Surfactant-Modified Ultrafine Gold Nanoparticles with Magnetic Responsiveness for Reversible Convergence and Release of Biomacromolecules.

It is difficult to synthesize magnetic gold nanoparticles (AuNPs) with ultrafine sizes (<2 nm) based on a conventional method via coating AuNPs using magnetic particles, compounds, or ions. Here, magnetic cationic surfactants C16H33N+(CH3)3[CeCl3Br]- (CTACe) and C16H33N+(CH3)3[GdCl3Br]- (CTAGd) are prepared by a one-step coordination reaction, i.e., C16H33N+(CH3)3Br- (CTABr) + CeCl3 or GdCl3 → CTACe or CTAGd. A simple strategy for fabricate ultrafine (<2 nm) magnetic gold nanoparticles (AuNPs) via surface modification with weak oxidizing paramagnetic cationic surfactants, CTACe or CTAGd, is developed. The resulting AuNPs can highly concentrate the charges of cationic surfactants on their surfaces, thereby presenting strong electrostatic interaction with negatively charged biomacromolecules, DNA, and proteins. As a consequence, they can converge DNA and proteins over 90% at a lower dosage than magnetic surfactants or existing magnetic AuNPs. The surface modification with these cationic surfactants endows AuNPs with strong magnetism, which allows them to magnetize and migrate the attached biomacromolecules with a much higher efficiency. The native conformation of DNA and proteins can be protected during the migration. Besides, the captured DNA and proteins could be released after adding sufficient inorganic salts such as at cNaBr = 50 mmol·L-1. Our results could offer new guidance for a diverse range of systems including gene delivery, DNA transfection, and protein delivery and separation.

[1]  M. Brunori,et al.  Enzyme Proteins. (Book Reviews: Hemoglobin and Myoglobin in Their Reactions with Ligands) , 1971 .

[2]  Complex formation between DNA and dodecyl-dimethyl-amine-oxide induced by pH , 2003 .

[3]  Stephen Mann,et al.  Reversible dioxygen binding in solvent-free liquid myoglobin. , 2010, Nature chemistry.

[4]  R. Dias,et al.  Condensation and decondensation of DNA by cationic surfactant, spermine, or cationic surfactant-cyclodextrin mixtures: macroscopic phase behavior, aggregate properties, and dissolution mechanisms. , 2012, Langmuir : the ACS journal of surfaces and colloids.

[5]  E. Smiley,et al.  Low molecular weight disulfide cross-linking peptides as nonviral gene delivery carriers. , 2000, Bioconjugate chemistry.

[6]  V. Bloomfield DNA condensation by multivalent cations. , 1997, Biopolymers.

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

[8]  J. Hao,et al.  Transfection efficiency of DNA enhanced by association with salt-free catanionic vesicles. , 2013, Biomacromolecules.

[9]  I. Grillo,et al.  Magnetic control over liquid surface properties with responsive surfactants. , 2012, Angewandte Chemie.

[10]  C. Putnam,et al.  Structure and function correlation in histone H2A peptide-mediated gene transfer , 2002, Proceedings of the National Academy of Sciences of the United States of America.

[11]  A. Perriman,et al.  Magnetizing DNA and Proteins Using Responsive Surfactants , 2012, Advances in Materials.

[12]  N. Abbott,et al.  Redox-based control of the transformation and activation of siRNA complexes in extracellular environments using ferrocenyl lipids. , 2013, Journal of the American Chemical Society.

[13]  Francis Vocanson,et al.  Gadolinium chelate coated gold nanoparticles as contrast agents for both X-ray computed tomography and magnetic resonance imaging. , 2008, Journal of the American Chemical Society.

[14]  J. Hao,et al.  Compaction and decompaction of DNA dominated by the competition between counterions and DNA associating with cationic aggregates. , 2015, Colloids and surfaces. B, Biointerfaces.

[15]  S. Reed,et al.  Improved Synthesis of Small (dCORE ≈ 1.5 nm) Phosphine-Stabilized Gold Nanoparticles , 2000 .

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

[17]  Kenneth A. Dawson,et al.  Protein–Nanoparticle Interactions , 2008, Nano-Enabled Medical Applications.

[18]  R. Dickson,et al.  Highly fluorescent, water-soluble, size-tunable gold quantum dots. , 2004, Physical review letters.

[19]  Brian F. G. Johnson,et al.  Selective oxidation with dioxygen by gold nanoparticle catalysts derived from 55-atom clusters , 2008, Nature.

[20]  K. Yoshikawa,et al.  TRANSITION OF DOUBLE-STRANDED DNA CHAINS BETWEEN RANDOM COIL AND COMPACT GLOBULE STATES INDUCED BY COOPERATIVE BINDING OF CATIONIC SURFACTANT , 1995 .

[21]  D. Otzen,et al.  Global study of myoglobin-surfactant interactions. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[22]  Taeghwan Hyeon,et al.  Ni/NiO core/shell nanoparticles for selective binding and magnetic separation of histidine-tagged proteins. , 2006, Journal of the American Chemical Society.

[23]  J. Hao,et al.  Controlling the capture and release of DNA with a dual-responsive cationic surfactant. , 2015, ACS applied materials & interfaces.

[24]  J. Hao,et al.  Loading capacity and interaction of DNA binding on catanionic vesicles with different cationic surfactants. , 2014, Soft matter.

[25]  M. Tabak,et al.  Spectroscopic studies on the interaction of bovine (BSA) and human (HSA) serum albumins with ionic surfactants. , 2000, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[26]  Yajuan Li,et al.  Comparative studies on interactions of bovine serum albumin with cationic gemini and single-chain surfactants. , 2006, The journal of physical chemistry. B.

[27]  P. Baker,et al.  Properties of new magnetic surfactants. , 2013, Langmuir : the ACS journal of surfaces and colloids.

[28]  J. Dobson,et al.  Gene therapy progress and prospects: magnetic nanoparticle-based gene delivery , 2006, Gene Therapy.

[29]  J. Hao,et al.  Magnetic controlling of migration of DNA and proteins using one-step modified gold nanoparticles. , 2015, Chemical communications.