Ultrasound controlled mechanophore activation in hydrogels for cancer therapy.

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.

Accelerated Activity-Based Sensing by Fluorogenic Reporter Engineering Enables to Rapidly Determine Unstable Analyte.

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 (∼2 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.

Exploring the decolorization efficiency and biodegradation mechanisms of different functional textile azo dyes by Streptomyces albidoflavus 3MGH.

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.

Sequence similarity network analysis of drug- and dye-modifying azoreductase enzymes found in the human gut microbiome.

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.

Photoresponsive Azobenzene Nanocluster-Modified Liposomes: Mechanism Analysis Combining Experiments and Simulations.

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.

Skin-Friendly Flexible Ultraviolet Detectors Based on Reversibly Deformable Worm-Like Polymer Nanoparticles.

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.

Sustainable efficient utilization of magnetic porous biochar for adsorption of orange G and tetracycline: Inherent roles of adsorption and mechanisms.

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.

Harnessing bromide ions to boost peroxymonosulfate for reactive yellow 145 dye degradation.

Bromide (Br-) was found in the fresh waters at concentrations from 0.1 to 1 mg/L and can be used to activate peroxymonosulfate (PMS) as a widely used chemical oxidation agent. In the present study, the reaction between PMS and Br- ions (PMS/Br- process) for the effective degradation of reactive yellow 145 (RY-145) dye was investigated by changing operational parameters vis solution pH, dosage of Br- ions and PMS, RY-145 concentration, and reaction time. Based on the results, the simultaneous presence of PMS and Br- ions in the solution led to efficient degradation of RY-145 with a synergistic index of 11.89. The degradation efficiency of RY-145 was decreased in severe basic pH and the presence of CO32- ions as a coexisting anion. Likewise, 4 mg/L of humic acid (HA), used as a classic scavenger, led to a 26.53% decrease in the RY-145 degradation efficiency. The free bromine (HOBr/OBr-), superoxide radical (●O2-), and singlet oxygen (1O2) was the dominant oxidation agents in RY-145 degradation, which confirmed the nonradical degradation pathway. In addition, PMS/Br- process showed excellent ability in mineralizing RY-145 in different aqueous solutions (total organic carbon (TOC) decreased 86.39% in deionized water and 78.23% in tap water). Although pollutants such as azo dyes can be effectively removed in the PMS/Br- process, the formation of byproducts should be strategically controlled and special attention should be paid when the PMS-based advance oxidation process is applied to treat Br- containing solutions.

Interface engineered cascade-type electronic structure of 2D/0D/2D CdS-CdCO3/SnO2 quantum dots/g-C3N4 nanocomposite for boosting solar-driven photocatalysis.

A rational design of heterojunctions with high-quality contacts is essential for efficiently separating photogenerated charge carries and boosting the solar-driven harvesting capability. Herein, we fabricated a novel heterojunction of SnO2 quantum dots-anchored CdS-CdCO3 with g-C3N4 nanosheets as a superior photocatalyst. SnO2 quantum dots (SQDs) with positively charged surfaces were tightly anchored on the negatively charged surface of CdS nanosheets (NSs). The resulting CdS@SnO2 was finally decorated with g-C3N4 NSs, and a new crystalline phase of CdS-CdCO3 was formed during the hydrothermal decoration process, g-C3N4 decorated CdS-CdCO3@SnO2 (CdS-CdCO3@SnO2@g-C3N4). The as-synthesized photocatalysts were evaluated for the degradation of methyl orange dye under solar light conditions. The CdS-CdCO3@SnO2@g-C3N4 exhibited 7.7-fold and 2.3-fold enhancements in photocatalytic activities in comparison to those of the bare CdS and CdS@SnO2 NSs, respectively. The optimal performance of CdS-CdCO3@SnO2@g-C3N4 is primarily attributed to the cascade-type conduction band alignments between 2D/0D/2D heterojunctions, which can harvest maximum solar light and effectively separate photoexcited charge carriers. This work provides a new inspiration for the rational design of 2D/0D/2D heterojunction photocatalyst for green energy generation and environmental remediation applications.

Bimetal Cu/Ni-BTC@SiO2 metal-organic framework as high performance photocatalyst for degradation of azo dyes under visible light irradiation.

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.

A hybrid electrocoagulation-biocomposite adsorption system for the decolourization of dye wastewater.

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.

Facile synthesis of lignin-based Fe-MOF for fast adsorption of methyl orange.

To rapidly remove dyes from wastewater, iron-based metal-organic frameworks modified with phenolated lignin (NH2-MIL@L) were prepared by a one-step hydrothermal method. Analyses of the chemical structure and adsorption mechanism of the NH2-MIL@L proved the successful introduction of lignin and the enhancement of its adsorption sites. Compared with NH2-MIL-101-Fe without phenolated lignin, the modification with lignin increased the methyl orange (MO) adsorption rate of NH2-MIL@L. For the best adsorbent, NH2-MIL@L4, the MO adsorption efficiency in MO solution reached 95.09% within 5 min. NH2-MIL@L4 reached adsorption equilibrium within 90 min, exhibiting an MO adsorption capacity of 195.31 mg/g. The process followed pseudo-second-order kinetics and the Dubinin-Radushkevich model. MO adsorption efficiency of NH2-MIL@L4 was maintained at 89.87% after six adsorption-desorption cycles. In mixed solutions of MO and methylene blue (MB), NH2-MIL@L4 achieved an MO adsorption of 94.02% at 5 min and reached MO adsorption equilibrium within 15 min with an MO adsorption capacity of 438.6 mg/g, while the MB adsorption equilibrium was established at 90 min with an MB adsorption rate and capacity of 95.60% and 481.34 mg/g, respectively. NH2-MIL@L4 sustained its excellent adsorption efficiency after six adsorption-desorption cycles (91.2% for MO and 93.4% for MB). The process of MO adsorption by NH2-MIL@L4 followed the Temkin model and pseudo-second-order kinetics, while MB adsorption followed the Dubinin-Radushkevich model and pseudo-second-order kinetics. Electrostatic interactions, π-π interactions, hydrogen bonding, and synergistic interactions affected the MO adsorption process of NH2-MIL@L4.

Green synthesis of magnetic azo-linked porous organic polymers with recyclable properties for enhanced Bisphenol-A adsorption from aqueous solutions.

Porous organic polymers (POPs) present superior adsorption performance to steroid endocrine disruptors. However, the effective recovery and high cost have been a big limitation for their large-scale applications. Herein, magnetic azo-linked porous polymers (Fe3O4@SiO2/ALP-p) were designed and prepared in a green synthesis approach using low-price materials from phloroglucinol and pararosaniline via a diazo-coupling reaction under standard temperature and pressure conditions, which embedded with Fe3O4@SiO2 nanoparticles to form three-dimensional interlayer network structure with flexible-rigid interweaving. The saturated adsorption capacity to bisphenol-A (BPA) was 485.09 mg/g at 298 K, which increased by 1.4 times compared with ALP-p of relatively smaller mass density. This enhanced adsorption was ascribed to increment from surface adsorption and pore filling with 2.3 times of specific surface area and 2.6 times of pore volume, although the total organic functional groups decreased with Fe3O4@SiO2 amendment. Also, the adsorption rate increased by about 1.1 and 1.5-fold due to enhancement in the initial stage of surface adsorption and subsequent stage pore diffusion, respectively. Moreover, this adsorbent could be used in broad pH (3.0-7.0) and salinity adaptability (<0.5 mol/L). The loss of adsorption capacity and magnetic recovery were lower than 1.1% and 0.8% in each operation cycle because of the flexible-rigid interweave. This excellent performance was contributed by synergistic effects from physisorption and chemisorption, such as pore filling, electrostatic attraction, π-π stacking, hydrogen bonding, and hydrophobic interaction. This study offered a cost-effective, high-performing, and ecologically friendly material along with a green preparation method.

Banana peel extract for CeO2 nanoflower synthesis: Enhancing photocatalytic activity for methyl orange dye removal and bactericidal effects.

The cube architecture associated with the CeO2 nanoflowers (NFs) that generated, which had an average crystallization width of 7 nm, has been confirmed by X-ray crystallographic investigations. The method used is environmentally acceptable since it converts wasted banana peel extracts into CeO2 nanoflower. On the basis of artwork obtained from a High-Resolution Transmission Electron Microscope (HR-TEM), CeO2 nanoparticles have been observed to possess a spherical shape and an average particle diameter of 21 nm. To take the purpose of this study, green-fabricated CeO2-NFs were used to investigate the photocatalytic oxidation of methyl orange (MO) dye when exposed to sunshine. CeO2 nanofibers showed a degradation performance of 98% when compared to methyl orange dye. Evidently is a possibility that this may be caused by the presence of CeO2 nanoflowers, whereby enhance the interaction of electrons, which are holes dissolution, and adherence. Upon a single day of being exposed, the biocidal potential was tested against both gram-positive and gram-negative bacteria, including E. coli, B. cereus, and S. aureus, among others. Due to the fact that its 32 mm minimum inhibitory concentration (MIC) for B. cereus was the highest among conventional medicines. As shown by the extraordinary capabilities of WBP@CeO2 tiny particles, manipulating of flexible tiny particles to feed the purpose of achieving effective and customizable infections and dermatologist advancements is really stunning.

Two protocols for the detection of oleaginous bacteria using Oil Red O.

The selection of oleaginous bacteria, potentially applicable to biotechnological approaches, is usually carried out by different expensive and time-consuming techniques. In this study, we used Oil Red O (ORO) as an useful dye for staining of neutral lipids (triacylglycerols and wax esters) on thin-layer chromatography plates. ORO could detect minimal quantities of both compounds (detection limit, 0.0025 mg of tripalmitin or 0.005 mg of cetylpalmitate). In addition, we developed a specific, rapid, and inexpensive screening methodology to detect triacylglycerol-accumulating microorganisms grown on the agar plate. This staining methodology detected 9/13 strains with a triacylglycerol content higher than 20% by cellular dry weight. ORO did not stain polyhydroxyalkanoates-producing bacteria. The four oleaginous strains not detected by this screening methodology exhibited a mucoid morphology of their colonies. Apparently, an extracellular polymeric substance produced by these strains hampered the entry of the lipophilic dye into cells. The utilization of the developed screening methodology would allow selecting of oleaginous bacteria in a simpler and faster way than techniques usually used nowadays, based on unspecific staining protocols and spectrophotometric or chromatographic methods. Furthermore, the use of ORO as a staining reagent would easily characterize the neutral lipids accumulated by microorganisms as reserve compounds. KEY POINTS: • Oil Red O staining is specific for triacylglycerols • Oil Red O staining is useful to detect oleaginous bacteria • Fast and inexpensive staining to isolate oleaginous bacteria from the environment.

An activatable azophenyl fluorescent probe for hypoxic fluorescence imaging in living cells.

Cellular hypoxia is a common pathological process in various diseases. Detecting cellular hypoxia is of great scientific significance for early diagnosis of tumors. The hypoxia fluorescence probe analysis method can efficiently and conveniently evaluate the hypoxia status in tumor cells. These probes are covalently linked by hypoxic recognition groups and organic fluorescent molecules. Currently, the fluorescent molecules used in these probes often exhibit the aggregation-caused quenching effect, which is not conducive to fluorescence imaging in water. Herein, an activatable hypoxia fluorescence probe was constructed by covalently linking aggregation-induced emission luminogens to the hypoxic recognition group azobenzene. It does not emit fluorescence in solution and in solid state under light excitation due to the presence of photosensitive azo bonds. It can be cleaved by intracellular azoreductase into fluorescent amino derivatives with aggregation-induced emission characteristic. As the concentration of oxygen in cells decreases, its fluorescence intensity increases, making it suitable for fluorescence imaging to detect hypoxic environment in live cancer cells. This work broadens the molecular design approach for activatable hypoxia fluorescent probes.

Theoretical Study of the Mechanism of the Formation of Azomethine Ylide from Isatine and Sarcosine and Its Reactivity in 1,3-Dipolar Cycloaddition Reaction with 7-Oxabenzonorbornadiene.

The reaction mechanism of tthe formation of azomethine ylides from isatins and sarcosine is addressed in the literature in a general manner. This computational study aims to explore the mechanistic steps for this reaction in detail and to assess the reactivity of formed ylide in a 1,3-dipolar cycloaddition reaction with 7-oxabenzonorbornadiene. For this purpose, density functional theory (DFT) calculations at the M06-2X(SMD,EtOH)/6-31G(d,p) level were employed. The results indicate that CO2 elimination is the rate-determining step, the activation barrier for 1,3-dipolar cycloaddition is lower, and the formed ylide will readily react with dipolarophiles. The substitution of isatine with electron-withdrawal groups slightly decreases the activation barrier for ylide formation.

Robust Photocatalytic MICROSCAFS® with Interconnected Macropores for Sustainable Solar-Driven Water Purification.

Advanced oxidation processes, including photocatalysis, have been proven effective at organic dye degradation. Tailored porous materials with regulated pore size, shape, and morphology offer a sustainable solution to the water pollution problem by acting as support materials to grafted photocatalytic nanoparticles (NPs). This research investigated the influence of pore and particle sizes of photocatalytic MICROSCAFS® on the degradation of methyl orange (MO) in aqueous solution (10 mg/L). Photocatalytic MICROSCAFS® are made of binder-less supported P25 TiO2 NPs within MICROSCAFS®, which are silica-titania microspheres with a controlled size and interconnected macroporosity, synthesized by an adapted sol-gel method that involves a polymerization-induced phase separation process. Photocatalytic experiments were performed both in batch and flow reactors, with this latter one targeting a proof of concept for continuous transformation processes and real-life conditions. Photocatalytic degradation of 87% in 2 h (batch) was achieved, using a calibrated solar light simulator (1 sun) and a photocatalyst/pollutant mass ratio of 23. This study introduces a novel flow kinetic model which provides the modeling and simulation of the photocatalytic MICROSCAFS® performance. A scavenger study was performed, enabling an in-depth mechanistic understanding. Finally, the transformation products resulting from the MO photocatalytic degradation were elucidated by high-resolution mass spectrometry experiments and subjected to an in silico toxicity assessment.

Microbial communities drive flux of acid orange 7 and crystal violet dyes in water-sediment system.

Unchecked dye effluent discharge poses escalating environmental and economic concerns, especially in developing nations. While dyes are well-recognized water pollutants, the mechanisms of their environmental spread are least understood. Therefore, the present study examines the partitioning of Acid Orange 7 (AO7) and Crystal Violet (CV) dyes using water-sediment microcosms and reports that native microbes significantly affect AO7 decolorization and transfer. Both dyes transition from infused to pristine matrices, reaching equilibrium in a fortnight. While microbes influence CV partitioning, their role in decolorization is minimal, emphasizing their varied impact on the environmental fate of dyes. Metagenomic analyses reveal contrasting microbial composition between control and AO7-infused samples. Control water samples displayed a dominance of Proteobacteria (62%), Firmicutes (24%), and Bacteroidetes (9%). However, AO7 exposure led to Proteobacteria reducing to 57% and Bacteroidetes to 3%, with Firmicutes increasing to 34%. Sediment samples, primarily comprising Firmicutes (47%) and Proteobacteria (39%), shifted post-AO7 exposure: Proteobacteria increased to 53%, and Firmicutes dropped to 38%. At the genus level, water samples dominated by Niveispirillum (34%) declined after AO7 exposure, while Bacillus and Pseudomonas increased. Notably, Serratia and Sphingomonas, known for azo dye degradation, rose post-exposure, hinting at their role in AO7 decolorization. Conversely, sediment samples showed a decrease in the growth of Bacillus and an increase in that of Pseudomonas and Serratia. These findings emphasize the significant role of microbial communities in determining the environmental fate of dyes, providing insights on its environmental implications and management.

Oxygen-deficient AgIO3 for efficiently photodegrading organic contaminants under natural sunlight.

Defect engineering is regarded as an effective strategy to boost the photo-activity of photocatalysts for organic contaminants removal. In this work, abundant surface oxygen vacancies (Ov) are created on AgIO3 microsheets (AgIO3-OV) by a facile and controllable hydrogen chemical reduction approach. The introduction of surface Ov on AgIO3 broadens the photo-absorption region from ultraviolet to visible light, accelerates the photoinduced charges separation and migration, and also activates the formation of superoxide radicals (•O2-). The AgIO3-OV possesses an outstanding degradation rate constant of 0.035 min-1, for photocatalytic degrading methyl orange (MO) under illumination of natural sunlight with a light intensity is 50 mW/cm2, which is 7 and 3.5 times that of the pristine AgIO3 and C-AgIO3 (AgIO3 is calcined in air without generating Ov). In addition, the AgIO3-OV also exhibit considerable photoactivity for degrading other diverse organic contaminants, including azo dye (rhodamine B (RhB)), antibiotics (sulflsoxazole (SOX), norfloxacin (NOR), chlortetracycline hydrochloride (CTC), tetracycline hydrochloride (TC) and ofloxacin (OFX)), and even the mixture of organic contaminants (MO-RhB and CTC-OFX). After natural sunlight illumination for 50 min, 41.4% of total organic carbon (TOC) for MO-RhB mixed solution can be decreased over AgIO3-OV. In a broad range of solution pH from 3 to 11 or diverse water bodies of MO solution, AgIO3-OV exhibits attractive activity for decomposing MO. The MO photo-degradation process and mechanism over AgIO3-OV under natural sunlight irradiation has been systemically investigated and proposed. The toxicities of MO and its degradation intermediates over AgIO3-OV are compared using Toxicity Estimation Software (T.E.S.T.). Moreover, the non-toxicity of both AgIO3-OV catalyst and treated antibiotic solution (CTC-OFX mixture) are confirmed by E. coli DH5a cultivation test, supporting the feasibility of AgIO3-OV catalyst to treat organic contaminants in real water under natural sunlight illumination.