制备trans-Fe(CO)_3(PR_3)_2的新的取代过程

报道了用H_2Fe(CO)_4制备trans-Fe(CO)_3(PR_3)_2的新的羰基取代反应。在 过量质子存在下，H_2Fe(CO)_4中的羰基被活化，中心铁原子对膦的亲核进攻更为 敏感。在这种条件下H_2Fe(CO)_4与膦反应时，首先失去氢生成Fe(CO)_4(PR_3), Fe(CO)_4-(PR_3)再与第二个膦反应可高产率的得到trans-Fe(CO)_3(PR_3)_2。用 PPh_3与Fe(CO)_4(PPh_3)在过量质子存在下反应生成trans-Fe(CO)_3(PR_3)_2，证 实了上述过程。     

Synthesis of a Tweezer—like Bis（Phenylthiapropoxy）calix[4]—arene as a Cation／π Enhanced Sensor for Ion—Selective Electrodes

Two novel 25,27-dihydroxy-26,28-bis(3-phenylthiapropxy)-calix[4]arene(3) and 25,27-dihydroxy-26,28-bis(3-phenylthiapropoxy)-5,11,17,23-tetra-tert-butylcalix[4] arene (4) were synthesized for the evaluation of their ion-selectivity in ion-selective electrodes(ISEs).ISEs based on 3 and 4 as neutral ionophores were prepared,and their selectivity coefficients for Ag^ (lg KAg,M^pot)were investigated against other alkali metal,alkaline-earth metal,aluminum,thallium(Ⅰ）,Lead and some transition metal ions using the separate solution method (SSM).These ISEs showed excellent Ag^ seletivity over most of the interfering cations examined,except for Hg^2 and Fe^2 having relative smaller interference(lg KAg,M^pot≤-2.1).     

Synthesis and reactivity of 3-(trichlorogermyl)propanoic acid and 3-(triphenylgermyl) propanoic acid

3-(Trichlorogermyl)propanoic acid (la) reacts with phenylmagnesium bromide in malar ratio 1:4 to give 3-(triphenylgermyl)propanoic acid (2a).In the compounds la and 2a theβ-carboxylic functional group shows some unusual properties when they react with excess of phenylmagnesium bromide.The compound la reacts with phenylmagnesium bromide in molar ratio 1:5 to give phenyl 2-(triphenylgermyl)ethylketone (3a) and in molar ratio 1:6 to give l,l-diphenyl-3-(triphenylgermyl)propanol (4a).The compound 2a reacts with phenylmagnesium bromide in molar ratio 1:2 to give 3a and in molar ratio 1:3 to give 4a also.Dehydration of the compound 4a with dilute hydrochloric acid seems especially easy.Moreover,the compound la reacted with phenylmagnsium bromide in molar ratio 1:6,then the mixture was treated with dilute hydrochloric acid to give 1,1-diphenyl-3-(triphenylgermyl)-1-propene (5a) in one pot reaction.Alkyl Ge-C bond in the compound 5a can be cleaved selectively by lithium aluminium hydride ( LiAlH4) in good yiel     

单氧代-二硒烷基-1, w-二氧取代杯[4]衍生物的合成,结构及萃取性能研究

Novel macrocyclic monooxa-diselkylene-1,ω-dioxy substituted calix[4]arene derivatives 1a-5a were synthesized by the reaction of calix[4]arene dibromides 1-5 with the disodium salt of bis（2-selenylethyl）ether in the yields between 28% and 64%. Their structures were characterized by proton and carbon NMR spectra. X-Ray structure analysis of la further confirmed the cone conformation of compounds 1a-5a. An interesting host-guest complex of la with dichloromethane via CH/π and C1/π interactions was elucidated. Extraction experiments showed that these novel monooxa-diselkylene-1,ω-dioxy substituted calix[4]arene derivatives 1a-5a had strong extraction ability towards mercury ion. The interaction of Hg^2＋with the calix ligand has also been investigated by 1^H NMR titration.     

高能强子–强子碰撞中喷注性质的蒙特卡洛研究

在喷注“圆锥判定法”的基础上,对高能强子–强子碰撞中产生的喷注(微喷注)的性质进行了蒙特卡洛研究.采用以喷注动量为z轴的“喷注坐标系”,给出了表征喷注性质的各物理量在新坐标系中的分布情况.结果表明,圆锥判定法能够作为一种有效手段来对高能强子–强子碰撞和相对论重离子碰撞中发生的硬和半硬过程开展实验研究.由有喷注事件和无喷注事件的多重数分布可以看到,E_t=2GeV是用圆锥法确定喷注的合理的横能截断值.     

Laser-hole boring into overdense plasmas measured with soft X-Ray laser probing

A laser self-focused channel formation into overdense plasmas was observed using a soft x-ray laser probe system with a grid image refractometry (GIR) technique. 1.053 &mgr;m laser light with a 100 ps pulse duration was focused onto a preformed plasma at an intensity of 2x10(17) W/cm (2). Cross sections of the channel were obtained which show a 30 &mgr;m diameter in overdense plasmas. The channel width in the overdense region was kept narrow as a result of self-focusing. Conically diverging density ridges were also observed along the channel, indicating a Mach cone created by a shock wave due to the supersonic propagation of the channel front.     

杯芳烃衍生物和丙烯酰胺作为复合功能单体的分子印迹聚合物对海因类化合物的选择性识别研究

以杯[4]芳烃衍生物+丙烯酰胺作为复合功能单体,将其运用到分子印迹技术中,对海因类化合物R-苄基海因进行选择性识别.研究结果表明,由单一的杯[4]芳烃衍生物或丙烯酰胺作为功能单体的分子印迹聚合物对R-苄基海因的选择性均不高,而由杯[4]芳烃衍生物+丙烯酰胺作为复合功能单体的分子印迹聚合物对模板分子具有较高的特异选择性.     

新型钳状芳杂环杯[4]芳烃修饰电极对银离子的分子识别研究

合成了25,27-二羟基-26,28-双(3-苯并噻唑基硫代丙氧基)-5,11,17,23-四叔丁基杯[4]芳烃,并将其研制成PVC膜化学修饰电极.探讨了膜电极的修饰方法及伏安性能对金属离子的识别及其识别机理.结果表明,采用涂层-刻痕法制备的修饰电极在0.2mol/LHNO₃溶液中对银离子有很灵敏的伏安响应,在5.0×10^-8～1.3×10^-6mol/L范围内氧化峰电流与银离子呈线性关系,检测限为3.8×10^-8mol/L.用该法测定了一些实际样品,结果令人满意.     

Curing theory of A_f-A_g type free radical polymerization (I)──Distribution function and its invariant property

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