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Surface-Enhanced Raman Scattering (SERS) for (Bio)chemical Sensing Applications

A special issue of Sensors (ISSN 1424-8220). This special issue belongs to the section "Chemical Sensors".

Deadline for manuscript submissions: closed (15 September 2023) | Viewed by 14290

Special Issue Editor


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Guest Editor
Department of Chemical Engineering, Queen's University, Kingston, ON, Canada
Interests: raman spectroscopy; surface-based sensors; biosensors; electrokinetics; interfacial phenomena; colloidal assembly
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

The need for analytical technologies that provide rapid, quantitative, and ultrasensitive detection of chemical and biological analytes in raw samples from environmental or biological fluids is globally on the rise. The early detection of biomarkers of devastating diseases such as cancer, or the in situ identification of food contaminants, illegal drugs, and terrorism agents such as bacteria, viruses, and explosives, can be better accomplished with the use of sensing devices that combine time efficiency, low limits of detection, portability, and cost-effectiveness. Surface-enhanced Raman Scattering (SERS) has emerged as a powerful spectroscopic technique and a versatile method for differentiation and detection of a wide variety of analytes, thus providing the potential for point-of-care testing. SERS is a label-free, non-destructive, field-deployable technique, which has held a great deal of promise for possible chemical and biological sensors over the last few decades. By enhancing the Raman signal by several orders of magnitude, the “molecular fingerprint” for single molecules can be measured.

For this Special Issue, we invite both reviews and original research articles discussing novel SERS-based (bio)chemical sensing techniques that can be applied to analyte detection, quantification, or mapping. Research articles may focus on the use of SERS-based sensors in biological analysis, medical diagnostics, illicit drug detection, science, public safety, or food and water quality inspection. Chemical, colloidal, nanofabrication or other methods that can lead to ultrasensitive analyte detection through Raman signal enhancement (e.g., ultrasensitive SERS substrates) are welcome. Of special interest are applications of SERS with the potential to lead to miniaturized sensors, such as microfluidic (lab-on-a-chip) devices, portable/handheld SERS-based sensors for point-of-need applications, etc. Reviews must offer a critical and up-to-date overview of the state-of-the-art in a particular application, or discuss present and future challenges of SERS-based sensors (limit of detection, multiplexing, detection in complex matrices, etc.).

Should you require clarifications, or wish to discuss your submission in advance, we encourage you to contact us. We look forward to receiving your contribution to this Special Issue!

Prof. Dr. Aris Docoslis
Guest Editor

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Keywords

  • SERS
  • SERS mapping
  • Portable sensors
  • Microfluidic sensors
  • In situ diagnostics
  • Point-of-need sensors
  • Standoff detection
  • Illicit drug and cannabis detection
  • Food and water quality monitoring
  • Homeland security
  • Multivariate analysis in sensing

Published Papers (5 papers)

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Research

Jump to: Review

15 pages, 3356 KiB  
Article
SERS for Detection of Proteinuria: A Comparison of Gold, Silver, Al Tape, and Silicon Substrates for Identification of Elevated Protein Concentration in Urine
by Sultan Aitekenov, Alisher Sultangaziyev, Aigerim Boranova, Aigerim Dyussupova, Aisha Ilyas, Abduzhappar Gaipov and Rostislav Bukasov
Sensors 2023, 23(3), 1605; https://doi.org/10.3390/s23031605 - 01 Feb 2023
Cited by 2 | Viewed by 1903
Abstract
Excessive protein excretion in human urine is an early and sensitive marker of diabetic nephropathy and primary and secondary renal disease. Kidney problems, particularly chronic kidney disease, remain among the few growing causes of mortality in the world. Therefore, it is important to [...] Read more.
Excessive protein excretion in human urine is an early and sensitive marker of diabetic nephropathy and primary and secondary renal disease. Kidney problems, particularly chronic kidney disease, remain among the few growing causes of mortality in the world. Therefore, it is important to develop an efficient, expressive, and low-cost method for protein determination. Surface enhanced Raman spectroscopy (SERS) methods are potential candidates to achieve these criteria. In this paper, a SERS method was developed to distinguish patients with proteinuria from the healthy group. Commercial gold nanoparticles (AuNPs) with diameters of 60 nm and 100 nm, and silver nanoparticles (AgNPs) with a diameter of 100 nm were tested on the surface of four different substrates including silver and gold films, silicon, and aluminum tape. SERS spectra were acquired from 111 unique human urine samples prepared and measured for each of the seven different nanoparticle plus substrate combinations. Data analysis by the PCA-LDA algorithm and the ROC curves gave results for the diagnostic figures of merits. The best sensitivity, specificity, accuracy, and AUC were 0.91, 0.84, 0.88, and 0.94 for the set with 100 nm Au NPs on the silver substrate, respectively. Among the three metal substrates, the substrate with AuNPs and Al tape performed slightly worse than the other three substrates, and 100 nm gold nanoparticles on average produced better results than 60 nm gold nanoparticles. The 60 nm diameter AuNPs and silicon, which is about one order of magnitude more cost-effective than AuNPs and gold film, showed a relative performance close to the performance of 60 nm AuNPs and Au film (average AUC 0.88 (Si) vs. 0.89 (Au)). This is likely the first reported application of unmodified silicon in SERS substrates applied for direct detection of proteins in any biofluid, particularly in urine. These results position silicon and AuNPs@Si in particular as a perspective SERS substrate for direct urine analysis, including clinical diagnostics of proteinuria. Full article
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19 pages, 7212 KiB  
Article
Rapid Detection of Amitriptyline in Dried Blood and Dried Saliva Samples with Surface-Enhanced Raman Spectroscopy
by Ramin Boroujerdi, Richard Paul and Amor Abdelkader
Sensors 2022, 22(21), 8257; https://doi.org/10.3390/s22218257 - 28 Oct 2022
Cited by 2 | Viewed by 2072
Abstract
There is growing demand for rapid, nondestructive detection of trace-level bioactive molecules including medicines, toxins, biomolecules, and single cells, in a variety of disciplines. In recent years, surface-enhanced Raman scattering has been increasingly applied for such purposes, and this area of research is [...] Read more.
There is growing demand for rapid, nondestructive detection of trace-level bioactive molecules including medicines, toxins, biomolecules, and single cells, in a variety of disciplines. In recent years, surface-enhanced Raman scattering has been increasingly applied for such purposes, and this area of research is rapidly growing. Of particular interest is the detection of such compounds in dried saliva spots (DSS) and dried blood spots (DBS), often in medical scenarios, such as therapeutic drug monitoring (TDM) and disease diagnosis. Such samples are usually analyzed using hyphenated chromatography techniques, which are costly and time consuming. Here we present for the first time a surface-enhanced Raman spectroscopy protocol for the detection of the common antidepressant amitriptyline (AMT) on DBS and DSS using a test substrate modified with silver nanoparticles. The validated protocol is rapid and non-destructive, with a detection limit of 95 ppb, and linear range between 100 ppb and 1.75 ppm on the SERS substrate, which covers the therapeutic window of AMT in biological fluids. Full article
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11 pages, 2346 KiB  
Article
Simultaneous Multiplexed Quantification of Banned Sudan Dyes Using Surface Enhanced Raman Scattering and Chemometrics
by Taghrid S. Alomar, Najla AlMasoud, Yun Xu, Cassio Lima, Baris Akbali, Simon Maher and Royston Goodacre
Sensors 2022, 22(20), 7832; https://doi.org/10.3390/s22207832 - 15 Oct 2022
Cited by 7 | Viewed by 1637
Abstract
Azo compounds such as the Sudan dyes I–IV are frequently used illegally as colorants and added to a wide range of foods. These compounds have been linked to a number of food safety hazards. Several methods have been proposed to detect food contamination [...] Read more.
Azo compounds such as the Sudan dyes I–IV are frequently used illegally as colorants and added to a wide range of foods. These compounds have been linked to a number of food safety hazards. Several methods have been proposed to detect food contamination by azo compounds and most of these are laboratory based; however, the development of reliable and portable methods for the detection and quantification of food contaminated by these chemicals in low concentration is still needed due to their potentially carcinogenic properties. In this study, we investigated the ability of surface enhanced Raman scattering (SERS) combined with chemometrics to quantify Sudan I–IV dyes. SERS spectra were acquired using a portable Raman device and gold nanoparticles were employed as the SERS substrate. As these dyes are hydrophobic, they were first dissolved in water: acetonitrile (1:10, v/v) as single Sudan dyes (I–IV) at varying concentrations. SERS was performed at 785 nm and the spectra were analyzed by using partial least squares regression (PLS-R) with double cross-validations. The coefficient of determination (Q2) were 0.9286, 0.9206, 0.8676 and 0.9705 for Sudan I to IV, respectively; the corresponding limits of detection (LOD) for these dyes were estimated to be 6.27 × 10−6, 5.35 × 10−5, 9.40 × 10−6 and 1.84 × 10−6 M. Next, quadruplex mixtures were made containing all four Sudan dyes. As the number of possible combinations needed to cover the full concentration range at 5% intervals would have meant collecting SERS spectra from 194,481 samples (214 combinations) we used a sustainable solution based on Latin hypercubic sampling and reduced the number of mixtures to be analyzed to just 90. After collecting SERS spectra from these mixture PLS-R models with bootstrapping validations were employed. The results were slightly worse in which the Q2 for Sudan I to IV were 0.8593, 0.7255, 0.5207 and 0.5940 when PLS1 models (i.e., one model for one dye) was employed and they changed to 0.8329, 0.7288, 0.5032 and 0.5459 when PLS2 models were employed (i.e., four dyes were modelled simultaneously). These results showed the potential of SERS to be used as a high-throughput, low-cost, and reliable methods for detecting and quantifying multiple Sudan dyes in low concentration from illegally adulterated samples. Full article
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12 pages, 1271 KiB  
Communication
Cicada Wing Inspired Template-Stripped SERS Active 3D Metallic Nanostructures for the Detection of Toxic Substances
by Srijit Nair, Juan Gomez-Cruz, Gabriel Ascanio, Aristides Docoslis, Ribal Georges Sabat and Carlos Escobedo
Sensors 2021, 21(5), 1699; https://doi.org/10.3390/s21051699 - 02 Mar 2021
Cited by 13 | Viewed by 3130
Abstract
This article introduces a bioinspired, cicada wing-like surface-enhanced Raman scattering (SERS) substrate based on template-stripped crossed surface relief grating (TS-CSRG). The substrate is polarization-independent, has tunable nanofeatures and can be fabricated in a cleanroom-free environment via holographic exposure followed by template-stripping using a [...] Read more.
This article introduces a bioinspired, cicada wing-like surface-enhanced Raman scattering (SERS) substrate based on template-stripped crossed surface relief grating (TS-CSRG). The substrate is polarization-independent, has tunable nanofeatures and can be fabricated in a cleanroom-free environment via holographic exposure followed by template-stripping using a UV-curable resin. The bioinspired nanostructures in the substrate are strategically designed to minimize the reflection of light for wavelengths shorter than their periodicity, promoting enhanced plasmonic regions for the Raman excitation wavelength at 632.8 nm over a large area. The grating pitch that enables an effective SERS signal is studied using Rhodamine 6G, with enhancement factors of the order of 1 × 104. Water contact angle measurements reveal that the TS-CSRGs are equally hydrophobic to cicada wings, providing them with potential self-cleaning and bactericidal properties. Finite-difference time-domain simulations are used to validate the nanofabrication parameters and to further confirm the polarization-independent electromagnetic field enhancement of the nanostructures. As a real-world application, label-free detection of melamine up to 1 ppm, the maximum concentration of the contaminant in food permitted by the World Health Organization, is demonstrated. The new bioinspired functional TS-CSRG SERS substrate holds great potential as a large-area, label-free SERS-active substrate for medical and biochemical sensing applications. Full article
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Review

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22 pages, 3713 KiB  
Review
Recent Advances in the Use of Surface-Enhanced Raman Scattering for Illicit Drug Detection
by Shamim Azimi and Aristides Docoslis
Sensors 2022, 22(10), 3877; https://doi.org/10.3390/s22103877 - 20 May 2022
Cited by 24 | Viewed by 4433
Abstract
The rapid increase in illicit drug use and its adverse health effects and socio-economic consequences have reached alarming proportions in recent years. Surface-enhanced Raman scattering (SERS) has emerged as a highly sensitive analytical tool for the detection of low dosages of drugs in [...] Read more.
The rapid increase in illicit drug use and its adverse health effects and socio-economic consequences have reached alarming proportions in recent years. Surface-enhanced Raman scattering (SERS) has emerged as a highly sensitive analytical tool for the detection of low dosages of drugs in liquid and solid samples. In the present article, we review the state-of-the-art use of SERS for chemical analysis of illicit drugs in aqueous and complex biological samples, including saliva, urine, and blood. We also include a review of the types of SERS substrates used for this purpose, pointing out recent advancements in substrate fabrication towards quantitative and qualitative detection of illicit drugs. Finally, we conclude by providing our perspective on the field of SERS-based drug detection, including presently faced challenges. Overall, our review provides evidence of the strong potential of SERS to establish itself as both a laboratory and in situ analytical method for fast and sensitive drug detection and identification. Full article
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