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Gd(3+)-ion-doped upconversion nanoparticles (UCNPs), integrating the advantages of upconversion luminescence and magnetic resonance imaging (MRI) modalities, are capturing increasing attention because they are promising to improve the accuracy of diagnosis. The embedded Gd(3+) ions in UCNPs, however, have an indistinct MRI enhancement owing to the inefficient exchange of magnetic fields with the surrounding water protons. In this study, a novel approach is developed to improve the MR imaging sensitivity of Gd(3+)-ion-doped UCNPs. Bovine serum albumin (BSA) bundled with DTPA-Gd(3+) (DTPA(Gd)) is synthesized both as the MR imaging sensitivity synergist and phase-transfer ligand for the surface engineering of UCNPs. The external Gd(3+) ion attachment strategy is found to significant improve the MR imaging sensitivity of Gd(3+)-ion-doped UCNPs. The relaxivity analysis shows that UCNPs@BSA·DTPA(Gd) exhibit higher relaxivity values than do UCNPs@BSA without DTPA(Gd) moieties. Another relaxivity study discloses a striking message that the relaxivity value does not always reflect the realistic MRI enhancement capability. The high concentration of Gd(3+)-ion-containing UCNPs with further surface-engineered BSA·DTPA(Gd) (denoted as UCNPs-H@BSA·DTPA(Gd)) exhibits a more pronounced MRI enhancement capability compared to the other two counterparts [UCNPs-N@BSA·DTPA(Gd) and UCNPs-L@BSA·DTPA(Gd) (-N and -L are denoted as zero and low concentrations of Gd(3+) ion doping, respectively)], even though it holds the lowest r1 of 1.56 s(-1) per mmol L(-1) of Gd(3+). The physicochemical properties of UCNPs are essentially maintained after BSA·DTPA(Gd) surface decoration with good colloidal stability, in addition to improving the MR imaging sensitivity. In vivo T1-weighted MRI shows potent tumor-enhanced MRI with UCNPs-H@BSA·DTPA(Gd). An in vivo biodistribution study indicates that it is gradually excreted from the body via hepatobiliary and renal processing with no obvious toxicity. It could therefore be concluded, with improved MR imaging sensitivity by an internal and external incorporation of Gd(3+) strategy, that UCNPs-H@BSA·DTPA(Gd) presents great potential as an alternative in tumor-targeted MR imaging.

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Six tetraphenylporphyrins (TRPPH2) with different horizontal substituents R (R = H, CH3, OH, F, Cl, Br) were synthesized, and the organic light‐emitting diode (OLED) devices with a general configuration of ITO/TPD/Alq3:2%TRPPH2/Alq3/Al were prepared. The substituted TRPPH2 was used as the host dopant, 4,4‐bis‐(m‐tolyphenylamino)biphenyl (TPD) was used as a hole‐transporting material, and aluminum tris(8‐quinolinolato) (Alq3) was used as an electron‐transporting material. The electroluminescent (EL) properties of these devices were studied to understand the light emitting properties of the substituted TRPPH2. Previous studies have found that the color emitted by the devices was dependent on the TRPPH2 dye concentration. The electronic effect of the horizontal substituents R of TRPPH2 influenced the turn‐on voltage, brightness, and power efficiency of the devices. Also, the electroluminescence performance of the porphyrin‐doped OLED devices depended on the effectual overlaps between the emission of electron‐transporting material and the absorption of the dopants. This means that it is possible to evaluate the electroluminescence performance of the porphyrin‐doped OLED devices based on the emission of electron‐transporting material and the absorption of the dopants. Copyright © 2009 John Wiley & Sons, Ltd.