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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 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Spiroligomer‐Based Macrocycles for Atomically Precise Membranes

Abstract Here, we report a new class of peptidomimetic macrocycles with well‐defined three‐dimensional structures and low conformational flexibility. They are assembled from fused‐ring spiro‐ladder oligomers (spiroligomers) by modular solid‐phase synthesis. Two‐dimensional nuclear magnetic resonance confirms their shape persistency. Triangular macrocycles of tunable sizes assemble into membranes with atomically precise pores, which exhibit size and shape‐dependent molecular sieving towards a series of structurally similar compounds. The exceptional structural diversity and stability of spiroligomer‐based macrocycles will be explored for more applications.

Xie, Yihui↗
DOE OSTI2022

Chelating Rare-Earth Metals (Ln 3+ ) and 225 Ac 3+ with the Dual-Size-Selective Macrocyclic Ligand Py 2 -Macrodipa

Radioisotopes of metallic elements, or radiometals, are widely employed in both therapeutic and diagnostic nuclear medicine. For this application, chelators that efficiently bind the radiometal of interest and form a stable metal–ligand complex with it are required. Toward the development of new chelators for nuclear medicine, we recently reported a novel class of 18-membered macrocyclic chelators that is characterized by their ability to form stable complexes with both large and small rare-earth metals (Ln 3+ ), a property referred to as dual size selectivity. A specific chelator in this class called py-macrodipa, which contains one pyridyl group within its macrocyclic core, was established as a promising candidate for 135 La 3+ , 213 Bi 3+ , and 44 Sc 3+ chelation. Building upon this prior work, here we report the synthesis and characterization of a new chelator called py 2 -macrodipa with two pyridyl units fused into the macrocyclic backbone. Its coordination chemistry with the Ln 3+ series was investigated by NMR spectroscopy, X-ray crystallography, density functional theory (DFT) calculations, analytical titrations, and transchelation assays. These studies reveal that py 2 -macrodipa retains the expected dual size selectivity and possesses an enhanced thermodynamic affinity for all Ln 3+ compared to py-macrodipa. By contrast, the kinetic stability of Ln 3+ complexes with py 2 -macrodipa is only improved for the light, large Ln 3+ ions. Based upon these observations, we further assessed the suitability of py 2 -macrodipa for use with 225 Ac 3+ , a large radiometal with valuable properties for targeted α therapy. Radiolabeling and stability studies revealed py 2 -macrodipa to efficiently incorporate 225 Ac 3+ and to form a complex that is inert in human serum over 3 weeks. Although py 2 -macrodipa does not surpass the state-of-the-art chelator macropa for 225 Ac 3+ chelation, it does provide another effective 225 Ac 3+ chelator. Furthermore, these studies shed light on the fundamental coordination chemistry of the Ln 3+ series and may inspire future chelator design efforts.

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

Database of low‐temperature absorption and fluorescence spectra of native photosynthetic tetrapyrrole macrocycles

Low-temperature (77 K) absorption and fluorescence spectra of 12 naturally occurring photosynthetic tetrapyrrole macrocycles have been recorded in a frozen glass (2-methyltetrahydrofuran). The compounds encompass distinct chromophore classes: porphyrin, chlorophyll c 2 ; chlorin, chlorophylls a, b, d, f and bacteriochlorophylls c, d, e, f; and bacteriochlorin, bacteriochlorophylls a, b, g. The spectra are compared with those of the same pigment in liquid solution (predominantly 2-methyltetrahydrofuran) at room temperature (293 K). The measured Stokes shifts at 77 K across the 12 macrocycles range from ~30 to 300 cm −1 . The spectral data in digital form are made available as part of the PhotochemCAD databases. Literature searches have revealed extensive published data for Chl a (often in biological matrices) but at best rather limited data for less common macrocycles. The availability of a systematic collection of curated spectral data collected at low temperature should be useful for a variety of assessments, including reconstruction of absorption spectra of (bacterio)chlorophyll-containing protein complexes, vibrational analysis of absorption and fluorescence spectra, and calculations where knowledge of energy levels is important.

Niedzwiedzki, Dariusz M. [Washington University in↗
DOE OSTI2025

Slow Electron Spin Relaxation at Ambient Temperatures with Copper Coordinated by a Rigid Macrocyclic Ligand

Paramagnetic transition metal complexes can serve as quantum bits, storing phase information through unpaired electrons. Despite their promise, these systems often require low temperatures and tend to rapidly decohere. Recent efforts have sought to improve longitudinal relaxation (T 1 ), which provides an upper limit for phase coherence (T m ), by investigating existing literature compounds with reduced vibrational coupling and orbital angular momentum. However, synthetic strategies for improving T 1 through novel ligand design have remained scant. Here, we disclose the synthesis of a new modular macrocyclic ligand framework with four nitrogen donors (N 4 ) derived from phenanthroline that supports room-temperature coherent Cu(II) spin centers. The optimized complex more than doubles the T 1 over the next best Cu(II)-N 4 compound and exhibits a room temperature coherence time (T m ) of 0.28 μs, close to previously reported values. This performance enhancement arises from a tight binding site with short Cu–N distances, resulting in a stronger ligand field and reduced thermal accessibility of symmetric vibrational modes. This work demonstrates a practical approach to enabling spin coherence at room temperature, a factor critical to accessing relevant quantum bits and biological sensors, through a designer macrocyclic ligand platform.

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

Computationally designed peptide macrocycle inhibitors of New Delhi metallo-β-lactamase 1

The rise of antibiotic resistance calls for new therapeutics targeting resistance factors such as the New Delhi metallo-β-lactamase 1 (NDM-1), a bacterial enzyme that degrades β-lactam antibiotics. We present structure-guided computational methods for designing peptide macrocycles built from mixtures of l - and d -amino acids that are able to bind to and inhibit targets of therapeutic interest. Our methods explicitly consider the propensity of a peptide to favor a binding-competent conformation, which we found to predict rank order of experimentally observed IC 50 values across seven designed NDM-1- inhibiting peptides. We were able to determine X-ray crystal structures of three of the designed inhibitors in complex with NDM-1, and in all three the conformation of the peptide is very close to the computationally designed model. In two of the three structures, the binding mode with NDM-1 is also very similar to the design model, while in the third, we observed an alternative binding mode likely arising from internal symmetry in the shape of the design combined with flexibility of the target. Although challenges remain in robustly predicting target backbone changes, binding mode, and the effects of mutations on binding affinity, our methods for designing ordered, binding-competent macrocycles should have broad applicability to a wide range of therapeutic targets.

42 ENGINEERING↗
DOE OSTI2025

Pyrrole‐Imine Macrocycle: Self‐Organizing Cross‐Reactive Anion Receptor and Sensor

Self-organizing macrocyclic receptor-sensors for phosphorus oxyanions, phosphates, and phosphonates comprising imine moieties were prepared by condensation of dipyrrolylmethane dicarbaldehyde with diethylene triamine. The incorporation of flexible ethylene moieties endows the macrocycle with unprecedented flexibility and ability to accommodate numerous phosphorus oxyanions from orthophosphate to large anions such as ATP or phosphonate glyphosate. The anion binding was elucidated by NMR titrations, low-temperature NMR, and NOESY NMR. The incorporation of dansyl fluorophore enables sensing of anions using the fluorescence signal, whereas the changes in fluorescence intensity, width of the fluorescence band, and position of the maxima are analyte-specific and useful in recognition and identification of eleven different P-oxyanions in water. The affinity (K assoc ) for Na + salts was H 2 PO 4 − ≈ Methylphosphonate > H 2 P 2 O 7 2− > Phenylphosphonate- > Glyphosate 2− > AMP 2− > ADP 2− > ATP 2− . Interestingly, phosphonates, including methylphosphonate and glyphosate anions, were also found to display a strong affinity (K assoc ∼10 6 M −1 ) while halides, nitrate, carbonates, or hydrogen sulfate did not show a significant affinity. The determined fluorescence spectral parameters were used to classify the 12 analytes (11 anions and water) using Linear Discriminant Analysis (LDA). Quantification was performed using LDA and Support Vector Machine (SVM), and the phosphonate concentrations in unknown samples were determined with an error of 3.5% or lower.

anions↗
DOE OSTI2025

Tuning gas separation performance of polyimide membranes with macrocyclic crown ether units

Membrane-based gas separation is an energy-efficient alternative to conventional thermally-driven separation processes. However, polymer membranes face the permeability-selectivity trade-off challenge, which stems from the broad size distribution of free volume voids. Here, this study reports a molecular design strategy to address this challenge through incorporating macrocyclic crown ether (CE) moieties into the backbone of Matrimid® polyimide, a commercial gas separation membrane. A series of CE-containing Matrimid®-like copolyimides were synthesized with systematically varied CE molar contents ranging from 3 to 20%. These copolyimides formed ductile, defect-free thin films suitable for membrane fabrication. Gas permeation tests revealed a non-monotonic relationship between permeability/selectivity and CE content. Notably, the copolyimide with only 5% CE demonstrated a 61% increase in CO 2 /CH 4 selectivity and a 13% increase in CO 2 permeability relative to pristine Matrimid®. Higher CE contents did not yield further performance improvements, which is likely due to the competing effects of chain packing disruption and π–π interactions among CE moieties at high content. This hypothesis was supported by wide-angle X-ray scattering (WAXS) analysis, density measurements, and fractional free volume calculations. These findings highlight the potential of macrocyclic crown ether incorporation strategies in fine tuning the microstructure of commercial polyimide gas separation membranes to surpass the traditional permeability-selectivity trade-off.

CO2 separation↗
DOE OSTI2025

VHH antibody loop guides design of a synthetic macrocyclic peptide that potently blocks influenza virus membrane fusion

Abstract Miniaturizing biologically complex structural motifs to produce synthetic functional mimetics holds significant promise for development of new therapeutic modalities. Here, we demonstrate a unique approach using the key binding loop of the single variable domain of a heavy chain (V H H) llama antibody as a starting point for peptide design. V H H antibodies of camelids and sharks generally have longer, but more ligand-efficient complementarity determining region 3 (CDR3) loops and are relatively stable structures. We harnessed these attributes as templates for design of a series of synthetic macrocyclic peptides. The designed peptides exhibit nanomolar binding to influenza hemagglutinin (HA) and heterosubtypic in vitro neutralization breadth against influenza A viruses by inhibiting the low pH mediated HA conformational changes that lead to membrane fusion. X-ray structures of peptide-HA complexes reveal high structural mimicry with the parent V H H antibody. One such macrocycle peptide candidate is promising for further development of broad protection against influenza A group 1 viruses.

Kadam, Rameshwar U.↗
DOE OSTI2020

Here aqueous solubilization of hydrophobic tetrapyrrole macrocycles by attachment to an amphiphilic single-chain nanoparticle (SCNP)

Solubilization of hydrophobic tetrapyrrole macrocycles and other fluorophores in aqueous solution has been achieved by covalent attachment to the terminus of an amphiphilic polymer, thereby affording a single-fluorophore–single-chain nanoparticle (SCNP). The polymer is a heterotelechelic random polyacrylate/polyacrylamide copolymer bearing hydrophobic and hydrophilic pendant groups. The polymer has a folded unimeric morphology (~13 nm hydrodynamic diameter) in 1 M NaCl aqueous solution as indicated by dynamic light-scattering spectroscopy. Five hydrophobic organic fluorophores (coumarin, perylene, two chlorins, one phthalocyanine) have been synthesized with a conjugatable tether. Covalent conjugation of the fluorophore–maleimide to the polymer terminus via thiol–maleimide reaction was carried out in DMF. The resulting fluorophore–SCNP in 1 M NaCl aqueous solution exhibited retained spectral features and fluorescence quantum yield comparable to those of the respective hydrophobic benchmark in toluene. This single-fluorophore–single-polymer strategy simplifies the challenging and often idiosyncratic syntheses of water-soluble tetrapyrrole macrocycles by using the polymer as a general aqueous solubilization package, and in so doing opens up opportunities for the application of hydrophobic fluorophores in the life sciences.

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

Tolyporphins A–R, unusual tetrapyrrole macrocycles in a cyanobacterium from Micronesia, assessed quantitatively from the culture HT-58-2

The ‘pigments of life’ family has been enlarged by the discovery of the tetrapyrrole macrocycles dubbed tolyporphins, which are present in a cyanobacterial culture (HT-58-2). Of the 18 known tolyporphins, fourteen (A–J and L–O) are dioxobacteriochlorins, three (K, Q and R) are oxochlorins, and one (P) is a porphyrin. The members with a given chromophore absorb similarly but not identically with each other, presenting the problem of absorption spectral aliasing. Tolyporphins G and H are isomers, as are tolyporphins L–O, given the nature of the peripheral ( C -glycoside, –OH, or –OAc) substituents, presenting the (isobaric) problem of mass spectrometric analysis. The distribution of tolyporphin members is known to change over time and under different growth conditions, however, the complexity of the tolyporphins mixture presents challenges toward characterization of the underlying factors that alter such distributions. Liquid chromatography-mass spectrometry with dynamic multiple reaction monitoring (LC-MS-dMRM) was employed to characterize the distribution of tolyporphins under distinct growth media, using two semisynthetic standards, tolyporphin A O,O -dibutyrate and tolyporphin D O,O,O,O -tetrabutyrate. Growth in media containing both ammonium and nitrate salts versus nitrate alone affords increased production of tolyporphins. The absorption spectra of tolyporphins A–R have been reevaluated with regards to molar absorption coefficients, are compared with those of selected tetrapyrrole macrocycles to better understand the effects of chromophores and substituents, and are made available here in print and digital forms for comparison with isolated tolyporphins and mixtures thereof. Together, the work provides the foundation for quantitative assessment of these unusual natural products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Rigidochromism of tetranuclear Cu( I )–pyrazolate macrocycles: steric crowding with trifluoromethyl groups

Macrocyclic Cu(I)–pyrazolate tetramers (Cu 4 pz 4 ) can fold into compact structures with luminescent Cu 4 cores whose emission wavelengths are sensitive to steric effects along the periphery of the macrocycle. Introducing CF 3 at the C 4 position of 3,5-di- t Bu-pyrazolate increases steric crowding that modifies the conformational behavior of the Cu 4 pz 4 complex, highlighted by a low-temperature martensitic transition. Variable-temperature analysis of solid-state luminescence reveal an unexpected blueshifting of emission with rising temperature.

Rajagopal, Shinaj K.↗
DOE OSTI2024

From small changes to big gains: pyridinium-based tetralactam macrocycle for enhanced sugar recognition in water

The complex distribution of functional groups in carbohydrates, coupled with their strong solvation in water, makes them challenging targets for synthetic receptors. Despite extensive research into various molecular frameworks, most synthetic carbohydrate receptors have exhibited low affinities, and their interactions with sugars in aqueous environments remain poorly understood. In this work, we present a simple pyridinium-based hydrogen-bonding receptor derived from a subtle structural modification of a well-known tetralactam macrocycle. This small structural change resulted in a dramatic enhancement of glucose binding affinity, increasing from 56 M −1 to 3001 M −1 . Remarkably, the performance of our synthetic lectin surpasses that of the natural lectin, concanavalin A, by over fivefold. X-ray crystallography of the macrocycle–glucose complex reveals a distinctive hydrogen bonding pattern, which allows for a larger surface overlap between the receptor and glucose, contributing to the enhanced affinity. Furthermore, this receptor possesses allosteric binding sites, which involve chloride binding and trigger receptor aggregation. This unique allosteric process reveals the critical role of structural flexibility in this hydrogen-bonding receptor for the effective recognition of sugars. We also demonstrate the potential of this synthetic lectin as a highly sensitive glucose sensor in aqueous solutions.

Zhai, Canjia↗
DOE OSTI2022

Role of Bimetallic Interactions in the Enhancement of Catalytic CO 2 Reduction by a Macrocyclic Cobalt Catalyst

The use of two metal centers in a CO 2 reduction catalyst that work together synergistically, with similar or complementary functions, can potentially lead to a significant reduction in overpotential, enhance catalytic activity and/or selectivity, and/or enable access to cascade strategies where each metal center catalyzes a different step in the conversion of CO 2 to a fuel. Here, the bimetallic reactivity of two metal centers has been identified as the primary route for the reduction of CO 2 to CO promoted by the macrocycle, [Co(HMD)] 2+ (HMD = 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene), based on the experimental characterization of all major steps of the proposed catalytic cycle using pulse radiolysis time-resolved IR (PR-TRIR) spectroscopy, corroborated by density functional theory (DFT) calculations and IR spectroelectrochemistry (IR-SEC). A bimetallic intermediate is formed in situ from two singly reduced [Co(HMD)] + species bridged by a CO 2 molecule, and the presence of a coordinating species, e.g., formate anion, appears to assist in the formation of such an intermediate. In this work, it has been demonstrated that this reactivity enables access to elementary steps with lower energy requirements, resulting in overall catalysis being kinetically more facile compared to the mononuclear pathway. A two-step approach that combines chemical reduction followed by PR-TRIR has been successfully used for probing the structure and reactivity of reactive intermediates involved in the advanced stages of a catalytic cycle, which are rarely interrogated using experimental techniques.

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↗
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 OSTI2023

Macrocyclic β‐Sheets Stabilized by Hydrogen Bond Surrogates

Abstract Mimics of protein secondary and tertiary structure offer rationally‐designed inhibitors of biomolecular interactions. β‐Sheet mimics have a storied history in bioorganic chemistry and are typically designed with synthetic or natural turn segments. We hypothesized that replacement of terminal inter‐β‐strand hydrogen bonds with hydrogen bond surrogates (HBS) may lead to conformationally‐defined macrocyclic β‐sheets without the requirement for natural or synthetic β‐turns, thereby providing a minimal mimic of a protein β‐sheet. To access turn‐less antiparallel β‐sheet mimics, we developed a facile solid phase synthesis protocol. We surveyed a dataset of protein β‐sheets for naturally observed interstrand side chain interactions. This bioinformatics survey highlighted an over‐abundance of aromatic–aromatic, cation‐π and ionic interactions in β‐sheets. In correspondence with natural β‐sheets, we find that minimal HBS mimics show robust β‐sheet formation when specific amino acid residue pairings are incorporated. In isolated β‐sheets, aromatic interactions endow superior conformational stability over ionic or cation‐π interactions. Circular dichroism and NMR spectroscopies, along with high‐resolution X‐ray crystallography, support our design principles.

Chemistry↗
DOE OSTI2021

Combining the Best of Two Chelating Titans: A Hydroxypyridinone-Decorated Macrocyclic Ligand for Efficient and Concomitant Complexation and Sensitized Luminescence of f-Elements

An ideal chelator for f-elements features rapid kinetics of complexation, high thermodynamic stability, and slow kinetics of dissociation. Here we present the facile synthesis of a macrocyclic ligand bearing four 1-hydroxy-2-pyridinone units linked to a cyclen scaffold that rapidly forms thermodynamically stable complexes with lanthanides (Sm 3+ , Eu 3+ , Tb 3+ , Dy 3+ ) and a representative late actinide (Cm 3+ ) in aqueous media and concurrently sensitizes them. Extended X-ray absorption fine structure (EXAFS) spectroscopy revealed an increase in the Ln/An-O bond lengths following the trend Cm>Eu>Tb and EXAFS data were compatible with time-resolved luminescence studies, which indicated one to two water molecules in the inner metal coordination sphere of Eu(III) and two water molecules for the Cm(III) complex. Spectrofluorimetric ligand competition titrations against DTPA confirmed the high thermodynamic stability of DOTHOPO complexes, with pM values between 19.9(1) and 21.9(2).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗