DNA-functionalized monolithic hydrogels and gold nanoparticles for colorimetric DNA detection

Highly sensitive and selective DNA detection plays a central role in many fields of research, and various assay platforms have been developed. Compared to homogeneous DNA detection, surface-immobilized probes allow washing steps and signal amplification to give higher sensitivity. Previously research was focused on developing glass or gold-based surfaces for DNA immobilization; we herein report hydrogel-immobilized DNA. Specifically, acrydite-modified DNA was covalently functionalized to the polyacrylamide hydrogel during gel formation. There are several advantages of these DNA-functionalized monolithic hydrogels. First, they can be easily handled in a way similar to that in homogeneous assays. Second, they have a low optical background where, in combination with DNA-functionalized gold nanoparticles, even ～0.1 nM target DNA can be visually detected. By using the attached gold nanoparticles to catalyze the reduction of Ag+, as low as 1 pM target DNA can be detected. The gels can be regenerated by a simple thermal treatment, and the regenerated gels perform similarly to freshly prepared ones. The amount of gold nanoparticles adsorbed through DNA hybridization decreases with increasing gel percentage. Other parameters including the DNA concentration, DNA sequence, ionic strength of the solution, and temperature have also been systematically characterized in this study.     

Third-harmonic generation from single gold nanoparticles

We report the first observation of third-harmonic signals from individual gold colloids down to 40 nm diameter. Excited with 1-ps pulses at 1500 nm, the colloids generate 500-nm light, close to the plasmon resonance. The third-harmonic intensity varies as the square of the colloid surface area. Although weak, the third-harmonic signals of gold labels as small as 15 nm in diameter are expected to be accessible with 100-fs pulses. They could be used in microscopy for single-biomolecule tracking.     

Detection of lysozyme magnetic relaxation switches based on aptamer-functionalized superparamagnetic nanoparticles

Magnetic relaxation switch (MRSw) detection is based on aggregate formation or dissociation when magnetic nanoparticles (MNPs) bind to target molecules. In the aggregated state, the dephasing rate of nearby proton spins is higher than in the dispersed state, resulting in a decrease in the spin-spin relaxation time, T(2). In this work, an MRSw-based nanosensor for lysozyme (Lys) protein detection was achieved using iron oxide nanoparticles conjugated with either Lys aptamer or linker DNA, which can hybridize with the extended part of the aptamer to form clusters. Upon the addition of Lys, the aptamers bind with their targets, leading to disassembly of clusters and an increase in T(2). A detection limit in the nanomolar range was achieved for Lys detection in both buffer and human serum. The determination of Lys level in different types of cancer cell lysates was also performed to demonstrate detection in real clinical samples.     

Highly efficient multiphoton-absorption-induced luminescence from gold nanoparticles

We demonstrate that highly efficient photoluminescence is generated from gold nanoparticles as small as a few nanometers in diameter upon irradiation with sub-100-fs pulses of 790-nm light. Strong emission is observed at excitation intensities comparable to or less than those typically used for multiphoton imaging of fluorescently labeled biological samples. The particles have polarized emission, can radiate more efficiently than single molecules, do not exhibit significant blinking, and are photostable under hours of continuous excitation. These observations suggest that metal nanoparticles are a viable alternative to fluorophores or semiconductor nanoparticles for biological labeling and imaging.     

DNA-controlled assembly of a NaTl lattice structure from gold nanoparticles and protein nanoparticles

The formation of diamond structures from tailorable building blocks is an important goal in colloidal crystallization because the non-compact diamond lattice is an essential component of photonic crystals for the visible-light range. However, designing nanoparticle systems that self-assemble into non-compact structures has proved difficult. Although several methods have been proposed, single-component nanoparticle assembly of a diamond structure has not been reported. Binary systems, in which at least one component is arranged in a diamond lattice, provide alternatives, but control of interparticle interactions is critical to this approach. DNA has been used for this purpose in a number of systems. Here we show the creation of a non-compact lattice by DNA-programmed crystallization using surface-modified Qβ phage capsid particles and gold nanoparticles, engineered to have similar effective radii. When combined with the proper connecting oligonucleotides, these components form NaTl-type colloidal crystalline structures containing interpenetrating organic and inorganic diamond lattices, as determined by small-angle X-ray scattering. DNA control of assembly is therefore shown to be compatible with particles possessing very different properties, as long as they are amenable to surface modification.     

A new and clean method on synthesis of gold nanoparticles from bulk gold substrates

In this work, we report a new pathway to prepare clean gold nanoparticles in neutral solutions with aid of natural chitosan. First, an Au substrate was cycled in a deoxygenated aqueous solution containing 0.1N NaCl and 1 g L^?1 chitosan from ?0.28 to +1.22 V vs. Ag/AgCl at 500 mV s^?1 for 200 scans. The durations at the cathodic and anodic vertices are 10 and 5 s, respectively. After this process, positively charged Au- and chitosan-containing complexes were produced in the solution. Then the solution was heated from room temperature to boiling at a heating rate of 6 °C min^?1 to prepare Au nanoparticles. The particle sizes of prepared Au (1 1 1) nanoparticles are ca. 10 nm. Moreover, the prepared Au nanoparticles in solutions are capable for anti-oxidation and stable in an ambient atmosphere for at least three months.     

Controlled release of insulin from PLGA nanoparticles embedded within PVA hydrogels

A simple and versatile delivery platform for peptide and protein based on physically cross-linked poly (vinyl alcohol) (PVA) hydrogels containing insulin-loaded poly (lactic-co-glycolic acid) (PLGA) nanoparticles was successfully fabricated. The particle morphology and size were characterized by SEM and laser light scattering method, respectively. Results showed that these particles had a mean diameter of 615 nm with a narrow size distribution and homogeneous particle production. The protein encapsulation efficiency was 72.6%. When insulin-loaded PLGA nanoparticles were administered intraperitoneally as a single dose (20 U/kg) to streptozotocin-induced diabetic mouse, blood glucose levels of these mice decreased and it could be sustained at such levels over 24 h. In vitro release further indicated that entrapment of the nanoparticles into the PVA hydrogels causes a reduction in both the release rate and the total amount of insulin released, which suggesting that PLGA nanoparticles entrapped into the PVA hydrogels showed more suitable controlled release kinetics for protein delivery.     

Biosynthesis of gold nanoparticles

Synthesis of nanoparticles with interesting physico-chemical properties using efficient as well as eco-friendly technology is one of the main objectives of nanotechnology. Biological systems have been reported to synthesize inorganic materials under certain circumstances. Exploiting the biosynthetic potential of different organisms, nanoparticles of varying morphologies and sizes have been synthesized. Among the nanomaterials, gold has received considerable attention owing to its varied applications in the fields of nano-medicine, catalysis, electronics, and optics. This review gives an account on the biosynthesis of gold nanoparticles from microorganisms, plants, and other biological sources, with particular emphasis on the probable mechanisms leading to the formation of gold nanoparticles and the extent of control over nanoparticle properties that has been achieved so far in the biosynthetic protocols. It has been speculated that enzymes and/or proteins secreted by the organisms are involved in the bio-reduction and stabilization of the nanoparticles. The biosynthetic procedures could compete with existing solvent-based chemical synthetic procedures in order to achieve stable and monodisperse gold nanoparticles in large scale.     

Shaped gold and silver nanoparticles

Advance in the synthesis of shaped nanoparticles made of gold and silver is reviewed in this article. This review starts with a new angle by analyzing the relationship between the geometrical symmetry of a nanoparticle shape and its internal crystalline structures. According to the relationship, the nanoparticles with well-defined shapes are classified into three categories: nanoparticles with single crystallinity, nanoparticles with angular twins, and nanoparticles with parallel twins. Discussion and analysis on the classical methods for the synthesis of shaped nanoparticles in each category are also included and personal perspectives on the future research directions in the synthesis of shaped metal nanoparticles are briefly summarized. This review is expected to provide a guideline in designing the strategy for the synthesis of shaped nanoparticles and analyzing the corresponding growth mechanism.     

Determination of size and concentration of gold nanoparticles from UV-vis spectra

The dependence of the optical properties of spherical gold nanoparticles on particle size and wavelength were analyzed theoretically using multipole scattering theory, where the complex refractive index of gold was corrected for the effect of a reduced mean free path of the conduction electrons in small particles. To compare these theoretical results to experimental data, gold nanoparticles in the size range of 5 to 100 nm were synthesized and characterized with TEM and UV-vis. Excellent agreement was found between theory and experiment. It is shown that the data produced here can be used to determine both size and concentration of gold nanoparticles directly from UV-vis spectra. Equations for this purpose are derived, and the precision of various methods is discussed. The major aim of this work is to provide a simple and fast method to determine size and concentration of nanoparticles.     

Determination of size and concentration of gold nanoparticles from extinction spectra

Extinction spectra of colloidal gold can be used for a simple and fast determination of the size and concentration of nanoparticles. It is generally accepted that experimental correlations of the particle size and concentration with the plasmon resonance properties are in agreement with Mie theory simulations. Here, we discuss this point in the context of a long-term collection of published experimental data and our T-matrix simulations, which account for deviations of the particle size from ideal monodisperse spheres. These deviations result in small but quite evident disagreements between the Mie calculations and the experimental calibration curves "particle size vs resonance wavelength". We present a long-term-averaged analytical particle-size calibration and also discuss the effects of the particle dielectric functions, shape and size polydispersity on simulated correlations between the extinction spectra and the average particle size, and concentration.     

金纳米粒子的制备及自组装

金纳米粒子以它独特的光学、电学和催化性质以及在纳米级电子线路中的应用潜力,受到人们越来越多的关注.本文主要评述了金纳米粒子的合成方法和自组装技术,即对各种制备方法和自组装的特点、纳米粒子的生长机理和自组装机理进行了介绍.展望了金纳米材料未来的研究方向和发展趋势.     

Ligand-assisted extraction for separation and preconcentration of gold nanoparticles from waters

A new two-step extraction procedure is proposed for separation and preconcentration of gold nanoparticles (Au-NPs) from aqueous samples. First, Au-NPs are loaded onto a reversed phase C-18 (RP-C18) column, and then ligand-assisted extraction into chloroform is performed. 1-Dodecanethiol (1-DDT, 5 mM) was used as selective ligand for quantitative extraction under ultrasonic condition. Parameters of the extraction procedure, such as sample volume, organic solvent, concentration and nature of the ligand, ultrasonication time, pH of the sample, and different coating as well as sizes of Au-NPs were investigated in regard to the extraction efficiency of Au-NPs. The optimized procedure allows separation and preconcentration of the Au-NPs with an enrichment factor of up to 250 assuring no changes in size and/or shape of the NPs. This was proved by investigation of the particles by UV-vis spectrometry and transmission electron microscopy (TEM). Furthermore, the presence of potentially interfering other metal nanoparticles (M-NPs) and dissolved organic matter (DOM) was studied. Observed minor recoveries of Au-NPs in DOM model solutions were overcome by hydrogen peroxide pretreatment up to a DOM concentration of about 4 mg/L. Feasibility of the proposed method was proved by application of the optimized procedure to 5 real water samples. Recoveries of Au-NPs in the real waters spiked in a concentration range from 0.15 to 5100 μg/L obtained by this method varied from 68.4% to 99.4%. Consequently, the proposed approach has great potential for the analysis of M-NPs in environmental waters.     

Plasmonic properties of gold nanoparticles separated from a gold mirror by an ultrathin oxide

That a nanoparticle (NP) (for example of gold) residing above a gold mirror is almost as effective a surface enhanced Raman scattering (SERS) substrate (when illuminated with light of the correct polarization and wavelength) as two closely coupled gold nanoparticles has been known for some time. The NP-overmirror (NPOM) configuration has the valuable advantage that it is amenable to top-down fabrication. We have fabricated a series of Au-NPOM substrates with varying but thin atomic layer-deposited oxide spacer and measured the SERS enhancement as a function of spacer thickness and angle of incidence (AOI). These were compared with high-quality finite-difference time-domain calculations, which reproduce the observed spacer thickness and AOI dependences faithfully. The SERS intensity is expected to be strongly affected by the AOI on account for the fact that the hot spot formed in the space between the NP and the mirror is most efficiently excited with an electromagnetic field component that is normal to the surface of the mirror. Intriguingly we find that the SERS intensity maximizes at ~60° and show that this is due to the coherent superposition of the incident and the reflected field components. The observed SERS intensity is also shown to be very sensitive to the dielectric constant of the oxide spacer layer with the most intense signals obtained when using a low dielectric constant oxide layer (SiO(2)).     

Layered nanocomposites from gold nanoparticles for neural prosthetic devices

Treatments of neurological diseases, diagnostics of brain malfunctions, and the realization of brain-computer interfaces require ultrasmall electrodes that are "invisible" to resident immune cells. Functional electrodes smaller than 50 μm are impossible to produce with traditional materials due to high interfacial impedance at the characteristic frequency of neural activity and insufficient charge storage capacity. The problem can be resolved by using gold nanoparticle nanocomposites. Careful comparison indicates that layer-by-layer assembled films from Au NPs provide more than 3-fold improvement in interfacial impedance and 1 order of magnitude increase in charge storage capacity. Prototypes of microelectrodes could be made using traditional photolithography. Integration of unique nanocomposite materials with microfabrication techniques opens the door for practical realization of the ultrasmall implantable electrodes. Further improvement of electrical properties is expected when using special shapes of gold nanoparticles.     

Localized-surface-plasmon enhanced emission from porous silicon by gold nanoparticles

The porous silicon (PS) samples, decorated by Au nanoparticles (NPs) possessing localized-surface-plasmon (LSP) resonance, are prepared by the conventional anodization method. Photoluminescence (PL) is studied systematically, in particular, its dependence on the excitation power. It is found that undecorated PS samples exhibit a saturation behavior in PL intensity with increasing the pumping laser power, while the luminescence of Au-decorated PS hybrid samples have a purely linear dependence on the excitation power. In the linear response region of PS samples, addition of metal NPs layer moderately suppresses the emission while, in the saturation region, the net emission is enhanced by approximately up to 4-fold. Several possible mechanisms are discussed. We believe that the observed PL enhancement in saturation region is dominantly due to the resonant coupling between the LSP of Au NPs and the electronic excitation of PS, which inhibits the nonradiative Auger recombination process at high excitation power. These results indicate that the plasmon effect could be useful for designing even more efficient optoelectronic devices such as super bright light emitting devices and solar cells with high efficiencies. Despite many challenges, Au NPs can potentially be applied to introduce LSP resonance for the future silicon-based optoelectronics or photonics.     

Size-dependent cytotoxicity of gold nanoparticles

Gold nanoparticles are widely used in biomedical imaging and diagnostic tests. Based on their established use in the laboratory and the chemical stability of Au(0), gold nanoparticles were expected to be safe. The recent literature, however, contains conflicting data regarding the cytotoxicity of gold nanoparticles. Against this background a systematic study of water-soluble gold nanoparticles stabilized by triphenylphosphine derivatives ranging in size from 0.8 to 15 nm is made. The cytotoxicity of these particles in four cell lines representing major functional cell types with barrier and phagocyte function are tested. Connective tissue fibroblasts, epithelial cells, macrophages, and melanoma cells prove most sensitive to gold particles 1.4 nm in size, which results in IC(50) values ranging from 30 to 56 microM depending on the particular 1.4-nm Au compound-cell line combination. In contrast, gold particles 15 nm in size and Tauredon (gold thiomalate) are nontoxic at up to 60-fold and 100-fold higher concentrations, respectively. The cellular response is size dependent, in that 1.4-nm particles cause predominantly rapid cell death by necrosis within 12 h while closely related particles 1.2 nm in diameter effect predominantly programmed cell death by apoptosis.     

Preparation of antibody-conjugated gold nanoparticles

We here describe a method for the simple synthesis of gold nanoparticles (~ 10 nm in diameter) conjugated with antibody to E. coli O157:H7. Gold nanoparticles with pendant carboxylic acid and alcohol functional groups were synthesized and characterized using transmission electron microscopy (TEM) and infrared spectroscopy. These nanoparticles were then reacted with anti-E. coli O157:H7, using EDC coupling chemistry, and the product was characterized with X-ray photoelectron spectroscopy. Furthermore, binding of the antibody-gold conjugates to E. coli O157:H7 was demonstrated using transmission electron microscopy.     

Electronic structure of gold nanoparticles

Using the B3LYP/LANL2DZ method, we have calculated the spatial and electronic structures of a Au₃₂ nanocluster with I _h symmetry. The results suggest that the highest occupied orbitals have a significant density of d states, in agreement with angle-resolved photoelectron spectroscopy data for metallic gold. Relying on the densities of states obtained for the occupied and excited orbitals, we discuss optical electronic transitions in a laser based on gold nanoparticles.