Sándor Góbi

Reliability of computed signs and intensities for vibrational circular dichroism spectra

We present in detail a novel measure that improves the reliability of the assignment procedure for vibrational circular dichroism (VCD) spectra extending the useful robustness concept introduced by Nicu and Baerends. This measure enables spectroscopists to single out bands with unreliable VCD intensities that can be disregarded during analysis and determination of absolute configuration. The previously proposed robustness criterion is shown to be gauge dependent and less reliable than the one proposed here.

Effects of strong and weak hydrogen bond formation on VCD spectra: a case study of 2-chloropropionic acid

The vibrational circular dichroism (VCD) spectrum of S-(-) and R-(+)-2-chloropropionic acid is thoroughly analyzed. Besides the VCD spectrum of the monomer, the dimers (stabilized by strong hydrogen bonds) and the 2-chloropropionic acid-CHCl(3) complexes (stabilized by a weak hydrogen bond) are studied both experimentally (in solution and in low-temperature Ar matrix) and by quantum chemical computations. It is shown that dimer formation drastically changes, and even weak complex formation can also substantially affect the overall shape of the VCD spectrum. The present and previous results can be generalized for the practice of absolute configuration determination of carboxylic acids by VCD spectroscopy. For these measurements, if bulky groups do not block dimer formation, comparison of the computed spectra of the dimers with the experimental spectra recorded in relatively concentrated (∼0.1 mol dm(-3)) solutions is suggested. Our study also shows that due to the stabilization of monomers and/or the formation of weak complexes, the VCD spectrum recorded in CHCl(3) is more complex and, like in the present case, can have a lower intensity than that of the spectrum recorded in CCl(4). Therefore, if solubility allows, CCl(4) is a much preferred solvent over CHCl(3).

Near-infrared radiation induced conformational change and hydrogen atom tunneling of 2-chloropropionic acid in low-temperature Ar matrix.

Former assignments of the matrix-isolation infrared (MI-IR) spectrum of 2-chloropropionic acid are revised with the help of near-infrared (NIR) laser irradiation induced change in conformer ratios. This method allows not only the unambiguous assignment of each band in the MI-IR spectrum to the two trans (Z) and the cis (E) conformers but also the assignment of the spectral bands to different matrix sites. The tunneling decay of the higher-energy cis conformer prepared from both trans conformers in different sites is also investigated. It is shown that the tunneling decay time is very sensitive to the matrix site, especially if the in situ prepared high-energy conformer has a strained geometry in the matrix cage. The analysis shows that the kinetics of some cis → trans back conversion processes cannot be fitted by a single exponential decay. The possible reasons of this observation are examined and discussed. The present and former results clearly show that, in addition to tunneling processes, the decay rates strongly depend on solid-state effects. Therefore, simple theoretical predictions of decay rates, which do not take into account the solid-state effects, can only be compared to experimental observations only if experimentally proven that these effects do not significantly affect the experimentally measured tunneling rates.

Is β-homo-proline a pseudo-γ-turn forming element of β-peptides? An IR and VCD spectroscopic study on Ac-β-HPro-NHMe in cryogenic matrices and solutions

In order to test the pseudo-γ-turn forming capability of β-homo-proline (β(3)-HPro) 2-[(2S)-1-acetylpyrrolidin-2-yl]-N-methylacetamide (Ac-β(3)-HPro-NHMe) was synthesized and its potential energy landscape was investigated by infrared (IR) and vibrational circular dichroism (VCD) spectroscopy combined with density functional calculations. Based upon a comparison between experimental and computed spectra three different pseudo-γ-turn-like trans conformers and a cis conformer were identified in low-temperature Ar and Kr matrices. The computations in agreement with the observations reveal that, in contrast to its α-Pro analogue, the room-temperature abundance of the cis conformer is significant, falling above 10% in the isolated phase. Furthermore, solution-phase vibrational spectra and computations show that the cis conformer is predominant in polar solvents. This result indicates that β(3)-HPro is significantly less apt to form pseudo-γ-turns when compared to the γ-turn forming tendency of α-proline. The present study also shows that the interpretation of solution-phase VCD spectra of flexible molecules should be done with extra caution.

Exploring the Conformational Space of Cysteine by Matrix Isolation Spectroscopy Combined with Near-Infrared Laser Induced Conformational Change

Six conformers of α-cysteine were identified by matrix isolation IR spectroscopy combined with NIR laser irradiation. Five of these conformers are identical with the five out of six conformers that have recently been identified by microwave spectroscopy. The sixth conformer observed in the present study is a short-lived conformer, which decays by H-atom tunneling; its half-life in a 12 K N2 matrix is (1.1 ± 0.5) × 10(3) s. This study proves that matrix isolation IR spectroscopy combined with NIR laser irradiation is a suitable method to identify conformers of a complex system for which computations predict several dozens of conformers, and that the reliability of this method for conformational assignment is comparable to that of microwave spectroscopy.

EFFECT OF PERCHLORATES ON ELECTRON RADIOLYSIS OF GLYCINE WITH APPLICATION TO MARS

This work explores the radiolytic decomposition of glycine (H2NCH2COOH) under simulated Martian conditions in the presence of perchlorates ( ClO4 ), which are abundant oxidizers on the surface of Mars, by energetic electrons at 10, 160, 210, and 260 K, mimicking the radiation exposure of the Martian regolith in the first 5–10 cm depths over about 250 million years. Our experiments present quantitative evidence that the rate constants of the glycine decomposition in the presence of magnesium perchlorate hexahydrate (Mg(ClO4)2 ·6H2O) were a factor of about two higher than that of the pure glycine, suggesting that energetic oxygen atoms (O) released from the ClO4 have a significant effect on the decomposition rates and accelerate them by providing a unique oxidizing environment in the radiolyzed samples. Hence, two decay mechanisms exist: radiolysis by the electrons and oxidation by the O atoms. Within the Mars-relevant temperature range covering 160–260 K, the destruction rates are nearly temperature invariant with rates varying as little as 5%. Further, the formation rates of carbon dioxide (CO2) and carbon monoxide (CO) are both accelerated in the presence of ClO4 by a factor of three to five, supporting our conclusion of an active oxygen-initiated chemistry. In addition, the degradation rates are significantly higher than the formation rates of CO2 and CO. This suggests that, besides the decarboxylation, alternative degradation pathways such as a polymerization of glycine must exist. Finally, besides CO2 and CO, three alternative products were identified tentatively: methylamine (CH3NH2), methane (CH4), and ammonia (NH3).

IN SITU DETECTION OF CHLORINE DIOXIDE (ClO2) IN THE RADIOLYSIS OF PERCHLORATES AND IMPLICATIONS FOR THE STABILITY OF ORGANICS ON MARS

Magnesium perchlorate hexahydrate (Mg(ClO4)2 6H2O) samples were exposed to energetic electrons to investigate the products of the decomposition of perchlorates in the Martian soil and to infer their role in the degradation of organics on Mars. The samples were monitored online and in situ via infrared spectroscopy as well as electron impact (EI-QMS) and reflectron time-of-flight mass spectrometry coupled with single photon ionization (PI-ReTOF-MS). Our study reveals that besides chlorates () and molecular oxygen (O2), the chlorine dioxide radical (ClO2) was observed online and in situ for the first time as a radiolysis product of solid perchlorates. Chlorine dioxide, which is used on Earth as a strong oxidizing agent in water disinfection and bleaching, represents a proficient oxidizer—potentially more powerful than molecular oxygen—to explain the lack of abundant organics in the Martian soil.

Electron Radiolysis of Ammonium Perchlorate: A Reflectron Time-of-Flight Mass Spectrometric Study

Thin films of ammonium perchlorate (NH4ClO4) were exposed to energetic electrons at 5.5 K to explore the radiolytic decomposition mechanisms. The effects of radiolysis were monitored on line and in situ via Fourier transform infrared spectroscopy (FTIR) in the condensed phase along with electron impact ionization quadrupole mass spectrometry (EI-QMS) and single-photon photoionization reflectron time-of-flight mass spectrometry (PI-ReTOF-MS) during the temperature-programmed desorption (TPD) phase to probe the subliming molecules. Three classes of molecules were observed: (i) nitrogen bearing species [ammonia (NH3), hydroxylamine (NH2OH), molecular nitrogen (N2), nitrogen dioxide (NO2)], (ii) chlorine carrying molecules [chlorine monoxide (ClO), chlorine dioxide (ClO2), dichlorine trioxide (Cl2O3)], and (iii) molecular oxygen (O2). Decay profiles of the reactants along with the growth profiles of the products as derived from the infrared data were fit kinetically to obtain a reaction mechanism with the initial steps involving a proton loss from the ammonium ion (NH4+) yielding ammonia (NH3) and the decomposition of perchlorate ion (ClO4-) forming chlorate ion (ClO3-) plus atomic oxygen. The latter oxidized ammonia to hydroxylamine and ultimately to nitrogen dioxide. Molecular oxygen and nitrogen were found to be formed via recombination of atomic oxygen and multistep radiolysis of ammonia, respectively.

VCD Robustness of the Amide‐I and Amide‐II Vibrational Modes of Small Peptide Models

The rotational strengths and the robustness values of amide-I and amide-II vibrational modes of For(AA)n NHMe (where AA is Val, Asn, Asp, or Cys, n = 1-5 for Val and Asn; n = 1 for Asp and Cys) model peptides with α-helix and β-sheet backbone conformations were computed by density functional methods. The robustness results verify empirical rules drawn from experiments and from computed rotational strengths linking amide-I and amide-II patterns in the vibrational circular dichroism (VCD) spectra of peptides with their backbone structures. For peptides with at least three residues (n ≥ 3) these characteristic patterns from coupled amide vibrational modes have robust signatures. For shorter peptide models many vibrational modes are nonrobust, and the robust modes can be dependent on the residues or on their side chain conformations in addition to backbone conformations. These robust VCD bands, however, provide information for the detailed structural analysis of these smaller systems.

Can perchlorates be transformed to hydrogen peroxide (H2O2) products by cosmic rays on the Martian surface

Due to their oxidizing properties, perchlorates (ClO4–) are suggested by the planetary science community to play a vital role in the scarcity of organics on the Martian surface. However, alternative oxidation agents such as hydrogen peroxide (H2O2) have received surprisingly little attention. In this study, samples of magnesium perchlorate hexahydrate (Mg(ClO4)2·6H2O) were exposed to monoenergetic electrons and D2+ ions separately, sequentially, and simultaneously to probe the effects of galactic cosmic ray exposure of perchlorates and the potential incorporation of hydrogen (deuterium) into these minerals. The experiments were carried out under ultra-high vacuum conditions at 50 K, after which the samples were slowly heated to 300 K while the subliming products were monitored by a quadrupole mass spectrometer (QMS). In all cases, molecular oxygen (O2) was detected upon the onset of irradiation and also during the warmup phase. In case of a simultaneous D2+ - electron exposure, deuterated water (D2O) and deuterium peroxide (D2O2) were also detected in the warmup phase, whereas only small amounts of D2O2 were found after an exclusive D2+ irradiation. These experiments yield the first data identifying hydrogen peroxide as a potential product in the interaction of cosmic rays with perchlorates in the Martian regolith revealing that perchlorates are capable of producing multiple oxidizing agents (O2, D2O2) that may account for the destruction of organics on the Martian surface.