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Present and future of surface-enhanced Raman scattering

2020, Langer, Judith, de Aberasturi, Dorleta Jimenez, Aizpurua, Javier, Alvarez-Puebla, Ramon A., Auguié, Baptiste, Baumberg, Jeremy J., Bazan, Guillermo C., Bell, Steven E.J., Boisen, Anja, Brolo, Alexandre G., Choo, Jaebum, Cialla-May, Dana, Deckert, Volker, Fabris, Laura, Faulds, Karen, de Abajo, F. Javier García, Goodacre, Royston, Graham, Duncan, Haes, Amanda J., Haynes, Christy L., Huck, Christian, Itoh, Tamitake, Käll, Mikael, Kneipp, Janina, Kotov, Nicholas A., Kuang, Hua, Le Ru, Eric C., Lee, Hiang Kwee, Li, Jian-Feng, Ling, Xing Yi, Maier, Stefan A., Mayerhöfer, Thomas, Moskovits, Martin, Murakoshi, Kei, Nam, Jwa-Min, Nie, Shuming, Ozaki, Yukihiro, Pastoriza-Santos, Isabel, Perez-Juste, Jorge, Popp, Juergen, Pucci, Annemarie, Reich, Stephanie, Ren, Bin, Schatz, George C., Shegai, Timur, Schlücker, Sebastian, Tay, Li-Lin, Thomas, K. George, Tian, Zhong-Qun, Van Duyne, Richard P., Vo-Dinh, Tuan, Wang, Yue, Willets, Katherine A., Xu, Chuanlai, Xu, Hongxing, Xu, Yikai, Yamamoto, Yuko S., Zhao, Bing, Liz-Marzán, Luis M.

The discovery of the enhancement of Raman scattering by molecules adsorbed on nanostructured metal surfaces is a landmark in the history of spectroscopic and analytical techniques. Significant experimental and theoretical effort has been directed toward understanding the surface-enhanced Raman scattering (SERS) effect and demonstrating its potential in various types of ultrasensitive sensing applications in a wide variety of fields. In the 45 years since its discovery, SERS has blossomed into a rich area of research and technology, but additional efforts are still needed before it can be routinely used analytically and in commercial products. In this Review, prominent authors from around the world joined together to summarize the state of the art in understanding and using SERS and to predict what can be expected in the near future in terms of research, applications, and technological development. This Review is dedicated to SERS pioneer and our coauthor, the late Prof. Richard Van Duyne, whom we lost during the preparation of this article.

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TopUp SERS substrates with integrated internal standard

2018, Patze, Sophie, Hübner, Uwe, Weber, Karina, Cialla-May, Dana, Popp, Jürgen

Surface-enhanced Raman spectroscopy (SERS) is known as a molecular-specific and highly sensitive method. In order to enable the routine application of SERS, powerful SERS substrates are of great importance. Within this manuscript, a TopUp SERS substrate is introduced which is fabricated by a top-down process based on microstructuring as well as a bottom-up generation of silver nanostructures. The Raman signal of the support material acts as an internal standard in order to improve the quantification capabilities. The analyte molecule coverage of sulfamethoxazole on the surface of the nanostructures is characterized by the SERS signal evolution fitted by a Langmuir–Freundlich isotherm.

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Using Raman spectroscopy in infection research

2022, Cialla-May, Dana, Rösch, Petra, Popp, Jürgen

Raman spectroscopy allows to analyze bacteria and other microorganisms label and destruction free. With different Raman techniques either colonies on agar plates or small structures like single bacterial cells can be analyzed allowing for their identification as well as enabling 2D and 3D information of intracellular bacteria or biofilms. Using surface enhanced Raman spectroscopy (SERS) allows detecting and identifying viruses as well as antibiotics relevant in the treatment of infections.

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Toward food analytics: fast estimation of lycopene and β-carotene content in tomatoes based on surface enhanced Raman spectroscopy (SERS)

2016, Radu, Andreea Ioana, Ryabchykov, Oleg, Bocklitz, Thomas Wilhelm, Huebner, Uwe, Weber, Karina, Cialla-May, Dana, Popp, Jürgen

Carotenoids are molecules that play important roles in both plant development and in the well-being of mammalian organisms. Therefore, various studies have been performed to characterize carotenoids’ properties, distribution in nature and their health benefits upon ingestion. Nevertheless, there is a gap regarding a fast detection of them at the plant phase. Within this contribution we report the results obtained regarding the application of surface enhanced Raman spectroscopy (SERS) toward the differentiation of two carotenoid molecules (namely, lycopene and β-carotene) in tomato samples. To this end, an e-beam lithography (EBL) SERS-active substrate and a 488 nm excitation source were employed, and a relevant simulated matrix was prepared (by mixing the two carotenoids in defined percentages) and measured. Next, carotenoids were extracted from tomato plants and measured as well. Finally, a combination of principal component analysis and partial least squares regression (PCA-PLSR) was applied to process the data, and the obtained results were compared with HPLC measurements of the same extracts. A good agreement was obtained between the HPLC and the SERS results for most of the tomato samples.

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Rapid Colorimetric Detection of Pseudomonas aeruginosa in Clinical Isolates Using a Magnetic Nanoparticle Biosensor

2019, Alhogail, Sahar, Suaifan, Ghadeer A.R.Y, Bikker, Floris J., Kaman, Wendy E., Weber, Karina, Cialla-May, Dana, Popp, Jürgen, Zourob, Mohammed M.

A rapid, sensitive, and specific colorimetric biosensor based on the use of magnetic nanoparticles (MNPs) was designed for the detection of Pseudomonas aeruginosa in clinical samples. The biosensing platform was based on the measurement of P. aeruginosa proteolytic activity using a specific protease substrate. At the N-terminus, this substrate was covalently bound to MNPs and was linked to a gold sensor surface via cystine at the C-terminus of the substrates. The golden sensor appears black to naked eyes because of the coverage of the MNPs. However, upon proteolysis, the cleaved peptide–MNP moieties will be attracted by an external magnet, revealing the golden color of the sensor surface, which can be observed by the naked eye. In vitro, the biosensor was able to detect specifically and quantitatively the presence of P. aeruginosa with a detection limit of 102 cfu/mL in less than 1 min. The colorimetric biosensor was used to test its ability to detect in situ P. aeruginosa in clinical isolates from patients. This biochip is anticipated to be useful as a rapid point-of-care device for the diagnosis of P. aeruginosa-related infections.

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Surface enhanced Raman spectroscopy-based evaluation of the membrane protein composition of the organohalide-respiring Sulfurospirillum multivorans

2021, Cialla-May, Dana, Gadkari, Jennifer, Winterfeld, Andreea, Hübner, Uwe, Weber, Karina, Diekert, Gabriele, Schubert, Torsten, Goris, Tobias, Popp, Jürgen

Bacteria often employ different respiratory chains that comprise membrane proteins equipped with various cofactors. Monitoring the protein inventory that is present in the cells under a given cultivation condition is often difficult and time-consuming. One example of a metabolically versatile bacterium is the microaerophilic organohalide-respiring Sulfurospirillum multivorans. Here, we used surface enhanced Raman spectroscopy (SERS) to quickly identify the cofactors involved in the respiration of S. multivorans. We cultured the organism with either tetrachloroethene (perchloroethylene, PCE), fumarate, nitrate, or oxygen as electron acceptors. Because the corresponding terminal reductases of the four different respiratory chains harbor different cofactors, specific fingerprint signals in SERS were expected. Silver nanostructures fabricated by means of electron beam lithography were coated with the membrane fractions extracted from the four S. multivorans cultivations, and SERS spectra were recorded. In the case of S. multivorans cultivated with PCE, the recorded SERS spectra were dominated by Raman peaks specific for Vitamin B12. This is attributed to the high abundance of the PCE reductive dehalogenase (PceA), the key enzyme in PCE respiration. After cultivation with oxygen, fumarate, or nitrate, no Raman spectral features of B12 were found. © 2020 The Authors. Journal of Raman Spectroscopy published by John Wiley & Sons Ltd

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Laser-induced spatially-selective tailoring of high-index dielectric metasurfaces

2020, Berzinš, Jona, Indrišiūna, Simonas, Fasold, Stefan, Steinert, Michael, Žukovskaja, Olga, Cialla-May, Dana, Gečys, Paulius, Bäumer, Stefan M.B., Pertsch, Thomas, Setzpfandt, Frank

Optically resonant high-index dielectric metasurfaces featuring Mie-type electric and magnetic resonances are usually fabricated by means of planar technologies, which limit the degrees of freedom in tunability and scalability of the fabricated systems. Therefore, we propose a complimentary post-processing technique based on ultrashort (= 10 ps) laser pulses. The process involves thermal effects: crystallization and reshaping, while the heat is localized by a high-precision positioning of the focused laser beam. Moreover, for the first time, the resonant behavior of dielectric metasurface elements is exploited to engineer a specific absorption profile, which leads to a spatially-selective heating and a customized modification. Such technique has the potential to reduce the complexity in the fabrication of non-uniform metasurface-based optical elements. Two distinct cases, a spatial pixelation of a large-scale metasurface and a height modification of metasurface elements, are explicitly demonstrated. © 2020 Optical Society of America under the terms of the OSA Open Access Publishing Agreement

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Towards on-site testing of Phytophthora species

2014, Schwenkbier, Lydia, Pollok, Sibyll, König, Stephan, Urban, Matthias, Werres, Sabine, Cialla-May, Dana, Weber, Karina, Popp, Jürgen

Rapid detection and accurate identification of plant pathogens in the field is an ongoing challenge. In this study, we report for the first time on the development of a helicase-dependent isothermal amplification (HDA) in combination with on-chip hybridization for the detection of selected Phytophthora species. The HDA approach allows efficient amplification of the yeast GTP-binding protein (Ypt1) target gene region at one constant temperature in a miniaturized heating device. The assay's specificity was determined by on-chip DNA hybridization and subsequent silver nanoparticle deposition. The silver deposits serve as stable endpoint signals that enable the visual as well as the electrical readout. Our promising results point to the direction of a near future on-site application of the combined techniques for a reliable detection of Phytophthora species.

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Molecular Specific and Sensitive Detection of Pyrazinamide and Its Metabolite Pyrazinoic Acid by Means of Surface Enhanced Raman Spectroscopy Employing In Situ Prepared Colloids

2019, Mühlig, Anna, Jahn, Izabella-Jolan, Heidler, Jan, Weber, Karina, Jahn, Martin, Sheen, Patricia, Zimic, Mirko, Cialla-May, Dana, Popp, Jürgen

The prodrug pyrazinamide (PZA) is metabolized by the mycobacteria to pyrazinoic acid (POA), which is expelled into the extracellular environment. PZA resistance is highly associated to a lack of POA efflux. Thus, by detecting a reduction of the concentration of POA in the extracellular environment, by means of lab-on-a-chip (LoC)-SERS (surface-enhanced Raman spectroscopy), an alternative approach for the discrimination of PZA resistant mycobacteria is introduced. A droplet-based microfluidic SERS device has been employed to illustrate the potential of the LoC-SERS method for the discrimination of PZA resistant mycobacteria. The two analytes were detected discretely in aqueous solution with a limit of detection of 27 µm for PZA and 21 µm for POA. The simultaneous detection of PZA and POA in aqueous mixtures could be realized within a concentration range from 20 μm to 50 μm for PZA and from 50 μm to 80 μm for POA.

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A manual and an automatic TERS based virus discrimination

2015, Olschewski, Konstanze, Kämmer, Evelyn, Stöckel, Stephan, Bocklitz, Thomas, Deckert-Gaudig, Tanja, Zell, Roland, Cialla-May, Dana, Weber, Karina, Deckert, Volker, Popp, Jürgen

Rapid techniques for virus identification are more relevant today than ever. Conventional virus detection and identification strategies generally rest upon various microbiological methods and genomic approaches, which are not suited for the analysis of single virus particles. In contrast, the highly sensitive spectroscopic technique tip-enhanced Raman spectroscopy (TERS) allows the characterisation of biological nano-structures like virions on a single-particle level. In this study, the feasibility of TERS in combination with chemometrics to discriminate two pathogenic viruses, Varicella-zoster virus (VZV) and Porcine teschovirus (PTV), was investigated. In a first step, chemometric methods transformed the spectral data in such a way that a rapid visual discrimination of the two examined viruses was enabled. In a further step, these methods were utilised to perform an automatic quality rating of the measured spectra. Spectra that passed this test were eventually used to calculate a classification model, through which a successful discrimination of the two viral species based on TERS spectra of single virus particles was also realised with a classification accuracy of 91%.