Domino Rh-catalyzed hydroformylation–doublecyclization of o-amino cinnamyl derivatives:applications to the formal total syntheses ofphysostigmine and physovenine

A parallel, versatile and efficient route to synthesis of pyrrolidinoindoline and tetrahydrofuranoindoline alkaloids from cinnamyl derivatives has been developed, featuring a domino Rh-catalyzed hydroformylation–double cyclization sequence. This method can be applied to the syntheses of anti-Alzheimer drugs such as physostigmine and physovenine

α-Lactosylceramide Protects Against iNKT-Mediated Murine Airway Hyperreactivity and Liver Injury Through Competitive Inhibition of Cd1d Binding.

Invariant natural killer T (iNKT) cells, which are activated by T cell receptor (TCR)-dependent recognition of lipid-based antigens presented by the CD1d molecule, have been shown to participate in the pathogenesis of many diseases, including asthma and liver injury. Previous studies have shown the inhibition of iNKT cell activation using lipid antagonists can attenuate iNKT cell-induced disease pathogenesis. Hence, the development of iNKT cell-targeted glycolipids can facilitate the discovery of new therapeutics. In this study, we synthesized and evaluated α-lactosylceramide (α-LacCer), an α-galactosylceramide (α-GalCer) analog with lactose substitution for the galactose head and a shortened acyl chain in the ceramide tail, toward iNKT cell activation. We demonstrated that α-LacCer was a weak inducer for both mouse and human iNKT cell activation and cytokine production, and the iNKT induction by α-LacCer was CD1d-dependent. However, when co-administered with α-GalCer, α-LacCer inhibited α-GalCer-induced IL-4 and IFN-γ production from iNKT cells. Consequently, α-LacCer also ameliorated both α-GalCer and GSL-1-induced airway hyperreactivity and α-GalCer-induced neutrophilia when co-administered in vivo. Furthermore, we were able to inhibit the increases of ConA-induced AST, ALT and IFN-γ serum levels through α-LacCer pre-treatment, suggesting α-LacCer could protect against ConA-induced liver injury. Mechanistically, we discerned that α-LacCer suppressed α-GalCer-stimulated cytokine production through competing for CD1d binding. Since iNKT cells play a critical role in the development of AHR and liver injury, the inhibition of iNKT cell activation by α-LacCer present a possible new approach in treating iNKT cell-mediated diseases

Asteroid Spin-Rate Study using the Intermediate Palomar Transient Factory

Two dedicated asteroid rotation-period surveys have been carried out using data taken on January 6-9 and February 20-23 of 2014 by the Intermediate Palomar Transient Factory (iPTF) in the $R$~band with $\sim 20$-min cadence. The total survey area covered 174~deg$^2$ in the ecliptic plane. Reliable rotation periods for 1,438 asteroids are obtained from a larger data set of 6,551 mostly main-belt asteroids, each with $\geq 10$~detections. Analysis of 1751, PTF based, reliable rotation periods clearly shows the "spin barrier" at $\sim 2$~hours for "rubble-pile" asteroids. We also found a new large-sized super-fast rotator, 2005 UW163 (Chang et al., 2014), and other five candidates as well. Our spin-rate distributions of asteroids with $3 < D < 15$~km shows number decrease when frequency greater than 5 rev/day, which is consistent to that of the Asteroid Light Curve Database (LCDB, Warner et al., 2009) and the result of (Masiero et al., 2009). We found the discrepancy in the spin-rate distribution between our result and (Pravec et al., 2008, update 2014-04-20) is mainly from asteroids with $\Delta m < 0.2$ mag that might be primarily due to different survey strategies. For asteroids with $D \leq 3$~km, we found a significant number drop at $f = 6$ rev/day. The YORP effect timescale for small-sized asteroid is shorter that makes more elongate objets spun up to reach their spin-rate limit and results in break-up. The K-S test suggests a possible difference in the spin-rate distributions of C- and S-type asteroids. We also find that C-type asteroids have a smaller spin-rate limit than the S-type, which agrees with the general sense that the C-type has lower bulk density than the S-type.Comment: Submitted to ApJ (Jan, 2015). Accepted by ApJ (June, 2015). The whole set of the folded lightcurves will be available on the published articl

Pair-density wave signature observed by x-ray scattering in La-based high-TcT_{\rm c} cuprates

Suggestive, but indirect evidence of the existence of pair-density wave (PDW) order in several high-$T_{\rm c}$ cuprates has been reported. As this constitutes a new quantum phase of matter, it is important to {\it establish} its existence at least somewhere in the phase diagram. However, a direct correspondence between experiment and theory has remained elusive. Here, we report the observation of a theoretically predicted PDW {\it bulk} signature in two La-based cuprates, Sr-doped La$_{1.875}$Ba$_{0.125}$CuO$_4$ and Fe-doped La$_{1.87}$Sr$_{0.13}$CuO$_4$, through a comprehensive study that incorporates zero-magnetic field x-ray scattering, neutron scattering, and transport measurements. Specifically, we observe the emergence of so-called "1Q" order, which is to say subharmonic order associated with the charge-density wave (CDW) stripes, in a range of temperatures in which independent evidence suggests the co-existence of PDW long-range order and fluctuating uniform superconducting order. The subharmonic order is most pronounced around a half-integer $l$-vector, where the CDW diffraction peak is also strongest. This is consistent with the theoretical proposal that the cancellation of the Josephson coupling ("layer-decoupling"), is a signature of PDW order and that it is commensurately locked to the density wave stripes that are known to alternate orientation between adjacent layers. Even if the PDW is not the "mother of all state", it is at least a close relative -- possibly a second cousin

313 new asteroid rotation periods from Palomar Transient Factory observations

A new asteroid rotation period survey have been carried out by using the Palomar Transient Factory (PTF). Twelve consecutive PTF fields, which covered an area of 87 deg$^2$ in the ecliptic plane, were observed in $R$ band with a cadence of $\sim$20 min during February 15--18, 2013. We detected 2500 known asteroids with a diameter range of 0.5 km $\leq D \leq$ 200 km. Of these, 313 objects had highly reliable rotation periods and exhibited the "spin barrier" at $\sim2$ hours. In contrast to the flat spin rate distribution of the asteroids with 3 km $\leq D \leq$ 15 km shown by Pravec et al. (2008), our results deviated somewhat from a Maxwellian distribution and showed a decrease at the spin rate greater than 5 rev/day. One super-fast-rotator candidate and two possible binary asteroids were also found in this work.Comment: 18 pages, 20 figures and 2 very long table

High pressure evolution of Fe2_{2}O3_{3} electronic structure revealed by X-ray absorption

We report the first high pressure measurement of the Fe K-edge in hematite (Fe$_2$O$_3$) by X-ray absorption spectroscopy in partial fluorescence yield geometry. The pressure-induced evolution of the electronic structure as Fe$_2$O$_3$ transforms from a high-spin insulator to a low-spin metal is reflected in the x-ray absorption pre-edge. The crystal field splitting energy was found to increase monotonically with pressure up to 48 GPa, above which a series of phase transitions occur. Atomic multiplet, cluster diagonalization, and density-functional calculations were performed to simulate the pre-edge absorption spectra, showing good qualitative agreement with the measurements. The mechanism for the pressure-induced phase transitions of Fe$_2$O$_3$ is discussed and it is shown that ligand hybridization significantly reduces the critical high-spin/low-spin pressure.Comment: 5 pages, 4 figures and 1 tabl