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1.
The cost‐effective self‐assembly of 80 nm Au nanoparticles (NPs) into large‐domain, hexagonally close‐packed arrays for high‐sensitivity and high‐fidelity surface‐enhanced Raman spectroscopy (SERS) is demonstrated. These arrays exhibit specific optical resonances due to strong interparticle coupling, which are well reproduced by finite‐difference time‐domain (FDTD) simulations. The gaps between NPs form a regular lattice of hot spots that enable a large amplification of both photoluminescence and Raman signals. At smaller wavelengths the hot spots are extended away from the minimum‐gap positions, which allows SERS of larger analytes that do not fit into small gaps. Using CdSe quantum dots (QDs) a 3–5 times larger photoluminescence enhancement than previously reported is experimentally demonstrated and an unambiguous estimate of the electromagnetic SERS enhancement factor of ≈104 is obtained by direct scanning electron microscopy imaging of QDs responsible for the Raman signal. Much stronger enhancement of ≈108 is obtained at larger wavelengths for benzenethiol molecules penetrating the NP gaps.  相似文献   

2.
Magnetic‐plasmonic nanoparticles have received considerable attention for widespread applications. These nanoparticles (NPs) exhibiting surface‐enhanced Raman scattering (SERS) activities are developed due to their potential in bio‐sensing applicable in non‐destructive and sensitive analysis with target‐specific separation. However, it is challenging to synthesize these NPs that simultaneously exhibit low remanence, maximized magnetic content, plasmonic coverage with abundant hotspots, and structural uniformity. Here, a method that involves the conjugation of a magnetic template with gold seeds via chemical binding and seed‐mediated growth is proposed, with the objective of obtaining plasmonic nanostructures with abundant hotspots on a magnetic template. To obtain a clean surface for directly functionalizing ligands and enhancing the Raman intensity, an additional growth step of gold (Au) and/or silver (Ag) atoms is proposed after modifying the Raman molecules on the as‐prepared magnetic‐plasmonic nanoparticles. Importantly, one‐sided silver growth occurred in an environment where gold facets are blocked by Raman molecules; otherwise, the gold growth is layer‐by‐layer. Moreover, simultaneous reduction by gold and silver ions allowed for the formation of a uniform bimetallic layer. The enhancement factor of the nanoparticles with a bimetallic layer is approximately 107. The SERS probes functionalized cyclic peptides are employed for targeted cancer‐cell imaging and separation.  相似文献   

3.
Mercuric ion (Hg2+) is one of the most toxic and serious environment polluting heavy metal ions, which can be accumulated in human body through food chains and drinking water, and causes serious damage to human organs. Therefore, development of the efficient and sensitive method for detection of Hg2+ is very necessary. In this study, the high surface sensitivity and fingerprint information about the chemical structures based on surface‐enhanced Raman scattering (SERS) for sensing applications are taken advantage of. Au triangular nanoarrays/n‐layer graphene/Au nanoparticles sandwich structure with large‐area uniform subnanometer gaps are fabricated and used to detect Hg2+ in water via thymine–Hg2+–thymine coordination; the detection limit of Hg2+ is as low as 8.3 × 10?9m . Moreover, this SERS substrate is used to detect the Hg2+‐contaminated sandy soil and shows excellent performance. This study indicates the sandwich structure has a great potential in detection of toxic metal ions and environmental pollutants.  相似文献   

4.
A novel magnetically responsive and surface‐enhanced Raman spectroscopy (SERS) active nanocomposite is designed and prepared by direct grafting of Au nanoparticles onto the surface of magnetic network nanostructure (MNN) with the help of a nontoxic and environmentally friendly reagent of inositol hexakisphosphate shortly named as IP6. The presence of IP6 as a stabilizer and a bridging agent could weave Fe3O4 nanoparticles (NPs) into magnetic network nanostructure, which is easily dotted with Au nanoparticles (Au NPs). It has been shown firstly that the huge Raman enhancement of Au‐MNN is reached by an external magnetic collection. Au‐MNN presenting the large surface and high detection sensitivity enables it to exhibit multifunctional applications involving sufficient adsorption of dissolved chemical species for enrichment, separation, as well as a Raman amplifier for the analysis of trace pesticide residues at femtomolar level by a portable Raman spectrometer. Therefore, such multifunctional nanocomposites can be developed as a smart and promising nanosystem that integrates SERS approach with an easy assay for concentration by an external magnet for the effective on‐site assessments of agricultural and environmental safety.  相似文献   

5.
A high‐sensitivity and low‐power theranostic nanosystem that combines with synergistic photothermal therapy and surface‐enhanced Raman scattering (SERS) mapping is constructed by mesoporous silica self‐assembly on the reduced graphene oxide (rGO) nanosheets with nanogap‐aligned gold nanoparticles (AuNPs) encapsulated and arranged inside the nanochannels of the mesoporous silica layer. Rhodamine 6G (R6G) as a Raman reporter is then encapsulated into the nanochannels and anti‐epidermal growth factor receptor (EGFR) is conjugated on the nanocomposite surface, defined as anti‐EGFR‐PEG‐rGO@CPSS‐Au‐R6G, where PEG is polyethylene glycol and CPSS is carbon porous silica nanosheets. SERS spectra results show that rGO@CPSS‐Au‐R6G enhances 5 × 106 magnification of the Raman signals and thus can be applied in the noninvasive cell tracking. Furthermore, it displays high sensitivity (detection limits: 10?8m R6G solution) due to the “hot spots” effects by the arrangements of AuNPs in the nanochannels of mesoporous silica. The highly selective targeting of overexpressing EGFR lung cancer cells (A549) is observed in the anti‐EGFR‐PEG‐rGO@CPSS‐Au‐R6G, in contrast to normal cells (MRC‐5). High photothermal therapy efficiency with a low power density (0.5 W cm?2) of near‐infrared laser can be achieved because of the synergistic effect by conjugated AuNPs and rGO nanosheets. These results demonstrate that the anti‐EGFR‐PEG‐rGO@CPSS‐Au‐R6G is an excellent new theranostic nanosystem with cell targeting, cell tracking, and photothermal therapy capabilities.  相似文献   

6.
Plasmonic nanostructures have raised the interest of biomedical applications of surface-enhanced Raman scattering (SERS). To improve the enhancement and produce sensitive SERS probes, porous Au–Ag alloy nanoparticles (NPs) are synthesized by dealloying Au–Ag alloy NP-precursors with Au or Ag core in aqueous colloidal environment through galvanic replacement reaction. The novel designed core–shell Au–Ag alloy NP-precursors facilitate controllable synthesis of porous nanostructure, and dealloying degree during the reaction has significant effect on structural and spectral properties of dealloyed porous NPs. Narrow-dispersed dealloyed NPs are obtained using NPs of Au/Ag ratio from 10/90 to 40/60 with Au and Ag core to produce solid core@porous shell and porous nanoshells, having rough surface, hollowness, and porosity around 30–60%. The clean nanostructure from colloidal synthesis exhibits a redshifted plasmon peak up to near-infrared region, and the large accessible surface induces highly localized surface plasmon resonance and generates robust SERS activity. Thus, the porous NPs produce intensely enhanced Raman signal up to 68-fold higher than 100 nm AuNP enhancement at single-particle level, and the estimated Raman enhancement around 7800, showing the potential for highly sensitive SERS probes. The single-particle SERS probes are effectively demonstrated in quantitative monitoring of anticancer drug Doxorubicin release.  相似文献   

7.
Surface‐enhanced Raman scattering (SERS) provides a dramatic increase of Raman intensity for molecules adsorbed on nanogap‐rich metal nanostructures, serving as a promising tool for molecular analysis. However, surface contamination caused by protein adsorption and low surface concentration of small target molecules reduce the sensitivity, which severely restricts the use of SERS in many applications. Here, charged microgels containing agglomerates of gold nanoparticles (Au NPs) are designed using droplet‐based microfluidics to provide a reliable SERS substrate with molecular selectivity and high sensitivity. The limiting mesh size of hydrogel enables the autonomous exclusion of large proteins and the charged matrix concentrates oppositely charged small molecules through electrostatic attraction. As nanogaps among Au NPs in the agglomerates enhance Raman intensity, Raman spectrum of the adsorbed molecules is selectively measured with high sensitivity in the absence of interruption from adhesive proteins. Therefore, the SERS‐active‐charged microgels can be used for direct analysis of pristine biological samples without the pretreatment steps of separation and concentration, which are commonly a prerequisite for Raman analysis. For the purpose of demonstration, a direct detection of fipronil sulfone with partial negative charges, a metabolite of toxic insecticide, dissolved in eggs using the positively charged microgels without any pretreatment of the samples, is shown.  相似文献   

8.
Fabricating perfect plasmonic nanostructures has been a major challenge in surface enhanced Raman scattering (SERS) research. Here, a double‐layer stacked Au/Al2O3@Au nanosphere structures is designed on the silicon wafer to bring high density, high intensity “hot spots” effect. A simply reproducible high‐throughput approach is shown to fabricate feasibly this plasmonic nanostructures by rapid thermal annealing (RTA) and atomic layer deposition process (ALD). The double‐layer stacked Au nanospheres construct a three‐dimensional plasmonic nanostructure with tunable nanospacing and high‐density nanojunctions between adjacent Au nanospheres by ultrathin Al2O3 isolation layer, producing highly strong plasmonic coupling so that the electromagnetic near‐field is greatly enhanced to obtain a highly uniform increase of SERS with an enhancement factor (EF) of over 107. Both heterogeneous nanosphere group (Au/Al2O3@Ag) and pyramid‐shaped arrays structure substrate can help to increase the SERS signals further, with a EF of nearly 109. These wafer‐scale, high density homo/hetero‐metal‐nanosphere arrays with tunable nanojunction between adjacent shell‐isolated nanospheres have significant implications for ultrasensitive Raman detection, molecular electronics, and nanophotonics.  相似文献   

9.
The last few years have witnessed rapid development of biological and medical applications of graphene oxide (GO), such as drug/gene delivery, biosensing, and bioimaging. However, little is known about the cellular uptake mechanism and pathway of GO. In this work, surface-enhanced Raman scattering (SERS) spectroscopy is employed to investigate the cellular internalization of GO loaded with Au nanoparticles (NPs) by Ca Ski cells. The presence of Au NPs on the surface of GO enables detection of enhanced intrinsic Raman signals of GO inside the cell. The SERS results reveal that GO is distributed inhomogeneously inside the cell. Furthermore, internalization of Au-GO into Ca Ski cells is mainly via clathrin-mediated endocytosis, and is an energy-dependent process.  相似文献   

10.
There is a need for intraoperative imaging technologies to guide breast‐conserving surgeries and to reduce the high rates of re‐excision for patients in which residual tumor is found at the surgical margins during postoperative pathology analyses. Feasibility studies have shown that utilizing topically applied surface‐enhanced Raman scattering (SERS) nanoparticles (NPs), in conjunction with the ratiometric imaging of targeted versus untargeted NPs, enables the rapid visualization of multiple cell‐surface biomarkers of cancer that are overexpressed at the surfaces of freshly excised breast tissues. In order to reliably and rapidly perform multiplexed Raman‐encoded molecular imaging of large numbers of biomarkers (with five or more NP flavors), an enhanced staining method has been developed in which tissue surfaces are cyclically dipped into an NP‐staining solution and subjected to high‐frequency mechanical vibration. This dipping and mechanical vibration (DMV) method promotes the convection of the SERS NPs at fresh tissue surfaces, which accelerates their binding to their respective biomarker targets. By utilizing a custom‐developed device for automated DMV staining, this study demonstrates the ability to simultaneously image four cell‐surface biomarkers of cancer at the surfaces of fresh human breast tissues with a mixture of five flavors of SERS NPs (four targeted and one untargeted control) topically applied for 5 min and imaged at a spatial resolution of 0.5 mm and a raster‐scanned imaging rate of >5 cm2 min?1.  相似文献   

11.
A facile fabrication approach of large‐scale flexible films is reported, with one surface side consisting of Ag‐nanoparticle (Ag‐NP) decorated polyacrylonitrile (PAN) nanohump (denoted as Ag‐NPs@PAN‐nanohump) arrays. This is achieved via molding PAN films with ordered nanohump arrays on one side and then sputtering much smaller Ag‐NPs onto each of the PAN‐nanohumps. Surface‐enhanced Raman scattering (SERS) activity of the Ag‐NPs@PAN‐nanohump array films can be improved by curving the flexible PAN film with ordered nanohump arrays during the Ag‐sputtering process to increase the density of the Ag‐NPs on the sidewalls of the PAN‐nanohumps. More 3D hot spots are thus achieved on a large‐scale. The Ag‐NPs@PAN‐nanohump array films show high SERS activity with good Raman signal reproducibility for Rhodamine 6G probe molecules. To trial their practical application, the Ag‐NPs@PAN‐nanohump array films are employed as SERS substrates for trace detection of trinitrotoluene and a congener of polychlorinated biphenyls. A lower detection limit of 10−12m and 10−5m can be achieved, respectively. Furthermore, the flexible Ag‐NPs@PAN‐nanohump array films can also be utilized as swabs to probe traces of methyl parathion on the surface of fruits such as apples. The as‐fabricated SERS substrates therefore have promising potential for applications in rapid safety inspection and environmental protection.  相似文献   

12.
A universal femtoliter surface droplet‐based platform for direct quantification of trace of hydrophobic compounds in aqueous solutions is presented. Formation and functionalization of femtoliter droplets, concentrating the analyte in the solution, are integrated into a simple fluidic chamber, taking advantage of the long‐term stability, large surface‐to‐volume ratio, and tunable chemical composition of these droplets. In situ quantification of the extracted analytes is achieved by surface‐enhanced Raman scattering (SERS) spectroscopy by nanoparticles on the functionalized droplets. Optimized extraction efficiency and SERS enhancement by tuning droplet composition enable quantitative determination of hydrophobic model compounds of rhodamine 6G, methylene blue, and malachite green with the detection limit of 10?9 to 10?11 m and a large linear range of SERS signal from 10?9 to 10?6 m of the analytes. The approach addresses the current challenges of reproducibility and the lifetime of the substrate in SERS measurements. This novel surface droplet platform combines liquid–liquid extraction and highly sensitive and reproducible SERS detection, providing a promising technique in current chemical analysis related to environment monitoring, biomedical diagnosis, and national security monitoring.  相似文献   

13.
It is a significant challenge to achieve controllable self‐assembly of superstructures for biological applications in living cells. Here, a two‐layer core–satellite assembly is driven by a Y‐DNA, which is designed with three nucleotide chains that hybridized through complementary sequences. The two‐layer core–satellite nanostructure (C30S5S10 NS) is constructed using 30 nm gold nanoparticles (Au NPs) as the core, 5 nm Au NPs as the first satellite layer, and 10 nm Au NPs as the second satellite layer, resulting in a very strong circular dichroism (CD) and surface‐enhanced Raman scattering. After optimization, the yield is up to 85%, and produces a g‐factor of 0.16 × 10?2. The hybridization of the target microRNA (miRNA) with the molecular probe causes a significant drop in the CD and Raman signals, and this phenomenon is used to detect the miRNA in living cells. The CD signal has a good linear range of 0.011–20.94 amol ngRNA?1 and a limit of detection (LOD) of 0.0051 amol ngRNA?1, while Raman signal with the range of 0.052–34.98 amol ngRNA?1 and an LOD of 2.81 × 10?2 amol ngRNA?1. This innovative dual‐signal method can be used to quantify biomolecules in living cells, opening the way for ultrasensitive, highly accurate, and reliable diagnoses of clinical diseases.  相似文献   

14.
Ag nanoparticles (NPs) modified graphene nanoribbons (GNRs) are proposed to function as the high-performance shared substrates for surface-enhanced Raman and infrared absorption spectroscopy (SERS and SEIRAS). This is realized by modulating the localized plasmonic resonances of Ag NPs in visible region and GNRs in mid-infrared region simultaneously, so as to selectively employ each resonance to acquire SERS and SEIRAS on a single substrate. As a proof of concept, shared substrates are prepared by fabricating GNRs on a Fabry–Pérot like cavity, followed by depositing a thin Ag film with annealing treatment to achieve Ag NPs. Complementary Raman and infrared active vibrational modes of rhodamine 6G molecules can be extracted from the SERS and SEIRAS spectra. By optimizing the dimension of Ag NPs, SERS enhancement factors at the order of 105 can be achieved, which are comparable with or even larger than that of the reported shared substrates. Meanwhile, various polyethylene oxide vibrational modes can be recognized with maximum SEIRAS amplification up to 170 times, which is one order larger than that of the reported graphene plasmonic infrared sensors. Such plasmonic nanosensor with excellent SERS and SEIRAS performance exhibits promising potential for biosensing applications on an integrated lab-on-a-chip strategy.  相似文献   

15.
A yolk–shell Fe/Fe4N@Pd/C (FFPC) nanocomposite is synthesized successfully by two facile steps: interfacial polymerization and annealing treatment. The concentration of Pd2+ is the key factor for the density of Pd nanoparticles (Pd NPs) embedded in the carbon shells, which plays a role in the oxygen reduction reaction (ORR) and surface‐enhanced Raman scattering (SERS) properties. The ORR and SERS performances of FFPC nanocomposites under different concentrations of PdCl2 are investigated. The optimal ORR performance exhibits that onset potential and tafel slope can reach 0.937 V (vs reversible hydrogen electrode (RHE)) and 74 mV dec?1, respectively, which is attributed to the synergistic effects of good electrical conductivity, large electrochemically active areas, and strong interfacial charge polarization. Off‐axis electron holography reveals that interfacial charge polarization could facilitate the ORR of Pd NPs and defective carbon simultaneously and the shell with low density of Pd NPs is easier to form strong interfacial charge polarization. Moreover, FFPC‐3 with maximum EF of 2.3 × 105 results from more hot‐spots, local positive charge centers to attract rhodamine 6G molecules, and magnetic cores. This work not only offers a recyclable multifunctional nanocomposite with excellent performance, but also has instructional implications for interfacial engineering for electrocatalysts design.  相似文献   

16.
An economical method of fabricating large‐area (up to a 100‐mm wafer) silver (Ag)‐coated black silicon (BS) substrates is demonstrated by cryogenic deep reactive ion etching with inductively coupled plasma. This method enables a simple adjustment of the spike structure (e.g., height, width, sidewall slope and density of the spikes) on the silicon substrate, which thus offers the advantages of accurate tuning the density and amplitude of the localized surface plasmons after Ag coating. Using this method, an enhancement factor of 109 is achieved for the probe molecule of rhodamine 6G (around two orders of magnitude higher than previous results based on Ag‐coated BS) in surface‐enhanced Raman scattering (SERS) measurement. The presented results pave the way to make Ag‐coated BS substrates as economic and large‐area platforms for diverse surface plasmon related applications (such as SERS and surface plasmon based biosensors).  相似文献   

17.
The paper reports a facile one‐pot synthesis of core@shell nanoparticles (NPs) composed of Au core and graphene oxide nanocolloid (GON) shell. Unique properties of Au NPs and GON can be incorporated into a single nanohybrid structure to provide desirable functions for theranosis such as localized surface plasmon resonance, Raman scattering, amphiphilic surface, and photothermal conversion. Synthesis of Au@GON NPs is achieved by simple one‐pot reaction in aqueous phase utilizing GON as a reducing and stabilizing agent without any additional reducing agent. The zinc phthalocyanine, a photosensitizer, loaded Au@GON NPs show excellent multifunctional properties for combinational treatment of photothermal and photodynamic therapy in addition to Raman bioimaging with low cytotoxicity.  相似文献   

18.
Assemblies of nanomaterials for biological applications in living cells have attracted much attention. Herein, graphene oxide (GO)–gold nanoparticle (Au NP) assemblies are driven by a splint DNA strand, which is designed with two regions at both ends that are complementary with the DNA sequence anchored on the surface of the GO and the Au NPs. In the presence of microRNA (miR)‐21 and epithelial cell‐adhesion molecule (EpCAM), the hybridization of miR‐21 with a molecular probe leads to the separation of 6‐fluorescein‐phosphoramidite‐modified Au NPs from GO, resulting in a decrease in the Raman signal, while EpCAM recognition reduces circular dichroism (CD) signals. The CD signals reverse from negative in original assemblies into positive when reacted with cells, which correlates with two enantiomer geometries. The EpCAM detection has a good linear range of 8.47–74.78 pg mL?1 and a limit of detection (LOD) of 3.63 pg mL?1, whereas miR‐21 detection displays an outstanding linear range of 0.07–13.68 amol ng?1RNA and LOD of 0.03 amol ng?1RNA. All the results are in good agreement with those of the Raman and confocal bioimaging. The strategy opens up an avenue to allow the highly accurate and reliable diagnosis (dual targets) of clinic diseases.  相似文献   

19.
Graphene as a substrate for enhancing Raman scattering, called graphene‐enhanced Raman scattering (GERS), has been reported in previous work. Herein, it is found that the “first‐layer effect”, which is widely used to explain the chemical‐enhanced mechanism in surface‐enhanced Raman scattering (SERS), exists in the GERS system. The Langmuir–Blodgett (LB) technique is used to construct mono‐ and multilayer ordered aggregates of protoporphyrin IX (PPP). Raman spectra of PPP with different layer numbers of the LB film on graphene are collected. The Raman signal from the first monolayer LB film of PPP has a larger contribution to the Raman enhancement than that from subsequent monolayers. Meanwhile, the Raman enhancement is dependent on the molecular configuration in contact with graphene, in which the functional group of PPP in direct contact with graphene has a stronger enhancement than other groups. These results reveal that GERS is strongly dependent on the distance between graphene and the molecule, which is convincing evidence that the Raman enhancement effect based on graphene belongs to the chemical‐enhanced mechanism. This discovery provides a convenient system for the study of the chemical‐enhanced mechanism and will benefit further understanding of SERS.  相似文献   

20.
Here we discuss the use in solar cells of graphene grown by chemical vapor deposition (CVD) and of plasmonic gold nanoparticles (Au NPs) deposited by sputtering. The Au NPs have been coupled with a-Si heterojunction solar cells, with an organic active layer used in organic photovoltaics, and with graphene. Extensive characterization of those three systems by the optical technique of spectroscopic ellipsometry, which is suitable to monitor and analyze the plasmon resonance of the Au NPs, by the microstructural technique of Raman spectroscopy, which is suitable to analyze graphene properties and doping, and by atomic force microscopy has been carried out. Those techniques highlighted interactions between Au NPs and silicon, polymer and graphene, which lead to variation in the plasmon resonance of Au NPs and consequently in the characteristics of the Au NPs/Si, Au NPs/polymer and Au NPs/graphene hybrids. Specifically, we found that an optimal size and density of Au NPs are able to enhance the efficiency of c-Si/a-Si heterojunction solar cells and that exceeding with Au NPs size and density causes device shortcut because of interface interdiffusion between silicon and gold. To discuss organic photovoltaics, Au NPs have been combined with an electro-donating conjugated polymer, the poly[1,4bis(2-thienyl)-2,5-bis-(2-ethyl-hexyloxyphenylenes)]. We found that there is a strong correlation between the thickness and morphology of the organic active layer, which affects the energy and amplitude of the Au NPs plasmon resonance. Finally, Au NPs have been deposited on graphene. We found that Au NPs show the plasmon resonance in the region where graphene is transparent and also yield p-type doping of graphene decreasing its sheet resistance.  相似文献   

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