Eight ferrocenyl derivatives were synthesized and characterised by NMR, elemental analyses and X-ray single crystal diffraction analysis. The anticancer activities of the eight compounds were assessed where applicable in the two breast cancer cell lines, MCF-7 and MDA-MB-231. It was found that the cytotoxicity of N -Phenyl- N -(2-Methyl-4-Methoxyphenyl)ferrocenecarboxamide ( 4 ) and N , N -bis(4-Methoxyphenyl)ferrocenecarboxamide ( 8 ) correlates to their relatively positive reduction potentials, which may suggest that the cytotoxicity stems from their involvement in electron transfer process. Furthermore, comparing the activity of N , N -bis(phenyl)ferrocenecarboxamide ( 3 ) to that of compounds 4 and 8 suggest that their methoxyl group may undergo demethylation under physiological conditions to generate biologically active species and thus they exhibited better activity in the two breast cancer cell lines compared to compound 3 .
The hydrodemethoxylation (HDMO) of lignin-derived monophenolics to alkylphenols is a crucial step for the conversion of lignin bio-oil into chemicals. A new FeNi 3 alloy catalyst was firstly prepared by being reduced in-suit from Fe, Ni oxides precursor. The FeNi 3 /FeNi 8 O 9.25 catalyst prepared using optimal 12:88 of molar ratio of iron nitrate to nickel nitrate showed good catalytic activity and selectivity to HDMO of lignin-derived monophenolics. In the HDMO process of lignin-derived 4-propylguaiacol, FeNi 3 /FeNi 8 O 9.25 contributed to a 94.53 % of conversion and a 90.67 % of demethoxylation selectivity under 0.4 MPa H 2 at 280 °C for 2 h. Compared with the Ni/Ni 1 O catalyst, the FeNi 3 /FeNi 8 O 9.25 catalyst increased by 6.19 times and 2.35 times of the specific surface area and total acid amount, respectively. FeNi 3 (111) possessed lower adsorption energy to substrate and changed adsorption configuration of the benzene ring in tilted mode. Consequently, prepared catalyst facilitated the removal of methoxy group, as well as suppressing hydrogenation saturation of the benzene ring. Moreover, FeNi 3 /FeNi 8 O 9.25 catalyst exhibited versatile capacity of HDMO to different lignin-derived monophenolics and high stability. This work offers a new strategy for constructing non-noble metallic alloy catalyst for highly selective HDMO reactions.
Polychlorinated biphenyls (PCBs) and their biotransformation products, hydroxylated (OH-PCBs) and methoxylated derivatives (MeO-PCBs), have been detected in the environment and biota, especially crops. However, to date, little information is available on the phytotoxicity and metabolic responses induced by these chemicals in crops. In this study, we exposed rice ( Oryza sative L.) seedlings to 2,3,4,5-tetrachlorobiphenyl (CB-61) and its hydroxylated (4′-OH-CB-61) and methoxylated derivatives (4′-MeO-CB-61) at 0, 10, 50, 100 and 500 μg/L, respectively. After exposure for 14 days, significantly growth inhibition and oxidative damage were observed, among which the toxicities of 4′-OH-CB-61 and 4′-MeO-CB-61 were greater than that of the parent PCBs. Metabolomics analysis indicated that exposure to the three chemicals induced different metabolic responses. 4′-MeO-CB-61 mainly affected the saccharide catabolism, including pyruvate metabolism, the TCA cycle, the transfer of acetyl groups into mitochondria and the Warburg effect, resulting in a greater energy consumption. Moreover, both CB-61 and 4′-OH-CB-61 promoted several amino acid metabolism and fatty acid biosynthesis, thereby alleviating the potential ROS damage. This study for the first time evaluates and reveals the phytotoxicity of OH-PCBs and MeO-PCBs at the metabolic level, which attempts to provide important information for accurately evaluating the environmental risks of PCBs from the perspective of metabolism.