Recent startling interest for lanthanide luminescence is stimulated by the continuously expanding need for luminescent materials meeting the stringent requirements of telecommunication, lighting, electroluminescent devices, (bio-)analytical sensors and bio-imaging set-ups. This critical review describes the latest developments in (i) the sensitization of near-infrared luminescence, (ii) “soft” luminescent materials (liquid crystals, ionic liquids, ionogels), (iii) electroluminescent materials for organic light emitting diodes, with emphasis on white light generation, and (iv) applications in luminescent bio-sensing and bio-imaging based on time-resolved detection and multiphoton excitation (500 references).

/pdf/lanthanide-luminescence-for-functional-materials-and-bio-1w9cppwf8r.pdf

Lanthanide luminescence for functional materials and bio-sciences

Lanthanide ions exhibit unique luminescent properties, including the ability to convert near infrared long-wavelength excitation radiation into shorter visible wavelengths through a process known as photon upconversion. In recent years lanthanide-doped upconversion nanocrystals have been developed as a new class of luminescent optical labels that have become promising alternatives to organic fluorophores and quantum dots for applications in biological assays and medical imaging. These techniques offer low autofluorescence background, large anti-Stokes shifts, sharp emission bandwidths, high resistance to photobleaching, and high penetration depth and temporal resolution. Such techniques also show potential for improving the selectivity and sensitivity of conventional methods. They also pave the way for high throughput screening and miniaturization. This tutorial review focuses on the recent development of various synthetic approaches and possibilities for chemical tuning of upconversion properties, as well as giving an overview of biological applications of these luminescent nanocrystals.

Recent advances in the chemistry of lanthanide-doped upconversion nanocrystals

Sasidharan Swarnalatha Lucky,†,§ Khee Chee Soo,‡ and Yong Zhang*,†,§,∥ †NUS Graduate School for Integrative Sciences & Engineering (NGS), National University of Singapore, Singapore, Singapore 117456 ‡Division of Medical Sciences, National Cancer Centre Singapore, Singapore, Singapore 169610 Department of Biomedical Engineering, Faculty of Engineering, National University of Singapore, Singapore, Singapore 117576 College of Chemistry and Life Sciences, Zhejiang Normal University, Zhejiang, P. R. China 321004

Nanoparticles in photodynamic therapy.

Applications in Theranostics Guanying Chen,*,†,‡ Hailong Qiu,†,‡ Paras N. Prasad,*,‡,§ and Xiaoyuan Chen* †School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin, Heilongjiang 150001, China ‡Department of Chemistry and the Institute for Lasers, Photonics, and Biophotonics, University at Buffalo, State University of New York, Buffalo, New York 14260, United States Department of Chemistry, Korea University, Seoul 136-701, Korea Laboratory of Molecular Imaging and Nanomedicine, National Institute of Biomedical Imaging and Bioengineering, National Institutes of Health, Bethesda, Maryland 20892-2281, United States

Upconversion Nanoparticles: Design, Nanochemistry, and Applications in Theranostics

Upconversion luminescent materials: advances and applications.

Successful further development of superhigh-constrast upconversion (UC) bioimaging requires addressing the existing paradox: 980 nm laser light is used to excite upconversion nanoparticles (UCNPs), while 980 nm light has strong optical absorption of water and biological specimens. The overheating caused by 980 nm excitation laser light in UC bioimaging is computationally and experimentally investigated for the first time. A new promising excitation approach for better near-infrared to near-infrared (NIR-to-NIR) UC photoluminescence in vitro or in vivo imaging is proposed employing a cost-effective 915 nm laser. This novel laser excitation method provides drastically less heating of the biological specimen and larger imaging depth in the animals or tissues due to quite low water absorption. Experimentally obtained thermal-graphic maps of the mouse in response to the laser heating are investigated to demonstrate the less heating advantage of the 915 nm laser. Our tissue phantom experiments and simulations verified that the 915 nm laser is superior to the 980 nm laser for deep tissue imaging. A novel and facile strategy for surface functionalization is utilized to render UCNPs hydrophilic, stable, and cell targeting. These as-prepared UCNPs were characterized by TEM, emission spectroscopy, XRD, FTIR, and zeta potential. Specifically targeting UCNPs excited with a 915 nm laser have shown very high contrast UC bioimaging. Highly stable DSPE-mPEG-5000-encapsulated UCNPs were injected into mice to perform in vivo imaging. Imaging and spectroscopy analysis of UC photoluminescence demonstrated that a 915 nm laser can serve as a new promising excitation light for UC animal imaging.

Using 915 nm Laser Excited Tm3+/Er3+/Ho3+-Doped NaYbF4 Upconversion Nanoparticles for in Vitro and Deeper in Vivo Bioimaging without Overheating Irradiation

We demonstrate that tridoping with Li+ ions enhances the visible green and red upconversion (UC) emissions in Er3+/Yb3+-codoped Y2O3 nanocrystals by up to half of the bulk counterpart, i.e., about 2 orders of magnitude higher than previous results. X-ray diffraction and decay time investigations give evidence that tridoping with Li+ ions can tailor the local crystal field of the Y2O3 host lattice. Theoretical calculations illustrate well that a significant UC intensity enhancement arises from the synthesized tailoring effect induced by the Li+ ions, which increase lifetimes in the intermediate 4I11/2 (Er) and 2F5/2 (Yb) states, increase optically active sites in the Y2O3 host lattice, and dissociate the Yb3+ and Er3+ ion clusters in the nanocrytals. The general theoretical description of the visible UC radiations shows that the Yb3+ ion sensitization and the tailoring effect induced by the Li+ ions are two independent enhancement mechanisms, which is expected to lead to an increasing number of photonic an...

Upconversion Emission Enhancement in Yb3+/Er3+-Codoped Y2O3 Nanocrystals by Tridoping with Li+ Ions

Upconversion (UC) emission tuning from green to red in monodisperse NaYF(4):Yb(3+)/Ho(3+) nanocrystals was successfully achieved by tridoping with Ce(3+) ions under diode laser excitation of 970 nm. It is proposed that two efficient cross-relaxation processes, 5S2/5F4(Ho) + 2F(5/2)(Ce) --> 5F5(Ho) + 2F(7/2)(Ce) and 5I6(Ho) + 2F(5/2)(Ce) --> 5I7(Ho) + 2F(7/2)(Ce)between Ho(3+) and Ce(3+) ions, have been employed to select UC pathways to tune the UC radiation. Theoretical investigations based on steady-state equations demonstrate the proposed UC mechanisms and explain well the observed linear increase of the UC red-to-green intensity ratio with the increment of Ce(3+) ion concentrations.

https://iopscience.iop.org/article/10.1088/0957-4484/20/38/385704/pdf

Upconversion emission tuning from green to red in Yb3+/Ho3+-codoped NaYF4 nanocrystals by tridoping with Ce3+ ions

Two-color upconversion (UC) emissions with anomalous power dependence were observed in spectrally tailored rare-earth-ion-doped $\mathrm{Zr}{\mathrm{O}}_{2}$ nanocrystals. Single green and red UC radiation in the visible range was induced by $980\phantom{\rule{0.3em}{0ex}}\mathrm{nm}$ diode laser excitation in $\mathrm{Zr}{\mathrm{O}}_{2}:{\mathrm{Er}}^{3+}$ and $\mathrm{Zr}{\mathrm{O}}_{2}:{\mathrm{Er}}^{3+}+{\mathrm{Yb}}^{3+}$ nanocrystals, yielding quadratic and linear laser power dependences, respectively. The UC spectrum design is enabled by the saturation of the $^{4}I_{13∕2}(\mathrm{Er})$ state through the efficient energy back-transfer process $^{4}S_{3∕2}(\mathrm{Er})+^{2}F_{7∕2}(\mathrm{Yb})\ensuremath{\rightarrow}^{4}I_{13∕2}(\mathrm{Er})+^{2}F_{5∕2}(\mathrm{Yb})$ induced by high ${\mathrm{Yb}}^{3+}$-ion concentration. The anomalous power dependence originates from the fact that the UC rate of the $^{4}I_{11∕2}(\mathrm{Er})$ state at high ${\mathrm{Yb}}^{3+}$-ion concentrations is fundamentally much larger than its decay rate. These conclusions obtained are confirmed by theoretical investigations based on steady-state rate equations.

Upconversion mechanism for two-color emission in rare-earth-ion-doped Zr O 2 nanocrystals

Room temperature bright white upconversion (UC) luminescence in Yb3+–Tm3+–Er3+ ions doped Y2O3 nanocrystals was obtained under single-wavelength diode laser excitation of 976nm The white light consists of the blue, green, and red UC radiations which correspond to the transitions G41→H63 of Tm3+, H11∕22∕S3∕24→I15∕24, and F9∕24→I15∕24 of Er3+ ions, respectively The UC mechanisms were proposed based on spectral, kinetic, and pump power dependence analyses The calculated color coordinates display that white light can be achieved in a wide range of pumping powers, which promises their potential applications in the field of displays, lasers, photonics, and biomedicine

Gabriel Somesfalean

Papers

Using 915 nm Laser Excited Tm3+/Er3+/Ho3+-Doped NaYbF4 Upconversion Nanoparticles for in Vitro and Deeper in Vivo Bioimaging without Overheating Irradiation

Upconversion Emission Enhancement in Yb3+/Er3+-Codoped Y2O3 Nanocrystals by Tridoping with Li+ Ions

Upconversion emission tuning from green to red in Yb3+/Ho3+-codoped NaYF4 nanocrystals by tridoping with Ce3+ ions

Upconversion mechanism for two-color emission in rare-earth-ion-doped Zr O 2 nanocrystals

Bright white upconversion luminescence in rare-earth-ion-doped Y2O3 nanocrystals