size up to 3.5 nm, increasing metal dispersion and widening the metal–metal oxide interface region. Chemometric analysis revealed that these structures could maintain high activity and selectivity in a wide range of reaction conditions, with methanol space-time yields up to 4 times higher than those of the uncoated catalysts.
{"title":"CO2 Hydrogenation to Methanol over Mesoporous SiO2-Coated Cu-Based Catalysts","authors":"Luiz H. Vieira, Marco A. Rossi, Letícia F. Rasteiro, José M. Assaf, Elisabete M. Assaf","doi":"10.1021/acsnanoscienceau.4c00016","DOIUrl":"https://doi.org/10.1021/acsnanoscienceau.4c00016","url":null,"abstract":"Although chemical promotion led to essential improvements in Cu-based catalysts for CO<sub>2</sub> hydrogenation to methanol, surpassing structural limitations such as active phase aggregation under reaction conditions remains challenging. In this report, we improved the textural properties of Cu/In<sub>2</sub>O<sub>3</sub>/CeO<sub>2</sub> and Cu/In<sub>2</sub>O<sub>3</sub>/ZrO<sub>2</sub> catalysts by coating the nanoparticles with a mesoporous SiO<sub>2</sub> shell. This strategy limited particle size up to 3.5 nm, increasing metal dispersion and widening the metal–metal oxide interface region. Chemometric analysis revealed that these structures could maintain high activity and selectivity in a wide range of reaction conditions, with methanol space-time yields up to 4 times higher than those of the uncoated catalysts.","PeriodicalId":29799,"journal":{"name":"ACS Nanoscience Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141745570","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-07-18DOI: 10.1021/acsnanoscienceau.4c0001610.1021/acsnanoscienceau.4c00016
Luiz H. Vieira*, Marco A. Rossi, Letícia F. Rasteiro, José M. Assaf and Elisabete M. Assaf*,
Although chemical promotion led to essential improvements in Cu-based catalysts for CO2 hydrogenation to methanol, surpassing structural limitations such as active phase aggregation under reaction conditions remains challenging. In this report, we improved the textural properties of Cu/In2O3/CeO2 and Cu/In2O3/ZrO2 catalysts by coating the nanoparticles with a mesoporous SiO2 shell. This strategy limited particle size up to 3.5 nm, increasing metal dispersion and widening the metal–metal oxide interface region. Chemometric analysis revealed that these structures could maintain high activity and selectivity in a wide range of reaction conditions, with methanol space-time yields up to 4 times higher than those of the uncoated catalysts.
{"title":"CO2 Hydrogenation to Methanol over Mesoporous SiO2-Coated Cu-Based Catalysts","authors":"Luiz H. Vieira*, Marco A. Rossi, Letícia F. Rasteiro, José M. Assaf and Elisabete M. Assaf*, ","doi":"10.1021/acsnanoscienceau.4c0001610.1021/acsnanoscienceau.4c00016","DOIUrl":"https://doi.org/10.1021/acsnanoscienceau.4c00016https://doi.org/10.1021/acsnanoscienceau.4c00016","url":null,"abstract":"<p >Although chemical promotion led to essential improvements in Cu-based catalysts for CO<sub>2</sub> hydrogenation to methanol, surpassing structural limitations such as active phase aggregation under reaction conditions remains challenging. In this report, we improved the textural properties of Cu/In<sub>2</sub>O<sub>3</sub>/CeO<sub>2</sub> and Cu/In<sub>2</sub>O<sub>3</sub>/ZrO<sub>2</sub> catalysts by coating the nanoparticles with a mesoporous SiO<sub>2</sub> shell. This strategy limited particle size up to 3.5 nm, increasing metal dispersion and widening the metal–metal oxide interface region. Chemometric analysis revealed that these structures could maintain high activity and selectivity in a wide range of reaction conditions, with methanol space-time yields up to 4 times higher than those of the uncoated catalysts.</p>","PeriodicalId":29799,"journal":{"name":"ACS Nanoscience Au","volume":null,"pages":null},"PeriodicalIF":4.8,"publicationDate":"2024-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsnanoscienceau.4c00016","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142011081","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-06-25DOI: 10.1021/acsnanoscienceau.4c0001210.1021/acsnanoscienceau.4c00012
Yongjiu Chen, Ruixia Wang* and Ming Xu,
The increasing use of silver nanoparticles (AgNPs) in consumer products has led to concerns about potential health risks after oral exposure as a result of the transformation and absorption in the gastrointestinal tract (GIT). However, the intricate condition of the GIT poses challenges in understanding the fate and toxicity of AgNPs as they traverse from the mouth to the rectum. For an in-depth understanding of the nanobio interactions, we employed a simulated digestion model to investigate alterations in the physicochemical properties of AgNPs in vitro. Meanwhile, we investigated the underlying toxicological mechanisms of digested AgNPs in enterocytes through metabolomics analysis. In contrast to route means that primarily apply salt solutions to mimic dietary digestion, this in vitro model is a semidynamic sequential digestion system that includes artificial oral, gastric, and intestinal fluids, which are similar to those under physiological conditions including electrolytes, enzymes, bile, pH, and time of digestion. Our results suggest that the formation of Ag–Cl and Ag–S species within the simulated digestion model can lead to an increase in the size of digested AgNPs and that the acidic condition promotes the release of Ag+ from particles. More critically, the presence of digestive enzymes and high concentrations of salt enhances the uptake of Ag by human colon enterocytes, ultimately promoting ROS generation and exacerbating cytotoxicity. Metabolomics analysis further reveals that the sequentially digested AgNPs may disorder lipid metabolism, including the biosynthesis of unsaturated fatty acids and arachidonic acid metabolism, thus increasing the possibility of ferroptosis activation in enterocytes. These findings offer significant insights into the fate and potential adverse effects of AgNPs in the GIT, providing important implications for assessing the health risks of AgNPs via oral exposure.
{"title":"Metabolomics Analysis for Unveiling the Toxicological Mechanism of Silver Nanoparticles Using an In Vitro Gastrointestinal Digestion Model","authors":"Yongjiu Chen, Ruixia Wang* and Ming Xu, ","doi":"10.1021/acsnanoscienceau.4c0001210.1021/acsnanoscienceau.4c00012","DOIUrl":"https://doi.org/10.1021/acsnanoscienceau.4c00012https://doi.org/10.1021/acsnanoscienceau.4c00012","url":null,"abstract":"<p >The increasing use of silver nanoparticles (AgNPs) in consumer products has led to concerns about potential health risks after oral exposure as a result of the transformation and absorption in the gastrointestinal tract (GIT). However, the intricate condition of the GIT poses challenges in understanding the fate and toxicity of AgNPs as they traverse from the mouth to the rectum. For an in-depth understanding of the nanobio interactions, we employed a simulated digestion model to investigate alterations in the physicochemical properties of AgNPs <i>in vitro</i>. Meanwhile, we investigated the underlying toxicological mechanisms of digested AgNPs in enterocytes through metabolomics analysis. In contrast to route means that primarily apply salt solutions to mimic dietary digestion, this <i>in vitro</i> model is a semidynamic sequential digestion system that includes artificial oral, gastric, and intestinal fluids, which are similar to those under physiological conditions including electrolytes, enzymes, bile, pH, and time of digestion. Our results suggest that the formation of Ag–Cl and Ag–S species within the simulated digestion model can lead to an increase in the size of digested AgNPs and that the acidic condition promotes the release of Ag<sup>+</sup> from particles. More critically, the presence of digestive enzymes and high concentrations of salt enhances the uptake of Ag by human colon enterocytes, ultimately promoting ROS generation and exacerbating cytotoxicity. Metabolomics analysis further reveals that the sequentially digested AgNPs may disorder lipid metabolism, including the biosynthesis of unsaturated fatty acids and arachidonic acid metabolism, thus increasing the possibility of ferroptosis activation in enterocytes. These findings offer significant insights into the fate and potential adverse effects of AgNPs in the GIT, providing important implications for assessing the health risks of AgNPs via oral exposure.</p>","PeriodicalId":29799,"journal":{"name":"ACS Nanoscience Au","volume":null,"pages":null},"PeriodicalIF":4.8,"publicationDate":"2024-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsnanoscienceau.4c00012","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142436540","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-06-25DOI: 10.1021/acsnanoscienceau.4c00012
Yongjiu Chen, Ruixia Wang, Ming Xu
The increasing use of silver nanoparticles (AgNPs) in consumer products has led to concerns about potential health risks after oral exposure as a result of the transformation and absorption in the gastrointestinal tract (GIT). However, the intricate condition of the GIT poses challenges in understanding the fate and toxicity of AgNPs as they traverse from the mouth to the rectum. For an in-depth understanding of the nanobio interactions, we employed a simulated digestion model to investigate alterations in the physicochemical properties of AgNPs in vitro. Meanwhile, we investigated the underlying toxicological mechanisms of digested AgNPs in enterocytes through metabolomics analysis. In contrast to route means that primarily apply salt solutions to mimic dietary digestion, this in vitro model is a semidynamic sequential digestion system that includes artificial oral, gastric, and intestinal fluids, which are similar to those under physiological conditions including electrolytes, enzymes, bile, pH, and time of digestion. Our results suggest that the formation of Ag–Cl and Ag–S species within the simulated digestion model can lead to an increase in the size of digested AgNPs and that the acidic condition promotes the release of Ag+ from particles. More critically, the presence of digestive enzymes and high concentrations of salt enhances the uptake of Ag by human colon enterocytes, ultimately promoting ROS generation and exacerbating cytotoxicity. Metabolomics analysis further reveals that the sequentially digested AgNPs may disorder lipid metabolism, including the biosynthesis of unsaturated fatty acids and arachidonic acid metabolism, thus increasing the possibility of ferroptosis activation in enterocytes. These findings offer significant insights into the fate and potential adverse effects of AgNPs in the GIT, providing important implications for assessing the health risks of AgNPs via oral exposure.
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Pub Date : 2024-06-25DOI: 10.1021/acsnanoscienceau.4c00013
Abigail R. Orun, Caroline K. Slaughter, Ethan T. Shields, Ananya Vajapayajula, Sara Jones, Rojina Shrestha, Christopher D. Snow
Biomolecular crystals can serve as materials for a plethora of applications including precise guest entrapment. However, as grown, biomolecular crystals are fragile in solutions other than their growth conditions. For crystals to achieve their full potential as hosts for other molecules, crystals can be made stronger with bioconjugation. Building on our previous work using carbodiimide 1-ethyl-3-(3-(dimethylamino)propyl)carbodiimide (EDC) for chemical ligation, here, we investigate DNA junction architecture through sticky base overhang lengths and the role of scaffold proteins in cross-linking within two classes of biomolecular crystals: cocrystals of DNA-binding proteins and pure DNA crystals. Both crystal classes contain DNA junctions where DNA strands stack up end-to-end. Ligation yields were studied as a function of sticky base overhang length and terminal phosphorylation status. The best ligation performance for both crystal classes was achieved with longer sticky overhangs and terminal 3′phosphates. Notably, EDC chemical ligation was achieved in crystals with pore sizes too small for intracrystal transport of ligase enzyme. Postassembly cross-linking produced dramatic stability improvements for both DNA crystals and cocrystals in water and blood serum. The results presented may help crystals containing DNA achieve broader application utility, including as structural biology scaffolds.
生物分子晶体可作为多种应用的材料,包括精确的客体夹持。然而,生物分子晶体在生长条件之外的溶液中很脆弱。为了充分发挥晶体作为其他分子宿主的潜力,可以通过生物共轭使晶体变得更坚固。在使用碳二亚胺 1-乙基-3-(3-(二甲基氨基)丙基)碳二亚胺(EDC)进行化学连接的前期工作基础上,我们在这里通过粘性碱基悬垂长度和支架蛋白在两类生物分子晶体(DNA 结合蛋白共晶体和纯 DNA 晶体)交联过程中的作用来研究 DNA 连接结构。这两类晶体都含有 DNA 连接点,在这些连接点上,DNA 链端对端地堆叠在一起。研究将连接产量作为粘性碱基悬垂长度和末端磷酸化状态的函数。两类晶体的最佳连接性能取决于较长的粘性悬垂长度和末端 3′磷酸化状态。值得注意的是,EDC 化学连接是在孔径太小、无法在晶体内运输连接酶的晶体中实现的。组装后的交联大大提高了 DNA 晶体和共晶体在水和血清中的稳定性。所展示的结果可能有助于含有 DNA 的晶体获得更广泛的应用,包括作为结构生物学支架。
{"title":"Tuning Chemical DNA Ligation within DNA Crystals and Protein–DNA Cocrystals","authors":"Abigail R. Orun, Caroline K. Slaughter, Ethan T. Shields, Ananya Vajapayajula, Sara Jones, Rojina Shrestha, Christopher D. Snow","doi":"10.1021/acsnanoscienceau.4c00013","DOIUrl":"https://doi.org/10.1021/acsnanoscienceau.4c00013","url":null,"abstract":"Biomolecular crystals can serve as materials for a plethora of applications including precise guest entrapment. However, as grown, biomolecular crystals are fragile in solutions other than their growth conditions. For crystals to achieve their full potential as hosts for other molecules, crystals can be made stronger with bioconjugation. Building on our previous work using carbodiimide 1-ethyl-3-(3-(dimethylamino)propyl)carbodiimide (EDC) for chemical ligation, here, we investigate DNA junction architecture through sticky base overhang lengths and the role of scaffold proteins in cross-linking within two classes of biomolecular crystals: cocrystals of DNA-binding proteins and pure DNA crystals. Both crystal classes contain DNA junctions where DNA strands stack up end-to-end. Ligation yields were studied as a function of sticky base overhang length and terminal phosphorylation status. The best ligation performance for both crystal classes was achieved with longer sticky overhangs and terminal 3′phosphates. Notably, EDC chemical ligation was achieved in crystals with pore sizes too small for intracrystal transport of ligase enzyme. Postassembly cross-linking produced dramatic stability improvements for both DNA crystals and cocrystals in water and blood serum. The results presented may help crystals containing DNA achieve broader application utility, including as structural biology scaffolds.","PeriodicalId":29799,"journal":{"name":"ACS Nanoscience Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141530001","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-06-25DOI: 10.1021/acsnanoscienceau.4c0001310.1021/acsnanoscienceau.4c00013
Abigail R. Orun, Caroline K. Slaughter, Ethan T. Shields, Ananya Vajapayajula, Sara Jones, Rojina Shrestha and Christopher D. Snow*,
Biomolecular crystals can serve as materials for a plethora of applications including precise guest entrapment. However, as grown, biomolecular crystals are fragile in solutions other than their growth conditions. For crystals to achieve their full potential as hosts for other molecules, crystals can be made stronger with bioconjugation. Building on our previous work using carbodiimide 1-ethyl-3-(3-(dimethylamino)propyl)carbodiimide (EDC) for chemical ligation, here, we investigate DNA junction architecture through sticky base overhang lengths and the role of scaffold proteins in cross-linking within two classes of biomolecular crystals: cocrystals of DNA-binding proteins and pure DNA crystals. Both crystal classes contain DNA junctions where DNA strands stack up end-to-end. Ligation yields were studied as a function of sticky base overhang length and terminal phosphorylation status. The best ligation performance for both crystal classes was achieved with longer sticky overhangs and terminal 3′phosphates. Notably, EDC chemical ligation was achieved in crystals with pore sizes too small for intracrystal transport of ligase enzyme. Postassembly cross-linking produced dramatic stability improvements for both DNA crystals and cocrystals in water and blood serum. The results presented may help crystals containing DNA achieve broader application utility, including as structural biology scaffolds.
生物分子晶体可作为多种应用的材料,包括精确的客体夹持。然而,生物分子晶体在生长条件之外的溶液中很脆弱。为了充分发挥晶体作为其他分子宿主的潜力,可以通过生物共轭使晶体变得更坚固。在使用碳二亚胺 1-乙基-3-(3-(二甲基氨基)丙基)碳二亚胺(EDC)进行化学连接的前期工作基础上,我们在这里通过粘性碱基悬垂长度和支架蛋白在两类生物分子晶体(DNA 结合蛋白共晶体和纯 DNA 晶体)交联过程中的作用来研究 DNA 连接结构。这两类晶体都含有 DNA 连接点,在这些连接点上,DNA 链端对端地堆叠在一起。研究将连接产量作为粘性碱基悬垂长度和末端磷酸化状态的函数。两类晶体的最佳连接性能取决于较长的粘性悬垂长度和末端 3′磷酸化状态。值得注意的是,EDC 化学连接是在孔径太小、无法在晶体内运输连接酶的晶体中实现的。组装后的交联大大提高了 DNA 晶体和共晶体在水和血清中的稳定性。所展示的结果可能有助于含有 DNA 的晶体获得更广泛的应用,包括作为结构生物学支架。
{"title":"Tuning Chemical DNA Ligation within DNA Crystals and Protein–DNA Cocrystals","authors":"Abigail R. Orun, Caroline K. Slaughter, Ethan T. Shields, Ananya Vajapayajula, Sara Jones, Rojina Shrestha and Christopher D. Snow*, ","doi":"10.1021/acsnanoscienceau.4c0001310.1021/acsnanoscienceau.4c00013","DOIUrl":"https://doi.org/10.1021/acsnanoscienceau.4c00013https://doi.org/10.1021/acsnanoscienceau.4c00013","url":null,"abstract":"<p >Biomolecular crystals can serve as materials for a plethora of applications including precise guest entrapment. However, as grown, biomolecular crystals are fragile in solutions other than their growth conditions. For crystals to achieve their full potential as hosts for other molecules, crystals can be made stronger with bioconjugation. Building on our previous work using carbodiimide 1-ethyl-3-(3-(dimethylamino)propyl)carbodiimide (EDC) for chemical ligation, here, we investigate DNA junction architecture through sticky base overhang lengths and the role of scaffold proteins in cross-linking within two classes of biomolecular crystals: cocrystals of DNA-binding proteins and pure DNA crystals. Both crystal classes contain DNA junctions where DNA strands stack up end-to-end. Ligation yields were studied as a function of sticky base overhang length and terminal phosphorylation status. The best ligation performance for both crystal classes was achieved with longer sticky overhangs and terminal 3′phosphates. Notably, EDC chemical ligation was achieved in crystals with pore sizes too small for intracrystal transport of ligase enzyme. Postassembly cross-linking produced dramatic stability improvements for both DNA crystals and cocrystals in water and blood serum. The results presented may help crystals containing DNA achieve broader application utility, including as structural biology scaffolds.</p>","PeriodicalId":29799,"journal":{"name":"ACS Nanoscience Au","volume":null,"pages":null},"PeriodicalIF":4.8,"publicationDate":"2024-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsnanoscienceau.4c00013","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142436539","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Significant endeavors have been dedicated to the advancement of materials for artificial photosynthesis, aimed at efficiently harvesting light and catalyzing reactions such as hydrogen production and CO2 conversion. The application of plasmonic nanomaterials emerges as a promising option for this purpose, owing to their excellent light absorption properties and ability to confine solar energy at the nanoscale. In this regard, coupling plasmonic particles with molecular catalysts offers a pathway to create high-performance hybrid catalysts. In this review, we discuss the plasmonic–molecular complex hybrid catalysts where the plasmonic nanoparticles serve as the light-harvesting unit and promote interfacial charge transfer in tandem with the molecular catalyst which drives chemical transformation. In the initial section, we provide a concise overview of plasmonic nanomaterials and their photophysical properties. We then explore recent breakthroughs, highlighting examples from literature reports involving plasmonic–molecular complex hybrids in various catalytic processes. The utilization of plasmonic materials in conjunction with molecular catalysts represents a relatively unexplored area with substantial potential yet to be realized. This review sets a strong basis and motivation to explore the plasmon-induced hot-electron mediated photelectrochemical small molecule activation reactions. Utilizing in situ spectroscopic investigations and ultrafast transient absorption spectroscopy, it presents a comprehensive template for scalable and sustainable antenna-reactor systems.
{"title":"Noble Metal Plasmon–Molecular Catalyst Hybrids for Renewable Energy Relevant Small Molecule Activation","authors":"Tannu Kaushik, Suchismita Ghosh, Thinles Dolkar, Rathindranath Biswas and Arnab Dutta*, ","doi":"10.1021/acsnanoscienceau.4c0000910.1021/acsnanoscienceau.4c00009","DOIUrl":"https://doi.org/10.1021/acsnanoscienceau.4c00009https://doi.org/10.1021/acsnanoscienceau.4c00009","url":null,"abstract":"<p >Significant endeavors have been dedicated to the advancement of materials for artificial photosynthesis, aimed at efficiently harvesting light and catalyzing reactions such as hydrogen production and CO<sub>2</sub> conversion. The application of plasmonic nanomaterials emerges as a promising option for this purpose, owing to their excellent light absorption properties and ability to confine solar energy at the nanoscale. In this regard, coupling plasmonic particles with molecular catalysts offers a pathway to create high-performance hybrid catalysts. In this review, we discuss the plasmonic–molecular complex hybrid catalysts where the plasmonic nanoparticles serve as the light-harvesting unit and promote interfacial charge transfer in tandem with the molecular catalyst which drives chemical transformation. In the initial section, we provide a concise overview of plasmonic nanomaterials and their photophysical properties. We then explore recent breakthroughs, highlighting examples from literature reports involving plasmonic–molecular complex hybrids in various catalytic processes. The utilization of plasmonic materials in conjunction with molecular catalysts represents a relatively unexplored area with substantial potential yet to be realized. This review sets a strong basis and motivation to explore the plasmon-induced hot-electron mediated photelectrochemical small molecule activation reactions. Utilizing in situ spectroscopic investigations and ultrafast transient absorption spectroscopy, it presents a comprehensive template for scalable and sustainable antenna-reactor systems.</p>","PeriodicalId":29799,"journal":{"name":"ACS Nanoscience Au","volume":null,"pages":null},"PeriodicalIF":4.8,"publicationDate":"2024-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsnanoscienceau.4c00009","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142450456","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-06-07DOI: 10.1021/acsnanoscienceau.4c00006
Andrea Ferreras, Ana Matesanz, Jabier Mendizabal, Koldo Artola, Y. Nishina, Pablo Acedo, José L. Jorcano, Amalia Ruiz, Giacomo Reina, Cristina Martín
{"title":"Light-Responsive and Antibacterial Graphenic Materials as a Holistic Approach to Tissue Engineering","authors":"Andrea Ferreras, Ana Matesanz, Jabier Mendizabal, Koldo Artola, Y. Nishina, Pablo Acedo, José L. Jorcano, Amalia Ruiz, Giacomo Reina, Cristina Martín","doi":"10.1021/acsnanoscienceau.4c00006","DOIUrl":"https://doi.org/10.1021/acsnanoscienceau.4c00006","url":null,"abstract":"","PeriodicalId":29799,"journal":{"name":"ACS Nanoscience Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-06-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141374848","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}