Valine Radiolysis by H+, He+, N+, and S15+ MeV Ions
Abstract
:1. Introduction
2. Results
2.1. Results from the Van de Graaff Laboratory: H+, He+ and N+ Ion Beams
2.1.1. 1.5 MeV H+ Beam Irradiation
2.1.2. 1.5 MeV He+ and N+ Beam Irradiations
2.2. Results from GANIL (CIMAP Laboratory)
- Compaction effects have been observed to occur at low fluences and differently for distinct bands. However, since this is a property of the material, the different absorbance evolutions are expected to be similar for any ion beam. Indeed, comparing Figure 3b with Figure 9b, it can be seen that—for both irradiations—the 948 cm−1 band absorbance is the one that decreases the most, while those of the 2900 and 1329 cm−1 bands decrease much less. The compaction effect modifies absorbances up to 20%.
- Product bands: For low fluences, the concentration of daughter molecules is still too low for disturbing the chemical environment in such a way to modify precursor’s absorbances (this effect is nevertheless expected to be seen at high fluences). Furthermore, the absorbance slopes do not seem to be correlated with product formation. Figure 8 and Figure 6b show that the 1271, 948, and 716 cm−1 bands are due only to valine and, consequently, their absorbances decrease to zero at the end of irradiation; the 3300–2400 and 1700–1300 cm−1 (large) regions contain contributions of daughter molecules and their absorbances decrease more slower. The 716 cm−1 band is well seen in the non-irradiated valine spectrum, but contrarily to what happens with H+ irradiation, this band is not observed at the last fluence (Figure 6a). This may be explained by the fact that thickness of the sample irradiated by the S15+ beam was half of that irradiated by the H+ beam, preventing small (valine or product) peaks to be observed in the highest fluence spectrum. The large background in the 1700–1200 cm−1 region is probably due to amide compounds. Consistently, Figure 9a shows that the 2900 and 716 cm−1 bands have a lower slope at high fluences, indicating overlapping with product’s bands.
- Baseline selection: Figure 7a,b show that the baseline is not critical, since the baseline and peak evolutions are similar. However, once baseline is generated by very large vibrational bands, these may have distinct sensitivities to compaction.
- Chemical environment changes: Irradiation modifies the crystalline structure (compaction, amorphization and crystallization). Therefore, a moderate dependence of A-value on constituent concentrations is expected. An overview of the A-value variation, before and after compaction, is presented in Table 2 for the four different ion beams.
- For non-irradiated samples, the dispersion of the relative A-values are about 20%. This is probably due to non-homogeneous samples. Porosities may be different. No particular correlation between the relative A-values with sample thickness is observed.
- For non-irradiated samples, the relative A-value variations are band-dependent. For the H+ beam, the relative A-values for the 2900 and 716 cm−1 bands have increased by a factor ~2 from F = 0 to F = Fref; these two bands are compaction sensitive (Figure 3b); for the other bands, the relative A-values are close.
- Relative A-value variations are lower for the N+ and S15+ beams. A possible explanation is that these beams have larger stopping power than the two others.
2.3. Cross Section Measurements
2.4. Summary of the Experimental Results
3. Discussion
3.1. Dependence of Cross Sections on the Electronic Stopping Power
3.2. Astrophysical Implications
4. Materials and Methods
4.1. Ion Beam Irradiation of Valine
4.2. Cross Sections from Modelling of Fluence Dependent Absorption
5. Conclusions
- Compaction effects are seen via absorption modification, which means band strength modification. This process is due to the destruction of pores and to phase changes in the solid sample.
- The chemical effects of the irradiation by distinct ion beams on valine are similar except for their molecular destruction rates (or destruction cross sections), which vary according to the deposited dose.
- The elimination of valine molecules from the irradiated sample proceeds by radiolysis and by sputtering. Radiolysis imposes that the sample column density decreases exponentially with beam fluence. Another consequence is that the precursor concentration on the sample surface varies also exponentially and, in turn, the precursor sputtering yield decreases accordingly.
- Strong evidence that the sputtering yield decays exponentially during irradiation is given by mass spectrometry measurements. Indeed, Salehpour et al. [23] found this behavior for valine bombarded by 127I14+ ions. Furthermore, Ferreira-Rodrigues et al. reported similar results analyzing the sample surface by TOF-252Cf–PDMS for glycine radiolysis [22]. FTIR spectroscopy determines the loss rate of precursors: the technique cannot distinguish those sputtered from those dissociated. Accordingly, the apparent destruction cross section, σdap, is measured: it quantifies the combined effect of both processes. It is found that σdap is approximately proportional to the electronic stopping power and, therefore, to the absorbed dose. This is an unexpected finding, since for condensed gases the literature indicates σdap proportional to Sen, where n ~ 3/2 [28].
- At the end of irradiation, valine was destroyed and their bands vanished. The still visible bands are due to valine’s daughter molecules. Structural attributions are attempted.
- Band strengths evolve with fluence but not linearly; moreover, some A-values are more sensitive to fluence than others. This feature does not depend on the processing ion and is attributed to compaction and to the increase of product concentrations.
- Concerning Astrophysics, using theoretical GCR flux distribution, the solid valine half-life is predicted to be about one million years. Recent work estimated solid adenine half-life to be 10 ± 8 million years (Vignoli Muniz et al. [30]). These results suggest that the search for valine by radio astronomy should be envisaged.
- Concerning Astrobiology, 1.1 × 107 Gy is the mean dose to destroy solid valine. This is a huge value for Biology standards. For human beings, 50 Gy is a typical lethal dose.
- Concerning radiotherapy, the current results, obtained for valine, are actually typical for amino acids in general and even for biological material. Stopping powers are calculated for ion-atom interactions and biological materials are mostly formed by carbon, oxygen, nitrogen and hydrogen—the same atoms of the molecular structure of valine; biological material mass densities are close to 1 g/cm3, so that penetration depths are similar to valine. Therefore, the findings of this work may be a useful contribution for the understanding of microscopic processes in the damage of biological targets, and in particular, radiation protection and ion beam therapy.
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
References
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Vibration Mode | Band (cm−1) | Band Collapses into (Possible Species) | |
---|---|---|---|
H+ | S15+ | ||
NH3+ asy str | 3150, 3050 | - | - |
CH3+ asy str | 2960, 2940 | 2955, 2918 (C2H6 *) | 2961, 2933 (C2H6 *) |
CH3+ asy str | 2880, 2850 | 2868, 2849 (C2H6 *) | 2874 (C2H6 *) |
N-H…O | 2690, 2630, 2580 | - | - |
CH3 bend + NH2 rocking b | ~2109 (2153 + 2013) a | - | - |
CO2− stretch c | 1640 | - | - |
NH3+ asy def. | 1600, 1555 | - | 1595 (Amine) |
- | - | 1544, 1507 | 1516 (Nitro) |
COO+ sy str | 1520, 1430, 1390 | 1457 | 1469 (C2H6), 1394 |
- | - | - | 1355 (Nitro) |
COO+/CO | 1340, 1320 | 1339 | 1329 |
CH3+ def. | 1271, 948 | - | 1271 |
885 (C2H6 **) | |||
CO2 Bend b | 775 | - | |
C-H out bend | 716 | 716 |
Ion Beam: | A-Value/A-Value (Fref) | ||||
---|---|---|---|---|---|
H+ 1.5 MeV | He+ 1.5 MeV | N+ 1.5 MeV | S15+ 230 MeV | ||
Sample Thickness | 2.4 μm | 0.96 μm | 0.23 μm | 0.58 μm | |
Band (cm−1) (interval) | Fref (ions cm−2) | 5.8 × 1014 | 1.1 × 1013 | 4.39 × 1012 | 3.2 × 1011 |
2900* (3300–2400) | 0 | 273 | 282 | 235 | 246 |
Fref | 768 | 602 | 270 | 303 | |
1329 (1335–1301) | 0 | 3.94 | 3.07 | 9.51 | 10.8 |
Fref | 5.23 | 6.34 | 10.5 | 13.8 | |
1271 (1279–1261) | 0 | 0.876 | 1.16 | 0.981 | 0.984 |
Fref | 0.955 | 1.70 | 0.997 | 1.22 | |
948 (957–937) | reference | 1 | 1 | 1 | 1 |
reference | 1 | 1 | 1 | 1 | |
716* (726–705) | 0 | 2.80 | 2.70 | 2.35 | 3.39 |
Fref | 5.05 | 3.31 | 2.54 | 3.85 |
Band (cm−1) | Ion Beam | ||||||
---|---|---|---|---|---|---|---|
1.5 MeV | 230 MeV | ||||||
Band Interval | Band Maximum | H+ | He+ | N+ | S15+ | ||
σdap (10−14 cm²) | Δσj = (σdap)mean − (σdap)j (10−14 cm2) | Observations | |||||
3300–2400 | 2900* | 14 | 3.3 | 7.2 | 29 | 4.7 | no compaction, tholins at the end |
1335–1304 | 1329 | 16 | 3.8 | 7.6 | 30 | 3.7 | no compaction |
1279–1261 | 1271 | 33 | 4.9 | 11 | 39 | −5.3 | disappears at the end |
957–937 | 948 | 27 | 7.8 | 13 | 37 | −3.3 | |
782–763 | 775 | - | 4.0 | - | 34 | -0.3 | σc(S) = 50 × 10−14 cm2σc(He) = 82 × 10−14 cm2 |
726–705 | 716 * | 42 | 7.2 | 15 | 33 | 0.7 | no compaction, tholins peaks too small |
Mean value | σd,jap ± Δσj | 26 ± 16 | 5.4 ± 2.1 | 11 ± 4 | 33.7 ± 4 | 0 | 12% rms error |
Ion Beam | H+ | He+ | N+ | S15+ |
---|---|---|---|---|
Energy (MeV) | 1.5 | 1.5 | 1.5 | 230 |
Se (keV µm−1) | 26.7 | 252 | 998 | 1690 |
Sn (keV µm−1) | 0.0187 | 0.256 | 7.84 | 1.03 |
Sp 716 cm−1 (cm−1) | 1.82 | 0.903 | 0.20 | 0.688 |
Sp 948 cm−1 (cm−1) | 0.173 | 0.345 | 0.0849 | 0.151 |
Valine sample | ||||
N0 (1017 molec/cm2) | 8.12 | 6.56 | 1.61 | 4.00 |
Tk (µm) | 2.4 | 0.96 | 0.23 | 0.58 |
Range (µm) | 35 | 5.8 | 2.4 | 97 |
σdap (10−14 cm2) | 26 ± 16 | 5.4 ± 2.1 | 11 ± 4 | 34 ± 4 |
j | Cj Ions cm−2 s−1 MeV−1.7 | Rj (10−16 s−1) | Rj (Ma−1) | τ1/2 = ln(2)/Rj (Ma) |
---|---|---|---|---|
H | 5.96 × 105 | 7.1 | 0.022 | 31 |
He | 4.11 × 104 | 7.5 | 0.024 | 29 |
C | 1.79 × 103 | 8.8 | 0.028 | 25 |
O | 2.22 × 103 | 28 | 0.088 | 7.9 |
Ne | 438 | 12 | 0.038 | 18 |
Fe | 425 | 170 | 0.54 | 1.2 |
Total | 6.42 × 105 | 230 | 0.74 | 0.94 |
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Costa, C.A.P.d.; Muniz, G.S.V.; Boduch, P.; Rothard, H.; Silveira, E.F.d. Valine Radiolysis by H+, He+, N+, and S15+ MeV Ions. Int. J. Mol. Sci. 2020, 21, 1893. https://doi.org/10.3390/ijms21051893
Costa CAPd, Muniz GSV, Boduch P, Rothard H, Silveira EFd. Valine Radiolysis by H+, He+, N+, and S15+ MeV Ions. International Journal of Molecular Sciences. 2020; 21(5):1893. https://doi.org/10.3390/ijms21051893
Chicago/Turabian StyleCosta, Cíntia A. P. da, Gabriel S. Vignoli Muniz, Philippe Boduch, Hermann Rothard, and Enio F. da Silveira. 2020. "Valine Radiolysis by H+, He+, N+, and S15+ MeV Ions" International Journal of Molecular Sciences 21, no. 5: 1893. https://doi.org/10.3390/ijms21051893