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.

Methanetriol─Formation of an Impossible Molecule.

Orthocarboxylic acids─organic molecules carrying three hydroxyl groups at the same carbon atom─have been distinguished as vital reactive intermediates by the atmospheric science and physical (organic) chemistry communities as transients in the atmospheric aerosol cycle. Predicted short lifetimes and their tendency to dehydrate to a carboxylic acid, free orthocarboxylic acids, signify one of the most elusive classes of organic reactive intermediates, with even the simplest representative methanetriol (CH(OH)3)─historically known as orthoformic acid─not previously been detected experimentally. Here, we report the first synthesis of the previously elusive methanetriol molecule in low-temperature mixed methanol (CH3OH) and molecular oxygen (O2) ices subjected to energetic irradiation. Supported by electronic structure calculations, methanetriol was identified in the gas phase upon sublimation via isomer-selective photoionization reflectron time-of-flight mass spectrometry combined with isotopic substitution studies and the detection of photoionization fragments. The first synthesis and detection of methanetriol (CH(OH)3) reveals its gas-phase stability as supported by a significant barrier hindering unimolecular decomposition. These findings progress our fundamental understanding of the chemistry and chemical bonding of methanetriol, hydroxyperoxymethane (CH3OOOH), and hydroxyperoxymethanol (CH2(OH)OOH), which are all prototype molecules in the oxidation chemistry of the atmosphere.

Prebiotic Synthesis and Isomerization in Interstellar Analog Ice: Glycinal, Acetamide, and Their Enol Tautomers.

Glycinal (HCOCH2 NH2 ) and acetamide (CH3 CONH2 ) are simple molecular building blocks of biomolecules in prebiotic chemistry, though their origin on early Earth and formation in interstellar media remain a mystery. These molecules are formed with their tautomers in low temperature interstellar model ices upon interaction with simulated galactic cosmic rays. Glycinal and acetamide are accessed via barrierless radical-radical reactions of vinoxy (⋅CH2 CHO) and acetyl (⋅C(O)CH3 ), and then undergo keto-enol tautomerization. Exploiting tunable photoionization reflectron time-of-flight mass spectroscopy and photoionization efficiency (PIE) curves, these results demonstrate fundamental reaction pathways for the formation of complex organics through non-equilibrium ice reactions in cold molecular cloud environments. These molecules demonstrate an unconventional starting point for abiotic synthesis of organics relevant to contemporary biomolecules like polypeptides and cell membranes in deep space.

Photochemically triggered cheletropic formation of cyclopropenone (c-C3H2O) from carbon monoxide and electronically excited acetylene.

For more than half a century, pericyclic reactions have played an important role in advancing our fundamental understanding of cycloadditions, sigmatropic shifts, group transfer reactions, and electrocyclization reactions. However, the fundamental mechanisms of photochemically activated cheletropic reactions have remained contentious. Here we report on the simplest cheletropic reaction: the [2+1] addition of ground state 18O-carbon monoxide (C18O, X1Σ+) to D2-acetylene (C2D2) photochemically excited to the first excited triplet (T1), second excited triplet (T2), and first excited singlet state (S1) at 5 K, leading to the formation of D2-18O-cyclopropenone (c-C3D218O). Supported by quantum-chemical calculations, our investigation provides persuasive testimony on stepwise cheletropic reaction pathways to cyclopropenone via excited state dynamics involving the T2 (non-adiabatic) and S1 state (adiabatic) of acetylene at 5 K, while the T1 state energetically favors an intermediate structure that directly dissociates after relaxing to the ground state. The agreement between experiments in low temperature ices and the excited state calculations signifies how photolysis experiments coupled with theoretical calculations can untangle polyatomic reactions with relevance to fundamental physical organic chemistry at the molecular level, thus affording a versatile strategy to unravel exotic non-equilibrium chemistries in cyclic, aromatic organics. Distinct from traditional radical-radical pathways leading to organic molecules on ice-coated interstellar nanoparticles (interstellar grains) in cold molecular clouds and star-forming regions, the photolytic formation of cyclopropenone as presented changes the perception of how we explain the formation of complex organics in the interstellar medium eventually leading to the molecular precursors of biorelevant molecules.

Excited state photochemically driven surface formation of benzene from acetylene ices on Pluto and in the outer solar system.

NASA's New Horizons mission unveiled a diverse landscape of Pluto's surface with massive regions being neutral in color, while others like Cthulhu Macula range from golden-yellow to reddish comprising up to half of Pluto's carbon budget. Here, we demonstrate in laboratory experiments merged with electronic structure calculations that the photolysis of solid acetylene - the most abundant precipitate on Pluto's surface - by low energy ultraviolet photons efficiently synthesizes benzene and polycyclic aromatic hydrocarbons via excited state photochemistry thus providing critical molecular building blocks for the colored surface material. Since low energy photons deliver doses to Pluto's surface exceeding those from cosmic rays by six orders of magnitude, these processes may significantly contribute to the coloration of Pluto's surface and of hydrocarbon-covered surfaces of Solar System bodies such as Triton in general. This discovery critically enhances our perception of the distribution of aromatic molecules and carbon throughout our Solar System.

Combined Spectroscopic and Computational Investigation on the Oxidation of exo-Tetrahydrodicyclopentadiene (JP-10; C10H16) Doped with Titanium-Aluminum-Boron Reactive Metal Nanopowder.

We report the results on the combustion of single, levitated droplets of exo-tetrahydrodicyclopentadiene (JP-10) doped with titanium-aluminum-boron (Ti-Al-B) reactive metal nanopowders (RMNPs) in an oxygen (60%)-argon (40%) atmosphere by exploiting an ultrasonic levitator with droplets ignited by a carbon dioxide laser. Ultraviolet-visible (UV-vis) emission spectroscopy revealed the presence of gas-phase aluminum (Al) and titanium (Ti) atoms. These atoms can be oxidized in the gas phase by molecular oxygen to form spectroscopically detected aluminum monoxide (AlO) and titanium monoxide (TiO) transients. Analysis of the optical ignition videos supports that the nanoparticles are ignited before JP-10. The detection of boron monoxide (BO) further proposes an active surface chemistry through the oxidation of the RMNPs and the release of at least BO into the gas phase. The oxidation of gas-phase BO by molecular oxygen to boron dioxide (BO2) plus atomic oxygen might operate in the gas phase, although the involvement of surface oxidation processes of RMNPs to BO2 cannot be discounted. The UV-vis emission spectra also revealed the key reactive intermediates (OH, CH, C2, and HCO) of the oxidation of JP-10. Electronic structure calculations reveal that the presence of reactive radicals has a profound impact on the oxidation of JP-10. Although titanium monoxide (TiO) reacts to produce titanium dioxide (TiO2), it does not engage in an active JP-10 chemistry as all abstraction pathways are endoergic by more than 217 kJ mol-1. This is similar for atomic aluminum and titanium, whose hydrogen abstraction reactions from JP-10 were revealed to be endoergic by at least 77 kJ mol-1. Therefore, aluminum and titanium react preferentially with molecular oxygen to produce their monoxides. However, the formation of BO, AlO, and BO2 supplies a pool of highly reactive radicals, which can abstract hydrogen from JP-10 via transition states ranging from only 1 to 5 kJ mol-1 above the separated reactants, forming JP-10 radicals along with the hydrogen abstraction products (boron hydride oxide, aluminum monohydroxide, and metaboric acid) in the overall exoergic reactions. These abstraction barriers are well below the barriers of abstractions for ground-state atomic oxygen and molecular oxygen. In this sense, gas-phase BO, AlO, and BO2 catalyze the oxidation of gas-phase JP-10 via hydrogen abstraction, forming highly reactive JP-10 radicals. Overall, the addition of RMNPs to JP-10 not only provides a higher energy density fuel but is also expected to lead to shorter ignition delays compared to pure JP-10 due to the highly reactive pool of radicals (BO, AlO, and BO2) formed in the initial stage of the oxidation process.

Identification of Glycolaldehyde Enol (HOHC═CHOH) in Interstellar Analogue Ices.

Glycolaldehyde is considered the entry point in the aqueous prebiotic formose (Butlerow) reaction although it mainly exists in its unreactive hydrated form in aqueous solution. The characterization of the more reactive nucleophilic enol form under interstellar conditions has remained elusive to date. Here we report on the identification of glycolaldehyde enol (1,2-ethenediol, HOHC═CHOH) in low temperature methanol-bearing ices at temperatures as low as 5 K. Exploiting isotope labeling and isomer-selective photoionization coupled with reflectron time-of-flight mass spectrometry, our results unravel distinct reaction pathways to 1,2-ethenediol, thus demonstrating the kinetic stability, availability for prebiotic sugar formation, and potential detectability in deep space.

Interstellar Enolization-Acetaldehyde (CH3 CHO) and Vinyl Alcohol (H2 CCH(OH)) as a Case Study.

Owing to the unique conditions in cold molecular clouds, enols-the thermodynamically less stable tautomers of aldehydes and ketones-do not undergo tautomerization to their more stable tautomers in the gas phase because they cannot overcome tautomerization barriers at the low temperatures. Laboratory studies of interstellar analog ices have demonstrated the formation of several keto-enol tautomer pairs in astrochemically relevant ice mixtures over the last years. However, so far only one of them, acetaldehyde-vinyl alcohol, has been detected in deep space. Due to their reactivity with electrophiles, enols can play a crucial role in our understanding of the molecular complexity in the interstellar medium and in comets and meteorites. To study the enolization of aldehydes in interstellar ices by interaction with galactic cosmic rays (GCRs), we irradiated acetaldehyde ices with energetic electrons as proxies of secondary electrons generated in the track of GCRs while penetrating interstellar ices. The results indicate that GCRs can induce enolization of acetaldehyde and that intra- as well as intermolecular processes are relevant. Therefore, enols should be ubiquitous in the interstellar medium and could be searched for using radio telescopes such as ALMA. Once enols are detected and abundances are established, they can serve as tracers for the non-equilibrium chemistry in interstellar ices thus eventually constraining fundamental reaction mechanisms deep inside interstellar ices.

On the Formation of the Popcorn Flavorant 2,3-Butanedione (CH3 COCOCH3 ) in Acetaldehyde-Containing Interstellar Ices.

Acetaldehyde (CH3 CHO) is ubiquitous throughout the interstellar medium and has been observed in cold molecular clouds, star forming regions, and in meteorites such as Murchison. As the simplest methyl-bearing aldehyde, acetaldehyde constitutes a critical precursor to prebiotic molecules such as the sugar deoxyribose and amino acids via the Strecker synthesis. In this study, we reveal the first laboratory detection of 2,3-butanedione (diacetyl, CH3 COCOCH3 ) - a butter and popcorn flavorant - synthesized within acetaldehyde-based interstellar analog ices exposed to ionizing radiation at 5 K. Detailed isotopic substitution experiments combined with tunable vacuum ultraviolet (VUV) photoionization of the subliming molecules demonstrate that 2,3-butanedione is formed predominantly via the barrier-less radical-radical reaction of two acetyl radicals (CH3 CO). These processes are of fundamental importance for a detailed understanding of how complex organic molecules (COMs) are synthesized in deep space thus constraining the molecular structures and complexity of molecules forming in extraterrestrial ices containing acetaldehyde through a vigorous galactic cosmic ray driven non-equilibrium chemistry.

Bottom-Up Synthesis of 1,1-Ethenediol (H2CC(OH)2)─The Simplest Unsaturated Geminal Diol─In Interstellar Analogue Ices.

Because of their nucleophilic character and high reactivity, enols─reaction intermediates carrying a hydroxyl group connected to a carbon-carbon double bond─play a key role in the formation of complex organic molecules in astrobiology and biochemistry. Here, we report the first bottom-up preparation of 1,1-ethenediol (H2CC(OH)2)─the simplest unsaturated geminal enol of acetic acid (CH3COOH) and potential precursor for the formation of glycine─in interstellar analogue ices of carbon dioxide and methane processed by proxies of galactic cosmic rays. These enols can easily form via nonequilibrium chemistry in low temperature (10 K) interstellar ices at abundances orders of magnitude higher than thermodynamically predicted. These energetically less favorable tautomers remain stable in ice-coated interstellar nanoparticles in molecular clouds and also upon sublimation into the gas phase in star forming regions thus providing the raw material to a complex and exotic organic chemistry under extreme conditions in deep space.

Gas phase identification of the elusive oxaziridine (cyclo-H2CONH) - an optically active molecule.

The hitherto elusive oxaziridine molecule (cyclo-H2CONH) - an optically active, high energy isomer of nitrosomethane (CH3NO) - is prepared in processed methane-nitrogen monoxide ices and detected upon sublimation in the gas phase. Electronic structure calculations reveal likely routes via addition of carbene (CH2) to the nitrogen-oxygen double bond of nitrosyl hydride (HNO). Our findings provide a fundamental framework to explore the preparation and stability of racemic oxaziridines exploited in chiral substrate-controlled diastereoselective preparation such as Sharpless asymmetric epoxidation, thus advancing our fundamental understanding of the preparation and chemical bonding of strained rings in small organic molecules.