SENSORS AND ACTUATORS B-CHEMICAL
·
2025
·
IF 7.7
Jiajun Li,Yunyun Mu,Guanwei Tao,Xinping Zhang
We report a line excitation scheme for surface enhanced Raman scattering (SERS) using a graphene substrate deposited with silver nanoparticles (AgNPs). Direct laser writing was employed for producing laser-induced graphene (LIG) layer on polyimide and electrochemical reaction was used to grow AgNPs onto the surface of LIG. In addition to the local-field enhancement on the plasmonic hotspots, the graphene-based charge-transfer and molecular adsorption properties make further contributions to the SERS mechanisms. Compared with conventional point excitation, the line excitation scheme allows much extended dynamic range of the excitation laser power before reaching the damage threshold of the target molecules, much enhanced Raman signal due to the integration over the focusing line, and high reliability/repeatability of the SERS signals. This also reduces significantly the sensitivity of the SERS signals to the randomly distributed nanostructures. Thus, much enlarged excitation area/volume for Raman interactions enables high stability of the signals with multiplied intensity through integration over the focusing line, as compared with point excitation scheme under the same excitation power density. The line excitation scheme shows a detection limit of 100 ppb in tracing melamine in water, attaining an enhancement factor of larger than 100, as compared with point excitation.
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Food Bioscience
·
2024
·
IF 4.8
Shunqian Zhuang,Jun Cheng,Songting Chen,Yuliang Li,Dazhi Ding,Zhilong Yu,Yunfei Xie
Lotus leaf is a super-hydrophobic material found in nature. Drawing inspiration from the micro-nano structure of lotus leaf surface, a hybrid surface-enhanced Raman spectroscopy (SERS) substrate owning both hydrophobic and hydrophilic properties was developed. The biomimetic part, which was fabricated by replicating the surface structure of lotus leaf using polydimethylsiloxane, exhibited a hydrophobic surface with a contact angle of 150.3°. Meanwhile, silver nanoparticles-coated filter paper was assembled on the top of the biomimetic part to render hydrophilic regions for SERS detection. Silver nanoparticles on the surface of filter paper owned a size of approximately 70–80 nm with an interval of about 5–10 nm. The hydrophobic/hydrophobic hybrid regions on the substrate significantly enhanced Raman signals of rhodamine 6g with mitigated coffee ring effects, showing a limit of detection low to 10 −10 M. Notably, the limit of detection of this technique for thiram on apple surface reached 0.5 ng/cm 2 , which was lower than the reported methods. The prepared substrate displayed exceptional uniformity and stability, with an RSD value of 7.21% calculated based upon 30 randomly selected Raman signals, and experienced a decrease in signal by only 29.7% after 30-d storage. This biomimetic substrate can be utilized for batch detection of pesticide residues on fresh produce with high sensitivity, thereby owning great potential for application as a rapid detection tool for food safety.
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Aggregate
·
2024
·
IF 13.9
Yu Yang,Hao Lu,Dan Fang,Yuyuan Zhang,Yuteng Tang,Songsong Zhao,Jun Yan,Xiaojie Qin,Jianlei Shen,Fan Yang
Solid bubbles have expanded the SERS assay toolbox, but their detection performance in biofluids is still hampered by the irrational design of the plasmonic sensing interface. A plasmonic bubble aggregate-driven DNA-encoded SERS assay is reported here that enables simultaneous, ultrasensitive, and specific detection of multiple miRNAs in blood samples for accurate cancer diagnosis. In this assay, the buoyancy of plasmonic bubbles allows them to self-aggregate at a droplet apex for SERS reconfiguration, form single-layer bubble aggregates with plasmonic nanogaps, and prevent the coffee ring effect during evaporation assembly. Furthermore, DNA-encoded plasmonic bubbles seamlessly couple with dual-color catalytic hybridization assembly to amplify the specific miRNA-responsive Raman signal, and function as both an analyte concentrator and a Raman signal aggregator without external forces. Using these merits, this magnet-free, portable assay achieves femtomolar dual-miRNA quantitation with single-base resolution, simultaneous miRNA detection across four cell lines, and accurate cancer diagnosis (AUC = 1) via analyzing 40 blood samples with machine learning, thus providing a promising tool for clinical diagnosis.
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INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
·
2024
·Vol. 25
·期 23
·12785
·
IF 4.9
Arina Pavlova,Ksenia Maleeva,Ivan V. Moskalenko,Vadim Belyaev,Mikhail V. Zhukov,Demid Kirilenko,Kirill V. Bogdanov,Evgeny Smirnov
Natural polyphenolic compounds play a pivotal role in biological processes and exhibit notable antioxidant activity. Among these compounds, chlorogenic acid stands out as one of the most widespread and important polyphenols. The accurate detection of chlorogenic acid is crucial for ensuring the quality and classification of the raw materials used in its extraction, as well as the final products in the food, pharmaceutical, and cosmetics industries that contain this bioactive compound. Raman spectroscopy emerges as a powerful analytical tool, particularly in field applications, due to its versatility and sensitivity, offering both qualitative and quantitative analyses. By using the self-assembly of gold nanoparticles at liquid–liquid interfaces and the developed “aqua-print” process, we propose a facile and inexpensive route to fabricate enhanced substrates for surface-enhanced Raman spectroscopy with high reproducibility. To ensure substrate reliability and accurate molecule detection in SERS experiments, a benchmarking procedure was developed. This process involved the use of non-resonant rhodamine 6G dye in the absence of charge transfer and was applied to all synthesized nanoparticles and fabricated substrates. The latter revealed the highest enhancement factor of 4 × 104for 72 nm gold nanoparticles among nanoparticle diameters ranging from 14 to 99 nm. Furthermore, the enhanced substrate was implemented in the detection of chlorogenic acid with a concentration range from 10 μM to 350 μM, demonstrating high accuracy (R2> 99%). Raman mapping was employed to validate the good uniformity of the signal (the standard deviation was below 15%). The findings of this study were also supported by DFT calculations of the theoretical Raman spectra, demonstrating the formation of the chlorogenic acid dimer. The proposed method is strategically important for the development of the class of in-field methods to detect polyphenolic compounds in raw materials such as plants, extracted plant proteins, and polyphenolic compounds.
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Biosensors-Basel
·
2024
·Vol. 14
·期 4
·202
·
IF 4.9
Zimeng Gu,Di Zhao,Hongyan He,Zhenhui Wang
Tyrosinase (TYR) emerges as a key enzyme that exerts a regulatory influence on the synthesis of melanin, thereby assuming the role of a critical biomarker for the detection of melanoma. Detecting the authentic concentration of TYR in the skin remains a primary challenge. Distinguished from ex vivo detection methods, this study introduces a novel sensor platform that integrates a microneedle (MN) biosensor with surface-enhanced Raman spectroscopy (SERS) technology for the in situ detection of TYR in human skin. The platform utilized dopamine (DA)-functionalized gold nanoparticles (Au NPs) as the capturing substrate and 4-mercaptophenylboronic acid (4-MPBA)-modified silver nanoparticles (Ag NPs) acting as the SERS probe. Here, the Au NPs were functionalized with mercaptosuccinic acid (MSA) for DA capture. In the presence of TYR, DA immobilized on the MN is preferentially oxidized to dopamine quinone (DQ), a process that results in a decreased density of SERS probes on the platform. TYR concentration was detected through variations in the signal intensity emitted by the phenylboronic acid. The detection system was able to evaluate TYR concentrations within a linear range of 0.05 U/mL to 200 U/mL and showed robust anti-interference capabilities. The proposed platform, integrating MN-based in situ sensing, SERS technology, and TYR responsiveness, holds significant importance for diagnosing cutaneous melanoma.
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ANALYTICAL CHEMISTRY
·
2025
·
IF 6.7
Yue Hu,Lei Xu,Xinyu Miao,Yujiao Xie,Zhouxu Zhang,Yuening Wang,Wenzhi Ren,Wenting Jiang,Xiaotian Wang,Aiguo Wu,Jie Lin
Early diagnosis and precise identification of breast cancer subtypes are vital. However, current detection methods are often hindered by high costs and complexity. This study aims to develop an efficient and noninvasive method to realize efficient breast cancer detection. First, hexoctahedral gold nanoparticles (Au HNPs) are constructed, which detect molecules with concentrations as low as 10–12 M, and the EF value is ∼3.8 × 108. Then, two optical bioprobes with a surface-enhanced Raman scattering (SERS)-fluorescence (FL) dual-modal function for breast cancer cell detection and subtype identification are designed. These bioprobes exhibit excellent SERS stability since the spectral relative standard deviation (RSD) of the SERS-FL bioprobe achieves a good level of ∼10.4%. Additionally, the clear distinction between breast cancer cells and white blood cells (WBCs) under a fluorescence microscope showed that bioprobes have a good fluorescence imaging ability. More importantly, by creatively stitching the SERS spectra of the two bioprobes, a “symphonic SERS spectra” is constructed, and a linear discriminant analysis (LDA) machine learning algorithm is employed, enabling high-precision classification of breast cancer subtypes with an accuracy of 94%. This study proposes an innovative strategy combined with SERS and FL technology, which provides the possibility for rapid and accurate detection of breast cancer subtypes.
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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY
·
2024
·
IF 4.3
Yuqing Gu,Siyi Wu,Zhewen Luo,Linley Li Lin,Jian Ye
Label-free surface-enhanced Raman spectroscopy (SERS) has attracted extensive attention as an emerging technique for molecular phenotyping of biological samples. However, the selective enhancement property of SERS mediated by complicated interactions between substrates and analytes is unfavorable for molecular profiling. The electrostatic force is among the most dominating interactions that can cause selective adsorption of molecules to charged substrates. This means if only negatively- or positively-charged SERS substrates are applied, then considerable SERS information from a portion of analytes would be lost, hindering comprehensive SERS sensing. In this work, we utilize both negatively- and positively-charged colloidal silver (Ag) nanoparticles (NPs) to detect various charged molecules. The negatively-charged citrate-stabilized Ag and the positively-charged Ag prepared via a cetyltrimethyl-ammonium chloride-based charge reversal protocol have been adopted as SERS substrates. The Ag NPs are all relatively well-dispersed with good uniformity. After applying the oppositely-charged NPs to the detection of charged molecules, we find the SERS results explicitly demonstrate the electrostatically-driven SERS selective enhancement, which is further supported and clarified by molecular electrostatic potential calculations. Our work highlights the importance of developing SERS substrates modified with appropriate surface charges for various analytes, and enlightens us that potentially more molecular SERS information can be acquired from complex bio-samples using combinations of oppositely-charged substrates.
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ANALYTICAL CHEMISTRY
·
2024
·
IF 6.7
Ping Wen,Feng Yang,Haixia Zhao,Yi Xu,Shunbo Li,Li Chen
In this work, we present a simple and novel digital surface-enhanced Raman spectroscopy (SERS)-microfluidic chip designed for the rapid and accurate quantitative detection of microorganisms. The chip employs a high-density inverted pyramid microcavity (IPM) array to separate and isolate microbial samples. The presence or absence of target microorganisms is determined by scanning the IPM array using SERS and identifying the characteristic Raman bands. This approach allows for the “digitization” of the SERS response of each IPM, enabling quantification through the application of mathematical statistical techniques. Significantly, precise quantitative detection of yeast was achieved within a concentration range of 106–109 cells/mL, with the maximum relative standard deviation from the concentration calibrated by the cultivation method being 5.6%. This innovative approach efficiently addresses the issue of irregularities in SERS quantitative detection, which arises due to fluctuations in SERS intensity and poor reproducibility. We strongly believe that this digital SERS-microfluidic chip holds immense potential for diverse applications in the rapid detection of various microorganisms, including pathogenic bacteria and viruses.
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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS
·
2024
·
IF 4.9
Weibing Wu,Sijie Li,Wen Deng,Shanshan Zhai,Youlu Chu,Xingyue Liu,Peng Li,Lei Zhang
Surface enhanced Raman scattering spectroscopy (SERS) technology has received increasing attention in the bioimaging field. Herein, based on the support of cellulose nanocrystal (CNC) with thiol groups, one-dimensional (1D) "hot spot" structure was constructed by the self-assembly of gold nanoparticles (AuNPs) via Au-S bonding. Silica shell was subsequently coated on the CNC loaded with AuNPs to fabricate core-shell SERS nanoprobe, which was further successfully applied for the SERS imaging of Hela cells. Owing to the presence of silica shell, the nanoprobe exhibited excellent water-dispersible stability in phosphate buffer salt solution (PBS). Moreover, the silica shell effectively protected both the "hot spot" structure and the adsorbed Raman reporter of 4-mercaptobenzoic acid from external interference, thereby improving the signal stability of SERS nanoprobe. In addition, the plasma coupling of electromagnetic field between AuNPs and silica significantly enhanced the Raman signal of "hot spots". The SERS nanoprobe possessed good biocompatibility even at relatively high concentrations, and successfully achieved bioimaging of Hela cell using the Raman signal at 1580 cm -1 channel.
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JOURNAL OF LUMINESCENCE
·
2024
·
IF 3.3
Haoquan Wang,Qi Yang,Yan Zhang,Bo Peng,Feng Wu,Zewei Quan
Developing a SERS nanotag with high signal intensity, excellent signal stability, and biocompatibility is of significant importance in the fields of food safety, drug testing, and virus detection. In this work, silica-encapsulated, indocyanine green (ICG)-modified Au octahedral core-small Au spherical nanoparticles (NPs) satellite nanostructures (Au/Au@ICG@SiO 2 ) are uniformly synthesized as surface-enhanced Raman scattering (SERS) tags, which provide abundant “hot spots” and also increase the stability of Raman reporter molecule ICG to greatly facilitate subsequent functionalization and detection. Both experimental and numerical results demonstrate that this Au/Au@ICG nanostructure achieve a detection limit of 10⁻⁷ M for ICG in aqueous solution ascribed to the increased number of hot spots compared with Au octahedral NPs. As-prepared Au/Au@ICG@SiO 2 SERS nanotags are further integrated with a lateral flow immunoassay (LFIA) for the detection of the SARS-CoV-2 nucleocapsid protein. Compared to the traditional bio-recognition method on LFIA strips with the detection limit of 8 pg/mL, the detection capability for the SARS-CoV-2 nucleocapsid protein is improved approximately 16 times (500 fg/mL) based on this novel SERS tag and custom-built adaptive Raman mapping spectrometer. This Au/Au@ICG@SiO 2 SERS tag is expected to play a significant role in early detection, prevention, and control of similar infectious viruses in the future.
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JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2025
·
IF 9.7
Xiangqian Kong,Wenyan Xia,Yuruo Qiu,Bingrui Zhao,Yuan Zhao,Wei Ma
Polystyrene (PS) plastics were potentially present in consumer products through the use of plastics packaging. The migration and enduring presence for bioaccumulation posed significant threats to human health and the environment. It was significant to develop a simple and reliable approach for sensitive PS plastics detection. In this study, Au-Bi 2 Se 3 hybrid nanosheets (NSs) were designed and utilized as SERS probes for the detection of PS plastics. The electron transfer from Bi 2 Se 3 to AuCl 4 − induced the formation of Au NPs on the surface of thin Bi 2 Se 3 NSs. Au-Bi 2 Se 3 hybrid NSs were found to display enhanced SERS activity by using PS plastics as Raman tags. Besides the unique electromagnetic enhanced mechanism from Au NPs, the introduction of Bi 2 Se 3 supported the Dirac plasmon polaritons in electromagnetic modes, and Bi 2 Se 3 with high dielectric constants inhibited the decay of electromagnetic waves. Au-Bi 2 Se 3 hybrid NSs engineered SERS sensor achieved stable and sensitive detection of PS plastics in essence liquid. Different sized PS plastics ranging from 89.3 nm to 1.48 μm were detected with the LODs of ppm levels. These findings highlight the potential of Au-Bi 2 Se 3 hybrid NSs as effective and universal SERS substrates for detecting different sized plastics in real samples.
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SENSORS AND ACTUATORS B-CHEMICAL
·
2024
·
IF 8
Changkun Song,Hongbiao Huo,Wei Shi,Jianyong Xu,Xiaoting Lei,Bonan Gu,Zhongbo Han,Wenchao Zhang
Surface-enhanced Raman spectroscopy (SERS) is strongly dependent on the metallic plasmonic nanostructures that can generate plasmon resonance coupling effects. Plasmonic nanostructures with sub-nanometer interparticle gaps or cavities have shown great potential in generating high local electromagnetic fields. Unfortunately, achieving precise control over the geometrical morphology of these nanostructures at the sub-nanometer scale presents significant challenges, particularly in applications where high consistency and homogeneity are required. Here, a reliable approach is proposed to construct plasmon-coupled Ag nanosphere-internalized nanocavity (SIC) arrays to enhance sensitivity and reproducibility in SERS sensing. This novel SIC nanostructure consists of a precise arrangement of Ag nanospheres located at the bottom of Au nanocavities, separated by a precisely controlled nano-Al 2 O 3 dielectric layer. The Al 2 O 3 dielectric layer plays a crucial role in inhibiting quantum tunneling effects at the nanogaps, thereby suppressing charge recombination and leading to strong plasmon resonance coupling. The SERS enhancement tends to significantly diminishes as the nanogap size increases from 4 to 10 nm, a spatially averaged SERS enhancement factor of 3.5 * 10 8 was obtained when the gap size is 4 nm, aligning well with the FDTD simulation results. As a representative application, an indirect detection strategy is utilized to selectively detect TNT with a high level of homogeneity and reproducibility, achieving a relative standard deviation of less than 7.8 %. Together with the capability to be fabricated on a flexible polyimide substrate, the SIC substrate shows significant potential for practical applications.
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