Abstract
G-Quadruplex (G4) structures of a human telomeric 24-mer (5′-TTAGGGTTAGGGTTAGGGTTAGGG-3′) sequence (Tel24) stabilized by sodium and potassium ions have been assessed using surface-enhanced Raman scattering (SERS) spectroscopy. The distinctive SERS spectra of Tel24 in the presence of 100 mM Na+ and 100 mM K+ were obtained and the SERS bands characteristic of the antiparallel basket-type and the mixed hybrid (3+1) structures, respectively, were identified and assigned. The influence of the SERS - active substrate on the scattering enhancement was studied using citrate- and chloride-covered silver nanoparticles, in the absence and presence of the aggregating agent (0.1 M Na2SO4 and 0.1 M K2SO4). The highly reproducible SERS spectra of Tel24 obtained in various SERS active media indicated the same adsorption mechanism of the cation - stabilized G-quadruplexes onto the metal surface, regardless of the silver colloid. The remarkable resemblance between the circular dichroism (CD) spectra of the Tel24 structures with and without the colloid confirmed that interaction with the enhancing silver surface did not affect the stability of the formed G4 structures. The presented study pointed to a great potential of the SERS spectroscopy for the sensitive structural analysis of various G4 topologies.
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References
Burge S, Parkinson GN, Hazel P, Todd AK, Neidle S. Quadruplex DNA: sequence, topology and structure. Nucleic Acids Res. 2006;34:5402–15.
Ioannis Karsisiotis A, O’Kane C, Webba da Silva M. DNA quadruplex folding formalism—a tutorial on quadruplex topologies. Methods. 2013;64:28–35.
Dai J, Carver M, Yang D. Polymorphism of human telomeric quadruplex structures. Biochimie. 2008;90:1172–83.
Phan AT. Human telomeric G-quadruplex: structures of DNA and RNA sequences. FEBS J. 2010;277:1107–17.
Bochman ML, Paeschke K, Zakian VA. DNA secondary structures: stability and function of G-quadruplex structures. Nat Rev Genet. 2012;3:770–80.
König SLB, Evans AC, Huppert JL. Seven essential questions on G-quadruplexes. Biomol Concepts. 2010;1:197–213.
Huppert JL. Four-stranded nucleic acids: structure, function and targeting of G-quadruplexes. Chem Soc Rev. 2008;27:1375–84.
Huppert JL. Four-stranded DNA: cancer, gene regulation and drug development. Phil Trans R Soc A. 2007;365:2969–84.
Luedtke NW. Targeting G-quadruplex DNA with small molecules. Chimia. 2009;63:134–9.
Balagurumoorthy P, Brahmachari SK. Structure and stability of human telomeric sequence. J Biol Chem. 1994;269:21858–69.
Luu KN, Phan AT, Kuryavyi V, Lacroix L, Patel DJ. Structure of the human telomere in K+ solution: an intramolecular (3 + 1) G-quadruplex scaffold. J Am Chem Soc. 2006;128:9963–70.
Ambrus A, Chen D, Dai J, Bialis T, Jones RA, Yang D. Human telomeric sequence forms a hybrid-type intramolecular G-quadruplex structure with mixed parallel/antiparallel strands in solution. Nucleic Acids Res. 2006;34:2723–35.
Phan AT, Luu KN, Patel DJ. Different loop arrangements of intramolecular human telomeric (3+1) G-quadruplexes in K+ solution. Nucleic Acids Res. 2006;34:5715–9.
Prislan I, Lah J, Milanic M, Vesnaver G. Kinetically governed polymorphism of d(G4T4G3) quadruplexes in K+ solutions. Nucleic Acids Res. 2011;39:1933–42.
Boncina M, Lah J, Prislan I, Vesnaver G. Energetic basis of human telomeric DNA folding into G-quadruplex structures. J Am Chem Soc. 2012;134:9657–63.
Aroca R. Surface-enhanced vibrational spectroscopy. Chichester: Wiley; 2006.
Schlücker S. Surface-enhanced Raman spectroscopy: analytical, biophysical and life science applications. Weinheim: Wiley-VCH; 2011.
Miljanić S, Kenđel A, Novak M, Deliqeorqiev TG, Crnolatac I, Piantanida I, et al. Distinguishing binding modes of a new phosphonium dye with DNA by surface-enhanced Raman spectroscopy. RSC Adv. 2016;6:41927–36.
Palacký J, Vorlíčková M, Kejnovská I, Mojzeš P. Polymorphism of human telomeric quadruplex structure controlled by DNA concentration: a Raman study. Nucleic Acids Res. 2013;41:1005–16.
Benevides JM, Overman SA, Thomas GJ. Raman, polarized Raman and ultraviolet resonance Raman spectroscopy of nucleic acids and their complexes. J Raman Spectrosc. 2005;36:279–99.
Pagba CV, Lane SM, Wachsmann-Hogiu S. Conformational changes in quadruplex oligonucleotide structures probed by Raman spectroscopy. Biomed Opt Express. 2011;2:207–17.
Krafft C, Benevides JM, Thomas GJ. Secondary structure polymorphism in Oxytricha nova telomeric DNA. Nucleic Acids Res. 2002;30:3981–91.
Friedman SJ, Terentis AC. Analysis of G-quadruplex conformations using Raman and polarized Raman spectroscopy. J Raman Spectrosc. 2016;47:259–68.
Pagba CV, Lane SM, Wachsmann-Hogiu S. Raman and surface-enhanced Raman spectroscopic studies of the 15-mer DNA thrombin-binding aptamer. J Raman Spectrosc. 2010;41:241–7.
Rusciano G, De Luca AC, Pesce G, Sasso A, Oliviero G, Amato J, et al. Label-free probing of G-quadruplex formation by surface-enhanced Raman scattering. Anal Chem. 2011;83:6849–55.
Gracie K, Dhamodharan V, Pradeepkumar PI, Faulds K, Graham D. Qualitative SERS analysis of G-quadruplex DNAs using selective stabilising ligands. Analyst. 2014;139:4458–65.
Breuzard B, Millot J-M, Riou J-F, Manfait M. Selective interactions of ethidiums with G-quadruplex DNA revealed by surface-enhanced Raman scattering. Anal Chem. 2003;73:4305–11.
Wei C, Jia G, Yuan J, Feng Z, Li C. A spectroscopic study on the interactions of porphyrin with G-quadruplex DNAs. Biochemistry. 2006;45:6681–91.
Miljanić S, Ratkaj M, Avdejev I, Meglić K, Kenđel A. Surface-enhanced Raman scattering enhancement factors for RNA mononucleotides on silver nanoparticles. Croat Chem Acta. 2015;88:387–96.
Munro CH, Smith WE, Garner M, Clarkson J, White PC. Characterization of the surface of a citrate-reduced colloid optimized for use as a substrate for surface-enhanced resonance Raman scattering. Langmuir. 1995;11:3712–20.
Leoplod N, Lendl B. A new method for fast preparation of highly surface-enhanced Raman scattering (SERS) active silver colloids at room temperature by reduction of silver nitrate with hydroxylamine hydrochloride. J Phys Chem B. 2003;107:5723–7.
Papadopulou E, Bell SEJ. Label-free detection of nanomolar unmodified single- and double-stranded DNA by using surface-enhanced Raman spectroscopy on Ag and Au colloids. Chem Eur J. 2012;18:5394–400.
Papadopulou E, Bell SEJ. Label-free detection of single-base mismatches in DNA by surface-enhanced Raman spectroscopy. Angew Chem Int Ed. 2011;50:9058–61.
Wu C-Y, Lo W-Y, Chiu C-R, Yang T-S. Surface enhanced Raman spectra of oligonucleotides induced by spermine. J Raman Spectrosc. 2006;27:799–807.
Ke W, Zhou D, Wu J, Ji K. Surface-enhanced Raman spectra of calf thymus DNA adsorbed on concentrated silver colloid. Appl Spectrosc. 2005;59:418–23.
Miljanić S, Dijanošić A, Matić I. Adsorption mechanisms of RNA mononucleotides on silver nanoparticles. Spectrochim Acta A. 2015;137:1357–62.
Sharma VR, Sheardy RD. The human telomere sequence, (TTAGGG)4, in the absence and presence of cosolutes: a spectroscopic investigation. Molecules. 2014;19:595–608.
Acknowledgements
This work was supported by the Ministry of Science, Education and Sports of the Republic of Croatia and the Croatian Science Foundation (grant number 1477).
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Miljanić, S., Ratkaj, M., Matković, M. et al. Assessment of human telomeric G-quadruplex structures using surface-enhanced Raman spectroscopy. Anal Bioanal Chem 409, 2285–2295 (2017). https://doi.org/10.1007/s00216-016-0172-y
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DOI: https://doi.org/10.1007/s00216-016-0172-y