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Biomedical subjects

Eugen Illenberger

Publications and source records attributed to Eugen Illenberger.

15 recordsLinked to original sources
PubMed2006

Reactivity induced at 25 K by low-energy electron irradiation of condensed NH3-CH3COOD (1 : 1) mixture.

Chemical reactivity is observed following electron irradiation of a binary mixture of ammonia (NH(3)) and acetic acid (CH(3)COOD) at 25 K, without any subsequent thermal activation, as evidenced by vibrational high resolution electron energy loss spectroscopy (HREELS). Analysis of the HREEL spectra and comparison with infrared and Raman data of different molecules are compatible with glycine formation in its zwitterionic form. The onset for electron induced reaction is found to be at about approximately 13 eV. The mechanisms may involve NH radicals interaction with CH(3)COOD molecules. Then glycine formation does not imply any displacement of reactants, so that it involves only NH(3) and CH(3)COOD neighboring molecules.

Acetic Acid↗
PubMed2006

Dissociative electron attachment to furan, tetrahydrofuran, and fructose.

We study dissociative electron attachment to furan (FN) (C(4)H(4)O), tetrahydrofuran (THF) (C(4)H(8)O), and fructose (FRU) (C(6)H(12)O(6)) using crossed electron/molecular beams experiments with mass spectrometric detection of the anions. We find that FN and THF are weak electron scavengers and subjected to dissociative electron attachment essentially in the energy range above 5.5 eV via core excited resonances. In striking contrast to that, FRU is very sensitive towards low energy electrons generating a variety of fragment ions via a pronounced low energy feature close to 0 eV. These reactions are associated with the degradation of the ring structure and demonstrate that THF cannot be used as surrogate to model deoxyribose in DNA with respect to the attack of electrons at subexcitation energies (<3 eV). The results support the picture that in DNA the sugar moiety itself is an active part in the initial molecular processes leading to single strand breaks.

Anions↗
PubMed2006

Dissociative electron attachment to phosphoric acid esters: the direct mechanism for single strand breaks in DNA.

We use dibutyl phosphate to simulate the behavior of the phosphate group in DNA towards the attack of low energy electrons. We find that the compound undergoes effective dissociative electron attachment within a low energy resonant feature at 1 eV and a further resonance peaking at 8 eV. The dissociative electron attachment (DEA) reactions are associated with the direct cleavage of the C-O and the P-O bond but also the excision of the PO-, PO3-, H2PO3- units. For the phosphate group coupled in the DNA network these reactions represent single strand breaks. We hence propose that the most direct mechanism of single strand breaks occurring in DNA at subexcitation energies (< 4 eV) is due to DEA directly to the phosphate group.

Computer Simulation↗
PubMed2006

Reactive scattering damage to DNA components by hyperthermal secondary ions.

We have observed reactive scattering damage to fundamental DNA building blocks by the type of hyperthermal secondary ions that are produced along heavy ion tracks in biological media. Reactions include carbon abstraction by N+, and hydrogen abstraction by O- and N+, at collision energies down to 1 eV. Our results show that localized reactive scattering by hyperthermal secondary fragments can lead to important physicochemical damage to DNA in cells irradiated by heavy ions. This suggests a fundamentally different picture of nascent DNA damage induced by heavy ion tracks, compared to conventional (x or gamma) radiation tracks.

Journal Article↗
PubMed2006

10-100 eV Ar+ ion induced damage to D-ribose and 2-deoxy-D-ribose molecules in condensed phase.

We report that 10-100 eV Ar+ ion irradiation induces severe damage to the biologically relevant sugar molecules D-ribose and 2-deoxy-D-ribose in the condensed phase on a polycrystalline Pt substrate. Ar+ ions with kinetic energies down to 15 eV induce effective decomposition of both sugar molecules, leading to the desorption of abundant cation and anion fragments, including CH3+, C2H3+, C3H3+, H3O+, CHO+, CH3O+, C2H3O+, H-, O-, and OH-, etc. Use of isotopically labelled molecules (5- 13C D-ribose and 1-D D-ribose) reveals the site specificity for some of the fragment origins, and thus the nature of the chemical bond breaking. It is found that all of the chemical bonds in both molecules are vulnerable to ion impact at energies down to 15 eV, particularly both the endo- and exocyclic C-O bonds. In addition to molecular fragmentation, several chemical reactions are also observed. A small amount of O-/O fragments abstract hydrogen to form OH-. It is found that the formation of the H3O+ ion is related to the hydroxyl groups of the sugar molecules, and is associated with additional hydrogen loss from the parent or adjacent molecules via hydrogen abstraction or proton transfer. The formation of several other cation fragments also requires hydrogen abstraction from its parent or an adjacent molecule. These fragmentations and reactions are likely to occur in a real biomedium during ionizing radiation treatment of tumors and thus bear significant radiobiological relevance.

Argon↗
PubMed2005

Beyond the Bragg peak: hyperthermal heavy ion damage to DNA components.

We have observed the destruction of fundamental building blocks of DNA (nucleoside, base, and sugar) by hyperthermal (0.25-1.75 eV/amu) heavy ion impact. Nucleoside damage pathways include base or sugar loss, and complete disintegration of either moiety. Sugar damage dominates, and in DNA will yield a complex strand break. Our results suggest that (a) heavy particle damage to biological media may extend to ion track ends beyond the Bragg peak, and (b) the nascent damage by hyperthermal secondary heavy particles, formed along the primary ion tracks, may be equally complex.

Journal Article↗
PubMed2005

Bond- and site-selective loss of H- from pyrimidine bases.

Electron attachment to gas phase thymine and uracil leads to H- loss within a broad and structured feature in the energy range between about 5 and 12 eV consisting of 4 overlapping resonances. By using thymine and uracil methylated at the N1 and N3 positions, respectively, and taking into account recent results from partly deuterated thymine, we find that by tuning the electron energy, H- loss turns out to be not only bond selective, i.e., (C-H) versus (N-H) bonds, but also site selective (N1 versus N3 site). Such a bond and site selectivity by energy has not been observed before in dissociative electron attachment. Implications for the mechanism of strand breaks observed in plasmid DNA are considered.

DNA↗
PubMed2004

Degradation of N-acetyl tryptophan by low-energy (<12 eV) electrons.

Secondary low-energy electrons are abundantly created during the early moments following the deposition of energy by radiation into cells. Here we show the ability of slow (<12 eV) electrons to effectively decompose gas-phase N-acetyl tryptophan (NAT) which can model a simple protein. The fragmentation of NAT, initiated via a resonant electron-molecule interaction exclusively at the peptide bridge, produces a large variety of negative species. The present findings contribute to the molecular description of the initial step in the radiation-induced damage.

Electrons↗
PubMed2004

Site-specific dissociation of DNA bases by slow electrons at early stages of irradiation.

At the very early time of irradiation, ballistic secondary electrons are produced as the most abundant of the radiolytic species directly within DNA or its environment. Here, we demonstrate the propensity of such low-energy (<3 eV) electrons to damage DNA bases via an effective loss of hydrogen located at the specific nitrogen positions. Since this site is directly implicated in the bonding of nucleobases within DNA and since dehydrogenation of the nucleic acid bases has been observed to be the predominant dissociative channel, the present findings foreshadow significant implications for the initial molecular processes leading to genotoxicity in living cells following unwanted or intended exposure to ionizing radiation (e.g., sunbathing, air travel, radiotherapy, etc.).

Adenine↗
PubMed2004

Electron attachment to chlorouracil: a comparison between 6-ClU and 5-ClU.

Low energy electron impact to the isomers 6-chlorouracil (6-ClU) and 5-chlorouracil (5-ClU) yields a variety of negative ion fragments with surprisingly high cross sections. These ions are dominantly formed via sharply structured resonance features at energies below the threshold for electronic excitation and result from dissociative electron attachment (DEA). The most dominant DEA channel is formation of (M-HCl)-, i.e., ejection of a neutral HCl molecule with the negative charge remaining on the ring. The reaction cross section is 9 x 10(-18) m2 and 5 x 10(-18) m2 for 6-Cl and 5-ClU, respectively, and thus about two orders of magnitude higher than the geometrical cross section of the molecule. Further reactions also operative via low energy resonances (<2.5 eV) are Cl- abstraction, dehydrogenation [formation of (M-H)-, M=ClU], and DEA processes associated with a ring opening. Most of the ion yield curves exhibit remarkably sharp structures which have not been observed before in DEA to a polyatomic system. Although some possibilities on their origin are discussed, their interpretation remains a challenge for theory and further experiments. While electron attachment to both 6-ClU and 5-ClU generates fragments of the same stoichiometric composition, their ion yields and also their relative intensities show some very pronounced differences which can be explained by the different structure but also the different energetic situation in the two isomers.

Computer Simulation↗
PubMed2003

Complete chemical transformation of a molecular film by subexcitation electrons (<3 eV).

The potential of slow electrons to act as a soft tool to control a chemical reaction in the condensed phase is demonstrated. By setting the energy of a well defined electron beam to values below 3 eV, the surface of a thin film of 1,2-C(2)F(4)C(l2) molecules can completely be transformed into molecular chlorine (and by-products, possibly perfluorinated polymers). At higher energies (>6 eV) some equilibrium state between product and educt composition can be achieved, however, accompanied by a gradual overall degradation of the film. The effect of complete transformation is based on both the selectivity and particular energy dependence of the initial step of the reaction which is dissociative electron attachment to C(2)F(4)C(l2), but also the fact that the initial molecule is efficiently decomposed by subexcitation electrons while the product C(l2) is virtually unaffected.

Journal Article↗