Selective Hydrogenolysis of Glycerol over Acid-Modified Co–Al Catalysts in a Fixed-Bed Flow Reactor

In this study, different acid-modified Co–Al catalysts were prepared and employed for glycerol hydrogenolysis by the addition of B, Ce, Zr, and heteropolyacids (HSiW, HPW, HPMo) to Co–Al catalysts. The catalysts prepared in this work were thoroughly examined by various characterization methods such as BET, ICP, SEM, H₂ chemisorption, TEM, XRD, H₂-TPR, NH₃-TPD, XPS, and FTIR. The results showed an increase in the acid strength and Co dispersion on the catalytic surface for the modified Co–Al catalysts. This facilitated the conversion of glycerol. When ethanol was used as a solvent, the selectivity of 1,2-propanediol (1,2-PDO) by the acid-modified Co–Al catalysts decreased slightly, attributable to the enhanced etherification activity of glycerol with ethanol. However, when water was used as a solvent, the modified Co–Al catalyst with the B, Ce, and Zr species increased the selectivity of 1,2-PDO. Addition of heteropolyacids to the Co–Al catalyst enhanced the selectivity of 1,3-propanediol (1,3-PDO) as compared to 1,2-PDO selectivity which was relatively low due to its association with Brønsted acid sites on the modified Co–Al catalysts. The optimal HSiW/Co–Al catalyst (in terms of both 1,2- and 1,3-PDO selectivity) showed 76.3% glycerol conversion and 18.3% 1,3-PDO selectivity with a good stability. This could be attributed to the existence of well-dispersed Co particles with strong interaction between Co and W species

Down-regulating BC expression suppressed cell growth in several mouse cell lines.

<p>(<b>A, C</b> and <b>E</b>) Quantitative PCR results showing knock-down efficiency of BC siRNAs in NIH/3T3, Hepa 1–6 or SV40 MES 13 cells at 48 h after siRNA transfection. Data were mean ± s.d. of at least three independent experiments. (<b>B, D</b> and <b>F</b>) Cell numbers of NIH/3T3, Hepa 1–6 and SV40 MES 13 cells at indicated times after siRNA transfection. Data were mean ± s.d. of at least three independent experiments performed in triplicate. Values shown on top of bars are <i>P</i> values <i>vs</i> nonsense.</p

Selection of sensitive and specific genotoxic stress responsive genes.

<p>(<b>A</b>) Hierarchical clustering of top 50 scored up-regulated genes shown in gene symbol. Red and green indicate up-regulation and down-regulation, respectively. The orange box represents genes whose expression could distinguish GTXs from NGTXs. The blue box represents the gene with the highest score, BC005512. (<b>B</b> and <b>C</b>) Microarray and quantitative PCR (qPCR) data showing BC expression levels in livers of mice dosed with indicated chemicals at 4 h or 20 h after administration. Microarray data represented pooled samples from 4 animals per group. Quantitative PCR data were mean ± s.d. (n = 4).</p

BC005512 is a member of the GLN family of murine endogenous retrovirus.

<p>Sequence alignment between BC005512, BC062922 and MMERGLN_I. Locations of the genechip probe, quantitative PCR primers (BC-F and BC-R) and BC siRNAs are shown.</p

Expression of BC was specifically induced by GTXs in NIH/3T3 cells.

<p>Data from quantitative PCR showing transcriptional expression of BC in NIH/3T3 cells treated with genotoxic or non-genotoxic chemicals for indicated time. Data were mean ± s.d. of three independent experiments.</p

Induced expression level of BC correlated with DNA damage in NIH/3T3 cells.

<p>(<b>A, B, D, E, G and H</b>) Comparison between expression level of BC and DNA damage in NIH/3T3 cells exposed to MMS (A, B) for 8 h, or to colchicine (D, E) or paclitaxel (G, H) for 24 h. DNA damage was measured by olive tail moment (tail length × percentage of DNA in tail) in an alkaline comet assay (representative figures are shown in B, E and H). Data were mean±s.d. of three independent experiments. (<b>C</b>) Linear regression analysis between expression level of BC and DNA damage, reflected by olive tail moment. Each dot represents the mean of data shown in (A), (D) and (G). (<b>F</b> and <b>I</b>) Micronucleus frequency in NIH/3T3 cells exposed to colchicine or paclitaxel for 24 h. Data were mean ± s.d. of three independent experiments. Values shown on top of bars are <i>P</i> values <i>vs</i> control.</p

Model compounds selected in the <i>in vivo</i> microarray study.

1<p>Abbr: Abbreviation;</p>2<p>CAS: Chemical Abstracts Service.</p

Model compounds selected in the <i>in vitro</i> BC induction study.

<p>Model compounds selected in the <i>in vitro</i> BC induction study.</p

Weight score for genotoxic stress responsive gene selection in the <i>in vivo</i> microarray study (liver, B6C3F1).

1<p>“V” represents values.</p>2<p>“S” represents score. Only the top 20 genes are shown. A full list is attached in <a href="http://www.plosone.org/article/info:doi/10.1371/journal.pone.0035010#pone.0035010.s012" target="_blank">Table S3</a>.</p><p>Detailed scoring rules are described in the supporting information. “Pink cells” represent up-regulation and “blue cells” represent down-regulation.</p><p><b>Specificity</b> = (number of total pink cells in GTXs)/(number of total pink cells in GTXs and NGTXs); <b>Ave ratio</b> = average of ratios of all pink cells in GTXs; <b>Positive condition</b> = number of total pink cells in GTXs. Since DEN was duplicated, each pink cell was considered 0.5; <b>Positive chemical</b> = number of GTXs with at least one pink cell; <b><i>P</i></b><b> value</b> was calculated by <i>t</i> test of signal intensity between GTXs and NGTXs in GeneSpring software; <b>Basal</b> represents basal expression level, equals to log₁₀ value of signal intensity of control animals; <b>Reverse change</b> reflects opposite change of gene expression in different treatment groups. Reverse change = number of blue cells in NGTXs - number of blue cells in GTXs; <b>CV%</b> = 100×SD/MEAN% based on the signal intensity of all control animals. <b>Total score</b> = Score of 2× Specificity + Ave ratio + Positive condition + Positive chemical + <i>P</i> value + 0.5× Basal + 0.5× Reverse change + 0.5× CV%.</p