Aggregation Of Gold Nanoparticles Research Articles

Plasmonic enzyme immunoassay via nanobody-driven controllable aggregation of gold nanoparticles for detection of ochratoxin A in pepper

Ochratoxin A (OTA) in food poses a serious challenge to public health. Herein, using the nanobody-driven controllable aggregation of gold nanoparticles (AuNPs) in a glucose oxidase-tyramine-horseradish peroxidase (GOx-TYR-HRP) system, we propose a direct competitive plasmonic enzyme immunoassay (dc-PEIA) for OTA detection. The OTA-GOx conjugate catalyzes glucose to produce hydrogen peroxide (H2O2), and then HRP catalyzes H2O2 to generate hydroxyl radical which induces the crosslink of TYR. Crosslinked TYR leads to aggregation of AuNPs through strong electrostatic interactions, which is tunable based on the competition of OTA-GOx and free OTA for binding the immobilized nanobody. The optimized dc-PEIA achieves an instrumental limit of detection (LOD) of 0.275 ng/mL and a visual LOD of 1.56 ng/mL. It exhibits good selectivity for OTA and accuracy in the analysis of pepper samples, with the confirmation of high-performance liquid chromatography. Overall, the dc-PEIA is demonstrated as a useful tool for detecting OTA in food.

Gold nanoshells with varying morphologies through templated surfactant‐assisted seed‐growth method

AbstractPlasmonic nanoparticles exhibit dramatic changes in optical properties depending on their spatial organization. Therefore, the ability to precisely control their assembly structure is important for both fundamental understanding and practical applications. In this personal account, we describe a templated surfactant‐assisted seed‐growth method to synthesize core–shell‐type gold nanoparticle assemblies with controllable surface morphologies and optical properties. This approach provides a simple procedure for simultaneous growth and assembly of metal nanoparticles on polymer templates, producing well‐defined nanostructures such as spiky nanoshells and raspberry‐like metamolecules with useful and interesting optical properties, such as strong and uniform surface‐enhanced Raman scattering and metamaterial properties. We discuss the factors that control the morphology and collective properties, describe the design rules acquired from the system, and suggest future directions of this research area.

Wet Chemical Engineering of Nanostructured GRIN Lenses

AbstractGradient‐index (GRIN) lenses have long been recognized for their importance in optics as a result of their ability to manipulate light. However, traditional GRIN lenses are limited on a scale of tens of microns, impeding their integration into nanoscale optical devices. This study presents a groundbreaking self‐assembled method that overcomes this limitation, allowing for constructing GRIN lenses at an extremely small dimension. The self‐assembly process offers several advantages, including creating highly precise, scalable, cost‐effective, and complex structures that eliminate the need for intricate and time‐consuming manual assembly. By engineering densely packed arrays of metallic nanoparticles, exceptional control over the local refractive index has been achieved. This is accomplished by layer‐by‐layer assembly of gold nanoparticles of different sizes over silica beads. A GRIN lens light‐sink is built where light is preferentially directed toward the center, which is corroborated by measuring the fluorescence of Rhodamine B (RhB) in the inside. Unlike traditional bulky macroscopic GRIN lenses, light‐sinks boast a size under 2.5 µm. Notably, the self‐focusing effects of this design allowed us to track the growth of single‐nanoparticle layers using SERS (Surface‐Enhanced Raman Spectroscopy). These results pave the way for designing and developing lens‐like devices at the nanoscale, allowing unprecedented light manipulation.

Colorimetric Concurrent Determination of Ultra-Trace Amounts of Pilocarpine and Timolol as anti-Glaucoma Drugs in Binary Mixtures Using a Multivariate Calibration Approach Based on the Aggregation of Gold Nanoparticles.

To study the ultra-trace simultaneous determination of drugs, the colorimetric method in combination with chemometrics can be used. In this study, a simple, rapid, and sensitive UV-Vis spectrophotometric method using gold nanoparticles (AuNPs) was introduced for the simultaneous determination of ultra-trace amounts of Pilocarpine (PIL) and Timolol (TIM) in binary mixtures and biological sample. AuNPs interacted with components and the aggregation mode of NPs occurred and finally, the color change of the solution (red to gray) was observed with the naked eye without the most modern and expensive instruments. The characterization of AuNPs was evaluated by transmission electron microscopy (TEM) and dynamic light scattering (DLS). The validation of the colorimetric way was studied in the concentration range of 100-800 and 100-600 μg/L with good linearity equal to 0.9772 and 0.9891 for PIL and TIM, respectively. The limit of detection (LOD) was found to be 165.00 and 92.40 μg/L, where the limit of quantitation (LOQ) was 500.00 and 280.00 μg/L for PIL and TIM, respectively. The effect of some factors such as interaction time, the concentration of components, and the volume of buffer on absorbance was investigated. Partial least squares (PLS) as an efficient multivariate calibration method was combined with colorimetry for the simultaneous determination of PIL and TIM in binary mixtures. The optimum number of latent variables was selected by k-fold cross-validation based on minimum mean square error prediction (MSEP) and the number of components equal to 1 with MSEP of 1.085 and 0.763 was considered for PIL and TIM, respectively. The mean recovery was obtained at 100.20% and 101.55% for PIL and TIM, respectively. The colorimetric method can be introduced as a proper option for the simultaneous determination of components in pharmaceutical formulations and other samples. A colorimetric method using AuNPs was proposed.PLS method was coupled with a colorimetric method for the ultra-trace simultaneous estimation of PIL and TIM in binary mixtures.Ultra-trace amounts of PIL and TIM were also determined in biological sample.The proposed method is simple, fast and less expensive than chromatography methods.

Sensitive osteoarthritis sensing by salt-induced aggregation and dispersion of gold nanoparticles.

Osteoarthritis occurs in any joints, and identification in its earlier stages helps to treat the disease and increase the recovery rate. The radiography method and imaging techniques are traditionally used to identify osteoarthritis. But these methods are expensive, and with the complicated steps. Researchers are working toward developing a highly sensitive biosensor in identifying the osteoarthritis biomarker. This research was focused on developing a C-terminal telopeptide of type II collagen (CTX-II) colorimetric sensor with gold nanoparticle (AuNP) for diagnosing osteoarthritis. Anti-CTX-II was conjugated with AuNP and then added with CTX-II and sodium chloride for the color change. In the presence of CTX-II, antibody releases from AuNP then binds with CTX-II, and the color of AuNP changed to purple. Without the CTX-II, AuNP remains its red color (dispersed). This easier colorimetric assay detected the CTX-II as low as 2ng/mL on linear regression [y=0.0131x-0.0051; R2=0.9205]. Furthermore, control performances with the relevant proteins osteopontin, IL-6, and nonimmune antibody failed to change the color confirming the specific identification of CTX-II.

Nanoantennas report dissipative assembly in oscillatory electric fields

Understanding driving forces for dissipative, i.e., out of equilibrium, assembly of nanoparticles from colloidal solution at liquid–solid interfaces provides the ability to design external cues for reconfigurable device response. Here electrohydrodynamic flow (EHD) at an electrode-liquid interface is investigated as a dissipative driving force for tuning optical response. EHD results from an oscillatory electric field in a liquid cell between two electrodes and drives assembly of gold nanoparticles (NP) into two-dimensional clusters on electrode surfaces. Clusters are chemically crosslinked during assembly to freeze assemblies for electron microscopy characterization in order to understand how to ‘nucleate’ cluster formation. Electron microscopy images show deposition with a potential having an amplitude of 5 V and frequency of 100 Hz produces surfaces with isolated NP, which can seed EHD flow. A second deposition step at 5 V and 500 Hz produces a high density of quadramers on surfaces. When exciting near the local surface plasmon resonance of the Au NP clusters formed during assembly, Au NPs serve as in situ nanoantenna reporters of assembly and disassembly. Surface enhanced Raman scattering (SERS) measurements of Au NP capped with 4-mercaptobenzoic acid show order of magnitude signal enhancements occur during cluster formation in the presence of an oscillatory field, which occurs on a time scale of seconds. Confocal fluorescence spectroscopy is used to monitor the dissipative assembly of Au NP over multiple cycles. Results provide insight on how electrical stimuli and seeding local perturbations affects formation of NP clusters and resultant optical response provides insight on how to tune response of optically active surfaces.

On-Chip Micro-Supercapacitor with High Areal Energy Density Based on Dielectrophoretic Assembly of Nanoporous Metal Microwire Electrodes.

Advances in the Internet of Things (IoT) technology have driven the demand for miniaturized electronic devices, prompting research on small-scale energy-storage systems. Micro-supercapacitors (MSCs) stand out in this regard because of their compact size, high power density, high charge-discharge rate, and extended cycle life. However, their limited energy density impedes commercialization. To resolve this issue, a simple and innovative approach is reported herein for fabricating highly efficient on-chip MSCs integrated with nanoporous metal microwires formed by dielectrophoresis (DEP)-driven gold nanoparticle (AuNP) assembly. Placing a water-based AuNP suspension onto interdigitated electrodes and applying an alternating voltage induces in-plane porous microwire formation in the electrode gap. The DEP-induced AuNP assembly and the gold microwire (AuMW) growth rate can be adjusted by controlling the applied alternating voltage and frequency. The microwire-integrated MSC (AuMW-MSC) electrically outperforms its unmodified counterpart and exhibits a 30% larger electrode area, along with 72% and 78% higher specific and areal capacitances, respectively, than a microwire-free MSC. Additionally, AuMW-MSC achieves maximum energy and power densities of 3.33 µWh cm-2 and 2629 µW cm-2 , respectively, with a gel electrolyte. These findings can help upgrade MSCs to function as potent energy-storage devices for small electronics.

Synthesis, functionalization and assembly of monodisperse gold nanoparticles with potassium sodium tartrate as reducing agent

AbstractMonodisperse gold nanoparticles (AuNPs) are an important guarantee of their scientific value and technical reproducibility in applications. The tartrate has a similar molecule structure and physicochemical properties to citrate, bur is much less reducibility and is usually not favorable for the formation of monodisperse AuNPs. We have prepared monodisperse AuNPs with tartrate (potassium sodium tartrate) as reducing and capping agent. Various parameters affecting the monodisperse properties during the preparation of tartrate‐capped AuNPs were analyzed, such as reversing the order of reactant addition and ripening of seeds, while adjusting the synthesis parameters such as time, temperature, and pH value. The final results show that the addition of a trace amount of silver (Ag) ion into chloroauric acid, the monodispersed tartrate‐capped AuNPs can be obtained with the size range of 9–40 nm. The fabricated gold seeds and grown tartrate‐capped AuNPs have narrow size dispersions (or polydispersity, σ<10 %). The minimum size dispersion of AuNPs with twice growth steps was as low as 5.73 %. So, the weak reducing agent of tartrate is one of good candidates to synthesize the monodispersity of AuNPs. Additionally, tartrate‐capped AuNPs have good stability and can be easily modified and form a large two‐dimensional (2D) monolayer nanostructure film.

Bioorthogonal "Click and Release" Reaction-Triggered Aggregation of Gold Nanoparticles Combined with Released Lonidamine for Enhanced Cancer Photothermal Therapy.

Cancer has been the most deadly disease, and 13 million cancer casualties are estimated to occur each year by 2030. Gold nanoparticles (AuNPs)-based photothermal therapy (PTT) has attracted great interest due to its high spatiotemporal controllability and noninvasiveness. Due to the trade-off between particle size and photothermal efficiency of AuNPs, rational design is needed to realize aggregation of AuNPs into larger particles with desirable NIR adsorption in tumor site. Exploiting the bioorthogonal "Click and Release" (BCR) reaction between iminosydnone and cycloalkyne, aggregation of AuNPs can be achieved and attractively accompanied by the release of chemotherapeutic drug purposed to photothermal synergizing. We synthesize iminosydnone-lonidamine (ImLND) as a prodrug and choose dibenzocyclooctyne (DBCO) as the trigger of BCR reaction. A PEGylated AuNPs-based two-component nanoplatform consisting of prodrug-loaded AuNPs-ImLND and tumor-targeting peptide RGD-conjugated AuNPs-DBCO-RGD is designed. In the therapeutic regimen, AuNPs-DBCO-RGD are intravenously injected first for tumor-specific enrichment and retention. Once the arrival of AuNPs-ImLND injected later at tumor site, highly photothermally active nanoaggregates of AuNPs are formed via the BCR reaction between ImLND and DBCO. The simultaneous release of lonidamine further enhanced the therapeutic performance by sensitizing cancer cells to PTT.

Bioorthogonal “Click and Release” Reaction‐Triggered Aggregation of Gold Nanoparticles Combined with Released Lonidamine for Enhanced Cancer Photothermal Therapy

AbstractCancer has been the most deadly disease, and 13 million cancer casualties are estimated to occur each year by 2030. Gold nanoparticles (AuNPs)‐based photothermal therapy (PTT) has attracted great interest due to its high spatiotemporal controllability and noninvasiveness. Due to the trade‐off between particle size and photothermal efficiency of AuNPs, rational design is needed to realize aggregation of AuNPs into larger particles with desirable NIR adsorption in tumor site. Exploiting the bioorthogonal “Click and Release” (BCR) reaction between iminosydnone and cycloalkyne, aggregation of AuNPs can be achieved and attractively accompanied by the release of chemotherapeutic drug purposed to photothermal synergizing. We synthesize iminosydnone‐lonidamine (ImLND) as a prodrug and choose dibenzocyclooctyne (DBCO) as the trigger of BCR reaction. A PEGylated AuNPs‐based two‐component nanoplatform consisting of prodrug‐loaded AuNPs‐ImLND and tumor‐targeting peptide RGD‐conjugated AuNPs‐DBCO‐RGD is designed. In the therapeutic regimen, AuNPs‐DBCO‐RGD are intravenously injected first for tumor‐specific enrichment and retention. Once the arrival of AuNPs‐ImLND injected later at tumor site, highly photothermally active nanoaggregates of AuNPs are formed via the BCR reaction between ImLND and DBCO. The simultaneous release of lonidamine further enhanced the therapeutic performance by sensitizing cancer cells to PTT.

Fabrication of complexed nanostructure using AAO template for ultrasensitive SERS detection

In the study of surface-enhanced Raman scattering (SERS) processes, a simple and fast approach is needed to ensure the large-scale preparation of SERS substrates. This article uses anodic aluminum oxide (AAO) as a template to assemble gold nanoparticles (Au NPs) into an ordered array. By changing the pore size of AAO and silanizing the pores, the number and density of Au NPs entering the pores through liquid–liquid two-phase self-assembly (LLSA) can be effectively regulated. Using Rh6G (Rhodamine 6G) and CV (Crystal Violet) molecules as probe molecules, substrate sensitivity was evaluated with an enhancement factor of up to 6.34 × 107. In addition, the uniformity of the substrate is good, with a relative standard deviation (RSD) of 9.94%, and the logarithmic concentration and the Raman signal presented significant linear correlations R2 was 0.997 and 0.985, respectively. The detection limit of the substrate for APM (aspartame) as a solvent is as low as 0.0078 g/L. Finally, the substrate was subjected to high sensitivity testing on two types of beverages containing APM sold, proving the practicality of the substrate. It is expected to achieve simple and rapid detection in food additive trace detection in the future.

Colorimetric detection of arsenite using Tris-mediated gold nanoparticle aggregation and chitosan lateral flow strip-based signal enhancement

Globally, over 200 million people are at risk of exposure to high levels of arsenic due to increasing environmental pollution; thus, there is high demand for detection methods to monitor arsenic contamination in the natural environment. In this study, we developed a cost-effective method for detecting arsenite [As(III)] ions using sodium dodecyl sulfate (SDS)-coated gold nanoparticles (AuNPs) and Tris. Positively charged Tris molecules induce aggregation of AuNPs by neutralizing the negative charge of SDS; however, this is prevented by the presence of As(III), which has a high affinity for AuNPs. This proposed method is able to detect 5 parts per billion (ppb) and 1.85 ppb of As(III) through naked eye and spectrophotometric measurements, respectively. Furthermore, a chitosan-based lateral flow (LF) strip was devised to enhance the visual signal intensity by concentrating AuNPs on its test zone, since AuNPs of lower concentration were more effective for detecting low As(III) concentrations. As a result, As(III) was detected at 500 parts per trillion (ppt) without any interference from other metal ions, which is a 10-fold improvement from solution-based assays. Importantly, the colorimetric signal amplification strategy (using the chitosan-based LF strip) is versatile and can be applied to many other AuNP- or nanomaterial-based technologies. The proposed system enables the detection of As(III) in facility-limited or point-of-care settings, making it ideal for use in underdeveloped countries because it requires a small sample volume (approximately 20–30 µL) with a small amount of AuNPs, and takes only 10 min to generate colorimetric results.

Acidity-activated aggregation and accumulation of self-complementary zwitterionic peptide-decorated gold nanoparticles for photothermal biofilm eradication

Drug-resistant biofilm infection is an extremely serious clinical problem, that easily leads to failure of antibiotic treatment. Although gold nanoparticles (AuNPs) as photothermal agents have been widely used in biofilm eradication, there are still challenges to be addressed, such as insignificantly redshifted absorption and slow assembly process of aggregated AuNPs. Herein, we developed an acidity-activated dispersion-to-aggregation transition to enhance the accumulation of self-complementary zwitterionic peptide-decorated AuNPs for photothermal eradication of drug-resistant biofilm infections. AuNPs were decorated with self-complementary zwitterionic peptides (ZP1 and ZP2) coupled with pH-sensitive anhydride (DMA) and pH-insensitive anhydride (SA), respectively. ZP2-decorated AuNPs with DMA modification (AuNP@ZP2(DMA)) exhibited prolonged blood circulation and enhanced accumulation in acidic biofilm microenvironment. Moreover, the electrostatic attraction between self-complementary ligands drove AuNPs to form closely packed aggregates with strong near-infrared absorption, leading to in vivo photoacoustic imaging ability and photothermal effect against drug-resistant bacteria and fungus, as well as microbial biofilms. AuNP@ZP2(DMA) with longer charge domains and a polyethylene glycol oligomer spacer showed greater photothermal antimicrobial and biofilm resistance in vitro and in vivo. This study develops an innovative acidity-activated AuNP photothermal agent, which provides an effective approach for treatment of biofilm infections.

Conductive Gold Thin Film Prepared by the Two-Dimensional Assembly of Gold Nanoparticles on a Plastic Surface

Conductive Gold Thin Film Prepared by the Two-Dimensional Assembly of Gold Nanoparticles on a Plastic Surface

Single-Particle Photoluminescence Measures a Heterogeneous Distribution of Differential Circular Absorbance of Gold Nanoparticle Aggregates near Constricted Thioflavin T Molecules.

The chirality of biomacromolecules is critical for their function, but the optical signal of this chirality is small in the visible range. Plasmonic nanoparticles are antennas that can couple to this chiral signal. Here, we examine the molecular-scale mechanism behind the induced circular dichroism of gold nanorods (AuNRs) in solution with insulin fibrils and the fibril-intercalating dye thioflavin T (ThT) with polarization-resolved single-molecule fluorescence and single-particle photoluminescence (PL) imaging. We compared the PL upon excitation by left- and right-handed circularly polarized light to calculate the differential absorbance of AuNRs near insulin fibrils with and without ThT. Overall, our results indicate that AuNRs do not act as chiral absorbers near constricted ThT molecules. Instead, we hypothesize that fibrils promote AuNR aggregation, and this templating is mediated by subtle changes in the solution conditions; under the right conditions, only a few chiral aggregates with significantly higher circular dichroism signal contribute to a large net circular dichroism.

Catalytic Gold Nanoparticle Assembly Programmed by DNAzyme Circuits.

Assembled gold nanoparticle (AuNP) superstructures can generate unique physicochemical characteristics and be used in various applications, thus becoming an attractive research field. Recently, several DNA-assisted gold nanoparticle assembly methods have been rigorously developed that typically require a non-catalytic equimolar molecular assembly to guarantee the designed assembly. Although efficient and accurate, exploring such non-catalytic nanoparticle assemblies in the complex cellular milieu under low trigger concentrations remains challenging. Therefore, developing a catalytic method that facilitates gold nanoparticle assemblies with relatively low DNA trigger concentrations is desirable. In this report, a catalytic method to program gold nanoparticle assemblies by DNAzyme circuits is presented, where only a small number of DNA triggers are able to induce the production of a large number of the desired nanoparticle assemblies. The feasibility of using logic DNAzyme circuits to control catalytic nanoparticle assemblies is experimentally verified. Additionally, catalytic AuNP assembly systems are established with cascading and feedback functions. The work provides an alternative research direction to enrich the tool library of nanoparticle assembly and their application in biosensing and nanomedicine.

Double phage displayed peptides co-targeting-based biosensor with signal enhancement activity for colorimetric detection of Staphylococcus aureus

The development of simple, fast, sensitive, and specific strategies for the detection of foodborne pathogenic bacteria is crucial for ensuring food safety and promoting human health. Currently, detection methods for Staphylococcus aureus still suffer from issues such as low specificity and low sensitivity. To address this problem, we proposed a sensitivity enhancement strategy based on double phage-displayed peptides (PDPs) co-targeting. Firstly, we screened two PDPs and analyzed their binding mechanisms through fluorescent localization, pull-down assay, and molecular docking. The two PDPs target S. aureus by binding to specific proteins on its outer membrane. Based on this phenomenon, a convenient and sensitive double PDPs colorimetric biosensor was developed. Double thiol-modified phage-displayed peptides (PDP-SH) enhance the aggregation of gold nanoparticles (AuNPs), whereas the specific interaction between the double PDPs and bacteria inhibits the aggregation of AuNPs, resulting in an increased visible color change before and after the addition of bacteria. This one-step colorimetric approach displayed a high sensitivity of 2.35 CFU/mL and a wide detection range from 10–2 × 108 CFU/mL. The combination with smartphone-based image analysis improved the portability of this method. This strategy achieves the straightforward, highly sensitive and portable detection of pathogenic bacteria.

Transformations in crystals of DNA-functionalized nanoparticles by electrolytes.

Colloidal crystals have applications in water treatments, including water purification and desalination technologies. It is, therefore, important to understand the interactions between colloids as a function of electrolyte concentration. We study the assembly of DNA-grafted gold nanoparticles immersed in concentrated electrolyte solutions. Increasing the concentration of divalent Ca2+ ions leads to the condensation of nanoparticles into face-centered-cubic (FCC) crystals at low electrolyte concentrations. As the electrolyte concentration increases, the system undergoes a phase change to body-centered-cubic (BCC) crystals. This phase change occurs as the interparticle distance decreases. Molecular dynamics analysis suggests that the interparticle interactions change from strongly repulsive to short-range attractive as the divalent-electrolyte concentration increases. A thermodynamic analysis suggests that increasing the salt concentration leads to significant dehydration of the nanoparticle environment. We conjecture that the intercolloid attractive interactions and dehydrated states favour the BCC structure. Our results gain insight into salting out of colloids such as proteins as the concentration of salt increases in the solution.

Ultra-rapid and highly selective colorimetric detection of hydrochloric acid via an aggregation to dispersion change of gold nanoparticles.

A rapid and highly selective naked-eye detection of hydrochloric acid (HCl) in an aqueous medium was established using HCl-triggered redispersion of gold nanoparticle aggregates.

Development of a label-free, sensitive gold nanoparticles-poly(adenine) aptasensing platform for colorimetric determination of aflatoxin B1 in corn.

In this work, a sensitive colorimetric bioassay method based on a poly(adenine) aptamer (polyA apt) and gold nanoparticles (AuNPs) was developed for the determination of aflatoxin B1 (AFB1). The polyA apt, adsorbed on the AuNPs, especially can bind to the analyte while deterring non-specific interactions. This nano aptasensor uses cationic polymer poly(diallyl dimethyl ammonium chloride) (PDDA), as an aggregating agent, to aggregate gold nanoparticles. PolyA apt-decorated gold nanoparticles (AuNPs/polyA apt) show resistance to PDDA-induced aggregation and maintains their dispersed state (red color) with the optical absorbance signal at λ = 520 nm. However, in the presence of AFB1 in the assay solution, the specific aptamer reacts with high affinity and folds into its three-dimensional form. Aggregation of AuNPs induced by PDDA caused their optical signal shift to λ = 620 nm (blue color). AFB1 concentration in the bioassay solution determines the amount of optical signal shift. Therefore, optical density ratio in two wavelengths (A620/520) can be used as a sturdy colorimetric signal to detect the concentration of aflatoxin B1. AFB1 was linearly detected between 0.5 and 20 ng mL-1, with a detection limit of 0.09 ng mL-1 (S/N = 3). The fabricated aptasensor was applied to the detection of AFB1 in real corn samples.