ACCOUNTS OF CHEMICAL RESEARCH 提供简短、简洁和批判性的文章，提供化学和生物化学所有领域的基础研究和应用的易于阅读的概述。此外，ACCOUNTS OF CHEMICAL RESEARCH 还出版了专门针对具有不寻常活动和意义的单一问题的特刊。访问 ACCOUNTS SPECIAL ISSUES 页面，查看所有特殊问题的列表、描述和 TOC。从 2008 年开始，ACCOUNTS OF CHEMICAL RESEARCH 将其传统的文章摘要替换为文章“CONSPECTUS”。这些新条目概述了研究，使读者可以更仔细地了解文章的内容和意义。通过对文章内容的更详细描述，CONSPECTUS 提高了文章在搜索引擎中的可发现性和研究的曝光率。

Accounts of Chemical Research publishes concise, clear, and critical articles that provide accessible overviews of fundamental research and applications across all areas of chemistry and biochemistry. Additionally, Accounts of Chemical Research publishes special issues focused on single topics of unusual activity and significance. You can visit the Accounts of Chemical Research Special Issues page to view a list of all special issues, their descriptions, and tables of contents. Since 2008, Accounts of Chemical Research has replaced traditional article abstracts with 'CONSPECTUS.' These new entries summarize the research, allowing readers to gain a deeper understanding of the content and significance of the articles. By providing a more detailed description of the article content, CONSPECTUS enhances the discoverability of articles in search engines and increases the visibility of the research.

《Accounts of Chemical Research》提供简短、清晰且具有批判性的文章，涵盖化学和生物化学各个领域的基础研究和应用，旨在为读者提供易于理解的概述。此外，《Accounts of Chemical Research》还出版专门针对具有特殊活动和重要性的单一主题的特刊。您可以访问《Accounts of Chemical Research》特刊页面，查看所有特刊的列表、描述和目录。从2008年开始，《Accounts of Chemical Research》将传统的文章摘要替换为“CONSPECTUS”，这些新条目概述了研究内容，使读者能够更深入地理解文章的内容和意义。通过对文章内容的详细描述，CONSPECTUS提高了文章在搜索引擎中的可发现性和研究的曝光率。

Accounts of Chemical Research

Peptide amphiphiles (PAs) are small molecules that contain hydrophobic components covalently conjugated to peptides. In this Account, we describe recent advances involving PAs that consist of a short peptide sequence linked to an aliphatic tail. The peptide sequence can be designed to form β-sheets among the amino acids near the alkyl tail, while the residues farthest from the tail are charged to promote solubility and in some cases contain a bioactive sequence. In water, β-sheet formation and hydrophobic collapse of the aliphatic tails induce assembly of the molecules into supramolecular one-dimensional nanostructures, commonly high-aspect-ratio cylindrical or ribbonlike nanofibers. These nanostructures hold significant promise for biomedical functions due to their ability to display a high density of biological signals on their surface for targeting or to activate pathways, as well as for biocompatibility and biodegradable nature. Recent studies have shown that supramolecular systems, such as PAs, often become kinetically trapped in local minima along their self-assembly reaction coordinate, not unlike the pathways associated with protein folding. Furthermore, the assembly pathway can influence the shape, internal structure, and dimension of nanostructures and thereby affect their bioactivity. We discuss methods to map the energy landscape of a PA structure as a function of thermal energy and ionic strength and vary these parameters to convert between kinetically trapped and thermodynamically favorable states. We also demonstrate that the pathway-dependent morphology of the PA assembly can determine biological cell adhesion and survival rates. The dynamics associated with the nanostructures are also critical to their function, and techniques are now available to probe the internal dynamics of these nanostructures. For example, by conjugating radical electron spin labels to PAs, electron paramagnetic resonance spectroscopy can be used to study the rotational diffusion rates within the fiber, showing a liquidlike to solidlike transition through the cross section of the nanofiber. PAs can also be labeled with fluorescent dyes, allowing the use of super-resolution microscopy techniques to study the molecular exchange dynamics between PA fibers. For a weak hydrogen-bonding PA, individual PA molecules or clusters exchange between fibers in time scales as short as minutes. The amount of hydrogen bonding within PAs that dictates the dynamics also plays an important role in biological function. In one case, weak hydrogen bonding within a PA resulted in cell death through disruption of lipid membranes, while in another example reduced hydrogen bonding enhanced growth factor signaling by increasing lipid raft mobility. PAs are a promising platform for designing advanced hybrid materials. We discuss a covalent polymer with a rigid aromatic imine backbone and alkylated peptide side chains that simultaneously polymerizes and interacts with a supramolecular PA structure with identical chemistry to that of the side chains. The covalent polymerization can be "catalyzed" by noncovalent polymerization of supramolecular monomers, taking advantage of the dynamic nature of supramolecular assemblies. These novel hybrid structures have potential in self-repairing materials and as reusable scaffolds for delivery of drugs or other chemicals. Finally, we highlight recent biomedical applications of PAs and related structures, ranging from bone regeneration to decreasing blood loss during internal bleeding.

Mark P. Hendricks

Kohei Sato

Liam C. Palmer

Samuel I. Stupp

Acc. Chem. Res.

Supramolecular Assembly of Peptide Amphiphiles

To meet the ever-increasing global demand for energy, conversion of solar energy to chemical/thermal energy is very promising. Light-mediated catalysis, including photocatalysis (organic transformations, water splitting, CO2 reduction, etc.) and photothermal catalysis play key roles in solar to chemical/thermal energy conversion via the light-matter interaction. The major challenges in traditional semiconductor photocatalysts include insufficient sunlight utilization, charge carrier recombination, limited exposure of active sites, and particularly the difficulty of understanding the structure-activity relationship. Metal-organic frameworks (MOFs), featuring semiconductor-like behavior, have recently captured broad interest toward photocatalysis and photothermal catalysis because of their well-defined and tailorable porous structures, high surface areas, etc. These advantages are beneficial for rational structural modulation for improved light harvesting and charge separation as well as other effects, greatly helping to address the aforementioned challenges and especially facilitating the establishment of the structure-activity relationship. Therefore, it is increasingly important to summarize this research field and provide in-depth insight into MOF-based photocatalysis and photothermal catalysis to accelerate the future development. In this Account, we have summarized the recent advances in these two directly relevant applications, photocatalysis and photothermal catalysis, mainly focusing on the results in our lab. Given the unique structural features of MOFs, we have put an emphasis on rational material design to optimize the components and performance and to understand related mechanisms behind the enhanced activity. This Account starts by presenting an overview of solar energy conversion by catalysis. We explain why MOFs can be promising photocatalysts and exemplify the semiconductor-like behavior of MOFs. More importantly, we show that MOFs provide a powerful platform to study photocatalysis, in which the involved three key processes, namely, light harvesting, electron-hole separation, and surface redox reactions, can be rationally improved. Meanwhile, the structure-activity relationship and charge separation dynamics are illustrated in this part. In addition, MOFs for photothermal catalysis have been introduced that are based on the photothermal effect of plasmonic metals and/or MOFs, together with light-driven electronic state optimization of active sites, toward enhanced heterogeneous organic reactions. Finally, our brief outlooks on the current challenges and future development of MOF photocatalysis and photothermal catalysis are provided. It is believed that this Account will afford significant understanding and inspirations toward solar energy conversion over MOF-based catalysts.

Juan-Ding Xiao

Hai-Long Jiang

Metal–Organic Frameworks for Photocatalysis and Photothermal Catalysis

The fixation of atmospheric dinitrogen to ammonia by industrial technologies (such as the Haber Bosch process) has revolutionized humankind. In contrast to industrial technologies, a single enzyme is known for its ability to reduce or "fix" dinitrogen: nitrogenase. Nitrogenase is a complex oxidoreductase enzymatic system that includes a catalytic protein (where dinitrogen is reduced) and an electron-transferring reductase protein (termed the Fe protein) that delivers the electrons necessary for dinitrogen fixation. The catalytic protein most commonly contains a FeMo cofactor (called the MoFe protein), but it can also contain a VFe or FeFe cofactor. Besides their ability to fix dinitrogen to ammonia, these nitrogenases can also reduce substrates such as carbon dioxide to formate. Interestingly, the VFE nitrogenase can also form carbon-carbon bonds. The vast majority of research surrounding nitrogenase employs the Fe protein to transfer electrons, which is also associated with the rate-limiting step of nitrogenase catalysis and also requires the hydrolysis of adenosine triphosphate. Thus, there is significant interest in artificially transferring electrons to the catalytic nitrogenase proteins. In this Account, we review nitrogenase electrocatalysis whereby electrons are delivered to nitrogenase from electrodes. We first describe the use of an electron mediator (cobaltocene) to transfer electrons from electrodes to the MoFe protein. The reduction of protons to molecular hydrogen was realized, in addition to azide and nitrite reduction to ammonia. Bypassing the rate-limiting step within the Fe protein, we also describe how this approach was used to interrogate the rate-limiting step of the MoFe protein: metal-hydride protonolysis at the FeMo-co. This Account next reviews the use of cobaltocene to mediate electron transfer to the VFe protein, where the reduction of carbon dioxide and the formation of carbon-carbon bonds (yielding the formation of ethene and propene) was realized. This approach also found success in mediating electron transfer to the FeFe catalytic protein, which exhibited improved carbon dioxide reduction in comparison to the MoFe protein. In the final example of mediated electron transfer to the catalytic protein, this Account also reviews recent work where the coupling of infrared spectroscopy with electrochemistry enabled the potential-dependent binding of carbon monoxide to the FeMo-co to be studied. As an alternative to mediated electron transfer, recent work that has sought to transfer electrons to the catalytic proteins in the absence of electron mediators (by direct electron transfer) is also reviewed. This approach has subsequently enabled a thermodynamic landscape to be proposed for the cofactors of the catalytic proteins. Finally, this Account also describes nitrogenase electrocatalysis whereby electrons are first transferred from an electrode to the Fe protein, before being transferred to the MoFe protein alongside the hydrolysis of adenosine triphosphate. In this way, increased quantities of ammonia can be electrocatalytically produced from dinitrogen fixation. We discuss how this has led to the further upgrade of electrocatalytically produced ammonia, in combination with additional enzymes (diaphorase, alanine dehydrogenase, and transaminase), to selective production of chiral amine intermediates for pharmaceuticals. This Account concludes by discussing current and future research challenges in the field of electrocatalytic nitrogen fixation by nitrogenase.

Ross D. Milton

Shelley D. Minteer

Nitrogenase Bioelectrochemistry for Synthesis Applications

Coherent light radiation down to the deep-ultraviolet spectral range (λ < 200 nm) produced by common laser sources is extensively used in diverse fields ranging from ultrahigh-resolution photolithography to photochemical synthesis to high-precision microprocessing. Actually, it is hard to immediately obtain certain wavelengths, deep-ultraviolet coherent light in particular, from commercial laser sources. However, the direct second harmonic generation process governed in part by nonlinear optical crystals is a feasible and effective approach to generate deep-ultraviolet coherent light, which motivates chemists and materials scientists to find potential deep-ultraviolet nonlinear optical materials that can practically meet the scientific requirements. The research progress required to go from a new single-crystal structure to final device applications involves many pivotal steps and is highly time-consuming and challenging, and therefore, it is necessary to commence systematic studies aimed at shortening the research cycle and accelerating the rational design of deep-ultraviolet nonlinear optical materials. In this Account, we choose borates as raw materials because they have ever-greater possibilities to form desired noncentrosymmetric structures, wide optical transparency windows, rich structural chemistry, and also large polarizabilities to guarantee the coexistence of large second-order nonlinear optical coefficients and suitable birefringence. Besides, the effects of fluorine atoms on the structural chemistry and optical properties of borates have been summarized and analyzed. On the basis of these favorable influences, three specific rational design strategies, including experimental and theoretical methods, have been proposed in order to shorten the investigational cycle of discovering the new expected compounds with high physicochemical performances required for practical applications. In this way, the progress of searching for candidates for the next generation of deep-ultraviolet nonlinear optical materials was accelerated from borates to borate fluorides to fluorooxoborates with three effective strategies: (1) expansion of the frontier from borates to borate fluorides with the introduction of fluorine to achieve enhanced optical performance; (2) computer-assisted design of new deep-ultraviolet nonlinear optical materials with a newly introduced systematic global structure optimization method; and (3) expansion of the frontier from borate fluorides to fluorooxoborates by proposed functionalized oxyfluoride [BO xF4- x]( x+1)- ( x = 1, 2, 3) chromophores to balance multiple criteria. The preliminary development of fluorooxoborates exhibiting high performance as a new fertile field to search for deep-ultraviolet nonlinear optical materials is highly encouraging and inspiring and can guide chemists and materials scientists with new directions and thoughts aimed at finding the next generation of practical deep-ultraviolet nonlinear optical materials.

Miriding Mutailipu

Min Zhang

Zhihua Yang

Shilie Pan

Targeting the Next Generation of Deep-Ultraviolet Nonlinear Optical Materials: Expanding from Borates to Borate Fluorides to Fluorooxoborates

ConspectusWhen molecular vibrational modes strongly couple to virtual states of photonic modes, new molecular vibrational polariton states are formed, along with a large population of dark reservoir modes. The polaritons are much like the bonding and antibonding molecular orbitals when atomic orbitals form molecular bonds, while the dark modes are like nonbonding orbitals. Because the polariton states are half-matter and half-light, whose energy is shifted from the parental states, polaritons are predicted to modify chemistry under thermally activated conditions, leading to an exciting and emerging field known as polariton chemistry that could potentially shift paradigms in chemistry. Despite several published results supporting this concept, the chemical physics and mechanism of polariton chemistry remain elusive. One reason for this challenge is that previous works cannot differentiate polaritons from dark modes. This limitation makes delineating the contributions to chemistry from polaritons and dark states difficult. However, this level of insight is critical for developing a solid mechanism for polariton chemistry to design and predict the outcome of strong coupling with any given reaction. My group addressed the challenge of differentiating the dynamics of polaritons and dark modes by ultrafast two-dimensional infrared (2D IR) spectroscopy. Specifically, (1) we found that polaritons can facilitate intra- and intermolecular vibrational energy transfer, opening a pathway to control vibrational energy flow in liquid-phase molecular systems, and (2) by studying a single-step isomerization event, we verified that indeed polaritons can modify chemical dynamics under strong coupling conditions, but in contrast, the dark modes behave like uncoupled molecules and do not change the dynamics. This finding confirmed the central concept of polariton chemistry: polaritons modify the potential energy landscape of reactions. The result also clarified the role of dark modes, which lays a critical foundation for designing cavities for future polariton chemistry. Aside from using 2D IR spectroscopy to study polariton chemistry, we also used the same technique to develop molecular polaritons into a potential quantum simulation platform. We demonstrated that polaritons have Rabi oscillations, and using a checkerboard cavity design, we showed that polaritons could have large nonlinearity across space. We further used the checkerboard polaritons to simulate coherence transfer and visualize it. A unidirectional coherence transfer was observed, indicating non-Hermitian dynamics. The highlighted efforts in this Account provide a solid understanding of the capability of polaritons for chemistry and quantum information science. I conclude this Account by discussing a few challenges for moving polariton chemistry toward being predictable and making the polariton quantum platform a complement to existing systems.

Wei Xiong

Molecular Vibrational Polariton Dynamics: What Can Polaritons Do?

分子振动极化激元动力学：极化激元能做什么？

Franklin Tao

Development of New Methods of Studying Catalyst and Materials Surfaces with Ambient Pressure Photoelectron Spectroscopy

新型催化剂与材料表面研究方法的发展：常压光电子能谱技术

ConspectusOrigin of Life research is a fast growing field of study with each year bringing new breakthroughs. Recent discoveries include novel syntheses of life's building blocks, mechanisms of activation and interaction between molecules, and newly identified environments that provide promising conditions for these syntheses and mechanisms. Even with these new findings, firmly grounded in rigorous laboratory experiments, researchers often find themselves uncertain about how to apply them. How can a bridge be built between the laboratory and the geochemical environment? A critical question to ask when seeking to apply new results in origins is: how can this chemistry occur without direct intervention from a chemist? We believe the first step toward answering this question lies in the determination of rate constants and the construction of chemical networks to describe prebiotic chemistry in geochemical environments.So far, our group has measured several rate constants relevant to different prebiotic reaction networks, starting with the synthetic pathways of the cyanosulfidic network. The reactions we explore often involve ultraviolet light-driven photochemistry, facilitated by our StarLab setup that accurately simulates the spectrum of the young Sun and other stars. Our latest work investigates environments with active photochemistry in the absence of cyanide. In this study, we measure the effective rate constant for the production of formate from the reduction of carbon species using sulfite within the context of early Martian waters. The underlying goal of the work done in our group is to predict the likelihood that certain geological conditions will result in a specific set of chemical products. These predictions can be combined with those we have made for the necessary astrophysical conditions in certain origins of life scenarios on extrasolar planets.In the near future we expect that a sufficient number of rate constants will be measured, by our group and others, to allow for aspects of prebiotic chemistry to be predicted using chemical kinetics models. Once these models have been benchmarked against experimental data, our next step will be applying them to natural environments that better mimic the conditions thought to have been present at the onset of life. Following this, we can test these models by comparing their predictions to additional experiments. After refinement, these models will be able to provide guidance on the optimal conditions for conducting laboratory experiments, while helping to minimize and characterize any interference from a chemist.This approach can provide valuable insights into what is possible within geochemical environments, where all chemistry is by necessity do-nothing chemistry.

Skyla B. White

Paul B. Rimmer

Do-Nothing Prebiotic Chemistry: Chemical Kinetics as a Window into Prebiotic Plausibility

无为益生元化学：化学动力学作为益生元可行性的窗口

Claudia Bonfio

Martina Preiner

Acc Chem Res

From the Chemistry of Life’s Emergence to the Chemistry of Life

从生命起源的化学到生命的化学

ConspectusThe redox reactivity of transition metal centers can be augmented by nearby redox-active inorganic or organic moieties. In some cases, these functional groups can even allow a metal center to participate in reactions that were previously inaccessible to both the metal center and the functional group by themselves. Our research groups have been synthesizing and characterizing coordination complexes with polydentate quinol-containing ligands. Quinol is capable of being reversibly oxidized by either one or two electrons to semiquinone or

Byron H. Farnum

Christian R. Goldsmith

Use of Intramolecular Quinol Redox Couples to Facilitate the Catalytic Transformation of O2 and O2-Derived Species

利用分子内醌类氧化还原对促进O2及其衍生物的催化转化

Nilay Hazari

Hannah S. Shafaat

Jenny Y. Yang

Transforming Highly Oxidized and Reduced Carbon Feedstocks: Strategies for Catalytic CO2 and CH4 Valorization

转化高氧化和还原性碳原料：催化CO2和CH4增值策略

Abbreviation	Acc. Chem. Res.
Journal Impact	16.35
Quartiles(Global)	CHEMISTRY, MULTIDISCIPLINARY(Q1)

ISSN	0001-4842, 1520-4898
h-index	453
Top Journals	Yes

Publication Information	Publisher: American Chemical Society，Publishing cycle: Monthly，Journal Type: journal，Open Access Journals: No
Basic data	Year of publication: 1968，Proportion of original research papers: 0.00%，Self Citation Rate:0.60%， Gold OA Rate: 12.32%
Average review cycle	网友分享经验：一般,3-6周
Average recruitment ratio	网友分享经验：极难

Accounts of Chemical Research

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