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SERS
Surfaces and Interfaces · 2024 · IF 5.7

Ag nanopines over Al nanoneedle arrays enable high SERS sensitivity and reproducibility for molecular sensing

Ningning Zhou,Huihui Zheng,Mengen Hu,Rui Liu,Guangchao Qin,Yilin Lu,Haibin Tang,Zhulin Huang

In this study, highly uniform 3D Al nanoneedle arrays (AlNNAs) decorated with Ag nanopines are synthesized by anodization of Al foil with prior nanoimprinting and subsequent electrodeposition method, demonstrating remarkable surface-enhanced Raman scattering (SERS) property. The AlNNAs possess a highly ordered periodicity of 1 μm and nanoneedle height of 800 nm, making it an optimal supporting matrix to host Ag-NPs as SERS substrate. Such well-ordered Ag@AlNNAs SERS substrate with precisely electrodeposited Ag nanopines generate high density SERS host spots and abundant sites to adsorb target molecules. As a result, Ag@AlNNAs exhibit high sensitivity for rhodamine 6 G down to 10 –13 M and good signal reproducibility with a relative standard deviation of 7.2 %, as well as an average enhancement factor of 4.23 × 10 9 . For practical detection of pollutants, 10 –8 M adenine , 10 –12 M bisphenol in water, and melamine (10 –7 M) in opaque milk are clearly identified by using the Ag@AlNNAs sensor. This study opens a bright way to fabricate SERS substrate with a good balance of sensitivity, reproducibility and cost, indicating promising potential for environmental monitoring and food safety.

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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2025 · IF 9.7

A local shrinkage approach for creating dynamic hot-spots on thermoresponsive nanocellulose-based SERS substrate

Wen Deng,Xingyue Liu,Yuzhou Yang,Liucheng Meng,Yanling Lou,Peng Li,Lei Zhang,Weibing Wu

Surface-enhanced Raman scattering (SERS) is a highly sensitive technology to detect target analytes. The construction of dynamic “hot-spots” represents a significant approach to enhancing detection sensitivity. Herein, a hybrid plasma platform with dynamic “hot-spots” was developed for SERS recognition based on the assembly of gold nanospheres (AuNSs) on temperature-sensitive bacterial cellulose (BC) film grafted with poly( N -isopropylacrylamide) (PNIPAM). The dynamic “hot-spots” structure was regulated in-situ by local conformational contraction of the grafted thermoresponsive PNIPAM around the BC backbone without changing the overall morphology of the substrate. Moreover, the heating process was simplified by utilizing the plasma photothermal effect of AuNSs to regulate the “hot-spot” structure. The dynamic regulation measured value of the Raman signal of Rhodamine 6G (R6G) was increased by 6.5-times, and the SERS substrate exhibited extremely high sensitivity with a limit of detection (LOD) of 8.47 × 10 −9 g/L and a relative standard deviation (RSD) of 9.24 %. Meanwhile, it can accurately detect the pesticide residues of thiram on apple peel with the detection limit of 6.54 × 10 −11 g/L. This dynamic “hot-spot” modulation strategy via local structural regulation has significant potential to improve the convenience, flexibility, and sensitivity of on-site SERS detection.

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Analytical Methods · 2025 · IF 2.6

An Ag-nanoplate decorated cavity-nanorod array SERS substrate for trace detection of PCB-77

Jinran Chen,Xiurui Ke,Zhou Zhou,Wenqi Ye,Hong Liu,Wei Zhang,Xiaohong Liu

We report the fabrication of a substrate with cavity-nanorods and decorated with Ag-nanoplates (C-NR@Ag). The cavities on the substrate are formed by metal assistant chemical etching, and the Ag-nanoplates in the cavities by galvanic cell deposition enhance the SERS performance effectively. Analytes in solution are adsorbed on Ag-nanoplates and located in hot spots, which enhance the SERS performance effectively. The enhancement factor of the Ag-nanoplates decorated on nanorod cavities is calculated to be 3.6 × 106, which is about 3 fold higher than that on the nanorods. The C-NR@Ag substrate is able to detect polychlorinated biphenyls (PCBs) with the lower limit of detection at 1.0 × 10−12 M. Additionally, due to the semi-volatile nature of PCB-77, the lower limit of detection of the C-NR@Ag substrate for PCB-77 was 1.0 × 10−11 M by the non-contact collection method. These results present a novel approach towards enhancing SERS performance and facilitating the rapid detection of PCB-77.

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ANALYTICA CHIMICA ACTA · 2024 · IF 5.7

An in-situ method for SERS substrate preparation and optimization based on galvanic replacement reaction

Xing Zhong,Peng Liu,Jiaxing Wen,Yongfu Qiu,Min Zhang,Dong Xie,Shoushan Wang,Shilei Xie,Faliang Cheng

Background Various surface-enhanced Raman spectroscopy (SERS) substrate preparation methods have been reported, however, how to tune the “gap” between nanostructures to make more “hot spots” is still a barrier that restricts their application. The gap between nanostructures is usually fixed when the substrates are prepared. In other words, it is hard to tune interparticle distances for maximum electromagnetic coupling during substrate preparation process. Therefore, an in-situ substrate optimization method that could monitor the SERS signal intensity changes, i.e., to find the optimum gap width and particle size, during substrate preparation process is needed. Results A method based on the galvanic replacement reaction (GRR) is proposed for the in-situ gap width tuning between nanostructures as well as for the optimization of SERS substrates. Noble metal nanoparticles (NPs) form and grow on the sacrificial templates' surface while noble metal ions are reduced by sacrificial metal (oxides) in GRR. Along with the fresh and clean NPs’ surface generated, the gap between two noble metal NPs decreases with the growth of the NPs . To demonstrate this strategy, cuprous oxide/Ti (Cu 2 O/Ti) sacrificial templates were prepared, and then a GRR was carried out with HAuCl 4 . The real-time SERS detection during GRR show that the optimum reaction time (ORT) is 300 ± 30 s. Furthermore, SERS performance testing was conducted on the optimized substrate, revealing that the detection limit for crystal violet can reach 1.96 × 10 −11  M, confirming the feasibility of this method. Significance and novelty By monitoring the in-situ SERS signal of probes during GRR will obtain an “optimal state” of the SERS substrate with optimal gap width and particle size. The SERS substrate preparation and optimization strategy proposed in this article not only provides a simple, efficient, and low-cost method to fabricate surface-clean noble NPs but also paves the way for the in-situ optimization of NPs size and gap width between NPs which could achieve wider applications of SERS.

CAS / MDL: 548-62-9
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Nanoscale · 2015 ·Vol. 7 ·期 48 ·20414-20425 · IF 7.394

The alloying effect and AgCl-directing growth for synthesizing a trimetallic nanoring with improved SERS

Shuhua Han,Guangju Zhou,Yunzhi Fu,Ying Ma,Li Xu,Chao Zou,Wei Chen,Yun Yang,Shaoming Huang

We report the synthesis of high quality trimetallic Au/Ag/Pt nanorings (TAAPNs) by using Au/Ag alloy decahedra (AAAD) as templates. The alloying effect and AgCl-directing growth have been investigated in detail during the formation of TAAPN. It was found that the doping of Ag in AAAD changes the surrounding environment of Au atoms and decreases the oxidization reduction potential (ORP) of [AuCl2]−/Au because of the alloying effect, resulting in the dissolved O2 molecules that serve as an effective etchant for oxidizing Au to Au(I). Ascorbic acid (AA) and chloroplatinic acid (H2PtCl6) are weak acids which can accelerate the etching by increasing the concentration of H+. The AgCl selectively absorbs on {100} of the decahedra and induces the preferential deposition of H2PtCl6 here via their complexing interaction. AA reduces Pt(IV) and Ag(I) to atoms which grow on {100} facets. The formed Pt/Ag layer changes the etching direction from along [100] to [111] and generates the TAAPN. Besides, it has been noted that the TAAPNs exhibit good Surface Enhanced Raman Scattering (SERS) performance.

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APPLIED SURFACE SCIENCE · 2015 · IF 2.711

Quaternized chitosan/silver nanoparticles composite as a SERS substrate for detecting tricyclazole and Sudan I

Kaihang Chen,Zuguang Shen,Jiwen Luo,Xiaoying Wang,Runcang Sun

There is an urgent need to develop a highly sensitive detection system for detecting trace amounts of food contaminants. In this study, optimal synthesis of silver nanoparticles (Ag NPs) with stable and narrow size distribution in the range of 15–25   nm was performed under microwave irradiation, using quaternized chitosan (QCS) as reducing and stabilizing agent. The results showed that the ratio of QCS to [Ag(NH 3 ) 2 ] + , reaction temperature, irradiation time, the degree of substitution ( DS ) and molecular weight ( Mw ) of QCS had obvious effects on the formation, particle size and size distribution of Ag NPs. In addition, utilizing QCS/Ag NPs composite as SERS substrate, tricyclazole and Sudan I could be rapidly and sensitively detected with the limit of detection (LOD) as low as 50   ppb and 10   ppm, respectively. Compared with previously reported works, our detection system are of great stability and operability. The QCS was coated on the surface of Ag core, avoiding aggregation of Ag NPs and creating hot spots, in turn, providing superior amplification of SERS. Thus, it is believed that the QCS/Ag NPs composite could be considered as an ideal SERS-active substrate for detection of food contaminants.

CAS / MDL: 842-07-9
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ACS Applied Materials & Interfaces · 2016 · IF 7.145

Highly Reproducible Ag NPs/CNT-Intercalated GO Membranes for Enrichment and SERS Detection of Antibiotics

Lu−Lu Qu,Ying-Ya Liu,Ming-Kai Liu,Guo-Hai Yang,Da-Wei Li,Hai-Tao Li

The increasing pollution of aquatic environments by antibiotics makes it necessary to develop efficient enrichment and sensitive detection methods for environmental antibiotics monitoring. In this work, silver nanoparticles and carbon nanotube-intercalated graphene oxide laminar membranes (Ag NPs/CNT-GO membranes) were successfully prepared for enrichment and surface-enhanced Raman scattering (SERS) detection of antibiotics. The prepared Ag NPs/CNT-GO membranes exhibited a high enrichment ability because of the π–π stacking and electrostatic interactions of GO toward antibiotic molecules, which enhanced the sensitivity of SERS measurements and enabled the antibiotics to be determined at sub-nM concentrations. In addition, the nanochannels created by the intercalation of CNTs into GO layers resulted in an 8-fold enhancement in the water permeance of Ag NPs/CNT-GO membranes compared to that of pure GO membranes. More importantly, the Ag NPs/CNT-GO membranes exhibited high reproducibility and long-term stability. The spot-to-spot variation in SERS intensity was less than 15%, and the SERS performance was maintained for at least 70 days. The Ag NPs/CNT-GO membranes were also used for SERS detection of antibiotics in real samples; the results showed that the characteristic peaks of antibiotics were obviously recognizable. Thus, the sensitive SERS detection of antibiotics based on Ag NPs/CNT-GO offers great potential for practical applications in environmental analysis.

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RSC Advances · 2016 ·Vol. 6 ·期 114 ·113115-113122 · IF 3.289

Design and preparation of a recyclable microfluidic SERS chip with integrated Au@Ag/TiO2 NTs

Chunyan Wang,Yi Xu,Conghui Deng,Zhixu Liu,Rong Wang,Huazhou Zhao

In the present paper, we report on the design and fabrication of a recyclable microfluidic SERS chip with an integrated Au@Ag/TiO2 NTs (gold core silver shell nanoparticles (NPs) with decorated TiO2 nanotube arrays (NTs)) composite SERS substrate. The stripped TiO2 NTs with regularly arranged pore structures were prepared on a Ti foil by easy tape lithography followed by anodic oxidation. The Au@Ag NPs were fabricated on the mouth surface and the inner walls of the TiO2 NTs within a microchannel without clogging via a facile self-assembly chemical plating composite method. Under optimized conditions, the microfluidic SERS chip provided excellent sensitivity to R6G molecules with a detection limit of 10−10 M and a SERS enhancement factor (EF) of 1.15 × 108. Versus single Au NPs, Au@Ag NPs and the Au@Ag/TiO2 plate, the optimized Au@Ag/TiO2 NTs showed improved SERS peak intensities for the C–C–C bending (613 cm−1) of 20, 2.3 and 1.6 times enhancement, respectively. The enhancement effect was attributed to both electromagnetic and chemical enhancement. The photocatalytic performance of the Au@Ag/TiO2 NTs was exploited to recycle the microfluidic SERS chip through UV light photocatalytic purification. The experimental result shows that the microfluidic SERS chip featured high reproducibility and could be used as an efficient SERS detector for many biochemical molecules.

CAS / MDL: 7761-88-8
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ANALYTICAL CHEMISTRY · 2017 · IF 6.32

Environmentally Safe Mercury(II) Ions Aided Zero-Background and Ultrasensitive SERS Detection of Dipicolinic Acid

Xiang-Ru Bai,Yi Zeng,Xiao-Dong Zhou,Xiao-Hua Wang,Ai-Guo Shen,Ji-Ming Hu

Field, reliable, and ultrasensitive detection of dipicolinic acid (DPA), a general biomarker of bacterial spores and especially Bacillus anthracis, is highly desirable but still challenging in current biometric security emergency response system. Herein we report an environmentally safe mercury(II) ions-mediated and competitive coordination interaction based approach for rationally designed surface-enhanced Raman scattering (SERS)-active gold nanoparticles (AuNPs), enabling rapid, ultrasensitive and zero-background detection of DPA without the pretreatment of samples. By means of competitiveness, these papain-capped gold nanoparticles (P-AuNPs) are induced to undergo controllable aggregation upon the addition of Hg2+ ions and DPA with a concentration range (1 nM∼8 μM), which correspondingly cause quantitative changes of SERS intensity of cresyl violet acetate (CVa) conjugated AuNPs. The decreased Raman intensity obtained by subtracting two cases of additives that contain only Hg2+ and the mixture of Hg2+ and DPA is proportional to the concentration of DPA over a range of 1 nM∼8 μM (R2 = 0.9824), with by far the lowest limit of detection (LOD) of 67.25 pM (0.01 ppb, S/N = 3:1). Of particular significance, mercury(II) ions actually play two roles in the process of measurements: a mediator for two designed competitive ligands (DPA and papain), and also a scavenger for the possibly blended ligands due to the different interaction time between DPA and the interferent with Hg2+ ions, which guarantees the interference-free detection of DPA even under real conditions.

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ANALYTICAL CHEMISTRY · 2015 · IF 5.636

Portable SERS-enabled Micropipettes for Microarea Sampling and Reliably Quantitative Detection of Surface Organic Residues

Wei Fang,Xinwei Zhang,Yong Chen,Liang Wan,Weihua Huang,Aiguo Shen,Jiming Hu

We report the first microsampling device for reliably quantitative, label-free and separation-free detection of multicomponents of surface organic residues (SORs) by means of a quality controllable surface-enhanced Raman scattering (SERS)-enabled micropipette. The micropipette is comprised of a drawn glass capillary with a tiny orifice (∼50 μm) at the distal tip, where the specially designed nanorattles (NRs) are compactly coated on the inner wall surface. SERS signals of 4-mercapto benzoic acid (MBA) anchored inside the internal gap of NRs could be used to evaluate and control the quality of micropipettes and, therefore, allow us to overcome the limitations of a reliably quantitative SERS assay using traditional substrates without an internal standard. By dropping a trace extraction agent on targeting SORs located on a narrow surface, the capillary and SERS functionalities of these micropipettes allow on-site microsampling via capillary action and subsequent multiplex distinction/detection due to their molecularly narrow Raman peaks. For example, 8 nM thiram (TMTD), 8 nM malachite green (MG), and 1.5 μM (400 ppb) methyl parathion (MPT) on pepper and cucumber peels have been simultaneously detected in a wide detection range. The portable SERS-enabled device could potentially be facilely incorporated with liquid–liquid or solid phase micro-extracting devices for a broader range of applications in rapid and field analysis of food/public/environment security related SORs.

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SENSORS AND ACTUATORS B-CHEMICAL · 2014 · IF 3.84

Shaped-controlled electrosynthesis of gold nanodendrites for highly selective and sensitive SERS detection of formaldehyde

Zhang-Ying Lv,Li-Ping Mei,Wan-Yi Chen,Jiu-Ju Feng,Jin-Yu Chen,Ai-Jun Wang

In this work, well-defined gold nanodendrites were simply synthesized by one-step electrodeposition by applying a constant potential of −0.2   V for 900   s in 0.5   mol/L H 2 SO 4 containing 7.5   ×   10 −3   mol/L HAuCl 4 and 0.15   mol/L l -asparagine, which were preferentially growing along the (1   1   1) directions. It was found that the morphology of the Au deposits was strongly dependent on the applied potential, deposition time, and the molar ratio of HAuCl 4 to l -asparagine. The as-prepared Au dendrites were used as highly Raman-active substrates for highly selective and sensitive detection of formaldehyde based on its reaction with 4-amino-3-hydrazino-5-mercapto-1, 2, 4-triazol (AHMT). The formaldehyde sensor displayed a wide linear range from 8.32   ×   10 −8   mol/L to 9.975   ×   10 −7   mol/L, along with a low detection limit of 7.2   ×   10 −9   mol/L ( S / N   =   3). The as-developed method was successfully used to detect trace amounts of formaldehyde in indoor air.

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ANALYST · 2013 ·Vol. 138 ·期 12 ·3450-3456 · IF 3.969

Simultaneous evaluation of p53 and p21 expression level for early cancer diagnosis using SERS technique

Lei Wu,Zhuyuan Wang,Shenfei Zong,Hui Chen,Chunlei Wang,Shuhong Xu,Yiping Cui

Simultaneous detection of tumor suppressor p53 and cyclin-dependent kinase inhibitor p21 has been achieved for the first time with a high sensitivity using surface enhanced Raman scattering (SERS) technique. In this immunoassay, gold@silver core–shell nanorods (Au@Ag NRs) with a high SERS activity and chemical stability were chosen to fabricate immuno-probes, which were conjugated with different antibodies to specifically target each analyte. Qualitative and quantitative analysis of p53 and p21 were achieved by characterizing SERS signals of two different Raman reporters (4MBA and DTNB), which were labeled on the corresponding optical probes. In addition, we investigated the detection of these biomarkers in the medium of blood serum. Our experimental results indicate the excellent specificity, high sensitivity (1 pg mL−1), as well as the great reproducibility of this immunoassay. More importantly, this assay presents a powerful ability to detect multiple analytes due to the great multiplexing capacity of SERS spectroscopy. Since the combined evaluation of p53 and p21 expression level acts as an indicator for early cancer prediction, our demonstrated immunoassay will potentially promote the application of SERS technique to practical clinical diagnoses.

CAS / MDL: 56-87-1
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