89 research outputs found

    Hydroquinone-Mediated Redox Cycling of Iron and Concomitant Oxidation of Hydroquinone in Oxic Waters under Acidic Conditions: Comparison with Ironā€“Natural Organic Matter Interactions

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    Interactions of 1,4-hydroquinone with soluble iron species over a pH range of 3ā€“5 in the air-saturated and partially deoxygenated solution are examined here. Our results show that 1,4-hydroquinone reduces FeĀ­(III) in acidic conditions, generating semiquinone radicals (Q<sup>ā€¢ā€“</sup>) that can oxidize FeĀ­(II) back to FeĀ­(III). The oxidation rate of FeĀ­(II) by Q<sup>ā€¢ā€“</sup>increases with increase in pH due to the speciation change of Q<sup>ā€¢ā€“</sup> with its deprotonated form (Q<sup>ā€¢ā€“</sup>) oxidizing FeĀ­(II) more rapidly than the protonated form (HQ<sup>ā€¢</sup>). Although the oxygenation of FeĀ­(II) is negligible at pH < 5, O<sub>2</sub> still plays an important role in iron redox transformation by rapidly oxidizing Q<sup>ā€¢ā€“</sup> to form benzoquinone (Q). A kinetic model is developed to describe the transformation of quinone and iron under all experimental conditions. The results obtained here are compared with those obtained in our previous studies of ironā€“Suwannee River fulvic acid (SRFA) interactions in acidic solutions and support the hypothesis that hydroquinone moieties can reduce FeĀ­(III) in natural waters. However, the semiquinone radicals generated in pure hydroquinone solution are rapidly oxidized by dioxygen, while the semiquinone radicals generated in SRFA solution are resistant to oxidation by dioxygen, with the result that steady-state semiquinone concentrations in SRFA solutions are 2ā€“3 orders of magnitude greater than in solutions of 1,4-hydroquinone. As a result, semiquinone moieties in SRFA play a much more important role in iron redox transformations than is the case in solutions of simple quinones such as 1,4-hydroquinone. This difference in the steady-state concentration of semiquinone species has a dramatic effect on the cycling of iron between the +II and +III oxidation states, with iron turnover frequencies in solutions containing SRFA being 10ā€“20 times higher than those observed in solutions of 1,4-hydroquinone

    High-Performance UVā€“Visibleā€“NIR Broad Spectral Photodetectors Based on One-Dimensional In<sub>2</sub>Te<sub>3</sub> Nanostructures

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    For the first time, high quality In<sub>2</sub>Te<sub>3</sub> nanowires were synthesized via a chemical vapor deposition (CVD) method. The synthesized In<sub>2</sub>Te<sub>3</sub> nanowires are single crystals grown along the [132] direction with a uniform diameter of around 150 nm and an average length of tens of micrometers. Further, two kinds of photodetectors made by 1D In<sub>2</sub>Te<sub>3</sub> nanostructures synthesized by CVD and solvothermal (ST) methods respectively were fabricated. To our best knowledge, this is the first time photoresponse properties of In<sub>2</sub>Te<sub>3</sub> nanowire have been studied. The CVD grown nanowire device shows better performance than the ST device, which demonstrates a fast, reversible, and stable photoresponse and also a broad light detection range from 350 nm to 1090 nm, covering the UVā€“visibleā€“NIR region. The excellent performance of the In<sub>2</sub>Te<sub>3</sub> nanowire photodetectors will enable significant advancements of the next-generation photodetection and photosensing applications

    Total and amplifiable DNA concentrations in plasma and plasma exosomes.

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    <p>A, Comparison of total DNA concentrations in plasma (median 6.86 ng/mL) and plasma exosomes (median 4.9 ng/mL). B, Comparison of total DNA concentrations in exosome pellet (median 5.6 ng/mL) and plasma supernatant (median 0.0 ng/mL). C, Comparison of Ī²-actin DNA concentrations in plasma and plasma exosomes detected by a ddPCR assay. There was no statistically significant difference between Ī²-actin DNA concentrations in plasma (median 1600 Ī²-actin copies/mL plasma) and plasma exosomes (median 1560 Ī²-actin copies/mL plasma). D, Comparison of Ī²-actin DNA concentrations in plasma exosome pellet (median 888 Ī²-actin copies/mL plasma) and plasma supernatant (median 52 Ī²-actin copies/mL plasma) detected by ddPCR assay. The line inside of the box indicates median value. The limits of the box represent the 75th and 25th percentiles. The whiskers indicate the 10th and 90th percentiles. Panels A and C; n = 23. Panels B and D; n = 16. * <i>p</i> < 0.01.</p

    Investigating Zigzag Film Growth Behaviors in Layer-by-Layer Self-Assembly of Small Molecules through a High-Gravity Technique

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    The zigzag film growth behavior in the layer-by-layer (LbL) assembly method is a ubiquitous phenomenon for which the growth mechanism was rarely investigated, especially for small molecules. To interpret the zigzag increasing manner, we hypothesized that the desorption kinetics of small molecules was dominant for the film growth behavior and demonstrated this hypotheis by introducing the high-gravity technique into the LbL assembly of a typical polyelectrolyte/small molecule system of polyethylenimine (PEI) and meso-tetraĀ­(4-carboxyphenyl)Ā­porphine (Por). The results showed that the high-gravity technique remarkably accelerated the desorption process of Por; the high-gravity LbL assembly provides a good platform to reveal the desorption kinetics of Por, which is tedious to study in conventional situation. We found that as much as 50 min is required for Por molecules to reach desorption equilibrium from the substrate to the bulk PEI solution for the conventional dipping method; however, the process could be accelerated and require only 100 s if a high-gravity field is used. Nonequilibrated desorption at 10 min for normal dipping and at 30 s for high-gravity-field-assisted assembly both exhibited a zigzag film growth, but after reaching desorption equilibrium at 100 s under a high-gravity field, film growth began to cycle between assembly and complete disassembly instead of LbL assembly. For the first time we have proven that the high-gravity technique can also accelerate the desorption process and demonstrated the desorption-dependent mechanism of small molecules for zigzag film growth behaviors

    Palladium-Catalyzed C(sp<sup>3</sup>)ā€“H Nitrooxylation of Aliphatic Carboxamides with Practical Oxidants

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    Here we report the palladium-catalyzed Ī²-C(sp3)āˆ’H nitrooxylation of aliphatic carboxamides using a modified quinoline auxiliary. Notably, Al(NO3)3Ā·9H2O was used as a nitrate source as well as a practical oxidant. The 5-chloro-8-aminoquinoline auxiliary was nitrated in situ during the reaction, which may enhance its directing ability and help its removal. The reaction has a broad substrate scope with a variety of aliphatic carboxamides. The multiple substituted auxiliary can be easily removed and recovered. Two Cā€“H-insertion palladacycle intermediates were isolated and characterized to elucidate the mechanism

    Improved Dielectric Properties and Energy Storage Density of Poly(vinylidene fluoride-<i>co</i>-hexafluoropropylene) Nanocomposite with Hydantoin Epoxy Resin Coated BaTiO<sub>3</sub>

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    Energy storage materials are urgently demanded in modern electric power supply and renewable energy systems. The introduction of inorganic fillers to polymer matrix represents a promising avenue for the development of high energy density storage materials, which combines the high dielectric constant of inorganic fillers with supernal dielectric strength of polymer matrix. However, agglomeration and phase separation of inorganic fillers in the polymer matrix remain the key barriers to promoting the practical applications of the composites for energy storage. Here, we developed a low-cost and environmentally friendly route to modifying BaTiO<sub>3</sub> (BT) nanoparticles by a kind of water-soluble hydantoin epoxy resin. The modified BT nanoparticles exhibited homogeneous dispersion in the ferroelectric polymer polyĀ­(vinylidene fluoride-<i>co</i>-hexafluoropropylene) (PĀ­(VDF-HFP)) matrix and strong interfacial adhesion with the polymer matrix. The dielectric constants of the nanocomposites increased significantly with the increase of the coated BT loading, while the dielectric loss of the nanocomposites was still as low as that of the pure PĀ­(VDF-HFP). The energy storage density of the nanocomposites was largely enhanced with the coated BT loading at the same electric field. The nanocomposite with 20 vol % BT exhibited an estimated maximum energy density of 8.13 J cm<sup>ā€“3</sup>, which was much higher than that of pure PĀ­(VDF-HFP) and other dielectric polymers. The findings of this research could provide a feasible approach to produce high energy density materials for practical application in energy storage

    Analysis of exosome DNA by agarose gel separation and Agilent Bioanalyzer.

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    <p>A, Exosome DNA without RNase treatment. B, Exosome DNA with RNase treatment. High molecular weight band is removed by RNase treatment indicating that band represents RNA. Low molecular weight band is resistant to RNase treatment indicating that it is DNA. Majority of exosome DNA are in 200 bp size range. C, Overlaid Agilent 2100 Bioanalyzer electropherograms. Exosome DNA was extracted from two individual donors. Exosome DNA from both donors were either treated with RNase or not treated. RNase treated and not treated DNA were analyzed by Agilent Bioanalyzer and RNase treated and not treated electropherograms were overlaid.</p

    Quantification and sizing of exosomes using NanoSight NS300 particle counter and analysis of protein exosome markers by western blotting.

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    <p>For ā€œFig 3ā€, panels A, B and C, x-axis represents particle size and y-axis represents the mode peak particle concentration. Mode peak concentration value is less than the total particle concentration. The total particle concentration is represented by the areas under the curves. Software used in the instrument automatically calculate the areas under the curves and gives estimated total particle concentration. Since sample was diluted 5-times, concentration value provided by software was multiplied by five. A, Exosomes were analyzed under light scatter mode. Size is heterogeneous ranging from 30ā€“260 nm. Mean size is 92.6 nm and mode is 39.7 nm. Concentration 9.25 Ɨ 10<sup>9</sup> particles/mL. B, Analysis of Exo-FTICā„¢ (green fluorescence) labeled exosomes using fluorescence mode. Exosomes are heterogeneous in size ranging from 30ā€“260 nm. Mean size is 113.3 nm and mode is 51.6 nm. Concentration 24 Ɨ 10<sup>9</sup> particles/mL plasma. C, Analysis of exosomes stained with Quant-iTā„¢ PicoGreen<sup>Ā®</sup> dsDNA reagent using fluorescence mode. Exosomes are heterogeneous in size ranging from 30ā€“260 nm. Mean size is 106.5 nm and mode is 45.5 nm. Concentration 18 Ɨ 10<sup>9</sup> particles/mL plasma.</p

    Characterization of plasma exosomes by Western blotting and transmission electron microscopy.

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    <p>A, Western blot analysis of exosome marker proteins, Hsp70 (MW 70 kDa), CD63 (MW 26 kDa) and CD9 (MW 24 kDa) in 4 donors. B, Western blot analysis of exosomes for microvesicles marker proteins, CD41 (MW 113 kDa) and CD45 (MW 147 kDa) in 3 donors. C, Analysis of density gradient fractions for CD9 and CD63 proteins. D, Electron microscopic analysis of exosomes isolated from human blood plasma, contrasted and embedded as described in Methods and Materials section. Note their cup shape, appearance, and heterogeneous size ranging from 15ā€“165 nm. Magnification110000 Ɨ.</p
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