Small Gold Nanoparticles Synthesized with Sodium Citrate and Heavy Water: Insights into the Reaction Mechanism

The effect of solvent isotopic replacement (H for D) on the size of gold nanoparticles (Au NPs) prepared by sodium citrate reduction has been investigated. With increasing replacement of water by deuterium oxide, smaller sizes of Au NPs are obtained, which is interpreted as a consequence of a faster reduction. A mechanism in which a substitution complex, [AuCl3(C6H5O7)−2]−, is formed from AuCl4 and citrate ions prior to its rate-limiting disproportionation into products is suggested. This novel procedure offers an attractive alternative to the existing ones and opens a full range of possibilities for biological studies.

[1]  Catherine J. Murphy,et al.  Seeding Growth for Size Control of 5−40 nm Diameter Gold Nanoparticles , 2001 .

[2]  R. Mehrotra,et al.  Kinetics and mechanism of the oxidation of oxalic acid by tetrachloroaurate(III) ion , 2007 .

[3]  D. Astruc,et al.  Gold nanoparticles: assembly, supramolecular chemistry, quantum-size-related properties, and applications toward biology, catalysis, and nanotechnology. , 2004, Chemical reviews.

[4]  B. C. Gilbert,et al.  Gold nanoparticle-initiated free radical oxidations and halogen abstractions. , 2007, Organic & biomolecular chemistry.

[5]  J. Hillier,et al.  The Formation of Colloidal Gold , 1953 .

[6]  Neus G Bastús,et al.  Peptides conjugated to gold nanoparticles induce macrophage activation. , 2009, Molecular immunology.

[7]  E. Matijević,et al.  Tailoring the particle size of monodispersed colloidal gold , 1999 .

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

[9]  M. Moeller,et al.  Effect of Solvent Isotopic Replacement on the Structure Evolution of Gold Nanorods , 2008 .

[10]  Xiaohua Huang,et al.  Surface plasmon resonance scattering and absorption of anti-EGFR antibody conjugated gold nanoparticles in cancer diagnostics: applications in oral cancer. , 2005, Nano letters.

[11]  D. Cole,et al.  Chapter 9 – Stable isotope partitioning in aqueous and hydrothermal systems to elevated temperatures , 2004 .

[12]  J. Hillier,et al.  A study of the nucleation and growth processes in the synthesis of colloidal gold , 1951 .

[13]  J. A. Peck,et al.  Speciation of aqueous gold(III) chlorides from ultraviolet/visible absorption and Raman/resonance Raman spectroscopies , 1991 .

[14]  André M. N. Silva,et al.  Determination of the pKa value of the hydroxyl group in the α-hydroxycarboxylates citrate, malate and lactate by 13C NMR: implications for metal coordination in biological systems , 2009, BioMetals.

[15]  C. Mirkin,et al.  Mechanistic study of photomediated triangular silver nanoprism growth. , 2008, Journal of the American Chemical Society.

[16]  C. Murphy,et al.  Gold nanoparticles are taken up by human cells but do not cause acute cytotoxicity. , 2005, Small.

[17]  G. Frens Controlled Nucleation for the Regulation of the Particle Size in Monodisperse Gold Suspensions , 1973 .

[18]  Antonio Turiel,et al.  Nanoparticle-mediated local and remote manipulation of protein aggregation. , 2006, Nano letters.

[19]  A. P. Alivisatos,et al.  Encapsulation of Metal (Au, Ag, Pt) Nanoparticles into the Mesoporous SBA-15 Structure , 2003 .

[20]  Mathias Brust,et al.  Synthesis of thiol-derivatised gold nanoparticles in a two-phase liquid-liquid system , 1994 .

[21]  Mostafa A. El-Sayed,et al.  Preparation and Growth Mechanism of Gold Nanorods (NRs) Using Seed-Mediated Growth Method , 2003 .

[22]  B. Chait,et al.  The molecular architecture of the nuclear pore complex , 2007, Nature.

[23]  Marc D. Porter,et al.  Alkanethiolate Gold Cluster Molecules with Core Diameters from 1.5 to 5.2 nm: Core and Monolayer Properties as a Function of Core Size , 1998 .

[24]  M. Steigerwald,et al.  Photovoltage mechanism for room light conversion of citrate stabilized silver nanocrystal seeds to large nanoprisms. , 2008, Journal of the American Chemical Society.

[25]  Mohan Srinivasarao,et al.  Shape separation of gold nanorods using centrifugation , 2005, Proceedings of the National Academy of Sciences.

[26]  L. Liz‐Marzán,et al.  An Electrochemical Model for Gold Colloid Formation via Citrate Reduction , 2007 .

[27]  P. White,et al.  Characterization of the Surface of a Citrate-Reduced Colloid Optimized for Use as a Substrate for Surface-Enhanced Resonance Raman Scattering , 1995 .

[28]  A. Williams-Jones,et al.  The disproportionation of gold(I) chloride complexes at 25 to 200°C , 1997 .

[29]  E. Giralt,et al.  Homogeneous conjugation of peptides onto gold nanoparticles enhances macrophage response. , 2009, ACS nano.

[30]  Allen J. Bard,et al.  Encyclopedia of Electrochemistry of the Elements , 1978 .

[31]  A. P. Alivisatos,et al.  Less is more in medicine. , 2001, Scientific American.

[32]  D. A. Palmer,et al.  Aqueous systems at elevated temperatures and pressures : physical chemistry in water, steam, and hydrothermal solutions , 2004 .

[33]  B. Nikoobakht,et al.  種結晶を媒介とした成長法を用いた金ナノロッド(NR)の調製と成長メカニズム , 2003 .

[34]  L. Kirschenbaum,et al.  Kinetics and mechanism of the oxidation of the hypophosphite ion by the tetrahydroxoargentate(III) ion , 1989 .

[35]  Jun Li,et al.  Size control of gold nanocrystals in citrate reduction: the third role of citrate. , 2007, Journal of the American Chemical Society.

[36]  Sanjeev Kumar,et al.  Modeling of Formation of Gold Nanoparticles by Citrate Method , 2007 .

[37]  Carsten Sönnichsen,et al.  Separation of nanoparticles by gel electrophoresis according to size and shape. , 2007, Nano letters.

[38]  R. Boese,et al.  Au55[P(C6H5)3]12CI6 — ein Goldcluster ungewöhnlicher Größe , 1981 .