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DNA Enabled Chiral Gold Nanoparticle - Chromophore Hybrid Structure with Resonant Plasmon – Exciton Coupling Gives Unusual and Strong Circular Dichroism
摘要: Circular dichroism (CD) from hybrid complexes of plasmonic nanostructures and chiral molecules has recently attracted significant interest. However, the hierarchical chiral self-assembly of molecules on surfaces of metal nanostructures has remained challenging. As a result, a deep understanding of plasmon-exciton coupling between surface plasmons and chiral collective molecular excitations has not been achieved. In particular, the critical impact of resonant plasmon-exciton coupling within the hybrid is unclear. Here, we employed DNA-templated strategies to control the chiral self-assembly of achiral chromophores with rationally tuned exciton transitions on gold nanosphere (AuNP) or gold nanorod (AuNR) surfaces. Unlike many previous chiral plasmonic hybrids utilizing chiral biomolecules with CD signals in the UV range, we designed structure with the chiral excitonic resonances at visible wavelengths. The constructed hybrid complexes displayed strong chiroptical activity that depends on the spectral overlap between the chiral collective molecular excitations and the plasmon resonances. We find that when spectral overlap is optimized, the molecular CD signal originating from the chiral self-assemblies of chromophores was strongly enhanced (maximum enhancement of nearly an order of magnitude) and a plasmonic CD signal was induced. Surprisingly, the sign of the molecular CD was reversed despite different self-assembly mechanisms of the Au nanoparticle-chromophore hybrids. Our results provide new insight into plasmonic CD enhancements and will inspire further studies on chiral light-matter interactions in strongly coupled plasmonic-excitonic systems.
关键词: DNA-templated strategies,gold nanorod,chiral molecules,chiroptical activity,gold nanosphere,Circular dichroism,plasmonic nanostructures
更新于2025-09-12 10:27:22
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Rapid Biofilm Elimination on Bone Implants Using Near‐Infrared‐Activated Inorganic Semiconductor Heterostructures
摘要: Bacterial infections often cause orthopedic surgery failures. It is hard for the immune system and antibiotics to clear bacteria adhered to implants after they form a mature biofilm, and a secondary surgery is required to remove the infected implants. To avoid this, a hybrid coating of Bi2S3@Ag3PO4/Ti is prepared to eliminate biofilm using near-infrared (NIR) light. Bi2S3 nanorod (NR) arrays are prepared on titanium (Ti) implants through hydrothermal methods, and Ag3PO4 nanoparticles (NPs) are loaded on Bi2S3 NR arrays using a stepwise electrostatic adsorption strategy. The introduction of Ag3PO4 NPs enhances the photocatalysis performances of Bi2S3, and the hybrid coating also exhibits good photothermal effects. After 808 nm light irradiation for 15 min, it shows superior bactericidal efficiency of 99.45% against Staphylococcus aureus, 99.74% against Escherichia coli in vitro, and 94.54% against S. aureus biofilm in vivo. Bi2S3@Ag3PO4/Ti also shows good cell viability compared to pure Ti. This NIR-activated-inorganic hybrid semiconductor heterojunction coating is biocompatible and could be employed to eliminate biofilm effectively, which makes it a very promising strategy for the surface modification of bone implant materials.
关键词: Bi2S3@Ag3PO4 nanorod arrays,biofilm elimination,bone implants,near-infrared photocatalysts,heterostructures
更新于2025-09-11 14:15:04
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Plasmon-Enhanced Fluorescence in Gold Nanorod-Quantum Dot Coupled Systems
摘要: Plasmon-exciton coupling is of great importance to many optical devices and applications. One of the coupling manifestations is plasmon-enhanced fluorescence. Although this effect is demonstrated in numerous experimental and theoretical works, there are different particle shapes for which this effect is not fully investigated. In this work electrostatic complexes of gold nanorods and CdSe/CdZnS quantum dots were studied. Double-resonant gold nanorods have an advantage of the simultaneous enhancement of the absorption and emission when the plasmon bands match the excitation and fluorescence wavelengths of an emitter. A relationship between the concentration of quantum dots in the complexes and the enhancement factor was established. It was demonstrated that the enhancement factor is inversely proportional to the concentration of quantum dots. The maximal fluorescence enhancement by 10.8 times was observed in the complex with the smallest relative concentration of 2.5 quantum dots per rod and approximately 5 nm distance between them. Moreover, the influence of quantum dot location on the gold nanorod surface plays an important role. Theoretical study and experimental data indicate that only the position near the nanorod ends provides the enhancement. At the same time, the localization of quantum dots on the sides of the nanorods leads to the fluorescence quenching.
关键词: quantum dot fluorescence,gold nanorod-quantum dot complexes,plasmon-enhanced fluorescence,plasmon-exciton coupling,gold nanorods
更新于2025-09-11 14:15:04
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A rotary plasmonic nanoclock
摘要: One of the fundamental challenges in nanophotonics is to gain full control over nanoscale optical elements. The precise spatiotemporal arrangement determines their interactions and collective behavior. To this end, DNA nanotechnology is employed as an unprecedented tool to create nanophotonic devices with excellent spatial addressability and temporal programmability. However, most of the current DNA-assembled nanophotonic devices can only reconfigure among random or very few defined states. Here, we demonstrate a DNA-assembled rotary plasmonic nanoclock. In this system, a rotor gold nanorod can carry out directional and reversible 360° rotation with respect to a stator gold nanorod, transitioning among 16 well-defined configurations powered by DNA fuels. The full-turn rotation process is monitored by optical spectroscopy in real time. We further demonstrate autonomous rotation of the plasmonic nanoclock powered by DNAzyme-RNA interactions. Such assembly approaches pave a viable route towards advanced nanophotonic systems entirely from the bottom-up.
关键词: DNA nanotechnology,nanophotonics,DNAzyme-RNA interactions,plasmonic nanoclock,gold nanorod
更新于2025-09-11 14:15:04
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Particulate Oxynitride Photoanodes Assembled with Transparent Electron-Collecting Oxide Nanorod Arrays
摘要: The collection of photogenerated electrons is commonly a bottleneck in photoelectrochemical water oxidation on a particulate photoanode. Herein, a new strategy called “array insertion” for particulate photoanode preparation is proposed to improve electron collection. ZnO nanorod arrays are inserted between LaTiO2N particles and Al-doped ZnO (AZO) substrates via epitaxial electrodeposition, which make electronic connections. Using this methodology, charge separation efficiency is improved drastically, and the photocurrent at 1.23 VRHE is enhanced by more than 1 order of magnitude, because the obstacle of electron collection in the particulate LaTiO2N photoanodes is overcome.
关键词: photoelectrochemical water oxidation,particulate photoanode,ZnO nanorod arrays,LaTiO2N,electron collection
更新于2025-09-11 14:15:04
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High-Speed Growth of ZnO Nanorods in Preheating Condition Using Microwave-Assisted Growth Method
摘要: In this study, we present the microwave-assisted growth (MAG) of ZnO nanorods (ZNRs) using a preheating hydrothermal method under tailored preheating and postheating growth conditions. The perimeters such as solution concentration, preheating time, and postheating time, were changed to optimize ZNR growth and the growth was carried out in a domestic 850 watt microwave oven. Preheated solution was utilized as an accelerator to increase the aspect ratio of the ZNRs and reduce the fabrication time. Because of a long fabrication time and limited length in the conventional MAG method, preheating condition was used for ef?cient growth of nanorods through homogeneous nucleation in the solution and then heterogeneous nucleation of the formed ZNRs on seeded substrate during postheating process. The nanostructures were characterized with scanning electron microscopy to look at the morphology and dimensions. Dimensions of ZNRs kept on increasing as the molar concentration went higher. Preheating time highly affected the morphology, dimensions, and aspect ratio of ZNRs and postheating time not only ensured the stability of ZNRs with substrate due to heterogeneous nucleation process but also in?uenced the morphology of ZNRs.
关键词: Hydrothermal,Aspect Ratio,Microwave,Preheating,ZnO Nanorod
更新于2025-09-11 14:15:04
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Ag-Ag2S quantum-dots modified TiO2 nanorod arrays with enhanced photoelectrochemical and photocatalytic properties
摘要: In this paper, highly ordered titanium dioxide nanorod (TNR) arrays decorated with Ag-Ag2S quantum-dots (QDs) were synthesized on FTO substrate through hydrothermal treatment and in-situ vulcanization. The content of Ag2S QDs on Ag/TNR was controlled by changing the immersion time of Ag/TNR in the N-N-dimethyl formamide (DMF) solution containing dissolved sulfur element. The morphology, structure, composition and optical, photoelectric and photocatalytic properties of QDs/TNR arrays were studied in detail. In the visible range, the QDs/TNR array with a soaking time of 12 h exhibits the maximal photocurrent density (0.082 mA/cm2) and photodegradation rate (62.2%), which is 5.5 and 1.85 times higher than that of pure TNR. The improvement of these properties could be attributed to synergy effect between Ag and Ag2S materials. That is, Ag QDs can stably capture and transmit photo-generated electrons from the TNR surface, whereas the Ag2S promoter is regarded as the interface active sites to enhance photocatalytic reactions. Therefore, the synergistic effect of Ag-Ag2S can significantly enhance the photoelectrochemical and photocatalytic propertise of the TNR arrays.
关键词: Ag-Ag2S quantum-dots,photoelectrochemical and photocatalytic properties,synergistic effect,TiO2 nanorod arrays
更新于2025-09-10 09:29:36
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Colorimetric Determination of Hypochlorite Based on the Oxidative Leaching of Gold Nanorods
摘要: Hypochlorite plays a critical role in killing microorganisms in the water. However, it can also cause cardiovascular diseases, neuron degeneration, and cancer to humans. Although traditional methods feature excellent sensitivity and reliability in detecting hypochlorite, the expensive instruments and strict determination conditions have limited their application in environmental analysis to some extent. Thus, it is necessary and urgent to propose a cheap, facile, and quick analytical assay for hypochlorite. This paper proposes a colorimetric assay for hypochlorite utilizing gold nanorods (AuNRs) as the nanoreactor and color reader. The AuNRs were acquired via a reported seed-mediated method. NaClO with strong oxidation property can cause the etching of gold from the longitudinal tips of AuNRs, which could shorten the aspect ratio of AuNRs, decrease the absorption in the UV–Vis spectrum and also induce the solution color changing from red to pale yellow. Thus, according to the solution color change and the absorbance of longitudinal surface plasmon resonance of AuNRs, we established the calibration curve of NaClO within 0.08 μM to 125 μM (?Abs = 0.0547 + 0.004 CNaClO, R2 = 0.9631). Compared to traditional method, we obtained the conversion formula between the concentration of residual-chlorine in tap water and the concentration of hypochlorite detected by the proposed colorimetric assay, which is Cresidual-chlorine = 0.24 CNaClO. Finally, the real application of the colorimetric assay in tap water was successfully performed, and the accuracy of the colorimetric method can reach from ?6.78% to +8.53%.
关键词: colorimetric determination,hypochlorite,gold nanorod
更新于2025-09-10 09:29:36
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Biocompatible Gold Nanorod Conjugates for Preclinical Biomedical Research
摘要: Gold nanorods with a peak absorption wavelength of 760 nm were prepared using a seed-mediated method. A novel protocol has been developed to replace hexadecyltrimethylammonium bromide on the surface of the nanorods with 16-mercaptohexadecanoic acid and metoxy-poly(ethylene glycol)-thiol, and the monoclonal antibody HER2. The physical chemistry properties of the conjugates were monitored through optical and zeta-potential measurements to confirm surface chemistry changes. The efficiency of the modifications was quantified through measurement of the average number of antibodies per gold nanorod. The conjugates were investigated for different cells lines: BT-474, MCF7, MCF10, MDCK, and fibroblast. The results show successful cell accumulation of the gold nanorod HER2 conjugates in cells with HER2 overexpression. Incubation of the complexes in heparinized mouse blood demonstrated the low aggregation of the metallic particles through stability of the spectral properties, as verified by UV/VIS spectrometry. Cytotoxicity analysis with LDH release and MTT assay confirms strong targeting and retention of functional activity of the antibody after their conjugation with gold nanorods. Silver staining confirms efficient specific binding to BT-474 cells even in cases where the nanorod complexes were incubated in heparinized mouse blood. This is confirmed through in vivo studies where, following intravenous injection of gold nanorod complexes, silver staining reveals noticeably higher rates of specific binding in mouse tumors than in healthy liver. The conjugates are reproducible, have strong molecular targeting capabilities, have long term stability in vivo and can be used in pre-clinical applications. The conjugates can also be used for molecular and optoacoustic imaging, quantitative sensing of biological substrates, and photothermal therapy.
关键词: Metallic nanoparticles,Gold nanorod fabrication,Cell particle targeting,Gold surface modification,Biocompatible targeting agent,Antibody conjugation
更新于2025-09-10 09:29:36
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A dual-targeted hyaluronic acid-gold nanorod platform with triple-stimuli responsiveness for photodynamic/photothermal therapy of breast cancer
摘要: Multi-stimuli-responsive theranostic nanoplatform integrating functions of both imaging and multimodal therapeutics holds great promise for improving diagnosis and therapeutic efficacy. In this study, we reported a pH, glutathione (GSH) and hyaluronidase (HAase) triple-responsive nanoplatform for HER2 and CD44 dual-targeted and fluorescence imaging-guided PDT/PTT dual-therapy against HER2-overexpressed breast cancer. The nanoplatform was fabricated by functionalizing gold nanorods (GNRs) with hyaluronic acid (HA) bearing pendant hydrazide and thiol groups via Au-S bonds, and subsequently chemically conjugating 5-aminolevulinic acid (ALA), Cy7.5 and anti-HER2 antibody onto HA moiety for PDT, fluorescence imaging and active targeting, respectively. The resulting versatile nanoplatform GNR-HA-ALA/Cy7.5-HER2 had uniform sizes, favorable dispersibility, as well as pH, GSH and HAase triple-responsive drug release manner. In vitro studies demonstrated that HER2 and CD44 receptor-mediated dual-targeting strategy could significantly enhance the cellular uptake of GNR-HA-ALA/Cy7.5-HER2. Under near-infrared (NIR) irradiation, MCF-7 cells could efficiently generate reactive oxygen species (ROS) and heat, and be more efficiently killed by a combination of PDT and PTT as compared with individual therapy. Pharmacokinetic and biodistribution studies showed that the nanoplatform possessed a circulation half-life of 1.9 h and could be specifically delivered to tumor tissues with an accumulation ratio of 12.8%. Upon the fluorescence imaging-guided PDT/PTT treatments, the tumors were completely eliminated without obvious side effects. The results suggest that the GNR-HA-ALA/Cy7.5-HER2 hold great potential for breast cancer therapy.
关键词: Triple-responsive drug release,Hyaluronic acid,Gold nanorod,Photodynamic and photothermal dual-therapy,Targeted delivery
更新于2025-09-10 09:29:36