How Tuning Interfaces Impacts the Dynamics and Structure of Polymer Nanocomposites Simultaneously

Fundamental understanding of macroscopic properties of polymer nanocomposites (PNCs) remains difficult due to the complex interplay of microscopic dynamics and structure, namely interfacial layer relaxations and three-dimensional nanoparticle arrangements. The effect of surface modification by alkyl methoxysilanes at different grafting densities has been studied in PNCs made of poly(2-vinylpyridine) and spherical 20 nm silica nanoparticles (NPs). The segmental dynamics has been probed by broadband dielectric spectroscopy, and the filler structure by small-angle X-ray scattering and reverse Monte Carlo simulations. By combining the particle configurations with the interfacial layer properties, it is shown how surface modification tunes the attractive polymer-particle interactions: bare NPs slow down the polymer interfacial layer dynamics over a thickness of ca. 5 nm, while grafting screens these interactions. Our analysis of interparticle spacing and segmental dynamics provides unprecedented insight into the effect of surface modification on the main characteristics of PNCs: particle interactions and polymer interfacial layers

Discovery and engineering of nylon hydrolases for PA66 recycling

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Enzymatic AND Logic Gates Operated Under Conditions Characteristic of Biomedical Applications

Experimental and theoretical analyses of the lactate dehydrogenase and glutathione reductase based enzymatic AND logic gates in which the enzymes and their substrates serve as logic inputs are performed. These two systems are examples of the novel, previously unexplored, class of biochemical logic gates that illustrate potential biomedical applications of biochemical logic. They are characterized by input concentrations at logic 0 and 1 states corresponding to normal and abnormal physiological conditions. Our analysis shows that the logic gates under investigation have similar noise characteristics. Both significantly amplify random noise present in inputs, however we establish that for realistic widths of the input noise distributions, it is still possible to differentiate between the logic 0 and 1 states of the output. This indicates that reliable detection of abnormal biomedical conditions is indeed possible with such enzyme-logic systems.Comment: PDF, 29 page

Single-Ion Conducting Polymer Nanoparticles as Functional Fillers for Solid Electrolytes in Lithium Metal Batteries

[EN]Composite solid electrolytes including inorganic nanoparticles or nanofibers which improve the performance of polymer electrolytes due to their superior mechanical, ionic conductivity, or lithium transference number are actively being researched for applications in lithium metal batteries. However, inorganic nanoparticles present limitations such as tedious surface functionalization and agglomeration issues and poor homogeneity at high concentrations in polymer matrixes. In this work, we report on polymer nanoparticles with a lithium sulfonamide surface functionality (LiPNP) for application as electrolytes in lithium metal batteries. The particles are prepared by semibatch emulsion polymerization, an easily up-scalable technique. LiPNPs are used to prepare two different families of particle-reinforced solid electrolytes. When mixed with poly(ethylene oxide) and lithium bis(trifluoromethane)sulfonimide (LiTFSI/PEO), the particles invoke a significant stiffening effect (E' > 106 Pa vs 105 Pa at 80 °C) while the membranes retain high ionic conductivity (sigma = 6.6 * 10-4 S cm-1). Preliminary testing in LiFePO4 lithium metal cells showed promising performance of the PEO nanocomposite electrolytes. By mixing the particles with propylene carbonate without any additional salt, we obtain true single-ion conducting gel electrolytes, as the lithium sulfonamide surface functionalities are the only sources of lithium ions in the system. The gel electrolytes are mechanically robust (up to G' = 106 Pa) and show ionic conductivity up to 10-4 S cm-1. Finally, the PC nanocomposite electrolytes were tested in symmetrical lithium cells. Our findings suggest that all-polymer nanoparticles could represent a new building block material for solid-state lithium metal battery applications.L.P. has received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska–Curie grant agreement no. 797295. P.S. has been funded by the SNSF (Swiss National Science Foundation) under project number P2FRP2_191846. J.R.L. and D.M. acknowledge the funding by the Basque Government (IT99-16). V.B. acknowledges support from the Laboratory Directed Research and Development Program of Oak Ridge National Laboratory (ORNL), managed by UT-Battelle, LLC, for the U.S. Department of Energy under contract no. DE-AC05-00OR22725. A.S. acknowledges financial support for dielectric measurements and data discussions by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division

Task-Specific Phosphonium Iongels by Fast UV-Photopolymerization for Solid-State Sodium Metal Batteries

Sodium metal batteries are an emerging technology that shows promise in terms of materials availability with respect to lithium batteries. Solid electrolytes are needed to tackle the safety issues related to sodium metal. In this work, a simple method to prepare a mechanically robust and efficient soft solid electrolyte for sodium batteries is demonstrated. A task-specific iongel electrolyte was prepared by combining in a simple process the excellent performance of sodium metal electrodes of an ionic liquid electrolyte and the mechanical properties of polymers. The iongel was synthesized by fast (<1 min) UV photopolymerization of poly(ethylene glycol) diacrylate (PEGDA) in the presence of a saturated 42%mol solution of sodium bis(fluorosulfonyl)imide (NaFSI) in trimethyl iso-butyl phosphonium bis(fluorosulfonyl)imide (P111i4FSI). The resulting soft solid electrolytes showed high ionic conductivity at room temperature (≥10−3 S cm−1) and tunable storage modulus (104–107 Pa). Iongel with the best ionic conductivity and good mechanical properties (Iongel10) showed excellent battery performance: Na/iongel/NaFePO4 full cells delivered a high specific capacity of 140 mAh g−1 at 0.1 C and 120 mAh g−1 at 1 C with good capacity retention after 30 cycles.L.P. has received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska–Curie grant agreement No. 797295. P.S. has been funded by the SNSF (Swiss National Science Foundation) under project number P2FRP2_191846. D.M., M.G., and A.F.A. acknowledge the funding by the Basque Government through Elkartek KK-2020/00078 and Agencia Estatal de Investigación (PLEC2021-007929). D.M. and M.G. also acknowledge the funding by Agencia Estatal de Investigación (PID2020-119026GB-100 and PID2019-107468RB-C22), respectively. A.P.S. acknowledges financial support for dielectric measurements and data discussions by NSF (award CHE-2102425)

Orally Bioavailable Androgen Receptor Degrader, Potential Next-Generation Therapeutic for Enzalutamide-Resistant Prostate Cancer

Acknowledgement. BGS acknowledges work performed at the Center for Nanophase Materials Sciences, a DOE Office of Science User Facility. VB acknowledges Laboratory Directed Research and Development program of Oak Ridge National Laboratory, managed by UTBattelle, LLC, for the U.S. Department of Energy.Peer reviewedPostprin