Synthesis, biocompatibility and cell labeling of L-arginine-functional beta-cyclodextrin-modified quantum dot probes.

A series of quantum dots (QDs), CdSe, CdSe/CdS and CdSe/ZnSe, coated with L-arginine-modified beta-cyclodextrin (beta-CD-L-Arg) were prepared in a solution of H2O and hexane by ultrasonic method and characterized using PL, UV-vis, TEM, EDX and FTIR techniques. We observed that beta-CD-L-Arg-coated QDs are water-soluble and stable with high colloidal properties in water. Their photophysical properties are similar to those of trioctylphosphine oxide (TOPO)-coated nanocrystals. The quantum yield (QY) of beta-CD-L-Arg/CdSe/ZnSe QDs in water is 68%, which is much higher than those of beta-CD-L-Arg/CdSe/CdS (26%) and beta-CD-L-Arg/CdSe (13%). The in vitro cytotoxicity of these QDs was evaluated in ECV-304, SH-SY5Y and Hela cells and low cytotoxicity was observed. In particular, the beta-CD-L-Arg/CdSe/ZnSe QDs presented lower cytotoxicity to these cells (CC(50) value is 173 microg/mL in ECV-304 cells for 48h). This may be due to the presence of the ZnSe and beta-CD-L-Arg outlayer, which may improve the biocompatibility of QDs. The QDs were further investigated for biological labeling in ECV-304 cells using confocal laser scanning fluorescence microscopy. We found that these QDs were capable of localing to the cytoplasm of cells. These results demonstrate that the beta-CD-L-Arg-coated QDs could be used as a potential photoluminescent nanocrystal probing agent with good biocompatibility.

[1]  M. Bruchez,et al.  Immunofluorescent labeling of cancer marker Her2 and other cellular targets with semiconductor quantum dots , 2003, Nature Biotechnology.

[2]  Vincent Noireaux,et al.  In Vivo Imaging of Quantum Dots Encapsulated in Phospholipid Micelles , 2002, Science.

[3]  S. Pathak,et al.  Hydroxylated quantum dots as luminescent probes for in situ hybridization. , 2001, Journal of the American Chemical Society.

[4]  Synthesis and characterization of water-soluble, stable and highly luminescent itaconic acid/methacrylic acid copolymer-coated CdSe/CdS quantum dots , 2009 .

[5]  L. Ji,et al.  Ester hydrolysis by a cyclodextrin dimer catalyst with a metallophenanthroline linking group. , 2008, Chemistry.

[6]  Y. Matsui,et al.  Host‐Guest Complexation of Mono(6‐(1‐pyridinio)‐6‐deoxy)‐α‐cyclodextrin with Several Inorganic Anions , 1989 .

[7]  D. Reinhoudt,et al.  Reversible phase transfer of (CdSe/ZnS) quantum dots between organic and aqueous solutions. , 2009, ACS nano.

[8]  Nigel Pickett,et al.  Nanocrystalline Semiconductors: Synthesis, Properties, and Perspectives , 2002 .

[9]  S. Nie,et al.  Quantum dot bioconjugates for ultrasensitive nonisotopic detection. , 1998, Science.

[10]  Matthew B. Johnson,et al.  Large-scale synthesis of nearly monodisperse CdSe/CdS core/shell nanocrystals using air-stable reagents via successive ion layer adsorption and reaction. , 2003, Journal of the American Chemical Society.

[11]  Cuiping Han,et al.  Sonochemical Synthesis of Cyclodextrin-Coated Quantum Dots for Optical Detection of Pollutant Phenols in Water , 2008 .

[12]  S. Hackney,et al.  Water-Soluble, Cyclodextrin-Modified CdSe−CdS Core−Shell Structured Quantum Dots , 2006 .

[13]  Xiaogang Peng,et al.  Luminescent CdSe/CdS core/shell nanocrystals in dendron boxes: superior chemical, photochemical and thermal stability. , 2003, Journal of the American Chemical Society.

[14]  Bao-hang Han,et al.  Molecular Recognition Study on Supramolecular Systems. 20. Molecular Recognition and Enantioselectivity of Aliphatic Alcohols by L-Tryptophan-Modified beta-Cyclodextrin. , 1999, The Journal of organic chemistry.

[15]  A. P. Alivisatos,et al.  Epitaxial growth and photochemical annealing of graded CdS/ZnS shells on colloidal CdSe nanorods. , 2002, Journal of the American Chemical Society.

[16]  Xiaogang Peng,et al.  Highly luminescent, stable, and water-soluble CdSe/CdS core-shell dendron nanocrystals with carboxylate anchoring groups. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[17]  Xiaogang Peng,et al.  Photochemical instability of CdSe nanocrystals coated by hydrophilic thiols. , 2001, Journal of the American Chemical Society.

[18]  C. Fan,et al.  The cytotoxicity of cadmium based, aqueous phase - synthesized, quantum dots and its modulation by surface coating. , 2009, Biomaterials.

[19]  Shimon Weiss,et al.  Bioactivation and cell targeting of semiconductor CdSe/ZnS nanocrystals with phytochelatin-related peptides. , 2004, Journal of the American Chemical Society.

[20]  Jong-Chul Park,et al.  Evaluation of the Extraction Method for the Cytotoxicity Testing of Latex Gloves , 2005, Yonsei medical journal.

[21]  M. Dahan,et al.  High-affinity labeling and tracking of individual histidine-tagged proteins in live cells using Ni2+ tris-nitrilotriacetic acid quantum dot conjugates. , 2009, Nano letters (Print).

[22]  D. Pang,et al.  CdSe/ZnS-labeled carboxymethyl chitosan as a bioprobe for live cell imaging. , 2005, Chemical communications.

[23]  Xiaogang Peng,et al.  Epitaxial Growth of Highly Luminescent CdSe/CdS Core/Shell Nanocrystals with Photostability and Electronic Accessibility , 1997 .

[24]  Xiaogang Peng,et al.  Size-dependent dissociation pH of thiolate ligands from cadmium chalcogenide nanocrystals. , 2005, Journal of the American Chemical Society.

[25]  Hans C. Fischer,et al.  Design and characterization of lysine cross-linked mercapto-acid biocompatible quantum dots , 2006 .

[26]  O. Pillai,et al.  Polymers in drug delivery. , 2001, Current opinion in chemical biology.

[27]  B. Kang,et al.  UV-enhanced cytotoxicity of thiol-capped CdTe quantum dots in human pancreatic carcinoma cells. , 2009, Toxicology letters.

[28]  Qisui Wang,et al.  Studies on CdSe/l-cysteine Quantum Dots Synthesized in Aqueous Solution for Biological Labeling , 2009 .

[29]  C. Niemeyer.  REVIEW Nanoparticles, Proteins, and Nucleic Acids: Biotechnology Meets Materials Science , 2022 .

[30]  M. El-Sayed.  Small is different: shape-, size-, and composition-dependent properties of some colloidal semiconductor nanocrystals. , 2004, Accounts of chemical research.

[31]  D. Balding,et al.  HLA Sequence Polymorphism and the Origin of Humans , 2006 .

[32]  M. Tong,et al.  Complexation, structure, and superoxide dismutase activity of the imidazolate-bridged dinuclear copper moiety with beta-cyclodextrin and its guanidinium-containing derivative. , 2006, Journal of the American Chemical Society.

[33]  Xiaogang Peng,et al.  Experimental Determination of the Extinction Coefficient of CdTe, CdSe, and CdS Nanocrystals , 2003 .

[34]  Q. Zeng,et al.  Photoluminescence quenching of CdSe core/shell quantum dots by hole transporting materials , 2009 .

[35]  D. Hunkeler,et al.  Rationalizing the design of polymeric biomaterials. , 1999, Trends in biotechnology.

[36]  C. Su,et al.  An effective metallohydrolase model with a supramolecular environment: structures, properties, and activities. , 2007, Chemistry.