Proton-induced Charge Transfer Research Articles

Proton-Induced Charge Transfer on Imidazole and 2-Aminoimidazole. Role of the Substituent and Influence of Stepwise Hydration.

The behavior of potential prebiotic species in space is of main concern in the chemistry at the origin of life. Their reactivity or stability in spatial conditions, under strong UV radiations or ion bombardments, remains an open question and needs wide investigations. As protons are by far the most abundant ions in space, we focus presently on proton-induced collisions on imidazole and 2-aminoimidazole evidenced as important prebiotic RNA intermediates. Unconstrained full optimization of the structures was performed with B3LYP/cc-pVTZ model chemistry. The calculations were performed in a wide collision energy range in order to model various astrophysical environments, from eV in the interstellar medium, up to keV for solar winds or supernovae shock-wave protons. Such a study provides for the first time a theoretical insight on the influence of the amino substituent on the proton-induced charge transfer. We evaluated the role of icy grain environments through a cluster approach modeling the effect of a stepwise microhydration on the process. Comparisons with oxygenated and sulfurated analogues address further qualitative trends on the respective stability or reactivity of such heterocycles which may be of tremendous interest in prebiotic chemistry. Charge transfer appears to be quite efficient for imidazole compounds and their sulfurated analogue compared to the oxygenated heterocycle.

Size-Induced Segregation in the Stepwise Microhydration of Hydantoin and Its Role in Proton-Induced Charge Transfer.

Recent photochemistry experiments provided evidence for the formation of hydantoin by irradiation of interstellar ice analogues. The significance of these results and the importance of hydantoin in prebiotic chemistry and polypeptide synthesis motivate the present theoretical investigation, in which we analyzed the effects of stepwise hydration on the electronic and thermodynamical properties of the structure of microhydrated hydantoin using a variety of computational approaches. We generally find microhydration to proceed around the hydantoin heterocycle until 5 water molecules are reached, at which stage hydration becomes segregated with a water cluster forming aside the heterocycle. The reactivity of microhydrated hydantoin caused by an impinging proton was evaluated through charge transfer collision cross sections for microhydrated compounds but also for hydantoin on icy grains modeled using a cluster approach mimicking the true hexagonal ice surface. The effects of hydration on charge transfer efficiency are mostly significant when few water molecules are present, and they progressively weaken and stabilize in larger clusters. On the ice substrate, charge transfer essentially contributes to a global increase in the cross sections.

Proton-induced collision dynamics on potential prebiotic sulfur species.

The formation of the building blocks of life and how they could survive under harsh astrophysical environments remains an open question of prebiotic chemistry. Effectively, ion bombardments or intense UV radiation may drive the destruction of prebiotic compounds. The possible role of sulfur in such processes is addressed here for the first time, by comparing directly proton-induced charge transfer for sulfur containing molecules and that for related COMs. The proton collision on mercaptoacetonitrile HSCH2C[triple bond, length as m-dash]N conformers has thus been investigated theoretically in a wide impact energy range modelling various astrophysical environments and compared to related COMs, namely HCN oligomers, in order to exhibit qualitative tendencies.

Theoretical investigation of proton collisions on prebiotic candidates: hydrogen cyanide polymers.

One of the major concerns in prebiotic chemistry is the formation and destruction routes of prebiotic compounds in space. As detected for a long time, hydrogen cyanide (HCN) has been suggested to be a feedstock molecule at the origin of life driving easy oligomerization, in particular to form adenine. This may focus on its first oligomers because its dimer cyanomethanimine was recently observed in star-forming regions, or its trimer aminomalononitrile. With regard to the assumption of an extra-terrestrial origin of life, the stability of such species under ultraviolet radiation or in ion-collisions is an open question. Thus, we investigated theoretically the proton collisions with dimer and trimer isomers of HCN in a wide impact energy range to model various astrophysical environments and exhibit qualitative tendencies.

Influence of microhydration on the structures and proton-induced charge transfer in RNA intermediates.

Solvation effects are of major interest in the context of radiation damage, due to their potential applications in cancer therapy. Reliable modeling of the solvent is, however, quite challenging, and numerous studies have been devoted to isolated biomolecules and stepwise-hydrated molecules in which the amount of solvent is controlled one molecule at a time. The influence of stepwise hydration on radiation damage is investigated here using the example of proton-induced charge transfer in two biomolecular targets. Uracil has been widely investigated both experimentally and theoretically in this context, and 2-aminooxazole was recently shown to be a potentially important intermediate in prebiotic chemistry. Focusing here on doubly hydrated biomolecules, stable structures and infrared spectra were obtained by combining the results of molecular dynamics simulations with those of quantum chemistry calculations performed at the density-functional theory level with the double hybrid M06-2X functional. The charge-transfer cross-sections upon proton impact were obtained from ab initio molecular calculations and after applying a semi-classical approach to investigate the collision. Our results suggest a significant relationship between the detailed hydration structure and the efficacy of proton-induced charge transfer, highlighting the competing roles of inter- and intramolecular hydrogen bonding.

Proton induced green emission from AIEE active 2,2′ biquinoline hydrosol and its selective fluorescence turn-on sensing property towards Zn2+ ion in water

A novel material showing aggregation induced enhanced emission (AIEE) is developed by reprecipitation method using 2,2′ biquinoline (BQN) in aqueous medium. Morphologies of the particles are characterized using optical and scanning electron microscopic (SEM) study. The selective fluorescence and absorbance response of aggregated BQN towards Zn2+ and H+ have been explained due to ground state complexation and protonation of BQN with Zn2+ and H+ respectively. Protonated BQN exhibits charge transfer character in transoid form with yellowish green emission but in BQN-Zn2+ complex, BQN changes to cis planer conformation and displays considerable intra ligand charge transfer (ILCT) character with sky blue color under UV excitation. A 2:1 BQN-Zn2+ complex have been confirmed using Job’s plot. Our study revealed that BQN hydrosol act as selective turn-on fluorescence sensor for Zn2+ ion both in acidic and alkaline medium. Further, the proton induced charge transfer character and the proposed binding modes of the receptor with Zn2+ have been supported by DFT based computational study.

Stepwise Hydration of 2-Aminooxazole: Theoretical Insight into the Structure, Finite Temperature Behavior and Proton-Induced Charge Transfer.

It was recently suggested that 2-aminooxazole (AO) could contribute to the formation of RNA nucleotides on primitive earth. In this article we have considered by means of computational modeling the influence of microhydration on the structural and spectral properties of this potential prebiotic molecule. The stable structures of AO(H2O)n were obtained first by sampling the potential energy landscapes of clusters containing up to n = 20 water molecules, using a simple but reasonably accurate force field and replica-exchange molecular dynamics simulations. Through reoptimization using an explicit description of electronic structure at the level of density functional theory with the M06-2X functional, the formation energies, ionization energies and electron affinities were determined in the vertical and adiabatic treatments, as well as vibrational and optical spectra covering the far-IR, mid-IR, and lower part of the UV ranges. The results generally show a clear segregation between the aminooxazole solute and the water molecules, a water cluster being formed near the nitrogen and amino group side leaving the hydrocarbon side dry even at temperatures corresponding to the liquid state. The spectral signatures generally concur and show distinct contributions of the solute and solvent, spectral shifts to lower energies being in agreement with earlier calculations in bulk solvent. We have also investigated the importance of microhydration on the charge transfer cross section upon collision with a proton, thereby extending an earlier investigation on the bare AO molecule. The presence of water molecules generally reduces the propensity for charge transfer at small sizes, but the influence of the solvent steadily decreases in larger droplets.

Nanohydration of uracil: emergence of three-dimensional structures and proton-induced charge transfer.

Stepwise hydration of uracil has been theoretically revisited using different methods ranging from classical force fields to quantum chemical approaches. Hydration initially begins within the uracil plane but proceeds at four molecules into three-dimensional configurations or even water clusters next to the nucleobase. The relative stability between the various structures is significantly affected by zero-point energy and finite temperature (entropy) effects and also gives rise to markedly different responses to an excitation by an impinging high-energy proton. In particular, charge transfer to the molecular complex is dramatically altered in collisions toward the coating cluster but barely modified for peripheral hydration patterns.

Proton-induced charge transfer degradation in CCDs for near-room temperature applications

An optical technique for measuring charge transfer inefficiency (CTI) in CCDs, operated under near-room temperature, high readout rate conditions, is described. It is possible to measure trap emission times and CTI dependence on signal size, background charge and clock waveform shape to high accuracy, both for serial and parallel transfers. It is shown that the presence of background charge (or "fat zero") can substantially improve charge transfer efficiency.< <ETX xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">&gt;</ETX>

Outstanding Conference Paper Award

The recipients of the 1994 NSREC Outstanding Conference Paper Award are Gordon Hopkinson of SIRA Ltd., Isobel Hopkins of SIRA/UCL Postgraduate Centre, and Bengt Johlander of ESA/ESTEC, for their paper entitled, Proton-Induced Charge Transfer Degradation in CCDs for Near-Room Temperature Applications. The paper describes an innovative optical technique for measuring charge transfer inefficiency in CCDs operated in the near-room-temperature-range of -30°C to 30°C. The optical spot technique enables the measurement of CTD dependence on signal size, background charge, and clock waveform shape, as well as trap emission times, as a function of these variables. The technique involves spot illumination of the CCD, followed by repeated charge transfer regimes. It is applicable to any CCD and yields improved accuracy over the x-ray method. The paper reflects strong current interest in CCD hardness issues as these devices become more pervasive in space applications