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DNA origami nanostructures are emerging as a bottom-up nanopatterning approach. Direct combination of this approach with top-down nanotechnology, such as ion beams, has not been considered because of the soft nature of the DNA material. Here we demonstrate that the shape of 2D DNA origami nanostructures deposited on Si substrates is well preserved upon irradiation by ion beams, modeling ion implantation, lithography, and sputtering conditions. Structural changes in 2D DNA origami nanostructures deposited on Si are analyzed using AFM imaging. The observed effects on DNA origami include structure height decrease or increase upon fast heavy ion irradiation in vacuum and in air, respectively. Slow- and medium-energy heavy ion irradiation results in the cutting of the nanostructures or crater formation with ion-induced damage in the 10 nm range around the primary ion track. In all these cases, the designed shape of the 2D origami nanostructure remains unperturbed. Present stability and nature of damages on DNA origami nanostructures enable fusion of DNA origami advantages such as shape and positioning control into novel ion beam nanofabrication approaches., (Copyright © 2024, Sala et al.)

As of early 2022, only six species bearing an N-O bond have been detected toward cold molecular clouds and regions of star formation. It is not clear yet if the small number of N-O bond species found in the interstellar medium so far stems from physical and technological limitations of astronomical detection techniques, or whether in fact molecules that bear an N-O bond are for some reason rare in these objects of the interstellar medium. Astronomical N-O bearing molecules are important because they are part of astrochemical models which propose that they are precursors of hydroxylamine (NH 2 OH), a species linked to the formation of prebiotic amino acids in space. The aim of this study is the better understanding of the open question of the interstellar synthesis of N-O bearing species. We have analyzed by infrared spectroscopy an astrophysically relevant polar ice mixture of N 2 O:H 2 O processed by 90 MeV 136 Xe 23+ ions, which can mimic the physicochemical processes triggered by cosmic rays in water-covered interstellar ice grains. The results show the formation of N 2 O 3 and of H 2 O 2 , but no HN-O species of any kind were detected. Such findings are discussed in light of recent studies from our group and from the literature.

Radiolysis of biomolecules by fast ions has interest in medical applications and astrobiology. The radiolysis of solid D-valine (0.2-2 μm thick) was performed at room temperature by 1.5 MeV H + , He + , N + , and 230 MeV S 15+ ion beams. The samples were prepared by spraying/dropping valine-water-ethanol solution on ZnSe substrate. Radiolysis was monitored by infrared spectroscopy (FTIR) through the evolution of the intensity of the valine infrared 2900, 1329, 1271, 948, and 716 cm -1 bands as a function of projectile fluence. At the end of sample irradiation, residues (tholins) presenting a brownish color are observed. The dependence of the apparent (sputtering + radiolysis) destruction cross section, σ d , on the beam stopping power in valine is found to follow the power law σ d = aS e n , with n close to 1. Thus, σ d is approximately proportional to the absorbed dose. Destruction rates due to the main galactic cosmic ray species are calculated, yielding a million year half-life for solid valine in space. Data obtained in this work aim a better understanding on the radioresistance of complex organic molecules and formation of radioproducts.

Several nitrogen-containing molecules have been unambiguously identified in the Solar System and in the Interstellar Medium. It is believed that such a rich inventory of species is a result of the energetic processing of astrophysical ices during the interaction with ionizing radiation. An intrinsic parameter of matter, the complex refractive index, stores all the "chemical memory" triggered by energetic processing, and therefore might be used to probe ice observations in the infrared. In this study, four N-containing ices have been condensed in an ultra-high vacuum chamber and processed by heavy ions (O and Ni) with energies between 0.2 and 15.7 MeV at the Grand Accélérateur National d'Ions Lourds (GANIL), in Caen, France. All chemical changes were monitored in situ by Infrared Absorption Spectroscopy. The complex refractive index was calculated directly from the absorbance spectrum, by using the Lambert-Beer and Kramers-Kroning relations, and the values are available in an online database: https://www1.univap.br/gaa/nkabs-database/data.htm. As a result, other than the database, it was observed that non-polar ices are more destroyed by sputtering than polar ones. Such destruction and chemical evolution lead to variation in the IR albedo of samples addressed in this paper., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Water ice exists on many objects in space. The most abundant icy species, among them water, are present in the icy satellites of the outer Solar System giant planets. The nuclei of comets, which are mainly composed of water ice, give another example of its abundance. In the interstellar medium (ISM), ice mantles, formed by molecular species sticking on dust grains, consist mainly of water ice. All these objects are exposed to ionizing radiation like ions, UV photons, and electrons. Sputtering of atoms, molecules, ions, and radicals from icy surfaces may populate and maintain exospheres of icy objects in the Solar System. In other respects, ionized hydrides such as OH + , H 2 O + , and H 3 O + have been detected in the gas phase in star-forming regions. Interactions with cosmic rays could be an additional explanation to the current models for the formation of those species. In fact, laboratory simulations showed that the main components of the sputtered ionic species from water ice are oxygen hydrides. In this work, water ice targets were irradiated at several temperatures (10-200 K) by 90 keV O 6+ ions, yielding an electronic stopping power of about 12 eV/Å, when the nuclear stopping power is comparable to the electronic stopping power. Sputtering of secondary ions after bombardment of the ice target was analyzed by time-of-flight mass spectrometry (TOF-SIMS). Besides hydrogen ions (H + , H 2 + , H 3 + ), also O + , O 2+ , OH + , (H 2 O) + , and clusters of (H 2 O) n H + with n = 1-8 are emitted. Our results show a progressive yield decrease with increasing temperature of all of the detected species. This is related to the structure of the ice: the ionic sputtering yield for crystalline ice is much lower than for an amorphous ice. For instance, amorphous ice at 10 K exhibits a yield of the order of 2 × 10 -6 secondary (H 2 O) n H + hydride ions/projectile (with n = 1-8). As the temperature is increasing toward the phase transition to crystalline ice, the yields decrease by about one order of magnitude.

We designed and built a mobile experimental set-up for studying the interaction of ion beams with solid samples in a wide temperature range from 9 to 300 K. It is either possible to mount up to three samples prepared ex situ or to prepare samples by condensation of molecules from gases or vapours onto IR or Visible-ultraviolet (Vis-UV) transparent windows. The physico-chemical evolution during irradiation can be followed in situ with different analysis techniques including Fourier transform infrared spectroscopy, Vis-UV, and quadrupole mass spectrometry.

In order to investigate the role of medium mass cosmic rays and energetic solar particles in the processing of N 2 -rich ice on frozen moons and cold objects in the outer solar system, the bombardment of an N 2  : H 2 O : NH 3  : CO 2 (98.2 : 1.5 : 0.2 : 0.1) ice mixture at 16 K employing 15.7 MeV 16 O 5+ was performed. The changes in the ice chemistry were monitored and quantified by Fourier transformed infrared spectroscopy (FTIR). The results indicate the formation of azide radicals (N 3 ), and nitrogen oxides, such as NO, NO 2 , and N 2 O, as well as the production of CO, HNCO, and OCN - . The effective formation and destruction cross-sections are roughly on the order of 10 -12 cm 2 and 10 -13 cm 2 , respectively. From laboratory molecular analyses, we estimated the destruction yields for the parent species and the formation yields for the daughter species. For N 2 , this value was 9.8 × 10 5 molecules per impact of ions, and for the most abundant new species (N 3 ), it was 1.1 × 10 5 molecules per impact of ions. From these yields, an estimation of how many species are destroyed or formed in a given timescale (10 8 years) in icy bodies in the outer solar system was calculated. This work reinforces the idea that such physicochemical processes triggered by cosmic rays, solar wind, and magnetospheric particles (medium-mass ions) in nitrogen-rich ices may play an important role in the formation of molecules (including pre-biotic species precursors such as amino acids and other "CHON" molecules) in very cold astrophysical environments, such as those in the outer region of the solar system (e.g. Titan, Triton, Pluto, and other KBOs).

This work presents a physicochemical study of frozen amorphous methane (at 16 K) under bombardment by medium-mass ions (15.7 MeV 16 O 5+ ) with implications for icy bodies in the outer Solar System exposed to the action of cosmic rays and energetic particles. The experiment was performed at the Grand Accélérateur National d'Ions Lourds (GANIL) located in Caen, France. The results demonstrate that irradiation of CH 4 -containing ices by swift medium mass ions with delivered energy covering both stopping power regimes until its implantation on ice (i.e. electronic and nuclear) leads to the production of many hydrocarbons, such as C 2 H 2 , C 2 H 4 , C 2 H 6 , and C 3 H 8 (the most abundant daughter species produced). Values for the effective dissociation cross section of CH 4 and the average value for the effective formation cross-sections of its daughter species were about 10 -14 cm 2 and 10 -15 cm 2 , respectively. The half-life of methane ice in the presence of swift medium mass ions extrapolated to some outer Solar System environments is estimated to be around 10 6 years. The measured sputtering yield of methane due to incoming swift ions was about 7.30 × 10 5 molecules per impact. Such parameters can be used as models to estimate the amount of CH 4 and other molecular species desorbed from the icy surfaces that are constantly being incorporated to the gaseous atmosphere in the vicinity of these outer Solar System bodies due to the presence of energetic particles and cosmic rays.

The presence of nucleobases in carbonaceous meteorites on Earth is an indication of the existence of this class of molecules in outer space. However, space is permeated by ionizing radiation, which can have damaging effects on these molecules. Adenine is a purine nucleobase that amalgamates important biomolecules such as DNA, RNA, and ATP. Adenine has a unique importance in biochemistry and therefore life. The aim of this work was to study the effects of cosmic ray analogues on solid adenine and estimate its survival when exposed to corpuscular radiation. Adenine films were irradiated at GANIL (Caen, France) and GSI (Darmstadt, Germany) by 820 MeV Kr 33+ , 190 MeV Ca 10+ , 92 MeV Xe 23+ , and 12 MeV C 4+ ion beams at low temperature. The evolution of adenine molecules under heavy ion irradiation was studied by IR absorption spectroscopy as a function of projectile fluence. It was found that the adenine destruction cross section (σ d ) follows an electronic stopping power (S e ) power law under the form: CS e n ; C is a constant, and the exponential n is a dimensionless quantity. Using the equation above to fit our results, we determined σ d  = 4 × 10 -17 S e 1.17 , with S e in kiloelectronvolts per micrometer (keV μm -1 ). New IR absorption bands arise under irradiation of adenine and can be attributed to HCN, CN - , C 2 H 4 N 4 , CH 3 CN, and (CH 3 ) 3 CNC. These findings may help to understand the stability and chemistry related to complex organic molecules in space. The half-life of solid adenine exposed to the simulated interstellar medium cosmic ray flux was estimated as (10 ± 8) × 10 6 years. Key Words: Heavy ions-Infrared spectroscopy-Astrochemistry-Cosmic rays-Nucleobases-Adenine. Astrobiology 17, 298-308.

We present new experimental results on thermal and ion irradiation processing of frozen ammonia-carbon dioxide mixtures. Some mixtures were deposited at low temperatures (T ≈ 16 K). Upon warming up to 160 K, complex chemical reactions occur leading to the formation of new molecules and, in particular, of ammonium carbamate. We also show that the same species are produced when water is the dominant species in the ternary mixture with ammonia and carbon dioxide. The samples have been irradiated with 144 keV S(9+) ions at 16 K and 50 K. Also in this case, new chemical species are formed as e.g. ammonium formate, CO and OCN(-). The results are discussed in the light of their relevance to the chemical evolution of ices in the interstellar medium and in the solar system. In particular, we suggest searching for them among the gas phase species sublimating from grains around young stellar objects and from the cometary nuclei approaching the Sun.

An experimental study of the interaction of highly charged, energetic ions (52 MeV (58)Ni(13+) and 15.7 MeV (16)O(5+)) with mixed H(2)O : C(18)O(2) astrophysical ice analogs at two different temperatures is presented. This analysis aims to simulate the chemical and the physicochemical interactions induced by cosmic rays inside dense, cold astrophysical environments, such as molecular clouds or protostellar clouds as well at the surface of outer solar system bodies. The measurements were performed at the heavy ion accelerator GANIL (Grand Accelerateur National d'Ions Lourds) in Caen, France. The gas samples were deposited onto a CsI substrate at 13 K and 80 K. In situ analysis was performed by a Fourier transform infrared (FTIR) spectrometer at different fluences. Radiolysis yields of the produced species were quantified. The dissociation cross section at 13 K of both H(2)O and CO(2) is about 3-4 times smaller when O ions are employed. The ice temperature seems to affect differently each species when the same projectile was employed. The formation cross section at 13 K of molecules such as C(18)O, CO (with oxygen from water), and H(2)O(2) increases when Ni ions are employed. The formation of organic compounds seems to be enhanced by the oxygen projectiles and at lower temperatures. In addition, because the organic production at 13 K is at least 4 times higher than the value at 80 K, we also expect that interstellar ices are more organic-rich than the surfaces of outer solar system bodies.