Engineering Coordination Environment of Cobalt Center in Molecular Catalysts for Improved Photocatalytic CO2 Reduction

Engineering Coordination Environment of Cobalt Center in Molecular Catalysts for Improved Photocatalytic CO2 Reduction

By regulating the coordination heteroatoms, we designed three Co(II)-based molecular catalysts with coordination microenvironments of [CoN3O]ClO4, [CoN4]ClO4, and [CoN3S]ClO4. Impressively, due to the slightly different coordination environments around Co(II) center, [CoN3O]ClO4 shows better photocatalytic activity for CO2 reduction to CO, 1.28 and 1.65 times higher than that of [CoN4]ClO4, and [CoN3S]ClO4, respectively.


Comprehensive Summary

The creation of effective and inexpensive catalysts is essential for photocatalytic CO2 reduction. Homogeneous molecular catalysts, possessing definite crystal structures, are desirable to study the relationship between catalytic performance and coordination microenvironment around catalytic center. In this report, we elaborately developed three Co(II)-based molecular catalysts with different coordination microenvironments for CO2 reduction, named [CoN3O]ClO4, [CoN4]ClO4, and [CoN3S]ClO4, respectively. The optimal [CoN3O]ClO4 photocatalyst has a maximum TON of 5652 in photocatalytic reduced CO2 reduction, which is 1.28 and 1.65 times greater than that of [CoN4]ClO4 and [CoN3S]ClO4, respectively. The high electronegativity of oxygen in L1 (N,N-bis(2-pyridylmethyl)-N-(2-hydroxybenzyl)amine) provides the Co(II) catalytic centers with low reduction potentials and a more stable *COOH intermediate, which facilitates the CO2-to-CO conversion and accounts for the high photocatalytic activity of [CoN3O]ClO4. This work provides researchers new insights in development of catalysts for photocatalytic CO2 reduction.

A Nearly 20‐Year Journey to Success of Azvudine for Antiviral Therapy

A Nearly 20-Year Journey to Success of Azvudine for Antiviral Therapy

The drug discovery campaign of Azvudine starts from 2′-deoxynucleoside, followed by extensive modifications. Azvudine receives approval from China and Russia for treating COVID-19 and represents a novel anti-HIV agent approved in China.


Comprehensive Summary

Modified nucleosides, particularly those with 4'-modifications, are significant nucleosides used in antiviral treatments. The drug discovery campaign of Azvudine starts from 2′-deoxynucleoside, followed by extensive modifications, such as introducing the 4’-position substitutions, a 2’-β-fluoro atom, and changing the nucleobases. Azvudine acts potently toward various HIV-1 strains by inhibiting HIV-1 reverse transcription and preventing Vif-induced A3G degradation, representing the first-in-class dual-acting antiviral agent. In July 2021, the NMPA conditionally approved Azvudine as an adjunct therapy for adult patients with high levels of HIV-1 virus load when combined with NRTIs or NNRTIs. Azvudine is capable of inhibiting SARS-CoV-2, as well as its variants, including Alpha, Beta, Delta, and Omicron. Clinical trials have revealed its real-world effectiveness among hospitalized severely or critically ill COVID-19 patients or those with pre-existing conditions. On July 25th, 2022, the NMPA granted conditional authorization approving Azvudine as China's first domestic oral anti-COVID-19 agent. Generally, Azvudine at therapeutic doses is safe and well-tolerated in clinical settings. Azvudine got approval from the National Health Commission and National Administration of Traditional Chinese Medicine on August 9th to be used in the "Diagnosis and Treatment Program for Novel Coronavirus Pneumonia (Ninth Edition)" for treating common COVID-19 adult patients. On August 12th, 2022, it was also approved by the National Healthcare Security Administration to be added to the list of medical reimbursements. Of note, the achievements related to Azvudine were indexed in the China Basic Research Development Report in Thirty-Five of 2022. Azvudine was also approved on January 5th, 2023, to be used in the "Diagnosis and Treatment Program for Novel Coronavirus Pneumonia (Tenth Edition)" for treating COVID-19 patients. In February 2023, the Ministry of Health of the Russian Federation approved the usage of Azvudine among individuals infected with SARS-CoV-2.

What is the most favorite and original chemistry developed in your research group?

My favorite chemistries are always those that enable efficient access to drug molecules.

How do you get into this specific field? Could you please share some experiences with our readers?

The virus uses nucleosides as raw materials for replication. Learned from this biological process, I have been devoted to, for decades, synthesizing nucleoside mimics. Once attached to the 3'-hydroxy group of the virus RNA chain, these nucleoside analogs can effectively inhibit virus replication. Hard work pays off! We have developed a series of novel 4’-modified nucleosides, among which Azvudine has been officially approved for treating HIV in China and COVID-19 in both China and Russia. Notably, Azvudine is the first Chinese oral anti-COVID-19 agent. The experiences I would like to share with the readers are many, but emphases are placed on thinking critically and working enthusiastically.

How do you supervise your students?

I generally supervise students differently according to their aptitudes. For those keen on scientific work, I always suggest them learn from the literature, and practice makes perfect, think critically, and work with passion.

What is the most important personality for scientific research?

The personalities such as curiosity, creativity, persistence, and the ability to think critically and solve problems matter most for scientific research. Furthermore, what sets successful scientists apart is their passion for their work and their ability to persevere in facing challenges and setbacks.

Who influences you mostly in your life?

My Ph.D. supervisor profoundly fuels my passion for academia and, to some extent, reshapes my personality.

Electrolysis of Direct Seawater: Challenges, Strategies, and Future Prospects

Electrolysis of Direct Seawater: Challenges, Strategies, and Future Prospects†


Comprehensive Summary

The use of renewable sources such as solar, ocean, geothermal, and wind energy to drive water electrolysis reactions to obtain green and clean hydrogen fuels is one of the important paths to achieve sustainable energy development. At present, most water electrolysis technologies need to conduct corresponding pre-processing, such as diluting water sources and purifying dehydration, which will greatly increase operating costs. The development of direct seawater electrolytic process can effectively solve the above problems. Here, we review the latest progress of the electrode materials and catalysts of the direct electrolysis process of seawater, and discuss how to design high activity and high-selective electrode materials for water electrolysis with familiar impurities (such as chloride, metal ions and biological organisms) existing in the future.

Diastereoselective Construction of α‐Fluoroalkyl Cycloalkanols via Radical Alkylation of α‐Fluoroalkyl Ketones

Diastereoselective Construction of α-Fluoroalkyl Cycloalkanols via Radical Alkylation of α-Fluoroalkyl Ketones†

A visible-light-induced cascade radical cyclization of alkenyl fluoroalkyl ketones is developed, producing various α-Rf cycloalkanols in promising yields with up to >20 : 1 dr selectivity. DFT calculations suggest that the fluorine effect plays an important role in this reaction.


Comprehensive Summary

α-Fluoroalkyl (Rf) alcohols are privileged motifs in drugs and pharmaceutically active compounds. As such, it is highly desirable to develop efficient methods for assembling these scaffolds. Herein, a visible-light-induced cascade radical cyclization of alkenyl fluoroalkyl ketones is developed, producing a variety of decorate α-Rf cycloalkanols in promising yields with up to >20 : 1 dr selectivity. A radical chain mechanism involving an intramolecular radical addition to the α-Rf carbonyl group and a subsequent intermolecular hydrogen atom transfer (HAT) has been proposed. Density functional theory (DFT) calculations indicate that a fluorine effect contributes to the radical addition to carbonyls by lowering the π* (C=O) orbital energy of CORf and energy barrier of the HAT between alkoxy radicals and THF, which may be valuable for controllable transformations of fluorinated molecules.

Machine Learning‐Aided Data Analysis in Single‐Protein Conductance Measurement with Electron Tunneling Probes

Comprehensive Summary

The electrical tunneling sensors have excellent potential in the next generation of single-molecule measurement and sequencing technologies due to their high sensitivity and spatial resolution capabilities. Electrical tunneling signals that have been measured at a high sampling rate may provide detailed molecular information. Despite the extraordinarily large amount of data that has been gathered, it is still difficult to correlate signal transformations with molecular processes, which creates great obstacles for signal analysis. Machine learning is an effective tool for data analysis that is currently gaining more significance. It has demonstrated promising results when used to analyze data from single-molecule electrical measurements. In order to extract meaningful information from raw measurement data, we have combined intelligent machine learning with tunneling electrical signals. For the purpose of analyzing tunneling electrical signals, we investigated the clustering approach, which is a classic algorithm in machine learning. A clustering model was built that combines the advantages of hierarchical clustering and Gaussian mixture model clustering. Additionally, customized statistical algorithms were designed. It has been proved to efficiently gather molecular information and enhance the effectiveness of data analysis.

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Efficient contact between H2O and N‐coordinate Ru nanoparticles in three‐dimensionally ordered macro/mesoporous carbon boosting alkaline HER

Comprehensive Summary

In this study, a novel approach is proposed to achieve the uniformly dispersed Ru nanoparticles with N coordination loaded on three-dimensionally ordered macro/mesoporous carbon (3DOMMC) through simultaneous pyrolysis of Ru3+ and cyanamide on 3DOMMC.In an alkaline medium, the synthesized catalysts exhibit exceptional hydrogen evolution reaction (HER) performance. Specifically, Ru-N/3DOMMC demonstrates a significantly low overpotential of 13.8 mV to achieve a current density of 10 mA cm-2, and it exhibits a mass activity 17.5 times higher than that of commercial Pt/C. The outstanding performance could be attributed to the ultrahigh Ru dispersion and more efficient contact between active sites and reactant, which derived from the large specific surface area and inter-connective three-dimensionally macro/mesoporous of 3DOMMC.

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Dcalycinumines A–E, alkaloids with cytotoxic activities of nasopharyngeal carcinoma cells from Daphniphyllum calycinum

Comprehensive Summary

Five novel Daphniphyllum alkaloids, named dcalycinumines A–E (14, 6), and eight previously described Daphniphyllum alkaloids (5, 713) were isolated from Daphniphyllum calycinum. Compound 1 is the first Daphniphyllum alkaloid possessing a highly rearranged 6/6/6/7/5/6 hexacyclic architecture with a unique 3-methyl-1-azabicyclo [4,4,0] decane ring system. Compound 2 represents a rare diamino Daphniphyllum alkaloid with an unprecedented 6/5/5/6/6/5 carbon skeleton featuring a unique 1-aza-6-azaspiro [4,5] decane unit, whereas 3 also represents a rare diamino Daphniphyllum alkaloid as a possible precursor of 2. Compound 4 is the second example of C-22-nor yuzurimine-type alkaloids. Their structures and absolute configurations were elucidated by HRESIMS, NMR spectroscopic analyses, ECD calculations, and single-crystal X-ray diffraction. Moreover, compound 1 showed remarkable antitumor activities, which could inhibit the proliferation, migration and invasion of nasopharyngeal carcinoma cells, and promoted nasopharyngeal carcinoma cells apoptosis.

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Recent Advances in Base‐Metal‐Catalyzed Carbonylation of Unactivated Alkyl Electrophiles

Recent Advances in Base-Metal-Catalyzed Carbonylation of Unactivated Alkyl Electrophiles†

This review summarizes the recent advances in base-metal-catalyzed carbonylative C—C, C—N, C—O, C—X coupling and other carbonylation reactions of unactivated alkyl electrophiles using CO as C1 source, providing efficient methods for the synthesis of diverse alkyl-substituted carbonyl compounds or their derivatives including ketones, amides, esters, acylsilanes, acylborons, acyl chlorides and alcohols.


Comprehensive Summary

Transition metal-catalyzed carbonylation reactions represent a direct and atom-economical approach to synthesize carbonyl compounds or their derivatives by using CO as a cheap and readily available C1 feedstock. While carbonylation of C(sp2)-hybridized electrophiles (e.g., aryl halides) is well developed, carbonylation of less reactive unactivated alkyl electrophiles remains challenging. Recently, the use of earth-abundant base metals including Cu, Co, Mn, Fe, Ni as catalysts has enabled advances in carbonylative coupling of alkyl electrophiles for approaching diverse carbonyl compounds or their derivatives, notably, some of which are of synthetic importance but difficult to be synthesized through previous reported methods. Herein, we have summarized and discussed these recent achievements in base-metal-catalyzed carbonylative C—C, C—N, C—O, C—X coupling and other carbonylation reactions of unactivated alkyl electrophiles using CO as C1 source.

Application of Biological Nanopore Sequencing Technology in the Detection of Microorganisms

Application of Biological Nanopore Sequencing Technology in the Detection of Microorganisms†


Comprehensive Summary

Environmental pollution and the spread of pathogenic microorganisms pose a significant threat to the health of humans and the planet. Thus, understanding and detecting microorganisms is crucial for maintaining a healthy living environment. Nanopore sequencing is a single-molecule detection method developed in the 1990s that has revolutionized various research fields. It offers several advantages over traditional sequencing methods, including low cost, label-free, time-saving detection speed, long sequencing reading, real-time monitoring, convenient carrying, and other significant advantages. In this review, we summarize the technical principles and characteristics of nanopore sequencing and discuss its applications in amplicon sequencing, metagenome sequencing, and whole-genome sequencing of environmental microorganisms, as well as its in situ application under some special circumstances. We also analyze the advantages and challenges of nanopore sequencing in microbiology research. Overall, nanopore sequencing has the potential to greatly enhance the detection and understanding of microorganisms in environmental research, but further developments are needed to overcome the current challenges.

Cationic conjugated oligomers for efficient and rapid antibacterial photodynamic therapy via both Type I and Type II pathways

Comprehensive Summary

Recently, photodynamic therapy (PDT) has attracted wide attention due to its less susceptibility to drug resistance, broad-spectrum biocidal activity and biosafety in normal tissues. However, the traditional photosensitizers (PSs) face the disadvantage of poor therapeutic efficacy due to the requirement of an aerobic environment to generate 1O2 through Type ІI pathway. Herein, we designed and synthesized a novel cationic conjugated oligomer OPV and studied its antibacterial photodynamic activity against both Gram-negative Escherichia coli (E. coli) and Gram-positive bacteria methicillin-resistant Staphylococcus aureus (MRSA). Importantly, the OPV can rapidly produce reactive oxygen species (ROS) through double pathways, Type I and II mechanism under white light irradiation, and efficiently kill E. coli and MRSA at a nanomolar level. The dual type photosensitizing capability makes OPV promising for enhanced PDT to treat pathogens and tumors in complex environments.

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