ACS Materials AuPub Date : 2025-03-27eCollection Date: 2025-05-14DOI: 10.1021/acsmaterialsau.4c00154
Bryan A Corzo, Hugo Hernández-Martínez, Eugenia Josefina Aldeco-Pérez, Jorge Cárdenas, Víctor Lara, Lilian I Olvera
{"title":"Functionalized Imidazolium Ether-Free Polymer Backbones with Ion Transport Channels and Catalytic Activity.","authors":"Bryan A Corzo, Hugo Hernández-Martínez, Eugenia Josefina Aldeco-Pérez, Jorge Cárdenas, Víctor Lara, Lilian I Olvera","doi":"10.1021/acsmaterialsau.4c00154","DOIUrl":"10.1021/acsmaterialsau.4c00154","url":null,"abstract":"<p><p>Novel ether-free bond polymer backbones were synthesized through polycondensation in a superacid medium by using <i>p</i>-terphenyl and 4-(1<i>H</i>-imidazol-1-yl)benzaldehyde. The presence of imidazolium groups enabled further modifications through a highly efficient nucleophilic substitution reaction introducing cationic sites essential for anionic transport. Characterization by NMR and FTIR analyses confirmed the structures and the complete functionalization of the base polymer. Critical properties for potential anion exchange membrane applications, including water uptake, ion exchange capacity, ion conductivity, morphology, and thermal and mechanical stabilities were investigated. Results indicated that these polymers form stable ion transport channels, with the formation of distinctive hydrophilic/hydrophobic microphase separation in the membranes observed through AFM, HR-TEM, and SAXS analyses. This structural configuration of the membranes exhibited high hydroxide conductivities of 61.33 and 80.33 mS/cm at 80 °C for 1AIM (quaternization with iodomethane) and 1ABPTA (quaternization with (3-bromopropyl)trimethylammonium bromide), respectively, with a thermal stability up to 240 °C, underscoring their suitability for electrochemical applications. Additionally, an organometallic polymer was successfully synthesized from the 1ABPTA polymer due to the presence of an imidazolium salt, <i>N</i>-heterocyclic carbene (NHC) ligand precursor. SEM images displayed the homogeneous distribution of metal atoms, and XPS spectra confirmed the formation of the C-M bond. The material obtained was utilized as a heterogeneous catalyst in a C-C Suzuki-Miyaura coupling reaction, achieving catalytic conversion percentages of 70% and 60% for the first and second cycles, respectively.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"5 3","pages":"508-521"},"PeriodicalIF":5.7,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12082359/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144094957","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}
ACS Materials AuPub Date : 2025-03-26DOI: 10.1021/acsmaterialsau.4c0015410.1021/acsmaterialsau.4c00154
Bryan A. Corzo, Hugo Hernández-Martínez, Eugenia Josefina Aldeco-Pérez, Jorge Cárdenas, Víctor Lara and Lilian I. Olvera*,
{"title":"Functionalized Imidazolium Ether-Free Polymer Backbones with Ion Transport Channels and Catalytic Activity","authors":"Bryan A. Corzo, Hugo Hernández-Martínez, Eugenia Josefina Aldeco-Pérez, Jorge Cárdenas, Víctor Lara and Lilian I. Olvera*, ","doi":"10.1021/acsmaterialsau.4c0015410.1021/acsmaterialsau.4c00154","DOIUrl":"https://doi.org/10.1021/acsmaterialsau.4c00154https://doi.org/10.1021/acsmaterialsau.4c00154","url":null,"abstract":"<p >Novel ether-free bond polymer backbones were synthesized through polycondensation in a superacid medium by using <i>p</i>-terphenyl and 4-(1<i>H</i>-imidazol-1-yl)benzaldehyde. The presence of imidazolium groups enabled further modifications through a highly efficient nucleophilic substitution reaction introducing cationic sites essential for anionic transport. Characterization by NMR and FTIR analyses confirmed the structures and the complete functionalization of the base polymer. Critical properties for potential anion exchange membrane applications, including water uptake, ion exchange capacity, ion conductivity, morphology, and thermal and mechanical stabilities were investigated. Results indicated that these polymers form stable ion transport channels, with the formation of distinctive hydrophilic/hydrophobic microphase separation in the membranes observed through AFM, HR-TEM, and SAXS analyses. This structural configuration of the membranes exhibited high hydroxide conductivities of 61.33 and 80.33 mS/cm at 80 °C for 1AIM (quaternization with iodomethane) and 1ABPTA (quaternization with (3-bromopropyl)trimethylammonium bromide), respectively, with a thermal stability up to 240 °C, underscoring their suitability for electrochemical applications. Additionally, an organometallic polymer was successfully synthesized from the 1ABPTA polymer due to the presence of an imidazolium salt, <i>N</i>-heterocyclic carbene (NHC) ligand precursor. SEM images displayed the homogeneous distribution of metal atoms, and XPS spectra confirmed the formation of the C–M bond. The material obtained was utilized as a heterogeneous catalyst in a C–C Suzuki–Miyaura coupling reaction, achieving catalytic conversion percentages of 70% and 60% for the first and second cycles, respectively.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"5 3","pages":"508–521 508–521"},"PeriodicalIF":5.7,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmaterialsau.4c00154","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143940702","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}
{"title":"Continuous Sustainable Production of Biobased Multicomponent Enhanced Resin for SLA 3D Printing.","authors":"Vojtěch Jašek, Otakar Bartoš, Veronika Lavrinčíková, Jan Fučík, Silvestr Figalla, Eliška Kameníková, Radek Přikryl","doi":"10.1021/acsmaterialsau.5c00014","DOIUrl":"10.1021/acsmaterialsau.5c00014","url":null,"abstract":"<p><p>This work focuses on biobased reactive diluents' synthesis, continuing with optimized oil-based resin precursor production. Our approach introduces vanillin methacrylate (VanMMA), cinnamyl methacrylate (CinMMA), and vanillyl dimethacrylate (VanDiMMA) synthesis using methacrylic anhydride. The introduced approach involves an innovative and available catalyst, potassium acetate, which possesses much suitable potential compared with the usually used 4-dimethylaminopyridine (DMAP). Moreover, we separated the formed secondary product, methacrylic acid (MA), and used it to modify rapeseed oil to prepare a curable thermoset. All synthesized products were structurally verified via complex cross-analysis (NMR, ESI-MS, and FTIR). The reactive systems were mixed to form a multicomponent mixture appropriate for stereolithography (SLA) and 3D printing. It was found that VanDiMMA exhibited comparable diluting properties to the commercially available and used compound, isobornyl methacrylate (IBOMA), while achieving better mechanical, thermo-mechanical, and thermal properties than IBOMA. VanDiMMA-containing SLA resin reached a tensile strength of 12.7 ± 0.3 MPa, a flexural strength of 16.8 ± 0.4 MPa, a storage modulus of 570 MPa at 30 °C, a glass-transition temperature of 83.7 °C, and the heat-resistant index of 169.5 °C.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"5 3","pages":"580-592"},"PeriodicalIF":5.7,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12082353/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144094950","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}
ACS Materials AuPub Date : 2025-03-19DOI: 10.1021/acsmaterialsau.5c0001410.1021/acsmaterialsau.5c00014
Vojtěch Jašek*, Otakar Bartoš, Veronika Lavrinčíková, Jan Fučík, Silvestr Figalla, Eliška Kameníková and Radek Přikryl,
{"title":"Continuous Sustainable Production of Biobased Multicomponent Enhanced Resin for SLA 3D Printing","authors":"Vojtěch Jašek*, Otakar Bartoš, Veronika Lavrinčíková, Jan Fučík, Silvestr Figalla, Eliška Kameníková and Radek Přikryl, ","doi":"10.1021/acsmaterialsau.5c0001410.1021/acsmaterialsau.5c00014","DOIUrl":"https://doi.org/10.1021/acsmaterialsau.5c00014https://doi.org/10.1021/acsmaterialsau.5c00014","url":null,"abstract":"<p >This work focuses on biobased reactive diluents’ synthesis, continuing with optimized oil-based resin precursor production. Our approach introduces vanillin methacrylate (VanMMA), cinnamyl methacrylate (CinMMA), and vanillyl dimethacrylate (VanDiMMA) synthesis using methacrylic anhydride. The introduced approach involves an innovative and available catalyst, potassium acetate, which possesses much suitable potential compared with the usually used 4-dimethylaminopyridine (DMAP). Moreover, we separated the formed secondary product, methacrylic acid (MA), and used it to modify rapeseed oil to prepare a curable thermoset. All synthesized products were structurally verified via complex cross-analysis (NMR, ESI-MS, and FTIR). The reactive systems were mixed to form a multicomponent mixture appropriate for stereolithography (SLA) and 3D printing. It was found that VanDiMMA exhibited comparable diluting properties to the commercially available and used compound, isobornyl methacrylate (IBOMA), while achieving better mechanical, thermo-mechanical, and thermal properties than IBOMA. VanDiMMA-containing SLA resin reached a tensile strength of 12.7 ± 0.3 MPa, a flexural strength of 16.8 ± 0.4 MPa, a storage modulus of 570 MPa at 30 °C, a glass-transition temperature of 83.7 °C, and the heat-resistant index of 169.5 °C.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"5 3","pages":"580–592 580–592"},"PeriodicalIF":5.7,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmaterialsau.5c00014","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143940699","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}
{"title":"Nickel-Doped Titanium Oxide with the Rutile Structure for High-Performance Sodium Storage","authors":"Hiroyuki Usui*, Yasuhiro Domi, Yuma Sadamori, Ryuto Tanaka, Takeo Hoshi, Toshiyuki Tanaka and Hiroki Sakaguchi*, ","doi":"10.1021/acsmaterialsau.5c0000810.1021/acsmaterialsau.5c00008","DOIUrl":"https://doi.org/10.1021/acsmaterialsau.5c00008https://doi.org/10.1021/acsmaterialsau.5c00008","url":null,"abstract":"<p >We prepared rutile TiO<sub>2</sub> particles doped with Ni<sup>2+</sup>, Al<sup>3+</sup>, Nb<sup>5+</sup>, and Ta<sup>5+</sup> by hydrothermal synthesis as anode materials for Na-ion batteries and investigated the effect of doping cation valence on the anode performance and the Na<sup>+</sup> diffusion behavior. <i>In situ</i> X-ray diffraction analyses confirmed the insertion and extraction of Na<sup>+</sup> while maintaining the rutile structure. Among the various doped TiO<sub>2</sub> electrodes, the Ni-doped TiO<sub>2</sub> one exhibited the best anode performance with a high reversible capacity of 135 mA h g<sup>–1</sup> even at 50<i>C</i> (16.75 A g<sup>–1</sup>). This electrode showed a very long cycle life: the capacity of 225 mA h g<sup>–1</sup> could be attained even after 10,000 cycles. The first-principles calculation suggested the formation of impurity levels in the forbidden band of TiO<sub>2</sub> by various cation dopings. Electrochemical impedance analyses revealed that the Ni-doped TiO<sub>2</sub> electrode showed lower charge-transfer resistance (<i>R</i><sub>ct</sub>) compared with other cation-doped TiO<sub>2</sub> electrodes. Measurements using the galvanostatic intermittent titration technique found that the Na<sup>+</sup> diffusion coefficient (<i>D</i><sub>Na+</sub>) of Ni-doped TiO<sub>2</sub> has a higher value of 1.2 × 10<sup>–13</sup> cm<sup>2</sup> s<sup>–1</sup> compared with <i>D</i><sub>Na+</sub> of 4.8 × 10<sup>–14</sup> cm<sup>2</sup> s<sup>–1</sup> in the case of undoped TiO<sub>2</sub>. The first-principle calculation supported this result: the Ni<sup>2+</sup> doping could reduce the activation energy required for Na<sup>+</sup> diffusion in rutile TiO<sub>2</sub>. Therefore, we suggest that an easier migration of Na<sup>+</sup> was promoted in the Ni-doped TiO<sub>2</sub>, effectively enhancing the charge–discharge capacity and the cycle life. Although rutile TiO<sub>2</sub> as an anode has had a difficult history, this study proved that impurity element doping such as Ni<sup>2+</sup> can transform it into a very attractive anode material.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"5 3","pages":"558–568 558–568"},"PeriodicalIF":5.7,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmaterialsau.5c00008","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143940698","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}
{"title":"Nickel-Doped Titanium Oxide with the Rutile Structure for High-Performance Sodium Storage.","authors":"Hiroyuki Usui, Yasuhiro Domi, Yuma Sadamori, Ryuto Tanaka, Takeo Hoshi, Toshiyuki Tanaka, Hiroki Sakaguchi","doi":"10.1021/acsmaterialsau.5c00008","DOIUrl":"10.1021/acsmaterialsau.5c00008","url":null,"abstract":"<p><p>We prepared rutile TiO<sub>2</sub> particles doped with Ni<sup>2+</sup>, Al<sup>3+</sup>, Nb<sup>5+</sup>, and Ta<sup>5+</sup> by hydrothermal synthesis as anode materials for Na-ion batteries and investigated the effect of doping cation valence on the anode performance and the Na<sup>+</sup> diffusion behavior. <i>In situ</i> X-ray diffraction analyses confirmed the insertion and extraction of Na<sup>+</sup> while maintaining the rutile structure. Among the various doped TiO<sub>2</sub> electrodes, the Ni-doped TiO<sub>2</sub> one exhibited the best anode performance with a high reversible capacity of 135 mA h g<sup>-1</sup> even at 50<i>C</i> (16.75 A g<sup>-1</sup>). This electrode showed a very long cycle life: the capacity of 225 mA h g<sup>-1</sup> could be attained even after 10,000 cycles. The first-principles calculation suggested the formation of impurity levels in the forbidden band of TiO<sub>2</sub> by various cation dopings. Electrochemical impedance analyses revealed that the Ni-doped TiO<sub>2</sub> electrode showed lower charge-transfer resistance (<i>R</i> <sub>ct</sub>) compared with other cation-doped TiO<sub>2</sub> electrodes. Measurements using the galvanostatic intermittent titration technique found that the Na<sup>+</sup> diffusion coefficient (<i>D</i> <sub>Na+</sub>) of Ni-doped TiO<sub>2</sub> has a higher value of 1.2 × 10<sup>-13</sup> cm<sup>2</sup> s<sup>-1</sup> compared with <i>D</i> <sub>Na+</sub> of 4.8 × 10<sup>-14</sup> cm<sup>2</sup> s<sup>-1</sup> in the case of undoped TiO<sub>2</sub>. The first-principle calculation supported this result: the Ni<sup>2+</sup> doping could reduce the activation energy required for Na<sup>+</sup> diffusion in rutile TiO<sub>2</sub>. Therefore, we suggest that an easier migration of Na<sup>+</sup> was promoted in the Ni-doped TiO<sub>2</sub>, effectively enhancing the charge-discharge capacity and the cycle life. Although rutile TiO<sub>2</sub> as an anode has had a difficult history, this study proved that impurity element doping such as Ni<sup>2+</sup> can transform it into a very attractive anode material.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"5 3","pages":"558-568"},"PeriodicalIF":5.7,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12082360/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144095020","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}
ACS Materials AuPub Date : 2025-03-05DOI: 10.1021/acsmaterialsau.5c0002410.1021/acsmaterialsau.5c00024
Pieremanuele Canepa*,
{"title":"Correction to “Pushing Forward Simulation Techniques of Ion Transport in Ion Conductors for Energy Materials”","authors":"Pieremanuele Canepa*, ","doi":"10.1021/acsmaterialsau.5c0002410.1021/acsmaterialsau.5c00024","DOIUrl":"https://doi.org/10.1021/acsmaterialsau.5c00024https://doi.org/10.1021/acsmaterialsau.5c00024","url":null,"abstract":"","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"5 3","pages":"609 609"},"PeriodicalIF":5.7,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmaterialsau.5c00024","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143940778","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}
ACS Materials AuPub Date : 2025-03-05eCollection Date: 2025-05-14DOI: 10.1021/acsmaterialsau.5c00024
Pieremanuele Canepa
{"title":"Correction to \"Pushing Forward Simulation Techniques of Ion Transport in Ion Conductors for Energy Materials\".","authors":"Pieremanuele Canepa","doi":"10.1021/acsmaterialsau.5c00024","DOIUrl":"https://doi.org/10.1021/acsmaterialsau.5c00024","url":null,"abstract":"<p><p>[This corrects the article DOI: 10.1021/acsmaterialsau.2c00057.].</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"5 3","pages":"609"},"PeriodicalIF":5.7,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12082348/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144094951","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}
ACS Materials AuPub Date : 2025-03-04DOI: 10.1021/acsmaterialsau.4c0017210.1021/acsmaterialsau.4c00172
Grace M.O. Tieman, Fatima Shatila, Stefania Ceschia, Jeremy E. Wulff and Heather L. Buckley*,
{"title":"Photobleaching of Light-Activated Porphyrin-Functionalized Plastic Coupons for Potential Antimicrobial Applications","authors":"Grace M.O. Tieman, Fatima Shatila, Stefania Ceschia, Jeremy E. Wulff and Heather L. Buckley*, ","doi":"10.1021/acsmaterialsau.4c0017210.1021/acsmaterialsau.4c00172","DOIUrl":"https://doi.org/10.1021/acsmaterialsau.4c00172https://doi.org/10.1021/acsmaterialsau.4c00172","url":null,"abstract":"<p >Developing greener alternatives for harmful conventional cleaning agents is an important focus for preventing negative impacts on both the environment and human health. One potential alternative of interest is photodynamic inactivation (PDI), where a photosensitizing molecule is used to generate singlet oxygen (<sup>1</sup>O<sub>2</sub>) and other reactive oxygen species (ROS). ROS, <sup>1</sup>O<sub>2</sub> in particular, are known to react with cellular membranes of bacteria, resulting in cellular death. Porphyrinoids are one of these known light sensitizing species. In this work, zinc(II) 5,10,15,20-tetrakis((<i>N</i>-4-[3-(trifluoromethyl)-3<i>H</i>-diazirin-3-yl]benzyl)-4-pyridyl)-21<i>H</i>,23<i>H</i>-porphine tetrabromide is covalently attached to polyethylene terephthalate (PET) via thermal activation of a diazirine to initiate a C–H insertion. With the porphyrin now covalently bonded to the PET, the functionalized PET was assessed at a range of light intensities on its ability to generate <sup>1</sup>O<sub>2</sub> and for antimicrobial activity against <i>Escherichia coli</i>; the results were found to be correlated. Because photobleaching and resultant loss of activity are one of the weaknesses of PDI, the material was further assessed for its ability to withstand various photobleaching conditions. The photobleaching conditions assessed were high intensity light in dry and underwater conditions and ambient light, along with a set of dark controls. Results indicate that after 2 weeks of high intensity irradiation, the material still mediates singlet oxygen generation, albeit less efficiently. This shows promise for the use of this approach as an alternative to conventional cleaning agents.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"5 3","pages":"537–546 537–546"},"PeriodicalIF":5.7,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmaterialsau.4c00172","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143940777","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}
ACS Materials AuPub Date : 2025-03-04eCollection Date: 2025-05-14DOI: 10.1021/acsmaterialsau.4c00172
Grace M O Tieman, Fatima Shatila, Stefania Ceschia, Jeremy E Wulff, Heather L Buckley
{"title":"Photobleaching of Light-Activated Porphyrin-Functionalized Plastic Coupons for Potential Antimicrobial Applications.","authors":"Grace M O Tieman, Fatima Shatila, Stefania Ceschia, Jeremy E Wulff, Heather L Buckley","doi":"10.1021/acsmaterialsau.4c00172","DOIUrl":"10.1021/acsmaterialsau.4c00172","url":null,"abstract":"<p><p>Developing greener alternatives for harmful conventional cleaning agents is an important focus for preventing negative impacts on both the environment and human health. One potential alternative of interest is photodynamic inactivation (PDI), where a photosensitizing molecule is used to generate singlet oxygen (<sup>1</sup>O<sub>2</sub>) and other reactive oxygen species (ROS). ROS, <sup>1</sup>O<sub>2</sub> in particular, are known to react with cellular membranes of bacteria, resulting in cellular death. Porphyrinoids are one of these known light sensitizing species. In this work, zinc(II) 5,10,15,20-tetrakis((<i>N</i>-4-[3-(trifluoromethyl)-3<i>H</i>-diazirin-3-yl]benzyl)-4-pyridyl)-21<i>H</i>,23<i>H</i>-porphine tetrabromide is covalently attached to polyethylene terephthalate (PET) via thermal activation of a diazirine to initiate a C-H insertion. With the porphyrin now covalently bonded to the PET, the functionalized PET was assessed at a range of light intensities on its ability to generate <sup>1</sup>O<sub>2</sub> and for antimicrobial activity against <i>Escherichia coli</i>; the results were found to be correlated. Because photobleaching and resultant loss of activity are one of the weaknesses of PDI, the material was further assessed for its ability to withstand various photobleaching conditions. The photobleaching conditions assessed were high intensity light in dry and underwater conditions and ambient light, along with a set of dark controls. Results indicate that after 2 weeks of high intensity irradiation, the material still mediates singlet oxygen generation, albeit less efficiently. This shows promise for the use of this approach as an alternative to conventional cleaning agents.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"5 3","pages":"537-546"},"PeriodicalIF":5.7,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12082355/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144095036","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}