Naked Gold Nanoparticles Research Articles

A dendrimer-based platform integrating surface-enhanced Raman scattering and class-incremental learning for rapidly detecting four pathogenic bacteria

Rapid monitoring of pathogens is crucial for preventing foodborne diseases, thus making it an urgent need to develop efficient, fast, and simple methods for on-site detection of multiple pathogens. With advances in SERS-based label-free biosensors and machine learning, progress is evident, yet challenges such as complex substrates and limited model interpretability persist. In this work, we reported a novel dendrimer-based platform that integrated surface-enhanced Raman scattering (SERS) with class-incremental learning (CIL) for quick and simultaneous detection of four pathogenic bacteria, namely Escherichia coli, Salmonella Paratyphi B, Pseudomonas aeruginosa, and Staphylococcus aureus. First, the poly(amidoamine) (PAMAM)-based gold nanoassemblies on silicon wafer (PGNAs/Si) was designed as a highly active SERS substrate with an easy fabrication process. Compared with naked gold nanoparticles, both sensitivity and repeatability were improved by introducing a controllable dendritic nanostructure with ultra-small internal nanogaps. The detection limits of four pathogens in water, food, and dietary supplement matrices were all on the order of 10 CFU/mL. Subsequently, to analyze the complex SERS spectra and distinguish samples with different pathogens, CIL models were established using the light gradient boosting machine (LightGBM) algorithm. Notably, the discriminative models demonstrated excellent classification performance with an accuracy of over 93.44 %. Further, the SHapley Additive exPlanations (SHAP) method was utilized to identify the key SERS features in accurately discriminating different pathogens. Together, these results demonstrate that the dendrimer-based platform, by integrating SERS with CIL, can rapidly detect four pathogenic bacteria, underscoring its potential for food safety testing or quality monitoring in medical supplies manufacturing.

Eco-Friendly Production of AuNPs and Their Impact on the Oil Oxidative Stability.

Vegetable oils have been used for different applications and, more recently, as an active host medium to obtain nanoparticles for employment in bionanotechnological applications. Nevertheless, oils are very susceptible to oxidation during production, storage, and transportation because of their chemical composition. Consequently, any modification in their production must be accompanied by an analysis of the oxidative stability. In this study, naked and biocompatible gold nanoparticles (AuNPs) were grown on sunflower oil during sputtering deposition using different deposition times. Size and morphology were determined by transmission electron microscopy (TEM) and their concentrations were found by inductively coupled plasma-optical emission spectroscopy (ICP-OES). Rancimat® method was employed to evaluate the AuNPs influence on the oxidative stability of the vegetable oil. Well-dispersed quasi-spherical NPs were produced with a mean diameter in the 2.9–3.7 nm range and they were concentration-dependent on the deposition time. A concentration of about 11 mg/L, 38 mg/L, and 225 mg/L of AuNPs was obtained for a deposition time of 5 min, 15 min, and 30 min, respectively. The results also revealed that AuNPs negatively affected the oxidative stability of the sunflower oil and exponentially reduced the induction period (IP) with the increase in AuNPs content. IP reductions of 63%, 77%, and 81% were determined for the AuNPs containing samples at 11 mg/L, 38 mg/L, and 225 mg/L. For the first time, it is reported that naked AuNPs promote the rapid degradation of vegetable oil and this points out the need for attention relative to the quality of vegetable oils used to host metal nanoparticles.

Effect of naked and PEG-coated gold nanoparticles on histopathology and cytokines expression in rat liver and kidneys.

Aim: To compare the effects of 5- and 50-nm naked and PEG-coated gold nanoparticles (AuNP) on proinflammatory cytokines (IL-1β, IL-6, TNF-α) expression and histopathological changes in liver and kidneys of rats. Materials & methods: Rats were injected with different nanoparticles and sacrificed after 24h. Results: Both 5- and 50-nm AuNPs, and 50-nm PEG-AuNPs caused granular clumping of cytoplasm, edema and hydropic dystrophy in hepatic cells. Naked AuNPs of both sizes caused mild shrinkage, whereas 50-nm PEG-AuNPs enlarged the Bowman's space and capsule. Larger nanoparticles produced more profound mRNA expression of cytokines in both the organs. Conclusion: These findings suggest the roles of particle size and coating on immunological response and histopathological changes.

Therapeutic effect of gold nanoparticles on DSS-induced ulcerative colitis in mice with reference to interleukin-17 expression

Ulcerative colitis (UC) is among the most challenging human diseases. Nanotechnology has incontestable promising outcomes in inflammatory bowel diseases. This study aimed to investigate the therapeutic effect of naked gold nanoparticles (AuNPs) on dextran sodium sulphate (DSS) induced ulcerative colitis in mice. We also examined the expression of interleukin-17 (IL-17) following AuNPs treatment. Mice were randomly divided into control, DSS and DSS+ AuNPs groups. Severity of colitis was assessed by disease activity index (DAI) measurement. At the end of the experiment, the final body weights were recorded. The colon was dissected and processed for histopathological examinations by light and electron microscopes. Colon homogenates were prepared for assay of tissue malondialdehyde (MDA) and real-time PCR analysis of IL-17A. Immunohistochemical localization of IL-17A was carried out. Scanning electron microscopy (SEM) and Energy Dispersive X-ray (EDX) detector were used to detect the presence of AuNPs in the colonic tissue of DSS+ AuNPs groups. Our results showed that AuNPs effectively targeted the colonic tissue, and reduced changes induced by DSS. The underlying mechanisms could be related to anti-oxidant effect (as evident by decreasing tissue MDA) and anti-inflammatory potential of AuNPs. Our study draws attention to as a novel therapeutic strategy for treating UC.

Surface plasmon resonance of naked gold nanoparticles for photodynamic inactivation of Escherichia coli

Although antimicrobial photothermal inactivation of naked gold nanostructures using powerful pulsed lasers has been previously studied, there are little reports about their photodynamic antimicrobial properties under the irradiation of low-power density continuous wave lasers. Therefore, this paper attempts to fill this gap. In this paper, we studied the effects of a 40-mW/cm2 continuous Nd:Yag laser at 532 nm and naked gold nanoparticles on inactivation of Escherichia coli ATCC25922. According to our results, 60 min illumination using the Nd:Yag laser caused a 0.15log reduction of the bacterial viability. Also, the employed gold nanoparticles with an average size of 15 nm were toxic to E. coli ATCC 25922 in the concentrations above 0.5 μg/ml. In addition, synergistic effects of 0.5 μg/ml gold nanoparticles and the light illumination led to a 2.43log reduction of the viability after a 60-min exposure and did not show any considerable temperature change on the media. The obtained results were justified based on the possible interaction mechanisms of low-power density laser lights and naked gold nanoparticles. The paper is proposed as a prelude for future research about localized inactivation of resistant pathogens with minimum side effects on neighbor tissues.

Fast and simple method for screening of single-stranded DNA breaking photosensitizers using graphene oxide

A fast and simple method for screening of ssDNA-breaking photosensitizers was developed using graphene oxide. The ultraviolet light-induced DNA breaks are one of the most harmful DNA damages and cause skin cancer if they are left unrepaired. Since graphene oxide showed relatively strong affinity to the broken DNA than intact DNA, and it quenched fluorescence of the DNA labeling dye effectively, the degree of ultraviolet light-induced broken DNAs could be analyzed by measuring decreased fluorescence after mixing the DNA with graphene oxide. The decrease of fluorescence was highly correlated with the ultraviolet light-irradiating time and concentration of the added drugs. As a result, it was possible to evaluate the efficacy of different ssDNA-breaking photosensitizers in a high-throughput manner. However, conventional methods for the damaged-DNA analysis are time-consuming and require additional manipulations such as purification, radio-labeling, enzymatic digestion, or chemical modification of DNA. The phototoxicity of five drugs such as benzophenone, ketoprofen, indomethacin, naproxen, and norfloxacin was tested using the proposed method. The ssDNA-breaking efficiency of the drugs was well matched with reported efficiency of the tested drugs. In contrast to naked gold nanoparticles, graphene oxide is stably dispersed in the presence of salt, the phototoxicity of the drugs could be successfully tested at a physiological condition using the graphene oxide based method.

A surface enhanced Raman scattering based colloid nanosensor for developing therapeutic drug monitoring

Competitive reactions, on the surface of plasmonic nanostructures, allow exploiting SERS signals for quantitative Therapeutic Drug Monitoring. As an example, the concentration of Erlotinib, an anti-EGFR small molecule, used for the treatment of non-small cell lung and pancreatic cancer, is determined. The numerous side effects and the variability of patient responses make Erlotinib a good candidate for monitoring. The new SERS based sensor can estimate Erlotinib down to nanomolar concentration and is based on the chemical reaction of the drug and of a competitor SERS reporter on the surface of gold nanostructures. Colloid solutions of naked gold nanoparticles obtained by laser ablation in solution were used for obtaining nanostructures with very efficient hot spots for SERS and with a clean surface for chemistry. Detection of the drug in the nanomolar concentration range is shown to be possible also in spiked plasma samples.

Promising therapeutic effect of gold nanoparticles against dinitrobenzene sulfonic acid-induced colitis in rats.

Aim: The aim of this study is to evaluate the therapeutic effect of two different doses of naked gold nanoparticles (AuNPs) in the experimental colitis in rats. Materials & methods: Colitis was induced in rats by single intracolonic instillation of dinitro-benzene sulfonic acid (250μl DNBS-25mg/rat). 4 days later the rats were intravenously injected with a single dose of AuNPs 40 and 400μg/kg of size 16-25nm. Results: In comparison with dinitro-benzene sulfonic acid-colitis group, the exposure to AuNPs for 72 h ameliorated the liver and kidney functions, increased the regenerative capacity of damaged colon tissues, suppressed the inflammatory cytokine response and diminished the colonic malondialdehyde and myeloperoxidase activities. In addition, there was a remarkable improvement in the antioxidant defense system. Conclusion: Our study suggested a new therapy for experimental colitis without noticeable drawbacks.

Naked Gold Nanoparticles and hot Electrons in Water

The ionizing radiation in aqueous solutions of gold nanoparticles, stabilized by electrostatic non-covalent intermolecular forces and steric interactions, with antimicrobial compounds, are investigated with picosecond pulse radiolysis techniques. Upon pulse radiolysis of an aqueous solution containing very low concentrations of gold nanoparticles with naked surfaces available in water (not obstructed by chemical bonds), a change to Cerenkov spectrum over a large range of wavelengths are observed and pre-solvated electrons are captured by gold nanoparticles exclusively (not by ionic liquid surfactants used to stabilize the nanoparticles). The solvated electrons are also found to decay rapidly compared with the decay kinetics in water. These very fast reactions with electrons in water could provide an enhanced oxidizing zone around gold nanoparticles and this could be the reason for radio sensitizing behavior of gold nanoparticles in radiation therapy.

Naked physically synthesized gold nanoparticles affect migration, mitochondrial activity, and proliferation of vascular smooth muscle cells.

IntroductionVascular smooth muscle cells (VSMCs) play an important role in the development and progression of atherosclerosis and vascular injuries in terms of proliferation and migration. Therefore, the aim of this study was to investigate the anti-migratory and proliferative effects of naked gold nanoparticles (AuNPs) on VSMCs.Materials and methodsOne set of physically synthesized AuNPs (pAuNPs) and three sets of chemically synthesized AuNPs (cAuNPs) were tested.Results and discussionAmong them, the pAuNPs were found to significantly and markedly inhibit platelet-derived growth factor (PDGF)-induced VSMC migration. Transmission electron microscopy revealed that the pAuNPs were ingested and aggregated in the cytoplasm at an early stage of treatment, while the viability of VSMCs was not affected within 24 hours of treatment. The pAuNP treatment enhanced cellular mitochondrial activity but inhibited basal and PDGF-induced VSMC proliferation, as determined by MTT, WST-1, and BrdU cell proliferation assays. Furthermore, the pAuNPs did not interfere with PDGF signaling or matrix metalloproteinase-2 expression/activity. Unlike the cAuNPs, the pAuNPs could markedly reduce VSMC adhesion to collagen, which was supported by the findings that the pAuNPs could inhibit collagen-induced tyrosine protein and focal adhesion kinase (FAK) phosphorylation and actin cytoskeleton reorganization during cell adhesion. The in vitro effects of the pAuNPs were confirmed in the in vivo rat balloon-injured carotid artery model by diminishing the proliferating VSMCs.ConclusionTaken together, the present study provides the first evidence that naked pAuNPs can reduce VSMC migration and compromise cell adhesion by affecting FAK and tyrosine-protein activation. The pAuNPs also have an inhibitory effect on PDGF-induced VSMC proliferation and can reduce proliferating/migrating VSMC expression in vivo.

Optimal method of gold nanoparticle administration in melanoma-bearing mice.

The present study assessed different methods of administering gold nanoparticles (GNPs) using different formulations to determine which of the methods achieved optimal radiosensitization. Cells from the B16F10 mouse melanoma cell line were implanted in the femoral area of mice, assigned to one of the eight following groups: i) Control; ii) intravenous (IV) injection of polyethylene glycol (PEG)-binding GNPs (Peg-GNPs) alone; iii) direct intratumoral (IT) injection of Peg-GNPs alone; iv) radiotherapy (RT)-alone; v) Peg-GNP IV + RT; vi) Peg-GNP IT + RT; vii) naked GNP (N-GNPs) IV + RT; and viii) N-GNP IT + RT. Injection volumes of the Peg-GNPs (particle size, 15 nm; dose, 2.8 mg/ml) and N-GNPs (particle size, 15 nm; dose, 200 mg Au/cc) were 0.3 and 0.2 ml per mouse, respectively, for IV and IT. The femoral area was irradiated with a single dose of 10 Gy. To evaluate the effects of GNPs, the current study measured the changes in the tumor volume ratio to the initial tumor volume over time and observed the survival rate. Administration of GNPs with RT did not improve the suppression of tumor growth or survival to a statistically significant extent. The administration of Peg-GNPs alone indicated a slight tumor suppressing effect at the early stage. The current study was not able to confirm the radiosensitization effect of GNPs in melanoma-bearing mice with tumors that were large in comparison to previous studies. Further research is required to validate the radiosensitizing effect on large tumors.

A SERRS/MRI multimodal contrast agent based on naked Au nanoparticles functionalized with a Gd(iii) loaded PEG polymer for tumor imaging and localized hyperthermia.

Multimodal contrast agents offer new interesting diagnostic possibilities, summing the benefits of multiple imaging techniques. Magnetic resonance and optical imaging are complementary techniques. The first allows total body screening, even though it suffers from low spatial resolution and needs high loadings, whereas the second shows lower penetration, but bright signals, and a higher spatial resolution and needs lower loadings. We present a plasmonic nanosystem as a MRI (magnetic resonance imaging) and SERRS (surface enhanced resonance Raman scattering) multimodal contrast agent. Naked gold nanoparticles, obtained by laser ablation synthesis in solution, are organized as a highly efficient SERRS substrate with a naphthalocyanine reporter and functionalized with a MRI contrast agent with a newly synthesized 3DOTA-PEG polymer, with a high GdIII loading. As a proof of concept, in vivo and ex vivo MRI and SERRS experiments are also performed. The plasmonic property of the nanosystem is then exploited to show its usefulness for localized hyperthermia.

Enhanced EGFR Targeting Activity of Plasmonic Nanostructures with Engineered GE11 Peptide.

Plasmonic nanostructures show important properties for biotechnological applications, but they have to be guided on the target for exploiting their potentialities. Antibodies are the natural molecules for targeting. However, their possible adverse immunogenic activity and their cost have suggested finding other valid substitutes. Small molecules like peptides can be an alternative source of targeting agents, even if, as single molecules, their binding affinity is usually not very good. GE11 is a small dodecapeptide with specific binding to the epidermal growth factor receptor (EGFR) and low immunogenicity. The present work shows that thousands of polyethylene glycol (PEG) chains modified with lysines and functionalized with GE11 on clusters of naked gold nanoparticles, obtained by laser ablation in water, achieves a better targeting activity than that recorded with nanoparticles decorated with the specific anti-EGFR antibody Cetuximab (C225). The insertion of the cationic spacer between the polymeric part of the ligand and the targeting peptide allows for a proper presentation of GE11 on the surface of the nanosystems. Surface enhanced resonance Raman scattering signals of the plasmonic gold nanoparticles are used for quantifying the targeting activity. Molecular dynamic calculations suggest that subtle differences in the exposition of the peptide on the PEG sea are important for the targeting activity.

A12 超音波還元法により調製された裸の金ナノ粒子の分散安定化機構の解明(口頭発表)

A12 超音波還元法により調製された裸の金ナノ粒子の分散安定化機構の解明(口頭発表)

Gold nanoparticle-decorated halloysite nanotubes – Selective catalysts for benzyl alcohol oxidation

Preparation of gold nanoparticle-decorated halloysite nanotubes (Au-Hal) by a deposition method and evaluation of their catalytic activity in an oxidation of benzyl alcohol are reported. An electrostatic attraction between positively charged polyethylenimine (PEI)-capped gold nanoparticles and the negatively charged external surfaces of halloysite nanotubes (Hal nanotubes) was the key factor in fabrication of Au-Hal nanotubes. Au-Hal catalysts showed good conversions and surprisingly high benzaldehyde selectivities (above 90%) in the benzyl alcohol oxidation. Influence of the amount of PEI used as a capping agent, the gold content and calcination of Au-Hal catalysts on the conversion and selectivity was investigated. A notable increase in the benzaldehyde selectivity at higher PEI contents and a significant drop in the benzaldehyde selectivity on calcination clearly indicate the central role of PEI in the selective formation of benzaldehyde. The high benzaldehyde selectivity of uncalcined catalysts are probably due to PEI donor molecules coordinating to certain surface sites on Au nanoparticles and thus blocking the catalytic sites required for further oxidation of benzaldehyde to benzoic acid. The high combined selectivity of benzoic acid and benzyl benzoate obtained with the calcined catalysts indicates that naked gold nanoparticles have the catalytic sites available for the benzoic acid formation.

Confined naked gold nanoparticles in ionic liquid films.

Surface-clean Au nanoparticles (NPs) confined in films of ionic liquids (ILs) can be easily fabricated by sputtering deposition. A silicon wafer coated with films of both hydrophobic (bis((trifluoromethyl)sulfonyl)amide, NTf2-) and hydrophilic (tetrafluoroborate, BF4-) imidazolium-based ILs forms an 'ionic carpet-like' structure that can be easily decorated with Au NPs of 5.1 and 6.5 nm mean diameter, respectively. The depth profile distribution of the Au NPs depends on the arrangement of the IL, which is controlled mainly by the anion volume. Higher concentrations of Au NPs are found closer to the IL surface for the system containing a larger anion (NTf2) whereas Au NPs are located deeper in the IL for the system containing a smaller anion (BF4). The Au NPs are well distributed over the IL/Si support and are strictly confined in a single layer of the IL. This method is among the most simple and versatile for the generation of liquid layers containing surface-clean, stable and confined Au NPs.

Coinhibition of overexpressed genes in acute myeloid leukemia subtype M2 by gold nanoparticles functionalized with five antisense oligonucleotides and one anti-CD33(+)/CD34(+) aptamer

The aim of this study was to evaluate an engineered nanostructure to silence five important oncogenes, including BAG1, MDM2, Bcl-2, BIRC5 (survivin) and XIAP, in acute myeloid leukemia subtype 2 (AML-M2). The smart nanostructures were functionalized gold nanoparticles (FGNs) containing five antisense oligonucleotides (AOs) and one anti-CD33(+)/CD34(+) aptamer. First, the best AO for each gene was selected with the OligoWalk online software, and then different arrangements of AOs were evaluated with the RNAstructure software. Thereafter, naked gold nanoparticles (NGNs) were synthesized by the reaction of 1000 mm HAuCl4 with 10 μg ml(-1) ascorbic acid. Next, five AOs and one anti-CD33(+)/CD34(+) aptamer were attached to NGNs through serial reactions. Later, 5 ml of heparinized blood samples from five AML-M2 patients were prepared, cancerous cells were isolated and then incubated with three concentrations (75, 150 and 300 μg ml(-1)) each of FGNs, NGNs, gold nanoparticles functionalized with scrambled oligonucleotides (GNFSONs) and doxorubicin. Finally, cell death percentage and gene expressions were measured by MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) assay and real-time PCR, respectively. This study showed that FGNs and doxorubicin led to more cell death compared with NGNs and GNFSONs (P<0.05). Interestingly, all concentrations of FGNs led to a decrease in gene expression. As an important finding, although all concentrations of doxorubicin could also inhibit the expression of genes, FGNs had more effect (P<0.05). Moreover, both NGNs and GNFSONs could silence all genes only at a concentration of 300 μg ml(-1). For BCL2 and XIAP, a dose-dependent pattern was observed, but there was no similar pattern for others.

SERS and integrative imaging upon internalization of quantum dots into human oral epithelial cells.

CdTe quantum dots (QDs) are widely used in bio-applications due to their size and highly efficient optical properties. However internalization mechanisms thereof for the variety of freshly extracted, not cultivated human cells and their specific molecular interactions remains an open topic for discussion. In this study, we assess the internalization mechanism of CdTe quantum dots (3.3 nm) capped with thioglycolic acid using non cultivated oral epithelial cells obtained from healthy donors. Naked gold nanoparticles (40 nm) were successfully used as nanosensors for surface-enhanced Raman spectroscopy to efficiently identify characteristic Raman peaks, providing new evidence indicating that the first interactions of these QDs with epithelial cells occurred preferentially with aromatic rings and amine groups of amino acid residues and glycans from trans-membrane proteins and cytoskeleton. Using an integrative combination of advanced imaging techniques, including ultra-high resolution SEM, high resolution STEM coupled with EDX spectroscopy together with the results obtained by Raman spectroscopy, it was determined that thioglycolic acid capped CdTe QDs are efficiently internalized into freshly extracted oral epithelial cells only by facilitated diffusion, distributed into cytoplasm and even within the cell nucleus in three minutes.

Preparation of Au/PAN nanofibrous membranes for catalytic reduction of 4-nitrophenol

Due to their high surface energy, naked gold nanoparticles (AuNPs) tend to form agglomerates, which could lead to the decrease of active sites and catalytic activity of AuNPs. Herein, the gold nanoparticles/polyacrylonitrile (AuNPs/PAN) nanofibrous membranes have been prepared via an environmentally friendly and efficient route combining electrospinning, amination, and electroless plating technique. The abundant amine and imine groups can be introduced onto the surface of PAN nanofibrous membranes via amination treatment which could be used as “anchoring sites” to immobilize AuNPs. The resultant composite membranes were applied as the new catalytic materials for reduction of 4-nitrophenol to 4-aminophenol under room temperature. The new catalytic membranes exhibited the significant advantages, such as low dosage, high catalytic activity, easy recycling, and excellent stability.

Surface enhanced Raman scattering of amino acids assisted by gold nanoparticles and Gd(3+) ions.

The surface enhanced raman scattering (SERS) signal from the l-tyrosine (tyr) molecule adsorbed on gold nanoparticles (Au-tyr) is compared with the SERS signal assisted by the presence of gadolinium ions (Gd(3+)) coordinated with the Au-tyr system. An enhancement factor of the SERS signal in the presence of Gd(3+) ions was ∼5 times higher than that produced by l-tyrosine adsorbed on gold nanoparticles. The enhancement of the SERS signal can be attributed to a corresponding increase in the local electric field due to the presence of Gd(3+) ions in the vicinity of a gold dimer configuration. This scenario was confirmed by solving numerically Maxwell equations, showing an increase of 1 order of magnitude in the local electric scattered field when the Gd(3+) ion is located in between a gold dimer compared with naked gold nanoparticles.