Norek Małgorzata, Neves Isabel C, Peters Joop A
Biocatalysis and Organic Chemistry, Department of Biotechnology, Delft University of Technology, Julianalaan 136, 2628 BL Delft, The Netherlands.
Inorg Chem. 2007 Jul 23;46(15):6190-6. doi: 10.1021/ic700699n. Epub 2007 Jun 23.
The results of a (1)H nuclear magnetic relaxation dispersion (NMRD) and EPR study on aqueous suspensions of Gd(3+)-loaded NaY nanozeolites and AlTUD-1 mesoporous material are described. Upon increase of the Si/Al ratio from 1.7 to 4.0 in the Gd(3+)-loaded zeolites, the relaxation rate per mM Gd(3+) (r1) at 40 MHz and 25 degrees C increases from 14 to 27 s(-)1 mM(-1). The NMRD and EPR data were fitted with a previously developed two-step model that considers the system as a concentrated aqueous solution of Gd(3+) in the interior of the zeolite that is in exchange with the bulk water outside the zeolite. The results show that the observed increase in relaxivity can mainly be attributed to the residence lifetime of the water protons in the interior of the material, which decreased from 0.3 to 0.2 micros, upon the increase of the Si/Al ratio. This can be explained by the decreased interaction of water with the zeolite walls as a result of the increased hydrophobicity. The importance of the exchange rate of water between the inside and the outside of the material was further demonstrated by the relatively high relaxivity (33 s(-1) mM(-1) at 40 MHz, 25 degrees C) observed for a suspension of the Gd(3+)-loaded mesoporous material AlTUD-1. Unfortunately, Gd(3+) leaches rather easily from that material, but not from the Gd(3+)-loaded NaY zeolites, which may have potential as contrast agents for magnetic resonance imaging.
描述了对负载Gd(3+)的NaY纳米沸石和AlTUD-1介孔材料水悬浮液进行的(1)H核磁共振弛豫分散(NMRD)和电子顺磁共振(EPR)研究结果。在负载Gd(3+)的沸石中,Si/Al比从1.7增加到4.0时,40 MHz和25℃下每毫摩尔Gd(3+)的弛豫率(r1)从14增加到27 s(-1) mM(-1)。NMRD和EPR数据用先前开发的两步模型进行拟合,该模型将系统视为沸石内部Gd(3+)的浓水溶液,其与沸石外部的大量水进行交换。结果表明,观察到的弛豫率增加主要归因于材料内部水质子的停留寿命,随着Si/Al比的增加,停留寿命从0.3微秒降至0.2微秒。这可以通过疏水性增加导致水与沸石壁之间的相互作用降低来解释。负载Gd(3+)的介孔材料AlTUD-1悬浮液在40 MHz、25℃下观察到的相对较高的弛豫率(33 s(-1) mM(-1))进一步证明了材料内外水交换速率的重要性。不幸的是,Gd(3+)很容易从该材料中浸出,但不会从负载Gd(3+)的NaY沸石中浸出,负载Gd(3+)的NaY沸石可能有作为磁共振成像造影剂的潜力。