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.

Preparation, characterization and comparison of biological potency in two new Zn(II) and Pd(II) complexes of butanedione monoxime derivatives.

A novel Schiff base ligand (2-iminothiophenol-2,3-butanedione monoxime, ITBM) and its complexes with Pd(II) and Zn(II) metal ions ([M(ITBM)2]Cl2) were synthesized and characterized in the present study. The formulated complexes were evaluated for in vitro antioxidant activity as radical scavengers against 1,1-diphenyl-2-picrylhydrazyl radicals (DPPH•). According to the results, antioxidant activity of Pd complex (IC50=36 mg L-1) was more effective than that of Zn(II) complex (IC50=72 mg L-1). Biophysical techniques along with computational modeling were employed to examine the binding of these complexes with human serum albumin (HSA) as the model protein. The trial findings revealed an interaction between Schiff base complexes and HSA with a modest binding affinity [Kb=6.31(±0.11)×104 M-1 for Zn(II) complex and 0.71(±0.05)×104 M-1 for Pd(II) complex at 310 K]. An intense fluorescence quenching of protein through a static quenching mechanism was occurred due to the binding of both complexes to HSA. Hydrogen bonds and van der Waals forces in both examined systems were the main stabilizing forces in the development of drug-protein complex. Based on far-UV-CD observations, the content of α-helical structure in the protein was reduced through induction by both complexes. Analysis of protein-ligand docking demonstrated binding of the two Schiff base complexes to residues placed in the IIA subdomain of HSA. In addition, Zn complex with HSA showed a stronger binding ability than that of Pd complex.Communicated by Ramaswamy H. Sarma.

Acetoin is a precursor to diacetyl in e-cigarette liquids.

Use of the e-liquid flavourings diacetyl and acetyl propionyl has raised concerns that they might cause respiratory diseases amongst vapers. Product surveys show that these compounds, plus a less toxic alternative, acetoin, are widely used in e-liquids. We have investigated the chemistry of acetoin, acetyl propionyl and diacetyl in e-liquids. They are reactive, with concentrations falling substantially over time. Acetyl propionyl is the most reactive, diacetyl less so, and acetoin significantly more stable. Their reactivity is pH-enhanced when nicotine is present in the e-liquid. Of major concern, we found that acetoin generates diacetyl in e-liquids. We found diacetyl formation in all acetoin-containing e-liquids, but it is not an acetoin-contaminant. Diacetyl concentrations were proportional to acetoin content, grew over time, and formation was accelerated by nicotine. E-liquids stored for up to 18 months contained significant diacetyl, and reduced acetoin levels, showing that acetoin is a long-term diacetyl source. Other reaction pathways operate, and we advance mechanisms to explain this area of e-liquid chemistry. Acetoin use in e-liquids is an inevitable source of diacetyl exposure for e-cigarette users. Acetoin, acetyl propionyl and diacetyl are avoidable hazards for vapers, and we recommend e-liquid manufacturers move away from their use in e-liquid formulations.

Formation of 4(5)-methylimidazole and its precursors, α-dicarbonyl compounds, in Maillard model systems.

Glyoxal, methylglyoxal, and diacetyl formed from sucrose alone and from a D-glucose/ammonia Maillard model system were analyzed by gas chromatography. They are known as precursors of 4(5)-methylimidazole (MI). Glyoxal and methylglyoxal formed more in acidic conditions than in basic conditions, whereas diacetyl formed the most at the highest basic condition of pH 12. Glyoxal formation from sucrose ranged from 0.33 to 32.90 µg/g under four different time and temperature conditions. Amounts of glyoxal, methylglyoxal, and diacetyl formed in Maillard model systems ranged from 2.98 to 46.12 µg/mL, from 8.27 to 156.61 µg/mL, and from 14.94 to 1588.45 µg/mL, respectively. 4(5)-MI formation in the same model systems ranged from 28.56 to 1269.71 µg/mL. Addition of sodium sulfite reduced formation of these chemicals significantly. Total α-dicarbonyl compounds in 12 commercial soft drinks ranged from 5.75 to 50.72 µg/mL. 4(5)-MI was found in levels ranging from 1.76 to 28.11 ng/mL in 10 commercial soft drinks.

Deacylation reactions of 20-acetyl dinorcholanic lactones and 20,23-diacetyl furost-22-enes.

We report the deacylation of (20R)-20-acetyl-23,24-dinorcholanic lactones by hydrazine hydrate, under microwave irradiation in high yields. The elimination of the 20-acetyl group proceeded with retention of configuration which contrast with other proved deacylation methods that yield a mixture of diastereoisomers. In this way, unnatural (20R)-23,24-dinorcholanic lactones can be produced rapidly on a large scale. Both (20R)- and (20S)-lactones were prepared starting from diosgenin, hecogenin and sarsasapogenin, in 72-80% overall yields.

A macrocyclic polyamine as an anion receptor in the capillary electrochromatographic separation of carbohydrates.

An analytical approach of the 32-membered macrocyclic polyamine, 1,5,9,13,17,21,25,29-octaazacyclodotriacontane ([32]ane-N8) was described for the capillary electrochromatographic (CEC) separation of derivatized mono- and disaccharides. The column displayed reversal electroosmotic flow (EOF) at pH below 7.0, while a cathodic EOF was shown at pH above 7.0. The reductive amination of saccharides was carried out with p-aminobenzoic acid. Some parameters that affect the CEC separations were investigated. Several competitive ligands, such as Tris, EDTA and phosphate were also examined for the effect on the performance. We achieved a complete separation of all compounds as well as the excess derivatizing agent by using borate buffer (pH 9.0) in a mode of concentration gradient (60 mM inlet side and 70 mM outlet side). The relative standard deviation of the retention time measured for each sample was less than 4% in six continuous runs, suggesting that the bonded phase along with the gradient formed inside the column was quite stable. With the mixing modes of anion coordination, anion exchange, and shape discrimination, the interaction adequately accomplishes the separation of carbohydrates which are epimers or have different glycosidic linkage, although the electrophoretic migration is also involved in the separation mechanism.