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At least 181 records · Page 10

Substrate-Directed Dimensional and Phase Control of Peptide Assemblies on Two-Dimensional van der Waals Materials

Understanding and controlling biomolecular self-assembly on van der Waals (vdW) materials has the potential to advance hybrid bioelectronic devices by enabling precise tuning of the interface and modulation of the resulting electronic properties of the biomolecule-vdW heterostructure. However, how surface properties of vdW materials direct biomolecule assembly remains poorly understood. To fill this knowledge gap, we investigated the assembly of a peptide known to assemble into two-dimensional (2D) crystalline films on MoS 2 on three representative vdW surfaces: WS 2 , MoS 2 , and highly oriented pyrolytic graphite (HOPG). Using in situ atomic force microscopy (AFM), we find that assembly is substrate-dependent, resulting in multilayers on WS 2 , monolayers on MoS 2 , and multiple coexisting phases on HOPG. WS 2 exhibits a higher negative charge, strong long-range electrostatic interactions, and extensive hydration layering that may promote multilayer stacking. In contrast, MoS 2 has stronger short-range interactions with the peptides but much weaker long-range interactions and hydration structure, which may favor monolayer formation. Molecular dynamics simulations predict a corresponding switch from monolayer to multilayer aggregates of the adsorbed monomers, reflected in their relative mobilities. On hydrophobic HOPG, the peptides bind most strongly and remain as monomers with high surface mobility. The peptide dimers comprising the basic unit of the crystals are more compact on HOPG, which has a smaller lattice constant than WS 2 or MoS 2 , suggesting strain contributes to stabilizing multiple phases. Our results provide mechanistic insights into how surface charge and hydration structure, and the lattice structure of the substrates governs peptide assembly on vdW materials, offering a framework to rationally control the 2D peptide-vdW heterostructures.

Molecular dynamics simulations↗

Quantifying Polaron Mole Fractions and Interpreting Spectral Changes in Molecularly Doped Conjugated Polymers

Molecular doping of conjugated polymers causes bleaching of the neutral absorbance and results in new polaron absorbance transitions in the mid and near infrared. In this report the concentration dependent changes in the spectra for a series of molecularly doped diketopyrrolopyrrole (DPP) co-polymers with a series of ultra-high electron affinity cyanotrimethylenecyclopropane-based dopants is analyzed. With these strong dopants the polaron mole fraction (Θ) reaches saturation. Analysis of the full spectrum enables separation of neutral and polaron signals and quantification of the polaron mole fraction using a simple noninteracting site model. The peak ratios for both neutral and polaron peaks change systematically with increasing polaron mole fraction for all measured polymers. Analysis of the spectral changes indicates that the polaron mole fraction can be quantified to within 5%. While the total change in the absorbance spectrum with increasing polaron mole fraction is linear, the lowest energy polaron peak (P1) grows nonlinearly, which indicates increased polarization/delocalization. Molecular doping of polymers that form either H- or J-aggregates shows systematically different spectral changes in the vibronic peak ratios of the neutral spectra and provides insights into the polymer configuration at undoped sites in the film.

36 MATERIALS SCIENCE↗

Asphaltene-induced spontaneous emulsification: Effects of interfacial co-adsorption and viscoelasticity

Asphaltenes are a class of high molecular weight aromatic compounds found in crude oil. They adsorb onto toluene-water interfaces and induce a spontaneous emulsification phenomenon, whereby stable water-in-oil emulsions form without the need of an external energy input. This work aims to control and understand the factors affecting spontaneous droplet formation in the presence of asphaltene adsorption. This is particularly useful for crude oil refining, where the presence of a stable emulsion hampers the efficiency of downstream processing operations. We explore the effect of the addition of copolymers designed as crude oil flow improvers as a means to control the extent of emulsion formation. We find that the polymers competitively adsorb onto the toluene-water interface and diminish spontaneous emulsification. Additionally, we conduct fluorescence microscopy experiments and measurements of the interfacial energy to determine the mechanism of spontaneous emulsification in asphaltene systems. We conclude that an emulsion forms via the diffusion of molecular water into the oil phase and subsequent binding with asphaltene aggregates, leading to the nucleation of micrometer-sized water droplets. We find that the polymer forms complexes with the dissolved asphaltenes, possibly hampering the ability of diffused water to bind to the asphaltenes and reducing the extent of spontaneous emulsification. Finally, we investigate the role of interfacial shear and dilatational viscoelasticity to better understand which fundamental interfacial properties are important in the emulsification of asphaltene-laden systems. We find that the rate of formation of an interfacial microstructural network is inversely correlated with the extent and rate of spontaneous emulsification.

42 ENGINEERING↗

Ultraviolet photometry from the orbiting astronomical observatory. XXX - The Orion reflection nebulosity

Surface-brightness measurements are presented that cover the region of Orion in nine intermediate-width bandpasses ranging from 4250 to 1550 A. The existence of an extended ultraviolet reflection nebulosity in this area is confirmed, and the characteristics of its spectrum and spatial distribution are derived. The observations are consistent with a model in which the dense molecular cloud complex in Orion is illuminated by the foreground Orion aggregate of early-type stars. The interpretation is complicated by the fact that foreground dust may contribute to the observed scattered light. The scattering particles in the cloud appear to exhibit a wavelength-dependent albedo similar to that found for interstellar grains in general, with a strong indication that the phase function changes to a less forward-scattering form in the ultraviolet.

Witt, A. N.↗

Energetics of water expulsion from intervening space between two particles during aggregation

Solvent expulsion away from an intervening region between two approaching particles plays important roles in particle aggregation yet remains poorly understood. Here, in this work, we use metadynamics molecular simulations to study the free energy landscape of removing water molecules from gibbsite and pyrophyllite slit pores representing the confined spaces between two approaching particles. For gibbsite, removing water from the intervening region is both entropically and enthalpically unfavorable. The closer the particles approach each other, the harder it is to expel water molecules. For pyrophyllite, water expulsion is spontaneous, which is different from the gibbsite system. A smaller pore makes the water removal more favorable. When water is being drained from the intervening region, single chains of water molecules are observed in gibbsite pore, while in pyrophyllite pore water cluster is usually observed. Water-gibbsite hydrogen bonds help stabilize water chains, while water forms clusters in pyrophyllite pore to maximize the number of hydrogen bonds among themselves. This work provides the first assessment into the energetics and structure of water being drained from the intervening region between two approaching particles during oriented attachment and aggregation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Robust chain aggregation of low-entropy rigid ladder polymers in solution

Conjugated polymers have been widely investigated where ladder-type conjugated polymers receive more attention due to their rigid backbones and extraordinary properties. However, the understanding of how the rigid conformation of ladder polymers translates to material properties is still limited. Here, we systematically investigated the solution aggregation properties of a carbazole-derived conjugated ladder polymer (LP) and its analogous non-ladder control polymer (CP) via light scattering, neutron scattering, and UV-vis absorption spectroscopy characterization techniques, revealing a highly robust, temperature-insensitive aggregation behavior of the LP. The experimental findings were further validated by computational molecular dynamics simulations. Here we found that the peak positions and intensities of the UV spectra of the LP remained constant between 20 °C and 120 °C in chlorobenzene solution. The polymer also showed a stable hydrodynamic radius measured by dynamic light scattering from 20 °C to 70 °C in the chlorobenzene solution. Using small-angle neutron scattering, no Guinier region was reached in the measured q range down to 0.008 Å –1 , even at elevated temperature. In contrast, the non-ladder control polymer CP was fully soluble in the chlorobenzene solvent without the observation of any notable aggregates. The Brownian dynamics simulation showed that during polymer aggregation, the entropy change of the LP was significantly less negative than that of the non-ladder control polymer. These findings revealed the low entropy nature of rigid conjugated ladder polymers and the low entropy penalty for their aggregation, which is promising for highly robust intermolecular interactions at high temperatures. Such a unique thermodynamic feature of rigid ladder polymers can be leveraged in the design and application of next-generation electronic and optoelectronic devices that function under unconventional high temperature conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hydroxyl radical mediated damage of proteins in low oxygen solution investigated using X-ray footprinting mass spectrometry

In the method of X-ray footprinting mass spectrometry (XFMS), proteins at micromolar concentration in solution are irradiated with a broadband X-ray source, and the resulting hydroxyl radical modifications are characterized using liquid chromatography mass spectrometry to determine sites of solvent accessibility. These data are used to infer structural changes in proteins upon interaction with other proteins, folding, or ligand binding. XFMS is typically performed under aerobic conditions; dissolved molecular oxygen in solution is necessary in many, if not all, the hydroxyl radical modifications that are generally reported. In this study we investigated the result of X-ray induced modifications to three different proteins under aerobic versus low oxygen conditions, and correlated the extent of damage with dose calculations. We observed a concentration-dependent protecting effect at higher protein concentration for a given X-ray dose. For the typical doses used in XFMS experiments there was minimal X-ray induced aggregation and fragmentation, but for higher doses we observed formation of covalent higher molecular weight oligomers, as well as fragmentation, which was affected by the amount of dissolved oxygen in solution. The higher molecular weight products in the form of dimers, trimers, and tetramers were present in all sample preparations, and, upon X-ray irradiation, these oligomers became non-reducible as seen in SDS-PAGE. The results provide an important contribution to the large body of X-ray radiation damage literature in structural biology research, and will specifically help inform the future planning of XFMS, and well as X-ray crystallography and small-angle X-ray scattering experiments.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Discussion on molecular dynamics (MD) simulations of the asphalt materials

The application of asphalt materials in pavement engineering has been increasingly widespread and sophisticated over the past several decades. Variations in the properties of asphalt binder during mixing, transportation, and paving can affect the performance of asphalt pavement. However, the asphalt material is a non-homogeneous and complex organic substance, consisting of various molecules with widely various molecular weights, elemental compositions, and structures. This complexity leads to difficulties for researchers to clearly and immediately understand the properties of asphalt materials and their variations. The multi-scale research approach combines macroscopic experimental data and microscopic simulation results from a practical engineering perspective. It helps to improve the understanding of asphalt materials. The molecular dynamics (MD) simulation proposes a corresponding molecular model of asphalt material based on experimental data, and the simulation algorithm is able to derive properties similar to those of real asphalt. Here, this paper provides a comprehensive review of the current studies on MD simulation of asphalt materials, including modeling, properties, and multi-scale analysis. As a key part of the computational simulation, this paper discusses the typical asphalt binder and asphalt-aggregate interface models constructed by different groups, and also presents their differences from real samples and their feasibility based on fundamental properties. After the introduction of molecular models, the extensive work made by researchers based on molecular models is categorically reviewed and discussed. The strengths and weaknesses of MD simulation methods in the study of asphalt materials are also summarized in order to provide the reader with a more comprehensive understanding of the relevant contents and to guide subsequent research.

36 MATERIALS SCIENCE↗

Enhanced hindrance from phenyl outer side chains on nonfullerene acceptor enables unprecedented simultaneous enhancement in organic solar cell performances with 16.7% efficiency

Inner side-chain engineering on Y6 has been a proven successful in improving short-circuit current density (JSC) through fine-tuning aggregated structures of acceptors. However, it fails in tuning the lowest unoccupied molecular orbital level (LUMO) and open-circuit voltage (V OC ). In this paper, we turn to focus on engineering the outer side chains on the flanking thienothiophene units with 4-hexylphenyl (PhC6) and 6-phenylhexyl (C6Ph) chains. Use of PhC6 enhances the steric effect between the attached phenyl and the ending group, which in combination with the additional conjugation effect provided by the linking phenyl leads to upshifted energy levels and increased V OC as a result. Again, substitution with the bulkier PhC6 unprecedentedly improves film-morphology with reduced paracrystalline disorder and long period and increased root-mean-square composition variations as well, leading to increased electron and hole mobilities and suppressed monomolecular recombination with J SC and fill-factor (FF) simultaneously enhanced. The PM6:BTP-PhC6-based devices yield a higher efficiency value of 16.7% than the PM6:BTP-C6Ph-based one (15.5%). Furthermore, this study shows a conceptual advance in materials design towards reducing the conflict between V OC and J SC in binary blended organic solar cells, which can be achieved by introducing bulkier chains to twist the backbone and simultaneously enhance the packing order.

14 SOLAR ENERGY↗

Molecular Mechanisms Underlying Surfactant-Based Plastics De-Inking

Surfactant-mediated binder removal is critical for de-inking pretreatment in plastics recycling, yet the molecular mechanisms governing surfactant performance remain poorly understood. We used all-atom (AA) and coarse-grained (CG) molecular dynamics (MD) simulations alongside alkaline surfactant washing experiments to investigate interactions between a series of surfactants and a polyether urethane (PEU) binder in solution and on a polyethylene (PE) surface. Experiments reveal a range of de-inking efficiencies, ranging from <25 to >95% depending upon surfactant headgroup charge and tail length. AA simulations reveal that charged surfactants reach stable levels of surfactant coverage, while nonionic surfactants aggregate on the binder. CG umbrella sampling calculations quantify the thermodynamics of binder desorption in water. In ∼0.25 M surfactant solutions, up to a 52% reduction in the free energy barrier is computed, with trends in good agreement (R 2 = 0.92, Pearson’s r = –0.96, Spearman’s ρ = –0.83) with experimental de-inking efficiencies. We find that charged surfactants are more effective than nonionic surfactants for de-inking and propose three regimes of surfactant de-inking processes: good de-inking occurs in surfactants that promote PEU desorption with a low radius of gyration (R g ); moderate de-inking occurs when surfactants stabilize PEU but increase R g ; poor de-inking occurs in surfactants that aggregate on the binder and promote extensive anchoring to the surface. Overall, these molecular-level insights have the potential to guide the design of surfactant formulations for plastics recycling applications.

ink removal↗

Layer-by-Layer-Processed Organic Solar Cells with 18.02% Efficiency Enabled by Regulating the Aggregation of Bottom Polymers

The fabrication of organic solar cells (OSCs) by a layer-by-layer (LBL) method has attracted growing attention in recent years. As already known, the pre-aggregates of conjugated polymers in solution have a profound impact on their microstructure morphology in films. Herein, by simply controlling the solution temperature and annealing processes, the pre-aggregation behavior of D18 polymer in solution can be fine-tuned and the microstructure of D18 bottom layer is well manipulated. The optimized D18 bottom layer can effectively regulate L8-BO upper-layer-forming suitable networks for efficient charge transportation. In addition, a vertical phase separation with a special D/D:A/A structure (P-i-N-type component distribution) is also formed. As a result, compared to the 16.43% power conversion efficiency (PCE) of the bulk heterojunction devices, such control enables bilayer OSC devices based on the polymer D18 and L8-BO to deliver an enhanced PCE of 18.02% with simultaneously improved short-circuit current density, open-circuit voltage, and fill factor. Importantly, it is also demonstrated in these results that the LBL deposition process utilizing the pre-aggregation of polymer and its fiber-network-forming ability is a very promising approach to improve charge dynamics, suppress carrier recombination, and fabricate highly efficient OSCs.

14 SOLAR ENERGY↗

Reinforcement learning based hybrid bond-order coarse-grained interatomic potentials for exploring mesoscale aggregation in liquid–liquid mixtures

Exploring mesoscopic physical phenomena has always been a challenge for brute-force all-atom molecular dynamics simulations. Although recent advances in computing hardware have improved the accessible length scales, reaching mesoscopic timescales is still a significant bottleneck. Coarse-graining of all-atom models allows robust investigation of mesoscale physics with a reduced spatial and temporal resolution but preserves desired structural features of molecules, unlike continuum-based methods. Here, we present a hybrid bond-order coarse-grained forcefield (HyCG) for modeling mesoscale aggregation phenomena in liquid–liquid mixtures. The intuitive hybrid functional form of the potential offers interpretability to our model, unlike many machine learning based interatomic potentials. We parameterize the potential with the continuous action Monte Carlo Tree Search (cMCTS) algorithm, a reinforcement learning (RL) based global optimizing scheme, using training data from all-atom simulations. The resulting RL-HyCG correctly describes mesoscale critical fluctuations in binary liquid–liquid extraction systems. cMCTS, the RL algorithm, accurately captures the mean behavior of various geometrical properties of the molecule of interest, which were excluded from the training set. The developed potential model along with the RL-based training workflow could be applied to explore a variety of other mesoscale physical phenomena that are typically inaccessible to all-atom molecular dynamics simulations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Printing 2D Conjugated Polymer Monolayers and Their Distinct Electronic Properties

Abstract Recently, 2D monolayer films of conjugated polymers have gained increasing attention owing to the preeminence of 2D inorganic films that exhibit unique optoelectronic and mechanical properties compared to their bulk analogs. Despite numerous efforts, crystallization of semiconducting polymers into highly ordered 2D monolayer films still remains challenging. Herein, a dynamic‐template‐assisted meniscus‐guided coating is utilized to fabricate continuous, highly ordered 2D monolayer films of conjugated polymers over a centimeter scale with enhanced backbone π–π stacking. In contrast, monolayer films printed on solid substrates confer upon the 1D fiber networks strong alkyl side‐chain stacking at the expense of backbone packing. From single‐layers to multilayers, the polymer π‐stacks change from edge‐on to bimodal orientation as the film thickness reaches ≈20 nm. Spectroscopic and cyclic voltammetry analysis reveals an abrupt increase in J‐aggregation and absorption coefficient and a decrease in bandgap and highest occupied molecular orbital level until critical thickness, possibly arising from the straightened polymer backbone. This is corroborated by an abrupt increase in hole mobility with film thickness, reaching a maximum of 0.7 cm 2 V −1 s −1 near the critical thickness. Finally, fabrication of chemical sensors incorporating polymer films of various thicknesses is demonstrated, and an ultrahigh sensitivity of the ≈7 nm thick ultrathin film (bilayers) to 1 ppb ammonia is shown.

Kafle, Prapti↗

Adsorption Mechanisms of Glyphosate on Ferrihydrite: Effects of Al Substitution and Aggregation State

Ferrihydrite is one of the most reactive iron (Fe) (oxyhydr)oxides in soils, but the adsorption mechanisms of glyphosate, the most widely used herbicide, on ferrihydrite remain unknown. Here, we determined the adsorption mechanisms of glyphosate on pristine and Al-substituted ferrihydrites with aggregated and dispersed states using macroscopic adsorption experiments, zeta potential, phosphorus K-edge X-ray absorption near-edge structure spectroscopy, in situ attenuated total reflectance Fourier transform infrared spectroscopy coupled with two-dimensional correlation spectroscopy, and multivariate curve resolution analyses. Aggregation of ferrihydrite decreases the glyphosate adsorption capacity. The partial substitution of Al in ferrihydrite inhibits glyphosate adsorption on aggregated ferrihydrite due to the decrease of external specific surface area, while it promotes glyphosate adsorption on dispersed ferrihydrite, which is ascribed to the increase of surface positive charge. Glyphosate predominately forms protonated and deprotonated, depending on the sorption pH, monodentate-mononuclear complexes (MMH 1 /MMH 0 , 77-90%) on ferrihydrites, besides minor deprotonated bidentate-binuclear complexes (BBH 0 , 23-10%). Both Al incorporation and a low pH favor the formation of the BB complex. The adsorbed glyphosate preferentially forms the MM complex on ferrihydrite and preferentially bonds with the Al-OH sites on Al-substituted ferrihydrite. In conclusion, these new insights are expected to be useful in predicting the environmental fate of glyphosate in ferrihydrite-rich environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Temperature-based reactive flow model for triaminotrinitrobenzene (TATB) plastic bonded explosives

A new reactive flow model is presented for triaminotrinitrobenzene (TATB)-based plastic bonded explosives, applicable to shock initiation and steady detonation problems of differing initial temperature. Temperature disequilibrium is assumed between unreacted explosive, material in the vicinity of compressed defects (called hot spots), and reaction products. The model incorporates temperature-dependent decomposition reaction rates. Particularly, Arrhenius model parameters were derived from quantum-based molecular dynamics simulations of TATB decomposition. Further, a model of detonation carbon aggregation is incorporated, describing the slow release of energy inherent to detonation in TATB-based materials. Model parameters were calibrated against gas gun shock initiation experiments and steady detonation rate stick tests. The predictive ability of the model in the shock initiation regime is tested against recent thin pulse experiments. The model is found to perform equally well in predicting the size-effect curve of ambient, cold, and hot rate sticks. The present work demonstrates the viability of incorporating results from subscale simulations into a continuum-scale reactive flow model.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Computer Modeling of Protocellular Functions: Peptide Insertion in Membranes

Lipid vesicles became the precursors to protocells by acquiring the capabilities needed to survive and reproduce. These include transport of ions, nutrients and waste products across cell walls and capture of energy and its conversion into a chemically usable form. In modem organisms these functions are carried out by membrane-bound proteins (about 30% of the genome codes for this kind of proteins). A number of properties of alpha-helical peptides suggest that their associations are excellent candidates for protobiological precursors of proteins. In particular, some simple a-helical peptides can aggregate spontaneously and form functional channels. This process can be described conceptually by a three-step thermodynamic cycle: 1 - folding of helices at the water-membrane interface, 2 - helix insertion into the lipid bilayer and 3 - specific interactions of these helices that result in functional tertiary structures. Although a crucial step, helix insertion has not been adequately studied because of the insolubility and aggregation of hydrophobic peptides. In this work, we use computer simulation methods (Molecular Dynamics) to characterize the energetics of helix insertion and we discuss its importance in an evolutionary context. Specifically, helices could self-assemble only if their interactions were sufficiently strong to compensate the unfavorable Free Energy of insertion of individual helices into membranes, providing a selection mechanism for protobiological evolution.

Rodriquez-Gomez, D.↗

Inhibition of Amyloid β-Induced Lipid Membrane Permeation and Amyloid β Aggregation by K162

Alzheimer's disease (AD) is characterized by progressive neurodegeneration associated with amyloid β (Aβ) peptide aggregation. The aggregation of Aβ monomers (AβMs) leads to the formation of Aβ oligomers (AβOs), the neurotoxic Aβ form, capable of permeating the cell membrane. Here, we investigated the effect of a fluorene-based active drug candidate, named K162, on both Aβ aggregation and AβO toxicity toward the bilayer lipid membrane (BLM). Electrochemical impedance spectroscopy (EIS), atomic force microscopy (AFM), and molecular dynamics (MD) were employed to show that K162 inhibits AβOs-induced BLM permeation, thus preserving BLM integrity. In the presence of K162, only shallow defects on the BLM surface were formed. Apparently, K162 modifies Aβ aggregation by bypassing the formation of toxic AβOs, and only nontoxic AβMs, dimers (AβDs), and fibrils (AβFs) are produced. Unlike other Aβ toxicity inhibitors, K162 preserves neurologically beneficial AβMs. This unique K162 inhibition mechanism provides an alternative AD therapeutic strategy that could be explored in the future.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The role of interfacial donor–acceptor percolation in efficient and stable all-polymer solar cells

Polymerization of Y6-type acceptor molecules leads to bulk-heterojunction organic solar cells with both high power-conversion efficiency and device stability, but the underlying mechanism remains unclear. Here we show that the exciton recombination dynamics of polymerized Y6-type acceptors (Y6-PAs) strongly depends on the degree of aggregation. While the fast exciton recombination rate in aggregated Y6-PA competes with electron-hole separation at the donor–acceptor (D–A) interface, the much-suppressed exciton recombination rate in dispersed Y6-PA is sufficient to allow efficient free charge generation. Indeed, our experimental results and theoretical simulations reveal that Y6-PAs have larger miscibility with the donor polymer than Y6-type small molecular acceptors, leading to D–A percolation that effectively prevents the formation of Y6-PA aggregates at the interface. Besides enabling high charge generation efficiency, the interfacial D–A percolation also improves the thermodynamic stability of the blend morphology, as evident by the reduced device “burn-in” loss upon solar illumination.

14 SOLAR ENERGY↗