Low-Temperature Approach to Highly Emissive Copper Indium Sulfide Colloidal Nanocrystals and Their Bioimaging Applications

Abstract

/npsi/ctrl?action=rtdoc&an=21270647&lang=en http://nparc.cisti-icist.nrc-cnrc.gc.ca/npsi/ctrl?action=rtdoc&an=21270647&lang=fr READ THESE TERMS AND CONDITIONS CAREFULLY BEFORE USING THIS WEBSITE.http://nparc.cisti-icist.nrc-cnrc.gc.ca/npsi/jsp/nparc_cp.jsp?lang=en Vous avez des questions? Nous pouvons vous aider. Pour communiquer directement avec un auteur, consultez la première page de la revue dans laquelle son article a été publié afin de trouver ses coordonnées. Si vous n'arrivez pas à les repérer, communiquez avec nous à PublicationsArchive-ArchivesPublications@nrc-cnrc.gc.ca. Questions?Contact the NRC Publications Archive team at PublicationsArchive-ArchivesPublications@nrc-cnrc.gc.ca. If you wish to email the authors directly, please see the first page of the publication for their contact information. NRC Publications Archive Archives des publications du CNRCThis publication could be one of several versions: author's original, accepted manuscript or the publisher's version. / La version de cette publication peut être l'une des suivantes : la version prépublication de l'auteur, la version acceptée du manuscrit ou la version de l'éditeur. For the publisher's version, please access the DOI link below./ Pour consulter la version de l'éditeur, utilisez le lien DOI ci-dessous.http://doi.org/10.1021/am302951k ACS Applied Materials and Interfaces, 5, 8, pp. 2870-2880, 2013 ABSTRACT: We report our newly developed low-temperature synthesis of colloidal photoluminescent (PL) CuInS 2 nanocrystals (NCs) and their in vitro and in vivo imaging applications. With diphenylphosphine sulphide (SDPP) as a S precursor made from elemental S and diphenylphosphine, this is a noninjection based approach in 1-dodecanethiol (DDT) with excellent synthetic reproducibility and large-scale capability. For a typical synthesis with copper iodide (CuI) as a Cu source and indium acetate (In(OAc) 3 ) as an In source, the growth temperature was as low as 160°C and the feed molar ratios were 1Cu-to-1In-to-4S. Amazingly, the resulting CuInS 2 NCs in toluene exhibit quantum yield (QY) of ∼23% with photoemission peaking at ∼760 nm and full width at half maximum (FWHM) of ∼140 nm. With a mean size of ∼3.4 nm (measured from the vertices to the bases of the pyramids), they are pyramidal in shape with a crystal structure of tetragonal chalcopyrite. In situ 31 P NMR (monitored from 30°C to 100°C) and in situ absorption at 80°C suggested that the Cu precursor should be less reactive toward SDPP than the In precursor. For our in vitro and in vivo imaging applications, CuInS 2 /ZnS core−shell QDs were synthesized; afterwards, dihydrolipoic acid (DHLA) or 11-mercaptoundecanoic acid (MUA) were used for ligand exchange and then bio-conjugation was performed. Two single-domain antibodies (sdAbs) were used. One was 2A3 for in vitro imaging of BxPC3 pancreatic cancer cells. The other was EG2 for in vivo imaging of a Glioblastoma U87MG brain tumour model. The bioimaging data illustrate that the CuInS 2 NCs from our SDPP-based low-temperature noninjection appr...

The phase transformation of CuInS2 from chalcopyrite to wurtzite

“…Cu + is a soft acid, In 3+ is a hard acid, and the TGA is a soft base which will react preferentially with soft acid Cu + [17]. The Cu-SR bond should be stronger than the In-SR bond [12,18]. Therefore, the excess of TGA can balance the reaction rate between Cu + and In 3+ and S 2− .…”

Structural and optical characterization of CuInS2 quantum dots synthesized by microwave-assisted continuous flow methods

“…The core CIS QDs showed essentially no visible PL as expected for OLA-capped CIS (Yu et al 2013). Cation exchange was used to increase the bandgap and passivate trap states on the QD surface to increase PLQY.…”

“…The synthesis of CuInS 2 nanocrystals was adapted from Yu et al (2013). All reagents were stored in an oxygen and moisture-free glovebox.…”

Small GSH-Capped CuInS2 Quantum Dots: MPA-Assisted Aqueous Phase Transfer and Bioimaging Applications

“…12,13 On the contrary, I-III-VI CuInS 2 and CuInSe 2 QDs have a large spectral tunable range (500~900 nm) and high photoluminescence quantum yields (PLQYs ~70%) and less toxicity, which make them promising candidates for bio-applicaitons. [14][15][16][17][18][19][20] Although, CuInS 2 based QDs could be directly fabricated in water, the available aqueous routes only give samples with narrow emissive ranges and low QYs. 21-23 Highquality I-III-VI CuInS 2 and CuInSe 2 QDs produced in organic solvents are insoluble in water.…”