羧甲基纤维素钠水凝胶的制备及其生物降解性研究

用羧甲基纤维素钠(CMC—Na)制得了含水量高达98％的水凝胶，考察了防腐剂、交联剂、无机态氮素、有机态氮素、碳水化合物的加入量以及环境中pH值等因素对生物降解性的影响。结果表明：制备条件不同，水凝胶的生物降解性不同；环境中一定量铵根离子的存在有利于水凝胶的生物降解；在pH=5．2的环境中纤维素酶活性最高，降解程度最大。     

Chlorobiphenyl (PCB) composition of extracts of subsurface soil, superficial dust and air from a contaminated landfill

Samples of 3 matrices (air, superficial dust and subsurface soil) from an aged PCB-containing landfill were extracted and the extracts refined for bioassay. Acetone:hexane extraction was modestly selected for non-planar compounds. Coplanar PCBs and PCDFs were enriched about 2-fold in the subsequent benzene:methylene chloride extracts of the soil. Extract refinement with Florisil slurry and alumina column chromatography did not appreciably change the composition of the extracts. CB 28 (2,4,4′-triCB) dominated in all extracts. The congener composition of soil and air were surprisingly similar, being enriched in tri- and tetraCBs while dust retained higher proportions of congeners with 4 and 5 chlorines. It is postulated that anaerobic dechlorination in the moist subsurface soil depleted the higher chlorinated congeners; more volatile congeners escaped into the atmosphere while moderately chlorinated congeners were trapped in the superficial dust and debris. The refined extracts represent distinct compositions of environmental PCB mixtures suitable for bioassay. Received: 21 November 1995 / Revised: 9 April 1996 / Accepted: 14 April 1996     

Structures and hydration enthalpies of cationized glutamine and structural analogues in the gas phase

The structures of lithiated and sodiated glutamine, both with and without a water molecule, are investigated using experiment and theory. Loss of water from these complexes and from lithiated and sodiated complexes of asparagine methyl ester, asparagine ethyl ester, and glutamine methyl ester is probed with blackbody infrared radiative dissociation experiments performed over a wide temperature range. Threshold dissociation energies, E(o), for loss of a water molecule from these complexes are obtained from master equation modeling of these data. The values of E(o) are 63 +/- 1 and 53 +/- 1 kJ/mol for the lithiated and sodiated glutamine complexes, respectively. These values are similar to those for the nonzwitterionic model complexes and are in excellent agreement with calculated values. In contrast, water binding to the zwitterionic form is calculated to be significantly higher. These results indicate that glutamine in these lithiated and sodiated complexes with a water molecule are nonzwitterionic. Complexes with the asparagine side chain have slightly higher E(o) values than those with the glutamine side chain, a result consistent with more effective solvation of the metal ion due to the slightly longer side chain of glutamine. Calculations indicate that lithiated and sodiated glutamine are nonzwitterionic, with the metal ion interacting with the amine nitrogen and carbonyl oxygen from the amino acid backbone and the amide oxygen of the side chain. Addition of a water molecule does not affect the lowest-energy structure of lithiated glutamine, whereas, for sodiated glutamine, the lowest-energy zwitterionic and nonzwitterionic structures are essentially isoenergetic.     

Synthesis of pisiferol revisited; control of stereochemistry in an intramolecular Diels-Alder reaction

Thermolysis of 4(X=H) gives 6a and 6b(X=H) in a ratio of 1:4 whereas 4 (X=SO₂Ph) gives more of the trans-ring junction product 6a(X=SO₂Ph) suitable for the synthesis of pisiferol [ratio 6a : 6b(X=SO₂Ph) = 1.5:1].     

Binding energies of water to sodiated valine and structural isomers in the gas phase: the effect of proton affinity on zwitterion stability

The structures of valine (Val) and methylaminoisobutyric acid (Maiba) bound to a sodium ion, both with and without a water molecule, are investigated using both theory and experiment. Calculations indicate that, without water, sodiated Val forms a charge-solvated structure in which the sodium ion coordinates to the nitrogen and the carbonyl oxygen (NO-coordination), whereas Maiba forms a salt-bridge structure in which the sodium ion coordinates to both carboxylate oxygens (OO-coordination). The addition of a single water molecule does not significantly affect the relative energies or structures of the charge-solvated and salt-bridge forms of either cluster, although in Maiba the mode of sodium ion binding is changed slightly by the water molecule. The preference of Maiba to adopt a zwitterionic form in these complexes is consistent with its higher proton affinity. Experimentally, the rates of water evaporation from clusters of Val.Na(+)(H(2)O) and Maiba.Na(+)(H(2)O) are measured using blackbody infrared radiative dissociation (BIRD). The dissociation rates from the Val and Maiba complexes are compared to water evaporation rates from model complexes of known structure over a wide range of temperatures. Master equation modeling of the BIRD kinetic data yields a threshold dissociation energy for the loss of water from sodiated valine of 15.9 +/- 0.2 kcal/mol and an energy of 15.1 +/- 0.3 kcal/mol for the loss of water from sodiated Maiba. The threshold dissociation energy of water for Val.Na(+)(H(2)O) is the same as that for the charge-solvated model isomers, while the salt-bridge model complex has the same water threshold dissociation energy as Maiba.Na(+)(H(2)O). These results indicate that the threshold dissociation energy for loss of a water molecule from these salt-bridge complexes is approximately 1 kcal/mol less than that for loss of water from the charge-solvated complexes.     

Ceramic Micro-Particles Synthesised using Emulsion and Sol–Gel Technology: An Investigation into the Controlled Release of Encapsulants and the Tailoring of Micro-Particle Size

Controlled release technologies have many applications in such diverse fields as the pharmaceutical, agricultural, cosmetic and food industries, where tailored release rates and protection of the active molecule for delivery at a specific site or time are advantageous. Silica microspheres, with controlled diameters of 10–50 m and containing Orange II dye as a model encapsulant, have been synthesised by combining water-in-oil (w/o) emulsion technology with sol–gel chemistry. The average particle size may be controlled by the microemulsion parameters, including the surfactant and solvent concentrations, and by the sol–gel processing parameters, particularly water-to-silicon alkoxide ratio, pH, temperature, ageing and mixing conditions. Physical properties of the SiO₂ microspheres, which modulate the release rates of the encapsulated molecule (including pore size and tortuosity), are also controlled by the sol–gel process parameters.The effect of synthesis parameters, including surfactant concentration, sol–gel solution pH and drying temperature, on the morphology of the SiO₂ microspheres produced will be discussed. The effect of such parameters on the corresponding release rates of the model encapsulants will also be presented.