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At least 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Self‐Limiting Polymerization‐Induced Crystallization‐Driven Self‐Assembly (SL‐PI‐CDSA) Enables Templated Synthesis of Chiral Plasmonic, Hybrid 2D Hexagonal Assemblies

Examples of self-regulating synthetic self-assembly are relatively few, with most known chemical systems relying on kinetic rather than thermodynamic control. Herein, we demonstrate the rapid generation (t ≤ 5 min) of size-tunable ultralow dispersity (Ð ≤ 1.01) 2D hexagonal nanosheets governed by self-limiting self-assembly (SLSA). Self-assembly in natural systems occurs with exquisite control of structure, function, and dimension. We demonstrate that key aspects of biological assembly can be rationally applied toward the development of bottom-up approaches for the construction of chiral nanomaterials. To this end, self-limiting polymerization-induced crystallization-driven self-assembly (SL-PI-CDSA) of modular and templating aryl isocyanide (AIC) monomers yields functional 2D assemblies permitting post-polymerization/assembly modifications. Detailed study of the internal and external structure of the hexagonal nanosheets reveals topological defects which offer mechanistic insights into both their assembly and subsequent utilization. Specifically, these features enable fabrication of chiral hybrid organic–inorganic nanomaterials incorporating chiral plasmonic metal nanoparticles (MNPs). Our results suggest that the synergistic interplay of template-driven confinement and hierarchical chirality induce symmetry breaking of in situ-generated gold MNPs. We anticipate that the platform presented will facilitate fabrication of new hybrid, chiral organic–inorganic nanostructures.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Cu-Catalyzed Atom Transfer Radical Polymerization: The Effect of Cocatalysts

Atom transfer radical polymerization (ATRP) is one of the most powerful methods to prepare well-defined (co)polymers. Cu-catalyzed ATRP methods are most commonly used because of the excellent control and tunable catalytic activities via ligand functionalization. This minireview summarizes the development of Cu-catalyzed ATRP in the presence of cocatalysts, which are used to regenerate Cu I complex activators during polymerizations. Fundamentals of Cu-based ATRP catalysts are first introduced, followed by the discussion of different types of cocatalysts in different Cu-catalyzed ATRP methods. Recent developments of photochemical cocatalysts for oxygen-tolerant ATRP and ATRP using long-wavelength irradiation are highlighted, which significantly expand the applications of Cu-catalyzed ATRP. Methods to study the properties of cocatalysts and their roles in Cu-catalyzed ATRP are discussed, with an outlook for the future development of cocatalysts.

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

Impacts of Disulfide‐Containing Monomers in Alternating Diene Metathesis Polymerization

ABSTRACT Among the classes of synthetic polymers, disulfide‐containing structures offer unique opportunities due to their accessibility to redox chemistry that allows for degradation or reversible disulfide formation and exchange under mild conditions. Here, we examine the role of disulfides in olefin metathesis polymerization, specifically alternating diene metathesis (ALTMET) polymerization, for synthesizing unsaturated polyolefins with embedded disulfides. Our synthetic strategy hinged on the use of α,ω‐diacrylate monomers, including those connected by a disulfide unit, via copolymerization by the ALTMET mechanism to yield copolymers containing a range of disulfide content. In addition, the potential impacts of sulfur‐ruthenium interactions on the ALTMET process were investigated spectroscopically, while the degradation of the resultant polymers was affected by mild reducing agents. Overall, this study contributes to the development of degradable synthetic polymers using olefin metathesis methods, with an increased understanding of the potential for further use of disulfide groups in such metathesis reactions.

Lee, Kyoungwon↗
DOE OSTI2019

Dimethyl‐methylphenyl copolysiloxanes by dimethylsilanolate‐initiated ring opening polymerization. Evidence for linearity of the resulting polymer structures

ABSTRACT Recently, we reported that dimethylsilanolate‐initiated anionic ring opening polymerization of dimethylsiloxy‐ and diphenylsiloxy‐cyclic siloxanes results in polymer chain branching by dimethylsilanolate‐induced cleavage of only one Si‐C Ar side bond in diphenylsiloxy repeat units, leading to formation of “Ph‐T‐branches”, and not extending to the cleavage of the second phenyl group. We attributed this behavior to electronic structures of the participating dimethylsiloxy‐, diphenylsiloxy and Ph‐T‐branch silicons and predicted that copolymers prepared by this synthetic route from dimethylsiloxy‐ and methylphenylsiloxy‐cyclics should not undergo branching at all but should have perfect linear chain configuration. Here, we describe results of a study of two such dimethylsilanolate‐initiated ring opening polymerizations of dimethylsiloxy‐ and methyphenylsiloxy‐cyclic tetramers and characterization of the resulting polymers by SEC‐MALS‐VIS, Mark‐Houwink‐Sakurada relationship and 29 Si NMR. The results obtained clearly confirmed our prediction of expected linearity of these polymer chains and also indicated that the resulting polymers were completely amorphous even at as low methylphenylsiloxy‐content as 3.9 mol %. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 1122–1129

Zlatanic, Alisa↗
DOE OSTI2020

Vacuum-Free, All-Solution, and All-Air Processed Organic Photovoltaics with over 11% Efficiency and Promoted Stability Using Layer-by-Layer Codoped Polymeric Electrodes

Nonfullerene organic photovoltaics (OPVs) have achieved a breakthrough in pushing the efficiency beyond 15%. Although this sheds light on OPV commercialization, the high cost associated with the scalable device fabrications remains a giant challenge. Herein, a vacuum-free, all-solution and all-air processed OPV is reported that yields 11.12% efficiency with a fill factor of 0.725, due to the usages of high-merit polymeric electrodes and modified active blends. The design principle toward the high-merit electrodes is to induce heavy acid doping into the matrices for a raised carrier concentration and mobility, make a large removal of insulating components in the whole matrices rather than surfaces, and restrain the formation of large-domain aggregates. A unique layer-by-layer doping is developed to enable the polymeric electrodes with record-high trade-offs between optical transmittance and electrical conductivity. Moreover, solvent vapor annealing is proposed to boost device efficiency and it has the advantages of finely adjusting the active blend morphology and raising the electron mobility. The resulting devices are highly efficient and most (≈91%) of the initial efficiency are maintained in 30 day storage. Finally, this work indicates bright future for making cost-effective all-solution processed OPVs in air.

14 SOLAR ENERGY↗
DOE OSTI2018

Spectral-Luminescent Properties of Alkoxysilane–Metallophthalocyanine Conjugates Covalently Bonded to the Polymeric Chains of Silicate Gel Materials

Conjugates of metal hydroxyl phthalocyanines (М(ОН){sub n}Рс; М = Si, Ge, Al, Ga) with 3-aminopropyltriethoxysilane (APTEOS) are synthesized. By means of the sol-gel method, polymeric silicate gel materials doped with the (APTEOS){sub n}–М(ОН){sub n}Рс conjugates are prepared: the latter form structural links in the composition of the copolymer with the siloxane fragments of the polymeric chains (in the case of n = 2) or are ″grafted″ to such chains in the form of side substituents (n = 1). It is shown by spectral-luminescent and kinetic spectroscopy methods that the (APTEOS){sub n}–М(ОН){sub n}Рс conjugates, on the introduction into a silicate gel material, retain their molecular structure and the photophysical characteristics of MPc in the monomeric form. The obtained macromolecular substances are promising as monomeric dopants in new functional materials for optics and quantum electronics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Tetranuclear heteroleptic mercury(II) complexes of the composition [Hg{sub 4}(S{sub 2}CNPr{sub 2}){sub 6}(NO{sub 3}){sub 2}] and [Hg{sub 4}(S{sub 2}CNPr{sub 2}){sub 4}Cl{sub 4}]: structural organization, principles of construction of supramolecular polymeric chains, and thermal behavior

New heteroleptic mercury(II) complexes [Hg{sub 4}(S{sub 2}CNPr{sub 2}){sub 6}(NO{sub 3}){sub 2}] (1) and [Hg{sub 4}(S{sub 2}CNPr{sub 2}){sub 4}Cl{sub 4}] (2) were synthesized and characterized by single-crystal X-ray dif raction and {sup 13}C and {sup 15}N MAS NMR spectroscopy. In these complexes, the metal atoms are linked in pairs by bridging dipropyldithiocarbamate ligands (Pr{sub 2}Dtc) to form tetranuclear cations and molecules. The further structural organization of compound 1 to the polymeric chains [Hg{sub 4}(S{sub 2}CNPr{sub 2}){sub 6}(NO{sub 3}){sub 2}]{sub n} occurs due to the linking of [Hg{sub 4}(S{sub 2}CNPr{sub 2}){sub 6}]{sup 2+} cations by pairs of bridging nitrate groups. The formation of the supramolecular polymeric structure of 2 is determined by pairwise secondary Hg⋯Cl bonds between the cyclic [Hg{sub 4}(S{sub 2}CNPr{sub 2}){sub 4}Cl{sub 4}] molecules, in which the central eight-membered metallocycle [Hg{sub 4}S{sub 4}] adopts a distorted chair conformation. The thermal behavior of compounds 1 and 2 was studied by simultaneous thermal analysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Activation of β- and α2-adrenergic receptors stimulate tubulin polymerization and promote the association of Gβγ with microtubules in cultured NIH3T3 cells

Highlights: • GPCR activation stimulates microtubule assembly in NIH3T3 cells. • GPCR activation increases Gβγ association with microtubules. • β- and α2-adrenergic receptors have similar effects on microtubule assembly. • Signaling via GPCR is important for MT assembly and regulation. Microtubules (MTs) constitute a crucial part of the cytoskeleton and are essential for cell division and differentiation, cell motility, intracellular transport, and cell morphology. Precise regulation of MT assembly and dynamics is essential for the performance of these functions. Although much progress has been made in identifying and characterizing the cellular factors that regulate MT assembly and dynamics, signaling events in this process is not well understood. Gβγ, an important component of the G protein-coupled receptor (GPCR) signaling pathway, has been shown to promote MT assembly in vitro and in cultured NIH3T3 and PC12 cells. Using the MT depolymerizing agent nocodazole, it has been demonstrated that the association of Gβγ with polymerized tubulin is critical for MT assembly. More recently, Gβγ has been shown to play a key role in NGF-induced neuronal differentiation of PC12 cells through its interaction with tubulin/MTs and modulation of MT assembly. Although NGF is known to exert its effect through tyrosine kinase receptor TrkA, the result suggests a possible involvement of GPCRs in this process. The present study was undertaken to determine whether agonist activation of GPCR utilizes Gβγ to promote MT assembly. We used isoproterenol and UK 14,304, agonists for two different GPCRs (β- and α2-adrenergic receptors, respectively) known to activate Gs and Gi respectively, with an opposing effect on production of cAMP. The results demonstrate that the agonist activation of β- and α2-adrenergic receptors promotes the association of Gβγ with MTs and stimulates MT assembly in NIH3T3 cells. Interestingly, the effects of these two agonists were more prominent when the cellular level of MT assembly was low (30% or less). In contrast to MT assembly, actin polymerization was not affected by isoproterenol or UK 14, 304 indicating that the effects of these agonists are limited to MTs. Thus, it appears that, upon cellular demand, GPCRs may utilize Gβγ to promote MT assembly. Stimulation of MT assembly appears to be a novel function of G protein-mediated signaling.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2022

Fused perylene diimide-based polymeric acceptors with different $\mathcal{π}$-conjugation and molecular conformation in all polymer solar cells

Two perylene diimide (PDI) based polymeric acceptors, PFPDIBT-TT2F and PFPDIT-TT2F, which consist of fused-PDI moieties (FPDIBT and FPDIT) and 3,3'-difluoro-2,2'-bithiophene (TT2F) units, has been designed and synthesized. Compared with the unfused-PDI polymer (PPDI-TT2F) as the control molecule, the influence of structural conformation and π-conjugation extension on the performance of all-polymer solar cells has been investigated. Due to both the extended π-conjugation and the torsional polymer skeleton, the device adopting PFPDIT-TT2F achieved an obviously improved PCE of 5.11% comparing with the devices using the other two polymeric acceptors. This study demonstrates that the fused PDIs bridged by a thiophene enables both extended π-conjugation and twisted molecular conformation, and the latter plays a dominant role in the improvement of device performance.

42 ENGINEERING↗
DOE OSTI2023

Synthesis of hyperbranched polymer films via electrodeposition and oxygen-tolerant surface-initiated photoinduced polymerization

Hypothesis Hyperbranched polymers, not only possess higher functionality, but are also easier to prepare compared to dendrimers and dendric polymers. Combining electrodeposition and surface-initiated photoinduced electron transfer-reversible addition-fragmentation chain transfer (SI-PET-RAFT) polymerization is hypothesized to be a novel strategy for preparing hyperbranched polymer films on conductive surfaces without degassing. Experiments In this study, polymer brush grafted films with four different architectures (i.e. linear, branched, linear- block -branched, and branched- block -linear) were prepared on gold-coated glass substrates using electrodeposition, followed by SI-PET-RAFT polymerization. The resulting film structure and thickness, surface topology, absorption property, and electrochemical behavior were confirmed by spectroscopy, microscopy, microbalance technique, and impedance measurement. Findings These hyperbranched polymer brushes were capable of forming a thicker but more uniformly covered films compared to linear polymer brush films, demonstrating that hyperbranched polymer films can be potentially useful for fabricating protective polymer coatings on various conductive surfaces.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Chemical Transformations of Captured CO2 into Cyclic and Polymeric Carbonates

Alkylcarbonate ionic liquids are shown to be chemically active CO2 surrogates for transcarboxylating cyclohexene oxide to produce poly-carbonates. Catalytic equivalents of alkylcarbonate ionic liquids can be added to copolymerizations of cyclohexene oxide/CO2 to in-crease the yield and selectivity of the polymer. On the other hand, in the case of propylene oxide, polymerization is suppressed, and pro-pylene oxide is converted to propylene carbonate. The suppression of polymerization is due to the high activity of the alkylcarbonate ionic liquids towards carboxylation of epoxides for cyclic carbonate formation. The reactivity of alkylcarbonate ionic liquids with propylene oxide is sufficient enough that propylene carbonate is produced in the absence of catalyst at pressures as low as 1 atm at 60 °C.

Kothandaraman, Jotheeswari↗
DOE OSTI2018

Fabrication of localised aluminium foam by a novel polymeric blowing agent

Highlights: • Polymeric blowing agent used to synthesize metallic foam for first time. • Localised region of a metallic part is foamed. • A novel semisolid route is used to control the pore size of the foams. • Heat-treatable foam with controllable absorption energy is obtained. - Abstract: Closed cell aluminium foams are highly pursued, due to their unique combination of properties. However, the current applicability of the aluminium foams is limited due to issues like high costs, density-gradient and brittleness of the cell walls, which are either related to use of metallic hydride as blowing agent or liquid-state processing. To address these issues, this study presents a first attempt to use polymer as a blowing agent to foam an aluminium alloy. A polymer is Poly (methyl hydro siloxane) was dispersed into an Al2024 sheet of 6 mm by Friction Stir Processing, in a localised region. This processed sample was pyrolysed at temperatures between solidus and liquidus (500–640 °C) of the alloy and at various durations (5–60 min) to foam the localised precursor. The density of resulting foams was measured by the Archemidies method and the resulting pore structures were characterised by Scanning Electron Microscopy (SEM) and micro X-ray Computed Tomography (CT). The results show that by as pyrolysis temperature increases relative density reaches a minimum of 0.65 at 560 °C. Beyond 590 °C, relative density increased from the optimum due to escape of foaming gasses. With increasing pyrolysis temperature, the pore size increased from few microns to several hundred microns. Further, quasi-static compression test was done on as processed, solutionized and aged foams. Due to increased strain hardening in aged samples energy absorbed during compression increased by 80% in the plateau region. Hence, polymeric a blowing agent can be used to synthesize heat-treatable foams with controllable absorption energy.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Glassy carbon formation from pyrolysis of polymeric coatings on fiber-optic sensors

Deploying fiber-optic sensors in nuclear reactors requires a detailed understanding of radiation effects on the fiber materials and the transmitted signals. Previous work has shown large wavelength shifts in the reflected spectra obtained from polymer-coated fiber-optic temperature sensors exposed to high neutron fluences. The sensor drift resulting from these wavelength shifts cannot be explained by radiation effects on fused silica glass. These shifts are hypothesized to be caused by the conversion of the polymeric fiber coating to a glassy carbon via radiolysis and/or pyrolysis and subsequent radiation-induced compaction. Here, thermal degradation of these polymeric coatings was studied to provide insight into the potential origins of the sensor drift phenomenon. Acrylate- and polyimide-coated fibers were heated under various temperatures (250–1300 °C) and environments (oxidative and inert), and the resulting coating products were characterized via mass-loss data, scanning electron microscope imaging, and Raman spectroscopy. Results suggest that the polymer decomposition product of both coating types, at least under inert conditions, is indeed a glassy carbon. Analytical models that account for radiation-induced glassy carbon coating compaction show significant compressive fiber strains and predicted wavelength shifts that agree well with experimental measurements, providing additional evidence that supports the hypothesized origins of the sensor drift.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Diffusion-limited hydrolysis in polymeric materials

Polymer degradation under aggressive environmental stressors often develops heterogeneities due to diffusion-limited reaction phenomena. This is well established for diffusion-limited oxidation (DLO), which is known to occur for most polymeric materials at elevated temperatures but has been less summarized for the conditions of diffusion-limited hydrolysis (DLH). Here, an overview of hydrolysis for several materials and a computational model, analogous to the underlying equations for DLO, able to define this diffusion-reaction system is presented. A systematic study of the influence of various parameters, such as water diffusivity, reaction rate and order, and a more in-depth focus on residual isocyanate hydrolysis in a polymeric methylene diphenyl diisocyanate (pMDI) based polyurethane (PU) foam is given. For this system, we present experimental data for model ‘input’ parameters and discuss predictions for different conditions. We conceptually compare the behavior of diffusion-limited oxidation to that of diffusion-limited hydrolysis (DLH). With the mathematical framework and key material properties presented herein, any DLH phenomena following Fickian diffusion behavior can be understood, modeled, and predicted.

36 MATERIALS SCIENCE↗
DOE OSTI2025

RNA–Polymer Conjugates via Direct Incorporation of the Chain Transfer Agent and PET–RAFT Polymerization

Covalent conjugation of RNA with synthetic polymers has emerged as a powerful approach for creating bioconjugates with synergistically enhanced properties. However, conventional methods require solid-phase synthesis to preinstall functional groups in RNA, significantly limiting practical applications. Here, we present a novel approach for synthesizing RNA–polymer conjugates via direct incorporation of chain transfer agent (CTA) into RNA through acylation chemistry and reversible addition–fragmentation chain transfer (RAFT) polymerization. A CTA-functionalized acyl imidazole reagent was synthesized to facilitate direct and covalent modification of various RNAs by reacting with their 2′-hydroxyl groups. Subsequent RAFT polymerization using RNA–CTA as a macro-CTA enabled direct grafting-from RNA, yielding RNA conjugates with controlled molecular weight and low dispersity. Notably, this postsynthetic modification strategy was successfully extended to modify biomass RNA, yielding thermoresponsive conjugates and biodegradable hydrogels. Overall, this advance allowed for the direct modification of synthetic and biomass RNAs, significantly enhancing the accessibility of functional RNA–polymer materials.

biomass↗
DOE OSTI2021

Toward Quantum Confinement in Graphitic Carbon Nitride-Based Polymeric Monolayers

raphitic carbon nitride (g-C 3 N 4 ) has garnered much attention due to its potential as an efficient metal-free photocatalyst. This study examines the evolution of properties in zero-dimensional quantum dots up to sizable clusters that mimic extended g-C 3 N 4 monolayers. We employ density functional theory to investigate systematically the structural, electronic, and optical properties of the g-C 3 N 4 -based melamine and heptazine building blocks using a “bottom-up” construction of polymeric monolayers. The results from our computations indicate that the melamine- and heptazine-based polymeric g-C 3 N 4 systems must be reduced to at least 2.74 and 4.00 nm, respectively, to observe an increase of its optical gap with a size reduction. The present study also examines the nature of the electronic transitions exhibited by g-C 3 N 4 -based monolayers through full natural transition orbital and density of state analyses. Furthermore, the most promising sites for water splitting and subsequent chemical doping studies are identified, which generally correspond to the nitrogen and carbon atoms, respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

In Situ Nanoscale Characterization of Water Penetration through Plasma Polymerized Coatings

The search continues for means of making quick determinations of the efficacy of a coating for protecting a metal surface against corrosion. One means of reducing the time scale needed to differentiate the performance of different coatings is to draw from nanoscale measurements inferences about macroscopic behavior. Here we connect observations of the penetration of water into plasma polymerized (PP) protective coatings and the character of the interface between the coating and an oxide-coated aluminum substrate or model oxide-coated silicon substrate to the macroscopically observable corrosion for those systems. A plasma polymerized film from hexamethyldisiloxane (HMDSO) monomer is taken as illustrative of a hydrophobic coating, while a PP film from maleic anhydride (MA) is used as a characteristically hydrophilic coating. The neutron reflectivity (NR) of films on silicon oxide coated substrates shows that water moves more readily through the hydrophilic PPMA film. Off-specular X-ray scattering indicates the PPMA film on aluminum is less conformal with the substrate than is the PPHMDSO film. Measurements with infraredvisible sum frequency generation spectroscopy (SFG), which probes the chemical nature of the interface, make clear that the chemical interactions between coating and aluminum oxide are disrupted by interfacial water. With this water penetration and interface disruption, macroscopic corrosion can occur much more rapidly. An Al panel coated with PP-MA corrodes after 1 day in salt spray, while a similarly thin (similar to 30 nm) PP-HMDSO coating protects an Al panel for a period on the order of one month.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Simple Monomers for Precise Polymer Functionalization During Ring-Opening Metathesis Polymerization

Controlling the monomer sequence of synthetic polymers is a grand challenge in polymer science. Conventional sequence control has been achieved in dispersed polymers by exploiting the kinetic tendencies of monomers and their order of addition. While the sequence of blocks in multiblock copolymers can be readily tuned using sequential addition of monomers (SAM), control over the sequence distribution is eroded as the targeted block size approaches a single monomer unit (i.e., X n ~ 1) due to the stochastic nature of chain-growth reactions. Thus, unique monomers are needed to ensure precise single additions. Herein, we investigate common classes of cyclic olefin monomers for ring-opening metathesis polymerization (ROMP) to identify monomers for single unit addition during sequential monomer addition synthesis. Through careful analysis of polymerization kinetics, we find that easily synthesized oxanorbornene imide monomers are suitable for single-addition reactions. With the identified monomers, we demonstrate the synthesis of multiblock copolymers containing up to three precise functionalization sites and singly cross-linked four-armed star copolymers. In conclusion, we envision that expanded kinetic analyses of monomer reactivities in ROMP reactions will enable novel polymer synthesis capabilities such as the autonomous synthesis of sequence-defined polymers or one-shot multiblock copolymer syntheses.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗