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ConspectusLight is ubiquitously available to probe the structure and dynamics of biomolecules and biological tissues. Generally, this cannot be done directly with visible light, because of the absence of absorption by those biomolecules. This problem can be overcome by incorporating organic molecules (chromophores) that show an optical response in the vicinity of those biomolecules. Since those optical properties are strongly dependent on the chromophore's environment, time-resolved spectroscopic studies can provide a wealth of information on biosystems at the molecular scale in a nondestructive way. In this work, we give an overview on the multiscale computational strategy developed by us in the last eight years and prove that theoretical studies and simulations are needed to explain, guide, and predict observations in fluorescence experiments. As we challenge the accepted views on existing probes, we discover unexplored abilities that can discriminate surrounding lipid bilayers and their temperature-dependent as well as solvent-dependent properties. We focus on three archetypal chromophores: diphenylhexatriene (DPH), Laurdan, and azobenzene. Our method shows that conformational changes should not be neglected for the prototype rod-shaped molecule DPH. They determine its position and orientation in a liquid-ordered (Lo) sphingomyelin/cholesterol (SM/Chol) bilayer and are responsible for a strong differentiation of its absorption spectra and fluorescence decay times in dioleoylphosphatidylcholine (DOPC) and dipalmitoylphosphatidylcholine (DPPC) membranes, which are at room temperature in liquid-disordered (Ld) and solid-gel (So) phases, respectively. Thanks to its pronounced first excited state dipole moment, Laurdan has long been known as a solvatochromic probe. Since this molecule has however two conformers, we prove that they exhibit different properties in different lipid membrane phases. We see that the two conformers are only blocked in one phase but not in another. Supported by fluorescence anisotropy decay simulations, Laurdan can therefore be regarded as a molecular rotor. Finally, the conformational versatility of azobenzene in saturated Ld lipid bilayers is simulated, along with its photoisomerization pathways. By means of nonadiabatic QM/MM surface hopping analyses (QM/MM-SH), a dual mechanism is found with a torsional mechanism and a slow conversion for trans-to-cis. For cis-to-trans, simulations show a much higher quantum yield and a so-called "pedal-like" mechanism. The differences are related to the different potential energy surfaces as well as the interactions with the surrounding alkyl chains. When tails of increased length are attached to this probe, cis is pushed toward the polar surface, while trans is pulled toward the center of the membrane.
Assuntos
Compostos Azo , Bicamadas Lipídicas , Bicamadas Lipídicas/química , Compostos Azo/química , Difenilexatrieno/química , 2-Naftilamina/análogos & derivados , 2-Naftilamina/química , Lauratos/química , Simulação de Dinâmica MolecularRESUMO
Mechanophores are molecular motifs that respond to mechanical perturbance with targeted chemical reactions toward desirable changes in material properties. A large variety of mechanophores have been investigated, with applications focusing on functional materials, such as strain/stress sensors, nanolithography, and self-healing polymers, among others. The responses of engineered mechanophores, such as light emittance, change in fluorescence, and generation of free radicals (FRs), have potential for bioimaging and therapy. However, the biomedical applications of mechanophores are not well explored. Herein, we report an in vitro demonstration of an FR-generating mechanophore embedded in biocompatible hydrogels for noninvasive cancer therapy. Controlled by high-intensity focused ultrasound (HIFU), a clinically proven therapeutic technique, mechanophores were activated with spatiotemporal precision to generate FRs that converted to reactive oxygen species (ROS) to effectively kill tumor cells. The mechanophore hydrogels exhibited no cytotoxicity under physiological conditions. Upon activation with HIFU sonication, the therapeutic efficacies in killing in vitro murine melanoma and breast cancer tumor cells were comparable with lethal doses of H2O2 This process demonstrated the potential for mechanophore-integrated HIFU combination as a noninvasive cancer treatment platform, named "mechanochemical dynamic therapy" (MDT). MDT has two distinct advantages over other noninvasive cancer treatments, such as photodynamic therapy (PDT) and sonodynamic therapy (SDT). 1) MDT is ultrasound based, with larger penetration depth than PDT. 2) MDT does not rely on sonosensitizers or the acoustic cavitation effect, both of which are necessary for SDT. Taking advantage of the strengths of mechanophores and HIFU, MDT can provide noninvasive treatments for diverse cancer types.
Assuntos
Fenômenos Biomecânicos , Biopolímeros/química , Hidrogéis/química , Ondas Ultrassônicas , Animais , Compostos Azo/química , Humanos , Hidrogéis/síntese química , Melanoma Experimental , Camundongos , Neoplasias/terapia , Polietilenoglicóis/química , Espécies Reativas de Oxigênio/química , Espécies Reativas de Oxigênio/metabolismo , Termodinâmica , Terapia por Ultrassom/métodosRESUMO
The extracellular matrix (ECM) is a complex assembly of proteins that provide interstitial scaffolding and elastic recoil for human lungs. The pulmonary extracellular matrix is increasingly recognized as an independent bioactive entity, by creating biochemical and mechanical signals that influence disease pathogenesis, making it an attractive therapeutic target. However, the pulmonary ECM proteome ("matrisome") remains challenging to analyze by mass spectrometry due to its inherent biophysical properties and relatively low abundance. Here, we introduce a strategy designed for rapid and efficient characterization of the human pulmonary ECM using the photocleavable surfactant Azo. We coupled this approach with trapped ion mobility MS with diaPASEF to maximize the depth of matrisome coverage. Using this strategy, we identify nearly 400 unique matrisome proteins with excellent reproducibility that are known to be important in lung biology, including key core matrisome proteins.
Assuntos
Matriz Extracelular , Pulmão , Proteômica , Humanos , Proteômica/métodos , Pulmão/metabolismo , Matriz Extracelular/metabolismo , Compostos Azo/química , Proteínas da Matriz Extracelular/metabolismo , Tensoativos/química , Proteoma/análise , Espectrometria de Massas/métodosRESUMO
Accurate detection of labile analytes through activity based fluorogenic sensing is meaningful but remains a challenge because of nonrapid reaction kinetic. Herein, we present a signaling reporter engineering strategy to accelerate azoreduction reaction by positively charged fluorophore promoted unstable anion recognition for rapidly sensing sodium dithionite (Na2S2O4), a kind of widespread used but harmful inorganic reducing agent. Its quick decomposition often impedes application reliability of traditional fluorogenic probes in real samples because of their slow responses. In this work, four azo-based probes with different charged fluorophores (positive, zwitterionic, neutral, and negative) were synthesized and compared. Among of them, with sequestration effect of positively charged anthocyanin fluorophore for dithionite anion via electrostatic attraction, the cationic probe Azo-Pos displayed ultrafast fluorogenic response (â¼2 s) with the fastest response kinetic (kpos' = 0.373 s-1) that is better than other charged ones (kzwi' = 0.031 s-1, kneu' = 0.013 s-1, kneg' = 0.003 s-1). Azo-Pos was demonstrated to be capable to directly detect labile Na2S2O4 in food samples and visualize the presence of Na2S2O4 in living systems in a timely fashion. This new probe has potential as a robust tool to fluorescently monitor excessive food additives and biological invasion of harmful Na2S2O4. Moreover, our proposed accelerating strategy would be versatile to develop more activity-based sensing probes for quickly detecting other unstable analytes of interest.
Assuntos
Corantes Fluorescentes , Corantes Fluorescentes/química , Humanos , Ditionita/química , Compostos Azo/química , CinéticaRESUMO
Organic Raman probes, including polymers and small molecules, have attracted great attention in biomedical imaging owing to their excellent biocompatibility. However, the development of organic Raman probes is usually hindered by a mismatch between their absorption spectra and wavelength-fixed excitation, which makes it difficult to achieve resonance excitation necessary to obtain strong Raman signals. Herein, we introduce a covalent organic framework (COF) into the fine absorption spectrum regulation of organic Raman probes, resulting in their significant Raman signal enhancement. In representative examples, a polymer poly(diketopyrrolopyrrole-p-phenylenediamine) (DPP-PD) and a small molecule azobenzene are transformed into the corresponding COF-structured Raman probes. Their absorption peaks show an accurate match of less than 5 nm with the NIR excitation. As such, the COF-structured Raman probes acquire highly sensitive bioimaging capabilities compared to their precursors with negligible signals. By further mechanism studies, we discover that the crystallinity and size of COFs directly affect the π-conjugation degree of Raman probes, thus changing their bandgaps and absorption spectra. Our study offers a universal and flexible method for improving the signal performance of organic Raman probes without changing their structural units, making it more convenient to obtain the highly sensitive organic Raman probes for in vivo bioimaging.
Assuntos
Análise Espectral Raman , Análise Espectral Raman/métodos , Animais , Humanos , Camundongos , Compostos Azo/química , Estruturas Metalorgânicas/química , Polímeros/química , Estrutura Molecular , Fenilenodiaminas/químicaRESUMO
Hypoxia is known as a specific signal of various diseases, such as liver fibrosis. We designed a hypoxia-sensitive fluorometric approach that cleaved the azo bond (NâN) in the presence of hypoxia-controlled agents (sodium dithionite and azoreductase). 4-(2-Pyridylazo) resorcinol (Py-NâN-RC) bears a desirable hypoxia-responsive linker (NâN), and its azo bond breakup can only occur in the presence of sodium dithionite and azoreductase and leads to the release of 2,4-dihydroxyaniline, which can react with 3-[2-(2-aminoethylamino)ethylamino]propyltrimethoxysilane to generate yellow fluorescent silicon nanoparticles. This approach exhibited high selectivity and sensitivity toward both sodium dithionite and azoreductase over other potential interferences. The mouse liver microsome, which is known to contain azoreductase, was applied and confirmed the feasibility of the designed platform. Py-NâN-RC is expected to be a practical substrate for hypoxia-related biological analyses. Furthermore, silicon nanoparticles were successfully applied for Hela cell imaging owing to their negligible cytotoxicity and superb biocompatibility.
Assuntos
Compostos Azo , Nanopartículas , Silício , Silício/química , Humanos , Nanopartículas/química , Células HeLa , Compostos Azo/química , Animais , Camundongos , Resorcinóis/química , Hipóxia/metabolismo , Hipóxia Celular , Estrutura Molecular , Nitrorredutases/metabolismoRESUMO
Efficiently mitigating and managing environmental pollution caused by the improper disposal of dyes and effluents from the textile industry is of great importance. This study evaluated the effectiveness of Streptomyces albidoflavus 3MGH in decolorizing and degrading three different azo dyes, namely Reactive Orange 122 (RO 122), Direct Blue 15 (DB 15), and Direct Black 38 (DB 38). Various analytical techniques, such as Fourier Transform Infrared (FTIR) spectroscopy, High-Performance Liquid Chromatography (HPLC), and Gas Chromatography-Mass Spectrometry (GC-MS) were used to analyze the degraded byproducts of the dyes. S. albidoflavus 3MGH demonstrated a strong capability to decolorize RO 122, DB 15, and DB 38, achieving up to 60.74%, 61.38%, and 53.43% decolorization within 5 days at a concentration of 0.3 g/L, respectively. The optimal conditions for the maximum decolorization of these azo dyes were found to be a temperature of 35 °C, a pH of 6, sucrose as a carbon source, and beef extract as a nitrogen source. Additionally, after optimization of the decolorization process, treatment with S. albidoflavus 3MGH resulted in significant reductions of 94.4%, 86.3%, and 68.2% in the total organic carbon of RO 122, DB 15, and DB 38, respectively. After the treatment process, we found the specific activity of the laccase enzyme, one of the mediating enzymes of the degradation mechanism, to be 5.96 U/mg. FT-IR spectroscopy analysis of the degraded metabolites showed specific changes and shifts in peaks compared to the control samples. GC-MS analysis revealed the presence of metabolites such as benzene, biphenyl, and naphthalene derivatives. Overall, this study demonstrated the potential of S. albidoflavus 3MGH for the effective decolorization and degradation of different azo dyes. The findings were validated through various analytical techniques, shedding light on the biodegradation mechanism employed by this strain.
Assuntos
Compostos Azo , Biodegradação Ambiental , Corantes , Streptomyces , Streptomyces/metabolismo , Compostos Azo/metabolismo , Compostos Azo/química , Corantes/metabolismo , Corantes/química , Espectroscopia de Infravermelho com Transformada de Fourier/métodos , Têxteis , Cromatografia Gasosa-Espectrometria de Massas , Concentração de Íons de Hidrogênio , Temperatura , Indústria Têxtil , Poluentes Químicos da Água/metabolismo , Cromatografia Líquida de Alta Pressão , Carbono/metabolismoRESUMO
Drug metabolism by human gut microbes is often exemplified by azo bond reduction in the anticolitic prodrug sulfasalazine. Azoreductase activity is often found in incubations with cell cultures or ex vivo gut microbiome samples and contributes to the xenobiotic metabolism of drugs and food additives. Applying metagenomic studies to personalized medicine requires knowledge of the genes responsible for sulfasalazine and other drug metabolism, and candidate genes and proteins for drug modifications are understudied. A representative gut-abundant azoreductase from Anaerotignum lactatifermentan DSM 14214 efficiently reduces sulfasalazine and another drug, phenazopyridine, but could not reduce all azo-bonded drugs in this class. We used enzyme kinetics to characterize this enzyme for its NADH-dependent reduction of these drugs and food additives and performed computational docking to provide the groundwork for understanding substrate specificity in this family. We performed an analysis of the Flavodoxin-like fold InterPro family (IPR003680) by computing a sequence similarity network to classify distinct subgroups of the family and then performed chemically-guided functional profiling to identify proteins that are abundant in the NIH Human Microbiome Project dataset. This strategy aims to reduce the number of unique azoreductases needed to characterize one protein family in the diverse set of potential drug- and dye-modifying activities found in the human gut microbiome.
Assuntos
Microbioma Gastrointestinal , NADH NADPH Oxirredutases , Nitrorredutases , Humanos , Nitrorredutases/metabolismo , Nitrorredutases/genética , NADH NADPH Oxirredutases/metabolismo , NADH NADPH Oxirredutases/genética , NADH NADPH Oxirredutases/química , Corantes/metabolismo , Simulação de Acoplamento Molecular , Especificidade por Substrato , Sulfassalazina , Proteínas de Bactérias/metabolismo , Proteínas de Bactérias/genética , Proteínas de Bactérias/química , Cinética , Clostridiales/enzimologia , Clostridiales/genética , Compostos Azo/metabolismo , Compostos Azo/químicaRESUMO
Stimuli-responsive behaviors and controlled release in liposomes are pivotal in nanomedicine. To this end, we present an approach using a photoresponsive azobenzene nanocluster (AzDmpNC), prepared from azobenzene compounds through melting and aggregation. When integrated with liposomes, they form photoresponsive vesicles. The morphology and association with liposomes were investigated by using transmission electron microscopy. Liposomes loaded with calcein exhibited a 9.58% increased release after UV exposure. To gain insights into the underlying processes and elucidate the mechanisms involved. The molecular dynamic simulations based on the reactive force field and all-atom force field were employed to analyze the aggregation of isomers into nanoclusters and their impacts on phospholipid membranes, respectively. The results indicate that the nanoclusters primarily aggregate through π-π and T-stacking forces. The force density inside the cis-isomer of AzDmpNC formed after photoisomerization is lower, leading to its easier dispersion, rapid diffusion, and penetration into the membrane, disrupting the densification.
Assuntos
Compostos Azo , Lipossomos , Simulação de Dinâmica Molecular , Compostos Azo/química , Compostos Azo/efeitos da radiação , Lipossomos/química , Nanopartículas/química , Raios Ultravioleta , Fluoresceínas/química , Processos FotoquímicosRESUMO
Enzyme-responsive self-assembled nanostructures for drug delivery applications have gained a lot of attention, as enzymes exhibit dysregulation in many disease-associated microenvironments. Azoreductase enzyme levels are strongly elevated in many tumor tissues; hence, here, we exploited the altered enzyme activity of the azoreductase enzyme and designed a main-chain azobenzene-based amphiphilic polyurethane, which self-assembles into a vesicular nanostructure and is programmed to disassemble in response to a specific enzyme, azoreductase, with the help of the nicotinamide adenine dinucleotide phosphate (NADPH) coenzyme in the hypoxic environment of solid tumors. The vesicular nanostructure sequesters, stabilizes the hydrophobic anticancer drug, and releases the drug in a controlled fashion in response to enzyme-triggered degradation of azo-bonds and disruption of vesicular assembly. The biological evaluation revealed tumor extracellular matrix pH-induced surface charge modulation, selective activated cellular uptake to azoreductase overexpressed lung cancer cells (A549), and the release of the anticancer drug followed by cell death. In contrast, the benign nature of the drug-loaded vesicular nanostructure toward normal cells (H9c2) suggested excellent cell specificity. We envision that the main-chain azobenzene-based polyurethane discussed in this manuscript could be considered as a possible selective chemotherapeutic cargo against the azoreductase overexpressed cancer cells while shielding the normal cells from off-target toxicity.
Assuntos
Antineoplásicos , Compostos Azo , Nitrorredutases , Poliuretanos , Compostos Azo/química , Compostos Azo/farmacologia , Humanos , Poliuretanos/química , Antineoplásicos/farmacologia , Antineoplásicos/química , Células A549 , Nitrorredutases/metabolismo , NADH NADPH Oxirredutases/metabolismo , Liberação Controlada de Fármacos , Nanoestruturas/química , Sistemas de Liberação de Medicamentos/métodosRESUMO
A set of arylazopyrazole-based inhibitors targeting the mitotic motor protein CENP-E was discovered through the chemical platform using the quantitative cyclization of 1,3-diketone intermediate with various hydrazines under mild conditions. Through this efficient platform, the structure-activity relationship pertaining to the pyrazole photoswitch in photoswitchable CENP-E inhibitors not only in vitro but also in cells was successfully clarified.
Assuntos
Proteínas Cromossômicas não Histona , Pirazóis , Ciclização , Pirazóis/química , Pirazóis/farmacologia , Pirazóis/síntese química , Relação Estrutura-Atividade , Humanos , Proteínas Cromossômicas não Histona/antagonistas & inibidores , Proteínas Cromossômicas não Histona/metabolismo , Estrutura Molecular , Compostos Azo/química , Compostos Azo/farmacologia , Compostos Azo/síntese química , Relação Dose-Resposta a DrogaRESUMO
Conjugated polymers (CPs) have been developed quickly as an emerging functional material with applications in optical and electronic devices, owing to their highly electron-delocalized backbones and versatile side groups for facile processibility, high mechanical strength, and environmental stability. CPs exhibit multistimuli responsive behavior and fluorescence quenching properties by incorporating azobenzene functionality into their molecular structures. Over the past few decades, significant progress has been made in developing functional azobenzene-based conjugated polymers (azo-CPs), utilizing diverse molecular design strategies and synthetic pathways. This article comprehensively reviews the rapidly evolving research field of azo-CPs, focusing on the structural characteristics and synthesis methods of general azo-CPs, as well as the applications of charged azo-CPs, specifically azobenzene-based conjugated polyelectrolytes (azo-CPEs). Based on their molecular structures, azo-CPs can be broadly categorized into three primary types: linear CPs with azobenzene incorporated into the side chain, linear CPs with azobenzene integrated into the main chain, and branched CPs containing azobenzene moieties. These systems are promising for biomedical applications in biosensing, bioimaging, targeted protein degradation, and cellular apoptosis.
Assuntos
Compostos Azo , Polímeros , Compostos Azo/química , Polímeros/química , Polímeros/síntese química , Técnicas Biossensoriais , Estrutura Molecular , HumanosRESUMO
Photo-responsive liquid crystal polymers (LCPs) have potential application value in flexible robots, artificial muscles, and microfluidic control. In recent years, significant progress has been made in the development of LCPs. However, the preparation of LCPs with continuous and controllable stepwise deformation capabilities remains a challenge. In this study, visible photo-responsive cyanostilbene monomer, UV photo-responsive azobenzene monomer, and multiple hydrogen bond crosslinker are used to prepare photo-responsive LCPs capable of achieving continuously and controllable stepwise deformation. The comprehensive investigation of the multiple light response ability and photo-induced deformation properties of these copolymers is conducted. The results reveal that in the first stage of photo-induced deformation under 470 nm blue light irradiation, the deformation angle decreases with a reduction in cyanostilbene content in the copolymer component, ranging from 40° in AZ0-CS4 to 0° in AZ4-CS0. In the second stage of photo-induced deformation under 365 nm UV irradiation, the deformation angle increases with the increase of azobenzene content, ranging from 0° of AZ0-CS4 to 89.4° of AZ4-CS0. Importantly, the deformation between these two stages occurs as a continuous process, allowing for a direct transition from the first-stage to the second-stage deformation by switching the light source from 470 to 365 nm.
Assuntos
Polímeros , Polímeros/química , Polímeros/síntese química , Raios Ultravioleta , Processos Fotoquímicos , Compostos Azo/química , Cristais Líquidos/química , Estrutura Molecular , Luz , Ligação de HidrogênioRESUMO
Flexible ultraviolet (UV) light detection technology has important applications in wearable devices, smart sensors, and other fields and attracts much attention in recent years. However, for most semiconductor-based UV detectors, the elastic modulus between rigid semiconductors and flexible substrates is mismatched, which makes it difficult to fabricate UV detectors that meet the needs of wearable devices. Herein, a fully flexible, large-scale, skin-friendly UV photodetector component centered on photo-responsive worm-like polymer nanoparticles (NPs) is developed, and the resulting device can quantitatively detect UV illumination. Skin-friendly poly(vinyl alcohol) (PVA), amphiphilic azobenzene-containing polymer NPs (AzNPs), and water-soluble ionic liquids (IL) are formed into (AzNPs-IL)/PVA fabrics by electrospinning. There are interactions such as hydrogen bonding among PVA, AzNPs, and IL, which make the material system stable. The UV detector made of the fabric realizes UV sensing through the illuminance-mechanical stress-electrical signal conversion mechanism. It is capable of achieving a response time of 9 s, a detection range of 10-150 mW cm-2, and stability for 1000 cycle tests upon 365 nm UV irradiation. Moreover, it has good skin affinity, and the water contact angle of the fabric is only 23.57°, which holds great promise for wearable smart devices.
Assuntos
Nanopartículas , Polímeros , Raios Ultravioleta , Dispositivos Eletrônicos Vestíveis , Nanopartículas/química , Polímeros/química , Álcool de Polivinil/química , Pele/química , Humanos , Líquidos Iônicos/química , Compostos Azo/químicaRESUMO
The conventional approach to developing light-sensitive glycosidase activity regulators, involving the combination of a glycomimetic moiety and a photoactive azobenzene module, results in conjugates with differences in glycosidase inhibitory activity between the interchangeable E and Z-isomers at the azo group that are generally below one-order of magnitude. In this study, we have exploited the chemical mimic character of sp2-iminosugars to access photoswitchable p- and o-azobenzene α-O-glycosides based on the gluco-configured representative ONJ. Notably, we achieved remarkably high switching factors for glycosidase inhibition, favoring either the E- or Z-isomer depending on the aglycone structure. Our data also indicate a correlation between the isomeric state of the azobenzene module and the selectivity towards α- and ß-glucosidase isoenzymes. The most effective derivative reached over a 103-fold higher inhibitory potency towards human ß-glucocerebrosidase in the Z as compared with the E isomeric form. This sharp contrast is compatible with ex-vivo activation and programmed self-deactivation at physiological temperatures, positioning it as a prime candidate for pharmacological chaperone therapy in Gaucher disease. Additionally, our results illustrate that chemical tailoring enables the engineering of photocommutators with the ability to toggle inhibition between α- and ß-glucosidase enzymes in a reversible manner, thus expanding the versatility and potential therapeutic applications of this approach.
Assuntos
Compostos Azo , Inibidores Enzimáticos , Glicosídeo Hidrolases , Glicosídeos , Imino Açúcares , Humanos , Compostos Azo/química , Compostos Azo/farmacologia , Compostos Azo/síntese química , Relação Dose-Resposta a Droga , Inibidores Enzimáticos/química , Inibidores Enzimáticos/farmacologia , Inibidores Enzimáticos/síntese química , Glicosídeo Hidrolases/antagonistas & inibidores , Glicosídeo Hidrolases/metabolismo , Glicosídeos/química , Glicosídeos/farmacologia , Glicosídeos/síntese química , Imino Açúcares/química , Imino Açúcares/farmacologia , Imino Açúcares/síntese química , Luz , Estrutura Molecular , Relação Estrutura-Atividade , Glucosilceramidase/química , Glucosilceramidase/metabolismo , Glucosilceramidase/farmacologiaRESUMO
Iron-doped biochar has been widely used as an adsorbent to remove contaminants due to the high adsorption performance, but it still suffers from complicated preparation methods, unstable iron loading, unsatisfactory specific surface area, and uneven distribution of active sites. Here, a novel magnetic porous biochar (FeCS800) with nanostructure on surface was synthesized by one-pot pyrolysis method of corn straw with K2FeO4, and used in orange G (OG) and tetracycline (TC) adsorption. FeCS800 exhibited outstanding adsorption capacities for OG and TC after K2FeO4 activation and the adsorption data were fitted satisfactorily to Langmuir isotherm and Pseudo-second-order kinetic model. The maximum adsorption capacities of FeCS800 for OG and TC were around 303.03 mg/g and 322.58 mg/g, respectively, at 25 °C and pH 7.0, which were 16.27 and 24.61 times higher than that before modification. Thermodynamic studies showed that the adsorption of OG/TC by FeCS800 were thermodynamically favorable and highly spontaneous. And the adsorption capacity of OG and TC by FeCS800 remained 77% and 81% after 5 cycles, respectively, indicating that FeCS800 had good stability. The outstanding adsorption properties and remarkable reusability of FeCS800 show its great potential to be an economic and environmental adsorbent in contaminants removal.
Assuntos
Carvão Vegetal , Tetraciclina , Poluentes Químicos da Água , Adsorção , Tetraciclina/química , Carvão Vegetal/química , Poluentes Químicos da Água/química , Porosidade , Compostos Azo/química , Benzenossulfonatos/química , Cinética , TermodinâmicaRESUMO
Among the various methods for the removal of azo dye, electrocoagulation is recognized to be highly efficient. However, the process is associated with high operation and maintenance cost, which demands the need for reducing the electrolysis time without compromising the performance efficiency. This can be achieved by adopting hybrid electrocoagulation process with a low-cost but effective process, such as adsorption. The study investigated the performance of a hybrid electrocoagulation-biocomposite system (H-EC-BC) for removing methyl orange dye. Firstly, the operating parameters of electrocoagulation process were optimized and a removal efficiency of 99% has been attained using Fe-SS electrodes at a pH of 6 for a reaction time of 30 min. The performance of EC process was found to be decreasing with increase in dye concentration. Secondly, biocomposite was synthesized from Psidium guajava leaves and characterized using SEM, FTIR, EDAX, and XRD analyses. The results suggested that it is having a porous nature and cellulose crystal structure and confirmed the presence of chemical elements such as carbon (65.2%), oxygen (29.1%) as primary with Fe, Cl, Na and Ca as secondary elements. The performance of the biocomposite was evaluated for the dye adsorption using spectrophotometric methods. Various operating parameters were optimized using experimental methods and a maximum removal efficiency of 65% was achieved at a pH of 6, dosage of 5 g/L and an adsorption contact time of 120 min. The maximum efficiency (92.78%) was obtained with Fe-SS electrodes and KCl as a sustaining electrolyte under acidic circumstances (pH 6). The biocomposite was observed to be more efficient for higher dye concentration. Langmuir and Freundlich adsorption isotherms were fitted with the experimental results with R2 values as 0.926 and 0.980 respectively. The adsorption kinetics were described using Pseudo-first and Pseudo-second order models, wherein Pseudo-second order model fits the experimental results with R2 value of 0.999. The energy consumption of electrocoagulation (EC) process in the hybrid H-EC-BC system was compared to that of a standard EC process. The results demonstrated that the hybrid system is approximately 7 times more energy efficient than the conventional process, thereby implicating its adaptability for field application.
Assuntos
Corantes , Águas Residuárias , Poluentes Químicos da Água , Adsorção , Corantes/química , Poluentes Químicos da Água/química , Águas Residuárias/química , Compostos Azo/química , Eletrocoagulação/métodos , Descoloração da Água/métodos , Purificação da Água/métodosRESUMO
There has been significant attention on the efficient degradation of pollutants in wastewater using metal-organic frameworks (MOFs) photocatalytic methods over the past decade. Herein, we examined the elimination of two different types of water-contaminating dyes, specifically cationic dye methylene blue (MB) and anionic dye methyl orange (MO), through the application of bimetal Cu/Ni-BTC@SiO2 MOF as high performance photocatalyst. The bimetal Cu/Ni-BTC@SiO2 photocatalyst was synthesized and characterized by XRD, FTIR, SEM, TEM, TGA, BET, DRS, and VSM techniques. The examination of the impact of different operational factors on the elimination of pollutants involved a comprehensive analysis of variables including the photocatalyst type, initial pollutant concentration, quantity of photocatalyst, and pH levels. The highest removal efficiency for MO and MB dyes by the photocatalyst was found to be 98 and 71%, respectively, within 60 min. In the fifth reaction stage, degradation efficiency for MO and MB was 76 and 56% respectively. Kinetic investigations demonstrated that, in the context of the uptake of MB and MO dyes, the interparticle diffusion, and pseudo-second-order models emerged as possessing the most robust correlation coefficients with the experimental data, registering values of 0.988 and 0.961, respectively. The examination of isotherms reveals that the isotherm models proposed by BET, and Anderson (V) demonstrate the highest level of conformity with the empirical data for the decomposition of MB and MO dyes, correspondingly. The TOC levels decreased significantly from 51 to 14 and 47 to 3 mg/L for MB and MO dyes, indicating the effective mineralization process using Cu/Ni-BTC@SiO2.
Assuntos
Cobre , Azul de Metileno , Dióxido de Silício , Poluentes Químicos da Água , Cobre/química , Cobre/análise , Poluentes Químicos da Água/química , Poluentes Químicos da Água/análise , Dióxido de Silício/química , Azul de Metileno/química , Compostos Azo/química , Corantes/química , Níquel/química , Níquel/análise , Catálise , CinéticaRESUMO
Highly colored azo dye-contaminated wastewater poses significant environmental threats and requires effective treatment before discharge. The anaerobic azo dye treatment method is a cost-effective and environmentally friendly solution, while its time-consuming and inefficient processes present substantial challenges for industrial scaling. Thus, the use of iron materials presents a promising alternative. Laboratory studies have demonstrated that systems coupled with iron materials enhance the decolorization efficiency and reduce the processing time. To fully realize the potential of iron materials for anaerobic azo dye treatment, a comprehensive synthesis and evaluation based on individual-related research studies, which have not been conducted to date, are necessary. This review provides, for the first time, an extensive and detailed overview of the utilization of iron materials for azo dye treatment, with a focus on decolorization. It assesses the treatment potential, analyzes the influencing factors and their impacts, and proposes metabolic pathways to enhance anaerobic dye treatment using iron materials. The physicochemical characteristics of iron materials are also discussed to elucidate the mechanisms behind the enhanced bioreduction of azo dyes. This study further addresses the current obstacles and outlines future prospects for industrial-scale application of iron-coupled treatment systems.
Assuntos
Compostos Azo , Corantes , Ferro , Águas Residuárias , Poluentes Químicos da Água , Compostos Azo/química , Corantes/química , Águas Residuárias/química , Poluentes Químicos da Água/química , Ferro/química , Eliminação de Resíduos Líquidos/métodos , Descoloração da Água/métodosRESUMO
Water pollution has caused problems in coastal areas, rivers, lakes, and other important water sources around the world as a result of inappropriate waste management. Meanwhile, these pollutants are harmful to humans and aquatic life. Textile dye effluent methyl orange (MO) was used in this work for dye degradation studies employing nanocomposites. As a result, the importance of synthesizing pure ZnO and Co3O4 nanoparticles with composites of ZnCo2O4 (zinc cobaltite) nanorods in three various proportions (90:10, 75:25, and 50:50) is emphasized in this study. Many advanced approaches were used to assess the various features of these materials, including size and shape. Fourier transform infrared (FT-IR) spectroscopy was used to determine the vibrational modes of the materials. The absorption measurements were then carried out using UV-vis spectroscopic techniques, and the photocatalytic breakdown of MO was done under visible light irradiation. The findings revealed that pure materials were inadequate for visible light activity, resulting in decreased degradation efficiencies. Spinel cobaltite structures have potential degradation efficiency under visible light, while ZnCo2O4 (50:50) catalyst has superior degradation efficiency of 59.8% over MO. The crystallite size, morphology, functional group, absorption wavelength, and band gap all play important roles in enhancing the material's photocatalytic activity under visible light. Meanwhile, ZnCo2O4 spinel structures are crucial for increasing charge carriers and reducing electron-hole recombination. As a result, zinc cobaltite minerals are widely used in industrial dye degradation applications.