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ACS Applied Nano Materials · 2023 · IF 5.9

Ag Nanoparticle/Au@Ag Nanorod Sandwich Structures for SERS-Based Detection of Perfluoroalkyl Substances

Yating Feng,Jiaxue Dai,Chuyun Wang,Hongyang Zhou,Jianhua Li,Gang Ni,Maofeng Zhang,Youju Huang

Perfluoro- and polyfluoroalkyl substances (PFAS) are widely used throughout the world and are extensively found in the environment. The detection of PFAS has become essential to ensuring environmental sustainability and human health. Herein, AuNRs were synthesized by the seed growth method and then the samples were coated with silver shells to form Au@Ag core–shell nanorods (Au@AgNRs). Au@AgNRs monolayer was prepared by oil–water self-assembly on a silicon wafer and then was constructed as a plasmonic AgNPs/Au@AgNRs sandwich structure for surface-enhanced Raman scattering (SERS) detection of PFAS. The shell thickness of Au@AgNRs was optimized and displayed a 11.9-fold SERS intensity higher than the pristine AuNRs. Moreover, the hotspots generated by the electromagnetic field coupling between the interlayer gap achieved 3.6-fold SERS signal enhancement compared to that of the Au@AgNRs monolayer. Besides, the excellent structural uniformity (RSD ∼ 8.0%) makes it ideal for quantitative SERS detection applications. More importantly, the use of the AgNPs/Au@AgNRs sandwich structure sensor enables the highly sensitive detection of model molecules (10–11 M) and quantitative detection of a wide range of fluorinated alkyl substances of perfluorooctanoic acid (PFOA), perfluorohexanoic acid (PFHxA), and potassium perfluorobutanesulfonate (PPFBS), even with a portable Raman device. And the detection concentration can be down to 0.1 ppm for PFAS. This sensitive and quantitative SERS technique has promising prospects in the monitoring of fluorinated alkyl substance contaminations.

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ANALYTICAL AND BIOANALYTICAL CHEMISTRY · 2023 · IF 4.3

Efficient interfacial self-assembled MXene/Ag NPs film nanocarriers for SERS-traceable drug delivery

Chen Yi,Jiang Cailing,Huang Feixiang,Yu Zizhen,Jiang Li

Combining the unique advantages of two-dimensional transition metal carbon/nitrogen compounds (MXene) and the excellent surface-enhanced Raman scattering (SERS) performance of noble metal materials, MXene/Ag NPs films were proposed as nanocarriers for SERS-traceable drug delivery. The films were prepared by two-step self-assembly on positively charged silicon wafers using virtue of the high evaporation of ethyl acetate, the Marangoni effect, and an oil/water/oil three-phase system. With 4-mercaptobenzoic acid (4-MBA) as the probe molecule, the SERS detection limit was 10 −8  M and had shown a good linear relationship in the range of 10 −8 –10 −3  M. Simultaneously, the film had good uniformity, repeatability, and stability. When Ti 3 C 2 T x /Ag NPs films were used as nanocarriers, the anticancer drug doxorubicin (DOX) was loaded onto the surface through 4-MBA, and the tracking and monitoring were realized by SERS. The addition of glutathione (GSH) triggered the thiol exchange reaction, resulting in the shedding of 4-MBA from the surface of the film, which indirectly achieved the efficient release of DOX. Furthermore, the loading of DOX and the drug release effect triggered by GSH maintained a certain stability in serum, which provided a potential possibility for the subsequent loading and release of drugs by films with three-dimensional structures as scaffolds in biological therapy. Graphical abstract Self-assembled MXene/Ag NPs film nanocarriers for SERS-traceable drug delivery and GSH-triggered high-efficiency drug release

CAS / MDL: 1074-36-8
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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY · 2023 · IF 4.4

SERS combined with the difference in bacterial extracellular electron transfer ability to distinguish Shewanella

Mingxia Jiang,Anxun Chen,Jinghong Chen,Hui Zeng,Weikang Zhang,Yong Yuan,Lihua Zhou

Shewanella plays an important role in geochemical cycle, biological corrosion, bioremediation and bioenergy. The development of methods for identifying Shewanella can provide technical support for its rapid screening, in-depth research into its extracellular respiratory mechanism and its application in ecological environment remediation. As a tool for microbial classification, identification and detection, Surface-enhanced Raman scattering (SERS) has high feasibility and application potential. In this work, bio-synthesized silver nanoparticles (AgNPs) were used as SERS substrates to effectively distinguish different types of Shewanella bacteria based on the difference in bacterial extracellular electron transfer (EET) ability. AgNPs were combined with the analyzed bacteria to prepare “Bacteria-AgNPs” SERS samples, which can strongly enhance the Raman signal of the target bacteria and reliably obtain spatial information of different molecular functional groups of each bacteria. Our developed approach can effectively distinguish between non-metal reducing and metal-reducing bacteria, and can further distinguish the three subspecies of Shewanella ( Shewanella oneidensis MR-1, Shewanella decolorationis S12, and Shewanella putrefaciens SP200) at the genus and species level. The Raman signal enhancement is presumably caused by the excitation of local surface plasma (LSP) and the enhancement of surrounding electric field. Therefore, our developed method can achieve interspecific and intraspecies discrimination of bacteria. The proposed method can be extended to distinguish other metal-reducing bacteria, and the novel SERS active substrates can be developed for practical applications.

CAS / MDL: 7761-88-8
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Nanoscale Advances · 2022 ·Vol. 4 ·期 22 ·4730-4738 · IF 5.598

SERS spectral evolution of azo-reactions mediated by plasmonic Au@Ag core–shell nanorods

Mengen Hu,Zhulin Huang,Rui Liu,Ningning Zhou,Haibin Tang,Guowen Meng

The mechanism and application of localized surface plasmon resonance induced photocatalytic reactions remain an issue of interest. In this work, we used Au@Ag core–shell nanorods as a platform for plasmon-driven photocatalysis, which was in situ investigated by surface-enhanced Raman scattering (SERS) spectroscopy. The para-aminothiophenol (PATP) and para-nitrothiophenol (PNTP) adsorbed on the nanorods were irradiated with different excitation wavelengths (633 nm, 785 nm) and transformed into 4,4′-dimercaptoazobenzene (DMAB) as evidenced by the emerging Raman peaks at 1142 cm−1, 1390 cm−1, 1440 cm−1, and 1477 cm−1, corresponding to hot carrier dominated oxidation of PATP and reduction of PNTP. Preliminary azo-reaction kinetics and in situ SERS measurements were conducted by comparing the relative intensity ratio of SERS peaks at 1440 cm−1 (DMAB stretching of NN) and 1080 cm−1 (C–S stretching of PATP and PNTP). These results indicate that the catalytic efficiency was dominated by the excitation wavelength as well as the resonance condition between the plasmon band of the nanorods and the excitation line. As a proof of concept, the Au@Ag core–shell nanorods were used to catalyze 4-nitrophenol molecules, and 4-hydroxyazobenzene molecules as the product were confirmed by in situ SERS spectra as well theoretical predictions, showing potential in plasmon driven catalysis and degradation of organic molecules.

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Foods · 2022 ·Vol. 11 ·期 21 ·3407 · IF 5.561

An Alkyne-Mediated SERS Aptasensor for Anti-Interference Ochratoxin A Detection in Real Samples

Hao Wang,Lu Chen,Min Li,Yongxin She,Chao Zhu,Mengmeng Yan

Avoiding interference and realizing the precise detection of mycotoxins in complex food samples is still an urgent problem for surface-enhanced Raman spectroscopy (SERS) analysis technology. Herein, a highly sensitive and specific aptasensor was developed for the anti-interference detection of Ochratoxin A (OTA). In this aptasensor, 4-[(Trimethylsilyl) ethynyl] aniline was employed as an anti-interference Raman reporter to prove a sharp Raman peak (1998 cm−1) in silent region, which could avoid the interference of food bio-molecules in 600–1800 cm−1. 4-TEAE and OTA-aptamer were assembled on Au NPs to serve as anti-interference SERS probes. Meanwhile, Fe3O4NPs, linked with complementary aptamer (cApts), were applied as capture probes. The specific binding of OTA to aptamer hindered the complementary binding of aptamer and cApt, which inhibited the binding of SERS probes and capture probes. Hence, the Raman responses at 1998 cm−1were negatively correlated with the OTA level. Under the optimum condition, the aptasensor presented a linear response for OTA detection in the range of 0.1–40 nM, with low detection limits of 30 pM. In addition, the aptasensor was successfully applied to quantify OTA in soybean, grape and milk samples. Accordingly, this anti-interference aptasensor could perform specific, sensitive and precise detection of OTA in real samples, and proved a reliable reference strategy for other small-molecules detection in food samples.Keywords:SERS;4-TEAE;aptamer;silent region;OTA;anti-interference

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JOURNAL OF FOOD COMPOSITION AND ANALYSIS · 2022 · IF 4.52

Sensitive determination of Patulin by aptamer functionalized magnetic surface enhanced Raman spectroscopy (SERS) sensor

Zhiming Guo,Lingbo Gao,Shuiquan Jiang,Hesham R. El-Seedi,Islam M. El-Garawani,Xiaobo Zou

Food pollution caused by Patulin (PAT) seriously threatens the safety of human diets and has attracted extensive attention. Early and accurate detections of PAT are essential to prevent further toxin spreading and contamination. A surface enhanced Raman scattering (SERS) aptasensor was fabricated by combining a gold-silver core-shell structure containing signal molecule (ADANRs) and chitosan modified magnetic nanoparticles (CS-Fe 3 O 4 ). The modified ADANRs with the complementary chain of the aptamer (SH-cDNA-ADANRs) which were served as the signal probes and the aptamer modified CS-Fe3O4 (NH 2 -apt-CS-Fe 3 O 4 ) were served as the capture probes. In addition to the ability to recognize the target PAT, the capture probe also showed a strong enrichment ability under the action of external magnetic force. The intraparticle plasma coupling between the inner gold core and the outer silver shell can greatly improve the SERS activity of the signal molecules. SERS aptasensor was used to collect the spectra of actual apple samples spiked with different PAT content. The minimum detection limit of SERS aptasensor for detecting PAT in actual samples was 0.0384 ng/mL and the recovery rate range was from 96.3% to 108%. In conclusion, the sensitive and specific SERS aptasensor detection of PAT based on aptamer functionalized nanoparticles exhibited great potential for practical application in mycotoxin detection and analysis.

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Biosensors-Basel · 2022 ·Vol. 12 ·期 10 ·881 · IF 5.743

Quantitative SERS Detection of TBBPA in Electronic Plastic Based on Hydrophobic Cu-Ag Chips

Pei Dai,Xianzhi Huang,Yaqian Cui,Lihua Zhu

Tetrabromobisphenol A (TBBPA) was one of the most widely used brominated flame retardants. However, it easily contaminates nature and harms the environment and human health during its production and use. Therefore, it is necessary to strictly control the content of TBBPA in electronics. Surface-enhanced Raman spectroscopy has the advantages of being fast and sensitive, but it is difficult to obtain the SERS spectra of TBBPA because the hydrophobic TBBPA molecule is difficult to approach with the hydrophilic surface of common noble metal SERS substrates. In the present work, a hydrophobic Cu-Ag chip was developed for the SERS detection of TBBPA. The integration of the hydrophobic interaction and the Ag-Br bonding promoted the adsorption of TBBPA on the Cu-Ag chip, allowing for SERS detection. It was observed that both the hydrophobicity and bimetallic composition of the Cu-Ag chip played important roles in the SERS detection of TBBPA. Under the optimized conditions, the low limit of detection of the established SERS method for TBBPA was 0.01 mg L−1, within a linear range of 0.1–10 mg L−1. Combined with ultrasonic-assisted extraction, the substrate could be used for the quantitative determination of TBBPA in electronic products. Compared with the HPLC-UV method used as a national standard, the relative error of the SERS method for quantifying the TBBPA content in a mouse cable and shell was ±3% and ±7.7%, respectively. According to the SERS results, the recovery of TBBPA in the spiked mouse shell was 95.6%.Keywords:tetrabromobisphenol A;surface-enhanced Raman scattering;hydrophobic interaction;bi-metal chips;synergistic coupling

CAS / MDL: 79-94-7
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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY · 2022 · IF 4.831

Mesoporous silica coated core-shell nanoparticles substrate for size-selective SERS detection of chloramphenicol

Heera Jayan,Da-Wen Sun,Hongbin Pu,Qingyi Wei

With the growing popularity of the non-destructive technique, surface-enhanced Raman spectroscopy (SERS) demands a highly sensitive and reproducible plasmonic nanoparticles substrate. In this study, a novel bimetallic core–shell nanoparticles (Au@Ag@mSiO 2 NP) substrate consisting of a gold core, silver shell, and a mesoporous silica coating was synthesized. The mesoporous coating structure was created by employing template molecules such as surfactant and their subsequent removal allowing selective screening based on the size of analyte molecules. Results showed that the plasmonic substrate could selectively enhance small molecules by preventing large macromolecules to reach the exciting zone of the substrate core, achieving the detection of chloramphenicol in milk samples with a detection limit of 6.68 × 10 −8 M. Moreover, the mesoporous coating provided additional stability to the Au@Ag nanoparticles, leading to the reusability of the substrate. Thus, this work offered a simple and smart Au@Ag@mSiO 2 NP substrate for effective SERS detection of analytes.

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Frontiers in Bioengineering and Biotechnology · 2022 · IF 6.064

AuNPs@MIL-101 (Cr) as a SERS-Active Substrate for Sensitive Detection of VOCs

Xie Dan,Wang Ruimeng,Fu Jinghao,Zhao Zhongxing,Li Min

Surface-enhanced Raman scattering (SERS) is an important and powerful analytical technique in chemical and biochemical analyses. Metal–organic frameworks (MOFs) can effectively capture volatile organic compounds (VOCs) with high adsorption capacity and fast kinetics, and the local surface plasmon resonance characteristics of gold nanoparticles can quickly and effectively distinguish different VOCs by SERS. Combining both, we designed a novel SERS substrate based on embedding gold nanoparticles (AuNPs) within MIL-101(Cr) for the recognition of various VOCs in the gaseous phase. Occupying of AuNPs inside MIL-101(Cr) increased the micropore-specific surface area of AuNPs@MIL-101(Cr), which enabled AuNPs@MIL-101(Cr) to absorb more toluene molecules and consequently realized its high detection sensitivity. The detection limits for toluene, 4-ethylbenzaldehyde, and formaldehyde were down to 6, 5, and 75, ppm respectively. Moreover, this substrate could be used for detecting different VOCs simultaneously. Finally, we discussed the enhancement of AuNPs outside and inside MIL-101(Cr) on the Raman signal.

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ANALYTICAL AND BIOANALYTICAL CHEMISTRY · 2022 ·Vol. 414 ·期 23 ·6965-6975 · IF 4.478

Electrostimulus-triggered reactive oxygen species level in organelles revealed by organelle-targeting SERS nanoprobes

Chen Jiaming,Qu Xiaozhang,Qi Guohua,Xu Weiqing,Jin Yongdong,Xu Shuping

Electrostimulation (ES) is an important therapeutic method for diseases caused by abnormal intracellular electrical activity. Also, it can induce apoptosis of cells, which is a potential tumor treatment method. At present, there are no relevant studies on changes in intracellular reactive oxygen species (ROS) levels produced in the process of ES, or on the effects of simultaneous implementation of conventional antioxidant inhibitor drugs and ES therapy. To reveal these, two organelle-targeting core–shell plasmonic probes were designed for measuring ROS produced during ES. The probes were delivered into target organelles (nucleus and mitochondrion) before the cells were electrically stimulated for different periods of time. Surface-enhanced Raman scattering (SERS) signals were detected in situ , and the sensing mechanism for the quantitative analysis of ROS is based on the signal reduction of SERS caused by the ROS-etching effect on the silver shell. The detection results revealed that ES could trigger ROS generation in cells, and the ROS levels localized around organelles were assessed by SERS. This study has great potential for exploring abnormal organelle microenvironments via organelle-targeting probes combined with SERS technology. Graphical abstract

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Nanoscale · 2022 ·Vol. 14 ·期 16 ·6212-6219 · IF 8.307

Polydopamine stabilizes silver nanoparticles as a SERS substrate for efficient detection of myocardial infarction

Ding Wang,Liping Bao,Huijun Li,Xiaoyu Guo,Weizhuo Liu,Xianying Wang,Xumin Hou,Bin He

Rapid and accurate detection of myocardial infarction (MI) can boost the patient's chance of survival. Surface enhanced Raman scattering (SERS) is an outstanding diagnostic technique because of its strong light stability, high resolution, and qualitative and quantitative analysis based on the characteristic fingerprint. However, its reliability, stability and specificity remain to be improved, especially in the quantitative analysis of serum samples. In this study, we developed in situ silver nanoparticles (Ag NPs) on the surface of polydopamine (PDA) as a SERS substrate and found that PDA could act as a reducing agent to support the nucleation and growth of Ag NPs and control the distance and aggregation of Ag NPs to stabilize the Raman signal. In a standard phosphate buffered saline (PBS) environment, PDA@Ag could reach a low detection limit of 0.01 ng mL−1 cardiac troponin I (cTn I) with a good linear relationship. At the same time, the PDA@Ag substrate also possessed excellent stability, specificity and biocompatibility for cTn I detection. In addition, we verified the application potentiality of PDA@Ag in real serum samples and found that the performance of SERS was almost the same as that in PBS. This excellent detection performance of PDA@Ag could be attributed to both the enhanced electromagnetic field and the increased Raman cross-section, dominated by the gap distance between Ag NPs, reaction force between the antigen and the antibody and excellent biocompatibility and reducibility of PDA. In conclusion, this work may provide a new perspective for the in situ synthesis and growth of a uniform SERS substrate on the carrier to achieve the stability and specificity of SERS-based biological detection of MI.

CAS / MDL: 25952-53-8 6066-82-6
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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY · 2022 · IF 4.831

SERS active fibers from wet-spinning of alginate with gold nanoparticles for pH sensing

Yue Zhang,Ji Zhou,Ying He,Yong Ye,Jing An

Functional composite fibers were prepared by a wet-spinning method and used for pH sensing based on surface enhanced Raman scattering (SERS). Alginate solution with gold nanoparticles (AuNPs) was spun to fibers that acting as active substrate showed distinct SERS enhancement for low concentrations of dyes (1.0 × 10 -9 M for rhodamine 6G and 1.0 × 10 -8 M for crystal violet). After AuNPs were modified with 4-mercaptopyridine (4-MPY), the as-synthesized composite fibers (AuNPs@4-MPY/Ca-ALG fibers) displayed pH dependent SERS spectra due to the changes of chemical structures of 4-MPY under different pH conditions. The AuNPs@4-MPY/Ca-ALG fibers achieved fast response to the pH changes between 1.00 and 13.00. The flexible composite fibers were woven to a wearable “wrist band”, which has potential applications in health monitoring involving pH variation.

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