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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Gold nanostars co-coated with the Cu(II) complex of a tetraazamacrocyclic ligand
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Gold nanostars co-coated with the Cu(II) complex of a tetraazamacrocyclic ligand

机译：金纳米星与四氮杂大环配体的Cu（II）配合物共包覆

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The twelve-membered tetraazamacrocyclic ligand L1 bears an appended lipoic acid unit, whose disulphide ring is an efficient grafting moiety for the surface of gold nanostars (GNS). The GNS that were used featured a localized surface plasmon resonance (LSPR) absorption at similar to 800 nm, i.e. in the near infrared (NIR). We investigated different approaches for coating them with the Cu2+ complex of L1. While the direct reaction of [CuL1](2+) with as-prepared GNS led to aggregation, an initial coating step with polyethyleneglycol- thiol (PEG-SH) was found to be advantageous. Displacement reactions were carried out on pegylated GNS either with [CuL1](2+), directly generating [Cu-n(L1@GNS)](2n+), or with void L1, thus obtaining L1@GNS that coordinates Cu2+ in a second step. In both cases, even with a large excess of the competing disulphide moiety, only partial displacement of PEG-SH is observed, obtaining ca. 500-1500 [CuL1](2+) per GNS depending on the conditions, with PEG-SH remaining in the [Cun(L1@GNS)](2n+) hybrids and imparting them with remarkable stability. Comparison of the photothermal and two-photon luminescence (TPL) properties of the GNS between the pegylated GNS and [Cu-n(L1@GNS)](2n+) revealed that the grafted copper complex does not change them to any extent. Finally, the stability against demetallation and trans-metallation of the complexes, as well as the fast kinetics of complexation of the monodispersed macrocycle and of L1@GNS, have been examined, suggesting [Cun(L1@GNS)](2n+) as a device capable of TPL optical tracking and NIR photothermal therapy and as a possible agent for PET imaging.
机译：十二元四氮杂大环配体L1带有附加的硫辛酸单元，其二硫环是金纳米星（GNS）表面的有效接枝部分。所使用的GNS具有类似于800 nm的局部表面等离子体共振（LSPR）吸收特性，即在近红外（NIR）中。我们研究了用L1的Cu2 +络合物涂覆它们的不同方法。尽管[CuL1]（2+）与制备的GNS的直接反应导致聚集，但是发现用聚乙二醇硫醇（PEG-SH）进行初始涂覆是有利的。用[CuL1]（2+）在聚乙二醇化的GNS上进行置换反应，直接生成[Cu-n（L1 @ GNS）]（2n +），或在空隙L1上进行聚苯乙烯化，从而在第二秒获得配位Cu2 +步。在这两种情况下，即使存在大量过量的竞争性二硫键部分，也只能观察到PEG-SH的部分置换，从而获得约。每个GNS 500-1500 [CuL1]（2+），具体取决于条件，[Cun（L1 @ GNS）]（2n +）杂化体中保留有PEG-SH，赋予它们显着的稳定性。聚乙二醇化的GNS和[Cu-n（L1 @ GNS）]（2n +）之间的GNS的光热和双光子发光（TPL）特性的比较表明，接枝的铜络合物不会在任何程度上改变它们。最后，研究了配合物对去金属化和反金属化的稳定性，以及单分散大环化合物和L1 @ GNS的快速复合动力学，表明[Cun（L1 @ GNS）]（2n +）作为能够进行TPL光学跟踪和NIR光热疗法的设备，并且可能是PET成像的媒介。

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