H2 -free Semi-hydrogenation of Butadiene by the Atomic Sieving Effect of Pd Membrane with Tree-like Pd Dendrites Array.

H2 -free semi-hydrogenation at room temperature shows great advantage for replacing the thermocatalytic process in industry owing to the high energy and resource saving, however, remains great challenges. Herein, a tree-like Pd dendrites array decorated Pd membrane was constructed as the core device in an electrochemistry assisted gas-fed membrane reactor for butadiene semi-hydrogenation. It reveals that hydrogen atomic sieving effect of this Pd-based membrane under electrochemical condition was the key for semi-hydrogenation. The configuration study of Pd nanostructured membrane demonstrates that the penetration of hydrogen atoms through Pd membrane from electrochemical side to chemical side is affected by the consumption of hydrogen atom in semi-hydrogenation step. Such atomic sieving property of nanostructured Pd membrane with 5.1 times increase in catalytic active surface area brings above 14 times higher in butadiene conversion than that of bare Pd foil, with ≈90 % of butenes selectivity at butadiene conversion ≈98 % over 300 h of H2 -free reaction under 15 mA cm-2 .

Characterization of Queen Supergene Pheromone in the Red Imported Fire Ant Using Worker Discrimination Assays.

Ants use chemical signals to communicate for various purposes related to colony function. Social organization in the red imported fire ant, Solenopsis invicta, is determined by the Sb supergene, with colonies of the monogyne (single-queen) form lacking the element and colonies of the polygyne (multiple-queen) form possessing it. Polygyne workers accept new reproductive queens in their nest, but only those carrying Sb; young winged queens lacking this genetic element are executed as they mature sexually in their natal nest or as they attempt to enter a foreign nest to initiate reproduction after mating and shedding their wings. It has been suggested that queen supergene genotype status is signaled to workers by unsaturated cuticular hydrocarbons, while queen reproductive status is signaled by piperidines (venom alkaloids). We used high-throughput behavioral assays to study worker acceptance of paper dummies dosed with fractions of extracts of polygyne queens, or blends of synthetic counterparts of queen cuticular compounds. We show that the queen supergene pheromone comprises a blend of monoene and diene unsaturated hydrocarbons. Our assays also reveal that unsaturated hydrocarbons elicit discrimination by polygyne workers only when associated with additional compounds that signal queen fertility. This synergistic effect was obtained with a polar fraction of queen extracts, but not by the piperidine alkaloids, suggesting that the chemical(s) indicating queen reproductive status are compounds more polar than cuticular hydrocarbons but are not the piperidine alkaloids. Our results advance understanding of the role of chemical signaling that is central to the regulation of social organization in an important invasive pest and model ant species.

Synthesis of Cyclic Fragrances via Transformations of Alkenes, Alkynes and Enynes: Strategies and Recent Progress.

With increasing demand for customized commodities and the greater insight and understanding of olfaction, the synthesis of fragrances with diverse structures and odor characters has become a core task. Recent progress in organic synthesis and catalysis enables the rapid construction of carbocycles and heterocycles from readily available unsaturated molecular building blocks, with increased selectivity, atom economy, sustainability and product diversity. In this review, synthetic methods for creating cyclic fragrances, including both natural and synthetic ones, will be discussed, with a focus on the key transformations of alkenes, alkynes, dienes and enynes. Several strategies will be discussed, including cycloaddition, catalytic cyclization, ring-closing metathesis, intramolecular addition, and rearrangement reactions. Representative examples and the featured olfactory investigations will be highlighted, along with some perspectives on future developments in this area.

Light-Assisted Semi-Hydrogenation of 1,3-Butadiene with Water.

Sustainable processes for semi-hydrogenation of alkynes/alkadienes impurities in alkenes feedstocks are in great demand in industry as the utilization of excessive hydrogen, high temperature and unsatisfactory alkenes selectivity of the current thermo-catalytic route, however, their development is still challenging. Herein, we innovate a light-assisted semi-hydrogenation process in gas-feed fixed bed reactor, with water as hydrogen atom source by in situ photocatalysis. Using Pd/TiO2 as model catalyst, this process shows an excellent catalytic performance for the semi-hydrogenation of 1,3-butadiene, with 100 % of butenes selectivity at ≈99 % of conversion over 180 h of reaction at ambient temperature driven by 66 mW cm-2 of irradiation intensity. This light-driven, H2 -free, ambient temperature semi-hydrogenation process, with superior performance to that of thermocatalytic route, shows attractive to bring an evolution in industrial hydrogenation technology to an economical and safe way.

Reactive carbon fiber ionization-mass spectrometry for characterization of unsaturated hydrocarbons from plant aroma.

Carbon fiber ionization (CFI)-mass spectrometry (MS) is an ambient technique that can be used to detect samples in gas, liquid, and solid forms simply by using a piece of carbon fiber as the ionization emitter. Reactive MS can be performed to selectively detect target analytes by conducting fast reactions during ionization. Most ambient ionization MS techniques used to monitor chemical reactions are limited to liquid-phase reactions. Herein, we develop reactive CFI-MS to be a suitable tool for monitoring of reaction products derived from volatile unsaturated hydrocarbons in the gas phase. Hydroamination is a fast reaction that can form a carbon-nitrogen bond through the addition of an amine to unsaturated hydrocarbons. In this study, reactive CFI-MS was used to selectively characterize aroma molecules, which are unsaturated hydrocarbons derived from plants, through hydroamination. A piece of carbon fiber was placed close (~ 1 mm) to the inlet of the mass spectrometer and deposited with dried methylamine. The sample in either liquid or solid form was placed underneath the carbon fiber. The volatiles derived from the sample reacted with amine on the carbon fiber were simultaneously determined once the mass spectrometer was switched on. For proof of concept, ethylene glycol dimethacrylate, which has double bonds and is highly volatile, was initially selected as the model sample to demonstrate the feasibility of using reactive CFI-MS to detect its hydroamination derivative. Banana, garlic, and ginger, which possess aroma molecules with unsaturated hydrocarbons, were selected as real-world samples. Graphical abstract.

'Wax bloom' on beeswax cultural heritage objects: Exploring the causes of the phenomenon.

The term 'wax bloom' is used to describe a thin whitish crystalline layer that develops on the surface of beeswax objects under specific conditions. This phenomenon is undesirable, especially in the cases of objects with aesthetic or informational value, such as wax sculptures or historical seals. A combination of solid-state NMR and FTIR measurements allowed to obtain fairly detailed insight into the problem and to suggest a probable mechanism of its development. Secondary crystallization of unsaturated hydrocarbons from beeswax was determined as a primary cause. After the macroscopic solidification of beeswax from the melt, these molecules remain for months in a highly mobile, liquid-like state. This facilitates their diffusion to the surface, where they eventually crystallize, forming the 'wax bloom' effect. Although these results are of particular interest with respect to the conservation of beeswax artifacts, they are relevant to this material in general and help with understanding its unique properties.

Patterns of odour emission, thermogenesis and pollinator activity in cones of an African cycad: what mechanisms apply?

BACKGROUND AND AIMS: Ontogenetic patterns of odour emissions and heating associated with plant reproductive structures may have profound effects on insect behaviour, and consequently on pollination. In some cycads, notably Macrozamia, temporal changes in emission of specific odour compounds and temperature have been interpreted as a 'push-pull' interaction in which pollinators are either attracted or repelled according to the concentration of the emitted volatiles. To establish which mechanisms occur in the large Encephalartos cycad clade, the temporal patterns of volatile emissions, heating and pollinator activity of cones of Encephalartos villosus in the Eastern Cape (EC) and KwaZulu Natal (KZN) of South Africa were investigated. METHODS AND KEY RESULTS: Gas chromatography-mass spectrometry (GC-MS) analyses of Encephalartos villosus cone volatiles showed that emissions, dominated by eucalyptol and 2-isopropyl-3-methoxypyrazine in EC populations and (3E)-1,3-octadiene and (3E,5Z)-1,3,5-octatriene in the KZN populations, varied across developmental stages but did not vary significantly on a daily cycle. Heating in male cones was higher at dehiscence than during pre- and post-dehiscence, and reached a maximum at about 1830 h when temperatures were between 7·0 and 12·0 °C above ambient. Daily heating of female cones was less pronounced and reached a maximum at about 1345 h when it was on average between 0·9 and 3·0 °C above ambient. Insect abundance on male cones was higher at dehiscence than at the other stages and significantly higher in the afternoon than in the morning and evening. CONCLUSIONS: There are pronounced developmental changes in volatile emissions and heating in E. villosus cones, as well as strong daily changes in thermogenesis. Daily patterns of volatile emissions and pollinator abundance in E. villosus are different from those observed in some Macrozamia cycads and not consistent with the push-pull pattern as periods of peak odour emission do not coincide with mass exodus of insects from male cones.

Co-Pyrolysis of Unsaturated C4 and Saturated C6+ Hydrocarbons-An Experimental Study to Evaluate Steam-Cracking Performance.

Unsaturated C4 hydrocarbons are abundant in various petrochemical streams. They can be considered as a potential feedstock for the steam-cracking process, where they must be co-processed with C6 and higher (C6+) hydrocarbons of primary naphtha fractions. Co-pyrolysis experiments aiming at the comparison of different C4 hydrocarbon performances were carried out in a laboratory micro-pyrolysis reactor under standardized conditions: 820 °C, 400 kPa, and 0.2 s residence time in the reaction zone. C4 hydrocarbons were co-pyrolyzed with different co-pyrolysis partners containing longer hydrocarbon chain to study the influence of the co-pyrolysis partner structure on the behavior of C4 hydrocarbons. The yields of the pyrolysis products and the conversion of C4 hydrocarbons were used as the performance factors. A regression model was developed and used as a valuable tool for quantifying the inhibition or acceleration effect of co-pyrolysis on the conversion of co-pyrolyzed hydrocarbons. It was found that the performance of different C4 hydrocarbons in co-pyrolysis is substantially different from the separate pyrolysis of the individual components.

C-H Infrared Absorption and Solubility of Ethylene, Propyne, 2-methyl-2-butene, and 2-methyl-1, 3-butadiene (Isoprene) in Liquid Argon Solutions.

The solubility of ethylene (H2C=CH2), propyne (CH3-C≡C-H), 2-methyl-2-butene (CH3-CH=C(CH3)2), and isoprene or 2-methyl-1, 3-butadiene (H2C=C(CH3)-CH=CH2) in liquid argon has been measured using mid-infrared and near-infrared (NIR) absorption. Spectra were recorded in the C-H infrared (IR) region. Spectra were obtained at increasing solution composition until the magnitude of the integrated absorption band reached a maximum value, indicating a saturated solution. The approximate experimental solubilities are: (600 ± 100) ppm at 92 K for ethylene, (22 ± 9) ppm at 100 K for propyne, (9 ± 5) ppm at 100 K for 2-methyl-2-butene, and (12 ± 2) ppm at 86 K for isoprene. The experimental solubility values at the corresponding temperature were used with solubility parameters of two separate models: the perturbed-chain statistical associating fluid theory (PC-SAFT) and the regular solution theory. Solvent-solute interaction parameters k12 (PC-SAFT) and [Formula: see text] (RST) were obtained for each solute in the presence of argon as the solvent. Data from experimental measurements are important for more realistic simulations of solubility of solids in cryogenic liquids.

Ni- and Fe-catalyzed Carboxylation of Unsaturated Hydrocarbons with CO2.

The sustainable utilization of available feedstock materials for preparing valuable compounds holds great promise to revolutionize approaches in organic synthesis. In this regard, the implementation of abundant and inexpensive carbon dioxide (CO2) as a C1 building block has recently attracted considerable attention. Among the different alternatives in CO2 fixation, the preparation of carboxylic acids, relevant motifs in pharmaceuticals and agrochemicals, is particularly appealing, thus providing a rapid and unconventional entry to building blocks that are typically prepared via waste-producing protocols. While significant advances have been realized, the utilization of simple unsaturated hydrocarbons as coupling partners in carboxylation events is undoubtedly of utmost academic and industrial relevance, as two available feedstock materials can be combined in a catalytic fashion. This review article aims to describe the main achievements on the direct carboxylation of unsaturated hydrocarbons with CO2 by using cheap and available Ni or Fe catalytic species.

Saturated vs. unsaturated hydrocarbon interactions with carbon nanostructures.

The interactions of various acyclic and cyclic hydrocarbons in both saturated and unsaturated forms with the carbon nanostructures (CNSs) have been explored by using density functional theory (DFT) calculations. Model systems representing armchair and zigzag carbon nanotubes (CNTs) and graphene have been considered to investigate the effect of chirality and curvature of the CNSs toward these interactions. Results of this study reveal contrasting binding nature of the acyclic and cyclic hydrocarbons toward CNSs. While the saturated molecules show stronger binding affinity in acyclic hydrocarbons; the unsaturated molecules exhibit higher binding affinity in cyclic hydrocarbons. In addition, acyclic hydrocarbons exhibit stronger binding affinity toward the CNSs when compared to their corresponding cyclic counterparts. The computed results excellently corroborate the experimental observations. The interaction of hydrocarbons with graphene is more favorable when compared with CNTs. Bader's theory of atoms in molecules has been invoked to characterize the noncovalent interactions of saturated and unsaturated hydrocarbons. Our results are expected to provide useful insights toward the development of rational strategies for designing complexes with desired noncovalent interaction involving CNSs.

Relevance of the Channel Leading to Formaldehyde + Triplet Ethylidene in the O((3)P) + Propene Reaction under Combustion Conditions.

Comprehension of the detailed mechanism of O((3)P) + unsaturated hydrocarbon reactions is complicated by the existence of many possible channels and intersystem crossing (ISC) between triplet and singlet potential energy surfaces (PESs). We report synergic experimental/theoretical studies of the O((3)P) + propene reaction by combining crossed molecular beams experiments using mass spectrometric detection at 9.3 kcal/mol collision energy (Ec) with high-level ab initio electronic structure calculations of the triplet PES and RRKM/master equation computations of branching ratios (BRs) including ISC. At high Ec's and temperatures higher than 1000 K, main products are found to be formaldehyde (H2CO) and triplet ethylidene ((3)CH3CH) formed in a reaction channel that has never been identified or considered significant in previous kinetics studies at 300 K and that, as such, is not included in combustion kinetics models. Global and channel-specific rate constants were computed and are reported as a function of temperature and pressure. This study shows that BRs of multichannel reactions useful for combustion modeling cannot be extrapolated from room-temperature kinetics studies.