Colloidal Stability Of Gold Nanoparticles Research Articles

Ultrashort Peptides and Gold Nanoparticles: Influence of Constrained Amino Acids on Colloidal Stability.

Poor colloidal stability of gold nanoparticles (AuNPs) in physiological environments remains one of the major limitations that contribute to their difficult translation from bench to clinic. For this reason, an active research field is the development of molecules able to hamper AuNPs aggregation tendency in physiological environments. In this context, synthetic peptides are gaining an increased interest as an alternative to the use of biomacromolecules and polymers, due to their easiness of synthesis and their profitable pharmacokinetic profile. In this work, we reported on the use of ultrashort peptides containing conformationally constrained amino acids (AAs) for the stabilization of AuNPs. A small library of non-natural self-assembled oligopeptides were synthesized and used to functionalize spherical AuNPs of 20 nm diameter, via the ligand exchange method. The aim was to investigate the role of the constrained AA, the anchor point (at C- or N-terminus) and the peptide length on their potential use as gold binding motif. Ultrashort Aib containing peptides were identified as effective tools for AuNPs colloidal stabilization. Furthermore, peptide coated AuNPs were found to be storable as powders without losing the stabilization properties once re-dispersed in water. Finally, the possibility to exploit the developed systems for binding proteins via molecular recognition was also evaluated using biotin as model.

Opposite Effects of Flexible Single-Stranded DNA Regions and Rigid Loops in DNAzyme on Colloidal Nanoparticle Stability for "Turn-On" Plasmonic Detection of Lead Ions.

Strains in biomolecules greatly restrict their structural flexibility. The effects of DNA's structural flexibility on nanoparticle stability have remained less explored in the field of plasmonic biosensors. In the present study, we discover the opposite effects of a rigid loop and a flexible single-stranded DNA (ssDNA) region in DNAzyme on the colloidal stability of gold nanoparticles (AuNPs), which afford "turn-on" plasmonic detection of Pb2+. In specific, DNAzyme-functionalized AuNPs undergo spontaneous assembly at high ionic strength upon hybridization to their substrate sequence because of a DNA base stacking interaction. In the presence of Pb2+, however, the DNAzyme grafted on the AuNP cleaves the substrate and forms an ssDNA region in the middle of the rigid loop. The induced structural flexibility of the surface-grafted DNAzyme by the ssDNA region in the middle helps elevate interparticle entropic repulsion, thereby bringing AuNP assemblies back to dispersion. We discover that this process can afford a dramatic increase of the AuNPs' plasmon resonance for determination of Pb2+ concentration. Under optimized conditions, a detection limit of 8.0 nM can be achieved for Pb2+ by this method with high selectivity. Its applicability to Pb2+ analysis in tap water samples has also been demonstrated.

Effect of the Surface Chemical Composition and of Added Metal Cation Concentration on the Stability of Metal Nanoparticles Synthesized by Pulsed Laser Ablation in Water

Metal nanoparticles (NPs) made of gold, silver, and platinum have been synthesized by means of pulsed laser ablation in liquid aqueous solution. Independently from the metal nature, all NPs have an average diameter of 10 ± 5 nm. The ζ-potential values are: −62 ± 7 mV for gold, −44 ± 2 mV for silver and −58 ± 3 for platinum. XPS analysis demonstrates the absence of metal oxides in the case of gold and silver NPs. In the case of platinum NPs, 22% of the particle surface is ascribed to platinum oxidized species. This points to a marginal role of the metal oxides in building the negative charge that stabilizes these colloidal suspensions. The investigation of the colloidal stability of gold NPs in the presence of metal cations shows these NPs can be destabilized by trace amounts of selected metal ions. The case of Ag+ is paradigmatic since it is able to reduce the NP ζ-potential and to induce coagulation at concentrations as low as 3 μM, while in the case of K+ the critical coagulation concentration is around 8 mM. It is proposed that such a huge difference in destabilization power between monovalent cations can be accounted for by the difference in the reduction potential.

Impact of critical micelle concentration of macroRAFT agents on the encapsulation of colloidal Au nanoparticles

HypothesisReversible addition fragmentation chain transfer (RAFT) - assisted encapsulating emulsion polymerization (REEP) has received considerable attention as an efficient strategy to prepare colloidal stable shell@core nanoparticles. Generally, amphipathic macroRAFT agents are used but the effect of working above or below the critical micelle concentration (CMC) of macroRAFT agents needs to be addressed. Hence, it is necessary to understand if this parameter has an impact not only on the stability of the colloids but also on the molecular mass of the polymer shell. MethodsHere, the CMC of three different macroRAFT agent was determined and the effect of macroRAFT agents concentration on the colloidal stability of gold nanoparticles coated with macroRAFT agents (macroRAFT@Au) assessed. The subsequent chain extension from macroRAFT@Au NPs, resulting in encapsulated Au nanoparticles (copolymer@Au), has also been systematically studied. FindingsUsing the REEP approach it was possible to obtain stable encapsulated Au NPs. Moreover, this strategy opens the possibility of adjusting the macroRAFT agents concentration to tune the length of the polymer chains grown around Au cores which is of major interest for the design of biosensors based on responsive polymer shells, such as pH, temperature and photoluminescence quenching.

Reducing Protein Corona Formation and Enhancing Colloidal Stability of Gold Nanoparticles by Capping with Silica Monolayers

A study demonstrated the reducing of protein corona (PC) formation and enhancing colloidal stability of gold nanoparticles (Au NP) by capping with silica monolayers. Au NP surface was needed to achieve silica monolayer formation. In a first attempt to have a high density ligand coverage around NS-1, an excess of 3-mercaptopropyltrimethoxysilane (MPTMS) was directly added to a Au NP hydrosol, but this resulted in immediate aggregation. The resulting trimethoxysilane moiety covering the surface of NS-3 was subsequently hydrolyzed by addition of 5 mM NaOH in a 2:1 methanol/water mixture, yielding a polymeric monolayer.

Improved Chemical and Colloidal Stability of Gold Nanoparticles through Dendron Capping

Nanoparticle (NP) stability is imperative for commercialization of nanotechnology. In this study, we compare the stability of Au NPs with surfaces functionalized with oleylamine, dodecanethiol, and two dendritic ligands of different generations. Dendrimer ligands provide a significant increase in the chemical stability of Au NPs when analyzed by cyanide-induced NP decomposition as well as an investigation into their colloidal stability at ambient conditions. These results were supported by absorption measurements, transmission electron microscopy, thermogravimetric analysis, nuclear magnetic resonance, and small-angle transmission X-ray scattering and show that dendrimers play a key role in improving the chemical and colloidal stability of NPs.

Zwitterionic Gel Coating Endows Gold Nanoparticles with Ultrastability.

Colloidal stability of gold nanoparticles (GNPs) is of great importance for their applications. Although a number of ligands have been developed to protect GNPs, irreversible aggregation still happens under some particular conditions. Herein, we report a zwitterionic encapsulation strategy to endow GNPs with ultrastability. Each single GNP is coated with a cross-linked zwitterionic poly(ornithine methacrylamide) hydrogel thin-layer, which prevents particleaggregation under extremely harsh conditions, including lyophilization, strong acid solution, saturated salt solution, and concentrated alkali solution. In addition, the zwitterionic gel layer resists protein adsorption in the biological milieu, keeping the nanoparticles stable in full human blood serum. Furthermore, the amino-acid-derived polymer gel provides numerous conjugation sites for on-demand biomolecular functionalization. With all these merits, the zwitterionic gel coated GNPs hold great potential in many applications such as sensing and theragnostics.

Effect of surface modification with various thiol compounds on colloidal stability of gold nanoparticles

Gold nanoparticles (AuNPs) are attractive materials due to their special optical and electronic properties. However, they tend to aggregate particularly in the presence of thiol‐containing compounds. In this study, to investigate the effect of surface conjugation with thiol‐containing compounds on colloidal stability, thiol compounds with various structures as modifying agents were used. To this end, AuNPs were synthesized and stabilized by trisodium citrate in aqueous solution, and then modified with thiol‐containing compounds, namely cysteamine hydrochloride (MEA, containing primary amine groups), 2‐mercaptoethanol (BME, containing hydroxyl groups), 1‐dodecanthiol (LCA, containing long‐chain alkyl groups) and thioglycolic acid (TGA, containing carboxylic acid groups). We studied the effect of thiol ligands on solution stability of colloidal AuNPs and on the formation of aggregates originating from the modification process using UV–visible spectroscopy, dynamic light scattering, field emission scanning electron microscopy and transmission electron microscopy. Results showed that surface modification with MEA, BME and LCA led to the formation of aggregates. However, conjugation with TGA showed a concentration‐dependent behaviour: surface modification with low concentration resulted in the formation of aggregates whereas that with high concentration of TGA did not disturb the colloidal stability of AuNPs. Finally, the effect of surface modification on temperature increase of solutions originating from infrared light irradiation was studied, where the temperature increase depends on the surface‐modifying compound.

Effects of surface coating character and interactions with natural organic matter on the colloidal stability of gold nanoparticles

Character of engineered surface coatings plays a significant role in controlling ENM interactions with model NOM macromolecules.

Proposing a Feasible Mechanism to Support the Exhibition of Superb Colloidal Stability of Gold Nanoparticles with Poly Vinyl Pyrrolidone in the form of a Nanofluid in N, N-Dimethyl Formamide

Proposing a Feasible Mechanism to Support the Exhibition of Superb Colloidal Stability of Gold Nanoparticles with Poly Vinyl Pyrrolidone in the form of a Nanofluid in N, N-Dimethyl Formamide

Colloidal stability of zwitterionic polymer-grafted gold nanoparticles in water

We investigate the colloidal stability of gold nanoparticles (AuNPs) coated with zwitterionic sulfobetaine polymers in aqueous solution. Zwitterionic polymers with different molar masses, synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization of N,N′-dimethyl(methacrylamido propyl)ammonium propanesulfonate (SPP) exhibit a well known Upper Critical Solution Temperature (UCST) in water, i.e., phase separate at low temperature. The colloidal stability of gold nanoparticles grafted with PSPP was studied as a function of the temperature. The effects of the molar mass of the grafted polymers, the salt concentration, and the presence of free polymer chains in solution were investigated. UV–vis spectroscopy and dynamic light scattering measurements show that whatever the molar mass of the grafted polymer, the nanoparticles never aggregate at low temperature in pure water. However, a reversible thermal-driven aggregation process of the gold nanoparticles is observed in presence of free polymer chains in solution and explained by a depletion process.

A highly efficient ligand exchange reaction on gold nanoparticles: preserving their size, shape and colloidal stability

Almost complete ligand exchange and excellent colloidal stability of gold nanoparticles can be achieved by a new solvent extraction based method.

Colloidal Stability of Gold Nanoparticles Coated with Multithiol-Poly(ethylene glycol) Ligands: Importance of Structural Constraints of the Sulfur Anchoring Groups

Gold nanoparticles (AuNPs) coated with a series of poly(ethylene glycol) (PEG) ligands appended with four different sulfur-based terminal anchoring groups (monothiol, flexible dithiol, constrained dithiol, disulfide) were prepared to explore how the structures of the sulfur-based anchoring groups affect the colloidal stability in aqueous media. The PEG-coated AuNPs were prepared by ligand exchange of citrate-stabilized AuNPs with each ligand. The colloidal stability of the AuNPs in different harsh environmental conditions was monitored visually and spectroscopically. The AuNPs coated with dithiol- or disulfide-PEG exhibited improved stability under high salt concentration and against ligand replacement competition with dithiothreitol compared with those coated with their monothiol counterpart. Importantly, the ligands with structurally constrained dithiol or disulfide showed better colloidal stability and higher sulfur coverage on the Au surface compared to the ligands with more flexible dithiol and monot...

Block copolymer-mediated synthesis of gold nanoparticles in aqueous solutions: Segment effect on gold ion reduction, stabilization, and particle morphology

We report here on the segment effects of poly(ethylene oxide)-containing block copolymers (PEO-BCP) on the reduction activity for tetrachloride gold(III) ([AuCl4]−), interfacial activity for gold surface, colloidal stability, and morphology of gold nanoparticles formed in aqueous solutions. In particular, the effects of poly(ethylene oxide) (PEO), poly(propylene oxide) (PPO), polyethylene (PE) segments and amino group (NH2) on the rate of [AuCl4]− reduction, adsorption of PEO-BCP onto gold surface, colloidal stability, and morphology of gold nanoparticles formed in aqueous solutions were examined using a poly(ethylene oxide)–poly(propylene oxide) triblock copolymer (PEO–PPO–PEO, Pluronic L44), an amino-terminated poly(ethylene oxide)-poly(propylene oxide) block copolymer (PEO–PPO–NH2, SURFONAMINE® L-207), a poly(ethylene oxide) homopolymer (PEO, poly(ethylene glycol)2000), and a polyethylene–poly(ethylene oxide) block copolymer (PE–PEO). We found that the reduction activity of PEO-BCP for [AuCl4]− became higher with the order of PEO–PPO–NH2<PE–PEO<PEO<PEO–PPO–PEO. The interfacial activity (affinity) of PEO-BCP for gold surface increased with the order of PEO<PE–PEO<PEO–PPO–PEO≪PEO–PPO–NH2. Consequently, the colloidal stability of gold nanoparticles formed in aqueous PEO–PPO–NH2 solutions was extremely high compared with that in PEO, PEO–PPO–PEO, and PE-PEO solutions. In addition, the size of gold nanoparticles formed in aqueous PEO–PPO–NH2 solutions was much smaller than that in aqueous solutions of PEO–PPO–PEO, PEO or PE–PEO.

Colloidal Stability of Gold Nanoparticles Modified with Thiol Compounds: Bioconjugation and Application in Cancer Cell Imaging

Gold nanoparticles (GNPs) are attractive alternative optical probes and good biocompatible materials due to their special physical and chemical properties. However, GNPs have a tendency to aggregate particularly in the presence of high salts and certain biological molecules such as nucleic acids and proteins. How to improve the stability of GNPs and their bioconjugates in aqueous solution is a critical issue in bioapplications. In this study, we first synthesized 17 nm GNPs in aqueous solution and then modified them with six thiol compounds, including glutathione, mercaptopropionic acid (MPA), cysteine, cystamine, dihydrolipoic acid, and thiol-ending polyethylene glycol (PEG-SH), via a Au-S bond. We systematically investigated the effects of the thiol ligands, buffer pH, and salt concentrations of the solutions on the colloidal stability of GNPs using UV-vis absorption spectroscopy. We found that GNPs modified with PEG-SH were the most stable in aqueous solution compared to other thiol compounds. On the basis of the above results, we developed a simple and efficient approach for modification of GNPs using a mixture of PEG-SH and MPA as ligands. These biligand-modified GNPs were facilely conjugated to antibody using 1-ethyl-3-[3-(dimethylamino)propyl]carbodiimide and N-hydroxysulfosuccinimide as linkage reagents. We conjugated GNPs to epidermal growth factor receptor antibodies and successfully used the antibody-GNP conjugates as targeting probes for imaging of cancer cells using the illumination of a dark field. Compared to current methods for modification and conjugation of GNPs, our method described here is simple, has a low cost, and has potential applications in bioassays and cancer diagnostics and studies.

Effects of Ligand Coordination Number and Surface Curvature on the Stability of Gold Nanoparticles in Aqueous Solutions

The colloidal stability of gold nanoparticles (AuNPs) cap-exchanged with either monothiol- or dithiolane-terminated PEG-OCH(3) ligands was investigated. Three distinct aspects were explored: (1) effects of excess salt concentration; (2) ligation competition by dithiothreitol (DTT); and (3) resistance to sodium cyanide digestion. We found that overall ligands presenting higher coordination numbers (dithiolane) exhibit much better stability to excess added salt and against competition from DTT compared to their monodentate counterparts. Resistance to NaCN digestion indicated that there is a balance between coordination number and density of ligand packing on the NP surface. For smaller NPs, where a larger surface curvature reduces the ligand packing density, a higher coordination number is clearly beneficial. In comparison, a higher ligand density allowed by the smaller curvature for larger nanocrystals makes monothiol-PEG-capped NPs more resistant to cyanide digestion. The present study indicates that balance between the coordination number and surface packing density is crucial to enhancing the colloidal stability of AuNPs.

DNA Aptamer Folding on Gold Nanoparticles: From Colloid Chemistry to Biosensors

We have investigated the effect of the folding of DNA aptamers on the colloidal stability of gold nanoparticles (AuNPs) to which an aptamer is tethered. On the basis of the studies of two different aptamers (adenosine aptamer and K+ aptamer), we discovered a unique colloidal stabilization effect associated with aptamer folding: AuNPs to which folded aptamer structures are attached are more stable toward salt-induced aggregation than those tethered to unfolded aptamers. This colloidal stabilization effect is more significant when a DNA spacer was incorporated between AuNP and the aptamer or when lower aptamer surface graft densities were used. The conformation that aptamers adopt on the surface appears to be a key factor that determines the relative stability of different AuNPs. Dynamic light scattering experiments revealed that the sizes of AuNPs modified with folded aptamers were larger than those of AuNPs modified with unfolded (but largely collapsed) aptamers in salt solution. From both the electrostatic and steric stabilization points of view, the folded aptamers that are more extended from the surface have a higher stabilization effect on AuNP than the unfolded aptamers. On the basis of this unique phenomenon, colorimetric biosensors have been developed for the detection of adenosine, K+, adenosine deaminase, and its inhibitors. Moreover, distinct AuNP aggregation and redispersion stages can be readily operated by controlling aptamer folding and unfolding states with the addition of adenosine and adenosine deaminase.

Colloidal Stability of Gold Nanoparticles in 2-Propanol under Laser Irradiation

The influence of laser light irradiation at the surface plasmon frequency of the gold nanoparticles suspended in 2-propanol is examined by the UV−vis absorption spectral measurement and also by a t...