A new approach for photoluminescence imaging in vitro and in vivo has been shown, utilizing near infrared to near infrared (NIR-to-NIR) up-conversion in nanophosphors. This NIR-to-NIR up-conversion process provides deeper light penetration into biological specimen and results in high contrast optical imaging due to absence of an autofluorescence background and decreased light scattering. Aqueous dispersible fluoride (NaYF4) nanocrystals (20–30 nm size) co-doped with the rare earth ions, Tm3+ and Yb3+, were synthesized and characterized by TEM, XRD and photoluminescence (PL) spectroscopy. In vitro cellular uptake was shown by the PL microscopy visualizing the characteristic emission of Tm3+ at ~ 800 nm excited with 975 nm. No apparent cytotoxicity was observed. Subsequent animal imaging studies were performed using Balb-c mice injected intravenously with up-converting nanophosphors, demonstrating the high contrast PL imaging in vivo.

Here, novel nanoprobes for combined optical and magnetic resonance (MR) bioimaging are reported. Fluoride (NaYF4) nanocrystals (20–30 nm size) co‐doped with the rare earth ions Gd3+ and Er3+/Yb3+/Eu3+ are synthesized and dispersed in water. An efficient up‐ and downconverted photoluminescence from the rare‐earth ions (Er3+ and Yb3+ or Eu3+) doped into fluoride nanomatrix allows optical imaging modality for the nanoprobes. Upconversion nanophosphors (UCNPs) show nearly quadratic dependence of the photoluminescence intensity on the excitation light power, confirming a two‐photon induced process and allowing two‐photon imaging with UCNPs with low power continuous wave laser diodes due to the sequential nature of the two‐photon process. Furthermore, both UCNPs and downconversion nanophosphors (DCNPs) are modified with biorecognition biomolecules such as anti‐claudin‐4 and anti‐mesothelin, and show in vitro targeted delivery to cancer cells using confocal microscopy. The possibility of using nanoprobes for optical imaging in vivo is also demonstrated. It is also shown that Gd3+ co‐doped within the nanophosphors imparts strong T1 (Spin‐lattice relaxation time) and T2 (spin‐spin relaxation time) for high contrast MR imaging. Thus, nanoprobes based on fluoride nanophosphors doped with rare earth ions are shown to provide the dual modality of optical and magnetic resonance imaging.

We report that non-contact optical temperature sensing can be achieved with the use of heavily Nd(3+) doped NaYF(4) nanoparticles. The temperature evaluation can be realized either by monitoring the absolute luminescence intensity or by measuring the intensity ratio of the two Stark components of the (4)F(3/2) multiplet in the Nd(3+) ions.

We report a method for fabricating predefined photopatterns of upconversion nanophosphors using a chemical amplification reaction for direct writing of films with multilayer color-coded patterning for security applications. To photopattern the nanocrystal film we have synthesized rare-earth ion (Er(3+)/Yb(3+) or Tm(3+)/Yb(3+)) co-doped sodium yttrium fluoride (alpha-NaYF(4)) nanophosphors and functionalized the nanocrystal surfaces by incorporation of a photopatternable ligand such as t-butoxycarbonyl (t-BOC). The surface modification allows photopatterning of the nanophosphor solid state film. Furthermore, upconversion nanophosphors show a nearly quadratic dependence of the upconversion photoluminescence (PL) intensity on the excitation light power, and tailoring of the PL wavelength is possible by changing the lanthanide ions. We have demonstrated the capability of anchoring nanophosphors at desirable locations by a photolithography technique. The photopatterned films exhibit fixed nanophosphor structures clearly identifiable by strong upconversion photoluminescence under IR illumination which is useful for a number of applications in security.

In this paper we show that biocompatible zinc oxide (ZnO) nanocrystals (NCs) having noncentrosymmetric structure can be used as non-resonant nonlinear optical probes for targeting in bioimaging applications in vitro by use of the second order processes of second harmonic and sum frequency generation, as well as the third order process of four wave mixing. These non-resonant processes provide advantages above and beyond traditional two-photon bioimaging: (i) the probes do not photo-bleach; (ii) the input wavelength can be judiciously selected; and (iii) no heat is dissipated into the cells, ensuring longer cell viability and ultimately longer imaging times. ZnO NCs have been synthesized in organic media by using a non-hydrolytic sol-gel process, and subsequently dispersed in aqueous media using phospholipid micelles, and incorporated with the biotargeting molecule folic acid (FA). Sum Frequency, Second Harmonic and non-resonant four wave mixing non-linear signals from this stable dispersion of ZnO NCs, targeted to the live tumor (KB) cells were used for imaging. Robust intracellular accumulation of the targeted (FA incorporated) ZnO nanocrystals could be observed, without any indication of cytotoxicity.

Förster resonance energy transfer (FRET) between nanoparticles of up-conversion lanthanide phosphor as donors and quantum dots as acceptors is demonstrated. Fluoride (NaYF4) nanocrystals (ca. 30 nm size) codoped with the Er3+ and Yb3+ ions were synthesized with a high-pressure solvothermal microwave assisted technique and dispersed in organic solvent. Up-converted luminescence from the rare-earth ions doped into fluoride nanomatrix was achieved with optical pumping in NIR (976 nm) region. The green erbium upconversion emission at 540 nm is efficiently quenched by quantum dots (QDs) leading to color change of the mixture for different relative concentrations. Simultaneously, orange emission from quantum dots appears due to energy transfer from Er3+/Yb3+:NPs donors to QDs acceptors. The concomitant decrease of the average lifetime of donor emission at 540 nm (from ∼153 to ∼130 μs) indicates that the excitation of CdSe QDs occurs not only through reabsorption but also through Förster Resonance Energy Transfer. Acceptor luminescence lifetime mimics that of the donor and reaches hundreds of microseconds. The Förster radius (R 0) was calculated to be short (∼15 Å), mostly due to low quantum yield of the multilevel emitting donor. This short-range interaction proves that in our system the FRET occurs mostly through Er3+ ions proximate to the surface, resulting in efficiency of energy transfer equal to η = 14.8%.

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A mixed-metal approach has been used to control the size and physicochemical properties of heterometallic Co/ZIF-8 nanomaterials. Intentional substitution of zinc with cobalt in a broad concentration range (from 0 to 100 molar percent with a 10% step) provided a series of Co/ZIF-8 nanoparticles, whose sizes could be tuned in the range from 20 to over 500 nm in diameter. Zinc ions from the ZIF-8 matrix were found to be uniformly substituted with the cobalt ions. The increase of nanoparticles size resulted in a change of their nitrogen sorption−desorption characteristics due to decreasing participation of the external surface area in the total surface area. Insights from UV−vis-NIR and IR spectroscopies, as well as remarks on nonlinear optical properties are also provided.