Stereoselective Synthesis of 1,3-Amino Alcohols by the Pd-Catalyzed Cyclization of Trichloroacetimidates

The synthesis of 4-vinyl-5,6-dihydro-1,3-oxazines, precursors of 1,3-amino alcohols, using the palladium-catalyzed cyclization of trichloroacetimidates is reported. The reaction favors the formation of the 4,6-<i>cis</i>-isomers with up to >20:1 diastereoselectivity. Chemoselective hydrolysis of the resulting 5,6-dihydro-1,3-oxazines was also investigated

Cosolvent Effects on Dechlorination of Soil-Sorbed Polychlorinated Biphenyls Using Bentonite Clay-Templated Nanoscale Zero Valent Iron

Zero-valent iron synthesized using bentonite clay as a template (CZVI) was tested for its reactivity toward polychlorinated biphenyl (PCB) dechlorination in soil slurries. Aqueous-phase decachlorobiphenyl (PCB209) was rapidly dechlorinated by CZVI with a reaction rate 10 times greater than that by conventional nanoscale zerovalent iron. This superior reactivity was due largely to the nanoscale size (∼0.5 nm) of the ZVI particles located in the clay galleries. In soil slurries where PCB209 was strongly soil-bound, adding ethanol as an organic cosolvent led to increased PCB209 desorption into the liquid phase, thereby enhancing the PCB209 dechlorination with CZVI. The more effective PCB209 dechlorination in such a cosolvent system also promoted the subsequent stepwise dechlorinative process, leading to a relatively more removal of chlorine in the product mixture. The dechlorination became more rapid as the ethanol fraction increased from 10% to 50%, due apparently to the increasingly greater PCB209 desorption and thus facilitated contact with CZVI. Further increase in ethanol fraction above 50% led to an insignificant enhancement in degradation rate, due partially to attenuated contact of PCB209 with CZVI and reduced proton source from limited water content in the liquid. It is suggested that addition of organic cosolvents may make CZVI potentially useful for remediation of soils containing halogenated organic contaminants

Changes in body weight, colon length and histological score of CD200^tg, WT, CD200R1KO and CD200KO mice with DSS-induced acute colitis.

<p>(A) Change in body weight. Percent weight loss from baseline (y-axis) is plotted versus time post initiation of DSS treatment (x-axis). Data points represent mean ± SD for 5 mice. (B) Change in colon length assessed on day 9 following initiation of DSS treatment for the same same mice as in panel A. Data are expressed as mean ± SD of five mice. (C) Change in histological score (again day 9 post start of DSS) for mice of panel A. All independent experiments were performed three times, yielding similar results. * p < 0.05; ** p < 0.01; *** p < 0.001 compared with WT controls on the same day.</p

Quantitation of staining of CD3⁺ and Foxp3⁺ cells in slides shown in Fig 5B and 5C.

<p>Quantitation of staining of CD3⁺ and Foxp3⁺ cells in slides shown in Fig <a href="http://www.plosone.org/article/info:doi/10.1371/journal.pone.0146681#pone.0146681.g005" target="_blank">5B and 5C</a>.</p

Effect of CD200 on expression of multiple cytokines and in DSS-induced acute colitis.

<p>Cytokines and chemokines were analyzed in colonic tissue from CD200^tg, WT, CD200R1KO and CD200KO mice with DSS-induced acute colitis. A and B, Real-time RT-PCR was performed using total RNA extracted from colonic tissue (5 samples/group) or LP cells (3 samples/group), with data normalized to the expression of GAPDH and HPRT in the same organ. Expression levels in CD200^tg, CD200R1KO and CD200KO mice (mean ± SD in 5 mice) are shown relative to that in WT at day 0 (designated as 1). * p < 0.05; ** p < 0.01; *** p < 0.001 compared to WT control (day 0). (C) Tissue explants from the four experimental groups were cultured and used for multi-analyte Elisarray. Again, relative expression levels of cytokine/chemokine (mean ± SD in 5 mice) in CD200^tg, CD200R1KO and CD200KO mice are shown compared to that in WT at day 0 (designated as 1), using the manufacturer’s software supplied. * p < 0.05; ** p < 0.01; *** p < 0.001, compared to this WT control (day 0). (D) Inflammatory cytokines measured by commercial ELISA (Biolegend: USA) in 36hr culture supernatants of colon-derived CD11c⁺, CD11b⁺, or CD4⁺ T cells (isolated by MACS columns) from WT, CD200^tg, CD200KO or CD200RKO mice 9 days post initiation of DSS treatment. Cells were obtained from a pool of 4 mice/group, and cultured without further stimulation for 36hrs in complete medium. In some cases, as shown, cells were cultured in the presence of CD200Fc (5mg/ml). Data show mean (<u>+</u>SD) of triplicate measurements. *, indicates p<0.05 compared with WT control; **indicates p<0.05 compared to equivalent group with no CD200Fc. E, Comparison of weight loss in 4 groups of DSS treated mice receiving anti-CD4mAb (right hand panel) or isotype control Ig (left hand panel)-see also <a href="http://www.plosone.org/article/info:doi/10.1371/journal.pone.0146681#pone.0146681.g001" target="_blank">Fig 1</a>. Data are for 4 mice/group, given 50mg Ig at days 4/7 post initiation of DSS treatment. Comparison of equivalent groups in right/left hand panels (Mann Whitney U-test) revealed no statistically significant differences.</p

Primers used for real- time PCR.

<p>Primers used for real- time PCR.</p

Quantitation of staining of F4/80⁺ and GR1⁺ cells in slides shown in Fig 2B and 2C.

<p>Quantitation of staining of F4/80⁺ and GR1⁺ cells in slides shown in Fig <a href="http://www.plosone.org/article/info:doi/10.1371/journal.pone.0146681#pone.0146681.g002" target="_blank">2B and 2C</a>.</p

Changes in body weight, colon length and histological score of CD200^tg, WT CD200R1KO and CD200KO mice with DSS-induced chronic colitis.

<p>(A) Change in body weight. Percent weight loss from baseline (y-axis) is plotted versus time post initiation of first cycle of DSS (x-axis). Data points represent mean ± SD for 5 mice. (B) Change in colon length assessed on 8 days post initiation of the third cycle of DSS for same mice. Data are expressed as mean ± SD of five mice. (C) Change in histological score (again 8 days post start of the third cycle of DSS) for same mice. All independent experiments were performed three times, yielding similar results. * p < 0.05; ** p < 0.01; *** p < 0.001 compared with WT controls on the same day-see also <a href="http://www.plosone.org/article/info:doi/10.1371/journal.pone.0146681#pone.0146681.g001" target="_blank">Fig 1</a>.</p

Effect of CD200 on histological changes and cell infiltration in colonic tissue from mice with DSS-induced acute colitis.

<p>Sections from colon (day 9 post start of DSS) of control (<i>a</i>), CD200^tg (<i>b</i>), WT (<i>c</i>), CD200R1KO (<i>d</i>) and CD200KO (<i>e</i>) mice were stained with (A) H&E, or with (B) rat anti-mouse F4/80, or (C) rat anti-mouse Gr1 mAbs, respectively. Percent staining in tissue is shown in <a href="http://www.plosone.org/article/info:doi/10.1371/journal.pone.0146681#pone.0146681.t001" target="_blank">Table 1</a>, counting 1000 cells for each group using 5 slides/group. (D) FACS staining with anti-F4/90 or anti-GR1 mAb using isolated LP cells obtained from the groups of mice documented above. Control cells were stained with Fluorochrome labeled mouse Ig.</p

Effect of CD200 on histological changes and cell infiltration in colons from mice with DSS-induced chronic colitis.

<p>Sections from colon (8 days post start of the third cycle of DSS) of control (<i>a</i>), CD200^tg (<i>b</i>), WT (<i>c</i>), CD200R1KO (<i>d</i>) and CD200KO (<i>e</i>) mice were stained with (A) H&E, or with (B) rat anti-mouse CD3, or (C) rat anti-mouse Foxp3 mAbs, respectively-see also <a href="http://www.plosone.org/article/info:doi/10.1371/journal.pone.0146681#pone.0146681.g002" target="_blank">Fig 2</a>. Percent staining in tissue is shown in <a href="http://www.plosone.org/article/info:doi/10.1371/journal.pone.0146681#pone.0146681.t003" target="_blank">Table 3</a> using counts of 1000 cells for each group (5 slides/group).</p