Pyran-Squaraine as Photosensitizers for Dye-Sensitized Solar Cells: DFT/TDDFT Study of the Electronic Structures and Absorption Properties

In an effort to provide, assess, and evaluate a theoretical approach which enables designing efficient donor-acceptor dye systems, the electronic structure and optical properties of pyran-squaraine as donor-acceptor dyes used in dye-sensitized solar cells were investigated. Ground state properties have been computed at the B3LYP/6-31+G** level of theory. The long-range corrected density functionals CAM-B3LYP, PBEPBE, PBE1PBE (PBE0), and TPSSH with 6-311++G** were employed to examine absorption properties of the studied dyes. In an extensive comparison between experimental results and ab initio benchmark calculations, the TPSSH functional with 6-311++G** basis set was found to be the most appropriate in describing the electronic properties for the studied pyran and squaraine dyes. Natural transition orbitals (NTO), frontier molecular orbitals (FMO), LUMO, HOMO, and energy gaps, of these dyes, have been analyzed to show their effect on the process of electron injection and dye regeneration. Interaction between HOMO and LUMO of pyran and squaraine dyes was investigated to understand the recombination process and charge-transfer process involving these dyes. Additionally, we performed natural bond orbital (NBO) analysis to investigate the role of charge delocalization and hyperconjugative interactions in the stability of the molecule

Nucleophilic Addition of Reactive Dyes on Amidoximated Acrylic Fabrics

Seven reactive dyes judiciously selected based on chemical structures and fixation mechanisms were applied at 2% owf of shade on amidoximated acrylic fabrics. Amidoximated acrylic fabric has been obtained by a viable amidoximation process. The dyeability of these fabrics was evaluated with respect to the dye exhaustion, fixation, and colour strength under different conditions of temperature and dyeing time. Nucleophilic addition type reactive dyes show higher colour data compared to nucleophilic substitution ones. FTIR studies further implicate the binding of reactive dyes on these fabrics. A tentative mechanism is proposed to rationalize the high fixation yield obtained using nucleophilic addition type reactive dyes. Also, the levelling and fastness properties were evaluated for all dyes used. Excellent to good fastness and levelling properties were obtained for all samples irrespective of the dye used. The result of investigation offers a new method for a viable reactive dyeing of amidoximated acrylic fabrics

Immobilization of horseradish peroxidase on Fe3O4 magnetic nanoparticles

Background: Iron magnetic nanoparticles have attracted much attention. They have been used in enzyme immobilization because of their properties such as product is easily separated from the medium by magnetic separation. The present work was designed to immobilize horseradish peroxidase on Fe3O4 magnetic nanopraticles without modification. Results: In the present study, horseradish peroxidase (HRP) was immobilized on non-modified Fe3O4 magnetic nanoparticles. The immobilized HRP was characterized by FT-IR spectroscopy, scanning electron microscopy, and energy dispersive X-ray. In addition, it retained 55% of its initial activity after 10 reuses. The optimal pH shifted from 7.0 for soluble HRP to 7.5 for the immobilized HRP, and the optimal temperature shifted from 40\ub0C to 50\ub0C. The immobilized HRP is more thermostable than soluble HRP. Various substrates were oxidized by the immobilized HRP with higher efficiencies than by soluble HRP. Km values of the soluble and immobilized HRP were 31 and 45 mM for guaiacol and 5.0 and 7.0 mM for H2O2, respectively. The effect of metals on soluble and immobilized HRP was studied. Moreover, the immobilized HRP was more stable against high concentrations of urea, Triton X-100, and isopropanol. Conclusions: Physical immobilization of HRP on iron magnetic nanoparticles improved the stability toward the denaturation induced by pH, heat, metal ions, urea, detergent, and water-miscible organic solvent

Functional Dyes, and Some Hi-Tech Applications

An overview of the recent developments in functional dyes, which are useful for hi-tech applications for those based on optoelectronics, such as dye sensitized solar cells, photochromic dyes and biomedical applications, such as photodynamic therapy for the treatment of cancer and fluorescent sensors is presented

Preparation and Characterization of Cationized Cellulose for the Removal of Anionic Dyes

The factors influencing the cationization of microcrystalline cellulose with 3-chloro-2-hydroxypropyl triethylammonium chloride in the presence of NaOH were investigated. The course of the reaction was followed by estimating the nitrogen content of the cationized product while its structural features were confirmed by IR analysis. The ability of cationized cellulose to adsorb anionic dyes, viz. Acid Orange 7, Direct Blue 75 and Direct Violet 31, was investigated at 25°C and 50°C. The equilibrium data obtained were fitted by the Langmuir and Freundlich isotherm models, allowing the corresponding adsorption parameters to be determined. The results showed that the adsorption capacity was dependent on the adsorbent, temperature, the nature of the dye and (to some extent) on van der Waals and hydrogen bonding. Cationized cellulose exhibited a much better adsorption capacity towards anionic dyes than cellulose

Geochemistry and Utilization of Montmorillonitic Soil for Cationic Dye Removal

Geochemical studies of Egyptian soil-clay minerals from three different depths and their utilization as cationic dye adsorbents are presented. X-Ray diffraction patterns revealed that the dominant clay minerals in the studied samples were montmorillonite, kaolinite and illite. The ability of montmorillonitic soil samples to adsorb cationic dyes, namely Basic Blue 9 and Basic Red 18, was investigated at 30°C. The equilibrium adsorption data were well fitted to the Langmuir model and their parameters determined. The results showed that the adsorption capacity was dependent on the structure of the dyes and the geochemical features of the soil samples

Synthesis and Characterization of Ag-Ag2O/TiO2@polypyrrole Heterojunction for Enhanced Photocatalytic Degradation of Methylene Blue

Hybrid multi-functional nanomaterials comprising two or more disparate materials have become a powerful approach to obtain advanced materials for environmental remediation applications. In this work, an Ag-Ag2O/TiO2@polypyrrole (Ag/TiO2@PPy) heterojunction has been synthesized by assembling a self-stabilized Ag-Ag2O (p type) semiconductor (denoted as Ag) and polypyrrole (π-conjugated polymer) on the surface of rutile TiO2 (n type). Ag/TiO2@PPy was synthesized through simultaneous oxidation of pyrrole monomers and reduction of AgNO3 in an aqueous solution containing well-dispersed TiO2 particles. Thus synthesized Ag/TiO2@PPy was characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), and UV-Vis diffuse reflectance spectroscopy (UV-vis DSR). The photocatalytic activity of synthesized heterojunction was investigated for the decomposition of methylene blue (MB) dye under UV and visible light irradiation. The results revealed that π-conjugated p-n heterojunction formed in the case of Ag/TiO2@PPy significantly enhanced the photodecomposition of MB compared to the p-n type Ag/TiO2 and TiO2@PPy (n-π) heterojunctions. A synergistic effect between Ag-Ag2O and PPy leads to higher photostability and a better electron/hole separation leads to an enhanced photocatalytic activity of Ag/TiO2@PPy under both UV and visible light irradiations