Influence of intermolecular entanglements on the glass transition and structural relaxation behaviors of macromolecules. 2. Polystyrene and phenolphthalein poly(ether sulfone)

The effect of entanglements on the glass transition and structural relaxation behaviors has been studied for polystyrene (PS) and phenolphthalein poly(ether sulfone) (PES-C) samples by fast evaporation of the solution of concentrations varying from above the overlapping concentration to far below it, and compared to the results we have studied previously in PC. It has been found that for all the polymers we have studied, in the concentrated solution region, the T-g of the samples obtained from solution are independent of the change of concentration and are very close to that of normal bulk samples, whereas in the dilute solution region the T-g of the samples decrease with the logarithm of decreasing concentration. The critical concentrations that divide the two distinct regions for the three polymers are 0.9% g/mL for PC, 0.1% g/mL for PS, and 1% g/mL for PES-C. The decrease of T-g of the samples is interpreted by the decrease of intermolecular entanglements as the isolation of polymer chains, and the entanglement of polymer chains restrained the mobility of the segments. The structural relaxation behavior of the polymers is also found to be different from that of normal bulk samples. The enthalpies of single-chain samples are lower than that of the bulk ones, which correspond to the lower glass transition temperature; the peaks are lower and broader, and the relaxed enthalpy is much lower as compared to that of bulk samples. In the three polymers we have studied, the influence of change of entanglements on both the decrease in glass transition temperature and relaxed enthalpy is the most significant for PS and the least for PES-C. It is indicated that the interactions in the flexible polymers are weak; thus, the restraint of the entanglements on the mobility of the segments plays a more important role in the flexible polymers, and the change of entanglement in the flexible polymers has a more significant influence on the physical properties.

Reactive blending of polyamide 6,6 and Vectra A

In this paper, blends of Nylon 6,6 with the liquid crystal polymer Vectra A950 are considered; specifically we focused our attention on Nylon 6,6 modifications by interchange reactions that can occur in the melt, as a function of mixing conditions and blend compositions. Two matrix samples have been used, characterised by a slightly different relative amount of amine and carboxylic end groups, being the latter predominant in both cases. The dried polymers Nylon 6,6/Vectra, combined in weight ratios between 95/5 and 50/50, were subjected to reactive blending with different methods (single-screw extruder, Brabender, pyrex reactor). Pure Nylon samples have been also investigated as reference materials. The soluble Nylon 6,6-rich fraction of each blend was separated from the insoluble Vectra-rich one and used for molecular and spectroscopic characterisations. Thermal and morphological analyses, as well as testing of tensile properties, were carried out on the blends. Evidences of the occurrence of interchange reactions are given and the most probable ones are suggested. (C) 2001 Elsevier Science Ltd. All rights reserved.

Influence of entanglements an the glass transition and structural relaxation behaviors of macromolecules. 1. Polycarbonate

We obtained the single-chain polycarbonate sample, by a new fast evaporation method and found that the polycarbonate sample obtained by this method is completely amorphous, while the polycarbonate sample obtained by other methods all have a certain degree of crystallinity. The glass transition temperature (T-g) of the sample decreases with the decreasing of concentration when the concentration of the prepared solution is below the critical value. The critical concentration we obtained from the T-g dependence of concentration is 0.9% g/mL and is in accord with that obtained by viscometry and light scattering methods directly from the solution. The structural relaxation behavior is found also different from that of a normal bulk sample of polycarbonate. The enthalpic peak of the single-chain sample is lower: than that of the bulk one, which corresponds to the lower glass transition temperature. The peak of the single-chain sample is lower and broader, and the relaxed enthalpy is much lower compared with that of the bulk sample. These results have been explained in terms of the effect of entanglement on the mobility of the segments in polymer and the compact conformation in the single-chain sample.

Catalysis of copper-containing transition metal hydrotalcite-like compounds in the phenol hydroxylation with hydrogen peroxide

Hydrotalcite-like compounds containing carbonate ion as the interlayer anion were prepared by coprecipitation under low supersaturation condition by mixing an aqueous solution of metal nitrates with an aqueous solutions of NaOH and Na2CO3, at room temperature, maintaining pH = 8-10 with vigorous stirring, Following the mixing, the resulting heavy slurry was aged at 353 K for 18 h with vigorous stirring, The precipitate was then filtered, washed several times with hot distilled water and dried in air at 353 K overnight, In this way, CuMI AlCO3-HTLcs and M-I AlCO3-HTLcs were synthesized and characterized by means of XRD and IR, The catalysis of the above mentioned HTLcs were investigated in the phenol hydroxylation with H2O2. The results indicated that all of the copper-containing HTLcs had a higher catalytic activity in the reaction, However, those catalysts that did not contain copper had no catalytic activity in this reaction, This means that copper was the active center in the phenol hydroxylation. Meanwhile, the mechanism was also proposed, which could be used to explain the main reason for higher activity for CuCuAlCO3-HTLcs in the phenol hydroxylation and the effect of Mg2+, Zn2+, Co2+, Ni2+ on activity of CuMI AlCO3-HTLcs.

A New Cadinane Sesquiterpene from the Marine Brown Alga Dictyopteris divaricata

A sample of the marine brown alga D. divaricata collected off the coast of Yantai (P. R. China) was dried, powdered, and extracted with the mixture of CHCl3 and MeOH (1: 1, v/v). By a combination of silica gel and Sephadex LH-20 column chromatography and preparative TLC, a new cadinane sesquiterpene 1,4-epoxymuurolan-5 beta-ol (1) was isolated from this species. Its structure was established by detailed MS and NMR spectroscopic analysis, as well as comparison with literature data.

Large-scale recovery of C-phycocyanin from Spirulina platensis using expanded bed adsorption chromatography

C-phycocyanin was purified on a large scale by a combination of expanded bed adsorption, anion-exchange chromatography and hydroxyapatite chromatography from inferior Spirulina platensis that cannot be used for human consumption. First, phycobiliproteins were extracted by a simple, scaleable method and then were recovered by Phenyl-Sepharose chromatography in an expanded bed column. The purity (the A(620)/A(280) ratio) of C-phycocyanin isolated with STREAMLINE (TM) Column was up to 2.87, and the yield was as high as 31 mg/g of dried S. platensis. After the first step, we used conventional anion-exchange chromatography for the purification steps, with a yield of 7.7 mg/g of dried S. platensis at a purity greater than 3.2 and with an A(620)/A(650) index higher than 5.0. The fractions from anion-exchange chromatography with a level of purity that did not conform to the above standard were subjected to hydroxyapatite chromatography, with a C-PC yield of 4.45 mg/g of dried S. platensis with a purity greater than 3.2. The protein from both purification methods showed one absolute absorption peak at 620 nm and a fluorescence maximum at 650 nm, which is consistent with the typical spectrum of C-phycocyanin. SDS-PAGE gave two bands corresponding to 21 and 18 kDa. In-gel digestion and LC-ESI-MS showed that the protein is C-phycocyanin. (c) 2006 Elsevier B.V. All rights reserved.

高原鼢鼠的挖掘行为及其与土壤硬度的关系(英文)

Burrowing behaviors of the plateau zokors ( Myospalax bailely) in relation to soil hardness were investigated by using radio2telemetry at Haibei Alpine Meadow Ecosystem Research Station ,Qinghai , China. The results showed that there were no differences of burrowing behaviors and the efficiencies of the excavating segment between male and female , except the digging duration of the male was longer than that of the female in the same soil. With increase of soil hardness , digging duration in incisors significantly increased , but dried soil mass dug out by the zokors in each bout reduced. Mean-while the field investigation also showed that soil hardness affected the distribution of the zokor.

中国南方热带地区田洋玛珥湖24万年以来的气候变化及湖泊演变

A continuous long (224m) and high-resolution core TY2 was recovered from paleo-maar-lake Tianyang, tropical South China. Based on the diatom records of the upper 130-m core, this paper focuses on exploring climate change and the lake evolution history in tropical South China during the past 240ka. The most typical and unique characteristics of the diatom assemblages is that, Aulacoseira granulata was dominant or absolutely dominant species (80-90%) during most parts of the 130-m core, while Cyclotella stelligera var. tenuis and Fragilaria construens var. venter were subdominant species in only limited parts of the lower and upper core, respectively. Time scale is always the biggest problem for the study of TY2 core, so although diatom is seldom used for establishing time scale, here we attempt this by correlating the diatom-reconstructed temperature sequence with the time scale of ODP core 806B from Equatorial Western Pacific. Verified by the few most reliable ages from TY2 core and the parallel core TYl, a rather reasonable and reliable time scale was established. 01S 7/6 falls at the depth of 100m (ca. 194kaBP), OIS 6/5 at 75m (ca. 132kaBP), OIS 5/4 at 46m (ca. 75kaBP), OIS 4-3 at 35m (ca. 60kaBP). Qualitative and quantitative environmental reconstructions are made on the basis of diatom assemblage ecotype and EDDI dataset. Correlation of diatom-reconstructed temperature and moisture changes of Core TY2 with pollen-reconstructed temperature and rainfall sequence of Core TYl proves that the results are quite consistent in most periods. Thus the reconstruction results from diatom are quite reliable, and probably have a much higher resolution than pollen results. Combined with lithological and magnetic susceptibility variations, the diatom analysis reveals that, the general climate in tropical South China during the past 240ka was warm and wet. On the time scale of glacial-interglacial, warm and wet, cool and dry are not always synchronous. It was relatively warm-wet during the penultimate interglacial, cool-dry during the penultimate glacial, warm-dry during the last interglacial, and cooler-drier during the last glacial. In contrast, on the time scale of subglacial-subinterglacial scales, warm and dry, cool and wet corresponds very obviously, showing very clear 21-23 ka precession cycle. Analysis also shows that, the water of Tianyang paleo-maar-lake was generally warm, turbulent, turbid, meso-trophic, slightly alkaline, low conductivity and fresh during the past 240 kaBP, with small variations in some parts. Tianyang paleolake experienced shallow to semi-deep lake in OIS7d, open shallow lake in OIS7c-OIS5b, shallow coastal lake in OIS5a-OIS4c, swamp in OIS4b, and then completely dried up in OIS3c. The lake evolution was mainly controlled by temperature and precipitation changes in tropical China. While temperature and precipitation changes were probably controlled by the migrations of monsoon rainband and the evaporation rate, which was in turn controlled by the evolution of East Asian monsoon. Therefore, when the summer monsoon was strongest the climate was warm-dry, when stronger the climate was warm-wet; when the winter monsoon was strongest the climate was cool-dry, stronger cool-wet. This mechanism caused the warm-dry sub interglacial and cool-wet subglacial climate in the tropical South China.

内蒙古草地植被群落生物量的梯度特征研究

Relationship between biology and environment is always the theme of ecology. Transect is becoming one of the important methods in studies on relationship between global change and terrestrial ecosystems, especially for analysis of its driving factors. Inner Mongolia Grassland is the most important in China Grassland Transect brought forward by Yu GR. In this study, changes in grassland community biomass along gradients of weather conditions in Inner Mongolia was researched by the method of transect. Methods of regression about biomass were also compared. The transect was set from Eerguna county to Alashan county (38° 07' 35" ~50° 12' 20" N, 101° 55' 25" -120° 20' 46" E) in Inner Mongolia, China. The sample sites were mainly chosen along the gradient of grassland type, meadow steppe-* typical steppe-*desert steppe-*steppification desert-^desert. The study was carried out when grassland community biomass got the peak in August or September, 2003 and 2004. And data of 49 sample sites was gotten, which included biomass, mean annual temperature, annual precipitation, accumulated temperature above zero, annual hours of sunshine and other statistical and descriptive data. The aboveground biomass was harvested, and the belowground biomass was obtained by coring (30 cm deep). Then all the biomass samples were dried within (80 + 5) °C in oven and weighted. The conclusion is as follows: 1) From the northeast to the southwest in Inner Mongolia, along the gradient of grassland type, meadow steppe-*typical steppe-*desert steppe-*steppification desert-* desert, the cover degree of vegetation community reduces. 2) By unitary regression analysis, biomass is negatively correlated with mean annual temperature, s^CTC accumulated temperature, ^10°C accumulated temperature and annual hours of sunshine, among which mean annual temperature is crucial, and positively with mean annual precipitation and mean annual relative humidity, and the correlation coefficient between biomass and mean annual relative humidity is higher. Altitude doesn't act on it evidently. Result of multiple regression analysis indicates that as the primary restrictive factor, precipitation affects biomass through complicated way on large scale, and its impaction is certainly important. Along the gradient of grassland type, total biomass reduces. The proportion of aboveground biomass to total biomass reduces and then increases after desert steppe. The trend of below ground biomass's proportion to total biomass is adverse to that of aboveground biomass. 3) Precipitation is not always the only driving factor along the transect for below-/aboveground biomass ratio of different vegetation type composed by different species, and distribution of temperature and precipitation is more important, which is much different among climatic regions, so that the trend of below-/aboveground biomass ratio along the grassland transect may change much through the circumscription of semiarid region and arid region. 4) Among reproductive allocation of aboveground biomass, only the proportion of stem in total biomass notably correlates to the given parameters. Stem/leaf biomass ratio decreases when longitude and latitude increase, caloric variables decrease, and variables about water increase from desert to meadow steppe. The change trends are good modeled by logarithm or binomial equations. 5) 0'-10 cm belowground biomass highly correlates to environmental parameters, whose proportion to total biomass changes most distinctly and increases along the gradient from the west to the east. The deeper belowground biomass responses to the environmental change on the adverse trend but not so sensitively as the surface layer. Because the change value of 0~10 cm belowground biomass is always more than that of below 10 cm along the gradient, the deference between them is balanced by aboveground biomass's change by the resource allocation equilibrium hypothesis.

A novel method to synthesize amorphous silica-alumina materials with mesoporous distribution without using templates and pore-regulating agents

In this study, a novel sol-gel method is used to synthesize amorphous silica-alumina materials with a narrow mesoporous distribution and various Si/Al molar ratios without using any templates and pore-regulating agents. During the preparation procedure, only inexpensive inorganic salts were used as raw materials, instead of expensive and harmful alkoxides. The precursor sol was dried at room temperature in a vacuum box kept at 60 mmHg until it began to form the gel. The results of a nitrogen sorption experiment indicate that the synthesized materials with different Si/Al molar ratios have similar mesoporous distributions (within 2-12 nm). Moreover, it was found that the material's pore size distribution remains at a similar value during the heat treatment from room temperature to 550 degreesC. On the basis of the nitrogen sorption, TEM, and AFM characterization results, a formation mechanism of mesopores which accounts for the experimental data is also suggested. This suggested mechanism involves rearrangement of the primary particles during the drying process to form the precursors of the similarly sized mesopores. The synthesized materials were characterized by XRD, thermal analysis (TG/DTA), Al-27 and Si-29 MAS NMR spectroscopy, SEM, TEM, and AFM. The results of Al-27 and 29Si MAS NMR indicate that the distribution of silicon and aluminum in the synthesized materials is more uniform and homogeneous than that in the mixed oxides prepared via the traditional sol-gel method even at high alumina contents. The type and density of the acid sites were studied using pyridine adsorption-desorption FTIR spectroscopy. It was shown that the acidity of the synthesized materials is higher than that of the silica-alumina materials prepared by conventional methods.

Ethanol crossover phenomena and its influence on the performance of DEFC

In the present work, Nafion (R) membrane porosity changes were determined in aqueous ethanol solutions with different concentrations by weighing vacuum-dried and ethanol aqueous solution equilibrated membranes at room temperature. The ethanol crossover rate through Nafion (R)-115 membrane at different temperatures and different concentrations had been investigated in a fuel cell test apparatus by using membrane gets higher as ethanol solution gas chromatography analysis. The experimental results show that the swelling degree of Nafion (R) concentration increases. The ethanol crossover rate increases with ethanol concentration and temperature increment. The single direct ethanol fuel cell (DEFC) tests were carried out to investigate the effect of ethanol concentration on ethanol crossover and consequently, on the open circuit voltage and the cell performance of DEFC. It can be found that ethanol crossover presented a negative effect on the OCV and the cell performance of DEFC. It can also be found that an improved DEFC performance was obtained as temperature increased although the ethanol crossover rate increased with temperature increment. (c) 2005 Elsevier B.V. All rights reserved.