Molecular dynamics simulation of the HOONO decomposition and the HO*/NO2* caged radical pair in water

The decomposition of HOONO in water gives nitrate and a reactive oxidant whose identity has been debated. This oxidant has been argued to be a hydroxyl radical, but reported yields of hydroxyl-radical-trapped products range from only 0% to 40% in different experiments. Other oxidants, including the metastable HOONO*, have been proposed as intermediates. CPMD metadynamics simulations reported here show the mechanism of HOONO decomposition in water and the nature of the caged radical pair.     

Synthesis, characterization, and transistor response of semiconducting silole polymers with substantial hole mobility and air stability. Experiment and theory

Realizing p-channel semiconducting polymers with good hole mobility, solution processibility, and air stability is an important step forward in the chemical manipulation of charge transport in polymeric solids and in the development of low-cost printed electronics. We report here the synthesis and full characterization of the dithienosilole- and dibenzosilole-based homopolymers, poly(4,4-di-n-hexyldithienosilole) (TS6) and poly(9,9-di-n-octyldibenzosilole) (BS8), and their mono- and bithiophene copolymers, poly(4,4-di-n-hexyldithienosilole-alt-(bi)thiophene) (TS6T1, TS6T2) and poly(9,9-di-n-octyldibenzosilole-alt-(bi)thiophene) (BS8T1, BS8T2), and examine in detail the consequences of introducing dithienosilole and dibenzosilole cores into a thiophene polymer backbone. We demonstrate air-stable thin-film transistors (TFTs) fabricated under ambient conditions having hole mobilities as large as 0.08 cm(2)/V x s, low turn-on voltages, and current on/off ratios > 10(6). Additionally, unencapsulated TFTs fabricated under ambient conditions are air-stable, an important advance over regioregular poly(3-hexylthiophene) (P3HT)-based devices. Density functional theory calculations provide detailed insight into the polymer physicochemical and charge transport characteristics. A direct correlation between the hole injection barrier and both TFT turn-on voltage and TFT polymer hole mobility is identified and discussed, in combination with thin-film morphological characteristics, to explain the observed OTFT performance trends.     

Air-stable, solution-processable n-channel and ambipolar semiconductors for thin-film transistors based on the indenofluorenebis(dicyanovinylene) core

We present here the synthesis, characterization, and field-effect performance of a novel n-channel semiconducting molecule TIFDMT and of the corresponding thiophene-based copolymer P-IFDMT4 based on the indenofluorenebis(dicyanovinylene) core. TIFDMT-based field-effect transistors fabricated by spin-coating exhibit high electron mobilities of 0.10-0.16 cm2/V s in air, low turn-on voltages (0 to +5 V), and high on/off ratios of 10(7)-10(8). These devices also exhibit excellent air stability over a prolonged time of storage in ambient conditions. P-IFDMT4-based devices exhibit the first example of an air-stable ambipolar polymer processable from solution     

Primes of superspecial reduction for QM abelian surfaces

We show that any abelian surface with multiplication by thequaternion -algebra of discriminant 6, with field of moduli and which is a Jacobian in characteristic 2 and 3, has infinitelymany primes of superspecial reduction. This is done by examiningcomplex multiplication points in characteristic 0 and p andthe values of a certain j-function on the associated modulispace at these points.     

Pulsed electron nuclear double resonance studies of carotenoid oxidation in Cu(II)-substituted MCM-41 molecular sieves

Carotenoid (Car) radical intermediates formed upon catalytic or photooxidation of lutein (I), 7'-apo-7',7'-dicyano-beta-carotene (II), and lycopene (III) inside Cu(II)-MCM-41 molecular sieves were studied by pulsed electron nuclear double resonance (ENDOR) spectroscopies. The Davies and Mims ENDOR spectra (15-20 K) were simulated using the hyperfine coupling constants predicted by density functional theory (DFT) calculations. The DFT calculations revealed that upon chemical oxidation, carotenoid radical cations (Car*+) are formed, whereas carotenoid neutral radicals (#Car*) are produced by proton loss (indicated by #) from the radical cation. This loss is to first order independent of polarity or hydrogen bonding for carotenoids I, II, or III inside Cu(II)-MCM-41 molecular sieves.     

Synthesis and characterization of polymer/clay nanocomposites by intercalated chain transfer agent

In situ synthesis of poly(methyl methacrylate) (PMMA) and polystyrene (PS) nanocomposites by free radical polymerization using intercalated chain transfer agent (I-CTA) in the layers of montmorillonite (MMT) clay is reported. MMT clay was ion-exchanged with diethyl octyl ammonium ethylmercaptan bromide, which acts both as suitable intercalant and as chain transfer agent. These modified clays were then dispersed in methyl methacrylate (MMA) or styrene (St) monomers in different loading degrees to carry out the in situ free radical polymerization. The intercalation ability of the chain transfer agent and exfoliated nanocomposite structure were evidenced by both X-ray diffraction spectroscopy (XRD) and transmission electron microscopy (TEM). Thermal properties and morphologies of the resultant nanocomposites were also studied.     

New Pt(0) Nanoparticles as Highly Active and Reusable Catalysts in the C1–C3 Alcohol Oxidation and the Room Temperature Dehydrocoupling of Dimethylamine-Borane (DMAB)

New Pt(0) nanoparticles were easily and reproducibly prepared by the simultaneous reduction method using 1-butylamine (BA) and tributylamine (TBA) for the first time as capturing ligands at room temperature. X-ray diffraction, X-ray photoelectron microscopy and transmission electron microscopy measurements verify the formation of well-dispersed Pt(0) nanoparticles [~3.63 and ~3.98 nm for catalysts prepared using BA (catalyst I) and TBA (catalyst II), respectively] on an activated carbon surface. The catalytic performances of these nanoparticles in terms of activity, isolability and reusability were investigated for both alcohol oxidation and the dehydrocoupling of dimethylamine-borane (DMAB). These nanoparticles were shown to be as active and reusable heterogeneous catalysts even at room temperature. The prepared catalysts can catalyze the dehydrogenation of DMAB with one of the highest known activities at room temperature and also C1–C3 alcohol oxidation with very high electrochemical activities.     

Monodisperse Mw-Pt NPs@VC as Highly Efficient and Reusable Adsorbents for Methylene Blue Removal

Addressed herein, monodisperse Vulcan carbon supported Pt nanoparticles (Mw-Pt NPs@VC) have been reproducibly synthesized using the microwave assisted method and their application for methylene blue (MB) removal from aqueous solutions was investigated through the adsorption mechanism. The prepared nanomaterials were characterized by X-ray diffraction, transmission electron microscopy, high resolution transmission electron microscopy and X-ray photoelectron spectroscopy. All results show that highly crystalline and colloidally stable nanoparticles have been formed and Mw-Pt NPs@VC were found to be one of the the most active catalyst. The results showed that the Mw-Pt NPs@VC nanoparticles had remarkable MB adsorption capacity of 271.15 mg/g. The equilibrium for MB adsorption was attained in ～55 min. Moreover, Mw-Pt NPs@VC is a reusable and promising material for MB removal since it preserves 95.6 % of its initial efficiency after six successive cycles of adsorption–desorption.     

Experimental Investigation on Flow Characteristics of Aqueous Foams through the Jet Device and Horizontal Pipe

Aqueous foam is regarded as a versatile medium in numerous scientific and engineering applications due to its high viscosity and low density. The objective of this study is to investigate the flow characteristics of aqueous foams through the jet device and horizontal pipe. The pressure distribution and foam production capacity are measured at different operating conditions. Experimental results show that the pressure fluctuations reduce significantly by increasing the foam liquid concentration, especially in the downstream of jet device. The bubble flow turns into homogeneous foams gradually when the concentration increases from 0.025% to 0.35%, while the foam behaviors take little change at a higher concentration, and the foamability reaches a limit. Subjected to the large pressure difference produced between the top and bottom of horizontal pipe, aqueous foams undergo a gas–liquid separation at a high terminal pressure, resulting in bubbles at the top and liquid at the bottom. Therefore, the terminal pressure should be kept less than a critical value to hold a good foam pattern. Based on the above contributions, it is believed that the study laid an important foundation for the widespread application of foam technology.     

Preparation of glutathione loaded nanoemulsions and testing of hepatoprotective activity on THLE-2 cells

To improve bioavailability and stability of hydrophobic and hydrophilic compounds, nanoemulsions are good alternatives as delivery systems because of their nontoxic and nonirritant nature. Glutathione (GSH) suffers from low stability in water, where its encapsulation in nanoemulsions is a powerful strategy to its stability in aqueous systems. The aim of this study was to obtain nanoemulsions from the hydrophobic/hydrophilic contents of N. sativa seed oil so as to improve GSH stability along with bioavailability of N. sativa seed oil. Then, the prepared nanoemulsions were tested for in vitro hepatoprotective activity against ethanol toxicity. To the best of our knowledge, there is no study on the test of nanoemulsions by the combination of Nigella sativa seed oils and GSH in hepatoprotective activity. Here, nanoemulsions with different contents were prepared using Nigella sativa seed oils. Content analyses and characterisation studies of prepared nanoemulsions were carried out. In order to investigate the protective effects against to ethanol exposure, THLE-2 cells were pretreated with nanoemulsions for 2 h with the maximum benign dose (0.5 mg/mL of nanoemulsions). Ethanol (400 mM) was introduced to pretreated cells and nontreated cells for 48- or 72-h periods, followed by cell viability assay was carried out. Fluorescence microscopy tests revealed the introduction of the nanoemulsions into THLE-2 cells. The findings show that nanoformulations have promising in vitro hepatoprotective effects on the THLE-2 cell line against ethanol exposure.