Release kinetics of esterified p-coumaric acid and ferulic acid from rice straw in mild alkaline solution.

The release kinetics of esterified p-coumaric acid (PCA) and ferulic acid (FA) from rice straw under a mild alkaline condition were investigated to collect fundamental data for the design of a recovery process. The results showed that the straw size, NaOH concentration, and temperature were the key parameters governing release kinetics. The analysis demonstrated that FA is released considerably faster than PCA. The close relationship between lignin and the PCA dissolution indicates a reciprocal and/or simultaneous release. Moreover, PCA is broadly distributed in the lignin network but tends to be located more densely in the lignin fraction which is not easily solubilized by alkaline treatment. In contrast, the release of FA is strongly affected by removal of lignin fraction which is easily solubilized. These results suggest that the release kinetics are controlled by the accessibility of NaOH to their ester sites in the lignin/hemicellulose network, and by their localization.

Dynamic transition of chemolithotrophic sulfur-oxidizing bacteria in response to amendment with nitrate in deposited marine sediments.

Although environmental stimuli are known to affect the structure and function of microbial communities, their impact on the metabolic network of microorganisms has not been well investigated. Here, geochemical analyses, high-throughput sequencing of 16S rRNA genes and transcripts, and isolation of potentially relevant bacteria were carried out to elucidate the anaerobic respiration processes stimulated by nitrate (20 mM) amendment of marine sediments. Marine sediments deposited by the Great East Japan Earthquake in 2011 were incubated anaerobically in the dark at 25∘C for 5 days. Nitrate in slurry water decreased gradually for 2 days, then more rapidly until its complete depletion at day 5; production of N2O followed the same pattern. From day 2 to 5, the sulfate concentration significantly increased and the sulfur content in solid-phase sediments significantly decreased. These results indicated that denitrification and sulfur oxidation occurred simultaneously. Illumina sequencing revealed the proliferation of known sulfur oxidizers, i.e., Sulfurimonas sp. and Chromatiales bacteria, which accounted for approximately 43.5% and 14.8% of the total population at day 5, respectively. These oxidizers also expressed 16S rRNA to a considerable extent, whereas the other microorganisms, e.g., iron(III) reducers and methanogens, became metabolically active at the end of the incubation. Extinction dilution culture in a basal-salts medium supplemented with sulfur compounds and nitrate successfully isolated the predominant sulfur oxidizers: Sulfurimonas sp. strain HDS01 and Thioalkalispira sp. strain HDS22. Their 16S rRNA genes showed 95.2-96.7% sequence similarity to the closest cultured relatives and they grew chemolithotrophically on nitrate and sulfur. Novel sulfur-oxidizing bacteria were thus directly involved in carbon fixation under nitrate-reducing conditions, activating anaerobic respiration processes and the reorganization of microbial communities in the deposited marine sediments.

Electrochemical properties of oxygenated cup-stacked carbon nanofiber-modified electrodes.

Oxygenated cup-stacked carbon nanofibers (CSCNFs), the surface of which provides highly ordered graphene edges and oxygen-containing functional groups, were investigated as electrode materials by using typical redox species in electrochemistry, Fe(2+/3+), [Fe(CN)6](3-/4-), and dopamine. The electron transfer rates for these redox species at oxygenated CSCNF electrodes were higher than those at edge-oriented pyrolytic graphite and glassy carbon electrodes. In addition, the oxygen-containing functional groups also contributed to the electron transfer kinetics at the oxygenated CSCNF surface. The electron transfer rate of Fe(2+/3+) was accelerated and that of [Fe(CN)6](3-/4-) was decelerated by the oxygen-containing groups, mainly due to the electrostatic attraction and repulsion, respectively. The electrochemical reaction selectivities at the oxygenated CSCNF surface were tunable by controlling the amount of nanofibers and the oxygen/carbon atomic ratio at the nanofiber surface. Thus, the oxygenated CSCNFs would be useful electrode materials for energy-conversion, biosensing, and other electrochemical devices.

Selective ethanol production from reducing sugars in a saccharide mixture.

Fermentation profiles of four different yeasts reportedly defective in sucrose utilization indicate that all strains tested removed particular sugar via selective conversion to ethanol in a saccharide mixture. At the temperature of pressed sugarcane juice, Saccharomyces dairenensis and Saccharomyces transvaalensis performed better in ethanol production rate and yield, respectively.

Numerical analysis of the impact of structural changes in cellulosic substrates on enzymatic saccharification.

Here, a simple cellulose conversion model that considers the cellulose surface area and surface density of adsorbed cellulase as substrate-derived and cellulase-derived factors controlling reaction rates is provided. Microcrystalline cellulose (Avicel) and delignifed softwood were used as controls, and structure-modified samples were prepared. It was shown that the initial cellulose conversion rate is largely controlled by the cellulose surface area. Moreover, the proposed model demonstrates that increases in cellulose surface area reduce retardation of the cellulase reaction. The proposed model was used to estimate the impact of structural changes in a substrate (i.e., cellulose surface area) by pre-treatment on enzymatic saccharification. It was found that increasing the cellulose surface area is the most effective way to optimize enzymatic saccharification of cellulose substrates.

Direct synthesis of cup-stacked carbon nanofiber microspheres by the catalytic pyrolysis of poly(ethylene glycol).

Uniformly sized microspheres tangled with cup-stacked carbon nanofibers (CSCNFs) were directly synthesized by the pyrolysis of poly(ethylene glycol) (PEG) with a nickel catalyst. A PEG/Ni membrane was prepared on a silicon wafer surface by heating it to 750 °C at a heating rate of 15 °C min(-1). The wafer was heated to a temperature of 400 °C and was held at that temperature for 1 h before raising the temperature to 750 °C for 10 min to form the CSCNF microspheres. The final CSCNF microspheres and the intermediates were evaluated using scanning electron microscopy, transmission electron microscopy, X-ray diffractometry, and Raman spectroscopy to elucidate the growth mechanism. Furthermore, the CSCNF microspheres were successfully dispersed and maintained their spherical shape in an aqueous solution containing 0.5% Nafion. The CSCNF microspheres have the potential to work as a sophisticated carrier with high adsorption and fast electron-transfer exchange properties based on the graphene edges of the nanofiber surface.

Chlorine effect on the formation of carbon nanofibers.

Platelet graphite nanofibers (GNFs) and turbostratic carbon nanofibers (CNFs) are synthesized by the thermal evaporation and decomposition of a polymer-based mixture at 700 degrees C using Ni as a catalyst. The mixture consists of poly(ethylene glycol) (PEG), serving as the carbon source, and hydrochloric acid solution (HCl(aq)), serving as the promoter/additive for the growth of CNFs. High-purity zigzag-shaped platelet GNFs form with 10 wt% HCl(aq) as an additive in the PEG. The diameters of the platelet GNFs are in the range of 40-60 nm, with lengths of a few micrometers. High-resolution transmission electron microscopy images indicate a high degree of graphitization and well ordered graphene layers along the fiber axis. In contrast, high-purity turbostratic CNFs form with 20 wt% HCl(aq) in the PEG. The diameter and length of the turbostratic CNFs are 20-40 nm and a few micrometers, respectively. The participation of HCl in the thermal process leads to the formation of Ni-Cl compounds. The amount of chlorine affects the shape of the Ni catalyst, which determines the type of CNF formed.

Structural changes of lignocelluloses by a nonionic surfactant, Tween 20, and their effects on cellulase adsorption and saccharification.

In this work, we found that Tween 20 treatment (0-8 mM) contributed to the cell wall collapse of most samples except for those with high lignin contents and high crystallinity. Cell wall collapse contributed to the formation of 10- to 50-nm pores and not only increased the monolayer saturation amount of adsorbed cellulase about 3-3.6 times but also increased the cellulase adsorption rate (D(e)/r(2)) about 160-880 times. Moreover, cellulose conversion at 72 h was also increased 8.7-21.5% by Tween 20 treatment. On the other hand, the adsorption of Tween 20 on Avicel (microcrystalline cellulose) hindered the cellulase reaction (adsorption and saccharification). The effect of Tween 20 treatment on the crystalline part was insignificant for both lignocelluloses and Avicel. It was found that some degree of pretreatment (e.g. lignin removal) that enhances Tween 20 diffusion into samples is necessary to obtain the structural effects of Tween 20.

Removal of copper from aqueous solution using iron-containing adsorbents derived from methane fermentation sludge.

Iron-containing adsorbents prepared from methane fermentation sludge (MFS) were characterized by N(2) adsorption, XRD, SEM, EDX, pH determination and elemental analysis. The experiments for copper removal from aqueous solution using the MFS-derived adsorbents were performed, and the effects of iron content, forms of the iron (hydr)oxides, surface basicity and pH of the aqueous solution on copper removal were elucidated respectively. The desorption studies were also performed and the mechanism of Cu(II) adsorption was proposed. The results indicated that the adsorbent obtained at 700 degrees C for 1h in a steam atmosphere possessed the highest capability for Cu(II) adsorption. The high copper removal ability of the MFS-derived materials is attributed to their intermediate surface area, strong surface basicity and the presence of iron (hydr)oxides on their surface. The Cu(II) adsorption onto the composite adsorbents is via ion-exchange with H, Ca and K ions, surface precipitation and binding with active sites on the surface of iron (hydr)oxides at various pH values. The desorption of copper in deionized water is quite low. The irreversibility of copper adsorption on the iron-containing adsorbents is attributed to the formation of strong bonds between Cu(II) and the iron (hydr)oxides. The adsorbent can be applied to remove copper from water or soil by fixation onto the surface.

Gramine-induced growth inhibition, oxidative damage and antioxidant responses in freshwater cyanobacterium Microcystis aeruginosa.

In recent years, the exploration and development of the effective methods of treatment and prevention to algal blooms, especially Microcystis aeruginosa blooms has been an important issue in the field of water environment protection. Allelochemicals (natural plant toxins) are considered promising sources of algicides to control algal blooms. The objective of this study is to determine the inhibitory effects and potential mechanisms of a well-known allelochemical gramine (N,N-dimethyl-3-amino-methylindole) on bloom-forming cyanobacterium M. aeruginosa. The results showed that this indole alkaloid effectively inhibited the growth of M. aeruginosa. The effective concentration causing a 50% inhibition at 3 d (EC(50, 3 d)) increased with the initial algal density (IAD) increasing. When IAD increased from 5x10(4) to 5x10(5)cellsmL(-1), the values of EC(50, 3 d) increased from 0.5 to 2.1mgL(-1). In the cells of M. aeruginosa, gramine caused an obvious increase in the level of reactive oxygen species (ROS). The lipid-peroxidation product malondialdehyde (MDA) increased significantly in gramine-treated cells. The effects of gramine on enzymatic and non-enzymatic antioxidants were in different manners. The activity of superoxide dismutase (SOD) was decreased after gramine exposure. The catalase (CAT) activity was increased after 4h but decreased from 60h. Both the contents and the regeneration rates of ascorbic acid (AsA) and reduced glutathione (GSH) were increased after 4h of exposure to gramine. However, only GSH content was still increased after 40h of exposure. These results suggested that the activation of antioxidants in M. aeruginosa played an important role to resist the stress from gramine at initial time, the inactivation of SOD is crucial to the growth inhibition of M. aeruginosa by gramine, and the phytotoxicity of gramine on M. aeruginosa may be due to oxidative damage via oxidation of ROS.

[Phosphorus rhizosphere depletion effect of four aquatic plants].

Four aquatic plants (Alternanthera philoxeroides, Typha latifolia, Sagittaria sagittifolia, Phragmites communis ) were cultured on P-enriched soil in a pot experiment to assess the phosphorus rhizosphere depletion effect and analysis the ratio of root to shoot, root morphology, phosphorus uptake efficiency and phosphorus use efficiency. An obvious variation in P concentration of the soil in the rhizophere and non- rhizophere was observed. Compared with the non-rhizosphere (available P: 167.53 microg x g(-1)), the available P in the rhizosphere soil of Alternanthera philoxeroides, Typha latifolia, Sagittaria sagittifolia and Phragmites communis was reduced to 80.17, 124.37, 155.38 and 161.75 microg x g(-1) respectively, with 81%, 42%, 18% and 16% reduction ratio of water-soluble phosphorus. More effective phosphorus depletion was achieved in Alternanthera philoxeroides by higher phosphorus uptake efficiency (1.32 mg x m(-1)), while rooting system was small and phosphorus use efficiency was low (0.34 g x mg(-1)). Phosphorus uptake efficiency of Typha latjfolia is much lower (0.52 mg x m(-1)) than that of Alternanthera philoxeroides, however, its strong rooting system enhanced soil exploration, with higher phosphorus use efficiency (0.64 g x mg(-1)) and the ratio of root to shoot (0.35). Alternantshera philoxeroides and Typha latfolia were more effective in phosphorus depletion of the rhizosphere soil than that in Sagittaria sagittifolia and Phragmites communis.

[Growth of Microcystis aeruginosa affected by allelochemicals of Arundo donax Linn. extracted with different solvents].

To study the effects of allelochemicals of Arundo donax Linn. on the growth of Microcystis aeruginosa, the allelochemicals were extracted with three solvents (methanol, ethyl acetate and hexane), respectively. Based on the observation of algal morphology and the measurement of algal density and cell size, the results showed the allelochemicals extracted with all the three solvents had inhibition on M. aeruginosa. The appearance time of allelochemical inhibition increased as follows, allelochemicals extracted with methanol < ethyl acetate < hexane. As treatment time extended, M. aeruginosa regrew at low doses of allelochemicals extracted with methanol. Their inhibitory effects at high doses were lower than those extracted with ethyl acetate and hexane. After 2 d and 4 d of treatment, the inhibition ratios of allelochemicals extracted with ethyl acetate and hexane reached almost 100%, respectively. The 50% effective concentrations (EC50, 6 d) of allelochemicals extracted with methanol, ethyl acetate and hexane were 0.17 g x L(-1), 0.05 g x L(-1) and 0.08 g x L(-1), respectively. The allelochemicals extracted with methanol caused cavities in cells, those with ethyl acetate caused cells into cavities, pieces and conglomeration, and those with hexane caused goffers on cells initially with conglomeration later. The allelochemicals extracted with all the three solvents decreased the cell size of M. aeruginosa, among which those extracted with ethyl acetate had the strongest action.

Separation of phenols and furfural by pervaporation and reverse osmosis membranes from biomass--superheated steam pyrolysis-derived aqueous solution.

The separation of valuable chemicals from raw products, where a great number of chemicals coexist, is the key technology in biomass refinery. In this study, the applicability of membrane separation of valuable chemicals from our currently developed portable superheated steam (SHS) biomass pyrolysis process was demonstrated. Phenols (phenol, p-cresol, guaiacol, methyl guaiacol, and ethyl guaiacol), furfural, and acetone were successfully separated by pervaporation using the silicone rubber membrane from model solutions and an actual SHS derived aqueous solution. The solution was also concentrated effectively by reverse osmosis separation using a polyamide membrane. When a high concentration of SHS solution was fed to the pervaporation process, a phase-separated permeate was obtained, which indicated that the reverse osmosis concentration combined with pervaporation separation is useful for the superheated steam process.

Superheated steam pyrolysis of biomass elemental components and Sugi (Japanese cedar) for fuels and chemicals.

To develop a novel noncatalytic biomass refinery process that can be used as a portable process, superheated steam pyrolysis was investigated to produce both carbonized solid fuels and chemicals using a large-scale reactor. Individual biomass components and native biomass (Sugi, Japanese cedar) were pyrolyzed. Between 150 and 400 degrees C, the vaporizing fractions of cellulose, xylan, and kraft lignin were summarized using a numerical model. Cellulose was converted to glycolaldehyde, furfural, 5-hydroxymethyl furfural and levoglucosan, whereas xylan was converted to glycolaldehyde, furfural, and acetic acid. Kraft lignin produced a slight yield of phenol and guaiacol. The total vaporization fraction of Sugi and its vaporizing rate were explained sufficiently using a numerical model based on the weighted average of the vaporizing properties of the individual components. However, the yields of phenol, guaiacol, and acetic acid were underestimated, while the yields of furfurals and levoglucosan were overestimated. Possible synergetic effects among chemicals in the superheated steam pyrolysis of native biomass were also discussed.

Adsorptive ozonation of 2-methylisoborneol in natural water with preventing bromate formation.

This paper presents an application of our newly developed adsorptive ozonation process using a high silica zeolite adsorbent (USY) for drinking water treatment. First, the adsorption of 2-methylisoborneol (2-MIB) on USY in a river water/pure water mixture was clarified by a batch-type adsorption experiment. The results showed that 2-MIB was adsorbed on USY; however, almost all of the adsorbed 2-MIB was desorbed over time. The desorption rate was increased with the ratio of river water to pure water, indicating that compounds dissolved in the river water, such as natural organic matter (NOM), prevent the adsorption of 2-MIB on USY. Second, the ability of the river water to consume ozone was confirmed in an experiment using a USY-packed column reactor. The ozone consumption was obviously increased by the presence of USY, indicating that USY-adsorbing compounds dissolved in the river water (probably small size NOM) consumed the ozone. However, the rapid ozone consumption was occurred by 6-8 s in the retention times when 3.14-4.38 mgL(-1) of water dissolved ozone was fed, this rapid ozone consumption lasted no more than these times. This result revealed that the rapid consumption of ozone by the adsorptive compounds in our process could be avoided within a certain retention time (6-8 s; especially for the river water used in this study) when enough concentration of ozone (3.14 mgL(-1) or more; same above) was supplied. We therefore performed a trial in which 2-MIB dissolved in river water was continuously decomposed using a USY-packed column with various ozone concentrations. In the process, the adsorptive compound dissolved in the river water adsorbed and reacted with ozone in the parts of the apparatus upstream of the column, while the adsorption and decomposition of 2-MIB took place in the parts of the apparatus downstream of the column. This resulted in a sufficient 2-MIB decomposition with minimizing bromate ion formation.

Ozone decomposition of 2-methylisoborneol (MIB) in adsorption phase on high silica zeolites with preventing bromate formation.

This work elucidates the applicability of our newly developed adsorptive ozonation process for the decomposition of 2-methylisoborneol (MIB), a typical taste and odor chemical, without the formation of possibly carcinogenic bromate ions. First, zeolite adsorbents were screened for their ability to adsorb MIB with a batch-type adsorption experimental apparatus and a flow-type decomposition experimental apparatus included an adsorbent-packed column. The USY zeolite with the highest silica to alumina ratio (SiO(2)/Al(2)O(3) molar ratio=70) showed the best performance as an adsorbent. Using this adsorbent, an ozonation experiment on an MIB solution including bromide ions was performed under various retention times using the flow-type apparatus. As a result, sufficient decomposition of MIB was achieved with preventing bromate formation.

Feasibility of a simple double-layered coculture system incorporating metabolic processes of the intestine and liver tissue: application to the analysis of benzo[a]pyrene toxicity.

A simple double-layered coculture system using Caco-2 cell and Hep G2 cell, which mimic metabolic processes occurring in humans such as absorption through the intestine and cytochrome P450 1A1/2 involving biotransformation in both the intestine and liver cells, was used to investigate the toxicity of model chemical, benzo[a]pyrene (B[a]P). It was found that both Caco-2 and Hep G2 cells can metabolize B[a]P to toxic metabolites including B[a]P-7,8-hydrodiol (7,8-diol), an immediate precursor to the highly-reactive ultimate toxicant of B[a]P, B[a]P-7,8-hydrodiol-9,10-epoxide (BPDE), possibly mediated by cytochrome P450 1A1/2 activity. However, in a double-layered coculture system, no significant reduction of Hep G2 cell viability was found, although an approximately 50% reduction in viability was observed in pure Hep G2 cells. HPLC analysis showed that Caco-2 cells transfer B[a]P and its toxic metabolites back to the apical side, thus decreasing the concentrations of toxic metabolites including B[a]P-7,8-hydrodiol (7,8-diol) in cocultured Hep G2 cells. These results appear to be correlated with in vivo data on the effects of orally administered B[a]P, that is, low (10%) bioavailability in the rats and almost no acute lethal toxicity in rats or mice. As such, the simple double-layered coculture system can provide more accurate information regarding the toxic actions of the hazardous chemicals in humans than a pure culture system, as it also gives the final toxicity as a result of many complicated phenomena such as selective permeation in the intestine and biotransformation in the intestine and liver.

Use of a perfusion co-culture system consisting of Caco-2 and Hep G2 cell compartments for the kinetic analysis of benzo[a]pyrene toxicity.

Conventional cytotoxicity tests cannot usually include various metabolic processes in humans. We therefore developed a physiologically based, multi-compartment perfusion co-culture system, using a Caco-2 cell monolayer on a semi-permeable membrane and a microcarrier-based, three-dimensional culture of Hep G2 cells to mimic permeation across the small intestine and biotransformation of the small intestine and the liver. Stable operations allowed us to maintain various activities of both cells for at least 4 days. Cocultivation improved the growth of Hep G2 cells and enhanced the cytochrome P450 1A1/2 capacities of both Hep G2 and Caco-2 cells. When benzo[a]pyrene (BaP) was loaded on the apical side of the Caco-2 cell layer, the enhanced P450 capacities produced a higher amount of BaP-7,8-hydrodiol, a precursor of the ultimate carcinogen of BaP, BaP-7,8-dihydrodiol-9,10-epoxide (BPDE). These phenomena led to the initially retarded, but later stronger, expression of BaP toxicity in the co-culture system than in pure cultures, which agreed with the actual load of BaP-7.8-hydrodiol to the Hep G2 cells. Because this kind of system can reproduce such complicated phenomena, including those influenced by organ-organ interactions, it is useful as a new in vitro experimental system, for understanding the unknown mechanisms involved in final toxicity in humans and thereby improving physiologically based pharmacokinetic (PBPK) simulation models.

Adsorption and decomposition of water-dissolved ozone on high silica zeolites.

The adsorption properties of water-dissolved ozone on high silica zeolites were investigated. Adsorbed ozone was desorbed almost reversibly. The adsorption equilibrium relations were described by a linear expression written as q=betaC, where q is the amount adsorbed, C is the equilibrium concentration and beta is the equilibrium constant. Also, the beta values were strongly dependent on the SiO(2)/Al(2)O(3) ratio (mol/mol) and on the pore structure of the high silica zeolites. The larger the SiO(2)/Al(2)O(3) ratio, the larger the value of beta. ZSM-5 (SiO(2)/Al(2)O(3) ratio: 3000), which gave the highest adsorption capacity of water-dissolved ozone, was able to highly concentrate water-dissolved ozone on the adsorbent. The decomposition behavior of adsorbed ozone was also investigated. Ozone adsorbed on high silica zeolite was observed to be a little more stable than ozone existing in bulk water. The decomposition rate was independent of SiO(2)/Al(2)O(3) ratios in the range of 30-3000 or a solution pH in the range of 4-6.