Lipidomic "deep profiling": an enhanced workflow to reveal new molecular species of signaling lipids.

Current mass spectrometry-based lipidomics aims to comprehensively cover wide ranges of lipid classes. We introduce a strategy to capture phospho-monoester lipids and improve the detection of long-chain base phosphates (LCB-Ps, e.g., sphingosine-1-phosphate). Ten novel LCB-Ps (d18:2, t20:1, odd carbon forms) were discovered and characterized in tissues from human and mouse, as well in D. melanogaster and S. cerevisiae. These findings have immediate relevance for our understanding of sphingosine-1-phosphate biosynthesis, signaling, and degradation.

Learning and discrimination of cuticular hydrocarbons in a social insect.

Social insect cuticular hydrocarbon (CHC) mixtures are among the most complex chemical cues known and are important in nest-mate, caste and species recognition. Despite our growing knowledge of the nature of these cues, we have very little insight into how social insects actually perceive and discriminate among these chemicals. In this study, we use the newly developed technique of differential olfactory conditioning to pure, custom-designed synthetic colony odours to analyse signal discrimination in Argentine ants, Linepithema humile. Our results show that tri-methyl alkanes are more easily learned than single-methyl or straight-chain alkanes. In addition, we reveal that Argentine ants can discriminate between hydrocarbons with different branching patterns and the same chain length, but not always between hydrocarbons with the same branching patterns but different chain length. Our data thus show that biochemical characteristics influence those compounds that ants can discriminate between, and which thus potentially play a role in chemical signalling and nest-mate recognition.

Deciphering the chemical basis of nestmate recognition.

Social insects maintain colony cohesion by recognizing and, if necessary, discriminating against conspecifics that are not part of the colony. This recognition ability is encoded by a complex mixture of cuticular hydrocarbons (CHCs), although it is largely unclear how social insects interpret such a multifaceted signal. CHC profiles often contain several series of homologous hydrocarbons, possessing the same methyl branch position but differing in chain length (e.g., 15-methyl-pentatriacontane, 15-methyl-heptatriacontane, 15-methyl-nonatriacontane). Recent studies have revealed that within species these homologs can occur in correlated concentrations. In such cases, single compounds may convey the same information as the homologs. In this study, we used behavioral bioassays to explore how social insects perceive and interpret different hydrocarbons. We tested the aggressive response of Argentine ants, Linepithema humile, toward nest-mate CHC profiles that were augmented with one of eight synthetic hydrocarbons that differed in branch position, chain length, or both. We found that Argentine ants showed similar levels of aggression toward nest-mate CHC profiles augmented with compounds that had the same branch position but differed in chain length. Conversely, Argentine ants displayed different levels of aggression toward nest-mate CHC profiles augmented with compounds that had different branch positions but the same chain length. While this was true in almost all cases, one CHC we tested elicited a greater aggressive response than its homologs. Interestingly, this was the only compound that did not occur naturally in correlated concentrations with its homologs in CHC profiles. Combined, these data suggest that CHCs of a homologous series elicit the same aggressive response because they convey the same information, rather than Argentine ants being unable to discriminate between different homologs. This study contributes to our understanding of the chemical basis of nestmate recognition by showing that, similar to spoken language, the chemical language of social insects contains "synonyms," chemicals that differ in structure, but not meaning.

The scent of supercolonies: the discovery, synthesis and behavioural verification of ant colony recognition cues.

BACKGROUND: Ants form highly social and cooperative colonies that compete, and often fight, against other such colonies, both intra- and interspecifically. Some invasive ants take sociality to an extreme, forming geographically massive 'supercolonies' across thousands of kilometres. The success of social insects generally, as well as invasive ants in particular, stems from the sophisticated mechanisms used to accurately and precisely distinguish colonymates from non-colonymates. Surprisingly, however, the specific chemicals used for this recognition are virtually undescribed. RESULTS: Here, we report the discovery, chemical synthesis and behavioural testing of the colonymate recognition cues used by the widespread and invasive Argentine ant (Linepithema humile). By synthesizing pure versions of these chemicals in the laboratory and testing them in behavioural assays, we show that these compounds trigger aggression among normally amicable nestmates, but control hydrocarbons do not. Furthermore, behavioural testing across multiple different supercolonies reveals that the reaction to individual compounds varies from colony to colony -- the expected reaction to true colony recognition labels. Our results also show that both quantitative and qualitative changes to cuticular hydrocarbon profiles can trigger aggression among nestmates. These data point the way for the development of new environmentally-friendly control strategies based on the species-specific manipulation of aggressive behaviour. CONCLUSION: Overall, our findings reveal the identity of specific chemicals used for colonymate recognition by the invasive Argentine ants. Although the particular chemicals used by other ants may differ, the patterns reported here are likely to be true for ants generally. As almost all invasive ants display widespread unicoloniality in their introduced ranges, our findings are particularly relevant for our understanding of the biology of these damaging invaders.

Phospholipid imprinted polymers as selective endotoxin scavengers.

Herein we explore phospholipid imprinting as a means to design receptors for complex glycolipids comprising the toxic lipopolysaccharide endotoxin. A series of polymerizable bis-imidazolium and urea hosts were evaluated as cationic and neutral hosts for phosphates and phosphonates, the latter used as mimics of the phospholipid head groups. The bis-imidazolium hosts interacted with the guests in a cooperative manner leading to the presence of tight and well defined 1:2 ternary complexes. Optimized monomer combinations were subsequently used for imprinting of phosphatidic acid as an endotoxin dummy template. Presence of the aforementioned ternary complexes during polymerization resulted in imprinting of lipid dimers - the latter believed to crudely mimic the endotoxin Lipid A motif. The polymers were characterized with respect to template rebinding, binding affinity, capacity and common structural properties, leading to the identification of polymers which were thereafter subjected to an industrially validated endotoxin removal test. Two of the polymers were capable of removing endotoxin down to levels well below the accepted threshold (0.005 EU/mg API) in pharmaceutical production.