Strategies for photoluminescence enhancement of AgInS2 quantum dots and their application as bioimaging probes

We report the effect of the initial Ag : In stoichiometry, capping ligand concentration, and reaction temperature on the optical properties (such as photoluminescence [PL] quantum yield, PL full width at half-maximum, and wavelength of maximum PL emission) of AgInS2 quantum dots (QDs). The fabricated QDs exhibit excellent optical characteristics, including PL quantum yields of up to 22% and the appearance of an excitonic absorption peak. This is the first reported observation of such a well-defined exciton absorption feature in AgInS2 QDs. Its appearance could indicate a relatively narrow size distribution or minimization of nonradiative recombination at the surface sites of the QDs. Moreover, we report one-pot two-step synthesis of highly luminescent AgInS2–ZnS QDs by injection of ZnS precursors directly into the same reactor with existing AgInS2 cores without any purification. In addition, to demonstrate their potential biomedical application, the AgInS2–ZnS QDs were coated with poly(maleic anhydride-alt-1-octadecene) and further conjugated with folic acid for human liver carcinoma (HepG2) tumor cell labeling. The folate-receptor-mediated cellular uptake of the folic-acid-conjugated AgInS2–ZnS QDs was confirmed by confocal imaging characterization. Additionally, the small dimensions and high solubility of the folic-acid-conjugated AgInS2–ZnS QDs were also exploited in prefixed-cell staining; the QDs entered the complex cellular matrix and stained both the nucleoli and cytoplasm of HepG2 cells.

[1]  H. Low,et al.  Preparation of Ag(2)S nanocrystals of predictable shape and size. , 2004, Angewandte Chemie.

[2]  Taeghwan Hyeon,et al.  Synthesis of monodisperse spherical nanocrystals. , 2007, Angewandte Chemie.

[3]  Tsukasa Torimoto,et al.  Facile synthesis of ZnS-AgInS2 solid solution nanoparticles for a color-adjustable luminophore. , 2007, Journal of the American Chemical Society.

[4]  Philip S Low,et al.  Discovery and development of folic-acid-based receptor targeting for imaging and therapy of cancer and inflammatory diseases. , 2008, Accounts of chemical research.

[5]  V. Klimov,et al.  Efficient synthesis of highly luminescent copper indium sulfide-based core/shell nanocrystals with surprisingly long-lived emission. , 2011, Journal of the American Chemical Society.

[6]  T. Omata,et al.  Colloidal Synthesis of Ternary Copper Indium Diselenide Quantum Dots and Their Optical Properties , 2009 .

[7]  Xiaogang Peng,et al.  Mechanisms of the Shape Evolution of CdSe Nanocrystals , 2001 .

[8]  W. Knoll,et al.  Embryonic Nuclei-Induced Alloying Process for the Reproducible Synthesis of Blue-Emitting ZnxCd1-xSe Nanocrystals with Long-Time Thermal Stability in Size Distribution and Emission Wavelength , 2004 .

[9]  Vincenzo Grillo,et al.  Topologically controlled growth of magnetic-metal-functionalized semiconductor oxide nanorods. , 2007, Nano letters.

[10]  S. Gambhir,et al.  Quantum Dots for Live Cells, in Vivo Imaging, and Diagnostics , 2005, Science.

[11]  Jin-Sil Choi,et al.  Shape control of semiconductor and metal oxide nanocrystals through nonhydrolytic colloidal routes. , 2006, Angewandte Chemie.

[12]  Y. Hamanaka,et al.  Photoluminescence Properties and Its Origin of AgInS2 Quantum Dots with Chalcopyrite Structure , 2011 .

[13]  R. P. Andres,et al.  Synthesis and grafting of thioctic acid-PEG-folate conjugates onto Au nanoparticles for selective targeting of folate receptor-positive tumor cells. , 2006, Bioconjugate chemistry.

[14]  Yuliang Zhang,et al.  Facile and Reproducible Synthesis of Red-Emitting CdSe Nanocrystals in Amine with Long-Term Fixation of Particle Size and Size Distribution , 2007 .

[15]  Jiang Tang,et al.  Infrared Colloidal Quantum Dots for Photovoltaics: Fundamentals and Recent Progress , 2011, Advanced materials.

[16]  Yadong Yin,et al.  Colloidal nanocrystal synthesis and the organic–inorganic interface , 2005, Nature.

[17]  Edward H Sargent,et al.  Colloidal quantum dot photovoltaics: a path forward. , 2011, ACS nano.

[18]  C. Youn,et al.  Origin of point defects in AgInS2/GaAs epilayer obtained from photoluminescence measurement , 2001 .

[19]  Hiroshi Yokoyama,et al.  Temperature-sensitive photoluminescence of CdSe quantum dot clusters. , 2005, The journal of physical chemistry. B.

[20]  Peter Wick,et al.  Nanotoxicology: an interdisciplinary challenge. , 2011, Angewandte Chemie.

[21]  Jia-Yaw Chang,et al.  Facile one-pot synthesis of copper sulfide-metal chalcogenide anisotropic heteronanostructures in a noncoordinating solvent. , 2011, Chemical communications.

[22]  J. Ying,et al.  Synthesis and Cell‐Imaging Applications of Glutathione‐Capped CdTe Quantum Dots , 2007 .

[23]  Sang-Wook Kim,et al.  Step-Wise Synthesis of InP/ZnS Core−Shell Quantum Dots and the Role of Zinc Acetate , 2009 .

[24]  P. Low,et al.  Tumor detection using folate receptor-targeted imaging agents , 2008, Cancer and Metastasis Reviews.

[25]  A. Zunger,et al.  Defect physics of the CuInSe 2 chalcopyrite semiconductor , 1998 .

[26]  M. Ruckh,et al.  Radiative recombination in CuInSe2 thin films , 1997 .

[27]  R. J. Lee,et al.  Targeted drug delivery via the folate receptor. , 2000, Advanced drug delivery reviews.

[28]  Xiaogang Peng,et al.  Formation of high-quality I-III-VI semiconductor nanocrystals by tuning relative reactivity of cationic precursors. , 2009, Journal of the American Chemical Society.

[29]  D. Dunlavy,et al.  Defect level identification in copper indium selenide (CuInSe2) from photoluminescence studies , 1990 .

[30]  P. S. Nair,et al.  Cadmium ethylxanthate: A novel single-source precursor for the preparation of CdS nanoparticles , 2002 .

[31]  K. Sumiyama,et al.  Synthesis of Ag–In binary sulfide nanoparticles—structural tuning and their photoluminescence properties , 2010 .

[32]  S. Tretiak,et al.  Type-II core/shell CdS/ZnSe nanocrystals: synthesis, electronic structures, and spectroscopic properties. , 2007, Journal of the American Chemical Society.

[33]  Haosen Zhou,et al.  Enhanced infrared response of Si base p–n diode with self-assembled Ge quantum dots by thermal annealing , 2008 .

[34]  N. Pradhan,et al.  Formation of nearly monodisperse In2O3 nanodots and oriented-attached nanoflowers: hydrolysis and alcoholysis vs pyrolysis. , 2006, Journal of the American Chemical Society.

[35]  S. Rosenthal,et al.  Ultrafast Carrier Dynamics in CdSe Nanocrystals Determined by Femtosecond Fluorescence Upconversion Spectroscopy , 2001 .

[36]  Stephen G. Hickey,et al.  Single-step synthesis to control the photoluminescence quantum yield and size dispersion of CdSe nanocrystals , 2003 .

[37]  Andrea Ragusa,et al.  Water solubilization of hydrophobic nanocrystals by means of poly(maleic anhydride-alt-1-octadecene) , 2008 .

[38]  C. Burda,et al.  Synthesis and Photophysical Properties of Ternary I–III–VI AgInS2 Nanocrystals: Intrinsic versus Surface States , 2011 .

[39]  S. Kuwabata,et al.  Remarkable photoluminescence enhancement of ZnS-AgInS2 solid solution nanoparticles by post-synthesis treatment. , 2010, Chemical Communications.

[40]  R. Nitschke,et al.  Quantum dots versus organic dyes as fluorescent labels , 2008, Nature Methods.

[41]  Xiaogang Peng,et al.  Side reactions in controlling the quality, yield, and stability of high quality colloidal nanocrystals. , 2005, Journal of the American Chemical Society.

[42]  E. Shevchenko,et al.  Study of nucleation and growth in the organometallic synthesis of magnetic alloy nanocrystals: the role of nucleation rate in size control of CoPt3 nanocrystals. , 2003, Journal of the American Chemical Society.

[43]  A. Alivisatos,et al.  Light-emitting diodes made from cadmium selenide nanocrystals and a semiconducting polymer , 1994, Nature.

[44]  Jaehyun Park,et al.  CuInS2/ZnS core/shell quantum dots by cation exchange and their blue-shifted photoluminescence , 2011 .

[45]  K. Char,et al.  Gram-Scale One-Pot Synthesis of Highly Luminescent Blue Emitting Cd1-xZnxS/ZnS Nanocrystals , 2008 .

[46]  T. Nann,et al.  Shape control of II-VI semiconductor nanomaterials. , 2006, Small.

[47]  Eugene Shi Guang Choo,et al.  Synthesis and characterization of AgInS2–ZnS heterodimers with tunable photoluminescence , 2011 .

[48]  P. Stroeve,et al.  Toxicity of nanomaterials. , 2012, Chemical Society reviews.

[49]  A. Rogach,et al.  Evolution of an Ensemble of Nanoparticles in a Colloidal Solution: Theoretical Study , 2001 .

[50]  Xiaogang Peng,et al.  Formation of High Quality InP and InAs Nanocrystals in a Noncoordinating Solvent , 2002 .

[51]  Pilar López-Larrubia,et al.  Engineering biofunctional magnetic nanoparticles for biotechnological applications. , 2010, Nanoscale.

[52]  V. Bulović,et al.  Electroluminescence from single monolayers of nanocrystals in molecular organic devices , 2002, Nature.