Synergetic Oxidation of the Hydroxyl Radical and Superoxide Anion Lowers the Benzoquinone Intermediate Conversion Barrier and Potentiates Effective Aromatic Pollutant Mineralization.

Regulation of the free radical types is crucial but challenging in the ubiquitous heterogeneous catalytic oxidation for chemosynthesis, biotherapy, and environmental remediation. Here, using aromatic pollutant (AP) removal as a prototype, we identify the massive accumulation of the benzoquinone (BQ) intermediate in the hydroxyl radical (•OH)-mediated AP degradation process. Theoretical prediction and experiments demonstrate that BQ is both a Lewis acid and base because of its unique molecular and electronic structure caused by the existence of symmetrical carbonyl groups; therefore, it is hard to be electrophilically added by oxidizing •OH as a result of the high reaction energy barrier (ΔG = 1.74 eV). Fortunately, the introduction of the superoxide anion (•O2-) significantly lowers the conversion barrier (ΔG = 0.91 eV) of BQ because •O2- can act as the electron donor and acceptor simultaneously, electrophilically and nucleophilically add to BQ synchronously, and break it down. Subsequently, the breakdown products can then be further oxidized by •OH until completely mineralized. Such synergistic oxidation based on •OH and •O2- timely eliminates BQ, potentiates AP mineralization, and inhibits electrode fouling caused by high-resistance polymeric BQ; more importantly, it effectively reduces toxicity, saves energy and costs, and decreases the environmental footprint, evidenced by the life cycle assessment.

Designing Internal Hierarchical Porous Networks in Polymer Monoliths that Exhibit Rapid Removal and Photocatalytic Degradation of Aromatic Pollutants.

This paper describes the preparation of 3D polymer monoliths containing internal hierarchical porosity. The porous networks are fabricated based on Pickering high-internal-phase emulsions (HIPEs) stabilized by microporous ß-cyclodextrin-based polymer particles (CDPs) as the emulsifier; CDPs are facilely synthesized by the polyaddition reactions without the need for catalysts. The designed Pickering agents enable to form a bicontinuous internal phase in 8:2 cyclohexane-water v/v, and the oil droplets in the continuous water phase is found to be fairly stable up to 1 month. Furthermore, the addition of acrylamide and N,N'-methylenebis(acrylamide) results in polymer networks after in situ thermal polymerization at 60 °C in the water phase, and the monoliths include both interconnected macropores from the HIPE template and micro- and mesopores from the CDPs embedded at the interface. The porous monoliths rapidly absorb a variety of solvents taking advantage of multiscale porosity and amphiphilicity. Furthermore, the materials can be efficiently used for the removal of aromatic pollutants and then reused after washing and drying without the deterioration of performance. Also, they exhibit high photocatalytic capability and good recyclability as being used as a catalytic support when embedded with titanium dioxide (TiO2 ).

Frequency-modulated alternating current-driven bioelectrodes for enhanced mineralization of Alizarin Yellow R.

The alternating current (AC)-driven bioelectrochemical process, in-situ coupling cathodic reduction and anodic oxidation in a single electrode, offers a promising way for the mineralization of refractory aromatic pollutants (RAPs). Frequency modulation is vital for aligning reduction and oxidation phases in AC-driven bioelectrodes, potentially enhancing their capability to mineralize RAPs. Herein, a frequency-modulated AC-driven bioelectrode was developed to enhance RAP mineralization, exemplified by the degradation of Alizarin Yellow R (AYR). Optimal performance was achieved at a frequency of 1.67 mHz, resulting in the highest efficiency for AYR decolorization and subsequent mineralization of intermediates. Performance declined at both higher (3.33 and 8.30 mHz) and lower (0.83 mHz) frequencies. The bioelectrode exhibited superior electron utilization, bidirectional electron transfer, and redox bifunctionality, effectively aligning reduction and oxidation processes to enhance AYR mineralization. The 1.67 mHz frequency facilitated the assembly of a collaborative microbiome dedicated to AYR bio-mineralization, characterized by an increased abundance of functional consortia proficient in azo dye reduction (e.g., Stenotrophomonas and Shinella), aromatic intermediates oxidation (e.g., Sphingopyxis and Sphingomonas), and electron transfer (e.g., Geobacter and Pseudomonas). This study reveals the role of frequency modulation in AC-driven bioelectrodes for enhanced RAP mineralization, offering a novel and sustainable approach for treating RAP-bearing wastewater.

Biosensing of multiple aromatic xenobiotics in water by in-house fabricated prototype device.

Portable, low-cost, and accurate monitoring of hazardous mono-aromatic pollutants, such as phenol or benzene group of compounds in water is a challenging task due to the lack of suitable detectable functional groups and complex matrix of environmental samples. Here, we use a series of protein-based biosensing recognition scaffolds to enable specific detection of several mono-aromatic classes of xenobiotics. The biosensor is tuned to perform in intricate environmental conditions and is interfaced with an in-house manufactured, multi-channel device (AroTrack) capable of direct and sensitive detection of several of these aromatic contaminants, such as phenol, benzene, and 2,3-dimethylphenol (2,3-DMP) in the low ppb range (10-200 ppb). The efficiency of the prototype device was benchmarked in both simulated wastewater and real environmental samples comprising 10 times higher isostructural aromatic pollutants or ions. It was established that AroTrack is reliable for environmental sample testing with a high degree of reproducibility and efficiency comparable to that of modern spectrophotometers (<5 % error). The battery-operated device costs less than $50 to fabricate and this low cost makes it effective to be implemented in rural and low-income settings which suggests immense field deployable potential.

Heat-resistant boron-nitrogen doped lignin-derived adsorbent-catalyst for gaseous aromatic pollutants removal.

Lignin-based carbon material can be utilized as carbonaceous adsorbents for the removal of toxic gaseous organic pollutants, while the poor heat-resistance limited its widely application. Here in, B-N co-doped lignin carbon (BN-C) with high thermal stability was synthesized, and the optimized BN-C (1:2) exhibited notably improved heat resistance with the decomposition temperature up to 505 °C, and excellent adsorption capacity for o-dichlorobenzene (o-DCB) (1510.0 mg/g) and toluene (947.3 mg/g), together with good cyclic stability over 10 cycles for o-dichlorobenzene. The existence of abundant hexagonal boron nitride (h-BN) with good thermal conductivity contributed to the superior heat-resistance of BN-C (1:2), and the high specific surface area (1764.5 m2/g), enriched hydroxyl functional groups and improved graphitization degree contributed to its enhanced adsorption performance. More importantly, BN-C (1:2) supported Ru could effectively remove o-DCB and toluene at wide temperature range (50-300 °C). The present work guided the development of heat-resistant lignin-derived adsorbent-catalyst for gaseous aromatic pollutants removal, which benefits both environmental protection and resource utilization.

Preparation of GO/COFs composites by interlayer-confined strategy for the adsorption of nitro aromatic pollutants.

With the continuous development of industrialization, the excessive emission of nitro aromatic with strong toxicity, high carcinogenicity and non-degradability has attracted great attention. How to efficiently remove nitro aromatic pollutants is an important research topic. In this work, graphene oxide/covalent organic frameworks (GO/COFs) composites were successfully synthesized via interlayer confinement strategy selecting GO, 2,5-dimethoxybenzene-1,4-dicarboxaldehyde (DMTP) and 1,3,5-tri(4-aminophenyl)benzene (TPB) as raw materials. Due to high specific surface area, hierarchical porous structure and good thermal stability, GO/COFs were utilized to adsorb and remove nitro aromatic hydrocarbons in the water environment. The adsorption behavior of GO/COFs for o-nitrophenol, 1,3-dinitrobenzene and 2,4,6-trinitrophenol were further investigated. The GO/COFs composites showed the strongest adsorption capacity for 2,4,6-trinitrophenol, and the maximum adsorption capacity for 2,4,6-trinitrophenol, o-nitrophenol, and 1,3-dinitrobenzene were 438, 317, and 173 mg g-1, respectively. The experimental results indicated that the GO/COFs composites provided great adsorption capability for nitro aromatic pollutants and can be reused, rendering it an extremely potential adsorbent for organic pollutants.

Changing the reaction pathway in TiO2 photocatalytic dehalogenation of halogenated aromatic pollutants by surface hydroxyl regulation.

Understanding the photocatalytic reductive dehalogenation mechanism of halogenated aromatic pollutants is of great research value. However, the proton source in the photocatalytic dehalogenation process of representative halogenated aromatic pollutants by TiO2 is not clear. In this study, the TiO2 surface was modified by hydrochloric acid, sodium hydroxide, and sodium fluoride to obtain TiO2 samples with different hydroxyl groups. It was found that the hydroxyl groups on the surface of TiO2 affects the sequence of proton and electron transfer in dehalogenation. The abundance of hydroxyl groups on the surface of TiO2 can accelerate the reductive dehalogenation process of representative halogenated aromatic pollutants. The kinetic solvent isotope effect was used to study the proton-coupled electron transfer process in the reaction. It shows that the enriching of protons on TiO2 bridging oxygen (bridging hydroxyl groups) is conducive to the rapid step of protonation of the reactant, and subsequent proton and electron transfer. On the contrary, the bridging hydroxyl groups can be removed by reacting with strongly basic sodium hydroxide and sodium ions can occupy the bridging oxygen. The substitution of bridging oxygen by fluorine ions can also lead to the destruction of bridge hydroxyl groups. Significantly, the absence of bridging hydroxyl groups on titanium dioxide will lead to the dehalogenation of representative halogenated aromatic pollutants initiated by electron transfer. This study is helpful to understand dehalogenation reaction paths catalyzed by TiO2.

Evaluation of scale-up effect on cold-active enzyme production and biodegradation tests using pilot-scale bioreactors and a 3D soil tank.

Despite recent attention being paid to the biodegradation of petroleum hydrocarbons in cold environments, scale-up studies of biodegradation are lacking. Herein, the effect of scale-up on the enzymatic biodegradation of highly contaminated soil at low temperatures was studied. A novel cold-adapted bacteria (Arthrobacter sp. S2TR-06) was isolated that could produce cold-active degradative enzymes (xylene monooxygenase (XMO) and catechol 2,3-dioxygenase (C2,3D)). Enzyme production was investigated on 4 different scales (lab to pilot scale). The results showed a shorter fermentation time, and the highest production of enzymes and biomass (107 g/L for biomass, 109 U/mL, and 203 U/mL for XMO and C2,3D after 24 h) was achieved in the 150-L bioreactor due to enhanced oxygenation. Multi-pulse injection of p-xylene into the production medium was needed every 6 h. The stability of membrane-bound enzymes can be increased up to 3-fold by adding FeSO4 at 0.1% (w/v) before extraction. Soil tests also showed that biodegradation is scale-dependent. The maximum biodegradation rate decreased from 100% at lab-scale to 36% in the 300-L sand tank tests due to limited access of enzymes to trapped p-xylene in soil pores, low dissolved oxygen in the water-saturated zone, soil heterogeneity, and the presence of the free phase of p-xylene. The result demonstrated that formulation of enzyme mixture with FeSO4 and direct injection of enzyme mixture (third scenario) can increase the efficiency of bioremediation in heterogeneous soil. In this study, it was demonstrated that cold-active degradative enzyme production can be scaled up to an industrial scale and enzymatic treatment can be used to effectively bioremediate p-xylene contaminated sites. This study could provide key scale-up guidance for the enzymatic bioremediation of mono-aromatic pollutants in water-saturated soil under cold conditions.

Tailored Sky-Parking Architectures of 3D Graphene Oxide Towards Highly-Efficient Water Purification.

The widespread use of chemicals has brought serious water pollution threatening human health and environment, which requires green, fast, and low-cost purification urgently. Here, we build up a novel material family of sky-parking-like 3D structured graphene oxides (SP-GOs) with adjustable interlayer-space of 0.8-1.7 nm via the insertion of different sized diamine compounds as support pillars between GO layers. The assembled 3D SP-GOs exhibit superior adsorption capacity and short removal time for various aromatic organic compounds in water, achieving record-breaking maximum adsorption capacity of 535.79 mg g-1 toward the most common water-pollutant bisphenol A (BPA) at ambient conditions as well as significantly improved removal of other organic pollutants including sulfapyridine, carbamazepine, ketoprofen and 2-naphthol. The construction of SP-GO provides a simple approach for evolving the GO material from 2D to 3D and a new avenue for the decontamination of pollutants in environmental remediation.

Modelling the octanol-air partition coefficient of aromatic pollutants based on the solvation free energy and the dimer effect.

In this study, generalized predictive models were developed to estimate KOA of four kinds of aromatic pollutants based on the calculated solvation free energy and taking the dimer effect into account. Uncorrected log KOA values, which were directly estimated from the calculated solvation free energy of individual molecules, underestimated experimental values, and the deviation increased with increasing log KOA. Dimers were found to greatly affect the apparent KOA values of these aromatic pollutants, which were driven by π-π interactions. London dispersion and exchange-repulsion terms were identified to be dominant components of the underlying π-π interactions. It is interesting to find that the π-π interactions of polybrominated diphenyl ethers correlate with not only the molecular polarizability but also the size of opposing aromatic surfaces, which leads to a different trend of π-π interactions from other aromatic pollutants. A universal quantitative structure-activity relationship model was developed to estimate the proportion of dimers based on five molecular structural descriptors relevant to the π-π interactions. After calibration with the dimer effect, estimations of log KOA were consistent with experimental values. Therefore, the dimer effect should be taken into consideration when investigating the partition behavior of aromatic pollutants, and the solvation free energy model could be an alternative method for the prediction of KOA.

A colorimetric supramolecular sensor array based on charge-transfer complexes for multiplex aniline and phenolic pollutants detection.

In order to effectively monitor toxic and harmful substances in sewage discharge, a rapid, highly sensitive detection of complex pollutants with similar structures has become an urgent problem to be solved. In this paper, a supramolecular colorimetric array sensor based on charge-transfer complex was constructed, which can quickly detect aniline and phenol pollutants (such as p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, m-aminophenol, hydroquinone, and resorcinol) with similar structures. When six anilines and phenol isomers with similar structures were added to the supramolecular colorimetric array sensor, different color changes were produced under natural light. Linear discriminant analysis (LDA) showed that the supramolecular colorimetric array sensor could recognize and distinguish these isomers, and a mixture with different concentration ratios could be well categorized. The total Euclidean distance (TED) of an array with pollutant concentrations had a good linear correlation, and the detection limit (LOD) was as low as 10-5-10-6 mol L-1. Six anilines and phenol isomers in real samples were identified by supramolecular colorimetric array sensor. 1H NMR results showed that the formation of charge transfer complexes in Q[8] cavity may be the cause of color change. This work provides a fast and convenient experimental basis for monitoring the complex structure pollutants in sewage discharge.

Thiol/methylthio-functionalized porous aromatic frameworks for simultaneous capture of aromatic pollutants and Hg(II) from water.

Simultaneously capturing organic pollutants and heavy metal can greatly reduce the water remediation time and cost, however it is still a great challenge presently. Herein, two novel thiol/methylthio-functionalized porous aromatic frameworks were synthesized as sorbents via the Sonogashira-Hagihara reaction of 1,3,5-triethynylbenzene and 1,3,5-tris(4-bromophenyl) benzene, the subsequent chloromethylation of the phenyl rings, and the final nucleophile substitution of -Cl groups by NaSH/NaSMe. These two sorbents were characterized by FT-IR spectra, energy dispersive X-ray spectra, scanning electron microscope, nitrogen adsorption analysis, thermo-gravimetric analysis, and elemental analyses. Adsorption experiments displayed that new sorbents had high uptake abilities and fast adsorption kinetics for aromatic pollutants and mercury (II) (Hg(II)). The maximum adsorption capacity (Qmax) of toluene and m-xylene on both new sorbents were 531.9-571.4 mg/g with the kinetic binding rate constants (kobs) of 0.00276-0.02422 g/mg/min, and the Qmax values of Hg(II) were 148.1-180.3 mg/g with kobs of 0.00592-0.01573 g/mg/min. Moreover, new sorbents indicated high simultaneous uptake abilities for these pollutants with good reusability, and finally they were successfully applied to the simultaneous remediation of these pollutants in two simulated sewages with high and low concentration, indicating their great practical application potential in wastewater remediation.

Garbage in garbage out: the contribution of our industrial advancement to wastewater degeneration.

Natural water sources are habitually marred by insidious anthropogenic practices and municipal wastewater discharges that contain either of xenobiotic pollutants and their sometimes more toxic degradation products, or both. Although wastewater is considered as both a resource and a problem, as explained in this review, it is however daunting that, while the global village is still struggling to decipher the mode of proper handling, subsequent discharge and regulation of already established aromatic contaminants in wastewater, there emanates some more aggressive, stealth and sinister groups of compounds. It is quite ironic that majority of these compounds are the 'go through' consumables in our present society and have been suspected to pose several health risks to the aquatic ecosystem, eliciting unfavourable clinical manifestations in aquatic animals and humans, which has heightened the uncertainties conferred on freshwater use and consumption of some aquatic foods. This review therefore serves to give a brief account on the metamorphosis of approach in detection of aromatic pollutants and ultimately their implications along the trophic chains in the community.

An innovative in vitro assay to study the effects of aromatic pollutants on porphyrin systems.

Interactions between aromatic pollutants (APs) and porphyrin nucleus as physiological receptors have a significant effect on biological functions of porphyrin-based systems in organism. However, the details on the interaction at molecule level are still elusive. Herein, interaction mechanisms between two typical APs (methylene blue, MB and benzo[a]pyrene, B[a]P) and meso-tetra (4-carboxyphenyl) porphine (TCPP) as physiological receptors were systematically investigated. Adsorption behaviors of TCPP to B[a]P was dominated by pi-pi interaction, while interaction between TCPP and MB coupled with a multi-force field including hydrophobic, pi-pi, electrostatic, and H-bonding interactions. The relative contributions of these four forces obeyed an order: H-bonding > pi-pi > electrostatic > hydrophobic, regardless of the pH value and the initial concentration of MB. H-bonding assisted by hydrogen/hydroxide ion was the most influential force. According to the effect of pH and temperature, organisms exposed to cellular environment with high alkalinity and high temperature might uptake more APs molecules with chemical properties similar to MB and suffered greater health risks. In detail, APs might replace amino acid molecules surrounding porphyrin and change the distortion type of porphyrin molecule, and then affect biological functions of porphyrin and related proteins. This study facilitates a better understanding of potential toxicity of organisms in contaminated environment.

Self-Amplified Fluorescent Nanoparticles for Rapid and Visual Detection of Xylene in Aqueous Media.

Pollutant detection is of great importance for quality control of drinking water and environmental protection. The common methods of pollutant detection suffer from time-consuming procedures, bulky and expensive instruments, and complicated sample pretreatment. Herein, a type of conceptually new self-amplified fluorescent nanoparticle (SAFN) is constructed based on aggregation-induced emission (AIE) luminogens for rapid and visual detection of xylene in aqueous media. AIE luminogens are self-assembled into SAFNs in aqueous media, which emit efficiently due to the aggregation of luminogen molecules. The SAFNs of AIE luminogens stick xylene molecules from aqueous media through multiple interactions including hydrophobic and π-π interactions. Upon capturing xylene, SAFNs swell, which quench the fluorescence of the whole SAFNs, showing the self-amplification effect. Such a self-amplification effect is entirely different from that of conjugated polymers in the literature. Importantly, fluorescence quenching of SAFNs by xylene can be readily observed by the naked eye, which enables visual xylene sensing. The SAFNs enable rapid and visual detection of xylene in aqueous media with a low detection limit (5 µg/L) in the order of seconds. Given high sensitivity, rapid response, simple and easy operation, and low cost, SAFNs of AIE luminogens present a promising platform for visual detection of organic pollutants in aqueous media.

Structure Elucidation and Biochemical Characterization of Environmentally Relevant Novel Extradiol Dioxygenases Discovered by a Functional Metagenomics Approach.

The release of synthetic chemical pollutants in the environment is posing serious health risks. Enzymes, including oxygenases, play a crucial role in xenobiotic degradation. In the present study, we employed a functional metagenomics approach to overcome the limitation of cultivability of microbes under standard laboratory conditions in order to isolate novel dioxygenases capable of degrading recalcitrant pollutants. Fosmid clones possessing dioxygenase activity were further sequenced, and their genes were identified using bioinformatics tools. Two positive fosmid clones, SD3 and RW1, suggested the presence of 2,3-dihydroxybiphenyl 1,2-dioxygenase (BphC-SD3) and catechol 2,3-dioxygenase (C23O-RW1), respectively. Recombinant versions of these enzymes were purified to examine their pollutant-degrading abilities. The crystal structure of BphC-SD3 was determined at 2.6-Å resolution, revealing a two-domain architecture, i.e., N-terminal and C-terminal domains, with the sequential arrangement of ßαßßß in each domain, characteristic of Fe-dependent class II type I extradiol dioxygenases. The structure also reveals the presence of conserved amino acids lining the catalytic pocket and Fe3+ metal ion in the large funnel-shaped active site in the C-terminal domain. Further studies suggest that Fe3+ bound in the BphC-SD3 active site probably imparts aerobic stability. We further demonstrate the potential application of BphC-SD3 in biosensing of catecholic compounds. The halotolerant and oxygen-resistant properties of these enzymes reported in this study make them potential candidates for bioremediation and biosensing applications.IMPORTANCE The disposal and degradation of xenobiotic compounds have been serious issues due to their recalcitrant properties. Microbial oxygenases are the fundamental enzymes involved in biodegradation that oxidize the substrate by transferring oxygen from molecular oxygen. Among oxygenases, catechol dioxygenases are more versatile in biodegradation and are well studied among the bacterial world. The use of catechol dioxygenases in the field is currently not practical due to their aerobically unstable nature. The significance of our research lies in the discovery of aerobically stable and halotolerant catechol dioxygenases that are efficient in degrading the targeted environmental pollutants and, hence, could be used as cost-effective alternatives for the treatment of hypersaline industrial effluents. Moreover, the structural determination of novel catechol dioxygenases would greatly enhance our knowledge of the function of these enzymes and facilitate directed evolution to further enhance or engineer desired properties.

In silico genome analysis reveals the metabolic versatility and biotechnology potential of a halotorelant phthalic acid esters degrading Gordonia alkanivorans strain YC-RL2.

Members of genus Gordonia are known to degrade various xenobitics and produce secondary metabolites. The genome of a halotorelant phthalic acid ester (PAEs) degrading actinobacterium Gordonia alkanivorans strain YC-RL2 was sequenced using Biosciences RS II platform and Single Molecular Real-Time (SMRT) technology. The reads were assembled de novo by hierarchical genome assembly process (HGAP) algorithm version 2. Genes were annotated by NCBI Prokaryotic Genome Annotation Pipeline. The generated genome sequence was 4,979,656 bp with an average G+C content of 67.45%. Calculation of ANI confirmed previous classification that strain YC-RL2 is G. alkanivorans. The sequences were searched against KEGG and COG databases; 3132 CDSs were assigned to COG families and 1808 CDSs were predicted to be involved in 111 pathways. 95 of the KEGG annotated genes were predicted to be involved in the degradation of xenobiotics. A phthalate degradation operon could not be identified in the genome indicating that strain YC-RL2 possesses a novel way of phthalate degradation. A total of 203 and 22 CDSs were annotated as esterase/hydrolase and dioxygenase genes respectively. A total of 53 biosynthetic gene clusters (BGCs) were predicted by antiSMASH (antibiotics & Secondary Metabolite Analysis Shell) bacterial version 4.0. The genome also contained putative genes for heavy metal metabolism. The strain could tolerate 1 mM of Cd2+, Co2+, Cu2+, Ni2+, Zn2+, Mn2+ and Pb2+ ions. These results show that strain YC-RL2 has a great potential to degrade various xenobiotics in different environments and will provide a rich genetic resource for further biotechnological and remediation studies.

TiO2/SiO2 decorated carbon nanostructured materials as a multifunctional platform for emerging pollutants removal.

Aquatic ecosystem contaminated with hazardous pollutants has become a high priority global concern leading to serious economic and environmental damage. Among various treatment approaches, carbon nanostructured materials have received particular interest as a novel platform for emerging pollutants removal owing to their unique chemical and electrical properties, biocompatibility, high scalability, and infinite functionalization possibility with an array of inorganic nanomaterials and bio-molecules. Within this framework, carbon nanotubes (CNTs) are widely used due to their hollow and layered structure and availability of large specific surface area for the incoming contaminants. Carbon nanotubes can be used either as single-walled, multi-walled, or functionalized nanoconstructs. TiO2/SiO2-functionalized CNTs are among the most promising heterogeneous photocatalytic candidates for the degradation of a range of organic compounds, heavy metals reduction, and selective oxidative reactions. Herein, we reviewed recent development in the application of TiO2 and SiO2 functionalized nanostructured carbon materials as potential environmental candidates. After a brief overview of synthesis and properties of CNTs, we explicitly discussed the potential applications of TiO2/SiO2 functionalized CNTs for the remediation of a variety of environmentally-related pollutants of high concern, including synthetic dyes or dye-based hazardous waste effluents, as polycyclic aromatic hydrocarbons (PAHs), pharmaceutically active compounds, pesticides, toxic heavy elements, remediation of metal-contaminated soil, and miscellaneous organic contaminants. The work is wrapped up by giving information on current challenges and recommended guidelines about future research in the field bearing in mind the conclusions of the current review.

Cu2O@ß-cyclodextrin as a synergistic catalyst for hydroxyl radical generation and molecular recognitive destruction of aromatic pollutants at neutral pH.

Wastewater systems contain a large number of compounds, such as anthropogenic aromatic pollutants and natural organic matter (NOM), and usually have pH higher than 4. Fenton-like reaction is the most widespread method for removal of organic pollutants, but their reactivity with H2O2 may be inhibited by NOM due to the competition of hydroxyl radicals and chelating agents. In this work, Cu2O@ß-cyclodextrin was developed to achieve the collaboration between molecular recognition and Fenton-like catalysis to destruct aromatic pollutants at neutral pH. In Cu2O@ß-CD, covalent CuOC bond was topotaxially converted from CuCl assisted by ß-CD at room temperature. Covalently linked ß-CD could keep humic acid from interfering catalytic performance of Cu2O surfaces and inhibit the leaching of copper. A higher catalytic ability was observed for Cu2O@ß-CD with rate constant 0.0331 min-1 than Cu2O (0.0064 min-1) at neutral pH. A mechanism of synergistic catalysis was proposed on the basis of Cu+, ß-CD and phenoxo-Cu2+ complexes in the Cu2O@ß-CD/BPA/H2O2 system. The strategy of coupling molecular recognition into Fenton-like reaction provides an efficient and promising approach to the destruction of aromatic pollutants at neutral pH.

Green-fabrication of gold nanomaterials using Staphylococcus warneri from Sundarbans estuary: an effective recyclable nanocatalyst for degrading nitro aromatic pollutants.

Microbial synthesis of gold nanoparticles (GNPs) has attracted considerable attention in recent times due to their exceptional capability for the bioremediation of industrial wastes and also for the treatment of wastewater. A bacterial strain Staphylococcus warneri, isolated from the estuarine mangroves of Sundarbans region produced highly stable GNPs by reducing hydrogen auric chloride (HAucl4) salt using intracellular protein extract. The nanoparticles were characterized utilizing ultraviolet-visible spectrophotometry, transmission electron microscopy, scanning electron microscopy, atomic force microscopy, X-ray diffraction, and surface enhanced Raman scattering. Highly dispersed, spherically shaped GNPs varied around 15-25 nm in size and were highly crystalline with face-centered cubic structures. Recyclable catalytic activity of as-synthesized GNPs was evidenced by complete degradation of nitro aromatic pollutants like 2-nitroaniline, 4-nitroaniline, 2-nitrophenol and 4-nitrophenol. Our GNPs show excellent and efficient catalytic activity with significantly high rate constant (10-1 order) and high turnover frequency (103 order) in recyclable manner up to three times. To our knowledge, this is the first report of Staphylococcus warneri in the production of gold nanoparticles. This green technology for bioremediation of toxic nitro aromatic pollutants is safe and economically beneficial to challenge the development and sustainability issue.