Pub Date : 2026-03-17DOI: 10.1021/acs.jpclett.6c00260
Jie Ma,Tianle Liu,Zhengzheng Dang,Yanming Wang,Yuljae Cho
Quasi-two-dimensional (Q2D) metal halide perovskites (PVSKs) have attracted great attention due to their improved environmental stability over three-dimensional ones. However, solution-based synthesis commonly yields mixed phases in the PVSKs that introduce an energetic disorder, limiting efficient carrier transport and thus device performance. In spite of its high demand, achieving phase-pure Q2D PVSKs remains challenging particularly for highly hydrophobic spacers due to supersaturation at the liquid-air interface and uncontrolled nucleation during crystallization. Here, we report a cosolvent-controlled crystallization method via an aqueous route, enabling the synthesis of phase-pure Q2D PVSKs single crystals based on 2-thiophenemethylammonium (TMA) with n = 1-3. Introducing sulfolane as the cosolvent increases the solubility of TMA and reduces the surface excess concentration of PVSK precursors, suppressing supersaturation and random nucleation. As a result, we obtain highly crystalline, phase-pure Q2D PVSK single crystals, confirmed by PL, XRD, and single-crystal XRD. Photodetectors fabricated from the phase-pure crystals exhibit low dark current, a high on/off ratio, high responsivity, high specific detectivity, and fast rise and fall time. This work establishes an effective strategy to overcome spacer-induced phase inhomogeneity and expands the library of phase-pure Q2D PVSKs for stable, high-performance optoelectronics.
{"title":"Phase-Pure Thiophene-Based Quasi-2D Perovskite Single Crystals via Cosolvent-Controlled Crystallization.","authors":"Jie Ma,Tianle Liu,Zhengzheng Dang,Yanming Wang,Yuljae Cho","doi":"10.1021/acs.jpclett.6c00260","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c00260","url":null,"abstract":"Quasi-two-dimensional (Q2D) metal halide perovskites (PVSKs) have attracted great attention due to their improved environmental stability over three-dimensional ones. However, solution-based synthesis commonly yields mixed phases in the PVSKs that introduce an energetic disorder, limiting efficient carrier transport and thus device performance. In spite of its high demand, achieving phase-pure Q2D PVSKs remains challenging particularly for highly hydrophobic spacers due to supersaturation at the liquid-air interface and uncontrolled nucleation during crystallization. Here, we report a cosolvent-controlled crystallization method via an aqueous route, enabling the synthesis of phase-pure Q2D PVSKs single crystals based on 2-thiophenemethylammonium (TMA) with n = 1-3. Introducing sulfolane as the cosolvent increases the solubility of TMA and reduces the surface excess concentration of PVSK precursors, suppressing supersaturation and random nucleation. As a result, we obtain highly crystalline, phase-pure Q2D PVSK single crystals, confirmed by PL, XRD, and single-crystal XRD. Photodetectors fabricated from the phase-pure crystals exhibit low dark current, a high on/off ratio, high responsivity, high specific detectivity, and fast rise and fall time. This work establishes an effective strategy to overcome spacer-induced phase inhomogeneity and expands the library of phase-pure Q2D PVSKs for stable, high-performance optoelectronics.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"213 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147471700","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-16DOI: 10.1021/acs.jpclett.6c00414
Yuming Shu, Hanghang Lei, Qing Pan, Wanyi Zhang, Shuang Yang, Guoqiang Zou, Hongshuai Hou, Wentao Deng, Di Chen, Xiaobo Ji
The practical reversibility of Li–O2 batteries is constrained by the electronically insulating discharge product Li2O2, which limits interfacial reaction kinetics, induces large charge polarization, and accelerates electrolyte decomposition. Here we introduce Pr(NO3)3 as an electrolyte additive to generate in situ an amorphous, three-dimensional PrOx framework on a Co3O4/CNT cathode during the first discharge. This framework confines Li2O2 growth to produce nanosized, poorly ordered Li2O2 and, at the same time, provides abundant active sites and continuous electron pathways for O2 redox and Li2O2 formation/decomposition. As a result, the voltage gap decreases from 1.66 to 1.16 V at 200 μA cm–2 under a limited capacity of 400 μAh cm–2. The lowered charging potential also suppresses Li2CO3 formation, leading to an improved cycling stability.
{"title":"In Situ PrOx Framework Enables Reversible Reaction Pathways in Li–O2 Batteries","authors":"Yuming Shu, Hanghang Lei, Qing Pan, Wanyi Zhang, Shuang Yang, Guoqiang Zou, Hongshuai Hou, Wentao Deng, Di Chen, Xiaobo Ji","doi":"10.1021/acs.jpclett.6c00414","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c00414","url":null,"abstract":"The practical reversibility of Li–O<sub>2</sub> batteries is constrained by the electronically insulating discharge product Li<sub>2</sub>O<sub>2</sub>, which limits interfacial reaction kinetics, induces large charge polarization, and accelerates electrolyte decomposition. Here we introduce Pr(NO<sub>3</sub>)<sub>3</sub> as an electrolyte additive to generate in situ an amorphous, three-dimensional PrO<sub><i>x</i></sub> framework on a Co<sub>3</sub>O<sub>4</sub>/CNT cathode during the first discharge. This framework confines Li<sub>2</sub>O<sub>2</sub> growth to produce nanosized, poorly ordered Li<sub>2</sub>O<sub>2</sub> and, at the same time, provides abundant active sites and continuous electron pathways for O<sub>2</sub> redox and Li<sub>2</sub>O<sub>2</sub> formation/decomposition. As a result, the voltage gap decreases from 1.66 to 1.16 V at 200 μA cm<sup>–2</sup> under a limited capacity of 400 μAh cm<sup>–2</sup>. The lowered charging potential also suppresses Li<sub>2</sub>CO<sub>3</sub> formation, leading to an improved cycling stability.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"31 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147461849","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-16DOI: 10.1021/acs.jpclett.6c00561
Sumit Sahu, Berk Delibas, Jahan M. Dawlaty
Controlling chemical reactivity by engineering the immediate electrostatic and solvation microenvironment of a reactant is a central goal of chemistry. Crown ethers covalently attached to reactive centers have emerged as a versatile supramolecular motif for modulating reactivity by selectively positioning metal ions near functional groups and generating localized electrostatic fields without altering covalent structure. Here, we demonstrate ion-controlled modulation of acidity in an archetypal benzoic acid system covalently functionalized with a metal-binding crown ether. Experimental pKa measurements, supported by density functional theory calculations, show that encapsulated metal ions act as effective electron-withdrawing units that stabilize the carboxylate conjugate base. We show that the induced acidity change depends on metal-ion identity, charge, size complementarity with crown ether, and hydration energy. This study establishes a quantitative framework for defining Hammett-like parameters for metal ions and provides design principles and limitations for controlling acid–base chemistry using crown ether motifs. More broadly, it demonstrates a general supramolecular strategy for tuning reactivity via noncovalent electrostatic effects.
{"title":"Ions as Substituents: A Supramolecular Hammett Approach for Electrostatic Control of Acidity","authors":"Sumit Sahu, Berk Delibas, Jahan M. Dawlaty","doi":"10.1021/acs.jpclett.6c00561","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c00561","url":null,"abstract":"Controlling chemical reactivity by engineering the immediate electrostatic and solvation microenvironment of a reactant is a central goal of chemistry. Crown ethers covalently attached to reactive centers have emerged as a versatile supramolecular motif for modulating reactivity by selectively positioning metal ions near functional groups and generating localized electrostatic fields without altering covalent structure. Here, we demonstrate ion-controlled modulation of acidity in an archetypal benzoic acid system covalently functionalized with a metal-binding crown ether. Experimental p<i>K</i><sub>a</sub> measurements, supported by density functional theory calculations, show that encapsulated metal ions act as effective electron-withdrawing units that stabilize the carboxylate conjugate base. We show that the induced acidity change depends on metal-ion identity, charge, size complementarity with crown ether, and hydration energy. This study establishes a quantitative framework for defining Hammett-like parameters for metal ions and provides design principles and limitations for controlling acid–base chemistry using crown ether motifs. More broadly, it demonstrates a general supramolecular strategy for tuning reactivity via noncovalent electrostatic effects.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"308 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147461850","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-16DOI: 10.1021/acs.jpclett.5c03651
Shahzad Alam,Yeon Lee,Bryan Voigt,William Moore,Bhaskar Das,Moumita Maiti,Chris Leighton,Renee R. Frontiera
Iron pyrite (FeS2) is a promising photovoltaic due to its strong light absorption, low-toxicity constituents, and low cost, yet pyrite devices suffer from poor open-circuit voltage and efficiency. The role of excited-state electron–phonon coupling (EPC), which drives structural distortion and energy loss following photoexcitation, remains underexplored in pyrite. Here, we use resonance Raman intensity analysis (RRIA) to quantify excited-state EPC in pristine, electron-doped, and hole-doped pyrite single crystals by determining the Huang–Rhys factors for three phonon modes. We find exceptionally strong excited-state EPC in pristine pyrite, dominated by the 347 cm–1 mode. Sulfur vacancies and phosphorus doping reduce the EPC strength for this mode, while cobalt doping significantly suppresses the EPC for all modes. Correlation analysis further reveals that higher doping systematically weakens EPC through electronic screening. These results demonstrate that excited-state EPC varies substantially with doping and impacts nonradiative energy loss, directly informing strategies to suppress vibrational losses in pyrite photovoltaics.
{"title":"Excited-State Electron–Phonon Coupling in Pristine and Doped Iron Pyrite","authors":"Shahzad Alam,Yeon Lee,Bryan Voigt,William Moore,Bhaskar Das,Moumita Maiti,Chris Leighton,Renee R. Frontiera","doi":"10.1021/acs.jpclett.5c03651","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c03651","url":null,"abstract":"Iron pyrite (FeS2) is a promising photovoltaic due to its strong light absorption, low-toxicity constituents, and low cost, yet pyrite devices suffer from poor open-circuit voltage and efficiency. The role of excited-state electron–phonon coupling (EPC), which drives structural distortion and energy loss following photoexcitation, remains underexplored in pyrite. Here, we use resonance Raman intensity analysis (RRIA) to quantify excited-state EPC in pristine, electron-doped, and hole-doped pyrite single crystals by determining the Huang–Rhys factors for three phonon modes. We find exceptionally strong excited-state EPC in pristine pyrite, dominated by the 347 cm–1 mode. Sulfur vacancies and phosphorus doping reduce the EPC strength for this mode, while cobalt doping significantly suppresses the EPC for all modes. Correlation analysis further reveals that higher doping systematically weakens EPC through electronic screening. These results demonstrate that excited-state EPC varies substantially with doping and impacts nonradiative energy loss, directly informing strategies to suppress vibrational losses in pyrite photovoltaics.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"237 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147462267","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-16DOI: 10.1021/acs.jpclett.5c04090
Xiang Sun, Zengkui Liu
Nonadiabatic dynamics in the condensed phase often involve correlated environments shared by multiple electronic states, challenging the traditional isolated bath assumption. We investigate these effects using the multistate harmonic (MSH) model and atomistic Hamiltonian applied to photoinduced charge transfer in a trimer consisting of a methylperylene donor and two tetracyanoethylene acceptors dissolved in a polar solvent. We propose a geometric metric based on the angular relationship of reorganization energies between transitions sharing an initial state to quantify bath correlation. Our analysis identifies distinct regimes: a correlated bath where synchronized energy gap fluctuations facilitate competing reactions, and an anticorrelated bath where fluctuations favoring one reaction suppress the other. These energetic correlations are modulated by molecular conformation and charge distribution, specifically through changes in dipole moments and solvent-accessible surface area. This study provides a connection between the energetic perspective of environmental correlations and the molecular details governing nonadiabatic dynamics in polar solvents.
{"title":"Molecular Origin of Correlated Bath Effects in Photoinduced Charge Transfer Dynamics in Polar Solvents","authors":"Xiang Sun, Zengkui Liu","doi":"10.1021/acs.jpclett.5c04090","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c04090","url":null,"abstract":"Nonadiabatic dynamics in the condensed phase often involve correlated environments shared by multiple electronic states, challenging the traditional isolated bath assumption. We investigate these effects using the multistate harmonic (MSH) model and atomistic Hamiltonian applied to photoinduced charge transfer in a trimer consisting of a methylperylene donor and two tetracyanoethylene acceptors dissolved in a polar solvent. We propose a geometric metric based on the angular relationship of reorganization energies between transitions sharing an initial state to quantify bath correlation. Our analysis identifies distinct regimes: a correlated bath where synchronized energy gap fluctuations facilitate competing reactions, and an anticorrelated bath where fluctuations favoring one reaction suppress the other. These energetic correlations are modulated by molecular conformation and charge distribution, specifically through changes in dipole moments and solvent-accessible surface area. This study provides a connection between the energetic perspective of environmental correlations and the molecular details governing nonadiabatic dynamics in polar solvents.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147461848","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Solid-state near-infrared (NIR)-to-visible triplet–triplet annihilation upconversion (TTA-UC) at the 1 μm edge is attractive for deep-tissue photonics and NIR energy harvesting but remains limited by sensitizer losses and restricted triplet transport in condensed media. Here we demonstrate porous poly(vinyl alcohol) (PVA)/rubrene films sensitized by spin-forbidden Ru complexes (DX1m–DX3m) with appreciable NIR absorption. Photon-flux-normalized action spectra show sensitizer-dependent red-edge response across the series, and DX3m affords quantifiable upconversion under 1000 nm femtosecond and 980 nm continuous-wave excitation, with detectable spectra to 1030 nm. Because spin-forbidden Ru sensitizers offer molecular tunability yet face threshold limitations from red-edge absorption and short triplet lifetimes, we examined what governs the operating thresholds in porous films. Transient kinetics indicate that excitation range is sensitizer-controlled, whereas thresholds are governed by triplet survival and encounter kinetics in porous domains rather than sensitizer-to-annihilator triplet–triplet energy transfer alone. These results establish a Ru-based route to 1-μm-class solid-state TTA-UC in polymer films.
{"title":"Spin-Forbidden Ru Sensitizers Enable 1 μm Excitation for Solid-State Triplet–Triplet Annihilation Photon Upconversion","authors":"Takumi Kinoshita, Takeshi Mori, Tomohiro Mori, Hiroshi Segawa, Hitoshi Saomoto","doi":"10.1021/acs.jpclett.6c00275","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c00275","url":null,"abstract":"Solid-state near-infrared (NIR)-to-visible triplet–triplet annihilation upconversion (TTA-UC) at the 1 μm edge is attractive for deep-tissue photonics and NIR energy harvesting but remains limited by sensitizer losses and restricted triplet transport in condensed media. Here we demonstrate porous poly(vinyl alcohol) (PVA)/rubrene films sensitized by spin-forbidden Ru complexes (<b>DX1m</b>–<b>DX3m</b>) with appreciable NIR absorption. Photon-flux-normalized action spectra show sensitizer-dependent red-edge response across the series, and <b>DX3m</b> affords quantifiable upconversion under 1000 nm femtosecond and 980 nm continuous-wave excitation, with detectable spectra to 1030 nm. Because spin-forbidden Ru sensitizers offer molecular tunability yet face threshold limitations from red-edge absorption and short triplet lifetimes, we examined what governs the operating thresholds in porous films. Transient kinetics indicate that excitation range is sensitizer-controlled, whereas thresholds are governed by triplet survival and encounter kinetics in porous domains rather than sensitizer-to-annihilator triplet–triplet energy transfer alone. These results establish a Ru-based route to 1-μm-class solid-state TTA-UC in polymer films.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"17 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147462060","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Single-molecule fluorescence blinking reflects reversible transitions between open emissive and closed nonemissive forms of rhodamine dyes. These transitions are strongly influenced by the local chemical environment. Here, we establish fluorescence blinking as a quantitative and interpretable readout of local physicochemical interactions. Hydroxymethyl silicon-rhodamine (HMSiR) was covalently linked to a series of short peptides designed to span defined electrostatic, hydrophobic, and hydrogen-bonding properties. Each peptide created a distinct microenvironment that modulated the spirocyclization equilibrium of the fluorophore. Blinking trajectories recorded under controlled conditions yielded descriptors such as on-state dwell times and state-transition statistics, which served as optical signatures of peptide-fluorophore interactions. Machine learning regression mapped these descriptors onto continuous physicochemical parameters, enabling accurate prediction of peptide net-charge, hydrophobicity, and hydrogen-bonding capacity. This work provides a direct connection between blinking dynamics and local physicochemical interactions, transforming stochastic fluorescence blinking into a mechanism-based chemical readout.
{"title":"Decoding Physicochemical Interactions Via Single-Molecule Fluorescence Blinking.","authors":"Yifeng Cheng,Jian Mao,Yue Li,Xintong Miao,Zheng Zhen,Guangyong Qin,Zhenzhen Feng,Xiaojuan Wang,Fang Huang,Hua He","doi":"10.1021/acs.jpclett.6c00001","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c00001","url":null,"abstract":"Single-molecule fluorescence blinking reflects reversible transitions between open emissive and closed nonemissive forms of rhodamine dyes. These transitions are strongly influenced by the local chemical environment. Here, we establish fluorescence blinking as a quantitative and interpretable readout of local physicochemical interactions. Hydroxymethyl silicon-rhodamine (HMSiR) was covalently linked to a series of short peptides designed to span defined electrostatic, hydrophobic, and hydrogen-bonding properties. Each peptide created a distinct microenvironment that modulated the spirocyclization equilibrium of the fluorophore. Blinking trajectories recorded under controlled conditions yielded descriptors such as on-state dwell times and state-transition statistics, which served as optical signatures of peptide-fluorophore interactions. Machine learning regression mapped these descriptors onto continuous physicochemical parameters, enabling accurate prediction of peptide net-charge, hydrophobicity, and hydrogen-bonding capacity. This work provides a direct connection between blinking dynamics and local physicochemical interactions, transforming stochastic fluorescence blinking into a mechanism-based chemical readout.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"44 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147461772","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The accurate modeling of the excited state landscapes in chiral materials requires an optimal balance between the description of their electronic structure and the influence of environmental effects. In this work, using a prototypical lead halide chiral perovskite, we show that embedding a chromophore in point charges has a beneficial effect in correcting the spurious representation of charge-transfer states arising from hybrid or semilocal approximations within density functional theory (DFT). Notably, the effect of the embedding also outperforms the benefits induced by the range-separated functionals. While the nature of the state remains similar, we demonstrate that the addition of point charges significantly decreases the electron–hole distance. The combination of hybrid functionals with embedding provides the best description of the experimental absorption spectrum, with the only exception being excitonic states that cannot be reproduced when considering a model constituted by a single cell.
{"title":"Optical Properties of Chiral Perovskites: The Role of Electrostatic Embedding in Correcting the Accuracy of Exchange-Correlation Functionals","authors":"Amina Alehyane,Elise Lognon,Mariagrazia Fortino,Eric Brémond,Florent Barbault,Adriana Pietropaolo,Antonio Monari","doi":"10.1021/acs.jpclett.6c00309","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c00309","url":null,"abstract":"The accurate modeling of the excited state landscapes in chiral materials requires an optimal balance between the description of their electronic structure and the influence of environmental effects. In this work, using a prototypical lead halide chiral perovskite, we show that embedding a chromophore in point charges has a beneficial effect in correcting the spurious representation of charge-transfer states arising from hybrid or semilocal approximations within density functional theory (DFT). Notably, the effect of the embedding also outperforms the benefits induced by the range-separated functionals. While the nature of the state remains similar, we demonstrate that the addition of point charges significantly decreases the electron–hole distance. The combination of hybrid functionals with embedding provides the best description of the experimental absorption spectrum, with the only exception being excitonic states that cannot be reproduced when considering a model constituted by a single cell.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"308 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147462265","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-16DOI: 10.1021/acs.jpclett.5c04106
Premashis Manna,Mark A. Hix,Srijit Mukherjee,Alice R. Walker,Ralph Jimenez
Developing bright and photostable red fluorescent proteins (RFPs) is one of the “holy grails” of the protein engineering community. Despite several attempts, such fluorescent proteins (FPs) have remained elusive. One bottleneck to engineering next-generation RFPs is our lack of understanding of nonfluorescent or dark-state properties in such constructs. Here, we develop a theoretical and experimental framework that describes how photobleaching decays in FPs relate to dark-state conversion and ground-state recovery. Our systematic photophysical investigation of mCherry and mCherry-d, an RFP with enhanced dark-state behavior, showed the presence of photodestructive dark states in such FPs. Molecular dynamics simulations reveal enhanced fluctuation around the imidazolinone end of the chromophore in mCherry-d, potentially facilitating conversion to nonfluorescent states. Collectively, this work quantifies dark-state kinetics and provides insights into engineering dark states in RFPs to develop bright, yet photostable, molecular probes.
{"title":"Dark-State-Mediated Photobleaching in mCherry-Based Red Fluorescent Proteins","authors":"Premashis Manna,Mark A. Hix,Srijit Mukherjee,Alice R. Walker,Ralph Jimenez","doi":"10.1021/acs.jpclett.5c04106","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c04106","url":null,"abstract":"Developing bright and photostable red fluorescent proteins (RFPs) is one of the “holy grails” of the protein engineering community. Despite several attempts, such fluorescent proteins (FPs) have remained elusive. One bottleneck to engineering next-generation RFPs is our lack of understanding of nonfluorescent or dark-state properties in such constructs. Here, we develop a theoretical and experimental framework that describes how photobleaching decays in FPs relate to dark-state conversion and ground-state recovery. Our systematic photophysical investigation of mCherry and mCherry-d, an RFP with enhanced dark-state behavior, showed the presence of photodestructive dark states in such FPs. Molecular dynamics simulations reveal enhanced fluctuation around the imidazolinone end of the chromophore in mCherry-d, potentially facilitating conversion to nonfluorescent states. Collectively, this work quantifies dark-state kinetics and provides insights into engineering dark states in RFPs to develop bright, yet photostable, molecular probes.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"17 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147462300","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The morphology and property of the high-temperature proton exchange membranes (PEMs) based on short-side-chain perfluorosulfonic acid (SSC-PFSA) are determined by the polymer structure in dispersion during solution casting. In this work, by using rheological analysis and structural characterization techniques, including Cryo-transmission electron microscope (Cryo-TEM) and small-angle X-ray scattering (SAXS), the rheology and microstructure of SSC-PFSA dispersions were collectively studied to spotlight the concentration dependent viscoelasticity across a large scale from dilute solution to gelation. Initially, SSC-PFSA forms rod-like primary aggregates exhibiting a scaling exponent (0.63) that deviates from the theoretical values of 0.5 (for semidilute solutions). As the concentration increases, these primary aggregates assemble into secondary aggregates, where the viscosity-concentration relationship deviates from the predicted scaling behavior. Further increasing the concentration, the secondary aggregates interact to form a percolating network, leading to gelation. This new multiscale self-assembly mechanism elucidates the fundamental connections underlying the gelation process toward membrane formation. It provides the first comprehensive understanding of the nonequilibrium morphology evolution across multiple magnitudes of concentration and length scales and finds the origin of the physical properties for SSC-PFSA electrolyte membranes.
{"title":"Viscoelasticity and Sol-Gel Transition via Multiscale Self-Assembled Nanostructures in Short-Side-Chain PFSA Dispersions.","authors":"Bonan Hao,Anyang Zhang,Jianpeng Jiang,Jingnan Song,Yanxin Zhao,Yecheng Zou,Zichun Zhou,Wei Yu,Feng Liu,Yongming Zhang","doi":"10.1021/acs.jpclett.6c00012","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c00012","url":null,"abstract":"The morphology and property of the high-temperature proton exchange membranes (PEMs) based on short-side-chain perfluorosulfonic acid (SSC-PFSA) are determined by the polymer structure in dispersion during solution casting. In this work, by using rheological analysis and structural characterization techniques, including Cryo-transmission electron microscope (Cryo-TEM) and small-angle X-ray scattering (SAXS), the rheology and microstructure of SSC-PFSA dispersions were collectively studied to spotlight the concentration dependent viscoelasticity across a large scale from dilute solution to gelation. Initially, SSC-PFSA forms rod-like primary aggregates exhibiting a scaling exponent (0.63) that deviates from the theoretical values of 0.5 (for semidilute solutions). As the concentration increases, these primary aggregates assemble into secondary aggregates, where the viscosity-concentration relationship deviates from the predicted scaling behavior. Further increasing the concentration, the secondary aggregates interact to form a percolating network, leading to gelation. This new multiscale self-assembly mechanism elucidates the fundamental connections underlying the gelation process toward membrane formation. It provides the first comprehensive understanding of the nonequilibrium morphology evolution across multiple magnitudes of concentration and length scales and finds the origin of the physical properties for SSC-PFSA electrolyte membranes.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"13 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147461681","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：