ACS Materials Au最新文献

{"title":"Prediction of the Apparent pKa Value of Lipid Nanoparticles by Density Functional Theory","authors":"Valentin H. K. Fell*,&nbsp;Tim Kramer,&nbsp;Andreas Heindl and Olivia M. Merkel*,&nbsp;","doi":"10.1021/acsmaterialsau.4c0015810.1021/acsmaterialsau.4c00158","DOIUrl":"https://doi.org/10.1021/acsmaterialsau.4c00158https://doi.org/10.1021/acsmaterialsau.4c00158","url":null,"abstract":"<p >One of the most important parameters for the development of novel ionizable lipids (ILs) for use in lipid nanoparticle (LNP) drug carriers is their p<i>K</i>_a value. Ideally, the LNP should be deprotonated outside the cell to prevent cytotoxicity and protonated inside the endosome, where pH is lower. To achieve this switch, the LNP’s p<i>K</i>_a value, the so-called “apparent p<i>K</i>_a value”, should range generally between 5.5 and 7. For specific applications, the range is narrower. We present a straightforward approach to computationally estimate this apparent p<i>K</i>_a value of LNPs using density functional theory (DFT). This method uses “surrogates” of the ILs, which are hypothetical derivatives featuring an <i>N</i>,<i>N</i>-dimethylethylaminium side group attached to the lipid’s nitrogen atom.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"5 3","pages":"451–457 451–457"},"PeriodicalIF":5.7,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmaterialsau.4c00158","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143940709","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":"Prediction of the Apparent p<i>K</i> _a Value of Lipid Nanoparticles by Density Functional Theory.","authors":"Valentin H K Fell, Tim Kramer, Andreas Heindl, Olivia M Merkel","doi":"10.1021/acsmaterialsau.4c00158","DOIUrl":"10.1021/acsmaterialsau.4c00158","url":null,"abstract":"<p><p>One of the most important parameters for the development of novel ionizable lipids (ILs) for use in lipid nanoparticle (LNP) drug carriers is their p<i>K</i> _a value. Ideally, the LNP should be deprotonated outside the cell to prevent cytotoxicity and protonated inside the endosome, where pH is lower. To achieve this switch, the LNP's p<i>K</i> _a value, the so-called \"apparent p<i>K</i> _a value\", should range generally between 5.5 and 7. For specific applications, the range is narrower. We present a straightforward approach to computationally estimate this apparent p<i>K</i> _a value of LNPs using density functional theory (DFT). This method uses \"surrogates\" of the ILs, which are hypothetical derivatives featuring an <i>N</i>,<i>N</i>-dimethylethylaminium side group attached to the lipid's nitrogen atom.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"5 3","pages":"451-457"},"PeriodicalIF":5.7,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12082357/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144095050","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":"Celebrating 5 Years of the ACS Au Journal Family.","authors":"Paul D Goring, Amelia Newman, Christopher W Jones, Shelley D Minteer","doi":"10.1021/acsmaterialsau.5c00021","DOIUrl":"https://doi.org/10.1021/acsmaterialsau.5c00021","url":null,"abstract":"","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"5 2","pages":"220-222"},"PeriodicalIF":5.7,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11907280/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143651148","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":"Celebrating 5 Years of the ACS Au Journal Family","authors":"Paul D. Goring,&nbsp;Amelia Newman,&nbsp;Christopher W. Jones* and Shelley D. Minteer*,&nbsp;","doi":"10.1021/acsmaterialsau.5c0002110.1021/acsmaterialsau.5c00021","DOIUrl":"https://doi.org/10.1021/acsmaterialsau.5c00021https://doi.org/10.1021/acsmaterialsau.5c00021","url":null,"abstract":"","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"5 2","pages":"220–222 220–222"},"PeriodicalIF":5.7,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmaterialsau.5c00021","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143590429","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":"ACS Materials Au: Announcing the 2024 Rising Stars in Materials Science","authors":"Stephanie L. Brock*,&nbsp;Maksym V. Kovalenko and Mary Ann Meador,&nbsp;","doi":"10.1021/acsmaterialsau.5c0002010.1021/acsmaterialsau.5c00020","DOIUrl":"https://doi.org/10.1021/acsmaterialsau.5c00020https://doi.org/10.1021/acsmaterialsau.5c00020","url":null,"abstract":"","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"5 2","pages":"211–219 211–219"},"PeriodicalIF":5.7,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmaterialsau.5c00020","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143590449","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":"<i>ACS Materials Au</i>: Announcing the 2024 Rising Stars in Materials Science.","authors":"Stephanie L Brock, Maksym V Kovalenko, Mary Ann Meador","doi":"10.1021/acsmaterialsau.5c00020","DOIUrl":"https://doi.org/10.1021/acsmaterialsau.5c00020","url":null,"abstract":"","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"5 2","pages":"211-219"},"PeriodicalIF":5.7,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11907279/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143651146","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":"Cu₂PdSnSe₄ and Cu₂PdSn(S,Se)₄ Palladium-Substituted Kesterite Nanomaterials for Thin-Film Solar Cells.","authors":"Kelechi Nwambaekwe, Sodiq Yussuf, Ziyanda Tshobeni, Chinwe Ikpo, Jaymi January, Meleskow Cox, Precious Ekwere, Shimelis Admassie, Xinwen Peng, Emmanuel Iwuoha","doi":"10.1021/acsmaterialsau.4c00129","DOIUrl":"10.1021/acsmaterialsau.4c00129","url":null,"abstract":"<p><p>Kesterites are being studied intensively as sustainable absorber materials for solar cell development. However, elements such as Zn and Cu exhibit antisite defects that function as charge traps and recombination centers that affect the light absorption and carrier transport efficiencies of kesterite solar cells. The substitution of Zn or Cu with other metals is one of the strategies used to improve the photovoltaic performance of kesterites. This study focuses on the preparation and photovoltaics of Cu₂PdSnSe₄ (CPTSe) and Cu₂PdSn(S,Se)₄ (CPTSSe) kesterite nanoparticles (containing Pd instead of Zn) by a modified solvothermal (polyol) microwave synthesis method. The nanomaterials exhibited a tetragonal kesterite crystal structure with polydispersed morphology and average crystallite sizes of 22 and 17 nm for CPTSe and CPTSSe, respectively. DAMMIF ab initio analysis of the small-angle X-ray scattering data determined the shape of CPTSe and CPTSSe nanomaterials to be ellipsoidal. Ultraviolet-visible (UV-vis) spectroscopy revealed red-shift absorption properties, with bandgap energy values of 1.13 eV (CPTSe) and 1.20 eV (CPTSSe), thereby making them suitable light absorber materials for photovoltaic applications. Photoluminescence spectroscopy characterization confirmed the attenuation of defect concentrations in CPTSe and CPTSSe compared to the Zn analogue, which positively impacts the charge-carrier transport and recombination properties. A preliminary test of the materials in superstrate photovoltaic cell devices yielded power conversion efficiency values of 1.32% (CPTSe) and 3.5% (CPTSSe). The CPTSe- and CPTSSe-based photovoltaic devices maintained ∼70% mean open-circuit voltage (<i>V</i>oc), which is a significant improvement over the ∼20% <i>V</i> _oc retained by Zn-based kesterites after 24 days.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"5 3","pages":"469-490"},"PeriodicalIF":5.7,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12082362/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144094938","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":"Cu2PdSnSe4 and Cu2PdSn(S,Se)4 Palladium-Substituted Kesterite Nanomaterials for Thin-Film Solar Cells","authors":"Kelechi Nwambaekwe,&nbsp;Sodiq Yussuf,&nbsp;Ziyanda Tshobeni,&nbsp;Chinwe Ikpo,&nbsp;Jaymi January,&nbsp;Meleskow Cox,&nbsp;Precious Ekwere,&nbsp;Shimelis Admassie,&nbsp;Xinwen Peng and Emmanuel Iwuoha*,&nbsp;","doi":"10.1021/acsmaterialsau.4c0012910.1021/acsmaterialsau.4c00129","DOIUrl":"https://doi.org/10.1021/acsmaterialsau.4c00129https://doi.org/10.1021/acsmaterialsau.4c00129","url":null,"abstract":"<p >Kesterites are being studied intensively as sustainable absorber materials for solar cell development. However, elements such as Zn and Cu exhibit antisite defects that function as charge traps and recombination centers that affect the light absorption and carrier transport efficiencies of kesterite solar cells. The substitution of Zn or Cu with other metals is one of the strategies used to improve the photovoltaic performance of kesterites. This study focuses on the preparation and photovoltaics of Cu₂PdSnSe₄ (CPTSe) and Cu₂PdSn(S,Se)₄ (CPTSSe) kesterite nanoparticles (containing Pd instead of Zn) by a modified solvothermal (polyol) microwave synthesis method. The nanomaterials exhibited a tetragonal kesterite crystal structure with polydispersed morphology and average crystallite sizes of 22 and 17 nm for CPTSe and CPTSSe, respectively. DAMMIF ab initio analysis of the small-angle X-ray scattering data determined the shape of CPTSe and CPTSSe nanomaterials to be ellipsoidal. Ultraviolet–visible (UV–vis) spectroscopy revealed red-shift absorption properties, with bandgap energy values of 1.13 eV (CPTSe) and 1.20 eV (CPTSSe), thereby making them suitable light absorber materials for photovoltaic applications. Photoluminescence spectroscopy characterization confirmed the attenuation of defect concentrations in CPTSe and CPTSSe compared to the Zn analogue, which positively impacts the charge-carrier transport and recombination properties. A preliminary test of the materials in superstrate photovoltaic cell devices yielded power conversion efficiency values of 1.32% (CPTSe) and 3.5% (CPTSSe). The CPTSe- and CPTSSe-based photovoltaic devices maintained ∼70% mean open-circuit voltage (<i>V</i>oc), which is a significant improvement over the ∼20% <i>V</i>_oc retained by Zn-based kesterites after 24 days.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"5 3","pages":"469–490 469–490"},"PeriodicalIF":5.7,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmaterialsau.4c00129","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143940707","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":"Investigating Ionic Diffusivity in Amorphous LiPON using Machine-Learned Interatomic Potentials","authors":"Aqshat Seth,&nbsp;Rutvij Pankaj Kulkarni and Gopalakrishnan Sai Gautam*,&nbsp;","doi":"10.1021/acsmaterialsau.4c0011710.1021/acsmaterialsau.4c00117","DOIUrl":"https://doi.org/10.1021/acsmaterialsau.4c00117https://doi.org/10.1021/acsmaterialsau.4c00117","url":null,"abstract":"<p >Due to its immense importance as an amorphous solid electrolyte in thin-film devices, lithium phosphorus oxynitride (LiPON) has garnered significant scientific attention. However, investigating Li⁺ transport within the LiPON framework, especially across a Li||LiPON interface, has proven challenging due to its amorphous nature and varying stoichiometry, necessitating large supercells and long time scales for computational models. Notably, machine-learned interatomic potentials (MLIPs) can combine the computational speed of classical force fields with the accuracy of density functional theory (DFT), making them the ideal tool for modeling such amorphous materials. Thus, in this work, we train and validate the neural equivariant interatomic potential (NequIP) framework on a comprehensive DFT-based data set consisting of 13,454 chemically relevant structures to describe LiPON. With optimized training (validation) energy and force mean absolute errors of 5.5 (6.1) meV/atom and 13.6 (13.2) meV/Å, respectively, we employ the trained potential to model Li transport in both bulk LiPON and across Li||LiPON interfaces. Amorphous LiPON structures generated by the optimized potential resemble those generated by <i>ab initio</i> molecular dynamics, with N being incorporated on nonbridging apical and bridging sites. Subsequent analysis of Li⁺ diffusivity in the bulk LiPON structures indicates broad agreement with prior computational and experimental literature. Further, we investigate the anisotropy in Li⁺ transport across the Li(110)||LiPON and Li(111)||LiPON interface, where we observe Li transport across the interface to be one order of magnitude slower than Li motion within the bulk Li and LiPON phases. Nevertheless, we note that this anisotropy of Li transport across the interface is minor, and we do not expect it to cause any significant impedance buildup. Finally, our work highlights the efficiency of MLIPs in enabling high-fidelity modeling of complex noncrystalline systems over large length and time scales.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"5 3","pages":"458–468 458–468"},"PeriodicalIF":5.7,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmaterialsau.4c00117","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143940711","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":"Investigating Ionic Diffusivity in Amorphous LiPON using Machine-Learned Interatomic Potentials.","authors":"Aqshat Seth, Rutvij Pankaj Kulkarni, Gopalakrishnan Sai Gautam","doi":"10.1021/acsmaterialsau.4c00117","DOIUrl":"10.1021/acsmaterialsau.4c00117","url":null,"abstract":"<p><p>Due to its immense importance as an amorphous solid electrolyte in thin-film devices, lithium phosphorus oxynitride (LiPON) has garnered significant scientific attention. However, investigating Li⁺ transport within the LiPON framework, especially across a Li||LiPON interface, has proven challenging due to its amorphous nature and varying stoichiometry, necessitating large supercells and long time scales for computational models. Notably, machine-learned interatomic potentials (MLIPs) can combine the computational speed of classical force fields with the accuracy of density functional theory (DFT), making them the ideal tool for modeling such amorphous materials. Thus, in this work, we train and validate the neural equivariant interatomic potential (NequIP) framework on a comprehensive DFT-based data set consisting of 13,454 chemically relevant structures to describe LiPON. With optimized training (validation) energy and force mean absolute errors of 5.5 (6.1) meV/atom and 13.6 (13.2) meV/Å, respectively, we employ the trained potential to model Li transport in both bulk LiPON and across Li||LiPON interfaces. Amorphous LiPON structures generated by the optimized potential resemble those generated by <i>ab initio</i> molecular dynamics, with N being incorporated on nonbridging apical and bridging sites. Subsequent analysis of Li⁺ diffusivity in the bulk LiPON structures indicates broad agreement with prior computational and experimental literature. Further, we investigate the anisotropy in Li⁺ transport across the Li(110)||LiPON and Li(111)||LiPON interface, where we observe Li transport across the interface to be one order of magnitude slower than Li motion within the bulk Li and LiPON phases. Nevertheless, we note that this anisotropy of Li transport across the interface is minor, and we do not expect it to cause any significant impedance buildup. Finally, our work highlights the efficiency of MLIPs in enabling high-fidelity modeling of complex noncrystalline systems over large length and time scales.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"5 3","pages":"458-468"},"PeriodicalIF":5.7,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12082356/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144095015","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}