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At least 1,369 records · Page 76
All sourcesNASA NTRSDOE OSTI
DOE OSTI2013

Temporal and spatial features of the formation of DNA adducts in sulfur mustard-exposed skin

Sulfur mustard (SM) is a chemical warfare agent that targets skin where it induces large blisters. DNA alkylation is a critical step to explain SM-induced cutaneous symptoms. We determined the kinetics of formation of main SM–DNA adducts and compare it with the development of the SM-induced pathogenesis in skin. SKH-1 mice were exposed to 2, 6 and 60 mg/kg of SM and treated skin was biopsied between 6 h and 21 days. Formation of SM DNA adducts was dose-dependent with a maximum immediately after exposure. However, adducts were persistent and still detectable 21 days post-exposure. The time-dependent formation of DNA adducts was also found to be correlated with the appearance of apoptotic cells. This temporal correlation suggests that these two early events are responsible for the severity of the damage to the skin. Besides, SM–DNA adducts were also detected in areas located next to contaminated zone, thus suggesting that SM diffuses in skin. Altogether, this work provides for the first time a clear picture of SM-induced genotoxicity using DNA adducts as a marker. - Highlights: • Sulfur mustard adducts are formed in DNA after skin exposure. • DNA damage formation is an early event in the pathological process of skin burn. • The amount of SM–DNA adducts is maximal at the earliest time point investigated. • Adducts are still detected 3 weeks after exposure. • Sulfur mustard diffuses in skin especially when large doses are applied.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2014

A synthetic mechano-growth factor E peptide promotes rat tenocyte migration by lessening cell stiffness and increasing F-actin formation via the FAK-ERK1/2 signaling pathway

Tendon injuries are common in sports and are frequent reasons for orthopedic consultations. The management of damaged tendons is one of the most challenging problems in orthopedics. Mechano-growth factor (MGF), a recently discovered growth repair factor, plays positive roles in tissue repair through the improvement of cell proliferation and migration and the protection of cells against injury-induced apoptosis. However, it remains unclear whether MGF has the potential to accelerate tendon repair. We used a scratch wound assay in this study to demonstrate that MGF-C25E (a synthetic mechano-growth factor E peptide) promotes the migration of rat tenocytes and that this promotion is accompanied by an elevation in the expression of the following signaling molecules: focal adhesion kinase (FAK) and extracellular signal regulated kinase1/2 (ERK1/2). Inhibitors of the FAK and ERK1/2 pathways inhibited the MGF-C25E-induced tenocyte migration, indicating that MGF-C25E promotes tenocyte migration through the FAK-ERK1/2 signaling pathway. The analysis of the mechanical properties showed that the Young's modulus of tenocytes was decreased through treatment of MGF-C25E, and an obvious formation of pseudopodia and F-actin was observed in MGF-C25E-treated tenocytes. The inhibition of the FAK or ERK1/2 signals restored the decrease in Young's modulus and inhibited the formation of pseudopodia and F-actin. Overall, our study demonstrated that MGF-C25E promotes rat tenocyte migration by lessening cell stiffness and increasing pseudopodia formation via the FAK-ERK1/2 signaling pathway. - Highlights: • Mechano-growth factor E peptide (MGF-C25E) promotes migration of rat tenocytes. • MGF-C25E activates the FAK-ERK1/2 pathway in rat tenocytes. • MGF-C25E induces the actin remodeling and the formation of pseudopodia, and decreases the stiffness in rat tenocytes. • MGF-C25E promotes tenocyte migration via altering stiffness and forming pseudopodia by the activation of the FAK-ERK1/2 pathway.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2014

Myotube formation is affected by adipogenic lineage cells in a cell-to-cell contact-independent manner

Intramuscular adipose tissue (IMAT) formation is observed in some pathological conditions such as Duchenne muscular dystrophy (DMD) and sarcopenia. Several studies have suggested that IMAT formation is not only negatively correlated with skeletal muscle mass but also causes decreased muscle contraction in sarcopenia. In the present study, we examined w hether adipocytes affect myogenesis. For this purpose, skeletal muscle progenitor cells were transfected with siRNA of PPARγ (siPPARγ) in an attempt to inhibit adipogenesis. Myosin heavy chain (MHC)-positive myotube formation was promoted in cells transfected with siPPARγ compared to that of cells transfected with control siRNA. To determine whether direct cell-to-cell contact between adipocytes and myoblasts is a prerequisite for adipocytes to affect myogenesis, skeletal muscle progenitor cells were cocultured with pre- or mature adipocytes in a Transwell coculture system. MHC-positive myotube formation was inhibited when skeletal muscle progenitor cells were cocultured with mature adipocytes, but was promoted when they were cocultured with preadipocytes. Similar effects were observed when pre- or mature adipocyte-conditioned medium was used. These results indicate that preadipocytes play an important role in maintaining skeletal muscle mass by promoting myogenesis; once differentiated, the resulting mature adipocytes negatively affect myogenesis, leading to the muscle deterioration observed in skeletal muscle pathologies. - Highlights: • We examined the effects of pre- and mature adipocytes on myogenesis in vitro. • Preadipocytes and mature adipocytes affect myoblast fusion. • Preadipocytes play an important role in maintaining skeletal muscle mass. • Mature adipocytes lead to muscle deterioration observed in skeletal muscle pathologies.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2018

Novel proteins that regulate cell extension formation in fibroblasts

Cell extensions are critical structures that enable matrix remodeling in wound healing and cancer invasion but the regulation of their formation is not well-defined. We searched for new proteins that mediated cell extension formation over collagen by tandem mass tagged mass spectrometry analysis of purified extensions in 3T3 fibroblasts. Unexpectedly, importin-5, ENH isoform 1b (PDLIM5) and 26 S protease regulatory subunit 6B (PSMC4) were more abundant (> 10-fold) in membrane-penetrating cell extensions than cell bodies, which was confirmed by immunostaining and immunoblotting and also observed in human gingival fibroblasts. After siRNA knockdown of these proteins and plating cells on grid-supported floating collagen gels for 6 h, formation of cell extensions and collagen remodeling were examined. Knockdown of importin-5 reduced collagen compaction (1.9-fold), pericellular collagen degradation (~ 1.8-fold) and number of cell extensions (~ 69%). Knockdown of PSMC4 reduced collagen compaction (~ 1.5-fold), pericellular collagen degradation (~ 1.7-fold) and number of cell extensions (~ 42%). Knockdown of PDLIM5 reduced collagen compaction (~ 1.6-fold) and number of cell extensions (~ 21%). Inhibition of the TGF-β RI kinase, Smad3 or ROCK-II signaling pathways reduced the abundance of PDLIM5 in cell extensions but PSMC4 and importin-5 were reduced only by Smad3 or ROCK-II inhibitors. }We conclude that these novel proteins are required for cell extension formation and their recruitment into extensions involves the Smad3 and ROCK signaling pathways.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2021

Differential localization patterns of pyruvate kinase isoforms in murine naïve, formative, and primed pluripotent states

Highlights: • PKM1/2 protein abundance is greater in formative mEpiLCs compared to naïve mESCs or primed mEpiSCs. The ratio of PKM1/2 is maintained. • PKM1/2 are localized in both nuclear and cytoplasmic regions relative to GAPDH and OCT4 across the pluripotent continuum. • PKM1 localization is strongly correlated to OCT4 localization, and moderately to GAPDH in formative mEpiLCs. • PKM1/2 localization is moderately correlated to OCT4 and GAPDH localization in naïve mESCs. • PKM1/2 localization are moderately correlated to GAPDH localization in primed mEpiSCs. Mouse embryonic stem cells (mESCs) and mouse epiblast stem cells (mEpiSCs) represent opposite ends of the pluripotency continuum, referred to as naïve and primed pluripotent states, respectively. These divergent pluripotent states differ in several ways, including growth factor requirements, transcription factor expression, DNA methylation patterns, and metabolic profiles. Naïve cells employ both glycolysis and oxidative phosphorylation (OXPHOS), whereas primed cells preferentially utilize aerobic glycolysis, a trait shared with cancer cells referred to as the Warburg Effect. Until recently, metabolism has been regarded as a by-product of cell fate, however, evidence now supports metabolism as being a driver of stem cell state and fate decisions. Pyruvate kinase muscle isoforms (PKM1 and PKM2) are important for generating and maintaining pluripotent stem cells (PSCs) and mediating the Warburg Effect. Both isoforms catalyze the final, rate limiting step of glycolysis, generating adenosine triphosphate and pyruvate, however, the precise role(s) of PKM1/2 in naïve and primed pluripotency is not well understood. The primary objective of this study was to characterize the cellular expression and localization patterns of PKM1 and PKM2 in mESCs, chemically transitioned epiblast-like cells (mEpiLCs) representing formative pluripotency, and mEpiSCs using immunoblotting and confocal microscopy. The results indicate that PKM1 and PKM2 are not only localized to the cytoplasm, but also accumulate in differential subnuclear regions of mESC, mEpiLCs, and mEpiSCs as determined by a quantitative confocal microscopy employing orthogonal projections and airyscan processing. Importantly, we discovered that the subnuclear localization of PKM1/2 changes during the transition from mESCs, mEpiLCs, and mEpiSCs. Finally, we have comprehensively validated the appropriateness and power of the Pearson's correlation coefficient and Manders's overlap coefficient for assessing nuclear and cytoplasmic protein colocalization in PSCs by immunofluorescence confocal microscopy. We propose that nuclear PKM1/2 may assist with distinct pluripotency state maintenance and lineage priming by non-canonical mechanisms. These results advance our understanding of the overall mechanisms controlling naïve, formative, and primed pluripotency.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2021

Tetramethylpyrazine inhibits neutrophil extracellular traps formation and alleviates hepatic ischemia/reperfusion injury in rat liver transplantation

Hepatic ischemia/reperfusion injury (IRI) is an adverse effect for liver transplantation which is characterized by immune response mediated inflammation. Recent studies report that neutrophil extracellular traps (NETs) are implicated in hepatic IRI. The aim of this study was to explore the mechanism of action of tetramethylpyrazine (TMP), the main chemical composition of Ligusticum chuanxiong in treatment of ischemic related diseases. Data showed that hepatic IRI increases the leak of alanine aminotransferase (ALT) and aspartate transaminase (AST), and stimulates formation of NETs. Extracellular DNA/NETs assay, hematoxylin-eosin (HE) staining, immunofluorescence assay, terminal deoxynucleotidyl transferase dUTP nick-end labeling (TUNEL) and Western blot assay, showed that TMP significantly reduces formation of NETs and alleviates hepatic IRI. Moreover, TMP and Diphenyleneiodonium (DPI) suppressed ROS production in neutrophils. In addition, analysis showed that activation of NADPH oxidase plays a role in formation of NETs triggered by hepatic IRI. Notably, TMP inhibited formation of NETs though inhibition of NADPH oxidase. Additionally, Combination treatment using TMP and DPI was more effective compared with monotherapy of either of the two drugs. These findings show that combination therapy using TMP and DPI is a promising method for treatment hepatic IRI.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2016

Probing the Crystal Structure and Formation Mechanism of Lanthanide-Doped Upconverting Nanocrystals

Lanthanide (Ln)-doped upconverting nanocrystals (UCNCs), such as NaLnF 4 (with Ln = lanthanide), constitute an important class of nanoscale materials due to their capacity to convert near-infrared photons into near-ultraviolet or visible light. Although under intense investigation for more than a decade, UCNCs have been relatively underexplored especially regarding their crystal structure and mechanisms of formation in organic media. The former is needed to explain the relationship between atomic scale structure and upconversion (UC) properties of UCNCs (i.e., local symmetry for 4f–4f transition probability, Ln 3+ distances for energy migration), while the latter is essential to finely tune the size, morphology, chemical composition, and architecture of well-defined upconverting nanostructures, which constitute the experimental levers to modify the optical properties. In this contribution, we use synchrotron-based diffraction experiments coupled to Rietveld and pair distribution function (PDF) analyses to understand the formation of NaGdF 4 :Yb:Er UCNCs in organic media and to investigate their crystal structure. Our results reveal a complex mechanism of the formation of NaGdF 4 :Yb:Er UCNCs based on chemical reactions involving molecular clusters and in situ-generated, crystalline sodium fluoride at high temperature. Additionally, a detailed crystallographic investigation of NaGdF 4 :Yb:Er UCNCs is presented. Our Rietveld and PDF analyses show that the space group P$\bar{6}$ is the one that best describes the crystal structure of NaGdF 4 :Yb:Er UCNCs contrary to what has been recently proposed. Further, our Rietveld and PDF data reveal the formation of bulk-like crystal structure down to 10 nm with limited distortions. Finally, the results presented in this paper constitute an important step toward the comprehensive understanding of the underlying picture that governs UC properties of lanthanide-doped nanostructures.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2018

Elementary Steps of Faujasite Formation Followed by in Situ Spectroscopy

Ex situ and in situ spectroscopy was used to identify the kinetics of processes during the formation of the faujasite (FAU) zeolite lattice from a hydrous gel. Using solid-state 27Al MAS NMR, the autocatalytic transformation from the amorphous gel into the crystalline material was monitored. Al-XANES shows that most Al already adopts a tetrahedral coordination in the X-ray-amorphous aluminosilicate at the beginning of the induction period, which hardly changes throughout the rest of the synthesis. Using 23Na NMR spectroscopy, environments in the growing zeolite crystal were identified and used to define the processes in the stepwise formation of the zeolite lattice. The end of the induction period was accompanied by a narrowing of the 27Al and 23Na MAS NMR peak widths, indicating the increased long-range order. The experiments show conclusively that the formation of faujasite occurs via the continuous formation and subsequent condensation of intermediary sodalite-like units that constitute the key building block of the zeolite. Acknowledgement The authors thank T. Huthwelker for assistance with XAFS experiment setup at the Swiss Light Source (PSI, Switzerland). Further, we would like to acknowledge V. Shutthanandan and B.W. Arey for performing Helium ion microscopy as well as Z. Zhao, N.R. Jaeger, M. Weng, C. Wan and M. Hu for aiding in the NMR experimental procedure. T. Varga is acknowledged for his help with the capillary XRD. A.V., D.M.C., J.H., J.L.F and J.A.L. were supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences. S.P. and M.A.D. acknowledge support by the Materials Synthesis and Simulation Across Scales (MS3 Initiative) conducted under Laboratory Directed Research & Development Program at PNNL. The in situ NMR experiments were supported by the U. S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Biosciences and Geosciences. Part of the research described in this paper was performed in the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated for the US DOE by Battelle.

faujasite↗
DOE OSTI2018

Evidence of a Nonphotochemical Mechanism for the Solid-State Formation of Uranyl Peroxide

Here, we have demonstrated the solid-state formation of a uranyl peroxide (UP) species from hydrated uranyl fluoride via a uranyl hydroxide intermediate, the first observation of a UP species formed in a solid-state reaction. Water vapor pressure is shown to be a driving factor of both the loss of fluorine and the subsequent formation of peroxo units. We have ruled out a photochemical mechanism for formation of the UP species by demonstrating that the same reaction occurs in the dark. A radiolytic mechanism is unlikely because of the low radioactivity of the sample material, suggesting the existence of a novel UP formation mechanism.

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

Formation of 1 H -Phenalene (C 13 H 10 ) in the Taurus Molecular Cloud via Methylidyne Addition-Cyclization-Aromatization (MACA)

The formation of 1H-phenalene (C 13 H 10 ) in cold molecular clouds, such as the Taurus Molecular Cloud-1 (TMC-1), presents a significant challenge to traditional astrochemical models, which predominantly suggest high-temperature pathways for polycyclic aromatic hydrocarbon (PAH) formation. In this study, we explore computationally the Methylidyne Addition-Cyclization-Aromatization (MACA) mechanism as a viable, barrierless pathway for phenalene synthesis under low-temperature conditions. Through electronic structure calculations and Rice–Ramsperger–Kassel–Marcus (RRKM) statistical methods, we demonstrate that the reaction of 1-vinylnaphthalene (C 10 H 7 C 2 H 3 ) with the methylidyne radical (CH) leads to the formation of 1H-phenalene via a bimolecular reaction, a process that is exoergic and without entrance barrier. The MACA mechanism facilitates the growth of the aromatic carbon backbone via a [5 + 1] ring annulation, providing a new insight into PAH formation in cold molecular clouds. Notably, the MACA mechanism has previously been shown to form indene (C9H8), which was detected in TMC-1 as well, via a [4 + 1] annulation, demonstrating its potential to produce a variety of complex PAHs by addition of a five- and six-membered ring to a benzene moiety via [4 + 1] and [5 + 1] annulation, respectively. As a result, this work highlights the importance of barrierless, exoergic reactions involving MACA in the synthesis of complex aromatic molecules in space, expanding our physicochemical understanding of carbon-rich chemistry in cold molecular clouds.

Aromatic compounds↗
DOE OSTI2021

Formation of Gas-Phase Allyl Radicals from Glycerol on Rutile TiO2(110)

The reaction pathways of glycerol on partially reduced TiO2(110) have been studied by a combination of molecular beam dosing and temperature-programmed desorption (TPD). Glycerol is found to bind more strongly to TiO2(110) than glycols due to an additional hydroxyl group in the molecule. When the Ti surface sites are saturated by glycerol, the majority of glycerol molecules (~ 95%) undergo further reactions to yield carbon-free (water and hydrogen) and carbon-containing products that are desorbed during the TPD ramp. In contrast to glycols for which both water and hydrogen arise exclusively from the cleavage of glycol O-H bonds, we identify two distinct reaction channels resulting from the cleavage of O-H and C-H bonds, respectively, for both water and hydrogen evolution from glycerol on TiO2(110). Quantitative determination of the desorption yields of water and hydrogen reveals that the C-H bond scission channel which occurs at higher temperature than the O-H bond scission channel, is a minor reaction channel for water formation, while it is a major reaction channel responsible for hydrogen evolution. For the carbon-containing products, we exclude both carbon deposition and carbon oxides (CO and CO2) formation, and identify the allyl radical as the major carbon-containing product. The formation of the allyl radical is accompanied by the formation of various minor carbon-containing products including propylene, acrolein, allyl alcohol, acetone, formaldehyde and ethylene. The different surface chemistries observed between glycerol and simpler alcohols and glycols on TiO2(110), suggest that smaller oxygenates cannot serve as models for larger oxygenates in probing their reaction pathways on oxide surfaces. The new reaction channels observed for glycerol on TiO2(110) may open up a new way to convert bio-renewable glycerol directly to pure hydrogen and hydrocarbons on TiO2. This work was supported by the US Department of Energy, Office of Sciences, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences, and performed in EMSL, a national scientific user facility sponsored by the Department of Energy’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is a multiprogram national laboratory operated for the DOE by Battelle.

Chen, Long↗
DOE OSTI2023

Effects of Sodium and Magnesium Ions on the Photochemically Induced Heterogeneous Formation of Manganese Oxides and Their Structural Evolution

Manganese (Mn) oxides are abundant in aquatic and terrestrial environments, where they play significant roles in redox cycling and biological metabolisms. We recently observed that Mn oxides were homogeneously formed during the abiotic oxidation of Mn 2+ (aq) to Mn(IV) by O 2 •– via nitrate photolysis, at a rate comparable to that of biotic Mn oxide formation. On the other hand, for the heterogeneous formation of Mn oxides, the presence of a substrate can alter the required thermodynamic driving force, which may affect their crystalline phases and further influence the oxidative capability of redox cycling in environmental systems. However, little is known about the photochemically induced heterogeneous formation of Mn oxides on substrates. In this study, we investigated the heterogeneous formation of Mn oxides on a quartz substrate in the presence of two environmentally abundant cations, Na + and Mg 2+ . In contrast to homogeneously generated Mn oxides, the heterogeneously formed Mn oxides displayed faster crystalline phase evolutions and morphological changes over time. Additionally, the coexistence of Na + and Mg 2+ ions greatly affected the initial crystalline phases and the phase evolution, as well as the surface morphologies of the Mn oxides. Finally, these discoveries contribute to our understanding of how various Mn oxides form in nature and provide insights into the processes involved in manufacturing specific Mn oxide crystalline structures for engineering applications.

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

AP-XPS Study of the Reaction of O 2 and CO 2 with Zn–Au(111) Surface Alloys: Activation of O–O/C–O Bonds and the Formation of ZnO

Synchrotron-based ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) was used to study the dissociation of O 2 and CO 2 on Zn-Au(111) alloys which contained 0.2-0.3 monolayers of zinc. Although Au(111) is inert, the alloys displayed a high activity for the cleavages of O-O and C-O bonds at room temperature with the formation of ZnO x species. Dissociative adsorption of O 2 at 300 K destroyed the alloys and the results of AP-XPS pointed to the co-existence of two types of oxygen species on the surface: ZnO x and chemisorbed O atoms (O chem ) on Au or the Au-ZnO interface. Annealing from room temperature to 600 K induced a O chem → ZnO x transformation that reflected the poor stability of O atoms on Au(111). The Zn-Au(111) systems exhibited a reactivity towards CO 2 that was much larger than that seen for Au(111), Cu(111) or surfaces of late transition metals like, Ni, Pd or Pt. At 300 K, CO 2 underwent partial dissociation depositing large amounts of O chem on the surface with minor formation of ZnO x . In addition, the deposited O chem reacted with CO 2 to form surface carbonate groups. Dosing of CO 2 at 500-600 K mainly led to the formation of ZnO x and the surface carbonate almost disappeared. In the presence of hydrogen, i.e. reaction feeds with a CO 2 to H 2 ratio of 1:3, the surface chemistry at 300 K was very similar to that seen for pure CO 2 with the formation of ZnO x and carbonate groups. In contrast, at 500-600 K, reaction with hydrogen induced the removal of ZnO x and CO 3 /HCOO species. Finally, our AP-XPS results are consistent with the idea that CO 2 hydrogenation on AuZn alloys involves a redox process where there is sequential oxidation by CO 2 and reduction by H 2 to yield methanol.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Revealing Au13 as Elementary Clusters During the Early Formation of Au Nanocrystals

Understanding the formation mechanism of nanocrystals in solution is very fundamental to the development of materials science. For a metal nanocrystal, the cluster mediated formation mechanism is still poorly understood. Particularly, identifying what types of clusters are dominant and how they evolve into a nanocrystal in the early nucleation stage remains a great challenge. Here, using liquid-cell transmission electron microscopy, we directly observe the formation of ultra-small Au clusters (~0.84 nm) in the presence of PAA-Na. These clusters, which correspond to the size of Au13 cluster, coalesce to form nanocrystals. Our molecular dynamics simulations suggest Au13 in an aqueous environment have higher stability when compared to other cluster sizes and provide atomistic details of growth by cluster coalescence. Collectively, our demonstration of Au13 as the dominant species with elaboration of their coalescence kinetics sheds light on nonclassical nanocrystal formation mechanisms and offers useful guidelines for designing innovative pathways for synthesis of nanomaterials.

Au13 clusters, cluster coalescence, liquid-cell TE↗
DOE OSTI2018

Effect of Poly(ethylene glycol) Grafting Density on Methylcellulose Fibril Formation

Herein we investigate the effect of short-chain poly(ethylene glycol) (PEG) graft density on the formation of methylcellulose (MC) fibrils at elevated temperatures. Thiol–ene click chemistry was used to systematically graft 800 and 2000 g/mol PEG onto the backbone of allylated MC, with a wide range of grafting densities from 0.7% to 33%. As determined from light scattering, grafting leads to an increase in the persistence length of this semiflexible copolymer, by as much as a factor of 10. Upon heating, SAXS and AFM studies show that fibril formation is suppressed at around 10% grafting density for shorter PEG grafts, corresponding to persistence lengths about ~22 nm. For longer grafts fibril formation is suppressed at 7% grafting density, at around the same ~22 nm persistence length. The radius of the fibrils increases with the square root of the persistence length of the chains, which is consistent with a theory for the radius of twisted chains. The ability to form networks at 80 °C is highly correlated to the ability to form fibrils, and accordingly the modulus systematically decreases with grafting density. When the fibril formation is suppressed, MC solutions no longer form solid networks. Therefore, grafting modulates the molecular architecture and gelation properties of MC and also provides new insight into the structure of MC fibrils.

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

Spontaneous Formation of 1D Pattern in Monolayer VSe 2 with Dispersive Adsorption of Pt Atoms for HER Catalysis

Creation of functional patterns in two-dimensional (2D) materials provides opportunities to extend their potential for applications. Transition-metal dichalcogenides (TMDCs) are suitable 2D materials for pattern generation because of properties including alterable polymorphic phases, easy chalcogen-vacancy formation, metal-atom insertion, and alloying. Such patterning can be used for selective functionalization. Here we report the spontaneous formation of long-range, well-ordered 1D patterns in monolayer vanadium diselenide (VSe 2 ) by a single annealing stage during growth. Atomic-resolution images in real space combined with density-functional-theory (DFT) calculations reveal the 1D features of patterned VSe 2 . Further experimental characterization of the intermediate states in the growth process confirm the spontaneous formation of the 1D pattern by annealing-induced Se-deficient linear defects. The 1D pattern can be reversibly transformed to homogenous VSe 2 monolayer by reintroducing Se atoms. Moreover, additional experiments demonstrate that a dispersive deposition of Pt atoms along the 1D structures of patterned VSe 2 is achieved, while DFT calculations find that their catalytic activity for hydrogen evolution reaction (HER) is as good as that of Pt surfaces. Further, the formation of long-range, well-ordered 1D patterns not only demonstrates an effective way of dimension modulation in 2D materials but also enriches the potential of intrinsically patterned 2D materials for promising catalytic activities.

Chemical structure↗
DOE OSTI2022

Formation of a Secondary Phase in Thermally Evaporated MAPbI 3 and Its Effects on Solar Cell Performance

Thermal evaporation is a promising deposition technique to scale up perovskite solar cells (PSCs) to large areas, but the lack of understanding of the mechanisms that lead to high-quality evaporated methylammonium lead triiodide (MAPbI 3 ) films gives rise to devices with efficiencies lower than those obtained by spin coating. Here this work investigates the crystalline properties of MAPbI 3 deposited by the thermal coevaporation of PbI 2 and MAI, where the MAI evaporation rate is controlled by setting different temperatures for the MAI source and the PbI 2 deposition rate is controlled with a quartz crystal microbalance (QCM). Using grazing incident wide-angle X-ray scattering (GIWAXS) and X-ray diffraction (XRD), we identify the formation of a secondary orthorhombic phase (with a Pnma space group) that appears at MAI source temperatures below 155 °C. With synchrotron-based X-ray fluorescence (XRF) microscopy, we show that the changes in crystalline phases are not necessarily due to changes in stoichiometry. The films show a stochiometric composition when the MAI source is heated between 140 to 155 °C, and the samples become slightly MAI rich at 165 °C. Increasing the MAI temperature beyond 165 °C introduces an excess of MAI in the film, which promotes the formation of films with low crystallinity that contain low-dimensional perovskites. When they are incorporated in solar cells, the films deposited at 165 °C result in the champion power conversion efficiency, although the presence of a small amount of low-dimensional perovskite may lead to a lower open-circuit voltage. We hypothesize that the formation of secondary phases in evaporated films limits the performance of PSCs and that their formation can be suppressed by controlling the MAI source temperature, bringing the film toward a phase-pure tetragonal structure. Control of the phases during perovskite evaporation is therefore crucial to obtain high-performance solar cells.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Gallstone-Formation-Inspired Bimetallic Supra-nanostructures for Computed-Tomography-Image-Guided Radiation Therapy

Inspired by the gallstone formation mechanism, we report here a fast one-pot synthesis of high-surface-area bimetallic hierarchical supra-nanostructures. As gallstones are generated from metal cholate complexes, cholate bile acid molecules with Au/Ag metal precursors formed stable nanocomplexes aggregated with metal Au ions and preformed ~2 nm silver halide nanoparticles before reduction. When a reducing agent was added, the metal cholate nanocomplexes quickly formed noble bimetallic hierarchical supra-nanostructures. The morphology of bimetallic supra-nanostructures could be tailored by changing the feeding ratio of each metal precursor. In situ synchrotron small-angle X-ray scattering measurement with a custom-designed reaction cell showed two-step growth and attachment behavior toward hierarchical supra-nanostructures from the gallstone-formation-inspired metal cholate nanocomplexes in a 60 s reaction. Additional wide-angle X-ray scattering, X-ray absorption near-edge structure, in situ Fourier transform infrared, and high-resolution scanning transmission electron microscopy investigations subsequently revealed the mechanism for the evolution of bimetallic hierarchical supra-nanostructures. The gallstone-formation-inspired synthesis mechanism can be universally applied to other metals, for example, Pt–Ag and Pd–Ag bimetallic nanostructures. The synthesized high-surface-area bimetallic supra-nanostructures demonstrated significantly enhanced X-ray computed tomography imaging contrast and radiosensitizing effect for a potential image-guided nanomedicine application. We believe that our synthetic method inspired by gallstone formation and understanding represents an important step toward the development of hierarchical nanoparticles for various applications.

62 RADIOLOGY AND NUCLEAR MEDICINE↗