ABSTRACT
Density functional theory calculations with a Hubbard U correction were used to investigate the selective oxidation of propylene on Cu2O(111) and Cu2O(110) surfaces, and the mechanism for the selective oxidation of propylene was discussed. On both surfaces, acrolein can be generated by two H-stripping reactions in the allylic hydrogen stripping path, while propylene oxide (PO), propanal, and acetone can be created through the propylene oxametallacycle intermediates in the epoxidation path. Our calculation results indicated that Cu2O has a high crystal plane-controlled phenomenon for the selective oxidation of propylene. It was found that the formations of propanal and acetone are unfavorable kinetically and acrolein is the main product on the (111) surface. On the (110) surface, the activation barrier of acrolein formation is too high to produce and PO becomes the favored product, which is different from the case of the (111) surface. Moreover, energetic span model analysis was carried out to discuss the selective oxidation of propylene on these two surfaces and confirm the above calculations. The present study can help people to design the proper crystal plane catalyst to get the target product of PO with high selectivity and activity in the selective oxidation of propylene.
ABSTRACT
Tamoxifen treatment is important assistant for estrogen-receptor-positive breast cancer (BRCA) after resection. This study aimed to identify signatures for predicting the prognosis of patients with BRCA after tamoxifen treatment. Data of gene-specific DNA methylation (DM), as well as the corresponding clinical data for the patients with BRCA, were obtained from The Cancer Genome Atlas and followed by systematic bioinformatics analyses. After mapping these DM CPG sites onto genes, we finally obtained 352 relapse-free survival (RFS) associated DM genes, with which 61,776 gene pairs were combined, including 1,614 gene pairs related to RFS. An 11 gene-pair signature was identified to cluster the 189 patients with BRCA into the surgical low-risk group (136 patients) and high-risk group (53 patients). Then, we further identified a tamoxifen-predictive signature that could classify surgical high-risk patients with significant differences on RFS. Combining surgical-only prognostic signature and tamoxifen-predictive signature, patients were clustered into surgical-only low-risk group, tamoxifen nonbenefit group, and tamoxifen benefit group. In conclusion, we identified that the gene pair PDHA2-APRT could serve as a potential prognostic biomarker for patients with BRCA after tamoxifen treatment.
