Two New Daphniphyllum Alkaloids from Daphniphyllum calycinum

Two new daphniphyllum alkaloids named 2‐hydroxyyunnandaphnine D ( 1 ) and methyl 7‐hydroxyhomodaphniphyllate ( 2 ), together with eight known alkaloids, daphnioldhanin D, calyciphylline F, calyciphylline B, deoxycalyciphylline B, daphnicyclidin H, macropodumine C, 9,10‐epoxycalycine A, and yunnandaphnine A, were isolated from the stems and leaves of Daphniphyllum calycinum. Their structures and relative configurations were established on the basis of spectral evidence (including 2D‐NMR) and subsequently confirmed by a single‐crystal X‐ray crystallographic diffraction analysis.     

Geometrical structures,electronic states,and stability of NinAl clusters

Density‐functional with generalized gradient approximation (GGA) for the exchange‐correlation potential has been used to calculate the energetically global‐minimum geometries and electronic states of Ni_nAl (n = 2–8) neutral clusters. Our calculations predict the existence of a number of previously unknown isomers. All structures may be derived from a substitution of a Ni atom at marginal positions by an Al atom in the Ni_n+1 cluster. Aluminum atom remains on the surface of the geometrical configurations. Moreover, these species prefer to adopt three‐dimensional (3D) spacial forms at the smaller number of nickel atoms compared with the pure Ni_n+1 (n ≥ 3) configuration. Atomization energies per atom for Ni_nAl (n = 2–8) have the same trend as the binding energies per atom for Ni_n (n = 3–9). The stabilization energies reveal that Ni₅Al is the relatively most stable in this series. In comparison with the magnetic moment of pure metal nickel (0.6 μ_B), the average magnetic moment of Ni atom increases in Ni Al clusters except the Ni₃Al. Moreover, except the case of Ni₅Al, Ni average magnetic moment decreases when alloyed with Al atoms than that in pure Ni clusters, which originate the effective charge transferring from Al to Ni atoms. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010     

Robin–Robin domain decomposition methods for the steady-state Stokes–Darcy system with the Beavers–Joseph interface condition

Domain decomposition methods for solving the coupled Stokes–Darcy system with the Beavers–Joseph interface condition are proposed and analyzed. Robin boundary conditions are used to decouple the Stokes and Darcy parts of the system. Then, parallel and serial domain decomposition methods are constructed based on the two decoupled sub-problems. Convergence of the two methods is demonstrated and the results of computational experiments are presented to illustrate the convergence.     

Microfluidic multi-analyte gradient generator

A microfluidic device was developed to produce temporal concentration gradients of multiple analytes. Four on-chip pumps delivered pulses of three analytes and buffer to a 14-cm channel where the pulses were mixed to homogeneity. The final concentration of each analyte was dependent on the temporal density of the pulses from each pump. The concentration of each analyte was varied by changing the number of pump cycles from each reservoir while maintaining the total number of pump cycles per unit time to ensure a constant total flow rate in the device. To gauge the independent nature of each pump, sinusoidal waves of fluorescein concentration were produced from each pump with independent frequencies and amplitudes. The resulting fluorescence intensity was compared with a theoretical summation of the waves and the experimental data matched the theoretical waves within 1%, indicating that the pumps were operating independently and outputting the correct frequency and amplitude. The device was used to demonstrate the role of adenosine triphosphate-sensitive K⁺ channels in glucose-stimulated increases in intracellular [Ca²⁺] in islets of Langerhans. Perfusion of single islets of Langerhans with combinations of glucose, diazoxide, and K⁺ resulted in intracellular Ca²⁺ patterns similar to what has been observed using conventional perfusion devices. The system will be useful in other studies with islets of Langerhans, as well as other assays that require the modulation of multiple analytes in time.     

An aspect ratio agglomeration multigrid for unstructured grids

A robust aspect ratio‐based agglomeration algorithm to generate high quality of coarse grids for unstructured and hybrid grids is proposed in this paper. The algorithm focuses on multigrid techniques for the numerical solution of Euler and Navier–Stokes equations, which conform to cell‐centered finite volume special discretization scheme, combines vertex‐based isotropic agglomeration and cell‐based directional agglomeration to yield large increases in convergence rates. Aspect ratio is used as fusing weight to capture the degree of cell convexity and give an indication of cell stretching. Agglomeration front queue is established to propagate inward from the boundaries, which stores isotropic vertex and also high‐stretched cell marked with different flag according to aspect ratio. We conduct the present method to solve Euler and Navier–Stokes equations on unstructured and hybrid grids and compare the results with single grid as well as MGridGen, which shows that the present method is efficient in reducing computational time for large‐scale system equations. Copyright © 2013 John Wiley & Sons, Ltd.     

A Shifted Double-Diamond Titania Scaffold

Photonic crystals are expected to be metamaterials because of their potential to control the propagation of light in the linear and nonlinear regimes. Biological single-network, triply periodic constant mean curvature surface structures are considered excellent candidates owing to their large complete band gap. However, the chemical construction of these relevant structures is rare and developing new structures from thermodynamically stable double-network self-organizing systems is challenging. Herein, we reveal that the shifted double-diamond titania scaffold can achieve a complete band gap. The largest (7.71 %) band gap is theoretically obtained by shifting 0.332 c with the dielectric contrast of titania (6.25). A titania scaffold with similar shifted double-diamond structure was fabricated using a reverse core–shell microphase-templating system with an amphiphilic diblock copolymer and a titania source in a mixture of tetrahydrofuran and water, which could result in a 2.05–3.78 % gap.     

Structure elucidation of four prenylindole derivatives from Streptomyces sp. isolated from Ailuropoda melanoleuca feces

Four new prenylindole derivatives, (R)‐6‐(2,3‐dihydroxy‐3‐methylbutyl)indole (1), (R)‐6‐(2,3‐dihydroxy‐3‐methylbutyl)indolin‐2‐one (2), and an unseparated mixture of (Z)‐6‐(4‐hydroxy‐3‐methylbut‐2‐en‐1‐yl)indolin‐2‐one (3a) and (E)‐6‐(4‐hydroxy‐3‐methylbut‐2‐en‐1‐yl)indolin‐2‐one (3b) with a ratio of 3 : 2, were isolated from the culture broth of a streptomycete isolated from Ailuropoda melanoleuca feces. Their structures were elucidated on the basis of 1D and 2D NMR spectroscopic techniques. The absolute configuration of 1 was determined by Mosher's method. Copyright © 2013 John Wiley & Sons, Ltd.     

Structure determination of selaginellins G and H from Selaginella pulvinata by NMR spectroscopy

Selaginellins G ( 1 ) and H ( 2 ), two new selaginellin derivatives, were isolated from the whole plant of Selaginella pulvinata. Their structures were elucidated, and complete assignments of the ¹H and ¹³C NMR spectroscopic data were achieved by 1D and 2D NMR experiments (HSQC, HMBC, COSY and ROESY). Compound 1 displayed good antifungal activity against Candida albicans with an IC₅₀ value of 5.3 µg/ml. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis and structure of a bowl-like molecule by threefold metathesis reactions

A bowl-like molecule was designed and efficiently synthesized by threefold metathesis reactions, and its structure was determined by NMR, MALDI-TOF MS spectrum, and X-ray crystallographic analysis.