Efficient adsorption of selenium (Se(IV) and Se(VI)) from water using Acacia senegal polysaccharide with multiple amine groups: Synthesis and application.

In this study, an amine-rich gel (ARAS) was prepared by chemically altering Acacia senegal (AS). ARAS acts as an adsorbent for selenium. Owing to the introduction of amino functional groups and a remarkable specific surface area (91.89 g/m2), ARAS shows maximum adsorption capacities at 75 and 130 mg g-1 for Se(IV) and Se(VI), respectively. The removal efficiency of ARAS is higher (ωSeIV = 98.2 % and ωSeVI = 98.6 %) at lower concentrations (CSeIV = 100 ppm and CSeVI = 95 ppm) and the adsorption equilibrium is achieved within 60 min. The adsorption process of Se (IV) and Se (VI) via ARAS is elucidated using the Quasi-Second-Order kinetic and Langmuir models. The enhanced adsorption capacity of the adsorbent could be attributed to the synergistic effects of electrostatic attraction, hydrogen bonding, and specific physicochemical properties. Thermodynamic studies reveal that the surface adsorption process is spontaneous and exothermic. Notably, ARAS maintains remarkable adsorption stability under a variety of solution conditions, including variable pH (4-11), NaCl concentrations (0-1 M), and the presence of organic solvents. It retains approximately 60 % of its initial adsorption capacity for Se(IV) and Se(VI) after three adsorption cycles. Therefore, ARAS with its cost-effectiveness and exceptional performance shows considerable potential for applications in water treatment.

Purification, Identification, and Mechanistic Investigation of Novel Selenium-Enriched Antioxidant Peptides from Moringa oleifera Seeds.

In this study, five novel Se-enriched antioxidant peptides (FLSeML, LSeMAAL, LASeMMVL, SeMLLAA, and LSeMAL) were purified and identified from Se-enriched Moringa oleifera (M. oleifera) seed protein hydrolysate. The five peptides showed excellent cellular antioxidant activity, with respective EC50 values of 0.291, 0.383, 0.662, 0.1, and 0.123 µg/mL. The five peptides (0.025 mg/mL) increased the cell viability from 78.72 to 90.71, 89.16, 93.92, 83.68, and 98.29%, respectively, effectively reducing reactive oxygen species accumulation and significantly increasing superoxide dismutase and catalase activities in damaged cells. Molecular docking results revealed that the five novel Se-enriched peptides interacted with the key amino acid of Keap1, thus directly blocking the interaction of Keap1-Nrf2 and activating the antioxidant stress response to enhance the ability of scavenging free radicals in vitro. In conclusion, Se-enriched M. oleifera seed peptides exhibited significant antioxidant activity and can be expected to find widespread use as a highly active natural functional food additive and ingredient.

Supporting nanoscale zero-valent iron onto shrimp shell-derived N-doped biochar to boost its reactivity and electron utilization for selenite sequestration.

Nanoscale zero-valent iron (nZVI) has been widely used in the reductive removal of contaminants from water, yet it still fights against the inherent passive cover and the raise of medium pH. In this study, nZVI was supported onto a nitrogen-doped biochar (NBC) that was prepared by pyrolyzing shrimp shell for efficiently sequestrating aqueous selenite (Se(IV)). The resultant composite (NBC-nZVI) revealed a higher reactivity and electron utilization efficiency (EUE) than the bare nZVI in Se(IV) sequestration because of the positive charge, the buffering effect and the good conductivity of NBC. The kinetic rate and EUE of NBC-nZVI were increased by 143.4% and 15.3% compared to the bare nZVI, respectively, at initial pH of 3.0. The high removal capacity of 605.4 mg g-1 for NBC-nZVI was obtained at Se(IV) concentration of 1000 mg L-1, initial pH of 3.0, NBC-nZVI dosage of 1.0 g L-1 and contact time of 12 h. Moreover, NBC-nZVI exhibited a strong tolerance to solution pHs and coexisting compounds (e.g., humic acid) and could reduce the Se(IV) concentration from 5.0 mg L-1 to below the limit of drinking water (50 µg L-1) in real-world samples. This work exemplified a utilization of shrimp shell-derived NBC to simultaneously enhance the reactivity and EUE of nZVI for reductively removing contaminants.

Rapid screening of novel tyrosinase inhibitory peptides from a pearl shell meat hydrolysate by molecular docking and the anti-melanin mechanism.

Pearls are an edible and medicinal resource with whitening activity and nutritional value in China. In the previous study, we found that the pearl shell meat hydrolysate showed dual activities of antioxidation and tyrosinase inhibition, which were similar to the activities of pearls. In this research, a pearl shell meat hydrolysate was isolated, identified and screened by molecular docking, and three peptides FLF, SPSSS and WLL with high tyrosinase inhibitory activities were obtained. The results indicated that FLF, SPSSS and WLL could effectively inhibit tyrosinase activities and the inhibition rates (1.0 mg mL-1) were 54.32%, 65.26% and 57.50%, respectively. The results of a zebrafish whitening experiment showed that the tyrosinase activities of zebrafish treated with FLF, SPSSS and WLL decreased by 75.41%, 62.87% and 64.99% (p < 0.05), respectively, and the melanin content decreased by 37.34%, 38.52% and 40.39% (p < 0.05), respectively. In a B16F10 cell whitening experiment, compared with a control group, FLF, SPSSS and WLL also showed a significant whitening effect, the tyrosinase activities decreased by 84.08%, 79.08% and 77.45% (p < 0.05), respectively, and the melanin content decreased by 42.23%, 34.37% and 34.02% (p < 0.05), respectively. Moreover, the active peptides could act on three signal pathways including Wnt/ß-catenin, MAPK and MC1R/α-MSH and significantly downregulated the expressions of the signaling factors WNT4, MITF, ß-catenin, ERK, JNK, TRP1 and TRP2 (p < 0.05). The results demonstrated that the whitening active peptides were edible natural antioxidants, tyrosinase inhibitors and skin anti-melanin agents, which could be added to functional foods as food ingredients.

Resource utilization of pig hair to prepare low-cost adsorbents with high density of sulfhydryl for enhanced and trace level removal of aqueous Hg(II).

Pig hair (PH), a keratinous waste, was modified by ammonium thioglycolate in a ball milling to promote its performance of Hg(II) sequestration. The ball milling broke the hydrophobic cuticle sheath and enhanced the reduction of disulfide bond, which increased the sulfydryl content of the modified PH (BTPH) from 0.07 to 11.05 µmol/g. BTPH exhibited a significantly higher capture capacity of Hg(II) (415.4 mg/g) than PH (3.1 mg/g), as well as the commercial activated carbon (219.7 mg/g), and persisted its performance over a wide range of solution pH. Meanwhile, BTPH with a distribution coefficient of 5.703 × 105 mL/g could selectively capture Hg(II) from the water with the coexisting metal ions such as Mg(II), Cd(II) and Pb(II). Moreover, the low-cost BTPH could reduce the Hg(II) from 1.0 mg/L to well below the limit of drinkable water (2 µg/L) in real-world samples. Density functional theory (DFT) calculations and state-of-the-art characterizations illustrated that the binding of Hg(II) to sulfydryl groups was the main adsorption mechanism. Notably, BTPH decreased the mercury content of water spinaches from 24.1 to 0.50 mg/kg and thereby significantly reduced the phytotoxicity of Hg(II). This work therefore provides a sustainable way to utilize keratinous wastes for the remediation of aqueous Hg(II).

Purification, identification, and antioxidative mechanism of three novel selenium-enriched oyster antioxidant peptides.

Natural organic selenium (Se) has multiple physiological health benefits and has become a hotspot of research in recent years. In this study, the Se-enriched antioxidant peptides were purified from Se-enriched oyster hydrolysate. Three novel Se-enriched antioxidant peptides LLVSeMY (685.2953 Da), MMDSeML (687.1875 Da) and VSeMDSeML (703.1599 Da) were identified from fraction F6-4, which all exhibited strong cellular antioxidant activity (CAA) with EC50 values of 0.739, 0.423, and 0.395 µg/mL, respectively. These three Se-enriched antioxidant peptides (0.025 mg/mL) could significantly enhanced cell viability to 84.60 ± 3.32% âˆ¼ 86.18 ± 1.36% compared with the AAPH injury group (75.99 ± 0.79%), and the cytoprotective effects were even better than that of GSH (80.47 ± 2.78%). Moreover, these three Se-enriched peptides also significantly protected HepG2 cells from AAPH-induced oxidative injury by inhibiting ROS production and enhancing the activities of antioxidant enzymes. The molecular docking results showed that these three Se-enriched peptides can form stable hydrogen and hydrophobic bonds with key amino acid residues of Keap1 protein, thereby potentially regulating the Keap1-Nrf2 pathway. In conclusion, the three novel Se-enriched oyster antioxidant peptides are expected to be used in medicine or functional food, providing a new theoretical basis for the high-value utilization of natural organic Se.

Enhancement of hydrothermal carbonization of chitin by combined pretreatment of mechanical activation and FeCl3.

In this work, a combined mechanical activation and FeCl3 (MA + FeCl3) method was applied to pretreat chitin to enhance the degree of hydrothermal carbonization. MA + FeCl3 pretreatment significantly disrupt the crystalline region of chitin and Fe3+ entered into the molecular chain, resulting in the destruction of the stable structure of chitin. The chemical and structural properties of hydrochars were characterized by EA, SEM, FTIR, XRD, XPS, 13C solid state NMR, and N2 adsorption-desorption analyses. The results showed that the H/C and O/C atomic ratios of HC-MAFCT/230 (the hydrochar derived from MA + FeCl3 pretreated chitin with hydrothermal reaction temperature of 230 °C) were 0.96 and 0.34, respectively. Van Krevelen diagram indicated that the hydrothermal carbonization of chitin underwent a series of reactions such as dehydration, decarboxylation, and aromatization. HC-MAFCT/230 had abundant oxygen- and nitrogen-containing functional groups. HC-MAFCT/230 exhibited a porous structure, with the specific surface area of 128 m2 g-1, which was a promising carbon material.

Preparation and catalytic behavior of antioxidant cassava starch with selenium active sites and hydrophobic microenvironments.

The preparation of antioxidant starch with the activity of glutathione peroxidase (GPx) for scavenging free radicals can not only enrich the types of modified starch but also alternate native GPx to overcome its drawbacks. In this work, an antioxidant cassava starch (AO-ca-starch) was prepared by the sequential esterification and selenylation of cassava starch. The process was optimized based on the selenium content. Various characterizations for the AO-ca-starch indicated that the catalytic center of GPx, the selenium, was anchored on the starch. The catalytic activity of AO-ca-starch, a starch-based biomimetic GPx, was about 4.95 × 105 times higher than that of the typical artificial selenoenzyme (diphenyl diselenide, PhSeSePh), and it exhibited a typical saturation kinetic catalytic behavior. The surface changes of the starch during the modification were conducive to the formation of hydrophobic microenvironments, which played an important role in the catalytic reaction of biomimetic GPx due to the binding of the hydrophobic substrates. The match of the catalytic center and the hydrophobic microenvironments was the key factor for maintaining the high catalytic activity of AO-ca-starch. Without cytotoxicity, AO-ca-starch exemplified a new and promising modified starch as a selenium-enriched functional food and antioxidant drug.

A Removable Artificial Cell Wall for Withstanding Ciprofloxacin.

The pollution of antibiotics in aquaculture environment is increasingly serious, and excessive antibiotics will kill the probiotics in aquaculture feed. How to improve the viability of probiotics in the antibiotics-contaminated environment is of significance. In this study, a new strategy for protecting Saccharomyces cerevisiae cells in situ against antibiotics is constructed based on cell surface engineering technology by putting on wearable protective layers for cells. The protective layer is constructed around cellular surface via the self-assembly of coacervate microdroplets that consist of carboxymethyl chitosan and carboxyl dextran. Without affecting the cell viability, the protective layer can grasp ciprofloxacin and decrease the contact of ciprofloxacin to cells and consequently improve the survival rate of cells when exposing to ciprofloxacin. This work highlights a facile strategy to establish removable artificial cell wall by biodegradable polysaccharides for improving the productivity of probiotics in antibiotic environments.

In-situ synthesis of poly(m-phenylenediamine) on chitin bead for Cr(VI) removal.

In this work, a user-friendly chitin-based adsorbent (CT-PmPD) was synthesized by in-situ polymerization of m-phenylenediamine on chitin bead, which could effectively remove Cr(VI) from water. The structure and morphology of the CT-PmPD were characterized by FT-IR, XRD, SEM, zeta potential and XPS. Specifically, the effect of adsorbed dosage, pH, contact time, adsorption temperature and coexisting salt on the adsorption of Cr(VI) were studied. Besides, the adsorption mechanism of CT-PmPD toward Cr(VI) were also analyzed. Consequently, CT-PmPD exhibited a monolayer adsorption and the Langmuir model fitted a Cr(VI) adsorption capacity reaching 185.4 mg/g at 298 K. The high adsorption capacity was attributed to the abundant amino groups of CT-PmPD, which could be protonated to boost the electrostatic attraction of Cr(VI) oxyanions, thus providing electron to reduce Cr(VI). Additionally, the CT-PmPD revealed a good regeneration and reusability capacity, maintaining most of its adsorption capacity even after five cycles of adsorption-desorption. This high adsorption capacity and excellent regeneration performance highlighted the great potential of CT-PmPD for the removal of Cr(VI).

A cellulose-based adsorbent with pendant groups of quaternary ammonium and amino for enhanced capture of aqueous Cr(VI).

As a promising candidate of Cr(VI) decontamination, cellulose is limited in the Cr(VI) uptake due to its poor accessibility. Herein, We describe the synthesis of a novel cellulose-based adsorbent (PQC, where P and QC designate the polyethylenimine and quaternized cellulose, respectively) with functional groups of quaternary ammonium and amino for enhanced capture of Cr(VI) from water. For preparing PQC, cellulose is first quaternized homogeneously, followed by grafting and/or cross-linking with polyethylenimine in the presence of epichlorohydrin. The PQC follows the Langmuir isotherm and presents a maximum Cr(VI) uptake capacity of 490.3 mg/g at 30 °C and initial pH about 2.0, much higher than many other reported cellulose-based adsorbents. The adsorption of PQC is spontaneous and endothermic, which follows the pseudo-second-order kinetic model and achieves the equilibrium after contacting about 50 min. Furthermore, the PQC, with favorable reusability, can work well in a high coexisting anion concentration. These excellent absorption performances are attributed to its physicochemical properties such as the robust porous structure and high density of functional groups including quaternary ammonium, amino and hydroxyl, which improve the availability to capture or reduce Cr(VI). This work demonstrates the significant potential of cellulose-based adsorbent for remediating aqueous Cr(VI).

Effective treatment and utilization of hazardous waste sulfuric acid generated from alkylation by lignocellulose ester-catalyzed oxidative degradation of organic pollutants.

Alkylation reaction catalyzed by concentrated H2SO4 generates hazardous waste H2SO4 containing a large amount of organic pollutants. This study focused on effective utilization and treatment of the waste H2SO4 for simultaneous consumption of H2SO4 and deep oxidative degradation of the organics. The waste H2SO4 could completely react with magnesium oxide ore to prepare crude MgSO4 solution, and the organic pollutants in the solution were deeply degraded and mainly mineralized to H2O and CO2 with H2O2 as oxidant and sugarcane bagasse citrate (SBC), a kind of lignocellulose ester, as catalyst. The total amount of acidic groups of SBC significantly affected its catalytic activity, attributing to that these oxygen-containing functional groups adsorbed and immobilized metal ions on SBC to form catalytic active sites, which could activate and catalyze H2O2 to generate •OH and HO2• radicals for effective degradation of the organics. The resulting purified MgSO4 solution with color removal of 93.71% and total organic carbon removal of 85.89% under optimum catalytic reaction conditions was used to produce qualified MgSO4∙7H2O product. These results highlighted the feasibility of using lignocellulose ester as effective catalyst for deep oxidative degradation of hazardous organic pollutants.

Aggregation of Gold Nanoparticles Caused in Two Different Ways Involved in 4-Mercaptophenylboronic Acidand Hydrogen Peroxide.

The difference in gold nanoparticle (AuNPs) aggregation caused by different mixing orders of AuNPs, 4-mercaptophenylboronic acid (4-MPBA), and hydrogen peroxide (H2O2) has been scarcely reported. We have found that the color change of a ((4-MPBA + AuNPs) + H2O2) mixture caused by H2O2 is more sensitive than that of a ((4-MPBA + H2O2) + AuNPs) mixture. For the former mixture, the color changes obviously with H2O2 concentrations in the range of 0~0.025%. However, for the latter mixture, the corresponding H2O2 concentration is in the range of 0~1.93%. The mechanisms on the color change originating from the aggregation of AuNPs occurring in the two mixtures were investigated in detail. For the ((4-MPBA + H2O2) + AuNPs) mixture, free 4-MPBA is oxidized by H2O2 to form bis(4-hydroxyphenyl) disulfide (BHPD) and peroxoboric acid. However, for the ((4-MPBA+AuNPs) + H2O2) mixture, immobilized 4-MPBA is oxidized by H2O2 to form 4-hydroxythiophenol (4-HTP) and boric acid. The decrease in charge on the surface of AuNPs caused by BHPD, which has alarger steric hindrance, is poorer than that caused by -4-HTP, and this is mainly responsible for the difference in the aggregation of AuNPs in the two mixtures. The formation of boric acid and peroxoboric acid in the reaction between 4-MPBA and H2O2 can alter the pH of the medium, and the effect of the pH change on the aggregation of AuNPs should not be ignored. These findings not only offer a new strategy in colorimetric assays to expand the detection range of hydrogen peroxide concentrations but also assist in deepening the understanding of the aggregation of citrate-capped AuNPs involved in 4-MPBA and H2O2, as well as in developing other probes.

One-pot synthesis of biomimetic glutathione peroxidase with temperature responsive catalytic behaviors.

Excessive reactive oxygen free radicals (ROS) are the main cause of various oxidative diseases. It is of great significance to develop antioxidant drugs that can intelligently regulate free radical concentrations. The biomimetic simulation of glutathione peroxidase (GPx) can provide an important theoretical basis for the development of antioxidant drugs. In order to explore a simple and efficient strategy for constructing biomimetic GPx, a microgel biomimetic GPx (PNTegel) with temperature responsive catalytic activity was prepared by a one-pot synthesis method. The PNTegel, with typical enzymatic catalytic characteristics, exhibited a maximum catalytic activity at 37 °C (υ 0 = 11.51 mM min-1). The investigation of the catalytic mechanism of PNTegel suggested that the binding of different hydrophobic substrates to PNTegel was altered by the change of hydrophobicity of poly(N-isopropylacrylamide) (PNIPAM) in the microgel scaffold of PNTegel during the temperature response process. The change of hydrophobicity was the main factor for regulating the catalytic activity of PNTegel, which resulted in a temperature responsive catalytic behavior of PNTegel. This new strategy for the simple and efficient construction of biomimetic GPx by a one-pot method provides important theoretical support for exploring the preparation of highly effective antioxidant drugs.

Mineralization of organics in hazardous waste sulfuric acid by natural manganese oxide ore and a combined MnO2/activated carbon treatment to produce qualified manganese sulfate.

To effectively dispose and utilize the hazardous waste H2SO4 generated from alkylation, an environmentally friendly and feasible technology for the simultaneous oxidative degradation of organics and consumption of H2SO4 was developed. Pyrolusite, a natural manganese oxide ore, was used for the oxidative degradation and mineralization of the organics, and reduction leaching of Mn from the pyrolusite occurred simultaneously. The total organic carbon (TOC) removal and Mn leaching efficiency were 46% and 16.44%, respectively. In addition, pyrites was applied as a reductant to extract Mn from the pyrolusite, and an Mn leaching efficiency of 98.31% was obtained under the optimized conditions of 4/1 liquid/solid ratio, 350 rpm stirring speed, 1.5 mol L-1 H2SO4 concentration, and 95 °C for 1 h in the first oxidative degradation stage and a molar ratio of FeS2/MnO2 of 0.55/1 for 4 h in the reduction leaching stage. Subsequently, a combined treatment of MnO2/activated carbon was developed for further oxidation and adsorption of the organics in the solution, with the TOC removal of 84.11%. The resulting purified MnSO4 solution was concentrated to produce qualified MnSO4∙H2O, which met the requirements of an industrial product. This technology showed application potential in highly-efficient removal of hazardous organic contaminates.

Solid-Phase Synthesis of Cellulose Acetate Butyrate as Microsphere Wall Materials for Sustained Release of Emamectin Benzoate.

Emamectin benzoate (EB), a widely used pesticide, is prone to decomposition by ultraviolet light and suffers from the corresponding loss of efficacy. The timed release of EB based on microspheres is one of the effective methods to solve this issue. As a non-toxic cellulose ester, cellulose acetate butyrate (CAB) is regarded as one of the best wall-forming materials for microcapsules with a good controlled release performance. Herein, two methods-mechanical activation (MA) technology and a conventional liquid phase (LP) method-were employed to synthesize different CABs, namely CAB-MA and CAB-LP, respectively. The molecular structure, rheological property, and thermal stability of these CABs were investigated. The two CABs were used to prepare microspheres for the loading and release of EB via an o/w (oil-in-water) solvent evaporation method. Moreover, the performances such as drug loading, drug entrapment, and anti-photolysis of the drug for these microspheres were studied. The results showed that both CABs were available as wall materials for loading and releasing EB. Compared with CAB-LP, CAB-MA presented a lower molecular weight and a narrower molecular weight distribution. Moreover, the MA method endowed the CAB with more ester substituent groups and less crystalline structure in comparison to the LP method, which had benefits including pelletizing and drug loading.

Efficient removal of Cr(VI) from water by quaternized chitin/branched polyethylenimine biosorbent with hierarchical pore structure.

A novel chitin-based biosorbent (QCP) was synthesized by cross-linking quaternized chitin and branched polyethylenimine with the aid of epichlorohydrin for efficient removal of Cr(VI) from water. Because it possessed both quaternary ammonium groups and amino groups as well as the hierarchical pore structure, QCP presented a maximum adsorption capacity of 387.7 mg/g according to the Langmuir isotherm at 25 °C. The biosorption of QCP achieved the equilibrium within 40 min and followed the pseudo-second-order kinetic model. QCP worked well even in the solution with high pH and high content of competing anions and, it exhibited an excellent reusability. The main Cr(VI) uptake mechanism was confirmed to be electrostatic attractions between Cr(VI) anions and quaternary ammonium groups as well as the protonated amino groups, and followed by partial reduction of Cr(VI) to Cr(III) by amines and hydroxyls. This work may provide a potential for Cr(VI) removal by chitin-based biosorbents.

Electrochemical removal of stains from paper cultural relics based on the electrode system of conductive composite hydrogel and PbO2.

Constructing methods for cleaning stains on paper artworks that meet the requirements of preservation of cultural relics are still challenging. In response to this problem, a novel electrochemical cleaning method and the preparation of corresponding electrodes were proposed. For this purpose, the conductive graphene (rGO)/polyacryamide (PAM)/montmorillonite (MMT) composite hydrogel as cathode and PbO2-based material as anode were prepared and characterized. The electrochemical cleaning efficiencies of real sample and mimicking paper artifacts were evaluated, and the effects of the electrochemical cleaning on paper itself were detected. Based on the above experiments, the following results were obtained. The composite hydrogel with attractive mechanical properties is mainly based on the hydrogen bond interactions between PAM chains and MMT. The results of cleaning efficiency revealed that the black mildew stains together with the yellowish foxing stains were almost completely eliminated within 6 min at 8 mA/cm2, and various stains formed by tideline, foxing, organic dyes and drinks could be thoroughly removed at 4 mA/cm2 within 5 min. In addition, the proposed cleaning method has advantages in local selectivity, easy control of cleaning course, and reusability, which represents a potential utility of this approach.