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At least 289 records · Page 16

Investigation of the iodate sorption mechanism by CoAl LDH through experiments and ab initio molecular dynamics simulations

Radioiodine released during the nuclear-fuel cycle constitutes a persistent radiological hazard. In this study, the IO 3 – uptake mechanism of CoAl LDH was resolved by combining pH-controlled sorption experiments, synchrotron XAFS, and DFT-based AIMD simulations. At pH close to 6, approximately 90% of IO 3 – was removed, and the equilibrium distribution coefficient reached about 1.7 × 10 4 mL g –1 . EXAFS analysis indicated an average iodine–oxygen bond length of 1.81 Å and a coordination number near 3, with the fit R-factor equal to 0.002. The simulations faithfully reproduced the experimental spectrum and revealed transient proton hopping events that generated metastable I–O–H species inside the interlayer, thereby confirming nitrate-to-iodate exchange as the controlling capture pathway. Atomic density profiles and radial distribution functions further showed that IO 3 – adopt an end-on orientation perpendicular to the hydroxide sheets, while water molecules mediate proton migration without disturbing the host lattice. In conclusion, the integrated experimental–computational evidence demonstrates that CoAl LDH can rapidly and selectively sequester IO 3 – under near-neutral conditions, offering atomic scale guidance for the rational engineering of layered sorbents for advanced radioactive-waste treatment.

Kang, Jaehyuk [Jeju National Univ. (Korea, Republi↗

Microbial Analysis of 100-N Borehole Samples: Estimation of Diesel and BTEX Degrading Bacterial Populations

Historical unplanned releases at the UPR-100-N-17 166-N Diesel Oil Supply Line Leak waste site located within the 100-NR-1 OU resulted in diesel fuel contamination of the unsaturated vadose zone and site groundwater. Enhanced in situ bioremediation of the deep vadose zone was the final remedy decision for the 100-NR-1 Operable Unit (OU) and the full-scale bioventing demo began in 2012. For this remedy, oxygen is actively supplied to the deep vadose zone to stimulate aerobic hydrocarbon degrading microorganisms to metabolize petroleum contamination. Degradation rate calculations based on vadose zone respirometry measurements, however, have indicated declining activity over recent years, though the precise reason for this apparent decline has not been determined. In this investigation 100-NR-1 OU sediment cores were analyzed for total microbial biomass, as well as enumeration of diesel and BTEX degrading bacteria to determine if these microbial populations have declined relative to previous measurements taken in 2009.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Structure of active methyl-CoM reductase, Earth’s main methane producer

Summary Our work reveals the structure of the active state of Methyl-Coenzyme M Reductase (MCR), the key and rate-limiting enzyme in biological methane formation. We find large differences between the active Ni(I) and inactive Ni(II) proteins and provide insight into how nature makes and breaks the C-H bond of methane. The Ni(II)-F430 center in inactive MCR contains four planar nitrogen ligands, a lower axial glutamine oxo, and an upper axial thiolate. The Ni(I)-enzyme replaces the axial ligands with a single water. The one-electron redox change results in movement of the Ni ion and upward swing of the β-lactam ring in the tetrapyrrole coupled to a domino-like protein quake through second sphere residues, inter-subunit interactions, a substrate tunnel, affecting even the dimensions of the unit cell. These structural changes lead Ni(I)-MCR to release a charge clamp that, in the Ni(II) state, locks down substrate Coenzyme B. Determining the Ni(I)-MCR structure required development of rigorous anaerobic crystallographic techniques. Validation of the MCR redox state was accomplished by in-line and parallel spectroscopic and unit cell analyses. This structure has large implications for developing technologies to limit methane emissions and efficiently produce biofuels. Methodology described here will enhance structural biology for other oxygen-sensitive enzymes.

09 BIOMASS FUELS↗

A Novel Sustainable Process for Multilayer Graphene Synthesis Using CO 2 from Ambient Air

Graphene produced by different methods can present varying physicochemical properties and quality, resulting in a wide range of applications. The implementation of a novel method to synthesize graphene requires characterizations to determine the relevant physicochemical and functional properties for its tailored application. We present a novel method for multilayer graphene synthesis using atmospheric carbon dioxide with characterization. Synthesis begins with carbon dioxide sequestered from air by monoethanolamine dissolution and released into an enclosed vessel. Magnesium is ignited in the presence of the concentrated carbon dioxide, resulting in the formation of graphene flakes. These flakes are separated and enhanced by washing with hydrochloric acid and exfoliation by ammonium sulfate, which is then cycled through a tumble blender and filtrated. Raman spectroscopic characterization, FTIR spectroscopic characterization, XPS spectroscopic characterization, SEM imaging, and TEM imaging indicated that the graphene has fifteen layers with some remnant oxygen-possessing and nitrogen-possessing functional groups. The multilayer graphene flake possessed particle sizes ranging from 2 µm to 80 µm in diameter. BET analysis measured the surface area of the multilayer graphene particles as 330 m 2 /g, and the pore size distribution indicated about 51% of the pores as having diameters from 0.8 nm to 5 nm. This study demonstrates a novel and scalable method to synthesize multilayer graphene using CO 2 from ambient air at 1 g/kWh electricity, potentially allowing for multilayer graphene production by the ton. The approach creates opportunities to synthesize multilayer graphene particles with defined properties through a careful control of the synthesis parameters for tailored applications.

36 MATERIALS SCIENCE↗

Structural dynamics in the water and proton channels of photosystem II during the S2 to S3 transition

Abstract Light-driven oxidation of water to molecular oxygen is catalyzed by the oxygen-evolving complex (OEC) in Photosystem II (PS II). This multi-electron, multi-proton catalysis requires the transport of two water molecules to and four protons from the OEC. A high-resolution 1.89 Å structure obtained by averaging all the S states and refining the data of various time points during the S 2 to S 3 transition has provided better visualization of the potential pathways for substrate water insertion and proton release. Our results indicate that the O1 channel is the likely water intake pathway, and the Cl1 channel is the likely proton release pathway based on the structural rearrangements of water molecules and amino acid side chains along these channels. In particular in the Cl1 channel, we suggest that residue D1-E65 serves as a gate for proton transport by minimizing the back reaction. The results show that the water oxidation reaction at the OEC is well coordinated with the amino acid side chains and the H-bonding network over the entire length of the channels, which is essential in shuttling substrate waters and protons.

59 BASIC BIOLOGICAL SCIENCES↗

Structural and mechanistic basis for redox sensing by the cyanobacterial transcription regulator RexT

Abstract Organisms have a myriad of strategies for sensing, responding to, and combating reactive oxygen species, which are unavoidable consequences of aerobic life. In the heterocystous cyanobacterium Nostoc sp. PCC 7120, one such strategy is the use of an ArsR-SmtB transcriptional regulator RexT that senses H 2 O 2 and upregulates expression of thioredoxin to maintain cellular redox homeostasis. Different from many other members of the ArsR-SmtB family which bind metal ions, RexT has been proposed to use disulfide bond formation as a trigger to bind and release DNA. Here, we present high-resolution crystal structures of RexT in the reduced and H 2 O 2 -treated states. These structures reveal that RexT showcases the ArsR-SmtB winged-helix-turn-helix fold and forms a vicinal disulfide bond to orchestrate a response to H 2 O 2 . The importance of the disulfide-forming Cys residues was corroborated using site-directed mutagenesis, mass spectrometry, and H 2 O 2 -consumption assays. Furthermore, an entrance channel for H 2 O 2 was identified and key residues implicated in H 2 O 2 activation were pinpointed. Finally, bioinformatics analysis of the ArsR-SmtB family indicates that the vicinal disulfide “redox switch” is a unique feature of cyanobacteria in the Nostocales order, presenting an interesting case where an ArsR-SmtB protein scaffold has been evolved to showcase peroxidatic activity and facilitate redox-based regulation.

54 ENVIRONMENTAL SCIENCES↗

Impacts of Sea‐Level Rise on Hypoxia and Phytoplankton Production in Chesapeake Bay: Model Prediction and Assessment

In this study, the influence of sea-level rise (SLR) on seasonal hypoxia and phytoplankton production in Chesapeake Bay is investigated using a 3D unstructured grid model. Three SLR scenarios (0.17, 0.5, and 1.0 m) were conducted from 1991 to 1995. Results show that the summer hypoxic volume (HV) increases about 2%, 8%, and 16%, respectively, for these three scenarios, compared with Base Scenario. The contributions of physical and biological processes on the increase in the HV were analyzed. With the projected SLR, enhanced gravitational circulation transports more oxygen-rich water in the bottom layer from the mouth. However, the pycnocline moves upwards along with increasing water depth, which largely prolongs the time for dissolved oxygen (DO) to be transported to the bottom. The altered physical processes contribute greatly to a larger HV bay-wide. Besides, SLR increases the whole Bay phytoplankton production, with a larger increase in shallow areas (e.g., 53% in areas with depth <1 m under SLR of 0.5 m). Enhanced light availability is suggested to be the major driver of blooming phytoplankton under SLR in shallow areas. While increased DO production over the euphotic zone is mostly released to the atmosphere and transported downstream, the increase in settled organic matter greatly promotes DO consumption in the water column. The increased respiration is another major cause of the HV increase besides the physical contributions.

54 ENVIRONMENTAL SCIENCES↗

Autoignition behavior of gasoline/ethanol blends at engine-relevant conditions

Ethanol is an attractive oxygenate increasingly used for blending with petroleum-derived gasoline yielding beneficial combustion and emissions behavior for a range of internal combustion engine schemes, including stoichiometric spark-ignition and low temperature combustion (LTC). As such, it is important to fundamentally understand the autoignition behavior of gasoline/ethanol blends. This work utilizes a rapid compression machine (RCM) and a homogeneous charge compression ignition (HCCI) engine to experimentally quantify changes in fuel reactivity, through ignition delay times and preliminary heat release, for blends of 0 to 30% vol./vol. into a full boiling range research gasoline (FACE-F). Diluted/stoichiometric and undiluted/fuel-lean conditions are explored covering a wide range of compressed temperatures and pressures relevant to conventional and advanced, gasoline combustion engines. Detailed chemical kinetic modeling is undertaken using a recently updated gasoline surrogate model in conjunction with a five-component surrogate to model the RCM experiments and provide chemical insight into the perturbative effects of ethanol on the autoignition process. The diluted/stoichiometric RCM measurements reveal that within the low-temperature regime ethanol retards first-stage and main ignition delay times, and suppresses both the rates and extents of low-temperature heat release (LTHR), while within the intermediate-temperature regime ethanol only causes slight changes. Good agreement of ignition delay time and preliminary heat release prediction is found between model and experimental results. Sensitivity and flux analyses further show that ethanol blending effects are dominated by the competition between the H-atom abstraction from ethanol and other fuel components by OH radical at low temperatures and by HO 2 radical at intermediate temperatures. These findings are consistent across both fuel loading conditions explored in this study. In addition, when HCCI engine experiments are mapped onto undiluted/lean RCM measurements under a constant combustion phasing scenario, good correspondence between the two apparatuses is observed for LTHR and start of high-temperature heat release. Finally, the current study highlights the importance of characterizing LTHR in predicting fuel behaviors in high-boost/low-temperature engines, and demonstrates that RCM experiments can provide an alternative, and more-efficient avenue for such characterization.

02 PETROLEUM↗

Continuous Wet Air Oxidation of the Hydrothermal Liquefaction Aqueous Product from Various Wet Wastes

Wet air oxidation (WAO) offers an effective method for treating waste streams, converting pollutants into benign substances, and holds significant potential for processing the aqueous product from the hydrothermal liquefaction (HTL-AP) of wet wastes, a promising renewable fuel technology. Here, we conducted a comprehensive study of the WAO of HTL-AP from four different wet wastes. Through continuous testing under various conditions, we produced samples with different chemical oxygen demand (COD) levels, enhancing understanding of reaction parameters necessary for substantial COD reduction (>95%). Chemical analysis revealed that alcohols and ketones in the HTL-AP rapidly oxidized to acetic acid through aldehyde intermediates, while acetic acid, other carboxylic acids, and phenols oxidized relatively slowly. The light N-containing compounds were found to exhibit a change in concentration only after the whole sample reaches an 80% COD reduction, indicating their refractory nature under applied conditions. Energy released in the WAO reaction was calculated, and anaerobic toxicity assay demonstrated that WAO treatment enhanced methane production kinetics due to reduced inhibitory effects, suggesting partial oxidative transformation of inhibitory compounds into less toxic derivatives. These findings provide insights into designing effective WAO processes for valorizing HTL aqueous products, addressing key barriers to HTL process commercialization.

anaerobic digestion↗

Synthesis and application of thermally responsive nanofiber coatings for overtemperature monitoring

This study presents a one-pot synthesis route to organometallic nanofibers based on copper thiolate, exhibiting distinctive chemical and physical characteristics. Electron microscopy analysis of morphology and composition revealed 2-10 μm-long, 50-90 nm-diameter hollow and non-hollow fibers composed of copper, sulfur, oxygen, hydrocarbon, and chlorine. Thermogravimetric analysis showed a pronounced mass loss within 120°C-135°C. To elucidate the thermal responsive pathways, the nanofibers were characterized before and after heating. X-ray photoelectron spectroscopy indicates that an initially mixed Cu(I)/Cu(II) oxidation states transition to predominantly Cu(I) upon heating. A layer of nanofiber was coated on battery pouch foil and evaluated as a candidate thermally sensitive coating. At elevated temperature (100-130°C), nanofiber coating released volatile organic compounds, sulfide and sulfur dioxide as detected using multiple gas sensors. This thermally responsive gas release/sensing approach provides a potential large-area temperature monitoring strategy, which is particularly relevant where direct temperature measurements of individual batteries is impractical. The results established proof of concept for nanofiber-coated battery pouch foil as overtemperature warning platform that can provide alerts when surface temperatures exceed a critical threshold. More broadly, the ability to form interconnected fiber networks positions copper thiolate nanofiber coatings as promising materials for advanced applications.

Ihala Gamaralalage, Chanaka [ORNL] (ORCID:00000002↗

Chlorophyllase from Arabidopsis thaliana Reveals an Emerging Model for Controlling Chlorophyll Hydrolysis

Chlorophyll (Chl) is one of Nature’s most complex pigments to biosynthesize and derivatize. This pigment is vital for survival and also paradoxically toxic if overproduced or released from a protective protein scaffold. Therefore, along with the mass production of Chl, organisms also invest in mechanisms to control its degradation and recycling. One important enzyme that is involved in these latter processes is chlorophyllase. This enzyme is employed by numerous photosynthetic organisms to hydrolyze the phytol tail of Chl. Although traditionally thought to catalyze the first step of Chl degradation, recent work suggests that chlorophyllase is instead employed during times of abiotic stress or conditions that produce reactive oxygen species. However, the molecular details regarding how chlorophyllases are regulated to function under such conditions remain enigmatic. Here, we investigate the Arabidopsis thaliana chlorophyllase isoform AtCLH2 using site-directed mutagenesis, mass spectrometry, dynamic light scattering, size-exclusion multiangle light scattering, and both steady-state enzyme kinetic and thermal stability measurements. Through these experiments, we show that AtCLH2 exists as a monomer in solution and contains two disulfide bonds. One disulfide bond putatively maps to the active site, whereas the other links two N-terminal Cys residues together. These disulfide bonds are cleaved by chemical or chemical and protein-based reductants, respectively, and are integral to maintaining the activity, stability, and substrate scope of the enzyme. This work suggests that Cys residue oxidation in chlorophyllases is an emerging regulatory strategy for controlling the hydrolysis of Chl pigments.

59 BASIC BIOLOGICAL SCIENCES↗

Target unit with ceramic capsule for producing cu-67 radioisotope

A target unit for producing Cu67 radioisotope is described herein, and comprises a cage body releasably coupled to a screw-on cap; and a ceramic capsule containing a solid Zn68 target ingot and having one open end and one closed end and defining an interior chamber for the target ingot. The ceramic capsule is releasably contained between the cage body and the screw-on cap with a lid disposed on the open end of the capsule and a washer positioned between the lid and the screw-on cap. The screw-on cap and the washer provide a water-tight seal between the lid and the capsule. The interior of the capsule is in intimate physical contact with the target ingot; and the Zn68 of the target ingot is free of traces of residual oxygen that interfere with contact of the Zn68 to the capsule.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

Effects of isoalcohol blending with gasoline on autoignition behavior in a rapid compression machine: Isopropanol and isobutanol

Alcohols, and particularly isoalcohols, are potentially advantageous blendstocks towards achieving efficient, low-carbon intensity internal combustion engines. Their use in advanced configurations, such as boosted spark-ignition or spark-assisted compression ignition, requires a comprehensive understanding of their blending effects on the low- and intermediate-temperature autoignition behavior of petroleum-derived gasoline. This work reports an experimental and modeling study of such autoignition characteristics quantified in a twin-piston rapid compression machine. Isopropanol and isobutanol are blended into a research-grade gasoline (FACE-F) at oxygenate blend levels of 0 to 30% vol/vol, with tests conducted at pressures of 20 and 40 bar, temperatures from 700 to 1000 K, and dilute stoichiometric fuel loadings. Changes to overall reactivity, including first-stage and main ignition times, and preliminary exothermicity are established, with comparisons made to previous measurements with ethanol-blended FACE-F gasoline. Furthermore, it is found that at low-temperature/NTC conditions (700–860 K) the isoalcohols suppress first-stage reactivity and associated heat release while main ignition times are extended. At NTC/intermediate-temperature (860–1000 K) conditions changes to fuel reactivity are less significant with isopropanol slightly suppressing reactivity and isobutanol promoting ignition. Detailed chemical kinetic modeling is used to interpret the experimental measurements. Overall trends of suppression or promotion in the blending behavior are reasonably captured by the model. Sensitivity and rate of production analyses indicate that at lower temperatures H-atom abstraction reactions from the surrogate fuel molecules (e.g., cyclopentane, isooctane) and the isoalcohols via OH are important leading to TC 3 H 6 OH and IC 4 H 8 OH–C radicals, for isopropanol and isobutanol respectively, which act as scavengers in the system. At higher temperatures, similar chemistries are dominant, but there is an increasing importance of abstraction by HO 2 . The kinetic modeling also indicates that the promoting effect of isobutanol at higher temperatures is due to the increased abstractions at the γ-sites, while at lower temperatures abstraction at the α-site leads to greater reactivity suppression.

36 MATERIALS SCIENCE↗

Tritiated Sulfur Hexafluoride Disposition Strategies

Tritium (T 2 ) is a radioactive isotope of hydrogen that is produced in nuclear fission reactions and is often used in nuclear fusion reactions and accelerator-based applications for medical isotope production. As a hydrogen isotope, tritium can readily bind to hydroxyl radicals (OH), forming tritiated water (HTO or T 2 0), and to carbon atoms. Tritium decays to helium-3 ( 3 He) via beta-decay with max decay energy of 18.6 keV. While it is not an external radiation hazard, it can be an internal radiation hazard if tritium is inhaled, ingested, or absorbed through the skin. In applications where tritium is handled, tritium confinement is performed using different barriers to minimize releases to the environment. For gaseous (elemental), liquid (oxide), and metal (hydride) tritium, process piping and components provide the primary confinement function. Secondary tritium confinement is typically provided by inert (i.e. non-flammable gases such as nitrogen, argon, or helium) gloveboxes which are connected to a tritium stripper system. Primary tritium confinement barriers typically produce low volumes of high tritium concentrations of tritiated methane from carbon in steels or organic materials along with tritiated water/tritium oxide (e.g. HTO) and tritiated ammonia from reactions with oxygen and nitrogen. Tritium escaping primary confinement into secondary confinement atmospheres (e.g. gloveboxes) produce higher volumes of lower activity contamination than found in process piping. Tritium contamination also occurs by leaks or tritium permeation/diffusion through confinement materials. Tritium from inside primary confinement barriers will diffuse or leak out of the primary confinement barrier and usually into the air, if the system is inside an air hood or ventilated hot cell, or into the secondary confinement (e.g. glovebox) atmosphere which is either exhausted or stripped based on the function of the secondary confinement (glovebox) system. Accelerator based processes for medical isotope production represent an atypical tritium contamination challenge. In medical isotope production, deuterium supply gas is ionized and accelerated to a tritium gas target to produce neutrons that are then used to produce the medical isotopes through additional nuclear fission reactions. To create large voltage differentials for accelerator operations, an electrical insulation medium is needed to prevent or rapidly quench electric discharges. A common electrical insulation medium utilized in accelerator applications is sulfur hexafluoride (SF 6 ) gas. SF 6 has a high dielectric strength and allows for the construction of smaller accelerator systems compared to other electrical insulation mediums such as air or dry nitrogen. Due to tritium permeation/diffusion through accelerator process and confinement materials, there is the possibility that tritium can contaminate the electrical insulation medium of the accelerator. Tritium contaminated SF 6 creates a material without any obvious processes for managing the contamination, reuse, or disposal of the used SF 6 . This document will discuss possible management strategies for tritium contaminated SF 6 for accelerator-based processes for Molybdenum-99 (Mo-99) production.

07 ISOTOPE AND RADIATION SOURCES↗

Understanding the Cathode Electrochemistry of Humidified Solid‐State Lithium‐Oxygen Batteries

Lithium-oxygen batteries (LOBs) possess a high theoretical energy density, making them potential candidates for next-generation energy storage. However, challenges such as reactive oxygen species-induced component degradation hinder their practical use. Inorganic solid-state electrolytes offer an alternative to degradation-prone aprotic electrolytes, while also protecting lithium anodes from potential atmospheric reactants. Here, this study explores the cathode electrochemistry of solid-state LOBs using humidified oxygen, which forms an aqueous catholyte during initial cycling, thereby improving cathode-electrolyte contact. To quantitatively analyze the cathode electrochemistry, a ‘Humidity-Incorporated’ Differential Electrochemical Gas Monitoring System (HiDEMS) is developed to control humidity and monitor gas consumption and evolution in real time. When studying a Li-O 2 cell that employs a NASICON-type Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 (LATP) solid electrolyte and a porous carbon cathode, a shift in discharge products from Li 2 O 2 to LiOH is observed over repeated cycles. While Li 2 O 2 evolves O 2 during charging, LiOH oxidation leads to minimal O 2 release and increased CO 2 production, originating from oxidation of carbon electrodes. Further, dissolution of Al and P from LATP is observed, likely driven by the formation of the alkaline catholyte. The findings highlight the need for carbon-free cathode materials and more stable solid-state conductors to minimize side reactions and improve rechargeability in humidified solid-state Li-O 2 batteries.

LATP degradation↗

Sintering Mechanism of Pt/Al 2 O 3 in Complex Emission Gases Elucidated via In Situ Environmental STEM

Emission control catalysts are crucial for protecting human health by preventing the release of harmful gases and unburnt fuel into the atmosphere. These catalysts often face deactivation through sintering processes in high-temperature, chemically reactive environments containing multiple gas species. Here, we use in situ environmental scanning transmission electron microscopy to monitor the sintering behavior and transient morphologies of Pt/Al 2 O 3 in various relevant gas environments through controlled experiments. Our results reveal the particle migration and atomic ripening behavior of Pt/Al 2 O 3 at the atomic scale in the presence of water vapor and oxygen, which differs from behaviors observed in single gas environments. We identify an atomic ripening mechanism involving the dissociation and migration of Pt adatom chains from Pt nanoparticles, observed only in combinational gases. Finally, these findings provide valuable insights into catalyst degradation behavior in complex gas environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structurally Defined Water‐Soluble Metallofullerene Derivatives towards Biomedical Applications

Abstract Endohedral metallofullerenes (EMFs) are excellent carriers of rare‐earth element (REE) ions in biomedical applications because they preclude the release of toxic metal ions. However, existing approaches to synthesize water‐soluble EMF derivatives yield mixtures that inhibit precise drug design. Here we report the synthesis of metallobuckytrio (MBT), a three‐buckyball system, as a modular platform to develop structurally defined water‐soluble EMF derivatives with ligands by choice. Demonstrated with PEG ligands, the resulting water‐soluble MBTs show superb biocompatibility. The Gd MBTs exhibit superior T 1 relaxivity than typical Gd complexes, potentially superseding current clinical MRI contrast agents in both safety and efficiency. The Lu MBTs generated reactive oxygen species upon light irradiation, showing promise as photosensitizers. With their modular nature to incorporate other ligands, we anticipate the MBT platform to open new paths towards bio‐specific REE drugs.

Li, Yanbang↗

Structurally Defined Water‐Soluble Metallofullerene Derivatives towards Biomedical Applications

Abstract Endohedral metallofullerenes (EMFs) are excellent carriers of rare‐earth element (REE) ions in biomedical applications because they preclude the release of toxic metal ions. However, existing approaches to synthesize water‐soluble EMF derivatives yield mixtures that inhibit precise drug design. Here we report the synthesis of metallobuckytrio (MBT), a three‐buckyball system, as a modular platform to develop structurally defined water‐soluble EMF derivatives with ligands by choice. Demonstrated with PEG ligands, the resulting water‐soluble MBTs show superb biocompatibility. The Gd MBTs exhibit superior T 1 relaxivity than typical Gd complexes, potentially superseding current clinical MRI contrast agents in both safety and efficiency. The Lu MBTs generated reactive oxygen species upon light irradiation, showing promise as photosensitizers. With their modular nature to incorporate other ligands, we anticipate the MBT platform to open new paths towards bio‐specific REE drugs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗