Pub Date : 2024-11-16DOI: 10.1021/acs.macromol.4c02206
Yaohang Cai, Lifei He, Lingyi Fang, Yuyan Zhang, Jing Zhang, Yi Yuan, Peng Wang
The advancement of p-type conjugated polymers with optimized electrical properties, morphology, and heat tolerance is essential for n-i-p-type perovskite solar cells. Herein, we present a novel conjugated polymer, p-PDT144-E, composed of alternating units of 4,4,7,7-tetrakis(4-hexylphenyl)-4,7-dihydropyreno[1,2-b:8,7-b′]dithiophene (PDT144) and 3,4-ethylenedioxythiophene. This copolymer was synthesized via a palladium-catalyzed direct arylation polycondensation method. Compared to the corresponding homopolymer p-PDT144 synthesized by oxidative polymerization, p-PDT144-E exhibited an elevated highest occupied molecular orbital energy level, facilitating faster hole extraction and enhanced hole conductivity. Additionally, p-PDT144-E demonstrated an increased glass temperature and a more uniform film morphology. When used as a hole transport material along with the air doping promoter 4-(tert-butyl)pyridinium 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonimide, perovskite solar cells incorporating p-PDT144-E achieved an average power conversion efficiency (PCE) of 25.5%, surpassing reference cells using spiro-OMeTAD (average PCE of 24.7%) under identical conditions. Furthermore, p-PDT144-E-based cells exhibited excellent operational stability at 45 °C and thermal storage stability at 85 °C.
{"title":"Engineering Pyreno[1,2-b:8,7-b′]dithiophene-Based Conjugated Polymers for Efficient and Stable Perovskite Solar Cells","authors":"Yaohang Cai, Lifei He, Lingyi Fang, Yuyan Zhang, Jing Zhang, Yi Yuan, Peng Wang","doi":"10.1021/acs.macromol.4c02206","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c02206","url":null,"abstract":"The advancement of p-type conjugated polymers with optimized electrical properties, morphology, and heat tolerance is essential for n-i-p-type perovskite solar cells. Herein, we present a novel conjugated polymer, p-PDT<sub>14</sub>4-E, composed of alternating units of 4,4,7,7-tetrakis(4-hexylphenyl)-4,7-dihydropyreno[1,2-<i>b</i>:8,7-<i>b</i><i>′</i>]dithiophene (PDT<sub>14</sub>4) and 3,4-ethylenedioxythiophene. This copolymer was synthesized via a palladium-catalyzed direct arylation polycondensation method. Compared to the corresponding homopolymer p-PDT<sub>14</sub>4 synthesized by oxidative polymerization, p-PDT<sub>14</sub>4-E exhibited an elevated highest occupied molecular orbital energy level, facilitating faster hole extraction and enhanced hole conductivity. Additionally, p-PDT<sub>14</sub>4-E demonstrated an increased glass temperature and a more uniform film morphology. When used as a hole transport material along with the air doping promoter 4-(<i>tert</i>-butyl)pyridinium 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonimide, perovskite solar cells incorporating p-PDT<sub>14</sub>4-E achieved an average power conversion efficiency (PCE) of 25.5%, surpassing reference cells using spiro-OMeTAD (average PCE of 24.7%) under identical conditions. Furthermore, p-PDT<sub>14</sub>4-E-based cells exhibited excellent operational stability at 45 °C and thermal storage stability at 85 °C.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"6 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2024-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142642632","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}
Pub Date : 2024-11-15DOI: 10.1021/acs.macromol.4c01993
Io Saito, Richard J. Sheridan, Stefan Zauscher, L. Catherine Brinson
Understanding the mechanical properties of polymer nanocomposite materials is essential for industrial use. Particularly, the determination of the polymer modulus at the nanofiller–polymer interphase is important for optimizing the interfacial mechanical properties. Nanoindentation via Atomic Force Microscopy (AFM) is well-established for measuring the modulus of the interphase region with nanoscale spatial resolution. However, indentation into heterogeneous materials presents a confounding issue often referred to as the “substrate effect”, i.e., the structural stress field caused by the rigid body is convoluted with the actual modulus of the interphase region. While finite element analysis (FEA)-based methods can be used to deconvolute the interphase modulus from measured apparent modulus–distance profiles, the experimental validation of this method is still needed. Here, we provide this validation using AFM nanoindentation on a layered model composite that consists of three layers with different moduli to recapitulate the properties of the matrix, the filler, and the interphase of real polymer nanocomposites. By systematically varying the thickness of the “artificial” interphase layer and the AFM probe radius, we obtain modulus–distance profiles over a wide range of indentation conditions. We validate a method to deconvolute the substrate effect using an empirically derived master curve obtained from FEA analysis. Furthermore, we showed that the effect of the artificial interphase on modulus– distance profiles can be distinguished only if the interphase layer is thick enough compared to the contact radius of the probe. Finally, we established an innovative and quantitative framework to predict the interphase thickness from mechanical nanoindentation measurements and discussed the lower, practical limit for interphase thickness determination. In summary, we provide a broadly applicable method to extract interphase mechanical properties of multiphase soft materials and practical guidelines for choosing optimal characterization conditions.
{"title":"Pushing AFM to the Boundaries: Interphase Mechanical Property Measurements near a Rigid Body","authors":"Io Saito, Richard J. Sheridan, Stefan Zauscher, L. Catherine Brinson","doi":"10.1021/acs.macromol.4c01993","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c01993","url":null,"abstract":"Understanding the mechanical properties of polymer nanocomposite materials is essential for industrial use. Particularly, the determination of the polymer modulus at the nanofiller–polymer interphase is important for optimizing the interfacial mechanical properties. Nanoindentation via Atomic Force Microscopy (AFM) is well-established for measuring the modulus of the interphase region with nanoscale spatial resolution. However, indentation into heterogeneous materials presents a confounding issue often referred to as the “substrate effect”, i.e., the structural stress field caused by the rigid body is convoluted with the actual modulus of the interphase region. While finite element analysis (FEA)-based methods can be used to deconvolute the interphase modulus from measured apparent modulus–distance profiles, the experimental validation of this method is still needed. Here, we provide this validation using AFM nanoindentation on a layered model composite that consists of three layers with different moduli to recapitulate the properties of the matrix, the filler, and the interphase of real polymer nanocomposites. By systematically varying the thickness of the “artificial” interphase layer and the AFM probe radius, we obtain modulus–distance profiles over a wide range of indentation conditions. We validate a method to deconvolute the substrate effect using an empirically derived master curve obtained from FEA analysis. Furthermore, we showed that the effect of the artificial interphase on modulus– distance profiles can be distinguished only if the interphase layer is thick enough compared to the contact radius of the probe. Finally, we established an innovative and quantitative framework to predict the interphase thickness from mechanical nanoindentation measurements and discussed the lower, practical limit for interphase thickness determination. In summary, we provide a broadly applicable method to extract interphase mechanical properties of multiphase soft materials and practical guidelines for choosing optimal characterization conditions.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"99 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142642634","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}
Polymer-grafted platelets (PGPLs) were prepared via atom transfer radical polymerization of butyl methacrylate with the initiator bonded to the surface of hematite platelets, and the conformation of the poly(butyl methacrylate) (PBMA) chains grafted onto the top and bottom of the platelets at a dimensionless graft density (σ*) of 0.3–0.9 was studied. PGPLs were shaped into films with platelets parallel to the film surface via dispersion casting followed by hot pressing. The face-to-face distance between platelets increases with the number-average molecular weight of the grafted polymer and equals 2Lcσ*, where Lc is the contour length of the grafted PBMA chains. This suggests that the polymer chains grafted onto a platelet are stretched perpendicular to the platelet face to a similar extent as those grafted onto flat substrates, and their ends are opposed to those grafted from the opposite platelets to fill the space between the platelets.
{"title":"Chain Conformation of Polymers Densely Grafted onto Plate-Shaped Particles","authors":"Yusuke Watanabe, Yusuke Kakizawa, Shinya Kato, Sayaka Yamagishi, Naruki Kurokawa, Masatoshi Tokita","doi":"10.1021/acs.macromol.4c01702","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c01702","url":null,"abstract":"Polymer-grafted platelets (PGPLs) were prepared via atom transfer radical polymerization of butyl methacrylate with the initiator bonded to the surface of hematite platelets, and the conformation of the poly(butyl methacrylate) (PBMA) chains grafted onto the top and bottom of the platelets at a dimensionless graft density (σ*) of 0.3–0.9 was studied. PGPLs were shaped into films with platelets parallel to the film surface via dispersion casting followed by hot pressing. The face-to-face distance between platelets increases with the number-average molecular weight of the grafted polymer and equals 2<i>L</i><sub>c</sub>σ*, where <i>L</i><sub>c</sub> is the contour length of the grafted PBMA chains. This suggests that the polymer chains grafted onto a platelet are stretched perpendicular to the platelet face to a similar extent as those grafted onto flat substrates, and their ends are opposed to those grafted from the opposite platelets to fill the space between the platelets.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"98 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142637489","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}
Pub Date : 2024-11-15DOI: 10.1021/acs.macromol.4c02233
Timo Sehn, Nicolai Kolb, Alexander Azzawi, Michael A. R. Meier
We herein present an efficient one-step synthesis route toward catechol containing polymers from liquid polybutadiene via a simple post polymerization modification (PPM) approach applying acid catalyzed Friedel–Crafts alkylation (FCA). Accordingly, 100% modification of polybutadiene was achieved within 30 min in bulk at 120 °C. The final structure of the polymer was analyzed by 1H, 13C, 2D nuclear magnetic resonance (NMR), infrared (IR), diffusion ordered spectroscopy (DOSY), and size exclusion chromatography (SEC). Material properties were investigated via thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Subsequent metal ion removal tests revealed excellent extraction efficiencies (86% ≤ Mn+removal < 100%) when using the catechol containing polymer as heavy metal sorbent and thus emphasize a potential application for water purification processes.
{"title":"Efficient One-Step Synthesis of Catechol Containing Polymers via Friedel–Crafts Alkylation and Their Use for Water Decontamination","authors":"Timo Sehn, Nicolai Kolb, Alexander Azzawi, Michael A. R. Meier","doi":"10.1021/acs.macromol.4c02233","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c02233","url":null,"abstract":"We herein present an efficient one-step synthesis route toward catechol containing polymers from liquid polybutadiene via a simple post polymerization modification (PPM) approach applying acid catalyzed Friedel–Crafts alkylation (FCA). Accordingly, 100% modification of polybutadiene was achieved within 30 min in bulk at 120 °C. The final structure of the polymer was analyzed by <sup>1</sup>H, <sup>13</sup>C, 2D nuclear magnetic resonance (NMR), infrared (IR), diffusion ordered spectroscopy (DOSY), and size exclusion chromatography (SEC). Material properties were investigated via thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Subsequent metal ion removal tests revealed excellent extraction efficiencies (86% ≤ M<sup><i>n</i>+</sup><sub>removal</sub> < 100%) when using the catechol containing polymer as heavy metal sorbent and thus emphasize a potential application for water purification processes.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"30 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142642639","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}
Pub Date : 2024-11-15DOI: 10.1021/acs.macromol.4c01779
Sara Zimny, Magdalena Tarnacka, Paulina Maksym, Żaneta Wojnarowska, Marian Paluch, Kamil Kamiński
In this paper, we investigated the molecular dynamics of polymer brushes based on poly(mercaptopropyl)methylsiloxane (PMMS), in which the thiol group was grafted with different homologous flexible acrylates (acrylate-based PMMS copolymers) and more rigid methacrylate (methacrylate-based PMMS copolymers) monomers of varying lengths of alkyl chain under ambient and elevated pressure conditions. It was found that the glass transition temperature, Tg, of PMMS homopolymer is significantly lower compared to the other systems. Moreover, surprisingly, in the methacrylate-grafted copolymers, there are two relaxation processes (α and α′), while in the systems grafted with various acrylates, only a single process is present in the supercooled phase. Complementary rheological investigations indicated that the faster α process comes from the segmental motions, while α′ is not detected in the mechanical response. Further high-pressure experiments showed that there is a superposition between segmental and α′ modes irrespective of applied pressure, p, in methacrylate-based PMMS copolymers. This result suggests that the latter process might be considered as a sub-Rouse mode, or alternatively, it may originate from the dielectric active relaxation of the rigid polar side chain (grafts). Moreover, analysis of the high-pressure data allowed us to estimate the pressure coefficient of the glass transition temperature, dTg/dp, which was much higher for polymer brushes with respect to the PMMS homopolymer. Interestingly, the values of dTg/dp for methacrylate-grafted copolymers are slightly higher compared to acrylate-based PMMS copolymers, which may be due to the different flexibility/rigidity of both groups of materials as all examined materials have the same degree of polymerization of homopolymer backbone (Nbb ∼ 12) and side chain (Nsc = 1). However, for both groups of studied systems, dTg/dp values did not scale with chain length. This unexpected result must be related to the structure of the studied grafted copolymers and the character of grafts, derivatives of acrylates/methacrylates. The data presented here extend our knowledge of the influence of the architecture of different molecules on the dynamics of polymers at ambient and high pressures.
{"title":"The Influence of Graft Rigidity on the Dynamical Behavior of PMMS-Based Polymer Brushes at Ambient and High Pressures","authors":"Sara Zimny, Magdalena Tarnacka, Paulina Maksym, Żaneta Wojnarowska, Marian Paluch, Kamil Kamiński","doi":"10.1021/acs.macromol.4c01779","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c01779","url":null,"abstract":"In this paper, we investigated the molecular dynamics of polymer brushes based on poly(mercaptopropyl)methylsiloxane (PMMS), in which the thiol group was grafted with different homologous flexible acrylates (acrylate-based PMMS copolymers) and more rigid methacrylate (methacrylate-based PMMS copolymers) monomers of varying lengths of alkyl chain under ambient and elevated pressure conditions. It was found that the glass transition temperature, <i>T</i><sub>g</sub>, of PMMS homopolymer is significantly lower compared to the other systems. Moreover, surprisingly, in the methacrylate-grafted copolymers, there are two relaxation processes (α and α′), while in the systems grafted with various acrylates, only a single process is present in the supercooled phase. Complementary rheological investigations indicated that the faster α process comes from the segmental motions, while α′ is not detected in the mechanical response. Further high-pressure experiments showed that there is a superposition between segmental and α′ modes irrespective of applied pressure, <i>p</i>, in methacrylate-based PMMS copolymers. This result suggests that the latter process might be considered as a sub-Rouse mode, or alternatively, it may originate from the dielectric active relaxation of the rigid polar side chain (grafts). Moreover, analysis of the high-pressure data allowed us to estimate the pressure coefficient of the glass transition temperature, d<i>T</i><sub>g</sub>/d<i>p</i>, which was much higher for polymer brushes with respect to the PMMS homopolymer. Interestingly, the values of d<i>T</i><sub>g</sub>/d<i>p</i> for methacrylate-grafted copolymers are slightly higher compared to acrylate-based PMMS copolymers, which may be due to the different flexibility/rigidity of both groups of materials as all examined materials have the same degree of polymerization of homopolymer backbone (<i>N</i><sub>bb</sub> ∼ 12) and side chain (<i>N</i><sub>sc</sub> = 1). However, for both groups of studied systems, d<i>T</i><sub>g</sub>/d<i>p</i> values did not scale with chain length. This unexpected result must be related to the structure of the studied grafted copolymers and the character of grafts, derivatives of acrylates/methacrylates. The data presented here extend our knowledge of the influence of the architecture of different molecules on the dynamics of polymers at ambient and high pressures.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"156 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142642633","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}
Pub Date : 2024-11-15DOI: 10.1021/acs.macromol.4c02074
Ikechukwu Martin Ogbu, Eli J. Fastow, Karen I. Winey, Marisa C. Kozlowski
To advance a strategy of polymer-to-polymer upcycling of waste polyolefin by dehydrogenation then functionalization, we report successful hydroesterification of polycyclooctene (PCOE), an analogue for partially unsaturated polyethylene. Here, we convert PCOE to a linear analog for poly(ethylene-co-ethyl acrylate) (EEA) across a range of ethyl acrylate incorporations (0 to 18 mol % of ethylene units). The ester incorporation was well controlled by reaction time, and the remaining C═C bonds were subsequently hydrogenated. The bulky ethyl acrylate groups did not incorporate into orthorhombic PE crystals, decreasing the crystallinity, crystallite size, and melting temperature with increasing functionalization. Additionally, hydroesterification tuned the dynamic mechanical properties, decreasing both the glass transition temperature and the storage modulus in the rubbery regime with greater functionalization. The linear EEA analogs reported here achieve remarkable extensibility (strain > 4000%) and high toughness, comparable to commercial random and branched EEA. Ultimately, we demonstrate successful conversion of an analogue to dehydrogenated PE to a linear EEA with favorable mechanical properties.
{"title":"Hydroesterification of Polycyclooctene to Access Linear Ethylene Ethyl Acrylate Copolymers as a Step Toward Polyolefin Functionalization","authors":"Ikechukwu Martin Ogbu, Eli J. Fastow, Karen I. Winey, Marisa C. Kozlowski","doi":"10.1021/acs.macromol.4c02074","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c02074","url":null,"abstract":"To advance a strategy of polymer-to-polymer upcycling of waste polyolefin by dehydrogenation then functionalization, we report successful hydroesterification of polycyclooctene (PCOE), an analogue for partially unsaturated polyethylene. Here, we convert PCOE to a linear analog for poly(ethylene-<i>co</i>-ethyl acrylate) (EEA) across a range of ethyl acrylate incorporations (0 to 18 mol % of ethylene units). The ester incorporation was well controlled by reaction time, and the remaining C═C bonds were subsequently hydrogenated. The bulky ethyl acrylate groups did not incorporate into orthorhombic PE crystals, decreasing the crystallinity, crystallite size, and melting temperature with increasing functionalization. Additionally, hydroesterification tuned the dynamic mechanical properties, decreasing both the glass transition temperature and the storage modulus in the rubbery regime with greater functionalization. The linear EEA analogs reported here achieve remarkable extensibility (strain > 4000%) and high toughness, comparable to commercial random and branched EEA. Ultimately, we demonstrate successful conversion of an analogue to dehydrogenated PE to a linear EEA with favorable mechanical properties.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"75 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142642635","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}
Pub Date : 2024-11-14DOI: 10.1021/acs.chemrev.4c00423
Colin S. Swenson, Gunasheil Mandava, Deborah M. Thomas, Raymond E. Moellering
The development of potent, specific, and pharmacologically viable chemical probes and therapeutics is a central focus of chemical biology and therapeutic development. However, a significant portion of predicted disease-causal proteins have proven resistant to targeting by traditional small molecule and biologic modalities. Many of these so-called “undruggable” targets feature extended, dynamic protein–protein and protein–nucleic acid interfaces that are central to their roles in normal and diseased signaling pathways. Here, we discuss the development of synthetically stabilized peptide and protein mimetics as an ever-expanding and powerful region of chemical space to tackle undruggable targets. These molecules aim to combine the synthetic tunability and pharmacologic properties typically associated with small molecules with the binding footprints, affinities and specificities of biologics. In this review, we discuss the historical and emerging platforms and approaches to design, screen, select and optimize synthetic “designer” peptidomimetics and synthetic biologics. We examine the inspiration and design of different classes of designer peptidomimetics: (i) macrocyclic peptides, (ii) side chain stabilized peptides, (iii) non-natural peptidomimetics, and (iv) synthetic proteomimetics, and notable examples of their application to challenging biomolecules. Finally, we summarize key learnings and remaining challenges for these molecules to become useful chemical probes and therapeutics for historically undruggable targets.
{"title":"Tackling Undruggable Targets with Designer Peptidomimetics and Synthetic Biologics","authors":"Colin S. Swenson, Gunasheil Mandava, Deborah M. Thomas, Raymond E. Moellering","doi":"10.1021/acs.chemrev.4c00423","DOIUrl":"https://doi.org/10.1021/acs.chemrev.4c00423","url":null,"abstract":"The development of potent, specific, and pharmacologically viable chemical probes and therapeutics is a central focus of chemical biology and therapeutic development. However, a significant portion of predicted disease-causal proteins have proven resistant to targeting by traditional small molecule and biologic modalities. Many of these so-called “undruggable” targets feature extended, dynamic protein–protein and protein–nucleic acid interfaces that are central to their roles in normal and diseased signaling pathways. Here, we discuss the development of synthetically stabilized peptide and protein mimetics as an ever-expanding and powerful region of chemical space to tackle undruggable targets. These molecules aim to combine the synthetic tunability and pharmacologic properties typically associated with small molecules with the binding footprints, affinities and specificities of biologics. In this review, we discuss the historical and emerging platforms and approaches to design, screen, select and optimize synthetic “designer” peptidomimetics and synthetic biologics. We examine the inspiration and design of different classes of designer peptidomimetics: (i) macrocyclic peptides, (ii) side chain stabilized peptides, (iii) non-natural peptidomimetics, and (iv) synthetic proteomimetics, and notable examples of their application to challenging biomolecules. Finally, we summarize key learnings and remaining challenges for these molecules to become useful chemical probes and therapeutics for historically undruggable targets.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"128 1","pages":""},"PeriodicalIF":62.1,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142610524","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}
Pub Date : 2024-11-13Epub Date: 2024-07-05DOI: 10.1021/acs.chemrev.4c00155
Štĕpán Kment, Aristides Bakandritsos, Iosif Tantis, Hana Kmentová, Yunpeng Zuo, Olivier Henrotte, Alberto Naldoni, Michal Otyepka, Rajender S Varma, Radek Zbořil
Anthropogenic activities related to population growth, economic development, technological advances, and changes in lifestyle and climate patterns result in a continuous increase in energy consumption. At the same time, the rare metal elements frequently deployed as catalysts in energy related processes are not only costly in view of their low natural abundance, but their availability is often further limited due to geopolitical reasons. Thus, electrochemical energy storage and conversion with earth-abundant metals, mainly in the form of single-atom catalysts (SACs), are highly relevant and timely technologies. In this review the application of earth-abundant SACs in electrochemical energy storage and electrocatalytic conversion of chemicals to fuels or products with high energy content is discussed. The oxygen reduction reaction is also appraised, which is primarily harnessed in fuel cell technologies and metal-air batteries. The coordination, active sites, and mechanistic aspects of transition metal SACs are analyzed for two-electron and four-electron reaction pathways. Further, the electrochemical water splitting with SACs toward green hydrogen fuel is discussed in terms of not only hydrogen evolution reaction but also oxygen evolution reaction. Similarly, the production of ammonia as a clean fuel via electrocatalytic nitrogen reduction reaction is portrayed, highlighting the potential of earth-abundant single metal species.
{"title":"Single Atom Catalysts Based on Earth-Abundant Metals for Energy-Related Applications.","authors":"Štĕpán Kment, Aristides Bakandritsos, Iosif Tantis, Hana Kmentová, Yunpeng Zuo, Olivier Henrotte, Alberto Naldoni, Michal Otyepka, Rajender S Varma, Radek Zbořil","doi":"10.1021/acs.chemrev.4c00155","DOIUrl":"10.1021/acs.chemrev.4c00155","url":null,"abstract":"<p><p>Anthropogenic activities related to population growth, economic development, technological advances, and changes in lifestyle and climate patterns result in a continuous increase in energy consumption. At the same time, the rare metal elements frequently deployed as catalysts in energy related processes are not only costly in view of their low natural abundance, but their availability is often further limited due to geopolitical reasons. Thus, electrochemical energy storage and conversion with earth-abundant metals, mainly in the form of single-atom catalysts (SACs), are highly relevant and timely technologies. In this review the application of earth-abundant SACs in electrochemical energy storage and electrocatalytic conversion of chemicals to fuels or products with high energy content is discussed. The oxygen reduction reaction is also appraised, which is primarily harnessed in fuel cell technologies and metal-air batteries. The coordination, active sites, and mechanistic aspects of transition metal SACs are analyzed for two-electron and four-electron reaction pathways. Further, the electrochemical water splitting with SACs toward green hydrogen fuel is discussed in terms of not only hydrogen evolution reaction but also oxygen evolution reaction. Similarly, the production of ammonia as a clean fuel via electrocatalytic nitrogen reduction reaction is portrayed, highlighting the potential of earth-abundant single metal species.</p>","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":" ","pages":"11767-11847"},"PeriodicalIF":5.1,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11565580/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141532883","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}
Pub Date : 2024-11-13DOI: 10.1021/acs.chemrev.4c00293
Anneliese M. M. Gest, Ayse Z. Sahan, Yanghao Zhong, Wei Lin, Sohum Mehta, Jin Zhang
Cellular function is controlled through intricate networks of signals, which lead to the myriad pathways governing cell fate. Fluorescent biosensors have enabled the study of these signaling pathways in living systems across temporal and spatial scales. Over the years there has been an explosion in the number of fluorescent biosensors, as they have become available for numerous targets, utilized across spectral space, and suited for various imaging techniques. To guide users through this extensive biosensor landscape, we discuss critical aspects of fluorescent proteins for consideration in biosensor development, smart tagging strategies, and the historical and recent biosensors of various types, grouped by target, and with a focus on the design and recent applications of these sensors in living systems.
{"title":"Molecular Spies in Action: Genetically Encoded Fluorescent Biosensors Light up Cellular Signals","authors":"Anneliese M. M. Gest, Ayse Z. Sahan, Yanghao Zhong, Wei Lin, Sohum Mehta, Jin Zhang","doi":"10.1021/acs.chemrev.4c00293","DOIUrl":"https://doi.org/10.1021/acs.chemrev.4c00293","url":null,"abstract":"Cellular function is controlled through intricate networks of signals, which lead to the myriad pathways governing cell fate. Fluorescent biosensors have enabled the study of these signaling pathways in living systems across temporal and spatial scales. Over the years there has been an explosion in the number of fluorescent biosensors, as they have become available for numerous targets, utilized across spectral space, and suited for various imaging techniques. To guide users through this extensive biosensor landscape, we discuss critical aspects of fluorescent proteins for consideration in biosensor development, smart tagging strategies, and the historical and recent biosensors of various types, grouped by target, and with a focus on the design and recent applications of these sensors in living systems.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"6 1","pages":""},"PeriodicalIF":62.1,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142601599","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}
Pub Date : 2024-11-13Epub Date: 2024-10-31DOI: 10.1021/acs.chemrev.4c00563
Takuya Higashi, Shuhei Kusumoto, Kyoko Nozaki
{"title":"Additions and Corrections to Cleavage of Si-H, B-H and C-H Bonds by Metal-Ligand Cooperation.","authors":"Takuya Higashi, Shuhei Kusumoto, Kyoko Nozaki","doi":"10.1021/acs.chemrev.4c00563","DOIUrl":"10.1021/acs.chemrev.4c00563","url":null,"abstract":"","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":" ","pages":"12381"},"PeriodicalIF":51.4,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142542858","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}
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