surface enhanced Raman spectroscopy

表面增强拉曼光谱
  • 文章类型: Journal Article
    17β-E2用于动物生长调节和农业肥料,甚至ngL-1质量浓度水平也能显示出生物学效应。在这项工作中,将AgNPs用作表面增强拉曼光谱(SERS)源,并通过简单的方法合成WS2,为AgNPs提供均匀分布平台。MIP是外壳,可以选择性地富集目标分子,拉靶分子和SERS源之间的距离,并保护AgNPs。构建了具有高灵敏度的可循环SERS底物,用于检测食品中的17β-E2。优化的WS2/Ag@MIP作为SERS基底具有高增强因子(EF=2.78×109)的优点,低检测限(LOD=0。0958pM),抗干扰能力强,和良好的回收性能。此外,实际样品中17β-E2的检测仍具有较好的准确性。本研究为食品中17β-E2的痕量检测提供了新的可能。
    17β-E2 is used in animal growth regulation and agricultural fertilizer, and even ng L-1 mass concentration levels can show biological effects. In this work, Ag NPs was used as surface-enhanced Raman spectroscopy (SERS) source and WS2 was synthesized by a simple method to provide a uniform distribution platform for Ag NPs. The MIP was the shell, which can selectively enrich the target molecule, pull the distance between the target molecule and SERS source, and protect Ag NPs. A cyclable SERS substrate with high sensitivity for detecting 17β-E2 in food was constructed. The optimized WS2/Ag@MIP as SERS substrate has the advantages of high Enhanced Factor (EF = 2.78 × 109), low detection limit (LOD = 0. 0958 pM), strong anti-interference ability, and good recycling performance. Moreover, the detection of 17β-E2 in real samples still has good accuracy. This work provides a new possibility for the trace detection of 17β-E2 in food.
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  • 文章类型: Journal Article
    根据许多国家的规定,食品和药物制剂中的大肠杆菌污染需要严格控制。然而,快速、灵敏的大肠杆菌检测仍然是一个挑战。在这项研究中,开发了一种基于适体的表面增强拉曼光谱(SERS)夹心方法,用于使用适体功能化的Au-Ag@Si三角金字塔(TP)底物快速灵敏地检测大肠杆菌。用大肠杆菌适体将Au-Ag@SiTP底物官能化,以通过与拉曼报道分子(6-羧基-X-罗丹明)整合作为捕获探针和SERS标签。捕获探针的制作,SH-apt@Au-Ag@SiTP,简单快速(20.5小时)。该方法能在约3h内选择性快速检测大肠杆菌,检出限为2.8CFU/mL。新皇片,回收率为90.19%至104.17%。结果表明,该方法简便、快速,它可能是一种有前途的替代方法,用于现场检测药物和食品样品中的大肠杆菌。
    Escherichia coli contamination in food and pharmaceutical preparations needs to be strictly controlled according to the regulations in many countries. However, rapid and sensitive E. coli detection is still a challenge. In this study, an aptamer-based surface-enhanced Raman spectroscopy (SERS) sandwich method was developed for the rapid and sensitive detection of E. coli using an aptamer-functionalized Au-Ag@Si triangular pyramid (TP) substrate. The Au-Ag@Si TP substrate was functionalized with E. coli aptamer to work as both the capture probe and SERS tag by integrating with Raman reporter (6-carboxy-X-rhodamine). The fabrication of the capture probe, SH-apt@Au-Ag@Si TP, was simple and rapid (20.5 h). This method could selectively and rapidly detect E. coli with a limit of detection of 2.8 CFU/mL within approximately 3 h. It was successfully applied to a traditional Chinese medicine preparation, Xinhuang tablets, with recoveries ranging from 90.19 % to 104.17 %. The results indicated that the developed method was simple and rapid, and it could be a promising alternative for the on-site detection of E. coli in pharmaceutical and food samples.
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  • 文章类型: Journal Article
    鼻咽癌(NPC)是一种在东南亚地区患病率高,具有高侵袭性和转移性特征的恶性肿瘤。放射治疗是鼻咽癌治疗的主要策略,然而,仍然缺乏预测治疗失败的主要原因辐射抗性的效果方法。在这里,放疗敏感和耐药组和健康组的鼻咽癌患者血浆的分子谱,分别,首次采用基于表面等离子体共振的无标记表面增强拉曼光谱(SERS)进行了研究。尤其是,通过分离过程分析了不同分子量大小的组分,有助于避免由于竞争性吸附而可能丢失的诊断信息。在此之后,采用基于主成分分析和线性判别分析的鲁棒机器学习算法(PCA-LDA)对血液SERS数据进行特征提取,建立了有效的预测模型,准确率达96.7%,100%用于识别健康的NPC受试者。这项工作证明了分子分离辅助无标记SERS结合机器学习在临床场景中用于NPC筛查和治疗策略指导的潜力。
    Nasopharyngeal cancer (NPC) is a malignant tumor with high prevalence in Southeast Asia and highly invasive and metastatic characteristics. Radiotherapy is the primary strategy for NPC treatment, however there is still lack of effect method for predicting the radioresistance that is the main reason for treatment failure. Herein, the molecular profiles of patient plasma from NPC with radiotherapy sensitivity and resistance groups as well as healthy group, respectively, were explored by label-free surface enhanced Raman spectroscopy (SERS) based on surface plasmon resonance for the first time. Especially, the components with different molecular weight sizes were analyzed via the separation process, helping to avoid the possible missing of diagnostic information due to the competitive adsorption. Following that, robust machine learning algorithm based on principal component analysis and linear discriminant analysis (PCA-LDA) was employed to extract the feature of blood-SERS data and establish an effective predictive model with the accuracy of 96.7% for identifying the radiotherapy resistance subjects from sensitivity ones, and 100% for identifying the NPC subjects from healthy ones. This work demonstrates the potential of molecular separation-assisted label-free SERS combined with machine learning for NPC screening and treatment strategy guidance in clinical scenario.
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  • 文章类型: Journal Article
    长链非编码RNA(lncRNA)作为转录调节因子在疾病中具有重要作用,mRNA加工调节剂和蛋白质合成因子。然而,传统的检测lncRNA的方法耗时耗力,lncRNA的功能仍在探索中。这里,我们提出了一种基于表面增强拉曼光谱(SERS)的生物传感器,用于检测与肝癌(LC)相关的lncRNA以及原位细胞成像。使用双SERS探头,lncRNA(DAPK1-215)的定量检测可以通过靶触发的核心卫星纳米结构的组装以952aM的超低检测限实现。并且该测定的可靠性可以通过能够进行信号动态校准的内标探针以0.9923的R2值进一步提高。同时,使用SERS成像方法,与正常细胞相比,在LC细胞中观察到DAPK1-215主要分布在细胞质中的高表达。此外,细胞功能检测结果显示,DAPK1-215通过显著降低死亡相关蛋白激酶结构域的表达,促进LC的迁移和侵袭。这种基于SERS的生物传感器的开发可以为探索lncRNA的表达提供灵敏而特异的方法,lncRNA将是筛选LC的潜在生物标志物。
    Long-stranded non-coding RNAs (lncRNA) have important roles in disease as transcriptional regulators, mRNA processing regulators and protein synthesis factors. However, traditional methods for detecting lncRNA are time-consuming and labor-intensive, and the functions of lncRNA are still being explored. Here, we present a surface enhanced Raman spectroscopy (SERS) based biosensor for the detection of lncRNA associated with liver cancer (LC) as well as in situ cellular imaging. Using the dual SERS probes, quantitative detection of lncRNA (DAPK1-215) can be achieved with an ultra-low detection limit of 952 aM by the target-triggered assembly of core-satellite nanostructures. And the reliability of this assay can be further improved with the R2 value of 0.9923 by an internal standard probe that enables the signal dynamic calibration. Meanwhile, the high expression of DAPK1-215 mainly distributed in the cytoplasm was observed in LC cells compared with the normal ones using the SERS imaging method. Moreover, results of cellular function assays showed that DAPK1-215 promoted the migration and invasion of LC by significantly reducing the expression of the structural domain of death associated protein kinase. The development of this biosensor based on SERS can provide a sensitive and specific method for exploring the expression of lncRNA that would be a potential biomarker for the screening of LC.
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  • 文章类型: Journal Article
    表面增强拉曼光谱(SERS)利用分子振动的指纹特征来识别和检测物质。然而,在传统的单焦点激励场景中,其目的的信号采集效率受到限制。此外,样品在SERS基底上的不均匀分布会导致信号稳定性差,同时限制激励功率以避免样品损坏。SERS检测系统总是需要精确调整焦距和光斑尺寸,这使得即时测试应用变得困难。这里,我们提出了一种采用真空自组装热压方法嵌入钛酸钡微球阵列(BTMA)的SERS微流控芯片,用于SERS检测,同时提高了灵敏度和稳定性。由于光子纳米射流和定向天线效应,高折射率微球是完美的微透镜,用于有效的光聚焦和信号收集。BTMA不仅可以将激发光束分散到均匀覆盖目标的焦点阵列中,并且信号波动非常低,但放大功率阈值以获得更高的信号强度。我们在芯片上进行了原理验证实验,以使用免疫磁性标签和免疫SERS标签检测细菌。连同磁性和超声波操作,流中的目标细菌均匀地聚集在BTMA的焦平面上。它显示了5个细胞/mL的检测限,优异的信号再现性(误差4.84%),在X-Y平面上具有500μm的出色位置公差(误差〜5.375%)。可见BTMA-SERS微流控芯片能有效解决SERS检测中灵敏度与稳定性的矛盾。
    Surface enhanced Raman spectroscopy (SERS) utilizes the fingerprint features of molecular vibrations to identify and detect substances. However, in traditional single focus excitation scenarios, its signal collection efficiency of the objective is restricted. Furthermore, the uneven distribution of samples on the SERS substrate would result in poor signal stability, while the excitation power is limited to avoid sample damage. SERS detection system always requires precise adjustment of focal length and spot size, making it difficult for point-of-care testing applications. Here, we proposed a SERS microfluidic chip with barium titanate microspheres array (BTMA) embedded using vacuum self-assembled hot-pressing method for SERS detection with simultaneous enhancement of sensitivity and stability. Due to photonic nano-jets and directional antenna effects, high index microspheres are perfect micro-lens for effective light focusing and signal collecting. The BTMA can not only disperse excitation beam into an array of focal points covering the target uniformly with very low signal fluctuation, but enlarge the power threshold for higher signal intensity. We conducted a proof-of-principle experiment on chip for the detection of bacteria with immuno-magnetic tags and immuno-SERS tags. Together with magnetic and ultrasonic operations, the target bacteria in the flow were evenly congregated on the focal plane of BTMA. It demonstrated a limit of detection of 5 cells/mL, excellent signal reproducibility (error∼4.84%), and excellent position tolerance of 500 μm in X-Y plane (error∼5.375%). It can be seen that BTMA-SERS microfluidic chip can effectively solve the contradiction between sensitivity and stability in SERS detection.
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  • 文章类型: Journal Article
    尽管薄膜技术(DGT)中的扩散梯度已经实现了磺胺二甲嘧啶(SMT)的原位采样,传统的DGT设备不能用作传感设备,而是原位采样设备。在这里,我们报告了一种可回收的表面增强拉曼散射(SERS)响应DGT传感设备(可回收的SERS-DGT传感设备),能够原位感测水中的SMT。这是通过创新性地利用负载在g-C3N4(Au@g-C3N4NS)上的Au纳米颗粒的可回收SERS响应液体悬浮液作为DGT结合相来实现的。Au@g-C3N4NS通过原位生长法合成并嵌入DGT结合阶段,表现出良好的SERS活性,水稳定性可回收和吸附性能。SERS-DGT传感设备在广泛的条件下(即,部署时间24-180小时,浓度范围为1.031~761.9ngmL-1,pH为5~9,离子强度为0.0001~0.05molL-1NaCl,DOM浓度0~100mgL-1,四次回收)。此外,底物与DGT结合阶段,可以集成采样,SMT的预处理和SERS检测,可以回收利用,提高环境监测的可靠性和效率。在这篇文章中,可回收SERS-DGT传感装置,一个可回收的抗生素原位传感平台,具有巨大的环境监测潜力。
    Although diffusion gradient in thin-film technique (DGT) has realized the in-situ sampling Sulfamethazine (SMT), the traditional DGT devices cannot be served as sensing devices but in-situ sampling devices. Here we report a recyclable surface enhanced Raman scattering (SERS) responsive DGT sensing device (recyclable SERS-DGT Sensing Device) capable of in-situ sensing of SMT in water. This is achieved by innovatively utilizing a recyclable SERS responsive liquid suspension of Au nanoparticles supported on g-C3N4 (Au@g-C3N4NS) as DGT binding phase. Au@g-C3N4NS is synthesized via in-situ growth method and embed in DGT binding phase, which exhibits good SERS activity, aqueous stability recyclable and adsorption performance. The SERS-DGT Sensing Device is valid for measuring SMT under a wide range of conditions (i.e., deployment time 24∼180 h, concentrations range of 1.031∼761.9 ng mL-1, pH 5∼9, ionic strength 0.0001∼0.05 mol L-1 NaCl, DOM concentrations 0∼100 mg L-1, four recycles). Furthermore, substrate combined with DGT binding phase, can integrate the sampling, pretreatment and SERS detection of SMT, which can be recycled, improving the reliability and efficiency of environmental monitoring. In this article, recyclable SERS-DGT Sensing Device, a platform for recyclable in-situ sensing of antibiotics, holds great potential for environmental monitoring.
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  • 文章类型: Journal Article
    贵金属一直被用作SERS衬底的优选基底。然而,这种材料的制备成本非常高。因此,许多研究人员已经开始寻找成本更低的sucedanea。在这项工作中,通过原位还原法合成了CsPbBr3@ZIF-8,并与石墨烯纳米片结合构建了SERS基底。钙钛矿量子点和石墨烯的协同作用可以进一步增强该基底的SERS性能。基于这种材料,由CsPbBr3@ZIF-8@G组成的敏感SERS策略,抗体,并建立了定量测定人血清中肌钙蛋白I(cTnI)的Bradford方法。值得注意的是,该方法的灵敏度和准确性可以接近其他使用贵金属的SERS方法的水平。“反向”-SERS方法可以明显提高检测平台的均匀性和稳定性。该方法的检测范围为0.01-100ng/mL,估计检出限(LOD)为4.7pg/mL。该方法的回收率在93.1%~104.8%之间,RSD范围为4.47%~7.06%。
    Noble metal has always been used as a preferred base for SERS substrate. However, the preparation cost of such materials is trully high. Therefore, many researchers have begun to search for succedanea which cost were lower. In this work, CsPbBr3@ZIF-8 was synthesized by in-situ reduction method and combined with graphene nanosheets to construct a SERS substrate. The SERS performance of this substrate could be further enhanced by the synergistic effect of perovskite quantum dots and graphene. Base on this material, a sensitive SERS strategy composed of CsPbBr3@ZIF-8@G, antibody, and Bradford method was developed for the quantitative determination of cardiac troponin I (cTnI) in human serum. It\'s worth noting that the sensitivity and accuracy of this method could approach the level of other SERS methods using noble metals. The \"reverse\"-SERS method could improve the uniformity and stability of detection platform obviously. The detection range of this method was 0.01-100 ng/mL, and the estimated detection of limit (LOD) was 4.7 pg/mL. The recovery rate of this method range was between 93.1 % and 104.8 %, and RSD range was between 4.47 % and 7.06 %.
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  • 文章类型: Journal Article
    尽管薄膜技术(DGT)中的扩散梯度在环境分析中受到高度重视,传统的DGT设备不能用作传感设备,而是原位采样设备。在这里,我们报告了一种表面增强拉曼散射(SERS)响应DGT传感设备(SERS-DGT传感器),能够现场确定水下有机污染物。这是通过创新性地利用负载在氧化石墨烯(AuNPs@GO)上的Au纳米颗粒的SERS响应液体悬浮液作为DGT结合相来实现的。液体悬浮液是通过组合的二次生长和分子焊接方法合成的,并用作DGT结合阶段AuNPs@GO表现出良好的SERS活性,水稳定性,和吸附性能。基于24-144小时的开发时间范围,SERS-DGT传感器对磺胺嘧啶(SMT)的测量在0.3289-2631ngmL-1的浓度范围内进行评估。SERS-DGT采样器适用于在各种环境条件下测量SMT(i。e,pH5-9,离子强度0.0001-0.05molL-1NaCl,DOM浓度0-100mgL-1,TC:SMT≤20和MNZ:SMT≤20的值)。SERS-DGT传感器应用于生猪养殖废水中SMT含量的实际测试,并与抓取抽样方法进行了比较,结果证实,这种新的连字符技术具有良好的准确性和精密度。通过将该方法扩展到罗丹明6G的监测,该平台被证明是通用的,甲硝唑,氟西汀,和恩诺沙星.在这篇文章中,SERS-DGT传感器,用于直接现场感测有机DGT的平台,对于各种有机物的原位采样和现场传感具有巨大的潜力,并为环境监测提供了新思路。
    Although diffusion gradient in the thin-film technique (DGT) is highly regarded in environmental analysis, the traditional DGT devices cannot serve as sensing devices but in situ sampling devices. Here we report a surface enhanced Raman scattering (SERS) responsive DGT sensing device (SERS-DGT Sensor) capable of on-site determination of organic contaminants underwater. This is achieved by innovatively utilizing a SERS responsive liquid suspension of Au nanoparticles supported on graphene oxide (AuNPs@GO) as the DGT binding phase. Liquid suspension is synthesized via a combined secondary growth and molecular welding approach and used as DGT binding phase AuNPs@GO exhibit good SERS activity, aqueous stability, and adsorption performance. Based on the development time range of 24-144 h, the measurement of sulfadiazine (SMT) by SERS-DGT Sensor is evaluated in the concentration range of 0.3289-2631 ng mL-1. The SERS-DGT sampler is valid for measuring SMT under a wide range of environmental conditions (i.e, pH 5-9, ionic strength 0.0001-0.05 mol L-1 NaCl, DOM concentrations 0-100 mg L-1, the values of TC: SMT ≤ 20 and MNZ: SMT ≤ 20). SERS-DGT Sensor is applied to the practical test of SMT content in pig breeding wastewater, and compared with the grab sampling method, the results confirm that this novel hyphenated technique exhibits good accuracy and precision. The platform proves to be versatile by extending the method to the monitoring of rhodamine 6G, metronidazole, fluoxetine, and enrofloxacin. In this article, SERS-DGT Sensor, a platform for directly on-site sensing of organic DGT, holds great potential for in situ sampling and on-site sensing for a wide range of organics and provides a new idea for environmental monitoring.
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  • 文章类型: Journal Article
    快速准确地检测人体血液中罕见的循环肿瘤细胞(CTC)仍然是一个挑战。我们提出了一种基于适体SERS生物探针识别和微孔膜过滤捕获的表面增强拉曼光谱(SERS)方法,用于在单细胞水平上检测CTC。具有优化微孔尺寸的聚对二甲苯微孔膜安装在过滤支架上,可以在不到10s的时间内通过重力捕获生物探针标记的CTC,只有很少的白细胞(WBC)残留。为了促进适体SERS生物探针的合成,建立了乙酸乙酯脱水方法。在乙酸乙酯的帮助下,通过将SH-适体与4-巯基苯甲酸(4-MBA)修饰的AuNPs结合,可以在2h内快速合成生物探针。具有选择的特异性适体的SERS生物探针可以基于其在1075cm-1处的拉曼信号强度差异,有效且可靠地将单个人非小细胞肺癌A549细胞与膜上的残留WBC区分开。通过滤膜与适体-SERS生物探针系统耦合,甚至可以检测到模拟CTC样本的血液溶液中的20个A549细胞,其回收率和识别率均在90%以上。这种方法是快速的,可靠且具有成本效益,表明CTCs检测具有良好的临床应用前景。
    Rapid and accurate detection of rare circulating tumor cells (CTCs) in human blood still remains a challenge. We present a surface enhanced Raman spectroscopy (SERS) method based on aptamer-SERS bio-probe recognition coupled with micropore membrane filtration capture for the detection of CTCs at single cell level. The parylene micropore membrane with optimized micropore size installed on a filtration holder could capture bio-probe labeled CTCs by gravity in less than 10 s, and only with very less white blood cells (WBCs) residual. In order to facilitate the synthesis of the aptamer-SERS bio-probe, ethyl acetate dehydration method was established. The bio-probe can be rapidly synthesized within 2 h by binding SH-aptamer to 4- mercaptobenzoic acid (4-MBA) modified AuNPs with the help of ethyl acetate. The SERS bio-probe with selected specific aptamer could distinguish single human non-small cell lung cancer A549 cells from residual WBCs on membrane efficiently and reliably based on their Raman signal intensity difference at 1075 cm-1. Through the filter membrane coupled with aptamer-SERS bio-probe system, even 20 A549 cells in blood solution simulating CTCs sample can be detected, which the recovery rate and recognition rate are more than 90%. This method is rapid, reliable and cost-effective, which indicates a good prospect in clinical application for CTCs detection.
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  • 文章类型: Journal Article
    由于环境中积累的微塑料(MPs)和纳米塑料(NPs)对野生动植物的潜在危害,已被确定为主要的全球问题。目前对MPs检测的研究已经建立。然而,NPs的检测仍然具有挑战性。本文的目的是研究高速离心PSNP和AgNP后,使用表面增强拉曼光谱(SERS)技术在超疏水基底上检测聚苯乙烯(PS)NP。疏水性基质减少了液滴的接触面积,将PSNPs和AgNPs集中在一个小地方,这消除了纳米颗粒的随机分布。浓缩的PSNP和AgNP提高了SERS强度,繁殖和检测灵敏度。结果表明,在疏水性基底上进行SERS测量可以显着提高PSNPs的检测灵敏度,PSNP的检测限低至0.5mg/L(500nmPSNP)和1mg/L(100nmPSNP)。该研究为痕量NPs的快速检测提供了一种有效的方法,证明了将来在水生环境中检测痕量NP的可能性更大。
    Microplastics (MPs) and Nanoplastics (NPs) accumulated in the environment have been identified as a major global issue due to their potential harm to wildlife. Current research in the detection of MPs is well established. However, the detection of NPs remains challenging. The aim of this paper is to investigate the detection of polystyrene (PS) NPs on a super-hydrophobic substrate using surface-enhanced Raman spectroscopy (SERS) technology after high-speed centrifugation of PS NPs and AgNPs. The hydrophobic substrate reduces the contact area of droplet, concentrating PS NPs and AgNPs on a small spot, which eliminates the random distribution of nano particles. The condensed PS NPs and AgNPs improve the SERS intensity, reproductivity and detection sensitivity. The results show that SERS measurement on a hydrophobic substrate could significantly improve the detection sensitivity of PS NPs, with the detection limits of PS NPs as low as 0.5 mg/L (500 nm PS NPs) and 1 mg/L (100 nm PS NPs). The study provides an effective and rapid method for the detection of NPs at trace concentration, demonstrating more possibility for the future detection of trace NPs in the aquatic environment.
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