Maochao Mao, Leon Ahrens, Julian Luka, Francisca Contreras, Tetiana Kurkina, Marian Bienstein, Marisa Sárria Pereira de Passos, Gabriella Schirinzi, Dora Mehn, Andrea Valsesia, Cloé Desmet, Miguel-Ángel Serra, Douglas Gilliland and Ulrich Schwaneberg
Material-binding peptides (MBPs) have emerged as a diverse and innovation-enabling class of peptides in applications such as plant-/human health, immobilization of catalysts, bioactive coatings, accelerated polymer degradation and analytics for micro-/nanoplastics quantification. Progress has been fuelled by recent advancements in protein engineering methodologies and advances in computational and analytical methodologies, which allow the design of, for instance, material-specific MBPs with fine-tuned binding strength for numerous demands in material science applications. A genetic or chemical conjugation of second (biological, chemical or physical property-changing) functionality to MBPs empowers the design of advanced (hybrid) materials, bioactive coatings and analytical tools. In this review, we provide a comprehensive overview comprising naturally occurring MBPs and their function in nature, binding properties of short man-made MBPs (<20 amino acids) mainly obtained from phage-display libraries, and medium-sized binding peptides (20–100 amino acids) that have been reported to bind to metals, polymers or other industrially produced materials. The goal of this review is to provide an in-depth understanding of molecular interactions between materials and material-specific binding peptides, and thereby empower the use of MBPs in material science applications. Protein engineering methodologies and selected examples to tailor MBPs toward applications in agriculture with a focus on plant health, biocatalysis, medicine and environmental monitoring serve as examples of the transformative power of MBPs for various industrial applications. An emphasis will be given to MBPs' role in detecting and quantifying microplastics in high throughput, distinguishing microplastics from other environmental particles, and thereby assisting to close an analytical gap in food safety and monitoring of environmental plastic pollution. In essence, this review aims to provide an overview among researchers from diverse disciplines in respect to material-(specific) binding of MBPs, protein engineering methodologies to tailor their properties to application demands, re-engineering for material science applications using MBPs, and thereby inspire researchers to employ MBPs in their research.
{"title":"Material-specific binding peptides empower sustainable innovations in plant health, biocatalysis, medicine and microplastic quantification","authors":"Maochao Mao, Leon Ahrens, Julian Luka, Francisca Contreras, Tetiana Kurkina, Marian Bienstein, Marisa Sárria Pereira de Passos, Gabriella Schirinzi, Dora Mehn, Andrea Valsesia, Cloé Desmet, Miguel-Ángel Serra, Douglas Gilliland and Ulrich Schwaneberg","doi":"10.1039/D2CS00991A","DOIUrl":"10.1039/D2CS00991A","url":null,"abstract":"<p >Material-binding peptides (MBPs) have emerged as a diverse and innovation-enabling class of peptides in applications such as plant-/human health, immobilization of catalysts, bioactive coatings, accelerated polymer degradation and analytics for micro-/nanoplastics quantification. Progress has been fuelled by recent advancements in protein engineering methodologies and advances in computational and analytical methodologies, which allow the design of, for instance, material-specific MBPs with fine-tuned binding strength for numerous demands in material science applications. A genetic or chemical conjugation of second (biological, chemical or physical property-changing) functionality to MBPs empowers the design of advanced (hybrid) materials, bioactive coatings and analytical tools. In this review, we provide a comprehensive overview comprising naturally occurring MBPs and their function in nature, binding properties of short man-made MBPs (<20 amino acids) mainly obtained from phage-display libraries, and medium-sized binding peptides (20–100 amino acids) that have been reported to bind to metals, polymers or other industrially produced materials. The goal of this review is to provide an in-depth understanding of molecular interactions between materials and material-specific binding peptides, and thereby empower the use of MBPs in material science applications. Protein engineering methodologies and selected examples to tailor MBPs toward applications in agriculture with a focus on plant health, biocatalysis, medicine and environmental monitoring serve as examples of the transformative power of MBPs for various industrial applications. An emphasis will be given to MBPs' role in detecting and quantifying microplastics in high throughput, distinguishing microplastics from other environmental particles, and thereby assisting to close an analytical gap in food safety and monitoring of environmental plastic pollution. In essence, this review aims to provide an overview among researchers from diverse disciplines in respect to material-(specific) binding of MBPs, protein engineering methodologies to tailor their properties to application demands, re-engineering for material science applications using MBPs, and thereby inspire researchers to employ MBPs in their research.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":null,"pages":null},"PeriodicalIF":46.2,"publicationDate":"2024-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/cs/d2cs00991a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140924321","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Xiaoyan Lu, Kun Zhang, Xinkai Niu, Dan-Dan Ren, Zhan Zhou, Li-Long Dang, Hong-Ru Fu, Chaoliang Tan, Lufang Ma and Shuang-Quan Zang
Delayed luminescence (DF), including phosphorescence and thermally activated delayed fluorescence (TADF), and circularly polarized luminescence (CPL) exhibit common and broad application prospects in optoelectronic displays, biological imaging, and encryption. Thus, the combination of delayed luminescence and circularly polarized luminescence is attracting increasing attention. The encapsulation of guest emitters in various host matrices to form host–guest systems has been demonstrated to be an appealing strategy to further enhance and/or modulate their delayed luminescence and circularly polarized luminescence. Compared with conventional liquid crystals, polymers, and supramolecular matrices, porous crystalline frameworks (PCFs) including metal–organic frameworks (MOFs), covalent-organic frameworks (COFs), zeolites and hydrogen-bonded organic frameworks (HOFs) can not only overcome shortcomings such as flexibility and disorder but also achieve the ordered encapsulation of guests and long-term stability of chiral structures, providing new promising host platforms for the development of DF and CPL. In this review, we provide a comprehensive and critical summary of the recent progress in host–guest photochemistry via the encapsulation engineering of guest emitters in PCFs, particularly focusing on delayed luminescence and circularly polarized luminescence. Initially, the general principle of phosphorescence, TADF and CPL, the combination of DF and CPL, and energy transfer processes between host and guests are introduced. Subsequently, we comprehensively discuss the critical factors affecting the encapsulation engineering of guest emitters in PCFs, such as pore structures, the confinement effect, charge and energy transfer between the host and guest, conformational dynamics, and aggregation model of guest emitters. Thereafter, we summarize the effective methods for the preparation of host–guest systems, especially single-crystal-to-single-crystal (SC–SC) transformation and epitaxial growth, which are distinct from conventional methods based on amorphous materials. Then, the recent advancements in host–guest systems based on PCFs for delayed luminescence and circularly polarized luminescence are highlighted. Finally, we present our personal insights into the challenges and future opportunities in this promising field.
{"title":"Encapsulation engineering of porous crystalline frameworks for delayed luminescence and circularly polarized luminescence","authors":"Xiaoyan Lu, Kun Zhang, Xinkai Niu, Dan-Dan Ren, Zhan Zhou, Li-Long Dang, Hong-Ru Fu, Chaoliang Tan, Lufang Ma and Shuang-Quan Zang","doi":"10.1039/D3CS01026K","DOIUrl":"10.1039/D3CS01026K","url":null,"abstract":"<p >Delayed luminescence (DF), including phosphorescence and thermally activated delayed fluorescence (TADF), and circularly polarized luminescence (CPL) exhibit common and broad application prospects in optoelectronic displays, biological imaging, and encryption. Thus, the combination of delayed luminescence and circularly polarized luminescence is attracting increasing attention. The encapsulation of guest emitters in various host matrices to form host–guest systems has been demonstrated to be an appealing strategy to further enhance and/or modulate their delayed luminescence and circularly polarized luminescence. Compared with conventional liquid crystals, polymers, and supramolecular matrices, porous crystalline frameworks (PCFs) including metal–organic frameworks (MOFs), covalent-organic frameworks (COFs), zeolites and hydrogen-bonded organic frameworks (HOFs) can not only overcome shortcomings such as flexibility and disorder but also achieve the ordered encapsulation of guests and long-term stability of chiral structures, providing new promising host platforms for the development of DF and CPL. In this review, we provide a comprehensive and critical summary of the recent progress in host–guest photochemistry <em>via</em> the encapsulation engineering of guest emitters in PCFs, particularly focusing on delayed luminescence and circularly polarized luminescence. Initially, the general principle of phosphorescence, TADF and CPL, the combination of DF and CPL, and energy transfer processes between host and guests are introduced. Subsequently, we comprehensively discuss the critical factors affecting the encapsulation engineering of guest emitters in PCFs, such as pore structures, the confinement effect, charge and energy transfer between the host and guest, conformational dynamics, and aggregation model of guest emitters. Thereafter, we summarize the effective methods for the preparation of host–guest systems, especially single-crystal-to-single-crystal (SC–SC) transformation and epitaxial growth, which are distinct from conventional methods based on amorphous materials. Then, the recent advancements in host–guest systems based on PCFs for delayed luminescence and circularly polarized luminescence are highlighted. Finally, we present our personal insights into the challenges and future opportunities in this promising field.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":null,"pages":null},"PeriodicalIF":40.4,"publicationDate":"2024-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140924319","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yuanbo Pan, Junjie Cheng, Yang Zhu, Jianmin Zhang, Wenpei Fan and Xiaoyuan Chen
Metastasis causes greater than 90% of cancer-associated deaths, presenting huge challenges for detection and efficient treatment of cancer due to its high heterogeneity and widespread dissemination to various organs. Therefore, it is imperative to combat cancer metastasis, which is the key to achieving complete cancer eradication. Immunotherapy as a systemic approach has shown promising potential to combat metastasis. However, current clinical immunotherapies are not effective for all patients or all types of cancer metastases owing to insufficient immune responses. In recent years, immunological nanomaterials with intrinsic immunogenicity or immunomodulatory agents with efficient loading have been shown to enhance immune responses to eliminate metastasis. In this review, we would like to summarize various types of immunological nanomaterials against metastasis. Moreover, this review will summarize a series of immunological nanomaterial-mediated immunotherapy strategies to combat metastasis, including immunogenic cell death, regulation of chemokines and cytokines, improving the immunosuppressive tumour microenvironment, activation of the STING pathway, enhancing cytotoxic natural killer cell activity, enhancing antigen presentation of dendritic cells, and enhancing chimeric antigen receptor T cell therapy. Furthermore, the synergistic anti-metastasis strategies based on the combinational use of immunotherapy and other therapeutic modalities will also be introduced. In addition, the nanomaterial-mediated imaging techniques (e.g., optical imaging, magnetic resonance imaging, computed tomography, photoacoustic imaging, surface-enhanced Raman scattering, radionuclide imaging, etc.) for detecting metastasis and monitoring anti-metastasis efficacy are also summarized. Finally, the current challenges and future prospects of immunological nanomaterial-based anti-metastasis are also elucidated with the intention to accelerate its clinical translation.
在与癌症相关的死亡病例中,90%以上都是由癌症转移造成的,由于癌症的高度异质性和向各器官的广泛扩散,给癌症的检测和有效治疗带来了巨大挑战。因此,抗击癌症转移势在必行,这是彻底根除癌症的关键。免疫疗法作为一种系统性方法,在抗癌转移方面已显示出良好的潜力。然而,由于免疫反应不足,目前的临床免疫疗法并非对所有患者或所有类型的癌症转移都有效。近年来,具有内在免疫原性的免疫纳米材料或高效负载的免疫调节制剂已被证明可增强免疫反应以消除转移。在这篇综述中,我们将总结各种类型的抗转移免疫纳米材料。此外,本综述还将总结一系列免疫纳米材料介导的抗肿瘤转移免疫疗法策略,包括免疫原性细胞死亡、趋化因子和细胞因子调节、改善免疫抑制性肿瘤微环境、激活 STING 通路、增强细胞毒性自然杀伤细胞活性、增强树突状细胞的抗原递呈以及增强嵌合抗原受体 T 细胞疗法。此外,还将介绍基于免疫疗法和其他治疗方式联合使用的协同抗肿瘤策略。此外,还总结了纳米材料介导的成像技术(如光学成像、磁共振成像、计算机断层扫描、光声成像、表面增强拉曼散射、放射性核素成像等)在检测转移和监测抗转移疗效方面的应用。最后,还阐明了基于免疫纳米材料的抗转移疗法目前面临的挑战和未来前景,以期加速其临床转化。
{"title":"Immunological nanomaterials to combat cancer metastasis","authors":"Yuanbo Pan, Junjie Cheng, Yang Zhu, Jianmin Zhang, Wenpei Fan and Xiaoyuan Chen","doi":"10.1039/D2CS00968D","DOIUrl":"10.1039/D2CS00968D","url":null,"abstract":"<p >Metastasis causes greater than 90% of cancer-associated deaths, presenting huge challenges for detection and efficient treatment of cancer due to its high heterogeneity and widespread dissemination to various organs. Therefore, it is imperative to combat cancer metastasis, which is the key to achieving complete cancer eradication. Immunotherapy as a systemic approach has shown promising potential to combat metastasis. However, current clinical immunotherapies are not effective for all patients or all types of cancer metastases owing to insufficient immune responses. In recent years, immunological nanomaterials with intrinsic immunogenicity or immunomodulatory agents with efficient loading have been shown to enhance immune responses to eliminate metastasis. In this review, we would like to summarize various types of immunological nanomaterials against metastasis. Moreover, this review will summarize a series of immunological nanomaterial-mediated immunotherapy strategies to combat metastasis, including immunogenic cell death, regulation of chemokines and cytokines, improving the immunosuppressive tumour microenvironment, activation of the STING pathway, enhancing cytotoxic natural killer cell activity, enhancing antigen presentation of dendritic cells, and enhancing chimeric antigen receptor T cell therapy. Furthermore, the synergistic anti-metastasis strategies based on the combinational use of immunotherapy and other therapeutic modalities will also be introduced. In addition, the nanomaterial-mediated imaging techniques (<em>e.g.</em>, optical imaging, magnetic resonance imaging, computed tomography, photoacoustic imaging, surface-enhanced Raman scattering, radionuclide imaging, <em>etc.</em>) for detecting metastasis and monitoring anti-metastasis efficacy are also summarized. Finally, the current challenges and future prospects of immunological nanomaterial-based anti-metastasis are also elucidated with the intention to accelerate its clinical translation.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":null,"pages":null},"PeriodicalIF":46.2,"publicationDate":"2024-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140924320","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Guang Chen, Jing Yu, Luling Wu, Xinrui Ji, Jie Xu, Chao Wang, Siyue Ma, Qing Miao, Linlin Wang, Chen Wang, Simon E. Lewis, Yanfeng Yue, Zhe Sun, Yuxia Liu, Bo Tang and Tony D. James
Small molecule donors (SMDs) play subtle roles in the signaling mechanism and disease treatments. While many excellent SMDs have been developed, dosage control, targeted delivery, spatiotemporal feedback, as well as the efficiency evaluation of small molecules are still key challenges. Accordingly, fluorescent small molecule donors (FSMDs) have emerged to meet these challenges. FSMDs enable controllable release and non-invasive real-time monitoring, providing significant advantages for drug development and clinical diagnosis. Integration of FSMDs with chemotherapeutic, photodynamic or photothermal properties can take full advantage of each mode to enhance therapeutic efficacy. Given the remarkable properties and the thriving development of FSMDs, we believe a review is needed to summarize the design, triggering strategies and tracking mechanisms of FSMDs. With this review, we compiled FSMDs for most small molecules (nitric oxide, carbon monoxide, hydrogen sulfide, sulfur dioxide, reactive oxygen species and formaldehyde), and discuss recent progress concerning their molecular design, structural classification, mechanisms of generation, triggered release, structure–activity relationships, and the fluorescence response mechanism. Firstly, from the large number of fluorescent small molecular donors available, we have organized the common structures for producing different types of small molecules, providing a general strategy for the development of FSMDs. Secondly, we have classified FSMDs in terms of the respective donor types and fluorophore structures. Thirdly, we discuss the mechanisms and factors associated with the controlled release of small molecules and the regulation of the fluorescence responses, from which universal guidelines for optical properties and structure rearrangement were established, mainly involving light-controlled, enzyme-activated, reactive oxygen species-triggered, biothiol-triggered, single-electron reduction, click chemistry, and other triggering mechanisms. Fourthly, representative applications of FSMDs for trackable release, and evaluation monitoring, as well as for visible in vivo treatment are outlined, to illustrate the potential of FSMDs in drug screening and precision medicine. Finally, we discuss the opportunities and remaining challenges for the development of FSMDs for practical and clinical applications, which we anticipate will stimulate the attention of researchers in the diverse fields of chemistry, pharmacology, chemical biology and clinical chemistry. With this review, we hope to impart new understanding thereby enabling the rapid development of the next generation of FSMDs.
{"title":"Fluorescent small molecule donors","authors":"Guang Chen, Jing Yu, Luling Wu, Xinrui Ji, Jie Xu, Chao Wang, Siyue Ma, Qing Miao, Linlin Wang, Chen Wang, Simon E. Lewis, Yanfeng Yue, Zhe Sun, Yuxia Liu, Bo Tang and Tony D. James","doi":"10.1039/D3CS00124E","DOIUrl":"10.1039/D3CS00124E","url":null,"abstract":"<p >Small molecule donors (SMDs) play subtle roles in the signaling mechanism and disease treatments. While many excellent SMDs have been developed, dosage control, targeted delivery, spatiotemporal feedback, as well as the efficiency evaluation of small molecules are still key challenges. Accordingly, fluorescent small molecule donors (FSMDs) have emerged to meet these challenges. FSMDs enable controllable release and non-invasive real-time monitoring, providing significant advantages for drug development and clinical diagnosis. Integration of FSMDs with chemotherapeutic, photodynamic or photothermal properties can take full advantage of each mode to enhance therapeutic efficacy. Given the remarkable properties and the thriving development of FSMDs, we believe a review is needed to summarize the design, triggering strategies and tracking mechanisms of FSMDs. With this review, we compiled FSMDs for most small molecules (nitric oxide, carbon monoxide, hydrogen sulfide, sulfur dioxide, reactive oxygen species and formaldehyde), and discuss recent progress concerning their molecular design, structural classification, mechanisms of generation, triggered release, structure–activity relationships, and the fluorescence response mechanism. Firstly, from the large number of fluorescent small molecular donors available, we have organized the common structures for producing different types of small molecules, providing a general strategy for the development of FSMDs. Secondly, we have classified FSMDs in terms of the respective donor types and fluorophore structures. Thirdly, we discuss the mechanisms and factors associated with the controlled release of small molecules and the regulation of the fluorescence responses, from which universal guidelines for optical properties and structure rearrangement were established, mainly involving light-controlled, enzyme-activated, reactive oxygen species-triggered, biothiol-triggered, single-electron reduction, click chemistry, and other triggering mechanisms. Fourthly, representative applications of FSMDs for trackable release, and evaluation monitoring, as well as for visible <em>in vivo</em> treatment are outlined, to illustrate the potential of FSMDs in drug screening and precision medicine. Finally, we discuss the opportunities and remaining challenges for the development of FSMDs for practical and clinical applications, which we anticipate will stimulate the attention of researchers in the diverse fields of chemistry, pharmacology, chemical biology and clinical chemistry. With this review, we hope to impart new understanding thereby enabling the rapid development of the next generation of FSMDs.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":null,"pages":null},"PeriodicalIF":46.2,"publicationDate":"2024-05-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/cs/d3cs00124e?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140919457","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Saba Daliran, Ali Reza Oveisi, Chung-Wei Kung, Unal Sen, Amarajothi Dhakshinamoorthy, Cheng-Hsun Chuang, Mostafa Khajeh, Mustafa Erkartal and Joseph T. Hupp
This comprehensive review explores the diverse applications of defective zirconium-based metal–organic frameworks (Zr-MOFs) in energy and environmental remediation. Zr-MOFs have gained significant attention due to their unique properties, and deliberate introduction of defects further enhances their functionality. The review encompasses several areas where defective Zr-MOFs exhibit promise, including environmental remediation, detoxification of chemical warfare agents, photocatalytic energy conversions, and electrochemical applications. Defects play a pivotal role by creating open sites within the framework, facilitating effective adsorption and remediation of pollutants. They also contribute to the catalytic activity of Zr-MOFs, enabling efficient energy conversion processes such as hydrogen production and CO2 reduction. The review underscores the importance of defect manipulation, including control over their distribution and type, to optimize the performance of Zr-MOFs. Through tailored defect engineering and precise selection of functional groups, researchers can enhance the selectivity and efficiency of Zr-MOFs for specific applications. Additionally, pore size manipulation influences the adsorption capacity and transport properties of Zr-MOFs, further expanding their potential in environmental remediation and energy conversion. Defective Zr-MOFs exhibit remarkable stability and synthetic versatility, making them suitable for diverse environmental conditions and allowing for the introduction of missing linkers, cluster defects, or post-synthetic modifications to precisely tailor their properties. Overall, this review highlights the promising prospects of defective Zr-MOFs in addressing energy and environmental challenges, positioning them as versatile tools for sustainable solutions and paving the way for advancements in various sectors toward a cleaner and more sustainable future.
{"title":"Defect-enabling zirconium-based metal–organic frameworks for energy and environmental remediation applications","authors":"Saba Daliran, Ali Reza Oveisi, Chung-Wei Kung, Unal Sen, Amarajothi Dhakshinamoorthy, Cheng-Hsun Chuang, Mostafa Khajeh, Mustafa Erkartal and Joseph T. Hupp","doi":"10.1039/D3CS01057K","DOIUrl":"10.1039/D3CS01057K","url":null,"abstract":"<p >This comprehensive review explores the diverse applications of defective zirconium-based metal–organic frameworks (Zr-MOFs) in energy and environmental remediation. Zr-MOFs have gained significant attention due to their unique properties, and deliberate introduction of defects further enhances their functionality. The review encompasses several areas where defective Zr-MOFs exhibit promise, including environmental remediation, detoxification of chemical warfare agents, photocatalytic energy conversions, and electrochemical applications. Defects play a pivotal role by creating open sites within the framework, facilitating effective adsorption and remediation of pollutants. They also contribute to the catalytic activity of Zr-MOFs, enabling efficient energy conversion processes such as hydrogen production and CO<small><sub>2</sub></small> reduction. The review underscores the importance of defect manipulation, including control over their distribution and type, to optimize the performance of Zr-MOFs. Through tailored defect engineering and precise selection of functional groups, researchers can enhance the selectivity and efficiency of Zr-MOFs for specific applications. Additionally, pore size manipulation influences the adsorption capacity and transport properties of Zr-MOFs, further expanding their potential in environmental remediation and energy conversion. Defective Zr-MOFs exhibit remarkable stability and synthetic versatility, making them suitable for diverse environmental conditions and allowing for the introduction of missing linkers, cluster defects, or post-synthetic modifications to precisely tailor their properties. Overall, this review highlights the promising prospects of defective Zr-MOFs in addressing energy and environmental challenges, positioning them as versatile tools for sustainable solutions and paving the way for advancements in various sectors toward a cleaner and more sustainable future.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":null,"pages":null},"PeriodicalIF":46.2,"publicationDate":"2024-05-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/cs/d3cs01057k?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140919646","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jingjing Liang, Guanghui Cao, Mengqi Zeng and Lei Fu
High-entropy alloys (HEAs) involving more than four elements, as emerging alloys, have brought about a paradigm shift in material design. The unprecedented compositional diversities and structural complexities of HEAs endow multidimensional exploration space and great potential for practical benefits, as well as a formidable challenge for synthesis. To further optimize performance and promote advanced applications, it is essential to synthesize HEAs with desired characteristics to satisfy the requirements in the application scenarios. The properties of HEAs are highly related to their chemical compositions, microstructure, and morphology. In this review, a comprehensive overview of the controllable synthesis of HEAs is provided, ranging from composition design to morphology control, structure construction, and surface/interface engineering. The fundamental parameters and advanced characterization related to HEAs are introduced. We also propose several critical directions for future development. This review can provide insight and an in-depth understanding of HEAs, accelerating the synthesis of the desired HEAs.
涉及四种以上元素的高熵合金(HEAs)作为新兴合金,为材料设计带来了范式转变。高熵合金具有前所未有的成分多样性和结构复杂性,因此具有多维的探索空间和巨大的实用潜力,同时也给合成带来了艰巨的挑战。为了进一步优化性能和促进先进应用,必须合成具有所需特性的 HEA,以满足应用场景的要求。HEA 的特性与其化学成分、微观结构和形态密切相关。本综述全面概述了 HEA 的可控合成,包括成分设计、形态控制、结构构建和表面/界面工程。文中介绍了与 HEAs 相关的基本参数和先进表征方法。我们还提出了未来发展的几个重要方向。本综述有助于深入了解 HEAs,加快合成所需的 HEAs。
{"title":"Controllable synthesis of high-entropy alloys","authors":"Jingjing Liang, Guanghui Cao, Mengqi Zeng and Lei Fu","doi":"10.1039/D4CS00034J","DOIUrl":"10.1039/D4CS00034J","url":null,"abstract":"<p >High-entropy alloys (HEAs) involving more than four elements, as emerging alloys, have brought about a paradigm shift in material design. The unprecedented compositional diversities and structural complexities of HEAs endow multidimensional exploration space and great potential for practical benefits, as well as a formidable challenge for synthesis. To further optimize performance and promote advanced applications, it is essential to synthesize HEAs with desired characteristics to satisfy the requirements in the application scenarios. The properties of HEAs are highly related to their chemical compositions, microstructure, and morphology. In this review, a comprehensive overview of the controllable synthesis of HEAs is provided, ranging from composition design to morphology control, structure construction, and surface/interface engineering. The fundamental parameters and advanced characterization related to HEAs are introduced. We also propose several critical directions for future development. This review can provide insight and an in-depth understanding of HEAs, accelerating the synthesis of the desired HEAs.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":null,"pages":null},"PeriodicalIF":46.2,"publicationDate":"2024-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140911520","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Zhenyue Chen, Irmak Gezginer, Quanyu Zhou, Lin Tang, Xosé Luís Deán-Ben and Daniel Razansky
Optoacoustic (OA) imaging offers powerful capabilities for interrogating biological tissues with rich optical absorption contrast while maintaining high spatial resolution for deep tissue observations. The spectrally distinct absorption of visible and near-infrared photons by endogenous tissue chromophores facilitates extraction of diverse anatomic, functional, molecular, and metabolic information from living tissues across various scales, from organelles and cells to whole organs and organisms. The primarily blood-related contrast and limited penetration depth of OA imaging have fostered the development of multimodal approaches to fully exploit the unique advantages and complementarity of the method. We review the recent hybridization efforts, including multimodal combinations of OA with ultrasound, fluorescence, optical coherence tomography, Raman scattering microscopy and magnetic resonance imaging as well as ionizing methods, such as X-ray computed tomography, single-photon-emission computed tomography and positron emission tomography. Considering that most molecules absorb light across a broad range of the electromagnetic spectrum, the OA interrogations can be extended to a large number of exogenously administered small molecules, particulate agents, and genetically encoded labels. This unique property further makes contrast moieties used in other imaging modalities amenable for OA sensing.
光声(OA)成像技术具有强大的功能,可利用丰富的光学吸收对比度对生物组织进行检测,同时保持较高的空间分辨率以进行深层组织观测。内源性组织发色团对可见光和近红外线光子的光谱吸收不同,这有助于从细胞器和细胞到整个器官和生物体等不同尺度的活体组织中提取各种解剖、功能、分子和代谢信息。OA 成像主要与血液相关,且穿透深度有限,这促进了多模态方法的发展,以充分利用该方法的独特优势和互补性。我们回顾了最近的杂交工作,包括 OA 与超声、荧光、光学相干断层扫描、拉曼散射显微镜和磁共振成像以及电离方法(如 X 射线计算机断层扫描、单光子发射计算机断层扫描和正电子发射断层扫描)的多模态组合。考虑到大多数分子在电磁波谱的广泛范围内吸收光,OA 检测可扩展到大量外源性小分子、微粒剂和基因编码标签。这种独特的特性还使其他成像模式中使用的对比剂也可用于 OA 检测。
{"title":"Multimodal optoacoustic imaging: methods and contrast materials","authors":"Zhenyue Chen, Irmak Gezginer, Quanyu Zhou, Lin Tang, Xosé Luís Deán-Ben and Daniel Razansky","doi":"10.1039/D3CS00565H","DOIUrl":"10.1039/D3CS00565H","url":null,"abstract":"<p >Optoacoustic (OA) imaging offers powerful capabilities for interrogating biological tissues with rich optical absorption contrast while maintaining high spatial resolution for deep tissue observations. The spectrally distinct absorption of visible and near-infrared photons by endogenous tissue chromophores facilitates extraction of diverse anatomic, functional, molecular, and metabolic information from living tissues across various scales, from organelles and cells to whole organs and organisms. The primarily blood-related contrast and limited penetration depth of OA imaging have fostered the development of multimodal approaches to fully exploit the unique advantages and complementarity of the method. We review the recent hybridization efforts, including multimodal combinations of OA with ultrasound, fluorescence, optical coherence tomography, Raman scattering microscopy and magnetic resonance imaging as well as ionizing methods, such as X-ray computed tomography, single-photon-emission computed tomography and positron emission tomography. Considering that most molecules absorb light across a broad range of the electromagnetic spectrum, the OA interrogations can be extended to a large number of exogenously administered small molecules, particulate agents, and genetically encoded labels. This unique property further makes contrast moieties used in other imaging modalities amenable for OA sensing.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":null,"pages":null},"PeriodicalIF":46.2,"publicationDate":"2024-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/cs/d3cs00565h?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140911521","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Triazole-derived N-heterocyclic carbenes, triazolylidenes (trz) have become an interesting alternative to the ubiquitous Arduengo-type imidazole-derived carbenes, in part because they are stronger donors, and in other parts due to their versatile synthesis through different types of click reactions. While the use of trz ligands has initially focused on their coordination to precious metals for catalytic applications, the recent past has seen a growing interest in their impact on first-row transition metals. Coordination of trz ligands to such 3d metals is more challenging due to the orbital mismatch between the carbene and the 3d metal center, which also affects the stability of such complexes. Here we summarize the strategies that have been employed so far to overcome these challenges and to prepare first-row transition metal complexes containing at least one trz ligand. Both properties and reactivities of these trz complexes are comprehensively compiled, with a focus on photophysical properties and, in particular, on the application of these complexes in homogeneous catalysis. The diversity of catalytic transformations entailed with these trz 3d metal complexes as well as the record-high performance in some of the reactions underpins the benefits imparted by trz ligands.
三唑衍生的 N-杂环碳烯、三唑亚基(trz)已成为无处不在的 Arduengo 型咪唑衍生碳烯的有趣替代品,部分原因是它们是更强的供体,另一部分原因是它们可以通过不同类型的点击反应进行多功能合成。虽然 trz 配体的使用最初主要集中在与贵金属的配位催化应用上,但最近人们对它们对第一排过渡金属的影响越来越感兴趣。由于碳烯与 3d 金属中心的轨道不匹配,trz 配体与此类 3d 金属的配位更具挑战性,这也影响了此类配合物的稳定性。在此,我们总结了迄今为止为克服这些挑战并制备至少含有一种 trz 配体的第一排过渡金属配合物而采用的策略。我们全面梳理了这些 trz 配合物的性质和反应活性,重点关注光物理性质,尤其是这些配合物在均相催化中的应用。这些 trz 3d 金属配合物催化转化的多样性以及在某些反应中创纪录的高性能证明了 trz 配体所带来的益处。
{"title":"Application of first-row transition metal complexes bearing 1,2,3-triazolylidene ligands in catalysis and beyond","authors":"Wowa Stroek and Martin Albrecht","doi":"10.1039/D4CS00021H","DOIUrl":"10.1039/D4CS00021H","url":null,"abstract":"<p >Triazole-derived N-heterocyclic carbenes, triazolylidenes (trz) have become an interesting alternative to the ubiquitous Arduengo-type imidazole-derived carbenes, in part because they are stronger donors, and in other parts due to their versatile synthesis through different types of click reactions. While the use of trz ligands has initially focused on their coordination to precious metals for catalytic applications, the recent past has seen a growing interest in their impact on first-row transition metals. Coordination of trz ligands to such 3d metals is more challenging due to the orbital mismatch between the carbene and the 3d metal center, which also affects the stability of such complexes. Here we summarize the strategies that have been employed so far to overcome these challenges and to prepare first-row transition metal complexes containing at least one trz ligand. Both properties and reactivities of these trz complexes are comprehensively compiled, with a focus on photophysical properties and, in particular, on the application of these complexes in homogeneous catalysis. The diversity of catalytic transformations entailed with these trz 3d metal complexes as well as the record-high performance in some of the reactions underpins the benefits imparted by trz ligands.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":null,"pages":null},"PeriodicalIF":46.2,"publicationDate":"2024-05-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/cs/d4cs00021h?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140896585","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
In the electrocatalytic CO2 reduction reaction (CO2RR), metal catalysts with an oxidation state generally demonstrate more favorable catalytic activity and selectivity than their corresponding metallic counterparts. However, the persistence of oxidative metal sites under reductive potentials is challenging since the transition to metallic states inevitably leads to catalytic degradation. Herein, a thorough review of research on oxidation-state stabilization in the CO2RR is presented, starting from fundamental concepts and highlighting the importance of oxidation state stabilization while revealing the relevance of dynamic oxidation states in product distribution. Subsequently, the functional mechanisms of various oxidation-state protection strategies are explained in detail, and in situ detection techniques are discussed. Finally, the prevailing and prospective challenges associated with oxidation-state protection research are discussed, identifying innovative opportunities for mechanistic insights, technology upgrades, and industrial platforms to enable the commercialization of the CO2RR.
{"title":"Stabilizing the oxidation state of catalysts for effective electrochemical carbon dioxide conversion","authors":"Zhitong Wang, Lizhi Xu, Yansong Zhou, Ying Liang, Jinlin Yang, Daoxiong Wu, Shuyu Zhang, Xingqi Han, Xiaodong Shi, Jing Li, Yuliang Yuan, Peilin Deng and Xinlong Tian","doi":"10.1039/D3CS00887H","DOIUrl":"10.1039/D3CS00887H","url":null,"abstract":"<p >In the electrocatalytic CO<small><sub>2</sub></small> reduction reaction (CO<small><sub>2</sub></small>RR), metal catalysts with an oxidation state generally demonstrate more favorable catalytic activity and selectivity than their corresponding metallic counterparts. However, the persistence of oxidative metal sites under reductive potentials is challenging since the transition to metallic states inevitably leads to catalytic degradation. Herein, a thorough review of research on oxidation-state stabilization in the CO<small><sub>2</sub></small>RR is presented, starting from fundamental concepts and highlighting the importance of oxidation state stabilization while revealing the relevance of dynamic oxidation states in product distribution. Subsequently, the functional mechanisms of various oxidation-state protection strategies are explained in detail, and <em>in situ</em> detection techniques are discussed. Finally, the prevailing and prospective challenges associated with oxidation-state protection research are discussed, identifying innovative opportunities for mechanistic insights, technology upgrades, and industrial platforms to enable the commercialization of the CO<small><sub>2</sub></small>RR.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":null,"pages":null},"PeriodicalIF":46.2,"publicationDate":"2024-05-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140895706","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Lixue Yang, Yiyao Zhang, Wenting Cai, Junlong Tan, Heather Hansen, Hongzhi Wang, Yan Chen, Meifang Zhu and Jiuke Mu
Soft actuators, pivotal for converting external energy into mechanical motion, have become increasingly vital in a wide range of applications, from the subtle engineering of soft robotics to the demanding environments of aerospace exploration. Among these, electrochemically-driven actuators (EC actuators), are particularly distinguished by their operation through ion diffusion or intercalation-induced volume changes. These actuators feature notable advantages, including precise deformation control under electrical stimuli, freedom from Carnot efficiency limitations, and the ability to maintain their actuated state with minimal energy use, akin to the latching state in skeletal muscles. This review extensively examines EC actuators, emphasizing their classification based on diverse material types, driving mechanisms, actuator configurations, and potential applications. It aims to illuminate the complicated driving mechanisms of different categories, uncover their underlying connections, and reveal the interdependencies among materials, mechanisms, and performances. We conduct an in-depth analysis of both conventional and emerging EC actuator materials, casting a forward-looking lens on their trajectories and pinpointing areas ready for innovation and performance enhancement strategies. We also navigate through the challenges and opportunities within the field, including optimizing current materials, exploring new materials, and scaling up production processes. Overall, this review aims to provide a scientifically robust narrative that captures the current state of EC actuators and sets a trajectory for future innovation in this rapidly advancing field.
{"title":"Electrochemically-driven actuators: from materials to mechanisms and from performance to applications†","authors":"Lixue Yang, Yiyao Zhang, Wenting Cai, Junlong Tan, Heather Hansen, Hongzhi Wang, Yan Chen, Meifang Zhu and Jiuke Mu","doi":"10.1039/D3CS00906H","DOIUrl":"10.1039/D3CS00906H","url":null,"abstract":"<p >Soft actuators, pivotal for converting external energy into mechanical motion, have become increasingly vital in a wide range of applications, from the subtle engineering of soft robotics to the demanding environments of aerospace exploration. Among these, electrochemically-driven actuators (EC actuators), are particularly distinguished by their operation through ion diffusion or intercalation-induced volume changes. These actuators feature notable advantages, including precise deformation control under electrical stimuli, freedom from Carnot efficiency limitations, and the ability to maintain their actuated state with minimal energy use, akin to the latching state in skeletal muscles. This review extensively examines EC actuators, emphasizing their classification based on diverse material types, driving mechanisms, actuator configurations, and potential applications. It aims to illuminate the complicated driving mechanisms of different categories, uncover their underlying connections, and reveal the interdependencies among materials, mechanisms, and performances. We conduct an in-depth analysis of both conventional and emerging EC actuator materials, casting a forward-looking lens on their trajectories and pinpointing areas ready for innovation and performance enhancement strategies. We also navigate through the challenges and opportunities within the field, including optimizing current materials, exploring new materials, and scaling up production processes. Overall, this review aims to provide a scientifically robust narrative that captures the current state of EC actuators and sets a trajectory for future innovation in this rapidly advancing field.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":null,"pages":null},"PeriodicalIF":46.2,"publicationDate":"2024-05-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140895440","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}