Accounts of Chemical Research最新文献

ConspectusLight is ubiquitously available to probe the structure and dynamics of biomolecules and biological tissues. Generally, this cannot be done directly with visible light, because of the absence of absorption by those biomolecules. This problem can be overcome by incorporating organic molecules (chromophores) that show an optical response in the vicinity of those biomolecules. Since those optical properties are strongly dependent on the chromophore's environment, time-resolved spectroscopic studies can provide a wealth of information on biosystems at the molecular scale in a nondestructive way. In this work, we give an overview on the multiscale computational strategy developed by us in the last eight years and prove that theoretical studies and simulations are needed to explain, guide, and predict observations in fluorescence experiments. As we challenge the accepted views on existing probes, we discover unexplored abilities that can discriminate surrounding lipid bilayers and their temperature-dependent as well as solvent-dependent properties. We focus on three archetypal chromophores: diphenylhexatriene (DPH), Laurdan, and azobenzene. Our method shows that conformational changes should not be neglected for the prototype rod-shaped molecule DPH. They determine its position and orientation in a liquid-ordered (Lo) sphingomyelin/cholesterol (SM/Chol) bilayer and are responsible for a strong differentiation of its absorption spectra and fluorescence decay times in dioleoylphosphatidylcholine (DOPC) and dipalmitoylphosphatidylcholine (DPPC) membranes, which are at room temperature in liquid-disordered (Ld) and solid-gel (So) phases, respectively. Thanks to its pronounced first excited state dipole moment, Laurdan has long been known as a solvatochromic probe. Since this molecule has however two conformers, we prove that they exhibit different properties in different lipid membrane phases. We see that the two conformers are only blocked in one phase but not in another. Supported by fluorescence anisotropy decay simulations, Laurdan can therefore be regarded as a molecular rotor. Finally, the conformational versatility of azobenzene in saturated Ld lipid bilayers is simulated, along with its photoisomerization pathways. By means of nonadiabatic QM/MM surface hopping analyses (QM/MM-SH), a dual mechanism is found with a torsional mechanism and a slow conversion for trans-to-cis. For cis-to-trans, simulations show a much higher quantum yield and a so-called "pedal-like" mechanism. The differences are related to the different potential energy surfaces as well as the interactions with the surrounding alkyl chains. When tails of increased length are attached to this probe, cis is pushed toward the polar surface, while trans is pulled toward the center of the membrane.

ConspectusRecent years have witnessed significant interest in two-dimensional metal-organic frameworks (MOFs) due to their unique properties and promising applications across various fields. These materials offer distinct advantages, including high porosity and excellent charge transport properties. Their tunability allows precise control over various factors, including the electronic structure adjustments and local reactivity modulation, facilitating a wide range of properties and applications, such as material sensing and spin dynamics control. Moreover, the precise crystal structure of 2D MOFs supports rational design and mechanism studies, providing insights into their potential applications and enhancing their utility in various scientific and technological endeavors.To fully unveil the latent capabilities of 2D MOFs and advance their applications across diverse fields, thin film synthesis is crucial. Thin films provide a platform for investigating the intrinsic electrical properties of 2D MOFs with anisotropic structures, enabling the exploration of their unique characteristics comprehensively. Additionally, thin films offer the advantage of minimizing interference at contacts and junctions, thereby enhancing the performance of 2D MOFs for various applications. Furthermore, the properties of thin films can vary with thickness, presenting an opportunity to tailor their characteristics based on specific requirements.In this Account, we present an overview of our research focusing on the synthesis of 2D conductive MOF thin films encompassing two primary methods: chemical vapor deposition and solution processing. The chemical vapor deposition method allows for one-step, all-vapor-phase processes resulting in MOFs with edge-on orientation, controllable film thicknesses ranging from 55 to 662.7 nm, and smooth, homogeneous surfaces. On the other hand, solution-processing introduces a novel MOF, Cu₃(HHTATP)₂, by reducing interlayer interactions through the addition of pendent Brønsted bases on a ligand, enabling spin coating for thin film synthesis. This method yields a concentrated 2D MOF solution, enabling spin coating for thin film synthesis, where reversible electrical conductivity changes occur through doping with an acid and dedoping with a base. Additionally, we discuss various other synthesis methods, such as interfacial synthesis, layer-by-layer assembly, and microfluidic-assisted synthesis, offering versatile approaches for fabricating large-area thin films with tailored properties. Finally, we address ongoing challenges and potential strategies for further advancement in 2D conductive MOF thin film synthesis. We hope that this Account provides insights for selecting synthesis methods tailored to specific purposes, contributes to the development of varied synthesis techniques, and facilitates the exploration of diverse applications, unlocking the full potential of 2D conductive MOFs for next-generation technolo

ConspectusTo tackle the energy and environmental concerns the world faces, much attention is given to catalytic reactions converting methane (CH₄) and carbon dioxide (CO₂) as abundant C1 resources into value-added chemicals with high efficiency and selectivity. In the oxidative conversion of CH₄ to methanol, it is necessary to solve the requirement of strong oxidants due to the large bond-dissociation energy (BDE) of the C-H bonds in methane and achieve suppression of overoxidation due to the smaller BDE of the C-H bond in methanol as the product. On the other hand, to efficiently perform CO₂ reduction, proton-coupled electron transfer (PCET) processes are required since the reduction potential of CO₂ becomes positive by using proton-coupled processes; however, under the acidic conditions required for PCET, hydrogen evolution by the reduction of protons becomes competitive with CO₂ reduction. Thus, it is indispensable to develop efficient catalysts for selective CO₂ reduction. Recently, we have developed efficient catalytic reactions toward the alleviation of the concerns mentioned above. Concerning CH₄ oxidation, inspired by metalloenzymes that oxidize hydrophobic organic substrates, a hydrophobic second coordination sphere (SCS) was introduced to an Fe^II complex bearing a pentadentate N-heterocyclic carbene ligand, and the Fe^II complex was used as a catalyst for CH₄ oxidation in aqueous media. Consequently, CH₄ was efficiently and selectively oxidized to methanol with 83% selectivity and a turnover number of 500. In contrast, when methanol was used as a substrate for catalytic oxidation by the Fe^II complex, oxidation products were obtained in a negligible yield, which was comparable to that of the control experiment without the catalyst. Therefore, the hydrophobic SCS of the Fe^II complex can capture only hydrophobic substrates such as CH₄ and release hydrophilic products such as methanol to the aqueous medium for suppressing overoxidation ("catch-and-release" mechanism). On the other hand, for photocatalytic CO₂ reduction, we have developed Ni^II complexes with N₂S₂-chelating ligands as catalysts, which have been inspired by carbon monoxide dehydrogenase, and have also introduced a binding site of Lewis-acidic metal ions to the SCS of the Ni complex. When Mg²⁺ was applied as a moderate Lewis acid, a Mg²⁺-bound Ni catalyst allowed us to achieve remarkable enhancement of the photocatalytic CO₂ reduction to afford CO as the product with over 99% selectivity and a quantum yield of 11.4%. Divalent metal ions besides Mg²⁺ also showed similar positive impacts on photocatalytic CO₂ reduction, whereas monovalent metal ions exhibited almost no effects and trivalent metal ions exclusi

ConspectusThe multifunctionality and resilience of living systems has inspired an explosion of interest in creating materials with life-like properties. Just as life persists out-of-equilibrium, we too should try to design materials that are thermodynamically unstable but can be harnessed to achieve desirable, adaptive behaviors. Studying minimalistic chemical systems that exhibit relatively simple emergent behaviors, such as motility, communication, or self-organization, can provide insight into fundamental principles which may enable the design of more complex and life-like synthetic materials in the future.Emulsions, which are composed of liquid droplets dispersed in another immiscible fluid phase, have emerged as fascinating chemically minimal materials in which to study nonequilibrium, life-like properties. As covered in this Account, our group has focused on studying oil-in-water emulsions, specifically those which destabilize by solubilization, a process wherein oil is released into the continuous phase over time to create gradients of oil-filled micelles. These chemical gradients can create interfacial tension gradients that lead to droplet self-propulsion as well as mediate communication between neighboring oil droplets. As such, oil-in-water emulsions present an interesting platform for studying active matter. However, despite being chemically minimal with sometimes as few as three chemicals (oil, water, and a surfactant), emulsions present surprising complexity across the molecular to macroscale. Fundamental processes governing their active behavior, such as micelle-mediated interfacial transport, are still not well understood. This complexity is compounded by the challenges of studying systems out-of-equilibrium which typically require new analytical methods and may break our intuition derived from equilibrium thermodynamics.In this Account, we highlight our group's efforts toward developing chemical frameworks for understanding active and interactive oil-in-water emulsions. How do the chemical properties and physical spatial organization of the oil, water, and surfactant combine to yield colloidal-scale active properties? Our group tackles this question by employing systematic studies of active behavior working across the chemical space of oils and surfactants to link molecular structure to active behavior. The Account begins with an introduction to the self-propulsion of single, isolated droplets and how by applying biases, such as with a gravitational field or interfacially adsorbed particles, drop speeds can be manipulated. Next, we illustrate that some droplets can be attractive, as well as self-propulsive/repulsive, which does not fall in line with the current understanding of the impact of oil-filled micelle gradients on interfacial tensions. The mechanisms by which oil-filled micelles influence interfacial tensions of nonequilibrium interfaces is poorly understood and requires deeper molecular understanding. Regardless,

ConspectusWith three valence electrons and four valence orbitals, boron (2s²2p¹) is an electron-deficient element, resulting in interesting chemical bonding and structures in both borane molecules and bulk boron materials. The electron deficiency leads to electron sharing and delocalization in borane compounds and bulk boron allotropes, characterized by polyhedral cages, in particular, the ubiquitous B₁₂ icosahedral cage. During the past two decades, the structures and bonding of size-selected boron clusters have been elucidated via combined photoelectron spectroscopy and theoretical investigations. Unlike bulk boron materials, finite boron clusters have been found to possess 2D structures consisting of B₃ triangles, dotted with tetragonal, pentagonal, or hexagonal holes. The discovery of the planar B₃₆ cluster with a central hexagonal hole provided the first experimental evidence for the viability of 2D boron nanostructures (borophene), which have been synthesized on inert substrates. The B₇^-, B₈^-, and B₉^- clusters were among the first few boron clusters to be investigated by joint photoelectron spectroscopy and theoretical calculations, and they were all found to possess 2D structures with a central B atom inside a B_n ring. Recently, the B₇^3- (C_6v), B₈^2- (D_7h), and B₉^- (D_8h) series of closed-shell species were shown to possess similar π bonding akin to that in the C₅H₅^-, C₆H₆, and C₇H₇⁺ series, respectively, and the name "borozene" was coined to highlight their analogy to the classical aromatic hydrocarbon molecules.Among the borozenes, the D_7h B₈^2- species is unique for its high stability originating from both its double aromaticity and the fact that the B₇ ring has the perfect size to host a central B atom. The B₈^2- borozene has been realized experimentally in a variety of MB₈ and M₂B₈ complexes. In particular, the B₈^2- borozene has been observed to stabilize the rare valence-I oxidation state of lanthanides in LnB₈^- complexes, as well as a Cu₂⁺ species in Cu₂B₈^-. The B₆ ring in B₇^3- is too small to host a B atom, resulting in a slight out-of-plane distortion. Interestingly, the bowl-shaped B₇ borozene is perfect for coordination to a metal atom, leading to the observation of a series of highly stable MB₇ borozene complexes. On the other hand, the B₈ ring is slightly too large to host the central B atom

ConspectusIn the field of neuroscience, understanding the complex interactions within the intricate neuron-motor system depends crucially on the use of high-density, physiological multiple electrode arrays (MEAs). In the neuron-motor system, the transmission of biological signals primarily occurs through electrical and chemical signaling. Taking neurons for instance, when a neuron receives external stimuli, it generates an electrical signal known as the action potential. This action potential propagates along the neuron's axon and is transmitted to other neurons via synapses. At the synapse, chemical signals (neurotransmitters) are released, allowing the electrical signal to traverse the synaptic gap and influence the next neuron. MEAs can provide unparalleled insights into neural signal patterns when interfacing with the nerve systems through their excellent spatiotemporal resolution. However, the inherent differences in mechanical and chemical properties between these artificial devices and biological tissues can lead to serious complications after chronic implantation, such as body rejection, infection, tissue damage, or device malfunction. A promising strategy to enhance MEAs' biocompatibility involves minimizing their thickness, which aligns their bending stiffness with that of surrounding tissues, thereby minimizing damage over time. However, this solution has its limits; the resulting ultrathin devices, typically based on plastic films, lack the necessary stretchability, restricting their use to organs that neither stretch nor grow.For practical deployments, devices must exhibit certain levels of stretchability (ranging from 20 to 70%), tailored to the specific requirements of the target organs. In this Account, we outline recent advancements in developing stretchable MEAs that balance stretchability with sufficient electrical conductivity for effective use in physiological research, acting as sensors and stimulators. By concentrating on the neuron-motor pathways, we summarize how the stretchable MEAs meet various application needs and examine their effectiveness. We distinguish between on-skin and implantable uses, given their vastly different requirements. Within each application scope, we highlight cutting-edge technologies, evaluating their strengths and shortcomings. Recognizing that most current devices rely on elastic films with a Young's modulus value between ∼0.5 and 5 MPa, we delve into the potential for softer MEAs, particularly those using multifunctional hydrogels for an optimizing tissue-device interface and address the challenges in adapting such hydrogel-based MEAs for chronic implants. Additionally, transitioning soft MEAs from lab to fab involves connecting them to a rigid adapter and external machinery, highlighting a critical challenge at the soft-rigid interface due to strain concentration, especially in chronic studies subject to unforeseen mechanical strains. We discuss innovative solutions to this integration