Au Nanostars Research Articles

Photothermal/NO combination therapy from plasmonic hybrid nanotherapeutics against breast cancer.

In this study, a plasmon-semiconductor nanotheranostic system comprising Au nanostars/graphene quantum dots (AuS/QD) hybrid nanoparticles loaded with BNN6 and surface modified with PEG-pyrene was developed for the photo-triggered hyperthermia effect and NO production as the dual modality treatment against orthotopic triple-negative breast cancer. The structure and morphology of the hybrid nanodevice was characterized and the NIR-II induced thermal response and NO production was determined. The hybrid nanodevice has shown enhanced plasmonic energy transfer from localized surface plasmonic resonance of Au nanostars to QD semiconductor that activates the BNN6 species loaded on QD surfaces, leading to the effective NO production and the gas therapy in addition to the photothermal response. The increased accumulation of the NIR-II-responsive hybrid nanotheranostic in tumor via the enhanced permeation and retention effects was confirmed by both in vivo fluorescence and photoacoustic imaging. The prominent therapeutic efficacy of the photothermal/NO combination therapy from the BNN6-loaded AuS@QD nanodevice with the NIR-II laser irradiation at 1064nm against 4T1 breast cancer was observed both in vitro and in vivo. The NO therapy for the cancer treatment was evidenced with the increased cellular nitrosative and oxidative stress, nitration of tyrosine residues of mitochondrial proteins, vessel eradication and cell apoptosis. The efficacy of the photothermal treatment was corroborated directly by severe tissue thermal ablation and tumor growth inhibition. The NIR-II triggered thermal/NO combination therapy along with the photoacoustic imaging-guided therapeutic accumulation in tumor shows prominent effect to fully inhibit tumor growth and validates the promising strategy developed in this study.

Hybrid Surface-Enhanced Raman Scattering Substrates for the Trace Detection of Ammonium Nitrate, Thiram, and Nile Blue.

We report the fabrication and performance evaluation of hybrid surface-enhanced Raman scattering (SERS) substrates involving laser ablation and chemical routes for the trace-level detection of various analyte molecules. Initially, picosecond laser ablation experiments under ambient conditions were performed on pure silver (Ag) and gold (Au) substrates to achieve distinct nanosized features on the surface. The properties of the generated surface features on laser-processed portions of Ag/Au targets were systematically analyzed using UV–visible reflection and field emission scanning electron microscopy studies. Later, hybrid-SERS substrates were achieved by grafting the chemically synthesized Au nanostars on the plain and laser-processed plasmonic targets. Subsequently, we employed these as SERS platforms for the detection of a pesticide (thiram), a molecule used in explosive compositions [ammonium nitrate (AN)], and a dye molecule [Nile blue (NB)]. A comparative SERS study between the Au nanostar-decorated bare glass, silicon, Ag, Au, and laser-processed Ag and Au targets has been established. Our studies and the obtained data have unambiguously determined that laser-processed Ag structures have demonstrated reasonably good enhancements in the Raman signal intensities for distinct analytes among other substrates. Importantly, the fabricated hybrid SERS substrate of “Au nanostar-decorated laser-processed Ag” exhibited up to eight times enhancement in the SERS intensity compared to laser-processed Ag (without nanostars), as well as up to three times enhancement than the Au nanostar-loaded plain Ag substrates. Additionally, the achieved detection limits from the Au nanostar-decorated laser-processed Ag SERS substrate were ∼50 pM, ∼5 nM, and ∼5 μM for NB, thiram, and AN, respectively. The estimated enhancement factors accomplished from the Au nanostar-decorated laser-processed Ag substrate were ∼106, ∼106, and ∼104 for NB, thiram, and AN, respectively.

Frontispiece: Peptoid‐Directed Formation of Five‐Fold Twinned Au Nanostars through Particle Attachment and Facet Stabilization

Nanoparticles The peptoid-directed formation of five-fold twinned Au nanostars through particle attachment and facet stabilization is reported by James J. DeYoreo, Chun-Long Chen et al. in their Research Article (e202201980).

Frontispiz: Peptoid‐Directed Formation of Five‐Fold Twinned Au Nanostars through Particle Attachment and Facet Stabilization

Nanopartikel Die peptoiddirigierte Bildung von verzwillingten Au-Nanosternen durch Partikelanlagerung und Facettenstabilisierung wird im Forschungsartikel von James J. DeYoreo, Chun-Long Chen et al. vorgestellt (e202201980).

Peptoid‐Directed Formation of Five‐Fold Twinned Au Nanostars through Particle Attachment and Facet Stabilization

AbstractWhile bio‐inspired synthesis offers great potential for controlling nucleation and growth of inorganic particles, precisely tuning biomolecule–particle interactions is a long‐standing challenge. Herein, we used variations in peptoid sequence to manipulate peptoid–Au interactions, leading to the synthesis of concave five‐fold twinned, five‐pointed Au nanostars via a process of repeated particle attachment and facet stabilization. Ex situ and liquid‐phase TEM observations show that a balance between particle attachment biased to occur near the star points, preferential growth along the [100] direction, and stabilization of (111) facets is critical to forming star‐shaped particles. Molecular simulations predict that interaction strengths between peptoids and distinct Au facets differ significantly and thus can alter attachment kinetics and surface energies to form the stars. This work provides new insights into how sequence‐defined ligands affect particle growth to regulate crystal morphology.

Peptoid-Directed Formation of Five-Fold Twinned Au Nanostars through Particle Attachment and Facet Stabilization.

While bio-inspired synthesis offers great potential for controlling nucleation and growth of inorganic particles, precisely tuning biomolecule–particle interactions is a long-standing challenge. Herein, we used variations in peptoid sequence to manipulate peptoid–Au interaction, leading to synthesis of concave five-fold twinned, five-pointed Au nanostars via a process of repeated particle attachment and facet stabilization. Ex situ and liquid-phase TEM observations show that a balance between particle attachment biased to occur near the star points, preferential growth along the [100] direction, and stabilization of (111) facets is critical to forming star-shaped particles. Molecular simulations predict that interaction strengths between peptoids and distinct Au facets differ significantly and thus can alter attachment kinetics and surface energies to form the stars. This work provides new insights into how sequence-defined ligands affect particle growth to regulate crystal morphology.

Abnormally Weak Surface-Enhanced Raman Scattering Activity of Tip-Rich Au Nanostars: The Role of Interfacial Defects.

Designing and regulating the geometry of a given plasmonic metal (Au, Ag, etc.) has become one of the most efficient approaches to achieve highly active surface-enhanced Raman spectroscopy (SERS) substrates, but this work demonstrates that plain efforts on this may not be enough. Here, we report that the often-neglected inner crystal defects also have huge impacts on the SERS activity, through a case of Au nanostars (NSs) with good SERS geometry but rich in defects. The results suggest that the interfacial defects (twin boundaries and superlattices) in the NSs aggravate the electronic oscillation damping via reducing the free path of electron scattering. This eventually results in weak local electromagnetic fields near the NS surfaces (or weak SERS activity of the NSs). This study has demonstrated the huge impact of interfacial defects on SERS activity and thus has a significant guideline for the design and fabrication of efficient SERS substrates.

Photochemical synthesis of Au nanostars on PMMA films by ethanol action as flexible SERS substrates for in-situ detection of antibiotics on curved surfaces

• Photochemical fabrication of Au NSs by the action of ethanol has been demonstrated. • Au NSs are employed directly on the flexible PMMA substrate for SERS application. • High enhancement factors about 10 9 are achieved for the antibiotics. • Effective multiplex SERS detection towards CPX and CAP is presented. • In-situ detection of antibiotics in chicken-wing samples was performed. Enormous Raman signal enhancement using gold nanostars (Au NSs) has attracted great attention due to the excitation of strong electric field on the nanostar tips. The synthetic methods of Au NSs mainly utilize specialized shape-directing agents, such as surfactants or polymers, to assist the tip formation. However, these agents passivate nanostar surfaces and weaken the interaction between Au NSs and analyte molecules. Herein, we report the synthesis of Au NSs with clean surface by the action of ethanol through a facile photoreduction process. The growth mechanism of Au NSs is elucidated and discussed with the action of ethanol as a polar protic solvent. The synthesis process of Au NSs is employed directly on poly(methyl methacrylate) (PMMA) films for the application of surface-enhanced Raman spectroscopy (SERS). The proposed flexible Au-NSs/PMMA SERS substrate is characterized by the SERS detection of two antibiotics, ciprofloxacin (CPX) and chloramphenicol (CAP). The superior detection performance includes high sensitivity, high enhancement factor (2.03 × 10 9 ), low limit of detection (3.41 × 10 -11 M), superior multiplex detection ability, good mechanical stability, excellent uniformity and reproducibility (<7.32 %). These superior sensing properties can be attributed to a large number of hotspots formed by diverse nanostructures at different positions of Au NSs on the Au-NSs/PMMA SERS substrate. The multiplex SERS detection ability is also explored for the simultaneous detection of multiple analytes. The transparent and flexible nature of the Au-NSs/PMMA SERS substrate enables the in-situ, real-time detection of CPX and CAP in chicken-wing samples by using the fiber-coupled Raman probe with the low LODs. The reported flexible SERS substrate opens the way to improve the practical detection of various antibiotics for the worldwide food safety issues.

Photothermal and Photodynamic Therapy of Tumors with Plasmonic Nanoparticles: Challenges and Prospects.

Cancer remains one of the leading causes of death in the world. For a number of neoplasms, the efficiency of conventional chemo- and radiation therapies is insufficient because of drug resistance and marked toxicity. Plasmonic photothermal therapy (PPT) using local hyperthermia induced by gold nanoparticles (AuNPs) has recently been extensively explored in tumor treatment. However, despite attractive promises, the current PPT status is limited by laboratory experiments, academic papers, and only a few preclinical studies. Unfortunately, most nanoformulations still share a similar fate: great laboratory promises and fair preclinical trials. This review discusses the current challenges and prospects of plasmonic nanomedicine based on PPT and photodynamic therapy (PDT). We start with consideration of the fundamental principles underlying plasmonic properties of AuNPs to tune their plasmon resonance for the desired NIR-I, NIR-2, and SWIR optical windows. The basic principles for simulation of optical cross-sections and plasmonic heating under CW and pulsed irradiation are discussed. Then, we consider the state-of-the-art methods for wet chemical synthesis of the most popular PPPT AuNPs such as silica/gold nanoshells, Au nanostars, nanorods, and nanocages. The photothermal efficiencies of these nanoparticles are compared, and their applications to current nanomedicine are shortly discussed. In a separate section, we discuss the fabrication of gold and other nanoparticles by the pulsed laser ablation in liquid method. The second part of the review is devoted to our recent experimental results on laser-activated interaction of AuNPs with tumor and healthy tissues and current achievements of other research groups in this application area. The unresolved issues of PPT are the significant accumulation of AuNPs in the organs of the mononuclear phagocyte system, causing potential toxic effects of nanoparticles, and the possibility of tumor recurrence due to the presence of survived tumor cells. The prospective ways of solving these problems are discussed, including developing combined antitumor therapy based on combined PPT and PDT. In the conclusion section, we summarize the most urgent needs of current PPT-based nanomedicine.

Refractive index sensitivity of Au nanostructures in solution and on the substrate

In this work, we present the synthesis and surface immobilization of Au nanostars, Au nanocubes and Au nanorods for localized surface plasmon resonance (LSPR)-based refractometric sensing applications. Au nanostructures exhibiting LSPR peak positions in 500–900 nm spectral range were prepared by seed-mediated synthesis method. The refractive index (RI) sensitivity of all these nanostructures in the colloidal solution were measured and the sample exhibiting highest sensitivity in each category were immobilized on the glass substrate. The surface immobilized nanostructures were investigated for RI sensing. Au nanostars having LSPR peak position at 767 nm exhibited highest RI sensitivity of 484 nm/RIU in solution and 318 nm/RIU on the substrate. This study gives an outline for selecting the Au nanostructures for developing plasmonic sensing platforms.

DNA Origami-Templated Bimetallic Nanostar Assemblies for Ultra-Sensitive Detection of Dopamine.

The abundance of hotspots tuned via precise arrangement of coupled plasmonic nanostructures highly boost the surface-enhanced Raman scattering (SERS) signal enhancements, expanding their potential applicability to a diverse range of applications. Herein, nanoscale assembly of Ag coated Au nanostars in dimer and trimer configurations with tunable nanogap was achieved using programmable DNA origami technique. The resulting assemblies were then utilized for SERS-based ultra-sensitive detection of an important neurotransmitter, dopamine. The trimer assemblies were able to detect dopamine with picomolar sensitivity, and the assembled dimer structures achieved SERS sensitivity as low as 1 fM with a limit of detection of 0.225 fM. Overall, such coupled nanoarchitectures with superior plasmon tunability are promising to explore new avenues in biomedical diagnostic applications.

Surfactant-free Synthesis of Spiky Hollow Ag-Au Nanostars with Chemically Exposed Surfaces for Enhanced Catalysis and Single-Particle SERS.

Spiky/hollow metal nanoparticles have applications across a broad range of fields. However, the current bottom-up methods for producing spiky/hollow metal nanoparticles rely heavily on the use of strongly adsorbing surfactant molecules, which is undesirable because these passivate the product particles’ surfaces. Here we report a high-yield surfactant-free synthesis of spiky hollow Au–Ag nanostars (SHAANs). Each SHAAN is composed of >50 spikes attached to a hollow ca. 150 nm diameter cubic core, which makes SHAANs highly plasmonically and catalytically active. Moreover, the surfaces of SHAANs are chemically exposed, which gives them significantly enhanced functionality compared with their surfactant-capped counterparts, as demonstrated in surface-enhanced Raman spectroscopy (SERS) and catalysis. The chemical accessibility of the pristine SHAANs also allows the use of hydroxyethyl cellulose as a weakly bound stabilizing agent. This produces colloidal SHAANs that remain stable for >1 month while retaining the functionalities of the pristine particles and allows even single-particle SERS to be realized.

Antibody mounting capability of 1D/2D carbonaceous nanomaterials toward rapid-specific detection of SARS-CoV-2

Carbonaceous immunosensors are ideal nanoplatforms for developing rapid, precise, and ultra-specific diagnostic kits capable of early detection of viral infectious illnesses such as COVID-19. However, developing a proper carbonic immunosensor requires stepwise protocols to find optimum operating conditions to minimize drawbacks. Herein, for the first time and through a stepwise protocol, activation, and monoclonal IgG antibody mounting capability of multi-walled carbon nanotubes (MWCNTs) at two diverse outer diameters (ODs), viz., 20–30 nm and 50–80 nm, and graphene deriv atives (graphene oxide (GO) and reduced graphene oxide (rGO)) were examined and compared with each other toward finding the prime carbonaceous nanomaterial(s) for maximized antibody loading efficiency along with an ideal detection limit (DL) and sensitivity. Next, the effect of common amplifying agents, i.e., Au nanostars (Au NSs) and Ag nanowires (Ag NWs), on the total performance of the best carbonaceous structure was carefully assessed, and the responsible detection mechanism is investigated in detail. Next, the developed carbonaceous immunosensors were assessed via voltammetric and impedance assays, and their performances toward specific detection of SARS-CoV-2 antigen through immunoreaction were examined in detail. The study's outcome showed the superior performance of conjugated rGO-based immunosensor with Au NSs toward specific and quick (1 min) detection of SARS-CoV-2 antigen in biological fluids compared with other 1D/2D carbonaceous nanomaterials.

Development of surface-enhanced Raman scattering-based immunoassay platforms using hollow Au nanostars for reliable SARS-CoV-2 diagnosis.

We developed a novel surface‐enhanced Raman scattering (SERS)‐based SARS‐CoV‐2 assay platform using hollow Au nanostars to realize high‐sensitivity diagnosis of SARS‐CoV‐2. The assay was performed using SARS‐CoV‐2 lysate as the target in a wide dynamic range with virus concentrations ranging from 0 to 104 PFU/ml and has a limit of detection (LOD) of 5.1 PFU/ml. This LOD value shows 100 times and 10 times better sensitivity compared to the LODs measured on the same sample using a commercially available rapid kit and enzyme‐linked immunosorbent assay, respectively. Therefore, we believe that this SERS‐based SARS‐CoV‐2 assay platform has high diagnostic accuracy for early or asymptomatic infected patients with low virus concentrations. Furthermore, the probability of a false‐negative diagnosis is likely to be very low.

Live Cell Poration by Au Nanostars to Probe Intracellular Molecular Composition with SERS.

A new type of flat substrate has been used to visualize structures inside living cells by surface-enhanced Raman scattering (SERS) and to study biochemical processes within cells. The SERS substrate is formed by stabilized aggregates of gold nanostars on a glass microscope slide coated with a layer of poly (4-vinyl pyridine) polymer. This type of SERS substrate provides good cell adhesion and viability. Au nanostars’ long tips can penetrate the cell membrane, allowing it to receive the SERS signal from biomolecules inside a living cell. The proposed nanostructured surfaces were tested to study, label-free, the distribution of various biomolecules in cell compartments.

Photoplasmonic assembly of dielectric-metal, Nd2O3-Gold soret nanointerfaces for dequenching the luminophore emission

Abstract A variety of materials such as low dimensional carbon substrates (1D, 2D, and 3D), nanoprisms, nanocubes, proteins, ceramics, and DNA to name a few, have been explored in surface plasmon-coupled emission (SPCE) platform. While these offer new physicochemical insights, investigations have been limited to silver as primary plasmonic material. Although, gold nanoparticles (AuNPs) exhibit robust performance, its intrinsic property to quench the emission from radiating dipoles (at distances &lt; 5 nm) has impeded its utility. Despite the use of metal-dielectric resonances (with Au decorated SiO2 NPs) and sharp nanotips (from Au nanostars) for dequenching the emission, the enhancements obtained has been less than 200-fold in SPCE platform. To address these long-standing challenges, we demonstrate the utility of gold soret colloids (AuSCs) and photonic crystal-coupled emission (PCCE) platform. The soret nano-assemblies synthesized using adiabatic cooling technique presented integrated hotspots when taken with high refractive index Nd2O3 ‘Huygens sources’. The collective and coherent coupling between localized Mie and delocalized Bragg plasmons (of sorets), dielectric plasmons (of Nd2O3), highly confined and intense Bloch surface waves (of PCCE platform) aided in realization of dequenched, as well as amplified &gt; 1500-fold enhancements at the photoplasmonic nanocavity interface, presenting new opportunities for multidisciplinary applications.

Broadband SERS Enhancement by DNA Origami Assembled Bimetallic Nanoantennas with Label-Free Single Protein Sensing.

Engineering hotspots in surface-enhanced Raman spectroscopy (SERS) through precisely controlled assembly of plasmonic nanostructures capable of expanding intense field enhancement are highly desirable to enhance the potentiality of SERS as a label-free optical tool for single molecule detection. Inspired by DNA origami technique, we constructed plasmonic dimer nanoantennas with a tunable gap decorated with Ag-coated Au nanostars on origami. Herein, we demonstrate the single-molecule SERS enhancements of three dyes with emission in different spectral regions after incorporation of single dye molecules in between two nanostars. The enhancement factors (EFs) achieved in the range of 109-1010 for all the single dye molecules, under both resonant and nonresonant excitation conditions, would enable enhanced photostability during time-series measurement. We further successfully explored the potential of our designed nanoantennas to accommodate and detect a single thrombin protein molecule after selective placement in the wide nanogap of 10 nm. Our results suggest that such nanoantennas can serve as a broadband SERS enhancer and enable specific detection of target biological molecules with single-molecule sensitivity.

Ultra-precise label-free nanosensor based on integrated graphene with Au nanostars toward direct detection of IgG antibodies of SARS-CoV-2 in blood.

Rapid distribution of airborne contagious pathogenic viruses such as SRAS-CoV-2 and their severely adverse impacts on different aspects of the human society, along with significant weaknesses of traditional diagnostic platforms, raised the global requirement for the design/fabrication of precise, sensitive, and rapid nanosystems capable of specific detection of viral illnesses with almost negligible false-negative results. To address this indispensable requirement, we have developed an ultra-precise fast diagnostic platform capable of detecting the trace of monoclonal IgG antibody against S1 protein of SARS-CoV-2 within infected patients' blood specimens with COVID-19 in about 1min. The as-developed electrochemical-based nanosensor consists of a highly activated graphene-based platform in conjunction with Au nanostars, which can detect SARS-CoV-2 antibodies with a fantastic detection limit (DL) and sensitivity of 0.18×10-19%V/V and 2.14 μA.%V/V.cm-2, respectively, in human blood plasma specimens even upon the presence of a high amount of interfering compound/antibodies. The nanosensor also exhibited remarkable sensitivity/specificity compared with the gold standard (i.e., ELISA assay), which furtherly confirmed its superb performance.

Au nanostars@PDA@Fe3O4-based multifunctional nanoprobe for integrated tumor diagnosis and photothermal therapy

A multifunctional nanoprobe (based on Au nanostars@PDA@Fe3O4) is developed for tumor targeted imaging and targeted photothermal therapy. Au nanostars and Fe3O4 are connected with polydopamine, and combined with antibody-FITC or antibody-quantum dots for in vitro or in vivo fluorescence labeling (FL), respectively, to form the composite nanoprobe. The shape and lattice structure of Au nanostars and Fe3O4 were confirmed with TEM, HRTEM and XRD experiments. Compared with other Au nanoparticles@Fe3O4 composite probes, the Au nanostars@PDA@Fe3O4 structure has a low photothermal conversion threshold. Compared with the corresponding pure Au nanostars, the photothermal efficiency of the probe has increased by 50%, while maintaining 171% and 32% fluorescence enhancement in vitro and in vivo, respectively. Due to the charge transfer channel, the phonon emission of Au can go on in Fe3O4 via the PDA linking. Under the precise guidance of multimodal imaging, the nanoprobe conducts homogeneous photothermal ablation of bulky solid tumors (~ 400 mm3) in a xenograft mouse model. Animal model magnetic resonance imaging (MRI) results found that the MRI T2 signal intensity of the probe was 65% stronger than that of pure Fe3O4 nanoparticles. These results suggest that this nanoplatform is promising for integrated tumor diagnosis and targeted cancer therapy.

Effectiveness of reducing the influence of CTAB at the surface of metal nanoparticles during in situ heating studies by TEM

In situ TEM is a valuable technique to offer novel insights in the behavior of nanomaterials under various conditions. However, interpretation of in situ experiments is not straightforward since the electron beam can impact the outcome of such measurements. For example, ligands surrounding metal nanoparticles transform into a protective carbon layer upon electron beam irradiation and may impact the apparent thermal stability during in situ heating experiments. In this work, we explore the effect of different treatments typically proposed to remove such ligands. We found that plasma treatment prior to heating experiments for Au nanorods and nanostars increased the apparent thermal stability of the nanoparticles, while an activated carbon treatment resulted in a decrease of the observed thermal stability. Treatment with HCl barely changed the experimental outcome. These results demonstrate the importance of carefully selecting pre-treatments procedures during in situ heating experiments.