{"title":"Using Dark Dyes for Fast Super-Resolution Imaging: A Proof-of-Concept Study","authors":"Srijayee Ghosh, , , Guillaume Barnoin, , , Benoît Y. Michel, , , Alain Burger*, , , Yves Mély*, , and , Ludovic Richert*, ","doi":"10.1021/acs.jpclett.5c02302","DOIUrl":"10.1021/acs.jpclett.5c02302","url":null,"abstract":"<p >DNA-PAINT (Point Accumulation for Imaging in Nanoscale Topography) exploits the transient hybridization of a short fluorescent DNA imager strand to a complementary docking strand to achieve super-resolution imaging. However, its application is hampered by the background noise caused by unbound imager strands and the subsequent slow image acquisition. Several variants of DNA-PAINT have already been developed to successfully overcome these limitations. Here we design and validate a new alternative, based on intermolecular dark resonance energy transfer (DRET) and the use of a fluorenyl nucleobase (X) substitute incorporated into the imager strand, acting as a dark donor. Upon annealing, the fluorescence of the bright acceptor (ATTO 647N) bound to the docking strand is turned on via DRET with X. Single-molecule experiments showed that an 11 nt X-labeled imager strand provides appropriate hybridization rates with the ATTO 647N-labeled docking strand to perform DNA-PAINT. Thanks to their low background, high concentrations of imager strands can be used, facilitating the acquisition of super-resolved images of cellular microtubules within 30 s. This study provides the first proof-of-concept for this novel route to fast DNA-PAINT nanoscopy.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 39","pages":"10087–10093"},"PeriodicalIF":4.6,"publicationDate":"2025-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145088936","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}
{"title":"Regulated Aggregation of Phenyl-C61-Butyric Acid Methyl Ester (PCBM) Electron-Transporting Layer via Solvent Engineering for Performance Improvement in Perovskite Solar Cells","authors":"Huilong Chen, , , Xingting Liu, , , Xiaoyuan Liu*, , , Xin Song*, , and , Weiguo Zhu*, ","doi":"10.1021/acs.jpclett.5c02212","DOIUrl":"10.1021/acs.jpclett.5c02212","url":null,"abstract":"<p >Fullerene derivatives, particularly phenyl-C61-butyric acid methyl ester (PCBM), are widely used as electron transport layers (ETLs) in inverted perovskite solar cells due to their excellent electron extraction capabilities. However, the relatively weak solvent–solute interactions in conventional chlorobenzene solvents often lead to intrinsic PCBM aggregation, resulting in interfacial charge accumulation and reduced device performance. In this study, an asymmetrical solvent, 2-chlorothiophene (2Cl–Th), is introduced to effectively regulate PCBM agglomeration by enhancing electrostatic interactions, which can efficiently regulate the molecular dispersion and boost the uniformity of PCBM molecules. The optimized morphology can coherently suppress interfacial charge recombination and promote the carrier extraction capability, leading to a champion power conversion efficiency of 23.22% with elevated operational stability.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 39","pages":"10080–10086"},"PeriodicalIF":4.6,"publicationDate":"2025-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145083885","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}
{"title":"Unraveling Tunable Optical Anisotropy in Colloidal Quantum Wells Using Mueller Matrix Ellipsometry","authors":"Chenlin Wang, , , Yueming Wang, , , Xian Zhao, , , Baoqing Sun, , , Jie Lian*, , and , Yuan Gao*, ","doi":"10.1021/acs.jpclett.5c02425","DOIUrl":"10.1021/acs.jpclett.5c02425","url":null,"abstract":"<p >Colloidal quantum wells (CQWs) combine atomic-level thickness control with strong excitonic effects, offering a versatile platform for nanophotonics. However, their intrinsic optical anisotropy has not been quantitatively resolved with high precision. Here, we employ Mueller matrix spectroscopic ellipsometry over 350–650 nm to reveal record-high birefringence (Δ<i>n</i><sub><i>max</i></sub> ≈ 1.95) and dichroism (Δ<i>κ</i><sub><i>max</i></sub> ≈ 1.53) in self-assembled CdSe CQW monolayers─values exceeding those of natural birefringent crystals such as rutile and black phosphorus. The Mueller matrix analysis uncovers pronounced differences between in-plane and out-of-plane dielectric responses, arising from heavy-hole exciton transitions confined to the <i>a</i>–<i>b</i> plane and thickness-tunable quantum confinement along the <i>c</i>-axis. The anisotropy strengthens systematically from 5.5 to 3.5 monolayers due to increased heavy-hole/light-hole splitting and preferential in-plane dipole alignment (∼97% in-plane, confirmed by back focal plane imaging). These results position CdSe CQWs as a solution-processable platform with giant, thickness-tunable optical anisotropy, providing a foundation for advanced polarization-resolved photonic studies.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 39","pages":"10094–10101"},"PeriodicalIF":4.6,"publicationDate":"2025-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145088935","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}
{"title":"Illumination Regulated Ion Migration in Metal Halide Perovskite","authors":"Jinbao Han, , , Shengjian Qin, , , Huan Liu, , , Menghan Chen, , , Zixuan Shang, , , Boru Tian, , , Zishang Liang, , , Mengxi Lv, , , Yanli Zeng, , and , Jinjin Zhao*, ","doi":"10.1021/acs.jpclett.5c02483","DOIUrl":"10.1021/acs.jpclett.5c02483","url":null,"abstract":"<p >Ion migration in CsPbBr<sub>3</sub> perovskites, crucial for device stability and performance, is investigated under combined illumination and direct current (DC) or alternating current (AC) bias using macroelectrical and nanoscale microscopy. DC measurements demonstrate that illumination suppresses bias-induced ion migration, reducing the current drop amplitude (Δ<i>I</i>/<i>I</i>) from 60.68% (dark) to 18.19% (3.80 mW/cm<sup>2</sup>), attributed to photogenerated carrier passivating vacancies. Photocurrent atomic force microscopy reveals grain boundaries as preferential migration pathways under light, exhibiting 9.6-fold higher mechanical work dissipation than grains. Under AC bias, illumination enhances polarization, evidenced by an +8° out-of-plane phase shift in piezoresponse force microscopy, and increases surface potential (Kelvin probe force microscopy: 2.35 V dark to 3.27 V), confirming light-promoted ion migration via polarization modulation. These findings elucidate the mechanism of light-regulated ion migration in CsPbBr<sub>3</sub>, facilitating optimization of the perovskite device stability and performance.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 39","pages":"10042–10048"},"PeriodicalIF":4.6,"publicationDate":"2025-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145083930","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}
Alessandro Bonardi, , , Shuai Xu, , , Giovanni Di Liberto*, , and , Gianfranco Pacchioni*,
{"title":"Role of Water in Modulating the Fe3+/Fe2+ Redox Couple in Iron-Based Complexes and Single-Atom Catalysts","authors":"Alessandro Bonardi, , , Shuai Xu, , , Giovanni Di Liberto*, , and , Gianfranco Pacchioni*, ","doi":"10.1021/acs.jpclett.5c02424","DOIUrl":"10.1021/acs.jpclett.5c02424","url":null,"abstract":"<p >A key challenge in modeling electrocatalysis with single-atom catalysts (SACs) is accurately capturing the redox behavior of transition metals across oxidation states. This is particularly true for iron, a widely used element in such systems. Iron phthalocyanine (FePc) serves as a model compound for graphene-based Fe SACs and is commonly used in reactions like the oxygen evolution reaction (OER). While FePc initially contains Fe(II), the active species under oxidative conditions is Fe(III), with an Fe(II)/Fe(III) transition occurring at intermediate potentials. Density functional theory (DFT) simulations must reflect this redox change. However, standard DFT predicts that oxidation removes an electron from the ligand, leaving the iron in the II state. This limitation arises not from DFT itself, but from an incomplete model. We show that adding at least one (preferably two) water molecules to the axial coordination sites of iron corrects this issue. The water ligands raise the energy of iron orbitals, making electron removal from the metal more favorable. This finding has two key implications: (1) the redox properties of transition metal complexes and graphene-based SACs are strongly influenced by the coordination environment, including solvent molecules; and (2) accurate description of the atomistic structure of the catalyst requires the explicit inclusion of axial water ligands, not just the in-plane ligands, to capture the true redox behavior.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 39","pages":"10049–10057"},"PeriodicalIF":4.6,"publicationDate":"2025-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.jpclett.5c02424","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145083887","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Weak Host Interactions Induced Thermal Transport Properties of Metal Halide Perovskites Deviating from the Rattling Model","authors":"Yu Wu, , , Linxuan Ji, , , Shuming Zeng, , , Ying Chen*, , , Chenhan Liu, , and , Liujiang Zhou*, ","doi":"10.1021/acs.jpclett.5c02208","DOIUrl":"10.1021/acs.jpclett.5c02208","url":null,"abstract":"<p >The low-frequency phonon branches of metal halide perovskites typically exhibit the characteristic of hardening with the increase of the cation mass, which leads to an anomalous thermal transport phenomenon. However, the underlying physical mechanism is not yet understood. Here, we theoretically compare the thermal transport properties of A<sub>2</sub>SnI<sub>6</sub> (A = K, Rb, and Cs) perovskites. The thermal transport in perovskites is widely explained using the rattling model, where “guest” cations inside the metal halide framework act as “rattlers”, but this fails to explain the following phenomenon: The low-frequency phonon branch of A<sub>2</sub>SnI<sub>6</sub> perovskites is insensitive to the mass of the A<sup>+</sup> cation and strongly correlated with the interaction of the A<sup>+</sup> cation with the I<sup>–</sup> anion in the octahedral structures. The failure of the rattling model stems mainly from the weak interactions between the octahedral structures. We find that this weak interaction is prevalent in other metal halide perovskites. By developing a new spring model, we successfully explain the thermal transport behavior in A<sub>2</sub>SnI<sub>6</sub> perovskites. Our work gives new insights into the thermal transport mechanism in metal halide perovskites, which has a guiding significance for designing extremely low thermal conductivity materials.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 39","pages":"10035–10041"},"PeriodicalIF":4.6,"publicationDate":"2025-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145083886","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}
Kristýna Bukvišová, , , Radek Kalousek, , , Marek Patočka, , , Jakub Zlámal, , , Jakub Planer, , , Vojtěch Mahel, , , Daniel Citterberg, , , Libor Novák, , , Tomáš Šikola, , , Suneel Kodambaka, , and , Miroslav Kolíbal*,
{"title":"Capillary Wave Driven Dynamics of Graphene Domains during Growth on Molten Metals","authors":"Kristýna Bukvišová, , , Radek Kalousek, , , Marek Patočka, , , Jakub Zlámal, , , Jakub Planer, , , Vojtěch Mahel, , , Daniel Citterberg, , , Libor Novák, , , Tomáš Šikola, , , Suneel Kodambaka, , and , Miroslav Kolíbal*, ","doi":"10.1021/acs.jpclett.5c02321","DOIUrl":"10.1021/acs.jpclett.5c02321","url":null,"abstract":"<p >Rheotaxy─growth of crystalline layers on molten surfaces─is considered as a promising approach for achieving large-scale monolayers of two-dimensional (2D) materials via seamless stitching of 2D domains during growth on molten metals. However, the mechanisms leading to this process are not well understood. Here, we present in situ microscopic observations of rheotaxy of graphene via chemical vapor deposition on molten gold and copper. We show that the graphene domains undergo translational and rotational motions, leading to self-assembly, during growth on molten metals. Using environmental and ultrahigh vacuum scanning electron microscopy and high-temperature (∼1300 K) atomic force microscopy, coupled with density functional theory and continuum modeling, we suggest that the observed graphene domain dynamics is due to forces arising from capillary waves on the surface of the liquid metal. Our results provide new insights into the mechanisms leading to self-assembly during rheotaxy of 2D layers.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 38","pages":"10020–10026"},"PeriodicalIF":4.6,"publicationDate":"2025-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.jpclett.5c02321","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145071709","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Conformational Pathways of Translational T-box Riboswitch Governing tRNA Recognition for Gene Regulation","authors":"Dibyendu Mondal, and , Govardhan Reddy*, ","doi":"10.1021/acs.jpclett.5c02341","DOIUrl":"10.1021/acs.jpclett.5c02341","url":null,"abstract":"<p >Amino acid availability is crucial for protein synthesis. T-box riboswitches regulate amino acid levels in bacteria by sensing tRNA aminoacylation, ensuring precise control of the biosynthesis and transport pathways. We used coarse-grained molecular dynamics simulations to probe the mechanism of tRNA recognition by a translational T-box riboswitch using the <i>iles</i> T-box riboswitch as a model system. We showed that the T-box aptamer transitions between undocked, predocked, and docked states with Mg<sup>2+</sup> concentration governing their relative abundance. In the undocked and predocked states, the freely moving stem I catches tRNA from the solution using the “fly casting” mechanism. The tRNA-bound stem I then docks to stem II in a specific orientation stabilized by noncanonical hydrogen bonds. This docking enables interaction with the discriminator domain to sense tRNA aminoacylation and regulate gene expression. As T-box riboswitches are key antibiotic targets, our proposed mechanism reveals critical druggable sites, and the results have broader implications for understanding RNA–RNA interactions in cellular regulation.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 38","pages":"10009–10019"},"PeriodicalIF":4.6,"publicationDate":"2025-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145071905","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}
{"title":"Phosphine-Free Synthesis of Monodisperse and Size-Tunable Silver Selenide Quantum Dots via Thermo-Regulated Selenium Dioxide Reactivity for High-Efficiency NIR-II Emission","authors":"Junjie Zhang, , , Zhe Liu, , , Qingyu Wang, , , Yifan Chen, , , Xingyu Hu, , , Cong Sun, , , Mengya Lu, , , Zifeng Liu, , , Ning Dai, , and , Yang Li*, ","doi":"10.1021/acs.jpclett.5c02547","DOIUrl":"10.1021/acs.jpclett.5c02547","url":null,"abstract":"<p >Colloidal silver selenide (Ag<sub>2</sub>Se) quantum dots (QDs) are promising NIR-II emitters owing to their tunable emission and nontoxic compositions. However, current studies suffer from limited size tunability and poor photoluminescence quantum yields (PL QYs) due to conventional toxic organophosphine-based Se precursors with low reactivity. Here, we demonstrate a thermo-regulated synthetic strategy for size-tunable Ag<sub>2</sub>Se QDs employing safe and cost-effective SeO<sub>2</sub> as the Se precursor. The mechanism of tuning the Se precursor reactivity derived from SeO<sub>2</sub> by temperature control is thoroughly elucidated, enabling the controllable synthesis of monodisperse Ag<sub>2</sub>Se QDs with tunable absorption spectra and a broad size range from 3 to 15 nm. Furthermore, with a Au alloying strategy, we have successfully achieved tunable NIR-II emission (950–1250 nm) with a record-high PL QY of 53.59% at 1140 nm, along with superior photostability. The results will pave the way for eco-friendly Ag-chalcogenide QDs toward applications in biological and infrared optoelectronics.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 38","pages":"10027–10034"},"PeriodicalIF":4.6,"publicationDate":"2025-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145071903","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}
Almudena Inchausti, , , Rosa Mollfulleda, , , Marcel Swart, , , Josefina Perles, , , Santiago Herrero, , , Valentín G. Baonza, , , Mercedes Taravillo, , and , Álvaro Lobato*,
{"title":"Chemical Tuning of the Electronic Structure in Diruthenium Compounds","authors":"Almudena Inchausti, , , Rosa Mollfulleda, , , Marcel Swart, , , Josefina Perles, , , Santiago Herrero, , , Valentín G. Baonza, , , Mercedes Taravillo, , and , Álvaro Lobato*, ","doi":"10.1021/acs.jpclett.5c02176","DOIUrl":"10.1021/acs.jpclett.5c02176","url":null,"abstract":"<p >This study explores how the electronic structure of mixed valence diruthenium paddlewheel complexes can be controlled through chemical modifications. These compounds exhibit a unique electronic configuration due to the quasidegeneracy of π* and δ* orbitals, making them very attractive for applications in electronic, magnetic, catalytic, and bioinorganic systems. Through synthesis, electrochemical and spectroscopic analyses, and density functional theory (DFT) calculations, we have investigated the impact of axial ligand interactions, equatorial ligand electronic effects, and structural distortions on the molecular orbital diagram, paying special attention to how the δ*-π* gap is modified. In contrast to prior assumptions, our results show that variations in equatorial ligand donor strength shift orbital energies in parallel and, therefore, the observed UV/vis trends with Hammett-type substituents are primarily due to solvent-dependent conformational changes. Overall, our findings highlight the role of axial Ru–Cl interactions and torsion angle modifications in stabilizing spin-admixed or low-spin states, offering new pathways for controlling electronic configurations in bimetallic complexes.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 38","pages":"10000–10008"},"PeriodicalIF":4.6,"publicationDate":"2025-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145068533","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}
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