Methoxyphenyl Groups Research Articles

Stable Xanthene Radicals and Their Heavy Chalcogen Analogues Showing Tunable Doublet Emission from Green to Near-infrared.

Organic luminescent radicals, unlike traditional closed-shell fluorescent emitters, exhibit distinct luminescence mechanisms, offering promising potential for optoelectronic devices. To date, stable luminescent radicals have predominantly been confined to polychlorinated triphenylmethyl radicals, underscoring the need for new platforms to expand their emission spectra. In this study, we report the synthesis of stable 9-aryl-substituted xanthene radicals and their heavy chalcogen analogues (1a-c and 2a-c), which exhibited excellent chemical stability and emission ranging from green to near-infrared (527~714 nm). Notably, the selenium-substituted radical (1c) demonstrates a significantly enhanced photoluminescence quantum yield of 41% when doped into its precursor solid. Additionally, the introduction of methoxyphenyl groups has largely enhanced the stability of the radical, showcasing an excellent photostability with the longest half-life of around 1792 h. The high internal quantum efficiency of up to 81% was further validated in organic light-emitting diode. This study introduces a novel class of stable carbon-centered radicals with high tunability and functionality for photoelectric applications.

Stable Xanthene Radicals and Their Heavy Chalcogen Analogues Showing Tunable Doublet Emission from Green to Near‐infrared

Organic luminescent radicals, unlike traditional closed‐shell fluorescent emitters, exhibit distinct luminescence mechanisms, offering promising potential for optoelectronic devices. To date, stable luminescent radicals have predominantly been confined to polychlorinated triphenylmethyl radicals, underscoring the need for new platforms to expand their emission spectra. In this study, we report the synthesis of stable 9‐aryl‐substituted xanthene radicals and their heavy chalcogen analogues (1a‐c and 2a‐c), which exhibited excellent chemical stability and emission ranging from green to near‐infrared (527~714 nm). Notably, the selenium‐substituted radical (1c) demonstrates a significantly enhanced photoluminescence quantum yield of 41% when doped into its precursor solid. Additionally, the introduction of methoxyphenyl groups has largely enhanced the stability of the radical, showcasing an excellent photostability with the longest half‐life of around 1792 h. The high internal quantum efficiency of up to 81% was further validated in organic light‐emitting diode. This study introduces a novel class of stable carbon‐centered radicals with high tunability and functionality for photoelectric applications.

Anti-inflammation Mechanisms of Flavones Are Highly Sensitive to the Position Isomers of Flavonoids: Acacetin vs Biochanin A.

Acacetin (ACA) and biochanin A (BCA) are isomeric monomethoxyflavones with different structural positions of the 4'-methoxy-phenyl group. Both of them are present in many commonly consumed foods, such as citrus fruits and vegetables, and have been discovered with anti-inflammatory activities, but their mechanisms of action are not clearly elucidated at the molecular level. Herein, we reported the structure-activity relationship of ACA and BCA regarding their potency in inhibiting nitric oxide (NO) production, proinflammatory enzyme expression, and mRNA expression of proinflammatory cytokines in the lipopolysaccharide (LPS)-induced RAW 264.7 cells. Furthermore, transcriptome analysis was conducted to map out the overall pathways impacted by these two isomers. Our results showed that ACA possessed higher suppressive activity in nitric oxide (NO) production (IC50 = 23.93 ± 1.74 μM for ACA and IC50 = 71.41 ± 8.07 μM for BCA), inducible nitric oxide synthase (iNOS) expression, and proinflammatory interleukin (IL)-1β mRNA expression, but lower inhibitory activity in IL-6 mRNA expression as compared with BCA. Although two compounds were revealed to bind to c-Src protein according to drug affinity responsive target stability (DARTS) and western blotting results, molecular docking and molecular dynamics (MD) simulation showed that they had different binding sites, which subsequently resulted in different signaling transduction. ACA primarily exerted anti-inflammatory activity through the mitogen-activated protein kinase (MAPK) signaling pathway, the tumor necrosis factor (TNF) signaling pathway, and the hypoxia-inducible factor (HIF)-1 signaling pathway, while BCA was particularly involved in the Janus kinase/signal transducers and activators of transcription (JAK/STAT) signaling pathway, the nuclear factor kappa B (NF-κB) signaling pathway, the TNF signaling pathway, and the toll-like receptor (TLR) signaling pathway. Moreover, two isomers remained stable in the cell culture medium and did not encounter the biotransformation process in RAW 264.7 cells. However, BCA exhibited insufficient cellular uptake ability and transport efficiency in macrophages compared to ACA. Taken together, ACA is more promising for controlling inflammation and worthy of further study for human use.

Design, synthesis, and evaluation of (1E,4E,6E)-1,7-diphenyl hepta-1,4,6-trien-3-one analogues-inspired o-methoxy phenyl group as potential anti–gastric cancer agents.

292 Background: Gastric cancer (GC) is a major global malignancy causing significant mortality. Most diagnoses occur at advanced stages. Current treatments involve surgery, chemotherapy, and targeted therapies. Targeted drugs face resistance and side effects. Curcumin, derived from Curcuma longa, shows promise against GC. Improved analogs addressing bioavailability have been developed. Some curcumin-based compounds with o-methoxy phenyl groups exhibit enhanced anticancer activity. We designed and synthesized (1E,4E,6E)-1,7-diphenyl hepta-1,4,6-trien-3-one analogs inspired by o-methoxy phenyl for anti-gastric cancer evaluation in vitro and in vivo. Methods: We designed and synthesized a series of analogs named (1E,4E,6E)-1,7-diphenyl hepta-1,4,6-trien-3-one analogues inspired by the o-methoxy phenyl group based on association theory. Anti-tumor activity was evaluated in vitro using gastric cancer cell lines BGC-823 and SGC-7901. Compound 2 was selected as a prime candidate based on its potency. Results: Compound 2 demonstrated potent anti-tumor effects in vitro by suppressing growth, migration, and invasion of SGC-7901 and BGC-823 cells. Impressively, it prompted cell cycle arrest at the G2/M phase and initiated apoptosis through Bax activation and caspase 3 inhibition. Moreover, in vivo trials on xenograft model nude mice validated the compound's substantial anti-gastric cancer potential while maintaining a favorable safety profile. Conclusions: A group of curcumin analogs exhibiting strong anti-gastric cancer activity was developed. The active compound 2 is capable of inhibiting the growth, colony formation, migration, and invasion of gastric cancer cells. It also arrests the cell cycle at the G2/M phase and stimulates the expression of apoptosis-related proteins, showcasing a powerful anti-gastric cancer effect in vitro. Furthermore, it demonstrates significant anti-gastric cancer activity in vivo while maintaining a favorable safety profile. Our research underscores the potential of (1E, 4E, 6E)-1,7-diphenylheptyl-1,4,6-trien-3-one analogs with o-methoxyphenyl in combatting tumors and highlights their promise as a secure anti-tumor candidate drug.

A further pocket or conformational plasticity by mapping COX-1 catalytic site through modified-mofezolac structure-inhibitory activity relationships and their antiplatelet behavior

Cyclooxygenase enzymes have distinct roles in cardiovascular, neurological, and neurodegenerative disease. They are differently expressed in different type of cancers. Specific and selective COXs inhibitors are needed to be used alone or in combo-therapies. Fully understand the differences at the catalytic site of the two cyclooxygenase (COX) isoforms is still opened to investigation. Thus, two series of novel compounds were designed and synthesized in fair to good yields using the highly selective COX-1 inhibitor mofezolac as the lead compound to explore a COX-1 zone formed by the polar residues Q192, S353, H90 and Y355, as well as hydrophobic amino acids I523, F518 and L352. According to the structure of the COX-1:mofezolac complex, hydrophobic amino acids appear to have free volume eventually accessible to the more sterically hindering groups than the methoxy linked to the phenyl groups of mofezolac, in particular the methoxyphenyl at C4-mofezolac isoxazole. Mofezolac bears two methoxyphenyl groups linked to C3 and C4 of the isoxazole core ring. Thus, in the novel compounds, one or both methoxy groups were replaced by the higher homologous ethoxy, normal and isopropyl, normal and tertiary butyl, and phenyl and benzyl. Furthermore, a major difference between the two sets of compounds is the presence of either a methyl or acetic moiety at the C5 of the isoxazole. Among the C5-methyl series, 12 (direct precursor of mofezolac) (COX-1 IC50 = 0.076 μM and COX-2 IC50 = 0.35 μM) and 15a (ethoxy replacing the two methoxy groups in 12; COX-1 IC50 = 0.23 μM and COX-2 IC50 > 50 μM) were still active and with a Selectivity Index (SI = COX-2 IC50/COX-1 IC50) = 5 and 217, respectively. The other symmetrically substituted alkoxyphenyl moietis were inactive at 50 μM final concentration. Among the asymmetrically substituted, only the 16a (methoxyphenyl on C3-isoxazole and ethoxyphenyl on C4-isoxazole) and 16b (methoxyphenyl on C3-isoxazole and n-propoxyphenyl on C4-isoxazole) were active with SI = 1087 and 38, respectively. Among the set of compounds with the acetic moiety, structurally more similar to mofezolac (SI = 6329), SI ranged between 1.4 and 943. It is noteworthy that 17b (n-propoxyphenyl on both C3- and C4-isoxazole) were found to be a COX-2 slightly selective inhibitor with SI = 0.072 (COX-1 IC50 > 50 μM and COX-2 IC50 = 3.6 μM). Platelet aggregation induced by arachidonic acid (AA) can be in vitro suppressed by the synthesized compounds, without affecting of the secondary hemostasia, confirming the biological effect provided by the selective inhibition of COX-1. A positive profile of hemocompatibility in relation to erythrocyte and platelet toxicity was observed. Additionally, these compounds exhibited a positive profile of hemocompatibility and reduced cytotoxicity. Quantitative structure activity relationship (QSAR) models and molecular modelling (Ligand and Structure based virtual screening procedures) provide key information on the physicochemical and pharmacokinetic properties of the COX-1 inhibitors as well as new insights into the mechanisms of inhibition that will be used to guide the development of more effective and selective compounds. X-ray analysis was used to confirm the chemical structure of 14 (MSA17).

Iterative Synthesis of Oligosilanes Using Methoxyphenyl- or Hydrogen-Substituted Silylboronates as Building Blocks: A General Synthetic Method for Complex Oligosilanes.

Organosilanes have attracted the attention of researchers for more than 150 years due to their unique properties, and they have become indispensable industrial assets. However, many synthesized oligosilanes with multiple Si-Si bonds are relatively simple, i.e., they often only contain a single repeating unit. More laborious customized synthetic routes can lead to more complex oligosilanes, but compared to carbon-based molecules, their structural diversity remains limited. The development of effective and practical synthetic routes to complex oligosilanes that contain mixed substituents constitutes a long-standing challenge. Here, we describe an iterative synthesis of oligosilanes using methoxyphenyl- or hydrogen-substituted silylboronates, which were obtained via transition-metal-catalyzed Si-H borylation reactions. The first key reaction is a cross-Si-Si bond-forming reaction between chloro(oligo)silanes and silylboronates activated by MeLi. The second key reaction is the selective chlorination of the methoxyphenyl group or the hydrogen atom at the terminal of the oligosilanes. Iteration of these two key reactions enables the synthesis of various oligosilanes that are otherwise difficult to access. As a demonstration of the synthetic utility of this iterative synthetic approach, oligosilanes with different sequences were prepared by simply changing the order of the reaction of four different silicon units. Furthermore, a bespoke tree-shaped oligosilane is easily obtained via the present iterative synthesis. The solid-state structures of several of these oligosilanes were unequivocally determined using single-crystal X-ray diffraction analysis.

Twisted Intramolecular Charge Transfer‐Based Fluorometric Detection of D‐fructose by Boronic Acid‐Containing BF2‐β‐Diketonate Complexes

AbstractNovel BF2‐β‐diketonate complexes 1–4 bearing phenylboronic acid moieties and methoxyphenyl or dimethylaminophenyl groups were synthesized and their photophysical properties, pH response, and reactivity to D‐fructose were evaluated. Complexes 1 and 2 bearing a methoxyphenyl group luminesced with high intensity in a range of non‐polar to polar solvents, except in DMSO, whereas complexes 3 and 4 containing a dimethylaminophenyl group with twisted intramolecular charge transfer (TICT) properties showed a dramatic decrease in luminescence intensity with increasing solvent polarity. The luminescence intensity of complexes 1 and 2 decreased with increasing pH due to intermolecular vibration which associated with hydrogen bonding between the complexes and solvent water molecules, whereas it increased when they reacted with D‐fructose due to the suppression of the intermolecular vibration. In contrast, the luminescence intensity of complexes 3 and 4 increased with increasing pH and upon reaction with D‐fructose due to the loss of its TICT properties. The photophysical properties of complexes 1–4 and the TICT properties of complexes 3 and 4 were supported by density functional theory calculations.

Curcumin and Its Derivatives as Potential Antimalarial and Anti-Inflammatory Agents: A Review on Structure-Activity Relationship and Mechanism of Action.

Curcumin, one of the major ingredients of turmeric (Curcuma longa), has been widely reported for its diverse bioactivities, including against malaria and inflammatory-related diseases. However, curcumin's low bioavailability limits its potential as an antimalarial and anti-inflammatory agent. Therefore, research on the design and synthesis of novel curcumin derivatives is being actively pursued to improve the pharmacokinetic profile and efficacy of curcumin. This review discusses the antimalarial and anti-inflammatory activities and the structure-activity relationship (SAR), as well as the mechanisms of action of curcumin and its derivatives in malarial treatment. This review provides information on the identification of the methoxy phenyl group responsible for the antimalarial activity and the potential sites and functional groups of curcumin for structural modification to improve its antimalarial and anti-inflammatory actions, as well as potential molecular targets of curcumin derivatives in the context of malaria and inflammation.

Is the Triggering of PD-L1 Dimerization a Potential Mechanism for Food-Derived Small Molecules in Cancer Immunotherapy? A Study by Molecular Dynamics.

Using small molecules to inhibit the PD-1/PD-L1 pathway is an important approach in cancer immunotherapy. Natural compounds such as capsaicin, zucapsaicin, 6-gingerol and curcumin have been proposed to have anticancer immunologic functions by downregulating the PD-L1 expression. PD-L1 dimerization promoted by small molecules was recently reported to be a potential mechanism to inhibit the PD-1/PD-L1 pathway. To clarify the molecular mechanism of such compounds on PD-L1 dimerization, molecular docking and molecular dynamics simulations were performed. The results evidenced that these compounds could inhibit PD-1/PD-L1 interactions by directly targeting PD-L1 dimerization. Binding free energy calculations showed that capsaicin, zucapsaicin, 6-gingerol and curcumin have strong binding ability with the PD-L1 dimer, where the affinities of them follow the trend of zucapsaicin > capsaicin > 6-gingerol ≈ curcumin. Analysis by residue energy decomposition, contact numbers and nonbonded interactions revealed that these compounds have a tight interaction with the C-sheet, F-sheet and G-sheet fragments of the PD-L1 dimer, which were also involved in the interactions with PD-1. Moreover, non-polar interactions between these compounds and the key residues Ile54, Tyr56, Met115 and Ala121 play a key role in stabilizing the protein-ligand complexes in solution, in which the 4'-hydroxy-3'-methoxyphenyl group and the carbonyl group of zucapsaicin, capsaicin, 6-ginger and curcumin were significant for the complexation of small molecules with the PD-L1 dimer. The conformational variations of these complexes were further analyzed by free energy landscape (FEL) and principal component analysis (PCA) and showed that these small molecules could make the structure of dimers more stable. This work provides a mechanism insight for food-derived small molecules blocking the PD-1/PD-L1 pathway via directly targeting the PD-L1 dimerization and offers theoretical guidance to discover more effective small molecular drugs in cancer immunotherapy.

Preliminary in Silico Studies of the Interactions of Certain Genotoxic Azo Dyes with Different Double-Stranded DNA Conformations

Organic azo dyes, which are widely used in industrial, health and cosmetic fields, pose genotoxic risks due to their chemical structures; however, the molecular details of the undesirable effects of these dyes on DNA have been poorly or insufficiently clarified. In this computational molecular docking study, the DNA binding modes and binding affinities of 14 azo dyes, previously determined to show DNA clastogenicity, were characterized using 2 different double-stranded DNA (dsDNA) conformations (an intact dsDNA and dsDNA with an intercalation gap). In this study, it was determined that 10 out of the 14 genotoxic azo dyes were strong dsDNA minor groove binders, while the remaining ones formed tight binding complexes with dsDNA through intercalation or threading intercalation modes. The azo, nitro, hydroxyl, ammonium, sulfonate, naphthalene, methoxyphenyl, bromine, nitrophenyl, imidazole, amino-phenylethanol and chloro-nitrophenyl groups were found to play primary role in the most favorable binding conformations of these dyes on dsDNA with an affinity ranging from −6.35 kcal/mol to −9.42 kcal/mol. It was determined that dsDNA sequences containing GT dinucleotides are frequently preferred in binding by these dyes, and that rings and polar groups are important features for tight binding with dsDNA. It was concluded that these dyes may be banned, or non-genotoxic congeners should be manufactured with appropriate molecular optimization for the genetic health of the human population and for future generations.

Synthesis, structures, and photophysical properties of three-coordinate copper(I) complexes bearing bidentate bis[(2-diphenylphosphino)phenyl]ether (POP) ligand and monodentate substituted-quinoline ligand

The three-coordinate Cu(I) complexes [Cu(POP)(X)]PF6, X = quinoline (P1), 2-(4-methoxyphenyl)quinoline (P2), 2-(4-(trifluoromethyl)phenyl)quinoline (P3), POP = bis[(2-diphenylphosphino)phenyl] ether were synthesized and characterized. The photophysical properties of these Cu(I) complexes were tuned by the addition of organic groups including methoxyphenyl and trifluoromethylphenyl groups into the quinoline ligand. The resulting complexes exhibit the metal-to-ligand charge transfer (MLCT) band in the lower energy. The emissions for all the complexes in solid state are in the range of 542–558 nm with higher quantum yields of 11.4–14.2% and long-lived excited lifetimes of 179–481 µs at room temperature. The photophysical properties were further explained by DFT and TDDFT methods.

Theoretical and X-ray studies on the cyclisation of 1-phenyl-5-(3-aryltriaz-1-en-1-yl)-1Hpyrazole- 4-carbonitriles and 2-amino-3-(3-aryltriaz-1-en-1-yl)maleonitriles: A comparison study

The present work investigates attempts to cyclise 1-phenyl-5-(3-aryltriaz-1-en-1-yl)-1H-pyrazole- 4-carbonitriles to the desired pyrazolo[3,4-d][1,2,3]triazinimine derivatives. The cyclisations were unfruitful, and a density functional theory study was performed. This revealed the 1-phenyl-5-(3-aryltriaz-1-en-1-yl)-1H-pyrazole-4-carbonitriles are more stable than the targeted pyrazolo[3,4-d][1,2,3]triazinimine derivatives, indicating that their cyclisation is thermodynamically disfavoured; the reactant 8c is more stable than the predicted six-membered ring products 9c by 5 kJ/mol. The effect of isomerisation of the methoxy-phenyl group in the self-assembly of 8c and 8d in the crystalline lattice was investigated. The intermolecular forces in solid state were analysed in the two structural isomers 8c and 8d using calculated HirshFeld surface; the analysis indicates that the intermolecular forces are stronger in 8c than 8d and hence 8c is denser than 8d by 0.071g/mL.

Y-shaped fluorophore: Synthesis, crystal structure and picric acid detection

Design and synthesis of a novel fluorescent probe for the detection of picric acid is a topic of an incessant research interest. In this context, we have developed a novel ‘Y’ shaped D-A-D type chromophore (TP171). Phenothiazine and methoxy phenyl groups are acting as donor whilst N-substituted imidazole as acceptor unit. As synthesized TP171 show an excellent fluorescent property with a quantum yield of 24%. Intriguingly, the TP171 fluorescent probe instantaneously responded towards the detection of picric acid with a concentration of 12 μM. The detection limit is found to be 7.95 nM.

Microwave-assisted synthesis and DNA-binding studies of half-sandwich ruthenium(II) arene complexes containing phenanthroimidazole-triarylamine hybrids

A new series of half-sandwich Ru(II)-arene complexes with phenanthroimidazole-triarylamine hybrid ligands were synthesized and scrutinized for DNA binding studies. The metal complexes were prepared via microwave-assisted synthesis with high yield and purity. The interaction of Ru(II)-arene complex with calf thymus DNA was studied by spectrophotometric methods. All six complexes exhibited significant interaction with CT-DNA. Methoxyphenyl-substituted metal complex showed the highest binding efficiency with a binding constant (Kb) of 5.053 × 104 M−1 due to its electron-rich nature. The methoxyphenyl group remarkably enhanced the interaction through stabilization of π-orbital of the metal complex which resulted in the efficient coupling. Phenyl- and thiophene-substituted ligands also showed good binding constants of 4.908 × 104 M−1 and 4.509 × 104 M−1, respectively. The absorption and ethidium bromide displacement studies declare that both the intercalation and groove binding is anticipated by these complexes. These Ru(II) complexes with phenanthroimidazole-triarylamine hybrid ligands can be realized as efficient DNA binding agents.

Easily Separable Cyclic Oligosilanes with p‐Methoxyphenyl Groups and Their Stereoselective Functionalization

AbstractNovel cyclic oligosilanes with trimethylsilylmethyl and aryl groups at each silicon ring atom were synthesized. The reductive condensation of a dichlorosilane having a phenyl group as an aryl group gave five‐ and six‐membered cyclic oligosilanes as mixtures of their stereoisomers. On the other hand, the use of p‐methoxyphenyl group instead of phenyl group resulted in the formation of four‐ and five‐membered cyclic oligosilanes, from which each stereoisomer was separable and identified spectroscopically and structurally. Interestingly, the dearylative pentatriflation of the isolated cyclic pentasilanes yielded the sole pentatriflated cyclopentasilane from any stereoisomer. In addition, its further chlorination, bromination, and iodination quantitatively afforded the sole stereoisomer of the corresponding pentahalocyclopentasilanes.

In Vitro Evaluation of Antibacterial and Antifungal Properties of Some New 1, 3, 4-Oxadiazole Derivatives Containing Phenyl Group

AimsAntibiotic resistance is recognized as one of the most challenging public health problems in the world. The need for new antibacterial and antifungal drugs is justified because many pathogens are currently resistant to available drugs. Several components of 1, 3, 4‑oxadiazoles have been shown to pose a wide range of antibacterial activities.Materials & MethodsThe new derivatives of 1, 3, 4-oxadiazole were synthesized using a single-stage method. The structure of derivatives was evaluated by IR, H-NMR, C-NMR, and GC-Mass methods. Then to measure the antibacterial and antifungal activities of the prepared derivatives at a concentration of 0.5 mg/mL, agar well diffusion method was employed, and the minimum inhibitory concentration (MIC) and the minimum bactericidal/fungicidal concentration (MBC/MFC) were determined with three replications.FindingsThe study of antibacterial properties of the prepared derivatives showed the highest activity of the compounds 4b-g against Enterococcus faecalis strains, among which the compound 4g with IZ= 55.66 ± 0.5 mm and MIC=31.25 mg/mL had the greatest effect compared to the others. Also, the compound 4f with MIC= 125 mg/mL had a powerful effect against E. faecalis strains. In the case of fungal samples, the highest activity of the compound 4b was with IZ=12.33±0.5 mm against Candida glabrata and with IZ=13.33±0.5 mm against C. krusei strains.ConclusionThe new 1, 3, 4‑oxadiazole derivatives (4b, 4d, and 4g) with tolyl, dimetylphenyl, and methoxyphenyl groups were shown to be a promising compounds for pharmaceutical applications so that by adding other functional groups to their structure, it is possible to increase the destructive power of these compounds.

Molecular Engineering of Hexaazatriphenylene Derivatives toward More Efficient Electron-Transporting Materials for Inverted Perovskite Solar Cells.

The electron-transporting material (ETM) in inverted perovskite solar cells (PSCs) plays important role in reducing hysteresis and realizing simple processing procedures, while the improvement of power conversion efficiency is limited by low electron mobility and weak perovskite/ETM interface interaction. In this work, three new ETMs (HAT-1, HAT-2, and HAT-3) were designed by introducing methoxyphenyl, imide, and naphthalene groups into the hexaazatriphenylene (HAT) skeleton, based on the ETM HATNASOC7 synthesized experimentally [Jen; Angew. Chem., Int. Ed. 2016, 55, 8999]. Theoretical calculations showed that the electron mobilities of HAT-1, HAT-2, and HAT-3 are 2.98, 3.79, and 13.21 times that of HATNASOC7, which is attributed to the increased C···C and O···H interactions in the newly designed ETMs. More importantly, the evidently decreased perovskite/ETM interface distances and the significantly increased adsorption energies revealed that the interface interactions were markedly enhanced with the newly designed ETMs by forming additional Pb···O interactions, which promote the electron injection. The deep understanding of perovskite/ETM interface properties sheds new light on the complex factors determining the PSC function and paves the way for the rational design of highly efficient and stable components for PSCs.

Crystal structure and Hirshfeld surface analysis of a new di-thio-glycoluril: 1,4-bis-(4-meth-oxy-phen-yl)-3a-methyl-tetra-hydro-imidazo[4,5-d]imidazole-2,5(1H,3H)-di-thione.

In the title di-thio-glycoluril derivative, C19H20N4O3S2, there is a difference in the torsion angles between the thio-imidazole moiety and the meth-oxy-phenyl groups on either side of the mol-ecule [C-N-Car-Car = 116.9 (2) and -86.1 (3)°, respectively]. The N-C-N bond angle on one side of the di-thio-glycoluril moiety is slightly smaller compared to that on the opposite side, [110.9 (2)° cf. 112.0 (2)°], probably as a result of the steric effect of the methyl group. In the crystal, N-H⋯S hydrogen bonds link adjacent mol-ecules to form chains propagating along the c-axis direction. The chains are linked by C-H⋯S hydrogen bonds, forming layers parallel to the bc plane. The layers are then linked by C-H⋯π inter-actions, leading to the formation of a three-dimensional supra-molecular network. Hirshfeld surface analysis and two-dimensional fingerprint plots were used to investigate the mol-ecular inter-actions in the crystal.

Effect of increasing methoxyphenyl substitution on pyrene pyrazoline enduring green light emitting materials

The pyrene pyrazoline derivatives containing mono, di and tri methoxy phenyl substituents were synthesized. Thermal stability and glass transition temperatures changed with progressive substitution of methoxy phenyl group. X-Ray Diffraction pattern revealed their crystalline nature. The photophysical properties of materials exhibited green emission at 510 nm (PP1My), 510 nm (PP2My) and 508 nm (PP3My) in solution and yellow emission at 580 nm (PP1My), 574 nm (PP2My) and 563 nm (PP3My) in solid state. The blue shift in the emission in solid state was owing to aggregation induced by methoxy substituent. The color chromaticity values were calculated for their color purity of green and yellow emissions. Ten different solvents were used to examine solvatochromism and red shifted emission observed in enhancing polarity of solvents and dual emission in cyclohexane were suggested twisted conformation of molecule that led to Intramolecular charge transfer becomes twisted Intramolecular charge transfer. Nonlinear optical properties of pyrazoline derivatives improved when electron donates methoxy groups and polyaromatic luminophore of pyrene were substituted on pyrazoline moiety. The third order nonlinear optical properties were investigated by Z-scan technique at 532 nm and exhibited strong reverse saturable absorption and self-defocusing natures. The optimized geometry evidences that molecules have twisted structures and looks like an antenna molecules. These kinds of molecules are demand in energy applications such as light harvesting solar materials and light emitting materials.

Synthesis of C[sbnd]C, C[sbnd]N coupled novel substituted dibutyl benzothiazepinone derivatives and evaluation of their thrombin inhibitory activity

The formation of a thrombus is a key event in thromboembolic disorders, that contribute to high mortality and morbidity in affected patients. In the present study, we synthesized a library of novel substituted 3,3-dibutyl-8-methoxy-2,3-dihydrobenzo [b] [1,4] thiazepin-4(5H)-one derivatives which were tested for their platelet aggregation and thrombin inhibitory activity. Among the tested compounds, 3,3-dibutyl-7-(2-chlorophenyl)-8-methoxy-2,3-dihydrobenzo[b] [1,4]thiazepin-4(5H)-one (DCT) displayed the maximum thrombin inhibition with an IC50 value of 3.85 μM and thus DCT was chosen for further studies. Next, the effect of DCT on primary hemostasis was evaluated using agonist-induced platelet aggregation model. The lead compound inhibited the collagen- or ADP- or thrombin-induced platelet aggregation in a dose-dependent manner. Furthermore, DCT prolonged the process of clot formation when evaluating plasma re-calcification time (320 ± 11 sec at 5 µg DCT), activated partial thromboplastin time (58.0 ± 0.01 sec at 2 µg), and prothrombin time (14.7 ± 0.01 sec at 5 µg). Molecular docking studies suggested that the benzothiazepinones evaluated here consistently display hydrogen bonding with Ser214 of thrombin, which is similar to that of the co-crystallized ligand (1-(2R)-2-amino-3-phenyl-propanoyl-N-(2,5dichlorophenyl)methylpyrrolidine-2-carboxamide). DCT displayed additional hydrogen bonding to Ser195 and π-π interactions between its methoxyphenyl groups and Trp60, thereby providing a structural rationale for the observed biological effect.