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 NaSO and 0.1 M KSO). 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. Graphical Abstract SERS spectroscopy allowed identification of Na stabilized antiparallel basket-type and K stabilized hybrid (3+1) structures of the same 24-mer human telomeric sequence.
Surface-enhanced Raman spectroscopy (SERS) and partial least squares (PLS) regression have been applied for the quantification of entacapone isomers E and Z in solution. Nine mixtures of isomers Z and E in ethanol ranging from 0% to 100% w/w were analyzed, for a total entacapone concentration of 1 × 10(-3) mol L(-1). Upon deposition onto commercially available Klarite® gold plates, highly intense and reproducible SERS spectra were obtained from the entacapone isomers. Based on the spectral measurements, a two-component PLS model for correlation of predicted and real content of the isomers mixtures was developed. Root-mean-square error of the predicted composition was found to be 8% of isomer Z in the isomers mixture, corresponding to the absolute concentration of 8 × 10(-5) mol L(-1) of isomer Z in solution.
Surface-enhanced Raman scattering (SERS) enhancement factors (EF) were evaluated for RNA mononucleotides: adenosine 5'-monophosphate (AMP), guanosine 5'-monophosphate (GMP), cytidine 5'-monophosphate (CMP) and uridine 5'-monophosphate (UMP), on silver nanoparticles, which differed in shape (nanospheres, nanostars) and stabilizing anionic layer (chlorides, citrates) on the metal surface. In freshly prepared silver colloids the enhanced Raman scattering was observed for all the RNA mononucleotides on the chloride coated silver nanospheres, Ag_Cl nsp (EF ≈ 10 4 ), for AMP only on the citrate coated silver nanospheres, Ag_cit nsp (EF ≈ 10 3 ), while not obtained at all for any of the mononucleotides on the citrate stabilized silver nanostars, Ag_cit nst. Upon aggregation, the SERS activity of all the silver colloids increased, whereby the purine mononucleotides, AMP and GMP, more strongly scattered radiation on Ag_Cl nsp, and the pyrimidine mononucleotides, CMP and UMP, on Ag_cit nsp. Regardless of the silver nanoparticles, the higher EFs were evaluated for AMP and GMP (EF up to 5 × 10 6 ), than for CMP and UMP (EF ≈ 5 × 10 4 ).
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