一种高效Pd探针.pptVIP

A Highly Sensitive FluorescentSensor for Palladium Based on the Allylic Oxidative InsertionMechanism Fengling Song, Amanda L. Garner, and Kazunori Koide Tsuji-Trost reaction 谢谢大家！ * J. Am. Chem. Soc., 2007, 129 (41), 12354-12355 ? DOI: 10.1021/ja073910q Compound 3 was 442 times more fluorescent than compound 2 at λ=526 nm (pH 10 borate buffer) and was as fluorescent as fluorescein. Figure 2. Metal specificity: “Pd” ) PdCl2, “Pt” ) PtCl2, “Fe” )FeCl3,“Ag” ) AgNO3, “Ni” ) NiCl2, “Pb” ) Pb(NO3)2, “Mn” ) MnCl2, “Cd”) CdCl2, “Au” ) AuCl3, “Rh” ) RhCl(PPh3)3, “Cu” ) CuCl2, “Mg” )MgSO4, “K” ) KCl, “Cr” ) CrCl3, “Co” ) CoCl2, “Hg” ) HgCl2, “Ru”) RuCl3. Figure 3. Quantitative fluorescent analysis of Pd: y-axis ) relative fluorescent intensity. The linear correlation between Pd quantity and fluorescence. Pd(0) and Pd(II) show nearly the same signals: (left) no Pd reagent; (center) [PdCl2] ) 2.0 μM; (right) [Pd(PPh3)4] ) 2.0 μM. Proof of concept for Pd detection in drugs: (left) no Pd; (center) PdCl2 (10ng); (right) PdCl2 (10 ng) + aspirin (1 mg). Figure 4. Further applications of 2. Detection of Pd on the surface of glassware: (left) The solution in a vial not exposed to Pd reagents; (right) the solution in a vial exposed to Pd2(dba)3 (10 mg) in THF and washed extensively. Photo of Pd/Pt detection in rocks: rock A, no metals; rock B, 120 ppm Pd/Pt; rock C, only Au/Ag; rock D, 35 ppm（Pd/Pt = 3.4:1). Naked eye detection of Pd: (vial 1) PdCl2 (1.6 mM), dimethylglyoxime (1% w/v in ethanol) in 0.25 N HCl; (vial 2) PdCl2 (1.6 mM), 2, NaBH4 in THF; (vial 3) PdCl2 (10μM), dimethylglyoxime (1% w/v in ethanol) in 0.25 N HCl;(vial 4) PdCl2 (10μM), 2, NaBH4 in THF. Tsuji-Trost reaction：Pd(0)催化烯丙基醚，C-0键断链，形成复合物Pd(II)B，B与不同亲核试剂反应，合成化合物C和副产物D 荧光素类化合物的酚羟基烷基化后没有荧光E，当其去质子化后，又显示荧光F。 烯丙基醚（2） 以通用DCF为原料，DIBALH、催化剂DDQ反应得到2，2与等量的四三苯基磷钯反应生产3. DCF:2,7-二氯荧光素 化合物 3是化合物2的 442 倍 526 nm (pH 10 borate buffer) 金属专一性，钯具有明显作用，铂有较小程度的作用，其它e-philic metals such as Ag, Ni,Au, Rh, Co, Hg, and Ru did not c