柱前衍生化RP-HPLC测定中药野马追中的氨基酸

采用柱前衍生反相高效液相色谱法(RP HPLC)测定了江苏地产药材野马追茎叶及其花蕾中的总氨基酸和游离氨基酸。用邻苯二甲醛(OPA)与一氯甲酸芴甲酯(FMOC)联用全自动柱前衍生化反相高效液相色谱仪,liozosphezeC18柱,pH=7.2的醋酸钠缓冲溶液和甲醇为流动相,流速为1.0mL/min,荧光检测器,波长为Ex=340nm、Em=450nm,样品中的氨基酸在30min内得到分离和检测。结果表明:野马追茎叶及其花蕾中含17种氨基酸,游离氨基酸17种,总氨基酸含量分别为2.40%和6.51%,游离氨基酸含量分别0.185%和0.508%,半胱氨酸(cys)和谷氨酸(glu)含量较高,其中7种为人体必需氨基酸。     

Free energy calculations of the mutation of Ile96 -> Ala in barnase: contributions to the difference in stability

Free energy calculations were carried out to determine the relativeunfolding free energy of the Ile96 wild type and Ala96 mutantbarnases. The total calculated free energies suggest that substitutionof Ile96 with Ala destabilizes barnase by 3.9 kcal/mol, whichis in good agreement with the independently determined experimentalvalues of 4.0 and 3.3 kcal/mol and a previous simulation. However,a decomposition of the free energy finds the dominant contributionsto this free energy arising from the noncovalent Interactionsbetween the perturbed group and distant residues of barnasein the sequence and water molecules and only a very small contributionfrom covalent interactions. This is in contrast to the previoussimulation, using the dual topology methodology, which produceda decomposition with an {small tilde}60% free energy contributionfrom changes in covalent interactions. The use of the singletopology employed in the present calculations and the dual topologyemployed in the previous study are analyzed in order to understandthe contrast between the present results and the results ofthe previous study.     

尿素－双醛淀粉胶粘剂的制备

将改性淀粉代替甲醛与尿素进行缩合反应 ,合成出全新无毒的尿素 双醛淀粉胶粘剂。讨论了双醛淀粉与尿素的反应机理 ,并对二者反应的影响因素进行概括分析     

铜锡合金的电动势热力学研究

在温度７００℃，组成０≤Ｘｓｎ≤０．２８的范围内，对固体Ｃｕ—Ｓｎ合金的α、β相的电池电动势测量研究表明，在固态高温相区，采用一固体电解质构成电池后，通过电动势测量，来获取热力学函数仍是一可靠方法。从锡活度的测定，体系的相对偏摩尔过剩自由能被确定。体系同理想混合行为的偏差可归结为在本质上是合金组份之间的互相作用，主要表现为在合金组成时的变形贡献和电子相互作用两个方面。     

取代基及分子量对非离子型纤维素醚表面特性的影响

根据Washburn的浸渍理论(Penetration Theory)和van Oss-Good- Chaudhury的组合理论(Combining Theory)及应用柱状灯芯技术(Column Wicking Technique),对几种非离子型纤维素醚,如甲基纤维素、羟丙基纤维素和羟丙基甲基纤维素的表面特性进行了测试。由于这些纤维素醚的取代基、取代度和分子量不同,所以它们的表面能及其组成部分有着明显的差异。数据说明,非离子型纤维素醚Lewis碱大于Lewis酸,表面自由能的主要成分是Lifshitz-van der Waals力。羟丙基的表面能及其成分都大于羟甲基。而在相同取代基和取代度的前提下,羟丙基纤维素的表面自由能正比于分子量;而羟丙基甲基纤维素的表面自由能则正比于取代度,反比于分子量。实验还发现非离子型纤维素醚中的取代基羟丙基和羟丙基甲基的表面能似乎都大于纤维素的表面能,而实验证明所测试得出的纤维素的表面能及其成分的数据是与文献所吻合的。     

乙酰丙酮分光光度法测定啤酒中甲醛

建立了检测啤酒中甲醛含量的新方法。在酸性条件下将溶解于水中的游离甲醛随水蒸出,馏出液中甲醛与乙酰丙酮作用,在100℃水浴中加热生成稳定的二乙酰基二氢吡啶化合物,冷却后在415nm处测吸光度,即可测的啤酒中甲醛含量。方法检出限为0.12μg/10mL,线性范围:0.0-8.0μg/10mL,RSD为0.73%-2.39%。样品加标回收率在98.4%-102.6%。该方法简便,灵敏度高,重线性好,适合啤酒中甲醛的测定。     

脲醛树脂的研究进展

综述了近年来脲醛树脂的研究进展,从低甲醛脲醛树脂的合成工艺研究、改性脲醛树脂的合成工艺研究、环保脲醛树脂的合成工艺研究等方面进行了归纳和评述,展望了脲醛树脂未来的研究方向和发展前景。     

Investigation of free volume,interfacial, and toughening behavior for cyanate ester/bentonite nanocomposites by positron annihilation

Effects of filler on microstructure and toughening behavior of cyanate ester (CE)/bentonite (BT) nanocomposites with different content of BT have been studied by positron annihilation lifetime spectroscopy, X‐ray diffraction, transmission electron microscopy, dynamic mechanical analysis, etc. The interesting results found by PALS indicate that the size and concentration of the free volume holes and the apparent free volume fraction increased with increasing the content of BT, which indicates that adding nano‐layers to thermosetting materials can lead to the high crosslinking density structure “looser.” The experimental results reveal that the increases in size of free volume holes and apparent free volume fraction are related to the increasing conversion of cure reaction. On the other hand, the mechanism of toughening (by adding the nano‐clay to the thermosetting material) has been discussed by combining free volume and interfacial property. It is shown that, for the high crosslinking thermosetting material‐based nanocomposites, both the property of free volume and dispersion state of nano‐layers are the two key factors in determining toughening property. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1509–1515, 2006     

Free‐radical grafting of acrylic acid onto isotactic polypropylene using styrene as a comonomer in supercritical carbon dioxide

Free‐radical grafting of acrylic acid (AAc) onto isotactic polypropylene (iPP) using styrene (St) as a comonomer in supercritical carbon dioxide (SCCO₂) medium was studied. The effects of temperature and pressure of reaction on functionalization degree (grafting degree of AAc) of the products were analyzed. The increase of reaction temperature increases the diffusion of monomers and radicals in the disperse reaction system of SCCO₂. In addition, the increase of temperature accelerates the decomposition rate of 2,2′‐azobisisobutyronitrile (AIBN), thus promoting grafting reaction. It was also observed that functionalization degree of the products decreases with the increase of pressure of SCCO₂ in the range of experiment. The effects of comonomer St on the functionalization degree of the products were investigated. The AAc graft degree of the resulting polymer was drastically higher in the present of St. It reached a maximum when the mass ratio of St and AAc was about 0.7 : 1. Because AAc is not sufficiently reactive toward iPP macroradicals, it would be helpful to use a second monomer that can react with them much faster than AAc. St preferentially reacts with the iPP macroradicals to form more stable styrene macroradicals, which then copolymerize with AAc to form branches. The highest functionalization degree was obtained when the AIBN was 0.75 wt %. When the initiator was used excessively, the functionalization degree decreased because of severe chain degradation of the iPP backbone. The morphologies of pure iPP and grafted iPP are different under the polarizing optical microscope. The diameter of the pure iPP spherulites is 20–38 μ and that of the grafted iPP spherulites is reduced with the increase of the functionalization degree of the products. This is proposed to be because the polar grafts formed during the reaction would have a tendency to associate in the hydrophobic PP environment. This might preserve some of the local crystalline order that existed during the reaction in the swollen iPP phase. It can be proven by a DSC cooling investigation that the crystallization temperature increased as the functionalization degree increased. This is proposed to be because the side‐chain of grafting polymer helps to bring about the heterogeneous nucleation in grafting polymer. Therefore, a large number of nuclei can emerge to a lesser supercooling degree. It can be also proven that the percent crystallization decreased as the functionalization degree increased, probably due to the grafted branches, which disrupted the regularity of the chain structure and increased the spacing between the chains. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2203–2210, 2004