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1.
The assembly of plasmonic metal nanoparticles into hot spot surface‐enhanced Raman scattering (SERS) nanocluster probes is a powerful, yet challenging approach for ultrasensitive biosensing. Scaffolding strategies based on self‐complementary peptides and proteins are of increasing interest for these assemblies, but the electronic and the photonic properties of such hybrid nanoclusters remain difficult to predict and optimize. Here, split‐green fluorescence protein (sGFP) fragments are used as molecular glue and the GFP chromophore is used as a Raman reporter to assemble a variety of gold nanoparticle (AuNP) clusters and explore their plasmonic properties by numerical modeling. It is shown that GFP seeding of plasmonic nanogaps in AuNP/GFP hybrid nanoclusters increases near‐field dipolar couplings between AuNPs and provides SERS enhancement factors above 108. Among the different nanoclusters studied, AuNP/GFP chains allow near‐infrared SERS detection of the GFP chromophore imidazolinone/exocyclic C?C vibrational mode with theoretical enhancement factors of 108–109. For larger AuNP/GFP assemblies, the presence of non‐GFP seeded nanogaps between tightly packed nanoparticles reduces near‐field enhancements at Raman active hot spots, indicating that excessive clustering can decrease SERS amplifications. This study provides rationales to optimize the controlled assembly of hot spot SERS nanoprobes for remote biosensing using Raman reporters that act as molecular glue between plasmonic nanoparticles.  相似文献   

2.
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   

3.
Directed assemblies of anisotropic metal nanoparticles exhibit attractive physical and chemical properties. However, an effective methodology to prepare differently directed assemblies from the same anisotropic nanoparticles is not yet available. Gold nanorods (AuNRs) region‐selectively modified with different DNA strands can form side‐by‐side (SBS) and end‐to‐end (ETE) assemblies in a non‐crosslinking manner. When the complementary DNA is hybridized to the surface‐bound DNA, stacking interaction between the blunt ends takes place in the designated regions. Such AuNRs assemble into highly ordered structures, assisted by capillary forces emerging on the substrate surface. Moreover, insertion of a mercury(II)‐mediated thymine–thymine base pair into the periphery of the DNA layer allows selective formation of the SBS or ETE assemblies from the strictly identical AuNRs with or without mercury(II).  相似文献   

4.
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   

5.
Semiconducting single‐walled carbon nanotubes (swCNTs) are a promising class of materials for emerging applications. In particular, they are demonstrated to possess excellent biosensing capabilities, and are poised to address existing challenges in sensor reliability, sensitivity, and selectivity. This work focuses on swCNT field‐effect transistors (FETs) employing rubbery double‐layer capacitive dielectric poly(vinylidene fluoride‐co‐hexafluoropropylene). These devices exhibit small device‐to‐device variation as well as high current output at low voltages (<0.5 V), making them compatible with most physiological liquids. Using this platform, the swCNT devices are directly exposed to aqueous solutions containing different solutes to characterize their effects on FET current–voltage (FET IV) characteristics. Clear deviation from ideal characteristics is observed when swCNTs are directly contacted by water. Such changes are attributed to strong interactions between water molecules and sp2‐hybridized carbon structures. Selective response to Hg2+ is discussed along with reversible pH effect using two distinct device geometries. Additionally, the influence of aqueous ammonium/ammonia in direct contact with the swCNTs is investigated. Understanding the FET IV characteristics of low‐voltage swCNT FETs may provide insights for future development of stable, reliable, and selective biosensor systems.  相似文献   

6.
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   

7.
Low‐bandgap diketopyrrolopyrrole (DPP)‐based polymers are used for the selective dispersion of semiconducting single‐walled carbon nanotubes (s‐SWCNTs). Through rational molecular design to tune the polymer–SWCNT interactions, highly selective dispersions of s‐SWCNTs with diameters mainly around 1.5 nm are achieved. The influences of the polymer alkyl side‐chain substitution (i.e., branched vs linear side chains) on the dispersing yield and selectivity of s‐SWCNTs are investigated. Introducing linear alkyl side chains allows increased polymer–SWCNT interactions through close π–π stacking and improved C–H–π interactions. This work demonstrates that polymer side‐chain engineering is an effective method to modulate the polymer–SWCNT interactions and thereby affecting both critical parameters in dispersing yield and selectivity. Using these sorted s‐SWCNTs, high‐performance SWCNT network thin‐film transistors are fabricated. The solution‐deposited s‐SWCNT transistors yield simultaneously high mobilities of 41.2 cm2 V?1 s?1 and high on/off ratios of greater than 104. In summary, low‐bandgap DPP donor–acceptor polymers are a promising class of polymers for selective dispersion of large‐diameter s‐SWCNTs.  相似文献   

8.
A novel droplet‐based surface‐enhanced Raman scattering (SERS) sensor for high‐throughput real‐time SERS monitoring is presented. The developed sensors are based on a droplet‐guiding‐track‐engraved superhydrophobic substrate covered with hierarchical SERS‐active Ag dendrites. The droplet‐guiding track with a droplet stopper is designed to manipulate the movement of a droplet on the superhydrophobic substrate. The superhydrophobic Ag dendritic substrates are fabricated through a galvanic displacement reaction and subsequent self‐assembled monolayer coating. The optimal galvanic reaction time to fabricate a SERS‐active Ag dendritic substrate for effective SERS detection is determined, with the optimized substrate exhibiting an enhancement factor of 6.3 × 105. The height of the droplet stopper is optimized to control droplet motion, including moving and stopping. Based on the manipulation of individual droplets, the optimized droplet‐based real‐time SERS sensor shows high resistance to surface contaminants, and droplets containing rhodamine 6G, Nile blue A, and malachite green are successively controlled and detected without spectral interference. This noble droplet‐based SERS sensor reduces sample preparation time to a few seconds and increased detection rate to 0.5 µ L s?1 through the simple operation mechanism of the sensor. Accordingly, our sensor enables high‐throughput real‐time molecular detection of various target analytes for real‐time chemical and biological monitoring.  相似文献   

9.
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   

10.
The measurement of ultralow concentrations of heavy metal ions (HMIs) in blood is challenging. A new strategy for the determination of mercury ions (Hg2+) based on an oriented ZnO nanobelt (ZnO‐NB) film solution‐gated field‐effect transistor (FET) chip is adopted. The FET chips are fabricated with ZnO‐NB film channels with different orientations utilizing the Langmuir–Blodgett (L–B) assembly technique. The combined simulation and IV behavior results show that the nanodevice with ZnO‐NBs parallel to the channel has exceptional performance. The sensing capability of the oriented ZnO‐NB film FET chips corresponds to an ultralow minimum detectable level (MDL) of 100 × 10?12 m in deionized water due to the change in the electrical double layer (EDL) arising from the synergism of the field‐induced effect and the specific binding of Hg2+ to the thiol groups (‐SH) on the film surface. Moreover, the prepared FET chips present excellent selectivity toward Hg2+, excellent repeatability, and a rapid response time (less than 1 s) for various Hg2+ concentrations. The sensing performance corresponds to a low MDL of 10 × 10?9 m in real samples of a drop of blood.  相似文献   

11.
The instability of few‐layer black phosphorus (FL‐BP) hampers its further applications. Here, it can be demonstrated that the instability of FL‐BP can also be the advantage for application in biosensor. First, gold nanoparticle/FL‐BP (BP‐Au) hybrid is facilely synthesized by mixing Au precursor with FL‐BP. BP‐Au shows outstanding catalytic activity (K = 1120 s?1 g?1) and low activation energy (17.53 kJ mol?1) for reducing 4‐nitrophenol, which is attributed to the electron‐reservoir and electron‐donor properties of FL‐BP, and synergistic interaction of Au nanoparticles and FL‐BP. Oxidation of FL‐BP after catalytic reaction is further confirmed by transmission electron microscope, X‐ray photoelectron spectroscopy, and zeta potentials. Second, the catalytic activity of BP‐Au can be reversibly switched from “inactive” to “active” upon treatment with antibody and antigen in solution, thus providing a versatile platform for label‐free colorimetric detection of biomarkers. The sensor shows a wide detection range (1 pg mL?1 to –10 µg mL?1), high sensitivity (0.20 pg mL?1), and selectivity for detecting carcinoembryonic antigen (CEA). Finally, the biosensor has been used to detect CEA in colon and breast cancer clinical samples with satisfactory results. Therefore, the instability of BP can also be the advantage for application in detecting cancer biomarker in clinic.  相似文献   

12.
Methods for the continuous monitoring and removal of ultra‐trace levels of toxic inorganic species (e.g., mercury, copper, and cadmium ions) from aqueous media such as drinking water and biological fluids are essential. In this paper, the design and engineering of a simple, pH‐dependent, micro‐object optical sensor is described based on mesoporous aluminosilica pellets with an adsorbed dressing receptor (a porphyrinic chelating ligand). This tailor‐made optical sensor permits ultra‐fast (≤ 60 s), specific, pH‐dependent visualization and removal of Cu2+, Cd2+, and Hg2+ at sub‐picomolar concentrations (~10?11 mol dm?3) from aqueous media, including drinking water and a suspension of red blood cells. The acidic active acid sites of the pellets consist of heteroatoms arranged around uniformly shaped pores in 3D nanoscale gyroidal mesostructures densely coated with the chelating ligand. The sensor can be used in batch mode, as well as in a flow‐through system in which sampling, target ion recognition and removal, and analysis are integrated in a highly automated and efficient manner. Because the pellets exhibit long‐term stability, reproducibility, and versatility over a number of analysis/regeneration cycles, they can be expected to be useful for the fabrication of inexpensive sensor devices for naked‐eye detection of toxic pollutants.  相似文献   

13.
The small size and low DNA amount of bacterial cells have hindered establishing phenome–genome links in a precisely indexed, one‐cell‐per‐reaction manner. Here, Raman‐Activated Gravity‐driven single‐cell Encapsulation and Sequencing (RAGE‐Seq) is presented, where individual cells are phenotypically screened via single‐cell Raman spectra (SCRS) in an aquatic, vitality‐preserving environment, then the cell with targeted SCRS is precisely packaged in a picoliter microdroplet and readily exported in a precisely indexed, “one‐cell‐one‐tube” manner. Such integration of microdroplet encapsulation to Raman‐activated sorting ensures high‐coverage one‐cell genome sequencing or cultivation that is directly linked to metabolic phenotype. For clinical Escherichia coli isolates, genome assemblies derived from precisely one cell via RAGE‐Seq consistently reach >95% coverage. Moreover, directly from a urine sample of urogenital tract infection, metabolic‐activity‐based antimicrobial susceptibility phenotypes and genome sequence of 99.5% coverage are obtained simultaneously from precisely one cell. This single‐cell global mutation map corroborates resistance phenotype and genotype, and unveils epidemiological features with high specificity and sensitivity. The ability to profile and correlate bacterial metabolic phenome and high‐quality genome sequences at one‐cell resolution suggests broad application of RAGE‐Seq.  相似文献   

14.
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   

15.
A novel fluorescence turn‐on strategy, based on the resistance of metal‐mediated molecular‐beacons (MBs) toward nuclease digestion and the remarkable difference in the affinity of graphene oxide (GO) with MBs and the mononucleotides, is designed for the biothiols assay. Specifically, the metal‐mediated base pairs facilitate the dye labeled MBs to fold into a hairpin structure preventing the digestion by exonuclease I, and thus allow the fluorescence quenching. The competition binding by biothiols removes metal ions from the base pairs, causing the nuclease reaction, and less decrease in the fluorescence is obtained after incubating with GO due to the weak affinity of the product‐mononucleotides to GO. Hg2+‐mediated MBs were firstly designed for the biothiols detection, and glutathione (GSH) was applied as the model target. Under the optimal conditions, the approach exhibits high sensitivity to GSH with a detection limit of 1.53 nM. Ag+‐mediated MBs based sensor was also constructed to demonstrate its versatility, and cysteine was studied as the model target. The satisfactory results in the determination of biothiols in serum demonstrate that the method possesses great potential for detecting thiols in biological fluids. This new approach is expected to promote the exploitation of metal‐mediated base pairs‐based biosensors in biochemical and biomedical studies.  相似文献   

16.
A novel surface‐enhanced Raman scattering (SERS) sensor is developed for real‐time and highly repeatable detection of trace chemical and biological indicators. The sensor consists of a polydimethylsiloxane (PDMS) microchannel cap and a nanopillar forest‐based open SERS‐active substrate. The nanopillar forests are fabricated based on a new oxygen‐plasma‐stripping‐of‐photoresist technique. The enhancement factor (EF) of the SERS‐active substrate reaches 6.06 × 106, and the EF of the SERS sensor is about 4 times lower due to the influence of the PDMS cap. However, the sensor shows much higher measurement repeatability than the open substrate, and it reduces the sample preparation time from several hours to a few minutes, which makes the device more reliable and facile for trace chemical and biological analysis.  相似文献   

17.
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   

18.
A method is developed to synthesize surface‐enhanced Raman scattering (SERS) materials capable of single‐molecule detection, integrated with a microfluidic system. Using a focused laser, silver nanoparticle aggregates as SERS monitors are fabricated in a microfluidic channel through photochemical reduction. After washing out the monitor, the aggregates are irradiated again by the same laser. This key step leads to full reduction of the residual reactants, which generates numerous small silver nanoparticles on the former nanoaggregates. Consequently, the enhancement ability of the SERS monitor is greatly boosted due to the emergence of new “hot spots.” At the same time, the influence of the notorious “memory effect” in microfluidics is substantially suppressed due to the depletion of surface residues. Taking these advantages, two‐step photoreduced SERS materials are able to detect different types of molecules with the concentration down to 10?13m . Based on a well‐accepted bianalyte approach, it is proved that the detection limit reaches the single‐molecule level. From a practical point of view, the detection reproducibility at different probing concentrations is also investigated. It is found that the effective single‐molecule SERS measurements can be raised up to ≈50%. This microfluidic SERS with high reproducibility and ultrasensitivity will find promising applications in on‐chip single‐molecule spectroscopy.  相似文献   

19.
Herein, a versatile and sensitive colorimetric sensor for Hg2+ based on aptamer–target specific binding and target‐mediated growth of AuNPs is reported. The 15 T bases are first designed to detect Hg2+ through T–Hg2+–T coordination. Aptamer–target binding results in the desorption of the aptamer from AuNP surface, the remaining aptamers adsorbed on AuNP surface trigger the growth of AuNPs with morphologically varied nanostructures, and then different colored solutions are formed. On this occasion, the limit of detection (LOD) of 9.6 × 10?9m is obtained. The other two aptamer strands (25‐ and 59‐mer) are designed by increasing A bases on either side and both sides of 15 T, respectively. The interaction of the binding domain and Hg2+ makes desorption of 15 T from AuNP surface, whereas excess bases not committed to the binding domain still adsorbed on AuNP surface. These excess bases control the growth of AuNPs, and enhance the sensitivity. The LODs are 4.05 and 3 × 10?9m for 25‐ and 59‐mer aptamers, respectively. In addition, the 59‐mer aptamer system is applied to identify Hg2+ in real river samples, the LOD of 6.2 × 10?9m is obtained.  相似文献   

20.
Single‐atom catalysts (SACs) have attracted extensive attention in the catalysis field because of their remarkable catalytic activity, gratifying stability, excellent selectivity, and 100% atom utilization. With atomically dispersed metal active sites, Fe‐N‐C SACs can mimic oxidase by activating O2 into reactive oxygen species, O2?? radicals. Taking advantages of this property, single‐atom nanozymes (SAzymes) can become a great impetus to develop novel biosensors. Herein, the performance of Fe‐N‐C SACs as oxidase‐like nanozymes is explored. Besides, the Fe‐N‐C SAzymes are applied in biosensor areas to evaluate the activity of acetylcholinesterase based on the inhibition toward nanozyme activity by thiols. Moreover, this SAzymes‐based biosensor is further used for monitoring the amounts of organophosphorus compounds.  相似文献   

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