Skip to main content
Log in

Synthesis of highly fluorescent and thio-linkers stabilize gold quantum dots and nano clusters in DMF for bio-labeling

  • Research Paper
  • Published:
Journal of Nanoparticle Research Aims and scope Submit manuscript

Abstract

This study demonstrates a one versus two-step synthesis of fluorescent gold quantum dots (F-AuQDs) and nano clusters (F-AuNCs) functionalized with thiolated organic linkers using reduction of gold precursor in N,N′-dimethylformamide in 1 h of reaction. The F-AuQDs and F-AuNCs show fluorescence emission at 425 ± 5 nm upon excitation at 345 ± 5 nm of wavelength, with good water solubility and stability. Five different thiolated organic binary linkers consisting of various functional groups including: carboxylic acid, hydroxyl, and aromatic amine, were conjugated with the F-AuQDs and F-AuNCs. The formation mechanism and functionalization of the F-AuQDs and F-AuNCs was characterized using UV–vis absorption spectra, UV–vis light, fluorescent emission spectra, pH, TEM, and FTIR. The fluorescence emission of the F-AuQDs and F-AuNCs is greatly dependent on the thio-linker. This novel one-step approach provides facile and fast synthesis of F-AuQDs and F-AuNCs over the two-step method, with less than 5 h of reaction and workup compared to more than 28 h of reaction for the two-step approach. These thio-linker functionalized F-AuQDs and F-AuNCs have a wide application in fluorescent labeling of biomolecules, optical devices, imaging, energy transfer, and biosensing.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Scheme 1
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9

Similar content being viewed by others

References

  • Alivisatos AP (1996) Semiconductor clusters, nanocrystals, and quantum dots. Science 271:933

    Article  CAS  Google Scholar 

  • Alivisatos AP, Gu W, Larabell C (2005) Quantum dots as cellular probes. Annu Rev Biomed Eng 7:55

    Article  CAS  Google Scholar 

  • Alvarez MM, Khoury JT, Schaaff TG, Shafigullin MN, Vezmar I, Whetten RL (1997) Optical absorption spectra of nanocrystal gold molecules. J Phys Chem B 101:3706

    Article  CAS  Google Scholar 

  • Apell P, Monreal R, Lundqvist S (1988) Photoluminescence of noble metals. Phys Scr 38:174

    Article  CAS  Google Scholar 

  • Bruchez M Jr, Moronne M, Gin P, Weiss S, Allivisatos AP (1998) Semiconductor nanocrystals as fluorescent biological labels. Small 281:2013

    CAS  Google Scholar 

  • Chen WC, Nie S (1998) Quantum dot bioconjugates for ultrasensitive nonisotopic detection. Small 281:2016

    Google Scholar 

  • Chen S, Ingram RS, Hostetler MJ, Pietron JJ, Murray RW, Schaaff TG, Khoury JT, Alvarez MM, Whetten RL (1998) Gold nanoelectrodes of varied size: transition to molecule-like charging. Science 280:2098

    Article  CAS  Google Scholar 

  • Duan H, Nie S (2007) Etching colloidal gold nanocrystals with hyperbranched and multivalent polymers: a new route to fluorescent and water-soluble atomic clusters. J Am Chem Soc 129:2412

    Article  CAS  Google Scholar 

  • Dubertret B, Skourides P, Norris DJ, Noireaux V, Brivanlou AH, Libchaber A (2002) In vivo imaging of quantum dots encapsulated in phospholipid micelles. Science 298:1759

    Article  CAS  Google Scholar 

  • George S (2004) Infrared and Raman characteristic group frequencies: tables and charts, III edn. Wiley, Chichester

    Google Scholar 

  • Hardman R (2006) A toxicologic review of quantum dots: toxicity depends on physicochemical and environmental factors. Environ Health Perspect 114:165

    Article  Google Scholar 

  • Hicks JF, Miles DT, Murray RW (2002) Quantized double-layer charging of highly monodisperse metal nanoparticles. J Am Chem Soc 124:13322

    Article  CAS  Google Scholar 

  • Hostetler MJ, Wingate JE, Zhong CJ, Harris JE, Vachet RW, Clark MR, Londono JD, Green SJ, Stokes JJ, Wignall GD (1998) Alkanethiolate gold cluster molecules with core diameters from 1.5 to 5.2 nm: core and monolayer properties as a function of core size. Langmuir 14:17

    Article  CAS  Google Scholar 

  • Huang CC, Yang Z, Lee KH, Chang HT (2007) Synthesis of highly fluorescent gold nanoparticles for sensing mercury(II). Angew Chem Int Ed 46:6824

    Article  CAS  Google Scholar 

  • Huang CC, Chiang CK, Lin ZH, Lee KH, Chang HT (2008) Bioconjugated gold nanodots and nanoparticles for protein assays based on photoluminescence quenching. Anal Chem 80:1497

    Article  CAS  Google Scholar 

  • Jin R, Egusa S, Scherer NF (2004) Thermally-induced formation of atomic Au clusters and conversion into nanocubes. J Am Chem Soc 126:9900

    Article  CAS  Google Scholar 

  • Konig L, Rabin I, Schulze W, Ertl G (1996) Chemiluminescence in the agglomeration of metal clusters. Science 274:1353

    Article  Google Scholar 

  • Lee TH, Gonzalez JI, Zheng J, Dickson RM (2005) Single-molecule optoelectronics. Acc Chem Res 38:534

    Article  CAS  Google Scholar 

  • Lin ZY, Kanters RPF, Mingos DMP (1991) Closed-shell electronic requirements for condensed clusters of the group-11 elements. Inorg Chem 30:91

    Article  CAS  Google Scholar 

  • Lin CJ, Lee CH, Yeh HI, Chang WH (2009) Fluorescent gold nanoclusters for biomedical applications. World congress on medical physics and biomedical engineering, September 7–12, 2009, Munich, Germany. IFMBE Proc 25(8):108

  • Link S, El-Sayed MA (2003) Optical properties and ultrafast dynamics of metallic nanocrystals. Annu Rev Phys Chem 54:331

    Article  CAS  Google Scholar 

  • Link S, Beeby A, FitzGerald S, El-Sayed MA, Schaaff TG, Whetten RL (2002) Visible to infrared luminescence from a 28-atom gold cluster. J Phys Chem B 106:3410

    Article  CAS  Google Scholar 

  • Liu X, Li C, Xu X, Lv J, Zhu M, Guo Y, Cui S, Liu H, Wang S, Li Y (2008) Surfactant-free synthesis and functionalization of highly fluorescent gold quantum dots. J Phys Chem C 112:10778

    Article  CAS  Google Scholar 

  • Michalet X, Pinaud FF, Bentolila LA, Tsay JM, Doose S, Li JJ, Sundaresan G, Wu AM, Gambhir SS, Weiss S (2005) Quantum dots for live cells, in vivo imaging, and diagnostics. Science 307:538

    Article  CAS  Google Scholar 

  • Mohamed MB, Volkov V, Link S, El-Sayed MA (2000) The ‘lightning’ gold nanorods: fluorescent enhancement of over a million compared to the gold metal. Chem Phys Lett 317:517

    Article  CAS  Google Scholar 

  • Muhammed MAH, Ramesh S, Sinha SS, Pal SK, Pradeep T (2008) Two distinct fluorescent quantum clusters of gold starting from metallic nanoparticles by pH-dependent linker etching. Nano Res 1:333

    Article  CAS  Google Scholar 

  • Negishi Y, Takasugi Y, Sato S, Yao H, Kimura K, Tsukuda T (2004) Magic-numbered Au-N clusters protected by glutathione monolayers (N = 18, 21, 25, 28, 32, 39): isolation and spectroscopic characterization. J Am Chem Soc 126:6518

    Article  CAS  Google Scholar 

  • Pastoriza-Santos I, Liz-Marzán LM (1999) Formation and stabilization of silver nanoparticles through reduction of N,N-dimethylformamide. Langmuir 15:948

    Article  CAS  Google Scholar 

  • Pastoriza-Santos I, Liz-Marzán LM (2002) Synthesis of silver nanoprisms in DMF. Nano Lett 2:903

    Article  CAS  Google Scholar 

  • Quinn BM, Liljeroth P, Ruiz V, Laaksonen T, Kontturi K (2003) Electrochemical resolution of 15 oxidation states for monolayer-protected gold nanoparticles. J Am Chem Soc 125:6644

    Article  CAS  Google Scholar 

  • Sánchez-Iglesias A, Pastoriza-Santos I, Pérez-Juste J, Rodríguez-González B, García de Abajo FJ, Liz-Marzán LM (2006) Synthesis and optical properties of nanodecahedra with size control. Adv Mater 18:2529

    Article  Google Scholar 

  • Schaaff TG, Shafigullin MN, Khoury JT, Vezmar I, Whetten RL, Cullen WG, First PN, Gutierrez WC, Ascensio J, JoseYacaman MJ (1997) Isolation of smaller nanocrystal Au molecules: robust quantum effects in optical spectra. J Phys Chem B 101:7885

    Article  CAS  Google Scholar 

  • Schaeffer N, Tan B, Dickinson C, Rosseinsky MJ, Laromaine A, McComb DW, Stevens MM, Wang Y, Petit L, Barentin C et al (2008) Fluorescent or not? Size-dependent fluorescence switching for polymer-stabilized gold clusters in the 1.1–1.7 nm size range. Chem Commun 7:3986

    Article  Google Scholar 

  • Selvan ST, Patra PK, Ang CY, Ying JY (2007) Synthesis of silica-coated semiconductor and magnetic quantum dots and their use in the imaging of live cells. Angew Chem Int Ed 46:2448

    Article  CAS  Google Scholar 

  • Shia W, Sahoob Y, Swiharta MT (2004) Gold nanoparticles surface-terminated with bifunctional linkers. Colloids Surf A 264:109

    Article  Google Scholar 

  • Smith AM, Dave S, Nie SM, True L, Gao XH (2006) Multicolor quantum dots for molecular diagnostics of cancer. Expert Rev Mol Diagn 6:231

    Article  CAS  Google Scholar 

  • Triulizi RC, Micic M, Giordani S, Serry M, Chiou WA, Leblance RM (2006) Immunoassay based on the antibody-conjugated PAMAM-dendrimer-gold quantum dot Complex. Chem Commun 48:5068

    Article  Google Scholar 

  • Vosch T, Antoku Y, Hsiang JC, Richards CI, Gonzalez JI, Dickson RM (2007) Strongly emissive individual DNA-encapsulated Ag nanoclusters as single-molecule fluorophores. Proc Natl Acad Sci 104:12616

    Article  CAS  Google Scholar 

  • Wilcoxon JP, Martin JE, Parsapour F, Wiedenman B, Kelley DF (1998) Photoluminescence from nanosize gold clusters. J Chem Phys 108:9137

    Article  CAS  Google Scholar 

  • Yang Y, Chen S (2003) Surface manipulation of the electronic energy of subnanometer-sized gold clusters: an electrochemical and spectroscopic investigation. Nano Lett 3:75

    Article  CAS  Google Scholar 

  • Zheng J, Dickson RM (2002) Individual water-soluble dendrimer-encapsulated silver nanodot fluorescence. J Am Chem Soc 124:13982

    Article  CAS  Google Scholar 

  • Zheng J, Petty JT, Dickson RM (2003) High quantum yield blue emission from water-soluble Au-8 nanodots. J Am Chem Soc 125:7780

    Article  CAS  Google Scholar 

  • Zheng J, Zhang CW, Dickson RM (2004) Highly fluorescent, water-soluble, size-tunable gold quantum dots. Phys Rev Lett 93:077402-1

    Google Scholar 

  • Zubarev ER, Xu J, Sayyad A, Gibson JD (2006) Amphiphilic gold nanoparticles with V-shaped arms. J Am Chem Soc 128:4958

    Article  CAS  Google Scholar 

Download references

Acknowledgments

This publication was made possible by NIH grant (P20RR016454) from the INBRE Program of the National Center of Research Resources as well as USDA grant (2009-34479-19833). The authors would like to thank Dr. Thomas J. Williams (Electron Microscopy Center, UI, Moscow) for the TEM imaging. Also they would like to thank Prof. Thomas E. Bitterwolf and Patrick J. Hrdlicka (Department of Chemistry, UI, Moscow) for use of their the fluorescent emission spectrometer. Finally a special thanks for Levi Inman, A. Dale Marcy, and the whole Department of Natural Sciences at North Idaho College for the use of the FT-IR spectrometer and as well as all the other aid given to complete the research.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Shiva K. Rastogi.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOC 420 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Rastogi, S.K., Denn, B.D. & Branen, A.L. Synthesis of highly fluorescent and thio-linkers stabilize gold quantum dots and nano clusters in DMF for bio-labeling. J Nanopart Res 14, 673 (2012). https://doi.org/10.1007/s11051-011-0673-8

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s11051-011-0673-8

Keywords

Navigation