Lyons Trevor, Kekedjian Chloe, Glaser Priscilla, Ohlin C André, van Eldik Rudi, Rodriguez Olga, Albanese Christopher, Van Keuren Edward, Stoll Sarah L
Department of Chemistry, Georgetown University, 37th and O Streets NW, Washington, D.C.20057, United States.
Department of Chemistry, Umeå University, Umeå907 36, Sweden.
ACS Appl Mater Interfaces. 2022 Oct 25. doi: 10.1021/acsami.2c12584.
We have investigated the mechanism of relaxivity for two magnetic resonance imaging contrast agents that both employ a cluster-nanocarrier design. The first system termed MnFe-coPS comprises the cluster MnFeO(L)(HO) or MnFe () (L = carboxylate) co-polymerized with polystyrene to form ∼75 nm nanobeads. The second system termed MnBpy-PAm used the cluster Mn(OCCH)(Bpy) or MnBpy () where Bpy = 2,2'-bipyridine, entrapped in ∼180 nm polyacrylamide nanobeads. Here, we investigate the rate of water exchange of the two clusters, and corresponding cluster-nanocarriers, in order to elucidate the mechanism of relaxivity in the cluster-nanocarrier. Swift-Connick analysis of O-17 NMR was used to determine the water exchange rates of the clusters and cluster-nanocarriers. We found distinct differences in the water exchange rate between MnFe and MnFe-coPS, and we utilized these differences to elucidate the nanobead structure. Using the transverse relaxivity from O-17 NMR line widths, we were able to determine the hydration state of the MnBpy () cluster as well as MnBpy-PAm. Using these hydration states in the Swift-Connick analysis of O-17 NMR, we found the water exchange rate to be extremely close in value for the cluster MnBpy and cluster-nanocarrier MnBpy-PAm.
我们研究了两种均采用簇状纳米载体设计的磁共振成像造影剂的弛豫率机制。第一个系统称为MnFe - coPS,由簇状的MnFeO(L)(HO)或MnFe ()(L = 羧酸盐)与聚苯乙烯共聚形成约75纳米的纳米珠。第二个系统称为MnBpy - PAm,使用簇状的Mn(OCCH)(Bpy)或MnBpy (),其中Bpy = 2,2'-联吡啶,包裹在约180纳米的聚丙烯酰胺纳米珠中。在此,我们研究这两种簇以及相应的簇状纳米载体的水交换速率,以阐明簇状纳米载体中弛豫率的机制。利用O - 17 NMR的Swift - Connick分析来确定簇以及簇状纳米载体的水交换速率。我们发现MnFe和MnFe - coPS之间的水交换速率存在明显差异,并利用这些差异来阐明纳米珠的结构。通过O - 17 NMR线宽的横向弛豫率,我们能够确定MnBpy ()簇以及MnBpy - PAm的水合状态。在O - 17 NMR的Swift - Connick分析中使用这些水合状态,我们发现簇状MnBpy和簇状纳米载体MnBpy - PAm的水交换速率在数值上极其接近。