Phase Transfer Of Quantum Dots Research Articles

Oligomeric Zinc Thiolates Tethering Multidentate Carboxylates for Nondestructive Aqueous Phase Transfer of Quantum Dots.

Functionalization of quantum dots (QDs) via ligand exchange is prone to debase their photoluminescence quantum yield (PL QY) owing to the unavoidable surface damage by excess reactants, and even worse in aqueous medium. Herein, the oligomeric zinc thiolate as the multidentate hydrophilic ligand featuring facile synthetic protocol is proposed. A simple reaction between ZnCl2 and 3-mercaptopropionic acid produces oligomeric ligands containing 3-6 zinc thiolate units, where the terminal moieties provide multidentate anchoring to the surface as well as hydrophilicity. 2D proton nuclear Overhauser effect spectroscopy (2D 1 H NOESY) and X-ray photoelectron spectroscopy (XPS) reveal that the oligomeric zinc thiolate ligands adsorb on the surface via multidentate metal carboxylate bindings without destruction of molecular structure, regardless of partial dissociation of thiolate branches in aqueous phase. Enhanced binding affinity granted by the multidentate nature allows for the effective exchange of original surface ligands without considerable surface deterioration. The zinc thiolate-capped Cd-free aqueous QDs exhibit a high photoluminescence quantum yield of ≈90% and extended stability against long-term storage and photochemical stress.

Quantum Dot Transfer from the Organic Phase to Acrylic Monomers for the Controlled Integration of Single-Photon Sources by Photopolymerization

This paper reports on a new strategy for obtaining homogeneous dispersion of grafted quantum dots (QDs) in a photopolymer matrix and their use for the integration of single-photon sources by two-photon polymerization (TPP) with nanoscale precision. The method is based on phase transfer of QDs from organic solvents to an acrylic matrix. The detailed protocol is described, and the corresponding mechanism is investigated and revealed. The phase transfer is done by ligand exchange through the introduction of mono-2-(methacryloyloxy) ethyl succinate (MES) that replaces oleic acid (OA). Infrared (IR) measurements show the replacement of OA on the QD surface by MES after ligand exchange. This allows QDs to move from the hexane phase to the pentaerythritol triacrylate (PETA) phase. The QDs that are homogeneously dispersed in the photopolymer without any clusterization do not show any significant broadening in their photoluminescence spectra even after more than 3 years. The ability of the hybrid photopolymer to create micro- and nanostructures by two-photon polymerization is demonstrated. The homogeneity of emission from 2D and 3D microstructures is confirmed by confocal photoluminescence microscopy. The fabrication and integration of a single-photon source in a spatially controlled manner by TPP is achieved and confirmed by auto-correlation measurements.

Water-Solubilizing Hydrophobic ZnAgInSe/ZnS QDs with Tumor-Targeted cRGD-Sulfobetaine-PIMA-Histamine Ligands via a Self-Assembly Strategy for Bioimaging.

Exploring the organic-to-aqueous phase transfer of quantum dots (QDs) is significant for achieving their versatile applications in biomedical fields. In this thematic issue, surface modification, size control, and biocompatibility of QDs and QDs-based nanocomposites are core problems. Herein, the new highly fluorescent tumor-targeted QDs-clusters consisting of ZnAgInSe/ZnS (ZAISe/ZnS) QDs and sulfobetaine-PIMA-histamine (SPH) polymer with the ανβ3 integrin receptor cyclic RGD (c-RGD) were developed via ligand exchange and an accompanying self-assembly process. It was found that the structure of RGD-SPH QDs-clusters was propitious to reduce the capture of reticulo-endothelial system (RES) in virtue of external stealth ligands, and benefit to selectively accumulate at the tumor site after intravenous injection via active tumor targeting cooperated with the enhanced permeability and retention (EPR) effect. In the meantime, those clusters also recognized and enriched the cell surface when cocultured with the ανβ3 integrin receptor overexpressed malignant cells (U87MG tumor). On the basis of the results, fabricating mutil-functional nanocomposites integrated with the long-term circulation and dual-targeting effects should be an interesting strategy for imaging cancer in vitro and in vivo.

Hydrophobin-Encapsulated Quantum Dots.

The phase transfer of quantum dots to water is an important aspect of preparing nanomaterials that are suitable for biological applications, and although numerous reports describe ligand exchange, very few describe efficient ligand encapsulation techniques. In this report, we not only report a new method of phase transferring quantum dots (QDs) using an amphiphilic protein (hydrophobin) but also describe the advantages of using a biological molecule with available functional groups and their use in imaging cancer cells in vivo and other imaging applications.

Reversible phase transfer of quantum dots by gas bubbling

Amine-capped, lipophilic CdSe/ZnS quantum dots can be transferred in the presence of a switchable surfactant, specifically N′-oleyl-N,N-dimethylacetamidine, from an organic phase to water and then reverted to the organic phase simply by the addition/removal of carbon dioxide. The strategy is based on interdigitation of the surfactant between the non-polar ligands of the nanoparticles. The reversibility of the phase transfer is possible in at least ten cycles, after which the initial quantum dots, with their optical features preserved, can be recovered by simple precipitation in methanol, followed by centrifugation. This approach is most appealing, since external stimulus (carbon dioxide bubbling) could be obtained from a waste product, which is easily removed from the system by nitrogen bubbling. This article contains supporting information that will be made available online once the issue is published.

SYNTHESIS, PHASE TRANSFER AND SURFACE MODIFICATION OF HYDROPHOBIC QUANTUM DOTS FOR BIOAPPLICATIONS

We review the preparation, phase transfer, surface modification and possible bioapplications of hydrophobic CdSe based quantum dots (QDs). CdSe cores with rod and spherical morphologies were prepared through adjusting preparation conditions. The photoluminescence (PL) of the QDs depended strongly on preparation conditions. The QDs were coated with semiconductor shells to improve their PL properties. Anisotropic growth occurred during shell coating. Core/shell QDs revealed tunable PL and high PL efficiencies up to 90%. The phase transfer of QDs from oil phase to water phase was carried out via polymer or a sol–gel process. The silanization of the QDs plays an important role for the sol–gel process. Because of a SiO2 coating, the surface modification of the QDs for bioapplications became easy. After transferring into water phase, the QDs still retained high PL efficiency. Because of their high PL, these biofunctional materials could provide a platform for various applications.

Natural Organic Matter-Mediated Phase Transfer of Quantum Dots in the Aquatic Environment

Imminent commercialization of semiconductor quantum dots (QDs) has raised concerns regarding the potential environmental impact of these materials. Understanding the partitioning behavior and obtaining information on the mobility and persistence of QDs in water is key to evaluating potential ecological hazards posed by QDs in the environment The role of natural organic matter (NOM) in the phase transfer of trioctylphosphine oxide-capped CdSe QDs from an organic solvent to water has been investigated. Results show that humic and fulvic acids, which have been used as model NOM, facilitate the stabilization of organic-capped QDs in water in less than 24 h. Spectroscopic studies indicate that some or all of the organic ligands of QDs are conserved during the phase transfer. The displacement of organic ligands by NOM also appears to play a role in phase transfer. This NOM-mediated phase transfer has also been demonstrated using two natural surface water samples. This study presents the first evidence of the stabilization of QDs in water by humic substances in real environmental samples, illustrating that interactions with NOM will play a significant role in the fate and transport of QDs in natural aquatic systems.

Tailor‐Made Ligands for Biocompatible Nanoparticles

Designer jackets: Polydentate amino-functionalized poly(ethylene oxide)s with various block lengths are synthesized and used for ligand exchange and phase transfer of quantum dots and magnetic nanoparticles (see scheme; TEM images of the particles before and after the exchange are also shown). The ligands enable the transfer of the previously water-insoluble particles into aqueous media.