Interfacial behavior, structural, and thermodynamic parameters in relation to the formation of water-in-oil (w/o) microemulsion (μE) with varied surfactant head groups and cosurfactants have been evaluated through dilution technique at different temperature and [water]/[surfactant] mole ratio. Dodecyltrimethylammonium bromide (DTAB), sodium dodecylsulphate (SDS), and polyoxyethylene sorbitan monolaurate (Tween-20) were used as surfactants and n-butanol and n-pentanol were used as cosurfactants. Distribution of cosurfactants between bulk oil and the interface using fixed amount of surfactant at varied [water]/[surfactant] mole ratio and temperature has been studied to evaluate thermodynamic parameters. Associated structural parameters, such as droplet dimension and aggregation number of surfactant and cosurfactant at the droplet interface, have also been evaluated. Spontaneity of the μE formation followed the order DTAB>SDS>Tween-20 for both butanol and pentanol in the studied range of temperature. Correlations of the results in terms of the evaluated physicochemical parameters have been attempted. 相似文献
Gold(I)‐chloride‐catalyzed synthesis of α‐sulfenylated carbonyl compounds from propargylic alcohols and aryl thiols showed a wide substrate scope with respect to both propargylic alcohols and aryl thiols. Primary and secondary aromatic propargylic alcohols generated α‐sulfenylated aldehydes and ketones in 60–97 % yield. Secondary aliphatic propargylic alcohols generated α‐sulfenylated ketones in yields of 47–71 %. Different gold sources and ligand effects were studied, and it was shown that gold(I) chloride gave the highest product yields. Experimental and theoretical studies demonstrated that the reaction proceeds in two separate steps. A sulfenylated allylic alcohol, generated by initial regioselective attack of the aryl thiol on the triple bond of the propargylic alcohol, was isolated, evaluated, and found to be an intermediate in the reaction. Deuterium labeling experiments showed that the protons from the propargylic alcohol and aryl thiol were transferred to the 3‐position, and that the hydride from the alcohol was transferred to the 2‐position of the product. Density functional theory (DFT) calculations showed that the observed regioselectivity of the aryl thiol attack towards the 2‐position of propargylic alcohol was determined by a low‐energy, five‐membered cyclic protodeauration transition state instead of the strained, four‐membered cyclic transition state found for attack at the 3‐position. Experimental data and DFT calculations supported that the second step of the reaction is initiated by protonation of the double bond of the sulfenylated allylic alcohol with a proton donor coordinated to gold(I) chloride. This in turn allows for a 1,2‐hydride shift, generating the final product of the reaction. 相似文献
CO2 and steam/CO2 electroreduction to CO and methane in solid oxide electrolytic cells (SOEC) has gained major attention in the past few years. This work evaluates, for the very first time, the performance of two different ZnO–Ag cathodes: one where ZnO nanopowder was mixed with Ag powder for preparing the cathode ink (ZnOmix–Ag cathode) and the other one where Ag cathode was infiltrated with a zinc nitrate solution (ZnOinf –Ag cathode). ZnOmix–Ag cathode had a better distribution of ZnO particles throughout the cathode, resulting in almost double CO generation while electrolysing both dry CO2 and H2/CO2 (4:1 v/v). A maximum overall CO2 conversion of 48% (in H2/CO2) at 1.7 V and 700 °C clearly indicated that as low as 5 wt% zinc loading is capable of CO2 electroreduction. It was further revealed that for ZnOinf –Ag cathode, most of CO generation took place through RWGS reaction, but for ZnOmix–Ag cathode, it was the synergistic effect of both RWGS reaction and CO2 electrolysis. Although ZnOinf –Ag cathode produced trace amount of methane at higher voltages, with ZnOmix–Ag cathode, there was absolutely no methane. This seems to be due to strong electronic interaction between Zn and Ag that might have suppressed the catalytic activity of the cathode towards methanation.
Ductility is a common phenomenon in many metals but is difficult to achieve in molecular crystals. Organic crystals bend plastically on one or two face‐specific directions but fracture when stressed in any other arbitrary directions. An exceptional metal‐like ductility and malleability in the isomorphous crystals of two globular molecules, BH3NMe3 and BF3NMe3, is reported, with characteristic tensile stretching, compression, twisting, and thinning. The mechanically deformed samples, which transition to lower symmetry phases, retain good long‐range order amenable to structure determination by single‐crystal X‐ray diffraction. Molecules in these high‐symmetry crystals interact through electrostatic forces (B??N+) to form columnar structures with multiple slip planes and weak dispersive forces between columns. On the other hand, the limited number of facile slip planes and strong dihydrogen bonding in BH3NHMe2 negates ductility. Our study has implications for the design of soft ferroelectrics, solid electrolytes, barocalorics, and soft robotics. 相似文献
Experimental Mechanics - The DIC Challenge 2.0 follows on from the work accomplished in the first Digital Image Correlation (DIC) Challenge Reu et al. (Experimental Mechanics 58(7):1067, 1). The... 相似文献
Quantum correlations provide dramatic advantage over the corresponding classical resources in several communication tasks. However, a broad class of probabilistic theories exists that attributes greater success than quantum theory in many of these tasks by allowing supra-quantum correlations in “space-like” and/or “time-like” paradigms. In this letter, a communication task involving three spatially separated parties is proposed where one party (verifier) aims to verify whether the bit strings possessed by the other two parties (terminals) are equal or not. This task is called authentication with limited communication, the restrictions on communication being: i) the terminals cannot communicate with each other, but (ii) each of them can communicate with the verifier through single use of channels with limited capacity. Manifestly, classical resources are not sufficient for perfect success of this task. Moreover, it is also not possible to perform this task with certainty in several nonclassical theories although they might possess stronger “space-like” and/or “time-like” correlations. Surprisingly, quantum resources can achieve the perfect winning strategy. The proposed task thus stands apart from all previously known communication tasks as it exhibits quantum advantage over other nonclassical strategies. 相似文献
We present herein a short tripeptide sequence (Lys–Phe–Gly or KFG) that is situated in the juxtamembrane region of the tyrosine kinase nerve growth factor (Trk NGF) receptors. KFG self‐assembles in water and shows a reversible and concentration‐dependent switching of nanostructures from nanospheres (vesicles) to nanotubes, as evidenced by dynamic light scattering, transmission electron microscopy, and atomic force microscopy. The morphology change was associated with a transition in the secondary structure. The tripeptide vesicles have inner aqueous compartments and are stable at pH 7.4 but rupture rapidly at pH≈6. The pH‐sensitive response of the vesicles was exploited for the delivery of a chemotherapeutic anticancer drug, doxorubicin, which resulted in enhanced cytotoxicity for both drug‐sensitive and drug‐resistant cells. Efficient intracellular release of the drug was confirmed by fluorescence‐activated cell sorting analysis, fluorescence microscopy, and confocal microscopy. 相似文献
The reactions of N-(aryl)pyridine-2-aldimines (L-R; R = OCH3, CH3, H, Cl and NO2), derived from pyridine-2-aldehyde and para-substituted anilines, with CuI in methanol under ambient conditions afford a series of brown complexes of the type [{Cu(L-R)I}2]. The structure of the [{Cu(L-OCH3)I}2] complex has been determined by X-ray crystallography. In these dimeric complexes the two copper centers are linked through an iodo-bridge, and the L-R ligands are coordinated to the metal center through the pyridine-nitrogen and imine-nitrogen. All the complexes show characteristic 1H NMR signals and intense MLCT transitions in the visible region. These complexes also show an emission near 465 nm, whilst they are excited at 340 nm, with relatively poor quantum yields (φ ∼0.002 at 298 K). Cyclic voltammetry on all the complexes shows two successive Cu(I)-Cu(II) oxidations on the positive side of SCE, and a reduction of the coordinated imine ligand on the negative side. These copper(I) complexes are found to efficiently catalyze Suzuki type C-C coupling reactions. 相似文献
Radio wave operating in millimetrewave and microwave frequency bands are adversely affected due to rain. Particularly the attenuation is of immense significance for sensitive remote measurements by satellites using frequencies greater than 10 GHz. Maintenance of an uninterrupted communication link requires a precise knowledge of the attenuation effect due to rain for commissioning right kind of transmitting sources for various purposes required in present day situation. Precise measurement of attenuation at various frequencies will enable us to choose the right frequency, polarization, incident angle and power of the source for different purposes. In this paper we have compared the results of earlier works using aRb Olsen et al, (1) and the formulation by Moupfouma, (2) on the basis of theoretical analysis for explaining the observed results. Effect of temperature, considered in detail in this communication, has contributed the necessary correction factor of the rain attenuation for explaining the observed results. Theoretical analyses to measure the attenuation of the propagating wave due to temperature variation in the rain path have been presented. Correction factor due to temperature profile (temperature from the ground to the rain height within which the radio wave traces its path) has been incorporated in two models by using the concept of dipole energy changes. The effect of this temperature is noted to be quite significant and incorporates an error to the extent of 7–8%. 相似文献
Three crescent shaped heterocycle-fused phenanthrene based systems 1–3 have been synthesized starting from benzene (or substituted benzene) 1,2-bis-propargyl alcohols. Bis-alkylation with propargylic bromides provided the key intermediate, the bis-propargyl bis-ethers. In spite of the possibility of many competing reactions, the latter underwent facile double Garratt-Braverman cyclization to provide compounds 1–3 in near quantitative yield, in a striking reaction involving the formation of four C–C bonds in a single step. Compounds 1–3 showed binding interaction with DNA, predominantly, via groove binding along with partial intercalation (combilexins). Molecular docking study supported the proposed binding modes. 相似文献