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SERS
Surfaces and Interfaces · 2023 · IF 6.2

Size-dependent SERS property of red phosphorous in the transition from bulk to nanosheet and its application in immunosensing

Jiayao Zhang,Danni Xue,Huan Liu,Zhao Wei,Chenjie Gu,Shuwen Zeng,Junhui Jiang,Tao Jiang,Xingfei Zhou,Kerong Wu

Attributed to their structure-dependent chemical enhancement capability and perfect biocompatibility, semiconductors have attracted significant concern in surface enhanced Raman scattering (SERS)-based immunoassay. By continually adjusting the size of red phosphorus (RP) in the transition process from bulk to nanosheet, we investigated in detail about the improvement of high-efficient charge transfer (CT) resonance dependent on the perfect energy level matching within the substrate-molecule combination. The nano-sized RP has achieved an impressive three-fold enhancement in SERS intensity in comparison to the RP nanosheet. Furthermore, the RP-based immunosubstrate was combined with MoS 2 nanoflowers-based immunoprobe to construct a sandwich immunostructure for the accurate and efficient diagnostics of cancer marker prostate-specific antigen. A limit of detection as low as 3.99 × 10 −10  M was obtained in the SERS-based immunoassay with reliable specificity. This study presents an innovative approach to promote the SERS performance of semiconductors, which may find potential biological applications in the early screening of cancer.

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ACS Applied Materials & Interfaces · 2023 · IF 9.5

Absolute Quantification of Serum Exosomes in Patients with an SERS-Lateral Flow Strip Biosensor for Noninvasive Clinical Cancer Diagnosis

Xiaoming Su,Yangcenzi Xie,Xinyu Liu,Mingyang Chen,Chao Zheng,Hong Zhong,Ming Li

Exosomes (exos) widely existing in body fluids show great potential for noninvasive cancer diagnosis. Quantitative analysis of exos is traditionally performed by targeting specific exosomal surface proteins, but it is often imprecise due to the common expression of exosomal proteins and subtle expression differences between different cancer subtypes. Herein, we report quantitative surface-enhanced Raman spectroscopy (SERS) of serum exos through a combination of a paper-based lateral flow strip (LFS) biosensor with multivariate spectral unmixing analysis rather than simply quantifying exosomal proteins. Our SERS-LFS biosensor enables absolute quantification of two different serum exos with a limit of detection down to ∼106 particles/mL for both exos. We further exemplify the application of this strategy in quantitative dual-plex detection of serum exos from breast cancer patients. We find that human epidermal growth factor receptor 2+ (HER2+) and luminal A breast cancer patients undergoing no surgery are enriched in serum exos derived from SKBR-3 cells and MCF-7 cells (denoted as SKBR and MCF exos), respectively. The surgical treatment of these breast cancer patients accompanies an obvious decrease of either SKBR or MCF exos in the serum. These results suggest the great potential of the combination of the SERS-LFS biosensor and multivariate spectral unmixing for breast cancer subtyping and therapeutic surveillance with the powerful quantitative capability of exos in clinical samples.

CAS / MDL: 4420-74-0
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ANALYTICA CHIMICA ACTA · 2023 · IF 6.2

Sensitive SERS aptasensor for histamine detection based on Au/Ag nanorods and IRMOF-3@Au based flexible PDMS membrane

Yue Pan,Shan Xu,Zhouping Wang,Caiyun Jiang,Xiaoyuan Ma

Background Histamine is a kind of biogenic amine with strong toxicity and potential carcinogenicity . Many traditional methods of detecting histamine have the disadvantages of cumbersome detection steps, expensive equipment, and high professional requirements for staff. In contrast, SERS has become the preferred method for quantitative analysis of histamine because of rich fingerprint information, rapidity and economy. However, most of SERS substrates still have technical problems, such as poor stability, low sample collection rate, and detection efficiency. Therefore, there is a great need for new strategies to develop high-performance SERS substrates based sensors. Results In our study, a sensitive SERS aptasensor for the detection of histamine was synthesized. The assembly was formed between IRMOF-3@Au/PDMS (flexible SERS substrate) and AuNR-DTNB@Ag-HA apt (Raman signal probe with both the target capture ability) via π-π stacking interaction from HA aptamer and IRMOF-3. Consequently, the SERS signal of the assembly derived from DTNB reached highest due to the synergistic enhancement effect by AuNR@Ag and IRMOF-3@Au. Meanwhile, HA aptamer can specifically capture histamine, therefore histamine addition competitively bound to the probe, leading to a corresponding decrease in the DTNB signal value on the SERS substrate. The SERS intensity at 1331 cm −1 presented a good linear relationship towards the logarithmic value of histamine concentrations ranging from 0.0001 mg/L to 400 mg/L (R 2  = 0.990) with the LOD of 3.6 × 10 −5  mg/L. Furthermore, the application in wine samples demonstrated the accuracy and applicability of the developed sensor. Significance This method effectively improves substrate stability, detection sensitivity and signal response immediacy to amplify the SERS sensor, thus satisfying the histamine detection requirements of various systems. According to this aptasensor design, our strategy can be extended to create other MOF-based SERS substrates for accurately detecting relative targets to ensure food safety.

CAS / MDL: 919-30-2
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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY · 2023 · IF 4.4

Ag microlabyrinth/nanoparticles coated large-area thin PDMS films as flexible and transparent SERS substrates for in situ detection

Meng Sun,Houjia Zhang,Hefu Li,Xuehui Hao,Changzheng Wang,Lijun Li,Zhenshan Yang,Cunwei Tian

Flexible and transparent surface-enhanced Raman scattering (SERS) substrates have   attracted   much   attention as a fast, sensitive and in situ detection platform for practical applications. However, the large-area fabrication of flexible and transparent SERS substrates with high performance is still challenging. Here, a flexible and transparent SERS substrate based on large-area thin PDMS film decorated with Ag microlabyrinth/nanoparticles hierarchical structures (denoted as ALNHS@PDMS) is fabricated by using the floating-on-water method and magnetron sputtering technology. By optimizing the sputtering time, the ALNHS with multiple hot spots are uniformly distributed on the PDMS surface. Based on characterizing the rhodamine 6G (R6G) with a portable Raman spectrometer, the optimal ALNHS@PDMS film exhibits a high enhancement factor (5.2 × 10 6 ), excellent uniformity and reproducibility, as well as superior mechanical stability. In addition, thanks to the good sticky feature and bi-directional activation property of the thin ALNHS@PDMS film, the prepared flexible and transparent SERS substrate can achieve in situ detection of malachite green residues (10 -6 M) on apple and tomato skins. This large-area, thin, mechanically robust, flexible and transparent ALNHS@PDMS film, integrated with a portable Raman spectrometer, shows great potential for point-of-care testing (POCT)   in practical applications.

CAS / MDL: 548-62-9 569-64-2
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TALANTA · 2023 · IF 6.1

Multifunctional Ni(OH)2/Ag composites for ultrasensitive SERS detection and efficient photocatalytic degradation of ciprofloxacin and methylene blue

Xiaojun Wen,Huan Cheng,Weilong Zhang,Lijun You,Jumei Li

To enable the widespread application of surface-enhanced Raman scattering (SERS) technique in practical sensing of organic pollutants, it is essential to develop a reliable SERS substrate that offers both high sensitivity and reusability. In this study, we employed a simple and rapid in-situ deposition method to coat Ag nanoparticles onto flower-like Ni(OH) 2 spheres, resulting in the formation of Ni(OH) 2 /Ag composites with excellent photocatalytic performance and SERS activity. These composites were used as a promising SERS analysis tool for effective detection of organic pollutants, including ciprofloxacin hydrochloride (CIP) and methylene blue (MB). Notably, the composites exhibited outstanding detection limits of 10 −8  M for MB and 10 −7  M for CIP, respectively, and showed a strong linear relationship between SERS intensities and the logarithmic concentration (R 2  ≥ 0.97). Moreover, under simulated sunlight irradiation, the Ni(OH) 2 /Ag composites efficiently degraded MB and CIP molecules within a short period of 120 min for MB and 130 min for CIP. This demonstrated their practical reusability, as evidenced by their consistent performance over five cycles of SERS sensing. These findings underscore the significant potential of these composites for SERS-based detection of trace pollutants and ecological restoration through photocatalytic reactions in the future.

CAS / MDL: 7220-79-3 61-73-4
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JOURNAL OF ALLOYS AND COMPOUNDS · 2023 · IF 6.2

Ultra-sensitive mercury detection from surface wrapping of carbon dots reduced and decorated silver nanoparticles on SERS fiber probes

Xiaoyu Han,Yan Wang,Tianyi Wang,Jihong Zhang,Jun Xie,Jianjun Han,Xiujian Zhao

Highly selective and sensitive detection of toxic mercury ions (Hg 2+ ) has become a critical issue in recent decades, due to increasing environmental and health requirements. Herein, carbon dots reduced and decorated Ag (CDs/Ag) nanoparticles based fiber probes were fabricated, providing a “turn-off” surface-enhanced Raman spectroscopy (SERS) for low-concentration Hg 2+ ions detection. The CDs/Ag nanoparticles fiber probe exhibits better SERS performance than that of Ag nanoparticles fiber, attributed to the stronger electromagnetic intensities induced by localized surface plasmon resonance (LSPR) and larger hot-spot areas resulting from the interaction between silver nanoparticles and carbon dots, under 532 nm beam excitation. As low as 10 −11 M Hg 2+ ions can be detected through the decrease in Raman scattering intensities of CV molecules, due to the SERS inactive Hg metal layer wrapping the surface of silver nanoparticles, through the reduction of Hg 2+ ions by carbon dots. The dropping of silver nanoparticles’ LSPR induced absorption peak, EDS elemental mapping, and XPS analysis all confirm that the wrapping decreases the LSPR effect and corresponding Raman intensity. Furthermore, the detection shows high selectivity and can only be applied for detecting Hg 2+ ions, owing to the reduction capability of carbon dots. The close analysis results obtained using SERS fiber probes and commercial inductively coupled plasma-mass spectrometry (ICP-MS) for detecting Hg 2+ ions in real water sample confirm the reliability of this detection method. This research indicates the CDs/Ag fiber probe has a great potential application for environmental Hg 2+ ions detection.

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FOOD CHEMISTRY · 2023 · IF 8.8

Au-Ag OHCs-based SERS sensor coupled with deep learning CNN algorithm to quantify thiram and pymetrozine in tea

Huanhuan Li,Xiaofeng Luo,Suleiman A. Haruna,Muhammad Zareef,Quansheng Chen,Zhen Ding,Yiyong Yan

Pesticide residue detection in food has become increasingly important. Herein, surface-enhanced Raman scattering (SERS) coupled with an intelligent algorithm was developed for the rapid and sensitive detection of pesticide residues in tea. By employing octahedral Cu 2 O templates, Au-Ag octahedral hollow cages (Au-Ag OHCs) were developed, which improved the surface plasma effect via rough edges and hollow inner structure, amplifying the Raman signals of pesticide molecules. Afterward, convolutional neural network (CNN), partial least squares (PLS), and extreme learning machine (ELM) algorithms were applied for the quantitative prediction of thiram and pymetrozine. CNN algorithms performed optimally for thiram and pymetrozine, with correlation values of 0.995 and 0.977 and detection limits (LOD) of 0.286 and 29 ppb, respectively. Accordingly, no significant difference ( P  greater than 0.05) was observed between the developed approach and HPLC in detecting tea samples. Hence, the proposed Au-Ag OHCs-based SERS technique could be utilized for quantifying thiram and pymetrozine in tea.

CAS / MDL: 50-81-7
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2023 · IF 9.9

An anisotropic nanobox based core-shell-satellite nanoassembly of multiple SERS enhancement with heterogeneous interface for stroke marker determination

Wei-Bin Wang,Jian-Jun Li,Guo-Jun Weng,Jian Zhu,Yu-Bo Guo,Jun-Wu Zhao

Herein, A novel gold-silver alloy nanobox (AuAgNB)@SiO 2 -gold nanosphere (AuNP) nanoassembly based on core–shell-satellite structure is fabricated and applied to the surface-enhanced Raman scattering (SERS) detection of S100 calcium-binding protein B protein (S100B). It contains an anisotropic hollow porous AuAgNB core with rough surface, an ultrathin silica interlayer labeled with reporter molecules, and AuNP satellites. The nanoassemblies were systematically optimized by tuning the reporter molecules concentration, silica layer thickness, AuAgNB size, and the size and number of AuNP satellite size. Remarkably, AuNP satellites are adjacent to [email protected] 2 , developing AuAg-SiO 2 -Au heterogeneous interface. With the strong plasmon coupling between AuAgNB and AuNP satellites, chemical enhancement from heterogeneous interface, and the tip “hot spots” of AuAgNB, the SERS activity of the nanoassemblies was multiply enhanced. Additionally, the stability of nanostructure and Raman signal was significantly improved by the silica interlayer and AuNP satellites. Eventually, the nanoassemblies were applied for S100B detection. It demonstrated satisfactory sensitivity and reproducibility with a wide detection range of 10 fg/mL-10 ng/mL and a limit of detection (LOD) of 1.7 fg/mL. This work based on the [email protected] 2 -AuNP nanoassemblies with multiple SERS enhancements and favorable stability demonstrates the promising application in stroke diagnosis.

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Plasmonics · 2023 ·Vol. 18 ·期 4 ·1541-1552 · IF 3

Highly Sensitive and Flexible GFF/Au/AgNPs SERS Substrate and Its Application for Rapid Hazardous Residues Detection on Food

Gu Ciyong,Meng Delong,Yu Xiaolei,Li Lin,Zhao Zhimin

In this work, we have developed a highly sensitive surface enhanced Raman scattering (SERS) substrate consisting of gold (Au) and silver (Ag) nanoparticles (NPs) loaded on glass fiber filter paper (GFF) by a two-step process of magnetron sputtering and sessile drop method. To test the SERS properties of the substrate, crystal violet (CV) was selected as the Raman probes. The influence of the amounts of NPs on the SERS signals was studied using field-emission scanning electron microscopy and theoretical methods. It is demonstrated that the hybrid structure of optimal GFF/Au/AgNPs has a much stronger SERS enhancement than that of GFF substrate coated only with AuNPs, which can provide a SERS enhancement factor (EF) of 3.52 × 10 8 , and the limit of detection is down to 10 −14  M for CV. Moreover, the Raman signal of the CV on the GFF/Au/Ag substrate presented good homogeneity, reproducibility and stability, also reproduce the SERS spectra after 15 days. Furthermore, the GFF/Au/AgNPs substrate was applied for the rapid on-site testing and identification of malachite green (MG) residual on contaminated fish scale, and the limit of detection was approximately 10 −7  M. Flexible GFF substrate with Au/Ag bimetallic hybrid structure has great potential in rapid sampling of hazardous ingredients on real samples and in SERS applications.

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Surfaces and Interfaces · 2023 · IF 6.2

Interfacial self-assembled dual-functional nanocomposite films for SERS monitoring of visible-light photocatalytic degradation of organic dye pollutants

Wanling Chen,Wanlin Wang,Hongyun Xing,Wan Li,Haiwei He,Wei Li,Paul K. Chu,Guofen Song,Huaiyu Wang,Penghui Li

Photocatalytic degradation by visible-light responsive photocatalysts is an efficient strategy to treat organic dye pollutants and monitoring of the photocatalytic reaction mechanisms and kinetics is important to the design of high-performance photocatalysts. Herein, a dual-functional graphitic carbon nitride/gold nanoparticles (g-C 3 N 4 /AuNPs) nanocomposite film is introduced to monitor the photocatalytic reactions by surface-enhanced Raman scattering (SERS) while degrading organic dyes photocatalytically. The nanocomposite film fabricated by two-step interfacial self-assembly consists of orderly arranged g-C 3 N 4 film anchored on a closely packed AuNPs monolayer film. The nanoplatform has excellent SERS characteristics such as a rhodamine 6G (R6G) detection limit of 8.8 × 10 −10 M, and good SERS detection uniformity with a relative standard deviation (RSD) of 9.62%, which is crucial to quantitative determination and accurate monitoring of the photocatalytic reactions. The nanoplatform is employed in visible-light photocatalytic degradation of organic dyes including R6G, methylene blue, acid orange II, and acid orange 74. The reactions follow the pseudo-first-order kinetics as revealed by SERS and the photocatalytic degradation mechanism is postulated to be the promoted charge separation. The results reveal a high-performance dual-functional nanoplatform suitable for visible-light photocatalytic degradation of organic dye pollutants and SERS monitoring of the reactions.

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ANALYTICA CHIMICA ACTA · 2023 · IF 6.2

Au/SiNCA-based SERS analysis coupled with machine learning for the early-stage diagnosis of cisplatin-induced liver injury

Shengjie Ge,Gaoyang Chen,Dawei Cao,Hechuan Lin,Ziyang Liu,Meng Yu,Shiyi Wang,Zhigang Wang,Ming Zhou

Cisplatin has been widely applied in the clinical treatment of various cancers, whereas liver injury induced by its hepatotoxicity is still a severe issue. Reliable identification of early-stage cisplatin-induced liver injury (CILI) can improve clinical care and help to streamline drug development. Traditional methods, however, cannot achieve enough information at the subcellular level due to the requirement of the labeling process and low sensitivity. To overcome these, we designed an Au-coated Si nanocone array (Au/SiNCA) to fabricate the microporous chip as the surface-enhanced Raman scattering (SERS) analysis platform for the early diagnosis of CILI. A CILI rat model was established, and the exosome spectra were obtained. The principal component analysis (PCA)-representation coefficient-based k-nearest centroid neighbor (RCKNCN) classification algorithm was proposed as the multivariate analysis method to build the diagnosis and staging model. The PCA-RCKNCN model has been validated to achieve a satisfactory result, with accuracy and AUC of over 97.5%, and sensitivity and specificity of over 95%, indicating that SERS combined with the PCA-RCKNCN analysis platform can be a promising tool for clinical applications.

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ANALYTICA CHIMICA ACTA · 2022 · IF 6.911

Controllable synthesis of flower-like AuNFs@ZIF-67 core-shell nanocomposites for ultrasensitive SERS detection of histamine in fish

Shan Xu,Peifang Chen,Xichi Lin,Imran Mahmood Khan,Xiaoyuan Ma,Zhouping Wang

Histamine is a significant biomarker to assess the freshness of fish products. In this study, a novel MOF-based SERS sensor for histamine determination was synthesized by wrapping PVP-capped Au nanoflowers with a ZIF-67 shell (Au [email protected] ). The highly branched Au NFs core exhibited a strong electromagnetic field enhancement effect and provided an ultra-sensitive SERS fingerprint spectrum, while ZIF-67 shell was the contributor to enrich the target and stabilize the substrate. The morphology of the core-shell structures can be easily controlled by the concentrations of the capping agent PVP and MOF precursor Co ion . Consequently, 4-MBA pre-grafted on the optimized SERS substrate can act as the Raman internal standard (IS) to eliminate signal fluctuations through standardizing all spectra against its peak at 1074 cm −1 . Moreover, as the specific receptor for histamine molecules, 4-MBA helped reach the low detection sensitivity, where the SERS intensity ratio, I 1172 /I 1074 presented a good linear relationship towards the histamine concentrations (10 −3 -10 −7  M) with the LOD of 0.87 × 10 −7  M (R 2  = 0.9930). Furthermore, the application in monitoring fish spoilage process demonstrated the feasibility and reliability of the developed sensor. This work provided a facile strategy to construct MOF-based SERS substrate as a potential platform for the shelf-life prediction of fish products.

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