FexO/FeNC modified activated carbon packing media for biological slow filtration to enhance the removal of dissolved organic matter in reused water.

The biological slow filtration reactor (BSFR) process has been found to be moderately effective for the removal of refractory dissolved organic matter (DOM) in the treatment of reused water. In this study, bench scale experiments were conducted using a mixture of landscape water and concentrated landfill leachate as feed water, to compare a novel iron oxide (FexO)/FeNC modified activated carbon (FexO@AC) packed BSFR, with a conventional activated carbon packed BSFR (AC-BSFR), operated in parallel. The results showed that the FexO@AC packed BSFR had a refractory DOM removal rate of 90%, operated at a hydraulic retention time (HRT) of 10 h at room temperature for 30 weeks, while under the same conditions the removal by the AC-BSFR was only 70%. As a consequence, the treatment by the FexO@AC packed BSFR substantially reduced the formation potential of trihalomethanes, and to a less extent, haloacetic acids. The modification of FexO/FeNC media raised the conductivity and the oxygen reduction reaction (ORR) efficiency of the AC media to accelerate the anaerobic digestion by consuming the electrons that are generated by anaerobic digestion itself, which lead to the marked improvement in refractory DOM removal.

Efficiently photocatalysis activation of peroxydisulfate by Fe-doped g-C3N5 for pharmaceuticals and personal care products degradation.

Peroxydisulfate (PDS) based advanced oxidation processes (AOPs) are widely used for the degradation of pharmaceutical and personal care products (PPCP) in wastewater treatment. In this study, a Fe-doped g-C3N5 (Fe@g-C3N5) was synthesized as a photocatalyst for catalyzing the PDS-based AOPs to degrade tetracycline hydrochloride (TH) at pH 3 and Naproxen (NPX) at pH 7. The photocatalytic performance of Fe@g-C3N5 was 19% and 67% higher than g-C3N5 and g-C3N4 for degradation of TH at pH 3, respectively, while it was 21% and 35% at pH 7. The Fe:N ratio in Fe@g-C3N5, was calculated as 1:3.79, indicating that the doped Fe atom formed a FeN4 structure with an adjacent two-layer graphite structure of g-C3N5, which improved the charge separation capacity of g-C3N5 and act as a new reaction center that can efficiently combine and catalyze the PDS to radicals. Although the intrinsic photo-degradation performance is weak, the photocatalytic performance of Fe@g-C3N5 has great room for the improvement and application in wastewater treatment.

The characters of dissolved organic matters from litter-mimic with the different humification states and their effects on drinking water treatment processes.

Dissolved organic matter (DOM) is one kind of the main pollutant in surface water that will cause many problems during drinking water treatment processes. In this study, a simulated humification process of forest litter-mimic was investigated for eight weeks continuously to study the variations in chemical properties such as DOM composition, polysaccharide/protein ratio, average molecular weight, oxidation degree, hydrophilicity, etc., as well as the impact of these variations on the coagulation, ultra-/nanofiltration (UF/NF). Results showed that the removal rate of coagulation (from 67.5 % to 37.0 %) and UF (from 14.4 % to 5.8 %) decreased significantly during the humification process as a function of time, while the removal rate of NF increased from 40.0 % to 72.9 % at first, and then decreased to 47.4 %. This study gave a deep insight into the effect of DOM with different humification ages on the drinking water treatment process with the influence of seasons and vegetation around the water source, which finally aimed to improve drinking water treatment.

Evaluating and improving the reliability of the UV-persulfate method for the determination of TOC/DOC in surface waters.

The UV-persulfate oxidation method is widely used for determining the total organic carbon concentration of aqueous samples (denoted for convenience as UVP-TOC). However, for some surface water samples, the measurement of TOC by this method can be unreliable, deviating significantly from the true carbon content. In this study, the performance of the UVP-TOC method has been investigated by comparing the results from the analysis of a variety of aqueous samples that included two kinds of surface water samples and related surface water model substances: bovine serum albumin (BSA), sodium alginate (SA), humic acid (HA), tannic acid (TA), benzoic acid (BA) and citric acid (CA), with those from a high-temperature combustion method (elemental analysis); the latter providing the true carbon content value. By comparing the above data, it was found that the UVP-TOC method significantly underestimated the TOC value of the surface water samples, and it was also found that the model components BSA (protein) and HA (humic substances, HS) had a substantial influence on the TOC underestimation, while the SA (polysaccharide), TA (complex organic molecule) and CA/BA (small molecules) had little effect. The results showed that the agglomeration within and between BSA and HA molecules was an important reason for the inaccurate UVP-TOC values of BSA and HA. A further limitation was that for BSA, surfactants (e.g. sodium dodecylbenzene sulfonate, SDBS) and other surfactant-like substances, foam was formed during the CO2 removal purging process by N2 that seriously interfered with the determination of TOC. The study provides new information and insight into the causes of inaccuracies in the UVP-TOC analysis of surface waters and possible approaches to improve the accuracy.

Carbon doped Fe3O4 peroxidase-like nanozyme for mitigating the membrane fouling by NOM at neutral pH.

Oxidation is a widely used method in drinking water treatment to mitigate the membrane fouling caused by the natural organic matters (NOM) from the surface water during ultra-filtration (UF) and nano-filtration (NF) processes, and H2O2 is one of the common oxidants for it. However, the oxidation capability of H2O2 at neutral pH is lower, compared to the acidic and alkaline conditions. In order to improve the efficiency of NOM oxidation at neutral pH, a carbon-doped Fe3O4 peroxidase-like nanozyme (CFPN) was synthesized in this study and used as a high-performance catalyst for H2O2 to generate hydroxyl radical. The oxygen-containing groups on the carbon structure of CFPN can form an acidic microenvironment, allowing H2O2 to produce hydroxyl radical by catalysis in neutral conditions. The results of hydrophilicity analysis, zeta potential, high-performance liquid size exclusion chromatography (HPSEC), Fourier transform infrared spectrum (FTIR) and flux indicated that the hydroxyl radical can oxidize the hydrophobic matters of humic acid (HA) into hydrophilic matters by Fenton reaction or electrophilic addition reaction, which can mitigate the fouling of NF membranes. The results of the same test for the bovine serum albumin (BSA) indicated that the hydroxyl radical can mitigate the fouling of UF membranes by degrading the tertiary and secondary structures of BSA and partly oxidizing the side chain groups. In addition, two types of surface water samples were used to verify the above mechanism, and the results indicated that the hydroxyl radical treatment at neutral pH is a new viable and effective strategy to significantly mitigate the NOM fouling of UF and NF membranes.

The Fe-N-C oxidase-like nanozyme used for catalytic oxidation of NOM in surface water.

The removal of natural organic matter (NOM), particularly humic substances (HS) from surface waters during drinking water treatment is necessary to avoid various water quality problems in supply, such as the formation of disinfection by-products. As an alternative to conventional processes (e.g. coagulation), and in the light of the rapidly increasing applications of nanozyme in bio-catalysis, a novel Fe-N-C oxidase-like nanozyme (FeNZ) has been prepared and used to catalyze the oxidative degradation of NOM during simple aeration. Using humic acid (HA) as a model NOM it was found that the HA removal (as TOC) was increased by a factor of 6 with a low dose (10 mg/L) of FeNZ compared to an aerated solution without FeNZ. A variety of analytical methods was used to investigate the oxygen reduction reaction, including cyclic voltammetry, electron spin resonance, and density functional theory (DFT) simulation. Based on these studies, a catalytic oxidation mechanism described as "adsorption-activation-oxidation" was proposed. The enhanced NOM removal performance of FeNZ catalytic oxidation was confirmed with samples of natural surface water in terms of organic mineralization and conversion of hydrophobic to hydrophilic components. The results show great potential for the use of oxidase-like nano catalytic materials in the field of water treatment.

Rational modification of Corynebacterium glutamicum dihydrodipicolinate reductase to switch the nucleotide-cofactor specificity for increasing l-lysine production.

l-lysine is an important amino acid in animals and humans and NADPH is a vital cofactor for maximizing the efficiency of l-lysine fermentation. Dihydrodipicolinate reductase (DHDPR), an NAD(P)H-dependent enzyme, shows a variance in nucleotide-cofactor affinity in bacteria. In this study, we rationally engineered Corynebacterium glutamicum DHDPR (CgDHDPR) to switch its nucleotide-cofactor specificity resulting in an increase in final titer (from 82.6 to 117.3 g L-1 ), carbon yield (from 0.35 to 0.44 g [g glucose]-1 ) and productivity (from 2.07 to 2.93 g L-1 hr-1 ) of l-lysine in JL-6 ΔdapB::Ec-dapBC115G,G116C in fed-batch fermentation. To do this, we comparatively analyzed the characteristics of CgDHDPR and Escherichia coli DHDPR (EcDHDPR), indicating that hetero-expression of NADH-dependent EcDHDPR increased l-lysine production. Subsequently, we rationally modified the conserved structure of cofactor-binding motif, and results indicated that introducing the mutation K11A or R13A in CgDHDPR and introducing the mutation R16A or R39A in EcDHDPR modifies the nucleotide-cofactor affinity of DHDPR. Lastly, the effects of these mutated DHDPRs on l-lysine production were investigated. The highest increase (26.2%) in l-lysine production was observed for JL-6 ΔdapB::Ec-dapBC115G,G116C , followed by JL-6 Cg-dapBC37G,G38C (21.4%) and JL-6 ΔdapB::Ec-dapBC46G,G47C (15.2%). This is the first report of a rational modification of DHDPR that enhances the l-lysine production and yield through the modulation of nucleotide-cofactor specificity.

NADPH metabolism: a survey of its theoretical characteristics and manipulation strategies in amino acid biosynthesis.

Reduced nicotinamide adenine nucleotide phosphate (NADPH), which is one of the key cofactors in the metabolic network, plays an important role in the biochemical reactions, and physiological function of amino acid-producing strains. The manipulation of NADPH availability and form is an efficient and easy method of redirecting the carbon flux to the amino acid biosynthesis in industrial strains. In this review, we survey the metabolic mode of NADPH. Furthermore, we summarize the research developments in the understanding of the relationship between NADPH metabolism and amino acid biosynthesis. Detailed strategies to manipulate NADPH availability are addressed based on this knowledge. Finally, the uses of NADPH manipulation strategies to enhance the metabolic function of amino acid-producing strains are discussed.

A dual-cell device designed as an oxidase mimic and its use for the study of oxidase-like nanozymes.

A dual-cell device has been designed as an oxidase-like mimic with the oxidation of 3,3',5,5'-tetramethylbenzidine as a model reaction. This dual-cell device could be also used to study oxidase-like nanozymes. It was found that only the catalytic sites for oxygen reduction are essential and necessary for oxidase-like nanozymes.

Oxidase-mimicking activity of the nitrogen-doped Fe3C@C composites.

Prussian blue cubes could be converted at a relatively low temperature (<600 °C) to the N-doped Fe3C@C composites, which showed oxidase-mimicking activity. This study also suggests that the four-electron oxygen reduction catalysts might be candidates for oxidase-mimics.

Reverse-Bumpy-Ball-Type-Nanoreactor-Loaded Nylon Membranes as Peroxidase-Mimic Membrane Reactors for a Colorimetric Assay for H2O2.

Herein we report for the first time fabrication of reverse bumpy ball (RBB)-type-nanoreactor-based flexible peroxidase-mimic membrane reactors (MRs). The RBB-type nanoreactors with gold nanoparticles embedded in the inner walls of carbon shells were loaded on nylon membranes through a facile filtration approach. The as-prepared flexible catalytic membrane was studied as a peroxidase-mimic MR. It was found that the obtained peroxidase-mimic MR could exhibit several advantages over natural enzymes, such as facile and good recyclability, long-term stability and easy storage. Moreover, the RBB NS-modified nylon MRs as a peroxidase mimic provide a useful colorimetric assay for H2O2.

Current control by electrode coatings formed by polymerization of dopamine at prussian blue-modified electrodes.

Electrode coating with polydopamine (PDA) is fast becoming a popular surface modification technique. In this study we report the investigation of the use of PDA as electrode coatings with Prussian blue (PB) as an electrode material model. The PB layer was galvanostatically deposited at an Au electrode, followed by PDA coating with the assistance of ammonium persulfate as an oxidant. The thickness of PDA coatings was measured to be ∼60 nm. Electrochemical characterization of the PDA-coated PB electrode revealed that the PDA coatings could stabilize the PB at neutral pH and allow the permeation of hydrogen peroxide (H2O2). Moreover, the PDA coatings were found to effectively exclude the common interfering compounds such as cysteine, ascorbic acid and uric acid, and exhibit selective electrocatalysis towards the electroreduction of H2O2. Accordingly, the PDA-coated PB electrode was applied for determination of H2O2 released from live cells.

Stability improvement of Prussian blue in nonacidic solutions via an electrochemical post-treatment method and the shape evolution of Prussian blue from nanospheres to nanocubes.

In this study we report the improved stability of Prussian blue (PB) films in neutral and alkaline solutions via an electrochemical post-treatment procedure. In this procedure, PB films synthesized via the electroless deposition method at glassy carbon electrodes were continuously cycled for 300 cycles (∼12 h) between the potential limits of +0.6 and -0.1 V (vs. Ag/AgCl) at a scan rate of 10 mV s(-1) in 2.0 M KCl solution of pH 3. It was found that after such electrochemical post-treatment the PB films exhibit dramatically improved stability in neutral and alkaline solutions. Control experiments confirmed that the longer potential cycling time and the higher KCl concentration are indispensable. In addition, interestingly, it was found that after the successive potential cycling treatments the shape of PB nanoparticles evolves from a sphere into a cube as well as a small amount of a rectangle, indicating the electrochemically induced shape evolution of nanocrystals. The electrochemical post-treatment procedure proposed here could be useful for the development of PB-based devices with improved stability, for instance, biosensors, biofuel cells, etc.