Alashinol H,an epoxylignan with an unusual six-membered cyclic hemiacetal from Syringa pinnatifolia

A new 7, 9′-epoxylignan, alashinol H (1), which features a rare six-membered cyclic hemiacetal, was isolated from the stem barks of Syringa pinnatifolia. The structure was elucidated based on spectroscopic data including HRESIMS and NMR. Its absolute configuration was resolved by GIAO NMR shifts and ECD calculations. A putative biosynthetic pathway of this compound is proposed. Alashinol H showed a moderate inhibitory effect against NO production in BV-2 murine microglia cells.     

Mechanofluorochromic behavior of anthracene-based acylhydrazone derivatives

Two anthracene-based derivatives, having one or two acylhydrazone branches attached on the anthracene, namely, asymmetrical AHP-1 and symmetrical AHBP-1 were designed. These compounds exhibited mechanofluorochromic behavior with the emission colors reversibly changing upon grinding and recrystallizing. The mechanofluorochromic mechanism was explored and ascribed to the crystalline-amorphous phase transformation. In addition, the red-shifted extent of fluorescent emission of the ground AHBP-1 samples was more than that of AHP-1.     

Syntheses,steric hindrance effects,luminescent properties and TD-DFT calculations for a series of copper(I) iodide coordination complexes

A series of copper(I) coordination complexes, CuI(Phen)[2-(Dpp)bp] (1) (Phen?=?phenanthroline, 2-(Dpp)bp?=?2-(Diphenylphosphino)-biphenyl), Cu₂I₂(Phen)[2-(Dpp)bp] (2), CuI(2-PBI)[2-(Dpp)bp] (3) and (2-PBI?=?2-(pyridin-2-yl)-1H-benzo[d]imidazole) and CuI(Bipy)[2-(Dpp)bp] (Bipy?=?2,2′-bipyridine) (4) have been synthesized. X-ray crystal structure studies revealed that complexes 1, 3 and 4 showed mononuclear structures with the copper atoms coordinated by iodide, a chelating nitrogen-donor ligand, and a monodentate phosphine ligand. However, the coordination centers display different distortions of their tetrahedral geometries, according to the steric hindrance of the bulky phosphine ligands. Complex 2 has a dinuclear structure, with trigonal and tetrahedral coordination centers. Variations in the aromatic system of the N-heterocyclic ligands result in different luminescence properties. Thus, the emission maxima for these complexes range from 580 to 642 nm, with lifetimes of τ?=?0.6–0.9 and 1.6–4.2 μs. TD-DFT calculations reveal the origin of the luminescence to be metal–ligand charge transfer, as well as halogen–ligand charge transfer. The optical absorption spectra and thermal stabilities of the complexes have also been studied.     

Experimental study of asphaltene deposition in transparent microchannels using the light absorption method

This study focuses on an experimental investigation of asphaltene deposition in a vertical transparent microchannel. Heptane-induced asphaltene precipitation is utilized to precipitate dissolved asphaltene in crude oil into asphaltene particles at ambient temperature and standard atmospheric pressure. These asphaltene particles deposit gradually on the surface of microchannels. The key parameters that influence the mechanism of asphaltene deposition are the ratio of crude oil to n-heptane and experimental elapsed time. At a constant flowrate, the amount of asphaltene deposited on a transparent channel wall is quantified using a new flow visualization technique based on reflected light intensity and image analysis. Asphaltene precipitation and deposition strongly affect the reflected light intensity through the change of mixture color in the recorded images. Experimental results show that asphaltene deposition process follows three stages, (i) slow asphaltene particle deposition at the beginning of the experiment, (ii) a rapid and continuous deposition occurring after few hours and (iii) a slower deposition (decreasing deposition rate) at the end of the experimentation. The experimental results for different crude oil to n-heptane ratios illustrate that deposition increases with this ratio, i.e. increasing concentration of n-heptane. An empirical equation is developed to correlate the intensity of the light absorption to the thickness of the deposited asphaltene in a transparent microchannel. Non-uniform deposition along the longitudinal direction of the microchannel is characterized. Deposits decrease with increasing longitudinal distance from the inlet. This non-uniform deposition distribution is due to local mass transport limitations and asphaltene aggregation size effect.     

Equilibrium and dynamic surface properties of long-chain quaternary ammonium hydroxides with different chain length and number

The equilibrium and dynamic surface tensions of five long-chain alkyl ammonium hydroxides (AAH) at the air/aqueous solution interface were investigated, and the effects of the length and number of alkyl chain on surface tensions had been discussed. With the increase of the length, the equilibrium surface tension (EST) increased from 28.65 to 40.52?mN/m. While, for the double chains at the critical micelle concentration (CMC), the EST decreased from 32.71 to 26.61?mN/m with the length increasing. In addition, the adsorption behaviors of the AAH were analyzed and the effective diffusion coefficients (D_eff) were calculated on basis of the Ward–Tordai equation. Moreover, the time required to attain the EST decreases with the increase of surfactant concentration. The longer the C–H chain is, the lower surface tension at initial concentration is. What’s more, the diffusion processing of the AAH to air/water interface mainly depends on the surfactant concentration, and the adsorption is controlled by diffusion mechanism in a dilute concentration, while under a high concentration the adsorption is controlled by mixed diffusion–kinetic mechanism.     

Aggregation behavior and adsorption properties of salt-free catanionic surfactant mixtures containing tetradecyltrimethyl ammonium salts

The aggregation behavior of salt-free catanionic surfactants, tetradecyltrimethyl ammonium hydroxide (TTAOH)/fatty acid (FA) including octanoic acid (OA), decylic acid (DA) and lauric acid (LA) in aqueous solutions were studied. The critical micelle concentration(cmc), surface tension at cmc (γ_cmc), surface excess (Г_max), mean molecular surface area (A_min), adsorption efficiency (pc₂₀) and surface tension reduction effectiveness (π_cmc) were obtained from surface tension isotherms. The influence of temperature on the surface tension of salt-free TTAOH/FA (TTAOF) systems was investigated. Data of adsorption dynamics indicated that at fixed adsorption time, the order of adsorption capacity was TTAOH?相似文献   

Theoretical investigation on cyclohexane dehydrogenation catalyzed by V<Subscript>2</Subscript><Superscript>+</Superscript> in gas-phase

The dehydrogenation reaction mechanism of cyclohexane catalyzed by dimer transition metal cluster V₂⁺ has been investigated at the B3LYP/6-31G (d, p) level of density functional theory. Density of states (DOS) graph is used to understand more deeply the roles of the front molecular orbital of the initial complexes. After the first molecular dehydrogenation, the reaction mainly consists of two competition mechanisms. First, the C-H bonds of cyclohexane can be effectively activated by the V₂⁺ cation, yielding the same-face dehydrogenation products. Second, the C-C bonds are activated, forming the different-face dehydrogenation products. Our calculations indicate that the reaction takes place more easily along the low-spin potential energy surface on the same-face and is a low-barrier or even barrier-free transformation. Carbon-carbon single bonds are nonpolar and generally far less reactive. A comparison of the reaction mechanism of V₂⁺ and congener Ti₂⁺ with cyclohexane has been presented. The bond dissociation energies (BDEs) of V₂⁺ are greater than that of Ti₂⁺, leading to difficulties in forming sandwich complexes in the different-face dehydrogenation of cyclohexane, and the same-face dehydrogenation is an important reaction channel.     

Antiglioma pseurotin A from marine Bacillus sp. FS8D regulating tumour metabolic enzymes

Pseurotin A was isolated from a culture of marine Bacillus sp. FS8D and showed to be active against the proliferation of four different glioma cells with IC₅₀ values of 0.51–29.3 μM. It has been found that pseurotin A downregulated the expression of tumour glycolytic enzymes pyruvate kinase M2 (PKM2) and lactate dehydrogenase 5 (LDH5) and upregulated the expression of pyruvate dehydrogenase beta (PDHB), adenosine triphosphate synthase beta (ATPB) and cytochrome C (Cyto-C), the important regulators for tricarboxylic acid cycle and oxidative phosphorylation. The data suggested that targeting multiple metabolic enzymes might be one of the antiglioma mechanisms of pseurotin A.     

The Fourth Alloying Mode by Way of Anti‐Galvanic Reaction

Anti‐galvanic reaction (AGR) not only defies classic galvanic theory but is a promising method for tuning the compositions, structures, and properties of noble‐metal nanoparticles. Employing AGR for the preparation of alloy nanoparticles has recently received great interest. Herein, we report an unprecedented alloying mode by way of AGR, in which foreign atoms induce structural transformation of the mother nanoparticles and enter the nanoparticles in a non‐replacement fashion. A novel, active‐metal‐doped, gold nanoparticle was synthesized by this alloying mode, and its structure resolved. A CdSH motif was found in the protecting staples of the bimetal nanoparticle. DFT calculations revealed that the Au₂₀Cd₄(SH)(SR)₁₉ nanoparticle is a 8e superatom cluster. Furthermore, although the Cd‐doping does not essentially alter the absorption spectrum of the mother nanocluster, it distinctly enhances the stability and catalytic selectivity of the mother nanoclusters.