Monthly Archives: September 2023

Meta‐Ortho Effect on the Excited State Pathways of Chloroanilines

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Meta-Ortho Effect on the Excited State Pathways of Chloroanilines

Computational chemistry allows to elucidate the observed selectivity in the photochemistry of chloroanilines. A meta-ortho effect of the substituents favours the population of the prefulvenic conical intersection which leads to rapid deactivation of the m- and o-isomers of chloroaniline, while the para derivative lives long enough to emit and populate the reactive triplet state which leads to C−Cl dissociation.


Abstract

Direct excitation of aromatic compounds grants access to high-energy intermediates that can be utilised in organic synthesis. Understanding and predicting the substituent effects at the excited state for aromatic molecules remains challenging for the synthetic photochemist. In this work, we present an experimental and computational investigation of the excited state of the isomeric chloroanilines, which promptly react by losing the chloride when the amino group is in para position, but are non-reactive and non-emissive in the meta and ortho isomers. XMS-CASPT2//CASSCF computations explain this apparent contradiction of the meta-ortho selectivity rule of Zimmerman, which originates from the substituent effects lowering to a different extent the barrier to populate the prefulvenic conical intersection that deactivates non-radiatively the singlet excited state of the chloroanilines.

Three Component Synthesis of 4‐Aryl‐2‐aminothiazoles under Transition‐Metal Free Conditions

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Three Component Synthesis of 4-Aryl-2-aminothiazoles under Transition-Metal Free Conditions

An efficient three-component synthesis of disubstituted 4-aryl-2-aminothiazoles was reported. The protocol features transition-metal free, short reaction time, easily available starting materials, good yields and broad substrates scope, showing potential synthetic value for the synthesis of a variety of biological or pharmaceutical active compounds.


Abstract

An efficient three-component synthesis of 4-aryl-2-aminothiazoles was reported. Phenyl-thioureas reacted with 2-bromoacetophenones to form 4-aryl-2-aminothiazoles through cyclization, and the subsequent C−N bonding with benzyl/allyl bromides gave the desired disubstituted thiazoles smoothly. The protocol features transition-metal free, short reaction time, easily available starting materials, good yields and broad substrate scope, showing potential synthetic value for the synthesis of a variety of biologically or pharmaceutically active compounds.

Practical Synthesis of Pharmaceutically Relevant Pyrroles from α,β‐Unsaturated Aldehydes and Phenacyl Azides

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Practical Synthesis of Pharmaceutically Relevant Pyrroles from α,β-Unsaturated Aldehydes and Phenacyl Azides

A method for the synthesis of 2-aroyl-5-aryl-pyrroles using phenacyl azide and α,β-unsaturated aldehyde at room temperature has been developed. High yield, atom economy and requirement of economic substrates, reagents and organocatalyst as well as non-involvement of cryogenic or very high temperature and inert or anhydrous conditions make this protocol a sustainable synthetic approach towards the synthesis of 2-aroyl-5-aroyl-pyrroles.


Abstract

Structurally diverse pyrroles were synthesized by direct coupling of α, β-unsaturated aldehydes and phenacyl azides. The scope of the synthetic method was successfully demonstrated by synthesizing 28 different phenyl(5-phenyl-1H-pyrrol-2-yl)methanones in high yields (87–95 %). Derivatization of a few synthesized pyrroles was demonstrated which shows the potential application of the developed protocol in new functional materials. To get a mechanistic insight of the reaction, a typical reaction was performed in a deuterated solvent and the progress of the reaction was monitored by recording its 1H NMR at regular time intervals.

Ring Transformation of α‐Amino‐β‐oxoesters to δ‐Butyrolactams

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Ring Transformation of α-Amino-β-oxoesters to δ-Butyrolactams

Lactams by Ring Transformation: δ-Butyrolactams with an exocyclic ester moiety in the δ-position were accessed by reduction of cyclic α-azido-β-oxocyclopentane carboxylates with Zn−AcOH. The ring transformation proceeded readily under the conditions of the reduction which is an unprecedented process.


Abstract

δ-Butyrolactams with an exocyclic ester moiety in the δ-position were accessed by reduction of 1-azido-2-cyclopentanone carboxylates with PBu3 or Zn−AcOH. The ring transformation proceeded readily under the conditions of this reduction which is an unprecedented process. Primary amines formed by catalytic hydrogenation of α-azido-β-oxoesters with larger ring sizes or with benzannulation do not show this rearrangement under the conditions of the azide reduction. In these cases, the ring transformation to respective lactams was achieved by treatment of the α-amino-β-oxoesters with a stoichiometric amount of lithium diisopropylamide.

Exploring the Therapeutic Properties of Alga‐Based Silver Nanoparticles: Anticancer, Antibacterial, and Free Radical Scavenging Capabilities

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Exploring the Therapeutic Properties of Alga-Based Silver Nanoparticles: Anticancer, Antibacterial, and Free Radical Scavenging Capabilities


Abstract

The current study was designed to evaluate the antioxidant, anticancer and antimicrobial activities of silver nanoparticles (AgNPs) biosynthesized by Spirulina platensis extract. The biosynthesized silver nanoparticles were characterized using Fourier transform infrared (FT-IR) analysis, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD) analysis. The antioxidant activity of the biosynthesized AgNPs were determined via DPPH radical scavenging assay while its anticancer activity was determined using the MTT assay. The antimicrobial activity of the biosynthesized AgNPs were analyzed by disc diffusion method. Spirulina platensis acts as a reducing and capping agent. The efficacy of silver nanoparticles (AgNPs) in inhibiting the growth of Gram-negative bacteria, specifically Acetobacter, Klebsiella, Proteus vulgaris, and Pseudomonas aeruginosa, was assessed by the utilisation of the diffusion method. The study aimed to evaluate the efficacy of biosynthesized silver nanoparticles (AgNPs) against many strains of Pseudomonas aeruginosa bacteria. The findings of the study revealed that when administered in doses of 50 μl, 75 μl, and 100 μl, the largest observed zone of inhibition corresponded to measurements of 10.5 mm, 14 mm, and 16 mm, respectively. A zone of inhibition with dimensions of 8 mm, 10.5 mm, and 12 mm was detected during testing against Acetobacter at concentrations of 50 μl, 75 μl, and 100 μl, respectively. The findings also indicate that there is a positive correlation between the concentration of AgNP and the DPPH scavenging ability of silver nanoparticles. The percentage of inhibition observed at concentrations of 500 μg/ml, 400 μg/ml, 300 μg/ml, 200 μg/ml, and 100 μg/ml were recorded as 80±1.98, 61±1.98, 52±1.5, 42±1.99, and 36±1.97, respectively. In addition, it was observed that the silver nanoparticles exhibited the greatest antioxidant activity at a concentration of 500 g/ml, with a measured value of 80.89±1.99. The IC-50 values, representing the inhibitory concentration required to achieve 50 % inhibition, were found to be 8.16, 19.15, 30.14, 41.13, and 63.11 at inhibition levels of 36±1.97, 42±1.99, 52±1.5, 61±1.98, and 80±1.98, respectively.

Structurally Diverse Sesquiterpenoids with NO Production and α‐Glucosidase Inhibitory Activities from the Fruits of Schisandra chinensis

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Structurally Diverse Sesquiterpenoids with NO Production and α-Glucosidase Inhibitory Activities from the Fruits of Schisandra chinensis


Abstract

Chemical fractionation of the AcOEt partition, generated from the EtOH extract of the fruits of Schisandra chinensis, afforded a series of sesquiterpenyl constituents including two new cadinanes, a new eudesmane, two new widdranes (a handling artefact and a new natural product), a new bisabolane and two new natural cuparane enantiomers, along with 15 known structurally related analogs. Structures of the new compounds were unambiguously characterized by interpretation of detailed spectroscopic data including ESI-MS and 1D/2D NMR, with their absolute configurations being established by electronic circular dichroism (ECD) calculation and induced ECD experiment. The inhibitory effects of all the isolates against α-glucosidase and lipopolysaccharide (LPS) induced nitric oxide (NO) production in murine RAW264.7 macrophages, as well as their antibacterial and cytotoxic potential, were evaluated, with selective compounds showing moderate α-glucosidase and NO inhibitory activity. Notably, canangaterpene III exhibited the most significant NO inhibitory effect with an IC50 value of 31.50±1.49 μM.

A New Harziane Diterpene, Harziaketal A, and a New Sterol, Trichosterol A, from the Marine‐Alga‐Epiphytic Trichoderma sp. Z43

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A New Harziane Diterpene, Harziaketal A, and a New Sterol, Trichosterol A, from the Marine-Alga-Epiphytic Trichoderma sp. Z43


Abstract

One new diterpene, harziaketal A (1), and one new highly degraded sterol, trichosterol A (2), along with three known compounds, including one diterpene, harzianone (3), and two steroids, (22E,24R)-5α,6α-epoxy-ergosta-8(14),22-dien-3β,7α-diol (4) and isoergokonin B (5), were isolated from the culture of the marine-alga-epiphytic fungus Trichoderma sp. Z43 by silica gel column chromatography (CC), Sephadex LH-20 CC, and preparative thin-layer chromatography (TLC). Their structures and relative configurations were assigned by nuclear magnetic resonance (NMR) and high resolution electrospray ionisation mass spectrometry (HR-ESI-MS) data, and the absolute configuration of 1 was established by X-ray diffraction. Compound 1 features a hemiketal unit situated at the four-membered ring of harziane-type diterpenes for the first time, while 2 represents the rare occurrence of sterols with rings A and B being degraded. Compounds 1 and 2 displayed weak inhibition against the tested phytoplankton (Amphidinium carterae, Heterocapsa circularisquama, Heterosigma akashiwo, and Prorocentrum donghaiense) with half maximal inhibitory concentration (IC50) ranging from 14 to 53 μg/mL.

Quantification of Phytochemicals and Metal Ions as well as the Determination of Volatile Compounds, Antioxidant, Antimicrobial and Antacid Activities of the Mimosa pudica L. Leaf: Exploration of Neglected and Under‐Utilized Part

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Quantification of Phytochemicals and Metal Ions as well as the Determination of Volatile Compounds, Antioxidant, Antimicrobial and Antacid Activities of the Mimosa pudica L. Leaf: Exploration of Neglected and Under-Utilized Part


Abstract

Mimosa pudica L. (MP) is well-known plant in traditional medicinal system, especially in India. Unfortunately, leaves of MP are less explored. To determine the food and nutritional value of the neglected part of Mimosa pudica L. (MP), that is MP leaves, phytochemicals and metal ions of MP were quantified by newly developed HPLC and ICPOES-based methods. The content of phytochemicals observed using HPLC analysis for chlorogenic acid, catechin, and epicatechin was 141.823 (±8.171), 666.621 (±11.432), and 293.175 (±12.743) μg/g, respectively. Using GC/MS/MS analysis, fatty acid like oleic acid were identified. In ICP-OES analysis, a significant content of Na, K, Ca, Cu, Fe, Mg, Mn, and Zn was observed. The observed TPC and TFC for MP leaf extracts was 44.327 (±1.041) mg GAE/ g of wt. and 214.217 (±4.372) mg QCE/ g of wt., respectively. The DPPH assay depicted a strong antioxidant activity of MP leaf extracts with IC50 values of 0.796 (±0.081) mg/mL and a TEAC value of 0.0356 (±0.0003). A significant antacid activity (666 mg MP+400 mg CaCO3 >400 mg CaCO3 ≫666 mg Gelusil) of MP leaves was noticed. The methanolic extract of MP leaves demonstrated anti-microbial activity against Staphylococcus aureus (15±2mm), Pseudomonas aeruginosa (12±2mm) and Escherichia coli (10±2mm). In silico studies confirmed the in vitro results obtained for antioxidant, antiacid, and anti-microbial activities. In addition, in silico studies revealed the anti-cancerous and anti-inflammatory potential of the MP leaves. In summary, this study demonstrated the medicinal significance of MP leaves and the conversion of agro-waste or the under-utilized part of MP into pharmaceutical potent materials. Consequently, the present study highlighted that MP leaves alone have medicinal importance with good nutritional utility and possess large promise in the pharma industry along with improving bio-valorization and the environment.

Isocucurbic Acid Derivatives and Soluble Epoxide Hydroxylase Inhibitors from the Flowers of Chrysanthemum indicum L.

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Isocucurbic Acid Derivatives and Soluble Epoxide Hydroxylase Inhibitors from the Flowers of Chrysanthemum indicum L.


Abstract

Soluble epoxide hydrolase (sEH) inhibitory activity guided fractionation and isolation of two new isocucurbic acid derivatives (1 and 2) and nine known compounds (3–11) from the flowers of Chrysanthemum indicum L. Their structures were elucidated on the basis of spectroscopic data interpretation and comparison with those reported in previous studies. Luteolin (3), acacetin-7-O-β-D-glucopyranoside (6), and methyl 3,4-di-O-caffeoylquinate (10) displayed sEH inhibitory activities with IC50 values ranging from 13.7±3.6 to 20.8±0.4 μM. Enzyme kinetic analysis revealed that 3, 6, and 10 were non-competitive inhibitors with K i values of 14.8±0.5, 31.2±0.8, and 3.9±0.2 μM, respectively. Additionally, molecular docking studies indicated compound 10 had the ability to form six hydrogen bonds at sEH active site, resulting binding energy as low as −9.58 Kcal/mol.

Chemiresistive Gas Sensing using Graphene‐Metal Oxide Hybrids

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Chemiresistive Gas Sensing using Graphene-Metal Oxide Hybrids

This review focuses on graphene-functionalized metal oxide nanostructures designed for gaseous molecules detection, mainly hydrogen gas sensing applications. Perfect structured pristine graphene (left-top), electron-hole transport mechanism in metal-graphene system (center) and a typical metal/metal oxide-graphene-based gas sensor (right-top) along with functional metal/metal oxide-graphene for hydrogen sensing material (background) is shown.


Abstract

Chemiresistive sensing lies in its ability to provide fast, accurate, and reliable detection of various gases in a cost-effective and non-invasive manner. In this context, graphene-functionalized metal oxides play crucial role in hydrogen gas sensing. However, a cost-effective, defect-free, and large production schemes of graphene-based sensors are required for industrial applications. This review focuses on graphene-functionalized metal oxide nanostructures designed for gaseous molecules detection, mainly hydrogen gas sensing applications. For the convenience of the reader and to understand the role of graphene-metal oxide hybrids (GMOH) in gas sensing activities, a brief overview of the properties and synthesis routes of graphene and GMOH have been reported in this paper. Metal oxides play an essential role in the GMOH construct for hydrogen gas sensing. Therefore, various metal oxides-decorated GMOH constructs are detailed in this review as gas sensing platforms, particularly for hydrogen detection. Finally, specific directions for future research works and challenges ahead in designing highly selective and sensitive hydrogen gas sensors have been highlighted. As illustrated in this review, understanding of the metal oxides-decorated GMOH constructs is expected to guide ones in developing emerging hybrid nanomaterials that are suitable for hydrogen gas sensing applications.