Cation-exchange fibers and silver nanoparticles-modified carbon electrodes for selective removal of hardness ions and simultaneous deactivation of microorganisms in capacitive deionization.

The hardness and microorganism contamination are common problems of water quality around the world. Capacitive deionization (CDI) is a much-discussed solution to help solve the water crisis by providing efficient water softening while killing microorganism. Carboxylic (Na) cation-exchange fiber (CCEF) is an adsorbent material with good affinity for hardness ions. Silver nanoparticles (AgNPs) is a broad-spectrum microbicide. In this paper, the CCEF modified activated carbon (CCEF-AC) was used as cathode and showed excellent hardness ion adsorption selectivity at the optimum CCEF doping level (αCa2+/Na of 15.0, αMg2+/Na of 13.5). Its electrosorption capacity of Ca2+ reached 311 µmol/g, much higher than that of the AC cathode (188 µmol/g). It also showed good regenerable performance, retaining over 85 % of Ca2+ electrosorption capacity after 50 cycles stability test. The activated carbon modified with AgNPs (AC-Ag) was used as anode. When enhanced by an electric field, it could kill bacteria and microalgae with over 99 % and 90 % inhibition rates, respectively. This work has opened up a new way to simultaneously remove multiple pollutants (organic or inorganic) from water.

Preparation and properties of phosphinic acid-functionalized polyacrylonitrile hollow fiber membrane for heavy metal adsorption.

In this study, phosphorylated polyacrylonitrile hollow fiber membrane was synthesized by reacting aminated polyacrylonitrile hollow fiber membrane with phosphinic acid in a Mannich reaction. The batch single-factor measurements revealed that the phosphorylated polyacrylonitrile (PPAN) membrane had an outstanding ability for Hg2+ adsorption. Thermodynamic investigations indicated that the adsorption process was homogenous, and the theoretical maximum adsorption capacity predicted by the Langmuir model was 371.75 mg·g-1. The PPAN membrane was able to successfully chelate Hg2+ ions and attain saturation in 4 h, demonstrating that the reaction was chemically controlled by the adsorption kinetics. Based on the FT-IR and XPS spectral characterization data, successful phosphinic acid group grafting was proven, and a plausible mechanism for Hg2+ adsorption by PPAN membranes was presented. Furthermore, the five adsorption-desorption cycle experiments revealed that PPAN hollow fiber membranes had outstanding reusability, indicating a possible use for removing heavy metal ions from wastewater.

Evaluation on antiosteoporosis of collagen peptides prepared by immobilized protease with eggshell membrane.

Collagen peptides are a potential treatment for osteoporosis due to their antiosteoporosis activity. In this study, we prepared immobilized protease with eggshell membrane as carrier, and then hydrolyzed collagen to obtain collagen peptide. The antiosteoporosis of collagen peptides was confirmed by hBMSC osteogenic differentiation and bone mineralization improvement results. Surprisingly, antiosteoporosis of collagen peptides was related to the molecular weight of collagen peptides. This was derived from the osteoblast marker gene expressions, and mineral elements in P1 treatment were higher than those in P3 treatment. Consequently, these results confirmed that antiosteoporosis of low molecular weight collagen peptides is higher than that of higher molecular weight collagen peptides. Furthermore, the antiosteoporosis activity of P1 was due to its peptide sequences with known antiosteoporosis activity in P1. PRACTICAL APPLICATION: Using eggshell membrane as carrier to prepare immobilized protease was meaningful for solving the problem of resource waste. In addition, the results showed that collagen peptides possessed antiosteoporosis, and the effect of low molecular weight collagen peptides was better. This study provides a theoretical basis for developing high antiosteoporosis collagen peptides able to treat osteoporosis.

The integrated production of ultrathing-C3N4and membrane assisted by edible syrup for the sustained photocatalytic treatment of Cr(VI) and tetracycline.

The exfoliation of bulk raw graphitic carbon nitride (g-C3N4) by edible glucose syrup to produce ultrathing-C3N4nanosheets in concentrations of up to 0.2 mg ml-1was achieved. Detailed characterization through TEM, AFM, FT-IR, XRD, Raman and TGA confirmed the formation of ultrathin structure and improved properties. Compared to rawg-C3N4, the prepared thing-C3N4layers exhibited a 18-fold enhancement in Cr(VI) reduction and a 3-fold enhancement in tetracycline hydrochloride degradation, which is ascribed to their larger specific surface area and more exposed active sites. The layeredg-C3N4membrane was constructed via direct vacuum filtration. The layer-stackedg-C3N4nanosheet membrane exhibited an excellent and sustained photocatalytic performance as the prepared thing-C3N4layers could maintain a layered lamella after stacking in filtration process. The recyclable synthesis of ultrathing-C3N4layers and layer-stackedg-C3N4membrane by our method provides a sustainable strategy to pollution treatment by 2D materials.

Scalable synthesis of monodisperse and recyclable sulphonated polystyrene microspheres for sustainable elimination of heavy metals in wastewater.

Herein, we demonstrate a scalable method for fabricating monodisperse sulphonated polystyrene (SPS) microspheres with abundant sulphonic acid groups and excellent heavy metal removal ability. A comprehensive characterization through SEM, EDS, FT-IR, TG, XRD and XPS confirmed the formation of the SPS microspheres. Take advantage of the abundant sulphonic acid groups on the surface of microspheres, as well as the superior monodisperse properties, adsorption ability of SPS microspheres both in quantity and speed have been enhanced. The adsorption equilibrium obeyed the Langmuir isotherm model with the theoretical maximum capacities of 49.16, 15.38 and 13.89 mg·g-1 for Pb2+, Zn2+ and Cu2+, respectively (30°C, pH = 3.5). Besides, the adsorption equilibriums of Pb2+ onto SPS microspheres can be achieved within only 1 min and the adsorption kinetics can be fitted by a pseudo-second-order kinetics model. More importantly, because of the micron structure of the SPS microspheres, it could overcome the excessive hydrophilia brought by rich sulphonic acid groups and thereby easily separated, which maintain a good recyclable capacity after five regeneration cycles. With the excellent adsorption ability and reusability, SPS microspheres can efficiently handle the polluted water in a convenience and rapid process, which satisfies the sustainable pollution treatment in heavy metals elimination.

Preparation of an Amidated Graphene Oxide/Sulfonated Poly Ether Ether Ketone (AGO/SPEEK) Modified Atmosphere Packaging for the Storage of Cherry Tomatoes.

The shelf life of cherry tomatoes is short so that new and efficient preservation techniques or procedures are required to reduce postharvest losses. This study focused on the development of a sulfonated poly ether ether ketone (SPEEK) film incorporated with amidated graphene oxide (AGO), for the storage of cherry tomatoes in modified atmosphere packaging. The mechanical properties, gas permeability, and moisture permeability were subsequently tested. The evolution of attributes related to shelf life, such as gas composition, physicochemical properties, and sensory properties were also monitored during storage trials. AGO, as an inorganic filler, increases the thermal stability and mechanical properties of SPEEK-based films, while it reduces the water absorption, swelling rate, and moisture permeability. Importantly, all the AGO/SPEEK films exhibited enhanced gas permeability and selective permeability of CO2/O2 relative to the SPEEK film. Moreover, 0.9% (w/w) AGO/SPEEK film showed an enhanced permeability coefficient of CO2, corresponding to an increase of 50.7%. It could further improve the selective coefficient of CO2/O2 to 67.1%. The results of preservation at 8 °C revealed that: 0.9% (w/w) AGO/SPEEK film was significantly effective at maintaining the quality and extending the shelf life of cherry tomatoes from 15 to 30 days, thereby suggesting the potential for applying AGO-incorporated SPEEK films for food packaging materials.

Facile and moderate immobilization of proteases on SPS nanospheres for the active collagen peptides.

Although collagen peptides have been proved to possess wide applications in functional foods, cosmetics, medical materials and pharmaceuticals, the production of collagen peptides are deeply affected by proteases and substrate. In this study, the scalable-synthesis sulfonated polystyrene (SPS) nanospheres were utilized as accessible supports for efficient subtilisin immobilization. Detailed characterizations through SEM-EDS, TEM, TGA and FT-IR confirmed the undamaged formation of the SPS-subtilisin. Owing to the moderate hydrophobic effect and electrostatic interaction, the SPS-subtilisin could achieve 397.15 mg/g enzyme loading and 77.3% activity recovery. The tilapia skin collagen, as a resource-rich raw material, was hydrolyzed by the prepared immobilized subtilisin. The antioxidant activity of the attained peptides was verified. With the mass spectrometry and molecular docking analysis of product peptides sequences, representative peptides were synthesized and their anti-oxidation capacity and mechanism were affirmed, which further verified the undiminished catalytic ability of immobilized subtilisin.

A novel approach for simultaneous analysis of perchlorate (ClO4-) and bromate (BrO3-) in fruits and vegetables using modified QuEChERS combined with ultrahigh performance liquid chromatography-tandem mass spectrometry.

Perchlorate (ClO4-) and bromate (BrO3-) are mainly determined by ion chromatography methods. The present work aims to develop a modified QuEChERS combined with ultrahigh performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) method for simultaneous analysis of ClO4- and BrO3- in fruits and vegetables including cherry tomato, strawberry, tomato, potato, lettuce and pakchoi. Two target inorganic anions were separated on a Diamonsil C18(2) column by gradient elution, scanned in ESI negative mode and detected under multiple reactions monitoring (MRM). Limit of detection (LOD) and method limit of quantification (MLOQ), matrix effect, accuracy and precision of the developed method were investigated. Results were linear in their concentration ranges, with coefficients of determination (r2) bigger than 0.999. LODs for ClO4- and BrO3- were 0.1 µg/L and 0.5 µg/L, respectively. The validated method provided sufficient selectivity, sensitivity and accuracy to screen for ClO4- and BrO3- with ignorable matrix effects. Recoveries for different kinds of negative samples at 3 spiked levels were between 82.0% and 99.5%. Both intraday-precision and interday-precision were satisfactory, showing RSDr values in the range of 2.1-7.1% and RSDR values in the range of 7.2-10.8%. The proposed method was successfully applied to determine target inorganic anions in several fruits and vegetables. Perchlorate was detected in 12 vegetable samples with the concentrations ranged from 21 µg/kg to 162 µg/kg. Results indicated that there was wide ClO4- contamination in vegetables, confirming its urgency for monitoring harmful inorganic anions in our daily consumed vegetables.

Development and comparison of single-step solid phase extraction and QuEChERS clean-up for the analysis of 7 mycotoxins in fruits and vegetables during storage by UHPLC-MS/MS.

A robust and sensitive UHPLC-MS/MS method was developed for the analysis of seven mycotoxins in fruits and vegetables. The variations of seven mycotoxins concentrations during storage were also determined for the first time. Solid phase extraction (SPE) and QuEChERS clean-up were compared, and extraction was finally performed with acetonitrile under acidic conditions followed by HLB SPE purification. Seven mycotoxins were separated on a C18 column by gradient elution, scanned by ESI+ and ESI- dynamic switching and detected with MRM mode. LOD and LOQ, matrix effect, accuracy and precision of the developed method were investigated. Results were linear in their concentration ranges for all mycotoxins with R2 being greater than 0.999. LODs and LOQs were ranged from 0.05 to 3.0 µg/kg and 0.2 to 10.0 µg/kg, respectively. Average recoveries were between 81.1% and 116% with intraday- and interday-precision being in the ranges of 3.0-6.2% and 4.2-6.1%, respectively. The validated method provides sufficient selectivity, sensitivity and accuracy to screen for seven mycotoxins at trace levels, without using standard addition or matrix-matched calibration to compensate for matrix effects. The method was successfully applied for mycotoxins analysis in fruits and vegetables. None were detected in fresh samples, but AOH and AME were detected in strawberry, and TeA was detected in tomato fruits during long-term storage. Their concentrations were in the range of 3.6-165.3 µg/kg from 3 days to 60 days and significantly increased along with storage time.

A novel superchilling storage - ice glazing (SS-IG) approach using biopolymer-based composite hydrogel to delay microbiological spoilage and organic oxidation of preserved tilapia.

BACKGROUND: Most aquatic products are highly susceptible to deterioration and microbial spoilage during storage. Cold storage is a frequently used method to preserve them. However, products preserved by traditional frozen method are prone to suffer damage. This can significantly impair the quality of the products. To solve the problem, this work established a novel superchilling storage-ice glazing (SS-IG) approach using chitosan-catechin composite material. It can maximize the postmortem quality of preserved products during storage, avoiding damage. RESULTS: During storage at -1.5 ± 0.2 °C for 25 days, the SS-IG approach using 5 g L-1 chitosan and 1∼3 g L-1 catechin as IG layers can effectively enhance the postmortem quality of preserved tilapia fillets. The sensory qualities of these fillets were effectively maintained. The microbial counts in these fillets were strongly suppressed. Oxidative rancidity in these fillets was observably inhibited. Less biogenic amine was produced in these fillets. CONCLUSION: The results indicated that the SS-IG with chitosan-catechin composite-ice glazing layers can be effective in maintaining the postmortem quality of tilapia fillets. This will have a wide potential application. © 2018 Society of Chemical Industry.

Authenticity determination of honeys with non-extractable proteins by means of elemental analyzer (EA) and liquid chromatography (LC) coupled to isotope ratio mass spectroscopy (IRMS).

The present work aims to systematically demonstrate the authenticity of honeys with non-extractable proteins for the first time, by means of EA-IRMS and LC-IRMS. Fifty-three pure honeys of various botanical and geographical origins were studied and a criterion on the basis of the stable carbon isotope ratio characterization of total honey and the main sugars was established for pure honeys. Parameters such as δ13C values of total honey and the main sugars were well utilized to identify honeys with non-extractable proteins. Thirty-five honeys from which protein could not be extracted were all identified as adulterated with C-4 sugars or C-3 sugars. The use of isotopic compositions and some systematic differences permit the honeys with non-extractable proteins to be reliably identified. The findings obtained in this work could supplement the AOAC 998.12 C-4 sugar method, with regard to honeys from which protein cannot be extracted.

Gram-scale synthesis of monodisperse sulfonated polystyrene nanospheres for rapid and efficient sequestration of heavy metal ions.

Herein, gram-scale monodisperse sulfonated polystyrene (SPS) nanospheres are synthesized and examined as a sorbent for the removal of heavy metal ions (Pb2+, Zn2+ and Cu2+). The resulting uniform SPS nanospheres exhibit remarkable adsorption capabilities and kinetics, facile regeneration and outstanding recyclability, affording promising applications in food engineering and water cleanup.

Modified QuEChERS combined with ultra high performance liquid chromatography tandem mass spectrometry to determine seven biogenic amines in Chinese traditional condiment soy sauce.

A rapid and sensitive UHPLC-MS/MS method followed by modified QuEChERS was developed for the simultaneous determination of seven biogenic amines in soy sauce. Samples were firstly diluted by water and pH values of which were adjusted using ammonia water. Modified QuEChERS method was adopted for the purification and 1, 7-heptyldiamine was used as the internal standard. Analysis of seven biogenic amines was within 4min. Under the optimized conditions, linear relations were favorable over the selected concentration ranges of 3.0-600µg/L with correlationcoefficients greater than 0.999. The average accuracy was between 84% and 115%. Intra- and inter- assay precisions for six replicates ranged from 2.2% to 8.8% or below 12%, respectively. The method limits of detection and the method limits of quantitation were 4-8µg/kg and 15-30µg/kg, respectively. The method was successfully applied to determine the concentrations of seven biogenic amines in soy sauces.

Quality Evaluation Focusing on Tissue Fractal Dimension and Chemical Changes for Frozen Tilapia with Treatment by Tangerine Peel Extract.

This work aimed to establish an effective approach to evaluate the quality of frozen fish, focusing on changes in fish tissue structure and chemical composition during storage. Fresh tilapia samples were treated by coating with tangerine peel (TP) extract and then stored at -4, -8 and -18 °C, respectively, for 40 days. The frozen fish tissues were analyzed for structural and chemical changes. Fractal dimension, which quantifies the porous structure formed in the tissue samples, texture properties including hardness and springiness, and moisture content and water activity all decreased during the storage, while the extents of lipid oxidation, measured as peroxide value and thiobarbituric acid concentration, and protein degradation, monitored with total volatile basic nitrogen and trichloroacetic acid soluble peptides, increased. The change rates of these parameters decreased with decreasing the storage temperature and by applying TP extract. A model was developed for predicting fractal dimension, which indicated the quality of preserved tilapia and thus can be used to predict the shelf life under different storage temperatures. The results demonstrated that TP extract could extend the shelf life of frozen tilapia by 35-45% by inhibiting changes in tissue structure, moisture loss, lipid oxidation and protein degradation during frozen storage.

In Situ Assembly of Ultrathin PtRh Nanowires to Graphene Nanosheets as Highly Efficient Electrocatalysts for the Oxidation of Ethanol.

One-dimensional (1D) anisotropic platinum-based nanowires are promising electrocatalysts in polymer electrolyte membrane fuel cells owing to the inherent structural merits. Herein, we report an in situ growth of ultrathin PtRh nanowires (diameters of 2-3 nm) on graphene nanosheets via the oriented attachment pathway. Mechanistic studies reveal that graphene nanosheets play a critical role in the nucleation and growth of PtRh nanowires. The resulting hybrid of PtRh nanowire decorated graphene nanosheets shows outstanding activity and durability toward ethanol electro-oxidation. It exhibits a specific current density of 2.8 mA cm-2 and a mass-normalized current density of 1 A mg-1 metal, which are 5.4 and 3.1 times those of the state-of-the-art Pt/C catalyst, respectively. After 2000 cyclic tests, it maintains 86% of the initial electrochemically active surface area, which is larger than that of 63% obtained from the Pt/C catalyst. The superior performance is attributed to the combination of the advantageous 1D morphological motif with the synergistic effects of PtRh alloys and graphene nanosheet support.

Adulteration Identification of Commercial Honey with the C-4 Sugar Content of Negative Values by an Elemental Analyzer and Liquid Chromatography Coupled to Isotope Ratio Mass Spectroscopy.

According to the AOAC 998.12 method, honey is considered to contain significant C-4 sugars with a C-4 sugar content of >7%, which are naturally identified as the adulteration. However, the authenticity of honey with a C-4 sugar content of <0% calculated by the above method has been rarely investigated. A new procedure to determine δ(13)C values of honey, corresponding extracted protein and individual sugars (sucrose, glucose, and fructose), δ(2)H and δ(18)O values, sucrose content, and reducing sugar content of honey using an elemental analyzer and liquid chromatography coupled to isotope ratio mass spectroscopy, was first developed to demonstrate the authenticity of honey with a C-4 sugar content of <0%. For this purpose, 800 commercial honey samples were analyzed. A quite similar pattern on the pentagonal radar plot (isotopic compositions) between honey with -7 < C-4 sugar content (%) < 0 and 0 < C-4 sugar content (%) < 7 indicated that honey with -7 < C-4 sugar content (%) < 0 could be identified to be free of C-4 sugars as well. A very strong correlation is also observed between δ(13)C honey values and δ(13)C protein values of both honey groups. For the δ(18)O value, the C-4 sugar content (%) < -7 group has lower (p < 0.05) values (16.30‰) compared to other honey, which could be a useful parameter for adulterated honey with a C-4 sugar content (%) < -7. The use of isotopic compositions and some systematic differences permits the honey with a C-4 sugar content of <0% to be reliably detected. The developed procedure in this study first and successfully provided favorable evidence in authenticity identification of honey with a C-4 sugar content of <0%.

Electrocatalytic activity of Pt subnano/nanoclusters stabilized by pristine graphene nanosheets.

Downsizing the Pt particle to the atomic level in the electro-catalysts is highly desirable to enhance its utilization efficiency in fuel cells. In this study, Pt subnano/nanoclusters were stabilized by the pristine graphene nanosheets (GNSs) derived from chemical vapor deposition and the resulting Pt/GNS hybrids were examined as catalysts for electro-oxidation of alcohols (methanol, ethanol, ethylene glycol and glycerol). In spite of the strong hydrophobic surface, the GNS was proved to be a promising catalyst support because the edges and defects in the GNS could effectively anchor and stabilize the Pt subnano/nanoclusters. The Pt/GNS catalyst showed an extremely high electrochemical active surface area and superior catalytic activity for alcohol oxidation compared with the commercial Pt/carbon black catalyst. The enhanced catalytic performance was attributed to the presence of the discrete Pt subnano/nanoclusters as well as the modulation of the electronic properties of Pt nanoparticles through the chemical interaction of Pt atoms with the edges and defects of the GNS support.

Synthesis of ultrafine Pt nanoparticles stabilized by pristine graphene nanosheets for electro-oxidation of methanol.

In this study, the pristine graphene nanosheets (GNS) derived from chemical vapor deposition process were employed as catalyst support. In spite of the extremely hydrophobic GNS surface, ultrafine Pt nanoparticles (NPs) were successfully assembled on the GNS through a surfactant-free solution process. The evolution of Pt NPs in the GNS support was studied using transmission electron microscopy. It was found that the high-energy surface sites in the GNS, such as edges and defects, played a critical role on anchoring and stabilizing Pt nuclei, leading to the formation of Pt NPs on the GNS support. The concentration of the Pt precursor, i.e., H2PtCl6 solution had significant effects on the morphology of Pt/GNS hybrids. The resulting Pt/GNS hybrids were examined as catalysts for methanol electro-oxidation. It was indicated that the electrochemical active surface area and catalytic activity of the Pt/GNS hybrids were highly dependent on Pt loadings. The superior activity of the catalysts with low Pt loadings was attributed to the presence of Pt subnanoclusters as well as the strong chemical interaction of Pt NPs with the GNS support.

Anti-inflammatory activity and chemical composition of the essential oils from Senecio flammeus.

Many species from Senecio genus have been used in traditional medicine, and their pharmacological activities have been demonstrated. This study investigated the chemical composition and anti-inflammatory activities of essential oils from Senecio flammeus. A total of 48 components representing 98.41 % of the total oils were identified. The main compounds in the oils were α-farnesene (11.26 %), caryophyllene (8.69 %), n-hexadecanoic acid (7.23 %), and α-pinene (6.36 %). The anti-inflammatory activity of the essential oils was evaluated in rodents (10-90 mg/kg bw) in classical models of inflammation [carrageenan-induced paw edema, 12-O-tetradecanoyl-phorbol-13-acetate (TPA)-induced ear edema, and cotton pellet-induced granuloma]. The essential oils at doses of 10, 30, and 90 mg/kg bw significantly reduced carrageenan-induced paw edema by 17.42 % (P < 0.05), 52.90 % (P < 0.05), and 66.45 % (P < 0.05) 4 h after carrageenan injection, respectively, and significantly reduced myeloperoxidase activity (P < 0.05). The essential oils (10, 30, and 90 mg/kg) also produced a significant dose-dependent response to reduce TPA-induced ear edema by 20.27 % (P < 0.05), 33.06 % (P < 0.05), and 53.90 % (P < 0.05), respectively. The essential oils produced significant dose-response anti-inflammatory activity against cotton pellet-induced granuloma that peaked at the highest dose of 90 mg/kg (49.08 % wet weight and 47.29 % dry weight). Results demonstrate that the essential oils of S. flammeus were effective in the treatment of both acute and chronic inflammatory conditions, thereby supporting the traditional use of this herb.