Synthesis of Multisubstituted 2,3-Allenamides via Palladium-Catalyzed Carbonylation of Propargylic Esters.

2,3-Allenamides are an important class of unsaturated group-substituted carbonyl compounds. A palladium-catalyzed aminocarbonylation of propargyl acetates with amines for the synthesized tri-/tetrasubstituted 2,3-allenamides has been developed. A broad range of tri-/tetrasubstituted 2,3-allenamides have been prepared from propargyl acetates in good to excellent yields. The reaction featured mild reaction conditions and good functional group tolerance. The applicability of this methodology was further highlighted by the late-stage modification of several natural products and pharmaceuticals.

Cooperative Cu/Pd-Catalyzed 1,5-Boroacylation of Cyclopropyl-Substituted Alkylidenecyclopropanes.

A Cu/Pd-cocatalyzed 1,5-boroacylation of cyclopropyl-substituted ACPs with B2pin2 and acid chlorides has been developed. Using cyclopropyl-substituted ACPs as the starting material, a broad range of 1,5-boroacylated products with multiple functional groups was prepared in good yields with excellent regio- and stereoselectively. Both aromatic and aliphatic acid chlorides were tolerated in this reaction.

Ruthenium-Catalyzed Carbonylation of α-Aminoaryl-Tethered Alkylidenecyclopropanes: Synthesis of Eight-Membered Benzolactams.

The synthesis of medium-sized lactams is a great challenge because of the unfavorable transannular interactions and entropic barriers in the transition state. We have developed a ruthenium-catalyzed carbonylation of α-aminoaryl-tethered alkylidenecyclopropanes (ACPs) that allows for the efficient preparation of valuable eight-membered benzolactams under ligand-free conditions. The amino group served a dual role of both directing group and nucleophile to facilitate the metallacycle formation and the carbonylation.

Palladium Catalyzed Dicarbonylation of α-Iodo-Substituted Alkylidenecyclopropanes: Synthesis of Carbamoyl Substituted Indenones.

A palladium catalyzed dicarbonylation of α-iodo-substituted ACPs for the synthesis of carbamoyl substituted indenones has been developed. Two carbonyl groups were incorporated into the product with the cleavage of the proximal C-C bond of the ACPs. A broad range of carbamoyl substituted indenones were efficiently prepared in good to excellent yields.

Longitudinal magnetic resonance imaging of spinal cord injury in mouse: changes in signal patterns associated with the inflammatory response.

Contusion-type spinal cord injury (SCI) in mice was followed longitudinally using in vivo magnetic resonance (MR) imaging along with neurobehavioral tests performed on postinjury Days 1, 7, 14 and 28. Magnetic resonance images were acquired from seven injured wild-type mice using a 9.4-T scanner and presented in sagittal and axial views to reflect the current state of the injured cord neuropathology on each day. The data were analyzed individually to gain more insights on the neuroinflammatory response unique to the mouse, to characterize the spatiotemporal evolution of the lesion and to quantify the changes in lesion volume and length with time. The MR intensity patterns on Day 1 showed acute injuries as focal in one group of three mice and as diffuse in the remaining group of four mice. The focal injuries appeared as a region of hypointensity with well-defined boundaries. These injuries first enlarged on Day 7, but then shrunk slightly by Days 14 and 28. In contrast, the diffuse injuries were initially obscure on Day 1, mainly because of loss of contrast between gray and white matters. On Day 7, lesions expanded asymptotically in both rostral and caudal directions with respect to the epicenter, and maintained its size on Days 14 and 28. Previous studies based on postmortem histological analysis have reported lesions behaving more like in the focal group. However, this new injury with diffuse characteristics may have important implications for SCI research carried out with mice. Unique experiments on genetically engineered mice with altered neuroinflammatory response should help clarify the origin of these differences in the lesion formation.

Studies on alkaloids from Melodinus moraei / 中国中药杂志

To study the alkaloids from Melodinus moraei,seven compounds were separated and purified by column chromatography over silica gel, reverse phase silica gel and preparative HPLC. Their chemical structures were elucidated by MS and spectral data (1H-NMR, 13C-NMR) as scandine(1),tabersonine(2),melodinine N(3),melodinine P(4), melodinine T(5),19-epimeloscandonine(6),16-hydroxy-19S-vindolinine(7). Compounds 1-7 were isolated from M. moraei for the first time．The bioassays showed all tested samples displayed antitumor activity against the cell lines such as A549,PC-3,HGC-27 and HL-60.

Chemical constituents of Physalis pubescens / 中国中药杂志

Chemical constituents of 95% ethanol extract of the dried persistent calyx of Physalis pubescens were investigated. By chromatography on a silica gel column and reverse-phase preparative HPLC, 10 compounds were isolated from the dichloromethane fraction. Based on the MS and 1D/2D NMR data, these compounds were identified as 5-O-(E-feruloyl) blumenol (1), isovanillin (2), (E) -ethyl 3-(4-hydroxyphenyl) acrylate (3), 4-hydroxybenzaldehyde(4), 4-methylphenol (5), (E) -methyl cinnamate (6), 7,3',4' trimethoxyquercetin (7), 5,3', 5'-trihydroxy-3,7,4'-trimethoxyflavone(8), danielone (9), and 5,5'-diisobutoxy-2,2'-bifuran (10).

Preparation of alginate-chitosan-poly (lactic-co-glycolic acid) composite microsphere and its regulation of protein release / 药学学报

<p><b>AIM</b>To elevate the encapsulation efficiency, decrease the burst release and improve the release of protein entrapped in poly (lactic-co-glycolic acid) (PLGA) microspheres. The bovine serum albumin (BSA) composite microspheres of alginate-chitosan-PLGA were prepared and the release characteristics of BSA from this composite microspheres were studied.</p><p><b>METHODS</b>The much smaller calcium alginate microcapsules were first prepared by a modified emulsification method in an isopropyl alcohol-washed way and coated with chitosan, then the alginate-chitosan microcapsules were further entrapped in PLGA to form the composite microspheres. The protein concentration was determined using a BCA protein assay kit. The release profiles were changed with various formulation factors.</p><p><b>RESULTS</b>The average diameter of the composite microcapsules was about 30 microm. Comparing with 60% to 70% of the conventional PLGA microspheres, the average encapsulation efficiency was more than 80%, and the burst releases in phosphate buffer solution of the composite microspheres decreased from 40% and 50% to 25% and further to 5% in saline solution.</p><p><b>CONCLUSION</b>The novel composite microspheres were prepared, the drug encapsulation efficiency increased and the burst release decreased. The desired release profiles could be obtained by regulating the ratios of PLG and PLA in the composite microspheres.</p>

Effects of xianggui pill on cytokine in endometriosis model rat / 中国中药杂志

<p><b>OBJECTIVE</b>To study the adjustment of Xianggui pill on the cytokine of endometriosis model rat, and investigate the mechanism of Xianggui pill on the treatment of endometriosis.</p><p><b>METHOD</b>To set up endometriosis model by rat self-endometria transplantation, drench sodium chloride, Xianggui pill elixation or Danazol after grouping, and to detect the contents of interleukin-8 (IL-8) and tumor necrosis factor-alpha (TNF-alpha) by ELISA.</p><p><b>RESULT</b>The contents of IL-8, TNF-alpha in the peripheral blood and peritoneal fluid of model group were higher than that of the blank group; The quality of allotopia growth intima tissue, the quantity of macrophage in peritoneal fluid and the contents of IL-8, TNF-alpha in the Xianggui pill group and Danazol group were all lower than those of the model group; but there was no significant difference of each target between the Xianggui pill group and Danazol group.</p><p><b>CONCLUSION</b>Xianggui pill can restrain significantly the growth of allotopia intima tissue, and has apparently adjustment to the cytokine.</p>