scholarly journals Enabling three-dimensional porous architectures via carbonyl functionalization and molecular-specific organic-SERS platforms

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Ibrahim Deneme ◽  
Gorkem Liman ◽  
Ayse Can ◽  
Gokhan Demirel ◽  
Hakan Usta
Keyword(s):  
Film Growth ◽  
Low Cost ◽  
Three Dimensional ◽  
Surface Enhanced Raman Spectroscopy ◽  
Molecular Engineering ◽  
Raman Signal ◽  
Chemical Enhancement ◽  
Out Of Plane ◽  
Surface Enhanced Raman ◽  
Anti Stokes

AbstractMolecular engineering via functionalization has been a great tool to tune noncovalent intermolecular interactions. Herein, we demonstrate three-dimensional highly crystalline nanostructured D(C7CO)-BTBT films via carbonyl-functionalization of a fused thienoacene π-system, and strong Raman signal enhancements in Surface-Enhanced Raman Spectroscopy (SERS) are realized. The small molecule could be prepared on the gram scale with a facile synthesis-purification. In the engineered films, polar functionalization induces favorable out-of-plane crystal growth via zigzag motif of dipolar C = O···C = O interactions and hydrogen bonds, and strengthens π-interactions. A unique two-stage film growth behavior is identified with an edge-on-to-face-on molecular orientation transition driven by hydrophobicity. The analysis of the electronic structures and the ratio of the anti-Stokes/Stokes SERS signals suggests that the π-extended/stabilized LUMOs with varied crystalline face-on orientations provide the key properties in the chemical enhancement mechanism. A molecule-specific Raman signal enhancement is also demonstrated on a high-LUMO organic platform. Our results demonstrate a promising guidance towards realizing low-cost SERS-active semiconducting materials, increasing structural versatility of organic-SERS platforms, and advancing molecule-specific sensing via molecular engineering.

scholarly journals New Trends in Raman Spectroscopy: From High-Resolution Geochemistry to Planetary Exploration

Elements ◽  
2020 ◽  
Vol 16 (2) ◽  
pp. 117-122 ◽  
Author(s):  
Olivier Beyssac
Keyword(s):  
Raman Spectroscopy ◽  
Surface Enhanced Raman Spectroscopy ◽  
Raman Signal ◽  
Time Resolved ◽  
The Earth ◽  
Surface Enhanced ◽  
Surface Enhanced Raman ◽  
Anti Stokes ◽  
Near Future ◽  
Very High

This article reviews nonconventional Raman spectroscopy techniques and discusses present and future applications of these techniques in the Earth and planetary sciences. Time-resolved spectroscopy opens new ways to limit or exploit luminescence effects, whereas techniques based on coherent anti-Stokes Raman scattering (CARS) or surface-enhanced Raman spectroscopy (SERS) allow the Raman signal to be considerably enhanced even down to very high spatial resolutions. In addition, compact portable Raman spectrometers are now routinely used out of the laboratory and are even integrated to two rovers going to Mars in the near future.

scholarly journals A simple and reliable approach for the fabrication of nanoporous silver patterns for surface-enhanced Raman spectroscopy applications

2021 ◽  
Vol 11 (1) ◽  
Author(s):  
Angela Capaccio ◽  
Antonio Sasso ◽  
Giulia Rusciano
Keyword(s):  
Raman Spectroscopy ◽  
Inductively Coupled Plasma ◽  
Low Cost ◽  
Cost Effective ◽  
Surface Enhanced Raman Spectroscopy ◽  
Raman Signal ◽  
Plasmonic Nanostructures ◽  
Surface Enhanced ◽  
Surface Enhanced Raman ◽  
Good Signal

AbstractThe fabrication of plasmonic nanostructures with a reliable, low cost and easy approach has become a crucial and urgent challenge in many fields, including surface-enhanced Raman spectroscopy (SERS) based applications. In this frame, nanoporous metal films are quite attractive, due to their intrinsic large surface area and high density of metal nanogaps, acting as hot-spots for Raman signal enhancement. In this paper, we report a detailed study on the fabrication of nanoporous silver-based SERS substrates, obtained by the application of two successive treatments with an Inductively Coupled Plasma (ICP) system, using synthetic air and Ar as feeding gases. The obtained substrates exhibit a quite broad plasmonic response, covering the Vis–NIR range, and an enhancement factor reaching 6.5 $$\times\, 10^7$$ × 10 7 , estimated by using 4-mercaptobenzoic acid (4-MBA) as probe molecule at 532 nm. Moreover, the substrates exhibit a quite good spatial reproducibility on a centimeter scale, which assures a good signal stability for analytical measurements. Globally, the developed protocol is easy and cost effective, potentially usable also for mass production thanks to the remarkable inter-batches reproducibility. As such, it holds promise for its use in SERS-based sensing platforms for sensitive detection of targets molecules.

scholarly journals 3D Hotspot Matrix of Au Nanoparticles on Au Nanostructures with a Spacer Layer of Dithiol Molecules for Highly Sensitive Surface-Enhanced Raman Spectroscopy

2021 ◽  
Author(s):  
Dong-Jin Lee ◽  
Dae Yu Kim
Keyword(s):  
Au Nanoparticles ◽  
Three Dimensional ◽  
Surface Enhanced Raman Spectroscopy ◽  
Raman Signal ◽  
Large Area ◽  
Spacer Layer ◽  
Highly Sensitive ◽  
Surface Enhanced ◽  
Surface Enhanced Raman ◽  
Enhanced Raman Scattering

Abstract Engineering of efficient plasmonic hotspots has been receiving great attention to enhance the sensitivity of surface-enhanced Raman scattering (SERS). In the present study, we propose a highly sensitive SERS platform based on Au nanoparticles (AuNPs) on Au nanostructures (AuNSs) with a spacer layer of 1,4-benzenedimethanethiol (BDMT). The three-dimensional (3D) hotspot matrix has been rationally designed based on the idea of employing 3D hotspots with a vertical nanogap between AuNSs and AuNPs after generating large area two-dimensional hotspots of AuNSs. AuNP@BDMT@AuNSs are fabricated by functionalizing BDMT on AuNSs and then immobilizing AuNPs. The Raman signal of the AuNP@BDMT@AuNSs is approximately twelve times higher than that of AuNSs at 100 nM of rhodamine 6G. The AuNP@BDMT@AuNSs are then employed to detect thiram, which is used as a fungicide, with a detection limit of 13 nM. Our proposed platform thus shows significant potential for use in highly sensitive SERS sensors.

scholarly journals Dual-enhancement and dual-tag design for SERS-based sandwich immunoassays: evaluation of a metal–metal effect in 3D architecture

2021 ◽  
Vol 189 (1) ◽  
Author(s):  
Ewelina Wiercigroch ◽  
Pawel Swit ◽  
Agnieszka Brzozka ◽  
Łukasz Pięta ◽  
Kamilla Malek
Keyword(s):  
Limit Of Detection ◽  
Specific Binding ◽  
3D Structure ◽  
Three Dimensional ◽  
Surface Enhanced Raman Spectroscopy ◽  
Raman Signal ◽  
Metal Metal ◽  
Surface Enhanced Raman ◽  
Active Substrate ◽  
Sandwich Type

Abstract The design of a sandwich-type SERS immunoassay (surface-enhanced Raman spectroscopy) is demonstrated operating in dual surface enhancement and dual-tag paradigm. The capture and detection antibodies are linked to two SERS-active substrates and form together the three-dimensional (3D) structure after specific binding to interleukin 6. A variety of metal combinations is tested (Au–Ag, Au–Au, and Ag–Ag), but an enhanced electromagnetic field is generated only due to coupling of Ag and Au nanoparticles with an Au hexagonal nanoarray. The amplified in that way Raman signals improve the limit of detection over 3 times in comparison to the assay with only one SERS-active substrate. It is also shown that the proper readout of the true-positive signal can be achieved in assays with two Raman tags, and this approach also improves LOD. For the optimal combination of the metal–metal junction and Raman tags, a linear relationship between the Raman signal and the concentration of IL-6 is obtained in the range 0–1000 pg⋅mL−1with LOD of 25.2 pg mL−1and RSD < 10%. The presented proof-of-concept of the SERS immunoassay with the dual-enhancement and dual-tag opens additional opportunities for engineering reliable SERS biosensing. Graphical abstract

scholarly journals A silver-nanoparticle/cellulose-nanofiber composite as a highly effective substrate for surface-enhanced Raman spectroscopy

2019 ◽  
Vol 10 ◽  
pp. 1270-1279 ◽  
Author(s):  
Yongxin Lu ◽  
Yan Luo ◽  
Zehao Lin ◽  
Jianguo Huang
Keyword(s):  
Silver Nanoparticles ◽  
Low Cost ◽  
Three Dimensional ◽  
Active Surface ◽  
Surface Enhanced Raman Spectroscopy ◽  
Sers Substrate ◽  
Highly Active ◽  
Surface Enhanced ◽  
Surface Enhanced Raman ◽  
Silver Mirror Reaction

A highly active surface-enhanced Raman scattering (SERS) substrate was developed by facile deposition of silver nanoparticles onto cellulose fibers of ordinary laboratory filter paper. This was achieved by means of the silver mirror reaction in a manner to control both the size of the silver nanoparticles and the silver density of the substrate. This paper-based substrate is composed of a particle-on-fiber structure with the unique three-dimensional network morphology of the cellulose matrix. For such a SERS substrate with optimized size of the silver nanoparticles (ca. 70 nm) and loading density of silver (17.28 wt %), a remarkable detection limit down to the sub-attomolar (1 × 10−16 M) level and an enhancement factor of 3 × 106 were achieved by using Rhodamine 6G as the analyte. Moreover, this substrate was applied to monitor the molecular recognition through multiple hydrogen bonds in between nucleosides of adenosine and thymidine. This low-cost, highly sensitive, and biocompatible paper-based SERS substrate holds considerable potentials for the detection and analyses of chemical and biomolecular species.

scholarly journals Rapid uropathogen identification using surface enhanced Raman spectroscopy active filters

2021 ◽  
Vol 11 (1) ◽  
Author(s):  
Simon D. Dryden ◽  
Salzitsa Anastasova ◽  
Giovanni Satta ◽  
Alex J. Thompson ◽  
Daniel R. Leff ◽  
...  
Keyword(s):  
Raman Spectroscopy ◽  
Bacterial Infections ◽  
Surface Enhanced Raman Spectroscopy ◽  
Active Filters ◽  
Raman Signal ◽  
Rapid Diagnostics ◽  
Bacterial Classification ◽  
Surface Enhanced ◽  
Surface Enhanced Raman

AbstractUrinary tract infection is one of the most common bacterial infections leading to increased morbidity, mortality and societal costs. Current diagnostics exacerbate this problem due to an inability to provide timely pathogen identification. Surface enhanced Raman spectroscopy (SERS) has the potential to overcome these issues by providing immediate bacterial classification. To date, achieving accurate classification has required technically complicated processes to capture pathogens, which has precluded the integration of SERS into rapid diagnostics. This work demonstrates that gold-coated membrane filters capture and aggregate bacteria, separating them from urine, while also providing Raman signal enhancement. An optimal gold coating thickness of 50 nm was demonstrated, and the diagnostic performance of the SERS-active filters was assessed using phantom urine infection samples at clinically relevant concentrations (105 CFU/ml). Infected and uninfected (control) samples were identified with an accuracy of 91.1%. Amongst infected samples only, classification of three bacteria (Escherichia coli, Enterococcus faecalis, Klebsiella pneumoniae) was achieved at a rate of 91.6%.

scholarly journals Sunflower-Like Nanostructure with Built-In Hotspots for Alpha-Fetoprotein Detection

Molecules ◽  
2021 ◽  
Vol 26 (4) ◽  
pp. 1197
Author(s):  
Xiaoyu Zhao ◽  
Aonan Zhu ◽  
Yaxin Wang ◽  
Yongjun Zhang ◽  
Xiaolong Zhang
Keyword(s):  
Rapid Detection ◽  
Clinical Medicine ◽  
Electromagnetic Coupling ◽  
Low Cost ◽  
Surface Enhanced Raman Spectroscopy ◽  
Alpha Fetoprotein ◽  
Low Concentrations ◽  
Surface Enhanced Raman ◽  
Active Substrate ◽  
Array Structures

In the present study, a sunflower-like nanostructure array composed of a series of synaptic nanoparticles and nanospheres was manufactured through an efficient and low-cost colloidal lithography technique. The primary electromagnetic field contribution generated by the synaptic nanoparticles of the surface array structures was also determined by a finite-difference time-domain software to simulate the hotspots. This structure exhibited high repeatability and excellent sensitivity; hence, it was used as a surface-enhanced Raman spectroscopy (SERS) active substrate to achieve a rapid detection of ultra-low concentrations of Alpha-fetoprotein (AFP). This study demonstrates the design of a plasmonic structure with strong electromagnetic coupling, which can be used for the rapid detection of AFP concentration in clinical medicine.

scholarly journals Bimetallic Core–Shell Nanoparticles of Gold and Silver via Bioinspired Polydopamine Layer as Surface-Enhanced Raman Spectroscopy (SERS) Platform

Nanomaterials ◽  
2020 ◽  
Vol 10 (4) ◽  
pp. 688 ◽  
Author(s):  
Asli Yilmaz ◽  
Mehmet Yilmaz
Keyword(s):  
Raman Spectroscopy ◽  
Low Cost ◽  
Silver Ions ◽  
Surface Enhanced Raman Spectroscopy ◽  
Core Shell ◽  
Silver Deposition ◽  
Shell Nanoparticles ◽  
Surface Enhanced ◽  
Surface Enhanced Raman ◽  
Core Shell Nanoparticles

Despite numerous attempts to fabricate the core–shell nanoparticles, novel, simple, and low-cost approaches are still required to produce these efficient nanosystems. In this study, we propose the synthesis of bimetallic core–shell nanoparticles of gold (AuNP) and silver (AgNP) nanostructures via a bioinspired polydopamine (PDOP) layer and their employment as a surface-enhanced Raman spectroscopy (SERS) platform. Herein, the PDOP layer was used as an interface between nanostructures as well as stabilizing and reducing agents for the deposition of silver ions onto the AuNPs. UV-vis absorption spectra and electron microscope images confirmed the deposition of the silver ions and the formation of core–shell nanoparticles. SERS activity tests indicated that both the PDOP thickness and silver deposition time are the dominant parameters that determine the SERS performances of the proposed core–shell system. In comparison to bare AuNPs, more than three times higher SERS signal intensity was obtained with an enhancement factor of 3.5 × 105.

scholarly journals Fabrication-friendly polarization-sensitive plasmonic grating for optimal surface-enhanced Raman spectroscopy

2020 ◽  
Vol 16 (1) ◽  
Author(s):  
Arpan Dutta ◽  
Tarmo Nuutinen ◽  
Khairul Alam ◽  
Antti Matikainen ◽  
Peng Li ◽  
...  
Keyword(s):  
Raman Spectroscopy ◽  
Fill Factor ◽  
Surface Enhanced Raman Spectroscopy ◽  
Transverse Magnetic ◽  
Raman Signal ◽  
Optical Resonance ◽  
Excitation Light ◽  
Surface Enhanced ◽  
Surface Enhanced Raman ◽  
Plasmonic Gratings

Abstract Plasmonic nanostructures are widely utilized in surface-enhanced Raman spectroscopy (SERS) from ultraviolet to near-infrared applications. Periodic nanoplasmonic systems such as plasmonic gratings are of great interest as SERS-active substrates due to their strong polarization dependence and ease of fabrication. In this work, we modelled a silver grating that manifests a subradiant plasmonic resonance as a dip in its reflectivity with significant near-field enhancement only for transverse-magnetic (TM) polarization of light. We investigated the role of its fill factor, commonly defined as a ratio between the width of the grating groove and the grating period, on the SERS enhancement. We designed multiple gratings having different fill factors using finite-difference time-domain (FDTD) simulations to incorporate different degrees of spectral detunings in their reflection dips from our Raman excitation (488 nm). Our numerical studies suggested that by tuning the spectral position of the optical resonance of the grating, via modifying their fill factor, we could optimize the achievable SERS enhancement. Moreover, by changing the polarization of the excitation light from transverse-magnetic to transverse-electric, we can disable the optical resonance of the gratings resulting in negligible SERS performance. To verify this, we fabricated and optically characterized the modelled gratings and ensured the presence of the desired detunings in their optical responses. Our Raman analysis on riboflavin confirmed that the higher overlap between the grating resonance and the intended Raman excitation yields stronger Raman enhancement only for TM polarized light. Our findings provide insight on the development of fabrication-friendly plasmonic gratings for optimal intensification of the Raman signal with an extra degree of control through the polarization of the excitation light. This feature enables studying Raman signal of exactly the same molecules with and without electromagnetic SERS enhancements, just by changing the polarization of the excitation, and thereby permits detailed studies on the selection rules and the chemical enhancements possibly involved in SERS.

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