Bi(III)-Catalyzed Michael Addition of Tautomerizable Heterocycles with α,ß-Unsaturated Carbonyl Compounds: Regioselective Construction of C-N Bonds.

A Bi(III)-catalyzed synthetic strategy for regioselective construction of C-N bonds via a simple Michael addition reaction is reported. A wide range of tautomerizable heterocycles such as benzoxazolones, benzothiazolones, benzimidazolinones, indolinones, and 2-pyridones along with α,ß-unsaturated carbonyls (ketones and esters) are employed to create a library of corresponding N-alkylated derivatives exclusively. High regioselectivity, high atom economy, and the participation of a range of tautomerizable heterocycles highlight the uniqueness and generality of the developed methodology.

Solvent- and Catalyst-Controlled Regioselective O- and N-Alkylation of 2-Pyridones by 2H-Azirines.

The synthesis of O-substituted 2-hydroxypyridines and N-substituted 2-pyridones, crucial for many bioactive compounds and drugs, faces challenges due to the tautomeric nature of 2-pyridones, which complicates selective alkylation. Here we developed an efficient method for regioselective O- and N-alkylation of 2-pyridones using BroÌ·nsted acid-catalyzed ring opening of 2H-azirines. The process involves triflic acid for O-alkylation and p-toluenesulfonic acid for N-alkylation, achieving high yields under optimized conditions. For O-alkylation, a variety of 2-pyridones and 2H-azirines were used, resulting in significant yields of the desired products. Similarly, for N-alkylation, the optimized conditions produced excellent yields, highlighting the method's versatility. This methodology was further demonstrated through scaled-up syntheses and subsequent transformations, showcasing its practicality for complex molecular architectures. The proposed mechanism involves the protonation of 2H-azirine, followed by a regioselective SN2-type attack and acid-catalyzed hydrolysis, leading to the desired alkylated products. This innovative approach, emphasizing BroÌ·nsted acid catalysis and careful control of reaction conditions, represents a significant advancement in the selective alkylation of 2-pyridones, with broad implications for medicinal chemistry.

Brønsted acid-catalyzed regioselective ring opening of 2H-azirines by 2-mercaptopyridines and related heterocycles; one pot access to imidazo[1,2-a]pyridines and imidazo[2,1-b]thiazoles.

A catalytic and versatile synthetic method for the synthesis of imidazo[1,2-a]pyridines has been developed. Brønsted acid-catalysis plays a major role in the regioselective ring opening of 2H-azirines. Nucleophilic attack via the N-centre of mercaptopyridines and their analogues, followed by cyclisation by cleaving the C-S bond, allowed a library of imidazo[1,2-a]pyridines and related heterocycles to be built. The reaction protocol has been applied to various 2H-azirines, 2-mercaptopyridines, and thiazole-2-thiols, illustrating the generality of reaction conditions. The practical applications include the synthesis of pharmaceuticals, such as anti-tumor agents. This study introduces a novel approach to the synthesis of functional molecules with extensive potential.

MeOTf-catalyzed Friedel-Crafts alkylation of benzoxazolones, benzothiazolones, indolinones and benzimidazolones with activated secondary alcohols.

Herein, we have revealed a methodology for the selective C-alkylation of benzoxazolones, benzothiazolones, indolinones, and benzimidazolones incorporating activated alcohols catalysed by methyltrifluoromethanesulfonate (MeOTf). This method offers a green, atom-economic alternative for the synthesis of alkylated heterocycles, producing water as the only byproduct. Alcohols, due to their abundance, ease of preparation, and environmental friendliness, have become attractive alkylating agents. The developed reaction conditions demonstrate high yields and broad applicability across various N-alkylated heterocycles, highlighting the versatility of the MeOTf catalysis. The method was also adapted for one-pot consecutive N- and C-alkylation and chemoselective C-alkylation in heterocycles containing a free -NH group. This approach provides a practical and efficient route for the functionalization of bioactive heterocyclic compounds.

Regioselective Transition Metal-Free Catalytic Ring Opening of 2H-Azirines by Phenols and Naphthols; One-Pot Access to Benzo- and Naphthofurans.

Benzofuran and naphthofuran derivatives are synthesized from readily available phenols and naphthols. Regioselective ring openings of 2H-azirine followed by in situ aromatization using a catalytic amount of Brønsted acid have established the novelty of the methodology. The involvement of a series of 2H-azirines with a variety of phenols, 1-naphthols, and 2-naphthols showed the generality of the protocol. In-depth density functional theory calculations revealed the reaction mechanism with the energies of the intermediates and transition states of a model reaction. An alternate pathway of the mechanism has also been proposed with computer modeling.

Hemin-Modified Multi-Walled Carbon Nanotube-Incorporated PVDF Membranes: Computational and Experimental Studies on Oil-Water Emulsion Separations.

The separation of oil/water emulsions has attracted considerable attention for decades due to the negative environmental impacts brought by wastewater. Among the various membranes investigated for separation, polyvinylidene fluoride (PVDF) membranes have shown significant advantages of ease of fabrication, high selectivity, and fair pore distribution. However, PVDF membranes are hydrophobic and suffer from severe fouling resulting in substantial flux decline. Meanwhile, the incorporation of wettable substrates during fabrication has significantly impacted the membrane performance by lowering the fouling propensity. Herein, we report the fabrication of an iron-containing porphyrin (hemin)-modified multi-walled carbon nanotube incorporated PVDF membrane (HA-MWCNT) to enhance fouling resistance and the effective separation of oil-in-water emulsions. The fabricated membrane was thoroughly investigated using the FTIR, SEM, EDX, AFM, and contact angle (CA) analysis. The HA-MWCNT membrane exhibited a water CA of 62° ± 0.5 and excellent pure water permeance of 300.5 L/m2h at 3.0 bar (400% increment), in contrast to the pristine PVDF, which recorded a CA of 82° ± 0.8 and water permeance of 59.9 L/m2h. The hydrophilic HA-MWCNT membrane further showed an excellent oil rejection of >99% in the transmembrane pressure range of 0.5−2.5 bar and a superb flux recovery ratio (FRR) of 82%. Meanwhile, the classical molecular dynamics (MD) simulations revealed that the HA-MWCNT membrane had greater solvent-accessible pores, which enhanced water permeance while blocking the hydrocarbons. The incorporation of the hemin-modified MWCNT is thus an excellent strategy and could be adopted in the design of advanced membranes for oil/water separation.

(3 + 2) cycloaddition of 2-alkoxynaphthalenes with azaoxyallyl cations: access to benzo[e]indolones.

A reaction between 2-alkoxynaphthalene and an in situ formed azaoxyallyl cation has been reported under ambient reaction conditions. The (3 + 2) cycloaddition reaction followed by aryl C-OMe/C-OEt bond cleavage produces a variety of benzo[e]indolone derivatives. Based on the isolated intermediate from the control experiment and previous results, a possible mechanism has been drawn. Reduction of the N-O bond of the benzo[e]indolone derivative manifests the possibility of further functionalization of the products towards biologically important heterocyclic molecules.

Mixed Dimensional Nanostructure (UiO-66-Decorated MWCNT) as a Nanofiller in Mixed-Matrix Membranes for Enhanced CO2 /CH4 Separation.

Mixed-matrix membranes (MMMs) with combination of two distinct dimensional nanofillers (such as 1D-3D, 2D-3D, or 3D-3D, etc.) have drawn special attention for gas separation applications due to their concerted effects on gas permeation and mechanical properties. An amine-functionalized 1D multiwalled carbon nanotube (NH2 -MWCNT) with exceptional mechanical strength and rapid gas transport was crosslinked with an amine-functionalized 3D metal-organic framework (UiO-66-NH2 ) with high CO2 affinity in a Schiff base reaction. The resultant crosslinked mixed-dimensional nanostructure was used as a nanofiller in a polysulfone (PSf) polymer matrix to explore the underlying synergy between 1D and 3D nanostructures on the gas separation performance of MMMs. Cross-sectional scanning electron microscopy and mapping revealed the homogenous dispersion of UiO-66@MWCNT in the polymer matrix. The MMM containing 5.0 wt. % UiO-66@MWCNT demonstrated a superior permeability 8.3 Barrer as compared to the 4.2 Barrer of pure PSf membrane for CO2 . Moreover, the selectivity (CO2 /CH4 ) of this MMM was enhanced to 39.5 from the 28.0 observed for pure PSf under similar conditions of pressure and temperature.

Conversion of Curcumin into Heterocyclic Compounds as Potent Anti-diabetic and Anti-histamine Agents.

Potential biologically active derivatives of the curcumin were prepared by the cyclocondensation reaction cyclohexanone 2, imino pyrimidine 3, pyrmidinones 4, thiopyrimidine 6 and pyranone 5, 7 when treated with acetylacetone, guanidine, ureaethylcyanoacetate, thiourea and ethylacetoacetate, respectively. The structures of compounds (2-7) were elucidated by means of microanalysis as well as spectral measurements such as IR, 1H-NMR, MS. The anti-diabetic potential of curcumin derivatives were evaluated by assessing amylase inhibition assay, also inhibition of histamine release activity of curcumin derivatives were assessed by U937 human monocytes. The results for amylase inhibition activity revels that the curcumin inhibits α-amylase in a concentration dependent manner. Compounds 4 and 5 exhibited significant inhibitory activity against amylase enzyme and was comparable with that of acrabose. Also, compounds 5, 6 and 7 exhibited significant inhibitory activity against histamine. Our results concluded that curcumin pyrmidinones and pyranone derivatives have highly effects as anti-diabetic and anti-histamine activities.

Effect of anisotropic electron momentum distribution of surface plasmon on internal photoemission of a Schottky hot carrier device.

We recently reported that an Au/TiO2 photonic crystal device for photochemical energy conversion showed a sub-bandgap photoresponse centered at the surface plasmon polariton (SPP) resonant wavelength of this device. Here we developed a theoretical modeling of the internal photoemission in this device by incorporating the effects of anisotropic hot electron momentum distribution caused by SPP. The influences of interband and intraband transition, anisotropic momentum distribution of hot electrons by SPP are integrated to model the internal quantum efficiency (IQE) of this device. Near resonant wavelength, SPP dominates the electric field in the thin Au layer, which generates hot electrons with high enough momentum preferentially normal to the Schottky interface. Compared with the widely used Fowler's theory of internal photoemission, our model better predicts hot electron collection in Schottky devices. This model will provide a design guidance for tuning and enhancing photoresponse of Schottky hot carrier devices.

Corrosion resistance of aluminum against acid activation in 1.0 M HCl by symmetrical ball - type zinc phthalocyanine.

The inhibition effect of symmetrical Ball - type Zinc Phthalocyanine on Aluminum in 1mol/L hydrochloric acid was analyzed by electrochemical techniques. A novel ball-type zinc phthalocyanine (Zn-Pc) inhibitor has been synthesized and verified utilizing FTIR, nuclear magnetic resonance (1H NMR and 13C NMR), MALDI-TOF MS, and absorption spectroscopy (UV-Vis). In addition, laser-induced breakdown and photoluminescence spectroscopy were employed for additional study. Weight loss technique was employed to investigate the corrosion inhibition effectiveness of the synthesized Zn-Pc on Aluminum in 1mol/L hydrochloric acid at the range of variation temperatures (293-333 K). The inhibition efficiency of Zn-Pc increased with higher concentrations of Zn-Pc and decreased as the temperature increased. Furthermore, Zn-Pc demonstrated outstanding outcomes, achieving 72.9% at a very low inhibitor concentration (0.4 mmol/L) at 298 K. The experimental data for Zn-Pc Aluminum in 1mol/L hydrochloric acid obeys the Langmuir adsorption isotherm. Moreover, the corrosion system's thermodynamic parameters and activation energy were determined. Quantum chemical calculations applying the (DFT) Density Functional Theory method was conducted and applied in this study. These calculations played a pivotal role in elucidating molecular structures and reactivity patterns. Through DFT, numerous reactivity indicators were computed, providing valuable insights into the chemical behavior of the studied compounds. These indicators, such as frontier molecular orbitals, electron density, and molecular electrostatic potential, were subsequently correlated with experimental data.

Methyltrifluoromethanesulfonate Catalyst in Direct Nucleophilic Substitution of Alcohols; One-Pot Synthesis of 4H-Chromene Derivatives.

The catalytic activity of methyltrifluoromethanesulfonate (MeOTf) has been explored toward direct nucleophilic substitution of the hydroxyl group of nonmanipulated alcohols such as benzylic, allylic, propargylic, and tertiary alcohols with a wide range of uncharged nucleophiles such as 1,3-dicarbonyl compounds, amides, alkynes, and indoles to generate functionalized 1,3-dicarbonyl compounds, amides, alkynes, and indoles, respectively. Thus, the present protocol defines an alternate pathway to construct new C-C, C-N, and C-O bonds with the formation of water as the byproduct under mild conditions without any acids or metals. A completely different mechanism was established through several control experiments to explain the reaction methodology. As an application of the reported protocol, 1H-indene derivatives have been synthesized in one pot when benzylic alcohols were subjected to react with internal alkynes. The scope of the reaction has been further extended toward a tandem benzylation-cyclization-dehydration of 1,3-dicarbonyl compounds with 2-hydroxybenzyl alcohols, which furnish biologically important 4H-chromene derivatives.

Synthesis of an Activatable Tetra-Substituted Nickel Phthalocyanines-4(3H)-quinazolinone Conjugate and Its Antibacterial Activity.

The aim of this study was to synthesize a series of nickel(II)phthalocyanines (NiPcs) bearing four 4(3H)-quinazolinone ring system units, (qz)4NiPcs 4a-d. The electronic factors in the 4(3H)-quinazolinone moiety that attached to the NiPc skeleton had a magnificent effect on the antibacterial activity of the newly synthesized (qz)4NiPcs 4a-d against Escherichia coli. The minimum MICs and MBCs value were recorded for compounds 4a, 4b, 4c, and 4d, respectively. The results indicated that the studied (qz)4NiPcs 4a-d units possessed a broad spectrum of activity against Escherichia coli. Their antibacterial activities were found in the order of 4d > 4c > 4b > 4a against Escherichia coli, and the strongest antibacterial activity was achieved with compound 4d.

Improved photodynamic efficacy of thiophenyl sulfonated zinc phthalocyanine loaded in lipid nano-carriers for hepatocellular carcinoma cancer cells.

BACKGROUND: The aim of the present study was to modify the structural activity of zinc(II)phthalocyanine by combining it with thiophenyl groups then loaded in lipid nano-carriers and evaluate its parameters required for the structure-activity relationship (SAR) for photodynamic therapy (PDT) of cancer. METHODS: Tetra (4-Thiophenyl) sulfonated phthalocyaninatozinc(II) (PhS·SO3Na)4ZnPc 5 was synthesized and characterized by various spectroscopic methods as a test compound. Liver hepatocellular carcinoma (HepG2) cells were treated with the synthesized (PhS·SO3Na)4ZnPc 5 derivative loaded in lipid nano carriers to understand the effect of combined compound on liver cancer cells. Furthermore, HepG2 cells were irradiated by visible red light at 60 mW/cm2 for 20 min. The phototoxicity of (PhS·SO3Na)4ZnPc 5 after being formulated in both (L) and transfersomes (T) was investigated. RESULTS: Overall, the results indicate that combination of thiophenyl groups substitution, in particular in the structure of sulfonated zinc phthalocyanine is able to improve the photodynamic properties of ZnPc, and (PhS·SO3Na)4ZnPc 5 loaded in lipid nano-carriers can be a promising combined PDT treatment strategy for Liver hepatocellular carcinoma (HepG2) cells. CONCLUSIONS: The new formulation ZnPc-lipid nano-carriers will be beneficial in the upcoming clinical trials and would enhance the inhibition of tumor growth.