Who Cares More About the Environment, Those with an Intrinsic, an Extrinsic, a Quest, or an Atheistic Religious Orientation?: Investigating the Effect of Religious Ad Appeals on Attitudes Toward the Environment.

There is a consensus among scientists that climate change is an existing, growing, and human-made threat to our planet. The topic is a divisive issue worldwide, including among people of faith. Little research has focused on the relationship between (non)religious belief and climate change. Hence, in Studies 1 and 2, the authors explore the impact of religious/non-religious orientations: intrinsic (religion as an end in itself), extrinsic (religion as a means to an end), quest (a journey toward religious understanding), and non-religious orientation (i.e., atheistic) on consumer attitudes toward the environment, focusing on recycling advertisements with (non)religious cues. Further, in Study 3, we examine the underlying causal mechanism of environmental identity and the moderating effect of political views on consumers' lack of belief in climate change. The results show that religious people are less committed to the environment and climate change and that atheism positively affects recycling and climate change identity. The findings offer practical implications in that advertising campaigns need to be endorsed by religious leaders and channeled within the confines of the religious institutions they represent.

Investigating C[double bond, length as m-dash]C positions and hydroxylation sites in lipids using Paternò-Büchi functionalization mass spectrometry.

Lipid oxidation plays a major role in biochemical processes and nutrition. Structural changes during oxidation can lead to alterations of lipid functions. Rancidification and production of secondary lipid messengers are well-known examples for the impact of oxidation on lipid function. Especially lipids with a high degree of unsaturation are prone to oxidize. In order to investigate structural changes of lipids upon oxidation, we here introduce a photochemical Paternò-Büchi functionalization workflow and subsequent mass spectrometric analysis for analysis of unsaturated, oxidized lipids. Results for hydroxylated fatty acids and triglycerides containing isolated and conjugated C[double bond, length as m-dash]C bonds will be presented making use of 3-acetylpyridine as a photochemically active compound. Photochemical derivatization is performed in nano-electrospray emitter tips in 30 s resulting in the formation of oxetanes without inducing light-triggered oxidation of analytes. Collisional-activation of photoproducts facilitates selective cleavage of oxetane moieties. Resulting fragment ions not only allow the determination of C[double bond, length as m-dash]C bond locations for isolated and conjugated C[double bond, length as m-dash]C bonds but also restrict the site of oxidation. By registering the mass shift in some fragment ions of +15.99 Da due to hydroxylation, the oxidized sections of lipids can be identified. In order to demonstrate its analytical robustness, the method is applied to determine the structural impact of non-selective ambient oxidation on fatty acids, triglycerides and complex triglyceride mixtures obtained from Sacha inchi oil.

Olefinic reagents tested for peptide derivatization with switchable properties: Stable upon collision induced dissociation and cleavable by in-source Paternò-Büchi reactions.

This contribution is part of our ongoing efforts to develop innovative cross-linking (XL) reagents and protocols for facilitated peptide mixture analysis and efficient assignment of cross-linked peptide products. In this report, we combine in-source Paternò-Büchi (PB) photo-chemistry with a tandem mass spectrometry approach to selectively address the fragmentation of a tailor-made cross-linking reagent. The PB photochemistry, so far exclusively used for the identification of unsaturation sites in lipids and in lipidomics, is now introduced to the field of chemical cross-linking. Based on trans-3-hexenedioic acid, an olefinic homo bifunctional amine reactive XL reagent was designed and synthesized for this proof-of-principle study. Condensation products of the olefinic reagent with a set of exemplary peptides are used to test the feasibility of the concept. Benzophenone is photochemically reacted in the nano-electrospray ion source and forms oxetane PB reaction products. Subsequent CID-MS triggered retro-PB reaction of the respective isobaric oxetane molecular ions and delivers reliably and predictably two sets of characteristic fragment ions of the cross-linker. Based on these signature ion sets, a straightforward identification of covalently interconnected peptides in complex digests is proposed. Furthermore, CID-MSn experiments of the retro-PB reaction products deliver peptide backbone characteristic fragment ions. Additionally, the olefinic XL reagents exhibit a pronounced robustness upon CID-activation, without previous UV-excitation. These experiments document that a complete backbone fragmentation is possible, while the linker-moiety remains intact. This feature renders the new olefinic linkers switchable between a stable, noncleavable cross-linking mode and an in-source PB cleavable mode.

Industrial Riboflavin Fermentation Broths Represent a Diverse Source of Natural Saturated and Unsaturated Lactones.

Fermentation broths of Ashbya gossypii from the industrial production of riboflavin emit an intense floral, fruity, and nutty smell. Typical Ehrlich pathway products, such as 2-phenylethan-1-ol and 2-/3-methylbutan-1-ol, were detected in large amounts as well as some intensely smelling saturated and unsaturated lactones, e.g., γ-decalactone and γ-(Z)-dodec-6-enlactone. An aroma extract dilution analysis identified 2-phenylethan-1-ol and γ-(Z)-dodec-6-enlactone as the main contributors to the overall aroma, with flavor dilution factors of 32 768. The position of the double bonds of unsaturated lactones was determined by the Paternò-Büchi reaction, and reference compounds that were not available commercially were synthesized to elucidate the structures of the uncommon lactones. The absolute configuration and enantiomeric excess values of the lactones were determined by converting the lactones to their corresponding Mosher's esters. In addition, the odor impressions and odor thresholds in air were determined.

Relative Quantification of Phosphatidylcholine sn-Isomers Using Positive Doubly Charged Lipid-Metal Ion Complexes.

Phosphatidylcholines are the major phospholipid component of most eukaryotic cell membranes. Phosphatidylcholines have been shown to actively participate in regulatory and metabolic processes. Dysfunctional metabolic processes have been linked to human disease and can result in altered phosphatidylcholine structural features, such as permutation of fatty acid connectivity. Assignment and relative quantitation of structural isomers that arise from fatty acid permutation on the phosphatidylcholine backbone, so-called sn-isomers, is difficult with routine tandem mass spectrometry or with liquid chromatography without authentic standards. In this work, we report on the observation that phosphatidylcholines form abundant doubly charged metal ion complexes during electrospray ionization (ESI) and show that these complexes can be used to assign fatty acid moieties, relatively quantify sn-isomers in MS2 experiments, and mass spectrometrically separate phosphatidylcholines from other phospholipid classes in positive ion mode. Addition of Fe2+ salts (20 mol %) to ESI spray solutions affords highly abundant doubly charged metal ion phosphatidylcholine complexes (∼110% of protonated compounds) and allows sensitive fragment ion detection (limit of detection = 100 pM). Higher energy collisional dissociation, collision-induced dissociation, and ultraviolet photodissociation of doubly charged complexes yield two fragment ions for every fatty acid moiety. The latter two tandem MS methods preferentially yield sn-2 associated product ions enabling relative sn-isomer quantification. The analytical utility of doubly charged phosphatidylcholine-metal ion complexes is demonstrated for polar lipid extracts, including extracts from diabetes type 1 and type 2 mouse models, and sn-isomer abundances are derived.

Charging and Charge Switching of Unsaturated Lipids and Apolar Compounds Using Paternò-Büchi Reactions.

The ability to control the charge state and ionization efficiency of lipids and hydrocarbons by means of in-source Paternò-Büchi functionalization in nano-electrospray ionization mass spectrometry experiments is investigated. Ultraviolet light irradiation of acetylpyridine filled nano-electrospray emitter tips, containing unsaturated analytes, generates protonated lipid and hydrocarbon ions. Comparison of reaction yields and fragment ion abundances of functionalized unsaturated fatty acids indicate that acetylpyridine Paternò-Büchi functionalization allows to readily detect fatty acids and determine double bond positions, but fragmentation efficiency and reactivity depend on double bond position and varies between different acetylpyridine isomers. Results for methyl oleate and olefins suggest that fragment ion abundances of unsaturated compounds depend on interactions between acetylpyridine and nearby functional groups. Paternò-Büchi functionalization with acetylpyridine was used to detect and assign double bond positions of mono- and polyunsaturated fatty acid, cholesterol ester, triglyceride, and hydrocarbon standards with ion abundances that are up to 631 times higher than abundances of the same compounds prior Paternò-Büchi reaction. To demonstrate the scope and analytical robustness of the newly developed method, free fatty acids in mouse brain as well as male Schistosoma mansoni extracts and hydrocarbons in an olefin mixture are investigated. For this complex set of analytes, charging and charge switching using acetylpyridine Paternò-Büchi functionalization enable double bond position assignment and relative quantification in positive ion mode. Graphical Abstract.

Selective phosphatidylcholine double bond fragmentation and localisation using Paternò-Büchi reactions and ultraviolet photodissociation.

The effect of double bond functionalisation for selective double bond localisation by ultraviolet photodissociation of phosphatidylcholines is investigated. Paternò-Büchi reactions in nanoESI emitter tips enable attachment of acetophenone to double bonds of unsaturated phosphatidylcholines after 100 s of 254 nm light irradiation with about 50-80% reaction yield. Functionalized phosphatidylcholines dissociate upon 266 nm irradiation yielding double bond selective fragment ions in contrast to results for ultraviolet photodissociation of unmodified lipids. Ultraviolet photodissociation of Paternò-Büchi modified lipids results in a selectivity increase of up to 2.2 towards double bond localisation compared collision-induced dissociation experiments. Double bond localisation is also possible with ultraviolet photodissociation when alkali metal ion attachment to Paternò-Büchi modified phosphatidylcholines occurs in contrast to classic collision-induced dissociation experiments. The developed methodology is used to differentiate lipid double bond isomers and applied to phosphatidylcholines from egg yolk to identify 15 phosphatidylcholines. Results from this study demonstrate that locally depositing energy in close vicinity to cleavable bonds via ultraviolet photodissociation can result in increased dissociation selectivity. This method can help to disentangle contributions from different structural elements in complex tandem mass spectra of lipids and aid to the structural characterization of phospholipids in a "top-down" approach.