Opto-Electronic Advances, Volume. 4, Issue 11, 210048-1(2021)

Flexible SERS substrates for hazardous materials detection: recent advances

Moram Sree Satya Bharati and Venugopal Rao Soma*
Author Affiliations
  • Advanced Centre of Research in High Energy Materials (ACRHEM), University of Hyderabad, Telangana 500046, India
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    Figures & Tables(14)
    A schematic depicting the various parameters influencing the SERS signal.
    The ideal requirements of SERS substrates are summarized in this schematic.
    Year wise publications on flexible SERS substrates obtained through a search in SCOPUS.
    Explosive trace detection using flexible SERS substrates detection of TNT, RDX, and PETN using self-assembly triangular nanoprisms on adhesive tape. Figure reproduced with permission from ref.58, Royal Society of Chemistry.
    Various fabrication techniques used for paper-based SERS substrates. (a) Vapor deposition. (b) Inkjet printing. (c) Dipping. (d) Pen-on-paper. (e) Drop-casting on hydrophilic wells. (f) Self assembling. (g) In-situ reduction. Figure reproduced with permission from: (a) ref.77, (b) ref.72, The Royal Society of Chemistry; ref.71, American Chemical Society; (d) ref.73, John Wiley and Sons; (e) ref.80, Springer Nature; (f) ref.84, (g) ref.79, American Chemical Society.
    Filter paper based SERS substrate by aggregated Ag/Au NPs for explosive molecule detection (Left side) (a) schematic of substrate preparation (b) and (c) FESEM images of bare filter and aggregated Ag NPs (Right side) SERS spectra of (a) PA (b) DNT (c) NTO using FP with optimized aggregated Ag NPs. Figure reproduced with permission from ref.94, American Chemical Society.
    (a) A schematic of the synthesis of dual-functional PDMS-assisted paper-based SERS platform. (b) (i) The photograph of a sample collection from orange surface. (ii) A comparison of SERS spectra of CV with and without PDMS. (iii) SERS spectra of different concentrations of thiram (0.5−50 ppm). (iv) The peak intensity at 1380 cm−1 of thiram in orange juice as a function of the spiked sample concentration. Figure reproduced with permission from ref.95, Royal Society of Chemistry.
    Fabrication of flexible SERS substrates for Ag@T-A@SiO2-Au nanofibrous substrates. Figure reproduced with permission from ref.100, under a Creative Commons Attribution 4.0 International License.
    (a) Reflectance spectra of the ASFPAN nanofibrous membranes with Ag NPs; Photographs of three nanofibrous membranes (PAN, ASFPAN, and ASFPAN-Ag NPs) are shown in the inset. (b) SEM image and (c) TEM image of ASFPAN nanofibers (3 min). Inset in (c) shows the size distribution of Ag NPs.107, American Chemical Society.
    (a) Schematic diagram representing the fabrication process of Au covered polymer nanostructure arrays using roll-to-roll ultraviolet nanoimprint lithography (R2R UV-NIL) technique (b) and (c) SERS spectra of R6G from 30 nm Au coating flexible substrate at different bending angles and bending cycles, respectively. Figure reproduced with permission from ref.114, under a Creative Commons Attribution 4.0 International License.
    (a) Schematic of flexible non-woven fabric based substrate and the (b) SERS spectra of carbyl on apples, oranges, and bananas surfaces. Figure reproduced with permission from ref.129, under a Creative Commons Attribution 4.0 International License.
    • Table 1. Important review articles on various applications of SERS that have been reported in the last three-years (2019–2021).

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      Table 1. Important review articles on various applications of SERS that have been reported in the last three-years (2019–2021).

      S. No.AuthorReview topicRef.
      1Zhang et al.Flexible SERS substrates and recent advances in food safety analysisref.43
      2Yin et al.Recent process of 2D materials in SERSref.30
      3Klapec et al.2016–2019 published literature on the forensic related molecules and their various detection techniques using SERSref.44
      4Li et al.Fabrication and applications of flexible, transparent SERS substratesref.45
      5Forbes et al.Developed and challenges of SERS sensor in the detection of inorganic based explosivesref.46
      6Ji Sun et al.SERS substrate developments and combination with other technologies in on-site analysis using portable Raman spectrometerref.19
      7Jingjing et al.Different dimensional (0D, 1D, 2D and 3D) SERS substrates for explosive detectionref.47
      8Shvalya et al.Plasmonic NPs and 3D plasmonic NSs sensors with biological, medical, military, and chemical applicationsref.48
      9To et al.Explosive trace detection technologies and latest advancesref.49
      10Ren et al.Qualitative and quantitative analysis; strategies of practical application of SERS substratesref.50
      11Huang et al.Paper SERS substrates in food safetyref.51
      12Chen et al.2D SERS substrates in chemical and biosensingref.52
      13Dinesh et al.Flexible sensor fabrication with various printing techniquesref.40
      14Xue et al.Flexible nanofiber-based substrates fabrication and applicationref.53
      15Ogundare et al.Cellulose-based SERS substrates: fundamentals and principlesref.39
      16Zamora Sequeira et al.Various methods for the determination of pesticidesref.2
      17Piolt et al.Key aspects of SERS and application in the biomedical fieldref.54
      18Ogundare et al.Cellulose substrate fundamental, preparation methods, and applicationsref.39
      19Lee et al.Analyte manipulation and hybrid SERS platforms for real-world applicationsref.55
      20Xu et al.Latest advances of flexible SERS substrates in point of care diagnostic in tunable, sample swapping and in-situ SERS detection highlightsref.56
      21Zhang et al.Electrospinning NPs based material and their sensing applicationref.57
      22Restaino et al.Plasmonic paper SERS substrates-preparation methods and sample collectionsref.36
    • Table 2. Summary of the recent flexible SERS substrates, their preparation methods, materials used, and the sensitivities achieved (2014-2021).

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      Table 2. Summary of the recent flexible SERS substrates, their preparation methods, materials used, and the sensitivities achieved (2014-2021).

      Flexible substrate typeHazardous material type studiedMethod usedSERS active materialMolecules investigated - sensitivityRef.
      Paper/CelluloseExplosivesInkjet printingPABT modified-Ag NPs-A4 paperTNT- pMref.132
      In-situAg NPs in agarose film supported on filter paperTNT- 10−8 M ref.78
      ImmersionAg nano triangles-filter paperPA- 10−6 M p-ATP- 10−8 M ref.88
      SoakingAggregated Ag/Au NPs-filter paperPA- 5 µM DNT- 1 µM NTO- 10 µM ref.94
      Drop castingStar-shaped Au NPsPA-5 µMref.133
      ReductionAg Nanostructures- filter paper Whatman 42Urea nitrate- 10−6 M CV- 10−8 M ref.134
      DrugsInkjet printingAg- chromatography paperOrganophosphate malathion –413 pg, Heroin –9 ng, Cocaine –15 ng ref.135
      Plasma assisted chemical depositionAu-Whatman filter paper grade 1 Cocaine- 1 ng/mlref.136
      DyesIn-situAg NPs-polydopamine -Filter paperR6g- 10−10 M MG residue on Fish scales- 0.04635 pg/cm2, Crab shells- 0.06952 pg/cm2 and Shrimp skins- 0.09270 pg/cm2ref.137
      Inkjet-printingMoO3−x nanosheets on Chromatographic paper, printing paper, filter paper R6g- 10–7 M CV- 10–6 M and MG- 10–6 M on fish surface ref.74
      In-situAu-filter paper (Advantec #1)MG-damped fish– 10 ppbref.138
      PesticidesSilver mirror reactionAg- filter paperThiram- 10−7 M ref.139
      Pen on paperAu NPs (15–120 nm); Au NRs (50 nm long, 14 nm thick); Ag NPs (50-80 nm) –A4 paper, Filter paperThiabendazole < 20 ppbref.73
      Airbrush spray methodAg NPs -glass fibre paperEnoxacin & Enrofloxacin- 10 −5 M ref.140
      PrintingAu@Ag 30 nm Au core & 7 nm Ag shell -filter paperThiram- 10−9 M ref.141
      Screen printingAg NPs/GO- paperThiram 0.26 ng cm−2Thiabendazole 28 ng cm−2Methylparathion 7.4 ng cm−2ref.142
      Immersion followed by APTMSAg NPs-PDMS spongeTriazophos 0.79 ng Methyl Parathion 1.58 ng ref.143
      Vacuum-assisted filtrationAuNPs- cellulose nanofiberThiram- 1 pM Tricyclazole- 10 pM ref.144
      In-situAu NPs-pseudo-paperThiram- 1.1 ng/cm2ref.145
      Laser techniquesAu/Ag film-print paperFungicide mancozeb (Dithane DG) and insecticide thiamethoxam (Aktara 25 BG)ref.146
      Immerson in NaCl solution for 5 min +dip-coatingAg NPs- filter PaperMelamine- 1 ppm Thiram- 1 ppm ref.147
      ImmersionFP-Au NPsMethyl parathion- 0.011 μg/cm2ref.148
      In-situNanocellulose fibers-Ag NPsThiram- 0.05 ppm Thiabendazole- 0.09 ppm, MG 0.0014 ppm Enrofloxaci- 0.069 ppm ref.149
      Silicon rubber mask and a vacuum filtration Au NRs -cellulose hydrogelsThiram- 100 fMref.92
      Drop castingQuartz paper/Cellulose nanofiber/ mixture (Ag NPs+Au NSs)Ferbam on kale leaves (50 µg/kg)ref.150
      Vacuum filtrationCellulose nanofibers-Au NPsThiram- 10−8M ref.151
      Drop casting, inkjet printingAu NPs-Whatman 44 FPBenzenethiol chemical aerosol Pyridine ref.152
      Vacuum filtrationGlass-fiber filter paper-Ag NWs coupled with polymerase chain reaction (PCR)DNAref.153
      Electrochemical depositionMesoporous Au film@Ag NWs@cellulose nanofiber paperR6g - 100 fM Thiram - 10 fM 2-naphthalenethiol-1 ppb ref.154
      Self-assemblingCellulose nanofibers -Ag@DNA/PDA (polydopamine)Rhodamine 6G. Thiamethoxamon- 0.003 mg/kg. ref.155
      Cotton budsAntibioticsIn situ reductionAg NPs-cellulose nanocrystals-Filter paperPhenylethanolamine A-10−9 M Metronidazole- 10−7 M ref.93
      ExplosivesSelf-assembly & In situAg NPs-cotton swab2,4 DNT- 5 ngref.156
      PesticidesSoaking, freezing, and dryingAg NPs-chitosan foamTriasophols Methidathion Isocrabophos ref.157
      Dipping & dryingAg NPs-cotton swab with NaClThiabendazole (TBZ), thiram, TBZ + thiram ref.158
      3D- spongeExplosivesIn situAg NPs -polyurethane spongePerchlorates- 0.13 ng CChlorates- 0.13 ng Nitrates- 0. 11 ng ref.159
      Nanofiber matPesticidesElectrospinningAu coated PVA nanofiberDeltamethrin- 0.33 mg/kg Quinalphos- 0.28 mg/kg Thiacloprid- 0.26 mg/kg ref.104
      CWA simulantsElectrospinningAu NPs –PVA nanofiberMethyl salicylateref.160
      DyesElectrospinningAg NPs-PVA nanofiberR6G-10−5 M ref.161
      Electrospinning and in-situAg NPs-Polyimide (PI) nanofabricp-Aminothiophenol (p-ATP)- 10−14 mol/L), ref.162
      FabricPesticidesSelf-assembly/in-situAg NPs- non woven fabricIsocarbophos Sumicidin Phosgene ref.163
      Dip coatingTriangular Ag nanoplates-Cotton fabricCarbaryl- 10−5M ref.164
      In situPolydopamine mediated Ag-Au NPs – cotton fabricCarbaryl- 10−6M ref.165
      Magneton sputteringAg NPs-cotton fabricThiram - 1 ppmref.127
      Magnetron sputteringAg-polyester fabricR6G on cucumber, MG and Thiramref.166
      Photochemical deposition (254 nm)Ag NPs on TiO2 coated polyester fiber membranes Sodium saccharin in soft drinks- 0.3 mg/L, (cola and sprite)ref.167
      In-situ growthAg NPs-Cotton fabricsPATP-10−8 M ref.168
      Vacuum evaporationAg coated (10 nm) nylon fabricsPATP-10−9 M Thiram on cucumber surface-10−7 M ref.169
      DyesVacuum thermal evaporation and high-temperature annealingAg NPs-carbon fiber clothR6g- 10−14 mol·L−1ref.170
      PolymersExplosivesOriented stacking and in-situAg and Au–Ag nanoplates- PETTNT- 10 nM RDX- 10 nM ref.171
      Self-assemblingAu triangular nanoprisms on adhesive film (Scotch magic-tape)TNT- 900 ppq RDX- 50 ppq and PETN- 50 ppq ref.58
      Incubated overnight followed by thorough rinsing dryingAu NPs,Au NRs and Au NCs on elastomeric film (PDMS)TNT vaporref.172
      Gravure printingAg NPs-PETDNT vaporref.173
      Sol–gel method and magnetron sputteringAg NPs-Porous silica aerogelsNTO- 7.94×10−10 M ref.174
      UV lithography and Au deposition Ag NPs-Au coated -nanowrinkled zigzag micropattern on PDMS layerTNT- 10−13 mol·L−1TNT residue(10−9 mol·L−1) on cloth bag ref.175
      DyesElectron-beam evaporation-uniaxial stretching Stretched Ag coated poly(ε-caprolactone) film MG-green mussel surface- 0.1×10−6 M ref.176
      Pyramid Si templateMoS2/AgNPs/inverted pyramidal PMMA R6G+MGref.177
      Pyramid Si templateGO/Ag NPs/ pyramidal PMMAMG on shrimpref.178
      Ar plasma etching and Au evaporationWorm-like Au NSs – PET filmR6G-10−9 M ref.179
      Self-assembly and in situ chemical reductionRaspberry-like polyamide@Ag hybrid nanoarray filmR6g-10−14 M Adenosine- 10−9 M ref.180
      PesticidesDrop-dry methodAu NPs (25 nm) - adhesive tapeParathion-methyl- 2.60 ng/cm2Thiram 0.24 ng/cm2Chlorpyrifos 3.51 ng/cm2on apples, oranges, cucumbers, and green vegetables surfaces ref.181
      Spin coating and manual peelingAgNP@AgNW network-PDMSThiram (0.1µM) on a leaf surface and MG (0.1µM) on a living fish scale ref.182
      Paste and peeling of self-assembled NPs from SiAdhesive acrylic polymer tape and polyethene terephthalate (PET) film (T/Au@Ag/PET)Thiram on apple, tomato, and cucumber peels (5 ng/cm2) ref.113
      Seed mediatedGold nanobush+PDMSThiabendazole (TBZ) on cherry – 0.64 ng/ml Carbaryl TBZ+Carbaryl ref.183
      Femtosecond laser induced plasma assisted ablationAg NPs and Au NPs FEP (fluorinated ethylene propylene) Thiram on apple- 7.96 ng/cm2ref.184
      Drop castingAg NS with spikes-adhesive tapePhosmet & carbaryl on apple-surface 10 −7M ref.185
    • Table 3. A summary of the commercially available SERS substrates, their costs, sensitivities and their stability (non-exhaustive).

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      Table 3. A summary of the commercially available SERS substrates, their costs, sensitivities and their stability (non-exhaustive).

      S. No.CompanySERS substrateSensitivityStabilityCostRef
      1StellarnetCellulose with Au NPs~1063 months$199 (pack of 30)ref.186
      2Horiba France SASGlass coated with Au nanorods processed by dynamic oblique vacuum evaporationref.187
      3SERSitiveElectrodeposition of silver and gold nanoparticles on an ITO glass surface~105–1064 months5 pcs Ag- €115 5 pcs Ag-Au- €138 ref.188
      4EnSpectr Inc.Si/Glass passivated with a thin transparent dielectic layer.~106Stable when unpackedref.189
      5SilmecoNanostructured Si deposited with Gold (Au), Silver (Ag)5 units €350ref.190
      6HamamatsuAu NS on polypropylene3 months when unpacked ref.191
      7Integrated OpticsAg/Au coating on silicate glass.2 monthsAg- €15 Au- €18 ref.192
      8Mesophotonics. Ltd. KlariteSi100 USD for single 2 mm × 2 mm sample.ref.193
      9Q SERS TMAu NSs on Si (5 mm × 5 mm)ppb to ppm6 months (package) 2 weeks (package opened) 2 units $50 USDref.194
      10MetrohmAg, Au based Filter paperref.195
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    Moram Sree Satya Bharati, Venugopal Rao Soma. Flexible SERS substrates for hazardous materials detection: recent advances[J]. Opto-Electronic Advances, 2021, 4(11): 210048-1

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    Paper Information

    Category: Review

    Received: Apr. 10, 2021

    Accepted: Jul. 18, 2021

    Published Online: Mar. 16, 2022

    The Author Email: Soma Venugopal Rao (soma_venu@uohyd.ac.in)

    DOI:10.29026/oea.2021.210048

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