Selectivity and delignification kinetics for oxidative short‐term lime pretreatment of poplar wood,part I: Constant‐pressure

Kinetic models applied to oxygen bleaching of paper pulp focus on the degradation of polymers, either lignin or carbohydrates. Traditionally, they separately model different moieties that degrade at three different rates: rapid, medium, and slow. These models were successfully applied to lignin and carbohydrate degradation of poplar wood submitted to oxidative pretreatment with lime at the following conditions: temperature 110–180°C, total pressure 7.9–21.7 bar, and excess lime loading of 0.5 g Ca(OH)₂ per gram dry biomass. These conditions were held constant for 1–6 h. The models properly fit experimental data and were used to determine pretreatment selectivity in two fashions: differential and integral. By assessing selectivity, the detrimental effect of pretreatment on carbohydrates at high temperatures and at low lignin content was determined. The models can be used to identify pretreatment conditions that selectively remove lignin while preserving carbohydrates. Lignin removal ≥50% with glucan preservation ≥90% was observed for differential glucan selectivities between ～10 and ～30 g lignin degraded per gram glucan degraded. Pretreatment conditions complying with these reference values were preferably observed at 140°C, total pressure ≥14.7 bars, and for pretreatment times between 2 and 6 h depending on the total pressure (the higher the pressure, the less time). They were also observed at 160°C, total pressure of 14.7 and 21.7 bars, and pretreatment time of 2 h. Generally, at 110°C lignin removal is insufficient and at 180°C carbohydrates do not preserve well. © 2011 American Institute of Chemical Engineers Biotechnol. Prog., 2011     

Sulfite pretreatment (SPORL) for robust enzymatic saccharification of spruce and red pine

This study established a novel process using sulfite pretreatment to overcome recalcitrance of lignocellulose (SPORL) for robust and efficient bioconversion of softwoods. The process consists of sulfite treatment of wood chips under acidic conditions followed by mechanical size reduction using disk refining. The results indicated that after the SPORL pretreatment of spruce chips with 8–10% bisulfite and 1.8–3.7% sulfuric acid on oven dry (od) wood at 180 °C for 30 min, more than 90% cellulose conversion of substrate was achieved with enzyme loading of about 14.6 FPU cellulase plus 22.5 CBU β-glucosidase per gram of od substrate after 48 h hydrolysis. Glucose yield from enzymatic hydrolysis of the substrate per 100 g of untreated od spruce wood (glucan content 43%) was about 37 g (excluding the dissolved glucose during pretreatment). Hemicellulose removal was found to be as critical as lignin sulfonation for cellulose conversion in the SPORL process. Pretreatment altered the wood chips, which reduced electric energy consumption for size reduction to about 19 Wh/kg od untreated wood, or about 19 g glucose/Wh electricity. Furthermore, the SPORL produced low amounts of fermentation inhibitors, hydroxymethyl furfural (HMF) and furfural, of about 5 and 1 mg/g of untreated od wood, respectively. In addition, similar results were achieved when the SPORL was applied to red pine. By building on the mature sulfite pulping and disk refining technologies already practiced in the pulp and paper industry, the SPORL has very few technological barriers and risks for commercialization.     

Further Studies on Factors Affecting the Efflux of Betacyanin from Beet Root: A Note on Thermal Effects

As judged by betacyanin efflux, beet root tissue differs in stability toward O₂ at low and high temperatures (45–60°C and 60–100°C respectively). The effect of temperature itself can he divided into a high activation energy (93 Kcal mol^?1) process in the lower temperature range and a low activation energy process (19 Kcal mor^?1) in the higher range (> 60°C). From these data it is suggested that initially, elevating temperatures bring about reversible conformational changes in the membrane. With continuing increase in temperature in the presence of O₂, membrane chemical groups susceptible to oxidation are exposed and, upon oxidation, render conformational changes irreversible.     

Oxygen-related processes in red blood cells exposed to tert-butyl hydroperoxide

The correlation between the oxidative processes in tert-butyl hydroperoxide (tBHP)-exposed red blood cells and the reactions of oxygen consumption and release were investigated. Red blood cell exposure to tBHP resulted in transient oxygen release followed by oxygen consumption. The oxygen release in red blood cells was associated with intracellular oxyhaemoglobin oxidation. The oxygen consumption proceeded in parallel with free radical generation, as registered by chemiluminescence, but not to membrane lipid peroxidation. The oxygen consumption was also observed in membrane-free haemolyzates. The order of the organic hydroperoxide-induced reaction of oxygen release with respect to the oxidant (tBHP) was estimated to be 0.9 +/- 0.1 and that of the oxygen consumption reaction was determined to be 2.4 +/- 0.2. The apparent activation energy values of the oxygen release and oxygen consumption were found to be 107.5 +/- 18.5 kJ/mol and 71.0 +/- 12.5 kJ/mol, respectively. The apparent pKa value for the functional group(s) regulating the cellular oxyHb interaction with the oxidant in tBHP-treated red blood cells was estimated to be 6.7 +/- 0.2 and corresponded to that of distal histidine protonation in haemoprotein. A strong dependence of tBHP-induced lipid peroxidation on the oxygen concentration in a red blood cell suspension was observed (P50 = 32 +/- 3 mmHg). This dependence correlated with the oxygen dissociation curve of cellular haemoglobin. The order of the membrane lipid peroxidation reaction with respect to oxygen was found to be 0.5 +/- 0.1. We can conclude that the intensity of the biochemical process of membrane lipid peroxidation in tBHP-exposed erythrocytes is controlled by small changes in such physiological parameters as the oxygen pressure and oxygen affinity of cellular haemoglobin. Neither GSH nor oxyhaemoglobin oxidation depended on oxygen pressure.     

Correlation of the neutron yield anisotropy with the electrical characteristics of a plasma focus discharge

The anisotropy of the yield and energy of neutrons generated in a small-size plasma focus chamber with a total neutron yield of about 4 × 10⁹ DD neutrons per shot was investigated experimentally. The neutrons were recorded using scintillation detectors on a 3-m-long flight base. The measurements were performed at the angles 0° and 90° with respect to the chamber axis. The maximum neutron energy measured by the time-of-flight method at the angles 0° and 90° was found to be 2.8 and 2.5 MeV, respectively. The measured anisotropy of the neutron yield was in the range 1.15–1.88. The integral DD neutron yield of the source was measured using the activation method (by activating silver isotopes). It is found that the neutron yield and the yield anisotropy depend linearly on the discharge current jump ΔI at the instant of neutron generation.     

Thermal degradation mechanisms of wood under inert and oxidative environments using DAEM methods

The pyrolytic behavior of wood is investigated under inert and oxidative conditions. The TGA experiment is given a temperature variation from 323 to 1173 K by setting the heating rate between 5 and 40 K/min. The results of DTG curves show that the hemicellulose shoulder peak for birch is more visible under inert atmosphere due to the higher content of reactive xylan-based hemicellulose (mannan-based for pine). When oxygen presents, thermal reactivity of biomass (especially the cellulose) is greatly enhanced due to the acceleration of mass loss in the first stage, and complex reactions occur simultaneously in the second stage when char and lignin oxidize. A new kinetic model is employed for biomass pyrolysis, namely the distributed activation energy model (DAEM). Under inert atmosphere, the distributed activation energy for the two species is found to be increased from 180 to 220 kJ/mol at the solid conversion of 10-85% with the high correlation coefficient. Under oxidative atmosphere, the distributed activation energy is about 175-235 kJ/mol at the solid conversion of 10-65% and 300-770 kJ/mol at the solid conversion of 70-95% with the low correlation coefficient (below 0.90). Comparatively, the activation energy obtained from established global kinetic model is correspondingly lower than that from DAEM under both inert and oxidative environments, giving relatively higher correlation coefficient (more than 0.96). The results imply that the DAEM is not suitable for oxidative pyrolysis of biomass (especially for the second mass loss stage in air), but it could represent the intrinsic mechanism of thermal decomposition of wood under nitrogen better than global kinetic model when it is applicable.     

Ultra-structural organisation of cell wall polymers in normal and tension wood of aspen revealed by polarisation FTIR microspectroscopy

Polarisation Fourier transform infra-red (FTIR) microspectroscopy was used to characterize the organisation and orientation of wood polymers in normal wood and tension wood from hybrid aspen (Populus tremula × Populus tremuloides). It is shown that both xylan and lignin in normal wood are highly oriented in the fibre wall. Their orientation is parallel with the cellulose microfibrils and hence in the direction of the fibre axis. In tension wood a similar orientation of lignin was found. However, in tension wood absorption peaks normally assigned to xylan exhibited a 90° change in the orientation dependence of the vibrations as compared with normal wood. The molecular origin of these vibrations are not known, but they are abundant enough to mask the orientation dependence of the xylan signal from the S₂ layer in tension wood and could possibly come from other pentose sugars present in, or associated with, the gelatinous layer of tension wood fibres.     

Solid-State NMR Investigation of Bio-chars Produced from Biomass Components and Whole Biomasses

Bio-char is a by-product from thermochemical treatment of biomass and has been identified as an energy condensed product with a comparable heating value as commercial coal. However, the combustion of such solid product as an energy resource is only a preliminary application. It is highly possible to convert bio-char, which always has a condensed aromatic and porous structure to various high-value products. The investigations of the structures and formation pathways for the bio-char are very important to any future applications. In this study, six different biomass components, including cellulose, lignin, and tannin, and three whole biomasses—pine wood, pine residue, and pine bark—have been used to produce bio-char at 400, 500, and 600 °C. Solid-state NMR and FT-IR have been employed in this study to characterize the structures for the bio-chars. The results indicated that the bio-chars produced from lignin contained some methoxyl groups, and the bio-chars produced from tannin contained significantly higher amount of phenolic hydroxyl groups. Compared to the bio-chars produced from pine wood and residue, the bio-chars produced from pine bark contained more aromatic C–O bonds, and aliphatic C–O and C–C bonds, which may be due to the significantly higher amount of lignin and tannin in the pine bark. However, the elevated amounts of aromatic C–O and aliphatic C–O and C–C bonds in the bio-chars from pine bark appeared to be completely decomposed at 600 °C.     

Identification and quantification of radical reaction intermediates by electron spin resonance spectrometry of laccase-catalyzed oxidation of wood fibers from beech (Fagus sylvatica)

During laccase-catalyzed oxidation of beech wood fibers in an aqueous suspension, phenoxy radicals were detected in steady-state concentrations by electron-spin resonance (ESR) spectrometry of the suspension liquid, suggesting that colloidal lignin functions as a mediator between laccase and the fiber lignin matrix. Phenoxy radicals were observed directly, whereas ESR spin-trapping techniques gave no evidence for reduced oxygen species, such as the superoxide or hydroxyl radical. A reaction mechanism involving parallel direct oxidation of the lignin on fiber surfaces and a phenol/phenoxy cyclic mediator process in the suspension liquid could accordingly describe laccase-catalyzed oxidation of beech wood fibers. Cytochrome c assays for detection of superoxide in systems involving lignin oxidized by oxidoreductases should be used with caution, as cytochrome c may be reduced by species other than superoxide. Received: 24 March 1997 / Received revision: 27 May 1997 / Accepted: 1 June 1997     

Heat stabilization dependence on redox state of cytochrome cd1 oxidase from Pseudomonas aeruginosa

The irreversible thermal denaturation of cytochrome cd₁ oxidase from $\text{P.}\text{aeruginosa}$ as a function of the oxidation-reduction states of its hemes was observed with a differential scanning calorimeter. Upon full reduction of the four hemes, the apparent denaturation temperature decreases by about 10° and the denaturation enthalpy decreases slightly: oxidized, 5.9 cal/gm; reduced, 5.4 cal/gm. At pH 7.5, the first order rate constants for denaturation at 90°C are: reduced, 33 × 10^?3s^?1; oxidized, 3 × 10^?3s^?1. Thus, oxidation of the hemes reuults in heat stabilization of the cytochrome oxidase. The activation energy for denaturation of fully reduced oxidase, 53 kcal/mol, is less than that for fully oxidized protein (73 kcal/mol).     

On the chemiluminescence in the oxidation of tetravalent uranium to the uranyl ion by dimethyldioxirane

The reaction of the tetravalent uranium [U(IV)] with dimethyldioxirane (DMD) in strongly acidic water–acetone solutions is accompanied by chemiluminescence (CL) in the visible (Vis) and infra‐red (IR) regions. At least three independent reaction pathways are involved in the U(IV)–DMD oxidation: the first entails the non‐chemiluminescent oxidation of U(IV) to the uranyl ion (UO₂²⁺); the second involves the catalytic decomposition of DMD by U(IV) to afford singlet oxygen, as manifested by its characteristic IR‐CL; and in the third process, slow Vis‐CL (510–540 nm) is emitted, following DMD consumption. Copyright © 2002 John Wiley & Sons, Ltd.     

Dilute sulfuric acid cycle spray flow-through pretreatment of corn stover for enhancement of sugar recovery

A cycle spray flow-through reactor was designed and used to pretreat corn stover in dilute sulfuric acid medium. The dilute sulfuric acid cycle spray flow-through (DCF) process enhanced xylose sugar yields and cellulose digestibility while increasing the removal of lignin. Within the DCF system, the xylose sugar yields of 90–93% could be achieved for corn stover pretreated with 2% (w/v) dilute sulfuric acid at 95 °C during the optimal reaction time (90 min). The remaining solid residue exhibited enzymatic digestibility of 90–95% with cellulase loading of 60 FPU/g glucan that was due to the effective lignin removal (70–75%) in this process. Compared with flow-through and compress-hot water pretreatment process, the DCF method produces a higher sugar concentration and higher xylose monomer yield. The novel DCF process provides a feasible approach for lignocellulosic material pretreatment.     

Characterization of Cold- and High-Pressure-Active Polygalacturonases from a Deep-Sea Yeast,Cryptococcus liquefaciens Strain N6

A deep-sea yeast, Cryptococcus liquefaciens strain N6, produces two polygalacturonases, p36 and p40 (N6-PGases). These N6-PGases were highly active at 0–10 °C in comparison to a PGase from Aspergillus japonicus. The hydrolytic activity of these N6-PGases remained almost unchanged up to a hydrostatic pressure of 100 MPa at 24 °C with a very small activation volume of ?1.1 ml/mol. At 10 °C, however, the activation volume increased to 3.3 or 5.4 ml/mol (p36 and p40, respectively), suggesting that the enzyme–substrate complexes can expand at their transition states. We speculate that such a volume expansion upon forming the enzyme–substrate complexes contributes to decreasing the activation energy for hydrolysis. This can account for the high activity of N6-PGases at low-temperature.     

Rhamnogalacturonan‐I is a determinant of cell–cell adhesion in poplar wood

The molecular basis of cell–cell adhesion in woody tissues is not known. Xylem cells in wood particles of hybrid poplar (Populus tremula × P. alba cv. INRA 717‐1B4) were separated by oxidation of lignin with acidic sodium chlorite when combined with extraction of xylan and rhamnogalacturonan‐I (RG‐I) using either dilute alkali or a combination of xylanase and RG‐lyase. Acidic chlorite followed by dilute alkali treatment enables cell–cell separation by removing material from the compound middle lamellae between the primary walls. Although lignin is known to contribute to adhesion between wood cells, we found that removing lignin is a necessary but not sufficient condition to effect complete cell–cell separation in poplar lines with various ratios of syringyl:guaiacyl lignin. Transgenic poplar lines expressing an Arabidopsis thaliana gene encoding an RG‐lyase (AtRGIL6) showed enhanced cell–cell separation, increased accessibility of cellulose and xylan to hydrolytic enzyme activities, and increased fragmentation of intact wood particles into small cell clusters and single cells under mechanical stress. Our results indicate a novel function for RG‐I, and also for xylan, as determinants of cell–cell adhesion in poplar wood cell walls. Genetic control of RG‐I content provides a new strategy to increase catalyst accessibility and saccharification yields from woody biomass for biofuels and industrial chemicals.     

Respiratory gas exchanges of termites from the Sabah (Borneo) assemblage

Abstract.Oxygen uptake and carbon dioxide release at 28°C were determined in worker castes of twenty-six species of forest termites from the Danum Valley Conservation Area, south-east Sabah, by Warburg manometry. Metabolic rate varied inversely with body weight in a suite of soil-, wood/soil- and wood-feeding species, giving a slope (in a log–log plot) of – 0.63. However, a number of large species, actively foraging forms such as Macrotermes malaccensis, M. gilvus, Havilanditermes atripennis and Hospitalitermes hospitalis, but also the wood-feeding Schedorhinotermes sarawakensis, showed an oxygen consumption greater than expected for their body weight. Rates of methane emission were above 0.100 μmol g^–1 h^–1 in seventeen species, with very high fluxes in two wood/soil-feeders, Termes borneensis (0.546 ± 0.163 μmol g^–1 h^–1) and Prohamitermes mirabilis (0.303 ± 0.123 μmol g^–1 h^–1). Of the fifteen remaining species, seven were soil-feeders, five were wood-feeders, two were wood/litter-feeders and a single species fed on lichen and moss. Low or negligible CH₄ emissions (< 0.100 μmol g^–1 h^–1) were observed in three other species, all wood-feeders. An apparent respiratory quotient (RQ_app) was calculated using xCO₂ and xO₂ (corrected for methane emission, but not hydrogen). Mean RQ_app was at or above 1.00 in eleven species and between 0.95 and 1.00 in a further six species, the two sets of species together representing all trophic groups, including lichen-feeders. This is argued to be consistent with carbohydrate being the principal substrate supporting respiration.     

Effect of forest thinning and wood quality on the short-term wood decomposition rate in a <Emphasis Type="Italic">Pinus tabuliformis</Emphasis> plantation

The effects of forest thinning and wood quality on wood decomposition in the mineral soil were investigated in a Chinese pine (Pinus tabuliformis Carriére) plantation in northern China by measuring mass loss and changes in wood properties (carbohydrates, lignin and nitrogen (N) concentrations) in wood stakes of two tree species—loblolly pine (Pinus taeda L.) and trembling aspen (Populus tremuloides Michx.). Stakes were inserted to a 20 cm soil depth in stands with three thinning levels (low, moderate, and heavy) and an unharvested control and removed after 1 year. There were significant differences in stake mass loss among the treatments. The species effect on the stake mass loss was marginally significant. Wood N content of both species increased during decomposition in all thinning treatments, and was only correlated with aspen mass loss. Wood properties of stakes placed in each stand before insertion (t?=?0) were similar, except for pine lignin concentration and aspen lignin: N ratio, but neither had any effect on thinning treatment results. Lignin concentration increased and carbohydrate concentration decreased in both aspen and pine wood stakes during decomposition across all thinning treatments, which suggests that brown-rot fungi are dominant wood-decomposers on our study site. We conclude that thinning has a significant influence on the wood decomposition in the mineral soil of this Chinese pine plantation.     

The fermentation stoichiometry of Thermotoga neapolitana and influence of temperature,oxygen, and pH on hydrogen production

The hyperthermophilic bacterium, Thermotoga neapolitana, has potential for use in biological hydrogen (H₂) production. The objectives of this study were to (1) determine the fermentation stoichiometry of Thermotoga neapolitana and examine H₂ production at various growth temperatures, (2) investigate the effect of oxygen (O₂) on H₂ production, and (3) determine the cause of glucose consumption inhibition. Batch fermentation experiments were conducted at temperatures of 60, 65, 70, 77, and 85°C to determine product yield coefficients and volumetric productivity rates. Yield coefficients did not show significant changes with respect to growth temperature and the rate of H₂ production reached maximum levels in both the 77°C and 85°C experiments. The fermentation stoichiometry for T. neapolitana at 85°C was 3.8 mol H₂, 2 mol CO₂, 1.8 mol acetate, and 0.1 mol lactate produced per mol of glucose consumed. Under microaerobic conditions H₂ production did not increase when compared to anaerobic conditions, which supports other evidence in the literature that T. neapolitana does not produce H₂ through microaerobic metabolism. Glucose consumption was inhibited by a decrease in pH. When pH was adjusted with buffer addition cultures completely consumed available glucose. © 2009 American Institute of Chemical Engineers Biotechnol. Prog., 2009     

Temperature-jump kinetics of the dC-G-T-G-A-A-T-T-C-G-C-G double helix containing a G . T base pair and the dC-G-C-A-G-A-A-T-T-C-G-C-G double helix containing an extra adenine

The kinetics of helix formation were investigated using the temperature-jump technique for the following two molecules: dC-G-T-G-A-A-T-T-C-G-C-G, which forms a double helix containing a G·T base pair(the G·T 12-mer), and dC-G-C-A-G-A-A-T-T-C-G-C-G, which forms a double helix containing an extra adenine (the 13-mer). When data were analyzed in an all-or-none model, the activation energy for the helix association process was 22 ± 4 kcal/mol for the G·T 12-mer and 16 ± 7 kcal/mol for the 13-mer. The activation energy for the helix-dissociation process was 68 ± 2 kcal/mol for the G·T 12-mer and 74 ± 3 kcal/mol for the 13-mer. Rate constants for recombination were near 10⁵s^?1M^?1 in the temperature range from 32 to 47°C; for the dissociation process, the rate constants varied from 1s^?1 near 32°C to 130s^?1 near 47°C. Possible effects of hairpin loops and fraying ends on the above data are discussed.     

Analysis of lignocelluloses and lignins from Arundo donax L. and Miscanthus sinensis Anderss., and hydroliquefaction of Miscanthus

In a comparative investigation of the chemical composition of Arundo donax L. and Miscanthus sinensis Anderss. the following experiments were performed: ash determination and ash characterization by energy dispersive X-ray analysis; determination of solubility in cyclohexane/ ethanol, hot water, 1% hydrochloric acid and sodium hydroxide; C, H and N determination; determination of Klason lignin and acid soluble lignin content; sulfuric acid hydrolysis followed by borate complex ion exchange chromatography of the monomeric sugars; isolation of milled wood lignins (MWL) and dioxane lignins (DIL) and their analysis by C, H, and OMe determination; quantitative FTIR spectroscopy of MWL; recording the molecular weight distribution curves using high performance size exclusion chromatography (HPSEC); calculation of average molecular weights, such as M_w and M_n; calculation of the heating values of the lignocellulosics and their components. The quantitative composition of the lignin from the three basic phenylpropane units is presented.M. sinensis was submitted to hydroliquefaction. The conversion process yielded 35% of a net product oil (NPO) with low oxygen content (11%), low viscosity (10⁻² NS m⁻²), low asphaltene content (3·5%) low molecular weight (M_w 200) and with a specific gravity of c. 0·93 g cm⁻³. The NPO has a heating value of 39·4 MJ kg⁻¹ and contains 55% of the carbon of the starting material and 59% of the combined heating value from the biomass and the hydrogen used for hydroliquefaction. The process yields 28% water which contains 58% of the original oxygen of the biomass. The process gives rise to 9 g solids and 32–35 g gases, whose energy content can easily be recovered.     

Properties of o-diphenol: O2 oxidoreductase from Musa cavendishii

Banana fruits (Musa cavendishii) contain a non-particulate o-diphenol: O₂ oxidoreductase that has been partially purified. The enzyme is inactivated during its catalytic action with a half time of 135 sec. The activation energy for the catalytic process is 4445 cal/mol. Classical thermal denaturation takes place only above 70°, with an entropy change of about 190 cal/mol °K at pH 6·0.