Alexandru-Cristi Iancu, George A. Lungu, Cristian A. Tache and Cristian M. Teodorescu
Carbon dioxide (CO2) is reversibly adsorbed and desorbed from ferroelectric (001) oriented, BaO-terminated barium titanate, as revealed in real time by high resolution and ultrafast photoelectron spectroscopy and certified by low energy electron diffraction. Desorption proceeds when the substrate is heated above its Curie temperature. The amount of CO2 adsorbed is derived to be between one molecule for a surface BaO unit cell (adsorption below room temperature) and one molecule for two unit cells (adsorption above room temperature). The molecule is bound with its carbon to surface oxygen, forming a CO3 structure. The BaTiO3(001) surface is unaffected by repeated cycles of adsorption–desorption. The relatively high amount of CO2 adsorbed and the stability of the substrate after repeated adsorption and desorption processes promotes barium titanate as a promising candidate for decarbonization technologies.
高分辨率和超快光电子能谱实时揭示了二氧化碳(CO2)在铁电(001)取向、BaO 端接的钛酸钡中的可逆吸附和解吸,低能电子衍射也证明了这一点。当基底被加热到居里温度以上时,就会发生解吸。据推算,一个表面 BaO 单胞吸附的二氧化碳量为一个分子(吸附温度低于室温),而两个单胞吸附的二氧化碳量为一个分子(吸附温度高于室温)。分子中的碳与表面的氧结合,形成 CO3 结构。BaTiO3(001) 表面不受反复吸附-解吸循环的影响。相对较高的二氧化碳吸附量以及基底在反复吸附和解吸过程后的稳定性,促使钛酸钡成为脱碳技术的理想候选材料。
{"title":"Ferroelectric-enabled significant carbon dioxide molecular adsorption on BaTiO3(001)†","authors":"Alexandru-Cristi Iancu, George A. Lungu, Cristian A. Tache and Cristian M. Teodorescu","doi":"10.1039/D4MA00856A","DOIUrl":"https://doi.org/10.1039/D4MA00856A","url":null,"abstract":"<p >Carbon dioxide (CO<small><sub>2</sub></small>) is reversibly adsorbed and desorbed from ferroelectric (001) oriented, BaO-terminated barium titanate, as revealed in real time by high resolution and ultrafast photoelectron spectroscopy and certified by low energy electron diffraction. Desorption proceeds when the substrate is heated above its Curie temperature. The amount of CO<small><sub>2</sub></small> adsorbed is derived to be between one molecule for a surface BaO unit cell (adsorption below room temperature) and one molecule for two unit cells (adsorption above room temperature). The molecule is bound with its carbon to surface oxygen, forming a CO<small><sub>3</sub></small> structure. The BaTiO<small><sub>3</sub></small>(001) surface is unaffected by repeated cycles of adsorption–desorption. The relatively high amount of CO<small><sub>2</sub></small> adsorbed and the stability of the substrate after repeated adsorption and desorption processes promotes barium titanate as a promising candidate for decarbonization technologies.</p>","PeriodicalId":18242,"journal":{"name":"Materials Advances","volume":" 22","pages":" 8798-8811"},"PeriodicalIF":5.2,"publicationDate":"2024-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ma/d4ma00856a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142598719","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}
Rui Feng, Chang-Yu Hung, Stoichko Antonov, Jonathan D. Poplawsky, Ke An, Paul D. Jablonski and Martin Detrois
The strong demands on increasing fuel efficiency have continuously driven the optimization of superalloys for high-performance applications. In this study, modifications to the chemistry and heat treatment of HAYNES® 282® alloy (H282) were performed by varying γ′ formers and refractory elements. It was found that increasing Ti and substituting W for some of the Mo in the newly designed alloy (Q) resulted in a significant improvement of creep resistance, up to 130% increase in creep life, compared to standard H282. It was found that Orowan loops and dislocation climb were the dominant creep deformation mechanisms in alloy Q, while extensive dislocation tangling as an additional configuration was observed in the baseline alloy. Moreover, phase stability investigations for up to 5000 h at 800 °C and 900 °C revealed a reduced formation of detrimental σ and μ phases in alloy Q when compared to H282. Atom-probe tomography (APT) revealed that the formation and growth of those phases were responsible for a decrease in Mo content in the matrix, thereby leading to a decrease in solid-solution strengthening in H282 over time. Furthermore, the coarsening of γ′ precipitates was retarded by the substitution of W for Mo, particularly under creep stress. The theoretical and experimental understanding of precipitation strengthening unraveled that higher optimal strengthening occurs at larger particle size for alloy Q, compared to the commercial formulation, further explaining the origin of enhanced creep resistance in the modified alloy.
对提高燃油效率的强烈要求不断推动着高性能应用领域超级合金的优化。在这项研究中,通过改变γ′形成剂和难熔元素,对瀚纳仕® 282® 合金(H282)的化学成分和热处理进行了改良。结果发现,与标准 H282 相比,在新设计的合金(Q)中增加 Ti 并用 W 替代部分 Mo,可显著提高抗蠕变性,蠕变寿命最多可提高 130%。研究发现,在合金 Q 中,奥罗万环和位错攀升是主要的蠕变变形机制,而在基线合金中则观察到广泛的位错缠结作为一种额外的构型。此外,在 800 °C 和 900 °C 下进行长达 5000 小时的相稳定性研究发现,与 H282 相比,合金 Q 中有害的 σ 和 μ 相的形成有所减少。原子探针断层扫描(APT)显示,这些相的形成和生长是基体中钼含量降低的原因,从而导致 H282 的固溶强化随时间推移而降低。此外,用 W 替代 Mo 会延缓 γ′ 沉淀的粗化,尤其是在蠕变应力下。通过对析出强化的理论和实验研究发现,与商用配方相比,合金 Q 的粒度越大,最佳强化效果越好,这进一步解释了改性合金抗蠕变性增强的原因。
{"title":"Variations in γ′ formers and refractory elements for enhanced creep resistance and phase stability of an advanced Ni-based superalloy†‡","authors":"Rui Feng, Chang-Yu Hung, Stoichko Antonov, Jonathan D. Poplawsky, Ke An, Paul D. Jablonski and Martin Detrois","doi":"10.1039/D4MA00334A","DOIUrl":"https://doi.org/10.1039/D4MA00334A","url":null,"abstract":"<p >The strong demands on increasing fuel efficiency have continuously driven the optimization of superalloys for high-performance applications. In this study, modifications to the chemistry and heat treatment of HAYNES® 282® alloy (H282) were performed by varying γ′ formers and refractory elements. It was found that increasing Ti and substituting W for some of the Mo in the newly designed alloy (Q) resulted in a significant improvement of creep resistance, up to 130% increase in creep life, compared to standard H282. It was found that Orowan loops and dislocation climb were the dominant creep deformation mechanisms in alloy Q, while extensive dislocation tangling as an additional configuration was observed in the baseline alloy. Moreover, phase stability investigations for up to 5000 h at 800 °C and 900 °C revealed a reduced formation of detrimental σ and μ phases in alloy Q when compared to H282. Atom-probe tomography (APT) revealed that the formation and growth of those phases were responsible for a decrease in Mo content in the matrix, thereby leading to a decrease in solid-solution strengthening in H282 over time. Furthermore, the coarsening of γ′ precipitates was retarded by the substitution of W for Mo, particularly under creep stress. The theoretical and experimental understanding of precipitation strengthening unraveled that higher optimal strengthening occurs at larger particle size for alloy Q, compared to the commercial formulation, further explaining the origin of enhanced creep resistance in the modified alloy.</p>","PeriodicalId":18242,"journal":{"name":"Materials Advances","volume":" 22","pages":" 8847-8863"},"PeriodicalIF":5.2,"publicationDate":"2024-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ma/d4ma00334a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142598673","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}
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":" 22","pages":" 8901-8908"},"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":" 22","pages":" 8961-8969"},"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":" 21","pages":" 8673-8683"},"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":" 22","pages":" 8927-8936"},"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":" 21","pages":" 8652-8664"},"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":" 22","pages":" 8878-8888"},"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":" 21","pages":" 8439-8443"},"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":" 21","pages":" 8665-8672"},"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}