Search Results (13)

A two-dimensional array of microfluidic ports with remote-controlled valve actuation is of great interest for applications involving localized chemical stimulation. Herein, a macroporous silicon-based platform where each pore contains an independently controllable valve made from poly(N-isopropylacrylamide) (PNIPAM) brushes is proposed. These valves are coated with silica-encapsulated gold nanorods (GNRs) for NIR-actuated switching capability. The layer-by-layer (LBL) electrostatic deposition technique was used to attach the GNRs to the PNIPAM brushes. The deposition of GNRs was confirmed by dark-field optical microscopy, and the localized surface plasmon resonance (LSPR) of the deposited GNRs was analyzed using UV-Vis spectra. To evaluate the chemical release behaviors, fluorescein dye was employed as a model substance. The chemical release properties, like OFF-state diffusion through the valve, the ratio between ON-state and OFF-state chemical release, and the rapidness of chemical modulation of the valve, were investigated, varying the PNIPAM brush thickness. The results indicate that enhancing the thickness of the PNIPAM brush in our platform improves control over the chemical modulation properties. However, excessive increases in brush length may lead to entanglement, which negatively impacts the chemical modulation efficiency. Full article

This paper explores a novel synthesis and characterization of silica-coated gold nanorods (AuNRs) embedding a highly emissive cyclometalated iridium(III) complex, denoted as Ir₁. We investigate the optical properties and the interplay between the metal compound and gold plasmon, observing how the emission of Ir₁ incorporated into the nanoparticles shows two emission bands, one in the blue and the other in the green-orange range of the visible spectrum. To obtain a clearer picture of what we were observing, we synthesized analogous nanosystems, from which it was possible to highlight the effect of different features. Based on what we observed, we proposed that the fraction of the iridium(III) complex in direct contact with the surface of the gold nanoparticle undergoes a “demixing” of the excited state, which, for cyclometalated iridium complexes, is generally considered a mixed LC+MLCT state. This preliminary study sheds light on the complexity of the “talking” between a fluorophore and a plasmonic system, highlighting the importance of considering the emitter typology when modeling such systems. Full article

In this paper, a self-assembly method was used to prepare gold nanorod composites, and a seed-growth method was used to adjust the amount of AgNO₃ solution, enabling the preparation of gold nanorods with different aspect ratios. AuNRs@SiO₂ nanocomposite particles were then prepared by using the Stöber method to coat the gold nanorod surface with silica. Transmission electron microscopy showed that the maximum aspect ratio of the gold nanorods was 4.53, which was achieved using 2 mL of 10 mM AgNO₃ solution. The Raman-scattering intensity of the gold nanorods was studied using rhodamine 6G, thiram, melamine, and piroxicam, and detection limits of 10⁻⁸ M, 10⁻⁵ M, and 10⁻³ M were, respectively, achieved. As a substrate, these gold nanorods showed good repeatability and reproducibility, and trace detection was successfully achieved. A transmission electron microscopy analysis shows that the SiO₂ shell became thicker with increasing tetraethyl orthosilicate addition. Using AuNRs@SiO₂ as the base and R6G, thiram, and piroxicam as the probes, measurable detection limits of 10⁻⁹ M, 10⁻⁶ M, and 10⁻⁵ M were achieved, and this composite also showed excellent repeatability and reproducibility. Full article

A nanocomposite based on silica-coated AuNRs with the aminated silica-covered spin-crossover nanoparticles (SCO NPs) of the 1D iron(II) coordination polymer with the formula [Fe(Htrz)₂(trz)](BF₄) is presented. For the synthesis of the SCO NPs, the reverse micelle method was used, while the gold nanorods (AuNRs) were prepared with the aspect ratio AR = 6.0 using the seeded-growth method and a binary surfactant mixture composed of cetyltrimethylammonium bromide (CTAB) and sodium oleate (NaOL). The final nanocomposite was prepared using the heteroaggregation method of combining different amounts of SCO NPs with the AuNRs. The nonlinear optical (NLO) properties of the hybrid AuNRs coated with different amounts of SCO NPs were studied in detail by means of the Z-scan technique, revealing that the third-order NLO properties of the AuNRs@SCO are dependent on the amount of SCO NPs grafted onto them. However, due to the resonant nature of the excitation, SCO-induced NLO switching was not observed. Full article

The versatile combination of metal nanoparticles with chemotherapy agents makes designing multifunctional drug delivery systems attractive. In this work, we reported cisplatin’s encapsulation and release profile using a mesoporous silica-coated gold nanorods system. Gold nanorods were synthesized by an acidic seed-mediated method in the presence of cetyltrimethylammonium bromide surfactant, and the silica-coated state was obtained by modified Stöber method. The silica shell was modified first with 3-aminopropyltriethoxysilane and then with succinic anhydride to obtain carboxylates groups to improve cisplatin encapsulation. Gold nanorods with an aspect ratio of 3.2 and silica shell thickness of 14.74 nm were obtained, and infrared spectroscopy and ζ potential studies corroborated surface modification with carboxylates groups. On the other hand, cisplatin was encapsulated under optimal conditions with an efficiency of ~58%, and it was released in a controlled manner over 96 h. Furthermore, acidic pH promoted a faster release of 72% cisplatin encapsulated compared to 51% in neutral pH. Full article

Gold nanoparticles are widely used in laser biomedical applications due to their favorable properties, mainly localized plasmon resonance. However, laser radiation can cause a change in the shape and size of plasmonic nanoparticles, thus resulting in an unwanted reduction of their photothermal and photodynamic efficiency due to a drastic alteration of optical properties. Most previously reported experiments were carried out with bulk colloids where different particles were irradiated by different numbers of laser pulses, thus making it difficult to accurately evaluate the laser power photomodification (PM) threshold. Here, we examine the one-shot nanosecond laser-pulse PM of bare and silica-coated gold nanoparticles moving in a capillary flow. Four types of gold nanoparticles, including nanostars, nanoantennas, nanorods, and SiO₂@Au nanoshells, were fabricated for PM experiments. To evaluate the changes in the particle morphology under laser irradiation, we combine measurements of extinction spectra with electron microscopy. A quantitative spectral approach is developed to characterize the laser power PM threshold in terms of normalized extinction parameters. The experimentally determined PM threshold increases in series were as follows: nanorods, nanoantennas, nanoshells, and nanostars. An important observation is that even a thin silica shell significantly increases the photostability of gold nanorods. The developed methods and reported findings can be useful for the optimal design of plasmonic particles and laser irradiation parameters in various biomedical applications of functionalized hybrid nanostructures. Full article

Gold nanorods (GNRs) coated with silica shells are excellent photothermal agents with high surface functionality and biocompatibility. Understanding the correlation of the coating process with both structure and property of silica-coated GNRs is crucial to their optimizing preparation and performance, as well as tailoring potential applications. Herein, we report a machine learning (ML) prediction of coating silica on GNR with various preparation parameters. A total of 306 sets of silica-coated GNRs altogether were prepared via a sol–gel method, and their structures were characterized to extract a dataset available for eight ML algorithms. Among these algorithms, the eXtreme gradient boosting (XGboost) classification model affords the highest prediction accuracy of over 91%. The derived feature importance scores and relevant decision trees are employed to address the optimal process to prepare well-structured silica-coated GNRs. The high-throughput predictions have been adopted to identify optimal process parameters for the successful preparation of dumbbell-structured silica-coated GNRs, which possess a superior performance to a conventional cylindrical core–shell counterpart. The dumbbell silica-coated GNRs demonstrate an efficient enhanced photothermal performance in vivo and in vitro, validated by both experiments and time domain finite difference calculations. This study epitomizes the potential of ML algorithms combined with experiments in predicting, optimizing, and accelerating the preparation of core–shell inorganic materials and can be extended to other nanomaterial research. Full article

Colorectal cancer (CRC) is the third most common cancer worldwide and the second leading cause of cancer-related deaths in the world. It is urgent to search for safe and effective therapies to address the CRC crisis. The siRNA-based RNA interference targeted silencing of PD-L1 has extensive potential in CRC treatment but is limited by the lack of efficient delivery vectors. In this work, the novel cytosine-phosphate-guanine oligodeoxynucleotides (CpG ODNs)/siPD-L1 co-delivery vectors AuNRs@MS/CpG ODN@PEG-bPEI (ASCP) were successfully prepared by two-step surface modification of CpG ODNs-loading and polyethylene glycol-branched polyethyleneimine-coating around mesoporous silica-coated gold nanorods. ASCP promoted dendritic cells (DCs) maturation by delivering CpG ODNs, exhibiting excellent biosafety. Next, mild photothermal therapy (MPTT) mediated by ASCP killed tumor cells and released tumor-associated antigens, further promoting DC maturation. Furthermore, ASCP exhibited mild photothermal heating-enhanced performance as gene vectors, resulting in an increased PD-L1 gene silencing effect. Enhanced DCs maturity and enhanced PD-L1 gene silencing significantly promoted the anti-tumor immune response. Finally, the combination of MPTT and mild photothermal heating-enhanced gene/immunotherapy effectively killed MC38 cells, leading to strong inhibition of CRC. Overall, this work provided new insights into the design of mild photothermal/gene/immune synergies for tumor therapy and may contribute to translational nanomedicine for CRC treatment. Full article

Photo-nanotheranostics integrates near-infrared (NIR) light-triggered diagnostics and therapeutics, which are combined into a novel all-in-one phototheranostic nanomaterial that holds great promise for the early detection and precise treatment of cancer. In this study, we developed methylene blue-loaded mesoporous silica-coated gold nanorods on graphene oxide (MB-GNR@mSiO₂-GO) as an all-in-one photo-nanotheranostic agent for intracellular surface-enhanced Raman scattering (SERS) imaging-guided photothermal therapy (PTT)/photodynamic therapy (PDT) for cancer. Amine functionalization of the MB-GNR@mSiO₂ surfaces was performed using 3-aminopropyltriethoxysilane (APTES), which was well anchored on the carboxyl groups of graphene oxide (GO) nanosheets uniformly, and showed a remarkably higher photothermal conversion efficiency (48.93%), resulting in outstanding PTT/PDT for cancer. The in vitro photothermal/photodynamic effect of MB-GNR@mSiO₂-GO with laser irradiation showed significantly reduced cell viability (6.32%), indicating that MB-GNR@mSiO₂-GO with laser irradiation induced significantly more cell deaths. Under laser irradiation, MB-GNR@mSiO₂-GO showed a strong SERS effect, which permits accurate cancer cell detection by SERS imaging. Subsequently, the same Raman laser can focus on highly detected MDA-MB-23l cells for a prolonged time to perform PTT/PDT. Therefore, MB-GNR@mSiO₂-GO has great potential for precise SERS imaging-guided synergistic PTT/PDT for cancer. Full article

In this work, the successful preparation and characterization of gold nanorods (AuNRs) coated with a mesoporous silica shell (AuNRs@Simes) was achieved. Conjugation with methylene blue (MB) as a model drug using ultrasound-stimulated loading has been explored for further application in light-mediated antibacterial studies. Lyophilization of this conjugated nanosystem was analyzed using trehalose (TRH) as a cryogenic protector. The obtained stable dry formulation shows potent antimicrobial activity against Gram-negative (Escherichia coli) and Gram-positive (Staphylococcus aureus) bacteria after a simple post-treatment irradiation method with a red laser during a short time period. Full article

Plasmonic nanoresonators consisting of a gold nanorod and a spherical silica core and gold shell, both coated with a gain layer, were optimized to maximize the stimulated emission in the near-field (NF-c-type) and the outcoupling into the far-field (FF-c-type) and to enter into the spasing operation region (NF-c*-type). It was shown that in the case of a moderate dye concentration, the nanorod has more advantages: smaller lasing threshold and larger slope efficiency and larger achieved intensities in the near-field in addition to FF-c-type systems’ smaller gain and outflow threshold, earlier dip-to-peak switching in the spectrum and slightly larger far-field outcoupling efficiency. However, the near-field (far-field) bandwidth is smaller for NF-c-type (FF-c-type) core–shell nanoresonators. In the case of a larger dye concentration (NF-c*-type), although the slope efficiency and near-field intensity remain larger for the nanorod, the core–shell nanoresonator is more advantageous, considering the smaller lasing, outflow, absorption and extinction cross-section thresholds and near-field bandwidth as well as the significantly larger internal and external quantum efficiencies. It was also shown that the strong-coupling of time-competing plasmonic modes accompanies the transition from lasing to spasing occurring, when the extinction cross-section crosses zero. As a result of the most efficient enhancement in the forward direction, the most uniform far-field distribution was achieved. Full article

Nanoparticles made of coinage metals are well known to display unique optical properties stemming from the localized surface plasmon resonance (LSPR) phenomenon, allowing their use as transducers in various biosensing configurations. While most of the reports initially dealt with spherical gold nanoparticles owing to their ease of synthesis, the interest in gold nanorods (AuNR) as plasmonic biosensors is rising steadily. These anisotropic nanoparticles exhibit, on top of the LSPR band in the blue range common with spherical nanoparticles, a longitudinal LSPR band, in all respects superior, and in particular in terms of sensitivity to the surrounding media and LSPR-biosensing. However, AuNRs synthesis and their further functionalization are less straightforward and require thorough processing. In this paper, we intend to give an up-to-date overview of gold nanorods in LSPR biosensing, starting from a critical review of the recent findings on AuNR synthesis and the main challenges related to it. We further highlight the various strategies set up to coat AuNR with a silica shell of controlled thickness and porosity compatible with LSPR-biosensing. Then, we provide a survey of the methods employed to attach various bioreceptors to AuNR. Finally, the most representative examples of AuNR-based LSPR biosensors are reviewed with a focus put on their analytical performances. Full article

Hybrid materials prepared by encapsulation of plasmonic nanoparticles in porous silica systems are of increasing interest due to their high chemical stability and applications in optics, catalysis and biological sensing. Particularly promising is the possibility of obtaining gold@silica nanoparticles (Au@SiO₂ NPs) with Janus morphology, as the induced anisotropy can be further exploited to achieve selectivity and directionality in physical interactions and chemical reactivity. However, current methods to realise such systems rely on the use of complex procedures based on binary solvent mixtures and varying concentrations of precursors and reaction conditions, with reproducibility limited to specific Au@SiO₂ NP types. Here, we report a simple one-pot protocol leading to controlled crystallinity, pore order, monodispersity, and position of gold nanoparticles (AuNPs) within mesoporous silica by the simple addition of a small amount of sodium silicate. Using a fully water-based strategy and constant content of synthetic precursors, cetyl trimethylammonium bromide (CTAB) and tetraethyl orthosilicate (TEOS), we prepared a series of four silica systems: (A) without added silicate, (B) with added silicate, (C) with AuNPs and without added silicate, and (D) with AuNPs and with added silicate. The obtained samples were characterised by transmission electron microscopy (TEM), small angle X-ray scattering (SAXS), and UV-visible spectroscopy, and kinetic studies were carried out by monitoring the growth of the silica samples at different stages of the reaction: 1, 10, 15, 30 and 120 min. The analysis shows that the addition of sodium silicate in system B induces slower MCM-41 nanoparticle (MCM-41 NP) growth, with consequent higher crystallinity and better-defined hexagonal columnar porosity than those in system A. When the synthesis was carried out in the presence of CTAB-capped AuNPs, two different outcomes were obtained: without added silicate, isotropic mesoporous silica with AuNPs located at the centre and radial pore order (C), whereas the addition of silicate produced Janus-type Au@SiO₂ NPs (D) in the form of MCM-41 and AuNPs positioned at the silica–water interface. Our method was nicely reproducible with gold nanospheres of different sizes (10, 30, and 68 nm diameter) and gold nanorods (55 × 19 nm), proving to be the simplest and most versatile method to date for the realisation of Janus-type systems based on MCM-41-coated plasmonic nanoparticles. Full article