Synthesis and structure of novel sugar-substituted bipyridine complexes of rhenium and 99m-technetium
Synthesis and structure of novel sugar-substituted bipyridine complexes of rhenium and 99m-technetium
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DOI：
10.1002/chem.200700296
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发表时间：
2007-01-01
影响因子：
4.3
通讯作者：
Yano, Shigenobu
中科院分区：
文献类型：
--
作者：
Gottschaldt, Michael;Koth, Daniel;Yano, Shigenobu
从4，4 ′-二溴甲基-2，2 ′-联吡啶与2，3，4，6-四-O-乙酰基-β-D-吡喃葡萄糖基硫醇、2，3，4，6-四-O-乙酰基-β-D-吡喃半乳糖基硫醇或2，3，4，6-四-O-乙酰基-α-D-硫代乙酰基吡喃甘露糖苷的反应中获得了新的配体，其中糖残基在4，4 ′-位与联吡啶硫代糖苷连接。乙酰基的裂解提供具有游离羟基的亲水性对称配体。新的糖基配体（L）与[Re（CO）（5）Cl]反应生成通式为[Re（L）-（CO）（3）Cl]的荧光配合物，其结构经质谱、元素分析、H-1和C-13 NMR、IR、UV/维斯和荧光光谱表征。这些配合物在有机溶剂或水中表现出优异的溶解性和稳定性，这取决于糖的残基。一种配合物，即三羰基-4，4 '-双[（2，3，4，6-四-O-乙酰基-β-D-吡喃葡萄糖基）硫甲基]-2，2'-联吡啶三羰基氯化物，已通过X射线晶体学表征。一个非对称结构的复合物可以被分配。用[Tc-99 m（H2O）（3）（CO）（3）]（+）放射性标记未保护的配体，得到相应的水溶性锝络合物（定量产率），其特征在于它们的HPLC辐射迹线。所形成的复合物在组氨酸存在下稳定数小时，但在一天后显示部分配体交换。
Novel ligands have been obtained from the reaction of 4,4'-dibromomethyl-2,2'-bipyridine with 2,3,4,6-tetra- O-acetyl-beta-D-glucopyranosylthiol, 2,3,4,6-tetra-O-acetyl-beta-D-galactopyra-nosylthiol or 2,3,4,6-tetra-O-acetyl-alpha-D-thioacetylmannopyranoside in which the sugar residues are thioglycosidically linked to the bipyridine in the 4,4'-position. Cleavage of the acetyl groups affords hydrophilic symmetric ligands with free hydroxyl groups. Reaction of the new glycoconjugated ligands (L) with [Re(CO)(5)Cl] yields fluorescent complexes of general formula [Re(L)-(CO)(3)Cl], which were characterised by mass spectrometry, elemental analysis and H-1 and C-13 NMR, IR, UV/Vis and fluorescence spectroscopy. These complexes exhibit excellent solubility and stability in organic solvents or water, depending on the residues of the sugar. One complex, namely tricarbonyl-4,4'-bis[(2,3,4,6-tetra-O-acetyl-beta-D-glycopyranosyl)thiomethyl]-2,2'-bipyridinerheniumtricarbonylo chloride, has been characterised by X-ray crystallography. A non-symmetric structure of the complexes could be assigned. Radiolabelling of the unprotected ligands with [Tc-99m(H2O)(3)(CO)(3)](+) affords the corresponding water-soluble technetium complexes (in quantitative yields), which were characterised by their HPLC radiation traces. The formed complexes are stable for several hours in the presence of histidine but show partial ligand-exchange after one day.