Control of N‐Heterocyclic Carbene Catalyzed Reactions of Enals: Asymmetric Synthesis of Oxindole‐γ‐Amino Acid Derivatives

A strategy to control the switch between a non‐cycloaddition reaction and a cycloaddition reaction of enals, using N‐heterocyclic carbene (NHC) catalyisis, has been developed. The new scalable protocol leads to γ‐amino‐acid esters bearing a tetrasubstituted stereocenter in good yields and high stereoselectivities by homo‐Mannich reactions of enals and isatin‐derived ketimines. By simply changing the N‐ketimine substituent to an ortho‐hydroxy phenyl group, the corresponding spirocyclic oxindolo‐γ‐lactams are obtained.     

Diarylheptanoids from the fresh pericarps of Juglans sigillata

One new diarylheptanoid (3S)-3′, 4″-epoxy-1-(4′-hydroxylphenyl)-7-(3″-hydroxylphenyl) heptane-3-hydroxy (1), together with eleven known ones (2–12), was isolated from the fresh pericarps of Juglans sigillata. Their structures were elucidated on the basis of extensive spectroscopic methods, including HR-ESI-MS, 1D and 2D-NMR. All isolates were evaluated for their cytotoxic activities in vitro against the growth of human cancer cells lines HT-29 and MCF-7 by MTT assay.     

Ag-Cu Nanoparticles Supported on N-Doped TiO\begin{document}$_2$\end{document} Nanowire Arrays for Efficient Photocatalytic CO\begin{document}$_2$\end{document} Reduction

Photocatalytic reduction of CO\begin{document}$_2$\end{document} into various types of fuels has attracted great interest, and serves as a potential solution to addressing current global warming and energy challenges. In this work, Ag-Cu nanoparticles are densely supported on N-doped TiO\begin{document}$_2$\end{document} nanowire through a straightforward nanofabrication approach. The range of light absorption by N-doped TiO\begin{document}$_2$\end{document} can be tuned to match the plasmonic band of Ag nanoparticles, which allows synergizing a resonant energy transfer process with the Schottky junction. Meanwhile, Cu nanoparticles can provide active sites for the reduction of CO\begin{document}$_2$\end{document} molecules. Remarkably, the performance of photocatalytic CO\begin{document}$_2$\end{document} reduction is improved to produce CH\begin{document}$_4$\end{document} at a rate of 720 \begin{document}$\mu$\end{document}mol\begin{document}$\cdot$\end{document}g\begin{document}$^{-1}$\end{document}\begin{document}$\cdot$\end{document}h\begin{document}$^{-1}$\end{document} under full-spectrum irradiation.     

Defects and microvoids in a-Si and a-Si:H

We report the first measurements of positron-annihilation spectra of samples of both pure and hydrogenated amorphous silicon. Comparison of these spectra with that of crystalline silicon indicates that the lowest-lifetime component can be identified as the contribution mainly from valence-band electrons. Both the pure (a-Si) and the hydrogenated (a-Si:H) samples exhibit a component with intermediate lifetime, which we attribute to small vacancies consisting of about 4 missing atoms. Finally, only a-Si:H shows a significant long-lived line (τ > 5 ns), which arises from large microvoids, with ～ 100 missing atoms. The existence of these microvoids in a-Si:H is consistent with recent reports of the presence of occluded H₂ gas under high pressure in such films.     

Modular synthesis of candidate indole-based insulin mimics by Claisen rearrangement

A modular synthetic route to (indolyl)kojic acid anti-diabetes agents has been developed. Sonogashira coupling of a protected iodoaniline with a propargyl kojate was used to construct an (indole)methyl kojate. Its heteroaromatic Claisen rearrangement, followed by tautomerization to return the indole and pyrone rings, was used to create the biaryl C-C bond. This route should enable collections of insulin mimic drug candidates to be prepared from a few basic building blocks.     

Distribution of Selmer groups of quadratic twists of a family of elliptic curves

We study the distribution of the size of the Selmer groups arising from a 2-isogeny and its dual 2-isogeny for quadratic twists of elliptic curves with full 2-torsion points in Q. We show that one of these Selmer groups is almost always bounded, while the 2-rank of the other follows a Gaussian distribution. This provides us with a small Tate-Shafarevich group and a large Tate-Shafarevich group. When combined with a result obtained by Yu [G. Yu, On the quadratic twists of a family of elliptic curves, Mathematika 52 (1-2) (2005) 139-154 (2006)], this shows that the mean value of the 2-rank of the large Tate-Shafarevich group for square-free positive integers n less than X is , as X→∞.     

Single-molecule detection of DNA via sequence-specific links between F1-ATPase motors and gold nanorod sensors

We report the construction of a novel biosensing nanodevice to detect single, sequence-specific target DNA molecules. Nanodevice assembly occurs through the association of an immobilized F1-ATPase molecular motor and a functionalized gold nanorod via a single 3',5'-dibiotinylated DNA molecule. Target-dependent 3',5'-dibiotinylated DNA bridges form by combining ligation and exonucleation reactions (LXR), with a specificity capable of selecting against a single nucleotide polymorphism (SNP). Using dark field microscopy to detect gold nanorods, quantitation of assembled nanodevices is sufficient to distinguish the presence of as few as 1800 DNA bridges from nonspecifically bound nanorods. The rotary mechanism of F1-ATPase can drive gold nanorod rotation when the nanorod is attached via the DNA bridge. Therefore, rotation discriminates fully assembled devices from nonspecifically bound nanorods, resulting in a sensitivity limit of one zeptomole (600 molecules).     

One-pot three component synthesis of heteroarylated arylacetates via VNSAr-SN reaction using N-methylpyrrolidone as general solvent

An efficient three component one-pot method was developed to assemble 2-heteroaryl-2-aryl acetates via VNS(Ar)-S(N)Ar and VNS(Ar)-S(N) reaction by using N-methylpyrrolidone (NMP) as general solvent.     

Cobalt-catalyzed hydrogen desorption from the LiNH2-LiBH4 system

A doping of 5 wt% CoCl2 considerably decreases the dehydrogenation temperature of a mixture of LiNH2 and LiBH4. More that 8 wt% of hydrogen can be released at ca. 155 degrees C. X-Ray absorption near edge structure (XANES) spectroscopy indicated the formation of metallic Co after ball milling CoCl2 with LiNH2 and LiBH4. Extended X-ray absorption fine structure (EXAFS) spectroscopy measurements revealed that Co particles have poor crystallinity and are finely dispersed in the sample, which could lead to a high catalytic efficiency.