Physical chemistry articles within Nature Chemistry

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  • News & Views |

    Surface heterogeneities lead to friction between droplets and solid surfaces, limiting the performance of the latter in a number of applications. A combination of friction force measurements and atomistic molecular dynamics simulations now sheds light on the influence of molecular scale heterogeneities on droplet friction.

    • Abhinav Naga
    •  & Doris Vollmer

  • Article |

    Key molecular features that drive protein liquid–liquid phase separation (LLPS) for biomolecular condensate have been reported. A spectrum of additional interactions that influence protein LLPS and material properties have now been characterized. These interactions extend beyond a limited set of residue types and can be modulated by environmental factors such as temperature and salt concentration.

    • Shiv Rekhi
    • , Cristobal Garcia Garcia
    •  & Jeetain Mittal

  • Article |

    Accessing longer-wavelength emitting organic fluorophores is critical for diagnostic imaging. Here a series of silicon-RosIndolizine fluorophores with emission maxima at 1,300 nm, 1,550 nm and 1,700 nm were synthesized. The fluorophores generate high-resolution in vivo fluorescence images in mice and establish design principles for future shortwave-infrared fluorophore designs.

    • William E. Meador
    • , Eric Y. Lin
    •  & Jared H. Delcamp

  • Article
    | Open Access

    Time-resolved femtosecond crystallography (TR-SFX) is a powerful technique to monitor structural transitions in protein crystals at the atomic level, but its use in non-protein synthetic materials remains limited. Now TR-SFX has been used to visualize the structural dynamics of metal–organic frameworks, showing the potential of this tool to study the dynamic motion of crystalline porous materials.

    • Jaedong Kang
    • , Yunbeom Lee
    •  & Hyotcherl Ihee

  • Article
    | Open Access

    The spontaneous recombination of photogenerated radicals surrounded by solvent molecules is an important energy-wasting elementary step in photoredox reactions. Now the decisive role that cage escape plays in these reactions is shown in three benchmark photocatalytic reactions, with quantitative correlations observed between photoredox product formation rates and cage escape quantum yields.

    • Cui Wang
    • , Han Li
    •  & Oliver S. Wenger

  • Article |

    Although photoinduced concerted multiple-bond-rotation processes are known in photoactive biological systems, the synthesis of compounds exhibiting similar behaviour has proven challenging. Now a thioamide-based system featuring chalcogen substituents has been shown to exhibit photoinduced C–N/C–C rotation; the rotation mode can be switched depending on external stimuli such as temperature and light irradiation.

    • Shotaro Nagami
    • , Rintaro Kaguchi
    •  & Akira Katsuyama

  • Article |

    The design of open-shell nanographenes is commonly limited to systems featuring a single magnetic origin. Now a strategy that combines topological frustration and electron–electron interactions has been developed to generate a butterfly-shaped nanographene that hosts four highly entangled π-spins and exhibits both ferromagnetic and anti-ferromagnetic coupling.

    • Shaotang Song
    • , Andrés Pinar Solé
    •  & Jiong Lu

  • Article
    | Open Access

    Although surface-bound molecular catalysts offer well-defined active sites on heterogeneous supports, it is challenging to identify key radical intermediates in the reaction mechanism. Now, a characterization method has been developed that combines film electrochemistry and EPR spectroscopy to track radical intermediates in real time, exemplified by alcohol oxidation with a surface-immobilized nitroxide.

    • Maryam Seif-Eddine
    • , Samuel J. Cobb
    •  & Maxie M. Roessler

  • Article |

    Chromophore supramolecular assemblies have long been studied for their exotic photophysical properties arising from their local geometry and long-range sensitive excitonic couplings. Now a high-resolution structure of a model nanotubular system has revealed a uniform brick-layer molecular arrangement and a non-biological supramolecular motif—interlocking sulfonates—enabling clear understanding of supramolecular structure–excitonic property relationships.

    • Arundhati P. Deshmukh
    • , Weili Zheng
    •  & Justin R. Caram

  • Article
    | Open Access

    Light-induced ultrafast switching between the molecular isomers norbornadiene and quadricyclane can reversibly store and release a substantial amount of chemical energy. Two competing pathways have now been identified by which electronically excited quadricyclane molecules relax to the electronic ground state, facilitating interconversion between the two isomers on different timescales.

    • Kurtis D. Borne
    • , Joseph C. Cooper
    •  & Daniel Rolles

  • Research Briefing |

    Dinitrogen (N2) fixation to ammonia (NH3) is typically challenging under mild conditions. Now, lithium hydride (LiH) is shown to mediate photodriven N2 fixation under ambient conditions. Under ultraviolet illumination, LiH is photolysed to release H2, leaving electrons residing in surface hydrogen vacancies, which facilitate N2 activation and photocatalytic NH3 synthesis.

  • Article
    | Open Access

    Single-atom alloys have emerged as highly active and selective catalysts that do not follow the traditional models of heterogeneous catalysis. Now it has been shown that the binding of adsorbates at their surface abides by a simple 10-electron count rule, which can identify promising catalysts for various applications.

    • Julia Schumann
    • , Michail Stamatakis
    •  & Romain Réocreux

  • Article |

    Although interfacial proton-coupled electron transfers are critical reaction steps in chemical and biological processes, studies investigating these reactions are complicated by surface heterogeneity. Now, interfacial proton-coupled electron transfer kinetics are studied and modelled at isolated, well-defined active sites to provide a foundation for understanding complex reactions involved in energy conversion and catalysis.

    • Noah B. Lewis
    • , Ryan P. Bisbey
    •  & Yogesh Surendranath

  • Research Briefing |

    Trans–cis photoisomerization is a fundamental photochemical reaction that is thought to proceed through an intermediate with a perpendicular conformation. However, unambiguous identification of this state has proved challenging. The combination of state-of-the-art ultrafast spectroscopy and quantum chemical calculations now provides evidence for its structural observation in stilbene photoisomerization.

  • Article |

    The prototypical trans–cis photoisomerization of stilbenes is thought to occur via a transient intermediate with a perpendicular conformation—often called ‘the phantom state’—but its unambiguous identification has thus far proved difficult. Now, using ultrafast ultraviolet Raman spectroscopy and ab initio molecular dynamics simulation, evidence for its existence and its perpendicular conformation has been obtained.

    • Hikaru Kuramochi
    • , Takuro Tsutsumi
    •  & Tahei Tahara

  • News & Views |

    Liquid–liquid phase separation (LLPS) within cells is a captivating phenomenon known to aid the organization of cellular components; however, its complex kinetics have remained a puzzle. Now, a new study elucidates the crosstalk between the phase state of an encapsulating membrane and LLPS dynamics.

    • Rumiana Dimova

  • Article |

    Light-induced azobenzene cis/trans isomerization has been extensively investigated, but the mechanical strength of its cis/trans structure is not well understood. Now it has been shown that cis azobenzene is mechanically less stable than the trans isomer due to its regiochemical structure, as revealed by single-molecule force spectroscopy.

    • Yiran Li
    • , Bin Xue
    •  & Yi Cao

  • Article |

    Many natural products are produced by non-ribosomal peptide synthetases in an assembly-line fashion. How these molecular machines orchestrate the biochemical sequences has remained elusive. It is now understood that an extended-conformation ensemble is needed to coordinate chemical-transformation steps whereas the biosynthesis directionality is driven by the enzyme’s innate conformational free energies.

    • Xun Sun
    • , Jonas Alfermann
    •  & Haw Yang

  • Article |

    Sequences of synthetic polymers are generally heterogeneous and dictate many of their physiochemical properties, but are challenging to determine. Now an imaging method, termed CREATS (coupled reaction approach toward super-resolution imaging), can count, localize and identify each monomer of single polymer chains during (co)polymerization.

    • Rong Ye
    • , Xiangcheng Sun
    •  & Peng Chen

  • News & Views |

    Open-shell organic molecules with properties that can be modulated by external stimuli are of interest for spintronics applications. Now, an overcrowded alkene with open-shell tetraradical character has been synthesized in which the interaction between the π-conjugated subunits depends on the charge and spin state.

    • Yoshito Tobe

  • Article |

    Although exciplex-forming systems are widely used for fabricating organic light-emitting diodes (OLEDs), their structural and thermodynamic characterization is limited. Now donor/acceptor inclusion complexes that demonstrate thermally activated delayed fluorescence have been generated. Their cocrystal structures have been resolved and the thermodynamics of exciplex formation determined, which has enabled the fabrication of efficient OLEDs.

    • Chun-Yen Lin
    • , Chao-Hsien Hsu
    •  & Pi-Tai Chou

  • Article
    | Open Access

    Tetrafluorenofulvalene (TFF) defies conventional rules of bond strength in organic chemistry. In particular, the central alkene bond of TFF becomes stronger in the quintet state and in the tetraanion. These changes arise from the unusual interplay between the twist, aromaticity and spin pairing in the π-electron system of TFF.

    • Bibek Prajapati
    • , Madan D. Ambhore
    •  & Marcin Stępień

  • News & Views |

    The factors that control the solubility of a salt are many and varied. Now a set of salts with closely related cations suggests that weak London dispersion-controlled CH···π interactions can dominate solubility, despite the presence of much stronger forces.

    • Steve Scheiner

  • Article
    | Open Access

    Although amorphous calcium carbonate represents an important biomineralization precursor, its structure has been difficult to understand. Now, amorphous calcium carbonate’s structure is shown to arise from the different bridging modes available to the calcium ions. This effective multi-well potential that drives calcium arrangements creates a geometric incompatibility between preferred Ca–Ca distances and frustrates crystallization.

    • Thomas C. Nicholas
    • , Adam Edward Stones
    •  & Andrew L. Goodwin

  • Article |

    While aromaticity is a useful concept for assessing the reactivity of organic compounds, the connection between aromaticity and on-surface chemistry remains largely unexplored. Now, scanning probe experiments on cyclization reactions of porphyrins on Au(111) show that the peripheral carbon atoms outside of the aromatic 18-π electron pathway exhibit a higher reactivity.

    • Nan Cao
    • , Jonas Björk
    •  & Alexander Riss

  • Article |

    Two-dimensional hybrid perovskites have gained substantial interest recently due to their controllable optoelectronic properties; however precise control over layer thickness has been synthetically challenging. Now a crystal growth method is shown to achieve high-quality single crystals of organic semiconductor-incorporated perovskites with control over their thickness and length through judicious solvent choice, affording precisely tuned optoelectronic properties.

    • Jee Yung Park
    • , Ruyi Song
    •  & Letian Dou

  • Research Briefing |

    Radiation damage in biological systems by radicals and low-energy electrons formed from water ionization is a consequence of ultrafast processes that follow core-level ionization of hydrated metal ions. More details of the complex pathway are now revealed from the study of aluminium-ion relaxation through sequential electron-transfer-mediated decay.

  • News & Views |

    When atoms first appeared in the Universe, molecules were needed to help coalesce them into stars. The trihydrogen cation H3+ is among the prime candidates for that process, and now two independent studies provide detailed insight into the ultrafast dynamics of the formation of this important ion from two hydrogen molecules.

    • Marcos Dantus

  • News & Views |

    Although Li–O2 batteries offer high theoretical energy storage capacities, few approach these limits. Now, a class of redox mediators is shown to send the discharge reaction from the electrode surface into the electrolyte solution, boosting device capacities and providing selection criteria for future efforts.

    • Zhangquan Peng

  • Article |

    Wavepacket dynamics around conical intersections are influenced by geometric phase, which can affect chemical reaction outcomes but has only been observed through indirect signatures. Now, by engineering a controllable conical intersection in a trapped-ion quantum simulator, the destructive wavepacket interference caused by a geometric phase has been observed.

    • C. H. Valahu
    • , V. C. Olaya-Agudelo
    •  & I. Kassal

  • Article |

    Geometric phase interference has been predicted to appear around conical intersections but has been experimentally illusive owing to competing effects in molecular systems. Now, this effect has been demonstrated in chains of trapped ions using state-of-the-art quantum simulation and read-out techniques.

    • Jacob Whitlow
    • , Zhubing Jia
    •  & Kenneth R. Brown

  • Article
    | Open Access

    Radiation damage in biology is largely mediated by radicals and low-energy electrons formed by water ionization and extensive, localized water ionization can be caused by ultrafast processes following the core-level ionization of hydrated metal ions. Now it has been shown that, for Al3+ ions, relaxation occurs via sequential solute–solvent electron transfer-mediated decay.

    • G. Gopakumar
    • , I. Unger
    •  & O. Björneholm

  • News & Views |

    Scientists have been studying how polymers break in solutions for decades, but the mechanism by which chains are stretched to the point of covalent bond scission is not trivial. Now, an experiment series provides ample support for a dynamic model in which chains uncoil from end to middle, while concurrently relaxing.

    • Charles E. Diesendruck

  • Article
    | Open Access

    Although noble metal coordination complexes typically show promising photophysical properties that enable applications in lighting, photocatalysis and solar energy conversion, first-row transition metal complexes rarely display properties as attractive. Now, two Cr(0) complexes are shown to afford excited-state lifetimes of ~50 ns and photophysical properties analogous to noble metal complexes, enabling efficient photoredox catalysis.

    • Narayan Sinha
    • , Christina Wegeberg
    •  & Oliver S. Wenger

  • Article
    | Open Access

    Pump–probe measurements conventionally achieve femtosecond time resolution for X-ray crystallography of reactive processes, but the measured structural dynamics are complex. Using coherent control techniques, we show that the ultrafast crystallographic differences of a fluorescent protein are dominated by ground-state vibrational processes that are unconnected to the photoisomerization reaction of the chromophore.

    • Christopher D. M. Hutchison
    • , James M. Baxter
    •  & Jasper J. van Thor

  • Article |

    The design and improvement of enzymes based on physical principles remain challenging. Now, the vibrational Stark effect has been used to demonstrate how an electrostatic model can unify the catalytic effects of distinct chemical forces in a quantitative manner and guide the design of enzyme variants that outperform their natural counterpart.

    • Chu Zheng
    • , Zhe Ji
    •  & Steven G. Boxer

  • Article |

    Although gas bubble dynamics during electrochemical processes dramatically affect performance, the fundamental understanding and manipulation of such dynamics have been limited. Now, electrolyte composition is found to be a key factor in inducing a solutal Marangoni instability that impacts both H2 gas detachment and coalescence between H2 microbubbles.

    • Sunghak Park
    • , Luhao Liu
    •  & Marc T. M. Koper

  • Article |

    While chiral hybrid organic–inorganic perovskites are promising materials for optoelectronic applications, the synthesis of three-dimensional single crystals has proven challenging. Now, a general strategy has been shown to synthesize chiral, three-dimensional perovskites by heterogeneous nucleation. The single-crystalline materials contain no chiral component; their chiroptical activity arises from supercells formed by chiral patterns of the A-site cations.

    • Gaoyu Chen
    • , Xiaoyu Liu
    •  & Xun Wang

  • Research Briefing |

    A multimodal imaging approach is developed to interrogate microorganism–semiconductor biohybrids at the single-cell and single-molecule level for light-driven CO2 fixation. Application to lithoautotrophic bacterium Ralstonia eutropha biohybrids reveals the roles of two hydrogenases in electron transport and bioplastic formation, the magnitude of semiconductor-to-single-cell electron transport and the associated pathways.

  • Article |

    Understanding interfacial and cellular electron transport is essential for guiding efficiency optimization in microbe–semiconductor biohybrids for energy conversion. A multimodal imaging platform that combines optical imaging and photocurrent mapping can now interrogate such electron-transport pathways at the single-cell level, uncovering different roles of hydrogenases and a microbe’s large electron-uptake capacity.

    • Bing Fu
    • , Xianwen Mao
    •  & Peng Chen

  • Research Briefing |

    Despite advances, understanding of the quantum state-to-state scattering dynamics between charged ions and neutral molecules at low collision energies remains limited. A high-resolution crossed-beam experiment with quantum state-selected ions prepared by laser photoionization and supporting trajectory surface-hopping calculations now provides insight into the quantum state-to-state collisional dynamics of a model charge-transfer reaction.

  • Article |

    Quantum state-to-state understanding of collisional charge transfer is a long-time goal of chemical dynamics. Now, using high-resolution molecular-beam experiments with spin–orbit state-selected ions and surface-hopping calculations, a vibrational-state-specific mechanism has been observed for the reaction Ar+(2P3/2) + N2 → Ar + N2+(v′, J′). Besides the well-known long-range harpooning mechanism, a hard-collision glory scattering mechanism was also identified.

    • Guodong Zhang
    • , Dandan Lu
    •  & Hong Gao

  • Article |

    Rapid solvent flows stretch dissolved polymer chains to their breaking point by hitherto-elusive molecular mechanisms. Now, analysis of competing mechanochemical reactions suggests a broad distribution of molecular geometries of fracturing chains. This occurs because, in each chain, fracture and kinetically destabilizing backbone stretching compete on submillisecond timescales.

    • Robert T. O’Neill
    •  & Roman Boulatov

  • Article |

    The kinetics of liquid–liquid phase separation (LLPS) in cell-like confinements remains poorly understood. Now it has been shown that it involves complex interplay between the incipient phases and the membrane boundary, which arrests phase coarsening, deforms the membrane and couples LLPS with lipid phase separation.

    • Wan-Chih Su
    • , James C. S. Ho
    •  & Atul N. Parikh

  • Article |

    In the atmosphere, photolysis of formaldehyde generates H and HCO radicals, which then react with O2 to form HO2 (important in converting atmospheric carbon to CO2). Now it has been shown that internally excited formaldehyde can also react with atmospheric O2 to make HO2 in a direct, one-step ‘photophysical oxidation’, a mechanism likely to be general in the troposphere.

    • Blair A. Welsh
    • , Maggie E. Corrigan
    •  & Scott H. Kable

  • Article
    | Open Access

    Allostery produces concerted functions of protein complexes by orchestrating the cooperative work between the constituent subunits. By restoring functions of pseudo-active sites that have been lost through evolution, allosteric sites have now been designed into a rotary molecular motor, V1-ATPase, resulting in its rotation being boosted allosterically.

    • Takahiro Kosugi
    • , Tatsuya Iida
    •  & Nobuyasu Koga

  • Article |

    Visualizing single-molecule reactions using electron microscopy can be difficult because of potential radiation damage from the electron beam. Now, however, it has been shown that a high-energy electron beam can be used to synthesize metallo-azafullerenes. Atomic-resolution, time-resolved transmission electron microscopy, with the help of computational calculations, is used to monitor the metal-encapsulation dynamics.

    • Helen Hoelzel
    • , Sol Lee
    •  & Dominik Lungerich

  • Article |

    Exciton–exciton annihilation is conventionally assumed to be limited by diffusion. Now, using time-resolved photoluminescence microscopy to determine exciton diffusion constants and annihilation rates in two substituted perylene diimide aggregates, along with a microscopic model, it has been shown that annihilation can be suppressed through quantum interference of the spatial phase of delocalized excitons.

    • Sarath Kumar
    • , Ian S. Dunn
    •  & Libai Huang

  • Article |

    Hybrid structures made up of quantum dots functionalized with molecules are highly tunable platforms for light-driven applications; however, the interaction between their components is often weak. Now it has been shown that by connecting molecules to silicon quantum dots via p-conjugated tethers, strongly coupled exciton states can be generated that prove advantageous for photon upconversion.

    • Kefu Wang
    • , R. Peyton Cline
    •  & Ming Lee Tang

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