Gold Nanorods Research Articles

Positron Emission Tomography‐Assisted Photothermal Therapy with Gold Nanorods

AbstractPhotothermal anticancer therapy based on plasmonic nanoparticles is proposed to enhance treatment efficacy while mitigating unintended side effects. However, most studies blindly rely on the accumulation of nanoparticles at the tumor site, which may result in inefficient treatment. In this study, the aim is to evaluate relevant parameters to improve plasmonic photothermal therapy. Gold nanorods (AuNRs) with an optimized aspect ratio and either amino or carboxylic acid surface functionalization are selected as photothermal agents. AuNR biocompatibility and photothermal activity in 2D and 3D human MDA‐MB‐231 triple‐negative breast cancer cell models, evaluating localized hyperthermal cell death upon irradiation with resonant near‐infrared (NIR) light, are analyzed first. To ensure reliable tracking of biodistribution in vivo, AuNRs are labeled with the positron emitter copper‐64 (64Cu), and their distribution in a murine MDA‐MB‐231 tumor model is studied via positron emission tomography (PET) imaging. PET images reveal enhanced tumor accumulation of carboxylic acid‐functionalized AuNRs compared to amino‐functionalized AuNRs post‐intravenous administration. Relatively low NIR laser power densities (0.5 W cm−2) are used for controlled heating – keeping local temperature below 50 °C – upon irradiation of intravenously and intratumorally administered AuNRs. As a result, tumor growth is significantly decelerated, even 9 days after application of photothermal therapy.

Plasmonic perovskite photodetector with high photocurrent and low dark current mediated by Au NR/PEIE hybrid layer

Hybrid organic-inorganic perovskite photodetectors have gained significant attention due to their superior potential for optoelectronic applications, offering various advantages such as low-cost processing, high charge carrier mobility, and lightweight properties. However, these perovskite photodetectors exhibit relatively low absorption in the near-infrared (NIR) range, which limits their potential applications. Here, to address this challenge, the integration of gold nanorods (Au NR) utilizing localized surface plasmon resonance (LSPR) effects in the NIR range has been developed, leading to enhanced light absorption in the active region and higher photocurrent generation. Additionally, ∼7.9 nm of thin polyethyleneimine ethoxylated (PEIE) interlayers were incorporated into the Au NR photodetectors, suppressing dark current by blocking charge injection. As a result, the synergistic effect of the Au NR/PEIE hybrid layer has led to a high-performance photodetector with a responsivity of 0.360 A/W and a detectivity of 1.81 × 1010 Jones, demonstrating a noticeable enhancement compared to the control device. Finite-difference time-domain (FDTD) simulations, morphological characterizations, and photoluminescence studies further support the mechanism for enhancing the performance of the device. We believe that our plasmon-enhanced protocol holds strong potential as a promising platform for perovskite optoelectronic devices.

Elucidating refractive index sensitivity on subradiant, superradiant, and fano resonance modes in single palladium-coated gold nanorods

Herein, we investigated the distinctive scattering properties exhibited by single gold nanorods coated with palladium (AuNRs@Pd), with variations in the Pd shell thicknesses and morphologies. AuNRs@Pd were synthesized through bottom-up epitaxial Pd growth using two different concentrations of Pd precursor. These single AuNRs@Pd displayed the characteristic of subradiant and superradiant localized surface plasmon resonance peaks, characterized by a noticeable gap marked by a Fano dip. We revealed the effect of local refractive index (RI) on the subradiant and superradiant peak energies, as well as the Fano dip in the scattering spectra of AuNRs@Pd with different Pd shell thicknesses. We demonstrated the applicability of the inflection points (IFs) method on detecting peaks and dip changes across different RIs. Thin AuNRs@Pd1mM displayed more pronounced sensitivity to peak shifts in response to variations in local RIs compared to thick AuNRs@Pd2mM. In contrast, thick AuNRs@Pd2mM exhibited greater sensitivity to changes in curvature near the subradiant and superradiant peak energies rather than peak shift sensitivity across different local RIs. Moreover, the Fano dip shift was more noticeable in thick AuNRs@Pd2mM compared to thin AuNRs@Pd1mM across different local RIs. Therefore, we provided new insight into the RI sensitivity on subradiant, superradiant, and Fano resonance modes in single AuNRs@Pd.

Improving treatment for Parkinson's disease: Harnessing photothermal and phagocytosis-driven delivery of levodopa nanocarriers across the blood-brain barrier

Parkinson's disease (PD) poses a significant therapeutic challenge, mainly due to the limited ability of drugs to cross the blood-brain barrier (BBB) without undergoing metabolic transformations. Levodopa, a key component of dopamine replacement therapy, effectively enhances dopaminergic activity. However, it encounters obstacles from peripheral decarboxylase, hindering its passage through the BBB. Furthermore, levodopa metabolism generates reactive oxygen species (ROS), exacerbating neuronal damage. Systemic pulsatile dosing further disrupts natural physiological buffering mechanisms. In this investigation, we devised a ROS-responsive levodopa prodrug system capable of releasing the drug and reducing ROS levels in the central nervous system. The prodrug was incorporated within second near-infrared region (NIR-II) gold nanorods (AuNRs) and utilized angiopep-2 (ANG) for targeted delivery across the BBB. The processes of tight junction opening and endocytosis facilitated improved levodopa transport. ROS scavenging helped alleviate neuronal oxidative stress, leading to enhanced behavioral outcomes and reduced oxidative stress levels in a mouse model of PD. Following treatment, the PD mouse model exhibited enhanced flexibility, balance, and spontaneous exploratory activity. This approach successfully alleviated the motor impairments associated with the disease model. Consequently, our strategy, utilizing NIR-Ⅱ AuNRs and ANG-mediated BBB penetration, coupled with the responsive release of levodopa, offers a promising approach for dopamine supplementation and microenvironmental regulation. This system holds substantial potential as an efficient platform for delivering neuroprotective drugs and advancing PD therapy.

Rapid Fingerprinting of Urinary Volatile Metabolites and Point-of-Care Diagnosis of Phenylketonuria on a Patterned Nanorod Sensor Array with Multiplexed Surface-Enhanced Raman Scattering Readouts.

Phenylketonuria (PKU) is one of the most common genetic metabolic diseases, especially among newborns. Traditional clinical examination of newborn blood samples for PKU is invasive, laborious, and limited to hospitals and healthcare facilities. We reported herein a SERS-based sensor array with three thiophenolic nanoreceptors built on a patterned nanorod vertical array for rapid and inexpensive detection of characteristic volatile biomarkers indicative of PKU in the urine and accurate classification of newborn baby patients all performed on a hand-held SERS spectrophotometer. The well-ordered array was generated from the volatility-driven assembly of gold nanorods (AuNRs) into an upright and closely packed hexagonal configuration. The uniformly distributed nanowells between AuNRs offered an intense and aspect-ratio-dependent plasmonic field for the molecular enhancement of SERS outputs. The SERS-based detector was integrated into a test chip for regular monitoring of volatile phenylketone bodies in the spiked solution or patients' urine within 5 min, allowing the quantification of a wide variety of normal or abnormal metabolites at their physiologically relevant concentration range. The detection limits for common biomarkers of PKU, including phenylpyruvic acid, 4-hydroxyphenylacetic acid, and phenylacetic acid, were at a few μM and well below the diagnostic thresholds. Moreover, the volatile headspace mixtures from a given urine sample could be fingerprinted by the sensor array and discriminated using machine-learning algorithms. Ultimately, the discrimination of baby patients among 26 cases of mild and classic PKU phenotypes and 17 cases of healthy volunteers could be realized with an overall accuracy of 97%. This hand-held SERS platform plays a pivotal role in advancing healthcare applications in quick screening of neonatal PKU through a facile urinary vapor test.

Gold nanorods as performance enhancers in planar perovskite solar cells: A numerical study

The quest for efficient and sustainable energy sources calls for an optimized optical design in photovoltaic technologies, particularly in perovskite solar cells (PSCs). This study focuses on the numerical analysis of integrating plasmonic non-spherical gold nanorods into realistic n-i-p MAPbI3 PSCs. The research addresses the light-harvesting enhancement, especially in near-infrared (NIR), a known limitation of metal halide PSCs. Nanorods were the selected nanostructures, as their longitudinal plasmon resonance has the potential to cover the NIR spectral limitation. The study aims to optimize the size, aspect ratio, orientation, and distance between nanorods, as well as provide insights into practical solutions for the positioning and encapsulation of the nanorods. The findings reveal that the aspect ratio and orientation of the nanorods significantly impact the absorption enhancement. Optimal outcomes are achieved with the vertical orientation of the nanorods, parallel to the stacking direction of the solar cell films. The most promising results from this study demonstrate that the incorporation of gold nanorods with small aspect ratios close to 1.5 leads to the potential enhancement of the perovskite photocurrent by at least 5 % (for spherical nanoparticles the maximum is 4.4 %). Additionally, it is also possible to reduce the layer thickness and the associated lead amount by at least 33 %, while maintaining the solar cell performance.

A dual-targeted electrochemical aptasensor for neuroblastoma-related microRNAs detection

Neuroblastoma (NB) is a significant pediatric cancer associated with high mortality rates, demanding innovative and appropriate approaches for its accurate detection. This paper described the design of a dual-target electrochemical aptasensor capable of simultaneously detecting neuroblastoma-associated microRNAs (miRNA-181 and miRNA-184) with exceptional sensitivity. Screen-printed carbon electrodes (SPCEs) were utilized with gold nanorods (AuNRs), and aptamers functionalized gold nanoparticles (AuNPs) to improve sensitivity, specificity, and portable detection ability. The detection method employed in this study includes differential pulse voltammetry (DPV) and cyclic voltammetry (CV). Our aptasensor exhibited remarkable limits of detections (LODs) of 5.10 aM for miRNA-181 and 9.39 aM for miRNA-184, respectively, along with a broad linear range spanning from 0.1 fM to 100 pM for both miRNAs. The practical significance of neuroblastoma diagnosis was shown through the validation of serum samples and comparison with quantitative polymerase chain reaction (qPCR). Our electrochemical aptasensor is user-friendly, easy to engineer, and offers a promising approach for accurately and selectively detecting important miRNA biomarkers in cancer screening and diagnosis, showing potential application in various clinical scenarios.

Near Infrared-Triggered Nitric Oxide-Release Nanovesicles with Mild-Photothermal Antibacterial and Immunomodulation for Healing MRSA-Infected Diabetic Wounds.

Bacterial infection-induced excessive inflammation is a major obstacle in diabetic wound healing. Nitric oxide (NO) exhibits significant antibacterial activity but is extremely deficient in diabetes. Hence, a near-infrared (NIR)-triggered NO release system is constructed through codelivery of polyarginine (PArg) and gold nanorods (Au) in an NIR-activatable methylene blue (MB)polypeptide-assembled nanovesicle (Au/PEL-PBA-MB/PArg). Upon NIR irradiation, the quenched MB in the nanovesicles is photoactivated to generate more reactive oxygen species (ROS) to oxidize PArg and release NO in an on-demand controlled manner. With the specific bacterial capture of phenylboronic acid (PBA), NO elevated membrane permeability and boosted bacterial vulnerability in the photothermal therapy (PTT) of the Au nanorods, which is displayed by superior mild PTT antibacterial activity against methicillin-resistant Staphylococcus aureus (MRSA) at temperatures<49.7°C in vitro. Moreover, in vivo, the antibacterial nanovesicles greatly suppressed the burst of MRSA-induced excessive inflammation, NO relayed immunomodulated macrophage polarization from M1 to M2, and the excessive inflammatory phase is successfully transferred to the repair phase. In cooperation with angiogenesis by NO, tissue regeneration is accelerated in MRSA-infected diabetic wounds. Therefore, nanoplatform has considerable potential for accelerating the healing of infected diabetic wounds.

Machine Learning and Small Data-Guided Optimization of Silica Shell Morphology on Gold Nanorods

Machine Learning and Small Data-Guided Optimization of Silica Shell Morphology on Gold Nanorods

Rainbow-inspired multicolor lateral flow immunoassay using multibranched platinum–rhodium-cobalt nanoparticles

Traditional lateral flow immunoassay (LFIA) using single-color labels has limitations in indistinct color change and restriction to the single-mode readout, which can hardly meet the demands of high-performance detection. Inspired by the multiple colors of the rainbow, we outline a multicolor LFIA using multibranched trimetallic platinum–rhodium-cobalt nanoparticles (PRCNPs) as signal labels to initiate multicolor conversion for diverse and multicolor readouts. The intrinsic properties of PRCNPs including their trimetallic composition, multibranched morphology, and strong absorption in the visible spectrum, confer advantages in catalytic activity, antibody utilization, and signal readout. Through the synergistic integration of the catalytic PRCNPs with the etching of gold nanorods, PRCNPs-LFIA enables multicolor readouts in a rainbow-like manner. PRCNPs-LFIA allows for qualitative analysis of acetamiprid, a widely-used neonicotinoid insecticide, at 2 ng mL−1. It also provides semi-quantitative analysis based on the discrimination of at least 10 colors. Furthermore, quantitative analysis can be conducted across multiple color spaces within the range of 0.01-10 ng mL−1, achieving a lowest detection result of 0.006 ng mL−1. The recoveries of acetamiprid in food samples detected by PRCNPs-LFIA in grayscale and multiple color space modes are 87.35%-103.59%, 85.56%-114.33%, 86.14%-114.77%, and 87.81%-112.01%, respectively, with all coefficients of variation below 15%. These results demonstrate the feasibility and accuracy of PRCNPs-LFIA in practical applications. Overall, this study illustrates the potential of multifunctional PRCNPs in the development of multicolor LFIA and broadens the biosensing strategies for point-of-care testing.

Photothermal-driven soft actuator capable of alternative control based on coupled-plasmonic effect

Recent advancements in small-scale soft actuators have showcased their ability to respond to various stimuli, making them ideal for biomedical engineering and robotics. Light-responsive actuators constructed from photothermal materials such as carbon-based materials have received great attention for their remote wireless control ability. However, conventional carbon-based actuators typically exhibit uniform responses to different light wavelengths, limiting the complexity of their control. To address this limitation, this study develops light-driven soft actuators utilizing gold nanorods (Au NRs) to enhance selective photo-responsiveness. Au NRs are incorporated given their superior ability to convert light energy into localized heat through localized surface plasmon resonances, with efficiency varying based on their size and the wavelength of incident light. By adjusting the specifications of the Au NRs and the wavelength of the optical field, tunable actuation efficiency can be achieved. Experimental calibration confirms that the actuator exhibits differential performance across various wavelengths, enabling more precise control over its behavior. Demonstrations of application devices highlight the actuator’s versatility in flexible robotics, showcasing its potential for advanced applications. This innovation represents a considerable step towards achieving more adaptable and functional soft robotic systems, paving the way for future developments in this area.

Interplay of kernel shape and surface structure for NIR luminescence in atomically precise gold nanorods

It is challenging to attain strong near-infrared (NIR) emissive gold nanoclusters. Here we show a rod-shaped cluster with the composition of [Au28(p-MBT)14(Hdppa)3](SO3CF3)2 (1 for short, Hdppa is N,N-bis(diphenylphosphino)amine, p-MBT is 4-methylbenzenethiolate) has been synthesized. Single crystal X-ray structural analysis reveals that it has a rod-like face-centered cubic (fcc) Au22 kernel built from two interpenetrating bicapped cuboctahedral Au15 units. 1 features NIR luminescence with an emission maximum at 920 nm, and the photoluminescence quantum yield (PLQY) is 12%, which is 30-fold of [Au21(m-MBT)12(Hdppa)2]SO3CF3 (2, m-MBT is 3-methylbenzenethiolate) with a similar composition and 60-fold of Au30S(S‑t‑Bu)18 with a similar structure. time-dependent DFT(TDDFT)calculations reveal that the luminescence of 1 is associated with the Au22 kernel. The small Stokes shift of 1 indicates that it has a very small excited state structural distortion, leading to high radiative decay rate (kr) probability. The emission of cluster 1 is a mixture of phosphorescence and thermally activated delayed fluorescence(TADF), and the enhancement of the NIR emission is mainly due to the promotion of kr rather than the inhibition of knr. This work demonstrates that the metal kernel and the surface structure are both very important for cluster-based NIR luminescence materials.

Highly selective localized surface plasmon resonance sensor for selenium diagnosis in selenium-rich soybeans

It is a challenge to determine selenium in acid aqueous for environmental monitoring and selenium-rich agricultural diagnosis. Herein, we developed a novel localized surface plasmon resonance (LSPR) sensor to detect Se(IV) ions based on the extraordinary laterals etching of gold nanorods (AuNRs). The etching started from the laterals in the low amount of Se(IV) ions, and accompanied by an apparent red shift of the longitudinal plasmon band (LPB), and then transformed to the tips etching with the upward of Se(IV) ions, the LPB band immediately shifted to the shorter wavelength. The red shift change (Δλ) of LPB band was utilized to quantitative analysis instead of blue shift or absorbance intensity, which gave a high selectivity for the proposed sensor. More importantly, this sensor could be performed in 0.1 mol/L of HCl solution, which achieved the seamlessly jointing with the pretreatment of complex samples, without time-consuming pH adjustment.Successful selenium detection was demonstrated in complex soybean samples that collected from the maturity after spraying organic chelated selenium at full flower period. The sensor provided a promising way to monitor and diagnose selenium in complex environmental samples and selenium-rich crops.

Near infrared photothermal inactivation of Candida albicans assisted by plasmonic nanorods

The use of photothermal processes has been proven effective in the control of microbial infections. Simultaneously, the localized surface plasmon resonance phenomena in metallic nanoparticles have been explored as an alternative strategy to achieve highly efficient localized heating. In this work, we propose the use of selected nanoheaters to improve the efficiency of fungal photothermal inactivation of Candida albicans through size optimization of plasmonic gold nanorods. Here, the optical heating of polyethylene glycol coated gold nanorods of varying sizes is evaluated, both theoretically and experimentally. A size-dependent computational approach was applied to identify metallic nanorods with maximized thermal performance at 800 nm, followed by the experimental comparison of optimal and suboptimal nanoheaters. Comparison among samples show temperatures of up to 53.0 °C for 41×10 nm gold nanorods against 32.3 °C for 90×25 nm, a percentage increase of ∼63% in photothermal inactivation assessments. Our findings reveal that gold nanorods of 41×10 nm exhibit superior efficiency in near-infrared (800 nm) photothermal inactivation of fungi, owing to their higher light-thermal conversion efficiency. The identification of high performance metallic nanoheaters may lead to the reduction of the nanoparticle dose used in plasmonic-based procedures and decrease the laser exposure time needed to induce cell death. Moreover, our results provide insights to better exploit plasmonic nanoparticles on photothermal inactivation protocols.

Gold nano densities: Relationship with drying parameters

Gold nanorod stain deposits have been studied using helium ion microscopy (HIM). The multilayer thick deposits can become well-organized monolayers when the density drops, as demonstrated by the density fluctuation of nanosuspension. However, once the density of nanoparticles approaches certain extremely low values, this tendency has disappeared. The difference in density associated with the liquid crystalline (LC) phases that have developed on the surface. There is a correlation between the density of nanoparticles in suspension and the relationship between droplet volume and UV-Vis absorbance. The physical characteristics that affect and generate such LC phases are contrasted and examined with the assembly method. To highlight noteworthy aspects, a quantitative comparison between the HIM analysis and the SEM is also made. Analyzing the correlation between the coffee stain range, nanoparticle density, and droplet contact angle is essential. It is possible to quantify the difference in the ring stains from the outside to the midle and from the midle to the inner boundary. HIM is typically useful when attempting to determine the true composition of surface deposits. The aim of this work is to investigate the effects of particle density on liquid crystalline superstructures and the coffee stain effect.

Single 5-nm quantum dot detection via microtoroid optical resonator photothermal microscopy

Label-free detection techniques for single particles and molecules play an important role in basic science, disease diagnostics, and nanomaterial investigations. While fluorescence-based methods are tools for single molecule detection and imaging, they are limited by available molecular probes and photoblinking and photobleaching. Photothermal microscopy has emerged as a label-free imaging technique capable of detecting individual nanoabsorbers with high sensitivity. Whispering gallery mode (WGM) microresonators can confine light in a small volume for enhanced light-matter interaction and thus are a promising ultra-sensitive photothermal microscopy platform. Previously, microtoroid optical resonators were combined with photothermal microscopy to detect 250 nm long gold nanorods and 100 nm long polymers. Here, we combine microtoroids with photothermal microscopy to spatially detect single 5 nm diameter quantum dots (QDs) with a signal-to-noise ratio exceeding 104. Photothermal images were generated by point-by-point scanning of the pump laser. Single particle detection was confirmed for 18 nm QDs by high sensitivity fluorescence imaging and for 5 nm QDs via comparison with theory. Our system demonstrates the capability to detect a minimum heat dissipation of 0.75 pW. To achieve this, we integrated our microtoroid based photothermal microscopy setup with a low amplitude modulated pump laser and utilized the proportional-integral-derivative controller output as the photothermal signal source to reduce noise and enhance signal stability. The heat dissipation of these QDs is below that from single dye molecules. We anticipate that our work will have application in a wide variety of fields, including the biological sciences, nanotechnology, materials science, chemistry, and medicine.

Study on the molecular mechanism of gold nanorods interacting with fibrinogen and transferrin to form protein corona

The molecular mechanism of the formation of protein corona by the interaction of gold nanorods (AuNRs) with fibrinogen and transferrin was studied by spectroscopic methods and molecular docking. Studies have shown that AuNRs can be used as quencher to quench the fluorescence of fibrinogen/transferrin. The quenching mechanism mainly comes from static quenching. Fibrinogen has two different binding sites on the longitudinal and the transverse plane of AuNRs respectively, while transferrin has only one binding site on the surface of AuNRs. The adsorption process conforms to Freundlich adsorption isotherm and the pseudo-second-order reaction. The chemisorption is the rate-limiting step. Fibrinogen/transferrin may be a component of the “hard corona” because they bind AuNRs with high binding affinity. The formation of protein corona leads to a decrease in the hydrophobicity of the microenvironment around transferrin tryptophan (Trp) residues and an increase in the hydrophobicity of the microenvironment around fibrinogen/transferrin tyrosine (Tyr) residues, affecting the tertiary and secondary structure of fibrinogen/transferrin. Molecular docking can clearly see the specific amino acid residues of fibrinogen and transferrin adsorbed on AuNRs, and verify the experimental results.

Multicolorimetric Sensor Array Based on Silver Metallization of Gold Nanorods for Discriminating Dopaminergic Agents.

Dopaminergic agents are compounds that modulate dopamine-related activity in the brain and peripheral nerves within the pathways on both sides of the blood-brain barrier. Atypical levels of them can precipitate a multitude of neurological disorders, whose timely diagnosis signifies not only stopping the advancement of the illness but also surmounting it. A silver metallized gold nanorod (AuNRs) conditional sensor array, designed to detect dopaminergic agents for assessing nervous system disorders, yielded significant results in simultaneous detection and discrimination of Benserazide (Benz), Levodopa (L-DOPA), and Carbidopa (Carb). The array was composed of two different concentrations of silver ions as sensor elements (SEs), which generated unique signatures indicative of the presence of reductive target analytes, triggered by the incongruent formation of the Au@Ag core-shell, causing visual and fingerprint colorimetric patterns. Generating diverse responses is the key to the functionality of array-based sensing, which facilitated achieving spectral and color variation originating from the blue shift of AuNRs longitudinal localized surface plasmon resonance (LLSPR) in the extinction spectrum. Also, employing a smartphone camera enables clear visual discrimination across an extensive concentration span. Pattern recognition through linear discriminant analysis (LDA) underscored the robust discrimination accuracies of this sensor, along with quantification by means of partial least-squares regression (PLSR), affirming its potential for practical applications. Notably, the array demonstrated high sensitivity in detecting varied concentrations of target analytes, even in commercial drug samples. The sensor responses exhibited a linear correlation with the concentrations of Benz, L-DOPA, and Carb ranging from 1.59 to 100.0, 5.26 to 100.0, and 5.32 to 100.0 μmol L-1, respectively, and the minimum detectable concentrations for Benz, L-DOPA, and Carb were measured at 0.53, 1.75, and 1.77 μmol L-1, respectively. The implemented machine-learning-empowered array-based sensor represents advancements in dopaminergic agent tracing and naked eye detection.

Electrostatically self-assembled gold nanorods with sulfated hyaluronic acid for targeted photothermal therapy for CD44-positive tumors

Gold nanorods (GNR) produce heat upon irradiation with near-infrared light, enabling a tumor-targeted photothermal therapy. In this study, we prepared GNR coated with sulfated hyaluronic acid (sHA) with a binding affinity for CD44 via electrostatic interactions to deliver GNR to tumors efficiently and stably, and evaluated their usefulness for photothermal therapy. Cationic GNR modified with trimethylammonium groups electrostatically interacted with native HA or sHA with varying degrees of sulfation to form complexes. While GNR/HA was unstable in saline, GNR/sHA maintained the absorbance peak in the near-infrared region, particularly for GNR/sHA with higher degrees of sulfation. GNR/sHA exhibited an intense photothermal effect upon irradiation with near-infrared light. Furthermore, in vitro and in vivo studies revealed that GNR coated with sHA containing approximately 1.2 sulfated groups per HA unit could accumulate in CD44-positive tumors via an HA-specific pathway. These findings indicate the effectiveness of GNR/sHA as a tumor-targeted photothermal therapeutic agent.

Etched-suppressed gold nanorods providing highly distinctive plasmonic patterns: Towards multiplex analysis of neuroblastoma biomarkers

BackgroundOn-site monitoring of vanillylmandelic acid (VMA), homovanillic acid (HVA), and dopamine (DA) as key diagnostic biomarkers for a wide range of neurological disorders holds utmost significance in clinical settings. Numerous colorimetric sensors with mechanistic approaches based on aggregation or silver metallization have been introduced for this purpose. However, these mechanisms have drawbacks, such as sensitivity to environmental factors and probe toxicity. Therefore, there is a great demand for a robust yet non-toxic colorimetric sensor that employs a novel route to monitor these biomarkers effectively. ResultsHere, we present a single-component multi-colorimetric probe based on the controllable etching suppression of gold nanorods (AuNRs) upon exposure to the mild etchant N-bromosuccinimide (NBS), designed to accurately detect and discriminate VMA, HVA, DA, and their corresponding mixtures, i.e., VMA:HVA, VMA:DA, HVA:DA, and VMA:HVA:DA. To enhance the sensitivity and automation capabilities of the designed multi-colorimetric sensor, two machine learning techniques were employed: linear discriminant analysis (LDA) for the qualitative classification and partial least-squares regression (PLSR) for the quantitative analysis of pure biomarkers and their mixtures. The outcomes revealed a high correlation between measured and predicted values, covering a linear range of 0.8–25, 1.2–25, and 2.7–100 μmol L−1, with remarkably low detection limits of 0.260, 0.397, and 0.913 μmol L−1 for VMA, HVA, and DA, respectively. Lastly, the performance of the probe was validated by successfully detecting the neuroblastoma biomarker VMA:HVA in human urine. SignificanceOur designed multi-colorimetric probe introduces a rapid, cost-effective, user-friendly, non-toxic, and non-invasive approach to detecting and discriminating not only the pure biomarkers but also their corresponding binary and ternary mixtures. The distinctive response profiles produced by the probe in the presence of different mixture ratios can indicate various disease states in patients, which is highly crucial in clinical diagnostics.