Copper-Catalyzed Asymmetric Nucleophilic Opening of 1,1,2,2-Tetrasubstituted Donor-Acceptor Cyclopropanes for the Synthesis of α-Tertiary Amines.

Catalytic asymmetric transformation of donor-acceptor cyclopropanes (DACs) has been proven to be a highly valuable and robust strategy to construct diverse types of enantioenriched molecules. However, the use of 1,1,2,2-tetrasubstituted DACs to form products bearing quaternary stereocenters remains a long-term unsolved challenge. Here, we report the copper-catalyzed asymmetric aminative ring opening of tetrasubstituted alkynyl DACs that delivers a myriad of α-tertiary amines with high levels of enantioselectivities.

Catalytic Asymmetric Transfer Hydrogenation of β,γ-Unsaturated α-Diketones.

Asymmetric transfer hydrogenation (ATH) has been recognized as a highly valuable strategy that allows access to enantioenriched substances and has been widely applied in the industrial production of drug molecules. However, despite the great success in ATH of ketones, highly efficient, regio- and stereoselective ATH on enones remains underdeveloped. Moreover, optically pure acyloins and 1,2-diols are both extremely useful building blocks in organic synthesis, medicinal chemistry, and materials science, but concise asymmetric approaches allowing access to different types of acyloins and 1,2-diols have scarcely been discovered.

Regio- and Stereoselective Transfer Hydrogenation of Aryloxy Group-Substituted Unsymmetrical 1,2-Diketones: Synthetic Applications and Mechanistic Studies.

Developing a general method that leads to the formation of different classes of chiral bioactive compounds and their stereoisomers is an attractive but challenging research topic in organic synthesis. Furthermore, despite the great value of asymmetric transfer hydrogenation (ATH) in both organic synthesis and the pharmaceutical industry, the monohydrogenation of unsymmetrical 1,2-diketones remains underdeveloped. Here, we report the aryloxy group-assisted highly regio-, diastereo-, and enantioselective ATH of racemic 1,2-diketones.

Rapid Construction of Polycyclic Skeletons via Brønsted-Base-Catalyzed Annulations of Ethylidene 1,3-Indenediones and Vinyl 1,2-Diketones.

Brønsted-base-catalyzed diversified annulations between ethylidene 1,3-indenediones and vinyl 1,2-diketones have been achieved, delivering three types of products containing oxabicyclo[3.2.1]octane, spiro[4.

Catalytic Asymmetric Transfer Hydrogenation of Acylboronates: BMIDA as the Privileged Directing Group.

Developing a general, highly efficient, and enantioselective catalytic method for the synthesis of chiral alcohols is still a formidable challenge. We report in this article the asymmetric transfer hydrogenation (ATH) of -methyliminodiacetyl (MIDA) acylboronates as a general substrate-independent entry to enantioenriched secondary alcohols. ATH of acyl-MIDA-boronates with (het)aryl, alkyl, alkynyl, alkenyl, and carbonyl substituents delivers a variety of enantioenriched α-boryl alcohols.

Narrow Bandgap Schottky Heterojunction Sonosensitizer with High Electron-Hole Separation Boosted Sonodynamic Therapy in Bladder Cancer.

Sonodynamic therapy (SDT) is applied to bladder cancer (BC) given its advantages of high depth of tissue penetration and nontoxicity due to the unique anatomical location of the bladder near the abdominal surface. However, low electron-hole separation efficiency and wide bandgap of sonosensitizers limit the effectiveness of SDT. This study aims to develop a TiO-Ru-PEG Schottky heterojunction sonosensitizer with high electron-hole separation and narrow bandgap for SDT in BC.

Asymmetric Transfer Hydrogenation of Cyclobutenediones.

Four-membered carbocycles are fundamental substructures in bioactive molecules and approved drugs and serve as irreplaceable building blocks in organic synthesis. However, developing efficient protocols furnishing diversified four-membered ring compounds in a highly regio-, diastereo-, and enantioselective fashion remains challenging but very desirable. Here, we report the unprecedented asymmetric transfer hydrogenation of cyclobutenediones.

Copper-Catalyzed Umpolung Reactivity of Propargylic Carbonates in the Presence of Diboronates: One Stone Four Birds.

Allylation and propargylation are two powerful synthetic strategies for making new substances that have been of significant importance in chemistry, medicine, and material fields. Conventional tactics employ various preformed allylation and propargylation reagents. In this study, a conceptually novel copper-catalyzed and Bpin-mediated Umpolung reactivity of propargylic carbonates has been achieved for the first time, realizing both allylation and propargylation of aldehydes and ketones without additional reductants.

Copper-Catalysed Rearrangement of Cyclic Ethynylethylene Carbonates: Synthetic Applications and Mechanistic Studies.

Transition-metal-catalysed reactions of cyclic ethynylethylene carbonates have been intensively studied because of their robustness in new bond formation and diversified molecule construction. Known reaction modes usually involve a substitution step occurring at either the propargylic or terminal alkyne positions. Here, we report an unprecedented reaction pattern in which cyclic ethynylethylene carbonates first undergo a rearrangement to release allenal intermediates, which subsequently react with diverse nucleophiles to furnish synthetically useful allylic and propargylic allenols, phosphorus ylides, and cyclopropylidene ketones through an addition process rather than a substitution pathway.

Dynamic Kinetic Resolution of β-Substituted α-Diketones via Asymmetric Transfer Hydrogenation.

Developing innovative dynamic kinetic resolution (DKR) modes and achieving the highly regio- and enantioselective semihydrogenation of unsymmetrical α-diketones are two formidable challenges in the field of contemporary asymmetric (transfer) hydrogenation. In this work, we report the highly regio- and stereoselective asymmetric semi-transfer hydrogenation of unsymmetrical α-diketones through a unique DKR mode, which features the reduction of the carbonyl group distal from the labile stereocenter, while the proximal carbonyl remains untouched. Moreover, the protocol affords a variety of enantioenriched acyclic ketones with α-hydroxy-α'-C(sp)-functional groups, which represent a new product class that has not been furnished in known arts.

Oxa-Nazarov Cyclization-Michael Addition Sequence for the Rapid Construction of Dihydrofuranones.

The Nazarov cyclization has been established as a powerful tool in constructing cyclopentenone skeletons. In sharp contrast, oxa-Nazarov cyclization that affords dihydrofuranones, a new type of product, has been less explored. In this work, we report the I-catalyzed oxa-Nazarov cyclization-Michael addition cascade between vinyl α-diketones and enones.

Traditional Chinese medicine active ingredients-based selenium nanoparticles regulate antioxidant selenoproteins for spinal cord injury treatment.

Background: As Traditional Chinese Medicine (TCM) drugs, Huangqi and Danshen are always applied in combination for spinal cord injury (SCI) treatment based on the compatibility theory of TCM. Astragalus Polysaccharidesis (APS) and Tanshinone IIA (TSIIA) are the main active ingredients of Huangqi and Danshen, and they both possess neuroprotective effects through antioxidant activities. However, low solubility and poor bioavailability have greatly limited their application.

A facile and general method for synthesis of antibiotic-free protein-based hydrogel: Wound dressing for the eradication of drug-resistant bacteria and biofilms.

Antibacterial protein hydrogels are receiving increasing attention in the aspect of bacteria-infected-wound healing. However, bacterial drug resistance and biofilm infections lead to hard healing of wounds, thus the construction of biological agents that can overcome these issues is essential. Here, a simple and universal method to construct antibiotic-free protein hydrogel with excellent biocompatibility and superior antibacterial activity against drug-resistant bacteria and biofilms was developed.

Uptake, transport, and metabolism of selenium and its protective effects against toxic metals in plants: a review.

Selenium (Se) is an essential trace element of fundamental importance to humans, animals, and plants. However, the uptake, transport, and metabolic processes of Se and its underlying mechanisms in plants have not been well characterized. Here, we review our current understanding of the adsorption and assimilation of Se in plants.

Access to enantioenriched compounds bearing challenging tetrasubstituted stereocenters via kinetic resolution of auxiliary adjacent alcohols.

Contemporary asymmetric catalysis faces huge challenges when prochiral substrates bear electronically and sterically unbiased substituents and when substrates show low reactivities. One of the inherent limitations of chiral catalysts and ligands is their incapability in recognizing prochiral substrates bearing similar groups. This has rendered many enantiopure substances bearing several similar substituents inaccessible.

N-Heterocyclic Carbene-Catalyzed Asymmetric Synthesis of Cyclopentenones.

N-Heterocyclic carbene-catalyzed asymmetric construction of cyclopentenones using enals and α-diketones is achieved, furnishing a series of highly functionalized cyclopentenones in a highly diastereo- and enantioselective manner. The protocol tolerates substrates with both aromatic and aliphatic groups, and further transformations of the products delivered a range of value-added molecules.

Induction of ferroptosis in human nasopharyngeal cancer cells by cucurbitacin B: molecular mechanism and therapeutic potential.

Cucurbitacin B (CuB) is a widely available triterpenoid molecule that exhibits various biological activities. Previous studies on the anti-tumour mechanism of CuB have mostly focused on cell apoptosis, and research on the ferroptosis-inducing effect has rarely been reported. Herein, we first discovered the excellent cytotoxicity of CuB towards human nasopharyngeal carcinoma cells and elucidated its potential ferroptosis-inducing mechanisms.

Ti(OPr)-Facilitated Formal Deoxygenative Annulation of Alkynyl 1,2-Diketones for the Synthesis of Highly Functionalized Furans.

A unique deoxygenative cyclodimerization of alkynyl 1,2-diketones facilitated by Ti(OPr) is achieved, affording a series of highly functionalized furan products. An unusual C-C bond and C═O bond cleavage of the substrates is observed, and Ti(OPr) plays triplicate roles in the reaction. Furthermore, the products show uncommon fluorescent emission in the solid state, indicating the potential practical applications of this work.

Bone mesenchymal stem cell-derived extracellular vesicles promote the repair of intervertebral disc degeneration by transferring microRNA-199a.

Extracellular vesicles (EVs) secreted by bone marrow mesenchymal stem cells (BMSCs) protect intervertebral disc degeneration (IDD) by regulating nucleus pulposus cell (NPC) apoptosis. But the mechanism of BMSCs-EVs-microRNA (miR)-199a in IDD remains unclear. In this study, after the acquisition and identification of BMSCs and BMSCs-EVs, IDD mouse model was established and treated with BMSCs-EVs.

Biomedical Application of Reactive Oxygen Species-Responsive Nanocarriers in Cancer, Inflammation, and Neurodegenerative Diseases.

Numerous pathological conditions, including cancer, inflammatory diseases, and neurodegenerative diseases, are accompanied by overproduction of reactive oxygen species (ROS). This makes ROS vital flagging molecules in disease pathology. ROS-responsive drug delivery platforms have been developed.

Divergent Synthesis of Bicyclo[3.2.1]octenes and Cyclohexenes via Catalytic Annulations of Nazarov Reagent and Vinyl 1,2-Diketones.

Bicyclo[3.2.1]octanes and related structures are unique units that widely exist in natural products, but the rapid and stereoselective construction of this skeleton is a challenging issue.

Catalytic Annulation of Alkynyl 1,2-Diketone Leading to Hydroxy Spirocyclopenteneindenedione: An Organic Dye with Strong Crystallization-Induced Emission and Data Storage Application.

An unprecedented cascade annulation between alkynyl 1,2-diketones and indene-1,3-diones is achieved for the first time, leading to a series of propeller-like large conjugated compounds in ≤99% yield. The products show strong crystallization-induced emission, with the colors changing from green to red. The fluorescence of the dye can be switched on and off by external acid/alkali stimuli, which can be utilized to develop a practical technology for rewritable information storage and security ink.

Percutaneous Full-Endoscopic Lumbar Foraminoplasty and Decompression by Using a Visualization Reamer for Lumbar Lateral Recess and Foraminal Stenosis in Elderly Patients.

Background: Percutaneous endoscopic lumbar discectomy has been widely used to treat lumbar disc herniation; its advantages are less trauma, faster recovery, lower costs, and higher percentage of patient satisfaction compared with open surgery. Treatment of lumbar spinal stenosis with percutaneous full-endoscopic surgery is still challenging, especially for elderly patients with multiple comorbidities and complex pathologic factors. The aim of this study was to introduce percutaneous full-endoscopic lumbar foraminoplasty and decompression using a visualization reamer in elderly patients with lateral recess and foraminal stenosis and evaluate efficacy and safety.

Regioselectivity-Switchable Catalytic Annulations of Alkynyl α-Diketones and α-Cyanoketones.

Regioselectivity-switchable reactions hold irreplaceable importance in the construction of diversified architectures. In this work, Brønsted base-catalyzed regioselectivity-switchable annulations between alkynyl α-diketones and α-cyanoketones have been achieved for the first time, delivering a series of skeletally thoroughly different dihydrofurofuran and furan derivatives. A range of novel transformations of the products can be realized.