9) and enabled site-specific delivery in the small intestine (pH 6.8). Cellular uptake results in RAW 264.7 macrophage, Caco-2, and LS174T cells confirming the efficient cellular uptake of nanoparticles in all three cell lines. More importantly, the bidirectional transport (absorptive and secretory) of MER across Caco-2 monolayer was significantly improved for both MSN-based formulations, particularly MSNs coated with a polymer (Eud-MER-MCM-NH2) where permeability was significantly enhanced (∼2.4-fold) for absorptive transport and significantly reduced (∼1.8-fold) for secretory transport. Finally, in vitro antibacterial activity [minimum inhibitory concentration (MIC)] and time-kill assay against S. aureus and P. aeruginosa showed that drug-loaded nanoparticles were able to retain antibacterial activity comparable to that of free MER in a solution at equivalent dose. Thus, Eudragit-coated silica nanoparticles could offer a promising and novel solution for oral delivery of Meropenem and other such drugs.We present an enhanced catalytic efficiency of palladium (Pd) nanoparticles (NPs) for the electrocatalytic hydrodechlorination (EHDC) reaction by incorporating the tetraethylammonium chloride (TEAC) ligand into the surface of NPs. Both experimental and theoretical analyses reveal that the surface-adsorbed TEAC is converted to molecular amine (primarily triethylamine) under reductive potentials, forming a strong ligand-Pd interaction that is beneficial to the EHDC kinetics. Using the EHDC of 2,4-dichlorophenol (2,4-DCP), a dominant persistent pollutant identified by the U.S. Environmental Protection Agency, as an example, the Pd/amine composite delivers a mass activity of 2.32 min-1 gPd-1 and a specific activity of 0.16 min-1 cm-2 at -0.75 V versus Ag/AgCl, outperforming Pd and most of the previously reported catalysts. The mechanistic study reveals that the amine ligand offers three functions the H+-pumping effect, the electronic effect, and the steric effect, providing a favorable environment for the generation of reactive hydrogen radicals (H*) for hydrogenolysis of the C-Cl bond. It also weakens the adsorption strength of EHDC products, alleviating their poisoning on Pd. Investigation into the intermediate products of EHDC on Pd/amine and the biological safety of the 2,4-DCP-contaminated water after EHDC treatment demonstrates that EHDC on Pd/amine is environmentally benign for halogenated organic pollutant abatement. This work suggests that the tuning of NP catalysis using facile ligand post-treatment may lead to new strategies to improve EHDC for environmental remediation applications.The knowledge concerning the influence of defects on the nonlinear optical response of materials remains scarce so far. In this work, we have successfully introduced defects into SnS2 nanosheets by plasma treatment and shown that a defect generation is an effective approach to significantly improve the reverse saturable absorption of SnS2. The SnS2 nanosheets treated with Ar plasma for 40 s exhibit a nonlinear absorption coefficient (β0) as large as (2.9 ± 0.12) × 104 cm GW-1, which is nearly 9 times that of the untreated sample. https://www.selleckchem.com/products/blu-451.html The influence of Ar-plasma-treatment time, defect type, and defect number on the nonlinear absorption of SnS2 nanosheets are also studied. Structure and spectroscopy characterization confirms the introduction of S and Sn vacancies with Ar-plasma etching. Surface photovoltage spectroscopy and density functional theory calculation indicate that S vacancies can induce in-gap states in the band gap. These in-gap states act as intermediate states for the successive absorption of photons during femtosecond laser excitation (namely, excited-state absorption). In contrast, Sn defects cannot lead to in-gap states and have a limited contribution to nonlinear absorption. Our result would provide a promising way to improve optical nonlinearities.The properties and, hence, the application of materials are dependent on the way their constituent atoms are arranged. Here, we report a facile approach to produce body-centered cubic (bcc) and face-centered cubic (fcc) phases of bimetallic FeCo crystalline nanoparticles embedded into nitrogen-doped carbon nanotubes (NCNTs) with equal loading and almost similar particle size for both crystalline phases by a rational selection of precursors. The two electrocatalysts with similar composition but different crystalline structures of the encapsulated nanoparticles have allowed us, for the first time, to account for the effect of crystal structure on the overall work function of electrocatalysts and the concomitant correlation with the oxygen reduction reaction (ORR). This study unveils that the electrocatalysts with lower work function show lower activation energy to facilitate the ORR. Importantly, the difference between the ORR activation energy on electrocatalysts and their respective work functions are found to be identical (∼0.2 eV). A notable decrease in the ORR activity after acid treatment indicates the significant role of encapsulated FeCo nanoparticles in influencing the oxygen electrochemistry by modulating the material property of overall electrocatalysts.The rational design of single-molecule electrical components requires a deep and predictive understanding of structure-function relationships. Here, we explore the relationship between chemical substituents and the conductance of metal-single-molecule-metal junctions, using functionalized oligophenylenevinylenes as a model system. Using a combination of mechanically controlled break-junction experiments and various levels of theory including non-equilibrium Green's functions, we demonstrate that the connection between gas-phase molecular electronic structure and in-junction molecular conductance is complicated by the involvement of multiple mutually correlated and opposing effects that contribute to energy-level alignment in the junction. We propose that these opposing correlations represent powerful new "design principles" because their physical origins make them broadly applicable, and they are capable of predicting the direction and relative magnitude of observed conductance trends. In particular, we show that they are consistent with the observed conductance variability not just within our own experimental results but also within disparate molecular series reported in the literature and, crucially, with the trend in variability across these molecular series, which previous simple models fail to explain.
9) and enabled site-specific delivery in the small intestine (pH 6.8). Cellular uptake results in RAW 264.7 macrophage, Caco-2, and LS174T cells confirming the efficient cellular uptake of nanoparticles in all three cell lines. More importantly, the bidirectional transport (absorptive and secretory) of MER across Caco-2 monolayer was significantly improved for both MSN-based formulations, particularly MSNs coated with a polymer (Eud-MER-MCM-NH2) where permeability was significantly enhanced (∼2.4-fold) for absorptive transport and significantly reduced (∼1.8-fold) for secretory transport. Finally, in vitro antibacterial activity [minimum inhibitory concentration (MIC)] and time-kill assay against S. aureus and P. aeruginosa showed that drug-loaded nanoparticles were able to retain antibacterial activity comparable to that of free MER in a solution at equivalent dose. Thus, Eudragit-coated silica nanoparticles could offer a promising and novel solution for oral delivery of Meropenem and other such drugs.We present an enhanced catalytic efficiency of palladium (Pd) nanoparticles (NPs) for the electrocatalytic hydrodechlorination (EHDC) reaction by incorporating the tetraethylammonium chloride (TEAC) ligand into the surface of NPs. Both experimental and theoretical analyses reveal that the surface-adsorbed TEAC is converted to molecular amine (primarily triethylamine) under reductive potentials, forming a strong ligand-Pd interaction that is beneficial to the EHDC kinetics. Using the EHDC of 2,4-dichlorophenol (2,4-DCP), a dominant persistent pollutant identified by the U.S. Environmental Protection Agency, as an example, the Pd/amine composite delivers a mass activity of 2.32 min-1 gPd-1 and a specific activity of 0.16 min-1 cm-2 at -0.75 V versus Ag/AgCl, outperforming Pd and most of the previously reported catalysts. The mechanistic study reveals that the amine ligand offers three functions the H+-pumping effect, the electronic effect, and the steric effect, providing a favorable environment for the generation of reactive hydrogen radicals (H*) for hydrogenolysis of the C-Cl bond. It also weakens the adsorption strength of EHDC products, alleviating their poisoning on Pd. Investigation into the intermediate products of EHDC on Pd/amine and the biological safety of the 2,4-DCP-contaminated water after EHDC treatment demonstrates that EHDC on Pd/amine is environmentally benign for halogenated organic pollutant abatement. This work suggests that the tuning of NP catalysis using facile ligand post-treatment may lead to new strategies to improve EHDC for environmental remediation applications.The knowledge concerning the influence of defects on the nonlinear optical response of materials remains scarce so far. In this work, we have successfully introduced defects into SnS2 nanosheets by plasma treatment and shown that a defect generation is an effective approach to significantly improve the reverse saturable absorption of SnS2. The SnS2 nanosheets treated with Ar plasma for 40 s exhibit a nonlinear absorption coefficient (β0) as large as (2.9 ± 0.12) × 104 cm GW-1, which is nearly 9 times that of the untreated sample. https://www.selleckchem.com/products/blu-451.html The influence of Ar-plasma-treatment time, defect type, and defect number on the nonlinear absorption of SnS2 nanosheets are also studied. Structure and spectroscopy characterization confirms the introduction of S and Sn vacancies with Ar-plasma etching. Surface photovoltage spectroscopy and density functional theory calculation indicate that S vacancies can induce in-gap states in the band gap. These in-gap states act as intermediate states for the successive absorption of photons during femtosecond laser excitation (namely, excited-state absorption). In contrast, Sn defects cannot lead to in-gap states and have a limited contribution to nonlinear absorption. Our result would provide a promising way to improve optical nonlinearities.The properties and, hence, the application of materials are dependent on the way their constituent atoms are arranged. Here, we report a facile approach to produce body-centered cubic (bcc) and face-centered cubic (fcc) phases of bimetallic FeCo crystalline nanoparticles embedded into nitrogen-doped carbon nanotubes (NCNTs) with equal loading and almost similar particle size for both crystalline phases by a rational selection of precursors. The two electrocatalysts with similar composition but different crystalline structures of the encapsulated nanoparticles have allowed us, for the first time, to account for the effect of crystal structure on the overall work function of electrocatalysts and the concomitant correlation with the oxygen reduction reaction (ORR). This study unveils that the electrocatalysts with lower work function show lower activation energy to facilitate the ORR. Importantly, the difference between the ORR activation energy on electrocatalysts and their respective work functions are found to be identical (∼0.2 eV). A notable decrease in the ORR activity after acid treatment indicates the significant role of encapsulated FeCo nanoparticles in influencing the oxygen electrochemistry by modulating the material property of overall electrocatalysts.The rational design of single-molecule electrical components requires a deep and predictive understanding of structure-function relationships. Here, we explore the relationship between chemical substituents and the conductance of metal-single-molecule-metal junctions, using functionalized oligophenylenevinylenes as a model system. Using a combination of mechanically controlled break-junction experiments and various levels of theory including non-equilibrium Green's functions, we demonstrate that the connection between gas-phase molecular electronic structure and in-junction molecular conductance is complicated by the involvement of multiple mutually correlated and opposing effects that contribute to energy-level alignment in the junction. We propose that these opposing correlations represent powerful new "design principles" because their physical origins make them broadly applicable, and they are capable of predicting the direction and relative magnitude of observed conductance trends. In particular, we show that they are consistent with the observed conductance variability not just within our own experimental results but also within disparate molecular series reported in the literature and, crucially, with the trend in variability across these molecular series, which previous simple models fail to explain.
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