Nickel‐Catalyzed 1,2‐Diarylation of Alkenyl Carboxylates: A Gateway to 1,2,3‐Trifunctionalized Building Blocks

A nickel‐catalyzed conjunctive cross‐coupling of alkenyl carboxylic acids, aryl iodides, and aryl/alkenyl boronic esters is reported. The reaction delivers the desired 1,2‐diarylated and 1,2‐arylalkenylated products with excellent regiocontrol. To demonstrate the synthetic utility of the method, a representative product is prepared on gram scale and then diversified to eight 1,2,3‐trifunctionalized building blocks using two‐electron and one‐electron logic. Using this method, three routes toward bioactive molecules are improved in terms of yield and/or step count. This method represents the first example of catalytic 1,2‐diarylation of an alkene directed by a native carboxylate group.     

Triterpene glycosides from the Vietnamese sea cucumber Holothuria edulis

Abstract

From the MeOH extract of the Vietnamese sea cucumber Holothuria edulis, eight triterpene glycosides (1–8), including one new compound namely holothurin A₅ (1), were isolated by using various chromatographic separations. Their structures were established by spectroscopic experiments including 1D, 2D NMR and HR-ESI-MS. Holothurin A₅ (1) has a hydroperoxy group at C-25. To the best of our knowledge, this is the first report of this group in triterpene saponins obtained from sea cucumbers to date. In addition, the in vitro cytotoxicity against five human cancer cell lines (HepG2, KB, LNCaP, MCF7 and SK-Mel2) of all isolated compounds was also evaluated using SRB assays.     

Acylated flavonoid glycosides from Barringtonia racemosa

Abstract

Using various chromatographic separations, three new acylated flavonoid glycosides, namely barringosides G–I (1–3), were isolated from the water-soluble extract of Barringtonia racemosa branches and leaves. The structure elucidation was performed by extensive analysis of the 1D and 2D NMR and HR-QTOF-MS data. Of the isolated compounds, barringoside I (3) showed moderate inhibitory effects on LPS-induced NO production in RAW264.7 cells with an IC₅₀ of 52.48?±?1.04?µM.     

Electronic structures of NbGen−/0/+ (n = 1–3) clusters from multiconfigurational CASPT2 and density matrix renormalization group-CASPT2 calculations

Density functional theory and multiconfigurational CASPT2 and density matrix renormalization group DMRG-CASPT2 have been employed to study the low-lying states of NbGe_n^−/0/+ (n = 1–3) clusters. With the DMRG-CASPT2 method, the active spaces are extended to a size of 20 orbitals. For most of the states, the CASPT2 relative energies are comparable with the DMRG-CASPT2 results. The leading configuration, bond distances, vibrational frequencies, and relative energies of the low-lying states of these clusters were calculated. The ground states of these clusters were computed to be ³Δ, ⁴Φ, and ⁵Φ of NbGe^−/0/+; ³A₂, ⁴B₁, and ³B₁ of cyclic-NbGe₂^−/0/+; and ¹A′, 1²A″ and 1²A′′ (²E), and ³A″ of tetrahedral-NbGe₃^−/0/+ isomers. For NbGe cluster, our calculations proposed that the ⁶∑ is almost degenerate with the ⁴Φ with the CASPT2 and DMRG-CASPT2 relative energies of 0.05 and 0.06 eV. The adiabatic detachment energies of NbGe_n⁻ (n = 1–3) clusters were estimated to be 1.46, 1.55, and 2.18 eV by the CASPT2 method. The relevant detachment energies of the anionic ground state and the ionization energies of the neutral ground states are evaluated at the CASPT2 level.     

Analysis of trace elements in the fingernails of breast cancer patients using instrumental neutron activation analysis

Journal of Radioanalytical and Nuclear Chemistry - The aim of this study was to find trace elements that increase risk of breast cancer based on the deviation of the concentration of trace elements...     

Nickel-Catalyzed 1,2-Diarylation of Alkenyl Carboxylates: A Gateway to 1,2,3-Trifunctionalized Building Blocks

A nickel-catalyzed conjunctive cross-coupling of alkenyl carboxylic acids, aryl iodides, and aryl/alkenyl boronic esters is reported. The reaction delivers the desired 1,2-diarylated and 1,2-arylalkenylated products with excellent regiocontrol. To demonstrate the synthetic utility of the method, a representative product is prepared on gram scale and then diversified to eight 1,2,3-trifunctionalized building blocks using two-electron and one-electron logic. Using this method, three routes toward bioactive molecules are improved in terms of yield and/or step count. This method represents the first example of catalytic 1,2-diarylation of an alkene directed by a native carboxylate group.     

TEM characterization of chemically synthesized copper–gold nanoparticles

Dodecanethiol-capped Cu–Au nanoparticles, synthesized via a successive two-phase (water/toluene) and galvanic-exchange procedure, were characterized using transmission electron microscopy (TEM). The size range of the particles is around 1–7 nm. Electron-induced morphological evolution was observed under high resolution (HR) TEM. Cuboctahedral morphology was found to be thermodynamically stable. Electron-induced aggregation of two particles was also observed. Chemical ordering of cuboctahedral particles was studied by atomic-resolution high angle annular dark field (HAADF) imaging in scanning TEM (STEM) mode and energy dispersive X-ray (EDX) element mapping using a silicon drift detector (SDD). The particles were found to be Cu–Au mixed, and to be stable in air. Surface plasmon resonance (SPR), which is dependent on local structure and morphology, was investigated by electron energy loss spectroscopy (EELS).     

Leading-Order Dynamics of Gravity-Driven Flows in?Free-Standing Soap Films

We derive the leading-order equations that govern the dynamics of the flow in a falling, free-standing soap film. Starting with the incompressible Navier?CStokes equations, we carry out an asymptotic analysis using parameters that correspond to a common experimental setup. We account for the effects of inertia, surface elasticity, pressure, viscous stresses, gravity, and air drag. We find that the dynamics of the flow is dominated by the effects of inertia, surface elasticity, gravity, and air drag. We solve the leading-order equations to compute the steady-state profiles of velocity, thickness, and pressure in an experiment in which the film is in the Marangoni elasticity regime. The computational results, which include a Marangoni shock, are in good accord with the experimental measurements.     

A parallel four step domain decomposition scheme for coupled forward–backward stochastic differential equations

Motivated by the idea of imposing paralleling computing on solving stochastic differential equations (SDEs), we introduce a new domain decomposition scheme to solve forward–backward stochastic differential equations (FBSDEs) parallel. We reconstruct the four step scheme in Ma et al. (1994) [1] and then associate it with the idea of domain decomposition methods. We also introduce a new technique to prove the convergence of domain decomposition methods for systems of quasilinear parabolic equations and use it to prove the convergence of our scheme for the FBSDEs.     

On an affirmative answer to S. Lin?s problem

In this paper, we give an affirmative answer to the problem posed by S. Lin (2002, 2007) in [7] and [8], and give another answer to the question posed by Y. Ikeda, C. Liu and Y. Tanaka (2002) in [5].