Samuel Mandin, Lorenzo Metili, Mohamed Karrouch, Didier Bleses, Christine Lancelon-Pin, Pierre Sailler, William Chèvremont, Erwan Paineau, Jean-Luc Putaux, Nicolas Hengl, Bruno Jean, Frédéric Pignon
The structural organization of cellulose nanocrystal (CNC) suspensions at the membrane surface during frontal ultrafiltration has been characterized, for the first time, at the nano- and microscale by in-situ small-angle X-ray and light scattering (SAXS and SALS, respectively). During filtration, the particles assembled at the membrane surface and formed the so-called concentration polarization layer (CPL), which contains CNCs arranged in a chiral nematic (cholesteric) helicoidal structure, with the long axis of the CNCs oriented parallel to the membrane surface, and the helical axis of the cholesteric structure oriented perpendicular to the membrane surface. The self-organization of CNCs in the form of oriented cholesteric structures was further characterized by a pitch gradient in the CPL. The structure of the CPL was also investigated upon release of the transmembrane pressure. SAXS data revealed a relaxation process associated with a diffusion of the CNCs from the membrane surface towards the bulk, while SALS measurements revealed a re-organization of the cholesteric phase that was preserved all along the deposit. The preservation of the observed structure after 14 days of continuous filtration followed by air-drying was confirmed using scanning electron microscopy and wide-angle X-ray diffraction, demonstrating the feasibility of the process scale-up.
{"title":"Multiscale study of the chiral self-assembly of cellulose nanocrystals during frontal ultrafiltration process","authors":"Samuel Mandin, Lorenzo Metili, Mohamed Karrouch, Didier Bleses, Christine Lancelon-Pin, Pierre Sailler, William Chèvremont, Erwan Paineau, Jean-Luc Putaux, Nicolas Hengl, Bruno Jean, Frédéric Pignon","doi":"10.1039/d4nr02840f","DOIUrl":"https://doi.org/10.1039/d4nr02840f","url":null,"abstract":"The structural organization of cellulose nanocrystal (CNC) suspensions at the membrane surface during frontal ultrafiltration has been characterized, for the first time, at the nano- and microscale by in-situ small-angle X-ray and light scattering (SAXS and SALS, respectively). During filtration, the particles assembled at the membrane surface and formed the so-called concentration polarization layer (CPL), which contains CNCs arranged in a chiral nematic (cholesteric) helicoidal structure, with the long axis of the CNCs oriented parallel to the membrane surface, and the helical axis of the cholesteric structure oriented perpendicular to the membrane surface. The self-organization of CNCs in the form of oriented cholesteric structures was further characterized by a pitch gradient in the CPL. The structure of the CPL was also investigated upon release of the transmembrane pressure. SAXS data revealed a relaxation process associated with a diffusion of the CNCs from the membrane surface towards the bulk, while SALS measurements revealed a re-organization of the cholesteric phase that was preserved all along the deposit. The preservation of the observed structure after 14 days of continuous filtration followed by air-drying was confirmed using scanning electron microscopy and wide-angle X-ray diffraction, demonstrating the feasibility of the process scale-up.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":null,"pages":null},"PeriodicalIF":6.7,"publicationDate":"2024-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142277065","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Metals exhibit unique characteristics in photocatalysis, and their incorporation into semiconductors can result in remarkable features. This study focuses on the preparation of graphdiyne with Cu (CG) by using Cu powder as a catalyst. The addition of Cu reduces the narrow band gap of graphdiyne and imparts metal-like properties to the material. By leveraging the electronegativity of CG, a spherical NiCo-MOF (NC) is grown and in situ anchored on CG, forming a strongly coupled electron transport interface. In addition, the CG with metal-like properties also displays distinct characteristics. The integration of CG and NC through an ohmic contact significantly enhances the spatial separation of photogenerated carrier holes. Efficient hydrogen evolution is achieved through a synergistic effect of the strongly coupled electron transport interface and the spatial separation of photogenerated carrier holes. This research provides a new perspective on the design and development of metal-like narrow band gap semiconductors.
{"title":"NiCo-MOFs in situ anchored on graphdiyne with metal-like properties form a strongly coupled electron transport interface and construct an ohmic contact to achieve efficient charge–hole spatial separation","authors":"Zhenkun Liu, Jing Wang, Guangbo Liu, Zhiliang Jin, Noritatsu Tsubaki","doi":"10.1039/d4nr03018d","DOIUrl":"https://doi.org/10.1039/d4nr03018d","url":null,"abstract":"Metals exhibit unique characteristics in photocatalysis, and their incorporation into semiconductors can result in remarkable features. This study focuses on the preparation of graphdiyne with Cu (CG) by using Cu powder as a catalyst. The addition of Cu reduces the narrow band gap of graphdiyne and imparts metal-like properties to the material. By leveraging the electronegativity of CG, a spherical NiCo-MOF (NC) is grown and <em>in situ</em> anchored on CG, forming a strongly coupled electron transport interface. In addition, the CG with metal-like properties also displays distinct characteristics. The integration of CG and NC through an ohmic contact significantly enhances the spatial separation of photogenerated carrier holes. Efficient hydrogen evolution is achieved through a synergistic effect of the strongly coupled electron transport interface and the spatial separation of photogenerated carrier holes. This research provides a new perspective on the design and development of metal-like narrow band gap semiconductors.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":null,"pages":null},"PeriodicalIF":6.7,"publicationDate":"2024-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142277056","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
This paper reports synthesis, aqueous self-assembly and relevance in the pH-triggered activable photodynamic therapy of an amphiphilic polyurethane (P1S), functionalized with a heavy-atom free organic photosensitizer. Condensation polymerization between 1,4-diisocyanatobutane and two different dihydroxy monomers (one having pendant hydrophilic wedge and the other having 1,3-dihydroxypropan-2-one with a reactive carbonyl-group) in presence of measured amount of (S)-2-methylbutan-1-ol (chain-stopper) and DABCO catalyst produces the reactive pre-polymer P1. Hydrazide- functionalized thionated-naphthalenemonimide (NMIS), that acts as a photosensitizer, was reacted with the carbonyl-functionality of P1 to get the desired polymer-photosensitizer conjugate P1S in which the dye was attached to the polymer backbone by the acid-labile hydrazone linker. In water, P1S adopted intra-chain H-bonding stabilized folded structure, which further assembled to produce polymersome structure (Dh ~ 200 nm), in which the hydrophobic membrane consists of aggregated NMIS and trialkoxy-benzene chromophores, as evident from the UV/Vis, CD and small-angle X-ray diffraction studies. In the aggregated state, the NMIS loses its reactive oxygen species (ROS)-generation ability and remains in the dormant state. However, in acidic condition (pH 5.5), the photosensitizer is detached (presumably due to the cleavage of the hydrazone-linker) and regains its full ROS-generation activity under photoirradiation, as evidenced from the standard DCFH assay. To test the possibility of such pH-activable intra-cellular ROS generation, P1S was treated with HeLa cells as it is known that cancer cells are more acidic than normal cells. Indeed, photoirradiation induced intra-cellular ROS generation was evident by the DCFH assay, resulting in efficient cell killing.
{"title":"pH-Responsive Self-assembled Polymer-Photosensitizer Conjugate for Activable Photodynamic Therapy","authors":"Tanushri Banerjee, Krishna Dan, Suhrit Ghosh","doi":"10.1039/d4nr03249g","DOIUrl":"https://doi.org/10.1039/d4nr03249g","url":null,"abstract":"This paper reports synthesis, aqueous self-assembly and relevance in the pH-triggered activable photodynamic therapy of an amphiphilic polyurethane (P1S), functionalized with a heavy-atom free organic photosensitizer. Condensation polymerization between 1,4-diisocyanatobutane and two different dihydroxy monomers (one having pendant hydrophilic wedge and the other having 1,3-dihydroxypropan-2-one with a reactive carbonyl-group) in presence of measured amount of (S)-2-methylbutan-1-ol (chain-stopper) and DABCO catalyst produces the reactive pre-polymer P1. Hydrazide- functionalized thionated-naphthalenemonimide (NMIS), that acts as a photosensitizer, was reacted with the carbonyl-functionality of P1 to get the desired polymer-photosensitizer conjugate P1S in which the dye was attached to the polymer backbone by the acid-labile hydrazone linker. In water, P1S adopted intra-chain H-bonding stabilized folded structure, which further assembled to produce polymersome structure (Dh ~ 200 nm), in which the hydrophobic membrane consists of aggregated NMIS and trialkoxy-benzene chromophores, as evident from the UV/Vis, CD and small-angle X-ray diffraction studies. In the aggregated state, the NMIS loses its reactive oxygen species (ROS)-generation ability and remains in the dormant state. However, in acidic condition (pH 5.5), the photosensitizer is detached (presumably due to the cleavage of the hydrazone-linker) and regains its full ROS-generation activity under photoirradiation, as evidenced from the standard DCFH assay. To test the possibility of such pH-activable intra-cellular ROS generation, P1S was treated with HeLa cells as it is known that cancer cells are more acidic than normal cells. Indeed, photoirradiation induced intra-cellular ROS generation was evident by the DCFH assay, resulting in efficient cell killing.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":null,"pages":null},"PeriodicalIF":6.7,"publicationDate":"2024-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142277051","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Increasing energy demands and low-carbon emission energy carriers are the global challenges for renewable energy resources. Regarding the aforementioned issues, magnesium-based composites are promising candidates for energy carriers. However, rapid initial hydrolysis kinetics and higher hydrogen yields are objectives for practical application. In this study, chromium-based catalysts (Cr2O3, Cr3C2) are employed via ball milling to activate Mg. Finally, we use Mg-Xwt%Y (X=1, 3, 5, and 10, Y= Cr2O3 and Cr3C2)composites to produce hydrogen. In seawater, Mg-10wt%Cr2O3 can produce 798 and 808 mL/g hydrogen, while 821 and 831.6 mL/g are achieved from Mg-10wt%Cr3C2 in seawater and 0.5 M MgCl2 solutions. Additionally, Cr2O3 and Cr3C2 significantly improve the Mg hydrolysis activation energies. However, incorporating Cr2O3 and Cr3C2, the activation energies for the hydrolysis of Mg with seawater are achieved to 19.447 kJ mol-1 and 17.290 kJ mol-1, while they are reduced to 15.69 kJ mol-1 and 14.369 kJ mol-1 with 0.5 M MgCl2 solutions, respectively. In comparison, Mg-10wt%Cr3C2 composite exhibits superior performance, which is attributed to the higher anode potential value of Cr3C2. This work accelerates the hydrolysis kinetics and provides a sufficient technique to produce hydrogen from Mg composite for the application of portable devices.
{"title":"The assessment of the importance and catalytic role of chromium oxide and chromium carbide for hydrogen generation via hydrolysis of Magnesium","authors":"Fei Qin, Yue Zhang, Kashif Naseem, Guoquan Suo, Waseem Hayat, Syed Hamza Safeer Gardezi, Zhanjun Chen","doi":"10.1039/d4nr02760d","DOIUrl":"https://doi.org/10.1039/d4nr02760d","url":null,"abstract":"Increasing energy demands and low-carbon emission energy carriers are the global challenges for renewable energy resources. Regarding the aforementioned issues, magnesium-based composites are promising candidates for energy carriers. However, rapid initial hydrolysis kinetics and higher hydrogen yields are objectives for practical application. In this study, chromium-based catalysts (Cr2O3, Cr3C2) are employed via ball milling to activate Mg. Finally, we use Mg-Xwt%Y (X=1, 3, 5, and 10, Y= Cr2O3 and Cr3C2)composites to produce hydrogen. In seawater, Mg-10wt%Cr2O3 can produce 798 and 808 mL/g hydrogen, while 821 and 831.6 mL/g are achieved from Mg-10wt%Cr3C2 in seawater and 0.5 M MgCl2 solutions. Additionally, Cr2O3 and Cr3C2 significantly improve the Mg hydrolysis activation energies. However, incorporating Cr2O3 and Cr3C2, the activation energies for the hydrolysis of Mg with seawater are achieved to 19.447 kJ mol-1 and 17.290 kJ mol-1, while they are reduced to 15.69 kJ mol-1 and 14.369 kJ mol-1 with 0.5 M MgCl2 solutions, respectively. In comparison, Mg-10wt%Cr3C2 composite exhibits superior performance, which is attributed to the higher anode potential value of Cr3C2. This work accelerates the hydrolysis kinetics and provides a sufficient technique to produce hydrogen from Mg composite for the application of portable devices.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":null,"pages":null},"PeriodicalIF":6.7,"publicationDate":"2024-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142276123","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Hesam Abouali, Michelle Przedborski, Mohammad Kohandel, Mahla Poudineh
Anti-PD1 immune checkpoint blockade (ICB) has shown promising results for treating several aggressive cancers, enhancing patient survival rates. The variability in clinical response to anti-PD1 ICB is thought to be driven by patient-specific biology and heterogeneity within the tumor microenvironment. Tumor-derived extracellular vesicles (TDEVs), nano-sized particles released from tumor cells, can modulate the tumor microenvironment, leading to immunosuppression and tumor progression. Hence, TDEVs may contribute to the variability in treatment response and play a crucial role in the failure of anti-PD1 immunotherapy. In this study, we develop a systems biology approach to interrogate the role of TDEVs on the response dynamics for anti-PD1 blockade. Our results suggest that the detection and profiling of TDEVs can help screen patients for anti-PD-1 immunotherapy. Moreover, the results in this study suggest that TDEVs and IL-12 can potentially be liquid biopsy biomarkers to profile patient response to anti-PD1 ICB and tailor patient-specific treatment protocols.
{"title":"Investigating Nano-Sized Tumor-Derived Extracellular Vesicles in Enhancing Anti-PD-1 Immunotherapy","authors":"Hesam Abouali, Michelle Przedborski, Mohammad Kohandel, Mahla Poudineh","doi":"10.1039/d4nr00729h","DOIUrl":"https://doi.org/10.1039/d4nr00729h","url":null,"abstract":"Anti-PD1 immune checkpoint blockade (ICB) has shown promising results for treating several aggressive cancers, enhancing patient survival rates. The variability in clinical response to anti-PD1 ICB is thought to be driven by patient-specific biology and heterogeneity within the tumor microenvironment. Tumor-derived extracellular vesicles (TDEVs), nano-sized particles released from tumor cells, can modulate the tumor microenvironment, leading to immunosuppression and tumor progression. Hence, TDEVs may contribute to the variability in treatment response and play a crucial role in the failure of anti-PD1 immunotherapy. In this study, we develop a systems biology approach to interrogate the role of TDEVs on the response dynamics for anti-PD1 blockade. Our results suggest that the detection and profiling of TDEVs can help screen patients for anti-PD-1 immunotherapy. Moreover, the results in this study suggest that TDEVs and IL-12 can potentially be liquid biopsy biomarkers to profile patient response to anti-PD1 ICB and tailor patient-specific treatment protocols.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":null,"pages":null},"PeriodicalIF":6.7,"publicationDate":"2024-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142276125","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Biljana Pejova, Arej Eid, Leonardo Lari, Ahmad Althumali, Lidija Šiller, Adam M. Kerrigan, L. Pejov, Vlado Lazarov
A surfactant-free ammonia and carbamide precursor-modulated engineering of self-assembled flower-like 3D NiO nanostructures based on ordered β-Ni(OH)2 and turbostratic Ni3(OH)4(NO3)2 nanoplate-structured intermediates is reported. Employing complementary structural and spectroscopic techniques, fundamental insight into structural and chemical transformation from intermediates to NiO nanoparticles (NPs) is provided. FTIR, Raman and DSC show that the transformation of intermediates to NiO NPs goes through subsequent loss of NO3− and OH− species, through double step phase transformation at 306 and 326 °C, corresponding to free interlayers ions and H2O species loss, followed by loss of chemically bonded OH− and NO3− ions. Transformation to NiO NPs via ammonia route proceeds as a single phase-transition, accompanied with loss of OH− species at 298 °C. The full transformation to NiO NPs of both intermediates is achieved at 350 °C by annealing in the air atmosphere. Ammonia derived NPs keep the nanoflower morphology by self-assembly into nanoplates, enabled by H2O mediated adhesion on the NiO NPs {100} neutral surfaces. Structural transformations of turbostratic Ni3(OH)4(NO3)2 nanoplates result in formation of NiO NPs dominantly shaped by inert polar OH terminated (111) atomic planes, leading to loss of initial self-assembled 3D structure. DFT calculations support these observations, confirming that H2O adsorbs dissociatively on polar {111} surfaces, while only physisorption is energetically feasible on {100} surfaces. NiO NPs obtained by two different routes have overall different properties: carbamide derived NPs are 3 times larger (15.5 vs 5.4 nm), possess larger band gap (3.6 vs 3.2 eV), and more Ni deficient. The intensity ratio of the surface optical (SO) modes to the transversal and longitudinal optical modes is ~ 40 times higher in the NiO NPs obtained from β-Ni(OH)2 compared to Ni3(OH)4(NO3)2-derived NPs. SO phonon lifetime is an order of magnitude shorter in NiO obtained from β-Ni(OH)2, reflecting the much smaller NP size. The choice of the precursor defines the size, morphology, crystallographic surface orientations and band gap of the NiO NPs, with Ni deficiency providing pathways of utilizing them as p-type material, and allows precise nanoengineering of polar and neutral surfaces dominated NiO NPs, of exceptional importance to the use in catalysis.
{"title":"3D self-assembled polar vs non-polar NiO nanoparticles nanoengineered from turbostratic Ni3(OH)4(NO3)2 and ordered β-Ni(OH)2 intermediates","authors":"Biljana Pejova, Arej Eid, Leonardo Lari, Ahmad Althumali, Lidija Šiller, Adam M. Kerrigan, L. Pejov, Vlado Lazarov","doi":"10.1039/d4nr03255a","DOIUrl":"https://doi.org/10.1039/d4nr03255a","url":null,"abstract":"A surfactant-free ammonia and carbamide precursor-modulated engineering of self-assembled flower-like 3D NiO nanostructures based on ordered β-Ni(OH)2 and turbostratic Ni3(OH)4(NO3)2 nanoplate-structured intermediates is reported. Employing complementary structural and spectroscopic techniques, fundamental insight into structural and chemical transformation from intermediates to NiO nanoparticles (NPs) is provided. FTIR, Raman and DSC show that the transformation of intermediates to NiO NPs goes through subsequent loss of NO3− and OH− species, through double step phase transformation at 306 and 326 °C, corresponding to free interlayers ions and H2O species loss, followed by loss of chemically bonded OH− and NO3− ions. Transformation to NiO NPs via ammonia route proceeds as a single phase-transition, accompanied with loss of OH− species at 298 °C. The full transformation to NiO NPs of both intermediates is achieved at 350 °C by annealing in the air atmosphere. Ammonia derived NPs keep the nanoflower morphology by self-assembly into nanoplates, enabled by H2O mediated adhesion on the NiO NPs {100} neutral surfaces. Structural transformations of turbostratic Ni3(OH)4(NO3)2 nanoplates result in formation of NiO NPs dominantly shaped by inert polar OH terminated (111) atomic planes, leading to loss of initial self-assembled 3D structure. DFT calculations support these observations, confirming that H2O adsorbs dissociatively on polar {111} surfaces, while only physisorption is energetically feasible on {100} surfaces. NiO NPs obtained by two different routes have overall different properties: carbamide derived NPs are 3 times larger (15.5 vs 5.4 nm), possess larger band gap (3.6 vs 3.2 eV), and more Ni deficient. The intensity ratio of the surface optical (SO) modes to the transversal and longitudinal optical modes is ~ 40 times higher in the NiO NPs obtained from β-Ni(OH)2 compared to Ni3(OH)4(NO3)2-derived NPs. SO phonon lifetime is an order of magnitude shorter in NiO obtained from β-Ni(OH)2, reflecting the much smaller NP size. The choice of the precursor defines the size, morphology, crystallographic surface orientations and band gap of the NiO NPs, with Ni deficiency providing pathways of utilizing them as p-type material, and allows precise nanoengineering of polar and neutral surfaces dominated NiO NPs, of exceptional importance to the use in catalysis.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":null,"pages":null},"PeriodicalIF":6.7,"publicationDate":"2024-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142276131","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Nanofiltration (NF) technologies have evolved into a stage ready for industrial commercialization. NF membranes with unique separation characteristics are widely used for ion selection in water environment. Although many materials have been synthesized and functionalized for specific ion separation, the permeability-selectivity trade-off is still a major challenge. Metal-organic frameworks (MOFs), as a class of promising materials to meet industrial demands, are gaining increasing attention. Many experimental and numerical studies have been conducted on the applications of MOF-based membranes in ion selection. This review focuses on MOF-based NF membranes for ion separation/selection from seawater and salt lake brines, including their applications in industry. First, a brief discussion on the development of membrane technology in ion selection is given, with the principles of ion separation via NF membranes, industrial implementations, and the technical difficulty being discussed. Then, the benefits and challenges using MOF membranes in NF processes are elaborated, including the basic properties of MOFs, approaches to fabricate MOF membranes for efficient ion selection and the challenges for constructing industrially viable membranes. Finally, the state-of-the-art studies on key characteristics of MOFs toward NF membranes are presented. It indicates that there is significant potential for the utilization of MOF-based membranes to improve the ion separation performance. However, the lack of sufficient data under industrial conditions highlights the need for further development in this area.
{"title":"Metal-Organic Framework-Based Ion Selection Membranes for Salt Lake Brines and Seawater","authors":"Lirong Li, Biyuan Liu, Zhigang Li","doi":"10.1039/d4nr02454k","DOIUrl":"https://doi.org/10.1039/d4nr02454k","url":null,"abstract":"Nanofiltration (NF) technologies have evolved into a stage ready for industrial commercialization. NF membranes with unique separation characteristics are widely used for ion selection in water environment. Although many materials have been synthesized and functionalized for specific ion separation, the permeability-selectivity trade-off is still a major challenge. Metal-organic frameworks (MOFs), as a class of promising materials to meet industrial demands, are gaining increasing attention. Many experimental and numerical studies have been conducted on the applications of MOF-based membranes in ion selection. This review focuses on MOF-based NF membranes for ion separation/selection from seawater and salt lake brines, including their applications in industry. First, a brief discussion on the development of membrane technology in ion selection is given, with the principles of ion separation via NF membranes, industrial implementations, and the technical difficulty being discussed. Then, the benefits and challenges using MOF membranes in NF processes are elaborated, including the basic properties of MOFs, approaches to fabricate MOF membranes for efficient ion selection and the challenges for constructing industrially viable membranes. Finally, the state-of-the-art studies on key characteristics of MOFs toward NF membranes are presented. It indicates that there is significant potential for the utilization of MOF-based membranes to improve the ion separation performance. However, the lack of sufficient data under industrial conditions highlights the need for further development in this area.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":null,"pages":null},"PeriodicalIF":6.7,"publicationDate":"2024-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142276126","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Two-dimensional multiferroic materials that exhibit both ferroelectricity and ferromagnetism provide a new platform for the discovery and regulation of magnetic skyrmions. In this study, we utilize first-principles calculations and Monte Carlo simulations to explore the properties and regulation of magnetic skyrmions in a novel multiferroic monolayer MnOBr. MnOBr exhibits skyrmions without the need for an external magnetic field. Upon applying an external magnetic field, we find the disappearance of Labyrinth Domains and the formation of a periodic arrangement Skyrmions Lattice. By employing machine learning techniques, we depict a phase diagram of MnOBr under varying magnetic fields and biaxial strain, which provides a detailed depiction of phase transitions of spin textures in monolayer MnOBr. Furthermore, in MnOBr/CdClBr heterostructures, we demonstrate that the creation and annihilation of magnetic skyrmions can be controlled by switching the polarization direction of the Janus CdClBr. These findings show potential applications of MnOBr as a 2D magnetic skyrmions materials in spintronic devices.
{"title":"Regulating magnetic skyrmions in multiferroic monolayer MnOBr","authors":"Cong Hou, Yibo Sun, Yuhang Lu, Zimo Li, Jun Ni","doi":"10.1039/d4nr02308k","DOIUrl":"https://doi.org/10.1039/d4nr02308k","url":null,"abstract":"Two-dimensional multiferroic materials that exhibit both ferroelectricity and ferromagnetism provide a new platform for the discovery and regulation of magnetic skyrmions. In this study, we utilize first-principles calculations and Monte Carlo simulations to explore the properties and regulation of magnetic skyrmions in a novel multiferroic monolayer MnOBr. MnOBr exhibits skyrmions without the need for an external magnetic field. Upon applying an external magnetic field, we find the disappearance of Labyrinth Domains and the formation of a periodic arrangement Skyrmions Lattice. By employing machine learning techniques, we depict a phase diagram of MnOBr under varying magnetic fields and biaxial strain, which provides a detailed depiction of phase transitions of spin textures in monolayer MnOBr. Furthermore, in MnOBr/CdClBr heterostructures, we demonstrate that the creation and annihilation of magnetic skyrmions can be controlled by switching the polarization direction of the Janus CdClBr. These findings show potential applications of MnOBr as a 2D magnetic skyrmions materials in spintronic devices.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":null,"pages":null},"PeriodicalIF":6.7,"publicationDate":"2024-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142276132","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Anubha Yadav, Netra Hiremath, Bhagirath Saini, Babasaheb Mansub Matsagar, Po Chun Han, Masaki Ujihara, M. H. Modi, Kevin C. W. Wu, Rakesh K Sharma, Raviraj Vankayala, Saikat Dutta
Installation of coordinately unsaturated FeNC structural units on polymer-composite derived N-doped carbon offers highly active FeNx sites for the electrochemical oxygen evolution reaction (OER) and reactive oxygen species (ROS) generation in tumor cells. An NH4Cl-driven high-temperature etching method offers the formation of Fe-SA950NC with coordinately unsaturated singleFeAtom in FeN(sp2)C structural unit along with N-vacancy (VN) and sp3 defects. The carbonization of Fe-phen@ZIF-8 at 800 C for 30 min under argon followed by grind Fe/ZIF-8@RF-Urea with NH4Cl at 950 C for 2 hours results sp3 carbon defect and VN site with a coordination unsaturation in FeNx by NH4Cl decomposition to NH3 and HCl, which produces substantial internal stress for etching the carbon matrix. Fe-SA950NC was used to treat both A549 lung cancer cells and NIH3T3 mouse fibroblast cells which determines the potential for efficient tumor therapeutic strategy via 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) and ROS assay. Additionally, Fe-SA950NC provides high stability and excellent OER activity through FeN(sp2)C structural unit on pyridinic nitrogen by delivering at a minimum of 210 mV which is much lower than structurally similar Fe-atom sites. Both significantly stronger ROS and OER activity of Fe-SA950NC suggest the role of VN and sp3-carbon defects with coordinately unsaturated FeN2 sites.
{"title":"Coordinately Unsaturated Single−Fe−Atom with N-Vacancy and Enhanced sp3 Carbon Defects in Fe−N(sp2)−C structural unit for Suppression of Cancer Cells Metabolism and Electrochemical Oxygen Evolution","authors":"Anubha Yadav, Netra Hiremath, Bhagirath Saini, Babasaheb Mansub Matsagar, Po Chun Han, Masaki Ujihara, M. H. Modi, Kevin C. W. Wu, Rakesh K Sharma, Raviraj Vankayala, Saikat Dutta","doi":"10.1039/d4nr02553a","DOIUrl":"https://doi.org/10.1039/d4nr02553a","url":null,"abstract":"Installation of coordinately unsaturated FeNC structural units on polymer-composite derived N-doped carbon offers highly active FeNx sites for the electrochemical oxygen evolution reaction (OER) and reactive oxygen species (ROS) generation in tumor cells. An NH4Cl-driven high-temperature etching method offers the formation of Fe-SA950NC with coordinately unsaturated singleFeAtom in FeN(sp2)C structural unit along with N-vacancy (VN) and sp3 defects. The carbonization of Fe-phen@ZIF-8 at 800 C for 30 min under argon followed by grind Fe/ZIF-8@RF-Urea with NH4Cl at 950 C for 2 hours results sp3 carbon defect and VN site with a coordination unsaturation in FeNx by NH4Cl decomposition to NH3 and HCl, which produces substantial internal stress for etching the carbon matrix. Fe-SA950NC was used to treat both A549 lung cancer cells and NIH3T3 mouse fibroblast cells which determines the potential for efficient tumor therapeutic strategy via 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) and ROS assay. Additionally, Fe-SA950NC provides high stability and excellent OER activity through FeN(sp2)C structural unit on pyridinic nitrogen by delivering at a minimum of 210 mV which is much lower than structurally similar Fe-atom sites. Both significantly stronger ROS and OER activity of Fe-SA950NC suggest the role of VN and sp3-carbon defects with coordinately unsaturated FeN2 sites.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":null,"pages":null},"PeriodicalIF":6.7,"publicationDate":"2024-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142276130","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Effective thermal management is essential for maintaining the operational stability and data security of magnetic devices across diverse fields, including thermoelectric, sensing, data storage, and spintronics. In this study, density functional theory calculations were conducted to explore the spin-induced modifications in the thermal properties of the H-phase monolayer VS₂, a two-dimensional (2D) semiconducting ferromagnet. Our investigation revealed that the 2D H-phase of VS2 exhibits a substantial thermal switching ratio, exceeding four at the Curie temperature, due to the coupling between magnetic order and lattice vibrations. This sensitivity arises from spin-dependent lattice anharmonicity, which results in a stiffening of the V-S bonds, thereby modifying the frequencies of different vibrational modes. Phonon-phonon interactions calculations indicated that phonon-magnon scattering was more predominant in the paramagnetic (PM) phase than in the ferromagnetic (FM) phase, which resulted in a reduced phonon lifetime, mean free path and group velocity. As a result, the lattice thermal conductivity was calculated to drop from 15.18 W/m/K in the ferromagnetic phase to 3.59 W/m/K in the paramagnetic phase. By elucidating heat transport in two-dimensional ferromagnets, our study offers valuable insights for manipulating and converting thermal energy.
{"title":"Unveiling Magnetic Transition-Driven Thermal Conductivity Switching in Semiconducting Monolayer VS2","authors":"Zimmi Singh, Abhishek Kumar, Sankha Mukherjee","doi":"10.1039/d4nr02375g","DOIUrl":"https://doi.org/10.1039/d4nr02375g","url":null,"abstract":"Effective thermal management is essential for maintaining the operational stability and data security of magnetic devices across diverse fields, including thermoelectric, sensing, data storage, and spintronics. In this study, density functional theory calculations were conducted to explore the spin-induced modifications in the thermal properties of the H-phase monolayer VS₂, a two-dimensional (2D) semiconducting ferromagnet. Our investigation revealed that the 2D H-phase of VS2 exhibits a substantial thermal switching ratio, exceeding four at the Curie temperature, due to the coupling between magnetic order and lattice vibrations. This sensitivity arises from spin-dependent lattice anharmonicity, which results in a stiffening of the V-S bonds, thereby modifying the frequencies of different vibrational modes. Phonon-phonon interactions calculations indicated that phonon-magnon scattering was more predominant in the paramagnetic (PM) phase than in the ferromagnetic (FM) phase, which resulted in a reduced phonon lifetime, mean free path and group velocity. As a result, the lattice thermal conductivity was calculated to drop from 15.18 W/m/K in the ferromagnetic phase to 3.59 W/m/K in the paramagnetic phase. By elucidating heat transport in two-dimensional ferromagnets, our study offers valuable insights for manipulating and converting thermal energy.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":null,"pages":null},"PeriodicalIF":6.7,"publicationDate":"2024-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142276127","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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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