Synthesis, anticancer evaluation and in silico studies of novel N‐substituted arylidenethiazolidine‐2,4‐dione derivatives as adenosine monophosphate‐activated protein kinase activators

Posted on by
Synthesis, anticancer evaluation and in silico studies of novel N-substituted arylidenethiazolidine-2,4-dione derivatives as adenosine monophosphate-activated protein kinase activators

Novel AMPK activator based on N-substituted arylidenethiazolidine-2,4-diones.


Abstract

Design and development of AMP-activated protein kinase (AMPK) activator emerged as a potential therapeutic approach for various types of cancers. In this context, thiazolidine 2,4-dione was invariably found as an important skeleton for the development of new lead compounds. The present study described the synthesis and antitumor evaluation of new hybrids of N-substituted arylidenethiazolidine-2,4-diones as AMPK activators. The in vitro results revealed that several of newly prepared compounds exhibited significant anticancer activity against human prostate cancer (PC3) and breast cancer (MDMB-231) cell growths with IC50 in the range of 2–10 μM. Particularly, molecular hybridization of thiazolidine 2,4-dione with N-2-(4-(trifluoromethyl)phenyl)ethanol and azaindole (compound 16) was the most effective among the series against both PC3 and MDMB-231 cell lines with IC50 4.28 and 2.5 μM, respectively. Western blot analysis of these thiazolidine 2,4-dione hybrids showed increased (p)-AMPK level in the PC-3 cells indicating direct activation of AMPK. The docking studies at the interface of activator binding site of the AMPK reinforced the in vitro results of potent compounds 13, 16, and 25 having low docking scores −9.0, −9.5, and −9.1 Kcal/mol, respectively.

Phosphate Triester Hydrolysis by Mononuclear Iron(III) Complexes: the Role of Benzimidazole in the Second Coordination Sphere

Posted on by
Phosphate Triester Hydrolysis by Mononuclear Iron(III) Complexes: the Role of Benzimidazole in the Second Coordination Sphere

The Front Cover shows the utilization of benzimidazole-derivatized ligands and their mononuclear iron(III) complexes as a viable alternative for hydrolyzing organophosphate pesticides and also to evaluate the second coordination sphere effect of the benzimidazole moieties. Organophosphates are widely employed in safeguarding crops against pests and insects. However, due to their inherent toxicity, catalysts become imperative to facilitate their efficient degradation. The manuscript explores the investigation of the catalytic role played by benzimidazole groups, employing a comprehensive approach that encompasses experimental facets, as well as computational methods like DFT calculations. The findings skillfully strike a balance between the incorporation of aromatic-nucleophilic groups within the second coordination sphere and the optimization of side chain length in order to augment phosphoesterase activity. More information can be found in the Research Article by F. R. Xavier, R. A. Peralta, and co-workers.


Carbonylation of Boranes – A Computational Study

Posted on by
Carbonylation of Boranes – A Computational Study

The Cover Feature shows a carbonyl trialkyl borate, R3B-CO, where three consecutive B-to-C alkyl group migrations are indicated by coloured (greenish, blue and violet) arrows, the last two being accompanied by the corresponding (blue and violet) arrows signaling the subsequent inverse (C-to-B) oxygen shift. This represents the consecutive formation of the formal acyl borane, boraepoxide and alkyl boron oxide intermediates resulting from the treatment of trialkyl boranes with carbon monoxide. The art work was designed by Pablo Espinosa Sánchez-Campillo. More information can be found in the Research Article by A. Espinosa Ferao.


Mesoporous SBA‐15 Supported CdS through Organosilane Ligand for Photo driven Cleavage of Aryl ether in Lignin and its Model Compound

Posted on by

Abstract: Mesoporous silica (SBA-15) synthesized hydrothermally followed by calcination and then functionalization with 3-(trimethoxysilyl)-1-propanethiol through surface grafting. The thiol moiety of the grafted ligand is utilized for uniform anchoring the cadmium into the channels of the material. The synthesised material was subjected for its photo catalytic applications after characterization through standard characterization protocol. The synthesised SAB-15, ligand modified SBA-15-S and Cd loaded SAB-15-CdS were characterized through standard characterization protocol like   powder XRD, FT-IR, UV-DRS,  MAS NMR, N2 sorption, FE-SEM, HR-TEM and TG-DTA studies. After successful characterization the screening of the catalyst was carried out on a model reaction involving photo catalytic cleavage of α-O-4 aryl ether linkage present in benzyl phenyl ether, which is an important lignin model compound. The catalyst exhibited good efficiency along with the selectivity for desired monoaromatic platform chemicals. The synthesized catalyst was also carried out for the photo catalytic depolymerization of alkali lignin at the optimized reaction conditions which further showed the promising results for getting value added chemicals from lignin. The reaction products were characterized by using Gas chromatography-mass spectrometry (GC-MS) techniques.

Ring‐Opening Mechanism of O‐heterocycles into α,ω‐Diols over Ni‐La(OH)3: C–O Bond hydrogenolysis of THFA to 1,5‐Pentanediol as a Case Study

Posted on by

The elucidation of the ring-opening reaction mechanism is a critical step towards improving the catalytic performance for the conversion of biomass into value-added chemicals. Herein, we focused on the stepwise C–O bond hydrogenolysis mechanism of oxygen-containing heterocycles (O-heterocycles) into α,ω-diols, in particular THFA to 1,5-PeD, over selective Ni-La(OH)3 in hydrogen-donor isopropanol. A mechanistic study was carried out on a structurally well-defined Ni-La(OH)3, where the mechanism was elucidated using a combination of kinetic and 13C NMR isotope labeling experiments. It was suggested that both Ni nanoparticles and La(OH)3 support play a critical role in the reaction mechanism, where basic hydroxide species of the support initially deprotonate the CH2OH and –OH modified furan, tetrahydrofuran and tetrahydropyran rings, adsorbing them chemically on the catalyst surface. This step is followed by a direct hydride attack on the second carbon atom of these rings, which is proposed to be the key step for ring cleavage, as indicated by the increased deuteration at this position. It is assumed that a catalytic transfer hydrogenolysis reaction (CTH) reaction of THFA is proposed to proceed via the dehydrogenation of isopropanol over isolated Ni species, forming hydrogen species that can be adsorbed on the Ni surface or desorb as H2.

Exploring the Effects Behind the Outstanding Catalytic Performance of PdAg Catalysts Supported on Almond Shell‐Derived Activated Carbon Towards the Dehydrogenation of Formic Acid

Posted on by

In this work, highly efficient carbon-supported Pd-based catalysts for formic acid dehydrogenation were synthesized by a straightforward wet impregnation-reduction method. The carbon support was obtained from a biomass residue (almond shell) prepared via H3PO4-assisted hydrothermal carbonization (HTC) and thermal activation. This carbon support was doped with nitrogen groups to study the effect on the electronic properties and catalytic performance of the catalysts. Investigating the formation of PdAg alloys with varying Pd:Ag molar ratios resulted in catalysts exhibiting enhanced catalytic activity compared to monometallic Pd counterparts. Notably, the Pd1Ag0.5/NAS catalyst displayed outstanding catalytic performance, achieving an initial TOF of 1716 h-1 (calculated in the first 3 minutes of reaction and expressed per mole of Pd) and maintaining substantial activity over 6 consecutive reaction cycles. This work elucidates the successful synthesis of effective catalysts, emphasizing the influence of nitrogen doping and PdAg alloy composition on catalytic behavior and stability.

Metal‐Organic Frameworks‐Derived Nanocarbon Materials and Nanometal Oxides for Photocatalytic Applications

Posted on by

Harnessing low-density solar energy and converting it into high-density chemical energy through photocatalysis has emerged as a promising avenue for the production of chemicals and remediation of environmental pollution, which contributes to alleviating the overreliance on fossil fuels. In recent years, metal-organic frameworks (MOFs) have gained widespread application in the field of photocatalysis due to their photostability, tunable structures, and responsiveness in the visible light range. However, most MOFs exhibit relatively low response to light, limiting their practical applications. MOFs-derived nanomaterials not only retain the inherent advantages of pristine MOFs but also show enhanced light adsorption and responsiveness. This review categorizes and summarizes MOFs-derived nanomaterials, including nanocarbons and nanometal oxides, providing representative examples for the synthetic strategies of each category. Subsequently, the recent research progress on MOFs-derived materials in photocatalytic applications are systematically introduced, specifically in the areas of photocatalytic water splitting to H2, photocatalytic CO2 reduction, and photocatalytic water treatment. The corresponding mechanisms involved in each photocatalytic reaction are elaborated in detail. Finally, the review discusses the challenges and further directions faced by MOFs-derived nanomaterials in the field of photocatalysis, highlighting their potential role in advancing sustainable energy production and environmental remediation.

Recent Progress in the Synthesis of α‐Hydroxy Carbonyl Compounds with ThDP‐dependent Carboligases

Posted on by

Carboligases catalyze the thiamine diphosphate (ThDP) dependent formation of carbon-carbon bonds. These enzymes are prominent biocatalysts for the production of valuable a-hydroxy carbonyl compounds, which serve as key building blocks in the synthesis of various pharmaceuticals and fine chemicals. Carboligases act in selective manner to afford regio- and stereochemically defined products from simple starting materials. This review explores the catalytic prowess of carboligases for synthetic purposes and is aimed at providing a selection tool of enzymes for particular sets of substrates or desired products. The comprehensive overview encompasses structural insights, relationships of the currently known sequence space and practical applications with a focus on recent literature, showcasing carboligases as potent tools for sustainable and efficient synthesis.