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At least 1,045 records · Page 58

Biological toxicity and environmental hazards associated with PLGA nanoparticles

There have been tremendous advances in nanotechnology. More recently, the use of nanoparticles has expanded to applications including materials, packaging, energy, and medical uses such as drug delivery, diagnostics, and therapeutics. The American Society for Testing and Materials (ASTM) and the International Organization for Standardization (ISO) define nanoparticles as particles with at least one dimension measuring between 1 and 100 nm (2), but this view is generally too limited, and recommendations have been made to consider all materials with a dimension measuring under 1,000 nm as nanoparticles. The biomedical uses of nanoparticles are particularly promising because of their ability to reach and target various sites and organs. However, some nanoparticles can be composed of toxic materials or are limited by issues of biodistribution and bioaccumulation, which have hampered their use in biomedicine. The copolymer poly lactic-co-glycolic acid (PLGA) has gained use in biomedical applications as a delivery system because it is considered biocompatible and can be formulated with controlled degradation in physiological environments. PLGA has a history in biomedicine that dates to the 1970s when biodegradable sutures were developed using PLGA. In addition, the United States (US) Food and Drug Administration (FDA) and the European Medicine Agency (EMA) have approved various PLGA particle formulations as therapeutic delivery vehicles. Interest in biocompatible materials to deliver a range of therapeutic drugs, proteins, nucleic acids, and other molecules has risen recently. In addition to drug delivery, sustained drug release can be achieved by tuning the physical properties of PLGA, such as the molecular weight, ratio of lactic to glycolic acid, drug concentration, stabilizing molecules, and particle size. Given the rise of nanoparticles, human and environmental exposure to them is inevitable as more applications use free, unbound, and highly mobile particles. Although PLGA is generally considered safe, a detailed understanding of how PLGA and the other components used to help formulate this copolymer into a nanoparticle delivery vehicle is useful for assessing potential harmful effects. Despite recent advances in PLGA nanoparticle formulations, residual stabilizing molecules, inconsistent preparations, and batch-to-batch variations can lead to toxicity. Poor preparations of PLGA can lead to common mechanisms of toxicity observed with nanoparticles, such as inflammation and oxidative stress. Consistency in PLGA formulations and accurate methods to evaluate nanoparticle toxicity are needed to ensure safety. In order to better assess PLGA nanoparticles as non-toxic delivery systems, it is critical to understand their physical and chemical properties and the formulation protocols that may introduce toxic components into particles.

Biology, nanoparticle, toxicity↗

Polymers from Levoglucosenone and Other Anhydrosugars (CRADA Final Report)

The goal of this work is to identify promising drop-in or novel polymers that can be produced from levoglucosenone (LGO), CyreneTM, or other anhydrous sugars. LGO is a potentially important feedstock for polymers produced from renewable sources and can be produced in high yields by the company Circa from the pyrolysis of cellulose and biomass. NLR has a long history with anhydrosugars, pyrolysis and biomass-based polymers and has recently developed machine learning (ML) tools for predicting polymer properties. The DOE has recently supported efforts to identify coproducts from pyrolysis of biomass and their use in the production of performance advantaged polymers. DOE is also supporting the development of ML and molecular modeling for predicting and understanding polymer properties. NLR will leverage this expertise and experience to map out the pathways to polymers from LGO, use ML to identify the properties of novel polymers and estimate the market application space. From this effort NLR will deliver a summary report that outlines the most promising pathways based on quantitative and qualitative metrics for producing polymers from LGO.

09 BIOMASS FUELS↗

The molecular content of interacting and isolated galaxies The effect of environment on the efficiency of star formation

Molecular gas observations of merging/interacting and isolated galaxies are presented in order to study the relationship between environment and the efficiency of star formation. The two galaxy samples differ primarily in their IR properties and are quite similar in their molecular gas contents. The ratios of IR luminosity to H2 mass have a mean value of 78 and 12 solar luminosity/solar mass for interacting and isolated galaxies, respectively. The highest star formation efficiencies (SFEs) appear to occur in the merging and interacting pairs. The SFE in merging/interacting galaxies is greater than that found in the spiral arms of M51 and may be roughly proportional to the rate of cloud-cloud collisions in the interacting systems.

Young, Judith S.↗

Medium-range atomic correlation in simple liquids. II. Theory of temperature dependence

The spatial atomic correlations in liquids and glasses extend often significantly beyond the nearest neighbors. Such correlations, called the medium-range order (MRO), affect many physical properties, but their nature is not well understood. In this article the variation of the MRO with temperature is calculated based upon the concept of the atomic-level pressure, focusing on simple liquids, such as metallic liquids. It is shown that the structural coherence length that characterizes MRO follows the Curie-Weiss law with a negative Curie temperature as observed by experiment and simulation. It is also shown that the glass transition is induced by freezing of the MRO, rather than the freezing of the nearest-neighbor shell. The implications of these results are discussed.

74 ATOMIC AND MOLECULAR PHYSICS↗

Uncovering the Functional Role of Coherent Phonons during the Photoinduced Phase Transition in a Molecular Crystal

The atomic motions that make up phonons and molecular vibrations in molecular crystals influence their photophysical and electronic properties, including polaron formation, carrier mobility, and phase transitions. Discriminating between spectator and driving motions is a significant challenge hindering optimization. Unlocking this information and developing fine-tuned controls over actively participating phonon modes would not only lead to a stronger understanding of photochemistry but also provide a significant new tool in controlling solid state chemistry. We present a strategy using rationally designed double pulses to unveil the unique function of specific excited state phonon modes. Using ultrafast spectroscopy, we identified 50 and 90 cm –1 phonons involved in modulating the photoinduced spin-Peierls melting of potassium tetracyanoquinodimethane crystals. Here, we show that the 50 cm –1 phonon specifically corresponds to the coherent nuclear wavepacket involved in the charge transfer component of the overall spin-Peierls phase melting process, while the 90 cm –1 phonon facilitates the phase transition component.

74 ATOMIC AND MOLECULAR PHYSICS↗

Heterogenized Pyridine-Substituted Cobalt(II) Phthalocyanine Yields Reduction of CO2 by Tuning the Electron Affinity of the Co Center

Conversion of CO 2 to reduced products is a promising route to alleviate irreversible climate change. In this paper we report the synthesis of a Co-based phthalocyanine with pyridine moieties (CoPc-Pyr), which is supported on a carbon electrode and shows Faradaic efficiency ~90% for CO at 490 mV of overpotential (-0.6 V vs reversible hydrogen electrode (RHE)). In addition, its catalytic activity at -0.7 V versus RHE surpasses other Co-based molecular and metal-organic framework catalysts for CO 2 reduction at this bias. Density functional theory calculations show that pyridine moieties enhance CO 2 adsorption and electron affinity of the Co center by an inductive effect, thus lowering the overpotential necessary for CO 2 conversion. Our study shows that CoPc-Pyr reduces CO 2 at lower overpotential and with higher activity than noble metal electrodes, such as silver.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Anomalous thermoelectricity at the two-dimensional structural transition of SnSe monolayers

The thermoelectric figure of merit ZT comprises electronic and vibrational contributions that drastically change across phase transitions, and the most common theoretical ab initio approach to thermoelectricity fails to describe the evolution of ZT across finite-temperature structural transitions in its entirety. Furthermore, while the thermoelectric behavior of bulk SnSe has been extensively studied, SnSe monolayers have been experimentally realized only recently, and the existent prediction of thermoelectricity on this two-dimensional material is unreliable because it misses its structural transition altogether. SnSe monolayers (and similar GeS, GeSe, GeTe, SnS, and SnTe monolayers) experience a temperature-induced two-dimensional Pnm2 1 → P4/nmm structural transition precipitated by the softening of vibrational modes, and we describe their thermoelectric properties across the phase transition, using molecular dynamics data to inform both electronic and vibrational coefficients directly and within the same footing. Similar to recent experimental observations pointing to an overestimated ZT past the transition temperature in bulk SnSe, we find a smaller ZT on SnSe monolayers when compared to its value predicted by the standard paradigm, due to the dramatic changes in the electrical conductivity and lattice thermal conductivity as the structural transition ensues. Here, the process described here lends a strong focus to both the vibrational and electronic evolutions throughout the structural transition, and it applies to thermoelectric materials undergoing thermally driven solid-to-solid structural phase transitions in one, two, and three dimensions.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Chemical characterization of selected LDEF polymeric materials

The chemical characterization of selected polymeric materials which received exposure on the LDEF is reported. The specimens examined include silvered fluorinated ethylene propylene (FEP) teflon thermal blanket material, polysulfone matrix resin/graphite fiber reinforced composites, and several high performance polymer films. These specimens came from numerous LDEF locations and, thus, received different environmental exposures. The results of infrared, thermal, x ray photoelectron, and various solution property analyses have shown no significant change at the molecular level in the polymer that survived exposure. However, scanning electron and scanning tunneling microscopies show resin loss and a texturing of the surface of some specimens which resulted in a change in optical properties. The potential effect of a silicon containing molecular contamination on these materials is addressed. The possibility of continued post-exposure degradation of some polymeric films is also proposed.

Young, Philip R.↗

Prediction of high-temperature superconductivity in C2/c-24 solid hydrogen

Recent experimental developments in hydrogen-rich materials at high pressures have put this class of materials above others in the race toward room-temperature superconductivity. As it is the basis of all the materials in this class, the efforts to determine the properties of pure solid hydrogen at high pressures remain intense. Most notably, a recent experimental study of the metallization of hydrogen identified the crystal phase of the solid as the C2/c-24 molecular phase up to ~425 GPa [Loubeyre et al., Nature (London) 577, 631 (2020)10.1038/s41586-019-1927-3]. It is possible that the observed metallization is caused by band structure effects and not a structural phase transition, and the material remains in this crystal phase up to higher pressures [Dogan et al., J. Phys.: Condens. Matter 33, 03LT01 (2020)10.1088/1361-648X/abba8a]. Therefore, it is of crucial importance to determine the superconducting properties of the C2/c-24 phase. Here, we employ a Wannier function-based dense k-point and q-point sampling to compute the electron-phonon coupling and superconducting properties of molecular hydrogen in the C2/c-24 phase. We find that the material has a high superconducting transition temperature of 242 K at 500 GPa. We also find that the transition temperature rapidly increases with pressure in the 400-500-GPa range.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Siloxane-modified polyethersulfideimide

BDSDA/APB, a novel linear polyethersulfideimide, was synthesized using siloxane units as flexible linkages in the backbone in an attempt to improve use properties and processability. The effect of these flexible linkages on molecular weight buildup, flexural strength and modulus, glass transition temperature, and melt-flow properties was determined.

Burks, Harold D.↗

Structure, bonding and electronic characteristics of amorphous Se

Ovonic threshold switching (OTS) selector can effectively improve the storage density and suppress the leakage current of advanced phase-change memory. As a prototypical OTS material, amorphous GeSe is widely investigated. But the attentions paid to amorphous Se (i.e., the functional constituent in amorphous GeSe) is very limited up to now. Here, in this work, we have explored the structure, bonding and electronic characteristics of amorphous Se using ab initio molecular dynamics simulations. The results reveal that the Se atoms in amorphous Se tend to form the 2-coordinated configurations, and they connect with each other to form the long chains. The fraction of vibrational density of state located in high frequency range is relatively large, and the formation energy of Se-Se bond is as large as 4.44 eV, hinting that the Se-Se bonds in chains possess a high stability. In addition, the mid-gap state related to the OTS behavior is also found in the amorphous Se despite of the small proportion. Our findings enrich the knowledge of the amorphous Se, which contributes to the applications of Se-based OTS selectors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ferroelectric Fractals: Switching Mechanism of Wurtzite AlN

The advent of wurtzite ferroelectrics is enabling new ferroelectric devices for computer memory that have the potential to bypass the von Neumann bottleneck due to their robust polarization and silicon compatibility. However, the atomistic switching mechanism of wurtzites is still undetermined due to the limitations of density functional theory simulation size and experimental temporal and spatial resolution. Thus, physics-informed materials engineering to reduce coercive field and breakdown in these devices has been limited. In this work, the atomistic mechanism of domain wall migration and domain growth in aluminum nitride-based wurtzites is uncovered using molecular dynamics and Monte Carlo simulations. We reveal the anomalous switching mechanism of fast 1D single columns of atoms propagating from a slow-moving 2D fractallike domain wall. We find that the critical nucleus is a single aluminum ion that breaks its bond with one nitrogen and bonds to another nitrogen; this creates a cascade that flips atoms directly only in the same column, due to the extreme locality (sharpness) of the domain walls in wurtzites. We further show how the fractallike shape of the domain wall in the 2D plane breaks assumptions in the Kolmogorov, Avrami, and Ishibashi (KAI) model and leads to the anomalously fast switching in wurtzite structured ferroelectrics.

36 MATERIALS SCIENCE↗

Observations of the CO J=6-5 transition in starburst galaxies

Over the past several years, short-submillimeter observations of carbon monoxide's (CO) mid-J rotational levels have revealed the presence of a large amount of excited molecular gas in luminous giant molecular clouds in our Galaxy. Submillimeter lines are specific probes of excited material: collisional excitation of the level energy of 116 K above ground, and 6-5 transition's critical density is approximately 10(exp 6) cm(exp -3) in optically thin gas. Radiative trapping effects reduce the excitation requirements to some extent, but detection of the CO J=6-5 line is nearly indisputable proof of the existence of gas that is both warm and dense. The excitation conditions also imply that cool (T less than 20 K) molecular clouds within the beam neither emit nor absorb in the short-submillimeter lines; in our Galaxy, clouds with active massive star formation emit the strongest short-submillimeter CO rotational lines. We used these properties to explore the distribution of excited molecular material and physical conditions within the star formation regions of several classical starburst nuclei: NGC253, M82, and IC342. We have used the 6-5 transition as a thermometer of warm molecular gas in starburst nuclei, unambiguously finding that the nuclear molecular gas in starburst galaxies is substantially warmer than in typical disk clouds.

Harris, A. I.↗

Evolution of structure and spectroscopic properties of a new 1,3-diacetylpyrene polymorph with temperature and pressure

A new polymorph of 1,3-diacetylpyrene has been obtained from its melt and thoroughly characterized using single-crystal X-ray diffraction, steady-state UV–Vis spectroscopy and periodic density functional theory calculations. Experimental studies covered the temperature range from 90 to 390 K and the pressure range from atmospheric to 4.08 GPa. Optimal sample placement in a diamond anvil cell according to our previously presented methodology ensured over 80% data coverage up to 0.8 Å for a monoclinic sample. Unrestrained Hirshfeld atom refinement of the high-pressure crystal structures was successful and anharmonic behavior of carbonyl oxygen atoms was observed. Unlike the previously characterized polymorph, the structure of 2°AP-β is based on infinite π-stacks of antiparallel 2°AP molecules. 2°AP-β displays piezochromism and piezofluorochromism which are directly related to the variation in interplanar distances within the π-stacking. The importance of weak intermolecular interactions is reflected in the substantial negative thermal expansion coefficient of -55.8 (57) MK -1 in the direction of C—H∙∙∙O interactions.

36 MATERIALS SCIENCE↗

Processible Polyazomethines

Processibility enhanced by incorporating trifluoromethylbenzene units into molecules. Results of two unexpected properties: high solubility in common organic solvents and lack of crystallinity. Properties coupled with ability of this class of polymers to undergo exchange reactions at elevated temperatures allow these materials to moderate their molecular weights during processing, which affects resulting mechanical properties after processing. Fluorinated polyazomethines form amorphous films that have excellent mechanical properties. Used in moisture-free environments as electronic semiconducting films and adhesives, and as matrix resins for advanced structural composites.

Bryant, Robert G.↗

Superresolved Motions of Single Molecular Catalysts during Polymerization Show Wide Distributions

The motion of single molecular ruthenium catalysts during and after single turnover events of ring-opening metathesis polymerization is imaged through single-molecule superresolution tracking with a positional accuracy of ±32 nm. This tracking is achieved through the real-time incorporation of spectrally tagged monomer units into active polymer chain ends during living polymerization; thus, by design, only active-catalyst motion is detected and imaged, without convolution by inactive catalysts. The catalysts show diverse individualistic diffusive behaviors with respect to time that persist for up to 20 s. Catalysts occupy three mobility populations: quasi-stationary (23%), intermediate (53%, 65 nm), and large (24%, 145 nm) step sizes. Differences in catalyst mobility populations also exist between individual aggregates (p < 0.001). Such differential motion indicates widely different local catalyst microenvironments during the catalytic turnover. These mobility differences are uniquely observable through single-catalyst microscopy and are not measurable through traditional ensemble analytical techniques for characterizing the behavior of molecular catalysts, such as nuclear magnetic resonance spectroscopy. The measured distributions of active molecular catalyst motions would not be readily predictable through modeling or first-principles, and the range likely impacts individual catalyst turnover rate and selectivity. This range plausibly contributes to property distributions observable in bulk polymers, such as molecular weight polydispersity (e.g., 1.9 in this system), leading to a revised understanding of the mechanistic, microscale origins of macroscale polymer properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Understanding the Influence of Chain Architecture on the Transport Quantities of Polymer Electrolytes with Covalently Bonded Anions

Here, we use a combination of experiments and coarse-grained molecular dynamics simulations to elucidate the structure–property relationships in polymer electrolytes obtained by the copolymerization of poly(vinyl ethylene carbonate─lithium styrene bis(trifluoromethanesulfonyl)imide) or p(VEC-LiSTFSI). Experiments show that the conductivity reduces with increasing anion (i.e., STFSI) fraction on the chain, and the cation transference number (t + ) is found to be dependent on the anion fraction. Furthermore, a significant fraction of unpolymerized VEC monomers are observed. Since it is inherently difficult to experimentally control the chain architecture and the amount of unpolymerized VEC in these systems, we perform coarse-grained molecular dynamics simulations on model polymer systems with different chain architectures to mimic the plausible experimental systems. Specifically, we look at the differences in transference numbers arising from (i) a random copolymer of VEC and STFSI monomers; (ii) a blend of VEC-STFSI copolymer with VEC monomers; and (iii) a ternary blend of the VEC homopolymer, STFSI homopolymers, and VEC monomers. The ternary blend model demonstrates the closest resemblance with the experimental transference numbers and diffusivities. The lithium diffusivity obtained from the coarse-grained models with VEC monomers (plasticizers) is about 1.5 times that of the model without VEC monomers, showing that the plasticizing effect of VEC monomers is modest. We rationalize the experimental observations based on aggregate and cluster analyses obtained from molecular simulations. This work reveals that polymer electrolyte chain architecture and plasticizers can critically influence the transport properties, and these parameters should be considered when designing single ion conducting polymeric electrolytes.

cluster distribution↗

Selective Depolymerization for Sculpting Polymethacrylate Molecular Weight Distributions

Chain-end reactivation of polymethacrylates generated by reversible-deactivation radical polymerization (RDRP) has emerged as a powerful tool for triggering depolymerization at significantly milder temperatures than those traditionally employed. In this study, we demonstrate how the facile depolymerization of poly(butyl methacrylate) (PBMA) can be leveraged to selectively skew the molecular weight distribution (MWD) and predictably alter the viscoelastic properties of blended PBMA mixtures. By mixing polymers with thermally active chain ends with polymers of different molecular weights and inactive chain ends, the MWD of the blends can be skewed to be high or low by selective depolymerization. This approach leads to the counterintuitive principle of the “destructive strengthening” of a material. As a result, we demonstrate, as a proof of concept, the encryption of information within polymer mixtures by linking Morse code with the MWDs before and after selective depolymerization, allowing for the encoding of data within blends of synthetic macromolecules.

36 MATERIALS SCIENCE↗