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TALANTA · 2020 · IF 5.339

Rapid nondestructive detection of mixed pesticides residues on fruit surface using SERS combined with self-modeling mixture analysis method

Bingxue Hu,Da-Wen Sun,Hongbin Pu,Qingyi Wei

Mixed pesticides are usually applied to agricultural products to enhance agricultural production. However, their presence in the environment and food poses serious health risks to humans. Therefore, rapid and reliable detection methods for mixed pesticides residues are in need to minimize potential health hazards. Herein, a nondestructive and sensitive strategy was developed to determine thiram and thiabendazole (TBZ) mixture on fruit surface using surface-enhanced Raman spectroscopy (SERS) technology coupled with interfacial self-assembly gold nanorods (Au NRs) array substrates together with self-modelling mixture analysis (SMA) method. Firstly, a large area high-density Au NRs array was fabricated by organic-aqueous interfacial self-assembly to serve as a sensitive SERS substrate for simultaneously screening of thiram and TBZ on the fruit surface. Then, an SMA method was employed to identify and separate the Raman spectrum for each pesticide from the Raman spectra of the pesticides mixture on the contaminated fruit surface. Results showed that using SERS technique with the SMA method, qualitative and quantitative analyses of a single component from the spectra of the mixture were simultaneously realized, and the resolved pure spectrum of each pesticide was presented. The limits of detection (LOD) of pesticides on the surface of apple, tomato and pear were 0.041, 0.029 and 0.047 ng/cm 2 for thiram, and 0.79, 0.76 and 0.80 ng/cm 2 for TBZ, respectively. It was anticipated that the proposed SERS detection approach combined with SMA methods should pave the way for detecting multi-analytes in practical applications for agriculture and food safety inspection.

✓ 已验证 产品关联 DOI PubMed 高影响因子
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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY · 2020 · IF 3.232

Facile synthesis of Au nanoparticle-coated Fe3O4 magnetic composite nanospheres and their application in SERS detection of malachite green

Zi Hao Li,Jia Hao Bai,Xin Zhang,Jia Meng Lv,Cheng Shan Fan,Yong Mei Zhao,Zheng Long Wu,Hai Jun Xu

A facile method for synthesizing Au nanoparticle-coated Fe 3 O 4 magnetic composite nanospheres (Fe 3 O 4 @Au MCS) via seed-mediated growth and iterative reduction is reported. The nanospheres were then successfully used to detect malachite green (MG) residues in water bodies via surface-enhanced Raman scattering (SERS) technique. Fe 3 O 4 @Au MCS has excellent optical properties and superparamagnetism ; it can be dispersed into the solution to fully adsorb target molecules and then collected with a magnet to increase the molecular density and the number of SERS hot spots. Magnetic enrichment was superior to conventional detection method. The limit of detection for MG was 10 −7  M and the enhancement factor was 1.1 × 10 5 . The logarithm of the SERS intensity of the characteristic peak at 1618 cm −1 exhibited a linear relationship with the logarithm of the MG concentration over the range of 10 −3 – 10 −7  M, with a correlation coefficient of 0.966. The Fe 3 O 4 @Au MCS had good uniformity of SERS signals, with a 18.59% relative standard deviation for the SERS intensity. MG detection in aquaculture water conformed with the established quantitative regulations. The SERS spectrum calculated with density function theory for MG adsorbed on Fe 3 O 4 @Au MCS was very close to the experimental spectrum, which verified enhancement by the substrate. Overall, Fe 3 O 4 @Au MCS enabled ultrasensitive, quantitative SERS detection of MG.

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ANALYTICAL CHEMISTRY · 2020 · IF 6.785

Fast Activation and Tracing of Caspase-3 Involved Cell Apoptosis by Combined Electrostimulation and Smart Signal-Amplified SERS Nanoprobes

Guohua Qi,Dan Sun,Yu Tian,Chen Xu,Ying Zhang,Dandan Wang,Kongshuo Ma,Shuping Xu,Yongdong Jin

Caspase-3 is considered as one of the key proteases that can spontaneously regulate the life activities of cells, and its activation (usually is a slow process) will execute the apoptosis process of cells. Rapid activation of caspase-3 on demand in living-cells is therefore highly desired toward precise cancer therapy but it is still a key challenge. Herein, we applied electrostimulus (ES) to achieve fast activation of caspase-3 and trigger cell apoptosis, and developed a smart magnetic-plasmonic assembly nanoprobes (A-nanoprobes) to real-time trace cellular caspase-3 activation at the single cell level. The designer core–satellite A-nanoprobe, working specific to the activated caspase-3 via a disassembly tactic, provides strong “hot spots” to improve the sensitivity and therefore enables SERS sensing of cellular caspase-3 upon activated by ES. Single-cell analysis revealed that the ES can rapidly activate the apoptosis pathway of caspase-3 on demand to make the DNA fragmentation and ultimately induce the cell apoptosis. Such method and nanoplatform were further used to monitor ES-triggered caspase-3 activation in cell apoptosis process of different cell types, revealing that more caspase-3 will be activated for cancerous cells than normal cells during the ES to induce cells apoptosis. This strategy and platform are promising for detecting cellular caspase-3 and other enzymes in the process of cancer diagnosis and treatments.

✓ 已验证 产品关联 DOI PubMed 高影响因子
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Sensors and Actuators Reports · 2020 · IF 0

Highly sensitive and selective colorimetric and SERS dual-mode detection of arsenic (III) based on glutathione functionalized gold nanoparticles

Jing Li,Biao Zheng,Zhongkai Zheng,Yuliang Li,Jun Wang

It is of very significance to strictly and precisely detect trace inorganic arsenic ions (As 3+ ), which may increase the risks of cancer in the skin, lungs, bladder, and diabetes diseases. Here, we report a simple and ultrasensitive method for dual-mode detection of arsenic by colorimetric and surface-enhanced Raman spectroscopy (SERS) based on glutathione functionalized gold nanoparticles (GSH/AuNPs). When As 3+ ion are present in GSH/AuNPs solution, the binding of As 3+ ion with GSH ligand induces the aggregation of AuNPs. The aggregation of GSH/AuNPs not only serves as indicator of As 3+ ion for the perceptible color change from wine-red to blue, but also a highly efficient on-site SERS detection of As 3+ ion due to the abundant hot spots. More importantly, the sensing system exhibits superior selectivity for As 3+ ion detection compared with other common metal ions (Pb 2+ , Hg 2+ , Cu + , K + , Cr 3+ , Co 2+ and Fe 3+ ). Meanwhile, the limit of detection (LOD) of colorimetric and SERS are estimated to be 0.11 ppb and 0.14 ppb, respectively, which is lower than the WHO defined limit (10 ppb). Our study would provide a novel method for detection of As 3+ ion in drinking water and marine environmental monitoring, as well as offers a strategy for developing multi-mode sensing system for different applications.

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MATERIALS CHEMISTRY AND PHYSICS · 2020 · IF 3.408

Improving the SERS enhancement and reproducibility of inkjet-printed Au NP paper substrates by second growth of Ag nanoparticles

Guojun Weng,Yue Yang,Jing Zhao,Jianjun Li,Jian Zhu,Junwu Zhao

The fabrication of paper-based SERS substrates, which provided the advantages of active Raman signal enhancement with good reproducibility is still a challenge for real-world applications. In this report, we showed how the SERS enhancement and reproducibility of Au NP paper substrates prepared by inkjet-printed method could be improved significantly by second growth of Ag NPs. The Au/Ag NP paper substrates fabricated with the improved protocol had a much higher SERS enhancement (about 1.356✕10 3 times) compared with printed Au NP paper substrates. Moreover, the reaction parameters affected the SERS enhancement of Au/Ag NP paper substrates were optimized by collecting rhodamine 6G (R6G) SERS spectra. Further, the reproducibility of Au/Ag NP paper substrates were evaluated on random spots of single substrate and batch to batch substrates by recording the intensity of R6G at 611 cm −1 . The SERS intensities at 611 cm −1 showed small relative standard deviation, which indicated the good reproducibility of Au/Ag NP paper substrates. This improved method enabled the printed Au NP paper substrates to possess the practical applicability for the on-site SERS sensing.

CAS / MDL: 989-38-8 7761-88-8
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ANALYTICAL AND BIOANALYTICAL CHEMISTRY · 2019 ·Vol. 411 ·期 27 ·7187-7196 · IF 3.286

Detection of systemic pesticide residues in tea products at trace level based on SERS and verified by GC–MS

Zhang De,Liang Pei,Ye Jiaming,Xia Jing,Zhou Yongfeng,Huang Jie,Ni Dejiang,Tang Lisha,Jin Shangzhong,Yu Zhi

Surface-enhanced Raman spectroscopy (SERS) has the potential to detect pesticide residues in agricultural products. However, some systemic pesticides, such as chlorpyrifos, can enter the plant tissue, and not just stay on the surface. Consequently, many SERS studies halted at practical application because of its complexity. In this work, SERS technology was used to detect chlorpyrifos residues in tea products at the semiquantitative level. A simple pretreatment method effectively avoided interference of other fluorescent substances, and all major peaks could be distinguished on the basis of a novel substrate. A principal component analysis algorithm was applied to form a regression model, and a nanogram detection limit was obtained. Furthermore, chlorpyrifos residues in the same tea products were also measured by gas chromatography–mass spectrometry, and the results show a small range of errors. From the comparative study of the two detection methods, the results suggest the great promise of SERS technology for rapid inspection of agricultural products.

✓ 已验证 产品关联 DOI PubMed 高影响因子
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ANALYTICAL AND BIOANALYTICAL CHEMISTRY · 2019 ·Vol. 411 ·期 30 ·8081-8089 · IF 3.286

Unraveling a self-assembling mechanism of isomeric aminothiophenol on Ag dendrite by correlated SERS and matrix-free LDI-MS

Ma Yankai,Nie Bei

Correlated spectroscopic analysis can provide complementary chemical insights that are often unattainable by either approach used in isolation. We distinguished the different self-assembling behavior of isomeric aminothiophenols (ATPs) on Ag dendrite by the correlation of surface-enhanced Raman spectroscopy and laser-induced desorption ionization mass spectrometry, demonstrating that steric effect impinged significantly upon surface molecular density and plasmon-driven catalytic reaction yield, which led to drastic variations in the resulting SERS spectra. The correlative measurement shows that ortho -substitute barely formed a self-assemble monolayer, relative to the para -isomer, which can form a close-packed self-assembled monolayer and perform a decent azo-coupling reaction. Comparison between normal and SERS spectra of ATP isomers supports the fact that additional disulfide- or hydrogen-bonding interactions are established in para -ATP solid crystal, but neither of ortho - nor meta -isomers. This work is expected to create a significant impact on the development of an orthogonally correlated spectroscopic tool in deciphering chemical insights and underlying reaction mechanism. Graphical abstract

✓ 已验证 产品关联 DOI PubMed 高影响因子
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TALANTA · 2019 · IF 4.916

Modified photochemical strategy to support highly-purity, dense and monodisperse Au nanospheres on graphene oxide for optimizing SERS detection

Linlin Xu,Hua Zhang,Yue Tian,Anxin Jiao,Shuang Li,Yang Tan,Ming Chen,Feng Chen

The integration of highly-purity, dense and monodisperse plasmonic nanoparticles (NPs) on two-dimensional (2D) graphene-like support possesses great potential for optimizing surface-enhanced Raman spectroscopy (SERS). Based on ultraviolet (UV) laser-induced modified photochemical reaction , we report an ingenious and green strategy to support highly dispersed Au NPs with controllable distribution on graphene oxide (GO). Without using any stabilizing agents or other complex chemical additives , the GO with abundant oxygen-containing functional groups can be effectively excited by 375 nm laser irradiation in HAuCl 4 solution, resulting in controlled reduction of Au ions and then overgrowth of highly-purity Au NPs. Highly dense and monodisperse Au NPs with uniform diameter of ~20 nm formed on GO supports can be achieved by 30 min irradiation, which can offer maximized SERS activity in comparison with GO/Au NPs obtained by other irradiation times. The optimized GO/Au NPs give rise to ultralow SERS analyses of (10 −14  M) methylene blue (MB), (10 −13  M) rhodamine 6G (R6G) and (10 −13  M) malachite green (MG), respectively. More importantly, it can also simultaneously analyze these three aromatic dyes in a mixture condition at detection limits as low as nano-mole level (10 −9 –10 −11  M), achieving the urgent requirement of mutually independent SERS trace detection. Therefore, the obtained GO/Au NPs with extremely high SERS activity and superior spectroscopic identification will be a prominent candidate for widespread SERS applications in real-word scenarios.

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ANALYTICAL CHEMISTRY · 2023 · IF 7.4

Smart Ratiometric SERS Nanoprobe for Real-Time Monitoring Hydrogen Peroxide in Living Cells during NADH Treatment Associated with Ferroptosis

Dan Sun,Guohua Qi,Xuan Yi,Hongyan Zhu,Yongdong Jin

Studying the oxidative stress, especially the reactive oxygen species (ROS) response of ferroptosis, is crucial for the diagnosis and treatment of cancer based on ferroptosis. However, reliable quantitative analysis of intracellular ROS in cancer treatment for drug screening is still a challenge. Herein, a superior ratiometric SERS nanoprobe was developed for in situ, real-time, and highly sensitive detection of content variation of H2O2 within living cells. The SERS nanoprobe was prepared by coassembly of the internal standard molecule p-mercaptobenzonitrile and the reporter molecule p-mercaptophenylboronic acid on the surface of gold nanoparticles, used for synergistic calibration and detection of H2O2, which enables reliable detection of the true content of intracellular H2O2 without the interference of other substances in cells. Based on the nanoprobe, we found that the level of intracellular H2O2 of cancer cells was increased after the nicotinamide adenine dinucleotide (NADH) treatment, with a dose-dependence to the concentration of NADH. High doses of NADH (above 20 mM) can induce cell death by means of ferroptosis associated with the level elevation of intracellular lipid hydroperoxides. This study highlights the potential of the SERS nanoprobe for tracking content variation of cellular H2O2 and understanding its roles in screening new anticancer drugs.

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ANALYST · 2023 · IF 4.2

Highly sensitive and selective SERS detection of caspase-3 during cell apoptosis based on the target-induced hotspot effect

Yueyuan Zhuang,Han Dong,Tianqing Liu,Yongmei Zhao,Yan Xu,Xiaojuan Zhao,Dan Sun

Caspase-3 is an important biomarker for the process of apoptosis, which is a key target for cancer treatment. Due to its low concentration in single cells and the structural similarity of caspase family proteins, it is exceedingly challenging to accurately determine the intracellular caspase-3 during apoptosis in situ. Herein, a biosensing strategy based on the target-induced SERS “hot spot” formation has been developed for the simultaneous highly sensitive and selective detection of intracellular caspase-3 level. The nanosensor is composed of gold nanoparticles modified with the probe molecule 4-mercaptophenylboronic acid (4-MPBA) and a peptide chain. The well-designed peptide chain contains two distinct functional domains, one with a sulfhydryl group for bonding to the gold nanoparticles and the other a fragment specifically recognized by caspase-3. When caspase-3 is present, the negatively charged segment (NH2–Asp–Asp–Asp–Glu–Val–Asp–OH) of the peptide chain is specifically hydrolyzed, leaving a positively charged fragment coated on the surface of the gold nanoparticles. At this time, the golden nanoparticles undergo significant coupling aggregation due to the electrostatic interaction, resulting in a large number of SERS “hot spot” formation. The SERS signal of the 4-MPBA located at the nano-gap is significantly boosted because of the local plasma enhancement effect. The highly sensitive determination of caspase-3 can be achieved according to the altered SERS signal intensity of 4-MPBA. The turn-on of the SERS signal-induced target contributes to the excellent selectivity and the formation of the SERS “hot spot” effect that further improves the sensitivity of caspase-3 detection. The advantages of this biosensing technique allow for the precise in situ monitoring of the dynamic changes in caspase-3 levels during apoptosis. In addition, the differences in caspase-3 levels during the apoptosis of various cell types were compared. Monitoring the caspase-3 levels can be used to track the cellular apoptosis process, evaluate the effect of drugs on cancer cells in real time, and provide guidance for the selection of the appropriate drug dosage.

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CHEMICAL ENGINEERING JOURNAL · 2023 · IF 15.1

Recyclable magnetic nanoparticles combined with TiO2 enrichment and “Off” to “On” SERS assay for sensitive detection of alkaline phosphatase

Jiansen Lie,Feili Luo,Yafang Liu,Yixuan Yang,Qingling Nie,Xiaochuan Chen,Ruiyun You,Yunzhen Liu,Xiufeng Xiao,Yudong Lu

As an important enzyme in human tissues, abnormally alkaline phosphatase (ALP) is strongly associated with many diseases, particularly breast and prostate cancer. In this study, we proposed a rapid and sensitive surface-enhanced Raman scattering (SERS)-based biosensor for ALP detection. The biosensor utilized Fe 3 O 4 @Au@TiO 2 nanoparticles (FAT NPs) as magnetic separation and enrichment materials to enrich grafted mediator Ag-4-mercaptophenylboronic acid (4-MPBA)-ascorbic acid 2-phosphate (AAP) NPs to form FAT-(AAP-4-MPBA-Ag) NPs, and 5,5′-dithiobis-(2-nitrobenzoic acid) (DTNB) was used as the internal standard tag molecule to prepare Au@DTNB@Ag as the signal source. The phosphate group in AAP was cleaved by ALP to form ascorbic acid (AA), which acts as a receptor for the boric acid to adsorb the 4-MPBA-Au@DTNB@Ag NPs. When the switch was “Off” to “On”, the Au@DTNB@Ag NPs were used to significantly improve the sensitivity of the proposed SERS platform, enabling detection as low as 1.17U/L of target ALP with a good linear range (R 2  = 0.991) of 2–10 U/L. Furthermore, the platform successfully detected ALP from 2 % human serum. The recoveries were 99.5–106 %. In addition, FAT-(AAP-4-MPBA-Ag) NPs could be transformed into FAT NPs to achieve recyclability by ultrasonication in acidic environments. Overall, this sensitive and fast SERS platform has promising potential for accurate and efficient identification of ALP from human serum.

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SENSORS AND ACTUATORS B-CHEMICAL · 2023 · IF 8.4

Ratiometric SERS sensing chip for high precision and ultra-sensitive detection of SARS-CoV-2 RNA in human saliva

Xueliang Lin,Youliang Weng,Yi Liu,Duo Lin,Huishan Yang,Zhiwei Chen,Shangyuan Feng

The rapid and high precision analysis of SARS-CoV-2 RNA in saliva is crucial for the efficient prevention and control of COVID-19. Herein, we developed a novel ratiometric surface-enhanced Raman spectroscopy (SERS) sensing chip based on a two-dimensional core-molecule-shell-molecule nanostructure for quantitative detection of SARS-CoV-2 RNA. Owing to the use of base-complementary pairing mechanism, this SERS sensing chip has better selectivity in discriminating SARS-CoV-2 RNA against other RNA. Besides, an internal standard molecule (4MBN) in the SERS sensing chip can used to calibrate the real-time changing Raman signals of the probe molecule during quantitative assay. Using this cleverly designed SERS sensing chip, the dynamic ranges from 10 –6 M to 10 –12 M with a low of detection limit (LOD = 7.61 ×10 –14 M) can be acquired for detection of SARS-CoV-2 RNA. Meanwhile, this SERS sensing chip was well adapted for point-of-care testing (POCT) in combination with portable Raman spectrometer, which is expected to achieve effective detection of early SARS-CoV-2 infection.

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