Responses of phenanthrene degradation to the changes in bioavailability and microbial community structure in soils amended with biochars pyrolyzed at low and high temperatures.

This study investigated the impact of wheat straw biochars pyrolyzed at temperatures of 100-700 â„ƒ (BC100-BC700) on biodegradation of phenanthrene in soils. During a 42-day experiment, biochar amendment reduced the biodegradation ratio of phenanthrene in soils by no change-77.0%. The biodegradation ratio decreased with the increase of pyrolysis temperature from 100 to 400 â„ƒ and then increased with the increase of pyrolysis temperature from 400 to 700 â„ƒ, exhibiting a U-shape. Meanwhile, desorbing fraction of phenanthrene extracted by n-butanol declined with increasing pyrolysis temperature. Biochar-derived dissolved organic carbon (DOC) obviously influenced the soil DOC contents which were negatively correlated with the total relative abundances of dominant polycyclic aromatic hydrocarbon (PAH)-degraders. These results indicated that in soils amended with biochars pyrolyzed at low temperatures (i.e. 100-400 â„ƒ), both the reduced bioavailability of phenanthrene and the reduced PAH-degrader abundance resulted in decreasing phenanthrene degradation with pyrolysis temperature. In soils amended with biochars pyrolyzed at high temperatures (i.e. 500-700 â„ƒ; HT-biochars), two possible reasons contribute to increasing phenanthrene degradation with pyrolysis temperature: (1) high sorbed-phenanthrene concentration due to large specific surface area and high aromaticity of the biochars, and (2) the increased dominant PAH-degrader abundance for the removal of sorbed-phenanthrene due to the impact of HT-biochars on soil properties (mainly on DOC content).

Removal of lead from two polluted soils by magnetic wheat straw biochars.

Due to high sorption capacity for heavy metals, magnetic biochar (MBC) has the potential to adsorb heavy metals in soils, which are then removed together with MBC from soils by a magnetic field. In this study, two magnetic biochars (MBC300 and MBC700) were derived from the magnetization of wheat straw biochars pyrolyzed at 300 and 700 °C. Strong binding of Pb with iron oxide particles deposited on biochar was observed. After the MBCs (7.5%, w/w) were applied to two naturally Pb-polluted soils (named as He-soil and Hu-soil) for 720 h, the removal efficiency of Pb from the soil by MBC300 (26.8-40.1%) was similar (p > 0.05) to that by MBC700 (25.1-42.1%). This is because MBC300 has lower sorption capacity for Pb but higher recovery percentage from soils as a result of lower saturation magnetization. The removal efficiencies of Pb by the two MBCs were 13-17% higher for He-soil than for Hu-soil, which was due to higher proportion of mobile forms of Pb in He-soil (82.3%) than in Hu-soil (51.5%). Spectroscopic analysis indicated that Pb in soils tended to bind onto the surface of MBC in more stable forms. Moreover, removing Pb from soils by MBC could decrease Pb concentration in ryegrass by about 30%. Therefore, it might be a potential method to remedy Pb-polluted soils.

Effects of microphytobenthos Cylindrotheca closterium on the fate of di-n-butyl phthalate in an aquatic microcosm.

Effects of Cylindrotheca closterium, a marine benthic diatom, on the fate of di-n-butyl phthalate (DBP) in a water-sediment system were investigated. Model calculation results showed that DBP residue was 38.5% lower in the system with C. closterium than in the system without C. closterium. The net flux from water to sediment increased by 7.3 times in the presence of C. closterium. As a result, the total biodegradation flux of DBP in the system with C. closterium was increased by 25.6%. According to the 16 s rDNA sequencing, the presence of C. closterium decreased the bacterial population as well as bacterial community diversity in sediments. Moreover, the population of C. closterium, capable of efficiently degrading DBP, was much higher than that of the dominant DBP-degrading bacteria, demonstrating that degradation of DBP by C. closterium should be the main reason for the degradation enhancement in sediments.

Calcium carbonate crystal growth beneath Langmuir monolayers of acidic ß-hairpin peptides.

Four amphiphilic peptides with designed hairpin structure were synthesized and their monolayers were employed as model systems to study biologically inspired calcium carbonate crystallization. Langmuir monolayers of hairpin peptides were investigated by surface pressure area isotherms, surface potential isotherms, Brewster angle microscopy (BAM), atomic force microscopy (AFM) and Fourier transform infrared (FTIR) spectroscopy. A ß-hairpin conformation was found for all peptides at the air-water interface although their packing arrangements seem to be different. Crystallization of calcium carbonate under these peptide monolayers was investigated at different surface pressures and growth times both by in situ optical microscopy, BAM and ex situ investigations such as scanning electron microscopy (SEM) and transmission electron microscopy (TEM). An amorphous calcium carbonate precursor was found at the initial crystallization stage. The crystallization process occurred in three stages. It starts from the nucleation of amorphous particles being a kinetically controlled process. Crystal nuclei subsequently aggregate to large particles and vaterite crystals start to form inside the amorphous layer, with the monolayer fluidity exerting an important role. The third process includes the re-crystallization of vaterite to calcite, which is thermodynamically controlled by monolayer structural factors including the monolayer flexibility and packing arrangement of the polar headgroups. Thus, the kinetic factors, monolayer fluidity and flexibility as well as structure factors govern the crystal morphology and polymorph distribution simultaneously and synergistically.

Self-assembly of amphiphilic hexapyridinium cations at the air/water interface and on HOPG surfaces.

Mono- and multilayers of a novel amphiphilic hexapyridinium cation with six eicosyl chains (3) are spread at the air/water interface as well as on highly ordered pyrolytic graphite (HOPG). On water, the monolayer of 3 is investigated by recording surface pressure/area and surface potential/area isotherms, and by Brewster angle microscopy (BAM). Self-organized tubular micelles with an internal edge-on orientation of molecules form at the air/water interface at low surface pressure whereas multilayers are present at high surface pressure, after a phase transition. Packing motifs suggesting a tubular arrangement of the constituting molecules were gleaned from atomic force microscopy (AFM) investigations of Langmuir-Blodgett (LB) monolayers being transferred on HOPG at different surface pressures. These LB film structures are compared to the self-assembled monolayer (SAM) of 3 formed via adsorption from a supersaturated solution, which is studied by scanning tunnelling microscopy (STM). On HOPG the SAM of 3 consists of nanorods with a highly ordered edge-on packing of the aromatic rings and an arrangement of alkyl chains which resembles the packing of molecules at the air/water interface at low surface pressure. Additional details of the molecular packing were gleaned from single-crystal X-ray structure analysis of the hexapyridinium model compound 2b, which possesses methyl instead of eicosyl residues.

Interaction and adhesion properties of polyelectrolyte multilayers.

The growth, morphology, and interaction/adhesion properties of supported poly(sodium 4-styrenesulfonate)/poly(allylamine hydrochloride) (PSS/PAH) and DNA/PAH multilayers were investigated by means of surface plasmon resonance spectroscopy, atomic force microscope (AFM) imaging, and AFM-related force measurements. Multilayers were assembled on a prelayer of poly(ethylenimine) (PEI) both with and without drying. SPR results showed a linear growth of the assembly in the case of PSS/PAH multilayers and nonlinear growth for DNA/PAH multilayers. Measurements of forces acting between a bare glass sphere and a multilayer-coated surface indicated repulsive or attractive forces, depending on surface charge, which suggests that, on approach, electrostatic forces dominate. On separation, we observed large pull-off forces in the case of positively charged multilayers and weak pull-off forces in the case negatively charged multilayers. Multiple adhesions and plateau regions observed on separation were interpreted in terms of a bridging of multiple polymer chains between the glass particle and the multilayer and a stretching of the polyelectrolyte loops. The dependence of the pull-off force on the number of deposited layers shows regular oscillations.

Multilayer DNA/poly(allylamine hydrochloride) microcapsules: assembly and mechanical properties.

We report the preparation, characterization, and mechanical properties of DNA/poly(allylamine hydrochloride) (PAH) multilayer microcapsules. The DNA/PAH multilayers were first constructed on a planar support to examine their layer-by-layer buildup. Surface plasmon resonance spectroscopy (SPR) showed a nonlinear growth of the assembly upon each bilayer deposited independently on a concentration of salt. A weak increase in the film thickness with the DNA concentration was, however, detected. A post-treatment of the multilayers in the salt solutions has shown a thinning of the film. The optimal conditions of the planar film growth were used to deposit the same multilayers on the surface of colloidal templates and to study their roughness and morphology with the atomic force microscope (AFM) imaging. When an outer layer is formed by DNA, we observe large domains of oriented parallel DNA loops, while an outer layer formed by PAH shows highly porous morphology. The dissolution of colloidal templates led to a formation of highly porous DNA/PAH microcapsules. We probe their mechanical properties by measuring force-deformation curves with the AFM-related setup. The experiment suggests that the DNA/PAH capsules are softer than capsules made from the flexible polyelectrolytes studied before. The softening is due to both higher permeability and smaller Young's modulus of the shell material. The Young's modulus of the DNA/PAH shells increases after post-treatment in salt solutions of relatively low concentration.

Photochemical reaction, acidichromism, and supramolecular nanoarchitectures in the Langmuir-Blodgett films of an amphiphilic styrylquinoxaline derivative.

An amphiphilic styrylquinoxaline derivative, 3-(4-(hexadecyloxy)styryl)quinoxalin-2(1H)-one (SQC16), was newly synthesized to investigate their photochemical and gas responsive properties in organized molecular films. It was observed that SQC16 can spread as a monolayer on the subphases with various pH values and be subsequently transferred onto solid substrates. While SQC16 showed predominantly reversible trans-cis photoisomerization in methanol solution, it showed both photoisomerization and photodimerization in Langmuir-Blodgett (LB) films. Photodimerization was only observed in the LB film due to the face-to-face arrangement of the functional headgroup in the LB film, and the process was irreversible. In addition, the LB film showed acidichromism, i.e., when the film was exposed to HCl gas its color changed from yellow to red, and the color could be recovered after exposure to NH(3) gas. The process was reversible and could be repeated many times. An interesting surface morphology of the SQC16 LB film was revealed. It was observed that SQC16 can form nanowire architecture in the transferred one-layer LB film. This morphology can be changed upon photoirradiation or in gas reactions. Through the atomic force microscopy measurements it was suggested that the photodimerization predominantly occurred from the nanowire structures, while during the acidichromism the reaction occurred preferentially in the flat region. X-ray diffraction studies revealed that while layer distance showed a slight change for the LB film during acidichromism and photoreaction, the layer structure of SQC16 LB film was retained.

Self-assembly and characterization of supramolecular [60]fullerene-containing 2,6-diacylamidopyridine with uracil derivative by hydrogen-bonding interaction.

[structure: see text] Novel self-assembly systems of uracil derivatives with organofullerene by a three-point hydrogen-bonding interaction were designed and established. The formation of hydrogen bonding was established by 1H NMR studies in CDCl3.