Synthesis of methanediol [CH2(OH)2]: The simplest geminal diol

Geminal diols—organic molecules carrying two hydroxyl groups at the same carbon atom—have been recognized as key reactive intermediates by the physical (organic) chemistry and atmospheric science communities as fundamental transients in the aerosol cycle and in the atmospheric ozonolysis reaction sequence. Anticipating short lifetimes and their tendency to fragment to water plus the aldehyde or ketone, free geminal diols represent one of the most elusive classes of organic reactive intermediates. Here, we afford an exceptional glance into the preparation of the previously elusive methanediol [CH2(OH)2] transient—the simplest geminal diol—via energetic processing of low-temperature methanol–oxygen ices. Methanediol was identified in the gas phase upon sublimation via isomer-selective photoionization reflectron time-of-flight mass spectrometry combined with isotopic substitution studies. Electronic structure calculations reveal that methanediol is formed via excited state dynamics through insertion of electronically excited atomic oxygen into a carbon–hydrogen bond of the methyl group of methanol followed by stabilization in the icy matrix. The first preparation and detection of methanediol demonstrates its gas-phase stability as supported by a significant barrier hindering unimolecular decomposition to formaldehyde and water. These findings advance our perception of the fundamental chemistry and chemical bonding of geminal diols and signify their role as an efficient sink of aldehydes and ketones in atmospheric environments eventually coupling the atmospheric chemistry of geminal diols and Criegee intermediates.

Direct and Indirect Chemiluminescence: Reactions, Mechanisms and Challenges

Emission of light by matter can occur through a variety of mechanisms. When it results from an electronically excited state of a species produced by a chemical reaction, it is called chemiluminescence (CL). The phenomenon can take place both in natural and artificial chemical systems and it has been utilized in a variety of applications. In this review, we aim to revisit some of the latest CL applications based on direct and indirect production modes. The characteristics of the chemical reactions and the underpinning CL mechanisms are thoroughly discussed in view of studies from the very recent bibliography. Different methodologies aiming at higher CL efficiencies are summarized and presented in detail, including CL type and scaffolds used in each study. The CL role in the development of efficient therapeutic platforms is also discussed in relation to the Reactive Oxygen Species (ROS) and singlet oxygen (1O2) produced, as final products. Moreover, recent research results from our team are included regarding the behavior of commonly used photosensitizers upon chemical activation under CL conditions. The CL prospects in imaging, biomimetic organic and radical chemistry, and therapeutics are critically presented in respect to the persisting challenges and limitations of the existing strategies to date.

ACTIVATION OF SINGLE-BUBBLE SONOLUMINESCENCE AND RADIOLUMINESCENCE OF GD3+ AND DY3+ IONS BY ELECTRON ACCEPTORS IN AQUEOUS SOLUTIONS AS CONSEQUENCE OF THE HYDRATED ELECTRON GENERATION DURING WATER SONOLYSIS AND RADIOLYSIS

Discovered the activation of moving single-bubble sonoluminescence and radioluminescence for Gd3+ and Dy3+ ions in aqueous solutions of GdCl3 and DyCl3 by the acceptor of a hydrated electron (eaq-): H+, Cd2+, etc. This activation is similar to the previously found activation by acceptors of eaq- radioluminescence and single-bubble sonoluminescence for the Tb3+ ion. Electron acceptors do not affect the quantum yield of the said lantha-nide ions photoluminescence. They also do not affect the yield of their multibubble sonoluminescence in aqueous solutions, since eaqdoes not appear in significant amounts during multibubble sonolysis. The found luminescence activation effects of lanthanide ions are interpreted as a consequence of the suppression of the quenching (reduction) reactions of these electronically excited ions eaq: *Ln3+ + eaq- → Ln2+ by acceptors. The feasibility of these reactions was predicted for all Ln3+ ions based on a theoretical estimate of their free energy. The discovery of the described effects of activation of the luminescence of Ln3+ ions is a consequence and serves as confirmation of not only the known generation of eaq- during radiolysis, but also its previously unknown generation during moving single-bubble sonolysis of water.

Electronically Excited States of Potential Interstellar, Anionic Building Blocks for Astrobiological Nucleic Acids

Functionalizing deprotonated polycyclic aromatic hydrocarbon (PAH) anion derivatives gives rise to electronically excited states in the resulting anions. While functionalization with −OH and −C2H, done presently, does not result in the richness of electronically excited states as it does with −CN done previously, the presence of dipole-bound excited states and even some valence excited states are predicted in this quantum chemical analysis. Most notably, the more electron withdrawing −C2H group leads to valence excited states once the number of rings in the molecule reaches three. Dipole-bound excited states arise when the dipole moment of the corresponding neutral radical is large enough (likely around 2.0 D), and this is most pronounced when the hydrogen atom is removed from the functional group itself regardless of whether functionalized by a hydroxyl or enthynyl group. Deprotonatation of the hydroxyl group in the PAH creates a ketone with a delocalized highest occupied molecular orbital (HOMO) unlike deprotonation of a hydrogen on the ring where a localized lone pair on one of the carbon atoms serves as the HOMO. As a result, hydroxyl functionlization and subsequent deprotonation of PAHs creates molecules that begin to exhibit structures akin to nucleic acids. However, the electron withdrawing −C2H has more excited states than the electron donating −OH functionalized PAH. This implies that the −C2H electron withdrawing group can absorb a larger energy range of photons, which signifies an increasing likelihood of being stabilized in the harsh conditions of the interstellar medium.

Nanocracks upon Fracture of Oligoclase

Abstract—The spectrum of fractoluminescence (FL) upon fracture of the surface of oligoclase is obtained. The analysis of the spectrum has shown that fracture of crystals leads to the formation of electronically excited free radicals ≡Si−O• and Fe3• ions as well as electron traps. FL consisted of a set of the signals with the intensities varying by an order of magnitude. The duration of the signals was ~50 ns and the time interval between them varied from ~0.1 to 1 μs. Each signal contained four maxima associated with the destruction of barriers preventing the motion of dislocations along the sliding planes. These breakthroughs cause the formation of the smallest (“primary”) cracks. All other, larger cracks are formed by the coalescence of the “primary” cracks. The sizes of “primary” cracks range from ~10 to 20 nm and the time of their formation is 16 ns. The distribution of cracks by size (surface areas of crack walls) is power law with the exponent –1.9.

The Reactive Oxygen Species Singlet Oxygen, Hydroxy Radicals, and the Superoxide Radical Anion—Examples of Their Roles in Biology and Medicine

Reactive oxygen species comprise oxygen-based free radicals and non-radical species such as peroxynitrite and electronically excited (singlet) oxygen. These reactive species often have short lifetimes, and much of our understanding of their formation and reactivity in biological and especially medical environments has come from complimentary fast reaction methods involving pulsed lasers and high-energy radiation techniques. These and related methods, such as EPR, are discussed with particular reference to singlet oxygen, hydroxy radicals, the superoxide radical anion, and their roles in medical aspects, such as cancer, vision and skin disorders, and especially pro- and anti-oxidative processes.