V. Vetokhina, N. Nepomniashchaia, E. de Prado, O. Pacherova, T. Kocourek, S. S. Anandakrishnan, Y. Bai, A. Dejneka and M. Tyunina
The ability to tailor the electronic band structure and optical absorption by appropriate cationic substitution in perovskite oxide ferroelectrics is essential for many advanced electronic and optoelectronic applications of these materials. Here, we explored weak (Ba,Ni)-doping for reducing optical bandgaps in (K,Na)NbO3 ferroelectric films and ceramics. The optical absorption in the broad spectral range of (0.7–8.8) eV was investigated in polycrystalline doped, pure, and oxygen deficient films, in doped epitaxial films grown on different substrates, and in doped ceramics. By comparing optical properties of all films and ceramics, it was established that 1–2 at% of cationic substitutions or up to 10 at % of oxygen vacancies have no detectable effect on the direct (∼4.5 eV) and indirect (∼3.9 eV) gaps. Concurrently, substantial sub-gap absorption was revealed and ascribed to structural band tailing in epitaxial films and ceramics. It was suggested that owing to fundamental strain-property couplings in perovskite oxide ferroelectrics, inhomogeneities of lattice strain can lead to increased sub-gap absorption. The uncovered structurally induced sub-gap optical absorption can be relevant for other ferroelectric ceramics and thin films as well as for related perovskite oxides.
{"title":"Tuning optical absorption in perovskite (K,Na)NbO3 ferroelectrics†","authors":"V. Vetokhina, N. Nepomniashchaia, E. de Prado, O. Pacherova, T. Kocourek, S. S. Anandakrishnan, Y. Bai, A. Dejneka and M. Tyunina","doi":"10.1039/D4MA00396A","DOIUrl":"10.1039/D4MA00396A","url":null,"abstract":"<p >The ability to tailor the electronic band structure and optical absorption by appropriate cationic substitution in perovskite oxide ferroelectrics is essential for many advanced electronic and optoelectronic applications of these materials. Here, we explored weak (Ba,Ni)-doping for reducing optical bandgaps in (K,Na)NbO<small><sub>3</sub></small> ferroelectric films and ceramics. The optical absorption in the broad spectral range of (0.7–8.8) eV was investigated in polycrystalline doped, pure, and oxygen deficient films, in doped epitaxial films grown on different substrates, and in doped ceramics. By comparing optical properties of all films and ceramics, it was established that 1–2 at% of cationic substitutions or up to 10 at % of oxygen vacancies have no detectable effect on the direct (∼4.5 eV) and indirect (∼3.9 eV) gaps. Concurrently, substantial sub-gap absorption was revealed and ascribed to structural band tailing in epitaxial films and ceramics. It was suggested that owing to fundamental strain-property couplings in perovskite oxide ferroelectrics, inhomogeneities of lattice strain can lead to increased sub-gap absorption. The uncovered structurally induced sub-gap optical absorption can be relevant for other ferroelectric ceramics and thin films as well as for related perovskite oxides.</p>","PeriodicalId":18242,"journal":{"name":"Materials Advances","volume":null,"pages":null},"PeriodicalIF":5.2,"publicationDate":"2024-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11492214/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142503326","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}
Farrel Dzaudan Naufal, Hasna Afifah, Marleni Wirmas, Mohammad Kemal Agusta, Adhitya Gandaryus Saputro, Hadi Teguh Yudistira, Aleksandar Staykov, Kazunari Yoshizawa and Muhammad Haris Mahyuddin
The direct conversion of methane to methanol has attracted increasing interests, owing to the necessity for an abundant low-carbon source of energy. However, numerous challenges are encountered in attaining a high conversion rate and selectivity using the existing approach and catalysts. One of them is the need for a reaction halt and a reactivation of the catalyst using an oxidant at high temperature, which makes the whole process non-cyclic. In this study, we employ density functional theory calculations to evaluate rutile-type IrO2(110), β-PtO2(110), and β-MnO2(110) surfaces not only for cleaving the H–CH3 bond but also for forming methanol. We find that IrO2(110) and β-PtO2(110) thermodynamically and kinetically favor the C–H activation on the bridging μO-atom terminations via a heterolytic pathway. However, the formation of strong Ir–C and Pt–C bonds, which initially help the C–H bond scission, hinders the methanol formation. In the β-MnO2(110) case, in contrast, the Mn–C interaction is quite weak, and the Mn(μ-O)Mn active site is electrophilic, thus allowing the formation of a stable ˙CH3 radical intermediate state that becomes the driving force for a low-barrier homolytic C–H bond scission as well as a low-barrier and highly exothermic formation of methanol. This first cycle of methane oxidation results in a reduced β-MnO2(110) surface, where no more μ-O active sites are available for the subsequent cycles of methane activation. Nonetheless, this reduced surface can also oxidize methane to methanol when the H2O2 oxidant is inserted in the mid-way reaction and forms new active sites of μ-OH. The second reaction is also highly exothermic although the C–H activation barrier is not as low as that for the fresh stoichiometric surface. This study suggests the β-MnO2(110) surface as a potential catalyst for the cyclic oxidation of methane to methanol using the H2O2 oxidant without halting for reactivation.
{"title":"Rutile-type metal dioxide (110) surfaces for the cyclic oxidation of methane to methanol†","authors":"Farrel Dzaudan Naufal, Hasna Afifah, Marleni Wirmas, Mohammad Kemal Agusta, Adhitya Gandaryus Saputro, Hadi Teguh Yudistira, Aleksandar Staykov, Kazunari Yoshizawa and Muhammad Haris Mahyuddin","doi":"10.1039/D4MA00827H","DOIUrl":"https://doi.org/10.1039/D4MA00827H","url":null,"abstract":"<p >The direct conversion of methane to methanol has attracted increasing interests, owing to the necessity for an abundant low-carbon source of energy. However, numerous challenges are encountered in attaining a high conversion rate and selectivity using the existing approach and catalysts. One of them is the need for a reaction halt and a reactivation of the catalyst using an oxidant at high temperature, which makes the whole process non-cyclic. In this study, we employ density functional theory calculations to evaluate rutile-type IrO<small><sub>2</sub></small>(110), β-PtO<small><sub>2</sub></small>(110), and β-MnO<small><sub>2</sub></small>(110) surfaces not only for cleaving the H–CH<small><sub>3</sub></small> bond but also for forming methanol. We find that IrO<small><sub>2</sub></small>(110) and β-PtO<small><sub>2</sub></small>(110) thermodynamically and kinetically favor the C–H activation on the bridging μO-atom terminations <em>via</em> a heterolytic pathway. However, the formation of strong Ir–C and Pt–C bonds, which initially help the C–H bond scission, hinders the methanol formation. In the β-MnO<small><sub>2</sub></small>(110) case, in contrast, the Mn–C interaction is quite weak, and the Mn(μ-O)Mn active site is electrophilic, thus allowing the formation of a stable ˙CH<small><sub>3</sub></small> radical intermediate state that becomes the driving force for a low-barrier homolytic C–H bond scission as well as a low-barrier and highly exothermic formation of methanol. This first cycle of methane oxidation results in a reduced β-MnO<small><sub>2</sub></small>(110) surface, where no more μ-O active sites are available for the subsequent cycles of methane activation. Nonetheless, this reduced surface can also oxidize methane to methanol when the H<small><sub>2</sub></small>O<small><sub>2</sub></small> oxidant is inserted in the mid-way reaction and forms new active sites of μ-OH. The second reaction is also highly exothermic although the C–H activation barrier is not as low as that for the fresh stoichiometric surface. This study suggests the β-MnO<small><sub>2</sub></small>(110) surface as a potential catalyst for the cyclic oxidation of methane to methanol using the H<small><sub>2</sub></small>O<small><sub>2</sub></small> oxidant without halting for reactivation.</p>","PeriodicalId":18242,"journal":{"name":"Materials Advances","volume":null,"pages":null},"PeriodicalIF":5.2,"publicationDate":"2024-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ma/d4ma00827h?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142598761","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}
Md Habibur Rahman, Yujie Sun and Arun Mannodi-Kanakkithodi
In recent years, ZnIn2S4 (ZIS) has garnered attention as a promising photocatalyst due to its attractive properties. However, its performance is hindered by its restricted range of visible light absorption and the rapid recombination of photoinduced holes and electrons. Single-atom co-catalysts (SACs) can improve photocatalytic activity by providing highly active sites for reactions, enhancing charge separation efficiency, and reducing the recombination rate of photo-generated carriers. In this work, we perform high-throughput density functional theory (DFT) computations to search for SACs in ZIS encompassing 3d, 4d, and 5d transition metals as well as lanthanides, considering both substitutional and interstitial sites. For a total of 172 SACs, defect formation energy (DFE) is computed as a function of chemical potential, charge, and Fermi level (EF), leading to the identification of low energy dopants and their corresponding shallow or deep defect levels. Statistical data analysis shows that DFE is highly correlated with the difference in electron affinity between the host (Zn/In/S) atom and the SAC, followed by the electronegativity and boiling point. Among the 60 lowest energy SACs, CoIn, Ybi, TcZn, AuS, Lai, Eui, Aui, TaIn, HfIn, ZrIn, and NiZn lead to a lowering of the Gibbs free energy for hydrogen evolution reaction, improving upon previous ZIS results. The computational dataset and insights from this work promise to accelerate the experimental design of novel dopants in ZIS with optimized properties for photocatalysis and environmental remediation.
{"title":"High-throughput screening of single atom co-catalysts in ZnIn2S4 for photocatalysis†","authors":"Md Habibur Rahman, Yujie Sun and Arun Mannodi-Kanakkithodi","doi":"10.1039/D4MA00616J","DOIUrl":"https://doi.org/10.1039/D4MA00616J","url":null,"abstract":"<p >In recent years, ZnIn<small><sub>2</sub></small>S<small><sub>4</sub></small> (ZIS) has garnered attention as a promising photocatalyst due to its attractive properties. However, its performance is hindered by its restricted range of visible light absorption and the rapid recombination of photoinduced holes and electrons. Single-atom co-catalysts (SACs) can improve photocatalytic activity by providing highly active sites for reactions, enhancing charge separation efficiency, and reducing the recombination rate of photo-generated carriers. In this work, we perform high-throughput density functional theory (DFT) computations to search for SACs in ZIS encompassing 3d, 4d, and 5d transition metals as well as lanthanides, considering both substitutional and interstitial sites. For a total of 172 SACs, defect formation energy (DFE) is computed as a function of chemical potential, charge, and Fermi level (<em>E</em><small><sub>F</sub></small>), leading to the identification of low energy dopants and their corresponding shallow or deep defect levels. Statistical data analysis shows that DFE is highly correlated with the difference in electron affinity between the host (Zn/In/S) atom and the SAC, followed by the electronegativity and boiling point. Among the 60 lowest energy SACs, Co<small><sub>In</sub></small>, Yb<small><sub>i</sub></small>, Tc<small><sub>Zn</sub></small>, Au<small><sub>S</sub></small>, La<small><sub>i</sub></small>, Eu<small><sub>i</sub></small>, Au<small><sub>i</sub></small>, Ta<small><sub>In</sub></small>, Hf<small><sub>In</sub></small>, Zr<small><sub>In</sub></small>, and Ni<small><sub>Zn</sub></small> lead to a lowering of the Gibbs free energy for hydrogen evolution reaction, improving upon previous ZIS results. The computational dataset and insights from this work promise to accelerate the experimental design of novel dopants in ZIS with optimized properties for photocatalysis and environmental remediation.</p>","PeriodicalId":18242,"journal":{"name":"Materials Advances","volume":null,"pages":null},"PeriodicalIF":5.2,"publicationDate":"2024-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ma/d4ma00616j?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142524278","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}
Bone defects represent a significant clinical challenge, traditionally addressed primarily through scaffold-based repair strategies. However, recent studies have revealed that relying solely on scaffolds may not fully overcome the bottlenecks in bone defect repair. Mounting evidence suggests that modulating the inflammatory response plays a crucial role in the bone healing process. While moderate inflammation can promote bone tissue regeneration, excessive or prolonged inflammatory responses may impede the repair process. Our previously developed calcium silicate (CS) scaffold, known to stimulate osteoblast proliferation and accelerate bone tissue formation, was enhanced with magnesium–strontium to boost cellular biological activity and foster bone formation and angiogenesis. In this study, the effects of 3D-printed CS scaffolds reinforced with astragalus (Ast) on inflammation regulation and osteogenic gene expression were examined. X-ray diffraction and Fourier transform infrared spectroscopy confirmed that the Ast phase structure and chemical functional groups were added to the materials. The findings revealed that integrating Ast improves scaffold biocompatibility, bioactivity, and bone and vascular tissue formation efficacy, enhances mechanical strength, and decelerates biodegradation. The 5% Ast-containing CS scaffold exhibited superior capabilities in promoting cell proliferation and differentiation, indicative of effective bone regeneration. Moreover, analysis of hMSC-seeded AstCS scaffold supernatants revealed significantly reduced levels of pro-inflammatory cytokines IL-1β and IL-6, coupled with elevated expression of the anti-inflammatory factor IL-1RA. These results suggest that Astragalus incorporation effectively modulates inflammatory signaling in the scaffold microenvironment. Transcriptome RNA sequencing revealed that this scaffold modulated multiple signaling pathways crucial for bone regeneration, such as WNT, AKT, and PI3K, and significantly influenced genes associated with cellular bone regeneration, angiogenesis, and immune responses. These results highlight the potential of combining Ast with CS in 3D-printed scaffolds for bone tissue engineering, offering new strategies for employing natural pharmaceutical ingredients as bioactivity enhancers and providing a substantial foundation for designing future bone regeneration materials with immune-modulating capabilities.
{"title":"Synergistic effects of astragalus on 3D-printed calcium silicate/poly-ε-caprolactone scaffolds to regulate inflammation/osteogenesis for bone regeneration","authors":"Jian-Jr Lee, Yen-Hong Lin, Ting-You Kuo, Alvin Kai-Xing Lee, Cheng-Yu Chen and Ming-You Shie","doi":"10.1039/D4MA00531G","DOIUrl":"https://doi.org/10.1039/D4MA00531G","url":null,"abstract":"<p >Bone defects represent a significant clinical challenge, traditionally addressed primarily through scaffold-based repair strategies. However, recent studies have revealed that relying solely on scaffolds may not fully overcome the bottlenecks in bone defect repair. Mounting evidence suggests that modulating the inflammatory response plays a crucial role in the bone healing process. While moderate inflammation can promote bone tissue regeneration, excessive or prolonged inflammatory responses may impede the repair process. Our previously developed calcium silicate (CS) scaffold, known to stimulate osteoblast proliferation and accelerate bone tissue formation, was enhanced with magnesium–strontium to boost cellular biological activity and foster bone formation and angiogenesis. In this study, the effects of 3D-printed CS scaffolds reinforced with astragalus (Ast) on inflammation regulation and osteogenic gene expression were examined. X-ray diffraction and Fourier transform infrared spectroscopy confirmed that the Ast phase structure and chemical functional groups were added to the materials. The findings revealed that integrating Ast improves scaffold biocompatibility, bioactivity, and bone and vascular tissue formation efficacy, enhances mechanical strength, and decelerates biodegradation. The 5% Ast-containing CS scaffold exhibited superior capabilities in promoting cell proliferation and differentiation, indicative of effective bone regeneration. Moreover, analysis of hMSC-seeded AstCS scaffold supernatants revealed significantly reduced levels of pro-inflammatory cytokines IL-1β and IL-6, coupled with elevated expression of the anti-inflammatory factor IL-1RA. These results suggest that Astragalus incorporation effectively modulates inflammatory signaling in the scaffold microenvironment. Transcriptome RNA sequencing revealed that this scaffold modulated multiple signaling pathways crucial for bone regeneration, such as <em>WNT</em>, <em>AKT</em>, and <em>PI3K</em>, and significantly influenced genes associated with cellular bone regeneration, angiogenesis, and immune responses. These results highlight the potential of combining Ast with CS in 3D-printed scaffolds for bone tissue engineering, offering new strategies for employing natural pharmaceutical ingredients as bioactivity enhancers and providing a substantial foundation for designing future bone regeneration materials with immune-modulating capabilities.</p>","PeriodicalId":18242,"journal":{"name":"Materials Advances","volume":null,"pages":null},"PeriodicalIF":5.2,"publicationDate":"2024-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ma/d4ma00531g?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142598740","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}
Kousumi Mukherjee, Denise Kreugel, Nga Phung, Cristian van Helvoirt, Valerio Zardetto and Mariadriana Creatore
Recent reports have shown that nickel oxide (NiO) when adopted as a hole transport layer (HTL) in combination with organic layers, such as PTAA or self-assembled monolayers (SAMs), leads to a higher device yield for both single junction as well as tandem devices. Nevertheless, implementing NiO in devices without PTAA or SAM is seldom reported to lead to high-performance devices. In this work, we assess the effect of key NiO properties deemed relevant in literature, namely- resistivity and surface energy, on the device performance and systematically compare the NiO-based devices with those based on PTAA. To this purpose, (thermal) atomic layer deposited (ALD) NiO (NiOBu-MeAMD), Al-doped NiO (Al:NiOBu-MeAMD), and plasma-assisted ALD NiO (NiOMeCp) films, characterized by a wide range of resistivity, are investigated. Although Al:NiOBu-MeAMD (∼400 Ω cm) and NiOMeCp(∼80 Ωcm) films have a lower resistivity than NiOBu-MeAMD (∼10 kΩ cm), the Al:NiOBu-MeAMD and NiOMeCp-based devices are found to have a modest open circuit voltage (VOC) gain of ∼30 mV compared to NiOBu-MeAMD-based devices. Overall, the best-performing NiO-based devices (∼14.8% power conversion efficiency (PCE)) still lag behind the PTAA-based devices (∼17.5%), primarily due to a VOC loss of ∼100 mV. Further investigation based on light intensity analysis of the VOC and FF and the decrease in VOC compared to the quasi-Fermi level splitting (QFLS) indicates that the VOC is limited by trap-assisted recombination at the NiO/perovskite interface. Additionally, SCAPS simulations show that the presence of a high interfacial trap density leads to a VOC loss in NiO-based devices. Upon passivation of the NiO/perovskite interface with Me-4PACz, the VOC increases by 170–200 mV and is similar for NiOBu-MeAMD and Al:NiOBu-MeAMD, leading to the conclusion that there is no influence of the NiO resistivity on the VOC once interface passivation is realized. Finally, our work highlights the necessity of comparing NiO-based devices with state-of-the-art HTL-based devices to draw conclusion about the influence of specific material properties on device performance.
{"title":"On the VOC loss in NiO-based inverted metal halide perovskite solar cells†","authors":"Kousumi Mukherjee, Denise Kreugel, Nga Phung, Cristian van Helvoirt, Valerio Zardetto and Mariadriana Creatore","doi":"10.1039/D4MA00873A","DOIUrl":"10.1039/D4MA00873A","url":null,"abstract":"<p >Recent reports have shown that nickel oxide (NiO) when adopted as a hole transport layer (HTL) in combination with organic layers, such as PTAA or self-assembled monolayers (SAMs), leads to a higher device yield for both single junction as well as tandem devices. Nevertheless, implementing NiO in devices without PTAA or SAM is seldom reported to lead to high-performance devices. In this work, we assess the effect of key NiO properties deemed relevant in literature, namely- resistivity and surface energy, on the device performance and systematically compare the NiO-based devices with those based on PTAA. To this purpose, (thermal) atomic layer deposited (ALD) NiO (NiO<small><sub>Bu-MeAMD</sub></small>), Al-doped NiO (Al:NiO<small><sub>Bu-MeAMD</sub></small>), and plasma-assisted ALD NiO (NiO<small><sub>MeCp</sub></small>) films, characterized by a wide range of resistivity, are investigated. Although Al:NiO<small><sub>Bu-MeAMD</sub></small> (∼400 Ω cm) and NiO<small><sub>MeCp</sub></small>(∼80 Ωcm) films have a lower resistivity than NiO<small><sub>Bu-MeAMD</sub></small> (∼10 kΩ cm), the Al:NiO<small><sub>Bu-MeAMD</sub></small> and NiO<small><sub>MeCp</sub></small>-based devices are found to have a modest open circuit voltage (<em>V</em><small><sub>OC</sub></small>) gain of ∼30 mV compared to NiO<small><sub>Bu-MeAMD</sub></small>-based devices. Overall, the best-performing NiO-based devices (∼14.8% power conversion efficiency (PCE)) still lag behind the PTAA-based devices (∼17.5%), primarily due to a <em>V</em><small><sub>OC</sub></small> loss of ∼100 mV. Further investigation based on light intensity analysis of the <em>V</em><small><sub>OC</sub></small> and FF and the decrease in <em>V</em><small><sub>OC</sub></small> compared to the quasi-Fermi level splitting (QFLS) indicates that the <em>V</em><small><sub>OC</sub></small> is limited by trap-assisted recombination at the NiO/perovskite interface. Additionally, SCAPS simulations show that the presence of a high interfacial trap density leads to a <em>V</em><small><sub>OC</sub></small> loss in NiO-based devices. Upon passivation of the NiO/perovskite interface with Me-4PACz, the <em>V</em><small><sub>OC</sub></small> increases by 170–200 mV and is similar for NiO<small><sub>Bu-MeAMD</sub></small> and Al:NiO<small><sub>Bu-MeAMD</sub></small>, leading to the conclusion that there is no influence of the NiO resistivity on the <em>V</em><small><sub>OC</sub></small> once interface passivation is realized. Finally, our work highlights the necessity of comparing NiO-based devices with state-of-the-art HTL-based devices to draw conclusion about the influence of specific material properties on device performance.</p>","PeriodicalId":18242,"journal":{"name":"Materials Advances","volume":null,"pages":null},"PeriodicalIF":5.2,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11472218/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142469171","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}
Olga Lem, Roosa Kekki, Artturi Koivuniemi, Alexander Efimov, Timo Laaksonen and Nikita Durandin
Reactive oxygen species (ROS)-mediated photooxidation is an efficient method for triggering a drug release from liposomes. In addition to the release of small molecules, it also allows the release of large macromolecules, making it a versatile tool for controlled drug delivery. However, the exact release mechanism of large macromolecules from ROS-sensitive liposomes is still unclear. There are no studies on the effect of lipid oxidation on the release of cargo molecules of different sizes. By using HPLC-HRMS method we analyzed the oxidation products of ROS-sensitive DOTAP lipid in phthalocyanine-loaded DOTAP:Cholesterol:DSPE-PEG liposomes after 630 nm light irradiation of different durations. Shorter illumination time (1–2 minutes) led to the formation of hydroperoxides and vic-alcohols predominantly. Longer 9-minute irradiation resulted already in aldehydes generation. Interestingly, the presence of epoxides/mono-hydroperoxides and vic-alcohols in a lipid bilayer ensured a high 90% release of small hydrophilic cargo molecules i.e. calcein, but not large (≥10 KDa) macromolecules. Oxidation till aldehydes was mandatory to deliver e.g. dextrans of 10–70 kDa with ca. 30% efficiency. Molecular dynamics simulations revealed that the formation of aldehydes is required to form pores or even fully disrupt the lipid membrane, while e.g. presence of hydroperoxides is enough to make the bilayer more permeable just for water and small molecules. This is an important finding that shed a light on the release mechanism of different cargo molecules from ROS-sensitive drug delivery systems.
{"title":"The role of lipid oxidation pathway in reactive oxygen species-mediated cargo release from liposomes†","authors":"Olga Lem, Roosa Kekki, Artturi Koivuniemi, Alexander Efimov, Timo Laaksonen and Nikita Durandin","doi":"10.1039/D4MA00535J","DOIUrl":"10.1039/D4MA00535J","url":null,"abstract":"<p >Reactive oxygen species (ROS)-mediated photooxidation is an efficient method for triggering a drug release from liposomes. In addition to the release of small molecules, it also allows the release of large macromolecules, making it a versatile tool for controlled drug delivery. However, the exact release mechanism of large macromolecules from ROS-sensitive liposomes is still unclear. There are no studies on the effect of lipid oxidation on the release of cargo molecules of different sizes. By using HPLC-HRMS method we analyzed the oxidation products of ROS-sensitive DOTAP lipid in phthalocyanine-loaded DOTAP:Cholesterol:DSPE-PEG liposomes after 630 nm light irradiation of different durations. Shorter illumination time (1–2 minutes) led to the formation of hydroperoxides and vic-alcohols predominantly. Longer 9-minute irradiation resulted already in aldehydes generation. Interestingly, the presence of epoxides/mono-hydroperoxides and vic-alcohols in a lipid bilayer ensured a high 90% release of small hydrophilic cargo molecules <em>i.e.</em> calcein, but not large (≥10 KDa) macromolecules. Oxidation till aldehydes was mandatory to deliver <em>e.g.</em> dextrans of 10–70 kDa with <em>ca.</em> 30% efficiency. Molecular dynamics simulations revealed that the formation of aldehydes is required to form pores or even fully disrupt the lipid membrane, while <em>e.g.</em> presence of hydroperoxides is enough to make the bilayer more permeable just for water and small molecules. This is an important finding that shed a light on the release mechanism of different cargo molecules from ROS-sensitive drug delivery systems.</p>","PeriodicalId":18242,"journal":{"name":"Materials Advances","volume":null,"pages":null},"PeriodicalIF":5.2,"publicationDate":"2024-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11491990/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142516502","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}
Kazuki Tabaru, Kanji Okada, Tatsuki Nagata, Takeyuki Suzuki, Hiromitsu Sogawa, Fumio Sanda, Takeshi Watanabe and Yasuhi Obora
We immobilised colloidal palladium nanoparticles on poly(N-vinylacetamide). The polymer and the immobilised Pd NPs were characterised with characterisation methods such as transmission electron microscopy, dynamic light scattering, thermogravimetric analysis, Fourier-transform infrared spectroscopy, X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy. Finally, we tested catalytic applications under Suzuki–Miyaura cross-coupling reaction conditions.
我们将胶体钯纳米粒子固定在聚乙烯乙酰胺上。我们采用透射电子显微镜、动态光散射、热重分析、傅立叶变换红外光谱、X 射线吸收光谱和 X 射线光电子能谱等表征方法对聚合物和固定化钯纳米粒子进行了表征。最后,我们测试了在铃木-宫浦交叉偶联反应条件下的催化应用。
{"title":"Synthesis of colloidal Pd nanoparticles immobilised on poly(N-vinylacetamide): characterisation and application in catalysis†","authors":"Kazuki Tabaru, Kanji Okada, Tatsuki Nagata, Takeyuki Suzuki, Hiromitsu Sogawa, Fumio Sanda, Takeshi Watanabe and Yasuhi Obora","doi":"10.1039/D4MA00674G","DOIUrl":"https://doi.org/10.1039/D4MA00674G","url":null,"abstract":"<p >We immobilised colloidal palladium nanoparticles on poly(<em>N</em>-vinylacetamide). The polymer and the immobilised Pd NPs were characterised with characterisation methods such as transmission electron microscopy, dynamic light scattering, thermogravimetric analysis, Fourier-transform infrared spectroscopy, X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy. Finally, we tested catalytic applications under Suzuki–Miyaura cross-coupling reaction conditions.</p>","PeriodicalId":18242,"journal":{"name":"Materials Advances","volume":null,"pages":null},"PeriodicalIF":5.2,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ma/d4ma00674g?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142524361","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}
James P. Warren, Ruth H. Coe, Matthew P. Culbert, Andrew R. Dixon, Danielle E. Miles, Marlène Mengoni, Paul A. Beales and Ruth K. Wilcox
We report the development of peptide-glycosaminoglycan hydrogels as injectable biomaterials for load-bearing soft tissue repair. The hydrogels are injectable as a liquid for clinical delivery, rapidly form a gel in situ, and mimic the osmotic swelling behaviour of natural tissue. We used a new in vitro model to demonstrate their application as a nucleus augmentation material for the treatment of intervertebral disc degeneration. Our study compared a complex lab gel preparation method to a simple clinical benchtop process. We showed pH differences did not significantly affect gel formation, and temperature variations had no impact on gel performance. Rheological results demonstrated consistency after benchtop mixing or needle injection. In our in vitro disc degeneration model, we established that peptide augmentation could restore the native biomechanical properties. This suggests the feasibility of minimally invasive peptide-GAG gel delivery, maintaining consistent properties across temperature and needle sizes while restoring disc height and stiffness in vitro.
{"title":"Injectable peptide-glycosaminoglycan hydrogels for soft tissue repair: in vitro assessment for nucleus augmentation†","authors":"James P. Warren, Ruth H. Coe, Matthew P. Culbert, Andrew R. Dixon, Danielle E. Miles, Marlène Mengoni, Paul A. Beales and Ruth K. Wilcox","doi":"10.1039/D4MA00613E","DOIUrl":"10.1039/D4MA00613E","url":null,"abstract":"<p >We report the development of peptide-glycosaminoglycan hydrogels as injectable biomaterials for load-bearing soft tissue repair. The hydrogels are injectable as a liquid for clinical delivery, rapidly form a gel <em>in situ</em>, and mimic the osmotic swelling behaviour of natural tissue. We used a new <em>in vitro</em> model to demonstrate their application as a nucleus augmentation material for the treatment of intervertebral disc degeneration. Our study compared a complex lab gel preparation method to a simple clinical benchtop process. We showed pH differences did not significantly affect gel formation, and temperature variations had no impact on gel performance. Rheological results demonstrated consistency after benchtop mixing or needle injection. In our <em>in vitro</em> disc degeneration model, we established that peptide augmentation could restore the native biomechanical properties. This suggests the feasibility of minimally invasive peptide-GAG gel delivery, maintaining consistent properties across temperature and needle sizes while restoring disc height and stiffness <em>in vitro</em>.</p>","PeriodicalId":18242,"journal":{"name":"Materials Advances","volume":null,"pages":null},"PeriodicalIF":5.2,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11474259/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142469170","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}
Collins Onyango, Wilfrida Nyairo, Bowa Kwach, Victor Shikuku, Tome Sylvain, Hermann Dzoujo Tamaguelon and Claus Rüscher
In this study, four geopolymer composites, GP-0, GP-10, GP-20 and GP-30, were synthesized from pumice, an abundant and inexpensive volcanic rock precursor, substituted with fractions of 0, 10, 20 and 30% by weight of medical waste incinerator fly ash (MWI-FA), respectively. The materials were characterized by standard methods (FTIR, XRF, BET surface area measurement, XRD, SEM-EDX and TGA). The materials were morphologically distinct and the specific surface areas (SSA) decreased with an increase in MWI-FA fraction. The adsorption performances of the geocomposites were evaluated in batch mode for the removal of methylene blue (MB), a toxic dye, from water. The study determined that the dye was optimally removed at circumneutral pH, 303 K temperature, 0.6 g/40 mL adsorbent dosage and 30 min contact time. The equilibrium data were best described using the Sips isotherm model. The geopolymers had ∼30 times higher adsorption capacities than pristine pumice. The maximum adsorption capacities of the geopolymers, ∼31 mg g−1, were indistinguishable despite an increase in MWI-FA indicating that MWI-FA provided new energetically favorable adsorption sites compensating diminished SSA. The adsorption kinetics was best described using the pseudo-second order kinetic model wherein the rate constant (K2) increased with the MWI-FA fraction suggesting porosity structures with reduced tortuosity. Thermodynamically, the adsorption process was exothermic (ΔH < 0), physical (ΔH and Ea < 40 kJ mol−1) spontaneous (ΔG < 0) and enthalpy-driven. Adsorption diminished in a saline environment. The exhausted adsorbent was recoverable and recycled twice using hot water before significant loss of adsorption potential. The composite geopolymers present a plausible strategy for stabilization of up to 30% MWI-FA without compromising the adsorptive properties for dye removal from water.
{"title":"Synthesis of pumice and medical waste incinerator fly ash based phosphate geopolymers for methylene blue dye adsorption: co-valorization, parameters and mechanism†","authors":"Collins Onyango, Wilfrida Nyairo, Bowa Kwach, Victor Shikuku, Tome Sylvain, Hermann Dzoujo Tamaguelon and Claus Rüscher","doi":"10.1039/D4MA00779D","DOIUrl":"https://doi.org/10.1039/D4MA00779D","url":null,"abstract":"<p >In this study, four geopolymer composites, GP-0, GP-10, GP-20 and GP-30, were synthesized from pumice, an abundant and inexpensive volcanic rock precursor, substituted with fractions of 0, 10, 20 and 30% by weight of medical waste incinerator fly ash (MWI-FA), respectively. The materials were characterized by standard methods (FTIR, XRF, BET surface area measurement, XRD, SEM-EDX and TGA). The materials were morphologically distinct and the specific surface areas (SSA) decreased with an increase in MWI-FA fraction. The adsorption performances of the geocomposites were evaluated in batch mode for the removal of methylene blue (MB), a toxic dye, from water. The study determined that the dye was optimally removed at circumneutral pH, 303 K temperature, 0.6 g/40 mL adsorbent dosage and 30 min contact time. The equilibrium data were best described using the Sips isotherm model. The geopolymers had ∼30 times higher adsorption capacities than pristine pumice. The maximum adsorption capacities of the geopolymers, ∼31 mg g<small><sup>−1</sup></small>, were indistinguishable despite an increase in MWI-FA indicating that MWI-FA provided new energetically favorable adsorption sites compensating diminished SSA. The adsorption kinetics was best described using the pseudo-second order kinetic model wherein the rate constant (<em>K</em><small><sub>2</sub></small>) increased with the MWI-FA fraction suggesting porosity structures with reduced tortuosity. Thermodynamically, the adsorption process was exothermic (Δ<em>H</em> < 0), physical (Δ<em>H</em> and <em>E</em><small><sub>a</sub></small> < 40 kJ mol<small><sup>−1</sup></small>) spontaneous (Δ<em>G</em> < 0) and enthalpy-driven. Adsorption diminished in a saline environment. The exhausted adsorbent was recoverable and recycled twice using hot water before significant loss of adsorption potential. The composite geopolymers present a plausible strategy for stabilization of up to 30% MWI-FA without compromising the adsorptive properties for dye removal from water.</p>","PeriodicalId":18242,"journal":{"name":"Materials Advances","volume":null,"pages":null},"PeriodicalIF":5.2,"publicationDate":"2024-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ma/d4ma00779d?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142524255","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}
Li Sun, Xiaochun Li, Constance Vandenbulcke, Nour El Islam Belmouri, Guillaume Bouchez, Koen Robeyns, Aurelian Rotaru, Kamel Boukheddaden and Yann Garcia
Structurally characterized porous spin crossover compounds are attractive types of materials due to their properties that can be regulated under several stimuli, resulting in drastic changes in their optical, electrical, and magnetic responses, leading to potential applications in chemical sensing, memory devices, actuators, etc. In this work, a new 3D FeII spin crossover porous coordination polymer, [Fe(tpe)2dca]ClO4·5CHCl3·3CH3OH (1, tpe = trans-1,2-bis(4-pyridyl)ethene; dca = N(CN)2−), which accommodates guest molecules in its cavities to modulate its magnetic and optical properties, was prepared. 1 was characterized by X-ray diffraction in its fully solvated form by flash cooling single crystals at 100 K, thermogravimetric analysis, elemental analysis and its spin crossover tracked by magnetic susceptibility, and studied by differential scanning calorimetry on single crystals. Compound 1 displays gradual and incomplete spin crossover behaviour with a transition temperature of T1/2 ∼ 155 K. An optical microscopy study carried out on one single crystal shows an abrupt transition around 180 K with a darkening of the crystal in the low-spin phase, although no clear evidence of an apparent size change was observed. When compound 1 loses its guest molecules partially, [Fe(tpe)2dca]ClO4·CHCl3·2H2O (2) is obtained in air atmosphere, which is paramagnetic. In addition, the complex [Fe(bpa)2(NCS)2]·solvent (bpa = 9,10-bis(4-pyridyl)anthracene, 3) remains paramagnetic down to 100 K, as confirmed by single crystal X-ray diffraction, due to the strong distortion of its octahedral coordination sphere as well as its rigid structure.
具有结构特征的多孔自旋交叉化合物是一种极具吸引力的材料类型,因为它们的特性可以在多种刺激下进行调节,从而使其光学、电学和磁学响应发生剧烈变化,有望应用于化学传感、记忆设备和致动器等领域。本研究制备了一种新型三维 FeII 自旋交叉多孔配位聚合物 [Fe(tpe)2dca]ClO4-5CHCl3-3CH3OH(1,tpe = 反式-1,2-双(4-吡啶基)乙烯;dca = N(CN)2-),它能在空穴中容纳客体分子以调节其磁性和光学特性。通过 X 射线衍射、热重分析、元素分析和磁感应强度跟踪其自旋交叉,并通过单晶体差示扫描量热法对化合物 1 进行了研究。对一个单晶体进行的光学显微镜研究表明,在 180 K 左右出现了突然的转变,晶体在低自旋相变暗,但没有观察到明显的尺寸变化。当化合物 1 部分失去客体分子后,在空气中会产生顺磁性的 [Fe(tpe)2dca]ClO4-CHCl3-2H2O (2)。此外,单晶 X 射线衍射证实,[Fe(bpa)2(NCS)2]-溶剂复合物(bpa = 9,10-双(4-吡啶基)蒽,3)在低至 100 K 的温度下仍具有顺磁性,这是因为其八面体配位球发生了强烈变形,而且结构坚硬。
{"title":"Stimuli-responsive spin crossover behavior in 3D Fe(ii) porous coordination polymers for guest molecules†","authors":"Li Sun, Xiaochun Li, Constance Vandenbulcke, Nour El Islam Belmouri, Guillaume Bouchez, Koen Robeyns, Aurelian Rotaru, Kamel Boukheddaden and Yann Garcia","doi":"10.1039/D4MA00527A","DOIUrl":"https://doi.org/10.1039/D4MA00527A","url":null,"abstract":"<p >Structurally characterized porous spin crossover compounds are attractive types of materials due to their properties that can be regulated under several stimuli, resulting in drastic changes in their optical, electrical, and magnetic responses, leading to potential applications in chemical sensing, memory devices, actuators, <em>etc.</em> In this work, a new 3D Fe<small><sup>II</sup></small> spin crossover porous coordination polymer, [Fe(<strong>tpe</strong>)<small><sub>2</sub></small>dca]ClO<small><sub>4</sub></small>·5CHCl<small><sub>3</sub></small>·3CH<small><sub>3</sub></small>OH (<strong>1</strong>, <strong>tpe</strong> = <em>trans</em>-1,2-bis(4-pyridyl)ethene; <strong>dca</strong> = N(CN)<small><sub>2</sub></small><small><sup>−</sup></small>), which accommodates guest molecules in its cavities to modulate its magnetic and optical properties, was prepared. <strong>1</strong> was characterized by X-ray diffraction in its fully solvated form by flash cooling single crystals at 100 K, thermogravimetric analysis, elemental analysis and its spin crossover tracked by magnetic susceptibility, and studied by differential scanning calorimetry on single crystals. Compound <strong>1</strong> displays gradual and incomplete spin crossover behaviour with a transition temperature of <em>T</em><small><sub>1/2</sub></small> ∼ 155 K. An optical microscopy study carried out on one single crystal shows an abrupt transition around 180 K with a darkening of the crystal in the low-spin phase, although no clear evidence of an apparent size change was observed. When compound <strong>1</strong> loses its guest molecules partially, [Fe(<strong>tpe</strong>)<small><sub>2</sub></small>dca]ClO<small><sub>4</sub></small>·CHCl<small><sub>3</sub></small>·2H<small><sub>2</sub></small>O (<strong>2</strong>) is obtained in air atmosphere, which is paramagnetic. In addition, the complex [Fe(<strong>bpa</strong>)<small><sub>2</sub></small>(NCS)<small><sub>2</sub></small>]·solvent (<strong>bpa</strong> = 9,10-bis(4-pyridyl)anthracene, <strong>3</strong>) remains paramagnetic down to 100 K, as confirmed by single crystal X-ray diffraction, due to the strong distortion of its octahedral coordination sphere as well as its rigid structure.</p>","PeriodicalId":18242,"journal":{"name":"Materials Advances","volume":null,"pages":null},"PeriodicalIF":5.2,"publicationDate":"2024-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ma/d4ma00527a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142524256","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}