Pd/Cu Dual Metal-Catalyzed Regioselective [2 + 2 + 2] Cycloaddition of Malononitriles with Alkynes to Densely Substituted Pyridines.

Transition metal-catalyzed [2 + 2 + 2] cycloaddition of nitriles and two alkynes is an efficient method for assembling pyridines. However, examples employing palladium catalysis have rarely been disclosed, and the processes of reactivity and selectivity remain unclear. We report here a palladium/copper dual metal-catalyzed [2 + 2 + 2] cycloaddition of diynyl-tethered malononitriles and terminal alkynes to synthesize densely substituted pyridines.

Real-space energy decomposition analysis method for qualitative and quantitative interpretations.

In the work, a real-space energy decomposition analysis method, called DM-EDA(RS), is introduced based on our recently developed DM-EDA method [Zhang et al., J. Chem.

Microwave Promoted Tandem Reaction of Free Primary Arylamines with Diazo Compounds Under Metal-Free Condition in Water: Clean Synthesis of 2,2-Disubstituted 3-Oxindoles.

Herein, a microwave promoted tandem reaction of free primary arylamines with diazo compounds in water for clean synthesis of 2,2-disubstituted 3-oxindoles is present. Water plays important roles in the whole cascade process: O-H insertion to diazo, air oxidation, ortho C-H functionalization, cyclization and 1,2-ester migration. In particular, water plays a mediation role in the site selective ortho-C-H addition.

Recent Advances of Metal-Organic Framework for Heavy Metal Ions Adsorption.

Heavy metal ion wastewater is a pressing and inescapable issue that is closely related to human health and ecological security due to its toxicity, carcinogenicity, and the unmanageable property of this type of wastewater. Metal-Organic Frameworks (MOFs) are a class of crystalline nanoporous materials with flexible designability and controllability, showing great potential in the field of adsorption and purification of heavy metals in wastewater. In this Perspective, we first discuss the harm of different heavy metal ions and briefly expound virtues of MOFs for pollutant adsorption.

Reversible Local Protonation-Deprotonation: Tuning Stimuli-Responsive Circularly Polarized Luminescence in Chiral Hybrid Zinc Halides for Anti-Counterfeiting and Encryption.

Precise control over the organic composition is crucial for tailoring the distinctive structures and properties of hybrid metal halides. However, this approach is seldom utilized to develop materials that exhibit stimuli-responsive circularly polarized luminescence (CPL). Herein, we present the synthesis and characterization of enantiomeric hybrid zinc bromides: biprotonated ((R/S)-CHN)ZnBr ((R/S-LH2)ZnBr) and monoprotonated ((R/S)-CHN)ZnBr ((R/S-LH1)ZnBr), derived from the chiral organic amine (R/S)-2,3,4,9-Tetrahydro-1H-carbazol-3-amine ((R/S)-CHN).

Cinquefoil Knot Possessing Dynamic and Tunable Metal Coordination.

While the majority of knots are made from the metal-template approach, the use of entangled, constrained knotted loops to modulate the coordination of the metal ions remains inadequately elucidated. Here, we report on the coordination chemistry of a 140-atom-long cinquefoil knotted strand comprising five tridentate and five bidentate chelating vacancies. The knotted loop is prepared through the self-assembly of asymmetric "3 + 2" dentate ligands with copper(II) ions that favor five-coordination geometry.

Primer exchange reaction assisted CRISPR/Cas9 cleavage for detection of dual microRNAs with electrochemistry method.

An electrochemical sensor assisted by primer exchange reaction (PER) and CRISPR/Cas9 system (PER-CRISPR/Cas9-E) was established for the sensitive detection of dual microRNAs (miRNAs). Two PER hairpin (HP) were designed to produce a lot of extended PER products, which could hybridize with two kinds of hairpin probes modified on the electrode and initiate the cleavage of two CRISPR/Cas9 systems guided by single guide RNAs (sgRNAs) with different recognition sequences. The decrease of the two electrochemical redox signals indicated the presence of dual-target miRNAs.

Adaptive accelerated reactive molecular dynamics driven by parallel collective variables overcoming dimensionality explosion.

ReaxFF reactive molecular dynamics has significantly advanced the exploration of chemical reaction mechanisms in complex systems. However, it faces several challenges: (1) the prevalent use of excessively high temperatures (>2000 K), (2) a time scale considerably shorter than the experimental timeframes (nanoseconds vs seconds), and (3) the constraining impact of dimensionality growth due to collective variables on the expansiveness of research systems. To overcome these issues, we introduced Parallel Collective Variable-Driven Adaptive Accelerated Reaction Molecular Dynamics (PCVR), which integrates metadynamics with ReaxFF.

Polyphyllin II Induces Apoptosis in Fibrosarcoma Cells via Activating Pyruvate Kinase M2.

Aerobic glycolysis is a metabolic reprogramming of tumor cells that is essential for sustaining their phenotype of fast multiplication by continuously supplying energy and mass. Pyruvate kinase M2 (PKM2) has a vital role in this process, which has given it high interest as a target for anticancer drug development. With potent toxicity to many types of cancer cells, polyphyllin II (), a steroidal saponin isolated from the herbaceous plant , brought to our attention that it might interfere with the PKM2 activity.

Manipulating AIE ligands into layers of pillar-layered MOFs for enhanced emission.

Four pillar-layered AIEgen-based MOFs exhibit higher thermal stability, tunable emission colors and improved QYs compared with that of non-pillar-layered AIEgen-based MOFs by confining the AIE ligands into layers. These results reveal that rationally manipulating AIE ligands into layers of pillar-layered MOFs is an effective strategy for the design and construction of tunable luminescent MOF systems.

Ultrasensitive Electrochemiluminescence Biosensing Platform Based on Polymer Dots with Aggregation-Induced Emission for Dual-Biotoxin Assay.

Multitarget assay has always been a hot topic in electrochemiluminescence (ECL) methods. Herein, a "on-off-on" ECL aptasensor was developed for the ultrasensitive and sequential detection of possible biological warfare agents, deoxynivalenol (DON) and abrin (ABR). As a luminophore, polymer dots (Pdots) with aggregation-induced emission exhibit high ECL efficiency in the aptasensor, i.

Asymmetric Intramolecular Amination Catalyzed with Cp*Ir-SPDO via Nitrene Transfer for Synthesis of Spiro-Quaternary Indolinone.

An asymmetric intramolecular spiro-amination to high steric hindering -C-H bond of 1,3-dicarbonyl via nitrene transfer using inactive aryl azides has been carried out by developing a novel Cp*Ir(III)-SPDO (spiro-pyrrolidine oxazoline) catalyst, thereby enabling the first successful construction of structurally rigid spiro-quaternary indolinone cores with moderate to high yields and excellent enantioselectivities. DFT computations support the presence of double bridging H-F bonds between [SbF] and both the ligand and substrate, which favors the plane-differentiation of the enol π-bond for nitrenoid attacking. These findings open up numerous opportunities for the development of new asymmetric nitrene transfer systems.

Empowering Exosomes with Aptamers for Precision Theranostics.

As information messengers for cell-to-cell communication, exosomes, typically small membrane vesicles (30-150 nm), play an imperative role in the physiological and pathological processes of living systems. Accumulating studies have demonstrated that exosomes are potential biological candidates for theranostics, including liquid biopsy-based diagnosis and drug delivery. However, their clinical applications are hindered by several issues, especially their unspecific detection and insufficient targeting ability.

Making Full Use of TMSCF: Deoxygenative Trifluoromethylation/Silylation of Amides.

As one of the most powerful trifluoromethylation reagents, (trifluoromethyl)trimethylsilane (TMSCF) has been widely used for the synthesis of fluorine-containing molecules. However, to the best of our knowledge, the simultaneous incorporation of both TMS- and CF- groups of this reagent onto the same carbon of the products has not been realized. Herein, we report an unprecedented SmI/Sm promoted deoxygenative difunctionalization of amides with TMSCF, in which both silyl and trifluoromethyl groups are incorporated into the final product, yielding α-silyl-α-trifluoromethyl amines with high efficiency.

Stimuli-Responsive mRNA Vaccines to Induce Robust CD8 T Cell Response via ROS-Mediated Innate Immunity Boosting.

The messenger RNA (mRNA) vaccines hold great significance in contagion prevention and cancer immunotherapy. However, safely and effectively harnessing innate immunity to stimulate robust and durable adaptive immune protection is crucial, yet challenging. In this study, we synthesized a library of stimuli-responsive bivalent ionizable lipids (srBiv iLPs) with smart molecular blocks responsive to esterase, HO, cytochrome P450, alkaline phosphatase, nitroreductase, or glutathione (GSH), aiming to leverage physiological cues to trigger fast lipid degradation, promote mRNA translation, and induce robust antitumor immunity via reactive oxygen species (ROS)-mediated boosting.

Inhalable Polymeric Microparticles for Phage and Photothermal Synergistic Therapy of Methicillin-Resistant Pneumonia.

Acute methicillin-resistant (MRSA) pneumonia is a common and serious lung infection with high morbidity and mortality rates. Due to the increasing antibiotic resistance, toxicity, and pathogenicity of MRSA, there is an urgent need to explore effective antibacterial strategies. In this study, we developed a dry powder inhalable formulation which is composed of porous microspheres prepared from poly(lactic--glycolic acid) (PLGA), internally loaded with indocyanine green (ICG)-modified, heat-resistant phages that we screened for their high efficacy against MRSA.