Enhanced artificial intelligence for electrochemical sensors in monitoring and removing of azo dyes and food colorant substances.

It is necessary to determine whether synthetic dyes are present in food since their excessive use has detrimental effects on human health. For the simultaneous assessment of tartrazine and Patent Blue V, a novel electrochemical sensing platform was developed. As a result, two artificial azo colorants (Tartrazine and Patent Blue V) with toxic azo groups (-NN-) and other carcinogenic aromatic ring structures were examined. With a low limit of detection of 0.06 µM, a broad linear concentration range 0.09µM to 950µM, and a respectable recovery, scanning electron microscopy (SEM) was able to reveal the excellent sensing performance of the suggested electrode for patent blue V. The electrochemical performance of an electrode can be characterized using cyclic and differential pulse voltammetry, and electrochemical impedance spectroscopy. Moreover, the classification model was created by applying binary classification assessment using enhanced artificial intelligence comprises of support vector machine (SVM) and Genetic Algorithm (GA), respectively, a support vector machine and a genetic algorithm, which was then validated using the 50 dyes test set. The best binary logistic regression model has an accuracy of 83.2% and 81.1%, respectively, while the best SVM model has an accuracy of 90.3% for the training group of samples and 81.1% for the test group (RMSE = 0.644, R2 = 0.873, C = 205.41, and = 5.992). According to the findings, Cu-BTC MOF (copper (II)-benzene-1,3,5-tricarboxylate) has a crystal structure and is tightly packed with hierarchically porous nanomaterials, with each particle's edge measuring between 20 and 37 nm. The suggested electrochemical sensor's analytical performance is suitable for foods like jellies, condiments, soft drinks and candies.

Volatile Nitrogenous Compounds from Bacteria: Source of Novel Bioactive Compounds.

Bacteria can produce nitrogenous compounds via both primary and secondary metabolic processes. Many bacterial volatile nitrogenous compounds produced during the secondary metabolism have been identified and reported for their antioxidant, antibacterial, antifungal, algicidal and antitumor activities. The production of these nitrogenous compounds depends on several factors, including the composition of culture media, growth conditions, and even the organic solvent used for their extraction, thus requiring their identification in specific conditions. In this review, we describe the volatile nitrogenous compounds produced by bacteria especially focusing on their antimicrobial activity. We concentrate on azo-compounds mainly pyrazines and pyrrolo-pyridines reported for their activity against several microorganisms. Whenever significant, extraction and identification methods of these compounds are also mentioned and discussed. To the best of our knowledge, this is first review describing volatile nitrogenous compounds from bacteria focusing on their biological activity.

Azodyrecins A-C: Azoxides from a Soil-Derived Streptomyces Species.

Azoxy compounds belong to a small group of natural products sharing a common functional group with the general structure RN = N+(O-)R. Three new azoxides, azodyrecins A-C (1-3), were isolated from a soil-derived Streptomyces sp. strain P8-A2. The cis-alkenyl unit in 1-3 was found to readily isomerize to the trans-congeners (4-6). The structures of the new compounds were determined by detailed spectroscopic (1D/2D NMR) and HRMS data analysis. Azodyrecins belong to a new class of natural azoxy compounds and are proposed to derive from l-alanine and alkylamines. The absolute configurations of 1-6 were defined by comparison of ECD spectra. While no antimicrobial effects were observed for 1 against Staphylococcus aureus, Vibrio anguillarum, or Candida albicans, azodyrecin B (2) exhibited cytotoxicity against the human leukemia cell line HL-60 with an IC50 value of 2.2 µM.

Chemical constituents from wetland soil fungus Penicillium oxalicum GY1.

A new azo compound, penoxalin (1), a new isochroman carboxylic acid, penisochroman B (3), two new natural products, penisochroman A (2) and 2,6-dihydroxy-4-[(2R)-2-hydroxyheptyl] benzoic acid (4), together with four known compounds (5-8) were isolated from wetland soil fungus Penicillium oxalicum GY1. All structures were elucidated by extensive NMR spectroscopic evidences together with mass spectrometry. The absolute configuration of penoxalin (1) was determined by calculated ECD spectrum, while the absolute configuration of new natural product penisochroman A (2) was established for the first time by single crystal X-ray diffraction. In addition, all compounds were evaluated for their cytotoxic activity in vitro. 2, 6-Dihydroxy-4-[(2R)-2-hydroxyheptyl] benzoic acid (4) displayed significant cytotoxicity against human esophageal carcinoma cells OE19 with an IC50 value of 5.50 µM.

TiO2 nanoparticles and C-Nanofibers modified magnetic Fe3O4 nanospheres (TiO2@Fe3O4@C-NF): A multifunctional hybrid material for magnetic solid-phase extraction of ibuprofen and photocatalytic degradation of drug molecules and azo dye.

Accurate sensitive analysis of drug ingredient substances in biological, pharmaceutical and environmental samples and removal of drug ingredient substances in environmental samples owngreat importance for sustaining viability. The realization of these processes using a single material offers significant advantages in terms of cost, time and ease of use. In this study, TiO2 nanoparticles and C-Nanofibers modified magnetic Fe3O4 nanospheres (TiO2@Fe3O4@C-NFs) synthesized as a multifunctional material employing a simple hydrothermal synthesis method. This innovative material was exploited in the magnetic solid-phase extraction (MSPE) method for the preconcentration of ibuprofen and photocatalytic degradation of antibiotics, non-steroidal anti-inflammatory drugs (NSAIDs), and azo dye. To our knowledge, no studies have been previously conducted using the same material as magnetic solid-phase extraction adsorbent and magnetically separable photocatalyst. The characterization of TiO2@Fe3O4@C-NFs was carried out by XRD, FE-SEM, EDX and Raman techniques. The main analytical parameters affecting MSPE performance of ibuprofen such as pH, sorbent amount eluent type and volume and sample volume were optimized. The optimum values of the method were determined at the following parameters: pH 4.0, adsorbent amount 150 mg and eluent 2 mL of acetone. Ibuprofen analysis after MSPE was carried out using a high-performance liquid chromatography diode array detection system (HPLC-DAD). The photocatalytic degradation efficiencies of TiO2@Fe3O4@C-NF hybrid material for probe-analytes reached 80-100% and the complete degradation attained within the range of 8-125 min under UV irradiation. Simple preparation, practical isolation from solutions, high efficiency, reproducibility, and sustainability are the main advantages of the TiO2@Fe3O4@C-NFs for MSPE and photocatalytic degradation applications.

Efficient removal of acid orange 7 using a porous adsorbent-supported zero-valent iron as a synergistic catalyst in advanced oxidation process.

This study focuses on the synthesis of granular red mud reinforced by zero-valent iron (Fe@GRM) and its application for the removal acid orange 7 (AO7) from aqueous solution. Then ZVI is employed as a catalyst for the activation of persulfate (PS) to produce sulfate radicals (SO4•-) that are produced at 900 °C in an anoxic atmosphere using the direct reduction of iron oxide in the red mud with maize straw as the reductant. Furthermore, scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) are used to illustrate the morphology and porous structure of the Fe@GRM. The X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) revealed that Fe@GRM was loaded with zero-valent iron. This characterization confirmed that the Fe@GRM was a porous structure material that contained zero-valent iron. The influence of conditions for AO7 elimination, including initial pH, Fe@GRM dosage, initial AO7 concentrations, and temperature, is also investigated. The removal efficiency of AO7 was 90.78% using Fe@GRM/PS, while only 18.15% was removed when Fe@GRM was used alone. The degradation kinetics were well fitted to a pseudo-first-order kinetic model, and the rate of removal increased with temperature, demonstrating an endothermic elimination process. The Arrhenius activation energy of the process was 20.77 kJ/mol, which indicated that the reduction of AO7 was a diffusion-mediated reaction. Fe@GRM is a low-cost material that demonstrated outstanding performance with great potential for wastewater treatment.

Preparation of novel aminated chitosan schiff's base derivative for the removal of methyl orange dye from aqueous environment and its biological applications.

A novel, eco-friendly aminated chitosan Schiff's base (ACSSB@ZnO) was developed and utilized to remove MO from aqueous environment. The impact of different significant parameters, for example, pH (3-11), adsorbent dose (0.1-0.6 g), contact time (0-120 min), and temperature (303-323 K) have been explored by batch process. Kinetic data was illustrated by pseudo-second-order model and the isotherms fitted well with Langmuir isotherm model. The highest sorption capacity of ACSSB@ZnO was observed to be 111.11 mg/g at 323 K. Positive enthalpy and entropy values demonstrated that the MO adsorption procedure was an endothermic. Negative Gibbs free energy values implied the spontaneous nature of the adsorption system. Moreover, reusability experiments were studied and it can be regenerated by using NaOH as effluent.

Potential Use of Probiotic Consortium Isolated from Kefir for Textile Azo Dye Decolorization.

Azo dyes are recalcitrant pollutants, which are toxic, carcinogenic, mutagenic and teratogenic, that constitute a significant burden to the environment. The decolorization and the mineralization efficiency of Remazol Brillant Orange 3R (RBO 3R) was studied using a probiotic consortium (Lactobacillus acidophilus and Lactobacillus plantarum). Biodegradation of RBO 3R (750 ppm) was investigated under shaking condition in Mineral Salt Medium (MSM) solution at pH 11.5 and temperature 25°C. The bio-decolorization process was further confirmed by FTIR and UV-Vis analysis. Under optimal conditions, the bacterial consortium was able to decolorize the dye completely (>99%) within 12 h. The color removal was 99.37% at 750 ppm. Muliplex PCR technique was used to detect the Lactobacillus genes. Using phytotoxicity, cytotoxicity, mutagenicity and biototoxicity endpoints, toxicological studies of RBO 3R before and after biodegradation were examined. A toxicity assay signaled that biodegradation led to detoxification of RBO 3R dye.

One-pot synthesis of multi-functional and environmental friendly tannic acid polymer with Fe3+ and formaldehyde as double crosslinking agents for selective removal of cation pollutants.

A novel multi-functional and environmental friendly tannic acid polymer (Fe3+-TA-HCHO) with Fe3+ and formaldehyde as double crosslinking agents together with cysteine as heteroatom source was prepared by a one-pot hydrothermal method. Characterization with transmission electron microscope (TEM), scanning electron microscopy (SEM), Fourier transform infrared spectrometer (FT-IR), and elemental analysis demonstrated that the Fe3+-TA-HCHO possessed uniform structure and particle size as well as plentiful functional groups. The resulted Fe3+-TA-HCHO material as a adsorbent to remove methylene blue, sunset yellow, Pb2+, Hg2+, and AsO33- from water. The results suggested that Fe3+-TA-HCHO polymer (pHpzc is 2.33) showed different adsorption properties for anionic pollutants (sunset yellow and AsO33-) and cationic pollutants (methylene blue, Pb2+, and Hg2+). The material exhibited remarkable selectivity for adsorption and separation of pollutants. The maximum adsorption capacities calculated from Langmuir model for methylene blue, Pb2+, and Hg2+ were 154.32, 819.67, and 699.30 mg g-1, respectively. This is the first time that tannic acid polymer is synthesized by double crosslinking method, which not only developed a promising adsorbent for selective removal of cation pollutants, but also opened up a new avenue for synthesis and application of tannic acid polymer.

A facile synthesis of CuAg nanoparticles on highly porous ZnO/carbon black-cellulose acetate sheets for nitroarene and azo dyes reduction/degradation.

A facile and highly porous heterostructure nanocomposite was designed for the support of zero-valent metal nanoparticles. This nanocomposite comprising of ZnO/carbon black (ZnO/CB) embedded in cellulose acetate polymer (CA), named as ZCA sheet, supported the metallic Cu, Ag and bimetallic CuAg nanoparticles (NPs). The ZnO/CB was incorporated to CA polymer host molecule in 3, 4 and 5 wt% and are designated as ZCA-3, ZCA-4 and ZCA-5. The catalytic tunability was evaluated for CuAg/ZCA-5 by adjusting the concentration of Cu and Ag ions in different molar ratio. Therefore, the CuAg/ZCA-5 was further selected for the removal of eight model pollutants comprising of o-nitrophenol (ONP), m-nitrophenol (MNP), p-nitrophenol (PNP), 2,6-dinitrophenol (DNP), methyl orange (MO), congo red (CR), methylene blue (MB) and rhodamine B (RB). The Kapp value for PNP was 1.9 × 10-1 min-1 and 9.0 × 10-2 min-1 for MO. Among the various nitrophenols, the rate of reaction with CuAg/ZCA-5 followed the ordered as PNP ˃ ONP ˃ MNP ˃ DNP, while methyl orange (MO) is degraded faster as compared to other dyes. The morphology, shape, elemental analysis, functional groups and peak crystallinity were scrutinized through FESEM, EDS, ATR-FTIR and XRD respectively.

Modified nickel ferrite nanocomposite/functionalized chitosan as a novel adsorbent for the removal of acidic dyes.

As a new type of magnetic adsorbent, a nickel ferrite nanocomposite modified by functionalized chitosan was developed to remove methyl orange and Congo red from aqueous solutions. This new adsorbent was characterized and utilizing batch adsorption approach, the mechanism of methyl orange and Congo red removal were probed. Following that the study on pertinent parameters which could influence the efficiency of the dyes removal, i.e. pH of the solution, initial dye concentration, dose of the adsorbent, and contact time were accomplished in order to arrive their optimized values by using response surface methodology. In addition, kinetics and isotherm studies were conducted on the developed system. Langmuir model was used to probe adsorption isotherm, acquiring adsorption capacity of 551.2 and 274.7 mg g-1 for methyl orange and Congo red, respectively. Both of methyl orange and Congo red adsorption kinetics obeyed a pseudo-second-order kinetic model, indicating that adsorption was the rate-limiting step and only 5 min was required to remove 50% of dyes. The fitting of experimental data was fulfilled with intra-particle diffusion reaching to conclusion that the adsorption kinetic could be controlled simultaneously by film diffusion and intra-particle diffusion. Furthermore, the desorption studies of dyes showed that the adsorbent is reusable.

Crown ether microfunctionalized carbon nanotubes for dispersive micro-solid-phase extraction of sudan dyes and their metabolites.

In this study, dispersive micro solid phase extraction (DMSPE) combined with ultrahigh-performance liquid chromatography coupled with quadrupole time-of-flight tandem mass spectrometry method was established to extract and determine sudan dyes and their metabolites in real samples. The crown ether microfunctionalized multi-walled carbon nanotubes (MWCNTs) was applied as the sorbent in DMSPE procedure. Several experimental parameters that can effect the extraction performance of the DMSPE method were investigated separately by a univariate method. The validation data showed that the limits of detection were in the range of 0.084-13.13 µg/kg, the mean recoveries were ranged from 80.15 to 103.58% for six samples. Compared with other published methods, the proposed method was more effective, more time-saving and more eco-friendly. Finally, the developed method was successfully applied to enrich and detect sudan dyes and their metabolites in real samples.

Preliminary Studies of Synthetic Dye Adsorption on Iron Sludge and Activated Carbons.

There is great interest in the search for multifunctional waste-based materials that may be applied as environmentally friendly adsorbents. Iron-rich sludge from ground drinking-water treatment plants may be considered a potential adsorbent for various water contaminants. This material is generated during ground water purification because of the excess of metal ions in water (Fe, Mn). In practice, this sludge is frequently disposed of as waste material and, so far, is not commonly applied as the adsorption base. Our research aims to explore the adsorption potential of iron sludge for selected synthetic dyes, including malachite green, ponceau 4R, and brilliant blue FCF. Experimental data were performed using iron sludge collected from the Groundwater Treatment Plant in Koszalin, Poland, and comparing it with adsorption properties of commercial activated carbons (Norit SA Super and Norit CA 1). The kinetics, adsorption isotherms, and temperature influence on the removal of target dyes were investigated and discussed. Preliminary experimental data have revealed that iron sludge can be considered an adsorbent for the removal of cationic dyes.

Aqueous biphasic systems formed by deep eutectic solvent and new-type salts for the high-performance extraction of pigments.

Deep eutectic solvent (DES) composed of polypropylene glycol 400 (PPG 400) and tetrabutylammonium bromide (TBAB) was combined with a series of new-type salts such as quaternary ammonium salts, amino acid and polyols to form Aqueous Biphasic Systems (ABSs). Phase-forming ability of the salts was investigated firstly. The results showed that polyols had a relatively weak power to produce phases within studied scopes. And the shorter of carbon chain length of salts, the easier to obtain phase-splitting. Then partitioning of three pigments in PPG 400/betaine-based ABSs was addressed to investigate the effect of pigments' hydrophobicity on extraction efficiency. It was found that an increase in hydrophobicity contributed to the migration of pigments in the DES-rich phase. On the other hand, with a decline in phase-forming ability of salts, the extraction efficiency of the whole systems started to go down gradually. Based on the results, selective separation experiment was conducted successfully in the PPG 400/betaine-based systems, including more than 93.00% Sudan Ⅲ in the top phase and about 80.00% sunset yellow FCF/amaranth in the bottom phase. Additionally, ABSs constructed by DES/betaine for partitioning amaranth were further utilized to explore the performances of influence factors and back extraction. It can be concluded that after the optimization above 98.00% amaranth was transferred into the top phase. And 67.98% amaranth can be transferred into the bottom phase in back-extraction experiment. At last, dynamic light scattering (DLS) and transmission electron microscope (TEM) were applied to probe into extraction mechanism. The results demonstrated that hydrophobicity played an important role in the separation process of pigments. Through combining with new-type DES, this work was devoted to introducing plentiful salts as novel compositions of ABSs and providing an eco-friendly extraction way for partitioning pigments, which boosted development of ABSs in the monitoring food safety field.

Development and optimization of a novel sample preparation method cored on functionalized nanofibers mat-solid-phase extraction for the simultaneous efficient extraction of illegal anionic and cationic dyes in foods.

A simple and efficient three-step sample preparation method was developed and optimized for the simultaneous analysis of illegal anionic and cationic dyes (acid orange 7, metanil yellow, auramine-O, and chrysoidine) in food samples. A novel solid-phase extraction (SPE) procedure based on nanofibers mat (NFsM) was proposed after solvent extraction and freeze-salting out purification. The preferred SPE sorbent was selected from five functionalized NFsMs by orthogonal experimental design, and the optimization of SPE parameters was achieved through response surface methodology (RSM) based on the Box-Behnken design (BBD). Under the optimal conditions, the target analytes could be completely adsorbed by polypyrrole-functionalized polyacrylonitrile NFsM (PPy/PAN NFsM), and the eluent was directly analyzed by high-performance liquid chromatography-diode array detection (HPLC-DAD). The limits of detection (LODs) were between 0.002 and 0.01 mg kg-1, and satisfactory linearity with correlation coefficients (R > 0.99) for each dye in all samples was achieved. Compared with the Chinese standard method and the published methods, the proposed method was simplified greatly with much lower requirement of sorbent (5.0 mg) and organic solvent (2.8 mL) and higher sample preparation speed (10 min/sample), while higher recovery (83.6-116.5%) and precision (RSDs < 7.1%) were obtained. With this developed method, we have successfully detected illegal ionic dyes in three common representative foods: yellow croaker, soybean products, and chili seasonings. Graphical abstract Schematic representation of the process of the three-step sample preparation.

Highly efficient simultaneous adsorption and biodegradation of a highly-concentrated anionic dye by a high-surface-area carbon-based biocomposite.

Mesoporous high-surface-area activated carbon (MHSA-AC), which has a honeycomb structure, was produced from coconut shells by simultaneous chemical and physical activation and used for the rapid adsorption of an anionic dye, namely acid orange 10 (AO10), from water. Owing to its porosity and high Brunauer-Emmett-Teller surface area (2283.91 m2g-1), MHSA-AC is a highly efficient adsorbent. It also has good biocompatibility and is a good immobilization carrier; the grooves on the MHSA-AC surface facilitate immobilization. Here, a new, highly efficient, and environmentally friendly simultaneous adsorption and biodegradation (SAB) process was developed. Highly concentrated AO10 (6000 mg L-1, 20 mL) was removed with an efficiency of 100% (pH = 7, 35 °C) by SAB using cells immobilized on MHSA-AC (500 mg). The immobilized cells were used directly, without pretreatment; the SAB process is therefore simple and has good potential for application in the treatment of dyes in industrial wastewater.

Enhanced bioelectricity generation and azo dye treatment in a reversible photo-bioelectrochemical cell by using novel anthraquinone-2,6-disulfonate (AQDS)/MnOx-doped polypyrrole film electrodes.

A novel anthraquinone-2,6-disulfonate/MnOx-doped polypyrrole film (AQDS/Mn/PPy) electrode was prepared by one-step electropolymerization method and was used to improve performance of a reversible photo-bioelectrochemical cell (RPBEC). The RPBEC was operated in polarity reversion depended on dark/light reaction of alga Chlorella vulgaris by which sequential decolorization of azo dye and mineralization of decolorization products coupled with bioelectricity generation can be achieved. The results showed that formation of uniform AQDS/Mn/PPy film significantly enhanced electroactive surface area and electrocatalytic activity of carbon electrode. The RPBEC with AQDS/Mn/PPy electrodes demonstrated 77% increases in maximum power and 73% increases in Congo red decolorization rate before polarity reversion, and 198% increases in maximum power and 138% increases in decolorization products mineralization rate after polarity reversion, respectively, compared to the RPBEC with bare electrode. This was resulted from simultaneous dynamics improvement in half-reaction rate of anode and photo-biocathode due to enhanced electron transfer and algal-bacterial biofilm formation.

Cross-linked beads of activated oil palm ash zeolite/chitosan composite as a bio-adsorbent for the removal of methylene blue and acid blue 29 dyes.

Cross-linked beads of activated oil palm ash zeolite/chitosan (Z-AC/C) composite were prepared through the hydrothermal treatment of NaOH activated oil palm ash followed by beading with chitosan. The effects of initial dye concentration (50-400mg/L), temperature (30°C-50°C) and pH (3-13) on batch adsorption of methylene blue (MB) and acid blue 29 (AB29) were studied. Adsorption of both dyes was better described by Pseudo-second-order kinetics and Freundlich isotherm model. The maximum adsorption capacities of Z-AC/C were 151.51, 169.49, and 199.20mg/g for MB and 212.76, 238.09, and 270.27mg/g for AB29 at 30°C, 40°C, and 50°C, respectively.

A highly efficient immobilized ZnO/Zn photoanode for degradation of azo dye Reactive Green 19 in a photocatalytic fuel cell.

Photocatalytic fuel cell (PFC) is a potential wastewater treatment technology that can generate electricity from the conversion of chemical energy of organic pollutants. An immobilized ZnO/Zn fabricated by sonication and heat attachment method was applied as the photoanode and Pt/C plate was used as the cathode of the PFC in this study. Factors that affect the decolorization efficiency and electricity generation of the PFC such as different initial dye concentrations and pH were investigated. Results revealed that the degradation of Reactive Green 19 (RG19) was enhanced in a closed circuit PFC compared with that of a opened circuit PFC. Almost 100% decolorization could be achieved in 8 h when 250 mL of 30 mg L-1 of RG19 was treated in a PFC without any supporting electrolyte. The highest short circuit current of 0.0427 mA cm-2 and maximum power density of 0.0102 mW cm-2 was obtained by PFC using 30 mg L-1 of RG19. The correlation between dye degradation, conductivity and voltage output were also investigated and discussed.

Delaminated montmorillonite with iron(III)-TiO2 species as a photocatalyst for removal of a textile azo-dye from aqueous solution.

A set of mesoporous delaminated montmorillonites containing iron(III)-titanium oxide species was synthesized using two minerals: a bentonite as support and an ilmenite as source of Fe-TiO2 species. Several values of both sulphuric acid concentration and temperature were employed to extract Fe-TiO2 species from an ilmenite. Analyses by X-ray fluorescence, X-ray diffraction, scanning electron microscopy and nitrogen adsorption-desorption confirmed the successful formation of delaminated (or exfoliated) mesoporous structures. Optical properties of solids were determined by UV-Vis diffuse reflectance spectroscopy, and their band gap energy values were also calculated. A small UV-shift of band gap values regarding that of commercial photo-active TiO2 was detected as consequence of the quantum size effect, suggesting that photocatalytic experiments should be performed under UV-radiation assistance. The synthesized solids showed good activity in the photocatalytic oxidation of a textile dye (reactive yellow 145: RY 145), achieving conversions higher than 70% and chemical oxygen demand removal between 60% and 80%.