Spectroscopic detection of chiral compounds is often hampered by a low sensitivity. For Raman optical activity (ROA), the signal can be dramatically increased in surface-enhanced experiments. So far, however, reproducible surface-enhanced ROA (SEROA) spectra were obtained for a reporter molecule only via induced chirality, and the intensities were just proportional to the Raman scattering. In the present study, we show that the signal can be substantially increased if colloidal silver nanoparticles are prepared already in the presence of a chiral analyte. In this case, both the analyte's and reporter's bands are visible. In addition, some experiments provided bisignate SEROA patterns, thus significantly enhancing information about the molecular structure provided by this spectroscopic method. Increased electronic circular dichroism (ECD) of the capped aggregated colloids suggests that ECD and polarized Raman scattering (ECD-Raman) contribute to the monosignate SEROA intensities, while well-dispersed nonaggregating colloids are important for observation of true (bisignate) molecular vibrational SEROA.

• Klíčová slova
• chiral analyte capped colloid, chirality, electronic circular dichroism, silver nanoparticles, surface-enhanced Raman optical activity,
• Publikační typ
• časopisecké články MeSH

Raman optical activity (ROA) is commonly measured with green light (532 nm) excitation. At this wavelength, however, Raman scattering of europium complexes is masked by circularly polarized luminescence (CPL). This can be avoided using near-infrared (near-IR, 785 nm) laser excitation, as demonstrated here by Raman and ROA spectra of three chiral europium complexes derived from camphor. Since luminescence is strongly suppressed, many vibrational bands can be detected. They carry a wealth of structural information about the ligand and the metal core, and can be interpreted based on density functional theory (DFT) simulations of the spectra. For example, jointly with ROA experimental data, the simulations make it possible to determine absolute configuration of chiral lanthanide compounds in solution.

• Klíčová slova
• Raman optical activity, chiral lanthanide complexes, circularly polarized luminescence, density functional theory, spectra simulations,
• Publikační typ
• časopisecké články MeSH

The broader availability of cost-effective methodologies like second-order vibrational perturbational theory (VPT2), also in general-purpose quantum chemical programs, has made the inclusion of anharmonic effects in vibrational calculations easier, paving the way to more accurate simulations. Combined with modern computing hardware, VPT2 can be used on relatively complex molecular systems with dozen of atoms. However, the problem of resonances and their corrections remains a critical pitfall of perturbative methods. Recent works have highlighted the sensitivity of band intensities to even subtle resonance effects, underlying the importance of a correct treatment to predict accurate spectral bandshapes. This aspect is even more critical with chiroptical spectroscopies whose signal is weak. This has motivated the present work in exploring robust methods and criteria to identify resonances not only in energy calculations but also on the transition moments. To study their performance, three molecules of representative sizes ranging from ten to several dozens of atoms were chosen. The impact of resonances, as well as the accuracy achievable once they are properly treated, is illustrated by the changes in spectral bandshapes, including chiroptical spectroscopies.

• Publikační typ
• časopisecké články MeSH

Resonance Raman optical activity (RROA) possesses all aspects of a sensitive tool for molecular detection, but its measurement remains challenging. We demonstrate that reliable recording of RROA of chiral colorful compounds is possible, but only after considering the effect of the electronic circular dichroism (ECD) on the ROA spectra induced by the dissolved chiral compound. We show RROA for a number of model vitamin B12 derivatives that are chemically similar but exhibit distinctively different spectroscopic behavior. The ECD/ROA effect is proportional to the concentration and dependent on the optical pathlength of the light propagating through the sample. It can severely alter relative band intensities and signs in the natural RROA spectra. The spectra analyses are supported by computational modeling based on density functional theory. Neglecting the ECD effect during ROA measurement can lead to misinterpretation of the recorded spectra and erroneous conclusions about the molecular structure.

• Klíčová slova
• Raman scattering, chirality, electronic circular dichroism, resonance Raman optical activity, vitamin B12,
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH