Reversible controlled assembly of thermosensitive polymer-coated gold nanoparticles

Aggregation of thermosensitive polymer-coated gold nanoparticles was performed in aqueous solution in the presence of a triblock copolymer poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) (Pluronic P123, PEO(20)-PPO(68)-PEO(20)). The gold nanoparticles, AuNPs, which are covered by thermosensitive statistical copolymers poly(EO(x)-st-PO(y)), aggregate when the temperature is higher than the phase transition temperature of the polymer, leading to a macroscopic precipitation. The presence of Pluronic chains in solution prevents the uncontrolled aggregation of the AuNPs at higher temperature than both the aggregation temperature of the AuNPs (T(agg)) and the critical micellization temperature (cmt) of the Pluronic. The size, the colloidal stability, and the optical properties of the AuNPs aggregates are modulated as a function of the P123-to-AuNP ratio, which constitutes the critical parameter of the system. Moreover, the AuNP aggregation is totally reversible upon decreasing the temperature below T(agg). Our approach constitutes an easy way to the formation of well-controlled nanoparticle aggregates with well-defined sizes. The resulting aggregates have been characterized by UV-vis spectroscopy, dynamic light scattering, and electron microscopy.     

Antibiofouling polymer-coated gold nanoparticles as a contrast agent for in vivo X-ray computed tomography imaging

Current computed tomography (CT) contrast agents such as iodine-based compounds have several limitations, including short imaging times due to rapid renal clearance, renal toxicity, and vascular permeation. Here, we describe a new CT contrast agent based on gold nanoparticles (GNPs) that overcomes these limitations. Because gold has a higher atomic number and X-ray absorption coefficient than iodine, we expected that GNPs can be used as CT contrast agents. We prepared uniform GNPs ( approximately 30 nm in diameter) by general reduction of HAuCl4 by boiling with sodium citrate. The resulting GNPs were coated with polyethylene glycol (PEG) to impart antibiofouling properties, which extends their lifetime in the bloodstream. Measurement of the X-ray absorption coefficient in vitro revealed that the attenuation of PEG-coated GNPs is 5.7 times higher than that of the current iodine-based CT contrast agent, Ultravist. Furthermore, when injected intravenously into rats, the PEG-coated GNPs had a much longer blood circulation time (>4 h) than Ultravist (<10 min). Consequently, CT images of rats using PEG-coated GNPs showed a clear delineation of cardiac ventricles and great vessels. On the other hand, relatively high levels of GNPs accumulated in the spleen and liver, which contain phagocytic cells. Intravenous injection of PEG-coated GNPs into hepatoma-bearing rats resulted in a high contrast ( approximately 2-fold) between hepatoma and normal liver tissue on CT images. These results suggest that PEG-coated GNPs can be useful as a CT contrast agent for a blood pool and hepatoma imaging.     

Interfacial surface properties of thiol-protected gold nanoparticles: a molecular probe EPR approach

We present a molecular probe technique for accessing interfacial surface electrostatics of ligand-protected gold nanoparticles. A series of ligands with variable length of the hydrocarbon bridge between the anchoring sulfur and the reporting pH-sensitive nitroxide is described. The protonation state of this probe is directly observed by EPR spectroscopy. For tiopronin-protected Au nanoparticles, we observed an increase in pKa of up to ca. 1.1 pH units that was affected by the position of the reporter moiety with respect to the monolayer interface.     

Controlled clustering and enhanced stability of polymer-coated magnetic nanoparticles

The clustering and stability of magnetic nanoparticles coated with random copolymers of acrylic acid, styrenesulfonic acid, and vinylsulfonic acid has been studied. Clusters larger than 50 nm are formed when the coatings are made using too low or too high molecular weight polymers or using insufficient amounts of polymer. Low-molecular-weight polymers result in thin coatings that do not sufficiently screen van der Waals attractive forces, while high-molecular-weight polymers bridge between particles, and insufficient polymer results in bare patches on the magnetite surface. The stability of the resulting clusters is poor, but when an insufficient polymer is used as primary coating, and a secondary polymer is added to coat remaining bare magnetite, the clusters are stable in high salt concentrations (>5 M NaCl), while retaining the necessary cluster size for efficient magnetic recovery. The magnetite cores were characterized by TEM and vibrating sample magnetometry, while the clusters were characterized by dynamic light scattering. The clustering and stability are interpreted in terms of the particle-particle interaction forces, and the optimal polymer size can be predicted well on the basis of these forces and the solution structure and hydrophobicity of the polymer. The size of aggregates formed by limited polymer can be predicted with a diffusion-limited colloidal aggregation model modified with a sticking probability based on fractional coating of the magnetite cores.     

Carboxylate-imidazole cooperativity in dipeptide-functionalized gold nanoparticles with esterase-like activity

We report here the first example of peptide-functionalized gold nanoparticles hydrolytically active against carboxylate esters. The active units are constituted by His-Phe-OH terminating thiols. The confinement of the catalytic units in the monolayer covering the nanoparticles triggers a cooperative hydrolytic mechanism operative at pH < 7 in which a carboxylate and an imidazolium ion act as general base and general acid, respectively. Such a mechanism is absent with an analogous monomeric dipeptide, and this results in a more than 300-fold rate acceleration of the hydrolytic process at low pH in the presence of the functional nanoparticles.     

Effect of aging on the electrocatalytic activity of gold nanoparticles

The electrocatalytic activities of freshly prepared nanomaterials do not represent normal activities, if they change with aging. We report the dependence of the electrocatalytic activity of gold nanoparticles (AuNPs) upon aging. The activities of AuNPs prepared by four different methods (electrodeposition; reduction of Au ions with NaBH₄, citrate, and ascorbate, respectively) slowly decrease with aging in the electrooxidation of H₂O₂ or formic acid, both in air and in solution. The possible origin of this effect is discussed.     

Novel colorimetric assay of LSD1 activity using gold nanoparticles

We have developed a simple and sensitive strategy for colorimetric LSD1 enzyme activity assay using avidin modified gold nanoparticles. The strategy is based on the vivid color change of a gold nanoparticle solution from red to violet upon addition of a test solution of peptide-antibody treated with LSD1. Thus, the presence of LSD1 in a sample can be determined by simple visual inspection with the naked eye. In addition, a wide range of LSD1 concentrations (13 pM to 0.13 μM) were quantitatively determined by spectrophotometry, which shows the possibility of quantitative analysis of the over expression levels of LSD1 in cancer tissue samples.     

Visual observation of the mercury-stimulated peroxidase mimetic activity of gold nanoparticles

Mercury-stimulated peroxidase mimetic activity of gold nanoparticles was presented, with which a sensitive label-free colorimetric method for Hg(2+) was developed.     

Regulation of alpha-chymotrypsin activity on the surface of substrate-functionalized gold nanoparticles

A gold nanoparticle functionalized with substrates for alpha-chymotrypsin was fabricated to afford an enzyme modulator that exhibited enzyme-specific activation coupled with general inhibition of other proteases.     

Thermosensitive gold nanoparticles

Thermosensitive gold nanoparticles were fabricated by conjugating Au with a thiol-terminated poly(N-isopropylacrylamide) or PPA; this polymer stabilizer exhibits a temperature transition while undergoing a hydrophilic to hydrophobic transformation. The introduction of PPA onto gold nanoparticles has sensitized Au nanoparticles with unique temperature dependence. At low temperature (25 degrees C), the solutions containing PPA-functionalized gold nanoparticles are transparent, whereas higher temperatures (30 degrees C) lead to opaque suspensions. The thermosensitive property of PPA-functionalized Au nanoparticles is reversible, and the clear-opaque suspensions can be repeated many times.     

Colloidal AgCl induced-growth of thorny gold nanoparticles and their SERS activity

In this paper, we exploited a unique procedure for obtaining thorny gold nanoparticles (Au NPs) with controllable length of thorns without using seeds and surfactants. The obtained Au NPs exhibited shape-determined surface-enhanced Raman spectroscopy activity toward rhodamine 6G.     

Patterned magnetic rings fabricated by dewetting of polymer-coated magnetite nanoparticles solution

Here we present a simple and controlled method for direct fabrication of ordered 2D arrays of magnetic rings. This method utilizes polystyrene-coated magnetite nanoparticles as a solution, and the magnetic rings are fabricated on patterned self-assembled monolayers by dewetting of the solution. Polystyrene-coated magnetite nanoparticles were synthesized by atom-transfer radical polymerization, which promoted the dispersibility and stability of magnetite nanoparticles in chloroform. Magnetic rings were studied using optical photograph, SEM, and magnetic force microscopy. This approach offers a new way for patterning nanoparticulate rings with deliberate control over feature composition, size, as well as interfeature distance.     

Alkanetelluroxide-protected gold nanoparticles

The synthesis and characterization of the first air-stable tellurium-containing ligand-protected gold nanoparticles (NPs) are reported. Although the synthesis largely followed the well-known Brust two-phase approach, the starting ligand was dioctyl ditelluride rather than alkanetellurol, which is an analogue of the widely used alkanethiol. Dioctyl ditelluride was used because alkanetellurol is unstable. The 1H and 13C NMR spectra, as well as infrared spectra (IR) of the formed Au NPs, indicated that the Te-Te bond in the starting ligand was broken but the octyl group was intact. This was further corroborated by the solid-state 125Te NMR spectrum that displayed a very broad and significantly downfield-shifted peak, indicating that tellurium was directly bound to the Au core. Furthermore, the O 1s and Te 3d XPS spectra of the Au NPs indicated that the capping ligands were octanetelluroxide. An average particle size of 2.7 nm diameter as measured by transmission electron microscopy (TEM) corresponded to an Au607 core. A two-step weight loss of approximately 22.2% in total was observed in the thermogravimetric analysis, which indicated about 53% ligand monolayer coverage (i.e., Au607(Te(=O)C8H17)133). Additionally, dioctyl ditelluride demonstrated an intriguing reductive power that led to a more sophisticated chemistry of forming the air-stable octanetelluroxide-protected gold NPs. It has been found that (1) when the ratio of Au to Te was about 1.5 a colorless intermediate state similar to Au(I)-SR (the intermediate state widely accepted in the synthesis of thiolate-protected Au NPs) could be obtained and (2) this kind of intermediate state played a key role in the formation of stable Au NPs.     

A molecularly imprinted polymer-coated nanocomposite of magnetic nanoparticles for estrone recognition

In this study, we synthesized Fe₃O₄ magnetic nanoparticles coated estrone-imprinted polymer with controlled size using a semi-covalent imprinting strategy. In this protocol, the estrone-silica monomer complex (EstSi) was synthesized by the reaction 3-(triethoxysilyl)propyl isocyanate with estrone, where the template was linked to the silica coating on the iron oxide core via a thermally reversible bond. The removal of the template by a simple thermal reaction produced specific estrone recognition sites on the surface of silica shell.The resulting estrone-imprinted polymer coating Fe₃O₄ magnetic hybrid nanoparticles exhibit a much higher specific recognition and saturation magnetization. The hybrid nanoparticles have been used for biochemical separation of estrone.     

Ciprofloxacin-protected gold nanoparticles

The antibacterial drug ciprofloxacin (cfH) has been used to protect gold nanoparticles of two different mean diameters, 4 and 20 nm. The protection is complete with about 65 and 585 cfH molecules covering 4 and 15 nm particles, respectively. The nature of binding has been investigated by several analytical techniques. The nitrogen atom of the NH moiety of piperazine group binds on the gold surface, as revealed by voltammetric and spectroscopic studies. The cfH-adsorbed particles are stable in the dry state as well as at room temperature, and as a result, redispersion is possible. The rate of release of the drug molecule from the nanoparticles is more in the basic medium than in pure water, and the kinetics depend on the size of the particle; faster desorption is seen in smaller particles. The bound cfH is fluorescent, and this property could be used in biological investigations. This study shows that metal nanoparticles could be useful carriers for cfH and fluoroquinolone molecules. Most of the bound molecules could be released over an extended period of time.     

Paclitaxel-functionalized gold nanoparticles

Here we describe the first example of 2 nm gold nanoparticles (Au NPs) covalently functionalized with a chemotherapeutic drug, paclitaxel. The synthetic strategy involves the attachment of a flexible hexaethylene glycol linker at the C-7 position of paclitaxel followed by coupling of the resulting linear analogue to phenol-terminated gold nanocrystals. The reaction proceeds under mild esterification conditions and yields the product with a high molecular weight, while exhibiting an extremely low polydispersity index (1.02, relative to linear polystyrene standards). TGA analysis of the hybrid nanoparticles reveals the content of the covalently attached organic shell as nearly 67% by weight, which corresponds to approximately 70 molecules of paclitaxel per 1 nanoparticle. The presence of a paclitaxel shell with a high grafting density renders the product soluble in organic solvents and allows for detailed (1)H NMR analysis and, therefore, definitive confirmation of its chemical structure. High-resolution TEM was employed for direct visualization of the inorganic core of hybrid nanoparticles, which were found to retain their average size, shape, and high crystallinity after multiple synthetic steps and purifications. The interparticle distance substantially increases after the attachment of paclitaxel as revealed by low-magnification TEM, suggesting the presence of a larger organic shell. The method described here demonstrates that organic molecules with exceedingly complex structures can be covalently attached to gold nanocrystals in a controlled manner and fully characterized by traditional analytical techniques. In addition, this approach gives a rare opportunity to prepare hybrid particles with a well-defined amount of drug and offers a new alternative for the design of nanosized drug-delivery systems.     

Spectrophotometric detection of tyrosinase activity based on boronic acid-functionalized gold nanoparticles

A spectrophotometric method for the detection of tyrosinase activity is developed by utilizing the product-triggered aggregation of boronic acid-functionalized gold nanoparticles. Based on the changes of absorbance in UV-visible spectra, the assay shows extremely high sensitivity and lowered limit of detection of 1 × 10(-10) u mL(-1).     

Phytochemical mediated gold nanoparticles and their PTP 1B inhibitory activity

Current discovery demonstrates the rapid formation of gold nanoparticles with guavanoic acid a phytochemical of Psidium guajava (Pg). The pharmacological capabilities of the phytochemicals present in the leaves of Pg and their ability to generate gold nanoparticles is presented herein. The new genre of green nanoparticles exhibit remarkable Protein Tyrosine Phosphatase 1B (PTP 1B) inhibitory activity and in vitro stability in various physiological medium including saline, histidine, cysteine, bovine serum albumin (BSA), human serum albumin (HSA) and buffers (pH 5, 7 and 9). It is predicted that this new technology will be felt greatly in several routes of pharmaceuticals.     

Photocatalytic activity of pyrazinoporphyrin in the presence of gold nanoparticles and nanoclusters

Russian Chemical Bulletin - The effect of gold nanoparticles and nanoclusters on the catalytic activity of dicarboxy-substituted pyrazinoporphyrin was studied using the photooxidation reaction of...