Sanyang Han

Imparting functionality to a metal–organic framework material by controlled nanoparticle encapsulation

Microporous metal-organic frameworks (MOFs) that display permanent porosity show great promise for a myriad of purposes. The potential applications of MOFs can be developed further and extended by encapsulating various functional species (for example, nanoparticles) within the frameworks. However, despite increasing numbers of reports of nanoparticle/MOF composites, simultaneously to control the size, composition, dispersed nature, spatial distribution and confinement of the incorporated nanoparticles within MOF matrices remains a significant challenge. Here, we report a controlled encapsulation strategy that enables surfactant-capped nanostructured objects of various sizes, shapes and compositions to be enshrouded by a zeolitic imidazolate framework (ZIF-8). The incorporated nanoparticles are well dispersed and fully confined within the ZIF-8 crystals. This strategy also allows the controlled incorporation of multiple nanoparticles within each ZIF-8 crystallite. The as-prepared nanoparticle/ZIF-8 composites exhibit active (catalytic, magnetic and optical) properties that derive from the nanoparticles as well as molecular sieving and orientation effects that originate from the framework material.

The effect of surface coating on energy migration-mediated upconversion.

Lanthanide-doped upconversion nanoparticles have been the focus of a growing body of investigation because of their promising applications ranging from data storage to biological imaging and drug delivery. Here we present the rational design, synthesis, and characterization of a new class of core-shell upconversion nanoparticles displaying unprecedented optical properties. Specifically, we show that the epitaxial growth of an optically inert NaYF(4) layer around a lanthanide-doped NaGdF(4)@NaGdF(4) core-shell nanoparticle effectively prevents surface quenching of excitation energy. At room temperature, the energy migrates over Gd sublattices and is adequately trapped by the activator ions embedded in host lattices. Importantly, the NaYF(4) shell-coating strategy gives access to tunable upconversion emissions from a variety of activators (Dy(3+), Sm(3+), Tb(3+), and Eu(3+)) doped at very low concentrations (down to 1 mol %). Our mechanistic investigations make possible, for the first time, the realization of efficient emissions from Tb(3+) and Eu(3+) activators that are doped homogeneously with Yb(3+)/Tm(3+) ions. The advances on these luminescent nanomaterials offer exciting opportunities for important biological and energy applications.

Enhancing Luminescence in Lanthanide-Doped Upconversion Nanoparticles

The enthusiasm for research on lanthanide-doped upconversion nanoparticles is driven by both a fundamental interest in the optical properties of lanthanides embedded in different host lattices and their promise for broad applications ranging from biological imaging to photodynamic therapy. Despite the considerable progress made in the past decade, the field of upconversion nanoparticles has been hindered by significant experimental challenges associated with low upconversion conversion efficiencies. Recent experimental and theoretical studies on upconversion nanoparticles have, however, led to the development of several effective approaches to enhancing upconversion luminescence, which could have profound implications for a range of applications. Herein we present the underlying principles of controlling energy transfer through lanthanide doping, overview the major advances and key challenging issues in improving upconversion luminescence, and consider the likely directions of future research in the field.

High-Efficiency in Vitro and in Vivo Detection of Zn2+ by Dye-Assembled Upconversion Nanoparticles

Development of highly sensitive and selective sensing systems of divalent zinc ion (Zn(2+)) in organisms has been a growing interest in the past decades owing to its pivotal role in cellular metabolism, apoptosis, and neurotransmission. Herein, we report the rational design and synthesis of a Zn(2+) fluorescent-based probe by assembling lanthanide-doped upconversion nanoparticles (UCNPs) with chromophores. Specifically, upconversion luminescence (UCL) can be effectively quenched by the chromophores on the surface of nanoparticles via a fluorescence resonant energy transfer (FRET) process and subsequently recovered upon the addition of Zn(2+), thus allowing for quantitative monitoring of Zn(2+). Importantly, the sensing system enables detection of Zn(2+) in real biological samples. We demonstrate that this chromophore-UCNP nanosystem is capable of implementing an efficient in vitro and in vivo detection of Zn(2+) in mouse brain slice with Alzheimers disease and zebrafish, respectively.

Multicolour synthesis in lanthanide-doped nanocrystals through cation exchange in water

Meeting the high demand for lanthanide-doped luminescent nanocrystals across a broad range of fields hinges upon the development of a robust synthetic protocol that provides rapid, just-in-time nanocrystal preparation. However, to date, almost all lanthanide-doped luminescent nanomaterials have relied on direct synthesis requiring stringent controls over crystal nucleation and growth at elevated temperatures. Here we demonstrate the use of a cation exchange strategy for expeditiously accessing large classes of such nanocrystals. By combining the process of cation exchange with energy migration, the luminescence properties of the nanocrystals can be easily tuned while preserving the size, morphology and crystal phase of the initial nanocrystal template. This post-synthesis strategy enables us to achieve upconversion luminescence in Ce3+ and Mn2+-activated hexagonal-phased nanocrystals, opening a gateway towards applications ranging from chemical sensing to anti-counterfeiting.

Photon Upconversion Through Tb3+‐Mediated Interfacial Energy Transfer

A strategy of interfacial energy transfer upconversion is demonstrated through the use of a terbium (Tb(3+) ) dopant as energy donor or energy migrator in core-shell-structured nanocrystals. This mechanistic investigation presents a new pathway for photon upconversion, and, more importantly, contributes to the better control of energy transfer at the nanometer length scale.

A BODIPY-functionalized bimetallic probe for sensitive and selective color-fluorometric chemosensing of Hg2+

A new BODIPY dye conjugate has demonstrated selective quenching by mercury over other metal ions. Coupling of this probe to Au-Fe(3)O(4) nanoparticles as well as platinum electrodes offered sensitive systems for suspension and surface based sensing, respectively.

Gold and Hairpin DNA Functionalization of Upconversion Nanocrystals for Imaging and In Vivo Drug Delivery

Although multifunctional upconversion imaging probes have recently attracted considerable interest in biomedical research, there are currently few methods for stabilizing these luminescent nanoprobes with oligonucleotides in biological systems. Herein, a method to robustly disperse upconversion nanoprobes in physiological buffers based on rational design and synthesis of nanoconjugates comprising hairpin-DNA-modified gold nanoparticles is presented. This approach imparts the upconversion nanoprobes with excellent biocompatibility and circumvents the problem of particle agglomeration. By combining single-band anti-Stokes near-infrared emission and the photothermal effect mediated by the coupling of gold to upconversion nanoparticles, a simple, versatile nanoparticulate system for simultaneous deep-tissue imaging and drug molecule release in vivo is demonstrated.

Intracellular Adenosine Triphosphate Deprivation through Lanthanide-Doped Nanoparticles

Growing interest in lanthanide-doped nanoparticles for biological and medical uses has brought particular attention to their safety concerns. However, the intrinsic toxicity of this new class of optical nanomaterials in biological systems has not been fully evaluated. In this work, we systematically evaluate the long-term cytotoxicity of lanthanide-doped nanoparticles (NaGdF4 and NaYF4) to HeLa cells by monitoring cell viability (mitochondrial activity), adenosine triphosphate (ATP) level, and cell membrane integrity (lactate dehydrogenase release), respectively. Importantly, we find that ligand-free lanthanide-doped nanoparticles induce intracellular ATP deprivation of HeLa cells, resulting in a significant decrease in cell viability after exposure for 7 days. We attribute the particle-induced cell death to two distinct cell death pathways, autophagy and apoptosis, which are primarily mediated via the interaction between the nanoparticle and the phosphate group of cellular ATP. The understanding gained from the investigation of cytotoxicity associated with lanthanide-doped nanoparticles provides keen insights into the safe use of these nanoparticles in biological systems.

Real-Time In Vivo Hepatotoxicity Monitoring through Chromophore-Conjugated Photon-Upconverting Nanoprobes

Drug toxicity is a long-standing concern of modern medicine. A typical anti-pain/fever drug paracetamol often causes hepatotoxicity due to peroxynitrite ONOO- . Conventional blood tests fail to offer real-time unambiguous visualization of such hepatotoxicity in vivo. Here we report a luminescent approach to evaluate acute hepatotoxicity in vivo by chromophore-conjugated upconversion nanoparticles. Upon injection, these nanoprobes mainly accumulate in the liver and the luminescence of nanoparticles remains suppressed owing to energy transfer to the chromophore. ONOO- can readily bleach the chromophore and thus recover the luminescence, the presence of ONOO- in the liver leads to fast restoring of the near-infrared emission. Taking advantages of the high tissue-penetration capability of near-infrared excitation/emission, these nanoprobes achieve real-time monitoring of hepatotoxicity in living animals, thereby providing a convenient screening strategy for assessing hepatotoxicity of synthetic drugs.