3D Long-Range Triplet Migration in a Water-Stable Metal-Organic Framework for Upconversion-Based Ultralow-Power in Vivo Imaging

被引:174
作者
Park, Jihye [1 ,4 ]
Xu, Ming [2 ,3 ]
Li, Fuyou [2 ,3 ]
Zhou, Hong-Cai [1 ]
机构
[1] Texas A&M Univ, Dept Chem, College Stn, TX 77843 USA
[2] Fudan Univ, Dept Chem, Shanghai 200433, Peoples R China
[3] Fudan Univ, State Key Lab Mol Engn Polymers, Shanghai 200433, Peoples R China
[4] Stanford Univ, Dept Chem Engn, Stanford, CA 94305 USA
基金
中国国家自然科学基金;
关键词
ENERGY MIGRATION; LIGAND COORDINATION; AQUEOUS-PHASE; ANNIHILATION; NANOPARTICLES; CANCER; PHOTOCATALYSIS; NANOCAPSULES; EMISSION; DYNAMICS;
D O I
10.1021/jacs.8b01613
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Triplet-triplet annihilation upconversion (TTA-UC) has gained increasing attention because it allows for harvesting of low-energy photons in the solar spectrum with high efficiency in relevant applications including solar cells and bioimaging. However, the utilization of conventional TTA-UC systems for low-power bioapplications is significantly hampered by their general incompatibility and low efficiency in aqueous media. Herein we report a metal-organic framework (MOF) as a biocompatible nanoplatform for TTA-UC to realize low-power in vivo imaging. Our MOF consists of a porphyrinic sensitizer in an anthracene-based Zr-MOF as a TTA-UC platform. In particular, closely aligned chromophores in the MOF facilitate a long-range 3D triplet diffusion of 1.6 mu m allowing efficient energy migration in water. The tunable ratio between sensitizer and annihilator by our synthetic method also allows an optimization of the system for maximized TTA-UC efficiency in water at a very low excitation power density. Consequently, the low-power imaging of lymph node in a live mouse was successfully demonstrated with an excellent signal-to-noise ratio (SNR > 30 at 5 mW cm(-2)).
引用
收藏
页码:5493 / 5499
页数:7
相关论文
共 49 条
[1]   Imaging Upconverting Polymersomes in Cancer Cells: Biocompatible Antioxidants Brighten Triplet-Triplet Annihilation Upconversion [J].
Askes, Sven H. C. ;
Pomp, Wim ;
Hopkins, Samantha L. ;
Kros, Alexander ;
Wu, Si ;
Schmidt, Thomas ;
Bonnet, Sylvestre .
SMALL, 2016, 12 (40) :5579-5590
[2]   Upconversion and anti-stokes processes with f and d ions in solids [J].
Auzel, F .
CHEMICAL REVIEWS, 2004, 104 (01) :139-173
[3]   Photon upconversion with directed emission [J].
Borjesson, K. ;
Rudquist, P. ;
Gray, V. ;
Moth-Poulsen, K. .
NATURE COMMUNICATIONS, 2016, 7
[4]   Upconversion Nanoparticles: Design, Nanochemistry, and Applications in Theranostics [J].
Chen, Guanying ;
Qju, Hailong ;
Prasad, Paras N. ;
Chen, Xiaoyuan .
CHEMICAL REVIEWS, 2014, 114 (10) :5161-5214
[5]   Kinetic Analysis of Photochemical Upconversion by Triplet-Triplet Annihilation: Beyond Any Spin Statistical Limit [J].
Cheng, Yuen Yap ;
Fueckel, Burkhard ;
Khoury, Tony ;
Clady, Raphael G. C. R. ;
Tayebjee, Murad J. Y. ;
Ekins-Daukes, N. J. ;
Crossley, Maxwell J. ;
Schmidt, Timothy W. .
JOURNAL OF PHYSICAL CHEMISTRY LETTERS, 2010, 1 (12) :1795-1799
[6]   Correlated defect nanoregions in a metal-organic framework [J].
Cliffe, Matthew J. ;
Wan, Wei ;
Zou, Xiaodong ;
Chater, Philip A. ;
Kleppe, Annette K. ;
Tucker, Matthew G. ;
Wilhelm, Heribert ;
Funnell, Nicholas P. ;
Coudert, Francois-Xavier ;
Goodwin, Andrew L. .
NATURE COMMUNICATIONS, 2014, 5
[7]   Annihilation Limit of a Visible-to-UV Photon Upconversion Composition Ascertained from Transient Absorption Kinetics [J].
Deng, Fan ;
Blumhoff, Joerg ;
Castellano, Felix N. .
JOURNAL OF PHYSICAL CHEMISTRY A, 2013, 117 (21) :4412-4419
[8]   A Water-Stable Porphyrin-Based Metal-Organic Framework Active for Visible-Light Photocatalysis [J].
Fateeva, Alexandra ;
Chater, Philip A. ;
Ireland, Christopher P. ;
Tahir, Asif A. ;
Khimyak, Yaroslav Z. ;
Wiper, Paul V. ;
Darwent, James R. ;
Rosseinsky, Matthew J. .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2012, 51 (30) :7440-7444
[9]   Ultrahigh Porosity in Metal-Organic Frameworks [J].
Furukawa, Hiroyasu ;
Ko, Nakeun ;
Go, Yong Bok ;
Aratani, Naoki ;
Choi, Sang Beom ;
Choi, Eunwoo ;
Yazaydin, A. Oezguer ;
Snurr, Randall Q. ;
O'Keeffe, Michael ;
Kim, Jaheon ;
Yaghi, Omar M. .
SCIENCE, 2010, 329 (5990) :424-428
[10]   Getting to the (Square) Root of the Problem: How to Make Noncoherent Pumped Upconversion Linear [J].
Haefele, Alexandre ;
Blumhoff, Joerg ;
Khnayzer, Rony S. ;
Castellano, Felix N. .
JOURNAL OF PHYSICAL CHEMISTRY LETTERS, 2012, 3 (03) :299-303