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- ItemConformations of a Long Polymer in a Melt of Shorter Chains: Generalizations of the Flory Theorem(Washington, DC : ACS, 2015) Lang, Michael; Rubinstein, Michael; Sommer, Jens-UweLarge-scale simulations of the swelling of a long N-mer in a melt of chemically identical P-mers are used to investigate a discrepancy between theory and experiments. Classical theory predicts an increase of probe chain size R ∼ P–0.18 with decreasing degree of polymerization P of melt chains in the range of 1 < P < N1/2. However, both experiment and simulation data are more consistent with an apparently slower swelling R ∼ P–0.1 over a wider range of melt degrees of polymerization. This anomaly is explained by taking into account the recently discovered long-range bond correlations in polymer melts and corrections to excluded volume. We generalize the Flory theorem and demonstrate that it is in excellent agreement with experiments and simulations.
- ItemSelf-propelled micromotors for cleaning polluted water(Washington, DC : ACS, 2013) Soler, L.; Magdanz, V.; Fomin, V.M.; Sanchez, S.; Schmidt, O.G.We describe the use of catalytically self-propelled microjets (dubbed micromotors) for degrading organic pollutants in water via the Fenton oxidation process. The tubular micromotors are composed of rolled-up functional nanomembranes consisting of Fe/Pt bilayers. The micromotors contain double functionality within their architecture, i.e., the inner Pt for the self-propulsion and the outer Fe for the in situ generation of ferrous ions boosting the remediation of contaminated water.The degradation of organic pollutants takes place in the presence of hydrogen peroxide, which acts as a reagent for the Fenton reaction and as main fuel to propel the micromotors. Factors influencing the efficiency of the Fenton oxidation process, including thickness of the Fe layer, pH, and concentration of hydrogen peroxide, are investigated. The ability of these catalytically self-propelled micromotors to improve intermixing in liquids results in the removal of organic pollutants ca. 12 times faster than when the Fenton oxidation process is carried out without catalytically active micromotors. The enhanced reaction-diffusion provided by micromotors has been theoretically modeled. The synergy between the internal and external functionalities of the micromotors, without the need of further functionalization, results into an enhanced degradation of nonbiodegradable and dangerous organic pollutants at small-scale environments and holds considerable promise for the remediation of contaminated water.
- ItemHydrolysis Stability of Bidentate Phosphites Utilized as Modifying Ligands in the Rh-Catalyzed n-Regioselective Hydroformylation of Olefins(Washington, DC : ACS, 2016) Zhang, Baoxin; Jiao, Haijun; Michalik, Dirk; Kloß, Svenja; Deter, Lisa Marie; Selent, Detlef; Spannenberg, Anke; Franke, Robert; Börner, ArminThe stability of ligands and catalysts is an almost neglected issue in homogeneous catalysis, but it is crucial for successful application of this methodology in technical scale. We have studied the effect of water on phosphites, which are the most applied cocatalysts in the n-regioselective homogeneous Rh-catalyzed hydroformylation of olefins. The stability of the bidentate nonsymmetrical diphosphite L1, as well as its two monophosphite constituents L2 and L3, toward hydrolysis was investigated by means of in situ NMR spectroscopy under similar conditions as applied in industry. Hydrolysis pathways, intermediates, and kinetics were clarified. DFT calculations were used to support the experimentally found data. The acylphosphite unit L2, which reacts with water in an unselective manner, was proven to be much less stable than the phenolphosphite L3. The stability of the bidentate ligand L1 can be therefore mainly attributed to its phenolphosphite moiety. With an excess of water, the hydrolysis of L1 and L2 as well as their Rh-complexes is first-order with respect to the phosphite. Surprisingly, coordination to Rh significantly stabilizes the monodentate ligand L2, while in strong contrast, the bidentate ligand L1 decomposes faster in the Rh complex. NMR spectroscopy provided evidence for the existence of species from decomposition of phosphites, which can likewise coordinate as ligands to the metal. Electron-withdrawing groups in the periphery of the acylphosphite moiety decrease the stability of L1, whereas 3,5-disubstituted salicylic acid derivatives with bulky groups showed superior stability. These modifications of L1 also give rise to different catalytic performances in the n-regioselective hydroformylation of n-octenes and 2-pentene, from which the 3,5-di-t-butyl-substituted ligand offered a higher n-regioselectivity accompanied by a lowering of the reaction rate in comparison to the parent ligand L1.
- ItemUnraveling the H2 Promotional Effect on Palladium-Catalyzed CO Oxidation Using a Combination of Temporally and Spatially Resolved Investigations(Washington, DC : ACS, 2018) Stewart, Caomhán; Gibson, Emma K.; Morgan, Kevin; Cibin, Giannantonio; Dent, Andrew J.; Hardacre, Christopher; Kondratenko, Evgenii V.; Kondratenko, Vita A.; McManus, Colin; Rogers, Scott; Stere, Cristina E.; Chansai, Sarayute; Wang, Yi-Chi; Haigh, Sarah J.; Wells, Peter P.; Goguet, AlexandreThe promotional effect of H2 on the oxidation of CO is of topical interest, and there is debate over whether this promotion is due to either thermal or chemical effects. As yet there is no definitive consensus in the literature. Combining spatially resolved mass spectrometry and X-ray absorption spectroscopy (XAS), we observe a specific environment of the active catalyst during CO oxidation, having the same specific local coordination of the Pd in both the absence and presence of H2. In combination with Temporal Analysis of Products (TAP), performed under isothermal conditions, a mechanistic insight into the promotional effect of H2 was found, providing clear evidence of nonthermal effects in the hydrogen-promoted oxidation of carbon monoxide. We have identified that H2 promotes the Langmuir-Hinshelwood mechanism, and we propose this is linked to the increased interaction of O with the Pd surface in the presence of H2. This combination of spatially resolved MS and XAS and TAP studies has provided previously unobserved insights into the nature of this promotional effect.
- ItemOxygen-deficient oxide growth by subliming the oxide source material: The cause of silicide formation in rare earth oxides on silicon(Washington, DC : ACS, 2013) Bierwagen, O.; Proessdorf, A.; Niehle, M.; Grosse, F.; Trampert, A.; Klingsporn, M.The fundamental issue of oxygen stoichiometry in oxide thin film growth by subliming the source oxide is investigated by varying the additionally supplied oxygen during molecular beam epitaxy of RE2O3 (RE = Gd, La, Lu) thin films on Si(111). Supplying additional oxygen throughout the entire growth was found to prevent the formation of rare earth silicides observed in films grown without an oxygen source. Postgrowth vacuum annealing of oxygen stoichiometric films did not lead to silicide formation thereby confirming that the silicides do not form as a result of an interface instability at growth temperature in vacuum but rather due to an oxygen deficiency in the source vapor. The average oxygen deficiency of the rare-earth containing species in the source vapor was quantified by the 18O tracer technique and correlated with that of the source material, which gradually decomposed during sublimation. Therefore, any oxide growth by sublimation of the oxide source material requires additional oxygen to realize oxygen stoichiometric films.
- ItemSynthesis, in Vitro Profiling, and in Vivo Evaluation of Benzohomoadamantane-Based Ureas for Visceral Pain: A New Indication for Soluble Epoxide Hydrolase Inhibitors(Washington, DC : ACS, 2022) Codony, Sandra; Entrena, José M.; Calvó-Tusell, Carla; Jora, Beatrice; González-Cano, Rafael; Osuna, Sílvia; Corpas, Rubén; Morisseau, Christophe; Pérez, Belén; Barniol-Xicota, Marta; Griñán-Ferré, Christian; Pérez, Concepción; Rodríguez-Franco, María Isabel; Martínez, Antón L.; Loza, M. Isabel; Pallàs, Mercè; Verhelst, Steven H. L.; Sanfeliu, Coral; Feixas, Ferran; Hammock, Bruce D.; Brea, José; Cobos, Enrique J.; Vázquez, SantiagoThe soluble epoxide hydrolase (sEH) has been suggested as a pharmacological target for the treatment of several diseases, including pain-related disorders. Herein, we report further medicinal chemistry around new benzohomoadamantane-based sEH inhibitors (sEHI) in order to improve the drug metabolism and pharmacokinetics properties of a previous hit. After an extensive in vitro screening cascade, molecular modeling, and in vivo pharmacokinetics studies, two candidates were evaluated in vivo in a murine model of capsaicin-induced allodynia. The two compounds showed an anti-allodynic effect in a dose-dependent manner. Moreover, the most potent compound presented robust analgesic efficacy in the cyclophosphamide-induced murine model of cystitis, a well-established model of visceral pain. Overall, these results suggest painful bladder syndrome as a new possible indication for sEHI, opening a new range of applications for them in the visceral pain field.
- ItemTracing Active Sites in Supported Ni Catalysts during Butene Oligomerization by Operando Spectroscopy under Pressure(Washington, DC : ACS, 2016) Rabeah, Jabor; Radnik, Jörg; Briois, Valérie; Maschmeyer, Dietrich; Stochniol, Guido; Peitz, Stephan; Reeker, Helene; La Fontaine, Camille; Brückner, AngelikaSupported Ni catalysts have been studied during the dimerization of butenes by operando electron paramagnetic resonance (EPR) and in situ X-ray absorption spectroscopy (XAS) at 353 K and up to 16 bar. Single NiI/NiII shuttles were identified as active sites, whereby the conversion of initial NiI to NiII by oxidative addition of butene is obviously faster than the re-reduction of NiII to NiI by reductive elimination of the C8 product, rendering the equilibrium percentage of NiI small. At p ≤ 2 bar, NiI single sites form inactive Ni0 aggregates, while this is suppressed at higher pressure (∼12 bar). A reaction mechanism is proposed.
- ItemMapping Nanoscale Absorption of Femtosecond Laser Pulses Using Plasma Explosion Imaging(Washington, DC : ACS, 2014) Hickstein, Daniel D.; Dollar, Franklin; Ellis, Jennifer L.; Schnitzenbaumer, Kyle J.; Keister, K. Ellen; Petrov, George M.; Ding, Chengyuan; Palm, Brett B.; Gaffney, Jim A.; Foord, Mark E.; Libby, Stephen B.; Dukovic, Gordana; Jimenez, Jose L.; Kapteyn, Henry C.; Murnane, Margaret M.; Xiong, WeiWe make direct observations of localized light absorption in a single nanostructure irradiated by a strong femtosecond laser field, by developing and applying a technique that we refer to as plasma explosion imaging. By imaging the photoion momentum distribution resulting from plasma formation in a laser-irradiated nanostructure, we map the spatial location of the highly localized plasma and thereby image the nanoscale light absorption. Our method probes individual, isolated nanoparticles in vacuum, which allows us to observe how small variations in the composition, shape, and orientation of the nanostructures lead to vastly different light absorption. Here, we study four different nanoparticle samples with overall dimensions of ∼100 nm and find that each sample exhibits distinct light absorption mechanisms despite their similar size. Specifically, we observe subwavelength focusing in single NaCl crystals, symmetric absorption in TiO2 aggregates, surface enhancement in dielectric particles containing a single gold nanoparticle, and interparticle hot spots in dielectric particles containing multiple smaller gold nanoparticles. These observations demonstrate how plasma explosion imaging directly reveals the diverse ways in which nanoparticles respond to strong laser fields, a process that is notoriously challenging to model because of the rapid evolution of materials properties that takes place on the femtosecond time scale as a solid nanostructure is transformed into a dense plasma. (Figure Presented).
- Item3D-Printed Self-Folding Electronics(Washington, DC : ACS, 2017) Sundaram, Subramanian; Kim, David S.; Baldo, Marc A.; Hayward, Ryan C.; Matusik, WojciechSelf-transforming structures are gaining prominence due to their general ability to adopt programmed shapes each tailored for specific functions. Composites that self-fold have so far relied on using the stimuli-responsive mechanisms focusing on reversible shape change. Integrating additional functions within these composites can rapidly enhance their practical applicability; however, this remains a challenging problem. Here, we demonstrate a method for spontaneous folding of three-dimensional (3D)-printed composites with embedded electronics at room temperature. The composite is printed using a multimaterial 3D-printing process with no external processing steps. Upon peeling from the print platform, the composite self-shapes itself using the residual forces resulting from polymer swelling during the layer-by-layer fabrication process. As a specific example, electrochromic elements are printed within the composite and can be electrically controlled through its folded legs. Our shape-transformation scheme provides a route to transform planar electronics into nonplanar geometries containing the overhangs. Integrating electronics within complex 3D shapes can enable new applications in sensing and robotics.