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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Hybrid Carbon Dioxide Reduction Photocatalysts Consisting of Macrocyclic Cobalt(III) Complexes Deposited on Semiconductor Surfaces

Hybrid photocatalysts can be prepared by coupling metal ligand complexes with light-harvesting semiconductors. It is often challenging and time consuming to derivatize ligands with anchoring groups to effectively attach onto surfaces. In this study, we synthesized hybrid carbon dioxide reduction photocatalysts by directly depositing two macrocyclic Co(III) complexes on three different semiconductor surfaces (TiO 2 , N-Ta 2 O 5 and C 3 N 4 ). The resulting hybrid photocatalysts were characterized with various techniques and tested in CO 2 reduction reactions under different light conditions. Excellent visible-light CO 2 -reduction activity was obtained using C 3 N 4 as the light-harvesting semiconductor. Furthermore, density functional theory calculations were conducted to help understand interactions between the cobalt complexes with a model TiO 2 surface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Synthesis and Characterization of Macrocyclic Ionic Liquids for CO 2 Separation

In this work, a series of ionic liquids with symmetric, macrocyclic cations composed of N-heterocycles connected by alkyl or ether linkages coupled with bis(trifluoromethylsulfonyl)imide or bis(pentafluoroethanesulfonyl)amide anions were synthesized to explore their application in CO 2 separation. These novel ionic liquids showed selective physical absorption of CO 2 compared to N 2 making them potential candidates for carbon capture. We examined the effect of cation structure on the physicochemical and separations properties of the ionic liquid and showed that these ionic liquids exhibit an inverse relationship between molar volume and CO 2 sorption capacity following the trend predicted by models based on regular solution theory. The fractional free volumes of the ionic liquids were lower than typical alkyl-imidazolium ionic liquids despite the cyclic structure of the cations which could be related to the flexibility of the alkyl and ether linkages. These results provide added insight into our understanding of structure–property relationships in CO 2 solubility in ionic liquids and afford a path toward enhancing the separations properties based on structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Mechanism of selective recognition of Lys48-linked polyubiquitin by macrocyclic peptide inhibitors of proteasomal degradation

Post-translational modification of proteins with polyubiquitin chains is a critical cellular signaling mechanism in eukaryotes with implications in various cellular states and processes. Unregulated ubiquitin-mediated protein degradation can be detrimental to cellular homeostasis, causing numerous diseases including cancers. Recently, macrocyclic peptides were developed that selectively target long Lysine-48-linked polyubiquitin chains (tetra-ubiquitin) to inhibit ubiquitin-proteasome system, leading to attenuation of tumor growth in vivo. However, structural determinants of the chain length and linkage selectivity by these cyclic peptides remained unclear. Here, we uncover the mechanism underlying cyclic peptide’s affinity and binding selectivity by combining X-ray crystallography, solution NMR, and biochemical studies. We found that the peptide engages three consecutive ubiquitins that form a ring around the peptide and determined requirements for preferential selection of a specific trimer moiety in longer polyubiquitin chains. The structural insights gained from this work will guide the development of next-generation cyclic peptides with enhanced anti-cancer activity.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

18-membered macrocycle appended on resin for selective rare earth element extraction and separation

The rare earth elements are critically important for a wide range of modern technologies. However, obtaining them selectively and efficiently from natural sources and recycled materials is challenging and often requires harsh or wasteful conditions. Here we show that a macrocyclic chelator appended to a solid resin can overcome this challenge by acting as a robust platform for both the extraction and separation of these elements. This resin preferably captures the large rare earth elements in mixtures of these ions, giving rise to higher extraction efficiencies for them over the smaller ions. We further demonstrate that this resin can be used to separate rare earth elements. As a proof-of-principle validation, this resin was demonstrated to selectively extract rare earth elements in the presence of many different types of competing metal ions in a bioleachate solution obtained from autoslag waste, leading to their enrichment.

Coordination chemistry↗
DOE OSTI2021

Towards the stable chelation of radium for biomedical applications with an 18-membered macrocyclic ligand

Targeted alpha therapy is an emerging strategy for the treatment of disseminated cancer. [ 223 Ra]RaCl 2 is the only clinically approved alpha particle-emitting drug, and it is used to treat castrate-resistant prostate cancer bone metastases, to which [ 223 Ra]Ra 2+ localizes. To specifically direct [ 223 Ra]Ra 2+ to non-osseous disease sites, chelation and conjugation to a cancer-targeting moiety is necessary. Although previous efforts to stably chelate [223Ra]Ra2+ for this purpose have had limited success, here we report a biologically stable radiocomplex with the 18-membered macrocyclic chelator macropa. Quantitative labeling of macropa with [ 223 Ra]Ra 2+ was accomplished within 5 min at room temperature with a radiolabeling efficiency of >95%, representing a significant advancement over conventional chelators such as DOTA and EDTA, which were unable to completely complex [ 223 Ra]Ra 2+ under these conditions. [ 223 Ra][Ra(macropa)] was highly stable in human serum and exhibited dramatically reduced bone and spleen uptake in mice in comparison to bone-targeted [ 223 Ra]RaCl 2 , signifying that [ 223 Ra][Ra(macropa)] remains intact in vivo. Upon conjugation of macropa to a single amino acid b-alanine as well as to the prostate-specific membrane antigen-targeting peptide DUPA, both constructs retained high affinity for 223 Ra, complexing >95% of Ra 2+ in solution. Furthermore, [ 223 Ra][Ra(macropa-b-alanine)] was rapidly cleared from mice and showed low 223 Ra bone absorption, indicating that this conjugate is stable under biological conditions. Unexpectedly, this stability was lost upon conjugation of macropa to DUPA, which suggests a role of targeting vectors in complex stability in vivo for this system. Nonetheless, our successful demonstration of efficient radiolabeling of the b-alanine conjugate with 223 Ra and its subsequent stability in vivo establishes for the first time the possibility of delivering [ 223 Ra]Ra 2+ to metastases outside of the bone using functionalized chelators, marking a significant expansion of the therapeutic utility of this radiometal in the clinic.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

A perspective on the redox properties of tetrapyrrole macrocycles

Tetrapyrrole macrocycles serve a multitude of roles in biological systems, including oxygen transport by heme and light harvesting and charge separation by chlorophylls and bacteriochlorophylls. Synthetic tetrapyrroles are utilized in diverse applications ranging from solar-energy conversion to photomedicine. Nevertheless, students beginning tetrapyrrole research, as well as established practitioners, are often puzzled when comparing properties of related tetrapyrroles. Questions arise as to why optical spectra of two tetrapyrroles often shift in wavelength/energy in a direction opposite to that predicted by common chemical intuition based on the size of a π-electron system. Gouterman's four-orbital model provides a framework for understanding these optical properties. Similarly, it can be puzzling as to why the oxidation potentials differ significantly when comparing two related tetrapyrroles, yet the reduction potentials change very little or shift in the opposite direction. In order to understand these redox properties, it must be recognized that structural/electronic alterations affect the four frontier molecular orbitals (HOMO, LUMO, HOMO-1 and LUMO+1) unequally and in many cases the LUMO+1, and not the LUMO, may track the HOMO in energy. This perspective presents a fundamental framework concerning tetrapyrrole electronic properties that should provide a foundation for rational molecular design in tetrapyrrole science.

chlorophyll↗
DOE OSTI2022

Proton-coupled electron transfer of macrocyclic ring hydrogenation: The chlorinphlorin

Significance The chemical reduction of unsaturated bonds occurs by hydrogenation with H 2 as the reductant. Conversely, in biology, the unavailability of H 2 engenders the typical reduction of unsaturated bonds with electrons and protons from different cofactors, requiring olefin hydrogenation to occur by proton-coupled electron transfer (PCET). Moreover, the redox noninnocence of tetrapyrrole macrocycles furnishes unusual PCET intermediates, including the phlorin, which is an intermediate in tetrapyrrole ring reductions. Whereas the phlorin of a porphyrin is well established, the phlorin of a chlorin is enigmatic. By controlling the PCET reactivity of a chlorin, including the use of a hangman functionality to manage the proton transfer, the formation of a chlorinphlorin by PCET is realized, and the mechanism for its formation is defined.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Fourfold alkyl wrapping of a copper(II) porphyrin thwarts macrocycle π–π stacking in a compact supramolecular package

Porphyrins are valuable constituents in optoelectronic, catalytic, and other applications, yet control of intermolecular π–π stacking is invariably essential to attain the desired properties. Superstructures built onto the porphyrin, often via meso -aryl groups, can afford facial encumbrance that suppresses π–π stacking, although some molecular designs have provided insufficient facial coverage and many have entailed cumbersome syntheses. In this study, a copper(II) porphyrin bearing four meso substituents, namely, {10,20-bis[2,6-bis(octyloxy)phenyl]-5,15-dibromoporphinato}copper(II), [Cu(C 64 H 82 Br 2 N 4 O 4 )], was prepared by metalation of the corresponding free-base porphyrin and was characterized by single-crystal X-ray diffraction. The crystal structure reveals a dihedral angle of 111.1 (2)° for the plane of the meso -aryl group relative to the plane of the porphyrin, with both aryl groups tilted in the same direction. Each of the four octyloxy groups exhibits a gauche conformation for the –OCH 2 CH 2 – unit but is extended with four or five anti (–CH 2 CH 2 –/H) conformations thereafter, causing each octyl group to span the dimension of the macrocycle. In a global frame of reference where the two Br atoms define the north/south poles and the two aryl groups are at antipodes on the equator, two octyl groups of one aryl unit project over the northern hemisphere (covering pyrroles A and B ), whereas those of the other aryl unit project over the southern hemisphere (covering pyrroles C and D ). Together, the four octyl groups ensheath the two faces of the porphyrin in a self-wrapped assembly. The closest approach of the Cu atom to an octyl methylene C atom (position 6) is 3.5817 (18) Å, the mean separations of neighboring porphyrin planes are 8.059 (4) and 4.693 (8) Å along the a and c axes, respectively, and the center-to-center distances between the Cu atoms of neighboring porphyrins are 10.2725 (4), 12.2540 (6), and 12.7472 (6) Å along the a , b , and c axes, respectively. The Hirshfeld surface analysis and two-dimensional (2D) fingerprint plots provide information concerning contact interactions in the supramolecular assembly of the solid crystal.

Chemistry↗
DOE OSTI2025

Uranyl Capture and Activation with Lewis Acids and Macrocyclic Hosts (Final Technical Report)

This document is the final report for the project with the title, “Uranyl Capture with Lewis Acids and Macrocyclic Hosts.” Nuclear power is attractive for meeting the current and future energy needs of society, in that it does not release carbon dioxide or other pollutants into the atmosphere during routine use. This motivated the project, because preparation of nuclear fuel, recovery of useful components from used fuel, and handling of waste materials remain significant impediments to further deployment of important nuclear technologies. In part, these problems arise from limited availability of chemical reactions that can reliably interconvert forms of uranium and other heavy elements during preparation and processing. For example, harsh and expensive chemicals are often required for making and breaking chemical bonds to uranium, and the reactions involved are inefficient. The overall objective of this research was to harness knowledge of chemical structure and bonding to develop a useful and predictive und

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Polymer Macrocycles: A novel topology to control dynamics of rubbery materials (Final Report)

We have successfully made synthetic polymer rings that are larger than previously reported having entanglement numbers as high as Z w ≈300 if the rings entangled as do linear chains. The synthesis was carried out using reversible radical recombination polymerization (R3P) of dithiols which produces a polymer with a very small persistence length. The reported results show surprising dilute solution behaviors due to the fact that polymeric rings expand more than their linear counterparts for polymer chains having a large number of persistence lengths, as developed in this study. The results strongly argue for a systematic investigation of the dilute solution properties of rings having different persistence lengths in different quality solvents, where the theta-condition should lead to results that are independent of the persistence length. For the rheological investigations related to chain entanglements, the polyDODT rings could be diluted so that the rheological data covered from less than one entanglement spacing relative to the linear counterpart to a value of Z w =300. Importantly, because we were able to dilute extremely high entanglement number polyDODT rings to a similar entanglement number as those reported for polystyrene rings that were highly purified using LCCC, we demonstrated that the dynamics of the polyDODT rings virtually overlaps with the dynamics of the polystyrene rings which is very strong evidence that these high molecular weight polyDODT rings are of high purity. Our results demonstrate that the onset of entanglement in rings, as evidenced by the appearance of a rubbery plateau G N 0 and by the onset of a strong power-law dependence of the viscosity on molecular weight (η~M w 5.8 ) or entanglement number (η~Z w 5.8 ), occurs at much higher molecular weights or polymer concentrations than is the case for linear chains. These results should serve as a benchmark for future investigations of the behavior of entangled, circular macromolecules.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2023

Polymer Macrocycles: A novel topology to control dynamics of rubbery materials

We have successfully made synthetic polymer rings that are larger than previously reported having entanglement numbers as high as $Z_w$≈300 if the rings entangled as do linear chains. The synthesis was carried out using reversible radical recombination polymerization (R3P) of dithiols which produces a polymer with a very small persistence length. The reported results show surprising dilute solution behaviors due to the fact that polymeric rings expand more than their linear counterparts for polymer chains having a large number of persistence lengths, as developed in this study. The results strongly argue for a systematic investigation of the dilute solution properties of rings having different persistence lengths in different quality solvents, where the theta-condition should lead to results that are independent of the persistence length. For the rheological investigations related to chain entanglements, the polyDODT rings could be diluted so that the rheological data covered from less than one entanglement spacing relative to the linear counterpart to a value of $Z_w$=300. Importantly, because we were able to dilute extremely high entanglement number polyDODT rings to a similar entanglement number as those reported for polystyrene rings that were highly purified using LCCC, we demonstrated that the dynamics of the polyDODT rings virtually overlaps with the dynamics of the polystyrene rings which is very strong evidence that these high molecular weight polyDODT rings are of high purity. Our results demonstrate that the onset of entanglement in rings, as evidenced by the appearance of a rubbery plateau $G_N^0$ and by the onset of a strong power-law dependence of the viscosity on molecular weight (η~$M_w^{5.8}$) or entanglement number (η~$Z_w^{5.8}$), occurs at much higher molecular weights or polymer concentrations than is the case for linear chains. These results should serve as a benchmark for future investigations of the behavior of entangled, circular macromolecules.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2020

Transactinide studies with sulfur macrocyclic extractant using mercury

Mercury extraction has been studied in nitric and hydrochloric acids with hexathia-18-crown-6 dissolved in carbon tetrachloride. Batch study experiments have been performed to determine the best conditions for maximum extraction. In both acids, Hg(II) was best extracted at low molarity while almost no extraction was observed above 2 M. Furthermore, speciation studies were carried out in an attempt to describe the extraction mechanism, but the exact composition of the extracted species was not determined. The extraction kinetics were studied to assess the feasibility of this crown ether for extracting Cn and/or Fl in a future online experiment.

197mHg↗