State Key Laboratory of Medicinal Chemical Biology (Nankai University), Synergetic Innovation Center of Chemical Science and Engineering (Tianjin), and Research Center for Analytical Sciences, College of Chemistry, and ‡College of Life Sciences, Nankai University , 94 Weijin Road, Tianjin 300071, China.
J Am Chem Soc. 2013 Sep 25;135(38):14125-33. doi: 10.1021/ja404243v. Epub 2013 Sep 17.
Near infrared (NIR)-emitting persistent luminescent nanoparticles (PLNPs) have great potential for in vivo bioimaging with the advantages of no need for in situ excitation, high signal-to-noise ratio, and deep tissue penetration. However, functional NIR-emitting PLNPs with long afterglow for long-term in vivo imaging are lacking. Here, we show the synthesis of NIR-emitting long-persistent luminescent nanoparticles (LPLNPs) Zn2.94Ga1.96Ge2O10:Cr(3+),Pr(3+) by a citrate sol-gel method in combination with a subsequent reducing atmosphere-free calcination. The persistent luminescence of the LPLNPs is significantly improved via codoping Pr(3+)/Cr(3+) and creating suitable Zn deficiency in zinc gallogermanate. The LPLNP powder exhibits bright NIR luminescence in the biological transparency window with a superlong afterglow time of over 15 days. A persistent energy transfer between host and Cr(3+) ion in the LPLNPs is observed and its mechanism is discussed. PEGylation greatly improves the biocompatibility and water solubility of the LPLNPs. Further bioconjugation with c(RGDyK) peptide makes the LPLNPs promising for long-term in vivo targeted tumor imaging with low toxicity.
近红外(NIR)发射持续发光纳米粒子(PLNPs)具有用于体内生物成像的巨大潜力,其优势在于无需原位激发、信噪比高、组织穿透深。然而,缺乏具有长余辉的功能性近红外发射 PLNPs 以进行长期体内成像。在这里,我们展示了通过柠檬酸溶胶-凝胶法结合随后的无还原气氛煅烧合成 NIR 发射长余辉纳米粒子(LPLNPs)Zn2.94Ga1.96Ge2O10:Cr(3+),Pr(3+)。通过共掺杂 Pr(3+)/Cr(3+)并在锌镓锗酸盐中创造合适的 Zn 缺乏,显著提高了 LPLNPs 的持续发光。LPLNP 粉末在生物透明窗口中表现出明亮的近红外发光,具有超过 15 天的超长余辉时间。观察到 LPLNPs 中主体和 Cr(3+)离子之间的持续能量转移,并讨论了其机制。PEG 化极大地提高了 LPLNPs 的生物相容性和水溶性。进一步与 c(RGDyK)肽进行生物偶联,使得 LPLNPs 具有低毒性的长期体内靶向肿瘤成像的应用前景。