RESUMO
More sustainable materials have been becoming an important concern of worldwide scientists, and cellulosic materials are one alternative in water decontamination. An efficient strategy to improve removal capacity is functionalizing or incorporating nanomaterials in cellulose-based materials. The new hybrid cDAC/ZnONPs was produced by green synthesis of zinc oxide nanoparticles (ZnONPs), promoting the in situ reduction and immobilization on the cationic dialdehyde cellulose microfibers (cDAC) surface to remove Congo red dye from water. cDAC/ZnONPs was characterized by scanning electron microscopy (SEM-EDS) and infrared spectroscopy (FTIR), which showed efficient nanoparticles reduction. Adsorption efficiency on cationic cellulose surface was investigated by pH, contact time, initial concentration, and dye selectivity tests. The material followed the H isotherm model, which resulted in a maximum adsorption capacity of 1091.16 mg/g. Herein, was developed an efficient and ecologically correct new adsorbent, highly effective in Congo red dye adsorption even at high concentrations, suitable for the remediation of contaminated industrial effluents.
Assuntos
Vermelho Congo , Poluentes Químicos da Água , Purificação da Água , Óxido de Zinco , Óxido de Zinco/química , Vermelho Congo/química , Vermelho Congo/isolamento & purificação , Poluentes Químicos da Água/química , Poluentes Químicos da Água/isolamento & purificação , Adsorção , Purificação da Água/métodos , Química Verde , Concentração de Íons de Hidrogênio , Celulose/química , Celulose/análogos & derivados , Corantes/química , Nanopartículas/química , Cinética , Nanopartículas Metálicas/química , Celulose Oxidada/química , Cátions/químicaRESUMO
This work aimed to describe the adsorption behavior of Congo red (CR) onto activated biochar material prepared from Haematoxylum campechianum waste (ABHC). The carbon precursor was soaked with phosphoric acid, followed by pyrolysis to convert the precursor into activated biochar. The surface morphology of the adsorbent (before and after dye adsorption) was characterized by scanning electron microscopy (SEM/EDS), BET method, X-ray powder diffraction (XRD), and Fourier-transform infrared spectroscopy (FTIR) and, lastly, pHpzc was also determined. Batch studies were carried out in the following intervals of pH = 4-10, temperature = 300.15-330.15 K, the dose of adsorbent = 1-10 g/L, and isotherms evaluated the adsorption process to determine the maximum adsorption capacity (Qmax, mg/g). Kinetic studies were performed starting from two different initial concentrations (25 and 50 mg/L) and at a maximum contact time of 48 h. The reusability potential of activated biochar was evaluated by adsorption-desorption cycles. The maximum adsorption capacity obtained with the Langmuir adsorption isotherm model was 114.8 mg/g at 300.15 K, pH = 5.4, and a dose of activated biochar of 1.0 g/L. This study also highlights the application of advanced machine learning techniques to optimize a chemical removal process. Leveraging a comprehensive dataset, a Gradient Boosting regression model was developed and fine-tuned using Bayesian optimization within a Python programming environment. The optimization algorithm efficiently navigated the input space to maximize the removal percentage, resulting in a predicted efficiency of approximately 90.47% under optimal conditions. These findings offer promising insights for enhancing efficiency in similar removal processes, showcasing the potential of machine learning in process optimization and environmental remediation.
Assuntos
Teorema de Bayes , Carvão Vegetal , Vermelho Congo , Aprendizado de Máquina , Carvão Vegetal/química , Adsorção , Vermelho Congo/química , Cinética , Poluentes Químicos da Água/química , Concentração de Íons de Hidrogênio , Espectroscopia de Infravermelho com Transformada de FourierRESUMO
Laccase is a superfamily of ligninolytic enzymes known to degrade a wide variety of xenobiotics, including synthetic dyes. Congo Red (CR) has a diazo dye function, carcinogenic and mutagenic potential, and is currently applied in clinical analysis. The objective of this work was to produce and characterize the crude extract of Lentinus sp. in semi-solid fermentation (FSS) and perform in vitro and in silico studies to assess the potential of the crude extract to discolor the CR dye. Laccase activity was determined using ABTS as substrate and characterized. The in vitro discoloration was carried out using experimental design 22 at room temperature and monitored at 340 nm for 24h. Molecular docking and molecular dynamics simulations were performed between laccase and CR. The maximum laccase activity production was 29.63 U L-1 with six days of FSS. The optimal temperature and pH were 50 °C and 3.0, respectively. Discoloration of the CR dye was obtained only in tests containing CuSO4. Laccase formed stable complexes with the dye, presenting negative binding energy values ranging from -70.94 to -63.16 kcal mol-1 and the occurrence of seven hydrogen bonds. Molecular dynamics results showed the stability of the system (RMSD ranging from 1.0 to 2.5 Ä) and protein-ligand interaction along simulation. RMSF values pointed residues at the end of chains A (residues 300 to 305, 480 to 500) and B (residues 650 to 655 and 950 to 1000) as the most flexible regions of the laccase. This study highlighted the enzymatic action in the bioremediation of CR in vitro in agreement with the in silico simulations that demonstrate the enzyme potential.Communicated by Ramaswamy H. Sarma.
Assuntos
Vermelho Congo , Lentinula , Vermelho Congo/química , Corantes/química , Lacase/química , Lacase/metabolismo , Simulação de Acoplamento Molecular , Lentinula/metabolismo , Projetos de Pesquisa , Misturas ComplexasRESUMO
The removal of dyes from effluents of textile industries represents a technological challenge, due to their significant environmental impact. The application of halloysite (Hal) and palygorskite (Pal) clay minerals as adsorbents for the removal of Congo red (CR) and methylene blue (MB) was evaluated in this work. The materials were applied both in natural and acid-treated forms, and characterized by XRD, XPS, SEM-EDS, FTIR, and N2 adsorption-desorption isotherm techniques to identify their properties and main active sites. The adsorbents showed potential to remove CR (> 98%) and MB (> 85%) within 180 min, using 0.3 g adsorbent and initial dye concentration of 250 mg L-1. Semi-empirical quantum mechanical calculations (SQM) confirmed the interaction mechanism between dyes and the adsorbents via chemisorption (- 69.0 kcal mol-1 < Eads < - 28.8 kcal mol-1), which was further observed experimentally due to the high fit of adsorption data to pseudo-second order kinetic model (R2 > 0.99) and Langmuir isotherm (R2 > 0.98). The use of Pal and Hal to remove dyes was proven to be economically and environmentally viable for industrial application.
Assuntos
Argila , Corantes , Compostos de Silício , Poluentes Químicos da Água , Adsorção , Argila/química , Corantes/química , Poluentes Químicos da Água/química , Compostos de Silício/química , Minerais/química , Azul de Metileno/química , Silicatos de Alumínio/química , Compostos de Magnésio/química , Cinética , Vermelho Congo/químicaRESUMO
In this article, we propose a simple photochemical method to synthesize pure La2Ti2O7 films and La2Ti2O7 films doped with silver at 1.0, 3.0, and 5.0 mol%. After annealing the photo-deposited films at 900 °C, XRD, SEM, and XPS analyses showed the formation of a monoclinic La2Ti2O7 phase and the presence of Ag and AgO in doped samples. Photocatalytic tests for Congo red degradation demonstrated that pure La2Ti2O7 achieved 25.4% degradation, while doped samples reached a maximum of 92.7% degradation. Moreover, increasing silver doping on La2Ti2O7 films significantly reduced the growth of Staphylococcus aureus, indicating potential antibacterial properties. The enhanced photoactivity was attributed to the formation of a type I heterojunction between La2Ti2O7 and AgO, and a degradation mechanism was proposed based on Congo red degradation.
Assuntos
Vermelho Congo , Staphylococcus aureus , Vermelho Congo/química , Prata/farmacologia , Prata/química , Titânio/química , Antibacterianos/farmacologia , Antibacterianos/químicaRESUMO
The thermodynamics and kinetics of arachin-Congo red (ARA-CR) and conarachin-Congo red (CON-CR) interactions were studied using surface plasmon resonance. KCl led to a reduction of up to 55% in the values of the associated kinetic constants, but it had less influence on the dissociation rates (less than 12%). The change in ionic strength had little effect on the thermodynamic stability of the complexes, but it did reduce their affinities ( [Formula: see text] from 3.52 to 2.44 × 103 M-1 and [Formula: see text] from 15.1 to 12.5 × 103 M-1). The shielding of the electrical double layer favored ARA-CR hydrophilic interactions ( [Formula: see text] decreased from -30.60 to -42.98 kJ mol-1). On the other hand, hydrophobic interactions came to dominate during the formation of [CON-CR]0 ( [Formula: see text] increased from -11.21 to 28.34 kJ mol-1 and [Formula: see text] increased from 12.64 to 51.73 kJ.mol-1). The data presented here improve our understanding of plant-based protein nanocarriers of small bioactive molecules.
Assuntos
Vermelho Congo , Sondas Moleculares , Vermelho Congo/química , Cinética , Proteínas de Plantas , TermodinâmicaRESUMO
A sensitive and selective strategy to identify insulin fibrils remains a challenge for researchers in amyloid protein research. Thus, it is critical to detect, in vitro, the species generated during amyloid aggregation, particularly the fibrillar species. Here we demonstrate that the luminescent complex cis-[Ru(phen)2(3,4Apy)2]2+ (RuApy; phen = 1,10-phenanthroline; 3,4Apy = 3,4-diaminopyridine) is a rapid, low-cost alternative to in vitro detection of fibrillar insulin, using conventional optical techniques. The RuApy complex displays emission intensity enhancement at 655 nm when associated with insulin, which enables imaging of the conformational changes of the protein's self-aggregation. The complex shows high sensitivity to fibrillar insulin with a limit of detection of 0.85 µM and binding affinity of 12.40 ± 1.84 µM which is comparable to those of Thioflavin T and Congo red, with the advantage of minimizing background fluorescence, absorption of light by biomolecules, and light scattering from physiologic salts in the medium.
Assuntos
Amiloide/análise , Corantes Fluorescentes/química , Insulina/análise , Rutênio/química , Amiloide/metabolismo , Peptídeos beta-Amiloides/metabolismo , Proteínas Amiloidogênicas/metabolismo , Animais , Benzotiazóis/química , Linhagem Celular , Vermelho Congo/química , Fluorescência , Insulina/metabolismo , Luminescência , Camundongos , Fenantrolinas/química , Agregados Proteicos , RatosRESUMO
GRASP55, one of the two human GRASP proteins, has been implicated in the organization of Golgi stacks and in unconventional protein secretion. However, the detailed molecular mechanisms supporting GRASP55 participation in those processes remain mostly unclear. We have shown that GRASP55 exists as monomers in solution, which transitions to amorphous aggregates with increasing temperatures. Here, we further investigated the formation of higher order structures of GRASP55 by exploring its amyloid fibrillation at 37 °C. Sequence-based AGGRESCAN analysis revealed that GRASP55 has ten aggregation "hot spots", preferentially concentrated in its N-terminal half. Congo Red, ThT, and circular dichroism assays suggested GRASP55 formed amyloid-like fibrils in a time-dependent manner at 37 °C. Dynamic light scattering showed the mean hydrodynamic radius of GRASP55 amyloid-like fibrils increased with increasing incubation times at 37 °C. Transmission electron microscopy and intrinsic fluorescence lifetime imaging showed that, upon increasing incubation time at 37 °C, GRASP55 yielded amyloid-like fibrils in a nucleation-dependent process via a sequence of events: lag-phase (monomers to oligomers), growth phase (oligomers to organized protofibrils), and plateau phase (protofibrils to amyloid-like fibrils). The insights gained herein may help in better understanding the mechanisms of GRASP55 amyloid fibrillation in vivo and its potential association with neurological disorders.
Assuntos
Amiloide/química , Complexo de Golgi/fisiologia , Proteínas da Matriz do Complexo de Golgi/química , Benzotiazóis/química , Dicroísmo Circular , Biologia Computacional , Vermelho Congo/química , Humanos , Hidrodinâmica , Cinética , Luz , Microscopia Eletrônica de Transmissão , Doenças do Sistema Nervoso/fisiopatologia , Conformação Proteica , Domínios Proteicos , Proteínas Recombinantes/química , Espalhamento de Radiação , TemperaturaRESUMO
AIM AND OBJECTIVE: A common method used for massive detection of cellulolytic microorganisms is based on the formation of halos on solid medium. However, this is a subjective method and real-time monitoring is not possible. The objective of this work was to develop a method of computational analysis of the visual patterns created by cellulolytic activity through artificial neural networks description. MATERIALS AND METHODS: Our method learns by an adaptive prediction model and automatically determines when enzymatic activity on a chromogenic indicator such as the hydrolysis halo occurs. To achieve this goal, we generated a data library with absorbance readings and RGB values of enzymatic hydrolysis, obtained by spectrophotometry and a prototype camera-based equipment (Enzyme Vision), respectively. We used the first part of the library to generate a linear regression model, which was able to predict theoretical absorbances using the RGB color patterns, which agreed with values obtained by spectrophotometry. The second part was used to train, validate, and test the neural network model in order to predict cellulolytic activity based on color patterns. RESULTS: As a result of our model, we were able to establish six new descriptors useful for the prediction of the temporal changes in the enzymatic activity. Finally, our model was evaluated on one halo from cellulolytic microorganisms, achieving the regional classification of the generated halo in three of the six classes learned by our model. CONCLUSION: We assume that our approach can be a viable alternative for high throughput screening of enzymatic activity in real time.
Assuntos
Celulose/química , Biblioteca Gênica , Redes Neurais de Computação , Reconhecimento Automatizado de Padrão , Celulose/metabolismo , Cor , Corantes/química , Vermelho Congo/química , Hidrólise , Aprendizado de Máquina , Modelos MolecularesRESUMO
GRASPs are proteins involved in cell processes that seem paradoxical: responsible for shaping the Golgi cisternae and involved in unconventional secretion mechanisms that bypass the Golgi. Despite its physiological relevance, there is still a considerable lack of studies on full-length GRASPs. Our group has previously reported an unexpected behavior of the full-length GRASP from the fungus C. neoformans: its intrinsically-disordered characteristic. Here, we generalize this finding by showing that it is also observed in the GRASP from S. cerevisae (Grh1), which strongly suggests it might be a general property within the GRASP family. Furthermore, Grh1 is also able to form amyloid-like fibrils either upon heating or when submitted to changes in the dielectric constant of its surroundings, a condition that is experienced by the protein when in close contact with membranes of cell compartments, such as the Golgi apparatus. Intrinsic disorder and fibril formation can thus be two structural properties exploited by GRASP during its functional cycle.