A general and convenient photoredox-catalyzed acylation and alkylcyanation of MBH acetates has been established, enabling the assembly of the C(sp²)–C(sp³) bond by a nitrogen-centered radical strategy for the synthesis of trisubstituted alkenes in moderate to excellent chemical yields (48 examples in total).

Comprehensive Summary

A general and convenient photoredox-catalyzed acylation and alkylcyanation of MBH acetates has been established, enabling the assembly of the C(sp²)–C(sp³) bond by a nitrogen-centered radical strategy for the synthesis of trisubstituted alkenes in moderate to excellent chemical yields (48 examples in total). The reaction of MBH acetates with acyl (indanone) oxime esters afforded trisubstituted alkenes containing 1,4-dicarbonyl groups. Interestingly, the use of Eosin Y as a photocatalyst in the catalytic system resulted in the formation of distal cyano group-anchored trisubstituted alkenes via deconstructive functionalization of cycloketone oxime esters. Notably, these resulting 1,4-dicarbonyl compounds could be applied to late-stage transformations, providing important methods for the synthesis of dihydropyridazin-3(2H)-one.

In this study, a strategy that employs the streptavidin-biotin interaction as a "brake system" for CRISPR/Cas9, effectively allowing for the shutdown of the enzymatic activity of CRISPR/Cas9 is developed.

Comprehensive Summary

Currently, CRISPR/Cas9 technology has found widespread applications across various domains. However, the utility of CRISPR/Cas9 is encumbered by issues pertaining to its reliability and safety, primarily stemming from the uncontrolled activity of the system. Therefore, the design and development of CRISPR/Cas9 systems with controllable activity is of paramount importance. Biotin, characterized by its small molecular weight, and streptavidin, distinguished by its substantial spatial steric hindrance, can be harnessed as an ideal OFF switch (termed a "bioactivity brake") due to their interaction characteristics. In this work, we present a strategy that employs the streptavidin-biotin interaction as a "brake system" for CRISPR/Cas9, effectively allowing for the shutdown of the enzymatic activity of CRISPR/Cas9.

A DNA force circuit was developed for detecting PPI anisotropy at the single-molecule level.

Comprehensive Summary

Protein-protein interactions (PPIs) play a crucial role in drug discovery and disease treatment. However, the development of effective drugs targeting PPIs remains challenging due to limited methodologies for probing their spatiotemporal anisotropy. Here, we propose a single-molecule approach using a unique force circuit to investigate PPI dynamics and anisotropy under mechanical forces. Unlike conventional techniques, this approach enables the manipulation and real-time monitoring of individual proteins at specific amino acids with defined geometry, offering insights into molecular mechanisms at the single-molecule level. The DNA force circuit was constructed using click chemistry conjugation methods and genetic code expansion techniques, facilitating orthogonal conjugation between proteins and nucleic acids. The SET domain of the MLL1 protein and the tail of histone H3 were used as a model system to demonstrate the application of the DNA force circuit. With the use of atomic force microscopy and magnetic tweezers, optimized assembly procedures were developed. The DNA force circuit provides an exceptional platform for studying the anisotropy of PPIs and holds promise for advancing drug discovery research targeted at PPIs.

A switchable strategy for the construction of diverse 4-fluoroalkyl-1,4-dihydropyrimidines and 4-fluoroalkyl-pyrimidines via a solvent/additive-free [3 + 2 + 1] annulation, starting from readily available enamines, trifluoroacetaldehyde hydrate or 1-ethoxy-2,2-difluoroethanol and amidines hydrochloride has been developed.

Comprehensive Summary

The development of switchable solvent-free multicomponent reactions to build high-value-added products is an important demand for organic synthesis. Herein, we detailed the successful implementation of a switchable strategy for the construction of diverse 4-fluoroalkyl-1,4-dihydropyrimidines and 4-fluoroalkyl-pyrimidines via a solvent/additive-free [3 + 2 + 1] annulation, starting from readily available enamines, trifluoroacetaldehyde hydrate or 1-ethoxy-2,2-difluoroethanol and amidines hydrochloride. This reaction conforms to the concept of green synthesis, and provides a new avenue to access valuable fluorinated heterocycles.

The selective electrochemical C—H sulfonylation of alkenes with selenium sulfonate was disclosed. Aerobic trifunctionalization of alkenes occurred by simply changing the conditions, which provides diverse β-keto selenosulfones.

Comprehensive Summary

The selective oxidative sulfonylation of alkenes with selenium sulfonate depended on the reaction conditions. The electrochemical C—H sulfonylation proceeded smoothly to afford (E)-vinyl sulfones with good selectivity in an undivided cell without external oxidant. While aerobic trifunctionalization of alkenes occurred in the presence of KI in the air, which provides β-keto selenosulfones via the formation of C—O, C—S, and C—Se bonds in one-pot. Following control experiments, a plausible mechanism is proposed to rationalize the experimental results.

A panel of furimazine-based bioluminescent probes has been developed for the detection of pathogenic bacterial nitroreductase. The probe containing 2-nitro-N-methyl-imidazolyl possessed up to a 560-fold increment in bioluminescent intensity, with detection limit as low as 16 ng/mL, making it suitable for bioluminescent visualization in vivo.

Comprehensive Summary

The detection of critical endogenous species, such as bacteria in microenvironments in the body, requires better imaging tools for visualization and monitoring of biological events. Bioluminescence imaging is the most popular strategy for obtaining real-time in living cells and organisms. Herein, we introduced a nitroaryl group on the C-3 position and a hydroxy group at the C-6 phenyl ring on furimazine to report the first bioluminescent probe (7) based on NanoLuc-furimazine bioluminescent pair for the detection of nitroreductase in bacteria. The probe, which possessed up to 560-fold intensity increase with a low detection limit of 16 ng/mL of nitroreductase, has the most efficient uncage efficiency in comparison with other bioluminescent congeners, thus enabling highly selective and sensitive visualization of NTR activity in a panel of clinical priority pathogens. Additionally, imaging of the recombinant strain as well as the NTR from mouse feces indicated the potential of this probe in the application of different mouse disease models.

A transition-metal-free allylic defluorination reductive cross-coupling between CF₃-alkenes and diaryliodonium salts mediated by rongalite has been described for the first time. This procedure was compatible with both linear and cyclic diaryliodonium salts, enabling a wide variety of substrates. The utility of this approach was demonstrated through gram-scale synthesis and efficient late-stage functionalizations of anti-inflammatory drugs.

Comprehensive Summary

The conversion of CF₃-alkenes to gem-difluoroalkenes using reductive cross-coupling strategy has received much attention in recent years, however, the use of green and readily available reducing salt to mediate these reactions remains to be explored. In this work, a concise construction of gem-difluoroalkenes, which requires neither a catalyst nor a metal reducing agent, was established. Rongalite, a safe and inexpensive industrial product, was employed as both a radical initiator and reductant. This procedure was compatible with both linear and cyclic diaryliodonium salts, enabling a wide variety of substrates (>70 examples). The utility of this approach was demonstrated through gram-scale synthesis and efficient late-stage functionalizations of anti-inflammatory drugs.

We report here the concise total syntheses of four laurane-type and guaiane-type sesquiterpenoids via oxidative Nazarov reaction, using unfunctionalized TDCs as the substrates.

Comprehensive Summary

As one of the most common structural motifs in natural products, cyclopentenones usually can be fabricated by Nazarov cyclization using divinyl ketones or functionalized tertiary divinyl carbinols (TDCs) as substrates. However, straightforward method for transforming unfunctionalized TDCs to their corresponding cyclopentenones is currently lacking. Herein, we wish to report the total syntheses of four structurally distinct terpenoids, namely laurane-type marine sesquiterpenoids isolaurene, debromoaplysin and aplysin, and guaiane sesquiterpenoid guaiadienone A, all using a novel synthetic method, named oxidative Nazarov cyclization, as the key step. This work demonstrated our robust method is suitable for synthesizing various highly substituted cyclopentenones.

A new strategy to design antitumor reagents has been developed based on artificial water channel (AWC)-promoted depolymerization of actin filaments. Its effectivity has been demonstrated in vitro and in vivo by using colorectal cancer as a disease model. The AWC conjugated with acetazolamide (AZA) moiety exhibited targeting behavior and water permeability to induce the depolymerization of the actin and apoptosis of the cancer cells.

Comprehensive Summary

Actin filaments play important physiological functions, which have become potential targets of antitumor drugs. Using chemicals to intervene their polymerization-depolymerization dynamics would generate new strategies for designing antitumor drugs. In this report, an artificial water channel appending acetazolamide moiety, a ligand that can selectively bind to carbonic anhydrase IX, has been prepared. We demonstrated that this conjugate can target colorectal cancer cells overexpressing carbonic anhydrase IX and trigger the depolymerization of actin filaments of the cancer cells by selectively mediating water transmembrane transport. Moreover, the conjugate-promoted actin depolymerization led to tumor cell apoptosis and its high antitumor activity in vitro and in vivo against colorectal cancer. The method described herein represents a new and general strategy for designing antitumor drugs by using artificial channel-mediated selective water transport to promote actin depolymerization.

In this review, we address the important role of hydrogen bonding in improving perovskite solar devices through various additives.

Comprehensive Summary

Owing to their distinctive optical and physical properties, organic-inorganic hybrid perovskite materials have gained significant attention in the field of electronic devices, especially solar cells. The achievement of high-performance solar cells hinges upon the utilization of top-notch perovskite thin films. Nevertheless, the fabrication process involving solutions and the polycrystalline nature of perovskite result in the emergence of numerous defects within the perovskite films, consequently exerting a deleterious influence on the overall performance and stability of the devices. Improving the performance and stability of perovskite solar cells by additive engineering to suppress/passivate defects is a viable approach, which involves hydrogen bond interactions in these device engineering processes. This review explores the intrinsic hydrogen bonds in methylammonium and formamidium lead triiodide, while also considering cation rotations, phase transitions, and stability. Moreover, the review classifies additives into distinct categories, including organic small molecules, polymers, nanodots, classical salts, ionic liquids, and molten salts. The various forms and characterization techniques of hydrogen bonds are discussed, as well as their potential synergistic effects in conjunction with other chemical interactions. Furthermore, this review offers insights into the potential utilization of hydrogen bonds to further enhance the performance and stability of devices.

Key Scientists

In 2009, Tsutomu Miyasaka et al. prepared the first perovskite solar cell, which kicked off the research on perovskite light-absorbing materials. However, the use of liquid electrolytes led to device instability. The transition to all-solid-state perovskite solar cells was realized by Nam-Gyu Park's team in 2012, which was the beginning of high-efficiency perovskite solar cells. Subsequently, a number of scientists have innovated the preparation ground process. Methods such as two-step deposition by Michael Grätzel in 2013 and anti-solvent extraction by Sang II Seok's team in 2014 were instrumental in advancing the development of perovskite. Liyuan Han's team then increased the cell's working area to 1 cm² without compromising performance, making it possible to compare the performance metrics of perovskite solar cells with those of other types of solar cells on the same scale. Recently, You's team and Pan's team kept updating the world record by obtaining certified efficiencies of 25.6% and 25.8% in 2022 and 2023, respectively.