Enantioselective, (−)-sparteine-mediated deprotonation of geranyl and neryl N,N-diisopropylcarbamate: configurational stability of the intermediate lithium compounds

(E)/(Z)-Isomeric allylic carbamate esters were deprotonated by n-butyllithium/(−)-sparteine in toluene. Trapping experiments with chlorotrimethylsilane afforded the α-substitution products, with (R)-configuration, revealing that the pro-S proton is removed predominantly to form the corresponding (S)-lithium·(−)-sparteine derivatives; k_S/k_R>15:1 and >7:1, respectively. A slow (S)→(R)-epimerization occurs at −78 °C (T_1/2>60 min). The allylic double bond is stable to (Z)-(E) isomerization under these conditions.     

Ru-catalyzed asymmetric hydrogenation of alpha-phthalimide ketones and 1,3-diaryl diketones using 4,4'-substituted BINAPs

[reaction: see text] A family of tunable precatalysts [NH2Et2][{Ru(4,4'-BINAP)Cl}2(mu-Cl)3] was synthesized and used for highly enantioselective hydrogenation of phthalimide-protected amino ketones and 1,3-diaryldiketones. The bulky groups on the 4,4'-positions of BINAP were believed to be responsible for the enhancement of enantioselectivity (and diasteroselectivity) in these reactions.     

A chiral porous 3D metal-organic framework with an unprecedented 4-connected network topology

A novel homochiral 3D metal-organic framework [CdL2(H2O)2][ClO4]2.2DMF.3EtOH.5/3H2O, 1, (L =(R)-6,6-dichloro-2,2-diethoxy-1,1-binaphthyl-4,4-bipyridine) exhibits an unprecedented 4-connected network topology owing to the cis- configuration of the Cd coordination and possesses permanent porosity as demonstrated by TGA, XRPD, and CO2 adsorption isotherm studies.     

Magnetically recoverable chiral catalysts immobilized on magnetite nanoparticles for asymmetric hydrogenation of aromatic ketones

Novel heterogenized asymmetric catalysts were synthesized by immobilizing preformed Ru catalysts on magnetite nanoparticles via the phosphonate functionality and were characterized by a variety of techniques, including TEM, magnetization, and XRD. These nanoparticle-supported chiral catalysts were used for enantioselective heterogeneous asymmetric hydrogenation of aromatic ketones with very high enantiomeric excess values of up to 98.0%. The immobilized catalysts were easily recycled by magnetic decantation and reused for up to 14 times without loss of activity and enantioselectivity. Orthogonal nature of the present catalyst immobilization approach should allow the design of other superparamagnetic nanoparticle-supported asymmetric catalysts for a wide range of organic transformations.     

Adaptive finite element methods for the identification of distributed parameters in elliptic equation

In this paper, adaptive finite element method is developed for the estimation of distributed parameter in elliptic equation. Both upper and lower error bound are derived and used to improve the accuracy by appropriate mesh refinement. An efficient preconditioned project gradient algorithm is employed to solve the nonlinear least-squares problem arising in the context of parameter identification problem. The efficiency of our error estimators is demonstrated by some numerical experiments.      

[Na4(H2O)7][Fe(OH)6Mo6O18]: A new [12] metallacrown-6 structure with an octahedrally coordinated iron at the center

The reaction of an aqueous solution of sodium molybdate with iron powder at low pH (～0.184) gives rise to the formation of a six-member Mo ring-shape cluster with an Fe (II) encapsulated at the center, [Na₄(H₂O)₇][Fe(OH)₆Mo₆O₁₈](1), which is further linked to a remarkable three-dimensional network via sodium ions.     

Maximum likelihood estimation in the proportional hazards cure model

The proportional hazards cure model generalizes Cox’s proportional hazards model which allows that a proportion of study subjects may never experience the event of interest. Here nonparametric maximum likelihood approach is proposed to estimating the cumulative hazard and the regression parameters. The asymptotic properties of the resulting estimators are established using the modern empirical process theory. And the estimators for the regression parameters are shown to be semiparametric efficient.     

Design, synthesis, and biological evaluation of a dansyled amino acid derivative as an imaging agent for apoptosis

To develop a small molecule-based biomarker for in vivo apoptosis imaging, a dansyled amino acid derivative (BNSBA) was designed and synthesized in good yield. The biological evaluation demonstrated that BNSBA selectively binds to apoptotic cancer cells and is localized within the cytoplasm of cells that bound annexin V on the plasma membrane.     

一类p-Laplace方程边值问题解的存在性

主要讨论一维p-Laplace方程在Neumann边值条件u(0)=0,u(1)=0下,对应的边值问题解的存在性.通过使用度理论,在适当的条件下,建立了对于p-Laplace方程在Neumann条件下解的存在性的充分条件.