甲基丙烯酸三苯甲酯不对称聚合过程中的立体化学

甲基丙烯酸三苯甲酯(TrMA)在不对称聚合中,当有手性配体鹰爪豆碱((—)-S_p)存在时,可形成具有单手螺旋链构象的旋光性聚合物。Vogt用TrMA的活性二聚体作引发剂,聚合TrMA,结果表明,右手螺旋链的聚甲基丙烯酸三苯甲酯(PTrMA)的主链上各不对称碳原子均为S型,而Okamoto借助色谱拆分PTrMA低聚物的方法得出了相反的结果,至于手性配体决定螺旋方向的原因则未见报道。本文从单体构象,配体(—)-S_p的构象及PTrMA活性端的烯醇式构型,研究了TrMA在不对称聚合过程中的立体化学。

中国北方中新世风尘物质来源及古气候的地球化学指示

The most prominent tectonic and environmental events during the Cenozoic in Asia are the uplift of the Himalaya-Tibetan plateau, aridification in the Asian interior, and onset of the Asian monsoons. These caused more humid conditions in southeastern China and the formation of inland deserts in northwestern China. The 22 Ma eolian deposits in northern China provide an excellent terrestrial record relative to the above environmental events. Up to date, many studies have focused on the geochemical characters of the late Mio-Pleistocene eolian deposits, however, the geochemical characteristics of the Miocene loess and soils is still much less known. In this study, the elemental and Sr-Nd isotopic compositions of the eolian deposits from the Qinan (from 22.0 to 6.2 Ma) and the Xifeng (from 3.5 Ma until now) loess-soil sections were analyzed to examine the grain size effects on the element concentrations and the implications about the dust origin and climate. The main results are as follows: 1. The contents of Si, Na, Zr and Sr are higher in the coarser fractions while Ti and Nb have the highest contents in the 2-8 μm fractions. Al, Fe, Mg, K, Mn, Rb, Cu, Ga, Zn, V, Cr, Ni, LOI have clear relationships with grain-size, more abundant in the fine fraction while non significant relationship is observed for Y. Based on these features, we suggest that K2O/Al2O3 ratio can be used to address the dust provenance, and that VR (Vogt ratio = (Al2O3+K2O)/(MgO+CaO+Na2O)) can be used as a chemical weathering proxy for the Miocene eolian deposits because of their relative independence on the grain size. Meanwhile, SiO2/Al2O3 molar ratio is a best geochemical indicator of original eolian grain size, as suggested in earlier studies. 2. Analyses on the Sr and Nd isotope composition of the last glacial loess samples (L1) and comparison with the data from the deserts in northern China suggest that that Taklimakan desert is unlikely to be the main source region of the eolian dust. In contrast, these data suggest greater contributions of the Tengger, Badain Jaran and Qaidam deserts to the eolian dust during the last glacial cycle. Since the geochemical compositions (major, trace, REE and Sr, Nd isotope) of loess samples for the past 22 Ma are broadly similar with the samples from L1, these data trend to suggest relatively stable and insignificant changes of dust sources over the past 22 Ma. 3. Chemical weathering is stronger for Miocene paleosol samples than for the Plio-Pleistocene ones, showing warmer/more humid climatic conditions with a stronger summer monsoon in the Miocene. However, chemical weathering is typical of Ca-Na removal stage, suggesting a climate range from semiarid to subhumid conditions. These support the notion about the formation of a semi-arid to semi-humid monsoonal regime by the early Miocene, as is consistent with earlier studies.