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It is interesting that (1)hyperconjugation of the solvent's CF3-donor group prefers H4/H5 of BMI cation to H2, which can be explained by the steric hindrance of PF6 anion;(2) the various-temperature 19F spin-lattice relaxation times (T1) of CF3 show phase change, e.g.

藉由分析阳离子和三氟乙醇的扩散速率求得DD值,可以看到改善在乙醇形成大的基团,产生较强的分解,三氟乙醇的性质利用19F、1H化学位移,得到(1)CF3和阳离子H4、H5形成超共轭大於对H2,因为立体效应的关系,而藉由19F迟缓时间的数据,三氟乙醇展现相变化,由一到两各堆叠的离子对,和一个阴离子形成超阴离子的情形,因为溶剂而开始崩解,在继续分解可得到自由的阴阳离子。

We developed new spectroscopic methods to create stable odorant gradients in which odor concentrations were experimentally measured.

结果,他们证实,果蝇幼虫的大脑不但能利用立体线索来定位气味,而且还能指导它们的化学趋性。

The induction of acylamide group can enhance the stereoselectivity of photochemistry and be used in other chemistry fields.

通过在二苯甲酮上引入酰胺羧酸类活性基团,不仅可以作为光化学前体用于提高光反应的立体选择性,而且还可直接应用于其他化学领域。

The constituents of bulb of F. puqiensis were studied. Five steroid alkaloids were isolated. The plane structure and stereoscopic configuration of 4 compounds were elucidated. They are named as puqienine A (FP-33), puqienine B (FP-3), N-demethyl-puqietinone (〓 FP-34) and puqietinone (〓, FP-9). Puqienine A and N-demethyl-puqietinone are new compounds. Puqienine B is as same as FPQ-3 elucidated by Prof.

对F.puqiensis鳞茎化学成份进行了研究,分得5个甾体类生物碱成分,并采用 UV、IR、EI-MS、1D-NMR,HHCOSY、CHCOSY、HMBC和X-RAY等光谱技术和理化常数测定,鉴定出4个化合物的平面结构和立体构型,分别为蒲圻贝母碱甲(puqienineA,FP-33)、蒲圻贝母碱乙(puqienineB,FP-3)、N-去甲蒲贝酮碱(N-demethyl-puqietinone,FP-34)和蒲贝酮碱(puqietinone,FP-9),其中蒲圻贝母碱甲和N-去甲蒲贝酮碱为新化合物。

In this thesis, we did modifications of alkyl groups upon benzyl fluorophosphonate. In order to study the influence of alkyl length and steric effect on activity and selectivity of probes, we synthesized benzyl fluorophosphonate recognition heads with modifications including ethyl, butyl, octyl and cyclohexyl. By way of connecting different kinds of tag like azido group, biotin and rhodamine with recognition heads separately through a higher hydrophilic ethylene glycol derived linker, a series of benzyl fluorophosphonate probes were made up. And they will apply to various biological testing strategies.

在本论文中,我们以苯甲基氟化磷酸酯为基础,於其上进行一系列烷基之修饰,为了探讨烷基长度与空间立体性质对於探针活性及选择性的影响,我们合成了包含乙烷基、丁烷基、辛烷基以及环己烷基修饰的苯甲基氟化磷酸酯辨识端,并藉由具较高亲水性的聚乙二醇衍生连接桥结合三种不同的发报端,分别有叠氮基团、生物素及萤光基团来构成不同的化学探针组合,这一系列苯甲基氟化磷酸酯类化学探针将可被应用於不同的生物测试策略。

The dissertation mainly consists of two parts:1. The Reaction Chemistry of Alkynes under Palladium Catalysis Part 1 studies the reaction α,β-unsaturated carbonyl compounds with alkenylpalladium intermediate generated by nucleopalladation, and discovered 1 the Pd-catalyzed tandem addition reaction of halides, alkynes and α,β-unsaturated carbonyls,2 the four-component tandem addition reaction of halides, alkynes and α,β-unsaturated carbonyls, 3 the tandem intramolecular oxypalladation-conjugate additionreaction of alkynoic acids with α,β-enals. These new reactions provide notonly efficient highly stereoselective methods for the synthesis of γ,δ-unsaturated,polyunsaturated carbonyl compounds and γ-lactonic aldehydes, but also thebasic transformations for a number of C-C bond formation reactions which can be usedto design synthesis of many acyclic, cyclic or polycyclic compounds.

本论文的主要工作分为两个部分:一、钯催化下炔烃的反应化学在本小组前人工作的基础上,我们详细研究了炔烃亲核钯化产生的烯基钯中间体与α,β-不饱和羰基化合物的反应,发现两价钯催化下卤离子-炔烃-α,β-不饱和醛酮的串联加成反应、卤离子-炔烃-α,β-不饱和醛酮的西组分串联加成及炔酸分子内氧钯化-串联Michael型加成反应;由此发展了γ,δ-不饱和醛酮、多不饱和羰基化合物和带有醛酮基侧链的γ-丁内酯衍生物的高立体选择性合成方法,这一过量卤离子存在下的烯基钯对α,β-不饱和羰基化合物共轭加成反应的发现,为大量碳-碳键形成反应的实现提供了基础,使我们能够从这一基本反应出发,设计和开发多种分子内、分子间的碳碳成键反应,以好的立体、区域选择性组建开链、环状及多环类型的化合物。

Organic matrixs coming from cells play role in nucleation, growth, morphology, polymorphology of inorganic materials. This control of organic matrixs are mainly behaved by the interfaction between organic matrix and inorganic materials .The processing of organic matrix controlling inorganic material is called as molecular recognition. The mechanism of organic-inorganic molecular recognition contains three facts such as electrostatic attraction, lattice geometry matching and stereochemical complimentary.

细胞分泌的有机基质在无机矿物的成核,生长,形貌,多型和结晶学定向等过程中起到了调控作用,基质对矿化的这种调控作用具体表现在有机或生物大分子和无机离子在界面上的相互作用,有机质对无机晶体的成核,生长,晶形及结晶学定向等的控制过程称为分子识别,有机-无机界面分子识别机制主要包括静电作用,晶格几何匹配和立体化学互补三个方面。

The present dissertation reviews the total synthesis of biotin, particularly on Hoffmann-La Roche\'s Lactone-Thiolactone approach. The Lactone-Thiolactone approach is presently the most competitive commercial route, which gives an excellent illustration of the gradual construction of the functionalized skeleton with the simultaneous solution of the stereochemical issues in a minimal number of steps.In 1970, Gerecke etc. of Roche Corp.

论文对生物素全合成的文献进行了综述,重点讨论了目前工业上最有竞争力的内酯—硫代内酯路线,展示了生物素是如何以最少的步骤去逐步构建目标产物的官能团骨架并同时解决立体化学问题的。1970年,Roche公司的Gerecke等报道了一条通过手性内酯,以较高收率并保持构型得到手性硫代内酯,从而直接合成d-生物素的方法后,该中间体内酯(3aS,6aR)-1,3-二苄基。

Chiral SalanCrX complexesa saturated version of SalenCr(ⅢX are designed,and in conjunction with an ionic quaternary ammonium salt or organic strong base can efficiently catalyze the asymmetric,regio-and stereoselective alternating copolymerization of CO_2 with rac-PO at mild conditions to afford isotactic-enriched polycarbonates with~95%head-to-tail linkages and moderate enantioselectivity.

本论文在Salen构型配体的基础上,设计合成了一系列手性Salan型铬配合物,并将其与季铵盐/有机强碱组成亲电-亲核双组分催化体系,在室温下可以有效的催化CO_2和环氧丙烷的不对称交替共聚反应,实现了CO_2和环氧丙烷的不对称交替共聚反应的区域和立体化学控制,得到95%的头尾连接单元和中等光学纯度(对映体过量值ee%≈70%)的全同结构的聚碳酸酯。

In our research,Wistar rats and SD rats which were parathyroidectomized were used as donors and recepients respectively.The parathyroid gland of the Wistar rat were allografted into the cerebroventricle and other different sites of the brains in SD rat s tereotaxically. Using methods of testing serum Ca~(2+) concentration,histological examination,histochemical and immunocytochemical methods and electron microscopic observation,we investigated the survival of the grafting tissue,its revascularization, infiltrating of monocytes, changes of microglia and astrocytes, the relationship of the CNS with the immune system, and the mechanism of rejection were investigated.The results as following: I .Effects on PTG after allografting into cerebroventricle and cerebral parenchyma of the brain: Testing serum Ca~(2+) conc.

本研究以Wistar大鼠作为供体,切除甲状旁腺的SD大鼠作为受体,在立体定位下将同种异体的PTG移植到大脑的不同部位,设计了侧脑室-内分泌系统移植的代替途径,比较了侧脑室内移植和脑实质内移植的异同,通过测定血清Ca~(2+)的浓度、组织学检查、组织化学和免疫细胞化学以及电镜观察对移植后PTG组织的存活、血管的再生、单核细胞的浸润、CNS内胶质细胞的变化、对免疫系统的影响及免疫排斥的机制进行了研究,结果如下:一、同种异体PTG侧脑室内移植与脑实质内移植的比较:血清Ca~(2+)的检查发现,PTG侧脑室内移植后第7天,血清Ca~(2+)的浓度恢复到8mg%以上,一直持续到移植后第8-12周;移植后第12周仍有60%移植PTG的动物血清Ca~(2+)维持在正常水平。

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As she looked at Warrington's manly face, and dark, melancholy eyes, she had settled in her mind that he must have been the victim of an unhappy attachment.

每逢看到沃林顿那刚毅的脸,那乌黑、忧郁的眼睛,她便会相信,他一定作过不幸的爱情的受害者。

Maybe they'll disappear into a pothole.

也许他们将在壶穴里消失

But because of its youthful corporate culture—most people are hustled out of the door in their mid-40s—it had no one to send.

但是因为该公司年轻的企业文化——大多数员工在40来岁的时候都被请出公司——一时间没有好的人选。