Synthesis of β-Stannyl Esters

A synthesis of β-stannyl esters from ester enolates and iodomethyl (tri-n-butyl) stannane (3) is described.     

A Convenient Synthesis of Monocationic 1-[(Cyclic Amidino)methyl]thymines

1-[(Cyclic amidino)methyl]thymines have been conveniently synthesized from thymine in a three-step procedure via 1-cyanomethyl- and 1-[(thiocarbamoyl) methyl]thymines. The above synthetic intermediates were obtained in good yields by improved methods.     

A cytotoxic dimeric furanoheliangolide from Piptocoma rufescens

A new sesquiterpene lactone, rufescenolide C (1), the first furanoheliangolide dimer, was isolated from the leaves of Piptocoma rufescens, collected in the Dominican Republic. Its structure was determined by interpretation of its spectroscopic data, with the absolute configuration being established by analysis of the CD spectrum. A plausible biogenesis of this dimer is proposed. This compound showed potent cytotoxicity with an IC₅₀ value of 150 nM, when tested against HT-29 human colon cancer cells.     

Monitoring abiotic degradation of branched polyethylenes formulated with pro-oxidants through different mechanical tests

The mechanical properties of two linear low density and low density polyethylenes containing a pro-oxidant additive were monitored during accelerated aging (60 °C in a convection oven) and weather exposure. Tearing tests (trouser) were performed for the first time in polyethylenes subjected to oxo-degradation revealing a transition from an extensible to a non-extensible material, at exposure times when standard tensile tests were not able to detect any changes in the materials. The essential work of fracture (EWF) technique was also applied and the results were in agreement with those of trouser tests. The specific essential work of fracture first increased with exposure time until the sample experienced a transition to a less ductile state where EWF was no longer applicable. EWF and trouser tear tests were more sensitive detecting the onset of degradation probably because they employ notched specimens that impose more critical stress concentration conditions than conventional tensile tests.     

Study of the degradation of a new PLA braided biomaterial in buffer phosphate saline,basic and acid media,intended for the regeneration of tendons and ligaments

The purpose of this study was to evaluate the effects of hydrolytic degradation on the properties of a PLA hollow braid designed as a new concept of biodegradable prosthesis for the regeneration of tendons and ligaments. The main function of the braided material is to bear mechanical loads while it is being replaced by the newly-generated tissue. The kinetics of braided material degradation is thus an important factor in determining the success of the product. In order to study this mechanism, PLA braid was subjected to a 12-month degradation process at 37 °C in PBS at pH 7.4 (to simulate the human physiological medium) and to accelerated degradation for one month in pH 12 and pH 3 solutions. Degradation of the braid subjected to hydrolysis was evaluated by weight loss, molecular weight distribution, mechanical properties, and calorimetric and morphologic analyses. The weight loss in a basic medium reached 21%, versus no significant change in the other media. Average molecular weight was reduced by approximately 50% in the three media, with loss of mechanical properties in all cases. The morphological changes were more evident in the PLA degraded in the basic medium. The crystallinity of the material increased at the first stages of degradation, regardless of the medium used.     

Evolution and solar modulation of 7Be during the solar cycle 23

The modulation of ⁷Be-aerosols concentration due to solar activity during the cycle 23 is studied in the present research. For that purpose, was analyzed the differences in the long-term variation of geomagnetic and solar activity to assess the physical effects over the evolution of ⁷Be during the period 1996–2010. Furthermore, exploratory data analysis was applied to understand better the behavior of ⁷Be-aerosols in the surface atmosphere. This study shows that there is an inverse relationship among ⁷Be measured in the near ground air and solar activity. The modulation of ⁷Be-aerosols during the cycle 23 was divided in two steps. In the first stage, ascending phase, 1996–2002, the solar activity played an important role in the production rate of ⁷Be, r = ?0.75. However, during the descending phase, 2002–2009, the role of the solar activity was secondary, r = ?0.30, allowing that ⁷Be-aerosols reached the maximum concentration, 9.33 mBq m^?3 in August-09 when the solar activity was zero. Moreover, the remaining solar activity after the end of the ascending phase and the last important solar storm (December-06) caused the slowdown of ⁷Be production rate from 2001 to 2004 and the rupture of the seasonal behavior of ⁷Be in 2007, respectively. Finally, this research highlight the necessity to take into account the solar cycle phase, ascending or descending, to model studies of atmospheric process with ⁷Be as tracer since the contribution of the variables studied are so different in these stages.     

微米及纳米丝光沸石分子筛上二甲醚羰基化反应的积碳分析

对比研究了在传统微米尺寸和新结构纳米丝光沸石催化剂上二甲醚羰基化合成乙酸甲酯的反应行为.结果表明,通过减小分子筛的尺寸到纳米水平,可以有效提高反应物和产物到达或者脱离反应活性位的效率,从而提高了二甲醚的转化率;更重要的是,抑制了硬积碳的生成,使催化剂保持了更高的稳定性.     

三价铑催化亚甲胺内盐与丙烯酰胺氧化合成三取代吡唑

将三价铑离子配合物用于催化甲亚胺内盐与取代的丙烯酰胺之间的氧化偶联反应,实现了三取代的吡唑化合物的合成.在这个过程中,取代的丙烯酰胺的烯烃发生了C-H键活化.此类反应和用丙烯酸酯时的反应具有不同的选择性.     

仿生制备有机-无机复合微囊固定化葡萄糖氧化酶

将层层自组装技术与仿生矿化技术相结合,由聚苯乙烯磺酸钠、聚二甲基二烯丙基氯化铵和二氧化硅成功制备(聚苯乙烯磺酸钠-聚二甲基二烯丙基氯化铵)₂-二氧化硅复合微囊.采用扫描电子显微镜、红外光谱和热重对微囊的形貌和化学结构进行了表征.以该复合微囊作为理想载体固定化葡萄糖氧化酶.结果表明,固定于复合微囊中的葡萄糖氧化酶的热稳定性、pH稳定性、操作稳定性得到了提高;在最适条件下,复合微囊固定化葡萄糖氧化酶的酶活回收率为72.85%,米氏常数是游离葡萄糖氧化酶的2.21倍.复合微囊在化学/生物催化、药物/基因传递系统和生物传感器应用方面具有一定的潜能.     

SAPO-11分子筛晶化过程研究

采用X射线衍射、X射线荧光光谱、扫描电镜和固体核磁等方法研究了SAPO-11分子筛的水热晶化过程.结果表明,晶化初期,SAPO-11和一种具有磷硅铝组成的未知晶相同时生成;随着晶化的进行,中间相溶解,SAPO-11的生成速率大大增加,呈现快速晶化的特征;至2.33h后,SAPO-11的结晶度接近100%,并保持至晶化结束.硅从晶化初期即参与了SAPO-11的形成,它在晶体中的含量随晶化时间的延长而逐渐增加.硅原子主要以硅岛的形式分布于SAPO-11分子筛骨架中,从而导致多种硅配位环境的存在.分析显示,SAPO-11分子筛呈现外表面富硅的特点,结合晶化过程的分析可推测,硅在SAPO-11分子筛晶体中的分布不均匀,其含量从内向外递增.