Search Results (13)

Tyrosinase (TYR) emerges as a key enzyme that exerts a regulatory influence on the synthesis of melanin, thereby assuming the role of a critical biomarker for the detection of melanoma. Detecting the authentic concentration of TYR in the skin remains a primary challenge. Distinguished from ex vivo detection methods, this study introduces a novel sensor platform that integrates a microneedle (MN) biosensor with surface-enhanced Raman spectroscopy (SERS) technology for the in situ detection of TYR in human skin. The platform utilized dopamine (DA)-functionalized gold nanoparticles (Au NPs) as the capturing substrate and 4-mercaptophenylboronic acid (4-MPBA)-modified silver nanoparticles (Ag NPs) acting as the SERS probe. Here, the Au NPs were functionalized with mercaptosuccinic acid (MSA) for DA capture. In the presence of TYR, DA immobilized on the MN is preferentially oxidized to dopamine quinone (DQ), a process that results in a decreased density of SERS probes on the platform. TYR concentration was detected through variations in the signal intensity emitted by the phenylboronic acid. The detection system was able to evaluate TYR concentrations within a linear range of 0.05 U/mL to 200 U/mL and showed robust anti-interference capabilities. The proposed platform, integrating MN-based in situ sensing, SERS technology, and TYR responsiveness, holds significant importance for diagnosing cutaneous melanoma. Full article

Silicon nanotubes (Si NTs) have a unique structure among the silicon nanostructure family, which is useful for diverse applications ranging from therapeutics to lithium storage/recycling. Their well-defined structure and high surface area make them ideal for sensing applications. In this work, we demonstrate the formation of Au nanoparticles (NPs) functionalized with 4-Mercaptophenylboronic acid (MPBA) on porous Si NTs (pSi NTs) fabricated using ZnO nanowires as a template. The system was characterized, and the proposed structure was confirmed using scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). Varying glucose concentrations in phosphate-buffered saline (PBS) (0.5–80 mM) were introduced to the Si NT nanocomposite system. The glucose is detectable at low concentrations utilizing surface-enhanced Raman spectroscopy (SERS), which shows a concentration-dependent peak shift in the benzene ring breathing mode (~1071 cm⁻¹) of MPBA. Complementing these measurements are simulations of the Raman hot spots associated with plasmonic enhancement of the Au NPs using COMSOL. This biocompatible system is envisioned to have applications in nanomedicine and microfluidic devices for real-time, non-invasive glucose sensing. Full article

In this paper, the silver-coated large-core suspended-core fiber (LSCF) probe was fabricated by the dynamic chemical liquid phase deposition method for surface-enhanced Raman scattering (SERS) sensing. The 4-mercaptophenylboronic acid (4-MPBA) monolayer was assembled in the LSCF as the recognition monolayer. Taking advantage of the appropriate core size of the LSCF, a custom-made Y-type optical fiber patch cable was utilized to connect the semiconductor laser, Raman spectrometer, and the proposed fiber SERS probe. The SERS signal is propagated in the silver-coated air channels, which can effectively reduce the Raman and fluorescence background of the silica core. Experiments were performed to measure the Raman scattering spectra of the 4-MPBA in the silver-coated LSCF in a non-enhanced and enhanced case. The experiment results showed that the Raman signal strength was enhanced more than 6 times by the surface plasmon resonance compared with the non-enhanced case. The proposed LSCF for SERS sensing technology provides huge research value for the fiber SERS probes in biomedicine and environmental science. The combination of SERS and microstructured optical fibers offers a potential approach for SERS detection Full article

A Ag@AuNP-functionalized capillary-based surface-enhanced Raman scattering (SERS) sensing platform for the interference-free detection of glucose using SERS tags with a built-in nitrile signal has been proposed in this work. Capillary-based SERS capture substrates were prepared by connecting 4-mercaptophenylboronic acid (MBA) to the surface of the Ag@AuNP layer anchored on the inner wall of the capillaries. The SERS tags with a built-in interference-free signal could then be fixed onto the Ag@AuNP layer of the capillary-based capture substrate based on the distinguished feature of glucose, which can form a bidentate glucose–boronic complex. Thus, many “hot spots” were formed, which produced an improved SERS signal. The quantitative analysis of glucose levels was realized using the interference-free SERS intensity of nitrile at 2222 cm⁻¹, with a detection limit of about 0.059 mM. Additionally, the capillary-based disposable SERS sensing platform was successfully employed to detect glucose in artificial urine, and the new strategy has great potential to be further applied in the diagnosis and control of diabetes. Full article

The rapid diagnosis and detection of respiratory bacteria at the early stage can effectively control the epidemic spread and bacterial infection. Here, we designed a rapid, ultrasensitive, and quantitative lateral flow immunoassay (LFA) strip for simultaneous detection of respiratory bacteria S. aureus and S. pneumoniae. In this assay, the surface enhanced Raman scattering (SERS) tags were designed through combining magnetite Raman enhancement nanoparticle Fe₃O₄@Au/DTNB and recognition element 4-mercaptophenylboronic acid (4-MPBA). Further, 4-MPBA could capture multiple bacteria in a complex environmental solution. Based on the strategies, Fe₃O₄@Au/DTNB-mediated magnetic enrichment and 4-MPBA-mediated universal capture capabilities improved the detection sensitivity, the limits of detection for S. aureus and S. pneumoniae were as low as 8 and 13 CFU mL⁻¹, respectively, which were more sensitive than those of colloidal gold method. The Fe₃O₄@Au/DTNB/Au/4-MPBA-LFA also exhibited good reproducibility, excellent specificity, and high recovery rates in sputum samples, indicating its potential application in the detection of respiratory bacteria samples. Full article

Large specific surface area nanostructures are desirable in a wide range of sensing applications due to their longer light-trapping path and increased absorption. Engineering of the specific nanotree structure which possesses a high branch density turned out to be challenging from the experimental point of view, and certainly not adequately explored. This paper shows how to design substrates with a silicon nanotree structure for surface-enhanced Raman spectroscopy (SERS) applications. Silicon nanotrees were synthesized by a Ag-Au nanocluster-catalyzed low-pressure chemical vapor deposition method (LPCVD). By the presented approaches, it is possible to manipulate branches’ number, length and thickness. The synthesized nanostructures are flexible after immersion in water which improves SERS performance. The amount of sputtered metal played a key role in preserving the flexibility of the nanotree structure. The obtained substrates with highly fractal nanostructure were tested on 4-mercaptophenylboronic acid (MPBA) to match the optimal SERS parameters. The silicon nanotrees fabrication, and particularly obtained SERS substrates plated with Ag and Au nanoparticles, demonstrated good features and a promising approach for further sensor development. Full article

The accurate and sensitive detection of biomolecules by surface-enhanced Raman spectroscopy (SERS) is possible, but remains challenging due to the interference from biomolecules in complex samples. Herein, a new SERS sensor is developed for background-free detection of hydrogen peroxide (H₂O₂) with an ultralow detection limit (1 × 10⁻¹⁰ mol/L), using a Raman-silent strategy. The Au microparticles (Au-RSMPs) resembling rose-stones are devised as SERS substrates with a high enhancement effect, and 4-mercaptophenylboronic acid (4-MPBA) is selected as an H₂O₂-responsive Raman reporter. Upon the reaction with H₂O₂, the phenylboronic group of 4-MPBA was converted to a phenol group, which subsequently reacted with 4-diazonium-phenylalkyne (4-DP), an alkyne-carrying molecule via the azo reaction. The formed product exhibits an intense and sharp SERS signal in the Raman-silent region, avoiding interference of impurities and biomolecules. As a proof-of-concept demonstration, we show that this SERS sensor possesses significant merits towards the determination of H₂O₂ in terms of broad linear range, low limit of detection, and high selectivity, showing promise for the quantitative analysis of H₂O₂ in complicated biological samples. Full article

A novel magnetic solid phase extraction based on mercaptophenylboronic acid (MPBA)-functionalized Fe₃O₄-NH₂@Au nanomaterial (Fe₃O₄-NH₂@Au-MPBA) was developed for selective separation and enrichment of catecholamines (including dopamine, norepinephrine and adrenaline). Fe₃O₄-NH₂@Au-MPBA nanoparticles were achieved by self-assembly-anchoring MPBA molecules on the surface of Fe₃O₄-NH₂@Au nanocomposites, which were synthesized via a facial ultrasonic auxiliary in situ reduction process. The interaction between cis-diol from catecholamines and boronic acid was reversible and could be flexibly controlled by adjusting pH value. The catecholamines could be quickly adsorbed by Fe₃O₄-NH₂@Au-MPBA in weak alkaline solution (pH 8.0–9.0) and subsequently released in acid solution (pH 1.0–2.0). The process of adsorption and dissociation was very fast. Furthermore, the three catecholamines could be detected in urine from children by high performance liquid chromatography (HPLC) with electrochemical detector. Under optimal conditions, norepinephrine (NE), epinephrine (EP) and dopamine (DA) were separated very well from internal standard and exhibited a good linearity in the range of 2.5–500.0 ng mL⁻¹, with correlation coefficients of r² > 0.9907. Limits of detection (LOD) (signal to noise = 3) were 0.39, 0.27 and 0.60 ng mL⁻¹ for NE, EP and DA, respectively. Recoveries for the spiked catecholamines were in the range of 85.4–105.2% with the relative standard deviation (RSD) < 11.5%. Full article

A dual strategy for the electrochemical detection for 20S proteasome (20S) is proposed, based on the oriented immobilization of a capture monoclonal antibody (Abβ) on a self-assembled monolayer of 4-mercaptophenylboronic acid (4-MPBA) on gold electrodes, which led to the Au/4-MPBA/Abβ immunosensor. The methodology comprises the correlation of 20S concentration with (i) its proteolytic activity toward the Z-LLE-AMC substrate, using the Au/4-MPBA/Abβ/20S, and (ii) the enzymatic activity of an alkaline phosphatase (AlkP) from the AlkP-labeled secondary antibody (Ab_core-AlkP), which involves the conversion of aminophenylphosphate to the electroactive aminophenol using Au/4-MPBA/Abβ/20S/Ab_core-AlkP. The step-by-step construction of the immunosensor and the interactions at its surface were evaluated by surface plasmon resonance and gravimetric analysis with quartz crystal microbalance, showing a high affinity between both antibodies and 20S. Morphological analysis by scanning electron microscopy demonstrated a pattern of parallel lines upon immobilization of Abβ on 4-MPBA and morphological changes to a well-organized granular structure upon binding of 20S. A voltametric and impedimetric characterization was performed after each step in the immunosensor construction. The two detection strategies were evaluated. It was shown that the immunosensor responds linearly with 20S concentration in the range between 5 and 100 µg mL⁻¹, which corresponds to proteasome levels in serum in the case of diverse pathological situations, and LoD values of 1.4 and 0.2 µg mL⁻¹ were calculated for the detection strategies. The immunosensor was applied to the detection of 20S in serum samples with recovery values ranging from 101 to 103%. Full article

The importance of glucose in many biological processes continues to garner increasing research interest in the design and development of efficient biotechnology for the sensitive and selective monitoring of glucose. Here we report on a surface-enhanced Raman scattering (SERS) detection of 4-mercaptophenyl boronic acid (4-MPBA)-immobilized gold-silver core-shell assembled silica nanostructure (SiO₂@Au@Ag@4-MPBA) for quantitative, selective detection of glucose in physiologically relevant concentration. This work confirmed that 4-MPBA converted to 4-mercaptophenol (4-MPhOH) in the presence of H₂O₂. In addition, a calibration curve for H₂O₂ detection of 0.3 µg/mL was successfully detected in the range of 1.0 to 1000 µg/mL. Moreover, the SiO₂@Au@Ag@4-MPBA for glucose detection was developed in the presence of glucose oxidase (GOx) at the optimized condition of 100 µg/mL GOx with 1-h incubation time using 20 µg/mL SiO₂@Au@Ag@4-MPBA and measuring Raman signal at 67 µg/mL SiO₂@Au@Ag. At the optimized condition, the calibration curve in the range of 0.5 to 8.0 mM was successfully developed with an LOD of 0.15 mM. Based on those strategies, the SERS detection of glucose can be achieved in the physiologically relevant concentration range and opened a great promise to develop a SERS-based biosensor for a variety of biomedicine applications. Full article

The difference in gold nanoparticle (AuNPs) aggregation caused by different mixing orders of AuNPs, 4-mercaptophenylboronic acid (4-MPBA), and hydrogen peroxide (H₂O₂) has been scarcely reported. We have found that the color change of a ((4-MPBA + AuNPs) + H₂O₂) mixture caused by H₂O₂ is more sensitive than that of a ((4-MPBA + H₂O₂) + AuNPs) mixture. For the former mixture, the color changes obviously with H₂O₂ concentrations in the range of 0~0.025%. However, for the latter mixture, the corresponding H₂O₂ concentration is in the range of 0~1.93%. The mechanisms on the color change originating from the aggregation of AuNPs occurring in the two mixtures were investigated in detail. For the ((4-MPBA + H₂O₂) + AuNPs) mixture, free 4-MPBA is oxidized by H₂O₂ to form bis(4-hydroxyphenyl) disulfide (BHPD) and peroxoboric acid. However, for the ((4-MPBA+AuNPs) + H₂O₂) mixture, immobilized 4-MPBA is oxidized by H₂O₂ to form 4-hydroxythiophenol (4-HTP) and boric acid. The decrease in charge on the surface of AuNPs caused by BHPD, which has alarger steric hindrance, is poorer than that caused by -4-HTP, and this is mainly responsible for the difference in the aggregation of AuNPs in the two mixtures. The formation of boric acid and peroxoboric acid in the reaction between 4-MPBA and H₂O₂ can alter the pH of the medium, and the effect of the pH change on the aggregation of AuNPs should not be ignored. These findings not only offer a new strategy in colorimetric assays to expand the detection range of hydrogen peroxide concentrations but also assist in deepening the understanding of the aggregation of citrate-capped AuNPs involved in 4-MPBA and H₂O₂, as well as in developing other probes. Full article

Herein we utilized coordination interactions to prepare a novel core-shell plasmonic nanosensor for the detection of glucose. Specifically, Au nanoparticles (NPs) were strongly linked with Ag+ ions to form a sacrificial Ag shell by using 4-aminothiophenol (4-PATP) as a mediator, which served as an internal standard to decrease the influence of the surrounding on the detection. The resultant Au-PATP-Ag core-shell systems were characterized by UV-vis spectroscopy, transmission electron microscopy, and surface-enhanced Raman scattering (SERS) techniques. Experiments performed with R6G (rhodamine 6G) and CV (crystal violet) as Raman reporters demonstrated that the Au@Ag nanostructure amplified SERS signals obviously. Subsequently, the Au@Ag NPs were decorated with 4-mercaptophenylboronic acid (4-MPBA) to specifically recognize glucose by esterification, and a detection limit as low as 10⁻⁴ M was achieved. Notably, an enhanced linearity for the quantitative detection of glucose (R² = 0.995) was obtained after the normalization of the spectral peaks using 4-PATP as the internal standard. Finally, the practical applicability of the developed sensing platform was demonstrated by the detection of glucose in urine with acceptable specificity. Full article

Phenylboronic acids can form tight covalent bonds with diol-containing biomolecules. In this work, water-dispersed bifunctional gold nanoparticles (AuNPs) modified with ferrecene (Fc)-derivatized peptides and 4-mercaptophenylboronic acids (MBA) (denoted as Fc–MBA–AuNPs) were synthesized and characterized by UV/vis spectrometry and transmission electron microscopy. To demonstrate the application and the analytical merits of the nanoparticles in biosensing, glycoprotein avidin was tested as a model analyte. Specifically, avidin was captured by the biotin-covered gold electrode via the strong biotin-avidin interaction. Then, Fc–MBA–AuNPs were attached by the captured avidin through the formation of tight covalent bonds between the boronic acid moieties of Fc–MBA–AuNPs and the oligosaccharides of avidin. As a result, a detection limit of 0.2 pM was achieved. We believe that the bifunctional nanoparticles would found many applications in amplified detection of diol-containing species by rational design of the surface chemistry of electrode. Full article