Controlling pH-Sensitive Chemical Reactions Pathways with Light - a Tale of Two Photobases: an Arrhenius and a Brønsted.

Light-gated chemical reactions allow spatial and temporal control of chemical processes. Here, we suggest a new system for controlling pH-sensitive processes with light using two photobases of Arrhenius and Brønsted types. Only after light excitation do Arrhenius photobases undergo hydroxide ion dissociation, while Brønsted photobases capture a proton. However, none can be used alone to reversibly control pH due to the limitations arising from excessively fast or overly slow photoreaction timescales. We show here that combining the two types of photobases allows light-triggered and reversible pH control. We show an application of this method in directing the pH-dependent reaction pathways of the organic dye Alizarin Red S simply by switching between different wavelengths of light, i. e., irradiating each photobase separately. The concept of a light-controlled system shown here of a sophisticated interplay between two photobases can be integrated into various smart functional and dynamic systems.

Evaluation of semi-quantitative colorimetric assays based on loop-mediated isothermal amplification indicators by using image analysis.

Colorimetric assays are some of the most convenient detection methods, creating discoloration in solutions that is visible to the naked eye. However, colorimetric reactions have some limitations regarding the variability in the color perception of individuals caused by factors such as color blindness, experience, and gender. Semi-quantitative chromatic analysis has been used as an alternative method to differentiate between two colors and accurately interpret the results from a numerical value, with high confidence. Therefore, we developed and determined the optimal model between Red-Green-Blue (RGB) and Commission Internationale de l'Eclairage (CIE) Lab color spaces to establish a semi-quantitative colorimetric assay via image analysis by the ImageJ program for loop-mediated isothermal amplification (LAMP), using the dyes malachite green and phenol red. The semi-quantitative colorimetric assays using the color distance values of the CIELab color space (ΔEab) were more suitable than those using the RGB color space (ΔERGB) for chromatic differentiation between positive and negative reactions in both indicator dyes, demonstrating the feasibility of this assay to be applied in the detection of a wide range of pathogens and infectious diseases.

Synthesis of SiO2@Ag Nanocomposite for Investigating Metal-Enhanced Fluorescence and Surface-Enhanced Raman Spectroscopy.

SiO2@Ag nanocomposite (NC) has been synthesized by the chemical reduction and StÓ§ber method for Metal-enhanced fluorescence (MEF) of Rhodmine 6G (R6G) and Surface-enhanced Raman spectroscopy (SERS) of Malachite green (MG). As-synthesized SiO2@Ag NC indicated SiO2 nanosphere (NS) and Ag nanoparticle (NP) morphologies. The SiO2@Ag NC was high quality with a well-defined crystallite phase with average sizes of 24 nm and 132 nm for Ag NP and SiO2 NC, respectively. By using SiO2@Ag NC, the photoluminescence (PL) intensity of the R6G (at 59.17 ppm) was increased approximately 133 times. The SERS of the MG (at 1.0 ppm) with SiO2@Ag NC as substrate clearly observed vibrational modes in MG dye at 798, 916, 1172, 1394, and 1616 cm-1. As a result, the SERS enhancement factor (EFSERS) at 1172 cm-1 obtained 6.3 × 106. This initial study points to the potential of SiO2@Ag NC as a promising material for MEF and SERS substrates to detect dyes at low concentrations.

References for Small Fluorescence Quantum Yields.

Three compounds with fluorescence quantum yields in the range of 10- 5 to 10- 4 and emission spectra covering the UV/Vis spectral range are suggested as new references for the determination of small fluorescence quantum yields. The compounds are thymidine (dT) in water, dibenzoylmethane (DBM) in ethanol, and malachite green chloride (MG) in water, representing the blue, green, and red regions of the spectrum, respectively. All compounds are easily handled, photostable, and commercially available. Furthermore, these compounds exhibit a mirror-image symmetry between their absorption and fluorescence spectra. This symmetry, along with closely aligned fluorescence excitation and absorption spectra, confirms that the observed emissions originate from the compounds themselves. The fluorescence quantum yields were determined via a relative approach as well as Strickler-Berg analysis in conjunction with time resolved fluorescence spectroscopy. Within the respective error margins, the two approaches yielded identical results.

Controlled solvothermal synthesis of self-assembled SrTiO3 microstructures for expeditious solar-driven photocatalysis dye effluents degradation.

In this work, the self-assembled SrTiO3 (STO) microstructures were synthesized via a facile one-step solvothermal method. As the solvothermal temperature increased from 140 °C to 200 °C, the STO changed from a flower-like architecture to finally an irregularly aggregated flake-like morphology. The photocatalytic performance of as-synthesized samples was assessed through the degradation of rhodamine B (RhB) and malachite green (MG) under simulated solar irradiation. The results indicated that the photocatalytic performance of STO samples depended on their morphology, in which the hierarchical flower-like STO synthesized at 160 °C demonstrated the highest photoactivities. The photocatalytic enhancement of STO-160 was benefited from its large surface area and mesoporous configuration, hence facilitating the presence of more reactive species and accelerating the charge separation. Moreover, the real-world practicality of STO-160 photocatalysis was examined via the real printed ink wastewater-containing RhB and MG treatment. The phytotoxicity analyses demonstrated that the photocatalytically treated wastewater increased the germination of mung bean seeds, and the good reusability of synthesized STO-160 in photodegradation reaction also promoted its application in practical scenarios. This work highlights the promising potential of tailored STO microstructures for effective environmental remediation applications.

Zinc oxide decorated plantain peel activated carbon for adsorption of cationic malachite green dye: Mechanistic, kinetics and thermodynamics modeling.

Reports have shown that malachite green (MG) dye causes various hormonal disruptions and health hazards, hence, its removal from water has become a top priority. In this work, zinc oxide decorated plantain peels activated carbon (ZnO@PPAC) was developed via a hydrothermal approach. Physicochemical characterization of the ZnO@PPAC nanocomposite with a 205.2 m2/g surface area, porosity of 614.68 and dominance of acidic sites from Boehm study established the potency of ZnO@PPAC. Spectroscopic characterization of ZnO@PPAC vis-a-viz thermal gravimetric analyses (TGA), Fourier Transform Infrared Spectroscopy (FTIR), Powdered X-ray Diffraction (PXRD), Scanning Electron Microscopy and High Resolution - Transmission Electron Microscopy (HR-TEM) depict the thermal stability via phase transition, functional group, crystallinity with interspatial spacing, morphology and spherical and nano-rod-like shape of the ZnO@PPAC heterostructure with electron mapping respectively. Adsorption of malachite green dye onto ZnO@PPAC nanocomposite was influenced by different operational parameters. Equilibrium data across the three temperatures (303, 313, and 323 K) were most favorably described by Freundlich indicating the ZnO@PPAC heterogeneous nature. 77.517 mg/g monolayer capacity of ZnO@PPAC was superior to other adsorbents compared. Pore-diffusion predominated in the mechanism and kinetic data best fit the pseudo-second-order. Thermodynamics studies showed the feasible, endothermic, and spontaneous nature of the sequestration. The ZnO@PPAC was therefore shown to be a sustainable and efficient material for MG dye uptake and hereby endorsed for the treatment of industrial effluent.

Enhancing Fenton-like reaction mediating performance of covalent organic frameworks through porosity modification.

Covalent organic framework (COF) catalytic photocatalysts mediating Fenton-like reactions have been applied to the treatment of organic dyes in printing and dyeing wastewater. However, the photocatalytic performance of original COF is often unsatisfactory. This study investigated the impact of porosity modification strategies on the performance of COF photocatalysts in mediating the removal of organic dyes via Fenton-like reaction. Porosity modification was achieved by increasing the concentration of acetic acid (HAc) catalyst during COF preparation. The modified TAPB-DMTA COF (12M COF) exhibited excellent adsorption and photocatalytic properties. The Fenton-like reaction mediated by 12M COF photocatalysis removed nearly 96% of malachite green (MG) within 20 min, with a rate constant of 0.091 min-1, which was 2.9 and 6.5 times higher than that of g-C3N4 and original COF under the same reaction conditions, respectively. Additionally, the modulation mechanism of porosity modification on COF photocatalysis was explored. The conduction band (CB) of COF was reduced from -0.14 eV to -0.38 eV after porosity modification, facilitating the generation of longer-lived O2•- in the reaction system, which was conducive to efficient MG removal. Anti-interference experiments showed that the photocatalytic Fenton-like reaction system based on 12 M COF was less affected by common anions, cations and dissolved organics, while maintaining a high MG removal rate in tap water, mid-water, secondary clarifier effluent and river water. In summary, porosity modification was an effective strategy to improve the catalytic performance of original COFs. This study presented an efficient metal-free photocatalyst modification strategy for the Fenton-like reaction while avoiding the production of toxic by-products during dye degradation.

Removal of malachite green from water: Comparison of adsorption in a residue-derived AC versus photocatalytic oxidation with TiO2 and study of the adsorption-photocatalysis synergy.

The literature rarely compiles studies devoted to the removal of pollutants in aqueous media comparing adsorption and photocatalytic degradation, and does not pay enough attention to the analysis of combined adsorption-photocatalytic oxidation processes. In the present manuscript, the removal of malachite green (MG) from aqueous solutions has been investigated in three different sustainable scenarios: i) adsorption on activated carbon (AC) derived from a residue, luffa cylindrica, ii) photocatalytic oxidation under simulated solar light using titanium dioxide (TP) and iii) combined adsorption-photocatalytic oxidation using TP-AC (70/30 wt./wt.) under simulated solar light. The study has revealed that in the three scenarios and studied conditions, the total removal of this endocrine-disrupting dye from the solution takes place in the assayed time, 2 h, in some cases just in a few minutes. MG adsorption in the AC is a very fast and efficient removal method. MG photocatalytic oxidation with TP also occurs efficiently, although the oxidized MG is not totally mineralized. MG removal using the TP-AC composite under simulated solar light occurs only slightly faster to the MG adsorption in the AC, being adsorption the dominating MG removal mechanism for TP-AC. Thus, more than 90% of the removed MG with TP-AC under simulated solar light is adsorbed in this carbon-containing composite. The obtained results highlight the interest in adsorption, being the selection of the most suitable removal method dependent on several factors (i.e., the cost of the AC regeneration, for adsorption, or the toxicity of the intermediate oxidation species, for photooxidation). Paying attention to MG photooxidation with TiO2, comparison of two working photodegradation schemes shows that the direct photodegradation of MG from solution, avoiding any initial dark equilibrium period, is more efficient from a time perspective. The use of scavengers has proved that MG photodegradation occurs via an oxidation mechanism dominated by superoxide anion radicals.

Carboxyl-functionalized covalent organic frameworks for the extraction of malachite green and crystal violet in environmental water samples prior to quantification by high-performance liquid chromatography.

In this study, monodisperse, uniform, and spherical covalent organic frameworks (COFs) were synthesized using 1,3,5-tris (4-aminophenyl) benzene and 1,3,5-tricarboxaldehyde benzene at room temperature. Post-modification of 6-aminocaproic acid on the COFs yielded carboxyl-modified COFs (COFs-COOH). The modification enhanced the hydrophilicity and adsorption efficiencies of COFs-COOH for malachite green (MG) and crystal violet (CV). A COFs-COOH-based dispersive solid-phase extraction coupled with high-performance liquid chromatography was developed for the analysis of MG and CV. The method showed a linear range from 10 to 1000 ng/mL with detection limits of 1.82 and 0.70 ng/mL for MG and CV detection, respectively. The recoveries of MG and CV from water samples collected from fish farms and markets ranged from 91.63% to 107.10% with relative standard deviations below 5%. Reproducibility tests demonstrated that the adsorption efficiencies of COFs-COOH were maintained at above 85.86% over 15 cycles. The study verified the potential of COFs-COOH as sorbents for the enrichment and separation of triphenylmethane dyes from complex samples.

Novel small multidrug resistance protein Tmt endows the Escherichia coli with triphenylmethane dyes bioremediation capability.

Dye contamination in printing and dyeing wastewater has long been a major concern due to its serious impact on both the environment and human health. In the quest for bioremediation of these hazardous dyes, biological resources such as biodegradation bacteria and enzymes have been investigated in severely polluted environments. In this context, the triphenylmethane transporter gene (tmt) was identified in six distinct clones from a metagenomic library of the printing and dyeing wastewater treatment system. Escherichia coli expressing tmt revealed 98.1% decolorization efficiency of triphenylmethane dye malachite green within 24 h under shaking culture condition. The tolerance to malachite green was improved over eightfold in the Tmt strain compared of the none-Tmt expressed strain. Similarly, the tolerance of Tmt strain to other triphenylmethane dyes like crystal violet and brilliant green, was improved by at least fourfold. Site-directed mutations, including A75G, A75S and V100G, were found to reinforce the tolerance of malachite green, and double mutations of these even further improve the tolerance. Therefore, the tmt has been demonstrated to be a specific efflux pump for triphenylmethane dyes, particularly the malachite green. By actively pumping out toxic triphenylmethane dyes, it significantly extends the cells tolerance in a triphenylmethane dye-rich environment, which may provide a promising strategy for bioremediation of triphenylmethane dye pollutants in the environments.

Preparation of 3D flexible SERS substrates by mixing gold nanorods in hydrogels for the detection of malachite green and crystal violet.

A simple and cost-effective fabrication method of gold nanorods (AuNRs) nanoparticles hybridized with polyvinyl alcohol hydrogel (AuNR/PVA) for SERS substrate is described. The AuNR/PVA achieves the control of inter-particle nanogap by modulating the density of gold nanorods, and inter-particle nanogap by the spatial deformation of the hydrogel, and the reduction of the gap between the AuNRs deposited on hydrogel makes the SERS enhancement. In addition, the AuNR/PVA substrate maintains high SERS activity after more than 100 cycles of bending and storage in air for 30 days, and the substrate possesses high sensitivity and high reproducibility. Combining a flexible and transparent surface-enhanced Raman spectroscopy (SERS) substrate for in situ detection with a small portable Raman can be applied to scenarios such as environmental detection and hazardous materials detection. The substrate showed excellent SERS activity against malachite green (MG) and crystal violet (CV) with limits of detection of 1.18 × 10-13 M and 7.17 × 10-12 M, respectively. The usability of the proposed SERS substrate was demonstrated by detecting the above contaminants in aquatic water. This work not only utilizes a cost-effective method for mass production but also provides a reliable and convenient platform for the preparation of other noble metal flexible substrates.

A ratiometric fluorescent sensor based on S-doped BCNO quantum dots and Au nanoclusters combined with 3D-printing portable device for the detection of malachite green.

Sulfur-doped BCNO quantum dots (S-BCNO QDs) emitting green fluorescence were prepared by elemental doping method. The ratiometric fluorescence probe with dual emissions was simply established by mixed S-BCNO QDs with gold nanoclusters (GSH-Au NCs). Because the emission spectrum of Au NCs (donor) at 615 nm overlapped well with the ultraviolet absorption of malachite green (MG), fluorescence resonance energy transfer (FRET) can be achieved. When the concentration of MG increased, the fluorescence intensity (F495) of S-BCNO QDs decreased slowly, while the fluorescence intensity (F615) of Au NCs decreased sharply. The fluorescence intensity ratio of F615/F495 decreased with the increase of MG. By plotting the F615/F495 values against MG concentration, a sensitive and rapid detection of MG was possible with a wide detection range (0.1-50 µM) and a low detection limit of 10 nM. Due to the accompanying fluorescence color change from pink to blue-green, it can be used for visual detection. A three dimensional-printing device utilizing digital image colorimetry to capture color changes through the built-in camera, enables quantitative detection of MG with a good linearity between the values of red/green ratio and MG concentrations at the range 1-50 µM. This sensing platform had a range of advantages, including high cost-effectiveness, portability, ease of operation, and high sensitivity. Furthermore, the sensing platform was successfully applied to the detection of MG in real water sample and fish samples, thereby verifying the reliability and effectiveness of this sensing platform in water quality monitoring and food safety.

A simple color absorption analysis of colorimetric loop-mediated isothermal amplification for detection of Raillietina spp. in clinical samples using a 3D-printed tube holder coupled with a smartphone camera and notebook screen.

A simple method has been developed for semi-quantitative analysis of the colorimetric output of loop-mediated isothermal amplification (LAMP) using a 3D-printed tube holder with a smartphone and notebook for the detection of Raillietina, which is the cause of Raillietiniasis affecting free-range chicken farming. In this method, a light is directed from a notebook screen to the LAMP products in the tube holder and the color absorption of the LAMP products is measured by using the appropriate smartphone application. It was found that the malachite green dye-coupled LAMP (MaG-LAMP) assay showed the highest sensitivity and specificity for detecting Raillietina without any cross-reaction with other related parasites and hosts. The limit of detection was 10 fg/µL of DNA. A total of 60 fecal samples were infectively confirmed by microscopic examination and the results of microscopy compared with those of MaG-LAMP and triplex PCR assays. Microscopy and MaG-LAMP based on the color absorption demonstrated high agreement in Raillietina detection with kappa = 1. Rapid, simple, cost-effective, and easy interpretation of colorimetric LAMP assays and their high sensitivity make them superior to PCR and morphological investigation, demonstrating the feasibility of this assay in point-of-care screening to support farm management and solve chicken health problems. Our study presents is an alternative diagnostic method using semi-quantitative analysis of colorimetric LAMP based on the differing solution color absorptions between positive and negative reactions for infectious disease diagnosis.

Cobalt oxyhydroxide nanosheet-modulated ratiometric fluorescence platform for the selective detection of malachite green in fish.

A ratiometric fluorescence platform was developed based on the cobalt oxyhydroxide (CoOOH) nanosheet-modulated fluorescence response of blue emissive copper nanoclusters (Cu NCs) and yellow emissive o-phenylenediamine (OPD). CoOOH nanosheets showed dual function of strong absorption and oxidation ability, which can effectively quench the blue fluorescence of Cu NCs, with an excitation and emission peak maximum at 390 and 450 nm, respectively , and transfer the OPD into yellow fluorescence products, with an excitation and emission peak maximum at 390 and 560 nm, respectively. Upon introducing butyrylcholinesterase (BChE) and its substrates, CoOOH nanosheets were decomposed into Co2+, and malachite green (MG) showed strong inhibition ability to this  process. This resulted in the obvious difference on the ratio of blue and yellow fluorescence recorded on the system in the presence and absence of MG, which was utilized for the quantitative detection of MG, with a limit of detection of 0.140 µM and a coefficient of variation of 3.5%. The fluorescence ratiometric assay showed excellent detection performances in practical sample analysis.

Malachite green (cationic dye) removal with modified Pinus brutia biochar.

Dyes are frequently used in industries such as textile, leather, paper and printing, to water sources causes harmful effects on the environment and human health. Therefore, it is crucial to effectively remove colored contaminants from water in order to protect the environment and public health, maintain biodiversity and preserve the esthetic aspects of water resources. In this study, wood chips obtained from Pinus brutia (PB) tree grown in many parts of the world were turned into biochar and then modified and used for the removal of malachite green, a cationic dye. For this purpose, biochar (PBB) was made by collecting PB wood and turning it into chips (PB). Later, PBB was modified to gain nano-magnetic properties. The structure of the obtained PBB and nM-PBB adsorbents was characterized by FT-IR. pH (2-9), temperature (25 °C-55 °C), time change (15 min-240 min), adsorbent amount change (0.05 g-0.45g) and MG concentration (25 mg/L-250 mg/L) were investigated in MG removal of PBB and nM-PBB. The process was found to be pseudo-second-order and spontaneous endothermic reaction. PBB and nM-PBB were found to be suitable for Langmuir isotherm in MG removal (qmax=13.004 mg/g for PBB, qmax=18.215 mg/g for nM-PBB).

Various adsorbents are used to remove different substances from water. The use of pinus brutia tree, which is a biochar product, in the removal of malachite green dyes from aqueous solutions has not been found in the literature. The findings revealed that Pinus brutia could be used to extract malachite green, a cationic dyestuff. Pinus brutia is a widely distributed, easy-to-access, low-cost species with many uses. Our study, in which Pinus brutian is used as an adsorbent, will contribute to the literature in this respect, and its use in the removal of different anionic and cationic dyes will be discussed in the future.

Enhancement of biosorption capability of imidazolium-based ionic liquid-treated Prosopis juliflora for the removal of malachite green from wastewater.

Due to its toxicity effect, treating toxic pollutants discharged from textile effluent is challenging for living beings. In the present study, the comparative biosorption potential of imidazolium-based ionic liquid-treated Prosopis juliflora (ILPJS) and untreated P. juliflora (PJS) was investigated for the removal of toxic pollutant, malachite green (MG) from aqueous solution. The textural, surface morphology, and functional analysis of ILPJS and PJS were examined using BET (Brunauer-Emmett-Teller) analysis, SEM (Scanning electron microscopy) analysis, and FTIR (Fourier-transform infrared spectroscopy) analysis. Textural property (BET surface area) and surface morphology containing irregular heterogeneous surface for ILPJS were significantly improved than PJS, thereby facilitating significant biosorption of MG. Based on the conventional optimization studies, the essential biosorption parameters for the removal of MG using ILPJS were found to be: initial pH (9.0), contact time (30 min), and biosorbent dosage (0.2 g). The maximum biosorption capacity of PJS and ILPJS were obtained to be 6.91 and 13.64 mg/g at 40 °C, respectively. The spontaneous and endothermic biosorption of MG was confirmed by thermodynamic analysis. The regeneration study indicated the greater reusability of ILPJS and PJS for MG removal till the fifth cycle. Based on the previous literature, this is the first report comparing the removal of toxic pollutant MG using ILPJS and PJS.

Prosopis juliflora is an invasive weed that causes a severe challenge to ecological diversity and rural livelihoods due to the continuous consumption of water throughout the year, leading to the depletion of groundwater reserves. To control its invasion and growth, weed has been applied as biosorbents to remove toxic pollutant, malachite green (MG). This is the first report comparing the pretreatment of P. juliflora using imidazolium-based ionic liquid (ILPJS) with raw P. juliflora (PJS) for the biosorption of MG. The biosorption capacity of ILPJS for MG removal was 1.97 times higher than PJS. The enhancement in biosorption capacity might be the possibility of better textural and surface morphology of chemically treated P. juliflora. Thermodynamic studies revealed the endothermic and spontaneous nature of the biosorption of MG on PJS. With the invasion of this weed over thousands of hectares of land in India, PJS is the ideal biosorbent for removing toxic chemical pollutants and preserving the groundwater level.

Acid-activated corn silk as a promising phytosorbent for uptake of Malachite green and Cd (II) ion from simulated wastewater: equilibrium, kinetic and thermodynamic studies.

Malachite green (MG) dye and cadmium metal ion are toxic pollutants that should be removed from aqueous environment. The recent study aimed to examine the adsorption behavior of MG dye and Cd (II) from wastewater onto low-cost adsorbent prepared by activating corn silk with nitric acid (ACS) and characterized by SEM, FTIR, XRD, BET and TGA. The optimum MG and Cd (II) adsorption was observed at pH 7 and pH 9 and maximum uptake of both pollutants was at 0.5 g dosage, 60 mins contact time and 20 mg/L initial concentration. The retention of dye and metal ion by the studied adsorbent was best fit to Langmuir isotherm and Pseudo-second order kinetics. The maximum monolayer coverage capacity of ACS for MG dye and Cd (II) ion was 18.38 mg/g and 25.53 mg/g, respectively. Thermodynamic studies predicted a spontaneous reaction with exothermic process for MG dye whereas an endothermic and spontaneous process was confirmed for Cd ion based on estimated parameters. The adsorption mechanism of MG dye and Cd (II) uptake was by combination of electrostatic interaction, pore diffusion, ion exchange, pie-pie attraction, hydrogen bonding, and complexation. The adsorbed pollutants were effectively desorbed with significant regeneration efficiency after successive five cycles that proved the potential of low-cost biosorbent for selective sequestration of cationic dye and divalent metal ion from effluents.

The use of nitric acid-modified corn silk has been reported to enhance its adsorption performance over the unmodified cob for pollutants such as cadmium ions and malachite green. Although there may be no recorded data on the adsorption efficiency of acid-treated corn silk for selected pollutants, it can be considered as a prospective bio-sorbent owing to its chemical composition and functional groups for exchange of hydrogen ions for other cations.

Removal of malachite green from wastewater using date seeds as natural adsorbent; isotherms, kinetics, Thermodynamic, and batch adsorption process design.

This research explores the feasibility of using date seeds (DS), an agricultural waste, for the adsorption of malachite green (MG) dye from synthesized wastewater. The characterization of the DS before and after adsorption was accomplished by FTIR, SEM, BET, and EDX measurements. Batch adsorption experiments were investigated for MG dye adsorption from aqueous solution onto the DS. The effect of different parameters such as solution pH, adsorbent dose, contact time, temperature, and the initial dye concentration were studied. The optimum pH, adsorbent dose, temperature, and contact time for the dye removal were found to be 5, 0.1 g, 25 °C, and 30 min, respectively. The equilibrium studies for the data with Langmuir, Freundlich, and Temkin isotherms showed that Freundlich isotherm is the best model to describe the adsorption of MG onto the DS particles which has a heterogeneous surface. It was found that the adsorption process follows a pseudo-second-order kinetic model which revealed that the intra-particle diffusion stage is the rate-controlling stage for the process. The thermodynamic parameters ΔG, ΔS, and ΔH suggest the possibility of chemisorption and physisorption simultaneously and indicate the exothermic and spontaneous characters of the adsorption of MG dye on DS with negative values of ΔH and ΔG.

This study used agriculture waste (date seeds) which is proved to be an environmentally friendly and low-cost adsorbent. The date seeds were shown to be a promising adsorbent, demonstrating high surface area and well-developed porosity. The prepared adsorbent will have a great impact on wastewater treatment technology and possible applications at a large scale. Thus, widespread and great progress in this area can be expected in the future.

Artificial neural network-based modeling of Malachite green adsorption onto baru fruit endocarp: insights into equilibrium, kinetic, and thermodynamic behavior.

In this study, artificial neural network (ANN) tools were employed to forecast the adsorption capacity of Malachite green (MG) by baru fruit endocarp waste (B@FE) under diverse conditions, including pH, adsorbent dosage, initial dye concentration, contact time, and temperature. Enhanced adsorption efficiency was notably observed under alkaline pH conditions (pH 10). Kinetic analysis indicated that the adsorption process closely followed a pseudo-second-order model, while equilibrium studies revealed the Langmuir isotherm as the most suitable model, estimating a maximum adsorption capacity of 57.85 mg g-1. Furthermore, the chemical adsorption of MG by B@FE was confirmed using the Dubinin-Radushkevich isotherm. Thermodynamic analysis suggested that the adsorption is spontaneous and endothermic. Various ANN architectures were explored, employing different activation functions such as identity, logistic, tanh, and exponential. Based on evaluation metrics like the coefficient of determination (R2) and root mean square error (RMSE), the optimal network configuration was identified as a 5-11-1 architecture, consisting of five input neurons, eleven hidden neurons, and one output neuron. Notably, the logistic activation function was applied in both the hidden and output layers for this configuration. This study highlights the efficacy of B@FE as an efficient adsorbent for MG removal from aqueous solutions and demonstrates the potential of ANN models in predicting adsorption behavior across varying environmental conditions, emphasizing their utility in this field.

The innovative aspect of this study lies in the utilization of a new and effective adsorbent for the removal of Malachite Green (MG), derived from the fruit endocarp of baru (Dipteryx alata Vog.). The baru fruit endocarp, typically discarded as solid waste during processing, was found to possess favorable characteristics for adsorption processes and provides an adsorption capacity that exceeds that of most other similar adsorbents. Additionally, integrating Artificial Neural Networks (ANNs) enables accurate modeling of the adsorption process, eliminating the need for extensive laboratory experiments. This contributes significantly to wastewater treatment research, enhancing effectiveness and sustainability in unwanted dye removal.

Modeling competitive biosorption for methylene blue removal on rape straw powders using response surface methodology in a ternary dye aqueous solution.

The improvement of biosorption efficiency for selective dye removal in a multi-dye aqueous system has become an increasingly significant research topic. However, the competitive effects of coexisting dyes and the target dye in such systems remain uncertain due to complex interactions between adsorbent and coexisting dyes. Therefore, in this research, response surface methodology (RSM) model was effectively employed to investigate the competitive effects of allura red (AR) and malachite green (MG) on methylene blue (MB) removal in a ternary dye aqueous system using three different parts of rape straw powders. In the current design of RSM, the initial concentrations of AR and MG dyes ranging from 0 mg·L-1 to 500 mg·L-1 were considered as influencing factors, while the removal rates of MB on adsorbents at an initial concentration of 500 mg·L-1 were established as response values. The RSM models exhibited high correlation coefficients with adjusted R2 values of 0.9908 (pith core), 0.9870 (seedpods), and 0.9902 (shells), respectively, indicating a close fitted between predicted and actual values. The proposed models indicated that the perturbation effects of initial AR and MG concentrations were observed on the removal rates of MB by three types of rape straw powders in a ternary dye aqueous system, resulting in a decrease in MB removal rates, particularly at higher initial AR concentration due to stronger competitive effects compared to initial MG concentration. The structures of rape straw powders, including pith core, seedpods and shell, were analyzed using scanning eletron microscoe (SEM), energy dispersive spectroscopy (EDS), N2 physisorption isotherm, frourier transform infared spectroscopy (FTIR), Zeta potential classes and fluorescence spectrum before and after adsorption of MB in various dye aqueous systems. The characteristics of rape straw powders suggested that similar adsorption mechanisms, such as electrostatic attraction, pore diffusion, and group complex formation for MB, AR, and MG, respectively, occurred on the surfaces of adsorbents during their respective adsorption processes. This leads to significant competitive effects on the removal rates of MB in a ternary dye aqueous system, which are particularly influenced by initial AR concentrations as confirmed through fluorescence spectrum analysis.

Impact of AR and MG on MB removal was analyzed using simple methodologies.Competitive behaviors between AR, MG and MB were understood through RSM.Intense restrain effects on MB removal were revealed by AR concentration.