Preparation, characterization and in vitro anticoagulant activity of corn stover xylan sulfates.

A new anticoagulant agent was prepared by introducing sulfate groups into corn stover xylan through homogeneous reactions. Three organic solvents, N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO) and formamide (FA), were adopted as reaction media, with the assistance of LiCl. Structural characterization by FT-IR and 13CNMR showed that xylan sulfate (XS) could be successfully synthesized with SO3∙Pyridine (SO3∙Py) complexes sulfation reagent in the three media. The effect of sulfation temperature, sulfation time, media type and molar ratio of -SO3/-OH on the degree of substitution (DS) and degree of the polymerization (DP) were studied. DMF/LiCl were more effective than DMSO/LiCl and FA/LiCl in preparation of xylan sulfate with high DS. The optimal conditions for sulfation were obtained when SO3∙Py complex was added to DMF/LiCl with -SO3/-OH ratio of 1.5:1 and maintained at 50 °C for 3 h. Degree of polymerization of xylan was decreased during the sulfation process and DMF/LiCl offered the least xylan degradation as compared with DMSO/LiCl or FA/LiCl. Anticoagulant activities of the resultant xylan sulfates with different DS were evaluated by using activated partial thromboplastin time (APTT), thrombin time (TT), and prothrombin time (PT). Results indicated that the introducing of sulfate groups into xylan did endow the polysaccharides with anticoagulant activity. The APTT and TT of XS with DS of 1.20 reached 141 and 45.3 s at a dosage of 20 µg/mL, while the APTT and TT values for the blank sample were only 35.5 and 15.6 s. Furthermore, coagulation time was prolonged with the increase of DS and the concentration of XS. Our findings provide new insights into the value-added utilization of agricultural biomass.

[A rapid method for the determination of hydrogen peroxide concentration].

The present paper reported a spectrophotometry for the determination of hydrogen peroxide concentration. It is based on the reaction between ceric sulfate and hydrogen peroxide in an acidic medium, in which orange tetravalent cerium is converted to colorless trivalent cerium that causeds the change in absorbance. According to the quantitative relationship between ceric sulfate and hydrogen peroxide, the hydrogen peroxide concentration can be calculated. The selected conditions were as follows: detection wavelength of 480 nm, H2SO4 concentration of 0.5 mol x L(-1), and reaction time of 3.0 min. The results showed that the method has an excellent measurement precision (RSD = 0.31%) and accuracy (RSD < or = 0.91%) for the quantification of hydrogen peroxide. The present method is simple and rapid, with high detection sensitivity and low cost. It is suitable for use in rapid industrial analyses.

Use of carboxylated cellulose nanofibrils-filled magnetic chitosan hydrogel beads as adsorbents for Pb(II).

Novel magnetic hydrogel beads (m-CS/PVA/CCNFs), consisting of carboxylated cellulose nanofibrils (CCNFs), amine-functionalized magnetite nanoparticles and poly(vinyl alcohol) (PVA) blended chitosan (CS), were prepared by an instantaneous gelation method. SEM, XRD, and TGA techniques were applied to investigate the structure of the hydrogel materials. The magnetic hydrogels were employed as absorbents for removal of Pb(II) ions from aqueous solutions and the fundamental adsorption behavior was studied. Experimental results revealed that the m-CS/PVA/CCNFs hydrogels exhibit higher adsorption capacity with the value of 171.0mg/g, and the carboxylate groups on the CCNFs surface play an important role in Pb(II) adsorption. Moreover, adsorption isotherm data were reliably described by the Langmuir model and the adsorption kinetics closely followed pseudo-second order model. Additionally, the Pb(II)-loaded m-CS/PVA/CCNFs hydrogels could be easily regenerated in weak acid solution and the adsorption effectiveness of 90% can be maintained after the 4 cycles.

Superabsorbent nanocomposite hydrogels made of carboxylated cellulose nanofibrils and CMC-g-p(AA-co-AM).

Superabsorbents based on carboxylated cellulose nanofibrils (CCNFs) and carboxymethyl cellulose-g-poly(acrylic acid-co-acrylamide) were synthesized. A series of experiments were performed to evaluate the influence of factors such as CCNFs amount, solution pH, temperature, salt solution type and concentration on the swelling behaviors of the hydrogels. The water uptake of the hydrogels strongly depended on the CCNF content, the swelling capacity in distilled water increased dramatically from 245.8 to 458.7 g/g with the addition of CCNFs up to 2.5 wt%. Furthermore, the incorporation of CCNFs improved salt resistance properties of the hydrogels with slower deswelling rate and higher water retention capacity at deswelling equilibrium. Besides, the CCNF nanocomposite hydrogels presented better responsive behavior in relation to pH presence and showed an increase in water retention capacity at various temperatures. Fourier transform infrared spectroscopy (FTIR) and scanning electron microscope (SEM) were employed to examine the structure and morphologies of the prepared superabsorbent hydrogels.

[Rapid determination of silicon content in black liquor of straw fibrous material].

The present paper reports a novel method for the determination of silicon content in straw fibrous material black liquor based on alpha-Si--Mo heteropoly acid spectrophotometry. The selected conditions were as follows: detection wavelength 360 nm, pH 4.0, and reaction time 10 min. It was found that the acidic soluble lignin in the sample liquor was the major interference species in the silicon content determination. The interference of acidic soluble lignin can be eliminated by hydrogen peroxide-nitric acid digestion method. The present method is not only simple, rapid, stable and less interferential, but also of good measurement precision and accuracy, with the relative standard deviations of 0.9%, and recoveries of 99.0%-102%. It is suitable for use in high silicon content of black liquor routine rapid analyses.

Colloidal stability of negatively charged cellulose nanocrystalline in aqueous systems.

Colloidal stability of negatively charged cellulose nanocrystalline (CNC) in the presence of inorganic and organic electrolytes was investigated by means of dynamic light scattering and atomic force microscopy. CNC could be well dispersed in distilled water due to the electrostatic repulsion among negatively charged sulfate ester groups. Increasing the concentration of inorganic cation ions (Na(+) and Ca(2+)) resulted in CNC aggregation. CNC in divalent cation ion Ca(2+) solution exhibited less stability than that in monovalent cation ion Na(+) solution. Organic low-molecular-weight electrolyte sodium dodecyl sulfate (SDS) favored the stability of CNC suspension, whereas organic high-molecular-weight electrolyte sodium carboxymethyl cellulose (CMC) induced CNC particle aggregation due to intermolecular bridging interaction or entanglement. Cationic polyacrylamide (CPAM) caused a serious aggregation of CNC particles even at low concentration of CPAM. At low ionic strength (Na(+), 1 mM), CNC were stable in aqueous solution at the pH range of 2-11.

Application of statistical design for the optimization of microbial community of synthetic domestic wastewater.

A fractional factorial design (FFD) and a response surface methodology (RSM) were used to optimize the inoculum composition of six strains for treatment of synthetic domestic wastewater. The model predicted the highest overall specific substrate utilization rate (q) of 6.88 g TOC/(d-gVSS). The value is in accordance with the actual maximum q, and is 1.5 and 1.97 times greater than those without optimization for 4 and 6 strains respectively. Additionally, the shortest time to reach stationary phase (3.5 h) and highest maximum total organic carbon (TOC) removal efficiency (92%) were also achieved under the optimum condition. The results indicated that the FFD and RSM are powerful screening and optimizing tools for the microbial community. The experimental approaches enhance the overall specific rate of substrate utilization as well as other biodegradation parameters.

Chemometrics-assisted spectrophotometry method for the determination of chemical oxygen demand in pulping effluent.

A new method has been developed for the determination of chemical oxygen demand (COD) in pulping effluent using chemometrics-assisted spectrophotometry. Two calibration models were established by inducing UV-visible spectroscopy (model 1) and derivative spectroscopy (model 2), combined with the chemometrics software Smica-P. Correlation coefficients of the two models are 0.9954 (model 1) and 0.9963 (model 2) when COD of samples is in the range of 0 to 405 mg/L. Sensitivities of the two models are 0.0061 (model 1) and 0.0056 (model 2) and method detection limits are 2.02-2.45 mg/L (model 1) and 2.13-2.51 mg/L (model 2). Validation experiment showed that the average standard deviation of model 2 was 1.11 and that of model 1 was 1.54. Similarly, average relative error of model 2 (4.25%) was lower than model 1 (5.00%), which indicated that the predictability of model 2 was better than that of model 1. Chemometrics-assisted spectrophotometry method did not need chemical reagents and digestion which were required in the conventional methods, and the testing time of the new method was significantly shorter than the conventional ones. The proposed method can be used to measure COD in pulping effluent as an environmentally friendly approach with satisfactory results.

Rapid determination of furfural in biomass hydrolysate by full evaporation headspace gas chromatography.

This paper reports a full evaporation (FE) headspace gas chromatographic (HS-GC) method for rapid determination of furfural in the biomass hydrolysate. The data show that a near-complete mass transfer of furfural in the sample from biomass hydrolysate to the vapor phase (headspace) was achieved within 3 min at 105°C when a very small (<40 µL) sample was added to a 20 mL headspace sample vial. The acid-catalyzed furfural decomposition under these conditions was negligible. The furfural in the vapor phase was then determined by HS-GC using a flame ionization detector. The results showed that the method has an excellent measurement precision (RSD<0.5%) and accuracy (recovery=100.2±1.7%) for furfural quantification in carbohydrate hydrolysate samples. The method requires no sample pretreatment, so it is simple, rapid and accurate, and suitable for applications in lignocellulosic biomass conversion to fuel ethanol or other high value-added products.

Effect of oxygen availability on the removal efficiency and sludge characteristics during pentachlorophenol (PCP) biodegradation in a coupled granular sludge system.

This study systematically investigated the metabolism of pentachlorophenol (PCP) in batch experiments using coupled sludge granules under various dissolved oxygen concentrations. Results indicated that the oxygen condition in serum bottles has a significant effect on the microorganism metabolism. A greater degree of mineralization of PCP was achieved under oxygen-limited conditions (e.g., 40 and 60 initial headspace oxygen percentage (IHOP)), producing trichlorophenol (TCP), dichlorophenol (DCP) and monochlorophenol (MCP) as intermediates and chloride as one of the final products. Reductive dechlorination was identified as the primary pathway for the PCP degradation. Under strictly anaerobic or slightly oxidative conditions (0 and 20 IHOP), the reductive dechlorination of PCP led to an accumulation of TCP. Under aerobic conditions (80 and 100 IHOP), PCP degradation was less significant due to the hindered reductive chlorination in the presence of oxygen. It is also observed that cell hydrophobicity, protein (PN) concentration, settling velocity and specific gravity of the sludge granules decreased with IHOP from 0 to 60, and then increased with IHOP from 60 to 100. Specific methanogenic activity (SMA) and specific oxygen uptake rate (SOUR) confirmed that degradation of PCP was achieved by methanogenic and methanotrophic populations coexisting in a single granule. Because of a combination of reductive and oxidative degradation mechanisms, aerobic or facultative bacteria were found to oxidize the intermediates of PCP degradation products produced by methanogens and strict anaerobes during fermentation.

[Rapid method for determination of furfural and 5-hydroxymethyl furfural in pre-extraction stream of biomass using UV spectroscopy].

The present paper reports a rapid method for the determination of furfural (F) and 5-hydroxymethyl furfural (HMF) in pre-extraction liquors of lignocellulosic biomass based on UV spectroscopy. In a concentrated acetic acid medium, F and HMF have an isosbestic point at 276 nm. It was found that the acidic soluble lignin in the pre-extraction sample is the major interference species in the F and HMF spectroscopic quantification However, only acidic soluble lignins have the absorption at the wavelengths above 325 nm. Based on the absorption of the acidic soluble lignins at 325 nm, their absorptions at either F or HMF absorbed wavelengths can be determined. Thus, with a simple triple-wavelength technique, both F and HMF in the pre-extraction liquors of lignocellulosic biomass can be quantified based on the spectroscopic measurement at the isosbestic point wavelength (276 nm), maximum absorption wavelength of F (272 nm) and the acid soluble lignin absorbed wavelength (325 nm). The present method does not require the hazardous organic compounds (such as phenolic compounds etc.) acting as a color reagent in the experiment. It is not only simple and rapid, but also has a good measurement precision and accuracy, with the relative standard deviations of 3.02% and 2.72%, and recoveries of 95%-107% and 96%-101%, respectively, in the F and HMF quantification. The present method is suitable for use in the research on pre-extraction hemicellulose of the lignocellulosic biomass in bio-refinery area in order to achieve a high selective sugar conversion.

Enhancing biodegradation of wastewater by microbial consortia with fractional factorial design.

Batch experiments were conducted on the degradation of synthetic and municipal wastewater by six different strains, i.e., Agrobacterium sp., Bacillus sp., Enterobacter cloacae, Gordonia, Pseudomonas stutzeri, Pseudomonas putida. By applying a fractional factorial design (FFD) of experiments, the influence of each strain and their interactions were quantified. An empirical model predicting the treatment efficiency was built based on the results of the FFD experiments with an R(2) value of 99.39%. For single strain, Enterobacter cloacae, Gordonia and P. putida (p=0.008, 0.009 and 0.023, respectively) showed significant enhancement on organic removal in the synthetic wastewater. Positive interaction from Enterobacter cloacae, Gordonia (p=0.046) was found, indicating that syntrophic interaction existed, and their coexistence can improve total organic carbon (TOC) degradation. Verification experiments were performed to evaluate the effect of bioaugmentation by introducing three selected strains into an activated sludge reactor for treating municipal wastewater. The removal efficiency of TOC with the bioaugmentation was increased from 67-72% to 80-84% at an influent TOC concentration of 200mg/L. The results derived from this study indicate that the FFD is a useful screening tool for optimizing the microbial community to enhance treatment efficiency.

Novel preparation and characterization of cellulose microparticles functionalized in ionic liquids.

Ionic liquid (IL)-reconstituted acrylic acid (AA)-functionalized cellulose microparticles were successfully prepared by a water-in-oil suspension technique preliminary modification with AA in homogeneous condition. Cellulose was fully dissolved in 1-butyl-3-methylimidazolium chloride ([Bmim]Cl) IL, and subsequently was grafted homogeneously with AA and N,N'-methylenebisacrylamide (N,N'-MBA) initiated with ammonium persulfate. The grafted cellulose was spheroidized using white silicone oil as the dispersion medium and Span 80 as a dispersant and then reconstituted from [Bmim]Cl. Reaction conditions were optimized to obtain microparticles with both the highest possible grafting efficiency and most uniform bead sizes. Fourier transform infrared spectroscopy, scanning electron microscopy, and an optical microscope were employed to provide structural information for the functionalized IL-reconstituted cellulose microparticles. These microparticles were shown to behave as good sorbents for Cu(II), Ni(II), Fe(III) ions.

Rapid determination of ethanol in fermentation liquor by full evaporation headspace gas chromatography.

This paper reports a full evaporation (FE) headspace gas chromatographic (GC) method for rapid determination of ethanol in fermentation liquor. The data show that ethanol in the fermentation liquor was transferred to the vapor phase (headspace) almost completely within 3 min at a temperature of 105 degrees C when a very small volume (< 50 microL) of sample was directly added to a sealed headspace sample vial (20 mL). The ethanol in the vapor phase was then measured by headspace GC using a flame ionization detector. The results show that the present method has an excellent measurement precision (RSD=1.62%) and accuracy (recovery=98.1 (+/-1.76%)) for the ethanol quantification in fermentation liquors. The method requires no sample pretreatment and is very simple and rapid.

Kinetic modeling of formic acid pulping of bagasse.

Organic solvent or organosolv pulping processes are alternatives to soda or kraft pulping to delignify lignocellulosic materials for the production of paper pulp. Formic acid, a typical organosolv system, has been presently examined under atmospheric pressure to pulp bagasse fibers. It was shown that efficient bagasse pulping was achieved when the formic acid concentration was limited to 90% (v/v). A statistical kinetic model based on the experimental results for the delignification of bagasse during formic acid pulping was developed that can be described as follows: D (delignification) = 0.747 x C(formicacid) (1.688) x (1 - e(-0.05171t)), an equation that can be used to predict the lignin content in formic acid during the pulping process. The delignification of bagasse by 90% formic acid was almost completed after approximately 80 min, while extended pulping did not improve the delignification but tended to degrade the carbohydrates in bagasse, especially the hemicelluloses, which were rapidly hydrolyzed at the onset of pulping.

Determination of oxalate in black liquor by headspace gas chromatography.

This study demonstrated a headspace gas chromatographic method (HS-GC) for the determination of oxalate content in black liquor (alkaline aqueous solution of inorganic chemicals and dissolved wood species from the alkaline pulping of wood). The method described in this paper is based on the reaction between oxalic and manganese dioxide in an acidic medium, in which oxalic acid is converted to carbon dioxide that is measured with a GC using a thermal conductivity detector. The challenge in developing this method was ensuring complete conversion of oxalic acid while minimizing the contribution of side reactions between carbohydrates, lignin and manganese dioxide to the carbon dioxide measured. It was found that a complete conversion of oxalate to carbon dioxide can be achieved within 3 min at a temperature of 70 degrees C; a MnO(2):C(oxalate) (concentration of H(2)C(2)O(4)+HC(2)O(4)(-)+C(2)O(4)(2-)) mole ratio of 60 and H(2)SO(4) concentration of 0.005-0.01 mol/L in the headspace vial. The method can detect concentrations as low as 0.39 microg of oxalate. The standard deviation was found to be 7% while recovery experiments with black liquor showed recoveries of 93-108% which were deemed acceptable for analysis of oxalate in an industrial sample such as black liquor.

Rapid determination of methanol in black liquors by full evaporation headspace gas chromatography.

This paper reported a full evaporation headspace gas chromatographic (GC) technique for determination of methanol content in black liquors (pulping spent liquor). In this method, a very small volume (10-20 microL) of liquor sample is introduced into a headspace sample vial (20 mL) and heated up to a temperature of 105 degrees C. A near-complete mass transfer of methanol from the liquid phase to vapor phase (headspace), i.e., a full evaporation, can be achieved within 3 min. The methanol in the headspace of the vial is then measured by GC. The present method is simple, rapid and accurate.

Simultaneous anaerobic-aerobic biodegradation of halogenated phenolic compound under oxygen-limited conditions.

The successful application of co-immobilized aerobic-anaerobic biomass under limited aeration in wastewater treatment systems would eliminate the problems associated with the intermediates mono-chlorophenol (MCP) and di-chlorophenol(DCP) accumulations. With low initial pentachlorophenol (PCP) concentration, all PCP could be completely removed under oxygen-limited strict anaerobic conditions, and the removal efficiencies with different initial headspace oxygen percentage (IHOP) were not obviously different from each other. While at high initial PCP concentration, under strictly anaerobic conditions PCP and their intermediates were clearly higher than that under other conditions, and produced obvious accumulation, the highest PCP reduction was achieved by the system receiving 30 IHOP, oxygen-limited system also exhibited lower residual TOC concentration and lower concentration of metabolic intermediates MCP and DCP. These results suggested that under strictly anaerobic condition the reductive dechlorination of low chlorinated compounds became rate limiting in the reductive dechlorination pathway, less chlorinated compounds be more amenable to aerobic degradation, and the aerobes of outer layers could function under limited oxygen. The co-immobilized aerobic-anaerobic biomass for methanogenesis under limited-aeration for chlorophenol degradation might be an attractive and efficient alternative for the sequential anaerobic/aerobic system to achieve mineralization of a broad range of recalcitrance highly chlorinated organics and low final TOC concentrations.

Adsorption/desorption behavior between a novel amphoteric granular lignin adsorbent and reactive red K-3B in aqueous solutions.

A novel amphoteric granular lignin adsorbent (AGLA) was prepared using magnesium lignosulfonate as a raw material which was provided by a straw sulfite pulp mill in Guangdong Province, China. A reactive dye (red K-3B) was used as an adsorbate to investigate the adsorption behavior by static and mobile ways. The removal of reactive red K-3B was found to be initially pH and concentration dependent. Moreover, an increase of solution temperature ranging from 5 degrees C to 60 degrees C helped to enhance the rate of intraparticle diffusion of adsorbate and changes in the size of the pores of the adsorbent and thus to reduce the adsorption time. The total breakthrough adsorption capacity was 531 mg/g, and the saturated adsorption capacity was 560 mg/g, which prevailed over the activated carbons evidently. The reactive red K-3B adsorbed on AGLA could be recovered with a mixture of alcohol, NaCl and HCl aqueous solutions. The recovery percentage could reach 92.4%.

Coupled anaerobic/aerobic biodegradation of 2,4,6 trichlorophenol.

Degradation of 2,4,6-trichlorophenol (TCP) with co-immobilizing anaerobic granular sludge and isolated aerobic bacterial species was studied in coupled anaerobic/aerobic integrated reactors. The synergism of aerobes and anaerobes within co-immobilized granule might facilitate degrading the TCP and exchange of anaerobic metabolites 4-CP, which promoted system organic removal efficiency and recovered from organic shock-loads more quickly. The biomass specific activities experiment further confirmed that strict anaerobes be not affected over the course of this experiment by the presence of an oxic environment, aerobic activity predominated in the outer co-immobilized granule layers, while the interior was characterized by anaerobic activity. The co-immobilized granule could thus enable both aerobic and anaerobic microbes function in the same reactor and thereby integrate the oxidative and reductive catabolism.