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11.
Dustin T. Savage Nicolas J. Briot J. Zach Hilt Thomas D. Dziubla 《Journal of polymer science. Part A, Polymer chemistry》2021,59(4):289-299
Per- and polyfluoroalkyl substances (PFAS) have rapidly accumulated in the environment due to their widespread use prior to commercial discussion in the early 21st century, and their slow degradation has magnified concerns of their potential toxicity. Monitoring their distribution is, therefore, necessary to evaluate and control their impact on the health of exposed populations. This investigation evaluates the capability of a simple polymeric detection scheme for PFAS based on crosslinked, thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) hydrogels. Surveying swelling perturbations induced by several hydrotropes and comparable hydrocarbon analogs, tetraethylammonium perfluorooctane sulfonate (TPFOS) showed a significantly higher swelling ratio on a mass basis (65.5 ± 8.8 at 15°C) than any of the other analytes tested. Combining swelling with the fluorimetric response of a solvachromatic dye, nile red, revealed the fluorosurfactant to initiate observable aggregation (i.e., its critical aggregation concentration) at 0.05 mM and reach saturation (i.e., its charge neutralization concentration) at 0.5 mM. The fluorosurfactant was found to homogeneously distribute throughout the polymer matrix with energy dispersive X-ray spectroscopy, marking the swelling response as a peculiar nexus of fluorinated interfacial positioning and delocalized electrostatic repulsion. Results from the current study hold promise for exploiting the physiochemical response of PNIPAM to assess TPFOS's concentration. 相似文献
12.
In this paper we prove that weak solutions to the Diffusive Wave Approximation of the Shallow Water equations are locally bounded. Here, u describes the height of the water, z is a given function that represents the land elevation and f is a source term accounting for evaporation, infiltration or rainfall. 相似文献
13.
Thomas Marmin Prof. Yves L. Dory 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(27):6707-6711
Cyclohexane and cyclotri-β-alanyl have been used as scaffolds for the design of new C3-symmetric rings incorporating conjugated alkenes and dienes. All three C3-symmetric lactams share the same triangular shape and their crystal system is trigonal. They all belong to the R3 space group, R3m, R3 and R3c, for the increasingly large 12-, 18- and 24-membered rigid rings, respectively. All lactams stack on top of each other, through H-bonds and van der Waals noncovalent interactions, leading to endless supramolecular cylinders and tubes. The largest member of the family leads to tubes, the central pores of which is wide enough to let water in. A common feature of all the lactams is their very large dipole, of around 9 D, according to DFT calculations. Surprisingly, all the resulting cylinders and tubes pack side by side in the crystals, with all the dipoles pointing to the same direction. As a result, all three crystals are anisotropic and appear to be the first members of a new kind of highly polar crystals. 相似文献
14.
Dr. Ritesh Haldar Kamal Batra Stefan Michael Marschner Dr. Agnieszka B. Kuc Dr. Stefan Zahn Prof. Dr. Roland A. Fischer Prof. Dr. Stefan Bräse Prof. Dr. Thomas Heine Prof. Dr. Christof Wöll 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(33):7847-7851
In organic photovoltaics, porphyrins (PPs) are among the most promising compounds owing to their large absorption cross-section, wide spectral range, and stability. Nevertheless, a precise adjustment of absorption band positions to reach a full coverage of the so-called green gap has not been achieved yet. We demonstrate that a tuning of the PP Q- and Soret bands can be carried out by using a computational approach for which substitution patterns are optimized in silico. The most promising candidate structures were then synthesized. The experimental UV/Vis data for the solvated compounds were in excellent agreement with the theoretical predictions. By attaching further functionalities, which allow the use of PP chromophores as linkers for the assembly of metal-organic frameworks (MOFs), we were able to exploit packing effects resulting in pronounced redshifts, which allowed further optimization of the photophysical properties of PP assemblies. Finally, we use a layer-by-layer method to assemble the PP linkers into surface-mounted MOFs (SURMOFs), thus obtaining high optical quality, homogeneous and crystalline multilayer films. Experimental results are in full accord with the calculations, demonstrating the huge potential of computational screening methods in tailoring MOF and SURMOF photophysical properties. 相似文献
15.
Oliver Back Dr. Christoph Förster Prof. Dr. Thomas Basché Prof. Dr. Katja Heinze 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(26):6542-6552
2-Iminopyrroles [HtBuL, 4-tert-butyl phenyl(pyrrol-2-ylmethylene)amine] are non-fluorescent π systems. However, they display blue fluorescence after deprotonation with alkali metal bases in the solid state and in solution at room temperature. In the solid state, the alkali metal 2-imino pyrrolates, M(tBuL), aggregate to dimers, [M(tBuL)(NCR)]2 (M=Li, R=CH3, CH(CH3)CNH2), or polymers, [M(tBuL)]n (M=Na, K). In solution (solv=CH3CN, DMSO, THF, and toluene), solvated, uncharged monomeric species M(tBuL)(solv)m with N,N′-chelated alkali metal ions are present. Due to the electron-rich pyrrolate and the electron-poor arylimino moiety, the M(tBuL) chromophore possesses a low-energy intraligand charge-transfer (ILCT) excited state. The chelated alkali cations rigidify the chromophore, restricting intramolecular motions (RIM) by the chelation-enhanced fluorescence (CHEF) effect in solution and, consequently, switch-on a blue fluorescence emission. 相似文献
16.
For a permanently manned outpost on the moon – a moon village – a first holistic concept of a sustainable material flow has been established. From this context three dedicated topics have been investigated to more depth: Additive manufacturing (AM) of Al from disused space crafts, AM of structural elements with local resources, and resource extraction from regolith via thermal processes. 相似文献
17.
In a previous study (Stahl and Bredow, Chem. Phys. Lett. 2018, 695, 28–33), we have studied structural, energetic, and electronic properties of two vanadium dioxide VO2 polymorphs with modified global and range-separated hybrid functionals. Since hybrid methods are computationally demanding, we evaluate the computationally more efficient DFT + U method in the present study. We assessed the widely used Dudarev PBE + U approach with a literature value of the effective Hubbard parameter Ueff = 3.4 eV. We compared the PBE + U results for the two VO2 polymorphs with our previous results, a self-consistent hybrid functional sc-PBE0, and the meta-GGA functional SCAN. It was found that the PBE + U method yields a strongly distorted monoclinic phase and does not reproduce the metal-to-insulator transition of VO2 correctly, even with modified values of Ueff. On the other hand, sc-PBE0 and SCAN describe the relative stability and the electronic structure of both polymorphs correctly and also provide reasonable lattice parameters. The functional SCAN yields the optimal balance between computational efficiency and accuracy. © 2019 The Authors. Journal of Computational Chemistry published by Wiley Periodicals, Inc. 相似文献
18.
Analytical and Bioanalytical Chemistry - 相似文献
19.