Pyrite-assisted degradation of methoxychlor by laccase immobilized on Fe3S4/earthworm-like mesoporous SiO2.

Laccase immobilized and cross-linked on Fe3S4/earthworm-like mesoporous SiO2 (Fe3S4/EW-mSiO2) was used to degrade methoxychlor (MXC) in aqueous environments. The effects of various parameters on the degradation of MXC were determined using free and immobilized laccase. Immobilization improved the thermal stability and reuse of laccase significantly. Under the conditions of pH 4.5, temperature 40 °C, and reaction time 8 h, the degradation rate of MXC by immobilized laccase reached a maximum value of 40.99% and remained at 1/3 of the original after six cycles. The excellent degradation performance of Fe3S4/EW-mSiO2 was attributable to the pyrite (FeS2) impurity in Fe3S4, which could act as an electron donor in reductive dehalogenation. Sulfide groups and Fe2+ reduced the activation energy of the system resulting in pyrite-assisted degradation of MXC. The degradation mechanism of MXC in aqueous environments by laccase immobilized on Fe3S4/EW-mSiO2 was determined via mass spectroscopy of the degradation products. This study is a new attempt to use pyrite to support immobilized laccase degradation.

Degradation of trichloroacetic acid by Fe/Ni bimetallic reactive PMS with hierarchical layered structure.

Overuse of chlorinated disinfectants leads to a significant accumulation of disinfection by-products. Trichloroacetic acid (TCA) is a typical carcinogenic disinfection by-product. The efficacy of the conventional degradation process is reduced by the complex nature of its structure, causing a yearly increase in its prevalence within the ecological environment and consequent infliction of significant harm. In this paper, TCA was chosen as the research subject, Fe/Ni bimetallic nanoparticles were employed as the reducing catalyst, ZIF-8@HMON as the catalytic carrier combined with Fe/Ni nanoparticles, and peroxymonosulfate (PMS) was introduced to construct the reducing-advanced oxidation synergistic system and investigated the effect of this system on the degradation performance and degradation pathway of TCA. Various characterization techniques, including TEM, SEM, XRD, FT-IR, XPS, BET, were employed to investigate the morphology, element composition and structure of composite materials analysis. Moreover, the conditions for TCA degradation can be optimized by changing the experimental environment. The results showed that 25 mg of composite catalyst (mole ratio Fe: Ni = 1:1) and 10 mg of PMS effectively degraded TCA within 20-80 mg/L range at pH = 3 and 55 °C, achieving maximum degradation within 20 min. Finally, the potential pathways of TCA degradation were analyzed using EPR and LC-MS, and the corresponding reaction mechanisms were proposed.

Hydrolytic degradation of methoxychlor by immobilized cellulase on LDHs@Fe3O4 nanocomposites.

In this study, we synthesized Fe3O4 using the co-precipitation method and then prepared magnetic carrier LDHs@Fe3O4 by immobilizing layered double hydroxide on Fe3O4 by in situ growth method. Cellulase was immobilized on this magnetic carrier by using glutaraldehyde as a coupling agent, which can be used for degrading Methoxychlor (MXC). The results demonstrated the maximum MXC removal efficiency of 73.4% at 45 °C and pH = 6.0 with excellent reusability. Through kinetic analysis, it was found that the degradation reaction conforms to the Langmuir-Hinshelwood model and is a first-order reaction. Finally, according to the EPR analysis, the active radicals in the system were found to be OH· and the degradation mechanism was proposed in combination with LC-MS. This study provides a feasible method for degrading organochlorine pesticides, which can be used for groundwater purification.

Preparation of Fe3O4@Fe(0) immobilized enzyme to enhance the efficient degradation of methoxychlor.

The presence of methoxychlor (MXC) in soil and wastewater is considered a nonnegligible environmental threat. Herein, Fe3O4@Fe(0) was obtained by NaBH4 reduction of Fe3O4 nanoparticles and served as a carrier for laccase to construct catalyst. The catalyst was evaluated for the degradation of MXC in treated wastewater and soil with 2, 2'-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) being used as cocatalyst. The removal rate of MXC in wastewater and soil was found to be 89% and 88% in optimum conditions, and the influences of initial MXC concentration, pH, and temperature on the degradation rate were evaluated. The metabolites including 2-methylpentane, 3-methylpentane, and n-pentane of MXC were identified, and possible degradation mechanisms were proposed. Overall, this work successfully demonstrates not only the ability to degrade MXC in different circumstances but also provides a new idea for environmental remediation in the future.

Graphene Oxide Covalently Grafted Fe2B@SiO2 Nanoparticles for Epirubicin Loading and Releasing.

In this work, stable superparamagnetic core-shell Fe2B@SiO2 nanoparticles were prepared by "one pot" chemical reduction of ferric ion salts with NaBH4 and silica shell coating in the presence of citric acid stabilizer. The X-ray (XRD) and selection of electron diffraction (SAED) revealed that Fe2B@SiO2 nanoparticles were chiefly composed of silica shell and Fe2B with a small amount of α-Fe. Then, graphene oxide (GO) was assembled onto core-shell Fe2B@SiO2 nanoparticles for Epirubicin (EPI) loading and releasing, and the adsorption isotherm of EPI on Fe2B@SiO2@GO was analyzed. The results showed, the adsorption process includes two steps, due to the π-π stacking effect of EPI on the Fe2B@SiO2@GO. The EPI loading efficiency of the magnetic nanoparticles was as high as 90%, while the EPI-loaded core-shell Fe2B@SiO2 nanoparticles showed an obvious pH controlled drug release behavior, and showed lower cumulative release rate when pH is 7.4 than that when pH is 5.7. The prepared nanoparticles demonstrated potential application in killing tumor cells while minimizing the toxicity to normal tissues.

Characterization of enzyme-immobilized catalytic support and its exploitation for the degradation of methoxychlor in simulated polluted soils.

Chiral mesoporous silica (SiO2) with helical structure was synthesized by using anionic surfactants as template. Pre-prepared graphene oxide (GO) was then loaded onto SiO2 to synthesize composite carrier chial-meso-SiO2@GO for the immobilization of laccase. The enzyme activity, thermostability, acid stability, and repeatability of the immobilized enzyme were significantly improved after immobilization. The chial-meso-SiO2@GO-immobilized laccase was then used for the degradation of MXC in aqueous phase. The degradation conditions, including temperature, time, pH, MXC concentration, and the dose of immobilized enzyme for cellulosic hydrolysis, were optimized. The optimum conditions for degradation of methoxychlor were selected as pH 4.5, MXC concentration 30 mg/L, immobilized enzyme dose 0.1 g, the maximum MXC removal of over 85% and the maximum degradation rate of 50.75% were achieved after degradation time of six h at temperature of 45 °C. In addition, the immobilized cellulase was added into the immobilized laccase system to form chial-meso-SiO2@GO-immobilized compound enzyme with the maximum MXC degradation rate of 59.58%, higher than that of 50.75% by immobilized laccase. An assessment was made for the effect of chial-meso-SiO2@GO-immobilized compound enzyme on the degradation of MXC in soil phase. For three contaminated soils with MXC concentration of 25 mg/kg, 50 mg/kg, and 100 mg/kg, the MXC removals were 93.0%, 85.8%, and 65.1%, respectively. According to the GC-MS analyses, it was inferred that chial-meso-SiO2@GO-immobilized compound enzyme had a different degradation route with that of chial-meso-SiO2@GO-immobilized laccase. The hydrolysis by immobilized cellulase might attack at a weak location of the MXC molecule with its free radical OH and ultimately removed three chlorine atoms from MXC molecule, leading to generating small molecular amount of degradation product.

Construction of Carbon Dots Coated Magnetic Hollow Silica Spheres.

Magnetic hollow silica spheres (MHSS) with uniform cavity size and shell thickness were prepared using functionalized SiO2 spheres as templates, on which the magnetic particles were uniformly deposited on their surface. The obtained MHSS exhibited a super-paramagnetic behavior at room temperature. Due to large hollow cavity space and super-paramagnetic characteristics, the MHSS were coated with carbon dots with assistance of (3-Aminopropyl) trimethoxysilane (APS). Thus, the preparedMHSS were mixed with citric acid and APS, followed by hydrothermal reaction at 180 °C, to generate carbon quantum dots coated MHSS (MHSS@CDs). Scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray powder scattering (XRD), X-ray energy dispersive spectral analysis (EDS), Raman spectra and laser scattering particle analyzer were applied to characterize the MHSS and MHSS@CDs.

Effect of Crystallization on the Catalytic Cracking Performance of Zeolite Socony Mobil-5.

In the research, zeolite socony mobil-5 (ZSM-5) catalyst was prepared by hydrothermal method and characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), NH3-temperature programmed desorption (NH3-TPD) and Brunauer- Emmett-Teller (BET). The catalytic products from Jatropha carcass L. oil were analyzed by gas chromatography-mass spectrometer (GC-MS). The effects of crystallization time and crystallization temperature on catalytic cracking performance of ZSM-5 were investigated. According to the results, the catalytic cracking performance of ZSM-5 was closely associated with its pore structure. When the crystallization time was 60 h and the crystallization temperature was 170 °C, ZSM-5 with optimal catalytic cracking performance was synthesized. Catalyzed by the optimal ZSM-5, Jatropha carcass L. oil showed the liquid conversion rate of 26.60% and the acid value of 1.24 mg KOH·g-1. The main catalytic products from Jatropha carcass L. oil included benzene (10.02%), methylbenzene (20.52%), o-xylene (14.45%) and p-xylene (6.59%).

Odd-Even Effect in Synthesis of Mesoporous Silica Using Long-Chain Acyl-L-Alanine Sodium Salt Templating.

In this research, hexagonal and cubic mesoporous silica with ordered parallel pore channels was synthesized using odd chain-length N-undecanoyl-L-alanine sodium salt and even chain-length N-lauroyl-L-alanine sodium salt as template respectively. Aminopropylsiloxane was used as the co-structure-directing agents (CSDA). The ordered mesostructure was characterized by infrared spectroscopy, small X-ray diffraction patterns (XRD), scanning electron microscope (SEM), trasmission electron microscope (TEM), and nitrogen sorption analysis. The results indicated that mesoporous silica which was prepared by asymmetric odd chain-length surfactants presented a looser strucuture with large volume than mesoporous silica prepared by the even chain-length surfactant. It led to the transformation from 2D hexagonal (p6mm) phase to cubic (Ia¯3d) mesophase.

Removal of Pb2+, Hg2+, and Cu2+ by Chain-Like Fe3O4@SiO2@Chitosan Magnetic Nanoparticles.

In this paper, the chain-like core-shell structure Fe3O4@SiO2@Chitosan composite nanoparticles were synthesized by a two-step coating and following crosslinking glutaraldehyde on chitosan shell. The composite particles showed nearly monodisperse 105 sized particles with a core diameter of 80 nm and chitosan shell thickness of 12 nm. The synthesis conditions of the product were studied, and the morphology and properties of the composite nanoparticles were characterized by IR, XRD, TEM, SEM, EDS and VSM. The adsorption properties of Hg2+, Pb2+ or Cu2+ ions on Fe3O4, Fe3O4@SiO2 and the composite particles were in detail studied using the colorimetric method based on forming colored mercuric dithizone, rhodamine-Pb2+ complex and DDTC-Cu(2+) complex. The results showed, adsorption isotherm, kinetics and separation coefficient of heavy metal ions on these three magnetic nanoparticles were concerned with pH, metal ions' electronic configuration, silica coating and chitosan shell respectively. In addition, the recycle efficiency was also studied. The findings demonstrated that Fe3O4@SiO2@Chitosan composite nanoparticles have great application value in the adsorption and separation of heavy metal ions.

Cagelike mesoporous silica encapsulated with microcapsules for immobilized laccase and 2, 4-DCP degradation.

In this study, cage-like mesoporous silica was used as the carrier to immobilize laccase by a physical approach, followed by encapsulating with chitosan/alginate microcapsule membranes to form microcapsules of immobilized laccase based on layer-by-layer technology. The relationship between laccase activity recovery/leakage rate and the coating thickness was simultaneously investigated. Because the microcapsule layers have a substantial network of pores, they act as semipermeable membranes, while the laccase immobilized inside the microcapsules acts as a processing plant for degradation of 2,4-dichlorophenol. The microcapsules of immobilized laccase were able to degrade 2,4-dichlorophenol within a wide range of 2,4-dichlorophenol concentration, temperature and pH, with mean degradation rate around 62%. Under the optimal conditions, the thermal stability and reusability of immobilized laccase were shown to be improved significantly, as the removal rate and degradation rate remained over 40.2% and 33.8% respectively after 6cycles of operation. Using mass spectrometry (MS) and nuclear magnetic resonance (NMR), diisobutyl phthalate and dibutyl phthalate were identified as the products of 2,4-dichlorophenol degradation by the microcapsules of immobilized laccase and laccase immobilized by a physical approach, respectively, further demonstrating the degradation mechanism of 2,4-dichlorophenol by microcapsule-immobilized laccase.

Clinical efficacy of 5-aminolevulinic acid photodynamic therapy in the treatment of moderate to severe facial acne vulgaris.

Acne vulgaris is considered as a therapeutic challenge in terms of managing ongoing symptoms and preventing scar formation. Although there are many available treatments for alleviating acne, therapies for resistant or moderate-to-severe forms have been limited to systemic agents that are accompanied by potentially severe side-effects. While, aminolevulinic acid (ALA) photodynamic therapy (PDT) has increasingly been used as a simple and safe therapeutic option of acne vulgaris, the clinical efficacy requires confirmation in further studies. The aim of this study was to investigate the efficacy and safety of 5-ALA-PDT in the treatment of moderate-to-severe facial acne vulgaris. A total of 50 patients with moderate-to-severe facial acne were enrolled in the study and randomly divided equally into a therapy group and a control group. In the therapy group, the patients were treated with 5% 5-ALA for 1.5 h, followed by three 20-min doses of infrared radiation once a week; in the control group, the patients were treated with three 20 min doses of infrared radiation without 5-ALA once a week. Both treatments lasted for 3 weeks. The clinical efficacy was determined by evaluating acne lesion counts at weeks 0, 2, 4 and 6. Total efficacy rate (TER) was the primary endpoint of the study, and was defined as the proportion of the patients whose treatment effectiveness evaluation was cured (≥90% of skin lesions improved) and excellent (60-89% improvement). Adverse effects were recorded throughout the study. The study was completed by 24 patients in the therapy group and 23 patients in the control group. The numbers of acne lesions significantly decreased. The TER of the therapy group was significantly higher than that of the control group at weeks 4 and 6. Adverse effects were observed in 12 patients of the therapy group and 2 patients of the control group. In the therapy group the most common adverse effect was a burning sensation (n=7), followed by transient hyperpigmentation (n=3) and acute acneform lesions (n=2), while in control group, the 2 patients experienced flushing and dryness. The adverse effects were all cured by a symptomatic approach prior to the end of the study. 5-ALA-PDT combined with infrared radiation is an effective and safe therapy for moderate-to-severe facial acne.

Preparation, Characterization of High-Luminescent and Magnetic Eu3+, Dy3+ Doped Superparamagnetic Nano-Fe3O4.

Pure superparamagnetic nano-Fe3O4 (SPMNPs) and Ln3+ (Eu3+, Dy3+) doped SPMNPs are successfully synthesized by reverse micelle method. The structure, morphology, magnetic properties and PL properties of the samples were characterized by XRD, FT-IR, TEM, PPMS, EDS and luminescence spectrometer respectively. The influences of Ln3+ doping amount on magnetic properties and PL properties were investigated in detail. The results show, with increasing of the Lna+ doping amount increasing, the morphologies and particle sizes of the doped Fe304 nanoparticles change, leading to saturation magnetization and coercivity changing accordingly. The change of lattice parameter and particle size was discussed based on Rietveld analysis of XRD pattern of the doped Fe3O4 nanoparticles. The coincidence of the ZFC and FC magnetization curves within the temperature range from 120.6 to 300 K, indicating that Fe3O4 nanoparticles are single domain super-paramagnetic.

Effects of different chain lengths and chiral branched amino acids on the synthesis of mesoporous silica.

Ordered mesoporous silica was successfully synthesized by using different chain-length chiral anionic surfactants, N-acylalanine and N-acylvaline as templates, and N-trimethoxy silylpropyl-N, N, N-trimethyl ammonium (TMAPS) as a co-structure-directing agent (CSDA) under weakly acidic conditions. The synthesized products were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and nitrogen sorption analysis. In the TMAPS/N-acylalanine system, the mesophase changed from a 3D disordered stucture into a 3D hexagonally structure for the first, and finally into a 3D cubic structure with increased hydrophobic chain lengths of the anionic surfactants. But in the TMAPS/N-acylvaline system, the mesophase changed into a 2D hexagonally structure for the first, and finally into a 3D hexagonally structured mesoporous silica with the helical pore channels. The changes of the pore diameter, the surface area and the pore volume with the chain lengths were also discussed.

Biomolecule-assisted green route to Sb2S3 crystals with three-dimensional dandelionlike patterns.

This paper describes a simple biomolecule-assisted solvothermal approach to fabricate the three-dimensional (3D) Sb2S3 microsphere with a wealth of novel morphologies in the presence of L-cysteine, which served as both the sulfur source and the directing molecule in the formation of antimony sulfide nanostructures. The effects of different solvents, and polyvinylpyrrolidone (PVP) on the morphology, structure, and phase composition of the as-prepared Sb2S3 products were discussed. The formation of 3D dandelionlike Sb2S3 microsphere was probably via the mechanism of the orientated aggregation growth of the Sb2S3 particles under the complexing action of L-cysteine, and co-action of the surfactant PVP. The absorption spectra of as-prepared 3D dandelionlike Sb2S3 structures show an optical shoulder band gap of 1.81 eV, which is near to the optimum for photovoltaic conversion.

Badh2, encoding betaine aldehyde dehydrogenase, inhibits the biosynthesis of 2-acetyl-1-pyrroline, a major component in rice fragrance.

In rice (Oryza sativa), the presence of a dominant Badh2 allele encoding betaine aldehyde dehydrogenase (BADH2) inhibits the synthesis of 2-acetyl-1-pyrroline (2AP), a potent flavor component in rice fragrance. By contrast, its two recessive alleles, badh2-E2 and badh2-E7, induce 2AP formation. Badh2 was found to be transcribed in all tissues tested except for roots, and the transcript was detected at higher abundance in young, healthy leaves than in other tissues. Multiple Badh2 transcript lengths were detected, and the complete, full-length Badh2 transcript was much less abundant than partial Badh2 transcripts. 2AP levels were significantly reduced in cauliflower mosaic virus 35S-driven transgenic lines expressing the complete, but not the partial, Badh2 coding sequences. In accordance, the intact, full-length BADH2 protein (503 residues) appeared exclusively in nonfragrant transgenic lines and rice varieties. These results indicate that the full-length BADH2 protein encoded by Badh2 renders rice nonfragrant by inhibiting 2AP biosynthesis. The BADH2 enzyme was predicted to contain three domains: NAD binding, substrate binding, and oligomerization domains. BADH2 was distributed throughout the cytoplasm, where it is predicted to catalyze the oxidization of betaine aldehyde, 4-aminobutyraldehyde (AB-ald), and 3-aminopropionaldehyde. The presence of null badh2 alleles resulted in AB-ald accumulation and enhanced 2AP biosynthesis. In summary, these data support the hypothesis that BADH2 inhibits 2AP biosynthesis by exhausting AB-ald, a presumed 2AP precursor.