Efficient degradation of bisphenol A and amino black 10B by magnetic composite Fe3O4@MOF-74 as catalyst.

Metal-organic frameworks (MOFs) exhibit high chemical stability and porosity, and have been widely applied in various fields including selective adsorption and separation, sensors, and catalysis. When combined with Fe3O4, they effectively address issues such as aggregation of Fe3O4 particles and the difficulty in recovering MOFs as catalysts. Therefore, in this study, we used a simple solvothermal method as a catalyst to synthesize a high specific surface area magnetic composite Fe3O4@MOF-74, which was used to catalyze the degradation of bisphenol A (BPA) and amino black 10B in wastewater. We activated Na2S2O8 to generate radicals for oxidizing and degrading BPA and amino black 10B. Experimental results showed that at 35 °C, with Fe3O4@MOF-74 (Fe3O4: MOF-74=1:1) concentration of 0.2 g/L and Na2S2O8 concentration of 2 g/L, the catalytic effect is efficient and economical. Meanwhile, removal rates of BPA and amino black 10B exceeded 95.58 % over a broad pH range (pH 3-9). Furthermore, even after multiple cycles of use, Fe3O4@MOF-74 maintained catalytic degradation rates of BPA and amino black 10B above 93.24 % and 95.01 %, respectively. Additionally, in water samples, removal rates of BPA and amino black 10B exceeded 91.55 %. This study provides a new and efficient catalyst material for wastewater treatment, which is expected to play an important role in environmental remediation.

Magnetic Property, Heat Capacity and Crystal Structure of Mononuclear Compounds Based on Substitute Tetrazole Ligand.

Three mononuclear compounds formulated as {M[(2-1H-tetrazol-5-yl)pyridine]2(H2O)2} (M = FeII (1), CoII (2), CuII (3)) were reported and synthesized. Their space group is monoclinic, P21/c, revealed by single-crystal X-ray diffraction. Antiferromagnetic interactions exist in Compounds 1, 2 and 3, as evidenced by magnetic and low-temperature heat capacity measurements. In addition, their thermodynamic functions were determined by a relaxation calorimeter, indicating that Compound 1 exhibits a Schottky anomaly in low-temperature heat capacity. This work can provide an important fundamental basis for the research of the thermophysical properties of molecular-based magnetic materials.

Adsorption Performance of Magnetic Covalent Organic Framework Composites for Bisphenol A and Ibuprofen.

As typical environmental endocrine disruptors and nonsteroidal anti-inflammatory drugs, bisphenol A and ibuprofen in water supplies can cause great harm to the ecological environment and human health. In this study, magnetic covalent organic framework composites Fe3O4@COF-300 were synthesized by the hydrothermal method and used to remove bisphenol A and ibuprofen from water. Fe3O4@COF-300 could be rapidly separated from the matrix by external magnetic fields, and could selectively adsorb bisphenol A and ibuprofen in the presence of coexisting compounds such as phenol, Congo red, and amino black 10B. The removal efficiency of ibuprofen was 96.12-98.52% at pH in the range of 2-4 and that of bisphenol A was 92.18-95.62% at pH in the range of 2-10. The adsorption of bisphenol A and ibuprofen followed a pseudo-second-order kinetic and Langmuir model, and was a spontaneous endothermic process with the maximum adsorption amounts of 173.31 and 303.03 mg∙g-1, respectively. The material presented favorable stability and reusability, and the removal efficiency of bisphenol A and ibuprofen after 5 cycles was still over 92.15% and 89.29%, respectively. Therefore, the prepared composite Fe3O4@COF-300 exhibited good performance in the adsorption of bisphenol A and ibuprofen in water.

Efficient activation of persulfate by Nickel-supported cherry core biochar composite for removal of bisphenol A.

In this study, low-cost and easily obtained biochar was chosen to prepare nickel-modified biochar materials (Ni/BC) through a one-step activation pyrolysis method. Characterization with X-ray diffraction, X-ray photoelectron spectroscopy and high-resolution transmission electron microscopy proved the existence of Ni0 and NiO nanocrystals in Ni/BC catalyst. The optimal Ni0.5/BC exhibited excellent peroxymonosulfate (PMS) and peroxydisulfate (PDS) activation efficiency toward bisphenol A (BPA) degradation. The Ni0.5/BC (0.03 g) reacted with 1.0 g L-1 PMS or PDS could completely remove 20 mg L-1 BPA in 10 min with the first-order kinetic constants (k1) of 0.322 min-1 (PMS) and 0.336 min-1 (PDS). More importantly, the composite has better structural and functional attributes for the BPA degradation with universal applicability at wide pH and temperature range, proving as a better degradation mediator with high adaptation for numerous organic pollutants. Catalytic activity decreased slightly even after 4 cycles. Based on the quenching experiment and electron paramagnetic resonance, it was found that SO4•-, •OH and 1O2 were the dominant active species in BPA degradation process. Therefore, this work not only supplies a promising catalyst for the removal of organic contaminants, but also is beneficial for the further development of alternative catalysts for sulfate radical based advanced oxidation processes.

Nanoscale zero-valent iron particles supported on MIL-96: a novel material for adsorption-degradation of trichloronitromethane.

As an emerging class of nitrogenous disinfection by-products, halonitromethanes have caused public health concerns owing to their high toxicity. More and more attention has been paid to the new materials and technologies for the removal of halonitromethanes. In this study, a novel material, nanoscale zero-valent iron (nZVI) supported on MIL-96 (nZVI@MIL-96) with favorable stability and reusability, was synthesized and applied to the adsorption-degradation of trichloronitromethane (TCNM) in the water. The results revealed that almost all the TCNM could be removed under 20 mg/L nZVI@MIL-96 dosage with a wide temperature range. The optimum mass ratio of nZVI to MIL-96 was 1:2, and the TCNM adsorption-degradation followed a pseudo-first-order model. The coexisting ions, such as SO42-, PO43-, and NO3-, with high concentration brought adverse effects on the removal of TCNM; however, the effects of Cl- and CO32- were insignificant. The concentrations of aluminum and iron ions in water were all within the standard value after adsorption with the nZVI@MIL-96. The degradation mechanism of TCNM by nZVI@MIL-96 included two steps, namely, adsorption and degradation, and methylamine was the terminal dechlorination and denitration products. In a word, the as-prepared nZVI@MIL-96 nanoparticles demonstrated the capabilities as a material of adsorption-degradation of TCNM in the water.

NDMA adsorption and degradation by a new-type of Ag-MONT material carrying nanoscale zero-valent iron.

Nitrosamines, which are emerging nitrogenous disinfection by-products, have raised great concern owing to their carcinogenicity and genotoxicity. Thus, exploring efficient materials to remove nitrosamines from the environment is of vital importance. In this work, NaBH4 was taken as a reducing agent and Ag-based metal organic nanotubes (Ag-MONTs) were impregnated in FeSO4·7H2O to prepare nanoscale zero-valent iron (nZVI) supported on the nanotubes (nZVI@Ag-MONTs). The new material was then characterized and applied to N-dimethylnitrosamine (NDMA) adsorption and degradation in water. The material had excellent ability to adsorb and degrade NDMA, and the total concentrations of iron and silver remaining in water did not exceed standard limits after 120 min of adsorption. Coexisting substances, such as NO3-, Cl-, CO32-, humic acid, trichloromethane, and trichloronitromethane, did not affect the NDMA removal efficiency of the adsorbent. The NDMA removal efficiency of the new material exceeded 88% even in the presence of SO42- and PO43-. The NDMA degradation mechanism of nZVI@Ag-MONTs included a catalytic hydrogenation reaction and resulted in dimethylamine as the final degradation product. The nZVI@Ag-MONTs showed favorable stability and reusability. Taking the results together, the nZVI@Ag-MONTs proposed in this work are applicable to NDMA adsorption and degradation in water.

A facile route for preparation of magnetic biomass activated carbon with high performance for removal of dye pollutants.

A novel and simple method for preparing magnetic biomass activated carbon (BAC) was developed. The BAC was prepared by decomposing fallen leaves, and magnetic nanoparticles were grown in situ on BAC using solvothermal method. The prepared magnetic BAC was characterized with FT-IR, XRD, vibrating sample magnetometer, thermo-gravimetric apparatus, SEM, and high-resolution transmission electron microscope, and results indicate that BAC and magnetic nanoparticles were combined together successfully. To investigate the adsorption ability of the composites, several dyes were selected as sample pollutants, and the sorbent showed high adsorption capacity for the dyes. The solution pH had no significant effect on the adsorption in the range of 5-9. The adsorption behavior of magnetic BAC for dyes followed the Langmuir isotherm model, and the adsorption capacity of congo red, neutral red, and methyl green were 396.8, 171.2, and 403.2 mg/g, respectively. The maximum adsorption capacity in natural water showed no obvious decrease, indicating the strong anti-interference ability of the sorbents. The Gibbs free energy calculated from the thermodynamics data was negative, demonstrating that the adsorption of these dyes on the magnetic BAC was spontaneous. The magnetic BAC showed a great potential for the removal of dye pollutants from environment water.

An unusual red-to-brown colorimetric sensing method for ultrasensitive silver(I) ion detection based on a non-aggregation of hyperbranched polyethylenimine derivative stabilized gold nanoparticles.

Here we have developed a facile and rapid colorimetric method for the sensitive and selective detection of Ag(+) based on the non-aggregation of gold nanoparticles (Au NPs) capped with hyperbranched polyethylenimine derivatives. In the detection process, an unusual colour change from red to brown was observed due to the formation of Au-Ag core-shell nanoparticles, which was more sensitive than that of the usual colorimetric assays (red to blue) based on the aggregation of Au NPs. After the colour changed, the non-aggregation-based Au-Ag core-shell nanomaterials did not aggregate further and could remain stable for a long time, which was convenient to record, detect and observe. The sensing probe exhibited a drastically long observing time for detecting Ag(+) owing to the stability of the Au-Ag core-shell non-aggregates, high sensitivity with a low detection limit of 8.76 nM by the naked eye and 1.09 nM by using a UV-vis spectrophotometer and a good linear relationship within the range from 1.09 to 109 nM. The colour change of the system is very fast, occurring within 1 to 2 minutes. Moreover, the proposed method also showed a remarkably high selectivity toward Ag(+) and was successfully used in tap water and drinking water samples. Therefore, this unusual colorimetric assay based on the non-aggregation of Au NPs has a great potential as a simple, rapid, sensitive and selective detection method for the detection of Ag(+).

Mussel-inspired polydopamine biopolymer decorated with magnetic nanoparticles for multiple pollutants removal.

The polydopamine polymer decorated with magnetic nanoparticles (Fe3O4/PDA) was synthesized and applied for removal of multiple pollutants. The resulted Fe3O4/PDA was characterized with elemental analysis, thermo-gravimetric analyses, vibrating sample magnetometer, high resolution transmission electron microscope, Fourier transform infrared spectra, and X-ray photoelectron spectroscopy. The self-polymerization of dopamine could be completed within 8h, and Fe3O4 nanoparticles were embedded into PDA polymer. Superparamagnetism and large saturation magnetization facilitated collection of sorbents with a magnet. Based on the catechol and amine groups, the PDA polymer provided multiple interactions to combine with pollutants. To investigate the adsorption ability of Fe3O4/PDA, heavy metal ions and dyes were selected as target pollutants. The adsorption of pollutants was pH dependent due to the variation of surface charges at different solution pH. The removal efficiencies of cation pollutants enhanced with solution pH increasing, and that of anion pollutant was just the opposite. Under the optimal solution pH, the maximum adsorption capacity calculated from Langmuir adsorption isotherm for methylene blue, tartrazine, Cu(2+), Ag(+), and Hg(2+) were 204.1, 100.0, 112.9, 259.1, and 467.3 mg g(-1), respectively. The Fe3O4/PDA shows great potential for multiple pollutants removal, and this study is the first application of PDA polymer in environmental remediation.

Formation of thermo-sensitive polyelectrolyte complex micelles from two biocompatible graft copolymers for drug delivery.

Thermo-sensitive polyelectrolyte complex (PEC) micelles assembled from two biocompatible graft copolymers chitosan-g-poly(N-isopropylacrylamide) (CS-g-PNIPAM) and carboxymethyl cellulose-g-poly(N-isopropylacrylamide) (CMC-g-PNIPAM) were prepared for delivery of 5-fluorouracil (5-FU). The PEC micelles showed a narrow size distribution with core-shell structure, in which the core formed from positively charged CS and negatively charged CMC by electrostatic interactions and the shell formed from thermo-sensitive PNIPAM. The synthesized PEC micelles have lower critical solution temperatures (LCST) in the region of 37°C, which is favorable for smart drug delivery applications. The hydrogen bondings between PEC micelles and 5-FU increased the drug loading. Changing temperature, pH or ionic strength, a sustained and controlled release was observed due to the deformation of PEC micelles. Adding glutaraldehyde, a chemical crosslinking reagent, was an efficient way to reinforce the micelles structure and decrease the initial burst release. Cytotoxicity assays showed that drug-loaded PEC micelles retained higher cell inhibition efficiency in HeLa cells.

pH-sensitive polyelectrolyte complex micelles assembled from CS-g-PNIPAM and ALG-g-P(NIPAM-co-NVP) for drug delivery.

In this paper, pH-sensitive polyelectrolyte complex micelles assembled from two oppositely charged graft copolymers chitosan-g-poly(N-isopropylacrylamide) (CS-g-PNIPAM) and sodium alginate-g-poly(N-isopropylacrylamide-co-N-vinyl-pyrrolidone) [ALG-g-P(NIPAM-co-NVP)] were prepared for controlled release of 5-fluorouracil (5-FU). The polyelectrolyte complex micelles showed a narrow size distribution with core-shell structure, where the core formed from positively charged CS and negatively charged ALG by electrostatic interactions. The hydrogen bonding interactions between micelles and 5-FU improved the drug loading. Changing temperature or pH, a controlled drug release was observed. Glutaraldehyde, as a chemical cross-linking agent, was used to improve the micelles stability and decrease the initial burst release. Cytotoxicity assays showed that drug-loaded micelles retained high cell inhibition efficiency in Hela cells. These novel complex micelles with environmentally sensitive properties are expected to be useful in the field of intelligent drug delivery system.

Dual cloud point extraction coupled with hydrodynamic-electrokinetic two-step injection followed by micellar electrokinetic chromatography for simultaneous determination of trace phenolic estrogens in water samples.

A dual cloud point extraction (dCPE) off-line enrichment procedure coupled with a hydrodynamic-electrokinetic two-step injection online enrichment technique was successfully developed for simultaneous preconcentration of trace phenolic estrogens (hexestrol, dienestrol, and diethylstilbestrol) in water samples followed by micellar electrokinetic chromatography (MEKC) analysis. Several parameters affecting the extraction and online injection conditions were optimized. Under optimal dCPE-two-step injection-MEKC conditions, detection limits of 7.9-8.9 ng/mL and good linearity in the range from 0.05 to 5 µg/mL with correlation coefficients R(2) ≥ 0.9990 were achieved. Satisfactory recoveries ranging from 83 to 108% were obtained with lake and tap water spiked at 0.1 and 0.5 µg/mL, respectively, with relative standard deviations (n = 6) of 1.3-3.1%. This method was demonstrated to be convenient, rapid, cost-effective, and environmentally benign, and could be used as an alternative to existing methods for analyzing trace residues of phenolic estrogens in water samples.

Adsorptive decolorization of methylene blue by crosslinked porous starch.

Crosslinked porous starch (CPS) was prepared by two steps. Native starch was crosslinked with epichlorohydrin and then CPS was prepared by hydrolyzing the crosslinked starch with α-amylase. As a biodegradable and safe adsorbent, CPS was used to remove methylene blue (MB) from the aqueous solution based on its characterizations, including surface area, pore volume and scanning electron microscopy (SEM). The results indicate that the adsorption capacity of CPS is much higher than native starch and relatively higher than porous starch. The effects of the initial concentration of MB, the time and temperature on the adsorption capacity were investigated. The pseudo-first-order kinetic model provides a better correlation of the experimental data in comparison with the pseudo-second-order model. The equilibrium adsorption data are well described by the Langmuir isotherm model with a maximum adsorption capacity of 9.46mg g(-1). The adsorption of MB on CPS is endothermic and spontaneous in nature. The thermodynamics data are in good agreement with physical adsorption mechanism.

Biocompatible phosphatidylcholine bilayer coated on magnetic nanoparticles and their application in the extraction of several polycyclic aromatic hydrocarbons from environmental water and milk samples.

In this work, phosphatidylcholine (PC) was coated on magnetic nanoparticles to form lipid bilayer as solid-phase extraction (SPE) sorbents for the enrichment of polycyclic aromatic hydrocarbons (PAHs) from environmental water and milk samples. The lipid bilayer was coated on Fe(3)O(4) nanoparticles using a modified dry lipid film hydration method. The resulted Fe(3)O(4)/PC could be readily isolated from solution with a magnet, and exhibited excellent adsorption performance to organic pollutants. Only 0.1g of sorbents was enough to extract PAHs from 500 mL aqueous solution, and 6 mL of acetonitrile was required to desorb them. The method was fast and relied on 10 min extraction time and 5 min magnetic separation. The proposed method was successfully applied to determine PAHs in some environmental water and milk samples. The detection limit was in the range of 0.2-0.6 ng L(-1). The recoveries of the spiked water samples ranged from 89% to 115% with relative standard deviations (RSD) varying from 1% to 8%. For spiked milk samples, RSD was satisfactory (1-9%), but the recoveries were relatively low (42-62%). We show the potentials of Fe(3)O(4)/PC sorbents in environmental water and biological sample analyses.

4'-Formyl-biphenyl-4-yl acetate.

In the title compound, C(15)H(12)O(3), the dihedral angle between the six-membered rings is 30.39 (1)°. The crystal packing is stabilized by inter-molecular C-H⋯O hydrogen bonds.

6-Formyl-2-naphthyl cis-1,5,7-trimethyl-2,4-dioxo-3-aza-bicyclo-[3.3.1]nonane-7-carboxyl-ate.

In the title compound, C(23)H(23)NO(5), the C(5)N ring adopts an envelope conformation with a C atom as the flap, whilst the saturated C(6) ring fused to it adopts a chair conformation. In the crystal, inversion dimers linked by pairs of N-H⋯O hydrogen bonds generate R(2) (2)(8) loops.

[Determination of trace elements in edible cactus by atomic absorption spectrometry].

The contents of 10 trace elements in edible cactus were determined by air-acetylene flame atomic absorption spectrometry. The sample was dissolved by ashing method. The experiment conditions were optimized by preparing mixed standard solution of these elements and adding LaCl3 and CsCl for interfering complements. The results show that the contents of following elements in the cactus are: 13-47 mg x g(-1) for Mg, K and Ca; 108-243 microg x g(-1) for Zn, Mn, Fe and Na; 34.8 microg x g(-1) for Cu, and 9.8-11.7 micro x g(-1) for Ni, Sr; and the contents of Mg, K, Ca, Zn, Mn, Fe, Na and Cu are higher than those in carrot.

Characteristics of aerobic granules grown on glucose a sequential batch shaking reactor.

Aerobic heterotrophic granular sludge was cultivated in a sequencing batch shaking reactor (SBSR) in which a synthetic wastewater containing glucose as carbon source was fed. The characteristics of the aerobic granules were investigated. Compared with the conventional activated sludge flocs, the aerobic granules exhibit excellent physical characteristics in terms of settleability, size, shape, biomass density, and physical strength. Scanning electron micrographs revealed that in mature granules little filamentous bacteria could be found, rod-shaped and coccoid bacteria were the dominant microorganisms.