New Insight into the Electronic Effect for Cu Porphyrin Catalysts in Electrocatalytic of CO2 into CH4.

Perturbation of the copper (Cu) active site by electron manipulation is a crucial factor in determining the activity and selectivity of electrochemical carbon dioxide (CO2 ) reduction reaction (e-CO2 RR) in Cu-based molecular catalysts. However, much ambiguity is present concerning their electronic structure-function relationships. Here, three molecular Cu-based porphyrin catalysts with different electron densities at the Cu active site, Cu tetrakis(4-methoxyphenyl)porphyrin (Cu─T(OMe)PP), Cu tetraphenylporphyrin (Cu─THPP), and Cu tetrakis(4-bromophenyl)porphyrin (Cu─TBrPP), are prepared. Although all three catalysts exhibit e-CO2 RR activity and the same reaction pathway, their performance is significantly affected by the electronic structure of the Cu site. Theoretical and experimental investigations verify that the conjugated effect of ─OCH3 and ─Br groups lowers the highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbitals (LUMO) gap of Cu─T(OMe)PP and Cu─TBrPP, promoting faster electron transfer between Cu and CO2 , thereby improving their e-CO2 RR activity. Moreover, the high inductive effect of ─Br group reduces the electron density of Cu active site of Cu─TBrPP, facilitating the hydrolysis of the bound H2 O and thus creating a preferable local microenvironment, further enhancing the catalytic performance. This work provides new insights into the relationships between the substituent group characteristics with e-CO2 RR performance and is highly instructive for the design of efficient Cu-based e-CO2 RR electrocatalysts.

Molecular Design of Porous Organic Polymer-Derived Carbonaceous Electrocatalysts for Pinpointing Active Sites in Oxygen Reduction Reaction.

The widespread application of fuel cells is hampered by the sluggish kinetics of the oxygen reduction reaction (ORR), which traditionally necessitates the use of high-cost platinum group metal catalysts. The indispensability of these metal catalysts stems from their ability to overcome kinetic barriers, but their high cost and scarcity necessitate alternative strategies. In this context, porous organic polymers (POPs), which are built up from the molecular level, are emerging as promising precursors to produce carbonaceous catalysts owning to their cost-effectiveness, high electrical conductivity, abundant active sites and extensive surface area accessibility. To enhance the intrinsic ORR activity and optimize the performance of these electrocatalysts, recognizing, designing, and increasing the density of active sites are identified as three crucial steps. These steps, which form the core of our review, serve to elucidate the link between the material structure design and ORR performance evaluation, thereby providing valuable insights for ongoing research in the field. Leveraging the precision of polymer skeletons based on molecular units, POP-derived carbonaceous catalysts provide an excellent platform for in-depth exploration of the role and working mechanism for the specific active site during the ORR process. In this review, the recent advances pertaining to the synthesis techniques and electrochemical functions of various types of active sites, pinpointed from POPs, are systematically summarized, including heteroatoms, surficial substituents and edge/defects. Notably, the structure-property relationship, between these active sites and ORR performance, are discussed and emphasized, which creates guidelines to shed light on the design of high-performance ORR electrocatalysts.

Construction of Low-Coordination Cu-C2 Single-Atoms Electrocatalyst Facilitating the Efficient Electrochemical CO2 Reduction to Methane.

Constructing Cu single-atoms (SAs) catalysts is considered as one of the most effective strategies to enhance the performance of electrochemical reduction of CO2 (e-CO2 RR) towards CH4 , however there are challenges with activity, selectivity, and a cumbersome fabrication process. Herein, by virtue of the meta-position structure of alkynyl in 1,3,5-triethynylbenzene and the interaction between Cu and -C≡C-, a Cu SAs electrocatalyst (Cu-SAs/HGDY), containing low-coordination Cu-C2 active sites, was synthesized through a simple and efficient one-step method. Notably, this represents the first achievement of preparing Cu SAs catalysts with Cu-C2 coordination structure, which exhibited high CO2 -to-CH4 selectivity (72.1 %) with a high CH4 partial current density of 230.7 mA cm-2 , and a turnover frequency as high as 2756 h-1 , dramatically outperforming currently reported catalysts. Comprehensive experiments and calculations verified the low-coordination Cu-C2 structure not only endowed the Cu SAs center more positive electricity but also promoted the formation of H•, which contributed to the outstanding e-CO2 RR to CH4 electrocatalytic performance of Cu-SAs/HGDY. Our work provides a novel H⋅-transferring mechanism for e-CO2 RR to CH4 and offers a protocol for the preparation of two-coordinated Cu SAs catalysts.

Application of near infrared reflectance (NIR) spectroscopy to identify potential PSE meat.

BACKGROUND: Pale, soft and exudative (PSE) meat is a quality problem that causes a large economic loss to the pork industry. In the present work, near infrared (NIR) quantification and identification methods were used to investigate the feasibility of differentiating potential PSE meat from normal meat. RESULTS: NIR quantification models were developed to estimate meat pH and colour attributes (L*, a*, b*). Promising results were reported for prediction of muscle pH (R(2) CV = 70.10%, RPDCV = 1.83) and L* (R(2) CV = 77.18%, RPDCV = 1.91), but it is still hard to promote to practical application at this level. The Factorisation Method applied to NIR spectra could differentiate potential PSE meat from normal meat at 3 h post-mortem. Correlation analysis showed significant relationship between NIR data and LF-NMR T2 components that were indicative of water distribution and mobility in muscle. PSE meat had unconventionally faster energy metabolism than normal meat, which caused greater water mobility. CONCLUSION: NIR spectra coupled with the Factorisation Method could be a promising technology to identify potential PSE meat. The difference in the intensity of H2 O absorbance peaks between PSE and normal meat might be the basis of this identification method. © 2015 Society of Chemical Industry.

The effect of perceived value on farmers' livestock manure resource utilization behavior: Evidence from Shandong, China.

Introduction: The rapid development of animal husbandry has brought many problems such as ecological environmental pollution and public health damage. The resource utilization of livestock manure is the key way to deal with the above crisis and turn waste into treasure. Methods: Based on the theory of perceived value, this paper uses multi-group structural equation model to explore the driving mechanism of perceived value on the resource utilization behavior of livestock manure. Results and discussion: The results showed that: (1) The resource utilization behavior of livestock manure followed the logic of "cognitive level → cognitive trade-off → perceived value → behavioral intention → behavioral performance." Perceived benefit and perceived risk have positive and reverse driving effects on perceived value, respectively. Perceived value has a positive driving effect on behavioral intention. The behavioral intention has a positive driving effect on utilization behavior. (2) Among the observed variables of perceived benefits, ecological benefits have the greatest impact; Among the observed variables of perceived risk, economic risk has the greatest impact. Among the observed variables of perceived value, Significance cognition has the greatest influence. Among the observed variables of behavioral intention, utilization intention has the greatest influence. (3) The perceived value has a differential effect on the utilization behavior of livestock manure resources of different part-time farmers, and the driving effect is more obvious for full-time farmers. Conclusions: Therefore, it is necessary to improve the resource utilization system of livestock manure, increase the channel for realizing the output of manure resources, strengthen technical assistance and policy subsidies, and implement policies according to local conditions to improve the overall perceived value of farmers.

Genomic and Transcriptomic Analyses of Prime Editing Guide RNA-Independent Off-Target Effects by Prime Editors.

Prime editors (PEs) were developed to induce versatile edits at a guide-specified genomic locus. With all RNA-guided genome editors, guide-dependent off-target (OT) mutations can occur at other sites bearing similarity to the intended target. However, whether PEs carry the additional risk of guide-independent mutations elicited by their unique enzymatic moiety (i.e., reverse transcriptase) has not been examined systematically in mammalian cells. Here, we developed a cost-effective sensitive platform to profile guide-independent OT effects in human cells. We did not observe guide-independent OT mutations in the DNA or RNA of prime editor 3 (PE3)-edited cells, or alterations to their telomeres, endogenous retroelements, alternative splicing events, or gene expression. Together, our results showed undetectable prime editing guide RNA-independent OT effects of PE3 in human cells, suggesting the high editing specificity of its reverse-transcriptase moiety.

Highly efficient prime editing by introducing same-sense mutations in pegRNA or stabilizing its structure.

Prime editor (PE), which is developed by combining Cas9 nickase and an engineered reverse transcriptase, can mediate all twelve types of base substitutions and small insertions or deletions in living cells but its efficiency remains low. Here, we develop spegRNA by introducing same-sense mutations at proper positions in the reverse-transcription template of pegRNA to increase PE's base-editing efficiency up-to 4,976-fold (on-average 353-fold). We also develop apegRNA by altering the pegRNA secondary structure to increase PE's indel-editing efficiency up-to 10.6-fold (on-average 2.77-fold). The spegRNA and apegRNA can be combined to further enhance editing efficiency. When spegRNA and apegRNA are used in PE3 and PE5 systems, the efficiencies of sPE3, aPE3, sPE5 and aPE5 systems are all enhanced significantly. The strategies developed in this study realize highly efficient prime editing at certain previously uneditable sites.

Eliminating base-editor-induced genome-wide and transcriptome-wide off-target mutations.

The fusion of CRISPR-Cas9 with cytidine deaminases leads to base editors (BEs) capable of programmable C-to-T editing, which has potential in clinical applications but suffers from off-target (OT) mutations. Here, we used a cleavable deoxycytidine deaminase inhibitor (dCDI) domain to construct a transformer BE (tBE) system that induces efficient editing with only background levels of genome-wide and transcriptome-wide OT mutations. After being produced, the tBE remains inactive at OT sites with the fusion of a cleavable dCDI, therefore eliminating unintended mutations. When binding at on-target sites, the tBE is transformed to cleave off the dCDI domain and catalyses targeted deamination for precise base editing. After delivery into mice through a dual-adeno-associated virus (AAV) system, the tBE system created a premature stop codon in Pcsk9 and significantly reduced serum PCSK9, resulting in a ~30-40% decrease in total cholesterol. The development of tBE establishes a highly specific base editing system and its in vivo efficacy has potential for therapeutic applications.

Comparison of cytosine base editors and development of the BEable-GPS database for targeting pathogenic SNVs.

A variety of base editors have been developed to achieve C-to-T editing in different genomic contexts. Here, we compare a panel of five base editors on their C-to-T editing efficiencies and product purity at commonly editable sites, including some human pathogenic C-to-T mutations. We further profile the accessibilities of 20 base editors to all possible pathogenic mutations in silico. Finally, we build the BEable-GPS (Base Editable prediction of Global Pathogenic SNVs) database for users to select proper base editors to model or correct disease-related mutations. The in vivo comparison and in silico profiling catalog the availability of base editors and their broad applications in biomedical studies.