Chemical Communication in the Gregarious Psocid Cerastipsocus sivorii (Psocoptera: Psocidae)

The objectives of this study were: (1) to test the existence of an aggregation pheromone in the gregarious psocid Cerastipsocus sivorii; (2) to compare the attractiveness of odors from different aggregations; (3) to test whether nymphs are able to chemically recognize damage-released alarm signals. In a choice experiment conducted in the laboratory, we showed that psocids are able to detect chemical cues from groups of conspecifics. Laboratory experiments also showed that nymphs are capable of chemically recognizing the aggregations where they came from. Finally, in a field experiment, most aggregations dispersed when exposed to the body fluids of a crushed conspecific, but no aggregations dispersed upon exposure to a crushed termite. The implications of these results for the evolution of sociality in psocopterans are discussed.

How the ladybird got its spots : effects of resource limitation on the honesty of aposematic signals

Prey species often possess defences (e.g. toxins) coupled with warning signals (i.e. aposematism). There is growing evidence that the expression of aposematic signals often varies within species and correlates with the strength of chemical defences. This has led to the speculation that such signals may be 'honest', with signal reliability ensured by the costliness of producing or maintaining aposematic traits. We reared larval seven-spot ladybirds (Coccinella septempunctata) on a Low or High aphid diet and measured the effects on warning signal expression (elytral carotenoid pigmentation, conspicuousness, spot size), levels of defensive alkaloids (precoccinelline, coccinelline), and relationships between these traits. High-diet individuals had greater total precoccinelline levels, and elytra carotenoid concentrations at adulthood which was detectable to a typical avian predator. However, larval diet did not significantly affect adult body mass or size, spot size or coccinelline levels. Elytra carotenoid concentrations correlated positively with total precoccinelline levels in both diet groups and sexes. However, the relationship between elytra carotenoid concentrations and total levels of coccinelline depended on sex: in both diet groups, elytra carotenoids and coccinelline levels were positively correlated in females, but negatively correlated in males. Spot size and coccinelline levels correlated positively in Low-diet individuals, but negatively in High-diet individuals. These results point to physiological linkages between components of aposematism, which are modulated by resource (i.e. food) availability and affect the honesty of signals. Developmental diet, but also sex, influenced the relationships between signals and toxin levels. Ladybirds are sexually size dimorphic, and thus in comparison with males, females may be more susceptible to resource limitation and more likely to be honest signallers. © 2012 The Authors. Functional Ecology © 2012 British Ecological Society.

Reaction pathway to the synthesis of anatase via the chemical modification of titanium isopropoxide with acetic acid

Anatase nanoparticles were obtained through a modified sol-gel route from titanium isopropoxide modified with acetic acid in order to control hydrolysis and condensation reactions. The modification of Ti(O(i)Pr)(4) with acetic acid reduces the availability of groups that hydrolyze and condense easily through the formation of a stable complex whose structure was determined to be Ti(OCOCH(3))(O(i)Pr)(2) by means of FTIR and (13)C NMR. The presence of this complex was confirmed with FTIR in the early stages of the process. A doublet in 1542 and 1440 cm(-1) stands for the asymmetric and symmetric stretching vibrations of the carboxylic group coordinated to Ti as a bidentate ligand. The gap of 102 cm(-1) between these signals suggests that acetate acts preferentially as a bidentate rather than as a bridging ligand between two titanium atoms. The use of acetic acid as modifier allows the control of both the degree of condensation and oligomerization of the precursor and leads to the preferential crystallization of TiO(2) in the anatase phase. A possible reaction pathway toward the formation of anatase is proposed on the basis of the intermediate species present in a 1:1 Ti(O(i)Pr)(4):CH(3)COOH molar system in which esterification reactions that introduce H(2)O into the reaction mixture were seen to be negligible. The Rietveld refinement and TEM analysis revealed that the powder is composed of isotropic anatase nanocrystallites.

Physico-chemical parameter correlations in the [RuCl2(CO)(L)(PPh3)2] complexes (L = N-heterocycles)

Fourteen complexes in the series [RuCl2(CO)(L)(PPh3)2] (where L = N-heterocycles) have been prepared and characterized by IR and NMR spectroscopies, and cyclic voltammetry. A good correlation is found between observed and calculated electrochemical potentials; E1/2 vs pKa or (Gp, σm for a series of similar ligands. It is now reported that the carbonyl stretching frequency, νCO, and the 13C and 31P NMR signals do not correlate well with any of the physico-chemical parameters used (E1/2, Taft's and Hammett's parameters). This behaviour is probably due to the characteristics of the Ru(II) species, which does not transmit the steric and electron donor/acceptor properties of the ligands to the carbonyl group, or because the measurements are not able to detect the effect induced by the changes in the ligand L. Indeed, good correlations are obtained when the measurements directly involve the metal centre, as is the case in the E1/2 measurements. Crystals of o[RuCl2(CO)(4-pic)(PPh3)2] are monoclinic, space group P21/n, a = 12.019(2), b = 13.825(3) and c = 22.253(3) . The structure was solved by the Patterson method and was refined by full-matrix least-squares procedure to R = 0.054 and Rw = 0.055, for 2114 reflections with I > 3σ(I). For L = 2-acetylpyridine and 2-methylimidazole, complexes with formulae [RuCl2(CO)(L)(PPh3)] · L and [RuCl2(CO)(L)2 (PPh3)], respectively, were obtained. © 1998 Elsevier Science Ltd. All rights reserved.

Attraction of the sand fly Nyssomyia neivai (Diptera: Psychodidae) to chemical compounds in a wind tunnel

Background: Similar to other hematophagous insects, male and female sand flies must feed on plants to obtain sugar and, subsequently, energy to complete their life cycles. A large number of compounds emitted by plants may act as volatile signals to these insects. Primary alcohols have been detected in some plants, but in small amounts. In a previous report, the attractiveness of saturated primary alcohols with 7 to 9 carbons was evaluated for Lutzomyia longipalpis, the vector of American visceral leishmaniasis, with positive results.Methods: In the present study, a wide range of primary alcohols, 3 to 10 carbons, were tested to investigate their attractiveness to another sand fly species, Nyssomyia neivai, a putative vector of American cutaneous leishmaniasis. The mixture of compounds that induced the best sand fly response was also evaluated.Results: Of the eight compounds evaluated, hexanol and octanol elicited the best attractive responses for sand fly females.Conclusion: Phytochemicals may be an interesting source of search for new sand fly attractants.

Mixed colonies of two species of congeneric stingless bees (Hymenoptera: Apinae, Meliponini) display environmentally-acquired and endogenously-produced recognition signals

Nestmate recognition is fundamental for the maintenance of social organization in insect nests. It is becoming well recognized that cuticle hydrocarbons mediate the recognition process, although the origin of recognition cues in stingless bees remains poorly explored. The present study investigates the effects of endogenously-produced and environmentally-acquired components in cuticular hydrocarbons in stingless bees. The tests are conducted using colonies of Plebeia droryana Friese and Plebeia remota Holmberg. Recognition tests are performed with four different groups: conspecific nestmates, conspecific non-nestmates, heterospecifics and conspecific, genetically-related individuals that emerge in a heterospecific nest. This last group is produced by introducing brood cells of P. droryana into a P. remota colony, and the resulting adult bees are tested for acceptance 10 days after emergence. For all groups, 15 individuals are sampled for chemical analysis. The results show the acceptance of all conspecific nestmates, and the rejection of almost every conspecific non-nestmate and every heterospecific bee. Genetically-related individuals emerging from heterospecific nests present intermediate rejection (66.7% rejection). Chemical analysis shows that P. droryana individuals emerging in a P. remota nest have small amounts of alkene and diene isomers found in P. remota cuticle that are not found in workers from the natal nest. The data clearly show that the majority of the compounds present in P. droryana cuticle are endogenously produced, although a few unsaturated compounds are acquired from the environment, increasing the chemical differences and, consequently, the rejection percentages.

Analysis of ion channel stochastic signals for biosensing

In biological world, life of cells is guaranteed by their ability to sense and to respond to a large variety of internal and external stimuli. In particular, excitable cells, like muscle or nerve cells, produce quick depolarizations in response to electrical, mechanical or chemical stimuli: this means that they can change their internal potential through a quick exchange of ions between cytoplasm and the external environment. This can be done thanks to the presence of ion channels, proteins that span the lipid bilayer and act like switches, allowing ionic current to flow opening and shutting in a stochastic way. For a particular class of ion channels, ligand-gated ion channels, the gating processes is strongly influenced by binding between receptive sites located on the channel surface and specific target molecules. These channels, inserted in biomimetic membranes and in presence of a proper electronic system for acquiring and elaborating the electrical signal, could give us the possibility of detecting and quantifying concentrations of specific molecules in complex mixtures from ionic currents across the membrane; in this thesis work, this possibility is investigated. In particular, it reports a description of experiments focused on the creation and the characterization of artificial lipid membranes, the reconstitution of ion channels and the analysis of their electrical and statistical properties. Moreover, after a chapter about the basis of the modelling of the kinetic behaviour of ligand gated ion channels, a possible approach for the estimation of the target molecule concentration, based on a statistical analysis of the ion channel open probability, is proposed. The fifth chapter contains a description of the kinetic characterisation of a ligand gated ion channel: the homomeric α2 isoform of the glycine receptor. It involved both experimental acquisitions and signal analysis. The last chapter represents the conclusions of this thesis, with some remark on the effective performance that may be achieved using ligand gated ion channels as sensing elements.

Complex chemical dynamics through engineering-like methods

Most of the problems in modern structural design can be described with a set of equation; solutions of these mathematical models can lead the engineer and designer to get info during the design stage. The same holds true for physical-chemistry; this branch of chemistry uses mathematics and physics in order to explain real chemical phenomena. In this work two extremely different chemical processes will be studied; the dynamic of an artificial molecular motor and the generation and propagation of the nervous signals between excitable cells and tissues like neurons and axons. These two processes, in spite of their chemical and physical differences, can be both described successfully by partial differential equations, that are, respectively the Fokker-Planck equation and the Hodgkin and Huxley model. With the aid of an advanced engineering software these two processes have been modeled and simulated in order to extract a lot of physical informations about them and to predict a lot of properties that can be, in future, extremely useful during the design stage of both molecular motors and devices which rely their actions on the nervous communications between active fibres.

Characterization of optical transduction-based molecular systems and nanoparticles for the development of chemical sensors

With the increasing importance that nanotechnologies have in everyday life, it is not difficult to realize that also a single molecule, if properly designed, can be a device able to perform useful functions: such a chemical species is called chemosensor, that is a molecule of abiotic origin that signals the presence of matter or energy. Signal transduction is the mechanism by which an interaction of a sensor with an analyte yields a measurable form of energy. When dealing with the design of a chemosensor, we need to take into account a “communication requirement” between its three component: the receptor unit, responsible for the selective analyte binding, the spacer, which controls the geometry of the system and modulates the electronic interaction between the receptor and the signalling unit, whose physico-chemical properties change upon complexation. A luminescent chemosensor communicates a variation of the physico-chemical properties of the receptor unit with a luminescence output signal. This thesis work consists in the characterization of new molecular and nanoparticle-based system which can be used as sensitive materials for the construction of new optical transduction devices able to provide information about the concentration of analytes in solution. In particular two direction were taken. The first is to continue in the development of new chemosensors, that is the first step for the construction of reliable and efficient devices, and in particular the work will be focused on chemosensors for metal ions for biomedical and environmental applications. The second is to study more efficient and complex organized systems, such as derivatized silica nanoparticles. These system can potentially have higher sensitivity than molecular systems, and present many advantages, like the possibility to be ratiometric, higher Stokes shifts and lower signal-to-noise ratio.

Mechano-Chemical Aspects of Organ Formation in Arabidopsis thaliana: The Relationship between Auxin and Pectin

How instructive signals are translated into robust and predictable changes in growth is a central question in developmental biology. Recently, much interest has centered on the feedback between chemical instructions and mechanical changes for pattern formation in development. In plants, the patterned arrangement of aerial organs, or phyllotaxis, is instructed by the phytohormone auxin; however, it still remains to be seen how auxin is linked, at the apex, to the biochemical and mechanical changes of the cell wall required for organ outgrowth. Here, using Atomic Force Microscopy, we demonstrate that auxin reduces tissue rigidity prior to organ outgrowth in the shoot apex of Arabidopsis thaliana, and that the de-methyl-esterification of pectin is necessary for this reduction. We further show that development of functional organs produced by pectin-mediated ectopic wall softening requires auxin signaling. Lastly, we demonstrate that coordinated localization of the auxin transport protein, PIN1, is disrupted in a naked-apex produced by increasing cell wall rigidity. Our data indicates that a feedback loop between the instructive chemical auxin and cell wall mechanics may play a crucial role in phyllotactic patterning.

Seasonally resolved chemical records of six ice cores from the Dronning Maud Land, Antarctica

The ammonium, calcium, and sodium concentrations from three intermediate depth ice cores drilled in the area of Dronning Maud Land, East Antarctica, have been investigated. Since all measurements were performed by a high-resolution Continuous Flow Analysis system, for the first time seasonal signals of chemical trace species could be obtained from the interior of central Antarctica over a period of approximately 2 millennia. Although the elevation as well as the accumulation rate differ between the drilling sites, similar values were obtained by comparing mean concentrations spanning the last 900 years. However, a distinct lack of intersite correlation was found on decadal timescales. Despite a noticeable accumulation change, apparent in one core, no significant concentration change of all three species has occurred. All the measured ions show clear seasonal signals over the whole records. While the sea-salt-related component sodium peaks simultaneously with calcium, the maximum ammonium concentration occurs in the snow with a time lag of 2 months after the sea-salt peak. More than 60% of the calcium concentration can be attributed to an ocean source. Elevated sodium concentrations were found within this millennium compared to mean values of the whole records, but the spatially varying shape of the increase suggests that a possible climatic signal is biased by local deposition effects.

Mean chemical characteristics and volcano signatures of ice cores from Belukha, the Everest and three Svalbard sites

Ice cores from outside the Greenland and Antarctic ice sheets are difficult to date because of seasonal melting and multiple sources (terrestrial, marine, biogenic and anthropogenic) of sulfates deposited onto the ice. Here we present a method of volcanic sulfate extraction that relies on fitting sulfate profiles to other ion species measured along the cores in moving windows in log space. We verify the method with a well dated section of the Belukha ice core from central Eurasia. There are excellent matches to volcanoes in the preindustrial, and clear extraction of volcanic peaks in the post-1940 period when a simple method based on calcium as a proxy for terrestrial sulfate fails due to anthropogenic sulfate deposition. We then attempt to use the same statistical scheme to locate volcanic sulfate horizons within three ice cores from Svalbard and a core from Mount Everest. Volcanic sulfate is <5% of the sulfate budget in every core, and differences in eruption signals extracted reflect the large differences in environment between western, northern and central regions of Svalbard. The Lomonosovfonna and Vestfonna cores span about the last 1000 years, with good extraction of volcanic signals, while Holtedahlfonna which extends to about AD1700 appears to lack a clear record. The Mount Everest core allows clean volcanic signal extraction and the core extends back to about AD700, slightly older than a previous flow model has suggested. The method may thus be used to extract historical volcanic records from a more diverse geographical range than hitherto.

Abundance patterns and isotopic signals of morphotypes of Globigerinoides ruber

The chemical composition of shells of the planktonic foraminifer Globigerinoides ruber (white) is frequently used to determine past sea surface conditions. Recently, it has been shown that arbitrarily defined morphotypes within this species exhibit different chemical and isotopic signatures. Here, we investigate the occurrence through time and in space of morphological types of G. ruber (white) in late Quaternary and Holocene sediments of the central and the eastern Mediterranean Sea. In 115 samples representing two distinct time intervals (MIS 1-2 and MIS 9-12) at ODP Site 964 and the piston core GeoTü-SL96, we have defined three morphological types within this species and determined their relative abundances and stable isotopic composition. A quantitative analysis of morphological variation within G. ruber (white) in four samples revealed that the subjectively defined morphotypes occupy separate segments of a continuous and homogenous morphospace. We further show that the abundance of the morphotypes changes significantly between glacials and interglacials and that the three morphotypes of G. ruber show significant offsets in their stable isotopic composition. These offsets are consistent within glacial and interglacial stages but their sign is systematically reversed between the two Sites. Since the isotopic shifts among the three G. ruber morphotypes are systematic and often exceed 1per mil, their understanding is essential for the interpretation of all G. ruber-based proxy records for the paleoceanographic development of the Mediterranean during the late Quaternary.