The phase map can provide information on the shape, dimensions and presence of cell defects that can be correlated with the biochemical information provided by single-point Raman spectra of the analyzed cells [58]. Adv. Phys. Acta 994, 6572 (2017). 12, 24932502 (2010). It was shown that, even for the lowest mixture, i.e., 1/100, the prediction based on the HTS-RS measurements provides highly accurate results, and the sampling of nearly 1000 cells could be achieved in 38 min. However, several groups are working to overcome this limitation [20,21]. The strong negative amide III (at 1247, 1270/1278 band ratio and 1438 cm1) Raman bands suggest a decreased HER2 amplification when control (HER2 control and HER2+ control) cell spectra were subtracted from that of BT474 cancer cells. 50, 240260 (2015). ACS Appl. Wang, H.-X., Zhao, Y.-W., Li, Z., Liu, B.-S. & Zhang, D. Development and application of aptamer-based surface-enhanced Raman spectroscopy sensors in quantitative analysis and biotherapy. The RM results were compared with confocal fluorescence analysis (Figure 4a). Kitagawa, T. & Ozaki, Y. in Metal Complexes with Tetrapyrrole Ligands volume I (ed. Mater. 136, 144704 (2012). 76, 4047 (2004). Raman Spectroscopy of Viruses and Viral Proteins - ScienceDirect This can be improved using advanced Raman spectrometers to achieve efficiency in Raman-acquisition and integration of the RACS system into the novel microfluidic devices. The same color code is maintained for images and for spectra. The following band assignment is therefore based on this evidence as well as on classical textbooks on vibrational assignments 5, 36, 37 and the literature published previously on similar compounds. High electromagnetic field enhancement of TiO2 nanotube electrodes. 70, 114126 (2017). Proposals for the immunological classification of acute leukemias. To determine the reproducibility of AuNPs prepared from different batches, SERS were examined by using R6G at a concentration of 10 6 mol L 1 as a probe, and three SERS spectra were randomly collected from each batch. In this review, we show the RS-based imaging technique, and provide biochemical identification and mapping of normal and cancer cells. It has been demonstrated that RS and DHM can be used simultaneously to provide a morphological and biochemical analysis of cells [58] and it can be applied to living white blood cells [59]. J. Raman. Angew. 16, 16851706 (2004). Chem. & Zhao, B. Label-free detection in biological applications of surface-enhanced Raman scattering. By combing RS and OCT, it is possible to provide a more complete description of the analyzed sample, correlating the biochemical information of the Raman analysis with microstructural and morphological information from the OCT. Actuators B Chem 262, 922927 (2018). This article is the first conceptual demonstration of SERS-active organic semiconductor films. Chip 19, 674681 (2019). In the last decade, Raman Spectroscopy (RS) was demonstrated to be a label-free, non-invasive and non-destructive optical spectroscopy allowing the improvement in diagnostic accuracy in cancer and analytical assessment for cell sensing. Mao, Z. et al. You can view the vibrations of a complex molecule as partly consisting of many simple diatomic vibrations. In the meantime, to ensure continued support, we are displaying the site without styles ), 21773080 (B.Z.) Chem. Keren S., Zavaleta C., Cheng Z., De la Zerda A., Gheysens O., Gambhir S.S. Noninvasive molecular imaging of small living subjects using Raman spectroscopy. The in-phase C-X stretch of the BP is seen as strong band at 1,360 cm 1 in Raman. Additional bands, which are apparently E2 modes, are observed at 308 and 676 cm1 at a sample temperature of 50C and at 389 and 741 cm1 at a sample temperature of 130C that are not observed in samples at room temperature. Nanoparticles for live cell microscopy: a surface-enhanced Raman scattering perspective. Chem. Chem. Anal. For each step, three or more cells were randomly analyzed, and the imaging analysis was repeated three times. Nanobi. Raman microscopy (RM) can be a complement to conventional staining methods that can be easily used for monitoring the sub-cellular components of normal and cancer cells [10,11]. 10, 96059612 (2019). Based on Raman spectral profile, differences in the composition of nucleic acids, proteins, lipids, and carbohydrates in cancer/normal cells helps in the evaluation, characterization, and discrimination of cancer stage [6,7,8,9]. This article presents the first conceptual demonstration of TERS. B. et al. Surface-enhanced Raman spectroscopy (SERS) is a highly sensitive technique that enhances the Raman scattering of molecules supported by some nanostructured materials. On a different note, Raman imaging can overcome problems resulting from limited stability, bleaching, the use of external biomarkers and long sample preparation associated with traditional morphological analysis like electron microscopy and fluorescence microscopy, opening the way to in vivo analysis. Between 3200 and 3500 cm-1, the Raman spectra of Valonia and ramie contain several closely spaced, medium-intensity bands. Shape, morphological defects and optical thickness are also useful parameters, particularly for the discrimination between cells, and may be recorded via holography. Lombardi, J. R. & Birke, R. L. The theory of surface-enhanced Raman scattering. This issue can be further improved by enhancing the Raman signal, as in the SERS experiments, or by integrating advanced Raman spectrometers into microfluidic devices [51] or using recently developed high-throughput screening RS (HTS-RS) [52]. At last, the Raman spectrum of vesicles reveals intense Raman bands assigned to lipid contents (at 1449, 1250 and 1660 cm1), in particular to vibrations in the hydrocarbon chains. In 2008, Anita Mahadevan-Jansen et al. In general, Raman spectra of DNA or RNA reveal structural information about base stacking and interbase hydrogen bonding interactions. The spectra/loadings of different components of the cells were converted into spatial distribution maps and translated into brightness pixels in the cell image. Qian, X. et al. Nanotechnol. Nat. open access Highlights Alkannin and shikonin are enantiomeric red natural dyes of Japanese origin. Intensities in Raman spectra I. In Figure 2a, the average Raman spectra of normal B-cells and B-ALL cell lines (RS4;11, REH, MN60) are compared and the differences in Raman spectra were used to classify and discriminate between normal and leukemia cell lines. Lu, G. et al. On a different note, the Raman spectra of B-ALL cells showed a higher intensity of the Raman amide III (at 1252 cm1), amide I (at 1660 cm1) and CH/CC region bands (at 1337, 14201485, 16071617 cm1) in comparison to the normal B-cells. Chem. ISSN 2662-8449 (online). Phys. This chapter considers the implementation of methods of Raman spectroscopy, ultraviolet resonance Raman (UVRR) spectroscopy, and polarized Raman spectroscopy as structural probes of native viruses, precursor viral assemblies, and their constituent proteins and nucleic acids. Nanoscale 9, 48474861 (2017). Park, K.-D. et al. WIRES Nanomed. In contrast, the Raman spectrum of the MN60 cell lines showed higher intensity of the Raman band around at 745 cm1, which is attributed to cytochrome C, suggesting it is at the most advanced stage of maturation. J. Phys. Chem. However, the transfer of the Raman spectral library, such as those available in FTIR analyses, remains a major challenge that stands in the way of clinical translation for Raman-based technologies, and continued effort is needed to facilitate the transition from benchtop to bedside by developing novel experimental designs and structured protocols for the objective method. El-Mashtoly S.F., Petersen D., Yosef H.K., Mosig A., Reinacher-Schick A., Ktting C., Gerwert K. Label-free imaging of drug distribution and metabolism in colon cancer cells by Raman microscopy. 118, 32093250 (2018). Interfaces 10, 3182531844 (2018). Phys. For the cancer cell sensing, RS is more advantageous than FM as it does not require an external contrast agent and works on the principle of Raman scattering, i.e., a vibrational phenomenon involving inelastic scattering [17]. 15 . Am. 2015, 316189 (2015). Chem. Raman C.V., Krishnan K.S. Search for other works by this author on: You do not currently have access to this content. A discrimination efficiency of up to 98% was obtained by combining RS with the statistical method and demonstrating its potential to discriminate normal and cancer cells, particularly in different differentiation/maturation stages. 86, 1150311507 (2014). Indeed, RS, detecting the fundamental vibrational states of biomolecules, is exploited as a label-free, non-invasive tool for monitoring the biochemical changes between normal and cancer cells [5]. 90, 29963000 (2018). Patil C.A., Bosschaart N., Keller M.D., Van Leeuwen T.G., Mahadevan-Jansen A. Spectrosc. Details about SERS equipment, SERS-active material preparation and SERS measurements are summarized, followed by results and typical methods for data analysis. Ed. The fact that Raman spectroscopy can provide molecular/chemical information of the cell of interest makes it a competitive contender in the molecular imaging arena. Furthermore, Raman spectra require specialized spectroscopic eyes for their precise interpretation, which has not facilitated its practical application in cancer diagnosis. Brozek-Pluska B., Kopec M., Surmacki J., Abramczyk H. Histochemical analysis of human breast tissue samples by IR and Raman spectroscopies. 171, 112748 (2021). On the contrary, the ATRA-treated leukemia cells did not exhibit important variations in the spectral region related to the proteinDNA ratio (at 1447 and 785 cm1). Besides this, a small increase can be seen in the intensity of band at 1350 cm1 in the red spectrum, once more suggesting a structural DNA modification. In MFS, Raman bands at 345-450, 575, 750, 973 and 1070 cm-1 are associated with various Si-O-Si . Raman mapping rather than single-point spectral analysis could benefit surgeons, allowing a more complete visualization of the cancer cells. Bantz, K. C. et al. Zhang, Z., Deckert-Gaudig, T. & Deckert, V. Label-free monitoring of plasmonic catalysis on the nanoscale. This increased Raman bands appeared to be more pronounced from RS4;11 to MN60 cells and confirm a good correlation with the differentiation/maturation stages of these B-leukemia cells. DNAzyme-based plasmonic nanomachine for ultrasensitive selective surface-enhanced Raman scattering detection of lead ions via a particle-on-a-film hot spot construction. Liebig, F. et al. Because of these unique properties, combined with an exceptional information depth, RS and RM are ideal for label-free high-throughput and high-content cell screening. 8, 677692 (2013). (a) Confocal (left) and Raman imaging (right) of DNP uptake in H1355 cells at different incubation times (0, 6, 18, 24, 48 and 72 h). Mater. 537573 (Wiley-VCH, 2019). Surface-enhanced Raman scattering and surface-enhanced infrared absorption by plasmon polaritons in three-dimensional nanoparticle supercrystals. & Tani, N. Surface-enhanced Raman scattering (SERS) of adsorbed molecules on smooth surfaces of metals and a metal oxide. 16, 918924 (2017). Both infrared (IR) and RS have been used in the analyses of biological samples and for the structural characterization of cellular components [15]. 47, 91319133 (2011). Preliminary Raman results of three clinical samples have shown that the Raman approach is promising for medical applications. Rev. Potential-dependent surface-enhanced resonance Raman spectroscopy at nanostructured TiO2: a case study on cytochrome b5. 93, 2340 (2021). & Zhao, Y. 84, 84488451 (2012). Chem. B 107, 74267433 (2003). While, MN60 cell line is a more differentiated B-ALL cell type which is classified as the L3-blast (i.e., B-cell leukemia) subtype [32,33,34]. Heavy atoms and weak bonds have low Raman shifts. Table 1 summarizes the assignments of Raman bands of proteins compiled from various literature reports. These changes were observed in both the fingerprint range (12651298 cm1) and in the high-frequency Raman range (between 27003100 cm1), that reflects the differences in lipid to protein distributions for the different cells [37,38]. Aside from chemical specificity, Raman spectroscopy also possesses many other desirable properties for imaging applications, such as high spatial resolution, high multiplexing capability and excellent photostability [10]. Ed. http://creativecommons.org/licenses/by/4.0/, Cytosine U, C, T ring breathing, DNA (nucleic acids assignment), Glycans, polysaccharides (-glucose), (C-O-C) skeletal mode, C-C Symmetric stretching ring breathing, phenylalanine (protein assignment), P=O symmetric vibration from nucleic acids/cell membrane phospholipids (protein assignment), Amide III, adenine, cytosine (protein assignment), C-H deformation (lipid/protein assignment), C-H deformation of proteins (protein assignment), The most pronounced saccharide band, Ring and C-N stretch, Amide II, aromatic amino acids within proteins of C=C olefinic stretch (protein assignment), C=C Symmetric stretching, tryptophan and phenylalanine (protein assignment), Amide I, Unsaturated fatty acids, C=O stretching (C-H) deformation/(C=C) stretch (lipid assignment), C=O Symmetric stretching; glycans and glycogen (lipid assignment), combination of ring stretching vibrations of CH, CH aromatic stretching (nucleic acids/proteins assignment). A collective oscillation of conduction band electrons at the interface of two materials that occurs upon stimulation by incident light. 91, 50435050 (2019). Soc. & Kawata, S. Metallized tip amplification of near-field Raman scattering. Changes in IR and Raman spectra (peak intensity and position) can be easily used to monitor the sub-cellular components of health or diseases cells/tissues, including proteins, lipids, carbohydrates and nucleic acids [15]. Analyst 140, 43254335 (2015). Raman spectroscopy band assignments of SK-BR3 breast cancer cells. Spiked gold nanotriangles: formation, characterization and applications in surface-enhanced Raman spectroscopy and plasmon-enhanced catalysis. 86, 1149411497 (2014). 92, 1263912646 (2020). Rodriguez, R. D. et al. Chem. 123, 243251 (2015). J. Phys. et al. Commun. A. Anomalously intense Raman spectra of pyridine at a silver electrode. 693, 175185 (2004). Rev. 88, 97669772 (2016). 115, 1048910529 (2015). The histochemical staining technique is the standard method for analyzing the cellular morphology such as size, shape and granularity, however, it suffers from some limitations and is not able to provide reliable information on the biochemical changes in or the specific immunophenotype of cells. Adv. Recently, it has been demonstrated that correlating the Raman signal with the destructive mass spectrometry analysis renders the drug and metabolite quantification at a single-cell level possible [62]. A false-color Raman image of the cell was constructed by acquiring about 2500 spectra in about 30 min, which clearly showed the main cellular compartments of the cells, such as nucleus, cytoplasm and vesicles. Nanoscale 10, 16221630 (2018). Abstract De Angelis A., Manag S., Ferrara M.A., Napolitano M., Coppola G., De Luca A.C. You can see more subtle effects if you inspect spectra closely. Diagnosing breast cancer by using Raman spectroscopy. Ed. The PCA loading can detect spectral differences in cell states and identify the associated biomolecular changes [4,5,6,7,8]. bands at. Soc. Kruse, F. et al. Recent advances in surface-enhanced Raman scattering-based sensors for the detection of inorganic ions: sensing mechanism and beyond. On a different note, the HTS-RS approach was truly valuing the advantage of RS; because a minimal sample preparation is required and large, statistically significant sample sizes in a mixed population, removes the human dependency from the data acquisition and a substantial amount of data can be accumulated for an explicit statistical evaluation. Raman band assignment a | Download Table - ResearchGate Sci. This is at a higher frequency than two carbon atoms lined by a weaker single bond (C-C, 800 cm-1). and A.C.D.L. See live demonstrations of Renishaw's latest products at events around the world and online. Raman imaging alone does not allow live, high-resolution imaging of large areas in complex matrices, for instance in tissues, where the cells and extracellular matrix coexist and interact. Long D.A. Division of Polymer Science, Case Western Reserve University, Cleveland, Ohio 44106. 205, 387407 (2017). Chem. 2 - Progress and Outcomes . Plasmon-mediated chemical reactions on nanostructures unveiled by surface-enhanced raman spectroscopy. Machine learning protocol for surface-enhanced Raman spectroscopy. Careers, Unable to load your collection due to an error. Nanostructure-based plasmon-enhanced Raman spectroscopy for surface analysis of materials. Adv. American Crystallographic Association, Inc. AVS: Science and Technology of Materials, Interfaces and Processing, DCP Future of Chemical Physics Lectureship, CP2K: An electronic structure and molecular dynamics software package - Quickstep: Efficient and accurate electronic structure calculations, Study on thermal decomposition characteristics of C, Effects of micro-water on decomposition of the environment-friendly insulating medium C, Operating results from the DELPHI ring imaging Cherenkov (RICH), Electron attachment to the perfluoroalkanes nC. Such new bands suggest that a phosphorylation process could be the potential reason for the faster cell proliferation of EGF-treated cells. & Nie, S. SERS nanoparticles in medicine: from label-free detection to spectroscopic tagging. App. For the Raman spectra of albite see also Frezzotti et al. Probing single-atom catalysts and catalytic reaction processes by shell-isolated nanoparticle-enhanced Raman spectroscopy. In the blue spectrum, the band at 752 cm1 is dominant, while the intensity of this band starts decreasing in the green spectrum, whereas the band at 784 cm1 starts increasing its contribution. ACS Nano 2, 377385 (2008). Lett. Rep. 7, 4471 (2017). This combination can be used for correlating the single-point Raman analysis information of biochemical changes in the cells with microstructural and morphological information. Kim, J., Nam, S. H., Lim, D.-K. & Suh, Y. D. SERS-based particle tracking and molecular imaging in live cells: toward the monitoring of intracellular dynamics. Rev. J. C. 117, 77917795 (2013). 26, 163166 (1974). The spectral acquisition time was 60 s with 1 accumulation averaged. RM combined with a microfluidic device, called the Raman-activated cell sorting (RACS) platform has been proposed for the fast diagnosis and selection of circulating tumor cells and for functional sorting of cells [51]. The assignments of the Raman bands given by Walrafen and Schultz and Hornig, are based on polari;.ation data'. Nat. ); Reproducibility and data deposition (X.X.H. In other words, as a result of the PCA, Raman spectra acquired from normal and cancer cell-lines appear as scores distributed in different regions of the score plot [8], allowing an immediate visualization and differentiation of the cell types. & Yu, S.-H. MRS Bull. Chim. Popp et al. Schie I.W., Kiselev R., Krafft C., Popp J. Surface-enhanced Raman spectroscopy and microfluidic platforms: challenges, solutions and potential applications. Han, X. X., Pienpinijtham, P., Zhao, B. Kneipp, K., Moskovits, M. & Kneipp, H. Surface-Enhanced Raman Scattering: Physics and Applications (Springer, 2006). 58, 1649916503 (2019). PDF Integrated LIBS-RAMAN-AI System for Real-Time, In-Situ Chemical C 116, 25152520 (2012). Wang, J. F., Wu, X. We briefly introduce the basic theories of SERS enhancement mechanisms. Zhang, Y., Gu, Y., He, J., Thackray, B. D. & Ye, J. Ultrabright gap-enhanced Raman tags for high-speed bioimaging. Bai, S., Serien, D., Hu, A. J. Phys. Communications Physics & Lednev, I. K. Surface enhanced Raman spectroscopy for single molecule protein detection. J. Phys. Aluminum and copper nanostructures for surface-enhanced Raman spectroscopy: a one-to-one comparison to silver and gold. and transmitted securely. Chem. Drexler H.G., Macleod R.A. History of leukemia-lymphoma cell lines. https://doi.org/10.1038/s43586-021-00083-6. Auner G.W., Koya S.K., Huang C., Broadbent B., Trexler M., Auner Z., Elias A., Mehne K.C., Brusatori M.A. The reported Raman results provide information on cancer progression and allow the identification, classification, and follow-up after chemotherapy treatments of the cancer cells from the liquid biopsy. Chem. Chem. Vibrational analysis of alkannin and shikonin were performed aided by DFT methods, allowing the assignment of the experimental bands. Introduction Macromolecular science has a major impact on the way we live today. SERS allows for the structural fingerprinting of low-concentration analytes through the plasmon-mediated amplification of electrical fields or chemical enhancement. Indeed, the detection of molecular targeted agents and their metabolites in cells/tissues by label-free RS is attractive because dyes or fluorescent labels may be toxic or invasive [19]. Nanoscale 11, 2172421727 (2019). 91, 79807984 (2019). Chem. The proposed device was able to compensate for the limitations of the two techniques alone. The median of each group is shown by the white dot and the line indicates the 50th percentile. Styles, M. J. et al. Antibody-free discrimination of protein biomarkers in human serum based on surface-enhanced Raman spectroscopy. According to a report, 30% of breast cancers have an amplification of the human epidermal growth factor receptor 2 (HER2)/neu gene or overexpression of HER2 protein [36]. Multiplex immunochips for high-accuracy detection of AFP-L3% based on surface-enhanced Raman scattering: implications for early liver cancer diagnosis. Infrared and Raman spectroscopy Near-infrared Visible and UV spectroscopy Optical materials Waveguide application 1. Chem. Anal. The site is secure. A review on surface-enhanced Raman scattering. Molecular sensitivities of substrate-supported gold nanocrystals. 53, 24812484 (2014). Ed. Liao, P. F. in Surface Enhanced Raman Scattering (eds Chang, R. K. & Furtak, T. E.) 379390 (Springer, 1982). This article is one of two presenting the first conceptual demonstration of single-molecule SERS. Yeo, B.-S., Stadler, J., Schmid, T., Zenobi, R. & Zhang, W. Tip-enhanced Raman spectroscopyits status, challenges and future directions. Kneipp, K., Ozaki, Y. Chem. The normalized averaged Raman spectrum of SK-BR3 HER2+ breast cancer cells. Unprocessed and Processed Raman Spectrum Identification of Raman Bands for Polystyrene . J. Phys. 46, 265281 (2006). 21773079 (X.X.H. Before Anal. This article is one of two demonstrating the discovery of SERS. The bands in the region between 1400 and 1500 cm1 are essentially due to C-H, CH2, and CH3 vibrations. Basically, OCT performed real-time, large-area imaging of the tissues and was used to guide the Raman analysis. Google Scholar. Highly sensitive and label-free determination of thiram residue using surface-enhanced Raman spectroscopy (SERS) coupled with paper-based microfluidics. PDF Raman Data and Analysis - Raman Bands - Horiba 12, 53695375 (2012). & Lombardi, J. R. Enhanced Raman scattering with dielectrics. Ozaki, Y., Wjcik, M. J., Popp, J. Molecular Spectroscopy: A Quantum Chemistry Approach (Wiley, 2019). Yang, B. et al. X. Bi et al. 14 . Lett. Having oriented molecules in Raman means that the band assignment is facilitated, especially for simple planar molecules like coniferyl alcohol. 22-24 Mater. J. Anderson, M. S. Locally enhanced Raman spectroscopy with an atomic force microscope. Chem. To accomplish global cell sensing that is effective for cancer diagnosis, the development of an automatic and objective method for discriminating cancer cells without any specialized knowledge of spectroscopy is . Zong, C. et al. The Raman intensity depends on the intensity of the laser source as well as the polarizability and concentration of the molecules in the samples [3]. Almehmadi, L. M., Curley, S. M., Tokranova, N. A., Tenenbaum, S. A. Nano Today 3, 3137 (2008). Hess, C. New advances in using Raman spectroscopy for the characterization of catalysts and catalytic reactions. Therefore, the PCA-SVM model was used to estimate the percentage of cell viabilities in the mixed population of all other test conditions.