Artificial metalloglycoclusters: compact saccharide shell to induce high lectin affinity as well as strong luminescence.
Artificial metalloglycoclusters: compact saccharide shell to induce high lectin affinity as well as strong luminescence.
复制标题
人工金属糖簇：致密的糖壳，诱导高凝集素亲和力以及强发光。
DOI：
10.1021/bc020026a
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发表时间：
2003
影响因子：
4.7
通讯作者：
Kazukiyo Kobayashi
中科院分区：
文献类型：
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作者：
Teruaki Hasegawa;Takahiro Yonemura;K. Matsuura;Kazukiyo Kobayashi
三-联吡啶亚铁和钌配合物携带各种糖的附件已被研究开发的传感系统监测糖结合的现象。亚铁O-糖簇之间插入的糖附件和复杂的核心间隔部分表现出增强的亲和力凝集素，但亚铁N-糖簇，其中的糖附件直接连接到复杂的核心通过酰胺键，具有低的凝集素亲和力。分子动力学计算表明，O-糖簇具有灵活的和密集的糖簇，与八面体固定的糖阵列的N-糖簇。糖簇的柔性对于其增强的亲和力是必不可少的，可能是为了诱导构象变化以适应凝集素的识别位点。根据这些见解，钌O-糖簇已被设计为发光生物传感器。带有α-甘露糖簇的钌配合物对伴刀豆球蛋白A（ConA）表现出优异的亲和力（IC（min）= 9.0 × 10（-）（8）M）。构象分析表明，密集的甘露糖簇可以很好地与ConA的识别位点相匹配。结合是热力学驱动的（Δ H度=-21.8kcal/mol）。这种结合行为与1-3/1-6三甘露糖苷与ConA的结合行为非常相似。它们具有强烈的放大发光（Phi（em）= 0.15），并且它们的发光强度在与特异性凝集素结合后改变（约40%）。钌糖簇可以是一个合适的感官系统的糖结合现象。
Tris-bipyridine ferrous and ruthenium complexes carrying various saccharide appendages have been investigated to develop sensory systems for monitoring saccharide-binding phenomena. Ferrous O-glycoclusters having spacer moieties inserted between saccharide appendages and the complex core showed enhanced affinities to lectins, but ferrous N-glycoclusters, in which the saccharide-appendages are directly linked to the complex core via amide linkage, had low lectin-affinities. Molecular dynamics calculation indicated that the O-glycoclusters have flexible and densely packed saccharide clusters, in contrast to the octahedrally fixed saccharide arrays of N-glycoclusters. Flexibility of saccharide clusters is essential for their enhanced affinity, probably to induce conformational change to fit the recognition sites of lectins. According to these insights, ruthenium O-glycoclusters have been designed as luminescence biosensors. The ruthenium complexes carrying alpha-manno clusters exhibited excellent affinities (IC(min) = 9.0 x 10(-)(8) M) to concanavalin A (ConA). It is suggested from conformational analysis that densely packed mannoclusters can be fit properly to the recognition site of ConA. The binding was enthalpicaly driven (deltaH degrees = -21.8 kcal/mol). This binding behavior is quite similar to that of 1-3/1-6 trimannoside to ConA. They have strongly amplified luminescence (Phi(em) = 0.15), and their luminescence intensities were changed (approximately 40%) upon binding to the specific lectins. The ruthenium glycoclusters can be a suitable sensory system for saccharide-binding phenomena.