Despite their charge neutrality, micelles composed of surfactants with zwitterionic headgroups selectively accumulate anions at their hydrophobic core/solution interphase due to electrostatic interactions if headgroup positive moieties are the innermost. This tendency may be markedly enhanced if polyions substitute simple ions. To investigate this possibility, solutions composed of zwitterionic micelles and hydrophilic polyanions have been investigated with Monte Carlo simulations representing the studied systems via primitive electrolyte models. Structural and energetic properties are obtained to highlight the impact of connecting simple ions into polyions on the interactions between electrolytes and micelles. Despite the latter, polyanions conserve their conformational properties. A marked increase in the concentration of charged species inside the micellar corona is, instead, found when polyions are present independently of their charge sign or the headgroup structure. Thus, polyelectrolytes act as "shuttle" for all charged species, with the potential of increasing reactions rates involving the latter due to mass effects. Besides, results for the polyions/micelles mixing free energy and Helmholtz energy profiles indicate that the critical micelle concentration is impacted minimally by hydrophilic polyelectrolytes, an outcome agreeing with experiments. This finding is entirely due to weak enthalpic effects while mixing hydrophilic polyions and micelles. A strong reduction in the screening of the micelle negative charge, acquired following the adsorption of anions in the corona and due to counterions layering just outside it (the so called "chameleon effect"), is forecasted when polyanions substitute monovalent anions.(-)-Homo-renieramycin G and its twenty derivatives were prepared from l-tyrosine methyl ester via a multi-step route. Their cytotoxicities were tested against four human cancer cell lines (A549, HeLa, KB and ****823). (-)-Renieramycin G and (-)-homo-renieramycin G showed comparable cytotoxicity against these four cancer cell lines, which indicated that the expansion of ring C from the six-membered 1,4-piperazinone to the seven-membered 1,4-diazepanone had no obvious impact on the cytotoxicity. Compound 42 with methyl side chain and compounds 38-41 with heterocyclic aromatic side chains at C-23 exhibited the most potent cytotoxicity with the IC50 values at the level of 10-6 M.The superparamagnetic magnetite nanoparticles have broad application prospects in the diagnosis and treatment of cancer. Herein, a series of monodispersed exceptionally small-sized superparamagnetic magnetite nanoparticles (ESM NPs) with tunable size were synthesized through thermal decomposition of an iron precursor by simply changing the reaction temperature and stabilizing agents. The underlying mechanisms of regulating the size and properties of ESM NPs were studied. The surface of hydrophobic ESM NPs was modified with a carboxyl-polyethylene glycol-phosphoric acid ligand, and the obtained water-soluble ESM NPs showed extremely high long-term stability under various aqueous environments and physiological conditions. The hemolysis and cytotoxicity evaluations showed that the ESM NPs had good blood compatibility and no obvious cytotoxicity. The 2.3 nm ESM NPs exhibited an extremely high longitudinal relaxivity (r1) of 6.0 mM-1 s-1, which was higher than that of the clinical gadolinium complex contrast agent (r1 = 3.8 mM-1 s-1), and had an appropriate r2/r1 ratio of 4.0. The in vivo results showed that the nanoparticles exhibited superior contrast effects in both T1 and T2 MR imaging, as well as high-resolution contrast in MR angiography. This study provides a general strategy for the controlled synthesis of ESM NPs and reveals the size and property regulation mechanisms, which undoubtedly provides the possibility of designing highly sensitive MR imaging probes based on small-sized magnetic nanoparticles for clinical diagnostic applications.For the efficient evolution of hydrogen, we designed a 3D quaternary BaCuZnS-graphene-TiO2 (BCZS-G-T) composite by an ultrasonic method. https://www.selleckchem.com/products/osmi-1.html Herein, we prepared a quaternary material to minimize the bandgap energy and size. We characterized the "as-prepared" composites by X-ray diffraction (XRD), scanning electron microscopy (SEM) with energy dispersive X-ray (EDX) analysis, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), UV-vis diffuse reflectance spectroscopy (DRS), photoluminescence (PL) spectroscopy, and electrochemical impedance spectroscopy (EIS). The high hydrogen evolution was attributed to the 3D quaternary BCZS-G-T composite with small bandgap energy because of its high photoelectron recombination properties. In addition, we demonstrated the combination effects with photocatalytic and sonocatalytic treatments with a scavenger. This work highlights the potential application of quaternary graphene-based composites in the field of energy conversion.Keto-substituted 1,2-cyclohexadienes were generated by base-mediated (KOt-Bu) elimination, and found to dimerize via an unprecedented formal hetero-Diels-Alder process, followed by hydration. These highly reactive cyclic allene intermediates were also trapped in Diels-Alder reactions by furan, 2,5-dimethylfuran, or diphenylisobenzofuran to afford cycloadducts with high regio- and diastereoselectivity, and could also be intercepted in a hetero-Diels-Alder process with enamine dienophiles. Endo/exo stereochemistry was unambiguously determined via X-ray crystallography in the case of nitrile-substituted 1,2-cyclohexadiene. DFT calculations indicate that the novel hetero-Diels-Alder processes observed with these allenes occur via a concerted asynchronous cycloaddition mechanism.This research provides an atomic-level insight into the synergic contribution of mono- and divalent ions to interfacial characteristics of calcite surfaces exposed to electrolyte solution containing organic compounds. The emphasis was placed on the ionic interactions responsible for charge developing mechanisms of calcite surfaces and also the capacity for adsorption of polar hydrocarbons, represented by benzoic acid (BA), at different brine compositions. For this purpose, molecular dynamics (MD) simulations were employed to explore the interplay of the main constituent ions of natural brines (Na+, Cl-, Mg2+, and SO42-) and BA at the interface of CaCO3. It was observed that surface accumulation of Na+ cations produces a positively charged layer immediate to the basal plane of calcite, validating the typical positive surface charge of carbonates reported by laboratory experiences. Meanwhile, a negatively charged layer appears beyond the sodium layer as a result of direct and solvent-mediated pairing of anions with Na+ cations lodged on the calcite substrate.
Despite their charge neutrality, micelles composed of surfactants with zwitterionic headgroups selectively accumulate anions at their hydrophobic core/solution interphase due to electrostatic interactions if headgroup positive moieties are the innermost. This tendency may be markedly enhanced if polyions substitute simple ions. To investigate this possibility, solutions composed of zwitterionic micelles and hydrophilic polyanions have been investigated with Monte Carlo simulations representing the studied systems via primitive electrolyte models. Structural and energetic properties are obtained to highlight the impact of connecting simple ions into polyions on the interactions between electrolytes and micelles. Despite the latter, polyanions conserve their conformational properties. A marked increase in the concentration of charged species inside the micellar corona is, instead, found when polyions are present independently of their charge sign or the headgroup structure. Thus, polyelectrolytes act as "shuttle" for all charged species, with the potential of increasing reactions rates involving the latter due to mass effects. Besides, results for the polyions/micelles mixing free energy and Helmholtz energy profiles indicate that the critical micelle concentration is impacted minimally by hydrophilic polyelectrolytes, an outcome agreeing with experiments. This finding is entirely due to weak enthalpic effects while mixing hydrophilic polyions and micelles. A strong reduction in the screening of the micelle negative charge, acquired following the adsorption of anions in the corona and due to counterions layering just outside it (the so called "chameleon effect"), is forecasted when polyanions substitute monovalent anions.(-)-Homo-renieramycin G and its twenty derivatives were prepared from l-tyrosine methyl ester via a multi-step route. Their cytotoxicities were tested against four human cancer cell lines (A549, HeLa, KB and BGC-823). (-)-Renieramycin G and (-)-homo-renieramycin G showed comparable cytotoxicity against these four cancer cell lines, which indicated that the expansion of ring C from the six-membered 1,4-piperazinone to the seven-membered 1,4-diazepanone had no obvious impact on the cytotoxicity. Compound 42 with methyl side chain and compounds 38-41 with heterocyclic aromatic side chains at C-23 exhibited the most potent cytotoxicity with the IC50 values at the level of 10-6 M.The superparamagnetic magnetite nanoparticles have broad application prospects in the diagnosis and treatment of cancer. Herein, a series of monodispersed exceptionally small-sized superparamagnetic magnetite nanoparticles (ESM NPs) with tunable size were synthesized through thermal decomposition of an iron precursor by simply changing the reaction temperature and stabilizing agents. The underlying mechanisms of regulating the size and properties of ESM NPs were studied. The surface of hydrophobic ESM NPs was modified with a carboxyl-polyethylene glycol-phosphoric acid ligand, and the obtained water-soluble ESM NPs showed extremely high long-term stability under various aqueous environments and physiological conditions. The hemolysis and cytotoxicity evaluations showed that the ESM NPs had good blood compatibility and no obvious cytotoxicity. The 2.3 nm ESM NPs exhibited an extremely high longitudinal relaxivity (r1) of 6.0 mM-1 s-1, which was higher than that of the clinical gadolinium complex contrast agent (r1 = 3.8 mM-1 s-1), and had an appropriate r2/r1 ratio of 4.0. The in vivo results showed that the nanoparticles exhibited superior contrast effects in both T1 and T2 MR imaging, as well as high-resolution contrast in MR angiography. This study provides a general strategy for the controlled synthesis of ESM NPs and reveals the size and property regulation mechanisms, which undoubtedly provides the possibility of designing highly sensitive MR imaging probes based on small-sized magnetic nanoparticles for clinical diagnostic applications.For the efficient evolution of hydrogen, we designed a 3D quaternary BaCuZnS-graphene-TiO2 (BCZS-G-T) composite by an ultrasonic method. https://www.selleckchem.com/products/osmi-1.html Herein, we prepared a quaternary material to minimize the bandgap energy and size. We characterized the "as-prepared" composites by X-ray diffraction (XRD), scanning electron microscopy (SEM) with energy dispersive X-ray (EDX) analysis, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), UV-vis diffuse reflectance spectroscopy (DRS), photoluminescence (PL) spectroscopy, and electrochemical impedance spectroscopy (EIS). The high hydrogen evolution was attributed to the 3D quaternary BCZS-G-T composite with small bandgap energy because of its high photoelectron recombination properties. In addition, we demonstrated the combination effects with photocatalytic and sonocatalytic treatments with a scavenger. This work highlights the potential application of quaternary graphene-based composites in the field of energy conversion.Keto-substituted 1,2-cyclohexadienes were generated by base-mediated (KOt-Bu) elimination, and found to dimerize via an unprecedented formal hetero-Diels-Alder process, followed by hydration. These highly reactive cyclic allene intermediates were also trapped in Diels-Alder reactions by furan, 2,5-dimethylfuran, or diphenylisobenzofuran to afford cycloadducts with high regio- and diastereoselectivity, and could also be intercepted in a hetero-Diels-Alder process with enamine dienophiles. Endo/exo stereochemistry was unambiguously determined via X-ray crystallography in the case of nitrile-substituted 1,2-cyclohexadiene. DFT calculations indicate that the novel hetero-Diels-Alder processes observed with these allenes occur via a concerted asynchronous cycloaddition mechanism.This research provides an atomic-level insight into the synergic contribution of mono- and divalent ions to interfacial characteristics of calcite surfaces exposed to electrolyte solution containing organic compounds. The emphasis was placed on the ionic interactions responsible for charge developing mechanisms of calcite surfaces and also the capacity for adsorption of polar hydrocarbons, represented by benzoic acid (BA), at different brine compositions. For this purpose, molecular dynamics (MD) simulations were employed to explore the interplay of the main constituent ions of natural brines (Na+, Cl-, Mg2+, and SO42-) and BA at the interface of CaCO3. It was observed that surface accumulation of Na+ cations produces a positively charged layer immediate to the basal plane of calcite, validating the typical positive surface charge of carbonates reported by laboratory experiences. Meanwhile, a negatively charged layer appears beyond the sodium layer as a result of direct and solvent-mediated pairing of anions with Na+ cations lodged on the calcite substrate.
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