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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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Bioinspired Macrocyclic Molecule Supported Two‐Dimensional Lamellar Membrane with Robust Interlayer Structure for High‐Efficiency Nanofiltration

Abstract 2D lamellar membranes (2DLMs) are used for efficient desalination and nanofiltration. However, weak interactions between adjacent stacked nanosheets result in susceptibility to swelling that limits practical applicability. Inspired by the super adhesion of multi‐point suction cups on octopus tentacles, a 2DLM is constructed from Ti 3 C 2 T x MXene supported by the macrocyclic “multi‐point” molecule cucurbit[5]uril (CB5) and demonstrated for nanofiltration of methyl blue (MB) and enrichment of uranyl carbonate. Experimental results and density functional theory calculations indicate that CB5 rivets to the surface of the nanoflakes through strong stable interactions between its multiple binding sites and surface hydroxyl functional groups on MXene nanosheets. This novel 2DLM exhibits excellent nanofiltration performance (69 L m −2 h −1 bar −1 permeance with 93.6% rejection for MB) and can be recycled at least 30 times without significant degradation. The 2DLM exhibits excellent swelling resistance at high salinity, with a demonstration of selective enrichment of uranyl carbonate from artificial water and natural seawater. The results provide a new strategy for constructing highly stable 2DLMs with interlayer spacing controllable from sub‐nano to nanometer scales, for size‐selective sieving of molecules and ions, high‐efficiency nanofiltration, and other applications.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2025

Discovery of Macrocyclic Myeloid Cell Leukemia 1 (Mcl-1)Inhibitors that Demonstrate Potent Cellular Efficacy and In Vivo Activity in a Mouse Solid Tumor Xenograft Model

Abstract The B cell lymphoma 2 (Bcl-2) family of proteins are key regulators of intrinsic apoptosis. The antiapoptotic protein myeloid cell leukemia 1 (Mcl-1), which is associated with high tumor grade, poor survival, and resistance to treatment, has emerged as a promising candidate for treating hematological and solid cancers. Herein, we report the structure-guided design of small molecule macrocyclic Mcl-1 inhibitors based on the (R)-methyl-dihydropyrazinoindolone scaffold our group has previously disclosed. The macrocyclic inhibitors bind Mcl-1 with subnanomolar affinity and offer improved potency in cell culture growth inhibition assays. Inhibitor 13 achieved tumor regression in a lung cancer-derived tumor xenograft model in mice as a monotherapy. The improved potency of the macrocyclic series allowed replacement of heretofore conserved indole carboxylic acid moiety, resulting in neutral inhibitors. Amide inhibitor 25 displayed a >10-fold increase in oral bioavailability as compared to acid-containing macrocyclic or acyclic inhibitors.

Pharmacology & Pharmacy↗
DOE OSTI2022

Selective Removal of Barium and Hardness Ions from Brackish Water with Chemically Enhanced Electrodialysis

The use of a nonconventional water resource for energy and industrial applications often requires extraction of low-level undesirable ions from matrices of benign dominant ions. In this study, the selective extraction of Ba 2+ and Mg 2+ from synthetic brine solutions was evaluated using strong acid cation-exchange membranes modified with the surface deposition of macrocyclic molecules including crown ethers and calixarenes. Compared to the bare membrane, vinylbenzo-18-crown-6 (VB18C6) and calix[4]arene-amended membranes showed increased selectivity for Ba 2+ and Mg 2+ with respect to the dominant ion (Na + ) by up to fourfolds, with the calix[4]arene-modified membrane achieving more selective separation than VB18C6. Optimal selectivity was achieved at a moderate-to-high current density (3.1–6.3 mA/cm 2 ), which was attributed to the alleviation of transport limitation in the boundary layer by the surface modification. Amendment of a calix[4]arene derivative with a crown-6 “boot strap” and two carboxylic groups resulted in reduced selectivity due to the formation of strong complexes with divalent ions. Furthermore, these results show that surface deposition of ion sequestrants can be a versatile approach to improve the membrane’s selectivity; however, the performance is sensitive to feed water salinity, current loading, and the macrocycle-ion chemistry, where there is a trade-off between ion affinity and mobility.

36 MATERIALS SCIENCE↗
DOE OSTI2022

On-Surface Single-Molecule Identification of Mass-Selected Cyclodextrin-Supported Polyoxovanadates for Multistate Resistive-Switching Memory Applications

Polyoxovanadate anions immobilized on conducting substrates are promising candidates for molecule-based memory technologies. However, strong electronic interactions with the substrate and the formation of larger agglomerates remain bottlenecks on the way to their technical application. We demonstrate that ion soft-landing of mass selected cyclodextrin- functionalized hexavanadates enables to deposit these host-guest complexes as single memory units on surfaces without their quaternary ammonium countercations from solution. The cyclodextrin provides a stabilizing “shell” for the dianions. Further, multistate switching evidenced by the change in molecular resistance has been detected using scanning tunneling microscopy and spectroscopy and attributed to reduction of individual vanadium (+V) centers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Metastable doubly threaded [3]rotaxanes with a large macrocycle

Ring size is a critically important parameter in many interlocked molecules as it directly impacts many of the unique molecular motions that they exhibit. Reported herein are studies using one of the largest macrocycles reported to date to synthesize doubly threaded [3]rotaxanes. A large ditopic 46 atom macrocycle containing two 2,6-bis(N-alkyl-benzimidazolyl)pyridine ligands has been used to synthesize several metastable doubly threaded [3]rotaxanes in high yield (65–75% isolated) via metal templating. Macrocycle and linear thread components were synthesized and self-assembled upon addition of iron(II) ions to form the doubly threaded pseudo[3]rotaxanes that could be subsequently stoppered using azide–alkyne cycloaddition chemistry. Following demetallation with base, these doubly threaded [3]rotaxanes were fully characterized utilizing a variety of NMR spectroscopy, mass spectrometry, size-exclusion chromatography, and all-atom simulation techniques. Critical to the success of accessing a metastable [3]rotaxane with such a large macrocycle was the nature of the stopper group employed. By varying the size of the stopper group it was possible to access metastable [3]rotaxanes with stabilities in deuterated chloroform ranging from a half-life of <1 minute to ca. 6 months at room temperature potentially opening the door to interlocked materials with controllable degradation rates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Truncating 2D Framework Materials Down to a Single Pore: Synthetic Approaches and Opportunities

Here, in this Accounts article, we summarize our recent work on truncating conjugated two-dimensional framework materials down to a single pore, or a single macrocycle. Conjugated 2D architectures have emerged as one of the most synthetically adaptable motifs for coupling semiconductivity and porosity in metal–organic frameworks (MOFs) and covalent organic frameworks (COFs). However, despite their prevalence, 2D architectures have several limitations. In particular, the strong interlayer π–π stacking can limit both processability and the accessibility of internal active sites. We have found that simple macrocycles preserve key aspects of 2D framework structure and function, including porosity and out-of-plane electrical conductivity, while providing improved processability, surface tunability, and mass transport properties. In this article, we first describe our synthetic approach and general design considerations. Specifically, we show how ditopic analogues of the tritopic ligands commonly found in the synthesis of 2D MOFs and COFs can be used to achieve a diverse library of conjugated macrocycles that resemble fragments of semiconducting frameworks in both form and function. The length of the peripheral side chains, the size of the aromatic core, and the solubility of intermediates are all key variables in favoring selective macrocycle formation over undesired linear polymers and oligomers. Next, we highlight the unique advantages that macrocycles provide, including improved processability, atomically precise surface tunability, and greater active site accessibility. In particular, the identity of the peripheral side chains dramatically impacts both solubility and colloidal stability as well as crystal size and morphology. We further show how the solution processability and nanoscale dimensions of macrocycles can simplify electronic device fabrication and improve electrochemical performance. Finally, we end with a forward-looking discussion on how macrocycles offer a unique bridge between conjugated molecules and extended frameworks, enabling new application areas and fundamental science.

charge transport↗
DOE OSTI2024

Chelator‐Assisted Precipitation‐Based Separation of the Rare Earth Elements Neodymium and Dysprosium from Aqueous Solutions

The rare earth elements (REEs) are critical resources for many clean energy technologies, but are difficult to obtain in their elementally pure forms because of their nearly identical chemical properties. Here, an analogue of macropa, G-macropa, was synthesized and employed for an aqueous precipitation-based separation of Nd 3+ and Dy 3+ . G-macropa maintains the same thermodynamic preference for the large REEs as macropa, but shows smaller thermodynamic stability constants. Molecular dynamics studies demonstrate that the binding affinity differences of these chelators for Nd 3+ and Dy 3+ is a consequence of the presence or absence of an inner-sphere water molecule, which alters the donor strength of the macrocyclic ethers. Leveraging the small REE affinity of G-macropa, we demonstrate that within aqueous solutions of Nd 3+ , Dy 3+ , and G-macropa, the addition of HCO 3 − selectively precipitates Dy 2 (CO 3 ) 3 , leaving the Nd 3+ −G-macropa complex in solution. With this method, remarkably high separation factors of 841 and 741 are achieved for 50 : 50 and 75 : 25 mixtures. Further studies involving Nd 3+ :Dy 3+ ratios of 95 : 5 in authentic magnet waste also afford an efficient separation as well. Finally, G-macropa is recovered via crystallization with HCl and used for subsequent extractions, demonstrating its good recyclability.

Gao, Yangyang↗
DOE OSTI2025

Anion Binding by Macrocyclic Receptors: Computational Landscape of 1:1 and 2:1 Stoichiometries

Macrocyclic receptors play a crucial role in supramolecular chemistry, enabling the selective binding of guest molecules through non-covalent interactions. This study investigates the anion binding properties of three shape-persistent macrocycles, triazolophane, cyanostar, and tricarb, each featuring preorganized cavities with polarized CH hydrogen bond donors. In the 1:1 binding stoichiometries, the macrocycles preferentially bind anions that fit inside their two-dimensional cavities, with this preference being more pronounced in solution. Specifically, the triazolophane favors smaller anions like chloride and bromide, while the larger cavities offered by cyanostar and tricarb macrocycles preferentially bind the larger iodide. For large, polyatomic anions (SCN − , BF$^{−}_{4}$, ClO$^{−}_{4}$, and PF$^{−}_{6}$), the macrocycles self-assemble to form stable 2:1 sandwich complexes, exhibiting stronger binding. This shift in selectivity highlights the versatility of the macrocycles, making them promising candidates for anion sensing and regulation with various complexation stoichiometries.

Che, Minwei [Indiana University, Bloomington, IN (↗
DOE OSTI2021

Active mechanisorption driven by pumping cassettes

Pumping macrocycles onto surfaces Numerous chemical processes, ranging from water purification to catalysis, involve sorption of small molecules onto surfaces. Typically, spontaneous attractive interactions favor the binding event. Feng et al . report a mechanisorption process that requires redox manipulations to pump macrocycles from bulk solution onto axles immobilized on a metal-organic framework. The resulting rotaxanes store energy through nonequilibrium charge concentration in their mechanical bonds. Ultimately, the technique could also prove useful for actively partitioning compounds with particular functionality between surface and bulk environments. —JSY

Science & Technology - Other Topics↗
DOE OSTI2021

Characterization of a Molecule Partially Confined at the Pore Mouth of a Zeotype

Abstract We investigate the interaction between a molecule and a pore mouth—a critical step in adsorption processes—by characterizing the conformation of a macrocyclic calix[4]arene‐Ti IV complex, which is grafted on the external surface of a zeotype (*‐SVY). X‐ray absorption and 13 C{ 1 H} CPMAS NMR spectroscopies independently detect a unique conformation of this complex when it is grafted at crystallographically equivalent locations that lie at the interface of 7 Å hemispherical microporous cavities and the external surface. Electronic structure calculations support the presence of this unique conformation, and suggest that it is brought about by a specific orientation of the macrocycle that maximizes non‐covalent interactions between calix[4]arene upper‐rim tert ‐butyl substituents and the microporous‐cavity walls. Our comparative study provides a rare “snapshot” of a molecule partially confined at a pore mouth, an essential intermediate for adsorption into micropores, and demonstrates how surrounding environment controls this confinement in a sensitive fashion.

Grosso‐Giordano, Nicolás A.↗
DOE OSTI2021

Interplays of electron and nuclear motions along CO dissociation trajectory in myoglobin revealed by ultrafast X-rays and quantum dynamics calculations

Significance In this multidisciplinary study, we investigated local and global structural responses upon carbon monoxide (CO) dissociation from the heme iron(II) in myoglobin in solution using ultrafast X-ray absorption and scattering. CO dissociation was optically triggered and pulsed X-rays probed structural and electronic changes as a function of time, revealing an iron(II) spin state transition and nuclear motions propagating from the active site throughout the entire protein. Quantum mechanical computational results were used to assign the iron K-edge absorption features, and to map out electronic and nuclear trajectories during Fe–CO bond elongation and heme macrocycle doming. The study has important implications for heme–protein function and the interaction of small molecule substrates with the metal active centers in enzymes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Abbr. Final report: Self-assembled molecular containers as artificial water channels: towards biomimetic desalination membranes

Global water scarcity demands advances in desalination technologies that can deliver more fresh water with less energy. Current reverse osmosis membranes are fundamentally limited by a trade-off between how much water they can pass and how well they block salts. To address this challenge, we developed a bottom-up strategy to design and test artificial water channels that mimic the efficiency of biological proteins but are built from robust synthetic molecules. Over two years, we synthesized and evaluated more than twenty molecular channel candidates, including supramolecular macrocycles and nanographene pores with atomically precise structures. We showed that small chemical modifications allow direct control over pore size and chemistry, which in turn govern water permeability and salt rejection. In collaboration with university partners, we reported the first experimental demonstration of water transport through a nanographene pore, bridging a long-standing gap between simulation and experiment. Several of the artificial channels we developed achieved water–salt selectivity beyond conventional polymer membranes, highlighting their potential for next-generation desalination and precision separations.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Recognition competes with hydration in anion-triggered monolayer formation of cyanostar supra-amphiphiles at aqueous interfaces

The triggered self-assembly of surfactants into organized layers at aqueous interfaces is important for creating adaptive nanosystems and understanding selective ion extraction. While these transformations require molecular recognition, the underlying driving forces are modified by the local environment in ways that are not well understood. Herein, we investigate the role of ion binding and ion hydration using cyanosurf, which is composed of the cyanostar macrocycle, and its binding to anions that are either size-matched or mis-matched and either weakly or highly hydrated. We utilize the supra-amphiphile concept where anion binding converts cyanosurf into a charged and amphiphilic complex triggering its self-organization into monolayers at the air–water interface. Initially, cyanosurf forms aggregates at the surface of a pure water solution. When the weakly hydrated and size-matched hexafluorophosphate (PF 6 - ) and perchlorate (ClO 4 - ) anions are added, the macrocycles form distinct monolayer architectures. Surface-pressure isotherms reveal significant reorganization of the surface-active molecules upon anion binding while infrared reflection absorption spectroscopy show the ion-bound complexes are well ordered at the interface. Vibrational sum frequency generation spectroscopy shows the water molecules in the interfacial region are highly ordered in response to the charged monolayer of cyanosurf complexes. Consistent with the importance of recognition, we find the smaller mis-matched chloride does not trigger the transformation. However, the size-matched phosphate (H 2 PO 4 - ) also does not trigger monolayer formation indicating hydration inhibits its interfacial binding. These studies reveal how anion-selective recognition and hydration both control the binding and thus the switching of a responsive molecular interface.

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

Stringing the Perylene Diimide Bow

Abstract This study explores a new mode of contortion in perylene diimides where the molecule is bent, like a bow, along its long axis. These bowed PDIs were synthesized through a facile fourfold Suzuki macrocyclization with aromatic linkers and a tetraborylated perylene diimide that introduces strain and results in a bowed structure. By altering the strings of the bow, the degree of bending can be controlled from flat to highly bent. Through spectroscopy and quantum chemical calculations, it is demonstrated that the energy of the lowest unoccupied orbital can be controlled by the degree of bending in the structures and that the energy of the highest occupied orbital can be controlled to a large extent by the constitution of the aromatic linkers. The important finding is that the bowing results not only in red‐shifted absorptions but also more facile reductions.

Liu, Taifeng↗
DOE OSTI2020

Stringing the Perylene Diimide Bow

This study explores a new mode of contortion in perylene diimides where the molecule is bent, like a bow, along its long axis. These bowed PDIs were synthesized through a facile fourfold Suzuki macrocyclization with aromatic linkers and a tetraborylated perylene diimide that introduces strain and results in a bowed structure. By altering the strings of the bow, the degree of bending can be controlled from flat to highly bent. Through spectroscopy and quantum chemical calculations, it is demonstrated that the energy of the lowest unoccupied orbital can be controlled by the degree of bending in the structures and that the energy of the highest occupied orbital can be controlled to a large extent by the constitution of the aromatic linkers. The important finding is that the bowing results not only in red-shifted absorptions but also more facile reductions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Molecular To Mesoscale Targeting of Oxoanions with Multi-Tasking Hosts

Achieving a better understanding of anion interactions both in solution and crystalline state was the overarching goal of this project. Anions are everywhere throughout Nature and play important roles in biological and environmental processes. They can be beneficial or deleterious or both in different situations and concentrations. For either reason it is important to have molecules that can bind anions for key needs that benefit society. However, recognition of specific anions is challenging due to the diffuse nature of their negative charge(s) as well as their various shapes and sizes. Understanding the basic properties of anions and how they interact with other molecules and ions in surrounding environments is key to selective recognition. In this project multi-tasking molecules for selective binding of targeted anions were designed to achieve cooperativity and synergism in one rather than multiple host molecules, including (1) cation:anion pair hosts for anions with charges of -2 or greater; (2) pH and redox activated hosts for on-off binding and release; and (3) multiple anion capture in extended host networks. Our design strategy was to combine the use of simple inexpensive building blocks and high yield synthetic pathways to provide economically feasible scale-up for applications. Oxoanions representing multiple shapes and charges were chosen based on having the potential for significant impact on DOE separations needs. Amide/amine-based macrocycles and urea/amine-based chelates and macrocycles with multiple hydrogen bonding sites provided the basic anion-binding frameworks. Successful multi-tasking outcomes were forthcoming in all three tasks. In Task 1, successful ion pair binding for anions with multiple charges was achieved. Furthermore, the ion pair molecules were capable of extended interactions through supramolecular intertwining, like fishing nets for capturing pools of fish (also fitting with Task 3). In Task 2, molecules were synthesized possessing on-off switches. These included a pH sensitive sensor for on-off binding of anions in general, as well as an electrochemical sensor selective for sulfate capture. Three new classes of extended anion host networks capable of binding multiple ions was a major outcome of Task 3. These systems included: anion sensitive, fluorescent organogels; channel-forming macrocycles for studying anion-water including larger macrocyclic cluster sandwiches; and, the offshoot of Task 1, fishing net ion-pair networks for higher valent anions. These strategies can be expanded in the future to other ions and molecules for a better understanding of intermolecular and interionic interactions.

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

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

Understanding the dynamics of polymers of different topologies is an important field of study and one of the most important unanswered questions in this field is "how do circular polymers move," particularly in the melt state. New information suggests that molecular topology, specifically circular rings, impacts the response of materials in nanometer- scale confinement. The work performed here tackles these subjects through a collaboration in which specialists in polymer synthesis, polymer rheology and scattering methods, and in the physics of nanoconfinement work together to investigate the thermophysical behavior of circular macromolecules. The project goals are to use a novel synthesis method of "green" oxidative polymerization to produce high purity macrocycles and to investigate their linear viscoelastic behavior in order to fully characterize the dynamics of circular macromolecules to sizes that correspond to linear molecule entanglement densities higher than previously obtainable with synthetic polymers. Chemical chain end characterization and critical edge fractionation coupled with direct visualization of the prepared polymers through the use of polymer amplification methods are proposed in order to quantify the numbers of circular and linear molecules in each sample. The study of the linear viscoelastic response of blends of linear and circular molecules is also to be undertaken in the project. Nonlinear viscoelastic measurements, including extensional viscosity, are to be made. Strong differences in behavior between linear chains and circular ones also provides an important opportunity for new technology to break the "magic triangle" for tires: it is believed that improving one of the three key attributes - traction, wear, rolling resistance - necessarily sacrifices at least one of the others. Rubber made from cyclic polymers has the potential to break out of this triangle by reducing the so-called Payne effect in reinforced rubbers because circular macromolecules are less sensitive to nanoconfinement than their linear counterparts. The work has as one objective to characterize the impact of nanoconfinement on the behavior of large circular macromolecules. In addition, the dynamics of carbon black filled circular macromolecules are to be studied to test the hypothesis that the resulting rubbery materials will exhibit a reduced Payne effect.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗