Gold Nanourchins Research Articles

Self-Assembled BODIPY@Au Core-Shell Structures for Durable Neuroprotective Phototherapy.

BODIPY analogs are promising photosensitizers for molecular phototherapy; however, they exhibit high dark cytotoxicity and limited singlet oxygen generation capacity. In this study, we developed self-assembled core-shell nanophotosensitizers by linking a bipyridine group to BODIPY (Bpy-BODIPY) and promoting J-aggregation on gold nanourchins. This design enhances photostability and reduces the energy gap between the lowest singlet excited state and the lower triplet state, facilitating efficient singlet oxygen production. We characterized these nanophotosensitizers using UV-visible spectroscopy, transmission electron microscopy (TEM), surface-enhanced Raman spectroscopy (SERS) and dynamic light scattering (DLS), which confirmed the formation of the desired core-shell structure and J-aggregates. Notably, Bpy-BODIPY@Au significantly suppresses tau protein aggregation and enhances neuroprotective action, even in the presence of a phosphatase inhibitor. This work broadens the application of BODIPY chemistry to nanoagents for neuroprotective therapy.

A gold nano-urchin-decorated quasi-freestanding graphene-based humidity sensor with enhanced responsivity and a wide relative humidity detection range for real-time applications

Excellent humidity response and detection threshold are essential attributes of a humidity sensor. In this study, quasi-freestanding graphene (QFSG) was grown epitaxially on vicinal silicon carbide via thermal annealing, followed by decoration with hydrophilic gold nano-urchins (AuNUs). The resulting humidity sensor consistently achieved highly effective non-contact humidity-sensing performance, which can be used to monitor breathing and skin moisture. The proposed humidity sensor demonstrated a non-linear response of ∼119.98 % over a wide relative humidity detection range of 4–96 % at a frequency of 1 kHz, outperforming a QFSG-only humidity-sensing device (∼11.92 % and 22–84 % relative humidity, respectively). This 10-fold increase in humidity response and wider detection range is attributed to the hydrophilicity and plasmonic behavior of the AuNUs. It also demonstrated transient impedance response/recovery time of 4.5 and 3.0 s, respectively; low hysteresis of 3.6 %; and stability over 25 days, which are key factors for effective humidity sensing. The fast response and sensitivity of the AuNUs/QFSG humidity sensor made it possible to test for various real-time monitoring applications such as human breathing and non-contact proximity testing.

Dynamic spectroscopic and optical characterization and modeling of bovine serum albumin corona during interaction with N-hydroxysulfo-succinimide-covalently functionalized gold nanourchins.

In this study, bovine serum albumin (BSA) is used as a globular protein model to examine the conformational changes that occur during the interaction of BSA with N-hydroxysulfo-succinimide (sodium salt)-functionalized gold nanourchins (GNUs), for which dynamic spectroscopic techniques are employed. The results showed that the absorbance of phosphate-buffered saline-BSA at 278 nm decreased when a GNU was added to the solution due to adsorption, and it decreased further when the GNU was increased. The intensity and width of the peak of local surface plasmon resonance increased, indicating the effect of corona formation. Dynamic UV-vis spectroscopy and scattering revealed a nonlinear behavior of BSA-GNU interaction. The bioplasmonic solution resulted in higher transmission and scattering than the BSA solution. Fourier transform-near-infrared spectra exhibited several bands due to overtones and combinations of the amide group and different proportions of α-helix and β-sheet components in BSA before and after the addition of the GNU. Time-resolved fluorescence spectroscopy demonstrated an initial increase in blueshifted emission, followed by a redshifted quenching of two major peaks of Tyr and tryptophan (Trp). The binding and dissociation constants were determined as Kb = 2.17 × 1010 M-1 and Kd = 4.6 × 10-11, respectively, using the Stern-Volmer relation. Both the dynamic CMOS-based imaging and the cadmium sulfide sensors demonstrated a nonlinear response of bioplasmonic solution. By increasing the GNU, the resistance of the solution decreased in the order of A > S1 > S3, where S3 exhibited the highest initial transmission with a longer desorption time. MATLAB modeling showed 80% surface coverage by the protein in 15 s at 0.05M, equivalent to a thickness of 1.7 nm, which was in agreement with the value determined by using the Stokes-Einstein relation.

Targeted FT-NIR and SERS Detection of Breast Cancer HER-II Biomarkers in Blood Serum Using PCB-Based Plasmonic Active Nanostructured Thin Film Label-Free Immunosensor Immobilized with Directional GNU-Conjugated Antibody.

This work describes our recent PCB-based plasmonic nanostructured platform patent (US 11,828,747B2) for the detection of biomarkers in breast cancer serum (BCS). A 50 nm thin gold film (TGF) was immersion-coated on PCB (i.e., PCB-TGF) and immobilized covalently with gold nanourchin (GNU) via a 1,6-Hexanedithiol (HDT) linkage to produce a plasmonic activated nanostructured thin film (PANTF) platform. A label-free SERS immunosensor was fabricated by conjugating the platform with monoclonal HER-II antibodies (mAb) in a directional orientation via adipic acid dihydrazide (ADH) to provide higher accessibility to overexpressed HER-II biomarkers (i.e., 2+ (early), 3+ (locally advanced), and positive (meta) in BCS. An enhancement factor (EF) of 0.3 × 105 was achieved for PANTF using Rhodamine (R6G), and the morphology was studied by scanning electron microscopy (SEM) and atomic force microscope (AFM). UV-vis spectroscopy showed the peaks at 222, 231, and 213 nm corresponding to ADH, mAb, and HER-II biomarkers, respectively. The functionalization and conjugation were investigated by Fourier Transform Near Infrared (FT-NIR) where the most dominant overlapped spectra of 2+, 3+, and Pos correspond to OH-combination of carbohydrate, RNH2 1st overtone, and aromatic CH 1st overtone of mAb, respectively. SERS data were filtered using the filtfilt filter from scipy.signals, baseline corrected using the Improved Asymmetric Least Squares (isals) function from the pybaselines.Whittaker library. The results showed the common peaks at 867, 1312, 2894, 3026, and 3258 cm-1 corresponding to glycine, alanine ν (C-N-C) assigned to the symmetric C-N-C stretch mode; tryptophan and α helix; C-H antisymmetric and symmetric stretching; NH3+ in amino acids; and N-H stretch primary amide, respectively, with the intensity of Pos > 3+ > 2+. This trend is justifiable considering the stage of each sample. Principal Component Analysis (PCA) and Linear Discrimination Analysis (LDA) were employed for the statistical analysis of data.

Time-resolved spectroscopic and SERS characterization of plasmonic optical fiber sensor using glutathione-capped gold nanourchins for detection of lead in water

Time-resolved spectroscopic and SERS characterization of plasmonic optical fiber sensor using glutathione-capped gold nanourchins for detection of lead in water

Gold nanourchin on multiple-point dielectrode for glucose biosensing by current-potential measurement.

Gestational diabetes (GD) is a condition characterized by elevated blood sugar levels during pregnancy. GD poses various health risks, such as serious birth injuries, the need for cesarean delivery, and the necessity of newborn care. Monitoring glucose levels is essential for ensuring safe delivery and reducing the risks to both the mother and fetus. Various sensors are readily available for monitoring glucose levels, and researchers are continually working to develop highly sensitive glucose sensors. This research aimed to develop a gold nanourchin (AuNU)-hybrid biosensor for quantifying glucose on a multi-point electrode sensor. Glucose oxidase (GOx) was attached to the AuNU and seeded on the sensing surface using an amine linker. The current-potential (1-2V at 0.1V sweep) was recorded for the GOx-glucose interaction, with a limit of detection of 560μM and a regression coefficient (R2) of 0.9743 [y = 0.9106x - 0.9953] on the linear curve. The sensitivity was estimated to be 3.5mAcm-2M-1. Furthermore, control experiments with galactose, sucrose, and fructose did not yield an increase in current-potential, confirming specific glucose detection. This experiment helps in monitoring glucose levels to manage conditions associated with GD.

Gold Nanoparticles: Tunable Characteristics and Potential for Nasal Drug Delivery.

A general procedure to prepare gold nanourchins (GNUs) via a seed-mediated method was followed using dopamine hydrochloride as a reducing agent and silver nitrate salt (AgNO3) as a shape-directing agent. The novelty of this study comes from the successful incorporation of the prepared gold urchins as an aqueous suspension in a nasal pressurized metered dose inhaler (pMDI) formulation and the investigation of their potential for olfactory targeting for direct nose-to-brain drug delivery (NTBDD). The developed pMDI formulation was composed of 0.025% w/w GNUs, 2% w/w Milli-Q water, and 2% w/w EtOH, with the balance of the formulation being HFA134a propellant. Particle integrity and aerosolization performance were examined using an aerosol exposure system, whereas the nasal deposition profile was tested in a sectioned anatomical replica of human nasal airways. The compatibility of the gold dispersion with the nasal epithelial cell line RPMI 2650 was also investigated in this study. Colloidal gold was found to be stable following six-month storage at 4 °C and during the lyophilization process utilizing a pectin matrix for complete re-dispersibility in water. The GNUs were intact and discrete following atomization via a pMDI, and 13% of the delivered particles were detected beyond the nasal valve, the narrowest region in the nasal cavity, out of which 5.6% was recovered from the olfactory region. Moreover, the formulation was found to be compatible with the human nasal epithelium cell line RPMI 2650 and excellent cell viability was observed. The formulated GNU-HFA-based pMDI is a promising approach for intranasal drug delivery, including deposition in the olfactory region, which could be employed for NTBDD applications.

Electrochemical Sensor Based on a MXene Nanosheet–Gold Nanourchin Hybrid as a Superoxide Dismutase Mimic for Real-Time Detection of Superoxide Anions Released from Living Cells

Electrochemical Sensor Based on a MXene Nanosheet–Gold Nanourchin Hybrid as a Superoxide Dismutase Mimic for Real-Time Detection of Superoxide Anions Released from Living Cells

Fabrication of and characterization of directional antibody-conjugated gold nanourchin colloid and effect of laser polarization on SERS detection of breast cancer biomarker in serum

We describe the results of citrate-stabilized 100 nm gold nanourchins (GNU) functionalized and conjugated with monoclonal antibody (mAb) in directional orientation to investigate the interaction with breast cancer serum (BCS) overexpressed with CA 15–3 biomarker. UV-Vis, fluorescence, FT-NIR spectroscopy, and SERS with 637 nm Raman probe were employed for non-destructive analysis. UV-Vis spectroscopy exhibited two distinct peaks at 230 and 280 nm related to tyrosine (Tyr) and tryptophan (Trp) with the corresponding fluorescence peaks at 285 and 315 nm respectively. FT-NIR showed some new lines after the interaction such as CH2 combination in carbohydrates, and NH2 amino acids. Directional orientation indicated a higher SERS intensity than random due to higher parallel dipole moments of asymmetric molecules and the polarization sensitivity of GNU. The SERS signals increased significantly after the interaction and the intensity of the Raman lines varied nonlinearly with the laser power. The data were filtered using the filtfilt filter from scipy.signals, baseline corrected using the Improved Asymmetric Least Squares (isals) function from the pybaselines.Whittaker library, and normalized using the minmax_scale function from sklearn.preprocessing. The scikit-learn Principal Component Analysis (PCA) function was used to analyze the dataset by identifying the directions of maximum variability in the data.

Gold structured nanourchin as anesthetic biosensor for determining neuroprotective effect

Research has proven that confusion, delirium, and cognitive dysfunction are the common symptoms caused by anesthesia. In general, neuroproteins fluctuation is common during the process of anesthetic treatment. Among others, tau protein was found to the higher fluctuations after the anesthetic process, and it is highly associated with various neuro-related diseases. Monitoring the level of tau protein helps to identify the neuro-related problems during and after the anesthetic processes. This research was focused on developing a tau electrochemical impedance biosensor on aptamer and antibody-modified electrodes. Aptamer and antibody were immobilized on the gold nanourchin with a chemical linker. Gold nanourchin enhances the probe of aptamer and antibody attachment on the electrode and improves the tau protein detection as low as 1 fM [y = 1.5604x − 1.5643; R2 = 0.9681], determined on a linear range from 1 fM to 1 nM. Further, control performances with complementary aptamer and non-immune antibodies fail to change the response of the current, indicating the specific detection of tau protein. This tau sensor detects the tau protein in its lower level and helps to identify the neuro-related problem caused by anesthetics.

Intrinsic tenase blood biomarker imprinted polymer-aptasensor with carbon nanohorn and gold nano-urchin construct for primitive-phase diagnosis of haemophilia B

The selective biomimetic aptasensor for blood coagulation factor IX protein (FIX) detection was developed using an interdigitated electrode with an Archimedean spiral pattern. In contrast to conventional molecularly imprinted polymer (MIP) techniques, aptamer was employed as a macromonomer to accelerate double binding affinity. To preserve the aptamer profile in its protein-binding orientation, FIX protein and thiol-modified RNA aptamers were complexed prior to MIP fabrication. The immobilized aptamer-FIX complex was surrounded by a polymer generated by the electropolymerization of 3-thiophene acetic acid (3TAA). Subsequent to FIX protein removal, leaves imprinted cavities facilitate selective FIX protein detection in conjunction with the affinity of embedded aptamer affinity. The Archimedean IDE surface was functionalized with carbon nanohorn (CNH) and gold nanourchin (GNU) to increase the imprinting ratios and sensor sensitivity. The developed FIX-aptasensor shows a detection limit of 0.06 fM, which is 660-fold higher than aptamer-embedded MIP nanoparticles. Moreover, the sensor exhibited greater selectivity for FIX, discriminating IgG and thrombin. As a preliminary study for clinical use, the sensor was used to analyze human serum without target spiking and detected FIX-protein with a relative standard deviation of 9.18%. It was ascertained that the sensor maintained 85% sustained performance for a duration of five weeks.

Highly branched and hollow gold nanourchins for bacterial killing and off-resonance SERS sensing

Highly branched and hollow gold nanourchins for bacterial killing and off-resonance SERS sensing

Template-Free Synthesized Gold Nanobowls Composed with Graphene Oxide for Ultrasensitive SERS Platforms.

Engineering of plasmonic properties of gold nanostructures expands the field of their applications from photocatalysis and photothermal effects to ultrasensitive surface-enhanced Raman spectroscopy (SERS). The known methods of preparation of gold nanobowls involve the deposition of gold layer on polymers or silicon nanotemplates and the removal of the top layer of gold together with the template. Such gold nanobowls are characterized by very broad plasmonic bands due to the plasmon hybridization. The sharp edges on the top of nanobowls are potential sources of the strong electromagnetic field beneficial for SERS. We present a novel template-free synthesis of gold nanobowls (AuNBs). The AuNB layers are deposited on graphene oxide (GO) layers. We compare AuNBs with gold nanospheres (AuNSs) and gold nanourchins (AuNUs) having similar size. The gold nanoparticles are combined with pristine GO or graphene oxide conditioned in ammonia (GONH3) or graphene oxide conditioned in sodium hydroxide (GONaOH). The SERS properties of the hybrid supports were studied using rhodamine 6G (R6G) as the SERS probe. The 633 nm laser line was used, which falls out of the molecular resonance with R6G. The results indicate that AuNBs show largely higher enhancement factors when compared to AuNUs and AuNSs. Furthermore, the GO materials are able to modify the SERS enhancement by 1 order of magnitude. We explain the influence of the GO material by three factors: (1) enabling or disabling the charge transfer between gold and R6G, which is crucial for the chemical part of SERS enhancement; (2) causing the aggregation of gold nanoparticles and formation of hot spots; (3) dipole contribution to the electromagnetic enhancement through the abundance of polar groups on the surface.

Label-free detection of porcine gelatin: A reliable immunosensor based on multi-walled carbon nanotubes and gold nano-urchins

Gelatin derived from porcine sources raises significant ethical and religious concerns worldwide, particularly due to its increasing use in food-based products without adequate monitoring and control. Once gelatin is incorporated into processed food items, determining its source animal becomes challenging, which consequently increases the risks of adulteration and mislabeling. In this study, we propose the utilization of a novel nanocomposite comprising multi-walled carbon nanotubes (MWCNTs), chitosan (CS), and gold nano-urchins (AuNUs) for constructing a label-free electrochemical immunosensor. The purpose of this immunosensor is to effectively detect Porcine skin gelatin (PSG) in food samples using differential pulse voltammetry (DPV) with a 5 mM [K3Fe(CN6)] redox probe. Under optimized conditions, the fabricated biosensor demonstrates superior sensitivity to PSG, exhibiting a linear detection range of 50 pg/mL to 1000 a pg/mL and a limit of detection (LOD) of 23.079 pg/mL. Moreover, the constructed biosensor exhibits excellent reproducibility, acceptable selectivity, and interference resistance. Notably, it achieves outstanding recovery rates when applied to real food samples spiked with PSG, thus indicating its potential for practical implementation in food safety monitoring.

Glass-Based Nanobiosensor Immobilized with Oriented Antibody-Conjugated Gold Nanourchin for Targeted Detection of Breast Cancer Biomarker in Serum Using FT-NIR and SERS

Glass-Based Nanobiosensor Immobilized with Oriented Antibody-Conjugated Gold Nanourchin for Targeted Detection of Breast Cancer Biomarker in Serum Using FT-NIR and SERS

Optimization of immersion direction and time of covalently self-assembled monolayer gold nanourchins on glass as SERS substrate

Optimization of immersion direction and time of covalently self-assembled monolayer gold nanourchins on glass as SERS substrate

Ion trapping, reduced rotational viscosity, and accelerated electro-optic response characteristics in gold nano-urchin-nematic suspensions.

The free-ion concentration in a nematic liquid crystal (LC) is found to be significantly reduced when gold nano-urchins (AuNUs) of 50-nm diameter are dispersed in the LC in dilute concentrations. The nano-urchins on AuNUs trap a significant amount of mobile ions, reducing the free-ion concentration in the LC media. The reduction of free ions results in a decreased rotational viscosity and accelerated electro-optic response of the LC. The study is carried out with several AuNUs concentrations in the LC, and the experimental results consistently suggest that there exists an optimal concentration of AuNUs, above which they tend to aggregate. At the optimal concentration, the ion trapping is maximum, rotational viscosity is at its lowest, and the electro-optic response is the fastest. Above this optimal AuNUs concentration, the rotational viscosity is found to increase, and consequently, the LC no longer exhibits an accelerated electro-optic response.

Novel H2S sensing mechanism derived from the formation of oligomeric sulfide capping the surface of gold nanourchins.

A gold nanourchin (AuNU) probe with a novel sensing mechanism for monitoring H2S was developed as a feasible colorimetric sensor. In this study, AuNUs that are selectively responsive to H2S were fabricated in the presence of trisodium citrate and 1,4-hydroquinone using a seed-mediated approach. Upon exposure of the AuNU solution to H2S, the hydrosulfide ions (HS-) in the solution are converted into oligomeric sulfides by 1,4-hydroquinone used as a reducing agent during the synthesis of AuNUs. The oligomeric sulfides formed in the AuNU solution upon the addition of H2S were found to coat the surface of the AuNUs, introducing a blue shift in absorption accompanied by a color change in the solution from sky blue to light green. This colorimetric alteration by the capping of oligomeric sulfides on the surface of AuNUs is unique compared to well-known color change mechanisms, such as aggregation, etching, or growth of nanoparticles. The novel H2S sensing mechanism of the AuNUs was characterized using UV-Vis spectroscopy, high-resolution transmission microscopy, X-ray photoelectron spectroscopy, surface-enhanced Raman spectroscopy, secondary ion mass spectroscopy, liquid chromatography-tandem mass spectrometry, and atom probe tomography. H2S was reliably monitored with two calibration curves comprising two sections with different slopes according to the low (0.3-15 μM) and high (15.0-300 μM) concentration range using the optimized AuNU probe, and a detection limit of 0.29 μM was obtained in tap water.

Non-invasive optical characterization and detection of CA 15-3 breast cancer biomarker in blood serum using monoclonal antibody-conjugated gold nanourchin and surface-enhanced Raman scattering.

A proof-of-concept of colloidal surface-enhanced Raman scattering (SERS) substrate for rapid selective detection of overexpressed CA 15-3 biomarker in breast cancer serum (BCS) is suggested using PEGylated gold nanourchins (GNUs) conjugated with anti-CA 15-3 monoclonal antibody (mAb). UV-vis spectroscopy provided conformational information about mAb where the initial aromatic amino acid peak was red-shifted from 271 to 291nm. The fluorescence peak of tyrosine in mAb was reduced by ≈ 77%, and red-shifted by ≈ 3nm after incubation in BCS. Fourier transform near-infrared spectroscopy and SERS were used to study the composition and the molecular structure of the mAb and BCS. Some of the most dominant Raman shifts after GNU-PEG-mAb interaction with BCS are 498, 736, 818, 1397, 1484, 2028, 2271, and 3227cm-1 mainly corresponding to C-N-C in amines, vibrational modes of amino acids, C-H out-of-plane bend, C-O stretching carboxylic acid, the vibrational mode in phospholipids, NH3+ amine salt, C≡N stretching in nitriles, and O-H stretching. The intensity of SERS signals varied per trial due to the statistical behavior of GNU in BCS, agglomeration, laser power, and the heating effect. Despite very small amount of plasmonic heating, the result of the ANOVA test demonstrated that under our experimental conditions, the heating effect on signal variation is negligible and that the differences in the laser power are insignificant for all SERS observations (p > 0.6); thus, other parameters are responsible. The absorbance of mAb-conjugated GNU was decreased after five minutes of irradiation at 8 mW in the BCS.

Gold Nanourchins Improve Virus Targeting and Plasmonic Coupling for Virus Diagnosis on a Smartphone Platform.

Point-of-care detection of pathogens is critical to monitor and combat viral infections. The plasmonic coupling assay (PCA) is a homogeneous assay and allows rapid, one-step, and colorimetric detection of intact viruses. However, PCA lacks sufficient sensitivity, necessitating further mechanistic studies to improve the detection performance of PCA. Here, we demonstrate that gold nanourchins (AuNUs) provide significantly improved colorimetric detection of viruses in PCA. Using respiratory syncytial virus (RSV) as a target, we demonstrate that the AuNU-based PCA achieves a detection limit of 1400 PFU/mL, or 17 genome equivalent copies/μL. Mechanistic studies suggest that the improved detection sensitivity arises from the higher virus-binding capability and stronger plasmonic coupling at long distances (∼10 nm) by AuNU probes. Furthermore, we demonstrate the virus detection with a portable smartphone-based spectrometer using RSV-spiked nasal swab clinical samples. Our study uncovers important mechanisms for the sensitive detection of intact viruses in PCA and provides a potential toolkit at the point of care.