Pub Date : 2024-09-14DOI: 10.1021/acsanm.4c0397310.1021/acsanm.4c03973
Shanshan Feng, Yang Liu and Yuxiang Bu*,
Reduction by one-electron activation or hydrogenation of N2 is extraordinarily difficult because of its extremely stable triple bond and symmetry-forbidden direct H2 addition. Demonstrated herein is reduction or hydrogenation of N2 in perfluorocarbon cage C70F70, a promising nanoreactor with synergetic confinement and electron-catalyzing effects. C70F70 pointing all dipolar C–F units toward its center not only traps reactants but also gives the cage and its guest species strong electron-hosting/binding abilities through lowering their orbital energies. Such a confinement effect can force one electron into the N2 π*-orbital, not only activating the N≡N bond but also making its frontier molecular orbitals symmetry matching with H2 and thus boosting its hydrogenation with a noticeable lowering of the energy barrier. The ability to initiate reduction reactions by absorbing electrons into the cage-reactor without surface adsorption and solid catalysts enables pathways that are not accessible using conventional electro-/photochemical processes.
{"title":"Synergetic Confinement and Electron-Catalysis Boost N2 Hydrogenation in C70F70 Nanoreactor: A Theoretical Investigation","authors":"Shanshan Feng, Yang Liu and Yuxiang Bu*, ","doi":"10.1021/acsanm.4c0397310.1021/acsanm.4c03973","DOIUrl":"https://doi.org/10.1021/acsanm.4c03973https://doi.org/10.1021/acsanm.4c03973","url":null,"abstract":"<p >Reduction by one-electron activation or hydrogenation of N<sub>2</sub> is extraordinarily difficult because of its extremely stable triple bond and symmetry-forbidden direct H<sub>2</sub> addition. Demonstrated herein is reduction or hydrogenation of N<sub>2</sub> in perfluorocarbon cage C<sub>70</sub>F<sub>70</sub>, a promising nanoreactor with synergetic confinement and electron-catalyzing effects. C<sub>70</sub>F<sub>70</sub> pointing all dipolar C–F units toward its center not only traps reactants but also gives the cage and its guest species strong electron-hosting/binding abilities through lowering their orbital energies. Such a confinement effect can force one electron into the N<sub>2</sub> π*-orbital, not only activating the N≡N bond but also making its frontier molecular orbitals symmetry matching with H<sub>2</sub> and thus boosting its hydrogenation with a noticeable lowering of the energy barrier. The ability to initiate reduction reactions by absorbing electrons into the cage-reactor without surface adsorption and solid catalysts enables pathways that are not accessible using conventional electro-/photochemical processes.</p>","PeriodicalId":6,"journal":{"name":"ACS Applied Nano Materials","volume":null,"pages":null},"PeriodicalIF":5.3,"publicationDate":"2024-09-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142326099","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Reduction by one-electron activation or hydrogenation of N2 is extraordinarily difficult because of its extremely stable triple bond and symmetry-forbidden direct H2 addition. Demonstrated herein is reduction or hydrogenation of N2 in perfluorocarbon cage C70F70, a promising nanoreactor with synergetic confinement and electron-catalyzing effects. C70F70 pointing all dipolar C–F units toward its center not only traps reactants but also gives the cage and its guest species strong electron-hosting/binding abilities through lowering their orbital energies. Such a confinement effect can force one electron into the N2 π*-orbital, not only activating the N≡N bond but also making its frontier molecular orbitals symmetry matching with H2 and thus boosting its hydrogenation with a noticeable lowering of the energy barrier. The ability to initiate reduction reactions by absorbing electrons into the cage-reactor without surface adsorption and solid catalysts enables pathways that are not accessible using conventional electro-/photochemical processes.
{"title":"Synergetic Confinement and Electron-Catalysis Boost N2 Hydrogenation in C70F70 Nanoreactor: A Theoretical Investigation","authors":"Shanshan Feng, Yang Liu, Yuxiang Bu","doi":"10.1021/acsanm.4c03973","DOIUrl":"https://doi.org/10.1021/acsanm.4c03973","url":null,"abstract":"Reduction by one-electron activation or hydrogenation of N<sub>2</sub> is extraordinarily difficult because of its extremely stable triple bond and symmetry-forbidden direct H<sub>2</sub> addition. Demonstrated herein is reduction or hydrogenation of N<sub>2</sub> in perfluorocarbon cage C<sub>70</sub>F<sub>70</sub>, a promising nanoreactor with synergetic confinement and electron-catalyzing effects. C<sub>70</sub>F<sub>70</sub> pointing all dipolar C–F units toward its center not only traps reactants but also gives the cage and its guest species strong electron-hosting/binding abilities through lowering their orbital energies. Such a confinement effect can force one electron into the N<sub>2</sub> π*-orbital, not only activating the N≡N bond but also making its frontier molecular orbitals symmetry matching with H<sub>2</sub> and thus boosting its hydrogenation with a noticeable lowering of the energy barrier. The ability to initiate reduction reactions by absorbing electrons into the cage-reactor without surface adsorption and solid catalysts enables pathways that are not accessible using conventional electro-/photochemical processes.","PeriodicalId":6,"journal":{"name":"ACS Applied Nano Materials","volume":null,"pages":null},"PeriodicalIF":5.9,"publicationDate":"2024-09-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142267549","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-09-14DOI: 10.1021/acsanm.4c0374910.1021/acsanm.4c03749
Elham Golafshan, Habib Nikukar, Shohreh Mashayekhan*, Mohammad Ali Shokrgozar and Abdolreza Simchi*,
The conductive microenvironment and pulsatile electromechanical cues in the native myocardium tissue regulate biological responses; hence, advanced nanomaterials must be developed to construct cardiac tissue-like constructs. In this work, we present a stretchable, electroconductive, and piezoelectric biphasic layered structure based on bilayer graphene nanolayers (BGF) modified polyvinylidene fluoride (PVDF) nanofibers to provide suitable electrophysiological microenvironments for the modulation of H9c2 embryonic rat cardiomyoblasts toward cardiomyocyte-like phenotypes. High-quality BGFs were synthesized by chemical vapor deposition, and PVDF nanofibrous webs were prepared by electrospinning. We demonstrate that the bilayer graphene nanosheets not only enhance the conductivity and piezoelectricity properties of PVDF nanofibers but also promote cardiomyocyte-like phenotypes by providing nanotopography cues. The BGF/PVDF biphasic layered structure (170 ± 15 μm thickness) provides an electrical conductivity of 2.82 μS/cm and a piezoelectric voltage of 0.47 mV/N, making it a suitable platform for cardiac cell stimulation under pulsatile electrical stimulation. Immunofluorescence staining analysis determines that the mechanism of graphene influence is associated with enhanced structural organization and expression of sarcomeric α-actinin (the cardiac-specific marker for H9c2 cells). Our results indicate that the synergistic effect of electroconductive (graphene) and piezoelectric (PVDF) nanomaterials provides a promising strategy for developing functional cardiac-like tissue substitutes, which can be used as an efficient tool for in vitro cardiac models for drug testing and screening.
{"title":"PVDF-Modified Graphene Nanosheets as a Piezoelectric and Electroconductive Bilayer Platform for Cardiac Cell Stimulation","authors":"Elham Golafshan, Habib Nikukar, Shohreh Mashayekhan*, Mohammad Ali Shokrgozar and Abdolreza Simchi*, ","doi":"10.1021/acsanm.4c0374910.1021/acsanm.4c03749","DOIUrl":"https://doi.org/10.1021/acsanm.4c03749https://doi.org/10.1021/acsanm.4c03749","url":null,"abstract":"<p >The conductive microenvironment and pulsatile electromechanical cues in the native myocardium tissue regulate biological responses; hence, advanced nanomaterials must be developed to construct cardiac tissue-like constructs. In this work, we present a stretchable, electroconductive, and piezoelectric biphasic layered structure based on bilayer graphene nanolayers (BGF) modified polyvinylidene fluoride (PVDF) nanofibers to provide suitable electrophysiological microenvironments for the modulation of H9c2 embryonic rat cardiomyoblasts toward cardiomyocyte-like phenotypes. High-quality BGFs were synthesized by chemical vapor deposition, and PVDF nanofibrous webs were prepared by electrospinning. We demonstrate that the bilayer graphene nanosheets not only enhance the conductivity and piezoelectricity properties of PVDF nanofibers but also promote cardiomyocyte-like phenotypes by providing nanotopography cues. The BGF/PVDF biphasic layered structure (170 ± 15 μm thickness) provides an electrical conductivity of 2.82 μS/cm and a piezoelectric voltage of 0.47 mV/N, making it a suitable platform for cardiac cell stimulation under pulsatile electrical stimulation. Immunofluorescence staining analysis determines that the mechanism of graphene influence is associated with enhanced structural organization and expression of sarcomeric α-actinin (the cardiac-specific marker for H9c2 cells). Our results indicate that the synergistic effect of electroconductive (graphene) and piezoelectric (PVDF) nanomaterials provides a promising strategy for developing functional cardiac-like tissue substitutes, which can be used as an efficient tool for in vitro cardiac models for drug testing and screening.</p>","PeriodicalId":6,"journal":{"name":"ACS Applied Nano Materials","volume":null,"pages":null},"PeriodicalIF":5.3,"publicationDate":"2024-09-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142326101","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Elham Golafshan, Habib Nikukar, Shohreh Mashayekhan, Mohammad Ali Shokrgozar, Abdolreza Simchi
The conductive microenvironment and pulsatile electromechanical cues in the native myocardium tissue regulate biological responses; hence, advanced nanomaterials must be developed to construct cardiac tissue-like constructs. In this work, we present a stretchable, electroconductive, and piezoelectric biphasic layered structure based on bilayer graphene nanolayers (BGF) modified polyvinylidene fluoride (PVDF) nanofibers to provide suitable electrophysiological microenvironments for the modulation of H9c2 embryonic rat cardiomyoblasts toward cardiomyocyte-like phenotypes. High-quality BGFs were synthesized by chemical vapor deposition, and PVDF nanofibrous webs were prepared by electrospinning. We demonstrate that the bilayer graphene nanosheets not only enhance the conductivity and piezoelectricity properties of PVDF nanofibers but also promote cardiomyocyte-like phenotypes by providing nanotopography cues. The BGF/PVDF biphasic layered structure (170 ± 15 μm thickness) provides an electrical conductivity of 2.82 μS/cm and a piezoelectric voltage of 0.47 mV/N, making it a suitable platform for cardiac cell stimulation under pulsatile electrical stimulation. Immunofluorescence staining analysis determines that the mechanism of graphene influence is associated with enhanced structural organization and expression of sarcomeric α-actinin (the cardiac-specific marker for H9c2 cells). Our results indicate that the synergistic effect of electroconductive (graphene) and piezoelectric (PVDF) nanomaterials provides a promising strategy for developing functional cardiac-like tissue substitutes, which can be used as an efficient tool for in vitro cardiac models for drug testing and screening.
{"title":"PVDF-Modified Graphene Nanosheets as a Piezoelectric and Electroconductive Bilayer Platform for Cardiac Cell Stimulation","authors":"Elham Golafshan, Habib Nikukar, Shohreh Mashayekhan, Mohammad Ali Shokrgozar, Abdolreza Simchi","doi":"10.1021/acsanm.4c03749","DOIUrl":"https://doi.org/10.1021/acsanm.4c03749","url":null,"abstract":"The conductive microenvironment and pulsatile electromechanical cues in the native myocardium tissue regulate biological responses; hence, advanced nanomaterials must be developed to construct cardiac tissue-like constructs. In this work, we present a stretchable, electroconductive, and piezoelectric biphasic layered structure based on bilayer graphene nanolayers (BGF) modified polyvinylidene fluoride (PVDF) nanofibers to provide suitable electrophysiological microenvironments for the modulation of H9c2 embryonic rat cardiomyoblasts toward cardiomyocyte-like phenotypes. High-quality BGFs were synthesized by chemical vapor deposition, and PVDF nanofibrous webs were prepared by electrospinning. We demonstrate that the bilayer graphene nanosheets not only enhance the conductivity and piezoelectricity properties of PVDF nanofibers but also promote cardiomyocyte-like phenotypes by providing nanotopography cues. The BGF/PVDF biphasic layered structure (170 ± 15 μm thickness) provides an electrical conductivity of 2.82 μS/cm and a piezoelectric voltage of 0.47 mV/N, making it a suitable platform for cardiac cell stimulation under pulsatile electrical stimulation. Immunofluorescence staining analysis determines that the mechanism of graphene influence is associated with enhanced structural organization and expression of sarcomeric α-actinin (the cardiac-specific marker for H9c2 cells). Our results indicate that the synergistic effect of electroconductive (graphene) and piezoelectric (PVDF) nanomaterials provides a promising strategy for developing functional cardiac-like tissue substitutes, which can be used as an efficient tool for in vitro cardiac models for drug testing and screening.","PeriodicalId":6,"journal":{"name":"ACS Applied Nano Materials","volume":null,"pages":null},"PeriodicalIF":5.9,"publicationDate":"2024-09-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142267544","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Protein scaffolds play a vital role in drug delivery systems. However, few research studies have been focused on loading hydrophobic drugs on protein scaffolds in biomedical fields. Here, we report on the development of protein microspheres and nanofibers by a simple ice-templating approach and their use as scaffolds for the controlled release of hydrophobic drugs, with bovine serum albumin (BSA) as the model protein and curcumin as the model hydrophobic drug. The BSA scaffolds display the unique nanofibrous and microspherical structures. This is a surprising discovery because there has been no report on the formation of microspheres via simple ice-templating of solutions or suspensions. To further understand the formation of microspheres by this approach, lysozyme, papain, and their composites with BSA are also studied. It is speculated that nanoparticles are first formed in aqueous BSA solution, attributed to the overlapping of hydration layers and autoassembly of inner hydrophobic cores of BSA globular molecules. Nanoprecipitation and soaking evaporation approaches are then used to load curcumin into the BSA scaffolds, followed by cross-linking with glutaraldehyde vapor to improve stability in an aqueous medium. The controlled release of curcumin is demonstrated, paving the way for various hydrophobic drugs loaded into this biodegradable and nonimmunogenic protein scaffold for potential treatments of diverse diseases.
{"title":"Protein Nanospheres and Nanofibers Prepared by Ice-Templating for the Controlled Release of Hydrophobic Drugs","authors":"Meina Zhang, Hong Cai, Haifei Zhang","doi":"10.1021/acsanm.4c03657","DOIUrl":"https://doi.org/10.1021/acsanm.4c03657","url":null,"abstract":"Protein scaffolds play a vital role in drug delivery systems. However, few research studies have been focused on loading hydrophobic drugs on protein scaffolds in biomedical fields. Here, we report on the development of protein microspheres and nanofibers by a simple ice-templating approach and their use as scaffolds for the controlled release of hydrophobic drugs, with bovine serum albumin (BSA) as the model protein and curcumin as the model hydrophobic drug. The BSA scaffolds display the unique nanofibrous and microspherical structures. This is a surprising discovery because there has been no report on the formation of microspheres via simple ice-templating of solutions or suspensions. To further understand the formation of microspheres by this approach, lysozyme, papain, and their composites with BSA are also studied. It is speculated that nanoparticles are first formed in aqueous BSA solution, attributed to the overlapping of hydration layers and autoassembly of inner hydrophobic cores of BSA globular molecules. Nanoprecipitation and soaking evaporation approaches are then used to load curcumin into the BSA scaffolds, followed by cross-linking with glutaraldehyde vapor to improve stability in an aqueous medium. The controlled release of curcumin is demonstrated, paving the way for various hydrophobic drugs loaded into this biodegradable and nonimmunogenic protein scaffold for potential treatments of diverse diseases.","PeriodicalId":6,"journal":{"name":"ACS Applied Nano Materials","volume":null,"pages":null},"PeriodicalIF":5.9,"publicationDate":"2024-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142181296","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Multilayer graphene (MLG) has attracted considerable attention as an interconnect material owing to its excellent electrical and mechanical properties. Several studies on the formation of MLG on insulators have been reported; however, the process temperature and shape controllability of MLG remain challenging. In this study, we investigated the formation of MLG strips for interconnect via metal-induced layer exchange (LE). The LE of strip-patterned amorphous carbon and Ni formed {002}-oriented high-crystallinity MLG strips at low temperatures (600 °C). While voids were formed inside the strip, continuous MLG was formed at the strip edge, likely due to the remarkable atomic diffusion at the edge. Smaller widths and larger thicknesses of the MLG strip allowed us to form uniform MLG strips without voids, and an electrical conductivity of 1100 S cm–1 was achieved. The technique developed in this study is unique because it overcomes the limitations of conventional MLG fabrication techniques and is promising for MLG interconnect applications.
{"title":"Multilayer Graphene Strips on Insulators Formed by Layer Exchange for Applications as Interconnects","authors":"Hiromasa Murata, Takamitsu Ishiyama, Katsuhisa Murakami, Masayoshi Nagao, Kaoru Toko","doi":"10.1021/acsanm.4c04902","DOIUrl":"https://doi.org/10.1021/acsanm.4c04902","url":null,"abstract":"Multilayer graphene (MLG) has attracted considerable attention as an interconnect material owing to its excellent electrical and mechanical properties. Several studies on the formation of MLG on insulators have been reported; however, the process temperature and shape controllability of MLG remain challenging. In this study, we investigated the formation of MLG strips for interconnect via metal-induced layer exchange (LE). The LE of strip-patterned amorphous carbon and Ni formed {002}-oriented high-crystallinity MLG strips at low temperatures (600 °C). While voids were formed inside the strip, continuous MLG was formed at the strip edge, likely due to the remarkable atomic diffusion at the edge. Smaller widths and larger thicknesses of the MLG strip allowed us to form uniform MLG strips without voids, and an electrical conductivity of 1100 S cm<sup>–1</sup> was achieved. The technique developed in this study is unique because it overcomes the limitations of conventional MLG fabrication techniques and is promising for MLG interconnect applications.","PeriodicalId":6,"journal":{"name":"ACS Applied Nano Materials","volume":null,"pages":null},"PeriodicalIF":5.9,"publicationDate":"2024-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142267548","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The tuning of optical, morphological, and structural properties through precise control of the size/thickness of transition-metal chalcogenide is one of the key aspects for practical applications. The present study reports that the microwave-synthesized MnSe1+xTe1–x (MST) nanocomposite by altering Se and Te concentrations is studied for optoelectronic applications. The gradual increase in its crystallinity through MnSe and MnTe2 crystalline phases with an increase in Se/Te ratio is confirmed by the structural study. The existence of different vibrational modes in the sample with alteration in the microstructural region is confirmed by a Raman study. The morphology study shows the nanosheet (nSh) structure as formed for the as-prepared MST samples, confirming the formation of 2D nanomaterial. The nSh thickness gradually decreased with a decrease in the Se concentration and increased Te. The reduction of the optical band gap of nSh is reflected by shifting the absorption edge to a higher wavelength regime. The refractive index values lie between 2.14 and 2.78 for different MST nSh as per theoretical calculation. The presence of various exothermal and endothermal peaks is confirmed by thermal analysis for the present sample. These materials undergo photodetection measurement, where they illustrate commendable responsivity across a range of values: 1.73, 8.88, and 28.88 nA W–1. Additionally, these materials showcase detectivity at levels of 1.14 × 1010, 2.52 × 1010, and 3.96 × 1011 Jones, respectively. The changes in different optical and structural parameters enable the material’s applicability in optoelectronic devices.
通过精确控制过渡金属卤化物的尺寸/厚度来调整其光学、形态和结构特性是实际应用的关键之一。本研究通过改变 Se 和 Te 的浓度，研究了微波合成的 MnSe1+xTe1-x （MST）纳米复合材料的光电应用。结构研究证实，随着 Se/Te 比例的增加，MnSe 和 MnTe2 结晶相的结晶度逐渐增加。拉曼研究证实，随着微结构区域的变化，样品中存在不同的振动模式。形貌研究显示，制备的 MST 样品形成了纳米片（nSh）结构，证实了二维纳米材料的形成。随着 Se 浓度的降低和 Te 浓度的增加，nSh 厚度逐渐减小。nSh 光带隙的减小反映在吸收边沿向高波长区移动。根据理论计算，不同 MST nSh 的折射率值介于 2.14 和 2.78 之间。热分析证实了本样品存在各种放热和内热峰。对这些材料进行了光电探测测量，结果表明它们的响应度在一定范围内值得称赞：1.73、8.88 和 28.88 nA W-1。此外，这些材料的探测率分别为 1.14 × 1010、2.52 × 1010 和 3.96 × 1011 琼斯。不同光学和结构参数的变化使这些材料能够应用于光电设备。
{"title":"Microwave-Assisted Synthesis of MnSeTe Nanocomposite Flowers for Optoelectronic and Photoresponse Applications","authors":"Subhashree Das, Subrata Senapati, Rajamanickam Ganesan, Ramakanta Naik","doi":"10.1021/acsanm.4c02591","DOIUrl":"https://doi.org/10.1021/acsanm.4c02591","url":null,"abstract":"The tuning of optical, morphological, and structural properties through precise control of the size/thickness of transition-metal chalcogenide is one of the key aspects for practical applications. The present study reports that the microwave-synthesized MnSe<sub>1+<i>x</i></sub>Te<sub>1–<i>x</i></sub> (MST) nanocomposite by altering Se and Te concentrations is studied for optoelectronic applications. The gradual increase in its crystallinity through MnSe and MnTe<sub>2</sub> crystalline phases with an increase in Se/Te ratio is confirmed by the structural study. The existence of different vibrational modes in the sample with alteration in the microstructural region is confirmed by a Raman study. The morphology study shows the nanosheet (nSh) structure as formed for the as-prepared MST samples, confirming the formation of 2D nanomaterial. The nSh thickness gradually decreased with a decrease in the Se concentration and increased Te. The reduction of the optical band gap of nSh is reflected by shifting the absorption edge to a higher wavelength regime. The refractive index values lie between 2.14 and 2.78 for different MST nSh as per theoretical calculation. The presence of various exothermal and endothermal peaks is confirmed by thermal analysis for the present sample. These materials undergo photodetection measurement, where they illustrate commendable responsivity across a range of values: 1.73, 8.88, and 28.88 nA W<sup>–1</sup>. Additionally, these materials showcase detectivity at levels of 1.14 × 10<sup>10</sup>, 2.52 × 10<sup>10</sup>, and 3.96 × 10<sup>11</sup> Jones, respectively. The changes in different optical and structural parameters enable the material’s applicability in optoelectronic devices.","PeriodicalId":6,"journal":{"name":"ACS Applied Nano Materials","volume":null,"pages":null},"PeriodicalIF":5.9,"publicationDate":"2024-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142267546","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Tatiana Yu. Komarova, Sergey E. Kushnir, Kirill S. Napolskii
Photonic crystal heterostructures (PhCHs) have emerged as a promising tool to control light propagation with high precision. Anodization techniques are widely used to prepare PhCHs based on porous silicon and valve metal oxides. These techniques rely on oscillating anodization voltage or current to modulate the effective refractive index along the normal to the porous film surface, thereby creating photonic band gaps (PBGs) in PhCHs. However, anodization regimes described in the literature lack direct control over the optical path length (L) of prepared photonic structures, which is essential for fine-tuning the optical properties of PhCHs. In this work we present an anodization method for the preparation of PhCHs based on anodic aluminum oxide (AAO). The proposed anodizing regime accounts for chromatic dispersion of the refractive index and dispersion of L of the porous AAO film, providing direct control over the L of the prepared PhCHs. The potential of this approach was demonstrated by preparing PhCHs with up to 21 PBGs in the wavelength range from 250 to 1050 nm. Furthermore, we showcase a promising practical application of PhCHs by encoding 10-letter words and storing 47 bits of data using AAO photonic barcodes. The developed anodizing approach opens up avenues for designing and fabricating PhCHs with enhanced optical properties and potential applications in optical communication, data storage, and sensing.
{"title":"Nanoscale Photonic Barcodes Based on Anodic Alumina Photonic Crystal Heterostructures: Implications for Optical Communications, Data Storage, and Sensing","authors":"Tatiana Yu. Komarova, Sergey E. Kushnir, Kirill S. Napolskii","doi":"10.1021/acsanm.4c03880","DOIUrl":"https://doi.org/10.1021/acsanm.4c03880","url":null,"abstract":"Photonic crystal heterostructures (PhCHs) have emerged as a promising tool to control light propagation with high precision. Anodization techniques are widely used to prepare PhCHs based on porous silicon and valve metal oxides. These techniques rely on oscillating anodization voltage or current to modulate the effective refractive index along the normal to the porous film surface, thereby creating photonic band gaps (PBGs) in PhCHs. However, anodization regimes described in the literature lack direct control over the optical path length (<i>L</i>) of prepared photonic structures, which is essential for fine-tuning the optical properties of PhCHs. In this work we present an anodization method for the preparation of PhCHs based on anodic aluminum oxide (AAO). The proposed anodizing regime accounts for chromatic dispersion of the refractive index and dispersion of <i>L</i> of the porous AAO film, providing direct control over the <i>L</i> of the prepared PhCHs. The potential of this approach was demonstrated by preparing PhCHs with up to 21 PBGs in the wavelength range from 250 to 1050 nm. Furthermore, we showcase a promising practical application of PhCHs by encoding 10-letter words and storing 47 bits of data using AAO photonic barcodes. The developed anodizing approach opens up avenues for designing and fabricating PhCHs with enhanced optical properties and potential applications in optical communication, data storage, and sensing.","PeriodicalId":6,"journal":{"name":"ACS Applied Nano Materials","volume":null,"pages":null},"PeriodicalIF":5.9,"publicationDate":"2024-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142181298","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ozce Durak, Ahmet Safa Aydogdu, Nitasha Habib, Hasan Can Gulbalkan, Zekihan Ozerdem, Sahika Sena Bayazit, Seda Keskin, Alper Uzun
Ionic liquid (IL)/metal–organic framework (MOF) (IL/MOF) nanocomposites have been shown to offer a broad potential in adsorption-based CO2 separation, especially at very low pressures. Selection of the most suitable ILs is crucial for synthesizing IL/MOF nanocomposites capable of achieving exceptionally high CO2 selectivities under more applicable conditions, such as at atmospheric pressure. However, the existence of a very wide range of IL-MOF pairs makes the design of such materials time-consuming when relying solely on experimental approaches. In this work, we employed a multitiered computational approach involving conductor-like screening model for realistic solvents, grand canonical Monte Carlo simulations, and density functional theory calculations. The goal was to screen 35,476 diverse ILs from various families to identify the IL that could boost the CO2 selectivity. Results of the computational screening highlighted 1-n-butyl-3-methylimidazolium tricyanomethanide ([BMIM][C(CN)3]) as the promising IL candidate offering significant potential for separation of CO2 from N2 and CH4. We then experimentally incorporated this IL into a robust MOF, UiO-66, and characterized the resulting structure in deep detail. Testing of [BMIM][C(CN)3]/UiO-66 for adsorption of CO2, N2, and CH4 demonstrated that the nanocomposite provides exceptional CO2 separation performance, offering an appreciable amount of CO2 uptake, while almost completely rejecting N2 and CH4 up to 1 and 0.3 bar, respectively, at 25 °C. Our results illustrated the importance of accurate selection of the IL for the design of IL/MOF nanocomposites with high performance for target gas separations.
离子液体（IL）/金属有机框架（MOF）（IL/MOF）纳米复合材料已被证明在基于吸附的二氧化碳分离方面具有广泛的潜力，尤其是在极低的压力下。选择最合适的 IL 对于合成 IL/MOF 纳米复合材料至关重要，因为它能够在更适用的条件下（如大气压下）实现极高的二氧化碳选择性。然而，IL-MOF 对的存在范围非常广泛，因此仅依靠实验方法来设计此类材料非常耗时。在这项工作中，我们采用了一种多层次的计算方法，包括针对现实溶剂的类似导体的筛选模型、大规范蒙特卡洛模拟和密度泛函理论计算。我们的目标是筛选出 35,476 种不同系列的 IL，从而找出能提高 CO2 选择性的 IL。计算筛选的结果表明，1-正丁基-3-甲基咪唑鎓三氰基甲烷化物（[BMIM][C(CN)3]）是很有前途的候选IL，在从N2和CH4中分离CO2方面具有很大的潜力。然后，我们通过实验将这种惰性离子纳入了一种坚固的 MOF UiO-66，并对由此产生的结构进行了深入细致的表征。对 [BMIM][C(CN)3]/UiO-66进行的二氧化碳、N2 和 CH4 吸附测试表明，这种纳米复合材料具有优异的二氧化碳分离性能，在 25 °C 下，它能吸附相当数量的二氧化碳，同时几乎完全排斥 N2 和 CH4，吸附压力分别高达 1 巴和 0.3 巴。我们的研究结果表明，在设计用于目标气体分离的高性能 IL/MOF 纳米复合材料时，准确选择 IL 非常重要。
{"title":"In Silico-Directed Design and Experimental Validation of an IL/UiO-66 Nanocomposite with Exceptional CO2 Selectivity across a Wide Pressure Range","authors":"Ozce Durak, Ahmet Safa Aydogdu, Nitasha Habib, Hasan Can Gulbalkan, Zekihan Ozerdem, Sahika Sena Bayazit, Seda Keskin, Alper Uzun","doi":"10.1021/acsanm.4c03699","DOIUrl":"https://doi.org/10.1021/acsanm.4c03699","url":null,"abstract":"Ionic liquid (IL)/metal–organic framework (MOF) (IL/MOF) nanocomposites have been shown to offer a broad potential in adsorption-based CO<sub>2</sub> separation, especially at very low pressures. Selection of the most suitable ILs is crucial for synthesizing IL/MOF nanocomposites capable of achieving exceptionally high CO<sub>2</sub> selectivities under more applicable conditions, such as at atmospheric pressure. However, the existence of a very wide range of IL-MOF pairs makes the design of such materials time-consuming when relying solely on experimental approaches. In this work, we employed a multitiered computational approach involving conductor-like screening model for realistic solvents, grand canonical Monte Carlo simulations, and density functional theory calculations. The goal was to screen 35,476 diverse ILs from various families to identify the IL that could boost the CO<sub>2</sub> selectivity. Results of the computational screening highlighted 1-<i>n</i>-butyl-3-methylimidazolium tricyanomethanide ([BMIM][C(CN)<sub>3</sub>]) as the promising IL candidate offering significant potential for separation of CO<sub>2</sub> from N<sub>2</sub> and CH<sub>4</sub>. We then experimentally incorporated this IL into a robust MOF, UiO-66, and characterized the resulting structure in deep detail. Testing of [BMIM][C(CN)<sub>3</sub>]/UiO-66 for adsorption of CO<sub>2</sub>, N<sub>2</sub>, and CH<sub>4</sub> demonstrated that the nanocomposite provides exceptional CO<sub>2</sub> separation performance, offering an appreciable amount of CO<sub>2</sub> uptake, while almost completely rejecting N<sub>2</sub> and CH<sub>4</sub> up to 1 and 0.3 bar, respectively, at 25 °C. Our results illustrated the importance of accurate selection of the IL for the design of IL/MOF nanocomposites with high performance for target gas separations.","PeriodicalId":6,"journal":{"name":"ACS Applied Nano Materials","volume":null,"pages":null},"PeriodicalIF":5.9,"publicationDate":"2024-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142267547","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Exhilarating breakthroughs in the treatment of autoimmune diseases through antigen-specific therapies offer new hope for patients. Herein, a novel antigen-specific reverse micelle platform is proposed: blank liposomes prepared with 1, 2-diolyl-sn-glycerol-3-phosphocholine (DOPC) and cholesterol (Chol) are mixed with an aqueous solution of the encapsulated antigens and immunomodulators, lyophilized, and then reconstituted in oil. Subcutaneous injection of 100 μL of a reverse micelle vaccine loaded with 10 μg of MOG35–55 and 30 μg of dexamethasone sodium phosphate (DSP) before experimental autoimmune encephalomyelitis (EAE, a multiple sclerosis model) establishment directly blocked the development of clinical symptoms. Furthermore, the same vaccine delayed and attenuated clinical symptoms in an established mouse model of EAE. Conversely, the reverse micelle vaccine loaded with an unrelated antigen OVA failed to alleviate paralysis in mice, highlighting the crucial aspect of antigen specificity. Dose-dependent effects were observed in both the prevention and treatment of EAE, with clinical scores of 0 being achieved during the treatment at single DSP doses of up to 50 μg at the MOG35–55 dose of 10 μg. The treatment of the reverse micelle vaccine induced Treg cell proliferation, accounting for the tolerance to the pathogenic antigens and improved outcomes. Overall, the designed reverse micelle vaccine provided a universal platform to encapsulate antigens and immunomodulators that restore tolerance of antigens and then demonstrated the therapeutic promise in autoimmune diseases.
{"title":"Tolerogenic Reverse Micelle Nanovaccine Prevents Onset and Progression of Multiple Sclerosis","authors":"Rui Zhang, Haolin Zhang, Yue Wang, Yuxin Hu, Qing Ma, Weijia Huang, Xin Li*, Yongjun Wang* and Hongzhuo Liu*, ","doi":"10.1021/acsanm.4c0330110.1021/acsanm.4c03301","DOIUrl":"https://doi.org/10.1021/acsanm.4c03301https://doi.org/10.1021/acsanm.4c03301","url":null,"abstract":"<p >Exhilarating breakthroughs in the treatment of autoimmune diseases through antigen-specific therapies offer new hope for patients. Herein, a novel antigen-specific reverse micelle platform is proposed: blank liposomes prepared with 1, 2-diolyl-<i>sn</i>-glycerol-3-phosphocholine (DOPC) and cholesterol (Chol) are mixed with an aqueous solution of the encapsulated antigens and immunomodulators, lyophilized, and then reconstituted in oil. Subcutaneous injection of 100 μL of a reverse micelle vaccine loaded with 10 μg of MOG<sub>35–55</sub> and 30 μg of dexamethasone sodium phosphate (DSP) before experimental autoimmune encephalomyelitis (EAE, a multiple sclerosis model) establishment directly blocked the development of clinical symptoms. Furthermore, the same vaccine delayed and attenuated clinical symptoms in an established mouse model of EAE. Conversely, the reverse micelle vaccine loaded with an unrelated antigen OVA failed to alleviate paralysis in mice, highlighting the crucial aspect of antigen specificity. Dose-dependent effects were observed in both the prevention and treatment of EAE, with clinical scores of 0 being achieved during the treatment at single DSP doses of up to 50 μg at the MOG<sub>35–55</sub> dose of 10 μg. The treatment of the reverse micelle vaccine induced Treg cell proliferation, accounting for the tolerance to the pathogenic antigens and improved outcomes. Overall, the designed reverse micelle vaccine provided a universal platform to encapsulate antigens and immunomodulators that restore tolerance of antigens and then demonstrated the therapeutic promise in autoimmune diseases.</p>","PeriodicalId":6,"journal":{"name":"ACS Applied Nano Materials","volume":null,"pages":null},"PeriodicalIF":5.3,"publicationDate":"2024-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142325982","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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