Toward efficient modification of large gold nanoparticles with DNA

DNA-coated gold nanoparticles are one of the most researched nano-bio hybrid systems. Traditionally their synthesis has been a long and tedious process, involving slow salt addition and long incubation steps. This stems from the fact that both DNA and gold particles are negatively charged, therefore efficient interaction is possible only at high salt concentration. However, unmodified particles are susceptible to aggregation at high salt concentrations. Most of the recent modification methods involve the use of surfactants or other small molecules to stabilize the nanoparticles against aggregation, enabling faster modification. Here we present our result on an alternative route to reach fast modification in low salt conditions, namely, reduction of the charge of DNA. We will discuss both the use of natural DNA under acidic pH conditions, and the use of DNA with a cationic, spermine-based “tail” which is commercially available under the name ZNA. Additionally we introduce a characterization method based on ensemble localized surface plasmon resonance measurement (LSPR) which enabled us to extract the kinetics of DNA absorbance without the need for fluorescent tags. Lastly we show that the same ZNA-based modification protocol can be effectively used for silver nanoparticle modification.

[1]  Alaaldin M. Alkilany,et al.  Gold nanoparticles in biology: beyond toxicity to cellular imaging. , 2008, Accounts of chemical research.

[2]  W. D. Geoghegan,et al.  Adsorption of horseradish peroxidase, ovomucoid and anti-immunoglobulin to colloidal gold for the indirect detection of concanavalin A, wheat germ agglutinin and goat anti-human immunoglobulin G on cell surfaces at the electron microscopic level: a new method, theory and application. , 1977, The journal of histochemistry and cytochemistry : official journal of the Histochemistry Society.

[3]  J. Behr,et al.  Zip Nucleic Acids: new high affinity oligonucleotides as potent primers for PCR and reverse transcription , 2009, Nucleic acids research.

[4]  Zhenxin Wang,et al.  Towards multistep nanostructure synthesis: programmed enzymatic self-assembly of DNA/gold systems. , 2003, Angewandte Chemie.

[5]  Robert Molenaar,et al.  Femtomolar DNA detection by parallel colorimetric darkfield microscopy of functionalized gold nanoparticles. , 2011, Biosensors & bioelectronics.

[6]  Ji-Xin Cheng,et al.  Gold Nanorods as Contrast Agents for Biological Imaging: Optical Properties, Surface Conjugation and Photothermal Effects † , 2009, Photochemistry and photobiology.

[7]  J. Storhoff,et al.  A DNA-based method for rationally assembling nanoparticles into macroscopic materials , 1996, Nature.

[8]  V. Subramaniam,et al.  Fast, single-step, and surfactant-free oligonucleotide modification of gold nanoparticles using DNA with a positively charged tail. , 2013, Chemical communications.

[9]  Sarit S. Agasti,et al.  Gold nanoparticles in chemical and biological sensing. , 2012, Chemical reviews.

[10]  Zhiqiang Gao,et al.  Facile and controllable loading of single-stranded DNA on gold nanoparticles. , 2009, Analytical chemistry.

[11]  J. Storhoff,et al.  Selective colorimetric detection of polynucleotides based on the distance-dependent optical properties of gold nanoparticles. , 1997, Science.

[12]  Chad A Mirkin,et al.  Multiplexed DNA detection with biobarcoded nanoparticle probes. , 2006, Angewandte Chemie.

[13]  Gary J. Blanchard,et al.  Direct Measurement of the Adsorption Kinetics of Alkanethiolate Self-Assembled Monolayers on a Microcrystalline Gold Surface , 1994 .

[14]  Mark R. Servos,et al.  Toward Fast and Quantitative Modification of Large Gold Nanoparticles by Thiolated DNA: Scaling of Nanoscale Forces, Kinetics, and the Need for Thiol Reduction , 2013 .

[15]  Mark R. Servos,et al.  Instantaneous and quantitative functionalization of gold nanoparticles with thiolated DNA using a pH-assisted and surfactant-free route. , 2012, Journal of the American Chemical Society.