Aggregation Of Gold Nanoparticles Research Articles

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.

Aggregable gold nanoparticles for cancer photothermal therapy.

Photothermal therapy (PTT) is an important non-invasive cancer treatment method. Enhancing the photothermal conversion efficiency (PCE) of photothermal agents (PTAs) and prolonging their tumor accumulation and retention are effective strategies to enhance the efficiency of cancer PTT. Recently, tremendous progress has been made in developing stimuli-responsive aggregable gold nanoparticles as effective PTAs for PTT. In this review, we discuss the chemical principles underlying gold nanoparticle aggregation and highlight the progress in gold nanoparticle aggregation triggered by different stimuli, especially tumor microenvironment-related factors, for cancer PTT. Covalent condensation reactions, click cycloaddition reactions, chelation reactions, and Au-S bonding, as well as non-covalent electrostatic interactions, hydrophobic interactions, hydrogen bonding, and van der Waals forces play key roles in the aggregation of gold nanoparticles. Enzymes, pH, reactive oxygen species, small molecules, salts, and light drive the occurrence of gold nanoparticle aggregation. Targeted aggregation of gold nanoparticles prolongs tumor accumulation and retention of PTAs and improves PCE, resulting in enhanced tumor PTT. Moreover, the major challenges of aggregable gold nanoparticles as PTAs are pointed out and the promising applications are also prospected at the end. With the deepening of research, we expect aggregable gold nanoparticles to become essential PTAs for tumor therapy.

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.

DNA-directed formation of plasmonic core-satellite nanostructures for quantification of hepatitis C viral RNA.

Hepatitis C virus (HCV) continues to be a significant public health challenge, affecting an estimated 71 million people globally and posing risks of severe liver diseases. Despite advancements in treatments, diagnostic limitations hinder the global elimination efforts targeted by 2030. This study introduces an innovative diagnostic approach, integrating catalytic hairpin assembly (CHA) with plasmonic core-satellite gold nanoparticle (AuNP) assemblies, to enable sensitive and specific detection of HCV RNA. We optimized the stoichiometry of DNA hairpins to form highly stable three-way junctions (3WJs), minimizing non-specific reactions in an enzyme-free, isothermal amplification process. The resulting dual-transduction biosensor combines colorimetric and surface-enhanced Raman spectroscopy (SERS) techniques, utilizing the Raman reporter malachite green isothiocyanate (MGITC) for signal generation. Our system targets a conserved 23-nucleotide sequence within the HCV 5'-UTR, essential for RNA replication, facilitating pan-genotypic HCV detection that complements direct-acting antiviral strategies. We evaluated the biosensor's efficacy using fluorescence spectroscopy, native PAGE, AFM, and TEM. Findings indicate that the 60 nm core AuNPs surrounded by 20 nm satellite AuNPs achieved a ten-fold increase in sensitivity over the 10 nm satellites, detecting HCV RNA concentrations as low as 1.706 fM. This sensitivity is crucial, given the extremely low viral loads present during early infection stages. Our research demonstrates the promise of enzyme-free molecular biosensors for HCV, with the potential to provide cost-efficient, rapid, point-of-care testing, although further sensitivity enhancements are needed to address the challenges of early-stage detection.

A colorimetric-aptamer-based assay for the determination of enrofloxacin through triggering the aggregation of gold nanoparticles.

Although enrofloxacin (ENR) is a widely used broad-spectrum antibiotic in veterinary medicine, its residues in animals can pose a risk to human health. Thus, we developed a new method for detecting ENR based on aptamers and AuNPs. In the absence of ENR, the aptamers attached to the surface of the AuNPs via electrostatic interactions to protect the AuNPs from NaCl, and the solution remained red. Conversely, the aptamer bonded with ENR, leading the aptamer to detach from the AuNP surface, and the color of the solution changed from red to blue. Based on this principle, ENR can be qualitatively detected by the naked eye and quantitatively detected by measuring the absorbance ratio at 650 nm and 530 nm. The experimental results showed a good linear relationship within the ENR concentration range of 0-400 nM, with a limit of detection (LOD) of 1.72 nM, which is satisfactory for detection in food safety. Additionally, this method has also been successfully applied to the detection of ENR in tap water, river water, milk, serum and urine, with good recovery rates and RSD values of less than 7%, indicating its great potential for ENR detection in environmental water samples. More importantly, the combination of this method with a smartphone platform provided great convenience for on-site and visual detection of ENR, offering promising applicability prospects.

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.

Improving DNA aptamers against a heart failure protein biomarker using structure-guided random mutation approaches for colourimetric biosensor development

The optimisation strategy successfully enhanced the DNA aptamer binding capability to its target. The docking, molecular dynamics, and gold nanoparticle aggregation assays showed the performance improvement of optimised aptamer as a bioreceptor.

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.

An electrochemical biosensor based on phage-encoded protein RBP 41 for rapid and sensitive detection of Salmonella

Salmonellosis caused by Salmonella contaminated food poses a serious threat to human health. The rapid and accurate detection of Salmonella is critical for preventing foodborne illness outbreaks. In this study, an electrochemical biosensor was developed using a newly identified biorecognition element, RBP 41, which is capable of specifically recognizing and binding to Salmonella. The biosensor was constructed through a layer-by-layer assembly of graphene oxide (GO), gold nanoparticles (GNPs), and RBP 41 on a glassy carbon electrode (GCE), with the GNPs amplifying the detection signal. The established biosensor was able to detect Salmonella in concentrations ranging from 3 to 106 CFU/mL within approximately 30 min by using differential pulse voltammetry (DPV) signal, and the estimated detection limit was to be 0.2984 Log10 CFU/mL. The biosensor demonstrated excellent specificity and was effective in detecting Salmonella in food matrices, such as skim milk and lettuce. Overall, this study highlights the potential of phage tail receptor binding proteins in biosensing and the proposed biosensor as a promising alternative for rapid and sensitive Salmonella detection in various samples.

Plasmonic and Photothermal Properties of Silica-Capped Gold Nanoparticle Aggregates.

Owing to their biocompatibility, gold nanoparticles have many applications in healthcare, notably for targeted drug delivery and the photothermal therapy of tumors. The addition of a silica shell to the nanoparticles can help to minimize the aggregation of the nanoparticles upon exposure to harsh environments and protect any Raman reporters adsorbed onto the metal surface. Here, we report the effects of the addition of a silica shell on the photothermal properties of a series of gold nanostructures, including gold nanoparticle aggregates. The presence of a Raman reporter at the surface of the gold nanoparticles also allows the structures to be evaluated by surface-enhanced Raman scattering (SERS). In this work, we explore the relationship between the degree of aggregation and the position and the extinction of the near-infrared plasmon on the observed SERS intensity and in the increase in bulk temperature upon near-infrared excitation. By tailoring the concentration of the silane and the thickness of the silica shell, it is possible to improve the photothermal heating capabilities of the structures without sacrificing the SERS intensity or changing the optical properties of the gold nanoparticle aggregates.

Novel rapid detection of melamine based on the synergistic aggregation of gold nanoparticles.

A simple and rapid colorimetric method for the detection of melamine in milk samples is described. Polythymidine oligonucleotide was adsorbed on to the surface of gold nanoparticles (AuNPs), protecting it from aggregation. In the presence of melamine, polythymidine oligonucleotide combined with melamine formed a double-strand DNA-like structure, allowing AuNPs aggregation. In the presence of positively charged SYBR Green I (SG I), AuNPs were further aggregated. In the presence of melamine and SG I, aggregation of AuNPs was synergistic. Thus, in this principle, melamine can be detected visually. Plasmon resonance peak changes enabled detection of melamine quantitatively using UV-vis spectroscopy. The limit of detection for this colorimetric method was 16μg L-1 with a good linear range from 19.5μg L-1 to 1.25×103 μg L-1, and detection took only 1min. The method was successfully applied for detection of melamine in milk samples.

Smartphone-based low-cost and rapid quantitative detection of urinary creatinine with the Tyndall effect

This research aims to develop a robust and quantitative method for measuring creatinine levels by harnessing the enhanced Tyndall effect (TE) phenomenon. The envisioned sensing assay is designed for practical deployment in resource-limited settings or homes, where access to advanced laboratory facilities is limited. Its primary objective is to enable regular and convenient monitoring of renal healthcare, particularly in cases involving elevated creatinine levels. The creatinine sensing strategy is achieved based on the aggregation of gold nanoparticles (AuNPs) triggered via the direct crosslinking reaction between creatinine and AuNPs, where an inexpensive laser pointer was used as a handheld light source and a smartphone as a portable device to record the TE phenomenon enhanced by the creatinine-induced aggregation of AuNPs. After evaluation and optimization of parameters such as AuNP concentrations and TE measurement time, the subsequent proof-of-concept experiments demonstrated that the average gray value change of TE images was linearly related to the logarithm of creatinine concentrations in the range of 1–50 μM, with a limit of detection of 0.084 μM. Meanwhile, our proposed creatinine sensing platform exhibited highly selective detection in complex matrix environments. Our approach offers a straightforward, cost-effective, and portable means of creatinine detection, presenting an encouraging signal readout mechanism suitable for point-of-care (POC) applications. The utilization of this assay as a POC solution exhibits potential for expediting timely interventions and enhancing healthcare outcomes among individuals with renal health issues.

Highly sensitive SERS detection of pesticide residues based on multi-hotspot buckypaper modified with gold nanoparticles

To effectively extract target analytes from complex sample surfaces is of great significance for the practical application of surface-enhanced Raman scattering (SERS) spectroscopy. A plasmonic substrate with multiple “hotspots” for highly sensitive detection of pesticide residues were prepared successfully by assembling gold nanoparticles on buckypaper (AuNPs-BP). The substrate exhibited high SERS enhancement and excellent detection sensitivity, with a detection limit (LOD) of 2.03 × 10-11 M and 6.88 × 10-12 M for the probe molecule R6G and MB, respectively. Combined with 3D finite-difference time-domain (3D-FDTD) simulation, the excellent SERS performance of the substrate was attributed to the enhancement of the electromagnetic field around the “hotspots”. Additionally, the substrates exhibited excellent flexibility, allowing easy contact with irregular surfaces and facilitating the collection of target molecules on the sample surface. Using a portable Raman spectrometer, the substrate achieved in situ analysis of chlorpyrifos residues on peach, with a LOD as low as 6.8 × 10-11 M. The method showed high accuracy, with a recovery value ranging from 94.2 % to 115.5 %. The results indicate that the substrate has great potential for rapid and highly sensitive detection of pollutants, especially on non-planar surfaces.

DNA-Based Gold Nanoparticle Assemblies: From Structure Constructions to Sensing Applications.

Gold nanoparticles (Au NPs) have become one of the building blocks for superior assembly and device fabrication due to the intrinsic, tunable physical properties of nanoparticles. With the development of DNA nanotechnology, gold nanoparticles are organized in a highly precise and controllable way under the mediation of DNA, achieving programmability and specificity unmatched by other ligands. The successful construction of abundant gold nanoparticle assembly structures has also given rise to the fabrication of a wide range of sensors, which has greatly contributed to the development of the sensing field. In this review, we focus on the progress in the DNA-mediated assembly of Au NPs and their application in sensing in the past five years. Firstly, we highlight the strategies used for the orderly organization of Au NPs with DNA. Then, we describe the DNA-based assembly of Au NPs for sensing applications and representative research therein. Finally, we summarize the advantages of DNA nanotechnology in assembling complex Au NPs and outline the challenges and limitations in constructing complex gold nanoparticle assembly structures with tailored functionalities.

Aptamer-based gold nanoparticle aggregates for ultrasensitive amplification-free detection of PSMA

Early diagnosis is one of the most important factors in determining the prognosis in cancer. Sensitive detection and quantification of tumour-specific biomarkers have the potential to improve significantly our diagnostic capability. Here, we introduce a triggerable aptamer-based nanostructure based on an oligonucleotide/gold nanoparticle architecture that selectively disassembles in the presence of the biomarker of interest; its optimization is based also on in-silico determination of the aptamer nucleotides interactions with the protein of interest. We demonstrate this scheme for the case of Prostate Specific Membrane Antigen (PSMA) and PSMA derived from PSMA-positive exosomes. We tested the disassembly of the system by diameter and count rate measurements in dynamic light scattering, and by inspection of its plasmon resonance shift, upon addition of PSMA, finding appreciable differences down to the sub-picomolar range; this points towards the possibility that this approach may lead to sensors competitive with diagnostic biochemical assays that require enzymatic amplification. More generally, this scheme has the potential to be applied to a broad range of pathologies with specific identified biomarkers.