{"title":"Redox-Gated Optical Modulation of Coumarin-Triphenyliminophosphorane Fluorophores.","authors":"Wei-Chu Huang, Yi-Yin Lu, Shiao-Chen Huang, Tai-Chung Lo, Shun-Yuan Luo, Wei-Hong Huang, Chih-Wei Luo, Vincent K-S Hsiao, Chih-Chien Chu","doi":"10.1021/acsphyschemau.4c00082","DOIUrl":"10.1021/acsphyschemau.4c00082","url":null,"abstract":"<p><p>Novel coumarin-triphenyliminophosphorane (TPIPP) fluorophores, synthesized via a nonhydrolytic Staudinger reaction, exhibit remarkable redox-responsive optical properties. Upon chemical and electrochemical oxidation, these compounds display a hypsochromic shift in absorption from 430 to 350 nm, accompanied by up to 11-fold fluorescence enhancement under 405 nm excitation. The fluorescence switching occurs at an electrochemical oxidation potential of approximately +2.0 V. This enhanced one-photon excited fluorescence is attributed to an emissive radical effect, stemming from in situ generated radical cations at the polarizable iminophosphorane (P=N) bond. The radical formation was confirmed by trapping experiments using tetracyanoquinodimethane, which produced characteristic absorption of radical anions around 850 nm, and by electron spin resonance studies using 5,5-dimethyl-1-pyrroline <i>N</i>-oxide as a spin trap. Conversely, two-photon excited fluorescence under 800 nm pulsed laser excitation decreases upon oxidation, likely due to reduced two-photon absorption resulting from altered π-conjugation. This work demonstrates that external redox modulation can induce significant changes in absorption profiles and enable switching between enhanced one-photon and diminished two-photon excited fluorescence, highlighting the potential of leveraging the controllable radical character of the P=N bond in designing redox-responsive fluorophores.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"5 1","pages":"92-100"},"PeriodicalIF":3.7,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11758267/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143047963","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 Physical Chemistry AuPub Date : 2024-11-02DOI: 10.1021/acsphyschemau.4c0005410.1021/acsphyschemau.4c00054
Chen Zhang*, Valerie A. Niemann, Peter Benedek, Thomas F. Jaramillo and Mathieu Doucet,
{"title":"Extracting Thin Film Structures of Energy Materials Using Transformers","authors":"Chen Zhang*, Valerie A. Niemann, Peter Benedek, Thomas F. Jaramillo and Mathieu Doucet, ","doi":"10.1021/acsphyschemau.4c0005410.1021/acsphyschemau.4c00054","DOIUrl":"https://doi.org/10.1021/acsphyschemau.4c00054https://doi.org/10.1021/acsphyschemau.4c00054","url":null,"abstract":"<p >Neutron-Transformer Reflectometry Advanced Computation Engine (<i>N-TRACE</i>), a neural network model using a transformer architecture, is introduced for neutron reflectometry data analysis. It offers fast, accurate initial parameter estimations and efficient refinements, improving efficiency and precision for real-time data analysis of lithium-mediated nitrogen reduction for electrochemical ammonia synthesis, with relevance to other chemical transformations and batteries. Despite limitations in generalizing across systems, it shows promises for the use of transformers as the basis for models that could accelerate traditional approaches to modeling reflectometry data.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"5 1","pages":"30–37 30–37"},"PeriodicalIF":3.7,"publicationDate":"2024-11-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsphyschemau.4c00054","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143091710","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 Physical Chemistry AuPub Date : 2024-11-02eCollection Date: 2025-01-22DOI: 10.1021/acsphyschemau.4c00054
Chen Zhang, Valerie A Niemann, Peter Benedek, Thomas F Jaramillo, Mathieu Doucet
{"title":"Extracting Thin Film Structures of Energy Materials Using Transformers.","authors":"Chen Zhang, Valerie A Niemann, Peter Benedek, Thomas F Jaramillo, Mathieu Doucet","doi":"10.1021/acsphyschemau.4c00054","DOIUrl":"10.1021/acsphyschemau.4c00054","url":null,"abstract":"<p><p>Neutron-Transformer Reflectometry Advanced Computation Engine (<i>N-TRACE</i>), a neural network model using a transformer architecture, is introduced for neutron reflectometry data analysis. It offers fast, accurate initial parameter estimations and efficient refinements, improving efficiency and precision for real-time data analysis of lithium-mediated nitrogen reduction for electrochemical ammonia synthesis, with relevance to other chemical transformations and batteries. Despite limitations in generalizing across systems, it shows promises for the use of transformers as the basis for models that could accelerate traditional approaches to modeling reflectometry data.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"5 1","pages":"30-37"},"PeriodicalIF":3.7,"publicationDate":"2024-11-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11758268/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143047875","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 Physical Chemistry AuPub Date : 2024-10-31DOI: 10.1021/acsphyschemau.4c0006210.1021/acsphyschemau.4c00062
André Rodrigues-Pinheiro, Amanda F. Gouveia, Elson Longo, Juan Andrés and Miguel A. San-Miguel*,
{"title":"Mechanistic Insights into Ag Nanoparticle Formation on β-Ag2WO4 Surfaces through Electron Beam Irradiation","authors":"André Rodrigues-Pinheiro, Amanda F. Gouveia, Elson Longo, Juan Andrés and Miguel A. San-Miguel*, ","doi":"10.1021/acsphyschemau.4c0006210.1021/acsphyschemau.4c00062","DOIUrl":"https://doi.org/10.1021/acsphyschemau.4c00062https://doi.org/10.1021/acsphyschemau.4c00062","url":null,"abstract":"<p >The formation of metal nanoparticles triggered by electron beam irradiations on the parent metal oxide is well-established, yet the precise mechanism remains elusive. To gain deeper insights into the time evolution of the electron beam-driven processes on (011), (111), (001), and (110) surfaces of β-Ag<sub>2</sub>WO<sub>4</sub>, we have employed density functional theory (DFT) calculations and ab initio molecular dynamics (AIMD) simulations to reveal the diffusion processes of Ag cations, the amorphization of the surfaces, and a straightforward interpretation of the time evolution for the formation of Ag nanoclusters at the β-Ag<sub>2</sub>WO<sub>4</sub> surfaces. Present findings advanced a clear visualization, at the atomic level, of how the added electrons induce structural and electronic transformations at β-Ag<sub>2</sub>WO<sub>4</sub> to render the formation of Ag metal nanoparticles/β-Ag<sub>2</sub>WO<sub>4</sub> n/p-type semiconductors.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"5 2","pages":"139–150 139–150"},"PeriodicalIF":3.7,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsphyschemau.4c00062","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143696576","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 Physical Chemistry AuPub Date : 2024-10-29eCollection Date: 2024-11-27DOI: 10.1021/acsphyschemau.4c00073
James D Shipp, Ricardo J Fernández-Terán, Alexander J Auty, Heather Carson, Andrew J Sadler, Michael Towrie, Igor V Sazanovich, Paul M Donaldson, Anthony J H M Meijer, Julia A Weinstein
{"title":"Two-Dimensional Infrared Spectroscopy Resolves the Vibrational Landscape in Donor-Bridge-Acceptor Complexes with Site-Specific Isotopic Labeling.","authors":"James D Shipp, Ricardo J Fernández-Terán, Alexander J Auty, Heather Carson, Andrew J Sadler, Michael Towrie, Igor V Sazanovich, Paul M Donaldson, Anthony J H M Meijer, Julia A Weinstein","doi":"10.1021/acsphyschemau.4c00073","DOIUrl":"10.1021/acsphyschemau.4c00073","url":null,"abstract":"<p><p>Donor-bridge-acceptor complexes (D-B-A) are important model systems for understanding of light-induced processes. Here, we apply two-color two-dimensional infrared (2D-IR) spectroscopy to D-B-A complexes with a <i>trans</i>-Pt(II) acetylide bridge (D-C≡C-Pt-C≡C-A) to uncover the mechanism of vibrational energy redistribution (IVR). Site-selective <sup>13</sup>C isotopic labeling of the bridge is used to decouple the acetylide modes positioned on either side of the Pt-center. Decoupling of the D-acetylide- from the A-acetylide- enables site-specific investigation of vibrational energy transfer (VET) rates, dynamic anharmonicities, and spectral diffusion. Surprisingly, the asymmetrically labeled D-B-A still undergoes intramolecular IVR between acetylide groups even though they are decoupled and positioned across a heavy atom usually perceived as a \"vibrational bottleneck\". Further, the rate of population transfer from the bridge to the acceptor was both site-specific and distance dependent. We show that vibrational excitation of the acetylide modes is transferred to ligand-centered modes on a subpicosecond time scale, followed by VET to solvent modes on the time scale of a few picoseconds. We also show that isotopic substitution does not affect the rate of spectral diffusion, indicating that changes in the vibrational dynamics are not a result of differences in local environment around the acetylides. Oscillations imprinted on the decay of the vibrationally excited acceptor-localized carbonyl modes show they enter a coherent superposition of states after excitation that dephases over 1-2 ps, and thus cannot be treated as independent in the 2D-IR spectra. These findings elucidate the vibrational landscape governing IR-mediated electron transfer and illustrate the power of isotopic labeling combined with multidimensional IR spectroscopy to disentangle vibrational energy propagation pathways in complex systems.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"4 6","pages":"761-772"},"PeriodicalIF":3.7,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11613348/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142781018","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 Physical Chemistry AuPub Date : 2024-10-29DOI: 10.1021/acsphyschemau.4c0004010.1021/acsphyschemau.4c00040
Masahiko Taguchi, Shun Sakuraba, Justin Chan and Hidetoshi Kono*,
{"title":"Unveiling the Photoactivation Mechanism of BLUF Photoreceptor Protein through Hybrid Quantum Mechanics/Molecular Mechanics Free-Energy Calculation","authors":"Masahiko Taguchi, Shun Sakuraba, Justin Chan and Hidetoshi Kono*, ","doi":"10.1021/acsphyschemau.4c0004010.1021/acsphyschemau.4c00040","DOIUrl":"https://doi.org/10.1021/acsphyschemau.4c00040https://doi.org/10.1021/acsphyschemau.4c00040","url":null,"abstract":"<p >OaPAC is a photoactivated enzyme that forms a homodimer. The two blue-light using flavin (BLUF) photoreceptor domains are connected to the catalytic domains with long coiled-coil C-terminal helices. Upon photoreception, reorganization of the hydrogen bonding network between Tyr6, Gln48, and the chromophore in the BLUF domain and keto–enol tautomerization of Gln48 are thought to occur. However, the quantitative energetics of the photoisomerization reaction and how the BLUF domain’s structural change propagates toward the catalytic domain are still unknown. We evaluate the free-energy differences among the dark-state and two different light-state structures by the free-energy perturbation calculations combined with QM/MM free-energy optimizations. Furthermore, we performed long-time MD simulations for the free-energetically optimized dark- and light-state structures to clarify the differences in protein dynamics upon photoisomerization. The free-energy difference between the two optimized light-state structures was estimated at ∼4.7 kcal/mol. The free-energetically optimized light-state structure indicates that the chemically unstable enol tautomer of Gln48 in the light state is stabilized by forming a strong hydrogen bonding network with the chromophore and Tyr6. In addition, the components of free-energy difference between the dark- and light-state structures show that the energy upon photoreception is stored in the environment rather than the internal photoreceived region, suggesting a mechanism to keep the photoactivated signaling state with the chemically unstable enol tautomer of Gln48. In the light state, a fluctuation of Trp90 near the C-terminal helix becomes large, which causes subsequent structural changes in the BLUF core and the C-terminal helix. We also identified residue pairs with significant differences concerning residue-wise contact maps between the dark and light states.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"4 6","pages":"647–659 647–659"},"PeriodicalIF":3.7,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsphyschemau.4c00040","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142713631","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 Physical Chemistry AuPub Date : 2024-10-29DOI: 10.1021/acsphyschemau.4c0007310.1021/acsphyschemau.4c00073
James D. Shipp*, Ricardo J. Fernández-Terán*, Alexander J. Auty, Heather Carson, Andrew J. Sadler, Michael Towrie, Igor V. Sazanovich, Paul M. Donaldson, Anthony J. H. M. Meijer and Julia A. Weinstein*,
{"title":"Two-Dimensional Infrared Spectroscopy Resolves the Vibrational Landscape in Donor–Bridge–Acceptor Complexes with Site-Specific Isotopic Labeling","authors":"James D. Shipp*, Ricardo J. Fernández-Terán*, Alexander J. Auty, Heather Carson, Andrew J. Sadler, Michael Towrie, Igor V. Sazanovich, Paul M. Donaldson, Anthony J. H. M. Meijer and Julia A. Weinstein*, ","doi":"10.1021/acsphyschemau.4c0007310.1021/acsphyschemau.4c00073","DOIUrl":"https://doi.org/10.1021/acsphyschemau.4c00073https://doi.org/10.1021/acsphyschemau.4c00073","url":null,"abstract":"<p >Donor–bridge–acceptor complexes (D–B–A) are important model systems for understanding of light-induced processes. Here, we apply two-color two-dimensional infrared (2D-IR) spectroscopy to D–B–A complexes with a <i>trans</i>-Pt(II) acetylide bridge (D–C≡C–Pt–C≡C–A) to uncover the mechanism of vibrational energy redistribution (IVR). Site-selective <sup>13</sup>C isotopic labeling of the bridge is used to decouple the acetylide modes positioned on either side of the Pt-center. Decoupling of the D-acetylide- from the A-acetylide- enables site-specific investigation of vibrational energy transfer (VET) rates, dynamic anharmonicities, and spectral diffusion. Surprisingly, the asymmetrically labeled D–B–A still undergoes intramolecular IVR between acetylide groups even though they are decoupled and positioned across a heavy atom usually perceived as a “vibrational bottleneck”. Further, the rate of population transfer from the bridge to the acceptor was both site-specific and distance dependent. We show that vibrational excitation of the acetylide modes is transferred to ligand-centered modes on a subpicosecond time scale, followed by VET to solvent modes on the time scale of a few picoseconds. We also show that isotopic substitution does not affect the rate of spectral diffusion, indicating that changes in the vibrational dynamics are not a result of differences in local environment around the acetylides. Oscillations imprinted on the decay of the vibrationally excited acceptor-localized carbonyl modes show they enter a coherent superposition of states after excitation that dephases over 1–2 ps, and thus cannot be treated as independent in the 2D-IR spectra. These findings elucidate the vibrational landscape governing IR-mediated electron transfer and illustrate the power of isotopic labeling combined with multidimensional IR spectroscopy to disentangle vibrational energy propagation pathways in complex systems.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"4 6","pages":"761–772 761–772"},"PeriodicalIF":3.7,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsphyschemau.4c00073","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142713632","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":"Unveiling the Photoactivation Mechanism of BLUF Photoreceptor Protein through Hybrid Quantum Mechanics/Molecular Mechanics Free-Energy Calculation.","authors":"Masahiko Taguchi, Shun Sakuraba, Justin Chan, Hidetoshi Kono","doi":"10.1021/acsphyschemau.4c00040","DOIUrl":"10.1021/acsphyschemau.4c00040","url":null,"abstract":"<p><p>OaPAC is a photoactivated enzyme that forms a homodimer. The two blue-light using flavin (BLUF) photoreceptor domains are connected to the catalytic domains with long coiled-coil C-terminal helices. Upon photoreception, reorganization of the hydrogen bonding network between Tyr6, Gln48, and the chromophore in the BLUF domain and keto-enol tautomerization of Gln48 are thought to occur. However, the quantitative energetics of the photoisomerization reaction and how the BLUF domain's structural change propagates toward the catalytic domain are still unknown. We evaluate the free-energy differences among the dark-state and two different light-state structures by the free-energy perturbation calculations combined with QM/MM free-energy optimizations. Furthermore, we performed long-time MD simulations for the free-energetically optimized dark- and light-state structures to clarify the differences in protein dynamics upon photoisomerization. The free-energy difference between the two optimized light-state structures was estimated at ∼4.7 kcal/mol. The free-energetically optimized light-state structure indicates that the chemically unstable enol tautomer of Gln48 in the light state is stabilized by forming a strong hydrogen bonding network with the chromophore and Tyr6. In addition, the components of free-energy difference between the dark- and light-state structures show that the energy upon photoreception is stored in the environment rather than the internal photoreceived region, suggesting a mechanism to keep the photoactivated signaling state with the chemically unstable enol tautomer of Gln48. In the light state, a fluctuation of Trp90 near the C-terminal helix becomes large, which causes subsequent structural changes in the BLUF core and the C-terminal helix. We also identified residue pairs with significant differences concerning residue-wise contact maps between the dark and light states.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"4 6","pages":"647-659"},"PeriodicalIF":3.7,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11613238/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142781198","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 Physical Chemistry AuPub Date : 2024-10-25eCollection Date: 2024-11-27DOI: 10.1021/acsphyschemau.4c00070
Jack Dalton, Natércia D N Rodrigues, Daniel Berndt, Vasilios G Stavros
{"title":"Evaluating the Fluorescence Quenching of Troxerutin for Commercial UV Sunscreen Filters.","authors":"Jack Dalton, Natércia D N Rodrigues, Daniel Berndt, Vasilios G Stavros","doi":"10.1021/acsphyschemau.4c00070","DOIUrl":"10.1021/acsphyschemau.4c00070","url":null,"abstract":"<p><p>2-Phenylbenzimidazole-5-sulfonic acid (PBSA) and disodium phenyl dibenzimidazole tetrasulfonate (DPDT) are commercially available ultraviolet (UV) sunscreen filters that are known to undergo radiative relaxation following the absorption of UV light. The release of high-energy photons from this relaxation can be detrimental to human health; therefore, fluorescence quenchers need to be incorporated in commercial sunscreen formulations containing PBSA or DPDT. Troxerutin is a fluorescence quencher utilized for DPDT commercially. Here, its ability to quench the fluorescence of both PBSA and DPDT is evaluated using a dual-pronged approach by breaking down the multicomponent problem into its constituent parts. First, PBSA and DPDT's femtosecond to nanosecond photodynamics are uncovered in solution and on the surface of a human skin mimic to ascertain a benchmark. Second, these results are compared to their photodynamics in the presence of troxerutin. A significant reduction in the fluorescence lifetime is observed for both PBSA and DPDT on a human skin mimic with the addition of troxerutin, which is attributed to a Dexter energy transfer (DET) or Förster resonance energy transfer (FRET) quenching mechanism. This finding demonstrates the hitherto unseen fluorescence quenching mechanism of troxerutin on a human skin mimic and its role in quenching the fluorescence of commercial UV sunscreen filters through a DET or FRET mechanism.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"4 6","pages":"750-760"},"PeriodicalIF":3.7,"publicationDate":"2024-10-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11613208/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142780745","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 Physical Chemistry AuPub Date : 2024-10-24DOI: 10.1021/acsphyschemau.4c0007010.1021/acsphyschemau.4c00070
Jack Dalton, Natércia d. N. Rodrigues, Daniel Berndt and Vasilios G. Stavros*,
{"title":"Evaluating the Fluorescence Quenching of Troxerutin for Commercial UV Sunscreen Filters","authors":"Jack Dalton, Natércia d. N. Rodrigues, Daniel Berndt and Vasilios G. Stavros*, ","doi":"10.1021/acsphyschemau.4c0007010.1021/acsphyschemau.4c00070","DOIUrl":"https://doi.org/10.1021/acsphyschemau.4c00070https://doi.org/10.1021/acsphyschemau.4c00070","url":null,"abstract":"<p >2-Phenylbenzimidazole-5-sulfonic acid (PBSA) and disodium phenyl dibenzimidazole tetrasulfonate (DPDT) are commercially available ultraviolet (UV) sunscreen filters that are known to undergo radiative relaxation following the absorption of UV light. The release of high-energy photons from this relaxation can be detrimental to human health; therefore, fluorescence quenchers need to be incorporated in commercial sunscreen formulations containing PBSA or DPDT. Troxerutin is a fluorescence quencher utilized for DPDT commercially. Here, its ability to quench the fluorescence of both PBSA and DPDT is evaluated using a dual-pronged approach by breaking down the multicomponent problem into its constituent parts. First, PBSA and DPDT’s femtosecond to nanosecond photodynamics are uncovered in solution and on the surface of a human skin mimic to ascertain a benchmark. Second, these results are compared to their photodynamics in the presence of troxerutin. A significant reduction in the fluorescence lifetime is observed for both PBSA and DPDT on a human skin mimic with the addition of troxerutin, which is attributed to a Dexter energy transfer (DET) or Förster resonance energy transfer (FRET) quenching mechanism. This finding demonstrates the hitherto unseen fluorescence quenching mechanism of troxerutin on a human skin mimic and its role in quenching the fluorescence of commercial UV sunscreen filters through a DET or FRET mechanism.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"4 6","pages":"750–760 750–760"},"PeriodicalIF":3.7,"publicationDate":"2024-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsphyschemau.4c00070","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142719580","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}