Protocol for the preparation and application of CeO2-CuO catalysts in the decarboxylative oxidation reaction of benzoic acids to phenols.

Phenolic chemicals are important building blocks in chemical and material industries. In this protocol, we describe the preparation of CeO2-CuO catalysts and the application in the decarboxylative oxidation reaction of benzoic acids to phenols. Furthermore, we describe how to modify the basic sites of CeO2-CuO catalysts by CO2 treatment to increase the selectivity of phenol and the regeneration process of used catalyst. For complete details on the use and execution of this protocol, please refer to Du et al. (2023).1.

Effect of feeding corn silage on semen quality and spermatogenesis of bulls.

Bovine reproduction, including male fertility traits like semen quality, are influenced by a variety of different factors like breed, nutrition, environment, and feeding management. Diet in a crucial determinant, and in this regard although corn silage is generally considered to be a favorable roughage for fattening meat type breeds, it tends to have a negative impact on semen quality. In the current study, alfalfa hay was substituted by corn silage as a roughage source in the diet of bulls to investigate its effects on the fertility of breeding bulls. A feeding trail spanning 140 days was conducted, with semen collection occurring twice a week commencing 60 days after the start of trial. Semen quality parameters, serum antioxidant indexes, sex hormone content in semen, rumen microflora, and sperm transcriptome were characterized. Feeding corn silage enhanced host antioxidant capacity, significantly decreased spermatozoal motility and increased sperm deformity rate in bulls. Furthermore, follicle-stimulating hormone (FSH) and luteinizing hormone (LH) content in semen were significantly decreased (P < 0.05), and the inhibin B (INHB) content was significantly increased (P < 0.01). Feeding corn silage led to significant changes in the diversity of rumen microbiota of cattle at the phylum and genus levels, some of which were significantly correlated with semen quality. Subsequent RNA sequencing indicated that DHH and PITHD1, two genes related to sperm and reproductive development, were differentially expressed, and enrichment analysis also identified several pathways and biological functions relevant to sperm development and reproduction. These results indicate that feeding corn silage modulates semen quality via different pathways. Firstly, corn silage metabolites likely affect the secretion of INHB through the testicular capillaries, which affects semen quality by regulating genes involved in spermatogenesis. Secondly, low lignin content in silage corn appears to reduce abundance of rumen flora that are positively correlated with semen quality. Overall, results indicate that feeding bulls corn silage as the primary source of forage could negatively impact semen quality and may not be appropriate as the primary roughage of forage for breeding bulls.

Selective nucleophilic α-C alkylation of phenols with alcohols via Ti=Cα intermediate on anatase TiO2 surface.

C-C bond forming reaction by alkylation of aryl rings is a main pillar of chemistry in the production of broad portfolios of chemical products. The dominant mechanism proceeds via electrophilic substitution of secondary and tertiary carbocations over acid catalysts, forming multiple aryl alkylation products non-selectively through all secondary and tertiary carbons in the alkyl chains but producing little α-C alkylation products because primary carbocations are poorly stable. Herein, we report that anatase TiO2 (TiO2-A) catalyzes nucleophilic α-C alkylation of phenols with alcohols in high selectivity to simply linear alkylphenols. Experimental and computational studies reveal the formation of Ti=C- bond with the α-carbon of the alkyl group at oxygen vacancies of the TiO2-A surface. The subsequent α-C alkylation by selective substitution of phenol ortho-C-H bond is verified by deuterium exchanged substrate and DFT calculations.

Selective synthesis of meta-phenols from bio-benzoic acids via regulating the adsorption state.

Phenols are important building blocks widely applied in many fields. The pronounced orientational effect of the phenolic hydroxyl group makes achieving selective synthesis of meta-phenols challenging. Accessing meta-phenols needs lengthy synthetic sequences. Herein, we first developed a heterogeneous CO2-mediated CeO2-5CuO catalyst for decarboxylative oxidation of benzoic acids with a more than 80% selectivity to meta-phenols. This technology is based on a traceless directing group relay method. The CeO2-CuO catalysts with different Ce/Cu ratios exhibited controllable reaction selectivity between decarboxylation and decarboxylative oxidation. Spectroscopy experiments and computational studies showed the adsorption state of benzoic acid was found to be crucial for subsequent reaction pathways. The moderate adsorption on CO2-mediated CeO2-5CuO catalyst contributes to the distinct selectivity of phenol. Furthermore, the paddlewheel intermediate facilitates the synthesis of meta-phenols from benzoic acids. This traceless directing group method would promote the development of useful one-pot meta-substituted phenols from bio-based benzoic acids.

Radical-Friedel-Crafts benzylation of arenes with benzyl ethers over 2H-MoS2: ether cleavage into carbon- and oxygen-centered radicals.

The selective activation of C-O ether bonds is an essential tool in organic synthesis and natural polymer depolymerization. However, the direct cleavage of the ether bond is still challenging work, especially breaking this inert and redox-neutral bond to provide one active carbon radical and another oxygen-centered fragment with oxidation capacity that can participate in the controllable radical reaction. We herein report that commercial 2H-MoS2 with negligible acidity can efficiently catalyze the benzylation of arenes with benzyl ethers, and a new Radical-Friedel-Crafts mechanism is proposed, which is quite different from the strong acid-catalyzed Friedel-Crafts mechanism. With dibenzyl ether as the model benzylation reagent, 2H-MoS2 can achieve the homolytic cleavage of the Bn-OR bond to generate the benzyl carbon radical and RO˙ species, identified by EPR measurement and radical trap experiments. The following radical-involved benzylation is confirmed by the Hammett results and a plausible pathway is proposed to clarify the Radical-Friedel-Crafts process. Heterogeneous 2H-MoS2 can be consecutively used four times without regeneration and it offers 94-95% yields of 2-benzyl-1,4-dimethylbenzene from dibenzyl ether and p-xylene in 30 min at 140 °C. Furthermore, this mechanism can provide some inspiration to activate the ether bond and to utilize ether as an oxidant in C-H bond activation.

Mitochondrial DNA polymorphisms in COX1 affect the lifespan of Caenorhabditis elegans through nuclear gene dct-15.

Mutations in the mitochondrial DNA (mtDNA) are closely related to age and age-related complex diseases, but the exact regulatory mechanism of mtDNA natural variation or polymorphism and ageing remains unclear. Recently, nuclear genes that regulate mitochondrial functions and thereby influence ageing have been widely studied. In this study, the relationship between the retrograde communication from the mitochondria to the nucleus and its ultimate effect on ageing has been elucidated. This study found that the natural variations in COX1 of the mitochondria in the Caenorhabditis elegans population do not correlate with multiple phenotypes, except for a mild correlation with lifespan. After excluding the differences in the nuclear genome, the correlation between natural mitochondrial variation and lifespan increased significantly. Moreover, mtDNA variation downregulated the nuclear dct-15 gene expression, which consequently reduced the lifespan, development rate and motility of C. elegans. dct-15 mutations decreased mitochondria copy number but increased ATP content and mitochondrial ultrastructure. Thus, the results indicated that dct-15 interacted with the mitochondrial DNA polymorphisms in COX1 and is associated with ageing. Finally, bioinformatic analyses revealed that mtDNA variation regulated the structural constituent of the cuticle via dct-15 and suggested that the structural constituent of the cuticle could have an important role in the development and ageing processes. These results provide insights into the mtDNA mechanism that can alter the nuclear gene and thereby regulate ageing and ageing-related diseases.

Screening and validation of reference genes for qRT-PCR of bovine skeletal muscle-derived satellite cells.

The accuracy of sixteen commonly used internal reference genes was assessed in skeletal muscle-derived satellite cells of Qinchuan cattle at different stages of proliferation and induction of differentiation to determine the most suitable ones. Quantitative real-time PCR and three commonly used algorithmic programs, GeNorm, NormFinder and BestKeeper, were used to evaluate the stability of expression of the candidate internal reference genes (GAPDH, ACTB, PPIA, LRP10, HPRT1, YWHAZ, B2M, TBP, EIF3K , RPS9, UXT, 18S rRNA, RPLP0, MARVELD, EMD and RPS15A) in skeletal muscle-derived satellite cells at 0, 12, 24, 36 and 48 h of growth and after differentiation for 0, 2, 4, 6 and 8 days. The expression of two satellite cell marker genes, CCNA2 and MYF5, was used for validation analysis. The results of the software analyses showed that GAPDH and RPS15A were the most stable reference gene combinations during in vitro proliferation of bovine skeletal muscle-derived satellite cells, RPS15A and RPS9 were the most stable reference gene combinations during in vitro induction of differentiation of the cells, and PPIA was the least stable reference gene during proliferation and differentiation and was not recommended. This study lays the foundation for the selection of reference genes for qRT-PCR during the proliferation and induction of differentiation of bovine skeletal muscle-derived satellite cells.

Performance of a recirculating aquaculture system using biofloc biofilters with convertible water-treatment efficiencies.

To achieve high water-treatment efficiencies and simplify the setup of recirculating aquaculture systems (RAS), this study examined the use of suspended growth reactors (R1 and R2) based on biofloc technology (BFT) as water-treatment biofilters. Moreover, the conversion of the heterotrophic R1 biofilter to a nitrifying role was investigated. During RAS operation using heterotrophic BFT biofilters, R1 and R2 simultaneously controlled total ammonium nitrogen, nitrite (NO2--N), nitrate (NO3--N), soluble reactive phosphate (SRP), and alkalinity, with relevant functional microbes including denitrifying bacteria (DNB), phosphorus accumulating organisms (PAOs), denitrifying PAOs (DNPAOs), glycogen accumulating organisms, ammonia oxidizing bacteria, and nitrite oxidizing bacteria. To achieve low concentrations of nitrogen, phosphorus, and save carbon sources, we were able to quickly convert R1 into a nitrifying BFT biofilter by stopping carbohydrate addition. Although there were dominant relative abundances of DNB, PAOs, and DNPAOs in the converted R1, the lack of carbon sources resulted in continuous rise of NO3--N in the effluent, stable NO2--N removal efficiency, and absence of SRP removal after 40 h. However, R2 retained the previous NO3--N and SRP removal efficiencies with carbohydrate addition. This indicated that this novel RAS using BFT biofilters achieved simultaneous nitrogen and phosphate removal, and that the convertible water-treatment efficiencies of BFT biofilters could be controlled by carbohydrate addition. This approach could simplify the RAS setup and meet real-time water quality demands.