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Nanoscale · 2023 ·Vol. 15 ·期 18 ·8424-8431 · IF 6.7

Design of Raman reporter-embedded magnetic/plasmonic hybrid nanostirrers for reliable microfluidic SERS biosensors

Bingfang Zou,Shiyun Lou,Jie Duan,Shaomin Zhou,Yongqiang Wang

Magnetic-based microfluidic SERS biosensors hold great potential in various biological analyses due to their integrated advantages including easy manipulation, miniaturization and ultrasensitivity. However, it remains challenging to collect reliable SERS nanoprobe signals for quantitative analysis due to the irregular aggregation of magnetic carriers in a microfluidic chamber. Here, magnetic/plasmonic hybrid nanostirrers embedded with a Raman reporter are developed as capture carriers to improve the reliability of microfluidic SERS biosensors. Experimental results revealed that SERS signals from magnetic hybrid nanostirrers could serve as microenvironment beacons of their irregular aggregation, and a signal filtering method was proposed through exploring the relationship between the intensity range of beacons and the signal reproducibility of SERS nanoprobes using interleukin 6 as a model target analyte. Using the signal filtering method, reliable SERS nanoprobe signals with high reproducibility could be picked out from similar microenvironments according to their beacon intensity, and then the influence of irregular aggregation of magnetic carriers on the SERS nanoprobe could be eliminated. The filtered SERS nanoprobe signals also exhibited excellent repeatability from independent tests, which lay a solid foundation for a reliable working curve and subsequent accurate bioassay. This study provides a simple but promising route for reliable microfluidic SERS biosensors, which will further promote their practical application in biological analysis.

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Food Additives and Contaminants Part A-Chemistry Analysis Control Exposure & Risk Assessment · 2019 · IF 2.17

SERS detection of urea and ammonium sulfate adulterants in milk with coffee ring effect

Abid Hussain,Da-Wen Sun,Hongbin Pu

In the current work, surface-enhanced Raman scattering (SERS) based on gold nanoparticles (AuNPs) and silver-coated gold nanoparticles (Au@AgNPs) with coffee ring effect was employed to simultaneously ascertain urea and ammonium sulfate (AmS) in milk. A small drop (2 µL) of milk with adulterants was dried on a gold-coated slide to examine concentrations ranging from 5, 10, 20, 40 and 80 mg/dL based on spectra ranging from 400 to 1500 cm.−1 A uniform distribution of analytes, with enhanced Raman signals was detected in a small region (maximum 1.9 mm) of coffee ring across the centre of coffee ring pattern. Nanoparticles with core (Au) diameter of 26 nm and shell thickness (Ag) of 6.5 nm were confirmed using transmission electron microscopy (TEM) images. A strong Raman peak at 980 cm−1 was assigned to AmS, while that at 1001 cm−1 was ascribed to urea. With AuNPs, coefficients of determination (R2) of 0.9873 and 0.9859 were achieved for urea and AmS, respectively, while for Au@AgNPs values of 0.9827 and 0.9855 were obtained for urea and AmS, respectively. This study revealed that SERS based on coffee ring effect has the potential to be further exploited for detecting other banned and hazardous adulterants in milk and milk products.

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APPLIED SURFACE SCIENCE · 2019 · IF 5.155

Size dependent SERS activity of Ag triangular nanoplates on different substrates: Glass vs paper

Guojun Weng,Yao Feng,Jing Zhao,Jianjun Li,Jian Zhu,Junwu Zhao

Ag triangular nanoplates have been widely used as the SERS substrate due to their anisotropic morphology and sharp corners. In this work, SERS activity of Ag triangular nanoplates on glass and paper substrates was investigated with different concentration and size. A tiny triangular nuclei based synthesis method was employed to produce Ag triangular nanoplates with different size. And the extinction coefficients of Ag triangular nanoplates with different size were quantified by inductively coupled plasma mass spectrometry (ICP-MS) and transmission electron microscopy (TEM). With definite concentration, Ag triangular nanoplates with small size showed stronger SERS intensity on glass substrate at high concentrations, while large Ag triangular nanoplates exhibited better SERS effect on paper substrate at low concentrations. The possible reasons for distinct SERS activity of Ag triangular nanoplates on glass and paper were discussed with scanning electron microscope (SEM) characterization. These results exhibited important implications for fabricating Raman substrates using Ag triangular nanoplates and could be applied to the SERS sensing with flexile substrate.

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Biosensors-Basel · 2018 ·Vol. 8 ·期 4 ·113 · IF 0

One-Pot Synthesis of Multi-Branch Gold Nanoparticles and Investigation of Their SERS Performance

Weifeng Lv,Chenjie Gu,Shuwen Zeng,Jiaguang Han,Tao Jiang,Jun Zhou

Gold nanoparticles with multiple branches have attracted intensive studies for their application in sensing of low trace molecules. A large number of the merits found on the gold nanoparticles for the above applications are attributed to the strong localized surface plasmon resonance excited by the incident radiation. However, a facile and flexible way of synthesizing the multi-branch gold nanoparticles with tunable localized surface plasmon resonance frequency is still a challenge for the plasmonic research field. Herein, we report an efficient one-pot synthesis of multi-branch gold nanoparticles method that resembles a seed-medicated approach while using no further chemicals except chloroauric acid, ascorbic acid and 4-(2-Hydroxyethyl)-1-piperazinyl]-ethanesulfonic acid. By controlling the amounts of ascorbic acid volumes in the reaction mixture, the morphology and the localized surface plasmon resonance frequency of the synthesized multi-branch gold nanoparticles can be manipulated conveniently. Moreover, using the 4-Mercaptobenzoic acid as the Raman reporter, the multi-branch gold nanoparticles show superior surface-enhanced Raman spectroscopy characteristics that can be potentially used in chemical and biological sensing.Keywords:gold nanoparticle with branches;one-pot synthesis;LSPR frequency tuning;surface enhanced Raman scattering

CAS / MDL: 1310-73-2
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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY · 2019 · IF 2.931

Developing cysteamine-modified SERS substrate for detection of acidic pigment with weak surface affinity

Huan He,Pan Li,Xianghu Tang,Dongyue Lin,Anjian Xie,Yuhua Shen,Liangbao Yang

In this paper, we developed cysteamine-modified surface-enhanced Raman scattering (SERS) substrate for detecting detect trace amount of acidic pigment that shows weak affinity with gold nanoparticles (Au NPs). To realize sensitive and reproducible detection of pigment with weak affinity, the SERS substrate was prepared by attaching cysteamine (CA) to the Au NPs, the acidic pigment molecule could rapidly reached to the surface of Au NPs because of the formation of multi‑hydrogen-bond and electrostatic interaction between the pigment and CA molecule. The proposed method allowed us to detect five kinds of acidic pigment with a limit of 1.0 ppm, which is below the strictest safety limit. Compared with the previous methods, the advantages of the present substrate were its simple substrate preparation, high reproducibility and good universality. Furthermore, the reliable and enough accurate results had been obtained by using of the proposed substrates in the assay of trace pigment in real samples.

CAS / MDL: 34819-78-8
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ACS Sensors · 2019 · IF 6.944

Reusable Silicon-Based SERS Chip for Ratiometric Analysis of Fluoride Ion in Aqueous Solutions

Xiaomin Yue,Yan Su,Xinnan Wang,Linfang Li,Wei Ji,Yukihiro Ozaki

An innovative ratiometric surface-enhanced Raman scattering (SERS) sensor using a 4-mercaptoboric acid (4-MPBA)-modified silver nanoparticle-decorated silicon wafer (Si@Ag NPs chip) was proposed for the ultrasensitive determination of F– ions in aqueous solutions. The principle of sensing strategy is based on fluoride-induced structural symmetry breaking and charge redistribution of phenylboronic acid, leading to a band shift of the C–C stretching mode of 4-MPBA from 1589 to 1576 cm–1. Accordingly, a ratiometric signal of the area ratio (A1576/A1589) between the fluoride-bond MPBA molecules and unoccupied MPBA molecules can be used for the quantitative response of F– ions. In comparison with other SERS-based sensing methods, this ratiometric method can avoid a large error resulting from the inhomogeneity of substrates. Under the optimized analytical conditions, the proposed SERS sensor possesses a quick response to F– ions within 2 min and exhibits high selectivity for F– ions with the determination limit of 10–8 M, which is over 3 orders of magnitude lower than the World Health Organization (WHO) guideline value for F– ions in drinking water. Of particular significance, the present sensor features favorable recyclability, which preserves suitable reproducibility during 6-time cyclic determination of F– ions. The practical utility of this sensing system for the determination of F– ions was tested with real water and toothpaste samples, and the results demonstrate that this sensor shows high recoveries (90–110%). Given its simple principle and easy operation, the present silicon-based SERS sensor could serve as a promising sensor for various practical applications.

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NANOTECHNOLOGY · 2019 ·Vol. 30 ·期 27 ·275604 · IF 3.399

Template growth of Au/Ag nanocomposites on phosphorene for sensitive SERS detection of pesticides

Penghui Li,Wanling Chen,Danni Liu,Hao Huang,Kun Dan,Xiangna Hu,Shaozhou Yu,Paul K Chu,Xue-Feng Yu

We report template growth and dense packing of noble metallic nanoparticles (NPs) on few-layer phosphorene for sensitive surface-enhanced Raman scattering (SERS) detection. Phosphorene obtained by electrochemical exfoliation serves as both the template and reductant in the fabrication of noble metallic NPs which are dispersed on phosphorene without aggregation or pile-up. The BP/Ag/Au and BP/Au/Ag nanocomposites with a nanogap structure exhibit excellent SERS sensitivity and reproducibility with respect to Rhodamine 6G. The BP/Au/Ag nanocomposite is further utilized as the SERS substrate for the detection of two fungicides, thiabendazole and thiram, and detection limits of 10–7 and 10–8 M are achieved. Template growth of Au/Ag nanocomposites is demonstrated to be a green strategy for the fabrication of SERS substrates and has large potential in applications such as pesticide detection.

CAS / MDL: 64-17-5
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Nanomaterials · 2019 ·Vol. 9 ·期 2 ·185 · IF 4.034

Seed-Mediated Electroless Deposition of Gold Nanoparticles for Highly Uniform and Efficient SERS Enhancement

Junqi Tang,Quanhong Ou,Haichun Zhou,Limin Qi,Shiqing Man

A seed-mediated electroless deposition (SMED) approach for fabrication of large-area and uniform gold nanoparticle films as efficient and reproducible as surface-enhanced Raman scattering (SERS) substrates was presented. This approach involved a seeding pretreatment procedure and a subsequent growth step. The former referred to activation of polylysine-coated glass slides in gold seed solution, and the latter required a careful control of the reactant concentration and reaction time. With the aid of gold seeds and appropriate reaction conditions, a large-area and uniform nanofilm with evenly distributed gold nanoparticles (Au NPs) was formed on the surface of the substrates after adding a mixed solution containing ascorbic acid and trisodium citrate. The morphology of the Au nanofilm was examined by scanning electron microscopy. The size evolution of Au NPs on the surface of the substrates was analyzed in detail. The nanofilm substrate was prepared by reaction conditions of the seeded activation process: 10 mL ascorbic acid and trisodium citrate mixture and 30 min of soaking time, which exhibited an excellent uniformity and reproducibility of SERS enhancement with relative standard deviation (RSD) values of less than 8% (particularly, a RSD value of 3% can be reached for the optimized measurement). Compared to the common electroless deposition, the seed-mediated electroless deposition possessed inherent advantages in controllability, reproducibility, and economic benefit.Keywords:electroless deposition;nanoparticles;nanofilm;SERS;in situ chemical reduction

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TALANTA · 2018 · IF 4.244

Design and preparation of centrifugal microfluidic chip integrated with SERS detection for rapid diagnostics

Xi Su,Yi Xu,Huazhou Zhao,Shunbo Li,Li Chen

A microfluidic SERS chip integrated with blood separation and in-situ detection was designed and fabricated for the rapid detection of clinical blood samples. Each functional unit in the microfluidic SERS chip consist of separation-decantation cavity based on centrifugal separation principle, mixing channels and SERS detection chamber built with integrated nano-Au on Ag film microstructure. The serum creatinine was selected as a typical sample to demonstrate the capability of microfluidic SERS chip. It was found that the creatinine SERS characteristic peaks at 678 cm −1 can be effectively identified and the detection limit could be as low as 4.42 × 10 −3 μmol mL −1 in water. The blood samples were also tested in microfluidic SERS chip. The whole separation and test process could be completed within 2 min, which is a significant improvement in the field of creatinine detection. The whole blood of six cases clinical blood samples were also tested, and the results were consistent with the enzymatic results. The developed microfluidic SERS chip has advantages including reduction of the required quantity of blood sample, reusable and easy to operate. It is expected to provide a new method for rapid diagnostics .

CAS / MDL: 7761-88-8
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OPTIK · 2019 · IF 1.914

Synthesis of a low-cost, stable, silicon-based SERS substrate for rapid, nondestructive biosensing

Xiaxia Yue,Xiangxiang Zheng,Guodong Lv,Jiaqing Mo,Xiaoyang Yu,Jie Liu,Zhenhong Jia,Xiaoyi Lv,Jun Tang

Uniform, low-cost, surface-enhanced Raman scattering (SERS) active substrates were prepared by sputtering silver onto porous silicon (pSi) fabricated by an electrochemical etching method. The resulting Ag/pSi SERS substrates were characterized by scanning electron microscopy (SEM), and the SERS effect of the substrates was investigated using rhodamine 6G (R6G) as a probe. Furthermore, the signal uniformity of the Ag/pSi SERS substrates was confirmed through mapping measurements. The Ag/pSi SERS substrates exhibited uniform shape and size and stable SERS activity. Then, we demonstrated the capacity of the prepared silicon-based SERS substrates for detecting bovine serum albumin (BSA) and serum samples. Therefore, our Ag/pSi SERS substrates can be easily employed in practical applications to effectively assess healthcare.

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CHEMISTRY OF MATERIALS · 2018 · IF 9.89

Light-Controlled Shrinkage of Large-Area Gold Nanoparticle Monolayer Film for Tunable SERS Activity

Xuefei Lu,Youju Huang,Baoqing Liu,Lei Zhang,Liping Song,Jiawei Zhang,Afang Zhang,Tao Chen

The two-dimensional (2D) monolayer gold nanoparticle (Au NP) film is of significant interest and importance in both fundamental and practical applications including optoelectronic devices, sensing, catalysis, and surface-enhanced Raman spectroscopy (SERS). Because of the weak physical interaction, the conventional monolayer Au NP film fabricated at the oil–water interface was unstable, easily breakable, and difficultly transferred. In the present work, we report on a simple and effective chemical cross-linking strategy at the air–water interface to achieve a large-scale monolayer gold nanoparticle film with intelligently tunable size of nanogaps, and excellent free-standing and easily transferable properties. In our strategy, acrylamide, a polymerizable molecule, was first modified on the surface of Au NPs for subsequent self-assembly into a monolayer film at the liquid–liquid interface. Through photopolymerization of acrylamide, a chemically cross-linked film was formed with closely packed nanoparticles, highly macroscopic uniformity, and excellent free-standing property, which allowed it to be easily transferred from the air–water interface onto various solid substrates while maintaining its integrity. It is interesting to find that the macroscopic film underwent an in situ shrinkage under irradiation of UV-light, and its area shrinkage ratio is close to 55% (equal to 2.2 times) of that from non-cross-linked counterparts. More importantly, UV-light-controlled in situ shrinkage of the Au NP film would lead to intelligently, precisely tuned nanogaps less than 0.5 nm between neighboring Au NPs for maximal amplification of SERS signals, and the macroscopic uniformity of the films ensured the reproducible performance of SERS signals, providing an ideal candidate for SERS applications.

CAS / MDL: 79-06-1 64-17-5
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ANALYTICAL LETTERS · 2019 · IF 1.248

Silver Nanostructures on Graphene Oxide as the Substrate for Surface-Enhanced Raman Scattering (SERS)

Ying Zhang,Hao Zhou,Qi Shen,Zhouwei Shao,Lin Xu,Zhimin Luo

Nanosized surface-enhanced Raman scattering (SERS) substrates fabricated by the controlled growth of metal nanostructures on water-dispersed two-dimensional nanomaterials can open a new avenue for SERS analysis of liquid samples in biological fields. In this work, regular and uniform Ag nanostructures were grown on the surface of graphene oxide (GO) through a microwave-assisted hydrothermal method. Polyamidoamine (PAMAM) dendrimers were assembled on the surface of GO to form GO/PAMAM templates for growing Ag nanostructures, which are primarily comprised of Ag dimers and trimers. The prepared Ag/GO nanocomposites are highly dispersed and stable in aqueous solution and may be used as substrates for enhanced Raman detection of rhodamine 6 G (R6G) in aqueous solution. This special substrate provides high-performance SERS and suppresses R6G fluorescence in aqueous solution and is promising as a nanosized material for the enhanced Raman detection of liquid samples in biological diagnostics.

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