TG-MS analysis for thermal decomposition of cellulose under different atmospheres

Cellulose degradation under inert (He) and oxidative atmospheres (7% O₂, 20% O₂ and 60% O₂) was investigated through thermogravimetric (TG) equipped with mass spectroscopy (MS) system. Two mass loss stages were observed for cellulose degraded under oxidative atmosphere, where the first mass loss stage is close to that under inert atmosphere, and the second one designated to char oxidation was enhanced by the increased oxygen concentration. The evolution of prominent volatiles including furfural, acetone, 2/5-hydromethyl furfural, formaldehyde, CO and CO₂ was examined considering the influence of oxygen concentration. The plateau for mass loss and evolution of some volatiles leads to the difficulty to determine the division-point for the two stages. However, the fitting parameter (Dev%) around 5% confirms the applicability of the proposed two-stage kinetic model accounting for partial pressure of oxygen.     

Mechanism for the depolymerization of cellulose under alkaline conditions

The mechanism for the hydroxyl-radical-induced depolymerization of cellulose under alkaline conditions in air was investigated using density functional theory at the B3LYP/6-31+G(d,p) level as well as electron transfer theory. The pathway for the depolymerization of cellulose was obtained theoretically and H abstraction from the C(3) atom of the pyran ring during the cleavage of the glucosidic bond was found to be the rate-limiting step due to its high energy barrier (16.81 kcal/mol) and low reaction rate constant (4.623?×?10⁴ mol L^?1 s^?1). Calculations of the electron transfer between O₂ and the saccharide radical performed with the HARLEM software package revealed that following the H abstraction, the oxygen molecule approaches C(2) on the saccharide radical and obtains an electron from the radical, even though no bond forms between the oxygen molecule and the radical. The rate constant for electron transfer could be as high as 1.572?×?10¹¹ s^?1. Furthermore, an enol intermediate is obtained during the final stage of the depolymerization.     

On hydrolysis of cellulose and nitrocellulose under sulfate-reducing conditions

Hydrolysis of cellulose and nitrocellulose in the presence of sulfate-reducing bacterium Desulfovibrio vulgaris 1388 was studied. The cellulolytic activity was found in culture medium after D. vulgaris growth (1.45 ± 0.04 nmol/mg protein/min). In the presence of cellulose or nitrocellulose the activity accounted for 4.82 ± 0.23 and 2.35 ± 0.11 nmol/mg protein/min, respectively. The initial rates of cellulose decomposition were measured using toluene to inhibit the microbial uptake of hydrolysis product—glucose. It was established that 7.6% of initially added cellulose was hydrolyzed in 3 weeks. The highest rate of glucose accumulation was observed on day 10 (2.13 μmol glucose/g dry-wt cellulose/h). At the same time only 3.3% of nitrocellulose was hydrolyzed, since nitro-groups of polymer exerted negative influence on the hydrolysis process. It is supposed that nonspecific extracellular hydrolases participate in the polymers hydrolysis.     

Quantitative colorimetric measurement of cellulose degradation under microbial culture conditions

We have developed a simple, rapid, quantitative colorimetric assay to measure cellulose degradation based on the absorbance shift of Congo red dye bound to soluble cellulose. We term this assay “Congo Red Analysis of Cellulose Concentration,” or “CRACC.” CRACC can be performed directly in culture media, including rich and defined media containing monosaccharides or disaccharides (such as glucose and cellobiose). We show example experiments from our laboratory that demonstrate the utility of CRACC in probing enzyme kinetics, quantifying cellulase secretion, and assessing the physiology of cellulolytic organisms. CRACC complements existing methods to assay cellulose degradation, and we discuss its utility for a variety of applications.     

Selective reactions of nucleobases under biological conditions.

Pentacyanonitrosylferrate/II/ complex reacts under biological conditions (pH= 7.5, T= 25-40 degrees C, dilute solution) selectively with nucleobases. The reaction with adenine and guanine probably leads to nitrosation. A new compound formed in the reaction with adenine is prepared; both this compound and the pentacyanonitrosylferrate/II/ inhibits the multiplication of Escherichia coli.     

Chemical stability of 2-arachidonylglycerol under biological conditions

Recent evidence indicates that 2-arachidonylglycerol (2-AG) is a potent and specific ligand for the central and peripheral cannabinoid receptors. Therefore, the chemical stability of this molecule under biological conditions is of interest. A method for the isolation and detection of 2-AG using HPLC with evaporative light scattering detection is described. The method provides an extraction recovery from aqueous media of 78%, and a limit of detection of 60 ng on column. Incubation of 2-AG in culture medium or biological buffers indicated that it is stable to oxidation and ester hydrolysis for up to 6 h at 37 degrees C. However, gradual disappearance of the compound was noted due to adherence to glass and plastic surfaces. During incubation in RPMI culture medium, 2-AG rearranged to 1(3)-arachidonylglycerol (1(3)-AG) in a first order process with a half-life of 10 min in the absence of serum and 2.3 min in the presence of 10% fetal calf serum. Further studies indicated that the acyl migration reaction is base catalyzed (k(cat)=78,000/min M), and that the reaction is affected slightly by changes in buffer (Tris) concentration and not at all by changes in ionic strength. The results indicate that 2-AG is readily converted to 1(3)-AG under conditions commonly used to study receptor-ligand interactions, findings that have significant implications for the interpretation of relative ligand potency between the two isomers.     

Studies on decomposition ofPhragmites australis leaves under laboratory conditions

Summary The decomposition ofPhragmites leaves was studied under experimental conditions in vessels during 147 days. This process was compared in vessels filled with (a) lake water, (b) lake water and sediment, and (c) lake water, sediment and plant material.In the course of time the ash-free dry weight and the N and C concentration in the plant material decreased gradually to, respectively, 64, 54 and 66% of the initial values. The P concentration fluctuated due to accumulation of bacteria and their excretion products. Almost all C and N which had disappeared from the plant material during the first 100 days of incubation was recovered in the water. Subsequently, these nutrients accumulated in the sediment. Only 10% of the C and N in the water was soluble (<0.33 m). Ortho-P increased substantially from 60 to 100 days of incubation in the vessels (b) and (c), possibly given off by the sediment or originating from decaying algae and bacteria. Only a minor part of the plant-P was recovered as ortho-P in the water.The effect of the decomposing plant material on the diversity within the microscopical primary producers was studied using paper chromatography of the pigments. The changes in bacterial numbers were followed by epifluorescence microscopy.     

Stabilization of nanoparticles under biological assembly conditions using peptoids

Sequence-specific polymers are proving to be a powerful approach to assembly and manipulation of matter on the nanometer scale. This has been most impressive in the case of DNA, and progress has been made toward templating inorganic nanoparticles using DNA nanostructures. One obstacle to this progress is that inorganic nanomaterials are often incompatible with DNA assembly conditions, which involve aqueous solutions high in either or both monovalent and divalent salt. Synthetic oligopeptide ligands have been shown by others to improve nanoparticle stability in high concentrations of monovalent salt. Ligands that are peptoids, or sequence-specific N-functional glycine oligomers, allow precise and flexible control over the arrangement of binding groups, steric spacers, charge, and other functionality. We have synthesized short peptoids that can prevent the aggregation of gold nanoparticles in high-salt environments including divalent salt, and allow coadsorption of a single DNA molecule. This degree of precision and versatility is likely to prove essential in bottom-up assembly of nanostructures and in biomedical applications of nanomaterials.     

Synergy of two thermophiles enables decomposition of poly-epsilon-caprolactone under composting conditions

The ultimate degradation (i.e. complete mineralization) of biodegradable polymers proceeds through hydrolysis to the production of degradation intermediates (primary degradation) that are then taken into the microbial cell and further degraded to CO2 and water. We first isolated thermophilic actinomycete (Streptomyces thermonitrificans PDS-1), which has the activity of ultimate degradability, from compost in which poly-epsilon-caprolactone (PCL) degraded vigorously. We next tried to investigate the detailed mechanisms of degradation of the PCL in compost by developing a new experimental method in which isolated microorganisms are used to inoculate sterilized compost raw materials containing PCL. It was confirmed that the ultimate degradation of PCL could not be achieved by the action of the strain PDS-1 alone, and that a supplementary microorganism (Bacillus licheniformis HA1) isolated from compost utilizes the degradation intermediates and also increases the activity of the other primary microorganism (PDS-1) by adjusting the pH. We could thus show experimental proof of synergy between two thermophiles in the ultimate degradation of a biodegradable polymer in compost.     

不同水分条件下杨树-玉米复合系统凋落物分解特性

为探讨水分变化对农林复合生态系统凋落物分解特性的影响,以河西走廊杨树（Populus）-玉米（Zea mays）凋落物为研究对象,设置正常水分（9200 m³/hm²,对照）,轻度干旱胁迫（减少15%,7800 m³/hm²）,中度干旱胁迫（减少30%,6400 m³/hm²）3种不同水分处理条件,采用分解袋法研究了不同水分条件下杨树叶和玉米秸秆的质量残留率、分解速率和养分含量变化特征。结果表明：（1）随着干旱胁迫的加剧,两种凋落物的质量残留率均增加,而分解速率降低。经过164 d的分解后,杨树叶和玉米秸秆的质量残留率分别为70.43%-77.49%、63.55%-68.29%。分析表明：水分和时间对各类型凋落物的质量残留率均有极显著的影响（P<0.001）,但二者的交互作用不显著（P>0.05）;干旱胁迫显著降低了玉米秸秆的分解速率,但杨树叶的分解速率却只是在中度干旱胁迫下显著降低（P<0.05）。对于不同类型凋落物而言,分解速率表现为玉米秸秆>杨树叶。（2）两种类型凋落物的氮（N）残留率在分解过程中表现为降低的趋势,但随着干旱程度的加大,N的残留率增加,表明水分抑制了N的释放过程。分解164d后,同一类型凋落物不同水分条件下的N残留率均存在显著差异。对于同一水分条件下不同凋落物而言,玉米秸秆的N残留率最低,而杨树叶最高。总的来说,水分降低对干旱区农林复合系统内凋落物的分解和氮元素含量具有显著的抑制作用。     

不同土壤培肥措施下农田有机物分解的生态过程

通过在河北曲周实验站的田间试验,研究了4种不同土壤培肥措施条件下农田生态系统中几种主要土壤生物随有机物分解的变化规律、有机物的分解及其主要影响因素。研究结果表明：除土壤线虫外,其他几种主要的土壤生物的分布规律基本上是堆肥区〉原貌区〉对照区〉化肥区,与施入的有机物（小麦秸秆）的分解规律一致。在受人为扰动的堆肥区、化肥区和对照区土壤中,细菌占绝对优势,而在未开垦的原貌区中,真菌起着重要作用。 在有机物分解初期,土壤微生物能比较快地迁移到秸秆表面,秸秆表面的生物数量最多的是细菌,随着细菌的数量增加,原生动物数量亦呈现增加趋势,蚯蚓数量增多,而线虫的数量则减少。而有机物分解后期,真菌的数量逐渐减少,蚯蚓的数量也呈下降趋势,有机物的分解速度减慢。通过灰色关联度分析,9种外界因素（生物因素和环境因素）对小麦秸秆分解作用的相对重要程度排序：土壤温度（0．844）〉蚯蚓（0．777）〉真菌（0．764）〉全氮（0．754）〉线虫（0．753）〉有机质（0．742）〉细菌（O．738）〉原生动物（0．693）〉土壤含水量（0．661）,其中土壤温度和蚯蚓是影响土壤有机物分解的最重要的两个因素。     

Analysis for temporal gene expressions under multiple biological conditions

Temporal gene expression data are of particular interest to researchers as they contain rich information in characterization of gene function and have been widely used in biomedical studies and early cancer detection. However, the current temporal gene expressions usually have few measuring time series levels; extracting information and identifying efficient treatment effects without temporal information are still a problem. A?dense temporal gene expression data set in bacteria shows that the gene expression has various patterns under different biological conditions. Instead of analyzing gene expression levels, in this paper we consider the relative change-rates of gene in the observation period. We propose a non-linear regression model to characterize the relative change-rates of genes, in which individual expression trajectory is modeled as longitudinal data with changeable variance and covariance structure. Then, based on the parameter estimates, a chi-square test is proposed to test the equality of gene expression change-rates. Furthermore, the Mahalanobis distance is used for the classification of genes. The proposed methods are applied to the data set of 18?genes in P. aeruginosa expressed in 24?biological conditions. The simulation studies show that our methods perform well for analysis of temporal gene expressions.     

Modelling MSW decomposition under landfill conditions considering hydrolytic and methanogenic inhibition

A landfill typically progresses through a series of microbial degradation phases, in which hydrolysis, production and consumption of fermentation products, such as fatty acids, and methane formation play important roles. For ultimate degradation of the waste, stable methanogenic conditions have to be attained, and maintained for sufficient time. Using experimental data from 100-L landfill simulation reactors containing municipal solid waste from a residential area, a distributed model, which accounts for vertical water flow, was developed. As a first step, the waste was divided into two fractions: readily degradable and recalcitrant waste. Secondly, the general hydrolysis of the recalcitrant waste was accounted for by including a specific, well-defined chemical substance in the model that generally occurs in Municipal Solid Waste (MSW) and is hydrolysed before its further degradation to methane. For this purpose we chose diethyl phthalate and its hydrolysis product monoethyl phthalate, for which leachate data are available from the reactors. The model indicated that inhibition of the hydrolytic and methanogenic processes occurred during␣the acidogenic phase and that it could be overcome either by improving the chemical environment or by the complete oxidation of the inhibiting, i.e. the easily degraded, fraction of the waste. The generality of the model was confirmed by the patterns of the phthalate di- and monoester transformations obtained. The validity of the model was further confirmed using experimental data from parallel reactors, which were subjected to either leachate exchange with an already methanogenic reactor or to initial aeration to force the reactor into stable methanogenic conditions.     

Enzymatic hydrolysis of cellulose: Evaluation of cellulase culture filtrates under use conditions

Culture filtrates from three mutant strains of Trichoderma reesei grown on lactose and on cellulose were compared under use conditions on four cellulose substrates. Cellulose culture filtrates contained five to six times as much cellulase as lactose culture filtrates. Unconcentrated cellulose culture filtrates produced up to 10% sugar solutions from 15% cellulose in 24 h. Specific activity in enzyme assays and efficiency in saccharification tests were low for enzymes from all the mutants. Over a wide range the percent saccharification of a substrate in a given times was directly proportional to the logarithm of the ratio of initial concentrations of enzyme and substrate. As a result of this, dilute enzyme is more efficient than concentrated enzyme, but if high sugar concentrations are desired, very large quantities of enzyme are required. Since the slopes of these plots varied, the relative activity of cellulase on different substrates may be affected by enzyme concentration.