Thermal Emulsion Polymerization without any Conventional Initiators and Emulsifiers

Stable poly(styrene-co-sodium styrene sulfonate) (P(St-NaSS) nanoparticles with broader size distribution were synthesized by thermal emulsion polymerization without any conventional initiators and emulsifiers. The obtained polymer nanoparticles have higher ξ potential, and the particle sizes have broad distribution. The stability of polymer particles originated from the addition of small amounts of ionic comonomer, NaSS, which can act as an emulsifier in somewhat. The monomer conversion could reach up to about 28 wt% in 48 h, and did not increase by further polymerization when higher polymerization temperature (120 ℃) was employed. This polymerization system may be give some further understand for mechanism of emulsion polymerization.     

Effects of cell-wall acetate,xylan backbone,and lignin on enzymatic hydrolysis of aspen wood

Aspen wood substrates with varying degrees of deacetylation, xylan, and lignin removal have been prepared and submitted to enzymatic hydrolysis with a cellulase/hemicellulase preparation for an extended constant period of hydrolysis. Controlled deacetylation has been achieved by treating wood with various alkali metal hydroxide solutions, at various alkali/wood ratios. It has been found that samples with the same extent of deacetylation produce the same sugar yields upon enzymatic hydrolysis. Increased degree of deacetylation increases the yield of sugars obtained from enzymatic hydrolysis, all other compositional parameters held constant. The acetyl group removal is proportional to the stoichiometric relation between added base and wood acetyl content, i.e., the same number of milliequivalents of base/weight of wood remove the same extent of acetyl groups, regardless of the concentration of the base solution. No cation effects are found among Li, Na, and K alkali hydroxide solutions, suggesting that swelling is not as important a parameter as is the removal of the acetyl groups from the xylan backbone in determining the extent of hydrolyzability of the resulting sample.     

FI－ICP－AES在线稀释间接测定表面活性剂─十二烷基苯磺酸钠

基于十二烷基苯磺酸钠（ＤＢＳ）与无机钠盐在无水乙醇中溶解度的差异，用乙醇选择提取ＤＢＳ，经水适当稀释，通过用ＦＩ－ＩＣＰ－ＡＥＳ测定其中的钠，从而间接测定ＤＢＳ的含量。     

Comparison between the adsorption behaviors of an organic cation and an organic anion on several reversed-phase liquid chromatography adsorbents

Adsorption data of an organic cation (propranololium chloride) and an organic anion (sodium 1-naphthalene sulfonate) were measured by frontal analysis on two RPLC adsorbents, Symmetry-C18 and XTerra-C18, with aqueous solutions of methanol as the mobile phases. The influence of supporting neutral salts on the adsorption behavior of these two ions are compared. The Henry constants are close (H approximately 5). The four sets of isotherm data are all well accounted for using the bi-Moreau model. However, the isotherms of the two ions behave differently at high concentrations. The initial behaviors of all the isotherms are antilangmuirian but remain so in a much wider concentration range for the cation than for the anion, due to its stronger adsorbate-adsorbate interactions on the low-energy adsorption sites. The retention times of both ions increase with increasing concentration of neutral salt in the mobile phase, suggesting the formation of ion-pair complexes, with Cl- for the cation and with Na+ for the anion. The adsorbate-adsorbate interactions vanish in the presence of salt and the bi-Moreau isotherm model tends toward a bi-Langmuir model. Differences in adsorption behavior are also observed between the cation and the anion when bivalent inorganic anions and cations, respectively, are dissolved in the mobile phase. High concentration band profiles of 1-naphthalene sulfonic acid are langmuirian, except in the presence of a trivalent cation, while those of propranolol are antilangmuirian under certain conditions even with uni- or divalent cations.     

TS和PTS单晶体的热刺激电流

测定了双(对甲基磺酸)2,4-己二炔-1,6-二醇酯(TS)及其不同聚合程度TS-PTS混合体和完全聚合的聚合物PTS在100-300K温度范围内的热刺激电流。在沿分子堆砌方向上(对PTS则是大分子链方向)上观察到了它们的热刺激电流,并在相应于它们相变152K和192K处呈现热刺激电流峰。研究了聚合程度对相变的影响,绘制了TS-PTS体系的相图。对另三个热刺激电流峰的归属作了定性解释。     

Strategies to enhance the enzymatic hydrolysis of pretreated softwood with high residual lignin content

Pretreatment of Douglas-fir by steam explosion produces a substrate containing approx 43% lignin. Two strategies were investigated for reducing the effect of this residual lignin on enzymatic hydrolysis of cellulose: mild alkali extraction and protein addition. Extraction with cold 1% NaOH reduced the lignin content by only approx 7%, but cellulose to glucose conversion was enhanced by about 30%. Before alkali extraction, addition of exogenous protein resulted in a significant improvement in cellulose hydrolysis, but this protein effect was substantially diminished after alkali treatment. Lignin appears to reduce cellulose hydrolysis by two distinct mechanisms: by forming a physical barrier that prevents enzyme access and by non-productively binding cellulolytic enzymes. Cold alkali appears to selectively remove a fraction of lignin from steam-exploded Douglas-fir with high affinity for protein. Corresponding data for mixed softwood pretreated by organosolv extraction indicates that the relative importance of the two mechanisms by which residual lignin affects hydrolysis is different according to the pre- and post-treatment method used.     

Mechanism and potential applications of bio-ligninolytic systems in a CELSS

A large amount of inedible plant material, generated as a result of plant growth in a Controlled Ecological Life Support System (CELSS), should be pretreated and converted into forms that can be recycled on earth as well as in space. The main portion of the inedible biomass is lignocellulosic material. Enzymatic hydrolysis of this cellulose would provide sugars for many other uses by recycling carbon, hydrogen, oxygen, and nitrogen through formation of carbon dioxide, heat, and sugars, which are potential foodstuffs. To obtain monosaccharides from cellulose, the protective effect of lignin should be removed. White-rot fungi degrade lignin more extensively and rapidly than other microorganisms.Pleurotus ostreatus degrades lignin effectively, and produces edible and flavorful mushrooms that increase the quality and nutritional value of the diet. This mushroom is also capable of metabolizing hemicellulose, thereby providing a food use of this pentose containing polysaccharide. This study presents the current knowledge of physiology and biochemistry of primary and secondary metabolisms of basidiomycetes, and degradation mechanism of lignin. A better understanding of the ligninolytic activity of white-rot fungi will impact the CELSS Program by providing insights on how edible fungi might be used to recycle the inedible portions of the crops.     

Entrapment and release of sodium polystyrene sulfonate (SPS) from calcium alginate gel beads

The release of sodium polystyrene sulfonate (SPS) from calcium alginate hydrogel beads has been studied. It has been shown that the structure of the cross-linked calcium alginate network is of primary importance in the retention and/or release of the SPS. This has been evidenced by studying the influence of Ca²⁺ concentration, molar masses (M_n) and the ratio of mannuronic acid/guluronic acid components. A minimum in the SPS release is observed in relation with the organization of the network structure. Conditions inducing the organization of a strong gel (e.g. high Ca²⁺ concentration for example) are not always related to a low release. A good control of release is found when a compromise between a well-structured hydrogel and sterical consideration of SPS is reached.     

Spectroscopic studies of water-soluble sulfonated calix[6]arene

Fluorescence and absorption studies of water-soluble sulfonated calix[6]arene (SCX6) are reported. Water-soluble calixarenes are potentially useful as host molecules for luminophores, and studies of their spectroscopic characteristics are therefore crucial. The absorption and fluorescence spectra of these molecules in aqueous solution were collected, analyzed, and compared with 4-hydroxybenzene sulfonate at different pHs. A red shift in the absorption spectrum and a change in the fluorescence spectrum of the calixarenes are observed upon an increase in pH from 2.0 to 13.0. Some of these spectroscopic changes are attributed to intramolecular hydrogen bonding between adjacent hydroxyl groups of SCX6 after proton disassociation. The formation of excimers between phenolic groups in the calixarene molecule is proposed. In addition, inner-filter effects of SCX6 are discussed. These inner-filter effects prove to be a disadvantage for the use of SCX6 as a host molecule for complexation studies by use of fluorescence probes whose absorption spectra overlap with those of calixarenes.     

The Thermokinetics of the Formation Reactions of Cerium(III) n-dodecylbenzene Sulfonate and Cerium(III) Stearate

The thermokinetics of the formation reactions of cerium(III) n-dodecylbenzene sulfonate and cerium(III) stearate are studied by using a microcalorimeter. On the basis of experimental and calculated results, three thermodynamics parameters (the activation enthalpies, the activation entropies, the activation free energies), the rate constant, three kinetic parameters (the activation energies, the pre-exponential constant and the reaction order) and the enthalpies of the reaction of preparing cerium(III) n-dodecylbenzene sulfonate in the temperature range of 20–35°C and cerium(III) stearate in the temperature range of44.6–62.8°C are obtained. The results showed that the title reactions easily took place in the studied temperature. This revised version was published online in July 2006 with corrections to the Cover Date.