The effect and mechanism of variable particle size microplastics and levofloxacin on the neurotoxicity of Rana nigromaculata based on the microorganism-intestine-brain axis.

Microplastics (MPs) usually appear in the aquatic environment as complex pollutants in combination with other environmental pollutants, such as levofloxacin (LVFX). After a 45-day exposure to LVFX and MPs with different particle sizes at environmental levels, LVFX was neurotoxic to Rana nigromaculata tadpoles. The order of the effects of the exposure treatment on tadpole behavior was: LVFX-MP3>LVFX-MP1>LVFX-MP2 ≥ LVFX. Results of transcriptome analysis of tadpole brain tissue showed that LVFX in combination with 0.10 and 10.00 µm MP interferes with the nervous system through the cell adhesion molecules pathway. Interestingly, the order of effects of the co-exposure on oxidative stress in the intestine was inconsistent with that of tadpole behavior. We found that Paraacteroides might be a microplastic indicator species for the gut microbiota of aquatic organisms. The results of the targeted metabolism of neurotransmitters in the intestine suggest that in the LVFX-MP2 treatment, LVFX alleviated the intestinal microbiota disorder caused by 1.00 µm MP, by regulating intestinal microbiota participating in the TCA cycle VI and gluconeogenesis and tetrapyrrole biosynthesis I, while downregulating Met and Orn, and upregulating 5HIAA, thereby easing the neurotoxicity to tadpoles exposed to LVFX-MP2. This work is of great significance for the comprehensive assessment of the aquatic ecological risks of microplastics-antibiotic compound pollutants.

Ultralow Loading of Silver Nanoparticles on Mn2O3 Nanowires Derived with Molten Salts: A High-Efficiency Catalyst for the Oxidative Removal of Toluene.

Using a mixture of NaNO3 and NaF as molten salt and MnSO4 and AgNO3 as metal precursors, 0.13 wt % Ag/Mn2O3 nanowires (0.13Ag/Mn2O3-ms) were fabricated after calcination at 420 °C for 2 h. Compared to the counterparts derived via the impregnation and poly(vinyl alcohol)-protected reduction routes as well as the bulk Mn2O3-supported silver catalyst, 0.13Ag/Mn2O3-ms exhibited a much higher catalytic activity for toluene oxidation. At a toluene/oxygen molar ratio of 1/400 and a space velocity of 40,000 mL/(g h), toluene could be completely oxidized into CO2 and H2O at 220 °C over the 0.13Ag/Mn2O3-ms catalyst. Furthermore, the toluene consumption rate per gram of noble metal over 0.13Ag/Mn2O3-ms was dozens of times as high as that over the supported Au or AuPd alloy catalysts reported in our previous works. It is concluded that the excellent catalytic activity of 0.13Ag/Mn2O3-ms was associated with its high dispersion of silver nanoparticles on the surface of Mn2O3 nanowires and good low-temperature reducibility. Due to high efficiency, good stability, low cost, and convenient preparation, 0.13Ag/Mn2O3-ms is a promising catalyst for the practical removal of volatile organic compounds.

Interfacial interactions between spider silk protein and cellulose studied by molecular dynamics simulation.

CONTEXT: Due to their excellent biocompatibility and degradability, cellulose/spider silk protein composites hold a significant value in biomedical applications such as tissue engineering, drug delivery, and medical dressings. The interfacial interactions between cellulose and spider silk protein affect the properties of the composite. Therefore, it is important to understand the interfacial interactions between spider silk protein and cellulose to guide the design and optimization of composites. The study of the adsorption of protein on specific surfaces of cellulose crystal can be very complex using experimental methods. Molecular dynamics simulations allow the exploration of various physical and chemical changes at the atomic level of the material and enable an atomic description of the interactions between cellulose crystal planes and spider silk protein. In this study, molecular dynamics simulations were employed to investigate the interfacial interactions between spider silk protein (NTD) and cellulose surfaces. Findings of RMSD, RMSF, and secondary structure showed that the structure of NTD proteins remained unchanged during the adsorption process. Cellulose contact numbers and hydrogen bonding trends on different crystalline surfaces suggest that van der Waals forces and hydrogen bonding interactions drive the binding of proteins to cellulose. These findings reveal the interaction between cellulose and protein at the molecular level and provide theoretical guidance for the design and synthesis of cellulose/spider silk protein composites. METHODS: MD simulations were all performed using the GROMACS-5.1 software package and run with CHARMM36 carbohydrate force field. Molecular dynamics simulations were performed for 500 ns for the simulated system.

Controlled generation of uniform spherical LaMnO3, LaCoO3, Mn2O3, and Co3O4 nanoparticles and their high catalytic performance for carbon monoxide and toluene oxidation.

Uniform hollow spherical rhombohedral LaMO3 and solid spherical cubic MOx (M = Mn and Co) NPs were fabricated using the PMMA-templating strategy. Hollow spherical LaMO3 and solid spherical MOx NPs possessed surface areas of 21-33 and 21-24 m(2)/g, respectively. There were larger amounts of surface-adsorbed oxygen species and better low-temperature reducibility on/of the hollow spherical LaMO3 samples than on/of the solid spherical MOx samples. Hollow spherical LaMO3 and solid spherical MOx samples outperformed their nanosized counterparts for oxidation of CO and toluene, with the best catalytic activity being achieved over the solid spherical Co3O4 sample for CO oxidation (T50% = 81 °C and T90% = 109 °C) at space velocity = 10,000 mL/(g h) and the hollow spherical LaCoO3 sample for toluene oxidation (T50% = 220 °C and T90% = 237 °C) at space velocity = 20,000 mL/(g h). It is concluded that the higher surface areas and oxygen adspecies concentrations and better low-temperature reducibility are responsible for the excellent catalytic performance of the hollow spherical LaCoO3 and solid spherical Co3O4 NPs. We believe that the PMMA-templating strategy provides an effective route to prepare uniform perovskite-type oxide and transition-metal oxide NPs.

P123-PMMA dual-templating generation and unique physicochemical properties of three-dimensionally ordered macroporous iron oxides with nanovoids in the crystalline walls.

Three-dimensionally (3D) ordered macroporous (3DOM) iron oxides with nanovoids in the rhombohedrally crystallized macroporous walls were fabricated by adopting the dual-templating [Pluronic P123 and poly(methyl methacrylate) (PMMA) colloidal microspheres] strategy with ferric nitrate as the metal precursor in an ethanol or ethylene glycol and methanol mixed solution and after calcination at 550 °C. The possible formation mechanisms of such architectured materials were discussed. The physicochemical properties of the materials were characterized by means of techniques such as XRD, TGA/DSC, FT-IR, BET, HRSEM, HRTEM/SAED, UV-vis, XPS, and H(2)-TPR. The catalytic properties of the materials were also examined using toluene oxidation as a probe reaction. It is shown that 3DOM-structured α-Fe(2)O(3) without nanovoids in the macroporous walls was formed in the absence of P123 during the fabrication process, whereas the dual-templating strategy gave rise to α-Fe(2)O(3) materials that possessed high-quality 3DOM structures with the presence of nanovoids in the polycrystalline macropore walls and higher surface areas (32-46 m(2)/g). The surfactant P123 played a key role in the generation of nanovoids within the walls of the 3DOM-architectured iron oxides. There was the presence of multivalent iron ions and adsorbed oxygen species on the surface of each sample, with the trivalent iron ion and oxygen adspecies concentrations being different from sample to sample. The dual-templating fabricated iron oxide samples exhibited much better low-temperature reducibility than the bulk counterpart. The copresence of a 3DOM-structured skeleton and nanovoids in the macropore walls gave rise to a drop in the band-gap energy of iron oxide. The higher oxygen adspecies amounts, larger surface areas, better low-temperature reducibility, and unique nanovoid-containing 3DOM structures of the iron oxide materials accounted for their excellent catalytic performance in the oxidation of toluene.

Polymer-Water Interaction Enabled Intelligent Moisture Regulation in Hydrogels.

The water-vapor transition is critical for hydrogels in a collection of applications. However, how the polymer-water interaction along with the nature of the structure affect the macroscopic water-vapor transition remains a challenging question to answer. In this work, we tested the moisture transfer behaviors of a series of hydrogels at different humidities and found some hydrogels capable of lowering their surface vapor pressure to stop dehydration at low humidity and absorbing water from ambient air to recover toward initial states at high humidity. Through molecular dynamic simulations, we demonstrate that water inside these hydrogels undergoes increasing intensive intermolecular bonding during evaporation. The increased intermolecular bonding reduces the vapor pressure of the hydrogels and leads to the self-regulation. More interestingly, we demonstrate the self-regulation is closely related to the Young's modulus of hydrogels. These results provide further insight into the mechanism of the water-vapor transition in hydrogels and show potential in a broad range of future applications.

Efficient harvesting of Chlorella pyrenoidosa and Scenedesmus obliquus cultivated in urban sewage by magnetic flocculation using nano-Fe3O4 coated with polyethyleneimine.

In this work, a novel flocculation process by using nano-Fe3O4 coated with polyethyleneimine (Fe3O4@PEI) as magnetic seeds was developed to harvest the microalgae cultivated in urban sewage. Experiment results indicated that the harvest efficiency of Chlorella pyrenoidosa (0.5 g/L) was 98.92 ±â€¯0.41% under the optimal conditions of Fe3O4@PEI dose of 20 mL/L, flocculation time of 20 min, and stirring speed of 800 rpm (3 min), while that of Scenedesmus obliquus (0.4 g/L) was 98.45 ±â€¯0.35% under a Fe3O4@PEI dose of 16 mL/L, flocculation time of 15 min, and stirring speed of 730 rpm (3 min). Moreover, the process did not reduce the lipid content of microalgae and quality of biodiesel. After microalgae harvest, Fe3O4@PEI could be recovered by ultrasonication, re-wrapped with polyethyleneimine and reused to reduce operational cost.

Cypate-mediated thermosensitive nanoliposome for tumor imaging and photothermal triggered drug release.

It is an emerging focus to explore controlled release drug delivery systems for simultaneous cancer imaging and therapy. Herein, we synthesized a photothermal sensitive multifunctional nano-liposome drug delivery system, with doxorubicin wrapped in the hydropholic layer as the therapeutical agent and cypate doped in the hydrophobic layer as the diagnostic agent. A series of in vitro and in vivo characterization demonstrated the stability of synthesized liposome, as the DL% was 9 ± 1.5 and the EE% was 82.7 ± 2.1. And the liposome achieved the functions of target-delivery, enhanced photochemical internalized drug release, and simultaneous chemotherapy and thermal therapy, indicating that this multifunctional nano-liposome is a promising drug delivery system for tumor diagnosis and targeting therapy.

Nano PdAu Bimetallic Alloy as an Effective Catalyst for the Buchwald-Hartwig Reaction.

It is highly challenging but desirable to develop efficient heterogeneous catalysts for C-Cl bond activation in coupling reactions. Here, we succeeded in synthesizing bimetallic Pd-Au nanoparticles through a convenient one-pot wet chemical route. The composition and alloyed structure of the as-prepared nanoparticles were fully characterized. We have evaluated the catalytic activity of these Pd-Au alloy catalysts in Buchwald-Hartwig reactions of aryl chlorides. The excellent catalytic activity of the as-obtained Pd-Au nanoparticles indicates that exploiting the catalytic power of nano-alloy catalysts could enable effective C-Cl bond activation suitable for cross-coupling reactions.

Drug co-loading and pH-sensitive release core-shell nanoparticles via layer-by-layer assembly.

Multifunctional core-shell nanoparticles are widely used for biomedical and catalytic applications. In this work, bilayers of chitosan (Cs) and phosphorylated polyvinyl alcohol (PPVA) were sequentially deposited on 3-Aminopropyltri-ethoxysilane-modified SiO2 nanoparticles via layer-by-layer electrostatic self-assembly. The good spherical shape and size distribution were observed by DLS and transmission electron microscope analysis. 7-Hydroxycoumarin (7-HC) and rhodamine B (RhB) as model drugs were loaded in the core and shell of the nanoparticles separately. Confocal laser scanning microscopy shows the core-shell structure of HC-SiO2(PPVA/Cs)n-RhB nanoparticles and the embedded location of 7-HC and RhB. The pH-sensitive release investigation of RhB indicates that the release profiles of RhB from HC-SiO2(PPVA/Cs)3PPVA-RhB core-shell nanoparticles are totally different at pH values of 2.0, 7.4, and 9.2. These results predict that the multifunctional nanoparticle SiO2(PPVA/Cs)n has a great potential for drug delivery.

Formation and characterization of natural polysaccharide hollow nanocapsules via template layer-by-layer self-assembly.

With natural polysaccharides carrageenan (Car) and chitosan (Cs) as the polyanion and polycation, respectively, multilayer hollow nanocapsules have been fabricated via sequential layer-by-layer (LbL) electrostatic self-assembly from the sacrificed templates nanospheres (SiO(2)-NH(2)). The LbL assembly process with the polysaccharides on SiO(2)-NH(2) core was followed by ζ-potential and size analysis. The fabrication of (Car/Cs)(x) nanocapsules and the removing of the SiO(2)-NH(2) core templates were confirmed by TGA and EDS analysis. The morphology of SiO(2)(Car/Cs)(x) nanospheres and (Car/Cs)(x) nanocapsules were observed by TEM analysis. The size analysis of (Car/Cs)(x) nanocapsules indicated that the cyst wall thickness and cavity volume of the nanocapsules are pH and ionic strength dual responsive. Due to the biocompatibility of the natural polysaccharides carrageenan and chitosan and the responsiveness of nanocapsules to pH and ionic strength, the (Car/Cs)(x) multilayer nanocapsules are expected to be used as nanoreactors or nanocontainers to control the synthesis, encapsulation, and releasing behaviors of bioactive molecules.

Three-dimensional ordered macroporous bismuth vanadates: PMMA-templating fabrication and excellent visible light-driven photocatalytic performance for phenol degradation.

Three-dimension ordered macroporous (3D-OM) bismuth vanadates with a monoclinic crystal structure and high surface area (18-24 m(2) g(-1)) have been prepared using ascorbic acid (AA)- or citric acid (CA)-assisted poly(methyl methacrylate) (PMMA)-templating strategy with bismuth nitrate and ammonium metavanadate as the metal sources, HNO(3) as the pH adjuster and ethylene glycol and methanol as the solvent. The materials were characterized by a number of analytical techniques. The photocatalytic performance of the porous BiVO(4) samples was evaluated for the degradation of phenol in the presence of a small amount of H(2)O(2) under visible light illumination. The effects of the initial phenol concentration and the H(2)O(2) amount on the photocatalytic activity of the photocatalyst were examined. It is shown that the chelating agent, AA or CA, and the amount in which it is added had a significant impact on the quality of the 3D-OM structure, with a "(Bi + V):chelating agent" molar ratio of 2:1 being the most appropriate. Among the as-prepared BiVO(4) samples, the one with a surface area of ca. 24 m(2) g(-1) showed the best visible light-driven photocatalytic performance for phenol degradation (phenol conversion = ca. 94% at phenol concentration = 0.1 mmol L(-1) and in the presence of 0.6 mL H(2)O(2)). A higher phenol conversion could be achieved within the same reaction time if the phenol concentration in the aqueous solution was lowered, but an excess amount of H(2)O(2) was not a favorable factor for the enhancement of the catalytic activity. It is concluded that the excellent photocatalytic activity of 3D-OM BiVO(4) is due to the high quality 3D-OM structured BiVO(4) that has a high surface area and surface oxygen vacancy density. We are sure that the 3D-OM material is a promising photocatalyst for the removal of organics from wastewater under visible light illumination.