Isolation, Characterization, and Single-Crystal X-ray Analysis of Lantabetulic Acid from Rhus alata: Insights into HSA and BSA Binding Interactions, with In-Silico Study.

This study investigated the bioactive potential of Rhus alata, a plant known for its rich phytochemicals. A previously unreported compound was isolated from R. alata and characterized using various spectroscopic techniques (IR, UV, NMR, MS) and confirmed for the first time by X-ray crystallography. In isolated compound 1, noncovalent interactions between H···H/H···H, C···C/C···C and O···H/H···O play a major role in its packing arrangement. This observation is consistent with the results of Hirshfeld surface analysis, which quantified these interactions as 14.2%, 84.6%, and 1.2%, respectively. The isolated compound was identified as lantabetulic acid (1) (3ß,25-expoxy-3α-hydroxylup-20(29)-en-28-oic acid). To understand its potential biological interactions, the binding affinity of lantabetulic acid to biomolecules such as bovine serum albumin (BSA), and human serum albumin (HSA), was assessed. The results showed significant binding efficacy, indicating potential interactions with these molecules. Furthermore, the DPPH assay demonstrated the potent antioxidant activity of this compound. We used in silico molecular docking to clarify the binding affinity between lantabetulic acid and a particular receptor. Furthermore, molecular dynamic simulation studies also explored the binding interaction. As well, MM/GBSA calculations corroborate the simulation results and the stability of the complex. Docking and dynamics studies revealed promising binding scores, suggesting further investigation into their potential therapeutic applications. Geometric parameters and the absorption spectrum of compound 1 were also determined using the DFT approach and compared with experimental findings.

Zn-MOF@rGO nanocomposite: a versatile tool for highly selective and sensitive detection of Pb2+ and Cu2+ ions in water.

In this work, a hybrid nanocomposite material (PUC2@rGO) was prepared by integrating our previously developed Zn-MOF (PUC2) with reduced graphene oxide (rGO) through the wet impregnation method. The characterization of PUC2@rGO was performed using various analytical techniques, including FTIR, PXRD, FE-SEM, HR-TEM, XPS, zeta potential, and time-resolved FL spectroscopy. Our investigation primarily focused on assessing the composite's capability to detect water pollutants. Notably, PUC2@rGO demonstrated remarkable selectivity and sensitivity towards Pb2+ and Cu2+ ions via fluorescence quenching, exhibiting low detection limits and high quenching constant values. Spectroscopic analysis revealed that electron transfer from PUC2@rGO (donor) to the metal ions (acceptor) resulted in the observed quenching effect induced by Pb2+ and Cu2+ ions. Time-resolved fluorescence studies of PUC2@rGO before and after adding Pb2+ and Cu2+ ions confirmed dynamic quenching, further affirming strong interactions between PUC2@rGO and the targeted metal ions. These findings highlight PUC2@rGO's potential for efficiently detecting heavy metal pollutants in water.

Au nanoparticles decorated graphitic carbon nitride nanosheets as a sensitive and selective fluorescence probe for Fe3+ and dichromate ions in aqueous medium.

Graphitic carbon nitride mutated with metal nanoparticles has captivated great interest as an effective fluorescent sensor for the detection of harmful ions present in water. In the present work, bulk-gCN was synthesized using melamine as precursor, and further Au-gCN nanocomposite were fabricated via in-situ direct reduction deposition method. The structural, morphological, compositional, stability and optical properties of bulk gCN and Au-gCN nanocomposite were examined using various scattering and spectroscopic techniques such as HRTEM, XPS, XRD and SEM. The synthesized bulk gCN straggles during selectivity studies with different cations and anions because of its uneven surface morphology, however in Au-gCN gold nanoparticles are uniformly distributed on the gCN sheets which results in its enhanced selectivity over bulk gCN. This leads to the fabrication of an optical sensor for Fe3+ and Cr2O72- ions with limit of detection of 4.62 and 2.77 µM, respectively. The sensing of Fe3+ ions corresponds to the photoinduced electron transfer (PET) mechanism, while the detection of chromate species is associated with an inner filter effect (IFE). The practical applicability of the sensor was also evaluated for different environmental water samples. The high stability, sensitivity, and specificity of Au-gCN nanocomposite make it a potential fluorescent probe for Fe3+ and Cr2O72- ions in water samples.

MOFs as versatile scaffolds to explore environmental contaminants based on their luminescence bustle.

Metal-Organic Frameworks (MOFs) with luminescent properties hold significant promise for environmental remediation. This review critically examines recent research on these materials design, synthesis, and applications, mainly focusing on their role in combating environmental pollutants. Through a comprehensive analysis of metal ions, ligands, and framework compositions, the review discusses the importance of tailored design and synthesis approaches in achieving desired luminescent characteristics. Key findings highlight the effectiveness of luminous MOFs as fluorescent sensors for a wide range of contaminants, including heavy metals, reactive species, antibiotics, and explosives. Considering all this, the review discusses future research needs and opportunities in the field of luminous MOFs. It emphasizes the importance of developing multifunctional materials, refining design methodologies, exploring sensing mechanisms, and ensuring environmental compatibility, scalability, and affordability. By providing insights into the current state of research and outlining future directions, this review is a valuable resource for researchers seeking to address environmental challenges using MOF-based solutions.

Facile synthesis of N-(α-furanyl) alkyl sulfoximines via gold catalyzed Michael addition/cyclization of enynones and sulfoximines.

Herein, we prepare a new array of N-(α-furanyl) alkyl sulfoximines via a gold catalyzed reaction of enynone with sulfoximine in moderate to very good yields. The reaction involves Michael addition of sulfoximine to enynone, followed by intramolecular cyclization. The presence of two chiral centres led to the formation of a mixture of diastereomers approximately in a 1 : 1 ratio. The salient features of the protocol include broad substrate scope, high efficiency and high yields. The synthetic utility of the protocol is explored using Suzuki-Miyaura cross-coupling and mild, metal-free opening of the furan ring.

Phenanthroline and Schiff Base associated Cu(II)-coordinated compounds containing N, O as donor atoms for potent anticancer activity.

As an inherent metal ion, copper has been the subject of investigation for developing a novel antitumoral compound that exhibits fewer adverse effects. Copper serves as a cofactor in multiple enzymes, generates reactive oxygen species (ROS), facilitates tumour evolution, metastasis and angiogenesis and has been detected at elevated concentrations in the serum and tissues of various human cancer types. In the given setting, utilising two methodologies in developing novel Copper-based pharmaceuticals for anti-cancer applications is standard practice. These approaches involve either the sequestration of unbound Copper ions or the synthesis of Copper complexes that induce cellular apoptosis. In the past four decades, the latter system has been used, leading to numerous reviews that have examined the anticancer characteristics of a wide range of Copper complexes. These analyses have consistently demonstrated that multiple factors frequently influence the efficacy of these compounds. This review examines the possible anticancer properties of copper and Cu(II) complexes that incorporate Schiff base ligands containing 1,10-phenanthroline. The present study will comprehensively analyse the examined cell lines and mechanistic research associated with each complex.

Visible Light Mediated Co-Catalyzed Isocyanide Insertion with Sulfonyl Azide: Synthesis of Sulfonyl Carbamimidic Azide and Sulfonyl Aminotetrazole via Carbodiimide Intermediate.

Herein, we report an operationally simple and efficient protocol to prepare sulfonyl carbamimidic azide and N-sulfonyl aminotetrazole via Co-catalyzed three component coupling of sulfonyl azide (acts as nitrene source), isocyanide, and TMS-azide at room temperature under visible light. Initially, the carbamimidic azide is formed, which cyclizes only in the presence of base to deliver N-sulfonyl aminotetrazole in very good yields. The sulfonyl aminotetrazole can also be synthesized directly without isolating the carbamimidic azide in the presence of base. The sulfonyl azide is anticipated to generate nitrene and reacts with isocyanide to produce carbodiimide. Subsequent addition of azide (TMS-N3 ) to carbodiimide results in the formation of carbamimidic azide.

Nanoscale designing of metal organic framework moieties as efficient tools for environmental decontamination.

Environmental pollutants, being a major and detrimental component of the ecological imbalance, need to be controlled. Serious health issues can get intensified due to contaminants present in the air, water, and soil. Accurate and rapid monitoring of environmental pollutants is imperative for the detoxification of the environment and hence living beings. Metal-organic frameworks (MOFs) are a class of porous and highly diverse adsorbent materials with tunable surface area and diverse functionality. Similarly, the conversion of MOFs into nanoscale regime leads to the formation of nanometal-organic frameworks (NMOFs) with increased selectivity, sensitivity, detection ability, and portability. The present review majorly focuses on a variety of synthetic methods including the ex situ and in situ synthesis of MOF nanocomposites and direct synthesis of NMOFs. Furthermore, a variety of applications such as nanoabsorbent, nanocatalysts, and nanosensors for different dyes, antibiotics, toxic ions, gases, pesticides, etc., are described along with illustrations. An initiative is depicted hereby using nanostructures of MOFs to decontaminate hazardous environmental toxicants.

Electro-organic synthesis of C-5 sulfenylated amino uracils: Optimization and exploring topoisomerase-I based anti-cancer profile.

Cancer is spreading worldwide and is one of the leading causes of death. The use of existing chemotherapeutic agents is frequently limited due to side effects. As a result, it is critical to investigate new agents for cancer treatment. In this context, we developed an electrochemical method for the synthesis of a series of thiol-linked pyrimidine derivatives (3a-3p) and explored their anti-cancer potential. The biological profile of the synthesized compounds was evaluated against breast (MDAMB-231 and MCF-7) and colorectal (HCT-116) cancer cell lines. 3b and 3d emerged to be the most potent agents, with IC50 values ranging between 0.98 to 2.45 µM. Target delineation studies followed by secondary anticancer parameters were evaluated for most potent compounds, 3b and 3d. The analysis revealed compounds possess DNA intercalation potential and selective inhibition towards human topoisomerase (hTopo1). The analysis was further corroborated by DNA binding studies and in silico-based molecular modeling studies that validated the intercalating binding mode between the compounds and the DNA.

Development of thiazole-appended novel hydrazones as a new class of α-amylase inhibitors with anticancer assets: an in silico and in vitro approach.

Hyperamylasemia is reported to be associated with numerous chronic diseases, including diabetes and cancer. Considering this fact, we developed a series of thiazole-clubbed hydrazones. The derivatives were explored for their in vitro α-amylase inhibitory activity, which was further corroborated with their anticancer assets using a panel of cancer cells, including colon cancer (HCT-116), lung cancer (A549), and breast cancer (MDA-MB-231). To better understand pharmacokinetics, the synthetic derivatives were subjected to in silico ADMET prediction. The in vitro based biological investigation revealed that compared to the reference drug acarbose (IC50 = 0.21 ± 0.008 µM), all the synthesized compounds (5a-5aa) exhibited in vitro α-amylase inhibitory response in the range of IC50 values from 0.23 ± 0.003 to 0.5 ± 0.0 µM. Along with this, the proliferations of the HCT-116, A549 and MDA-MB-231 cells were inhibited when treated with the synthesized compounds. Notable cancer cell growth inhibition was observed for compounds 5e, 5f and 5y, which correlated with their α-amylase inhibition. Additionally, the kinetics investigation revealed that 5b, 5e, 5f and 5y exhibit uncompetitive inhibition. 5b was found to be the least cytotoxic and most potent α-amylase inhibitor and was further validated by absorption and fluorescence quenching technique.

Ni-Catalyzed Mild Synthesis of Sulfonylurea via Tandem Coupling of Sulfonyl Azide, Isocyanide, and Water.

An efficient, mild, and novel route is developed to synthesize sulfonylurea via the nickel-catalyzed tandem coupling of sulfonyl azide, isocyanide, and water in aqueous media. The sulfonyl azide is expected to act as a nitrene precursor, which upon reaction with isocyanide generates carbodiimide. Herein, water acts as a nucleophile and reacts with carbodiimide to deliver the product. The protocol uses an inexpensive nickel catalyst, environmentally friendly water (as the nucleophile), and room temperature and provides products in moderate to good yields.

A highly sensitive and specific luminescent MOF determines nitric oxide production and quantifies hydrogen sulfide-mediated inhibition of nitric oxide in living cells.

The synthesis of a novel carboxylate-type organic linker-based luminescent MOF (Zn(H2L) (L1)) (named PUC2) (H2L = 2-aminoterephtalic acid, L1 = 1-(3-aminopropyl) imidazole) is reported by the solvothermal method and comprehensively characterized using single-crystal XRD, PXRD, FTIR, TGA, XPS, FESEM, HRTEM, and BET. PUC2 selectively reacts with nitric oxide (▪NO) with a detection limit of 0.08 µM, and a quenching constant (0.5 × 104 M-1) indicating a strong interaction with ▪NO. PUC2 sensitivity remains unaffected by cellular proteins or biologically relevant metals (Cu2+/ Fe3+/Mg2+/ Na+/K+/Zn2+), RNS/ROS, or H2S to score ▪NO in living cells. Lastly, we used PUC2 to demonstrate that H2S inhibition increases ▪NO production by ~ 14-30% in various living cells while exogenous H2S suppresses ▪NO production, indicating that the modulation of cellular ▪NO production by H2S is rather generic and not restricted to a particular cell type. In conclusion, PUC2 can successfully detect ▪NO production in living cells and environmental samples with considerable potential for its application in improving the understanding of the role of ▪NO in biological samples and study the inter-relationship between ▪NO and H2S.

Design, synthesis, spectroscopic characterization, single crystal X-ray analysis, in vitro α-amylase inhibition assay, DPPH free radical evaluation and computational studies of naphtho[2,3-d]imidazole-4,9-dione appended 1,2,3-triazoles.

In our quest to design and develop N/O-containing inhibitors of α-amylase, we have tried to synergize the inhibitory action of 1,4-naphthoquinone, imidazole and 1,2,3-triazole motifs by incorporating these structures into a single matrix. For this, a series of novel naphtho[2,3-d]imidazole-4,9-dione appended 1,2,3-triazoles is synthesized by a sequential approach involving [3 + 2] cycloaddition of 2-aryl-1-(prop-2-yn-1-yl)-1H-naphtho[2,3-d]imidazole-4,9-diones with substituted azides. The chemical structures of all the compounds are established with the help of 1D-NMR, 2D-NMR, IR, mass and X-ray studies. The developed molecular hybrids are screened for their inhibitory action on the α-amylase enzyme using the reference drug, acarbose. Different substituents present on the attached aryl part of the target compounds show amazing variations in inhibitory action against the α-amylase enzyme. Based on the type of substituents and their respective positions, it is observed that compounds containing -OCH3 and -NO2 groups show more inhibition potential than others. All the tested derivatives display α-amylase inhibitory activity with IC50 values in the range of 17.83 ± 0.14 to 26.00 ± 0.17 µg/mL. Compound 2-(2,3,4-trimethoxyphenyl)-1-{[1-(4-methoxyphenyl)-1H-1,2,3-triazol-4-yl]methyl}-1H-naphtho[2,3-d]imidazole-4,9-dione (10y) show maximum inhibition of amylase activity with IC50 value 17.83 ± 0.14 µg/mL as compared to reference drug acarbose (18.81 ± 0.05 µg/mL). A molecular docking study of the most active derivative (10y) is performed with A. oryzae α-amylase (PDB ID: 7TAA) and it unveils favourable binding interactions within the active site of the receptor molecule. The dynamic studies reveal that the receptor-ligand complex is stable as the RMSD of less than 2 is observed in 100 ns molecular dynamic simulation. Also, the designed derivatives are assayed for their DPPH free radical scavenging ability and all of them exhibit comparable radical scavenging activity with the standard, BHT. Further, to assess their drug-likeness properties, ADME properties are also evaluated and all of them demonstrate worthy in silico ADME results.

Non-Covalent Interactions in the Self-Assembly of Dihydropyridone Supramolecules and In Vitro Anti-Cancer Assessment in Human Lung Adenocarcinoma Cell Line (A549).

The synthesis of dihydropyridone derivatives has been reported by ring rearrangement of pyrans using iodine and formic acid as a catalyst separately. Dihydropyridones were crystallized subjected for single-crystal X-ray crystallography to acquire their structural parameters. The different non-covalent interactions involved within the supramolecular systems were studied and validated using Hirshfeld surface plot analysis. N-H⋅⋅⋅O interactions between the lactam group dominate. Still, other non-covalent interactions such as C-H⋅⋅⋅N, C-H⋅⋅⋅O, C-H⋅⋅⋅C, N-H⋅⋅⋅N, C-H⋅⋅⋅π, and lone pair⋅⋅⋅π systems act as the driving force in facilitating the self-assembly of the dihydropyridone supramolecules. The synthesized compounds were analyzed by in vitro techniques using human lung adenocarcinoma (A549) to evaluate their cytotoxic activities. Ethyl 4-(4-chlorophenyl)-5-cyano-2-methyl-6-oxo-1,4,5,6- tetrahydropyridine-3-carboxylate has shown the highest cytotoxicity among all the synthesized compounds. Molecular recognition properties of the dihydropyridone compounds were also studied, employing molecular docking tools to gain insight into the binding mode inside the allosteric binding pocket of the Eg5 protein through non-covalent interactions.

Effect of Synthesis Methods and Conditions on Properties and Applications of Carbon Dots for the Detection of Potential Water Contaminants: A Review.

The worldwide pollution of water bodies by potential contaminants such as heavy metals, dyes, and pesticides etc. have severely affected the entire eco-system due to their toxic mobility and tough degradation in water. Consequently, there is a requirement to develop cost-competitive and easily handleable sensing materials which can detect targets sensitively and with selectivity. Among the low-cost sensory materials, carbon dots (CDs) constitute an important class of carbon nanomaterial with unique photostability, electronic and fluorescent properties. This review is an effort to comprehend the recent improvements in the sensing applications of CDs with prominence on synthetic routes, the effect of various synthesis parameters on physical properties (quantum yield, size range), detection mechanisms, and detection parameters (limit of detection, interference etc.). Particularly, the scope and progress for the detection of potential water contaminants using CDs have been explored and a holistic view of mechanisms of their detection has been included.

Holistic view of mechanisms for different types of signals generated by CDs.

Cobalt-based co-ordination complex-derived nanostructure for efficient oxygen evolution reaction in acidic and alkaline medium.

Electrochemical water splitting is one of the most important method for energy conversion and storage. For this, the design and development of a low-cost robust electrocatalyst are highly desirable. In this study, Cobalt-based electrocatalyst for Oxygen Evolution Reaction was synthesized by thermal treatment of Cobalt-dehydroacetic acid (Co-DHA). The as-synthesized Co nanostructures and Co-DHA crystals were characterized with powder X-ray diffraction, X-ray photoelectron spectroscopy thermo-gravimetric analysis, and field emission scanning electron microscopy. The electrochemical O2 evolution study shows the overpotential (at 10 mV/cm-2) correspond to 294 mV vs reference hydrogen electrode (RHE) for K-300 (Co3O4@300), whereas K-500 (Co3O4@500) shows 170 mV vs RHE values in 1 M KOH solution, respectively. Similar trends have been observed for electrochemical O2 evolution studies in 0.5 M H2SO4, where K-300 and K-500 shows the overpotential (at 10mV/cm-2) of 234 mV vs RHE, and 199 mV vs RHE, respectively. The outcomes show better catalytic efficiency of K-500 as compared to K-300.

One-pot synthesis of α-sulfoximinophosphonate via Kabachnik-Fields reaction.

Herein, we disclose a novel approach for the synthesis of hitherto unknown α-sulfoximinophosphonate via the Kabachnik-Fields reaction of aldehyde, dialkylphosphite and sulfoximine in the presence of InCl3 in THF at 70 °C. α-Sulfoximinophosphonate is synthesized in good yields and its synthetic utilities are proved by functionalizing bromine through the Pd-catalyzed Suzuki-Miyaura cross-coupling reaction and reduction of a nitro group through the Béchamp reduction.

Halogen Bond Mediated Self-Assembly of Mononuclear Lanthanide Complexes: Perception of Supramolecular Interactions, Slow Magnetic Relaxation, and Photoluminescence Properties.

Five new mononuclear lanthanide complexes, [LnL2][Et3NH]·THF/H2O (Ln = Nd, Tb, Dy) (H2LCl = 2-bis(2-hydroxy-3,5-dichloro benzyl)aminomethyl]pyridine), Ln = Nd (1), Tb (2), and Dy (3), and (H2LBr = 2-bis(2-hydroxy-3,5-dibromo benzyl)aminomethyl]pyridine), Ln = Nd (4, H2O) and Tb (5), were synthesized and structurally characterized by single-crystal X-ray diffraction analyses. Being isostructural in all the five cases, the metal center is octa-coordinated with a triangular dodecahedron (D2d symmetry) geometry, and it is independent of the halogen substitution (Cl/Br). This close similarity is due to the composite interplay of hydrogen/halogen bond interactions that control the overall crystal packing, yet notable differences in association patterns among the individual ones arise from the subtle stereo-electronic requirement of individual molecules in the three-dimensional (3D) architecture. Hirshfeld surface and density functional theory (DFT) calculations clearly vouch for the importance of the hydrogen bond and halogen bond interactions observed in the structure. Detailed magnetic measurements using direct-current and alternating-current susceptibility measurements show slow magnetic relaxation in 3, a characteristic feature of the single-molecule magnets (SMMs), which is not shown by 1 and 2. Steady-state and time-resolved photoluminescence of Tb(III) complexes shows a strong ligand-to-metal energy transfer that can be modulated by changing the substitution on phenolic ligands. The results from these analyses indicate that it may be advantageous to consider the subtle role of hydrogen bond (HB)/halogen bond (XB) intermolecular interactions judiciously for the design of SMMs and luminescent materials based on halogen-substituted ligands.

A luminescent Zn-MOF for the detection of explosives and development of fingerprints.

A luminescent 3D metal-organic framework [Zn(NDA)(AMP)] = PUC1 (where, NDA = naphthalene-2,6-dicarboxylic acid and AMP = 4-aminomethyl pyridine) was synthesized under solvothermal conditions. The synthesized 3D framework was fully characterized with the help of different analytical techniques such as SCXRD, FTIR, TGA, PXRD, SEM, BET, etc. PUC1 exhibited a strong emission peak at 371 nm when excited at 290 nm and the resulting emission was efficiently quenched in the presence of various organic explosive substances like pentaerythritol tetranitrate (PETN), 2,4,6-trinitrophenyl-N-methylnitramine (Tetryl), trinitrotoluene (TNT), 1,3,5-trinitroperhydro-1,3,5-triazine (RDX), and 1,3,5,7-tetranitro-1,3,5,7-tetrazoctane (HMX). PUC1 revealed highly sensitive and selective detection of PETN and Tetryl with high quenching constant values of 0.1 × 106 and 0.12 × 105 M-1 and low detection limits of 0.315 and 0.404 µM respectively. The strong luminescent properties of PUC1 lead to its successful application in the development of latent fingermarks on different non-porous surfaces using the powder dusting method. The accuracy and applicability of the synthesized material were determined by developing fingerprints by using secretions from eccrine and apocrine glands on a glass slide and various other surfaces, followed by dusting the surfaces. The results so obtained were found to be very accurate and promising.

Methyl-linked Pyrazoles: Synthetic and Medicinal Perspective.

Pyrazoles, an important and well-known class of the azole family, have been found to show a large number of applications in various fields, especially medicinal chemistry. Pyrazole derivatives, particularly methyl-substituted pyrazoles, have been reported as potent medicinal scaffolds that exhibit a wide spectrum of biological activities. The present review is an attempt to highlight the detailed synthetic approaches for methyl-substituted pyrazoles along with an in-depth analysis of their respective medical significances till March 2021. It is hoped that literature sum-up in the form of present review article would certainly be a great tool in assisting medicinal chemists in generating new leads possessing pyrazole nucleus with high efficacy and less microbial resistance.