Aggregation Of Gold Nanoparticles Research Articles

PH-Triggered Aggregation of Gold Nanoparticles for Enhanced Labeling and Long-Term CT Imaging Tracking of Stem Cells in Pulmonary Fibrosis Treatment.

Gold nanoparticles (AuNPs) pose a great challenge in the development of nanotracers that can self-adaptively alter their properties in response to certain cellular environments for long-term stem cell tracking. Herein, pH-sensitive Au nanotracers (CPP-PSD@Au) are fabricated by sequential coupling of AuNPs with sulfonamide-based polymer (PSD) and cell-penetrating peptide (CPP), which can be efficiently internalized by mesenchymal stem cells (MSCs) and undergo pH-induced self-assembly in endosomes, facilitating long-term computed tomography (CT) imaging tracking MSCs in a murine model of idiopathic pulmonary fibrosis (IPF). Using the CPP-PSD@Au, the transplanted MSCs for the first time can be monitored with CT imaging for up to 35 days after transplantation into the lung of IPF mice, clearly elucidating the migration process of MSCs in vivo. Moreover, we preliminarily explored the mechanism of the CPP-PSD@Au labeled MSCs in the alleviation of IPF, including recovery of alveolar integrity, decrease of collagen deposition, as well as down-regulation of relevant cytokine level. This work facilitates our understanding of the behavior and effect of MSCs in the therapy of IPF, thereby providing an important insight into the stem cell-based treatment of lung diseases.

HOCl-Activated Aggregation of Gold Nanoparticles for Multimodality Therapy of Tumors.

Tumor microenvironment‐responsive nanodrugs offer promising opportunities for imaging‐guided precision therapy with reduced side effects. Considering that the antitumor effect is closely related to the size of the nanodrugs, it is particularly important to develop a therapeutic system with size adjustability in the tumor microenvironment, which is still a great challenge in the field of nanotheranostics. Herein, a reactive oxygen species (ROS)‐activated aggregation strategy is reported for imaging‐guided precision therapy of tumors. The ROS‐activated nanoplatform is constructed based on gold nanoparticles (AuNPs) coated with an HOCl probe on its surface (namely, Au–MB–PEG NPs). The Au–MB–PEG NPs show high sensitivity toward HOCl, resulting in the modulation of surface charge and rapid aggregation of AuNPs, and simultaneous release of methylene blue as a photosensitizer for photodynamic therapy (PDT). In the tumor environment, the aggregated AuNPs ensure higher tumor accumulation and retention. Furthermore, the redshift of the absorption of aggregated AuNPs leads to activated photoacoustic imaging signals and photothermal therapy (PTT) under near‐infrared irradiation. Au–MB–PEG NPs thus efficiently inhibit the tumor growth through combined PTT–PDT therapy. This work contributes to the design of stimuli‐induced size‐aggregation nanodrugs, thereby attaining advanced performance in cancer diagnosis and treatment.

Structure and Optical Property of Gold Nanoparticles Synthesized by Modified Polyol Method

In this research, Au nanoparticles were successfully synthesized by modified polyol method with commercial precursors to be gold (III) chloride trihydrate (HAuCl4·3H2O), ethylene glycol (EG), poly(vinylpyrrolidone) (PVP), sodium borohydride (NaBH4). The structure and properties of as-prepared Au nanoparticles have been investigated by X ray diffraction (XRD), transmission electron microscopy (TEM), and UV-vis-NIR spectroscopy. As a result, Au nanoparticles with the average particle size of 28.80 nm were successfully synthesized in the range of about 50 nm. It is evidenced that the assembly of gold nanoparticles was presented in their nucleation, growth, and formation.

A trigger-based aggregation of aptamer-functionalized gold nanoparticles for colorimetry: An example on detection of Escherichia coli O157:H7

Abstract A pH-triggered colorimetric assay has been established by using aptamer anchored gold nanoparticles to detect Escherichia coli O157:H7 (E. coli O157:H7). Gold nanoparticles (AuNPs) functionalized by aptamer via thiol groups were used as probes (HS-Apt@AuNPs).Solvents of HCl (acid), NaOH (alkaline) and MgCl2 (nearly neutral) were used as triggers to initiate the movement of HS-Apt@AuNPs in the presence of E. coli O157:H7 bacteria respectively. Due to the pH effect of trigger on the surface charges of E. coli O157:H7 and the contribution of aptamer to capture E. coli O157:H7, the movement of HS-Apt@AuNPs with the presence of E. coli O157:H7 exhibit dispersion and aggregation respectively, which leads the change of colorimetric signal to an opposite direction. Taking the solvent of NaCl frequently used as trigger for gold nanoparticle based colorimetric sensor into consideration, the utilization of pH dependent triggers provide an alternative for this kind of trigger-based sensor. Design of gold nanoparticle-based colorimetric biosensing assay suiting a wide range of trigger is more flexible for specific diagnosis. These results demonstrate a great potential to design bacterial sensor with high sensitivity to defend public health.

Rapid visual detection for nitroreductase based on the copper ions-induced and NADH-mediated aggregation of gold-silver alloy nanoparticles

Hypoxia refers to the lack of oxygen supply to cells or tissues. The overexpression of nitroreductase has been shown to be closely related to the degree of hypoxia, which leads to the level of nitroreductase (NTR) being used as an indicator of hypoxia. We reported a facile visual detection of NTR based on the aggregation of gold and silver alloy nanoparticles. Compared with gold nanoparticles (AuNPs), the aggregation behavior of Au80Ag20 NPs caused a more prominent color change. Copper ions (Cu2+) can be rapidly reduced by nicotinamide adenine dinucleotide (NADH) under the catalysis of Au80Ag20 NPs. But NADH is consumed as an electron donor during the catalytic reduction reaction of p-nitrophenol (pNP) by NTR. A decrease of NADH amount results in the aggregation of Au80Ag20 NPs by the excess Cu2+ and different aggregation degrees of Au80Ag20 NPs lead to observable color change. A linear correlation of A600/A505 = 0.0285 [NTR]+0.361 (R2 = 0.980) was obtained with a limit of detection (LOD) of 0.23 μg/mL for UV–vis spectrophotometer. For visual detection, the values of R/B against the concentration of NTR obtains a calibration curve of R/B = −0.031 [NTR]+ 1.54 (R2 = 0.985) with a LOD of 0.76 μg/mL, which is of the same order of magnitude as the UV–vis spectrophotometer analysis. As a comparison, Au80Ag20 NPs was replaced by several different composition nanoparticles (Au NPs, Au70Ag30 NPs, Au50Ag50 NPs) to be a chromogenic substrate, and the results suggest the Au80Ag20 NPs is the most sensitive substrate in our assay. Selectivity tests showed that the detection system did not respond to other common substances, and the reaction mechanism was verified by inhibitor research. Finally, the assay was used on the human serum samples with spiking NTR, and the recovery rates of this assay with UV–vis spectrophotometer were basically consistent with RGB analysis.

Colorimetric method based on salt-induced aggregation of gold nanoparticles and aptamer does not work for detection of tacrolimus

Objective(s): Tacrolimus (TAC) is used in autoimmune diseases, organ transplantation, and nephrotic syndrome treatment. Therapeutic drug monitoring (TDM) of TAC is critical since it has narrow therapeutic index. Thus, the development of an easy and sensitive method is critical for detecting TAC in blood samples.Materials and Methods: In this study, we aimed to design a fast, simple,and specific colorimetric sensor based on aptamer/AuNPs to detect. Initially, the aptamer was adsorbed on the surface of the gold nanoparticles (AuNPs). Results: Then, it was expected that when the aptamer bound to TAC, AuNPs were aggregated by salt, and the color changed from red to blue. However, in our study, color did not change, and NaCl could not aggregate the AuNPs. In this approach, the optical properties of AuNPs and high affinity of aptamer were used for the detection of TAC.Conclusion: However, according to our data, this colorimetric aptasensor was not appropriate for the detection of TAC.

Highly Controlled Janus Organic-Inorganic Nanocomposite as a Versatile Photoacoustic Platform.

Controlling the structural order of nanoparticles (NPs), morphology, and composition is of paramount significance in tailoring the physical properties of nanoassembly. However, the commonly reported symmetrical nanocomposites often suffer an interference or sacrifice of the photophysical properties of the original components. To address this challenge, we developed a novel type of organic-inorganic Janus nanocomposite (JNCP) with an asymmetric architecture, offering unique features such as the precisely controlled localization of components, combined modular optical properties, and independent stimuli. As a proof of concept, JNCPs were prepared by incorporating two photoacoustic (PA) imaging agents, namely an organic semiconducting dye and responsive gold nanoparticles (AuNP) assembly in separate compartments of JNCP. Theoretical simulation results confirmed that the formation mechanism of JNCPs arises from the entropy equilibrium in the system. The AuNP assembly generated a PA images with the variation of pH, while the semiconducting molecule served as an internal PA standard agent, leading to ratiometric PA imaging of pH. JNCP based probe holds great potential for real-time and accurate detection of diverse biological targets in living systems.

Highly Controlled Janus Organic‐Inorganic Nanocomposite as a Versatile Photoacoustic Platform

AbstractControlling the structural order of nanoparticles (NPs), morphology, and composition is of paramount significance in tailoring the physical properties of nanoassembly. However, the commonly reported symmetrical nanocomposites often suffer an interference or sacrifice of the photophysical properties of the original components. To address this challenge, we developed a novel type of organic‐inorganic Janus nanocomposite (JNCP) with an asymmetric architecture, offering unique features such as the precisely controlled localization of components, combined modular optical properties, and independent stimuli. As a proof of concept, JNCPs were prepared by incorporating two photoacoustic (PA) imaging agents, namely an organic semiconducting dye and responsive gold nanoparticles (AuNP) assembly in separate compartments of JNCP. Theoretical simulation results confirmed that the formation mechanism of JNCPs arises from the entropy equilibrium in the system. The AuNP assembly generated a PA images with the variation of pH, while the semiconducting molecule served as an internal PA standard agent, leading to ratiometric PA imaging of pH. JNCP based probe holds great potential for real‐time and accurate detection of diverse biological targets in living systems.

Surface topography and free energy regulate osteogenesis of stem cells: effects of shape-controlled gold nanoparticles.

ABSTRACTThe surface free energy of a biomaterial plays an important role in the early stages of cell–biomaterial interactions, profoundly influencing protein adsorption, interfacial water accessibility, and cell attachment on the biomaterial surface. Although multiple approaches have been developed to engineer the surface free energy of biomaterials, systematically tuning their surface free energy without altering other physicochemical properties remains challenging. In this study, we constructed an array of chemically-equivalent surfaces with comparable apparent roughness through assembly of gold nanoparticles adopting various geometrically-distinct shapes but all capped with the same surface ligand, (1-hexadecyl)trimethylammonium chloride, on cell culture substrates. We found that bone marrow stem cells exhibited distinct osteogenic differentiation behaviours when interacting with different types of substrates comprising shape-controlled gold nanoparticles. Our results reveal that bone marrow stem cells are capable of sensing differences in the nanoscale topographical features, which underscores the role of the surface free energy of nanostructured biomaterials in regulating cell responses. The study was approved by Institutional Animal Care and Use Committee, School of Medicine, University of South Carolina.

Smartphone-assisted colorimetric sensing of enzyme-substrate system using pH-responsive gold nanoparticle assembly

Gold nanoparticle (AuNP)-based colorimetric biosensors have been widely used for pH sensing and monitoring its changes. However, few AuNP-based pH sensors have been developed through the manipulation of the aggregation states of AuNPs via i-motif DNA. We herein report i-motif DNA-assisted pH-responsive gold nanoparticle assembly (termed RGA), which shows a reversible and highly sensitive response to pH variation between 6.20 and 7.40. The acidic pH triggers the disassembly of the RGA, thus converting the AuNPs from aggregation state to disperse state, which leads to a color transition from blue-purple to red. Therefore, the pH value can be estimated by naked-eye determination or UV–vis spectroscopy analysis. More significantly, the visually detectable color change is monitored using the built-in camera of a smartphone. The RGB (red, green, blue) values of the RGA solution are measured by a smartphone application (APP). Following data processing, the RGB values can be converted into pH value, providing a new strategy for the on-site and real-time pH sensing. Furthermore, the pH-induced conformation change of i-motif DNA allows the RGA to detect a slight pH fluctuation in the catalytic oxidation of glucose by glucose oxidase and the hydrolysis of urea by urease.

Furin Enzyme and pH Synergistically Triggered Aggregation of Gold Nanoparticles for Activated Photoacoustic Imaging and Photothermal Therapy of Tumors

Specific and effective accumulation of nanoparticles within tumors is highly crucial for precise cancer diagnosis and treatment. Therefore, spatiotemporally manipulating the aggregation of small gold nanoparticles (AuNPs) in a tumor microenvironment is of great significance for enhancing the diagnostic and therapeutic efficacy of tumors. Herein, we reported a novel furin enzyme/acidic pH synergistically triggered small AuNP aggregation strategy for activating the photoacoustic (PA) imaging and photothermal (PTT) functions of AuNPs in vivo. Smart gold nanoparticles decorated with furin-cleavable RVRR (Arg-Val-Arg-Arg) peptides (Au-RRVR) were rationally designed and fabricated. Both in vitro and in vivo experiments demonstrated that such Au-RRVR nanoparticles could be simultaneously induced by furin and acidic pH to form large aggregates within tumorous tissue resulting in improved tumor accumulation and retention, which can further activate the PA and PTT effect of AuNPs for sensitive imaging and efficient therapy of tumors. Thus, we believe that this dual-stimuli-responsive aggregation system may offer a universal platform for effective cancer diagnosis and treatment.

Dimeric-serotonin bivalent ligands induced gold nanoparticle aggregation for highly sensitive and selective serotonin biosensor

Chemically modulating monoamine neurotransmitter serotonin undergoes a physiological reaction of enzyme intermediated peroxidation to reconstruct dimeric self-assembled complex. A standard bivalent ligand approach dimeric serotonin increases structural and functional scaffolding with recognition-binding sites that are fundamentally more friendly than monovalent binding sites. Dimerization reaction accelerates the catalytic activity of one-electron oxidation at the C(4) position of serotonin to generate dual phenolic radicals in the presence of horseradish (HRP) and hydrogen peroxide (H2O2). Herein, we suggest the dimeric serotonin-based colorimetric assay, which presents a new rapid, sensitive, selective, and quantitative visualization. The dimeric serotonin possesses the capability to recognize intermolecular interaction units that cause aggregation scaffold of gold nanoparticles (GNPs), providing inexpensive and straightforward analytical needs. As a proof of visual and spectral analysis, peroxidative dimeric serotonin demonstrated sensitive and robust results. The calorimetric method enables highly sensitive detection of serotonin in phosphate buffer, and in human serum samples at nanomolar levels with a LOD of 2.6 nM and 2.81 nM, respectively, and the sensor possesses a dynamic range of 100–300 nM in buffer condition. Also, as proof of concept, visible color imaging of immunosensors which is appropriate for fast visible testing at detection limits as low as 2.90 nM concentration.

Dual-mode detection of organophosphate pesticides in pear and Chinese cabbage based on fluorescence and AuNPs colorimetric assays

Herein, a dual-mode method based on fluorescent and colorimetric sensor was developed for determination of organophosphate pesticides (OPs). In this study, indoxyl acetate (IDA) was hydrolyzed by esterase into indophenol. Indophenol leads to changes in fluorescence signal and aggregation of gold nanoparticles (AuNPs); ultimately changing the color from red to blue. When OPs exist, the formation of indophenol was inhibited. With increasing the concentrations of OPs, the enhancement rate of fluorescence signal decreases, and the color change of AuNPs weakened gradually. The assay was applied for determination of dichlorvos, trichlorfon, and paraoxon, and the limits of detection (LODs) were 0.0032 mg/kg, 0.0096 mg/kg, and 0.0074 mg/kg (fluorometric assay), and 0.0120 mg/kg, 0.0224 mg/kg, and 0.0106 mg/kg (colorimetric assay), respectively. Finally, such a convenient and sensitive sensing assay was successfully applied for quantification of OPs in pear and Chinese cabbage with good recoveries ranged between 80.19 and 116.93%.

Encapsulation of cells in gold nanoparticle functionalized hybrid Layer-by-Layer (LbL) hybrid shells – Remote effect of laser light

Encapsulation of cells has been an active area of research. Among various methods for encapsulation, Layer-by-Layer (LbL) offers extensive flexibility in the design of surfaces and their interfacial nanoarchitectonics. A diverse range of functionalities have been recently demonstrated for cell encapsulation including protection and improved circulation. Here, we present a new strategy of cell encapsulation in a hybrid coating containing LbL assembly functionalized with gold nanoparticle aggregates. The effect of this hybrid coating on cell viability was assessed. Subsequently, upon laser illumination the encapsulated cells undergo immediate necrosis caused by the localized heat generated by the laser beam on gold nanoparticle aggregates. Similarly to affecting polyelectrolyte multilayer capsules, one envisions controlling surface properties of cells remotely by a laser beam. Further applications of the proposed approach are expected to be in biomedicine.

Noninvasive Point-of-Care Nanobiosensing of Cervical Cancer as an Auxiliary to Pap-Smear Test.

A potential cancer antigen (Ag), protein-phosphatase-1-gamma-2 (PP1γ2), with a restricted expression in testis and sperms has been identified as a biomarker specific to cervical cancer (CaCx). Detection of this cancer biomarker antigen (NCB-Ag) in human urine opens up the possibility of noninvasive detection of CaCx to supplement the dreaded and invasive Pap-smear test. A colorimetric response of an assembly of gold nanoparticles (Au NPs) has been employed for the quantitative, noninvasive, and point-of-care-testing of CaCx in the urine. In order to fabricate the immunosensor, Au NPs of sizes ∼5-20 nm have been chemically modified with a linker, 3,3'-di-thio-di-propionic-acid-di(n-hydroxy-succinimide-ester) (DTSP) to attach the antibody (Ab) specific to the NCB-Ag. Interestingly, the addition of Ag to the composite of Ab-DTSP-Au NPs leads to a significant hypsochromic shift due to a localized surface plasmon resonance phenomenon, which originates from the specific epitope-paratope interaction between the NCB-Ag and Ab-DTSP-Au NPs. The variations in the absorbance and wavelength shift during such attachments of different concentrations of NCB-Ag on the Ab-DTSP-Au NPs composite have been employed as a calibration to identify NCB-Ag in human urine. An in-house prototype has been assembled by integrating a light-emitting diode of a narrow range wavelength in one side of a cuvette in which the reaction has been performed while a sensitive photodetector to the other side to transduce the transmitted signal associated with the loading of NCB-Ag in the Ab-DTSP-Au NPs composite. The proposed immunosensing platform has been tested against other standard proteins to ensure noninterference alongside proving the proof-for-specificity of the NCB detection.

Gold/ultra‐high molecular weight polyethylene nanocomposites for electrical energy storage: Enhanced recovery efficiency upon uniaxial deformation

AbstractThe growing demand for renewable energy sources has prompted the development of dielectric materials with the ability to store and efficiently recover electrical energy. Here, we correlate the structure and thermal conductivity of uniaxially oriented disentangled ultra‐high molecular weight polyethylene (dis‐UHMWPE) composites reinforced with gold nanoparticles with their electrical properties and potential application as electrical energy storage devices. Stretching increases the orientation of the polymer chains and thus the crystallinity and reduces the aggregation of gold nanoparticles while the thermal conductivity enhances significantly along the orientation axis. The structural changes driven by stretching result in two competing effects; on the one hand, the crystallinity increase reduces the permittivity of the composites and increases the resistivity, while on the other hand the recovery efficiency of oriented materials excels that of unstretched samples by up to 6 times at 5 s. Therefore, our work shows the structure–property relationship in electrical energy storage materials.

Heat-enhancing aggregation of gold nanoparticles combined with loop-mediated isothermal amplification (HAG-LAMP) for Plasmodium falciparum detection

Malaria infection represents a major public health and economic issue that leads to morbidity and mortality globally. A highly effective and uncomplicated detection tool is required for malaria control in geographical hotspots of transmission. We developed a simple and more sensitive novel approach for the detection of the 18S rRNA gene of Plasmodium falciparum based on loop-mediated isothermal amplification (LAMP) and visualization using colorimetric, streptavidin-functionalized gold nanoparticles (SA-GNPs). Two loop primers of LAMP were biotinylated to produce biotin-containing products during amplification. After the addition of SA-GNPs, clusters of avidin-biotin complexes were established in the LAMP structure. While the positive reactions remained wine red, the negative reactions became colorless with partial aggregations induced by hydrochloric acid (HCl) under heat enhancement (60 °C). All steps of the assay were completed within 50 min, its detection limit was 1 parasite/μL, and it was highly specific for P. falciparum. This effortless detection system with high sensitivity and specificity could provide an alternative choice for malaria diagnostics in resource-limited regions.

Reliable colorimetric aptasensor exploiting 72-Mers ssDNA and gold nanoprobes for highly sensitive detection of aflatoxin M1 in milk

The development of a label-free colorimetric aptasensor has been accomplished for rapid quantification of aflatoxin M1 (AFM1) based on localized surface plasmon resonance (LSPR) and aggregation of gold nanoparticles (AuNPs). The sensor utilizes competitive interactions of the aptamer to the AFM1 or the AuNPs under a specific condition exploiting sodium chloride to aggregate AuNPs. In principle, the aptamer interacts with AFM1 selectively, resulting in a change of its structure; consequently, the aptamer cannot prevent AuNPs aggregation induced by sodium chloride. A new color tone of the solution caused by the LSPR peak shift of aggregated AuNPs can be measured by a colorimetric method. The detection limit of the sensor was 0.002 ng mL−1, providing exceptionally analytical sensitivity that conforms to the maximal residue limits of AFM1. Moreover, the current method has been successfully utilized to determine AFM1 in milk. Recoveries obtained were higher than 80 %, with RSD lower than 10 %, denominating that the colorimetric aptasensor devotes practicability for real samples.

3-Aminophenylboronic acid-mediated aggregation of gold nanoparticles for colorimetric sensing of iohexol in environmental and biological samples

Iohexol (IHO), as one of iodinated X-ray contrast, is often used as not only a chemical marker for tracking wastewater contamination in aquatic environment, but also an ideal glomerular filtration rate marker for explorating kidney disease. To these aims, it is important to establish reliable, fast, and cheap methods to detect IHO in environmental and biological samples. This work describes for the first time the development of a selective, sensitive and reliable colorimetric sensing assay for the fast determination of IHO in environmental and biological samples based on 3-aminophenylboronic acid (3-APBA) mediated aggregation of gold nanoparticles (AuNPs). In this approach, 3-APBA can assemble on the AuNPs surface through electrostatic interaction between its amino groups with the negatively charged citrate stabilizer of AuNPs to form AuNP@3-APBA. Subsequently, the aggregation and visual color change of the assembled AuNP@3-APBA are induced by the covalent reaction between boronic acid ligands of 3-APBA and cis-diols of IHO. The developed assay presented a very simple operating procedure and a rapid analysis time of around 10 min. The developed assay also exhibited good selectivity and a low limit of detection (LOD) of 0.005 mM for detecting IHO. Moreover, the developed assay showed comparable accuracy and precision to the high-performance liquid chromatography-diode array detector (HPLC-DAD) method when used for the rapid determination of IHO in river water and human urine samples. The recoveries of IHO at three spiking levels were in the range of 91.5–106.3% with relative standard deviation (RSD) values below 6.39%.

Colorimetric Aptasensor for Detecting Bacillus carboniphilus Using Aptamer Isolated with a Non-SELEX-Based Method

B. carboniphilus is a naphtha-degradative strain (NDS) that uses hydrocarbons for its growth and causes microbiologically influenced corrosion (MIC) in naphtha pipelines. To date, there have been no studies on receptors or sensors for the detection of B. carboniphilus. We isolate B. carboniphilus-specific aptamers with a non-SELEX-based method, which employs repetitive cycles of centrifugation-based partitioning. The binding affinities of three aptamers are evaluated by obtaining their dissociation constants (Kd), which range from 13.2 to 26.3 nM. The BCA-05 aptamer with the lowest Kd value is employed for a two-stage label-free aptasensing platform to verify the aptamer selectivity using colorimetric detection of B. carboniphilus. This platform starts with the aptamer-bacteria binding step, and the concentration of residual aptamer after binding depends on the amount of the target bacteria. Then, the amount of separated residual aptamer determines the degree of salt-induced aggregation of gold nanoparticles (AuNPs), which results in a color change from red to blue. The AuNP color change is expressed as the ratio of absorbances at 630 and 520 nm (A630/A520). Under optimized conditions, this aptasensor shows reliable performance with a linear correlation in the range 104–107 CFU mL−1 and a limit of detection of 5 × 103 CFU mL−1.