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Described herein are devices and methods utilizing cascade photocatalysis to drive multiple chemical reactions via a series of photoelectrochemical catalysts driven by the conversion of light into current by one or more photovoltaic devices. The described devices and methods are tunable and may be used in conjunction with different reactants and products, including the conversion of carbon dioxide into valuable hydrocarbon products.
The spectra of predicted particles from elementary quark models (CQMs) are expansive, accurate for the low-lying spectra, but incomplete. The GlueX experiment at Jefferson Lab is a vehicle to study medium energy photoproduction of hadronic states. The primary goal of the GlueX collaboration is to study Quantum Chromodynamics (QCD, also known as the strong nuclear force) and the nature of quark confinement. The GlueX collaboration uses a polarized photon beam incident on a liquid hydrogen target (LH 2 ) to investigate the aftermath of photon-proton interactions. The cascade baryons, denoted by Ξ, are defined by having two, second-generation, strange quarks with an additional first-generation light quark (u or d). Experimentally, few cascades have been discovered, which is the antithesis of what most models expect. The cascades have some favorable attributes but are difficult to detect because the production cross sections are small and direct production is unlikely. Fortunately, in the 12 GeV era of the GlueX experiment, there is sufficient energy, beam time and data analysis tools for the detection of excited cascade states and their properties. From the reaction γ p →Κ + Κ + Ξ - π 0 , the invariant mass spectra of Ξ - π 0 system was surveyed for new possible resonances. The invariant mass spectrum has a strong Ξ(1530) signal with other smaller resonances throughout the spectrum. Preliminary cross sections for the Ξ(1530) that was photoproduced from the proton are presented at energies never before explored. While the Ξ(1530) couples almost exclusively to the Ξπ channel, there is an easily identifiable Ξ(1690) signal decaying Ξπ. Through the use of a simultaneous fitting routing of the Ξ*- mass spectra, I was able to observe the Ξ(1690) decaying to the KΛ, as well as to the Ξ - π 0 branch. With additional statistics, a measurement of the branching ratio should be possible. Lastly, a partial wave analysis (PWA) was completed to verify that the total angular momentum of Ξ(1530) is J = 3/2 and consistent with having positive parity. Additionally, there is evidence of a potentially interesting feature slightly above the mass of the Ξ(1530) that should be more fully explored as new GlueX data becomes available.
Abstract Nonstandard amino acids (nsAAs) that are l ‐phenylalanine derivatives with aryl ring functionalization have long been harnessed in natural product synthesis, therapeutic peptide synthesis, and diverse applications of genetic code expansion. Yet, to date, these chiral molecules have often been the products of poorly enantioselective and environmentally harsh organic synthesis routes. Here, we reveal the broad specificity of multiple natural pyridoxal 5′‐phosphate (PLP)‐dependent enzymes, specifically an l ‐threonine transaldolase, a phenylserine dehydratase, and an aminotransferase, toward substrates that contain aryl side chains with diverse substitutions. We exploit this tolerance to construct a one‐pot biocatalytic cascade that achieves high‐yield synthesis of 18 diverse l ‐phenylalanine derivatives from aldehydes under mild aqueous reaction conditions. We demonstrate the addition of a carboxylic acid reductase module to this cascade to enable the biosynthesis of l ‐phenylalanine derivatives from carboxylic acids that may be less expensive or less reactive than the corresponding aldehydes. Finally, we investigate the scalability of the cascade by developing a lysate‐based route for preparative‐scale synthesis of 4‐formyl‐ l ‐phenylalanine, a nsAA with a bio‐orthogonal handle that is not readily market‐accessible. Overall, this work offers an efficient, versatile, and scalable route with the potential to lower manufacturing costs and democratize synthesis for many valuable nsAAs.
Cell-free biocatalysis (CFB) is an efficient and environmentally friendly method to synthesize molecules such as pharmaceuticals, biochemicals, and biofuels through the in vitro use of enzyme cascades. These enzymes often require redox cofactors to drive chemical reactions. Natural redox cofactors (NAD(P)H) are expensive to isolate, motivating synthetic nicotinamide cofactor biomimetics (NCBs) as a cost-effective solution. A select handful of NCBs have been identified as potential NAD(P)H alternatives with comparable or improved redox capabilities, however, they display a tendency to degrade in common buffers. In this study, a library of 132 NCB candidates is systematically generated, over 85% of which have not been characterized in the literature, to expand the diversity of currently explored NCBs. The decomposition mechanism of NCBs in phosphate is evaluated using density functional theory (DFT), revealing protonation at the nicotinamide C5 position as a reporter of cofactor stability. Based on this result, we trained a linear regression model on DFT calculated descriptors to predict NCB stability in phosphate buffer, achieving mean absolute error (MAE) and root mean squared error (RMSE) values within computational accuracy. Analysis of key atomic descriptors and qualitative trends in our dataset informed the design of novel NCB candidates we propose with optimized stability. This work enables researchers to predict the relative stability of NCBs before synthesis, thereby streamlining the process to make CFB more affordable and viable at industry scales.
Plastic imposes a critical threat to the environment, ecosystems, and human health because of the low utilization efficiency of plastics. Here, we demonstrate a sustainable, highly efficient cascade photocatalysis for upcycle plastics to value-added acetic acid using Fe single-atom catalysts (Fe@C 3 N 4 SAC) at ambient conditions. Inspired by Phanerochaete chrysosporium microbial, the defective Fe@C 3 N 4 SAC acts as a bifunctional cascade photocatalyst for both Fenton-like and CO 2 reduction reactions. During the reaction, hydroxyl radicals (*OH) form and subsequently oxidize plastics into CO 2 intermediates. These CO 2 intermediates are then photo-reduced to CH 3 COOH on the same catalyst via cascade photocatalysis. The mechanism is confirmed by in situ multimodal microscopy and spectroscopies, with density functional theory calculations. A state-of-art CH 3 COOH yield of 63.8 mg h −1 gcat −1 from PVC, 12.7 mg h −1 gcat −1 from PE, 5.4 mg h −1 gcat −1 from PET, and 5.3 mg h −1 gcat −1 from PP are directly obtained under AM1.5G solar irradiation and further validated under real sunlight (≈0.6 sun), achieving 5.6 mg h −1 gcat −1 from PET, using low-cost Fe@C 3 N 4 SAC in a sealed reactor by enhancing the photon transport and utilization efficiency. The techno-economic analysis shows it is promising to practically mitigate plastic based on broader social welfare assessments.
Pre-equilibrium de-excitation is a well-established stage of nucleon-induced nuclear reactions but has not previously been incorporated into neutrino event generators. This work implements the Koning-Duijvestijn exciton model within the MARLEY neutrino event generator to simulate energy redistribution and particle emission before compound nucleus equilibrium. The implementation includes modular calculations of particle-hole state densities, internal transition rates, emission rates, and Monte Carlo cascade sampling, and is validated against the TALYS-2.2 nuclear reaction code. A new event record is also proposed to enable future uncertainty reweighting studies. This work establishes the first framework for studying pre-equilibrium effects in neutrino-induced reactions, with the goal of improving predictions of particle multiplicities, γ-ray production, and MeV-scale detector signals relevant to experiments such as DUNE.
We report the first measurement of the atmospheric neutrino-oxygen neutral-current quasielastic (NCQE) cross section in the gadolinium-loaded Super-Kamiokande (SK) water Cherenkov detector. In June 2020, SK began a new experimental phase, named SK-Gd, by loading 0.011% by mass of gadolinium into the ultrapure water of the SK detector. The introduction of gadolinium to ultrapure water has the effect of improving the neutron-tagging efficiency. Using a 552.2 day dataset from August 2020 to June 2022, we measure the NCQE cross section to be 0.74 ± 0.22 ( stat ) − 0.15 + 0.85 ( syst ) × 10 − 38 cm 2 / oxygen in the energy range from 160 MeV to 10 GeV, which is consistent with the atmospheric neutrino-flux-averaged theoretical NCQE cross section and the measurement in the SK pure-water phase within the uncertainties. Furthermore, we compare the models of the nucleon-nucleus interactions in water and find that the binary cascade model and the Liège intranuclear cascade model provide a somewhat better fit to the observed data than the Bertini cascade model. Since the atmospheric neutrino-oxygen NCQE reactions are one of the main backgrounds in the search for diffuse supernova neutrino background (DSNB), these new results will contribute to future studies—and the potential discovery—of the DSNB in SK. Published by the American Physical Society 2024
Abstract The reduction of CO 2 to synthetic fuels is a valuable strategy for energy storage. However, the formation of energy‐dense liquid fuels such as methanol remains rare, particularly under low‐temperature and low‐pressure conditions that can be coupled to renewable electricity sources via electrochemistry. Here, a multicatalyst system pairing an electrocatalyst with a thermal organometallic catalyst is introduced, which enables the reduction of CO 2 to methanol at ambient temperature and pressure. The cascade methanol synthesis proceeds via CO 2 reduction to formate by electrocatalyst [Cp*Ir(bpy)Cl] + (Cp*=pentamethylcyclopentadienyl, bpy=2,2′‐bipyridine), Fischer esterification of formate to isopropyl formate catalyzed by trifluoromethanesulfonic acid (HOTf), and thermal transfer hydrogenation of isopropyl formate to methanol facilitated by the organometallic catalyst (H‐PNP)Ir(H) 3 (H‐PNP=HN(C 2 H 4 P i Pr 2 ) 2 ). The isopropanol solvent plays several crucial roles: activating formate ion as isopropyl formate, donating hydrogen for the reduction of formate ester to methanol via transfer hydrogenation, and lowering the barrier for transfer hydrogenation through hydrogen bonding interactions. In addition to reporting a method for room‐temperature reduction of challenging ester substrates, this work provides a prototype for pairing electrochemical and thermal organometallic reactions that will guide the design and development of multicatalyst cascades.
The reduction of CO 2 to synthetic fuels is a valuable strategy for energy storage. However, the formation of energy-dense liquid fuels such as methanol remains rare, particularly under low-temperature and low-pressure conditions that can be coupled to renewable electricity sources via electrochemistry. Here, in this study, a multicatalyst system pairing an electrocatalyst with a thermal organometallic catalyst is introduced, which enables the reduction of CO 2 to methanol at ambient temperature and pressure. The cascade methanol synthesis proceeds via CO 2 reduction to formate by electrocatalyst [Cp*Ir(bpy)Cl] + (Cp*=pentamethylcyclopentadienyl, bpy=2,2'-bipyridine), Fischer esterification of formate to isopropyl formate catalyzed by trifluoromethanesulfonic acid (HOTf), and thermal transfer hydrogenation of isopropyl formate to methanol facilitated by the organometallic catalyst (H-PNP)Ir(H) 3 (H-PNP=HN(C 2 H 4 P i Pr 2 ) 2 ). The isopropanol solvent plays several crucial roles: activating formate ion as isopropyl formate, donating hydrogen for the reduction of formate ester to methanol via transfer hydrogenation, and lowering the barrier for transfer hydrogenation through hydrogen bonding interactions. In addition to reporting a method for room-temperature reduction of challenging ester substrates, this work provides a prototype for pairing electrochemical and thermal organometallic reactions that will guide the design and development of multicatalyst cascades.
Basic solutions are essential for gas-involved catalytic transformations, yet their ultralow free volume limits gas solubility and diffusivity. Engineering permanent porosity in such reactive liquids has remained a longstanding challenge. Here, we introduce a surface-sacrifice strategy that incorporates Brønsted-acidic zeolite nanocrystals into strong organic bases to create permanently porous reactive liquids. Stereochemically controlled acid–base neutralization at the external zeolite surface forms a thin ionic solvation shell that stabilizes the dispersion while fully preserving the internal microporosity and crystallinity of the zeolite framework. The resulting basic media exhibit persistent microporosity, confirmed by inert-gas sorption, 129Xe nuclear magnetic resonance, neutron scattering, and theoretical simulations. These porous liquids show significantly enhanced catalytic performance in CO2 conversion and hydrogenation reactions. The coexisting acidic and basic sites further enable antagonistic cascade catalysis within a single liquid phase. This surface-sacrifice approach provides a general route to introduce permanent porosity into reactive media, enabling boosted gas transformations.
A family of heterometallic metal-organic frameworks (MOFs) (CPM200s) harmoniously coexisting as Lewis acids and base (azo) sites were prepared. Seven CPM200s were employed as multifunctional heterogeneous cascade catalysts for the one-pot deacetalization-Knoevenagel reaction in a solvent-free system. Benefiting from the cooperation between Lewis acids from the open metal sites and base sites from the ligands, the CPM200s showed high activity and selectivity for the tandem reaction. The heterometallic 3D porous framework reported here not only offers a combination of two opposite active sites in the same framework of materials but also increases mass transfer of the substrate, thus maximizing the efficiency and substrate selectivity of the bifunctional catalysts. The CPM200s showed the highest turnover frequency (TOF), outperforming that of the reported MOFs in tandem with the deacetalization-Knoevenagel reaction. A strong correlation between the TOF and charge-to-radius ratio (z/r) of metal ions in the CPM200s was observed for the first time. The bifunctional CPM200s catalysts can be reused five times without significant loss of activity.
Syngas, a combination of carbon monoxide (CO) and hydrogen (H2), is a precursor to many chemicals and fuels, contributing to the billion-dollar global hydrocarbon industry. Chemical looping reforming (CLR) of the greenhouse gases methane (CH4) and carbon dioxide (CO2) allows for energy-efficient production of syngas. 5wt.% nickel (Ni) on ceria-zirconia (5wt%Ni@Ce0.6Zr0.4O2) mixed metal oxide catalyst was investigated here to explore pathways for enhanced syngas production on sustainable earth-abundant transition metal supported catalysts. The role of reduction-oxidation (redox) state of the catalyst, and carbon formation on the catalyst surface during chemical looping is explored to drive superior reaction kinetics, conversions, selectivity, and syngas ratios (H2/CO). The bulk and surface structure of the catalyst, along with carbon deposition features were characterized by electron microscopy, X-Ray diffraction, and ex situ Raman spectroscopy. The dynamic evolution of catalysts under CLR reaction conditions and the intrinsic reaction mechanisms were probed with in situ Raman spectroscopy, in situ Fourier transform spectroscopy, dynamic oxygen storage capacity (DOSC), and the Temporal Analysis of Products (TAP) reactor studies. Intrinsic kinetics of syngas production via CLR was correlated to the redox state of catalyst and the participation of nickel-catalyzed multiwalled carbon nanotube (CNT) growth, allowing enhanced CLR reaction performance.
Cascade photoelectrocatalysis (PEC) is a possible method to improve the selectivity of solar-driven CO 2 reduction (CO 2 R). This concept can be realized by coupling different CO 2 R catalysts to different subcells in a multijunction photovoltaic (PV) stack. Efficient implementation will require careful tuning of the photocurrents and design of the photovoltages provided by the subcells to the CO 2 R catalysts in such a way as to facilitate the target reaction. Here, we outline the design principles of the tandem PEC approach using two-step conversion of CO 2 to ethylene in aqueous electrolyte, via a CO intermediate, as a model system. To perform this reaction, the first coupled PV-catalyst component should provide 4 electrons to reduce 2 molecules of CO 2 to CO; the second component should provide 8 electrons to reduce 2 CO molecules to C 2 H 4 . Based on known CO 2 R catalysts, the overpotential required to produce CO can be less than that required to reduce it to ethylene, creating the opportunity for improved efficiency. Cascade PEC can be realized in a three-terminal tandem (3TT) configuration using III–V-semiconductor based subcells coupled to Au (produces CO intermediate) and Cu (converts CO to ethylene). The current to each catalyst can be controlled by the area of the subcell exposed to the electrolyte, and the photovoltage is determined by the materials selected and device configuration. Operating conditions are found by simulating the coupled system using the open-source circuit simulator SPICE (Simulation Program with Integrated Circuits Emphasis). We identify conditions under which a 3TT configuration can have a higher solar to chemical conversion efficiency compared to a two-terminal two-junction tandem (2T 2J) with the same absorbers and a Cu catalyst only. We also show that 3TT PEC devices can be less sensitive to variations in catalyst activity compared to 2T devices. Lastly, we discuss the applications of cascade PEC to CO 2 reduction, using different intermediates, and to other chemical networks.
The development of benign methylation reactions utilizing CO 2 as a one-carbon building block would enable a more sustainable chemical industry. Electrochemical CO 2 reduction has been extensively studied, but its application for reductive methylation reactions remains out of the scope of current electrocatalysis. Here, in this work, we report the first electrochemical reductive N-methylation reaction with CO 2 and demonstrate its compatibility with amines, hydroxylamines, and hydrazine. Catalyzed by cobalt phthalocyanine molecules supported on carbon nanotubes, the N-methylation reaction proceeds in aqueous media via the chemical condensation of an electrophilic carbon intermediate, proposed to be adsorbed or near-electrode formaldehyde formed from the four-electron reduction of CO 2 , with nucleophilic nitrogenous reactants and subsequent reduction. By comparing various amines, we discover that the nucleophilicity of the amine reactant is a descriptor for the C-N coupling efficacy. We extend the scope of the reaction to be compatible with cheap and abundant nitro-compounds by developing a cascade reduction process in which CO 2 and nitro-compounds are reduced concurrently to yield N-methyl amines with high mono-methylation selectivity via the overall transfer of 12 electrons and 12 protons.
Hemoprotein-catalyzed carbene and nitrene transformations have emerged as powerful tools for constructing complex molecules; they also nicely illustrate how new protein catalysts can emerge, evolve and diversify. These laboratory-invented enzymes exploit the ability of proteins to tame highly reactive carbene and nitrene species and direct their fates with high selectivity. New-to-nature carbene and nitrene transferases catalyze many useful reactions, including some that have no precedent using chemical methods. Here we cover recent advances in this field, including alkyne cyclopropenation, arene cyclopropanation, carbene C–H insertion, intramolecular nitrene C–H insertion, alkene aminohydroxylation, and primary amination. For such transformations, biocatalysts have exceeded the performance of reported small-molecule catalysts in terms of selectivity and catalyst turnovers. Lastly, we offer our thoughts on using these new enzymatic reactions in chemical synthesis, integrating them into biological pathways and chemo-enzymatic cascades, and on their current limitations.
Multicompartment micelles (MCMs) containing acid and base sites in discrete domains are prepared from poly(norbornene)-based amphiphilic bottlebrush copolymers in aqueous media. Here, the acid and base sites are localized in different compartments of the micelle, enabling the nonorthogonal reaction sequence: deacetalization – Knoevenagel condensation – Michael addition of acetals to 2-amino chromene derivatives. Computational simulations using dissipative particle dynamics (DPD) elucidated the bottlebrush composition required to effectively site-isolate the nonorthogonal catalysts. This contribution presents MCMs as a new class of nanostructures for one-pot multistep nonorthogonal cascade catalysis, laying the groundwork for the isolation of three or more incompatible catalysts to synthesize value-added compounds in a single reaction vessel, in water.
Although existing technology cannot yet directly produce fields at the Schwinger level, experimental facilities can already explore strong-field QED phenomena by taking advantage of the Lorentz boost of energetic electron beams. Recent studies show that QED cascades can create electron-positron pairs at sufficiently high density to exhibit collective plasma effects. Signatures of the collective pair plasma effects can appear in exquisite detail through plasmainduced frequency upshifts and chirps in the laser spectrum. Maximizing the magnitude of the QED plasma signature demands high pair density and low pair energy, which suits the configuration of colliding an over 10 18 Jm -3 energy-density electron beam with a 10 22 -10 23 Wcm -2 intensity laser pulse. The collision creates pairs that have a large plasma frequency, made even larger as they slow down or reverse direction due to both the radiation reaction and laser pressure. This paper explains at a tutorial level the key properties of the QED cascades and laser frequency upshift, and at the same time finds the minimum parameters that can be used to produce observable QED plasma.
Measurements of multistep cascade gamma-ray spectra from several low-lying 1 + resonances in the Pu 239 ( n , γ ) reaction were made using the DANCE detector. The measured spectra are compared to spectra simulated using several models for the photon strength function and the nuclear level density, representing the first analysis of this nature on a fissile nucleus. In general, models of the photon strength function that included a strong M 1 “scissors mode” contribution coupled with a Gilbert-Cameron nuclear level density provided a reasonable description of the spectra. Simulations using photon strength functions and nuclear level densities specifically for Pu 240 , extracted by the Oslo method, resulted in a very good representation of the measured spectra. Neutron-capture cross section calculations that included the scissors mode provided a good estimate of the previously measured values, without additional normalization. However, the scissors-mode energy that produced the best description of the multistep cascade spectra was different from the value that best reproduced the capture cross section. In addition, the 〈 Γ γ 〉 inferred from the multistep cascade calculations was somewhat less than the tabulated value, which was determined from resonance analysis. Published by the American Physical Society 2025