Facing Challenges in Real-Life Application of Surface-Enhanced

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Facing Challenges in Real-Life Application of Surface-Enhanced Raman Scattering (SERS): Design and Nanofabrication of SERS Substrates for Rapid Field Test of Food Contaminants Ruyi Shi, Xiangjiang Liu, and Yibin Ying J. Agric. Food Chem., Just Accepted Manuscript • DOI: 10.1021/acs.jafc.7b03075 • Publication Date (Web): 18 Sep 2017 Downloaded from http://pubs.acs.org on September 18, 2017

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Journal of Agricultural and Food Chemistry

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Facing Challenges in Real-Life Application of

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Surface-Enhanced Raman Scattering (SERS):

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Design and Nanofabrication of SERS Substrates for

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Rapid Field Test of Food Contaminants

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Ruyi Shi,† Xiangjiang Liu,† Yibin Ying*,†, ‡

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†

College of Biosystems Engineering and Food Science, Zhejiang University, 866 Yuhangtang

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Road, Hangzhou, Zhejiang 310058, China ‡

Zhejiang A&F University, 88 Huanchengdong Road, Hangzhou, Zhejiang 311300, China

* Corresponding author: Email: [email protected] (Y. B. Ying)

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RECEIVED DATE (to be automatically inserted after your manuscript is accepted if

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required according to the journal that you are submitting your paper to)

ACS Paragon Plus Environment

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ABSTRACT

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Surface-enhanced Raman scattering (SERS) is capable of detecting single molecule with high

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specificity and has become a promising technique for rapid chemical analysis of agricultural

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products and foods. With a deeper understanding of the SERS effect and advances in

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nanofabrication technology, SERS is now on the edge of going out of the laboratory and

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becoming a sophisticated analytical tool to fulfill various real-world tasks. This review focuses

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on the challenges that SERS has met in this progress, such as how to obtain a reliable SERS

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signal, improve the sensitivity and specificity in a complex sample matrix, develop simple and

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user-friendly practical sensing approach, reduce the running cost, etc. This review highlights the

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new thoughts on design and nanofabrication of SERS-active substrates for solving these

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challenges and introduces the recent advances of SERS applications in this area. We hope that

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our discussion will encourage more researches to address these challenges and eventually help to

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bring SERS technology out of the laboratory.

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KEYWORDS: SERS, SERS-active substrate, nanofabrication, food contaminant, rapid field test

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1. Introduction

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Surface-enhanced Raman scattering (SERS) was first observed in 1974 by Fleischmann when

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pyridine was adsorbed on a roughened silver electrode1 and was correctly interpreted later by

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Van Duyne and Creighton in 1977.2,3 Since its discovery, SERS remained interesting only to a

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relatively small scientific community, e.g., to the electrochemistry or Raman spectroscopy fields.

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It was not until the discovery in 1997 that SERS can boost the weak Raman signal to a

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surprisingly high level, which is sufficient for single-molecule detection,4,5 that it suddenly

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attracted enormous attention. Currently, due to the high sensitivity and high specificity inherited

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from the unique molecular spectral fingerprints of the Raman spectrum, a large range of

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disciplines (including chemistry,6,7 physics,8 materialogy9 and life sciences10) have begun to

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exploit the huge potential of this technique.

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Specifically, in analysis of foods and agricultural products, SERS technique has been used as a

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rapid and sensitive tool for detecting chemical and microbial hazards. Compared with the well-

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established “wet chemistry” methods and modern analytical instrumental techniques (HPLC,

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GC-MS, etc.), SERS can avoid complicated and time-consuming sample pretreatment, therefore

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being more preferred in rapid field screening. Another advantage of SERS is that it has less

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interference from water, which is very important in analyzing biological samples such as

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agricultural products. Various food contaminants, such as pesticide,11–13 illegal food

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additives,14,15 veterinary drug,16,17

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technique. Besides, SERS has also been developed as a rapid diagnostic tool for food-borne

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pathogenic microorganisms.20,21 In all, SERS shows great promise in rapid safety assessment of

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foods and agricultural products.

toxins,18,19 have been successfully detected by SERS


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Several excellent review articles related to SERS have been recently published. Most reviews

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focus on the mechanism of the SERS effect,22–24 applications of SERS in various fields,25–33

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fabrication of SERS-active substrates,34–36 and advances in new SERS devices,37–41 which are of

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interest to a heterogeneous readership. Naturally, this review cannot cover the entire picture of

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the corresponding topics of SERS, but instead presents the reader with the recent advances of

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SERS from a different angle.

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With a deeper understanding of the SERS effect and advances in nanofabrication technique,

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SERS is now on the edge of going out of the laboratory and becoming a sophisticated analytical

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tool to fulfill various real-world tasks. This review focuses on the major challenges that SERS

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has met in this progress, such as how to obtain a reliable SERS signal, how to reduce the running

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cost of this technology, etc, which are the keys to developing any practical applications.

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Specifically, in analysis of food contaminants in these real-world samples (e.g. fruits, vegetables,

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meats, oils, beverages, etc.), how to increase specificity and avoid interferences from complex

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sample matrix, and how to simplify the sampling and practicing approach become especially

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important. This review highlights the new thoughts on design and nanofabrication of SERS-

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active substrates for solving these challenges and introduces the recent advances of SERS

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applications in the analysis of agricultural products and foods, as well as the future developments

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and several prospects of SERS.

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2. Brief Introduction of SERS

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It has been generally accepted that two enhancement mechanisms may contribute to the

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enormous enhancement of SERS: an electromagnetic (EM) mechanism42–44 and a chemical

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enhancement.45 The former one is considered as the dominant reason for SERS,46 which

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originates from collectively oscillating conduction electrons in metal or metal-like nanomaterials


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under light excitation (see Figure 1a, b), the so-called surface plasmon resonance (SPR),

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including localized surface plasmon resonance (LSPR) and propagating surface plasmons

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(PSP).47–50 This effect can focus the incident light to nanoscale edges, gaps, tips, or crevices,

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therefore creating many electromagnetic “hotspots” in these sites, whose intensity can achieve 2-

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5 orders of magnitude of the incident light (Figure 1c).51,52 Molecules trapped in these hotspots

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can experience an enormous enhancement of their Raman intensity.4 Therefore, it would be more

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appropriate to call this effect plasmon-enhanced Raman scattering (PERS).50 However, we still

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use the common term, SERS, in this review, considering its long history and broad acceptance.

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For interested readers, these fundamental aspects of SERS can be referred to the review by

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Schlücker.53

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These metallic plasmonic nanostructures, also referred to as SERS-active substrates, are the

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prerequisite for observing SERS. The performance of a SERS-active substrate is usually

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evaluated based on two aspects: the enhancement factor (EF) and signal uniformity. Generally,

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the EF of a SERS substrate determines how sensitively it can detect a certain analyte. The EF is

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approximated to be proportional to the fourth power of the enhancement of the local

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electromagnetic field (|E/E0|4), where E and E0 are the intensities of the local electromagnetic

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field in the presence and absence of the substrates. The experimental determination of EFs

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requires measurements of the SERS intensity for the adsorbed molecules on the substrate relative

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to the normal Raman intensity of the same molecule using the following equation,

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EF =

ூೄಶೃೄ /ேೄಶೃೄ ூೃೄ /ேೃೄ

,

(1)

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where ISERS is the total SERS intensity and IRS is the normal Raman intensity of the probe

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molecules. NSERS and NRS are the numbers of molecules contributing under SERS and normal


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Raman conditions, respectively. The EF in the hotspot can be as high as 1014, which is sufficient

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for single-molecule detection.4,5 However, in most cases, the average EF of the entire SERS

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substrate is approximately 105-108.43,46,54 To further increase the EF of a SERS substrate requires

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a rational design and precise fabrication. However, it is a formidable task since so many factors

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need to be considered, such as the incident laser wavelength, optical properties of the analyte, the

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material of the substrate and, most importantly, the morphology of the metal plasmonic

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nanostructures of the substrate.55

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The signal uniformity of a SERS substrate is another crucial parameter since it decides how

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reliable a SERS measurement can be, which is the key to quantitative analysis. However, the

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SERS approach is known for poor reproducibility, mainly aroused by the traditional colloidal

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SERS substrates. To improve the reproducibility, a variety of approaches have been employed,

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such as controllable assembly, introducing an internal standard and employing a highly ordered

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SERS substrate, which we will address later. Evaluation of the reproducibility of SERS-active

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substrates is usually carried out by the relative standard deviation (RSD) value of the SERS

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intensity obtained on randomly selected spots. However, the complexity of evaluation the EF and

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the signal uniformity of a substrate should not be underestimated since several factors need to be

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taken into consideration together,56,57 such as the excitation wavelength and LSPR modes, the

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choice of probe molecule (avoiding resonance Raman effect), determination of the coverage of

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the probe on the substrates, etc. A full consideration of these factors should be given before

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comparing different SERS substrates.

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SERS-active substrates are the foundation for any SERS applications. An ideal SERS-active

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substrate generally needs to possess ultrafine features, large-scale uniformity, great EF, good

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signal reproducibility and a low fabrication cost. Thus far, the development of SERS-active


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substrates has gone through four stages: (1) metallic colloid substrates; (2) highly reproducible

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rigid substrates; (3) mechanically flexible substrates; and (4) universal “all-task” substrates

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(Figure 2). We will later discuss how to use these substrates to deal with the challenges in

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developing real-life applications and highlight the recent breakthroughs aiming to bring the

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SERS technique out of the laboratory.

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3. Challenges in Real-Life SERS Applications

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Despite the long history since its discovery, SERS has not yet become a sophisticated tool for

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practical applications. A major obstacle has been the poor reproducibility and poor stability of

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the wildly used metallic colloid substrates, limiting its applications in quantitative analysis. Also,

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when applying SERS technology to real-world applications, the cost is another major concern.

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Additionally, for practical applications, sample matrix interference cannot be overlooked. Since

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target molecules that are usually in low concentration and the matrix has the same access to the

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hotspots, a significant spectral “contamination” can often be observed in a complex sample

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matrix, which causes difficulty in analyzing the results and decrease of the sensitivity and

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specificity. Needless to say, there are many more challenges need to be addressed before further

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expanding SERS to real-life applications.

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3.1 Strategies to Improve the Signal Reproducibility of SERS

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Although the discovery of SERS was made on electrochemically roughened silver electrodes,1

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the first type of wildly used SERS-active substrates were metallic nanoparticles, e.g., gold, silver,

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and copper nanoparticles, freely suspended in a homogeneous medium. Due to the advantages of

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easy preparation, low cost, and tunable optical properties, these substrates have been preferred

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for several decades and extensively used in studies. These substrates significantly reduced the


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technical barrier for performing a SERS experiment and made SERS popular. For the preparation

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methods of various metallic colloids, the reader can refer to previously published reviews.58,59

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However, the EFs from single isolated nanoparticle are relatively low, which can be further

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increased by two approaches: either by increasing the intensity or the density of the EM hotspot.

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Because of the “lightning rod effect”,51 metal nanoparticles with sharp edges and corners exhibit

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a much higher enhancement of the local EM field compared to the spheres.60 Therefore, various

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heteromorphic nanoparticles have been employed to improve the EF, such as a triangle,61

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polyhedron,62 rod,63,64 cube,62,65 wire,66 star,67,68 popcorn,69 dendrite70 and so on. Another

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approach is to increase the density of hotspot in the substrates, by adding salt (e.g., NaCl, KCl, or

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NaNO3) to trigger the aggregation of nanoparticles. This process generates abundant hotspots

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between the gaps of aggregated nanoparticles. Aggregation can also be induced by centrifugal

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force71 and magnetic force.72,73 Sometimes, aggregation is inevitable, as simply introducing the

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analyte can induce it.74 However, these hotspots generated by aggregation are randomly

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organized and impossible to control (Figure 3a),75,76 and the aggregated nanoparticles are not

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stable and tend to sediment under gravity,77 causing both a fluctuation of the strength and

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number of EM hotspots in the detecting volume. Thus, the obtained SERS signals vary

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significantly from experiment to experiment and from time to time. It is quite often that the

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signal variation exceeds more than 50% using aggregated NPs.75,78 Therefore, it is almost

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impossible to use them for quantitative analysis. This is the reason that SERS gained its fame for

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lacking reproducibility.

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Controllable Assembly. To solve this problem, one of the strategies by using a controllable

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assembly technique is to synthesize well-defined superstructures based on small nanoparticles.

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With the help of some ligands, such as organic molecules,79–81 polymers,82 antibody/antigens,83


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biotin/avidin connectors,84 nanoparticles can be assembled into ordered superstructures, such as

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dimers or trimers,85 core-satellites,86–89 etc. One smart approach is based on the unique base-

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pairing rules and structural features of DNA, which can be used to program the assembly of

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ordered plasmonic superstructures,90 such as dimers,91–95 trimers,96 regularly spaced

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nanoparticles chains97 and two- or three-dimensional ordered arrays98–104 (Figure 3b). Another

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interesting approach is the liquid/liquid interfacial assembly technique. Based on soft ligand-

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ligand interactions, including steric hindrance, hydrogen bonding interactions, electrostatic

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forces,105–107 a variety of morphologies and structures have been successfully assembled, such as

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nanosheets,108–112 nanoribbons,113 folding structure,114,115 spherical supercluster,116 liquid-like

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metal droplets,117–120 and so forth (Figure 3c). These densely packed interfacial nanoparticle

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films have also been developed as SERS-active substrates.106,107 Due to dynamic nanogaps in

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the liquid interfacial structure, interfacial GNP arrays can cause surrounding molecules to easily

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diffuse into the nanogaps (hotspot).121 In these superstructures, the hotspots are evenly

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distributed, which ensures the good reproducibility of the signal (RSD% below 10%).121,122 Thus,

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these interfacial nanoparticle films overcomes the main drawbacks of conventional aggregated

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colloid substrates. However, the ligands required in the assembly process usually are strongly

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adsorbed on the nanoparticle and rest in the hotspot, therefore preventing the analyte from

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entering the hotspots for detection. Removing the ligands often involves harsh treatments and

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can cause complete or partial disassembly of the superstructures, therefore, limiting their

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practical applications.

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Internal Standard. A smart strategy for reducing the fluctuation of SERS intensity caused by

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uncontrollable aggregation of nanoparticles is to use an internal standard. The internal standard

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and target molecules normally have similar molecular structures and coexist in the same physical


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and chemical environment of the hotspot; therefore, its signal can be used to calibrate the

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absolute signal of each SERS measurement.123 It has been proven that the implementation of an

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internal standard can reduce the SERS signal fluctuation to the 10% level,124 which is enough for

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quantitative analysis. However, the reproducibility of this approach could be compromised, due

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to an unstable internal signal caused by interference from the external environment or

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competitive adsorption with the analytes, etc. In recent years, several new types of internal

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standards have been introduced (Figure 4). A special core/shell nanoparticle with internal

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standards embedded was developed (Figure 4a). Since internal standards are embedded inside

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the shell, they will not compete with the target molecules for the surface hotspots and will not be

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influenced by the external environment, providing a stable signal for calibration.125–132 For

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example, after correction with internal standards, the reproducibility of SERS signals between

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batches was significantly improved with a RSD% less than 8% (Figure 4a).126 This approach has

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also been used to develop a real-life application, namely quantification of the melamine

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concentration in milk with a detection limit of ~ 5 µM.129 Figure 4b also shows graphitic

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nanocapsules, in which the stable and unique Raman signal of graphene is used as internal

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standard.133 The RSD% of SERS intensity of Rhodamine B (RhB) can be reduced from 20.4% to

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6.8%. Sometimes, the signal of the target molecule itself can also be used as a stable intrinsic

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internal standard,134–136 such as the Raman peaks of the phosphate backbone of DNA135 and

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tryptophan of proteins (Figure 4c).136 Accordingly, with the assistance of a proper internal

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standard, it is possible to obtain reliable SERS signals from randomly aggregated nanoparticles

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for quantitative analysis, but requiring careful and rational design of the experiment.

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Highly Ordered Rigid SERS Substrates. With the rapid advancement of nanofabrication

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technology, researchers are able to fabricate SERS-active substrates with ultrafine features and


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large-area uniformity, therefore ensuring a good reproducibility for SERS signals. These

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substrates often contain a hotspot-rich metallic film that is supported by a rigid substrate. For

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more details on the fabrication methods for these SERS substrates, the reader can refer to the

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previously published review.137 In general, these approaches can be categorized as top-down and

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bottom-up techniques. Top-down techniques, such as electron beam (E-beam) lithography,

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focused-ion beam and photon lithography, nano-indentation, and metal-induced chemical etching,

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can fabricate well-controlled nanoscale patterns, and they are promising techniques for

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fabricating SERS-active substrates (Figure 5a).138–146 These approaches have difficulty in

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fabricating sub-5-nm structures (the size of a typical SERS hotspot is approximately 2 nm),

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however, the main challenges of top-down nanotechnology lie in the high technique barrier

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involved, low fabrication speed, and extremely high production cost, limiting their practical

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applications.

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Compared to the top-down approaches, the bottom-up techniques to fabricate ordered

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plasmonic nanostructures are often simpler and more cost-effective (Figure 5b). Usually, this

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approach is realized by assembling smaller nanoparticles into an ordered nanostructures array.

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The wildly used assembly techniques include Langmuir-Blodgett,147 Langmuir-Schaefer,148 gel

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trapping,149 electrophoretic deposition,150 etc. Recently, an interesting approach has been the

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liquid/liquid interface (LLI) or liquid/air interface (LAI) self-assembly technique in which the

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nanoparticle array is assembled on the interface and subsequently transferred to a solid

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supporter.114,151–155 However, substrates fabricated via the bottom-up approaches can only

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achieve moderate reproducibility and batch-to-batch reproducibility. Compared to the top-down

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approaches, these approaches are of a low degree of freedom and are unable to fabricate any


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user-defined structure; therefore, the precise control of substrate shape, distribution, and density

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is impossible.

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Another method for assembling highly-ordered SERS substrates is template-assisted

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fabrication (Figure 5c). The templates include anodized aluminum oxide (AAO),156,157 zinc oxide

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nanowires,158,159 carbon nanotubes,160 and imprinted polymers,161 etc.162–164 Among them, the

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AAO template is extensively used. SERS substrates prepared via the template-assisted method

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are characterized by low cost, high reproducibility, high throughput, and low interference from

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the background signal. In all, compared with nanoparticle colloids, rigid SERS substrates often

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exhibit far better signal reproducibility and sensitivity, which can serve as a solid foundation for

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SERS quantification applications.

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Shell-Isolated Substrates. An irreproducible SERS measurement could also come from a

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physically/chemically unstable SERS-active substrate. For instance, nanoparticle colloids tend to

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aggregate when their surrounding environment changes.165 Meanwhile, metallic plasmonic

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nanostructures often suffer from oxidation and corrosion, both leading to degradation of the

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plasmonic characteristics and changes in the surface morphology, thereby compromising

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effective generation of SERS. Nevertheless, a fluctuation in the SERS measurement can also be

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caused by the photocarbonization, photobleaching or metal-catalyzed site reactions. Therefore, to

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develop any reliable SERS quantifications, these aspects must be paid attention to besides the

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reproducibility of the substrate itself.

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To improve the poor stability of SERS colloid, a chemically inert shell is coated on the

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nanoparticles. With this shell protection, the nanoparticles show good stability in various

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environments. Until now, there have been a variety of materials, such as SiO2,166,167 Al2O3,168,169

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Fe3O4,170,171 TiO2,172–176 MnO2,177 TiN178 and polymers,179 developed for the shell. A typical


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example is shell-isolated nanoparticles (SHINs),169,180 as shown in Figure 6a. It has been

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confirmed that a mixture of concentrated SHINs with pyridine is stable for more than 240 hours.

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In contrast, the mixture of bare gold nanoparticles completely aggregates after 15 mins (Figure

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6a).181 Based on these stable SERS substrates, a simpler quantification method for melamine in

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milk is developed and the LOD can be achieved as low as 0.03 ppm.182 The above coating

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strategy can also be used to prevent oxidation and corrosion of the rigid SERS substrates. This

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approach also helps to prevent photocarbonization, photobleaching or metal-catalyzed site

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reactions for the isolation of the substrate and analyte; therefore, a more reproducible SERS

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signal can be expected. However, this approach is over delicate. Given the rapid decay of the

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LSPR, the inert layer should be very thin (a couple of nanometers) to avoid significant loss of the

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SERS activity. Otherwise, the coating layer must be extremely uniform since any tiny variation

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in the thickness can cause a huge fluctuation in the SERS signal.166,183 The deposition of a

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uniform ultra-thin layer requires sophisticated experimental skills, meticulous treatments or a

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long reaction time, which are very challenging.

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An alternative approach has been proposed in which instead of coating the surface with an

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ultra-thin and uniform inert shell in a highly controllable manner, a thin film with a uniform

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thickness is directly transferred to the substrate as the passivate layer (Figure 6c). CVD-grown

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monolayer graphene is prefect for such an application since it is a mechanically strong and

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chemical inert atomic monolayer with a uniform thickness and is impenetrable to most gas

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molecules and liquids,184,185 which was also developed for fabricating SHINs (Figure 6b).186–188

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By passivating the SERS substrate with monolayer graphene, the substrate exhibited a

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significantly enhanced physical/chemical stability.189–192 Furthermore, graphene-shielded

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substrates also exhibit some new features (Figure 6c), such as alleviating photo-induced damage


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due to the extremely high thermal conductivity of graphene and improving the sensitivity for

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certain analytes due to graphene’s high affinity to many aromatic molecules and biomolecules

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(for the π-π stacking interactions).192 In particular, graphene exhibits excellent biological

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compatibility. These features make graphene-shielded substrates a promising platform for SERS

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quantification.

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3.2 Strategies to Develop SERS Detection in a Complex Sample Matrix

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SERS is known to be a first layer effect, which is only amplified at distances less than ~ 5 nm.

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When applying SERS technology to real-world detection, competitive adsorption or nonspecific

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fouling becomes another major problem for researchers, which significantly reduces the

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sensitivity and specificity of SERS sensing, especially for quantitative analysis. Although this

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problem can be resolved via a sample pretreatment process, it will certainly prolong the

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processing time and comprise the advantages of SERS as a rapid detection method compared to

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other methods. On other hand, target molecules with a weak affinity to substrates or with small

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cross sections present further difficulties. The gap distances with the hotspots only extend a few

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nanometers (~2 nm); accordingly, it is very difficult for analytes with a low affinity to enter such

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small, confined spaces. Therefore, surface modification of the SERS substrate to improve the

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contact between the analyte or to avoid competitive adsorption is essential for real-world SERS

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applications (Figure 7). A table summarizing the surface modification method is shown in Table

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1.

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Electrostatic and Hydrophobic Interactions. Among the various approaches for improving

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the affinity of analytes to substrates, the simplest one is based on electrostatic and hydrophobic

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interactions. In most cases, the capping agent of common colloidal systems for SERS (i.e., citrate

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or borohydride reduced gold or silver particles) is mainly formed via citrate ions and is thus


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negatively charged. As a consequence, to improve the affinity to most of organic molecules that

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often carry negative charges, the commonly used method is to modify the SERS substrates with a

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monolayer of positive-charged capping molecules (Figure 7a).16,193–198 For example, by

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functionalizing the amino group on the surface, negative-charged methylene blue can be

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selectively separated from the sample matrix containing acid blue and be detected.196 An

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alternative approach is to adjust the solution pH to enhance the affinity of the analyte to SERS

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substrate.199,200 By lowering the suspension pH below the analyte pKa, the surface affinity of

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SERS substrates can be improved because of the consistent electrostatic alignment. For example,

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using this method, limits of detection (LOD) of 3 × 10-9 M and 1.1 × 10-8 M for carbamazepine

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and atrazine, respectively, were obtained. By contrast, the LOD of 4.6 × 10-7 M for atrazine in

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drinking water obtained by non-modified SERS substrate (Table 1).201 This method based on

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adjusting pH (without surface modification) overcomes the drawback of interfering background

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signal due to the modified molecules. However, uncontrolled aggregation and flocculation of

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metallic colloid at low pH need to be avoided.

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Furthermore, for analytes with no affinity for gold or silver or are highly hydrophobic, surface

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functionalization is commonly employed to attract target molecules to the SERS substrate via

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hydrophobic interactions, such as an alkanethiol self-assembled monolayer.202–206 Based on the

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strong Au-S bonds, a monolayer of alkanethiol can be easily assembled on the substrates, in

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order to entrap hydrophobic targets. Compared with unmodified SERS substrate, a lower LOD

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can often be achieved for these modified SERS substrates, as shown in Table 1.206 Another

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interesting surface modification strategy is based on the so called host-guest interactions, in

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which a hydrophobic inner cavity and a hydrophilic outline to entrap the target molecules to the

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inner cavity.207–209 This method has gained special attention owing to its ability to capture a batch


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of small hydrophobic non-polar molecules in complex matrix (Figure 7b). For example, three

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PCB molecules captured by β-cyclodextrin on the substrate surface is confirmed to be detected

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simultaneously,207 however, with a compromising LOD compared with decanethiol-modified

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method,206 as shown in Table 1.The above approaches have been successfully applied to analyze

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real-world samples, such as blood plasma and serum for clinical diagnostics and contaminant

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tracing in food samples.

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As we know, competitive adsorption of other molecules or proteins on targets, which results in

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an appreciable background noise, is a critical problem for real-world applications. To solve this

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problem, it is common to modify a mixed self-assembled monolayer (SAMs) of thiol molecules

332

and non-fouling zwitterionic polymer, where the former is to attract or probe the target

333

molecules and the latter is to repel nonspecific fouling from the complex sample matrix (Figure

334

7e).210,211 A modified substrate with a surface composition of 94% N,N-dimethyl-cysteamine-

335

carboxybetaine showed that low nonspecific fouling was obtained.212 Using this modified

336

substrate-based SERS system, several analytes in undiluted plasma could be successfully

337

detected, such as drugs, blood pH, fructose and so on. Herein, it is worthy to note that modified

338

zwitterionic molecules not only effectively resist nonspecific fouling but also need to have very

339

weak Raman activity to avoid interference for an effective Raman signal of the target molecules.

340

Another mixed self-assembled monolayer of thiolazide and phosphocholine was also developed

341

for detecting C-reactive protein in serum, where the thiol molecules acts as a linker of

342

phosphocholine and SERS substrate, and the latter one is to attract the target.213 Using this SERS

343

platform, C-reaction protein could be selectively detected with a lower LOD of 10-10 g/mL

344

compared to that obtained by conventional Raman method (Table 1).214 For detecting Sudan dyes

345

in food samples, the Cialla-May group developed a SERS substrate modified with aliphatic


16

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346

hydrocarbons to repel non-specific fouling from water-soluble components.215 Via this

347

hydrophobic surface modification, 9 µM Sudan III in paprika powder extract was successfully

348

detected in the presence of riboflavin as a water-soluble competitor. Besides, this lipophilic

349

SERS substrate was also successfully applied to lipids analysis which need lower sampling

350

volume compared to that of Raman technique.216

351

However, surface coatings often lead to a decrease in the SERS signal intensity due to the

352

separation of the analyte and the hotspot in substrates, and noisy background due to the pre-

353

existing modification layer before the detection that may cause difficulties in interpreting the

354

signal or poor signal-to-noise (S/N) ratios.203 More importantly, the specificity of modification

355

layer based on electrostatic and hydrophobic interactions is not very high.203

356

Specific Molecular Receptors. To improve the specific affinity of a SERS substrate to an

357

analyte, molecular receptors have also been employed to modify the substrate surface. Due to the

358

small size of the hotspot, commonly used large molecular receptors in bio/chemical sensing,

359

such as antigen/antibodies, biotin/avidin, aptamers, etc., are not well suited in this case.

360

Therefore, small molecules are usually preferred as the specific molecular receptors.217,218 For

361

example, SERS substrates modified with 4-mercaptophenylboronic acid are widely used for

362

glucose sensing via reversible boronate ester formation.219–226 A triosmium carbonyl cluster-

363

boronic acid conjugate functionalized SERS substrate was successfully used to detect glucose

364

with concentrations as low as 10-4 M (Figure 7c).219 Compared with other methods or SERS

365

substrate without surface modification, specific molecular receptors offer the lower detection

366

limits and simpler operation procedure (Table 1).227 Another typical example is using the proper

367

molecules with both sensitive pH response and strong Raman signals for in vivo SERS-based pH

368

sensing. The most commonly used probe molecules are 4-mercaptobenzoic acid228–230 and 4-


17


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369

mercaptopyridine.231

370

mercaptoethanesulfonate exhibit high selectivity for detecting alkaline and alkaline earth metal

371

cations.217 This method depends on the formation of contact-ion pairs between sulfonate groups

372

of 2-mercaptoethanesulfonate and metal cations. A typically low LOD was obtained by this

373

method, e.g., the LOD for Ca2+ was 10-8 M (Table 1). Thus, with the assistance of specific

374

molecular receptors, molecules with weak affinity to SERS substrates or Raman-inactive ions

375

could be detected.

Additionally,

Ag

nanoparticles

functionalized

with

2-

376

Mechanical Trapping. The mechanical trapping of analytes is achieved by stimuli-responsive

377

SERS substrates. The most commonly used stimuli are pH,232,233 temperature234–236 and light.237

378

For example, Au nanorod-doped poly(N-isopropylacrylamide) microgels were presented and

379

applied for SERS application.236 It was demonstrated that the poly(N-isopropylacrylamide)

380

microgels could collapse when heating the temperature beyond 32 ºC; thus, the distance between

381

the Au nanorods could be shortened correspondingly to generate the hotspots. When the

382

temperature cooled down to 32 ºC, the responsive matrix could recover to expanding status

383

(Figure 7d). Therefore, analytes could be trapped in the hotspots by adjusting the temperature.

384

Because of this, the sensitivity of this SERS substrate could be significantly improved compared

385

to conventional SERS substrate (Table 1).238 In addition, dual stimuli-responsive microgels

386

modified SERS substrates were also developed recently. For example, the hybrid microgels were

387

confirmed to be utilized as for measuring both pH value and the temperature of their

388

surroundings.239,240 Another alternative approach is molecularly imprinted polymer-based SERS

389

detection, which usually consists of an ultrathin polymer layer imprinted with the

390

targets.16,161,241,242 This method has been used in various fields, especially for biomolecules

391

analysis (Table 1).243 This method was also successfully applied to selectively adsorb and


18

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392

separate α-tocopherol from vegetable oils.244 Nevertheless, the enlarged distance between the

393

analytes and surface of SERS substrates due to the polymer structure results in a modest SERS

394

enhancement.

395

3.3 Strategies to Develop User-Friendly Real-Life SERS Applications

396

With the significant progress that has been made in solving the above fundamental problems

397

such as poor signal reproducibility and low selectivity towards real samples, the SERS technique

398

has thus reached the stage of developing real-life applications. In terms of practical applications,

399

cost is a primary concern, and a good method should above all be an affordable one. However,

400

most of the nanofabricated SERS substrates do not satisfy this prerequisite. Another concern is

401

the convenience and easy usability of the application. For example, the above-mentioned SERS

402

substrates, nanoparticle colloids and rigid substrates, can be conveniently used to analyze liquid

403

forms of samples, but this is much more difficult in the quantification of a target molecule on

404

roughed, irregular, and non-planer surfaces, which is the most common case in real-life

405

applications. Extra extraction processes are thus often required.

406

In-Situ Synthesized SERS Substrates. To meet the requirement of economic viability and

407

operational simplicity, in situ synthesis of SERS substrates has been developed. For example,

408

combined with conductive ink, traditional pens (e.g., fountain pens and ball pens) can be

409

employed to write conductive patterns on multiple substrates, such as glass245 or paper (Figure

410

8a).246,247 Using inkjet technology, micro-volumes of metallic nanoparticle colloids have been

411

directly sprayed onto the surface of artwork and textile fibers, which have been employed to in

412

situ identify the organic colorants of Japanese woodblock print dating to the end of the 19th

413

century (Figure 8a).248 It is worth mentioning that the former one, so-called “pen-on-paper”

414

approach, can obtain a lower LOD of thiabendazole of 20 ppb.247 Similarly, this assay was also


19


Page 20 of 64

415

applied to quantitatively determine melamine in milk with the LOD of 0.27 mg/L.249 Another in

416

situ synthesis approach is to directly immobilize the plasmonic nanoparticles on the sample

417

surface (e.g., bacteria cell wall20,250). The SERS signal of an analyte, e.g., bacteria, using this

418

strategy is approximately 30-fold higher than in the case of a simply mixed colloid-analyte

419

suspension and a lower LOD of 103 CFU/mL of L. innocua can be obtained.250 These methods

420

are relatively low-cost, fast and user-friendly, which have recently led to substantial research

421

interest. However, the poor reproducibility of the Raman signal due to the irregularity of sample

422

surfaces still remains a problem.

423

Flexible SERS Substrates. A flexible SERS substrate refers to a SERS-active plasmonic

424

nanostructure constructed on a flexible solid supporter. Such substrates exhibit several

425

advantages over conventional rigid substrates in terms of easy usability and fabrication cost.

426

Unlike the intrinsic rigid, fragile SERS substrates, these substrates can be attached to rough,

427

irregular (i.e., non-planar or ripply) surfaces and directly collect samples, offering a non-invasive

428

or minimally invasive method of sample analysis. This advantage is especially useful for

429

analyzing fragile and valuable samples. Examples of flexible SERS substrates include cellulose

430

papers,251–254 polymers,255–257 graphene,258 etc (Figure 8b). Our group has also developed a

431

flexible patterned plasmonic metafilm by combining bottom-up self-assembly and top-down

432

laser engraving. With tunable plasmonic properties and excellent flexibility, this plasmonic

433

material could be applied in various fields.259 Nevertheless, flexible SERS can be fabricated via a

434

simple and cost-efficient approach, such as the dip-coating method,252 printing technology,260 or

435

interface self-assembly technique.261 An excellent review on flexible SERS substrates can be

436

referred to for more details.262 The characteristics afforded by a flexible supporter enable flexible

437

SERS substrates several new functionalities and extend to applications that were not possible


20

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438

before. For example, flexible SERS substrates can be easily cut into arbitrary shapes and

439

integrated with other devices, such as for capillary-actuated fluid transport and selective

440

molecular retention. Flexible SERS substrates can integrate the sample collection and the SERS

441

detection into one, which is very convenient for in-situ analysis.263,264 It offers other attractive

442

advantages, such as being easy to transport or stable for storage. All of these advantages are

443

expected to bring SERS technology closer to real-world applications.

444

Currently, several groups have used the flexible SERS substrates to analyze chemicals in

445

agricultural products and food. For example, via a simple “paste and peel off” approach,

446

pesticide residues (e.g. parathion-methyl, thiram and chlorpyrifos) in fruits and vegetables could

447

be directly extracted to the as-prepared flexible SERS substrates and analyzed.256,265 The

448

sensitivity of this approach can achieve a few nanogram per square centimeter (ng/cm2).

449

Moreover, using a Ag decorated sandpaper substrate, the triazophos on fruit surface can be

450

directly detected by swabbing the sample surface.266 The LOD can be achieved as low as 4.2

451

pM/cm2. Although flexible substrates can be easily attached on the irregular surface, limited by

452

their poor optical transparency, additional sample exaction procedures (e.g. paste and peel off or

453

swab256,265,266) are always needed for the detection. Therefore, in-situ analysis of residues on

454

sample surface cannot be realized by these opaque SERS substrates.

455

“All Tasks” SERS Substrates. The in situ quantification of chemical molecules on an

456

ambient surface without any sample pretreatment has been a long-standing pursuit in analytical

457

science. Among the few optional techniques, SERS is particularly attractive because of its ultra-

458

high sensitivity and selectivity. However, the most commonly used substrates, such as

459

nanoparticle colloids or rigid substrates, cannot accomplish this task because nanoparticle

460

colloids can hardly generate a reproducible signal over large areas and because rigid substrates


21


Page 22 of 64

461

cannot be attached to irregular surfaces. Additionally, conventional flexible substrates due to

462

their poor optical transparency can completely block the signal after attaching to sample surfaces.

463

Thus, the invention of flexible and transparent SERS-active substrates overcomes these

464

dilemmas and can make the idea of in situ SERS detection a reality.

465

Recently, various flexible substrates with transparent properties have been fabricated.261,267–273

466

There are two critical factors for the preparation of transparent flexible SERS substrates. Not

467

only the flexible supporter must be transparent, the SERS-active metallic layer should also

468

exhibit good optical transparency, which is difficulty since metallic layer is often not. A possible

469

approach is using top-down method to fabricate thin metal nanostructures on a transparent

470

polymer film, but is limited by its high cost and low hotspot density.274 The commonly used

471

method is to transfer an as-prepared nanoparticle monolayer array onto a polymer thin film. Our

472

group also introduced a flexible and transparent SERS metafilm.275 A large-area 2D array of

473

silver nanocubes (Ag NCs) was assembled via the LAI approach and then transferred onto

474

cellophane adhesive tape. The obtained Ag NCs array-attached tape exhibited excellent SERS

475

activity and a homogeneous enhancement factor; more importantly, its high mechanical

476

flexibility and good transparency ensure its conformal contact with sample surfaces and enable

477

excitation and collection of the signal from the backside of the substrate. Because of this feature,

478

flexible substrates with transparent properties has become a promising method for in situ

479

analysis of real-world samples. Recently, several groups have employed the flexible and

480

transparent SERS substrate to direct analysis of chemicals in agricultural products and foods,

481

such as pesticide residues and food additives (Figure 8c).261,268–270,276–279 By simply covering

482

these substrates on the surface of samples, the contaminants can be directly detected. For

483

example, pesticide residues can be in situ detected by attaching these substrates to the sample


22

Page 23 of 64


484

surfaces (e.g. fruit, fish). The sensitivity via this approach for detecting thiram on fruit peel and

485

methylene-blue on fish surface can be down to 72 ng/cm2 and 10-13 M, respectively.268,273

486

Besides foods and agricultural products, residues on food packages such as malachite green on

487

the inner wall of container can also be rapidly determined by transparent and flexible SERS

488

substrates.275

489

Therefore, flexible and transparent SERS substrates could serve as a form of “all task”

490

substrates since they suit all forms of samples, such as liquids, gases, solids, and especially

491

analytes dispersed on an underlying nonplanar solid surface.275 It is far more suitable than other

492

substrates for real-world applications, such as in homeland security, forensic science,

493

environmental analysis, food safety, etc. Altogether, these features suggest the high versatility of

494

flexible and transparent SERS-active substrates.

495

Integrated Portable SERS Sensing Devices. To enable SERS technology to be applied to on

496

field detection, portability is another important factor to be concerned. Most of the conventional

497

techniques commonly require sophisticated sampling and separation procedures, which hamper

498

their use in on field analysis. Recently, a variety of portable SERS sensing devices are developed,

499

such as microfluidic chip or device,236,280–284 capillary or microcolumn,12,245,285,286 SERS enabled

500

micropipette,287 paper-based SERS chip,263,288–290 SERS swab,291,292 lab-on-chip device,293 SERS

501

test kit (Figure 8d).294 These on-site SERS platforms usually combine with portable Raman

502

spectrometers which usually integrate separation, concentration and quantification process all in

503

one. For example, a SERS-enabled micropipette integrated with microsampling device was

504

developed to on-site capture and detect surface organic residues on real-world samples. By

505

dropping a proper extraction agent on sample surface, several pesticide residues (thiram,

506

malachite green and methyl parathion) on vegetable surface could be simultaneously detected.


23


Page 24 of 64

507

The LOD obtained via this device can be down to 8 nM, 8 nM, 1.5 µM for thiram, malachite

508

green and methyl parathion, respectively.287 Another SERS-enabled cotton swab was also

509

fabricated for sensing surface residues. By simply swabbing the sample surfaces, the targeting

510

contaminants could be collected and then detected. For example, 10-5 M carbaryl on a cucumber

511

surface could be successfully discriminated.291 Many materials, such as glass capillary, paper,

512

micropipette, are employed to fabricate these devices which are cost-effective and easy to obtain.

513

Thus, these portable and low-cost SERS-enabled devices make on-field application come true.

514

4. Perspectives

515

Since its discovery, a tremendous amount of work has been invested in the field of SERS,

516

which has successfully promoted our theoretical and experimental understanding of SERS.

517

Especially with recent breakthroughs in nanotechnology, researchers have gained the ability to

518

fabricate rationally designed and uniform plasmonic nanostructures as high-performance SERS

519

substrates, extremely expanding the potential applications of SERS in various fields. However,

520

most of the applications have, thus far, been limited to solving problems in the laboratory. To

521

further expand the real-life applications of SERS, several challenges need to be addressed. This

522

review attempted to emphasize these crucial but often overlooked problems and summarize

523

possible solutions. We hope that our discussion will encourage more research to address these

524

challenges and eventually help to bring SERS technology out of the laboratory.

525

The success of SERS application relies on the development of SERS-active substrates.

526

Although SERS has been famous for its poor reproducibility, currently, reliable SERS

527

applications can be developed based on highly uniform SERS substrates fabricated via top-down

528

nanofabrication approaches, such as E-beam lithography. The real reason for restraining SERS to

529

the laboratory is the high fabrication cost, which is one of the primary concerns for developing


24

Page 25 of 64


530

real-life applications. Therefore, the further expansion of SERS depends on developing cost-

531

efficient and high-performance substrates. Several possible strategies to address this challenge

532

are listed above, either by improving conventional SERS colloids or by developing low-cost

533

assembly techniques to fabricate uniform substrates. We can expect to see some practical SERS

534

applications based on these advances in the near future.

535

The design of SERS substrates used to focus on SERS-active nanostructures to achieve a

536

higher EF and better uniformity, but what is often neglected is the affinity of the substrates to the

537

analytes, which is a prerequisite for obtaining a reliable and sensitive SERS signal. Moreover,

538

nonspecific fouling of a SERS substrate in a real sample matrix and weak affinity of the analytes

539

to SERS-active substrates are the two main problems that need to be solved. Thus, how to

540

combine a proper molecular capture strategy (such as preconcentration methods,295–297 aptamer

541

recognition298) with repelling fouling approaches to improve the sensitivity and selectivity of

542

SERS detection is still an important issue for the future. A more delicate design approach should

543

be carried out.

544

One of the most promising and practicable application of SERS is the rapid testing for

545

chemical residues in foods or agricultural products, such as pesticide. By simply spreading the

546

SERS colloids on sample surface or swabbing the sample surface with a soft SERS substrates,

547

the residues could be rapidly analyzed.299–301 Besides, various user-friendly SERS sensing

548

devices have been developed, such as microfluidic device,236 capillary,285,286 SERS enabled

549

micropipette,287 paper-based SERS test strip,289 and SERS swab,291 which were rationally

550

designed for this purpose. The entire process, including preconcentration, separation and SERS

551

detection, can be completed within a few mintutes.299,302 Furthermore, recent development in

552

transparent flexible SERS substrates can even allow analysis of chemical residues directly on the


25


Page 26 of 64

553

sample surface, by directly attaching this substrate to the sample surface and recording SERS

554

signal from its back.303 These advances will definitely benefit to bring SERS technology closer

555

to real-world applications.

556

Further Challenges.

557

The mismatch between the size of the hotspot and that of the target is one of the main

558

problems for SERS detection of biomolecules. Thus, we can obtain only a partial SERS signal of

559

biomolecules; therefore, a fluctuation in the SERS signal is expected due to intrinsic distance-

560

dependent effects of SERS and the relatively large and complex structures of the biomolecules.

561

Several approaches have been employed to overcome this problem, such as surface modification,

562

which aimed to slightly enlarge the distance between analytes and substrates to ensure

563

enhancement of the absolute biomolecule signal.135,136 However, how to sensitively and

564

selectively detect biomolecules using SERS still remains a challenge.

565

Furthermore, to shorten the distance between laboratory research and real applications,

566

portable Raman devices need to be considered. For example, a smartphone-based point-of-care

567

genetic testing device that is inexpensive, user-friendly and compact has been developed.304 And

568

a lot of mobile Raman spectrometers have also been developed in various on-site SERS

569

applications.305 Combining rationally designed SERS-active substrates with portable Raman

570

spectrometer, these SERS-enabled platforms, usually integrated separation, concentration and

571

quantification processes all in one, are worth for future research.

572 573

Acknowledgements


26

Page 27 of 64


574

This work was financially supported by the National Natural Science Foundation of China (No.

575

21305125), the Natural Sciences Fund of Zhejiang Province (No. LY14B050004) and Zhejiang

576

Provincial Public Welfare Technology Applied Research Project (No. 2016C32006).

577

Notes

578

The authors declare no competing financial interest.

579


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580 581 582 583

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1414 1415 1416

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1420 1421 1422

(293) Mühlig, A.; Bocklitz, T. W.; Labugger, I.; Dees, S.; Henk, S.; Richter, E.; Andres, S.; Merker, M.; Stöckel, S.; Weber, K.; et al. LOC-SERS: a promising closed system for the identification of mycobacteria. Anal. Chem. 2016, 88 (16), 7998–8004.

1423 1424 1425

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1428 1429

dipicolinic acid, an anthrax biomarker, considerably below the infective dose. Chem. Commun. 2016, 52 (64), 9925–9928.

1430 1431 1432

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1451 1452 1453

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1459

FIGURE CAPTIONS

1460

Figure 1. Working principle of SERS. (a) Schematic diagram of the targets on the surface of

1461

SERS substrates under light excitation. (b) Illustration of the localized surface plasmon

1462

resonance effect; (c) Finite-element simulations of SERS enhancement distribution in single and

1463

coupled Au nanostructures. Copyright with the permission from ref.47,48,50.

1464

Figure 2. Key developing stages of SERS-active substrates. Copyright with the permission from

1465

ref.62,64,65,68,69,140,143,146,159,164,178,252,257,259,271,275.

1466

Figure 3. Comparation of random aggregation and controllable assembly of metallic colloid

1467

substrates. (a) Random SERS-active nanostructures. (b) DNA motif-guided assembly. (c)

1468

Liquid/liquid interfacial assembly. Copyright with the permission from ref.72,73,76,77,90,93,95–

1469

98,100,102,106,108,112,114,119

1470

Figure 4. New types of internal standards for quantitative SERS detection. (a) Extrinsic internal

1471

standards (core-shell structure). (b) Extrinsic internal standards (Graphitic internal standard). (c)

1472

Intrinsic internal standards. Copyright with the permission from ref.125,126,133,135.

1473

Figure 5. Highly ordered rigid SERS substrates fabricated by different methods. (a) Top-down

1474

fabrication. (b) Bottom-up assembly. (c) Template-assisted fabrication. Copyright with the

1475

permission from ref.114,138,139,141–145,148,149,151,153,155,157–159,162–164.

1476

Figure 6. Shell-isolated SERS substrates. (a) Traditional shell-isolated nanoparticle. (b)

1477

Graphene-encapsulated nanoparticle. (c) Graphene-isolated substrate. Copyright with the

1478

permission from ref.180,181,186,187,192.

.


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1479

Figure 7. Strategies to develop SERS detection in complex sample matrix. (a) Electrostatic

1480

interaction. (b) Hydrophobic effect (Host-guest interaction). (c) Specific molecular receptors. (d)

1481

Mechanical trapping. (e) Mixed self-assembly monolayers (SAMs). Copyright with the

1482

permission from ref.197,209,211,219,235.

1483

Figure 8. User-friendly SERS substrates. (a) In situ synthesized SERS substrates. (b) Low cost

1484

flexible SERS substrates. (c) Universal flexible substrates. (d) Integrated portable SERS devices.

1485

Copyright with the permission from ref.236,247,248,254–256,258–260,268,269,276,283,287,292.

1486


53


1487

TABLE CAPTIONS

1488

Table 1 Comparation of SERS platforms with or without surface functionalization.

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1489


54

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1490 1491


Figure 1.

1492 1493 1494 1495 1496


55


1497

Page 56 of 64

Figure 2

1498 1499 1500 1501 1502 1503 1504 1505


56

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1506


Figure 3

1507 1508 1509


57


1510

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Figure 4

1511 1512 1513 1514 1515 1516


58

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1517


Figure 5

1518 1519 1520 1521 1522 1523 1524 1525


59


1526

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Figure 6

1527 1528 1529 1530 1531 1532


60

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1533


Figure 7

1534 1535 1536


61


1537

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Figure 8

1538 1539


62

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1540 1541


Table 1 strategy electrostatic interaction

N.A.

modified molecule

hydrophobic interaction

decanethiol

hydrophobic interaction

β-cyclodextrin

target atrazine poly-chlorinated biphenyls-77 poly-chlorinated biphenyls(-3, -29, -77)

LODb 4.6 × 10-7 M 201

10-7 M

10-6 M

206

10-6 M

N.A.

207

3 × 10-5 g/mL214

213

N.A. 5 × 10-3 M 227

217

N.A.

231

N.A.

228

~10-5 M 238

236

10-5 M 243

161

thiolazide C-reactive protein 10-10 g/mL phosphocholine 2+ 10-8 M molecular receptor 2-mercaptoethanesulfonate Ca molecular receptor 4-mercaptophenylboronic acid glucose 10-4 M 4-mercaptopyridine molecular receptor pH 4.0-9.0 bull serum albumin 4-mercaptobenzoic acid molecular receptor pH 4.5-8.5 peptide poly(N-isopropylacrylamide) mechanical trapping methyl parathion 10–7 M microgel molecularly imprinted polymers mechanical trapping transferrin 10-8 M (dopamine) a : Except the result for pH (pH response range), the results refer to the LOD of the targets. b : LOD obtained by a SERS substrate without surface modification. hydrophobic interaction

1542 1543 1544

resultsa 1.1 × 10-8 M

ref. 200

219


63


1545 1546

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For Table of Content Only

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Facing Challenges in Real-Life Application of Surface-Enhanced

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