Hinged Bipodal Furoylthiourea-Based Ru(II)-Arene Complexes: Effect of (ortho, meta, or para)-Substitution on Coordination and Anticancer Activity.

We set out to design and synthesize bipodal ligands with the phenyl group as the spacer and varied the substitution on the spacer between ortho (L1), meta (L2), and para (L3). The respective ligands and complexes containing either p-cymene (PL1-PL3) or benzene (BL1-BL3) as the arene unit were synthesized and characterized successfully. The influence of the ligands due to substitution change on their coordination behavior was quite minimal; however, the differences were seen in the anticancer activity of the complexes. DFT studies revealed the structural variations between the three different substitutions, which was further confirmed by single-crystal X-ray diffraction studies. The anticancer activity of the complexes could be correlated with their rate of hydrolysis and their lipophilicity index as determined by UV-visible spectroscopy. The cell death mechanism of the active complexes was deduced to be apoptotic via staining assays, flow cytometry, and Western blot analysis.

Ru(II)-p-Cymene Complexes of Furoylthiourea Ligands for Anticancer Applications against Breast Cancer Cells.

Half-sandwich Ru(II) complexes containing nitro-substituted furoylthiourea ligands, bearing the general formula [(η6-p-cymene)RuCl2(L)] (1-6) and [(η6-p-cymene)RuCl(L)(PPh3)]+ (7--12), have been synthesized and characterized. In contrast to the spectroscopic data which revealed monodentate coordination of the ligands to the Ru(II) ion via a "S" atom, single crystal X-ray structures revealed an unusual bidentate N, S coordination with the metal center forming a four-membered ring. Interaction studies by absorption, emission, and viscosity measurements revealed intercalation of the Ru(II) complexes with calf thymus (CT) DNA. The complexes showed good interactions with bovine serum albumin (BSA) as well. Further, their cytotoxicity was explored exclusively against breast cancer cells, namely, MCF-7, T47-D, and MDA-MB-231, wherein all of the complexes were found to display more pronounced activity than their ligand counterparts. Complexes 7-12 bearing triphenylphosphine displayed significant cytotoxicity, among which complex 12 showed IC50 values of 0.6 ± 0.9, 0.1 ± 0.8, and 0.1 ± 0.2 µM against MCF-7, T47-D, and MDA-MB-231 cell lines, respectively. The most active complexes were tested for their mode of cell death through staining assays, which confirmed apoptosis. The upregulation of apoptotic inducing and downregulation of apoptotic suppressing proteins as inferred from the western blot analysis also corroborated the apoptotic mode of cell death. The active complexes effectively generated reactive oxygen species (ROS) in MDA-MB-231 cells as analyzed from the 2',7'-dichlorofluorescein diacetate (DCFH-DA) staining. Finally, in vivo studies of the highly active complexes (6 and 12) were performed on the mice model. Histological analyses revealed that treatment with these complexes at high doses of up to 8 mg/kg did not induce any visible damage to the tested organs.

A Simple Selective Probe for Lysine Detection in Tablets, Food Samples and Cells.

A novel probe ITQ (9-(((E)-1 H-inden-1-ylidene)methyl)-8-(3-(((E)-1 H-inden-1-ylidene)methyl)phenoxy)-2,3,6,7-tetrahydro-1 H,5 H-pyrido[3,2,1ij]quinolone) was successfully designed and synthesized to detect amino acid lysine (Lys). The selective sensing behavior of the probe ITQ was observed using absorption and emission spectral results. Further, the probe ITQ exhibits a strong binding affinity for Lys [1.4 × 104 M- 1] and detects and quantifies Lys even in its nanomolar concentration. Moreover, the probe ITQ detects Lys at 1:2 binding stoichiometry with suitable biological pH [4-11]. Furthermore, the probe ITQ was also successfully utilized to detect Lys in tablets, real samples (avocado, soyabean and pork) and in live HeLa cells.

A Reversible Fluorescent Chemosensor for the Selective Detection of Cu2+ and CN- ions by Displacement Approach.

A novel fluorescence chemosensor BDP (2-(1-(benzothiazol-2-yl)-5-(4-(diphenylamino)phenyl)-4,5-dihydro-1H-pyrazol-3-yl)phenol) has been synthesized and its sensing behavior has been screened towards various cations by absorption, emission and mass spectroscopic techniques. The probe BDP detects Cu2+ ions preferentially over other metal ions, and the resulting BDP-Cu2+ ensemble acts as a secondary sensor for cyanide anion detection over other anions. The fluorescence intensity of the probe BDP is quenched when it comes into contact with Cu2+ ions, but it is increased reversibly when it comes into contact with cyanide anion, according to spectroscopic measurements. Along with this, optical studies indicate that the sensor BDP has capability to sense Cu2+ and CN- ions selectively over other examined competitive ions with the LOD of 2.57×10-8 M and 2.98×10-8 M respectively. The detection limit of Cu2+ ions is lower than the WHO recommended Cu2+ ions concentration (31.5 µM) in drinking water. On the basis of "on-off-on" fluorescence change of the probe BDP upon interaction with Cu2+ and CN- ions, a possible mechanism for this selective sensing behavior was presented and IMPLICATION logic gate was successfully designed. Furthermore, cell imaging investigations were used to investigate the probe BDP's biological applicability.

Effective and Selective Ru(II)-Arene Complexes Containing 4,4'-Substituted 2,2' Bipyridine Ligands Targeting Human Urinary Bladder Cancer Cells.

Cisplatin-based chemotherapy is a common regimen for bladder cancer, a life-threatening cancer with more than 500,000 new cases worldwide annually. Like many other metallodrugs, cisplatin causes severe side effects for its general toxicity. Organoruthenium is known for its structural stability, good anticancer activity, and possible low general toxicity. Here, we have prepared and characterized a series of water-soluble ruthenium-arene complexes with N,N'-chelating ligands: [Ru(II)-η6-arene-(4,4'-(X)2-2,2'-bipyridine)Cl]Cl (arene = p-cymene, X = C4H9 (1), COOH (2), COOCH3 (3), COOC2H5 (4); arene = benzene, X = C4H9 (5), COOCH3 (6), COOC2H5 (7)). These complexes are carefully characterized using single-crystal X-ray diffraction, UV-vis, IR, 1H NMR, and MALDI-TOF MS spectroscopy. Their DFT-calculated structural and thermodynamic properties are consistent with the experimental observations. Biophysicochemical studies of complex interaction with CTDNA and BSA supported by molecular docking simulations reveal suitable properties of 1-7 as anticancer agents. Cytotoxicities of 1-7 are evaluated on healthy human MCF-10a-breast epithelial and African green monkey Vero cells, and carcinoma human HepG-2-hepatic, T24-bladder, and EAhy-926-endothelial cells. All complexes exhibit much higher cytotoxicity for T24 than cisplatin. Particularly, 1 and 2 are also highly selective toward T24. Fluorescence imaging and flow cytometry demonstrate that 1 and 2 penetrate T24 cell membrane and induce early apoptosis at their respective IC50 concentrations, which ultimately lead to cell death. Statistical analysis suggests that the order of importance for T24 cell antiproliferation is protein binding, Log p, Ru-Cl bond length, while DNA binding is the least important. This study is the first to report the anti-bladder cancer efficacy of Ru-arene-2,2'-bipyridine complexes, and may provide insights for rational design of organoruthenium drugs in the enduring search for new chemotherapeutic agents.

Design and synthesis of heterocyclic azole based bioactive compounds: Molecular structures, quantum simulation, and mechanistic studies through docking as multi-target inhibitors of SARS-CoV-2 and cytotoxicity.

Two heterocyclic azole compounds, 3-(2,3-dihydrobenzo[d]thiazol-2-yl)-4H-chromen-4-one (SVS1) and 5-(1H-indol-3-yl)-4-methyl-2,4-dihydro-3H-1,2,4-triazole-3-thione (SVS2) were obtained unexpectedly from 2-aminothiophenol and 4-oxo-4H-chromene-3-carbaldehyde (for SVS1), and (E)-2-((1H-indol-3-yl)methylene)-N-methylhydrazine-1-carbothioamide in the presence of anhydrous FeCl3 (for SVS2), respectively. The compounds were well characterized by analytical and spectroscopic tools. The molecular structures of both the compounds were determined by single crystal X-ray diffraction (XRD) study. The results obtained from density functional theory (DFT) study revealed the molecular geometry and electron distribution of the compounds, which were correlated well with the three-dimensional structures obtained from the single crystal XRD. DMol3 was used to calculate quantum chemical parameters [chemical potential (µ), global hardness (η), global softness (σ), absolute electronegativity (χ) and electrophilicity index (ω)] of SVS1 and SVS2. Molecular docking study was performed to elucidate the binding ability of SVS1 and SVS2 with SARS-CoV-2 main protease and human angiotensin-converting enzyme-2 (ACE-2) molecular targets. Interestingly, the binding efficiency of the compounds with the molecular targets was comparable with that of remdesivir (SARS-CoV-2), chloroquine and hydroxychloroquine. SVS1 showed better docking energy than SVS2. The molecular docking study was complemented by molecular dynamics simulation study of SARS-CoV-2 main protease-SVS1 complex, which further exemplified the binding ability of SVS1 with the target. In addition, SVS1, SVS2 and cisplatin were assessed for their cytotoxicity against a panel of three human cancer cells such as HepG-2 (hepatic carcinoma), T24 (bladder) and EA.hy926 (endothelial), as well as Vero (kidney epithelial cells extracted from an African green monkey) normal cells using MTT assay. The results showed that SVS2 has significant cytotoxicity against HepG-2 and EA.hy926 cells with the IC50 values of 33.8 µM (IC50 = 49.9 µM-cisplatin and 8.6 µM-doxorubicin) and 29.2 (IC50 = 26.6 µM-cisplatin and 3.8 µM-doxorubicin), respectively.

Tunable Anticancer Activity of Furoylthiourea-Based RuII -Arene Complexes and Their Mechanism of Action.

Fourteen new RuII -arene (p-cymene/benzene) complexes (C1-C14) have been synthesized by varying the N-terminal substituent in the furoylthiourea ligand and satisfactorily characterized by using analytical and spectroscopic techniques. Electrostatic potential maps predicted that the electronic effect of the substituents was mostly localized, with some influence seen on the labile chloride ligands. The structure-activity relationships of the Ru-p-cymene and Ru-benzene complexes showed opposite trends. All the complexes were found to be highly toxic towards IMR-32 cancer cells, with C5 (Ru-p-cymene complex containing C6 H2 (CH3 )3 as N-terminal substituent) and C13 (Ru-benzene complex containing C6 H4 (CF3 ) as N-terminal substituent) showing the highest activity among each set of complexes, and hence they were chosen for further study. These complexes showed different behavior in aqueous solutions, and were also found to catalytically oxidize glutathione. They also promoted cell death by apoptosis and cell cycle arrest. Furthermore, the complexes showed good binding ability with the receptors Pim-1 kinase and vascular endothelial growth factor receptor 2, commonly overexpressed in cancer cells.

Effective inhibition of insulin amyloid fibril aggregation by nickel(II) complexes containing heterocyclic thiosemicarbazones.

The sensitivity of protein molecular structures makes them susceptible to aggregation in conditions unfavorable for the maintenance of their native folds. The aggregation of proteins leads to many disorders, but the inhibition of amyloid fibril formation using metal-containing small molecules is gaining popularity. Herein we report the effect of nickel(II) complexes (N1, N2, N3, and N4) bearing thiosemicarbazones on the inhibition of amyloid fibril formation by insulin. The interactions of the complexes with amyloid fibrils were investigated using various biophysical techniques, including light scattering, intrinsic fluorescence assay, thioflavin T (ThT) assay, and Fourier transform-infrared spectroscopy. The results revealed that the phenyl-substituted N3 was an efficient inhibitor of amyloid fibril formation and maintained the insulin in its native structure despite conditions promoting fibrillation. Nickel(II) complexes containing indole based thiosemicarbazones were efficient in inhibiting the amyloid fibril formation and maintaining the insulin in its native structure in unfavorable conditions.

Synthesis, cytotoxicity and docking studies (with SARS-CoV-2) of water-soluble binuclear Ru-p-cymene complex holding indole thiosemicarbazone ligand.

A water-soluble binuclear organometallic Ru-p-cymene complex [Ru(η6-p-cymene)(η2-L)]2 (1) was prepared from (E)-2-((1H-indol-3-yl)methylene)-N-phenylhydrazine-1-carbothioamide (HL) and [RuCl2(p-cymene)]2 in methanol at room temperature under inert atmosphere. The structure of binuclear complex was analyzed by UV-Visible, FT-IR, NMR and mass spectroscopic methods. The solid-state structure of the complex was ascertained by single crystal X-ray diffraction technique. The complex exhibited pseudo-octahedral (piano-stool) geometry around Ru(II) ion. The cytotoxic property of the ligand and complex along with cisplatin was investigated against A549-lung, MCF-7-breast, HeLa-cervical, HepG-2-liver, T24-urinary bladder and EA.hy926-endothelial cancer cells, and Vero-kidney epithelial normal cells. The complex exhibited superior activity than cisplatin against A549, HeLa and T24 cancer cells with the IC50 values of 7.70, 11.2, and 5.05 µM, respectively. The complexes were cytotoxic specifically to the cancer cells. Molecular docking studies showed good binding potential of the ligand and complex with the spike protein and main protease of SARS-CoV-2, indicating the promising role of these compounds as antiviral compounds.

Cyclometalated Iridium(III) Complex-Cationic Peptide Hybrids Trigger Paraptosis in Cancer Cells via an Intracellular Ca2+ Overload from the Endoplasmic Reticulum and a Decrease in Mitochondrial Membrane Potential.

In our previous paper, we reported that amphiphilic Ir complex-peptide hybrids (IPHs) containing basic peptides such as KK(K)GG (K: lysine, G: glycine) (e.g., ASb-2) exhibited potent anticancer activity against Jurkat cells, with the dead cells showing a strong green emission. Our initial mechanistic studies of this cell death suggest that IPHs would bind to the calcium (Ca2+)-calmodulin (CaM) complex and induce an overload of intracellular Ca2+, resulting in the induction of non-apoptotic programmed cell death. In this work, we conduct a detailed mechanistic study of cell death induced by ASb-2, a typical example of IPHs, and describe how ASb-2 induces paraptotic programmed cell death in a manner similar to that of celastrol, a naturally occurring triterpenoid that is known to function as a paraptosis inducer in cancer cells. It is suggested that ASb-2 (50 µM) induces ER stress and decreases the mitochondrial membrane potential (ΔΨm), thus triggering intracellular signaling pathways and resulting in cytoplasmic vacuolization in Jurkat cells (which is a typical phenomenon of paraptosis), while the change in ΔΨm values is negligibly induced by celastrol and curcumin. Other experimental data imply that both ASb-2 and celastrol induce paraptotic cell death in Jurkat cells, but this induction occurs via different signaling pathways.

Synthesis of Palladium(II) Complexes via Michael Addition: Antiproliferative Effects through ROS-Mediated Mitochondrial Apoptosis and Docking with SARS-CoV-2.

Metal complexes have numerous applications in the current era, particularly in the field of pharmaceutical chemistry and catalysis. A novel synthetic approach for the same is always a beneficial addition to the literature. Henceforth, for the first time, we report the formation of three new Pd(II) complexes through the Michael addition pathway. Three chromone-based thiosemicarbazone ligands (SVSL1-SVSL3) and Pd(II) complexes (1-3) were synthesized and characterized by analytical and spectroscopic tools. The Michael addition pathway for the formation of complexes was confirmed by spectroscopic studies. Distorted square planar structure of complex 2 was confirmed by single-crystal X-ray diffraction. Complexes 1-3 were subjected to DNA- and BSA-binding studies. The complex with cyclohexyl substituent on the terminal N of thiosemicarbazone (3) showed the highest binding efficacy toward these biomolecules, which was further understood through molecular docking studies. The anticancer potential of these complexes was studied preliminarily by using MTT assay in cancer and normal cell lines along with the benchmark drugs (cisplatin, carboplatin, and gemcitabine). It was found that complex 3 was highly toxic toward MDA-MB-231 and AsPC-1 cancer cells with IC50 values of 0.5 and 0.9 µM, respectively, and was more efficient than the standard drugs. The programmed cell death mechanism of the complexes in MDA-MB-231 cancer cells was confirmed. Furthermore, the complexes induced apoptosis via ROS-mediated mitochondrial signaling pathway. Conveniently, all the complexes showed less toxicity (≥50 µM) against MCF-10a normal cell line. Molecular docking studies were performed with VEGFR2, EGFR, and SARS-CoV-2 main protease to illustrate the binding efficiency of the complexes with these receptors. To our surprise, binding potential of the complexes with SARS-CoV-2 main protease was higher than that with chloroquine and hydroxychloroquine.

Synthesis of Ni(II) complexes bearing indole-based thiosemicarbazone ligands for interaction with biomolecules and some biological applications.

A series of new Ni(II) complexes containing indole-based thiosemicarbazone ligands was synthesized and characterized by elemental analyses, and UV-visible, FT-IR, 1H & 13C NMR and mass spectroscopic techniques. The Ni(II) complexes (1-4) bear the general formula [Ni{C10H9N2NHCSNH(R)}2] where R = hydrogen (1), 4-methyl (2), 4-phenyl (3) and 4-cyclohexyl (4). Molecular structure of ligands (L3 and L4) and complexes (2, 3 and 4) was confirmed by single crystal X-ray crystallography. Four coordinated Ni(II) complexes showed square planar geometry. The interaction of the Ni(II) complexes with calf thymus DNA (CT-DNA) has been evaluated by absorption spectroscopic and ethidium bromide (EB) competitive binding studies, which revealed the intercalative interaction of the complexes with CT-DNA. Gel electrophoresis experiments showed the cleavage of DNA by the complexes without any external agent. Further, the interaction of the complexes with bovine serum albumin (BSA) was investigated using UV-visible, fluorescence and synchronous fluorescence spectroscopic methods, which showed that the complexes could bind strongly with BSA. Molecular docking was employed to understand the binding of the Ni(II) complexes with the molecular target B-DNA, human DNA topoisomerase I and BSA. All the Ni(II) complexes possess high antioxidant activity against 2-2-diphenyl-1-picrylhydrazyl (DPPH) radical and antihaemolytic activity. In addition, in vitro cytotoxicity of the Ni(II) complexes against lung cancer (A549), human breast cancer (MCF7) and mouse embryonic fibroblasts (L929) cell lines was investigated. Complex 4 has high cytotoxicity. The mode of cell death effected by complex 4 has been explored using Hoechst 33258 staining. Nickel(II) complexes of thiosemicarbazone ligands were synthesized and their DNA/protein binding, DNA cleavage and cytotoxicity abilities were studied.

Crystal structure of (E)-2-[(4-chloro-2H-chromen-3-yl)methyl-idene]-N-cyclo-hexyl-hydrazinecarbo-thio-amide.

In the title compound, C17H20ClN3OS, the mean plane of the central thio-urea core makes dihedral angles of 26.56 (9) and 47.62 (12)° with the mean planes of the chromene moiety and the cyclo-hexyl ring, respectively. The cyclo-hexyl ring adopts a chair conformation. The N-H atoms of the thio-urea unit adopt an anti conformation. The chromene group is positioned trans, whereas the cyclo-hexyl ring lies in the cis position to the thione S atom, with respect to the thio-urea C-N bond. In the crystal, mol-ecules are linked by N-H⋯S hydrogen bonds, forming inversion dimers enclosing R (2) 2(8) ring motifs. The dimers are linked by C-H⋯Cl hydrogen bonds, enclosing R (6) 6(44) ring motifs, forming sheets lying parallel to (010).

A substituent-modified new salicylaldehyde-diphenyl-azine based AIEgen: A promising skeleton for copper ion sensor.

In this study, we have reported a novel 4-bromo-salicylaldehyde-diphenyl-azine (B-1), a new member of salicylaldehyde-diphenyl-azine (SDPA) family known for its excellent sensing properties. In contrast to the previously reported AIEgens, we found that the bromo-substitution at the 4th position of the salicylaldehyde moiety blue-shifted the emission by 10 and 15 nm as compared to the unsubstituted (Tong et.al 2017) and Bromo at the 5th position (Jain et.al 2023) respectively. Moreover, B-1 crystallizes instantly as the cooling process starts, which was not observed in the previously reported scaffolds. The sensing investigation again demonstrated the precise and ultrasensitive behavior of B-1 for copper ions. B-1 has a very low LOD value i.e. 29.2 x 10-8 M with a high association constant and binds with copper ion in 2:1 mode. This time we also analyzed the practical applicability in the solid phase using cotton swabs and performed the real-time estimation of copper ions in water and biological samples like urine and blood serum. The excellent percentage recovery and the RSD value suggest the precision of the experiments. Further, we also perform the sensing in living cancer HeLa cells. Altogether, we found that the SDPA skeleton is precise and ultrasensitive for copper ions and versatile which can be used variously to detect copper ions in the real world. This research will surely help in developing new specific skeleton-based AIEgens with desirable emission properties and precise applications in the future.

Biomolecular Interactions and Anticancer Mechanisms of Ru(II)-Arene Complexes of Cinnamaldehyde-Derived Thiosemicarbazone Ligands: Analysis Combining In Silico and In Vitro Approaches.

Our study focuses on synthesizing and exploring the potential of three N-(4) substituted thiosemicarbazones derived from cinnamic aldehyde, alongside their Ru(II)-(η6 -p-cymene)/(η6-benzene) complexes. The synthesized compounds were comprehensively characterized using a range of analytical techniques, including FT-IR, UV-visible spectroscopy, NMR (1H, 13C), and HRMS. We investigated their electronic and physicochemical properties via density functional theory (DFT). X-ray crystal structures validated structural differences identified by DFT. Molecular docking predicted promising bioactivities, supported by experimental observations. Notably, docking with EGFR suggested an inhibitory potential against this cancer-related protein. Spectroscopic titrations revealed significant DNA/BSA binding affinities, particularly with DNA intercalation and BSA hydrophobic interactions. RuPCAM displayed the strongest binding affinity with DNA (Kb = 6.23 × 107 M-1) and BSA (Kb = 9.75 × 105 M-1). Assessed the cytotoxicity of the complexes on cervical cancer cells (HeLa), and breast cancer cells (MCF-7 and MDA-MB 231), revealing remarkable potency. Additionally, selectivity was assessed by examining MCF-10a normal cell lines. The active complexes were found to trigger apoptosis, a vital cellular process crucial for evaluating their potential as anticancer agents utilizing staining assays and flow cytometry analysis. Intriguingly, complexation with Ru(II)-arene precursors significantly amplified the bioactivity of thiosemicarbazones, unveiling promising avenues toward the creation of powerful anticancer agents.

Copper-mediated cyclization of thiosemicarbazones leading to 1,3,4-thiadiazoles: Structural elucidation, DFT calculations, in vitro biological evaluation and in silico evaluation studies.

Cancer's global impact necessitates innovative and less toxic treatments. Thiosemicarbazones (TSCs), adaptable metal chelators, offer such potential. In this study, we have synthesized N (4)-substituted heterocyclic TSCs from syringaldehyde (TSL1, TSL2), and also report the unexpected copper-mediated cyclization of the TSCs to form thiadiazoles (TSL3, TSL4), expanding research avenues. This work includes extensive characterization and studies such as DNA/protein binding, molecular docking, and theoretical analyses to demonstrate the potential of the as-prepared TSCs and thiadiazoles against different cancer cells. The DFT results depict that the thiadiazoles exhibit greater structural stability and reduced reactivity compared to the corresponding TSCs. The docking results suggest superior EGFR inhibition for TSL3 with a binding constant value of - 6.99 Kcal/mol. According to molecular dynamics studies, the TSL3-EGFR complex exhibits a lower average RMSD (1.39 nm) as compared to the TSL1-EGFR complex (3.29 nm) suggesting that both the thiadiazole and thiosemicarbazone examined here can be good inhibitors of EGFR protein, also that TSL3 can inhibit EGFR better than TSL1. ADME analysis indicates drug-likeness and oral availability of the thiadiazole-based drugs. The DNA binding experiment through absorption and emission spectroscopy discovered that TSL3 is more active towards DNA which is quantitatively calculated with a Kb value of 4.74 × 106 M-1, Kq value of 4.04 × 104 M-1and Kapp value of 5 × 106 M-1. Furthermore, the BSA binding studies carried out with fluorescence spectroscopy showed that TSL3 shows better binding capacity (1.64 × 105 M-1) with BSA protein. All the compounds show significant cytotoxicity against A459-lung, MCF-7-breast, and HepG2-liver cancer cell lines; TSL3 exhibits the best cytotoxicity, albeit less effective than cisplatin. Thiadiazoles demonstrate greater cytotoxicity than the TSCs. Overall, the promise of TSCs and thiadiazoles in cancer research is highlighted by this study. Furthermore, it unveils unexpected copper-mediated cyclization of the TSCs to thiadiazoles.

Host-guest interactions of coumarin-based 1,2-pyrazole using analytical and computational methods: Paper strip-based detection, live cell imaging, logic gates and keypad lock applications.

A novel Coumarin-based 1,2-pyrazole, HCPyTSC is synthesised and characterized. The chemosensor has been shown to have efficient colourimetric and fluorescence sensing capabilities for the quick and selective detection of fluoride and copper ions. At 376 and 430 nm, the HCPyTSC exhibits selective sensing for Cu2+ and F- ions. By examining the natural bond orbital (NBO) analysis and the potential energy curve (PES) of the ground state for the function of the C-H bond, it has been determined from the theoretical study at hand that the deprotonation was taken from the 'CH' proton of the pyrazole ring. For F- and Cu2+, the HCPyTSC detection limits were 4.62 nM and 15.36 nM, respectively. Similarly, the binding constants (Kb) for F- and Cu2+ ions in acetonitrile medium were found to be 2.06 × 105 M-1 and 1.88 × 105 M-1. Chemosensor HCPyTSC with and without F- and Cu2+ ions have an emission and absorption response that can imitate a variety of logic gates, including the AND, XOR, and OR gates. Additionally, a paper-based sensor strip with the HCPyTSC was created for use in practical, flexible F- sensing applications. The paper-based sensor was more effective in detecting F- than other anions. The effectiveness of HCPyTSC for the selective detection of F- in living cells as well as its cell permeability were examined using live-cell imaging in T24 cells.

An aqueous mediated ultrasensitive facile probe incorporated with acrylate moiety to monitor cysteine in food samples and live cells.

A colorimetric probe TQA ((E)-4-(((8-(sec-butoxy)-2,3,6,7-tetrahydro-1H,5H-pyrido[3,2,1-ij]quinolin-9-yl)methylene)amino)benzylacrylate) possessing greater potent towards the sensing of cysteine was successfully synthesized and characterized. The aqueous soluble probe TQA detects Cys based on "ON-OFF" effect with excellent absorbance and emission properties. The probe TQA detects Cys up to its ultra-low level concentration of 1.5 nM and also quantifies the Cys up to 5.05 nM with the quicker response time of 140 s (2.3 min). In addition, the color change produced by the probe TQA on integrated with Cys was also identified easily via paper strip, cotton wool buds and RGB color picker app in smart mobiles. Further, the admirable selectivity and sensitivity of the probe TQA towards Cys extends its utility towards food samples and imaging of live HeLa cells.

A new nitrile vinyl linked ultrafast receptor to track cyanide ions: Utilization on realistic samples and HeLa cell imaging.

A simple D - A (donor - acceptor) type receptor ((2E, 2'E)-3, 3'-(10-octyl-10H-phenothiazine-3,7-diyl)bis(2-(benzo[d]thiazol-2-yl)acrylonitrile)) (PBTA) containing nitrile-vinyl linkage was designed and completely characterized. The receptor PBTA detects CN- ions based on "turn-off" effect with admirable spectral properties. It also owns some of the merits like "naked-eye" color change, ultrafast response (90 s), lowest detection limit (1.25 × 10-10 M) as well as quantitation limit (4.17 × 10-10 M) with the pH range 4-11 which is more suitable pH to make use of the receptor PBTA in physiological medium. The instant detecting ability of the receptor over CN- ions was proved using paper test strip and cotton balls. Further, the utilization of the receptor PBTA was also extended to track CN- ions in realistic samples (water and food samples) and in HeLa cells bioimaging.

MOFs as Versatile Catalysts: Synthesis Strategies and Applications in Value-Added Compound Production.

Catalysts played a crucial role in advancing modern human civilization, from ancient times to the industrial revolution. Due to high cost and limited availability of traditional catalysts, there is a need to develop cost-effective, high-activity, and nonprecious metal-based electrocatalysts. Metal-organic frameworks (MOFs) have emerged as an ideal candidate for heterogeneous catalysis due to their physicochemical properties, hybrid inorganic/organic structures, uncoordinated metal sites, and accessible organic sections. MOFs are high nanoporous crystalline materials that can be used as catalysts to facilitate polymerization reactions. Their chemical and structural diversity make them effective for various reactions compared to traditional catalysts. MOFs have been applied in gas storage and separation, ion-exchange, drug delivery, luminescence, sensing, nanofilters, water purification, and catalysis. The review focuses on MOF-enabled heterogeneous catalysis for value-added compound production, including alcohol oxidation, olefin oligomerization, and polymerization reactions. MOFs offer tunable porosity, high spatial density, and single-crystal XRD control over catalyst properties. In this review, MOFs were focused on reactions of CO2 fixation, CO2 reduction, and photoelectrochemical water splitting. Overall, MOFs have great potential as versatile catalysts for diverse applications in the future.