Stabilizing Alginate Confinement and Polymer Coating of CO-Releasing Molecules Supported on Iron Oxide Nanoparticles To Trigger the CO Release by Magnetic Heating.
Stabilizing Alginate Confinement and Polymer Coating of CO-Releasing Molecules Supported on Iron Oxide Nanoparticles To Trigger the CO Release by Magnetic Heating.
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DOI：
10.1021/acs.inorgchem.5b01675
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发表时间：
2015-11
影响因子：
4.6
通讯作者：
H. Meyer;F. Winkler;P. Kunz;A. Schmidt;A. Hamacher;M. Kassack;C. Janiak
中科院分区：
文献类型：
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作者：
H. Meyer;F. Winkler;P. Kunz;A. Schmidt;A. Hamacher;M. Kassack;C. Janiak
合成了磁赤铁矿（Fe 2 O3）氧化铁纳米颗粒（IONP），用三（羰基）-氯-苯丙氨酸-钌（II）络合物（CORM）的共价表面结合的CO释放分子修饰，并用葡聚糖聚合物包覆。从该CORM-3类似物的时间和温度依赖性CO释放之后进行肌红蛋白测定。开发了一种新的肌红蛋白测定方法，该方法基于将“水溶性”聚合物涂覆的Dextran500k@CORM@IONP颗粒限制在无毒且易于制备的海藻酸钙空心球中。将右旋糖酐500k@CORM@IONP和海藻酸钠的混合物滴入CaCl 2溶液中，产生含有右旋糖酐500k@CORM@IONP颗粒的Ca（2+）交联海藻酸盐的稳定中空球体。这种“藻酸盐方法”（i）保护CORM-3类似物免于与蛋白质的快速CO置换反应，（ii）使得能够用充当CO渗透膜的藻酸盐将CORM与其周围的肌红蛋白测定空间分离，以及（iii）允许在肌红蛋白测定中使用具有高吸收率的物质（例如氧化铁纳米颗粒）而不干扰UV池的光路。将CORM@IONP纳米颗粒包埋在藻酸盐容器中代表反应性组分的区室化，并允许与周围的肌红蛋白测定物紧密接触，但容易分离。在20 °C下，从藻酸盐包围的Dextran500k@CORM@IONP颗粒释放的CO的半衰期被确定为890 ± 70分钟。CO释放加速发生在较高温度下，37 °C下的半衰期为172 ± 27 min，50 °C下为45 ± 7 min。CO的释放可以在交流磁场（31.7 kA m（-1），247 kHz，39.9 mT）中通过敏感的氧化铁纳米颗粒的局部磁加热来触发。在本体溶液中在20 °C下进行磁加热时，从Dextran500k@CORM@IONP颗粒释放的CO的半衰期降低至155 ± 18分钟，而分散体中没有明显的温度升高。在37 ° C和50 °C下，由局部磁加热触发的CO释放的半衰期分别为65 ± 5 min和30 ± 3 min。因此，在37 °C的生理温度下，磁加热使IONP结合的CORM的CO释放加速了2.6倍。CORM-3类似物释放CO的活化能为EA = 78 kJ/mol。
Maghemite (Fe2O3) iron oxide nanoparticles (IONPs) were synthesized, modified with covalent surface-bound CO-releasing molecules of a tri(carbonyl)-chlorido-phenylalaninato-ruthenium(II) complex (CORM), and coated with a dextran polymer. The time- and temperature-dependent CO release from this CORM-3 analogue was followed by a myoglobin assay. A new measurement method for the myoglobin assay was developed, based on confining "water-soluble" polymer-coated Dextran500k@CORM@IONP particles in hollow spheres of nontoxic and easily prepared calcium alginate. Dropping a mixture of Dextran500k@CORM@IONP and sodium alginate into a CaCl2 solution leads to stable hollow spheres of Ca(2+) cross-linked alginate which contain the Dextran500k@CORM@IONP particles. This "alginate-method" (i) protects CORM-3 analogues from rapid CO-displacement reactions with a protein, (ii) enables a spatial separation of the CORM from its surrounding myoglobin assay with the alginate acting as a CO-permeable membrane, and (iii) allows the use of substances with high absorptivity (such as iron oxide nanoparticles) in the myoglobin assay without interference in the optical path of the UV cell. Embedding the CORM@IONP nanoparticles in the alginate vessel represents a compartmentation of the reactive component and allows for close contact with, yet facile separation from, the surrounding myoglobin assay. The half-life of the CO release from Dextran500k@CORM@IONP particles surrounded by alginate was determined to be 890 ± 70 min at 20 °C. An acceleration of the CO release occurs at higher temperature with a half-life of 172 ± 27 min at 37 °C and 45 ± 7 min at 50 °C. The CO release can be triggered in an alternating current magnetic field (31.7 kA m(-1), 247 kHz, 39.9 mT) through local magnetic heating of the susceptible iron oxide nanoparticles. With magnetic heating at 20 °C in the bulk solution, the half-life of CO release from Dextran500k@CORM@IONP particles decreased to 155 ± 18 min without a noticeable temperature increase in the dispersion. At 37 and 50 °C, the half-life for the CO release triggered by local magnetic heating was 65 ± 5 min and 30 ± 3 min, respectively. Thus, at a physiological temperature of 37 °C, magnetic heating accelerates the CO release of the IONP-bound CORM by a factor of ∼ 2.6. The activation energy for CO release from a CORM-3 analogue was determined to be EA = 78 kJ/mol.