Biomimetic Aggregation-Induced Emission Luminogens Mediated Effective Phototherapy and Immune Checkpoint Blockade for the Synergistic Treatment of Lung Cancer.

Background: Lung cancer has become one of the most fatal cancers at present. Traditional treatments showed limited therapeutic effects on lung cancer. The phototherapy has emerged as a powerful approach for lung cancer treatment.

Organocatalytic asymmetric synthesis of axially and centrally chiral heterotriarylmethanes by a Friedel-Crafts reaction.

A highly enantioselective Friedel-Crafts reaction between C2-unsubstituted naphthyl-indoles and racemic 3-methylated-3-pyrrolides catalyzed by chiral phosphoric acids has been developed. This reaction provides an efficient and facile route to a series of heterotricyclic triarylmethanes containing axially chiral naphthyl-indole and centrally chiral pyrrole moieties under mild conditions. Moreover, biological evaluation discovered one of these products with promising antitumor activity, and demonstrates its potential application in medicinal chemistry.

Alumina-supported highly dispersed platinum-copper nanocatalyst with good dehydrogenation performance for perhydromonobenzyltoluene as a hydrogen carrier.

Precious metal catalysts are widely used in the field of heterogeneous catalysis in general and, in particular, for the dehydrogenation process of liquid organic hydrogen carriers (LOHCs). However, improving their catalytic activity and selectivity simultaneously is challenging owing to the characteristics of transition metals. Herein, a catalyst, namely, PtCu/AlO-H, was developed that could break the negative correlation between catalytic activity and selectivity, improving the overall dehydrogenation performance and reducing costs.

Divergent Total Syntheses of Phragmalin and Khayanolide-Type Limonoids: A Torquoselective Interrupted Nazarov Approach.

The asymmetric and divergent total syntheses of two phragmalin (moluccensins G and H) and two khayanolide-type (krishnolide F and khayseneganin F) limonoids were disclosed, which employed a torquoselective interrupted Nazarov cyclization as the key step. Taken together with a Liebeskind-Srogl coupling, a benzoin condensation, and bidirectional acyloin rearrangements, our strategy would simplify the synthetic design of both phragmalin and khayanolide-type limonoids and facilitate their modular syntheses. Moreover, the described approach also provides additional insights into the biosynthetic relationships between these two distinct skeletons.

Bulk Stereoselective Cationic Polymerization of Vinyl Ethers by the Coordination of ZrCl with Tunable Spirocyclic Phosphoric Acids.

Control over stereochemistry in poly(vinyl ether)s leads to a notable change in their physical properties, yet remains a grand challenge. Here, we demonstrate the bulk stereoselective cationic polymerization of vinyl ethers using ZrCl coordinated with a spirocyclic phosphoric acid (SPA). The widely variable substituents in SPAs exert a profound impact on the stereochemical and activity outcome of the polymerization: the % m of poly(vinyl ether)s linearly increases with the Hammett substituent constant (σ) of SPAs; the catalytic activity increases with the σ; the large steric hindrance groups lead to decreased polymerization activity.

Theoretical exploration of siloxy carbenes: photogeneration and [2+1] photocyclization mechanisms.

Carbenes are highly reactive intermediates central to various organic transformations, particularly within photochemistry. This study investigates siloxy carbenes generated from acyl silanes a 1,2-silyl shift, focusing on their generation and reactivity in excited states, using the multiconfiguration perturbation theory (CASPT2//CASSCF/PCM). Our findings reveal that the presence of an aryl group conjugated with the carbonyl moiety substantially lowers the excitation energy of the singlet nπ* state, enabling the 1,2-Brook rearrangement to proceed directly on the singlet hypersurface.

Organocatalytic Asymmetric [3 + 2] Cyclization: Enantioselective Synthesis of α-Indolyl Pyrrolo[1,2-a]indole Scaffolds.

A novel asymmetric [3 + 2] cyclization of α-indolyl propargylic alcohols with 3-alkyl-1H-indoles via chiral phosphoric acid catalysis has been established. This strategy allowed the synthesis of chiral α-indolyl pyrrolo[1,2-a]indole derivatives with high yields (up to 91%) and excellent enantioselectivities (up to 99% ee), facilitating both the reaction activity and enantioselectivity by using the solvent of CHCFCl. Significantly, this protocol will provide an effective synthetic approach for constructing enantioenriched α-indolyl pyrrolo[1,2-a]indole cores of antimalarial natural product isoborreverine analogues.

Organocatalytic Asymmetric (4 + 3) Cycloaddition toward Optically Active Cyclohepta Fused Diindoles.

A novel asymmetric (4 + 3) cycloaddition of indole-2,3-quinodimethanes in situ generated from 3-methyl-2-indolylmethanols with 3-indolylmethanols via chiral phosphoric acid catalysis has been established. The cycloaddition reaction exhibits a broad substrate scope affording the diverse enantioenriched cyclohepta fused diindoles in high yields with good enantioselectivities. Significantly, this work represents the first application of 3-methyl-2-indolylmethanols as 4C synthons instead of the commonly reported three-atom synthons in cycloaddition reactions.

Strong metal-support interactions of TiO interface-loaded Pt constructed under different atmospheres for adjusting the hydrogen storage reaction performance of -ethylcarbazole.

In this study, two series of samples (r-Pt/TiO prepared with a hydrogen pretreatment and r-Pt/TiO prepared with an oxygen pretreatment) were prepared by treating commercial TiO supports in different atmospheres to establish different TiO interfacial structures, followed by the addition of platinum nanoparticles (NPs) for the catalyzed hydrogenation/dehydrogenation cycle of -ethylcarbazole (NEC). The kinetic analysis and reaction mechanism were investigated by combining XRD, Raman, CO-DRIFT, HRTEM, XPS, H-TPD and DFT calculations. It was found that the performance of the samples for the NEC system's cyclic hydrogen storage could be modulated by treating the TiO interfacial structure with different atmospheres varying the extent of strong metal-support interaction (SMSI).

Organocatalytic enantioselective (4+3) cyclization for the synthesis of spiro-fused heterocyclic compounds containing isoindolinone, oxepine and indole moieties.

A refined strategy has been developed to control the regioselective asymmetric (4+3) cyclization of α-(3-isoindolinonyl) propargylic alcohols with 2-indolylmethanols, utilizing chiral phosphoric acid catalysis. This innovative organocatalytic cyclization yields spiro isoindolinone-oxepine-fused indoles featuring a spiro-quaternary stereocenter in high yields and enantioselectivities, facilitated by the solvent of 1,1-dichloro-1-fluoroethane and the additive of hexafluoroisopropanol. Additionally, the photophysical properties of product 3k are examined, revealing bright fluorescence both in the solution and the solid state.

Temporally resolved proteomics identifies nidogen-2 as a cotarget in pancreatic cancer that modulates fibrosis and therapy response.

Pancreatic ductal adenocarcinoma (PDAC) is characterized by increasing fibrosis, which can enhance tumor progression and spread. Here, we undertook an unbiased temporal assessment of the matrisome of the highly metastatic KPC (, , ) and poorly metastatic KPC (, , ) genetically engineered mouse models of pancreatic cancer using mass spectrometry proteomics. Our assessment at early-, mid-, and late-stage disease reveals an increased abundance of nidogen-2 (NID2) in the KPC model compared to KPC, with further validation showing that NID2 is primarily expressed by cancer-associated fibroblasts (CAFs).

Exploring Tunable Properties, Solvent-Modulated Dynamics, and Novel C(sp)-H Activation Mechanisms in Electron Donor-Acceptor Complexes.

Electron donor-acceptor (EDA) complex photochemistry has emerged as a vibrant area in visible-light-mediated synthetic radical chemistry. However, theoretical insights into the reaction mechanisms remain limited. Our study investigates the influence of solvent polarity and halogen atom types on radical reaction pathways in EDA complexes.

Wet peroxide oxidation process catalyzed by Cu/AlO: phenol degradation and Cu dissolution behavior.

Catalytic wet peroxide oxidation (CWPO) has become an important deep oxidation technology for organics removal in wastewater treatments. Supported Cu-based catalysts belong to an important type of CWPO catalyst. In this paper, two Cu catalysts, namely, Cu/AlO-air and Cu/AlO-H were prepared and evaluated through catalytic degradation of phenol.

Support Effect of Boron Nitride on the First N-H Bond Activation of NH on Ru Clusters.

Support effect is an important issue in heterogeneous catalysis, while the explicit role of a catalytic support is often unclear for catalytic reactions. A systematic density functional theory computational study is reported in this paper to elucidate the effect of a model boron nitride (BN) support on the first N-H bond activation step of NH on Ru ( = 1, 2, 3) metal clusters. Geometry optimizations and energy calculations were carried out using density functional theory (DFT) calculation for intermediates and transition states from the starting materials undergoing the N-H activation process.

Retraction: Enantioselective synthesis of α-tetrasubstituted (3-indolizinyl) (diaryl)methanamines chiral phosphoric acid catalysis.

[This retracts the article DOI: 10.1039/D2RA03750E.].

Enantioselective synthesis of α-tetrasubstituted (1-indolizinyl) (diaryl)-methanamines chiral phosphoric acid catalysis.

An enantioselective Friedel-Crafts reaction of cyclic α-diaryl -acyl imines with indolizines catalyzed by a chiral spirocyclic phosphoric acid has been developed. The asymmetric transformation proceeds smoothly to afford α-tetrasubstituted (1-indolizinyl) (diaryl)methanamines in good yields with up to 98% ee under mild conditions.

Selective Adsorptive Desulfurization with Alkaline-Earth Metal-Modified Zeolites in Oil in the Presence of Olefin.

Adsorptive desulfurization (ADS) was a hopeful method for deep desulfurization of oil in mild conditions. In this paper, based on the alkaline-earth (AE) metal-modified Y zeolite (AEY), synthesis, systematic characterization, ADS performance test, and analysis of related adsorption mechanisms were carried out. The crystal and pore structure of Y zeolite were not damaged after ion exchange of AE, while the amount of acid sites and the ratio of Lewis/Bronsted acid sites were both decreased.

A density functional theory study on the adsorption of different organic sulfides on boron nitride nanosheet.

The adsorption of methanethiol (MT), thiophene (T), benzothiophene (BT), dibenzothiophene (DBT) on hexagonal boron nitride (h-BN) has been investigated by the framework of the density functional theory (DFT) calculations in this work. The prefer adsorption sites and interfacial angles of different sulfur compounds on the surface of the h-BN are investigated and analyzed. The adsorption energy results indicated that the adsorption of MT ( ≈ -6 kcal mol), T ( ≈ -10 kcal mol), BT ( ≈ -15 kcal mol), and DBT ( ≈ -21 kcal mol) on monolayer h-BN is physical interaction, and the value of on bilayer h-BN is more than that on monolayer h-BN 0.

Supported Ni Catalysts: Simple Vapor Deposition Preparation Method and Improved Catalytic Performance for Oxidative Dehydrogenation of Ethane.

Developing new methods of catalyst preparation is one of the most important tasks in the field of catalysis. A simple one-tube vapor deposition (VD) is provided in this paper for preparing the supported Ni catalyst. Ni(acac) was used as the Ni precursor.

Organocatalytic Tandem Synthesis of Chiral Hexacyclic Bisindoles from Propargylic 3-Methyleneindoles with 2-Indolylmethanols.

A novel chiral phosphoric acid-catalyzed tandem regioselective 1,6-addition/double intramolecular nucleophilic addition annulation of the propargylic 3-methyleneindoles in situ generated from α-indolyl propargylic alcohols with 2-indolylmethanols has been developed. The methodology afforded the new chiral trifluoromethyl pentalenobisindoles bearing an all-carbon quaternary stereogenic center in generally good yields with excellent enantioselectivities.

On the mechanism of acceptorless dehydrogenation of N-heterocycles catalyzed by BuOK: a computational study.

The catalytic acceptorless dehydrogenation (ADH) of saturated N-heterocycles has recently gained considerable attention as a promising strategy for hydrogen release from liquid organic hydrogen carriers (LOHCs). Recently, a simple BuOK base-promoted ADH of N-heterocycles was developed by Yu ( 2019, , 3958). However, it is still open as to how the BuOK plays a catalytic role in the ADH process.