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Transition-metal-catalyzed reductive coupling reactions have been considered as a powerful tool to convert two electrophiles into value-added products. Numerous related reports have shown the fascinating potential. Mechanistic studies, especially theoretical studies, can provide important implications for the design of novel reductive coupling reactions. In this review, we summarize the representative advancements in theoretical studies on transition-metal-catalyzed reductive coupling reactions and systematically elaborate the mechanisms for the key steps of reductive coupling reactions. The activation modes of electrophiles and the deep insights of selectivity generation are mechanistically discussed. In addition, the mechanism of the reduction of high-oxidation-state catalysts and further construction of new chemical bonds are also described in detail. [ABSTRACT FROM AUTHOR]

The cardiovascular and cerebrovascular safety of ranibizumab, bevacizumab, and aflibercept for ocular diseases is unclear. This study aimed to evaluate and compare the cardiovascular and cerebrovascular safety in patients receiving ranibizumab, bevacizumab, and aflibercept for ocular disease. A cross‐sectional study was conducted from 2017 (Q1) to 2021 (Q4) in the US Food and Drug Administration Adverse Event Reporting System (FAERS) database. The outcomes of interest were central nervous system vascular disorders, ischemic heart disease, hypertension, pulmonary hypertension, torsade de pointes/QT prolongation, embolic and thrombotic events, cardiac arrhythmias, cardiac failure, and cardiomyopathy. Data mining was performed by a disproportional method with a compression, using compressed reporting odds ratios (sRORs) with 95% confidence intervals (CIs) to measure signals. The results showed 1462 cardiovascular and cerebrovascular events associated with aflibercept, 834 with ranibizumab, and 150 with bevacizumab. Ranibizumab, bevacizumab, and aflibercept were linked to central nervous system vascular disorders (sROR, 5.57[95%CI, 4.95‐6.26] vs sROR, 2.23 [95%CI, 1.75‐2.85] vs sROR, 2.73[95%CI, 2.43–3.06]), ischemic heart disease (sROR, 3.31[95%CI, 2.65–4.13] vs sROR, 1.98 [95%CI, 1.24‐3.16] vs sROR, 3.00 [95%CI, 2.46‐3.65]), embolic and thrombotic (sROR, 3.36 [95%CI, 3.04‐3.72] vs sROR, 2.16 [95%CI, 1.70‐2.74] vs sROR, 5.25 [95%CI, 4.82‐5.72]). Both ranibizumab and bevacizumab produced hypertension (sROR, 1.73 [95%CI, 1.41‐2.12] vs sROR, 1.46 [95%CI, 1.03‐2.06]) and arrhythmias (sROR, 2.82 [95%CI, 1.99‐3.99] vs sROR, 2.13 [95%CI, 1.08‐4.22]) signals. The signals of heart failure were detected in ranibizumab (sROR, 5.64 [95%CI, 4.08‐7.79]) and aflibercept (sROR, 2.80 [95%CI, 2.03‐3.86]). Ranibizumab, bevacizumab, and aflibercept for ocular disease have different safety profiles in cardiovascular and cerebrovascular. The overall cardiovascular and cerebrovascular risk of the patient should be thoroughly assessed in order to select the safest drug for treatment. [ABSTRACT FROM AUTHOR]

The adjusting charge kinetics of g-C 3 N 4 and the CBZ molecular NBO charge distribution and Fukui index. [Display omitted] • Elaborated the roles of the LSPR effect in adjusting charge generation kinetics. • Proved both the LSPR-mediated energy transfer and charge transfer worked. • Further deduced the mechanism of LSPR-mediated energy transfer. The charge kinetics of semiconductors determines the efficiency of photocatalysis reactions. Herein, the adjusting charge kinetics was investigated based on the integration of LSPR effect with homojunction. To this end, a novelty phosphorus (P)-doped fiber tubular graphitic carbon nitride (g-C 3 N 4)/g-C 3 N 4 /titanium nitride (TiN) composite (FCN/CN/TiN) was designed for this work. The features of adjusting charge kinetics were reflected in optical and photo-electrochemical measurements. The availability of the adjusting charge kinetics was evaluated by the photocatalytic degradation of the typical recalcitrant fungicide carbendazim. The mechanism of integrating LSPR effect with homojunction for adjusting charge kinetics of g-C 3 N 4 was systematically investigated and deepened the understanding of the thermodynamic reaction through DFT calculations. Especially, the specific roles of LSPR effect in adjusting charge generation kinetics, i.e. charge transfer, or energy transfer or both they was elaborated. The integration of LSPR effect with homojunction would provide a new strategy for adjusting charge kinetics of semiconductors in photocatalysis. [ABSTRACT FROM AUTHOR]

Diclofenac (DCF), a nonsteroidal anti-inflammatory drug, is one of the most commonly detected pharmaceuticals in wastewater treatment plants. However, the fate of DCF in waste activated sludge (WAS) anaerobic fermentation has not been well-understood so far. This work therefore aims to comprehensively reveal whether and how DCF is transformed in WAS mesophilic anaerobic fermentation through both experimental investigation and density functional theory (DFT) calculation. Experimental results showed that ∼28.8% and 45.8% of DCF were respectively degraded during the batch and long-term fermentation processes. Based on the detected intermediates and DFT-predicted active sites, three metabolic pathways, i.e., chlorination, hydroxylation, and dichlorination, responsible for DCF transformation were proposed. DFT calculation also showed that the Gibbs free energy (ΔG) of the three transformation pathways was respectively 19.0, −4.3, and −19.3 kcal/mol, suggesting that the latter two reactions (i.e., hydroxylation and dichlorination) were thermodynamically favorable. Illumina MiSeq sequencing analyses revealed that DCF improved the populations of complex organic degradation microbes such as Proteiniclasticum and Tissierellales , which was in accord with the chemical analyses above. This work updates the fundamental understanding of the degradation of DCF in WAS anaerobic fermentation process and enlightens engineers to apply theoretical calculation to the field of sludge treatment or other complex microbial ecosystems. [Display omitted] • Approximately 28.8% of DCF was degraded during anaerobic fermentation system. • DCF reduced the diversity and complexity of microbial community. • Hydroxylation and dichlorination reactions were thermodynamically favorable. • Proteiniclasticum and Tissierellales may be microbes related to DCF degradation. [ABSTRACT FROM AUTHOR]

This study examined the dissolution release performance of slow-release phosphate glass (SRPG), and the role this element plays in water and soil contaminated with heavy metals. It is known that the rate of dissolution ternary phosphate glass asXMgO–(50-X)Na2O–50P2O5(mol %) may be controlled by adjusting its content of MgO. The results showed that SRPG was uniformly dissolved in deionized water. Acidic or basic conditions induced the dissolution of SRPG; in contrast, lysate of SRPG in water decreased its rate of dissolution. Phosphate glass treatment of heavy metal lead (Pb)-contaminated soil effectively reduced the Pb content in H2O and MgCl2extracts by 81.6% and 75.7%, respectively. Comparative tests showed that leaf and root portion of Pb uptake in cabbage grown in soil treated with SRPG was reduced by 65.1% and 51.6% compared to untreated soil. Analysis of SRPG with Pb immobilization in water and soil environment by X-ray diffraction demonstrated that low-solubility phosphate (PbHPO4) and hydroxyphosphate [Pb5(PO4)3OH] complex was formed. Data indicate that SRPG may be effective in removal of Pb from contaminated soils and diminish risk of toxicity from ingestion of this heavy metal by consumers. [ABSTRACT FROM PUBLISHER]