Anomalous Reaction Pathways to Methane Production in Photocatalytic Ethanol Oxidation.

Photocatalytic reduction reactions occasionally utilize sacrificial agents to scavenge photogenerated holes, thus enhancing the kinetics and efficiency of electron harvesting. However, exploring alternative hole-mediated oxidation reactions and their potential impact on photoredox processes is limited. This study investigates the products resulting from the oxidation of ethanol, a commonly used hole scavenger, and the underlying mechanisms involved. We examine a homogeneous eosin Y photoreaction scheme containing a Cu complex coordinated with an N-heterocyclic carbene, a combination often employed in CO2 conversion. Under visible-light excitation, this photosystem yields methane as an unusual product, alongside acetaldehyde and carbon monoxide. Mechanistic analysis reveals that ethanol undergoes a catalytic cascade involving oxidative processes, C-C bond cleavage, and intermolecular hydrogen atom transfer. Notably, the Lewis-acidic metal center of the Cu complex activates a novel pathway for ethanol oxidation. This work presents the influence of catalyst selection and reaction condition optimization on the emergence of new or unexpected catalytic processes.

Facile synthesis and optimization of Acacia senegal gum hydrogel for kinetically treated adsorptive removal of targeted industrial effluents.

This context summarizes a detail on the fabrication of Acacia senegal Gum Hydrogel (ASGh) within well-engineered microemulsion, and thereafter chemical modification for environmental remediation. In brief, Divinylsulfone was used to crosslink polymeric chains and produce ASGh in ˂50 µm size within the reverse-microemulsion of Natrium-bis-(2-ethylhexyl) sulfosuccinate in gasoline. ASGh were subjected to chemical modification via versatile diethylenetriamine to produce m-[ASGh] for adsorptive removal of methyl orange (MO), eosin Y (EY) and congo red (CR) from waste-water. ASGh and m-[ASGh] were characterized through Scanning Electron Microscopy (SEM), Fourier Transform Infrared Spectroscopy (FTIR), and zeta potential measurements. For instance, FT-IR spectra depicted new bands upon Diethylenetriamine modification. The zeta potential measurements confirm a positively charged surface of m-[ASGh] upon Diethylenetriamine addition. Interestingly, 0.05 g m-[ASGh] demonstrated 91.0, 84.1, and 73.0 % removal efficiency towards MO, EY and CR, respectively in 2 h equilibrium time. Langmuir, Freundlich and modified-Freundlich isotherms were applied to further delineate adsorption data. Modified-Freundlich model depicted comparatively more agreeable fit, and delivered R2 value nearer to unity. Further, 143 mg·g-1, 130 mg·g-1 and, 116 mg·g-1 maximum adsorption capacity (QM) was represented by m-[ASGh] towards MO, EY and CR, respectively in 2 h. Interestingly, real water sample were tested whereby, the QM against MO, EY and CR was 146 mg·g-1, 132 mg·g-1 and, 111 mg·g-1, respectively in 2 h equilibrium time. To conclude, m-[ASGh] could be treated as decolorizing agent in real waste-water polluted through negatively charged organic pollutants, particularly MO.

Effective removal of acetamiprid and eosin Y by adsorption on pristine and modified MIL-101(Fe).

In this work, the efficacy of two metal-organic frameworks (MIL-101(Fe) and NH2-MIL-101(Fe)) in eliminating acetamiprid (ATP) insecticide and eosin Y (EY) dye from aqueous solution is tested. An analysis was conducted on the developed nanocomposite's optical, morphological, and structural characteristics. The adsorption isotherm, kinetics, thermodynamics, reusability, and mechanisms for ATP and EY dye removal were assessed. NH2-MIL-101(Fe) adsorbed 76% and 90% of ATP pesticide and EY dye, respectively after 10 to 15 min in optimum conditions. For both adsorbents, with regard to explaining the isotherm data, the Langmuir model offered the most accurate description. Moreover, the adsorption of ATP and EY dye is described by the pseudo-second-order kinetic model. The maximum adsorption capacities of ATP and EY dye on MIL-101(Fe) were 57.6 and 48.9 mg/g compared to 70.5 and 97.8 mg/g using NH2-MIL-101(Fe). The greatest amount of ATP and EY dye clearance was obtained at a neutral medium for both adsorbents. The results of this investigation demonstrate the effectiveness of MIL-101(Fe) and NH2-MIL-101(Fe) as effective substances in the adsorption process for removing pesticides and dyes from aqueous solution.

organo acid-activated clays for water treatment as removal agent of Eosin-Y: Properties, regeneration, and single batch design absorber.

Organoclays have been proposed as efficient removal agents for colored wastewater treatment. In this study, organo-acid-activated clays were investigated for their ability to remove eosin Y dye molecules. Firstly, the clay was acid activated using sulfuric solution at 90 °C for overnight. Secondly, the resulting materials were treated by hexadecyltetramethylammonium bromide solutions to obtain organo-acid-activated clays. Several techniques were used, such as X-ray diffraction, carbon hydrogen nitrogen analysis, silicon-29 and carbon-13 solid-state nuclear magnetic resonance, and nitrogen adsorption isotherms. The cation exchange capacity values were reduced and the specific surface area values increased from 80.1 m2/g to 183.2 m2/g during the acid activation process. The resulting organo-acid-activated clays had a similar expansion of interlayer spacing of 3.90 nm with less intercalated hexadecyltetramethylammonium surfactants, ranging from 0.80 mmol/g to 1.22 mmol/g; 13C solid NMR indicated that the intercalated surfactants exhibited different degree of conformation. Many factors, including the solid dose, solution pH, amount of intercalated surfactants, and starting eosin-Y concentrations, were studied in relation to the removal capabilities of organo acid-activated clays. Based on the Langmuir model, the removal capacity of the organo acid-activated clays ranged from a minimum of 43.5 mg/g to a maximum of 79.3 mg/g, dependent on the surfactant quantities and acid activation degree. , and the pH. The removal percentage of eosin-Y was increased from 50.5 % to 80.8 % by treating the organo acid-activated clay with HCl solution before the removal procedure. Regeneration and reuse of two selected organo acid-activated clays were carried out for seven successive cycles, and a reduction in the initial efficiency was in the range of 26.4 %-30.1 %. However, for organoclay (without acid activation), approximately 52.1 % efficiency was maintained. Using the Langmuir model and mass balance equations, a single-stage adsorber design was suggested for different dye volumes at a constant starting concentration.

A green reaction-based turn-off fluorescence sensor for determination of copper ions: DFT calculations, quenching mechanism, green chemistry metrics, and application in environmental samples.

When Cu(II) reacts with ascorbic acid (AA) to form Cu(I), Cu(I) can combine with eosin Y (EY) to form ionic associations, resulting in significant fluorescence quenching of the EY. Based on the turn-off of fluorescence in the chemosensor EY, a green reaction is proposed herein for the detection of Cu(II). The novel detection method for Cu(II) demonstrates simplicity, high sensitivity, and excellent selectivity, rendering it suitable for analyzing environmental samples. A static fluorescence quenching mechanism is validated through the Stern-Volmer relationship, and the thermodynamic parameters of the reaction are explored using a van 't Hoff plot. The reaction mechanism is investigated via fluorescence spectra, absorption spectra, and density-functional theory (DFT) calculations. The probe's green nature is confirmed by applying four green analytical chemistry metrics.

Wheat flour-derived amyloid fibrils for efficient removal of organic dyes from contaminated water.

Amyloid fibrils derived from different proteins have been proved as a promising material for adsorption of various pollutants from wastewater, which showed advantages of low cost and eco-friendliness. However, most of the amyloid fibrils derived from animal-based proteins with high environmental footprint, while more sustainable amyloid fibrils derived from plant materials are desirable. In this study, a plant-derived amyloid fibril was extracted from the commonly used wheat flour with a simple and scalable protein purification and fibrillization process. Interestingly, the amyloid fibrils showed good adsorption capacity towards typical organic dyes (Eosin Y (EY) and Congo red (CR)) from contaminated water. Adsorption kinetic analysis indicated the adsorption process to EY or CR by wheat flour amyloid well fitted with a pseudo-second-order model. The adsorption also followed a Langmuir isothermal model with adsorption capacities of 333 mg/g and 138 mg/g towards CR and EY, respectively. This work demonstrated the feasibility to utilize the plant-based amyloid fibril for organic dyes removal from contaminated water, which provided an affordable, sustainable and scalable tool for organic dyes removal from wastewater.

Development of Eco-Friendly Scattering and Fluorimetric Methods for the Determination of Clemastine Through Its Interaction with Eosin Y: Assessment of Whiteness, Blueness, and Greenness Tools.

For the first time, clemastine was estimated in this work utilizing two validated resonance Rayleigh scattering (RRS) and fluorimetric methods. The methods relied on forming an association complex in an acidic medium between eosin Y reagent and clemastine. In the spectrofluorimetric approach, the investigated drug was quantified by quenching the fluorescence-emission intensity of eosin Y at 543.5 nm. The RRS method relied on enhancing the RRS spectrum at 331.8 nm, which is produced when eosin Y interacts with clemastine. Suitable conditions were established for the reaction to achieve maximum sensitivity. The linear values obtained from the spectrofluorimetric approach and the RRS method fall into the ranges of 0.2-1.5 µg mL- 1 and 0.25-2.0 µg mL- 1, respectively. It was established that the detection limits for these methods were 0.045 µg mL- 1 and 0.059 µg mL- 1, respectively. The developed methodologies yielded acceptable recoveries when used to estimate the quantity of clemastine in its pharmaceutical tablet dosage form. Regarding the use of greener solvents that were chosen, the suggested and reported methods were compared with the help of the Green Solvents Selecting (GSST) tool for assessing hazardous solvents to achieve sustainability. Furthermore, analytical Eco scale and comprehensive assessments of whiteness, blueness, and greenness were carried out utilizing Modified NEMI, ComplexGAPI, and AGREE evaluation tools. Additionally, recently developed tools such as BAGI and RGB 12 were applied to assess the blueness and the whiteness of the suggested methods.

Determination of antihistaminic drugs alcaftadine and olopatadine hydrochloride via ion-pairing with eosin Y as a spectrofluorimetric and spectrophotometric probe: application to dosage forms.

Four sensitive and fast analytical approaches relied on ion pairing with eosin Y were built up and evaluated using spectroscopy for determination of Alcaftadine and Olopatadine hydrochloride with high sensitivity and selectivity. Two spectrofluorimetric techniques were employed to observe the quenching effect of Alcaftadine or Olopatadine hydrochloride on the intrinsic fluorescence of eosin Y in a 0.1 M acetate buffer solution at pH 3.8 and 3.3 for Alcaftadine and Olopatadine hydrochloride, respectively. Those methods are considered the first spectrofluorimetric methods for Alcaftadine and Olopatadine hydrochloride assay. The fluorescence quenching effect was linear with concentration ranging from 150 to 2000 and 200 to 2000 ng mL-1 for Alcaftadine and Olopatadine hydrochloride, respectively. In the two spectrophotometric techniques, the absorbance of the produced ion-pair was monitored at 548 and 547 nm in aqueous buffered solution at pH 3.8 and 3.3 for Alcaftadine and Olopatadine hydrochloride, respectively. Beer's law was obeyed in the concentrations range of 0.8-8.0 and 1.0-10.0 µg mL-1. The four techniques were evaluated in accordance with ICH requirements and were effectively used to analyze dosage forms with a high percent recovery.

Spectral Investigations of Fluorescence Tracers in Automotive and Aviation Fuels under Cryogenic Conditions.

This study investigated spectral laser-induced fluorescence signals of dyes in fuels for automotive and aerospace applications under low temperatures and cryogenic conditions down to 183 K. For this purpose, a fluorescence chamber was developed based on cooling with liquid nitrogen. The design enabled a minimal inner chamber temperature of 153 K. Furthermore, the applicability of two-color LIF for liquid thermometry was evaluated under these conditions. The temperature determination was based on the temperature-sensitive fluorescence intensity ratio of the special dyes doped into the fuels determined in suitable spectral regions, which represented common bandpass filters. For this purpose, the fluorescence signals of the dye doped into the gasoline and jet fuel surrogate isooctane were tested as well as blends of isooctane and the ethanol biofuels E20 (comprising 80 vol.% isooctane and 20 vol.% ethanol), E40, and E100. Additionally, a realistic multi-component fuel Jet A-1 mixed with a suitable fluorescence dye was investigated. E100 was doped with Eosin-Y, and the remaining fuels were doped with Nile red. Temperature-dependent spectral LIF intensities were recorded in the range of 183 K-293 K, which simulate extreme environments for aerospace and automotive applications. Frozen fuel-dye mixtures cause significant extinction effects and prevent sufficient signal detection at low and cryogenic temperatures, defining the detection limit. A temperature decrease led to a spectral shift in the emission peaks of E100 doped with Eosin-Y toward shorter wavelengths, while the spectra of mixtures doped with Nile red were shifted toward longer wavelengths. The suggested bandpass filters produced the temperature-sensitive intensity ratio (the average over the temperature interval) of the dyes with the largest sensitivity for Jet A-1 (5.2%/K), followed by E100 (4.95%/K), E40 (4.07%/K), E20 (3.23%/K), and isooctane (3.07%/K), even at cryogenic temperatures.

3D-Printed Eosin Y-Based Heterogeneous Photocatalyst for Organic Reactions.

Heterogenization of Eosin Y by 3D-printing and its application in photocatalysis are reported. The approach allows a fine tuning of the photocatalyst morphology and its rapid preparation. Photocatalytic activity was evaluated through model organic reactions involving oxidation, reduction, and photosensitization pathways. The efficiency, recyclability and stability of 3D printed EY is remarkable paving the way to new generation of heterogeneous photocatalysts with a perfect control of their shape and adaptable to any photoreactors.