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  • Open access
  • 5 Reads
Photoelectroactive Corrole Monomer Functionalized with a Triphenylamine–Chalcone Derivative: Synthesis, Electropolymerization, and Electrochromic Applications

In this work, we report a divergent synthesis of a novel corrole macrocycle featuring a T-shaped geometry and peripheral functionalization with triphenylamine (TPA) units. The synthesis began with 5-(pentafluorophenyl)dipyrromethane, prepared via a green protocol by Dehaen. This aryldipyrromethane was condensed with pentafluorobenzaldehyde in a MeOH/HCl aqueous mixture to yield a bilane intermediate, which was subsequently oxidized with DDQ to afford the target corrole bearing three pentafluorophenyl groups at the meso positions. In parallel, a TPA-based chalcone derivative was synthesized through Claisen–Schmidt condensation. Finally, a regioselective nucleophilic aromatic substitution in dry DMF using K₂CO₃ as base displaced the para-fluorine atoms, delivering the functionalized monomer in high yield. This molecule features a photoactive corrole core covalently linked to the electron-donating and electropolymerizable TPA moiety, making it a promising building block for photoactive and electroactive materials. The TPA groups were selected to promote electrochemical radical coupling: upon anodic oxidation, TPA radical cations dimerize to form tetraphenylbenzidine (TPB) linkages, producing covalently connected corrole films on Pt and ITO electrodes. Electropolymerization by cyclic voltammetry showed steadily increasing redox currents, consistent with conductive polymer growth. CV and UV–Vis spectroelectrochemistry confirmed retention of the corrole macrocycle (Soret and Q bands) and revealed additional absorptions at 300–350 nm from TPA/TPB species. Spectroelectrochemical switching exhibited reversible green-to-blue color changes, demonstrating strong electrochromic behavior and potential for electrochromic device applications.

  • Open access
  • 4 Reads
Process Optimization of Keratin Extraction from Chicken Feathers Using Alkaline Oxidation: A Taguchi L9 Orthogonal Array Study
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The valorization of poultry feather waste as a sustainable source of keratin aligns with circular economy principles and offers an environmentally responsible solution to managing agro-industrial residues. In this study, an eco-friendly alkaline oxidative extraction method using hydrogen peroxide (H₂O₂) was investigated for recovering keratin from chicken feathers. The process was optimized through a Taguchi experimental design to enhance both extraction efficiency and protein regeneration. Four critical parameters: H₂O₂ concentration, pH, temperature, and extraction time, were studied at three levels each using an L9 orthogonal array. Their effects on solubilization and regeneration yields were systematically evaluated. Statistical analysis revealed that pH and H₂O₂ concentration had the most significant influence on keratin yield. The optimal conditions for maximum solubilization (2 M H₂O₂, pH 12, 75 °C, 1.5 h) yielded high extraction efficiency, whereas a lower H₂O₂ concentration (1 M) favored better regeneration, indicating that excessive oxidation may compromise protein reassembly. Regression models and ANOVA confirmed the statistical significance of these findings, with R² values of 94.25% for solubilization and 78.23% for regeneration. The extracted keratin maintained essential structural features, as verified through subsequent characterization. This work not only improves the sustainability and effectiveness of keratin recovery but also establishes a statistically robust optimization approach. The methodology and insights provided can support future efforts in developing high-quality keratin-based biomaterials for biomedical, cosmetic, or environmental applications.

  • Open access
  • 2 Reads
Screening of the Antibacterial Potential of the Biosurfactant Produced by Pseudomonas fluorescens ICCF 392 Against Bacillus sp.

Biosurfactants are amphiphilic biocompounds produced by microorganisms, recognized for their surface-active properties and broad biotechnological applicability. The rising concern over antimicrobial resistance and environmental impact of synthetic chemicals has increased the demand for natural and eco-friendly alternatives. Biosurfactants, due to their unique chemical structure and multifunctional properties, have emerged as promising candidates in this regard. These compounds have gained increasing attention due to their biodegradability, low toxicity, and potential to replace synthetic surfactants in various industries. In particular, their antimicrobial properties make them promising agents for applications in food safety, pharmaceuticals, and environmental protection. Pseudomonas fluorescens, a well-known biosurfactant-producing bacterium, has been extensively studied for its capacity to produce rhamnolipids with antimicrobial activity. Therefore, this study aimed to assess the antibacterial potential of the biosurfactant synthesized by Pseudomonas fluorescens ICCF 392 against Bacillus cereus, a Gram-positive bacterium frequently associated with foodborne illnesses. The biosurfactant was obtained through submerged fermentation and partially purified. The antibacterial activity was evaluated using the agar well diffusion method, which revealed a clear zone of inhibition measuring 20 mm in diameter. These findings indicate that microbial biosurfactants can serve as effective and sustainable alternatives to conventional antimicrobial agents. Further studies will focus on detailed characterization of the biosurfactant, its spectrum of activity, and formulation potential in various delivery systems.

  • Open access
  • 6 Reads
Chiral Diketopyrrolopyrrole Thin Films: Unlocking Circularly Polarized Light for Next-Gen Optoelectronics

We report the synthesis and characterization of the two enantiomeric forms—(R)- and (S)-configured—of a chiral thienyl-substituted diketopyrrolopyrrole (DPP) derivatives functionalized with optically active alkyl side chains. The introduction of chirality into the molecular framework enables the exploration of its chiroptical properties and potential applications in emerging optoelectronic technologies.

Thin films of both enantiomers were fabricated using two different deposition techniques: spin coating and drop casting. These methods were selected to evaluate the influence of film morphology and molecular organization on the optical and chiroptical responses. Comprehensive spectroscopic characterization was conducted, including UV–Vis absorption, circular dichroism (CD), and circularly polarized luminescence (CPL) measurements.

The CD and CPL spectra revealed clear signatures of opposite chirality for the two enantiomers, confirming the successful transfer of molecular chirality into the solid-state films. Notably, distinct differences in spectral features were observed between the films prepared by spin coating and those obtained via drop casting, indicating the crucial role of processing conditions in modulating chiroptical performance.

Furthermore, preliminary device fabrication was carried out to assess the potential of these chiral DPP-based materials in practical applications. The initial results are promising and suggest that this class of compounds may serve as suitable candidates for use in chiral photodetectors or circularly polarized organic light-emitting diodes (CP-OLEDs).

  • Open access
  • 4 Reads
New molecular clips based on diazacrown-n ethers and p-tert-butylcalix[4]arenes molecules? Unusually behavior.

Previously, we demonstrated the complexing abilities of a molecular clip based on diaza-18-crown-6 as a central fragment and p-tert-butylcalix[4]arene molecules which are attached to the diazacrown via an amide groups. This work discloses the comparison of the complexing properties of clips based on diazacrown-n ethers (n = 4, 5, 6). It was found that the molecular clip based on diaza-12-crown-4, demonstrates high selectivity towards rubidium cations among alkali metals, and is able to form binuclear complexes with Mg and Ca cations among alkaline earth metals. The clip based on the unsymmetrical diaza-15-crown-5 ether is an exclusively selective ligand for Cs cations in the alkali metal series, and forms 1:2 (L:M) complexes with cesium and biligand complexes with barium cations. The clip based on diaza-18-crown-6 demonstrates exceptional selectivity for barium cations in the alkaline earth metal series with the formation of 1:1 complexes. The study of the interaction of the obtained clips with transition metal cations indicates that the ligand based on diaza-18-crown-6 is capable of forming predominantly 1:1 complexes with nickel, lead, cadmium, manganese, and cobalt cations (logK>4). In the case of diaza-12-crown-4, the formation of 1:1 complexes with manganese, cadmium, copper and cobalt cations, and biligand mononuclear complexes with nickel, lead and iron cations is observed. A different behavior is characteristic of the clip with diaza-15-crown-5 ether: interaction with nickel, lead, manganese and iron cations leads to the formation of 1:2 (L:M) complexes, but with cadmium, copper and cobalt cations the formation of stable biligand complexes is observed.

  • Open access
  • 3 Reads
Comparative adsorption performance of chitosan and iron-modified chitosan for the removal of a synthetic textile dye
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This work focuses on the removal of a synthetic textile dye trisodium ferric complex of N-methyl-1,8-naphtalimide-4-sulfonate from contaminated aqueous solutions using two types of biosorbents: industrial-grade chitosan and iron-modified chitosan. The objective of the study was to assess and compare the adsorption performance of both materials under various experimental conditions, with particular attention to their physicochemical characteristics and adsorption behavior.

The adsorbents were characterized using Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and pH at the point of zero charge (pHpzc), confirming structural differences induced by iron incorporation. Batch adsorption experiments were conducted to evaluate the effect of several parameters including contact time, initial pH, and agitation speed on dye removal efficiency.

The results revealed a remarkable enhancement in adsorption capacity for the iron-chitosan composite, achieving up to 96% removal efficiency, with equilibrium attained within 120 minutes for both materials. Kinetic studies showed better fitting with a pseudo-second-order model, while adsorption isotherms were best described by the Freundlich model, suggesting a multilayer adsorption on a heterogeneous surface.

A significant pH-dependent behavior was observed: industrial chitosan performed optimally under alkaline conditions, whereas the iron-modified form showed superior efficiency in acidic media. Additionally, a moderate agitation speed was identified as optimal, balancing diffusion kinetics and surface contact efficiency.

These findings underline the promising potential of iron-functionalized chitosan as an effective and sustainable material for the treatment of dye-laden industrial wastewater, offering a low-cost, environmentally friendly alternative to conventional adsorbents.

  • Open access
  • 3 Reads
Chitosan-Based Biosorption: A Sustainable Approach for Heavy Metal Removal from Wastewater
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With the rapid growth of industrial activities, water contamination has become one of the most pressing environmental issues worldwide. Among various pollutants, heavy metals are of particular concern due to their toxicity, persistence, and bioaccumulative nature. The control and remediation of such pollution is therefore of increasing scientific and societal interest.

In this context, our study investigates the potential of a natural, biodegradable, and eco-friendly biosorbent chitosan, derived from chitin extracted from marine crustacean shell for the removal of heavy metal ions from synthetic wastewater. The adsorption behavior of chitosan was explored using the batch equilibrium technique. A series of experiments was conducted to evaluate the influence of key operating parameters, including contact time, initial metal ion concentration, temperature, and pH of the solution, on the adsorption efficiency.

The experimental data were analyzed to determine the sorption capacity of chitosan and to identify the optimal conditions for maximum metal ion removal. The results indicate that chitosan exhibits a significant affinity towards heavy metal ions, and its adsorption performance is highly dependent on the physicochemical conditions of the aqueous medium.

These findings highlight the potential of chitosan as a low-cost and sustainable alternative for water purification, especially in the context of developing low-impact treatment technologies for industrial effluents.

  • Open access
  • 10 Reads
Transforming Anionic Reverse Micelles: The Potential of Hydrophobic Natural Deep Eutectic Solvents. How the mixture between camphor and menthol can be an excellent choice for reverse micelle preparation.
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Introduction: Reverse micelles are nanostructures formed by dissolving surfactants in low-polarity organic solvents. A commonly used anionic surfactant is AOT (sodium dioctyl sulfosuccinate), which forms aggregates capable of encapsulating water in their core. The amount of water solubilized is expressed as W₀ = [H₂O]/[Surfactant]. In green chemistry, Natural Deep Eutectic Solvents (NADES), such as the 1:1 mixture of camphor and menthol (CM), offer a sustainable alternative as non-polar external phases. This study evaluated the formation of reverse micelles with AOT, water, and CM, using NMR techniques.
Results: The CM NADES dissolved AOT up to 0.5 M and allowed the incorporation of water, achieving a maximum W₀ of 5. DOSY NMR studies confirmed the presence of reverse micelles and the encapsulation of water. Micellar diameters ranged from 1.5 to 3.5 nm, increasing with water content. ¹H NMR chemical shift changes revealed hydrogen bonding interactions between water and the polar region of AOT, affecting the interfacial conformation and reducing NADES penetration into the polar core.
Conclusion: The study demonstrated the formation of reverse micelles and allowed for the evaluation of the interface formed by CM/AOT at different water contents. Thus, it is possible to generate reverse micelles using a hydrophobic NADES, easily prepared, as the non-polar external solvent, paving the way for a new era in biocompatible organized systems. This is particularly interesting for future applications in the food industry or medicine.

  • Open access
  • 24 Reads
Supramolecular assemblies driven by N-H…O and O-H…O hydrogen bonding interactions: Experimental and theoretical investigation into the supramolecular architectures of dihydropyrimidin-2(1H)-ones

Extensive theoretical and experimental research has been conducted in the last few decades regarding non-covalent interactions and their function in chemical reactions, molecular recognition, and metabolic processes. The most emphasis has been paid to hydrogen bonding among them because of how frequently it occurs in chemical and biological processes. In addition to hydrogen bonding, other weak contacts including π-π interaction and chalcogen bonding has been acknowledged as a valuable instrument for supramolecular system design and crystal engineering. Understanding the origin and strength of the non-covalent bonds for different compounds has been a major focus of recent efforts, both computationally and experimentally. Theoretical computations such as Hirshfeld surface analysis, MEPS (molecular electrostatic potential surface), and QTAIM (quantum theory of atoms in molecules) were carried out in order to obtain insight into the nature of hydrogen-bonding interactions. The solid state structure of the compound using for this study shows the present of N-H…O and O-H…O hydrogen bonding interactions. The N-H…O bond lengths are 2.102 Å and 2.037 Å, respectively. The study focus on dihydropyrimidin-2(1H)-ones, specifically how these molecules with multiple hydrogen bonding sites interact within crystals to establish a synthon hierarchy. The research aims to understand the preferred hydrogen bonding patterns and their impact on the overall crystal structure.

  • Open access
  • 3 Reads
Synthesis and in silico evaluation 7-hydroxycoumarin-4-acetic acid as possible cytochromes P450 substrate
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Cytochromes P450 (CYPs) are superfamily of oxidoreductases with a hem-thiolate moiety. CYPs catalyze hydroxylation and some other oxidation reactions, including C-N, C-O and C-C bond cleavage. Their biological functions include xenobiotic detoxification and biosynthesis of hormone and other bioregulators using hydrophobic substrates like steroid and fatty acids. Coumarin derivatives are known to be substrates or inhibitors for some CYPs [1], but due to high amounts of coumarins and CYPs exist, some interactions of particular CYP-coumarin pairs is still undetermined. In this paper we report about of synthesis of 7-hydroxycoumarin-4-acetic acid (7-hydroxy-4-methyl-2H-chroman2-one, Pubchem ID CID: 5338490) using published method [2]. The product was found to by pure according to TLC assay and absorbance maxima at 320 and 365 nm in HCl acidified and K2CO3-buffered water:ethanol (10 : 1, v:v), respectively. To evaluate in silico its possible interactions with CYPs Autodock Vina (AV) together with authored helper software FYTdock [3] for highthroughput virtual screening (HTVS) were used together with majority of 3D structures of CYPs from PDB database. It was found that affine binding with AV scores in range -9 - -9.4 were found for human CYP1A1 structure (PDB code 6DWM), bacterial P450-BM3 (3BEN), OleT (5M0N, 4L40, 4L54), CYP260A1 S276I mutant (6F8C) and P450-CAM (1PHE). To the best of our knowledge the interactions have not been reported yet even in silico. Our results indicate on possibility to check such interactions in vitro, e.g. to develop fluorescence-based screening system for the aforementioned enzymes.

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