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At least 721 records · Page 40

Coordination Chemistry as a Universal Strategy for a Controlled Perovskite Crystallization

The most efficient and stable perovskite solar cells (PSCs) are made from complex mixture of precursors, which are practically always dissolved in combinations of the volatile (and toxic) N, N-Dimethylformamide (DMF), and the non-volatile (and green) dimethyl sulfoxide (DMSO) solvents. Typically, to then form a thin film, an extreme oversaturation of the perovskite precursor is initiated to trigger nucleation sites, e.g. by vacuum, an airstream or a so-called antisolvent. Unfortunately, most such oversaturation triggers do not expel the lingering (and highly coordinating) DMSO, which is highly coordinating, from the thin films; this detrimentally affects long-term stability. Here, for the first time, we introduce (the green) dimethyl sulfide (DMS) as a novel nucleation trigger for perovskite films combining, uniquely, high coordination and high vapor pressure. More precisely, DMS coordinates more strongly than all currently used solvents, hence replacing them, including DMSO, effectively during film formation. Crucially, DMS also has among the highest vapor pressures reported in literature, thus effectively leaving the thin film shortly after formation. This gives DMS a universal scope: DMS replaces other solvents by coordinating more strongly and removes itself once the film formation is finished. To demonstrate this novel coordination chemistry approach, we process MAPbI 3 PSCs, typically dissolved in hard-to-remove (and green) DMSO achieving 21.6% efficiency, among the highest reported efficiencies for this system. To confirm the universality of our strategy, we tested DMS for FAPbI 3 as another composition, which showed higher efficiency of 23.5% compared to 20.9% for fabricated device with CB. Finally, this work provides a universal strategy to control perovskite crystallization using coordination chemistry heralding the revival of perovskite compositions with pure DMSO, such as MAPbI 3 .

36 MATERIALS SCIENCE↗

Videos, photos, and AI-derived grain size data associated with “High-throughput AI Video Surveys Enable Reproducible Multiscale Sediment Size Mapping, with Implications for Hydrobiogeochemical Parameterization”

NOTE: The manuscript associated with this data package is currently in review. The data may be revised based on reviewer feedback. Upon manuscript acceptance, this data package will be updated with the final dataset and additional metadata. This data package is associated with the manuscript “High-throughput AI Video Surveys Enable Reproducible Multiscale Sediment Size Mapping, with Implications for Hydrobiogeochemical Parameterization” under review. This data package includes five data types: 1) raw photos and videos from drone survey and walking smartphone surveys; 2) images derived from raw videos; 3) manual labeling of reference scales; 4) metadata for all images and photo resolution derived from artificial intelligence (AI) models or manual labels, 5) grain size data obtained from AI models for all photos, 6) metadata and grain size data after quality control, 7) summaries of sample efficiency for all data, and 8) computational fluid dynamics (CFD) data used to support hydro-biogeochemical (HBGC) parameter estimation. Such data is used to 1) demonstrate significant improvements in accuracy, efficiency, and quality control for grain size data collection with the help of AI models, 2) study the spatial heterogeneity of grain size and observation reproducibility based on tens of thousands of data points generated by the AI models, and 3) evaluate the impacts of grain size heterogeneity on key HBGC parameters across sediment-to-reach and hourly-to-yearly scales. In particular, the data package contains 116 folders and 179696 files. The files include 41 videos in .mov format, 64047 photos in .jpg format, 13541 video-derived photos in .png format, 12747 segmentation mask data in .tif format, 12747 segmentation data in .json format, 24771 .csv files that with metadata and grain size for each individual photo as well as water depth and velocity data from CFD and observation, 51791 .txt files of raw AI predicted labels, and 11 flight record data in .srt format. The summary for all metadata and grain size statistics information is included in “Scales_V3_NG.csv” and “Statistics_V3_NG.csv”. The summary for data that pass data quality control (QC) level 0-2 is included in “QCStatistics_V3_NG.csv”. The QC level 0 represents photos whose photo resolution is positive, excluding photos that miss reference scale. The QC level 1 means reference scale circularity uncertainty is less than 5% for smartphone images while representing photo resolution is larger than 0.44 mm/pixel for drone images. The QC level 2 means excluding photos whose grain number is less than 100, a minimum number of grains recommended by classic literature. The summary for each video’s name, length, frame rates, survey area, grain number, survey efficiency, etc. can be found in “QCSummary_V3_NG.csv”. The summary for site name, GPS coordinates, and number of images at each site can be found in “SitesSummary_V3_*.csv” files. Overall computational efficiency summary is reported in Table 4 of accompanying manuscript. Additionally, the nitrate concentration data used in this work was downloaded from an existing dataset published on ESS-DIVE (Boat-Dragged Sensor Hanford Reach.csv; Conner A. et al., 2020). We thank the United States Forest Service, Washington Department of Fish and Wildlife, Washington Department of Natural Resources, Cowiche Canyon Conservatory, Port of Benton, and the Confederated Tribes and Bands of the Yakama Nation for access to field locations where the data were collected. We also thank the Yakama Nation Tribal Council and Yakama Nation Fisheries for working with us to facilitate data collection and optimization of data usage according to their values and worldview.

54 ENVIRONMENTAL SCIENCES↗

Active Thermochemical Tables: Enthalpies of Formation of Bromo- and Iodo-Methanes, Ethenes and Ethynes

Here, the thermochemistry of halocarbon species containing iodine and bromine is examined through an extensive interplay between new Feller–Peterson–Dixon (FPD) style composite methods and a detailed analysis of all available experimental and theoretical determinations using the thermochemical network that underlies the Active Thermochemical Tables (ATcT). From the computational viewpoint, a slower convergence of the components of composite thermochemistry methods is observed relative to species that solely contain first row elements, leading to a higher computational expense for achieving comparable levels of accuracy. Potential systematic sources of computational uncertainty are investigated, and, not surprisingly, spin-orbit coupling is found to be a critical component, particularly for iodine containing molecular species. The ATcT analysis of available experimental and theoretical determinations indicates that prior theoretical determinations have significantly larger uncertainties than originally reported, particularly in cases where molecular spin-orbit effects were ignored. Accurate and reliable heats of formation are reported for 38 halogen containing systems, based on combining the current computations with previous experimental and theoretical work via the ATcT approach.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Denudation, solute export, landscape evolution modeling, and geographic information system data for the East River watershed, Colorado, USA (2020-2024)

This data package contains geographic information system (GIS) layers and tabular datasets associated with the study of lithologic controls on denudation, solute export, carbon-scaling relationships, and transient landscape evolution in the East River watershed near Crested Butte, Colorado, USA. The package includes GIS layers used to produce the Figure 2 map, including drainage, hillshade, lithology, sample locations, and basin polygons, together with comma-separated value (CSV) tables and matching CSV data dictionaries. One group of tables reports sample-level and catchment-level information for river-sediment samples analyzed for in situ-produced cosmogenic beryllium-10 (10Be), including sample names, outlet elevations, geographic coordinates, upstream drainage area, rock-type classes, production-rate scaling scheme, analyzed nuclide, catchment-averaged denudation rates, and associated lower and upper analytical uncertainties. Sample and catchment attributes provide the basis for comparing denudation rates across intrusive, shale, sedimentary, and mixed-lithology settings. A second group of tables reports supporting information for landscape-evolution modeling and the mapped geologic framework of the study area. Included files list parameter values and definitions for the two-phase landscape-evolution simulations, summarize full-domain model erosion fluxes and topographic metrics for different simulation configurations, provide a fixed-area carbon-model scaling table, and summarize mapped geologic units within the East River study domain, including geologic code, formation name, lithologic description, mapped area, and lithologic class grouping. Model outputs and geologic summaries support interpretation of transient landscape behavior and its relation to the mapped distribution of shale, intrusive, sedimentary, and surficial units. A third group of tables reports hydrologic and hydrochemical information used to quantify dissolved export from the watershed. Included files provide site-level values for drainage area, mean annual solute export, standard error of annual export, area-normalized solute yield, and equivalent weathering rate for five East River monitoring sites, along with metadata describing the number, sampling cadence, and date range of discharge records and partial and full total dissolved solids observations used in the solute-yield analyses. The package also contains a supplementary daily ion-load time series with daily mean discharge, discharge observation counts, dissolved concentrations, and daily loads for calcium, magnesium, sodium, potassium, chloride, sulfate, nitrate, fluoride, dissolved silica, charge-balance bicarbonate, and total dissolved solids. The package contains GIS files, comma-separated value files (.csv), CSV data dictionaries, a file-level metadata table, a package-tree text file, and a readme text file.

10Be↗

Computed Tomography Scanning and Geophysical Measurements of Core from the Boggess 17H Well

The computed tomography (CT) facilities and the Multi-Sensor Core Logger (MSCL) at the National Energy Technology Laboratory (NETL) in Morgantown, West Virginia were used to characterize the Marcellus Shale and underlying formations. The core is from a vertical pilot well (Boggess 17H) drilled in western Monongalia County near Core, West Virginia by Northeast Natural Energy for the second Marcellus Shale Energy and Environmental Laboratory (MSEEL). MSEEL is a joint venture between NETL, Northeast Natural Energy, and West Virginia University. The primary impetus for this report is to characterize the core to better understand the structure and variation of the Marcellus Shale and surrounding formations. This report, and the associated scans, provide detailed datasets not typically available from unconventional shales for analysis.

58 GEOSCIENCES↗

Entropically engineered formation of fivefold and icosahedral twinned clusters of colloidal shapes

Fivefold and icosahedral symmetries induced by multiply twinned crystal structures have been studied extensively for their role in influencing the shape of synthetic nanoparticles, and solution chemistry or geometric confinement are widely considered to be essential. Here we report the purely entropy-driven formation of fivefold and icosahedral twinned clusters of particles in molecular simulation without geometric confinement or chemistry. Hard truncated tetrahedra self-assemble into cubic or hexagonal diamond colloidal crystals depending on the amount of edge and vertex truncation. By engineering particle shape to achieve a negligible entropy difference between the two diamond phases, we show that the formation of the multiply twinned clusters is easily induced. The twinned clusters are entropically stabilized within a dense fluid by a strong fluid-crystal interfacial tension arising from strong entropic bonding. Our findings provide a strategy for engineering twinning behavior in colloidal systems with and without explicit bonding elements between particles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dynamic x-ray diffraction and nanosecond quantification of kinetics of formation of β -zirconium under shock compression

We report the atomic- and nanosecond-scale quantification of kinetics of a shock-driven phase transition in Zr metal. We uniquely make use of a multiple shock-and-release loading pathway to shock Zr into the β phase and to create a quasisteady pressure and temperature state shortly after. Coupling shock loading with in situ time-resolved synchrotron x-ray diffraction, we probe the structural transformation of Zr in the steady state. Our results provide a quantified expression of kinetics of formation of β-Zr phase under shock loading: transition incubation time, completion time, and crystallization rate.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Mechanisms of Asymmetric Membrane Formation in Nonsolvent-Induced Phase Separation

We report the first simulations of nonsolvent-induced phase separation (NIPS) that predict membrane microstructures with graded asymmetric pore size distribution. In NIPS, a polymer solution film is immersed in a nonsolvent bath, enriching the film in nonsolvent, and leading to phase separation that forms a solid polymer-rich membrane matrix and polymer-poor membrane pores. We demonstrate how mass-transfer-induced spinodal decomposition, thermal fluctuations, and glass-transition dynamics implemented with mobility contrast between the polymer-rich and polymer-poor phases are essential to the formation of asymmetric membrane microstructures. Specifically, we show that the competition between the propagation of the phase-separation and glass-transition fronts determines the degree of pore-size asymmetry. In conclusion, we also explore the sensitivity of these microstructures to the initial film composition, and compare their formation in 2D and 3D.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Using Digital and Web-Based Platforms to Enhance Nuclear Power Plant Knowledge Transfer - 20203

As the workforce ages, the loss of experienced personnel can result in a loss of important knowledge. Updating Electric Power Research Institute (EPRI) research and guidance with the latest technology developments and operating experience is an important method to transfer knowledge between the retiring and incoming workforce. Studies suggest that the incoming workforce is accustomed to using digital and/or internet-based platforms to find information and may have a higher comfort with these types of platforms than they have with static, written reports. Additionally, the ease and speed of updating and delivering content through digital formats may offer an effective method for knowledge transfer and combining information from multiple reports into a single access point. EPRI has recently produced an online Decommissioning Hub available to members and is working on replicating the effort in the area of radioactive waste management called the Radwaste Web References. EPRI has extensive guidance in both disciplines. The Decommissioning Hub uses a wiki format to provide a platform that allows for both the updating of that guidance resulting from new research and new operating experiences, and combining related topical information from multiple reports. It also allows users to access the information based on key words and topical searches, and can be a tool for users to input experience to share with others. The Decommissioning Hub is accessed via a web-based portal and includes topical pages; experience summaries; a question and answer capability; and a smart search function of all EPRI decommissioning reports. Use of a wiki format allows users to input new experiences or modify existing experience summaries to add additional detail. EPRI moderates all content. The experience data base has been initially populated with information available in published EPRI reports and unpublished information currently available within EPRI. Moving forward, population of the database will continue with information available within the open literature, new information developed from current decommissioning projects, and user inputs. The web site became active in late 2017, and a major update will be issued in early 2020. Larger scale updates are planned biannually, and smaller-scale updates will occur continuously. Capturing and applying lessons learned from industry experiences is a hallmark of the global nuclear industry. This is even more important in the decommissioning technology area since very few plant staff have relevant experience and thus there is a steep learning curve. Moreover, decommissioning involves a number of complex, non-routine and specialized tasks. The web-accessible and searchable experience database provides an easy-to-use resource for capturing and disseminating practical experiences from completed and ongoing decommissioning projects. The EPRI Radwaste Web References will build upon the philosophy and objectives of the Radwaste Desk References that were published in the 1990's. The purpose of the original Radwaste Desk References was to provide nuclear power plant professionals with a how-to manual for managing radioactive waste. The Radwaste Web References will adopt this original purpose and will be a wiki type web site that provide fundamental practical and theoretical information, operating experience (OE), and information about advanced technologies and methods. As much as practicable, features that allow for interaction between users to share OE, best practices, and benchmarking will be added. Where they exist and are appropriate, the various EPRI Guidelines documents on radwaste topics will be updated and incorporated into the Radwaste Web References. The first Radwaste Web Reference will be on Low Level Waste Characterization and will build upon the EPRI Low Level Waste Characterization Guidelines (EPRI Report TR-107201, 1996) and will be available in 2020. The next Radwaste Web Reference will be on the topic of liquid radioactive waste processing and management, tentatively set for unveiling in 2021. This paper summarizes the EPRI's previous experiences with web-based platforms and future plans in this area. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Mitigating keyhole pore formation by nanoparticles during laser powder bed fusion additive manufacturing

Keyhole pore formation is one of the most detrimental subsurface defects in the laser metal additive manufacturing process. However, effective ways to mitigate keyhole pore formation beyond tuning laser processing conditions during keyhole mode laser melting are still lacking. Here we report a novel approach to mitigate keyhole pore formation during laser powder bed fusion (LPBF) process by using stable nanoparticles. The critical keyhole depth for keyhole pore generation (i.e., the largest keyhole depth without keyhole pore formation) during LPBF of Al6061 increases from 246 µm to 454 µm (85% increase) after adding TiC nanoparticles. In-depth x-ray imaging studies and thermo-fluid dynamics simulation enable us to identify that two mechanisms work together to mitigate keyhole pore generation: (1) adding nanoparticles prevents the keyhole from collapsing by increasing the liquid viscosity to impede the protrusion development; (2) adding nanoparticles slows down the keyhole pore movement by increasing the liquid viscosity, resulting in the recapturing of the pore by the keyhole. We further demonstrate that adding TiC nanoparticles can also eliminate the keyhole fluctuation induced keyhole pore during LPBF of Al6061. Our research provides a potential way to mitigate keyhole pore formation for defect lean metal additive manufacturing.

36 MATERIALS SCIENCE↗

Elucidation of Structure and Physical Properties of Pyrolytic Sugar Oligomers Derived from Cellulose Depolymerization/Dehydration Reactions: A Density Functional Theory Study

Fast pyrolysis of lignocellulosic materials is a promising research area to produce renewable fuels and chemicals. Dehydration is known to be among the most important reaction families during cellulose pyrolysis; water is the most important product. Together with water, dehydration reactions also form a range of poorly known oligomer species of varying molecular sizes, often collected as part of bio-oil water-soluble (WS) fraction. In this work, we used electronic structure calculations to evaluate the relative thermodynamic stabilities of several oligomer species resulting from up to three consecutive dehydration events from cellulose depolymerization intermediates. A library of the thermodynamically favored candidate molecular structures was compiled. Results revealed that most of the water molecules are eliminated from the non-reducing end, forming thermodynamically more stable conjugated compounds. This is consistent with results reported by other researchers in literature where dehydration reactions occur preferably at the non-reducing ends of oligomers. The physical-chemical properties of the proposed structures were estimated using quantitative structure-property relationships (QSPRs) and quantitative property-property relationships (QPPRs). The anhydro-sugars derived from cellulose are often blamed for coke formation during bio-oil hydrotreatment. Understanding their chemical structure could help to develop rational strategies to mitigate coke formation. Furthermore, the thermo-physical properties reported (boiling point, melting point, Gibb’s free energy of formation, enthalpy of formation, and solubility parameters among others) are also fundamental to conducting first principle engineering calculations to design and analyze new pyrolysis reactors and bio-oil up-grading units.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hole formation effect on surface morphological response of plasma-facing tungsten

We report simulation results on the effect of helium (He) bubble bursting-mediated surface hole formation on the surface morphological response of tungsten plasma-facing components (PFCs) in nuclear fusion devices. Our analysis is based on an atomistically informed, continuum-scale model, which is capable of accessing the spatiotemporal scales relevant to the fuzz nanostructure formation process on the surface of PFC tungsten. Our simulations account, in an empirical fashion, for two types of subsurface bubble dynamical phenomena in the nanobubble region of PFC tungsten during He plasma irradiation, involving bubble bursting and surface crater formation. We demonstrate that the hole formation effect on the PFC tungsten surface accelerates the growth rate of nanotendrils and the onset of fuzz formation. As a result, the predicted incubation time for surface nanotendril growth is shortened, in agreement with experimental data of incubation fluence at comparable plasma exposure conditions. We also explore systematically the dependence of the PFC surface morphological response on the areal density of holes introduced at regular time intervals onto the He-implanted tungsten surface, a parameter in our analysis that serves as a proxy for the rate of He bubble bursting. More importantly, our simulations capture fine surface features in the PFC tungsten surface morphology and predict that the average spacing between nanotendrils is on the order of 100 nm, consistent with the experimental findings.

Chen, Chao-Shou (ORCID:0000000307910042)↗

Direct observation of the formation and stabilization of metallic nanoparticles on carbon supports

Direct formation of ultra-small nanoparticles on carbon supports by rapid high temperature synthesis method offers new opportunities for scalable nanomanufacturing and the synthesis of stable multi-elemental nanoparticles. However, the underlying mechanisms affecting the dispersion and stability of nanoparticles on the supports during high temperature processing remain enigmatic. In this work, we report the observation of metallic nanoparticles formation and stabilization on carbon supports through in situ Joule heating method. We find that the formation of metallic nanoparticles is associated with the simultaneous phase transition of amorphous carbon to a highly defective turbostratic graphite (T-graphite). Molecular dynamic (MD) simulations suggest that the defective T-graphite provide numerous nucleation sites for the nanoparticles to form. Furthermore, the nanoparticles partially intercalate and take root on edge planes, leading to high binding energy on support. This interaction between nanoparticles and T-graphite substrate strengthens the anchoring and provides excellent thermal stability to the nanoparticles. These findings provide mechanistic understanding of rapid high temperature synthesis of metal nanoparticles on carbon supports and the origin of their stability.

36 MATERIALS SCIENCE↗

Green synthesis of cellulose formate and its efficient conversion into 5-hydroxymethylfurfural

5-hydroxymethylfurfural (HMF) production from cellulose is a hot topic, while the rigidity of cellulose limits its efficient conversion into HMF. Cellulose formate has exhibited the great potential for HMF production but it’s synthesis via direct formylation of cellulose in formic acid is difficult. We reported a green synthetic route of cellulose formate and its efficient conversion into HMF. Ball milled cellulose formate (BCF) was synthesized via ball milling followed by formylation in formic acid at 80 °C for 0.5 h. The structure of BCF was thoroughly characterized and BCF was subsequently converted to HMF catalyzed by AlCl3 and HCl in dimethyl sulfoxide (DMSO)-H 2 O media. Results showed that ball milling of cellulose for 1–1.5 h efficiently deconstructed its crystallinity and degree of polymerization, boosting its further formylation and catalytic conversion. An overall 66.9% HMF yield from cellulose was achieved at 150 °C for 20 min using BCF derived from cellulose ball milled for 1.5 h as the substrate. BCF exhibits high reactivity toward HMF due to its excellent solubility and accessibility in DMSO-H 2 O media, and the release of formic acid in reaction further facilitates HMF production. BCF synthesized with different ball milling times shows different degrees of substitution of formyl groups, which could serve as an indicator and regulate the HMF production. The green synthesis of cellulose formate creates an efficient pathway for HMF production.

5-hydroxymethylfurfural↗

The Geology of The Mt. Simon Sandstone Storage Complex at the Wabash #1 Well, Vigo Co., Indiana (Subtask 7.2, Technical Report)

The Wabash CarbonSAFE project drilled the Wabash #1 stratigraphic test well (ID# 168045) at the Wabash Valley Resources (WVR) IGCC facility in Vigo County, Indiana, to characterize and evaluate the basal Cambrian Mt. Simon Sandstone for commercial-scale CO 2 storage near the site. This report presents an extensive geologic characterization of the Mt. Simon storage complex and relevant data collected from the Wabash #1 well, such as lithologic data collected from cuttings and core, geophysical logging, geomechanical analysis of core samples, and well testing and fluid sampling within the Mt. Simon Sandstone. The Mt. Simon storage complex comprises two major sections: the Mt. Simon Sandstone as the potential reservoir and the overlying Eau Claire Formation as its primary seal. Within the report, an extensive depositional, sedimentological, and geochronologic characterization of the Mt. Simon is included with supportive chapters on the regional geology and the geophysical, petrophysical, and petrologic data collected during the project. An overview of 2D seismic reflection data collected from and around the test well is presented. Also presented are chapters on the characterization of the sealing Eau Claire Formation, including a chapter on the capacity of the primary and secondary seals to the Mt. Simon as well as a chapter on geomechanical testing results of the Eau Claire Formation and Mt. Simon Sandstone. Some of the information discussed in this report was used in the development of static and dynamic geologic models of the Mt. Simon Sandstone storage complex. The static and dynamic modeling of CO 2 injection in the Mt. Simon Sandstone are discussed in a separate report (Dessenberger et al., 2022) under the Wabash CarbonSAFE project.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Vibrational Signatures of Unrealized Phosphorus Suboxide Intermediates in White Phosphorus Oxidation Reactions

White phosphorus ignition notoriously produces the phosphoric acid anhydride P 4 O 10 , yet the intermediate oxidation steps remain undetermined. Here, we report the first geometric and vibrational characterization of two P 4 O 2 isomers, P 3 OPO and P 3 PO 2 , and substantiate a previously proposed cyclic P 4 O 2 isomer. We formally assign the infrared bands observed by Andrews and Mielke at 898 and 891 cm −1 to the antisymmetric P− O−P vibrations of P 3 OPO species. Additional bands corresponding to terminal P=O and −PO 2 stretches of P 3 OPO and P 3 PO 2 discussed herein also went unrecognized due to the peculiar bonding of P 4 O 2 species compared to oxo-bridged P 4 O x (x = 3−6) species. Sequential addition of oxygen atoms to the P 4 tetrahedron appears to form P 3 OPO and P 3 PO 2 , while cyclic P 4 O 2 is formed from P 2 O dimerization. CCSD(T) geometries, CCSD(T) + MP2[δVPT2] fundamental frequencies, and enthalpies of formation extrapolated using focal-point analysis are reported. The predicted enthalpies of formation relative to tetrahedral P 4 plus 3 Σ g − O 2 for bent-P 3 OPO, extended-P 3 OPO, P 3 PO 2 , and cyclic-P 4 O 2 are −93, −88, −85, and −63 kcal mol −1 , respectively.

Molecular structure↗

Structural basis of the stereoselective formation of the spirooxindole ring in the biosynthesis of citrinadins

Prenylated indole alkaloids featuring spirooxindole rings possess a 3 R or 3 S carbon stereocenter, which determines the bioactivities of these compounds. Despite the stereoselective advantages of spirooxindole biosynthesis compared with those of organic synthesis, the biocatalytic mechanism for controlling the 3 R or 3 S -spirooxindole formation has been elusive. Here, we report an oxygenase/semipinacolase CtdE that specifies the 3 S -spirooxindole construction in the biosynthesis of 21 R -citrinadin A. High-resolution X-ray crystal structures of CtdE with the substrate and cofactor, together with site-directed mutagenesis and computational studies, illustrate the catalytic mechanisms for the possible β-face epoxidation followed by a regioselective collapse of the epoxide intermediate, which triggers semipinacol rearrangement to form the 3 S -spirooxindole. Comparing CtdE with PhqK, which catalyzes the formation of the 3 R -spirooxindole, we reveal an evolutionary branch of CtdE in specific 3 S spirocyclization. Our study provides deeper insights into the stereoselective catalytic machinery, which is important for the biocatalysis design to synthesize spirooxindole pharmaceuticals.

59 BASIC BIOLOGICAL SCIENCES↗