Accounts of Chemical Research最新文献

{"title":"Biocompatible 2D Material Inks Enabled by Supramolecular Chemistry: From Synthesis to Applications.","authors":"Khaled Parvez, Cinzia Casiraghi","doi":"10.1021/acs.accounts.4c00596","DOIUrl":"10.1021/acs.accounts.4c00596","url":null,"abstract":"<p><p>ConspectusThe emergence of two-dimensional (2D) materials, such as graphene, transition-metal dichalcogenides (TMDs), and hexagonal boron nitride (h-BN), has sparked significant interest due to their unique physicochemical, optical, electrical, and mechanical properties. Furthermore, their atomically thin nature enables mechanical flexibility, high sensitivity, and simple integration onto flexible substrates, such as paper and plastic.The surface chemistry of a nanomaterial determines many of its properties, such as its chemical and catalytic activity. The electronic properties can also be modified by surface chemistry through changes in charge transfer or by the presence of surface states. Surface defects and functional groups can act as trap sites for excitons, hence affecting the optical properties. Furthermore, surface chemistry determines the stability and dispersibility of nanomaterials in colloidal dispersions as well as their biocompatibility and toxicity. In addition, the surface chemistry dictates how nanomaterials interact with biological systems, influencing cellular uptake, immune response, and biodistribution, to name a few examples. It is, therefore, crucial to be able to produce 2D materials with tunable surface chemistry to match target applications.Because of their dimensionality, 2D materials can be easily functionalized with noncovalent and covalent approaches. This review delves into the role of supramolecular chemistry, which is based on noncovalent interactions, in achieving stable and highly concentrated water-based dispersions of 2D materials with specific surface chemistry.In particular, we provide an overview of the recent progress made by our group in the field of solution-processed 2D materials produced by liquid-phase exfoliation with pyrene derivatives used as supramolecular receptors. We highlight the relationship between the structure of the pyrene derivative stabilizer and the concentration, stability, and lateral size and thickness distributions of the produced nanosheets. Subsequently, we give a short overview of the applications enabled by the supramolecular approach in printed electronics, sensing, bioelectronics, and in the biomedical field. We show that the careful design of the pyrene derivative enables us to achieve excellent stability of the material in the cellular medium, which is essential to accurately assess biological effects. We also highlight seminal case studies on the use of cationic graphene in the therapeutics of lysosomal storage disorders, and on the use of TMD nanosheets for trained immunity and as immune-compatible nanoplatforms, traceable at the single-cell and tissue (suborgan) levels.This Account aims to provide a comprehensive guide for readers on the potential of the supramolecular approach for the design of 2D material dispersions with tailored surface chemistry. This approach is expected to be extremely attractive for many applications, from tissue engineering to energy stora","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":"189-198"},"PeriodicalIF":16.4,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11756635/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142941378","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Selecting Initial Conditions for Trajectory-Based Nonadiabatic Simulations.","authors":"Jiří Janoš, Petr Slavíček, Basile F E Curchod","doi":"10.1021/acs.accounts.4c00687","DOIUrl":"10.1021/acs.accounts.4c00687","url":null,"abstract":"<p><p>ConspectusPhotochemical reactions have always been the source of a great deal of mystery. While classified as a type of chemical reaction, no doubts are allowed that the general tenets of ground-state chemistry do not directly apply to photochemical reactions. For a typical chemical reaction, understanding the critical points of the ground-state potential (free) energy surface and embedding them in a thermodynamics framework is often enough to infer reaction yields or characteristic time scales. A general working principle is that the energy profile along the minimum energy paths provides the key information to characterize the reaction. These well-developed concepts, unfortunately, rarely stretch to processes involving the formation of a nonstationary state for a molecular system after light absorption.Upon photoexcitation, a molecule is likely to undergo internal conversion processes, that is, changes of electronic states mediated by couplings between nuclear and electronic motion, precisely what the celebrated Born-Oppenheimer approximation neglects. These coupled electron-nuclear processes, coined <i>nonadiabatic processes</i>, allow for the molecule to decay from one electronic state to the other nonradiatively. Understanding the intricate nonadiabatic dynamics is pivotal to rationalizing and predicting the outcome of a molecular photoexcitation and providing insights for experiments conducted, for example, in advanced light sources such as free-electron lasers.Nowadays, most simulations in nonadiabatic molecular dynamics are based on approximations that invoke a near-classical depiction of the nuclei. This reliance is due to practical constraints, and the classical equations of motion for the nuclei must be supplemented by techniques such as surface hopping to account for nonadiabatic transitions between electronic states. A critical but often overlooked aspect of these simulations is the selection of initial conditions, specifically the choice of initial nuclear positions and momenta for the nonadiabatic dynamics, which can significantly influence how well the simulations mimic real quantum systems across various experimental scenarios. The conventional approach for generating initial conditions for nonadiabatic dynamics typically maps the initial state onto a nuclear phase space using a Wigner quasiprobability function within a harmonic approximation, followed by a second approximation where the molecule undergoes a sudden excitation.In this Account, we aim to warn the experienced or potential user of nonadiabatic molecular dynamics about the possible limitations of this strategy for initial-condition generation and its inability to accurately describe the photoexcitation of a molecule. More specifically, we argue that the initial phase-space distribution can be more accurately represented through molecular dynamics simulations by using a quantum thermostat. This method offers a robust framework that can be applied to large, flexibl","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":"261-270"},"PeriodicalIF":16.4,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11756641/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142941380","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Visible-Light-Fueled Polymerizations for 3D Printing.","authors":"Lynn M Stevens, Nirvana T Almada, Hyeong Seok Kim, Zachariah A Page","doi":"10.1021/acs.accounts.4c00680","DOIUrl":"10.1021/acs.accounts.4c00680","url":null,"abstract":"<p><p>ConspectusLight-driven polymerizations and their application in 3D printing have revolutionized manufacturing across diverse sectors, from healthcare to fine arts. Despite the popularized notion that with 3D printing \"imagination is the only limit\", we and others in the scientific community have identified fundamental hurdles that restrict our capabilities in this space. Herein, we describe the <i>ZAP</i> group's efforts in developing photochemical systems that respond to nontraditional colors of light to elicit the rapid, spatiotemporally controlled formation of plastics. Our research addresses key limitations in current photopolymerization methods, such as the reliance on high-energy UV light, oxygen sensitivity, and narrow materials scope. We present a comprehensive overview of our advancements in both light-fueled radical and nonradical chemistry and its implementation in vat photopolymerization 3D printing using panchromatic resins. In radical chemistry, we have developed a class of boron dipyrromethene (BODIPY) dye molecules that act as photoradical generators (PRGs). Upon exposure to visible or near-infrared (NIR) light, these molecules induced efficient polymerization of acrylics. Structural modifications, including the installment of halogens, twisted aromatic groups, nitrogen bridgeheads, and thiophenes, have imbued activity across this wide spectral range. Systematic photophysical characterization of these dyes revealed the presence of long-lived excited (high in energy) states, from which we accredited the enhancements in polymerization efficiency. In turn, curing (converting a liquid to solid) with low intensity visible-to-NIR light was possible in mere seconds; a requirement for many light-based 3D printing technologies. Our efforts in nonradical chemistry have been motivated by the need for new materials with properties and functionality currently inaccessible using radical-based 3D printing approaches (e.g., tough and recyclable), while also providing an avenue toward multimaterial fabrication. We have developed photobase generators (PBGs) - dyes that release basic cargo upon light exposure-to catalyze polymerizations beyond acrylic-only resins. These include coumarinylmethyl- and BODIPY-tetramethylguanidine (TMG) derivatives, as well as onium photocages, which enabled photocuring of thiol-ene and thiol-isocyanate resins. Lastly, we have pioneered rapid, high-resolution visible-to-NIR light-based 3D printing. Our work includes the development of reactive photoredox catalyst systems for speed, additives for oxygen-tolerance, NIR-light reactivity for nanoparticle composites, models for streamlined optimization, and triplet fusion for high resolution. These advancements led to build speeds up to 45 mm/h with features <100 μm, rivaling contemporary UV-based technologies. The impact of our research extends beyond academic interest, offering practical solutions for additive manufacturing of (multi)functional materials. By enabling","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":"250-260"},"PeriodicalIF":16.4,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142929857","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Sequence-Defined DNA Polymers: New Tools for DNA Nanotechnology and Nucleic Acid Therapy.","authors":"Muhammad Ghufran Rafique, Quentin Laurent, Michael D Dore, Hassan H Fakih, Tuan Trinh, Felix J Rizzuto, Hanadi F Sleiman","doi":"10.1021/acs.accounts.4c00580","DOIUrl":"10.1021/acs.accounts.4c00580","url":null,"abstract":"<p><p>ConspectusStructural DNA nanotechnology offers a unique self-assembly toolbox to construct soft materials of arbitrary complexity, through bottom-up approaches including DNA origami, brick, wireframe, and tile-based assemblies. This toolbox can be expanded by incorporating interactions orthogonal to DNA base-pairing such as metal coordination, small molecule hydrogen bonding, π-stacking, fluorophilic interactions, or the hydrophobic effect. These interactions allow for hierarchical and long-range organization in DNA supramolecular assemblies through a DNA-minimal approach: the use of fewer unique DNA sequences to make complex structures.Here we describe our research group's work to integrate these orthogonal interactions into DNA and its supramolecular assemblies. Using automated solid phase techniques, we synthesized <u><b>s</b></u>equence-defined <u><b>D</b></u>NA <u><b>p</b></u>olymers (SDPs) featuring a wide range of functional groups, achieving high yields in the process. These SDPs can assemble into not only isotropic spherical morphologies─such as spherical nucleic acids (SNAs)─but also into anisotropic nanostructures such as 1D nanofibers and 2D nanosheets. Our structural and molecular modeling studies revealed new insights into intermolecular chain packing and intramolecular chain folding, influenced by phosphodiester positioning and SDP sequence. Using these new self-assembly paradigms, we created hierarchical, anisotropic assemblies and developed systems exhibiting polymorphism and chiroptical behavior dependent on the SDP sequence. We could also precisely control the size of our nanofiber assemblies via nucleation-growth supramolecular polymerization and create compartmentalized nanostructures capable of precise surface functionalization.The exquisite control over sequence, composition, and length allowed us to combine our SDPs with nanostructures including DNA wireframe assemblies such as prisms, nanotubes, and cubes to create hybrid, stimuli-responsive assemblies exhibiting emergent structural and functional modes. The spatial control of our assemblies enabled their use as nanoreactors for chemical transformations in several ways: via hybridization chain reaction within SNA coronas, through chemical conjugation within SNA cores, and through a molecular \"printing\" approach within wireframe assemblies for nanoscale information transfer and the creation of anisotropic \"DNA-printed\" polymer particles.We have also employed our SDP nanostructures toward biological and therapeutic applications. We demonstrated that our SNAs could serve as both extrinsic and intrinsic therapeutic platforms, with improved cellular internalization and biodistribution profiles, and excellent gene silencing activities. Using SDPs incorporating hydrophobic dendrons, high-affinity and highly specific oligonucleotide binding to human serum albumin was demonstrated. These structures showed an increased stability to nuclease degradation, reduced nonspecific ce","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":"177-188"},"PeriodicalIF":16.4,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142941382","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Tripodal Triptycenes as a Versatile Building Block for Highly Ordered Molecular Films and Self-Assembled Monolayers.","authors":"Michael Zharnikov, Yoshiaki Shoji, Takanori Fukushima","doi":"10.1021/acs.accounts.4c00743","DOIUrl":"10.1021/acs.accounts.4c00743","url":null,"abstract":"<p><p>ConspectusThe design of properties and functions of molecular assemblies requires not only a proper choice of building blocks but also control over their packing arrangements. A highly versatile unit in this context is a particular type of triptycene with substituents at the 1,8,13-positions, called tripodal triptycene, which offers predictable molecular packing and multiple functionalization sites, both at the opposite 4,5,16- or 10 (bridgehead)-positions. These triptycene building blocks are capable of two-dimensional (2D) nested hexagonal packing, leading to the formation of 2D sheets, which undergo one-dimensional (1D) stacking into well-defined \"2D+1D\" structures. This ability makes it possible to form large-area molecular films having long-range structural integrity even on polymer substrates, which can be used to enhance the performance of organic devices. Importantly, the 2D assembly ability of tripodal triptycenes is robust and not impaired when chemically modified with functional molecular units and even with polymer chains. In addition, introducing suitable functionalities that act as anchoring groups results in reliable tripodal monomolecular assembly on application-relevant inorganic substrates, which is generally considered quite a challenging task. Self-assembled monolayers (SAMs) have been formed on Au(111), Ag(111), and indium tin oxide. On gold, these SAMs feature the nested hexagonal packing typical of 2D triptycene sheets, whereas, on silver, a distinct polymorphism with several different packing motifs occurs. Along with basic, nonsubstituted tripodal SAMs, specifically functionalized monolayers have been designed. A substitution pattern in which three nitrile tail groups build the outermost surface of a tripodal triptycene-based SAM has allowed for the study of femtosecond charge transfer dynamics across the triptycene framework, with a particular emphasis on the so-called matrix effects involving intramolecular pathways. The functionalization of the bridgehead position with a ferrocene tail group has enabled single-molecule observation of redox reactions and the creation of assemblies of unique molecular rectifiers, exhibiting highly effective rectification at a very low bias voltage. Complementary to the synthesis of these complex functional triptycenes, a strategy of on-surface click reactions has been designed. Indeed, a tripodal triptycene having an ethynyl tail group at the 10-position, capable of click reactions with azide functionalities, works well, allowing successive molecular layer deposition. The performance of tripodal triptycene-based SAMs has also been tested in the context of electron beam lithography (EBL) and nanofabrication, leading to the finding that these SAMs can serve as negative resists for EBL due to the efficient cross-linking, giving rise to triptycene-stemming carbon nanomembranes (CNM). These membranes feature the lowest lateral material densities used to date for CNM preparation, which m","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":"312-324"},"PeriodicalIF":16.4,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11756639/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142941383","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Rare Earth Complex-Based Functional Materials: From Molecular Design and Performance Regulation to Unique Applications.","authors":"Pingru Su, Fujia Song, Jing Cao, Chun-Hua Yan, Yu Tang","doi":"10.1021/acs.accounts.4c00649","DOIUrl":"10.1021/acs.accounts.4c00649","url":null,"abstract":"<p><p>ConspectusRare earth (RE) elements, due to their unique electronic structures, exhibit excellent optical, electrical, and magnetic properties and thus have found widespread applications in the fields of electronics, optics, and biomedicine. A significant advancement in the use of RE elements is the formation of RE complexes. RE complexes, created by the coordination of RE ions with organic ligands, not only offer high molecular design flexibility but also incorporate features such as a broad absorption band and efficient energy transfer of organic ligands. Through the \"antenna effect\", organic ligands can transfer energy to RE ions, enhancing their luminescence efficiency. Moreover, the modification of the ligands can influence the local environment of the RE ions, thereby regulating their electronic structures and energy-level distributions. This makes it one of the important avenues for the efficient development and utilization of RE resources.The meticulous design of organic ligands during molecular synthesis enables the precise construction and regulation of RE complex structures, which are essential for probing molecular-level structure-performance relations and developing functional materials in fields such as optoelectronics, sensing, and catalysis/energy. Despite notable advancements, challenges persist in refining synthesis methodologies, innovating RE complex-based materials, enhancing stability, gaining better control over device functionality, and realizing high-value applications. This Account summarizes the recent advancements in molecular design and performance regulation achieved by our research group, particularly focusing on the synthesis and functional regulation of RE complex-based materials. We have employed strategies such as coordination self-assembly, in situ coordination, and microstructural evolution to achieve the precise synthesis and functional modulation of RE complex-based materials. These approaches have allowed us to finely tune properties such as the luminescence, electrical performance, and catalytic performance of various material systems. Consequently, we have made considerable strides in multidimensional optical information storage, the development of intelligent biological probes, the preparation of nanocatalysts, and the enhancement of inorganic-organic hybrid perovskite solar cell devices. Finally, we are committed to conducting an in-depth analysis of the challenges and opportunities that arise from the precise synthesis methods, performance regulation strategies, and innovative applications of RE complex-based functional materials. Additionally, we aim to propose potential solutions to current issues. This Account comprehensively summarizes the developments in RE complex-based materials to stimulate innovative thinking and new research directions and to establish a foundation for function-oriented precise synthesis methods.</p>","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":"218-230"},"PeriodicalIF":16.4,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142918660","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Correction to \"Tuning Reactive Crystallization Pathways for Integrated CO₂ Capture, Conversion, and Storage via Mineralization\".","authors":"Prince Ochonma, Xun Gao, Greeshma Gadikota","doi":"10.1021/acs.accounts.4c00164","DOIUrl":"10.1021/acs.accounts.4c00164","url":null,"abstract":"","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":"325"},"PeriodicalIF":16.4,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142941379","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Self-Assembling Peptides, Conjugates, and Mimics: A Versatile Platform for Materials and Beyond","authors":"Honggang Cui, Matthew Tirrell","doi":"10.1021/acs.accounts.4c00805","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00805","url":null,"abstract":"Peptides are fundamental components of biological systems that are also readily synthesized chemically. Alongside polypeptides, proteins, and their mimics, peptides have emerged over the past few decades as versatile and indispensable molecular building blocks for creating myriad functional materials. While early studies on peptide assembly focused primarily on their pathological roles, such as the formation of amyloid fibrils implicated in neurodegenerative diseases, their potential as materials gained broader recognition in the 1990s. (1−5) Their ability to mediate a wide range of intermolecular interactions─hydrophobic, electrostatic, hydrogen bonding, and more─makes peptides uniquely suited not only for creating advanced functional materials with intricate internal structures and surface patterns but also for exploring fundamental scientific concepts, such as complex phase behavior and dynamic interfacial phenomena. With nearly all the chemical functionalities of proteins, but generally of smaller size and structural simplicity, peptides are readily conjugated with other moieties such as fatty acids, lipids, drugs, sugars, or synthetic macromolecules, to engineer new molecular architectures. (2,3,6) This thematic issue of &lt;i&gt;Accounts of Chemical Research&lt;/i&gt; highlights cutting-edge peptide materials research, showcasing how these molecular building blocks are leveraged to drive innovations across diverse scientific and technological domains. The selected Accounts in this collection emphasize the chemical principles underlying the development of structures and materials formed through the self-assembly of peptides, polypeptides, proteins, and their mimics. For example, Xu and colleagues delve into enzyme-instructed self-assembly (EISA), where enzymatic reactions guide the formation of local peptide assemblies. (7) By leveraging chemistry at the molecular scale, EISA enables the creation of dynamic, stimuli-responsive materials with applications in cancer therapeutics. The insights provided by this work illuminate how enzymatic catalysis can be a powerful tool for controlling peptide assembly and functionality. Similarly, Deming highlights sulfur-containing amino acids as chemical switches that modulate polypeptide material properties under physiologically relevant conditions. (8) This strategy integrates chemical specificity with material functionality, enabling applications ranging from therapeutics to diagnostics. Next, Yan and co-workers examine the transition from ordered to disordered peptide assemblies, providing molecular-level insights into how chemical factors drive these transitions. (9) Their work highlights the potential of peptide chemistry in developing sustainable biomaterials. Building on the theme of chemical control, Yu et al. focus on collagen-inspired peptides, emphasizing their applications in regenerative medicine. (10) By detailing their synthesis, hybridization strategies, and structural properties, this Account demonst","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"14 1","pages":""},"PeriodicalIF":18.3,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990917","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Self-Assembling Peptides, Conjugates, and Mimics: A Versatile Platform for Materials and Beyond","authors":"Honggang Cui*,&nbsp; and ,&nbsp;Matthew Tirrell*,&nbsp;","doi":"10.1021/acs.accounts.4c0080510.1021/acs.accounts.4c00805","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00805https://doi.org/10.1021/acs.accounts.4c00805","url":null,"abstract":"","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 2","pages":"163–164 163–164"},"PeriodicalIF":16.4,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143089884","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Expanding Horizons in Quantum Chemical Studies: The Versatile Power of MRSF-TDDFT.","authors":"Seunghoon Lee, Woojin Park, Cheol Ho Choi","doi":"10.1021/acs.accounts.4c00640","DOIUrl":"10.1021/acs.accounts.4c00640","url":null,"abstract":"&lt;p&gt;&lt;p&gt;ConspectusWhile traditional quantum chemical theories have long been central to research, they encounter limitations when applied to complex situations. Two of the most widely used quantum chemical approaches, Density Functional Theory (DFT) and Time-Dependent Density Functional Theory (TDDFT), perform well in cases with relatively weak electron correlation, such as the ground-state minima of closed-shell systems (Franck-Condon region). However, their applicability diminishes in more demanding scenarios. These limitations arise from the reliance of DFT on a single-determinantal framework and the inability of TDDFT to capture double and higher excited configurations in its response space.The recently developed Multi-Reference Spin-Flip Time-Dependent Density Functional Theory (MRSF-TDDFT) successfully overcomes these challenges, pushing the boundaries of DFT methods. MRSF-TDDFT is exceptionally versatile, making it suitable for various applications, including bond-breaking and bond-forming reactions, open-shell singlet systems such as diradicals, and a more accurate depiction of transition states. It also provides the correct topology for conical intersections (CoIns) and incorporates double excitations into the response space for a more precise description of excited states. With the help of its formal framework, core-hole relaxation for accurate X-ray absorption prediction can be also done readily. Notably, MRSF-TDDFT achieves an equal footing description of ground and excited states, with its dual-reference framework ensuring a balanced treatment of both dynamic and nondynamic electron correlations for high accuracy.In predictive tasks, such as calculating adiabatic singlet-triplet gaps, MRSF-TDDFT achieves accuracy comparable to that of far more computationally expensive coupled-cluster methods. The missing doubly excited state of H&lt;sub&gt;2&lt;/sub&gt; observed in TDDFT is accurately captured by MRSF-TDDFT, which also reproduces the correct asymptotic bond-breaking potential energy surface. Furthermore, the CoIns of butadiene, missed by both TDDFT and Complete-Active Space Self-Consistent Field (CASSCF) methods, are successfully recovered by MRSF-TDDFT, achieving results consistent with high-level theories, an important aspect for successful study of photochemical processes. Additionally, the common issue of CASSCF overestimating bright states (ionic states) due to the missing dynamic correlation is effectively resolved by MRSF-TDDFT.Despite its numerous advancements, MRSF-TDDFT retains the computational efficiency of conventional TDDFT, making it a practical tool for routine calculations. In addition, it has been demonstrated that the prediction accuracy of MRSF-TDDFT can be further enhanced through the development of tailor-made exchange-correlation functionals, paving the way for the creation of new, specialized functionals. Consequently, with its remarkable versatility, high accuracy, and computational practicality, this innovative method si","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":"208-217"},"PeriodicalIF":16.4,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11756640/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142913132","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}