Experimental and theoretical studies of linear and non-linear optical properties of novel fused-triazine derivatives for advanced technological applications.

Controlling photophysical properties is critical for the continued development of electroluminescent devices and luminescent materials. The preparation and study of novel molecules suitable as luminescent for the development of optoelectrical devices have recently received a lot of attention. Even though the as-triazine unit is a good building block for organic active substances, it is rarely used in this context. We created here novel bis-triazine derivative dyes in the far UV-Vis range by alkylation of triazine-thione derivatives with appropriate dibromo compounds. At the B3LYP/6-311**G(d,p) basis set, their optimal molecular structures were obtained. DFT technique confirmed that the new triazine derivatives are in noncoplanar with one of the two phenyl rings and the triazine plane rotating out by 102.09. Also, depending on the energy gap difference between HOMO and LUMO, some important parameters including chemical potential (π), electronegativity (χ), and chemical hardness (η) were calculated. The compounds may be readily polarized and have significant NLO characteristics, as seen by the tiny HOMO-LUMO energy gap. The calculated values for the polarizability (α) of the two new triazine derivatives have the range 6.09-10.75 × 10-24 (esu). The emission peaks seemed to move to the long-wavelength (redshift), with a rise in the fluorescence band, suggesting that the singlet excited state is more polar than the ground state. The influence of solvent polarity and the intermolecular charge transfer (ICT) processes are reflected in the photophysical properties of new fused triazine derivatives. These properties such as extinction coefficient, absorption and emission cross-sections, fluorescence quantum yield, fluorescence lifetime, oscillator strength, the dipole moment, radiative decay rate constant, the energy yield of fluorescence, and the attenuation length were assessed and discussed.

Growth Inhibition of Sulfate-Reducing Bacteria during Gas and Oil Production Using Novel Schiff Base Diquaternary Biocides: Synthesis, Antimicrobial, and Toxicological Assessment.

Upstream crude oil production equipment is always exposed to destruction damagingly which is caused by sulfate-reducing bacterium (SRB) activities that produce H2S gas, which leads to increased metal corrosion (bio-fouling) rates and inflicts effective infrastructure damage. Hence, oil and gas reservoirs must be injected with biocides and inhibitors which still offer the foremost protection against harmful microbial activity. However, because of the economic and environmental risks associated with biocides, the oil and gas sectors improve better methods for their usage. This work describes the synthesis and evaluation of the biological activities as the cytotoxicity and antimicrobial properties of a series of diquaternary cationic biocides that were studied during the inhibition of microbial biofilms. The prepared diquaternary compound was synthesized by coupling vanillin and 4-aminoantipyrene to achieve the corresponding Schiff base, followed by a quaternization reaction using 1,6-bromohexane, 1,8-bromooctane, and 1,12-bromododecane. The increase of their alkyl chain length from 6 to 12 methylene groups increased the obtained antimicrobial activity and cytotoxicity. Antimicrobial efficacies of Q1-3 against various biofilm-forming microorganisms, including bacteria and fungi, were examined utilizing the diameter of inhibition zone procedures. The results revealed that cytotoxic efficacies of Q1-3 were significantly associated mainly with maximum surface excess and interfacial characteristics. The cytotoxic efficiencies of Q1-3 biocides demonstrated promising results due to their comparatively higher efficacies against SRB. Q3 exhibited the highest cytotoxic biocide against the gram +ve, gram -ve, and SRB species according to the inhibition zone diameter test. The toxicity of the studied microorganisms depended on the nature and type of the target microorganism and the hydrophobicity of the biocide molecules. Cytotoxicity assessment and antimicrobial activity displayed increased activity by the increase in their alkyl chain length.

Valuation of rice straw residues: Production of silylated methylcellulose containing propylamine and propylethylenediamine for use as anticorrosion and antibacterial.

Green technology is a scientific movement seeking to eliminate industrial chemicals and replace them with natural products by valorizing natural resources or biological waste. In this work, we present the extraction of cellulose from rice straw and chemically modified water-dispersible cellulose (methylcellulose) by performing a methylation process. The methylcellulose is chemically bonded to N-[3-(trimethoxysilyl)propyl]ethylenediamine, and (3-aminopropyl)triethoxysilane compounds to produce a cellulose-organosilane hybrid. The prepared compounds were studied with appropriate techniques such as 1H NMR, XRD, FTIR, TGA, Raman spectroscopy, FE-SEM, and AFM. The prepared materials were used as corrosion inhibitors of steel in 1 N H2SO4 for studies of potentiodynamic polarization measurements and electrochemical impedance spectroscopy. The materials were also studied as antibacterial agents. The results indicate the successful use of a modified extracted cellulose hybrid in the corrosion field and as an antibacterial agent. Quantum chemical assessments based on density functional theory (DFT) of the trimethoxysilyl propylamine and dimethoxymethylsilyl propylethylenediamine grafted methylcellulose were calculated. The results obtained showed the agreement of the theoretical data with the experimental data.

Effect of Reaction Parameters on Catalytic Pyrolysis of Waste Cooking Oil for Production of Sustainable Biodiesel and Biojet by Functionalized Montmorillonite/Chitosan Nanocomposites.

The use of waste oils as pyrolysis feedstocks to manufacture high-grade biofuels has prompted researchers to focus on developing renewable energy to overcome the depletion of fossil fuel supplies and the global warming phenomena. Because of their high hydrogen and volatile matter concentration, waste oils are ideal raw materials for the production of biofuels. It is challenging to attain satisfactory results with conventional methods, such as transesterification, gasification, solvent extraction, and hydrotreating due to flaws such as high energy demand, long time, and high operating costs. Catalytic pyrolysis of waste edible oils was employed as a resource for the generation of biodiesel. The application of the catalytic cracking process has the potential to alleviate the existing situation. In this study of catalytic cracking conversion of waste cooking oil to produce different biofuels, grades were investigated using two heterogeneous catalysts. The catalysts were activated montmorillonite (PAMMT) clay and its modified form using a chitosan biopolymer (PAMMT-CH) nanocomposite. The catalysts were identified using infrared spectroscopy, X-ray diffraction patterns, transmittance electron microscopy images, surface area, and thermal stability. The catalysts were tested for their performances using different amounts (0.1-1% by weight) at a temperature assortment of 200-400 °C during a time range of 60-300 min. The experimental studies were carried out in a batch reactor. GC mass spectra were used to investigate the catalytic cracking products. Fractional distillation is used to separate the final products from various reaction conditions. The physicochemical properties of resulting biofuels were profiled by quantifying their densities, viscosities, specific gravities, pour points, flash and fire points, cetane numbers, carbon and ash residues, and sulfur contents. The optimum conditions of the yield product were 300 and 400 °C, catalyst weights of 0.7 and 0.8% w/v, and reaction times of 120 and 180 min concerning the (PAMMT) and (PAMMT-CH) nanocomposite, respectively. The determined properties were located within the limits of the specific standards of ASTM specifications. As a result, the PAMMT nanocomposite produced biofuel comparable to biodiesel according to ASTM specifications, while the PAMMT-CH nanocomposite produced biofuel comparable to biojet.

Corrosion Inhibition of Carbon Steel in Hydrochloric Acid Solution Using Ethoxylated Nonionic Surfactants Based on Schiff Base: Electrochemical and Computational Investigations.

Two ethoxylated nonionic surfactants (L400 and L600) based on Schiff base are prepared from polyoxyethylene, glyoxalic acid, and phenylenediamine. They are evaluated electrochemically as carbon steel corrosion inhibitors in 1 M HCl by electrochemical impedance spectroscopy (EIS) and Tafel techniques and complemented with microscopic analysis methods. The obtained Tafel data indicate the mixed-type behavior of the inhibitor used. The inhibition efficiency touches the peak at 1 × 10-4 M, exhibiting 92 and 94% for L400 and L600, respectively. The presence of the tested inhibitors decreases corrosion current density (i corr) and double-layer capacitance (C dl) due to the formation of a protective adsorption layer in place of the already adsorbed water and aggressive Cl- ions. Both L400 and L600 adsorption modes follow Langmuir adsorption isotherm. The density functional theory (DFT) calculated indices (ΔE gap and E HOMO) indicate the superiority of L600 over the L400 counterpart as a reactive compound. Adsorption of L600 and L400 over the Fe(1 1 0) in simulated acidic medium is investigated by Monte Carlo (MC) simulation to verify their inhibition performance and are matched with adsorption free energy ΔG ads calculated values. Both experimental and theoretical data are in agreement.

Performance of chitosan polymer as platform during sensors fabrication and sensing applications.

Chitosan is an important polymer produced from deacetylation of several sea and insects crusts. Due to its environmental fate and biological biocompatibility, it can be used in several biological and environmental applications. Sensing of biological compounds in human bodies and also in serum, blood, and different body fluids has found an important application instead of direct determination of the body fluids using complicated tools. Sensing process of biological compounds during bio-analysis of the biological systems, especially human fluids lack of several parameters including: high sensitivity, repeatability, speed of analysis and biocompatibility of the used analytical methods, especially in-vivo analysis. That was due to the time between sample handling and sample determination can change various components and concentrations of the bio-compounds. The need for in-situ analysis was directed the researchers for biosensors to overcome the upgrading problems of bio-analysis. Biosensors were the future of this issue. Chitosan can reserve as great platform for fabrication of different sensors to determine the elements, compounds and body bioactive compounds. The presence of different terminal amino and hydroxyl groups within chitosan framework facilitates the immobilization of different biomarkers to be used as sensing elements for the determined compounds. The use of chitosan as sensors platform was enhanced by using chitosan in its nanoforms.

Effectuality of chitosan biopolymer and its derivatives during antioxidant applications.

Chitosan is an important biopolymer produced from the deacetylation of several seas and insect crusts. Due to its environmental fate and biological biocompatibility, it can be used in several biological and environmental applications. In this review, the potential application of chitosan biopolymer was reviewed due to it is considered an environmental, sustainable, and biologically safe plate form for producing several antioxidants. The different antioxidants fabricated from chitosan biopolymer- an active substrate- and the functional role of the diverse groups, either in chitosan backbone or in the coupled species with chitosan, were reviewed. Different antioxidant types were described, reviewed, and compared with the most famous and traditional antioxidants, such as ascorbic acid, citric acid, and gallic acid. Additionally, the different methods and techniques used in determining the antioxidative tendencies of the antioxidants were extensively described and reviewed.

Advancement on modification of chitosan biopolymer and its potential applications.

Chitosan is the second abundant biopolymer present on earth after cellulose. Chitosan is extracted from the shells of shrimp and other crustaceans. Several methods were reported for its extraction, but the most commercial is the deacetylation of chitin. Chitosan as a biopolymer has numerous applications and uses. But, its mechanical, chemical and biological characteristics can be enhanced by modification of its chemical structures. Several modification methods and derivatives were reviewed in the literatures, and several were collected in this review. The reviewed modified chitosan derivatives herein were five types of derivatives. The first is substituted chitosan derivatives including thiolated, phosphorylated, and N-phthaloylated derivatives. The second is crosslinked chitosan derivatives including chitosan-glutaraldehyde, chitosan-ethylene diamine tetraacetic acid, and chitosan-epichlorohydrin derivatives. The third is carboxylic acid derivatives of chitosan obtained from carboxyalkylation, acrylation, methacrylation, and benzoylation of chitosan. The fourth is ionic chitosan derivatives including highly cationic and sulfated derivatives. The last is bounded chitosan to specific molecules including cyclodextrin, thiosemicarbazone, dioxime, and crown ether precursors. The review also highlights the reported advantages and applications of the modified chitosan and the synthetic routes of the biopolymer modification.

Spectroscopic Study of Solvent Polarity on the Optical and Photo-Physical Properties of Novel 9,10-bis(coumarinyl)anthracene.

Novel 7,7'-((anthracene-9,10-diylbis(methylene))bis(oxy))bis(4-methyl-2H-chromen-2-one) (BisCA) was prepared as fluorescent probe. The chemical structure of the novel BisCA was confirmed by spectroscopic data as well as elemental analyses. The solvatochromic characteristics of the new proble and its precursors were investigated in different solvents including, ethanol, DMF and toluene as protic polar, aprotic polar and non-polar solvents, respectively. Photo-physical parameters of probes, such as fluorescence quantum yields, fluorescence lifetime of excited state, radiative and non-radiative decay, were assessed in different media. The intermolecular H-bond effect on absorption and excitation spectra of the novel probe was reported in different solvents. Also, Onsager cavity radius and dipole moment of ground state and excited state of the probe were calculated as described by Bakhshiev and Reichardt methods.

Fluorescein dye derivatives and their nanohybrids: Synthesis, characterization and antimicrobial activity.

Fluorescein (resorcinolphthalein) is a synthetic organic photoactive dye compound soluble in water, alcohol and polar solvents. It is widely used as a fluorescent tracer in medicinal and biological applications and tumor infected tissues tracer. In this study, fluorescein (F) was condensed by five coupling agents namely: p,p-phenylene diamine, p-hydroxy aniline, o-hydroxy aniline, p-methoxy aniline and p-methyl aniline in a molar ratio of 2(F):1 (coupling agent). The chemical structures of the synthesized fluorescein derivatives were confirmed using: microelemental analysis, FTIR spectroscopy, 1H-NMR spectroscopy, and mass spectroscopy. The synthesized compounds were loaded on chemically prepared silver nanoparticles via reduction reaction of silver nitrate. The structures and properties of the formed fluorescein derivatives silver nanohybrids were determined using: UV/Vis spectroscopy, TEM images and dynamic light scattering (DLS). The synthesized compounds and their nanohybrids were evaluated for their antimicrobial activities against different bacterial strains and fungi. The results showed that the formed fluorescein derivatives silver nanohybrids are in moderate diameter range, and the loading of the synthesized compounds protect the silver nanoparticles against coagulation. The antimicrobial activity against the studied microorganisms was comparable to the standard used. Moreover, the antimicrobial activity was increased considerably in case of using fluorescein derivatives silver nanohybrids. The antimicrobial activities were correlated to the chemical structures of the compounds, diameter of the formed nanohybrids and to the nature of the tested bacterial strains. The mechanism of the antimicrobial action of the synthesized compounds and their nanohybrids was proposed.

Metal adsorption by agricultural biosorbents: Adsorption isotherm, kinetic and biosorbents chemical structures.

Biosorption of Cu(II), Co(II) and Fe(III) ions from aqueous solutions by rice husk, palm leaf and water hyacinth was investigated as a function of initial pH, initial heavy metal ions concentration and treatment time. The adsorption process was examined by two adsorption isotherms: Langmuir and Freundlich isotherms. The experimental data of biosorption process were analyzed using pseudo-first order, pseudo-second order kinetic models. The equilibrium biosorption isotherms showed that the three studied biosorbents possess high affinity and sorption capacity for Cu(II), Co(II) and Fe(III) ions. Rice husk showed more efficiency than palm leaf and water hyacinth. Adsorption of Cu(II) and Co(II) was more efficient in alkaline medium (pH 9) than neutral medium due to the high solubility of metal ion complexes. The metal removal efficiency of each biosorbent was correlated to its chemical structure. DTA studies showed formation of metal complex between the biosorbents and the metal ions. The obtained results showed that the tested biosorbents are efficient and alternate low-cost biosorbent for removal of heavy metal ions from aqueous media.

Structural and biological behaviors of some nonionic Schiff-base amphiphiles and their Cu(II) and Fe(III) metal complexes.

Novel series of nonionic Schiff bases was synthesized and characterized using microelemental analysis, FTIR and (1)H NMR spectra. These Schiff bases and their complexes with Cu and Fe have been evaluated for their antibacterial activity against bacterial species such as Staphylococcus aureus, Pseudomonas aureus, Candida albi, Bacillus subtilis and Escherichia coli and their fungicidal activity against Aspcrgillus niger and Aspcrgillus flavus. The results of the biocidal activities showed high potent action of the synthesized Schiff bases towards both bacteria and fungi. Furthermore, complexation of these Schiff bases by Cu(II) and Fe(III) show the metal complexes to be more antibacterial and antifungal than the Schiff bases. The results were correlated to the surface activity and the transition metal type. The mode of action of these complexes was discussed.

Biocidal activity of some Mannich base cationic derivatives.

A novel series of cationic surfactants was prepared based on Mannich base (produced from the condensation of piperidine and/or morpholine as secondary amine and paraformaldehyde in the presence of 8-hydroxyquinoline). The chemical structures of the synthesized cationic surfactants were confirmed using elemental analyses, FTIR spectroscopy and 1H NMR. Surface activities of the prepared surfactants were measured including: surface tension (gamma), critical micelle concentration (CMC), effectiveness (pi(CMC)), efficiency (Pc20), maximum surface excess (Gamma(max)), minimum surface area (A(min)), interfacial tension (gamma(IT)), emulsification power and foaming power at 25 degrees C. The structural influences on their surface activities and adsorption free energy were discussed. The synthesized cationic surfactants were evaluated for their biocidal activity towards Gram +ve bacteria (Staph. Cocu., Bacillus), Gram -ve bacteria (Salmonella, E. coli), fungi (A. terrus., A. flav.) and yeast (Candida) at 1.0, 2.5 and 5.0mg/mL, respectively. The target compounds showed good inhibition towards Gram +ve bacteria, Gram -ve bacteria and yeast. Meanwhile, excellent fungicidal results were obtained against the various types of fungi under investigation.