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PubMed2001

Species diversity of nematode communities in the digestive tract of domestic ruminants: multivariate versus univariate estimations.

The evaluation of species diversity can be performed using species richness (number of species), diversity (number and relative proportions of species) or evenness (equitability of the proportion of each species). A large number of indices related to diversity or evenness is available but their mathematical properties remain unexplained, and hence their use is somewhat unreliable. We intended to present an array of well defined methods, based on discriminant analysis, to evaluate diversity in helminth communities of ruminants. The database used concerned seven cattle farms and seven sheep farms located in temperate areas, from which at least three necropsies were undertaken in autumn. The hosts were chosen because they had experienced nearly a complete grazing period and no anthelmintic treatment was performed for a minimum of 2 months before the necropsies were undertaken, so that the helminth communities could be considered as representative of each farm at one specific moment. We used discriminant analyses to evaluate diversity, based either on proportions of species, or on proportions of species arranged in decreasing order, or on a set of six indices of diversity selected from the most commonly used. We showed that actual proportions were the most efficient in cattle but not in lambs, and that discriminant analyses based on six indices of diversity or based on actual proportions of species ranked in decreasing order yielded very similar results in both host communities. We rejected the use of one single index for evaluating diversity in all cases and proposed the following procedure: actual proportions of species provide information on interactions between species and, when there is limited or no interaction, a combination of diversity indices or single indices could be used for estimating diversity. When interactions between species have to be taken into account, the best information will be obtained either from species proportions arranged in decreasing order or a combination of biodiversity indices.

Animal Husbandry↗

PubMed2003

Sympatry and allopatry in two desert ant sister species: how do Cataglyphis bicolor and C. savignyi coexist?

Two extremely morphologically similar sister species of desert ants, Cataglyphis bicolor and C. savignyi, exhibit broadly overlapping distributional ranges within Tunisia. In order to analyse the microhabitats of C. bicolor and C. savignyi within the sympatric and allopatric areas of both ant species, the plant species located at 113 different nest sites of the two ant species were determined. In the sympatric area, the two species exhibit a clear-cut nest site segregation. This is not the case in the allopatric areas. Hence the two species differentiate their microhabitat only when they are sympatric. The plant species associated mainly with the nest sites of C. bicolor indicate that this species prefers a type of vegetation that needs irrigation. This is in contrast to the nest sites of C. savignyi, which are usually found around plants that characterize typical dry steppe areas. As the ants' foraging paths recorded in the sympatric area reveal, C. bicolor performs significantly shorter foraging runs with respect to both length and time, and covers a much smaller foraging range than C. savignyi does. This result reflects the fact that the microhabitat occupied by the colonies of C. bicolor is richer in food abundance. When direct interspecific interactions were investigated by placing a bait midway between two heterospecific nests, C. bicolor foragers dominated over those of C. savignyi. The same dominance of C. bicolor over C. savignyi occurred in laboratory experiments. These results suggest that the dominant species drives the subordinate one out of the high quality microhabitats, and that the subordinate species is forced to survive in the less lucrative habitats. In conclusion, coexistence seems to be maintained by the asymmetric competitive relationship between the two species and the fact that the subordinate species has the ability to endure in the less favourable microhabitat.

Animals↗

PubMed2003

Plant species persistence and turnover on small Bahamian islands.

I conducted surveys of the plant species occupying 136 small islands in the Exuma Cays and 58 small islands near Andros, Bahamas. Most species occurred on relatively few islands, and most islands contained relatively few species. Identities of the most common species differed between the two archipelagos. Comparisons with earlier surveys revealed species extinctions and immigrations. Turnover was relatively low on both a per island and a per species basis on both archipelagos, although significant spatial variation in turnover rates between archipelagos was found. Most islands experienced no turnover; islands on which turnover did occur were larger and had higher species richness. Likewise, most species did not turnover, although much variation existed in turnover rates among those that did. Experimental introductions of two species to very small islands naturally devoid of vegetation revealed that these islands could support plant life. One species survived on eight of ten islands for >9 years, including the effects of a moderate (class 2) hurricane. This hurricane caused substantial damage and loss of plant biomass, but resulted in no species extinctions on 30 small islands. Data for the small islands in this region, now spanning almost a decade, reveal that most populations are persistent over periods of years to decades, rarely going extinct or immigrating. Even moderate hurricanes seem to have little impact on species compositions.

Bahamas↗

PubMed2003

The relationship between species richness and productivity in metazoan parasite communities.

Biodiversity is not distributed homogeneously in space, and it often covaries with productivity. The shape of the relationship between diversity and productivity, however, varies from a monotonic linear increase to a hump-shaped curve with maximum diversity values corresponding to intermediate productivity. The system studied and the spatial scale of study may affect this relationship. Parasite communities are useful models to test the productivity-diversity relationship because they consist of species belonging to a restricted set of higher taxa common to all host species. Using total parasite biovolume per host individual as a surrogate for community productivity, we tested the relationship between productivity and species richness among assemblages of metazoan parasites in 131 vertebrate host species. Across all host species, we found a linear relationship between total parasite biovolume and parasite species richness, with no trace of a hump-shaped curve. This result remained after corrections for the potential confounding effect of the number of host individuals examined per host species, host body mass, and phylogenetic relationships among host species. Although weaker, the linear relationship remained when the analyses were performed within the five vertebrate groups (fish, amphibians, reptiles, mammals and birds) instead of across all host species. These findings agree with the classic isolationist-interactive continuum of parasite communities that has become widely accepted in parasite ecology. They also suggest that parasite communities are not saturated with species, and that the addition of new species will result in increased total parasite biovolume per host. If the number of parasite species exploiting a host population is not regulated by processes arising from within the parasite community, external factors such as host characteristics may be the main determinants of parasite diversity.

Animals↗

PubMed2003

Species-specific patterns of hydraulic lift in co-occurring adult trees and grasses in a sandhill community.

Plants can significantly affect ecosystem water balance by hydraulic redistribution (HR) from dry to wet soil layers via roots (also called hydraulic lift, HL, when the redistribution is from deep to shallow soil). However, the information on how co-occurring species in natural habitats differ in HL ability is insufficient. In a field study, we compared HL ability of four tree species (including three congeneric oak species) and two C4 bunch grass species that co-occur in subxeric habitats of fall-line sandhills in southeastern USA. Soil water potentials (psi(s)) were recorded hourly for 3 years both in large chambers that isolated roots for each species and outside the chambers. Outside of root chambers, soil drying occurred periodically in the top 25 cm and corresponded with lack of precipitation during the summer growing season. Soil moisture was continuously available at a 1 m depth. HL activity was observed in three of the tree species, with greater frequency for Pinus palustris than for Quercus laevis and Q. incana. The fourth tree species Q. margaretta did not exhibit HL activity even though it experienced a similar psi(s) gradient. For the C4 bunch grasses, Aristida stricta exhibited a small amount of HL activity, but Schizachyrium scoparium did not. The capacity for HL activity may be linked to the species ecological distribution. The four species that exhibited HL activity in this subxeric habitat are also dominant in adjacent xeric sandhill habitats, whereas the species that did not exhibit HL are scarcely found in the xeric areas. This is consistent with other studies that found greater fine root survival in dry soil for the four xeric species exhibiting HL activity. The differential ability of these species to redistribute water from the deep soil to the rapidly drying shallow soil likely has a strong effect on the water balance of sandhill plant communities, and is likely linked to their differential distribution across edaphic gradients.

Ecosystem↗

PubMed2004

Scale-dependent relationships between the spatial distribution of a limiting resource and plant species diversity in an African grassland ecosystem.

One cornerstone of ecological theory is that nutrient availability limits the number of species that can inhabit a community. However, the relationship between the spatial distribution of limiting nutrients and species diversity is not well established because there is no single scale appropriate for measuring variation in resource distribution. Instead, the correct scale for analyzing resource variation depends on the range of species sizes within the community. To quantify the relationship between nutrient distribution and plant species diversity, we measured NO(3)(-) distribution and plant species diversity in 16 paired, modified Whittaker grassland plots in Serengeti National Park, Tanzania. Semivariograms were used to quantify the spatial structure of NO(3)(-) from scales of 0.4-26 m. Plant species diversity (Shannon-Weiner diversity index; H ') was quantified in 1-m(2) plots, while plant species richness was measured at multiple spatial scales between 1 and 1000 m(2). Small-scale variation in NO(3)(-) (<0.4 m) was positively correlated with 1-m(2) H ', while 1000-m(2) species richness was a log-normal function of average NO(3)(-) patch size. Nine of the 16 grassland plots had a fractal (self-similar across scales) NO(3)(-) spatial distribution; of the nine fractal plots, five were adjacent to plots that had a non-fractal distribution of NO(3)(-). This finding offered the unique opportunity to test predictions of Ritchie and Olff (1999): when the spatial distribution of limiting resources is fractal, communities should display a left-skewed log-size distribution and a log-normal relationship between net primary production and species richness. These predictions were supported by comparisons of plant size distributions and biomass-richness relationships in paired plots, one with a fractal and one with a non-fractal distribution of NO(3)(-). In addition, fractal plots had greater large-scale richness than paired non-fractal plots (1,0-1000 m(2)), but neither species diversity ( H') nor richness was significantly different at small scales (1 m(2)). This result is most likely explained by differences in the scale of resource variation among plots: fractal and non-fractal plots had equivalent NO(3)(-) variation at small scales but differed in NO(3)(-) variation at large scales (as measured by the fractal dimension). We propose that small-scale variation in NO(3)(-) is largely due to the direct effects of plants on soil, while patterns of species richness at large scales is controlled by the patch size and fractal dimension of NO(3)(-) in the landscape. This study provides an important empirical step in understanding the relationship between the spatial distribution of resources and patterns of species diversity across multiple spatial scales.

Africa↗

PubMed2004

Assessing determinants of community biomass composition in two-species plant competition studies.

A method is proposed for assessing the relative importance of species identity, neighbour species influence and environment as determinants of change in community biomass composition in two-species short-term competition experiments. The method is based on modelling the differences in relative growth rates (RGR) of species (hence called the RGRD method). Using a multiple regression approach it quantifies the effects of initial species' abundance, species identity and environment on RGRD and hence on change in community biomass composition. The RGRD approach is relatively simple to use and deals readily with statistical difficulties associated with correlated responses between species from the same stand. It can be easily adapted to analyse sequential harvest data. An example based on data from two-species mixtures of the annual species Stellaria media and Poa annua is used to illustrate the method. The main determinant of change in community biomass composition was species identity, reflected in the difference in growth rates between the species. Change in community composition was not, in general, significantly affected by the influence of neighbours or fertiliser level. The unimportance of the influence of neighbours in affecting the composition of these communities contrasts with the strong role of intra- and interspecific competition in determining the size of individuals of both species (Connolly et al. in Oecologia 82:513-526, 1990).

Biomass↗

PubMed2005

An experimental assessment of biodiversity and species turnover in terrestrial vs canopy leaf litter.

Forest canopies support diverse assemblages of free-living mites. Recent studies suggest mite species complementarity between canopy and terrestrial soils is as high as 80-90%. However, confounding variation in habitat quality and resource patchiness between ground and canopy has not been controlled in previous comparative studies. We used experimental litter bags with standardized microhabitat structure and resource quality to contrast the colonization dynamics of 129 mite species utilizing needle accumulations on the ground vs in the canopy of Abies amabilis trees in a temperate montane forest in Canada. Mite abundance and species richness per litter bag were five to eight times greater on the ground than in the canopy, and composition differed markedly at family-, genus-, and species-level. Seventy-seven species (57%) were restricted to either ground or canopy litter bags, but many of these species were rare (n<5 individuals). Of 49 'common' species, 30.6% were entirely restricted to one habitat, which is considerably lower than most published estimates. In total, 87.5% of canopy specialists had rare vagrants on the ground, whereas only 51.9% of ground specialists had rare vagrants in the canopy. Canonical correspondence analysis of mite community structure showed high species turnover through time and a high degree of specialization for early-, mid-, and late-successional stages of litter decomposition, in both ground and canopy mites. In addition, distinct assemblages of ground-specialist mites dominated each elevation (800, 1000, and 1200 m), whereas few canopy-specialist mites had defined elevational preferences. This suggests that canopy mites may have greater tolerance for wide variation in environmental conditions than soil mites. The degree of species turnover between adjacent mountains also differed markedly, with 46.5% turnover of ground species, but 63.4% turnover of canopy species between the two montane areas. While ground and canopy assemblages are similar in total biodiversity, it appears that local mite richness (alpha diversity) is higher on the ground, whereas species turnover between sites (beta diversity) is higher in the canopy.

Acari↗

PubMed1989

Enhancement of monocyte-mediated tumoricidal activity by multiple interferon-alpha species.

Twenty-one interferon (IFN)-alpha species were evaluated for their ability to enhance monocyte-mediated lysis of the human melanoma cell line, A375. A wide variation in the potency of the different species in inducing monocyte tumoricidal action was observed. In addition, many IFN-alpha species were found to induce as much or more tumoricidal activity than recombinant IFN-gamma. The degree of monocyte activation induced by the various species generally correlated with their antiviral activity. Those which were better at inducing monocyte tumoricidal action also gave the highest antiviral specific activities. Studies were conducted to determine if the relative potency of the IFN-alpha species could be changed by altering certain parameters of the cytotoxicity assay. All IFN-alpha species tested required only 30 min in culture with the monocytes to induce activation. There were no changes in the relative potency of the species when cytotoxicity was measured at different times, nor when the effector:target ratio was altered. Competitive binding studies revealed that those IFN-alpha species which induced little activity in the bioassays were also generally poor in their ability to bind the IFN-alpha receptor on human monocytes, while the IFN-alpha species which induced relatively more activity in the bioassays were better able to bind to the IFN-alpha receptor. These data indicate that there are dramatic differences in activities among the IFN-alpha species which may, in part, be explained by different binding affinities. In addition, the differences observed among the IFN-alpha species demonstrate the need for further functional and structural characterization of the individual IFN-alpha species which could lead to a more effective clinical application of IFN-alpha.

Antiviral Agents↗

PubMed1991

A theoretical analysis of radiation interception in a two-species plant canopy.

Classical radiation interception laws for monospecific canopies cannot be used directly for bispecific canopies. They are always based on the gap frequency concept (i.e., the probability of no interception), which does not provide any information about the sharing of intercepted radiation between species. A theoretical analysis is reported that relates the radiation interception probabilities to the geometrical structure of the crop (i.e., the leaf area density and the leaf angle distribution of each component) and the foliage dispersion. The leaf dispersion globally describes the spatial relations between the leaf elements; it may be regular if the leaves avoid mutual shading, random, or clumped if they tend to overlap. For such two-species canopies, the leaf dispersions within each component (WSLD: within-species leaf dispersion) and between two species (BSLD: between-species leaf dispersion) are distinguished. Using bivariate multinomial distributions, general expressions for the gap frequency and the interception probabilities of a homogeneous vegetation layer were set as exponential functions of the foliage thickness, taking into account a number of dispersion parameters as small as possible. First, one WSLD for each species describes the rate of foliage overlap between the leaves of this species; it is quite similar to the leaf dispersion of single-species canopies. Second, the rate of foliage overlap between species is characterized by one BSLD. As in monospecific canopies, this parameter is positive, zero, or negative, respectively, for regular, random, or clumped BSLD. Third, another BSLD parameter has to be used if the foliage overlap between species is more than random (i.e., in the case of clumped BSLD); the latter shows the direction of overlap between species and may be taken as the probability of finding a leaf element of the first species in the case of marked overlapping. Suggestions for estimating the leaf dispersion parameters and possible uses of such relations are also discussed.

Agriculture↗

PubMedDate not supplied

Differentiation of Acinetobacter calcoaceticus sensu stricto from related Acinetobacter species by electrophoretic polymorphism of malate dehydrogenase, glutamate dehydrogenase and catalase.

Acinetobacter baumannii, unnamed Acinetobacter species 3 (studied by P.J.M. Bouvet and P.A.D. Grimont) and unnamed DNA group 13 (studied by I. Tjernberg and J. Ursing) are the most prevalent Acinetobacter species in hospitals. Using the identification scheme of Bouvet and Grimont, it is sometimes difficult to differentiate these species from A. calcoaceticus sensu stricto, a species of the natural environment that has seldom been found associated with human infection. Genetically identified Acinetobacter isolates belonging to A. calcoaceticus sensu stricto (n = 12), A. baumannii (n = 22), Acinetobacter species 3 (n = 15) and DNA group 13 of Tjernberg and Ursing (n = 26), Acinetobacter species 10 (n = 2), Acinetobacter species 11 (n = 2) and 3 strains ungrouped by DNA-DNA hybridization were investigated for electrophoretic separations of L-malate dehydrogenase (MDH), glutamate dehydrogenase (GDH) and catalase (CAT). All A. calcoaceticus sensu stricto isolates were easily differentiated from those of other species investigated by their high MDH values (relative mobility (Rf) = 78), their low GDH values (Rf range: 24-28) and CAT values (Rf range: 34-42). Acinetobacter species 3 was differentiated from A. baumannii and DNA group 13 of Tjernberg and Ursing by high CAT values. A. baumannii could not be differentiated from Tjernberg and Ursing DNA group 13. Acinetobacter species 10 was clearly differentiated from Acinetobacter species 11. Once an Acinetobacter is phenotypically identified with the four closely related species investigated here, electrophoretic analysis of MDH, GDH and CAT might be a useful complement to the identification scheme of Bouvet and Grimont for accurately identifying A. calcoaceticus sensu stricto.

Acinetobacter↗

PubMed2005

Cross-taxonomic potential and spatial transferability of an umbrella species index.

Validation that conservation of certain species effectively protects a high proportion of co-occurring species is rare. Our previous work has suggested that an umbrella index based on geographic distribution and life history characteristics would maximize the proportion of conspecifics protected per unit area conserved. Using bird and butterfly data from three mountain ranges in the Great Basin, we examined whether umbrella species also would confer protection to species in different taxonomic groups. Further, we addressed the spatial transferability of umbrella species by considering whether species identified as umbrellas in one mountain range would be effective umbrellas in other mountain ranges. Overall, equal proportions of species would be protected using either cross-taxonomic umbrella species or same-taxon umbrella species. Our data suggested that in a given mountain range, umbrella species identified using data from the same mountain range versus a different mountain range would be equally effective. The ability of one set of umbrella species to confer protection to co-occurring species, however, may vary among taxonomic groups and geographic regions.

Animals↗

PubMed1996

Quantifying vesicle/mixed micelle partitioning of phosphatidylcholine in model bile by using radiolabeled phosphatidylcholine species.

Phospholipid in vesicles and mixed micelles of (model) bile has been traced or quantitated (or both) by adding radioactively labeled phosphatidylcholine species. The question is whether these labeled species mix homogeneously with the phosphatidylcholine species mixture present, such that the label distribution reflects the already established mass partitioning of species. In this study, model bile containing egg yolk phosphatidylcholine was incubated with radioactive phosphatidylcholine species. Vesicle and mixed micelle fractions were separated by gel filtration. Radiochemical analysis of the species distribution confirmed chemical analysis: 1,2-di(14C)palmitoyl-phosphatidylcholine was enriched in the vesicles, the 1-palmitoyl-2-(14C)oleoyl species evenly distributed, and the 1-palmitoyl-2-(14C)linoleoyl species more expressed in mixed micelles. This indicates that the distribution of an added radioactive phosphatidylcholine species represents the vesicle/mixed micelle distribution of that particular phosphatidylcholine species. Consequently, the label distribution of a particular added radioactive phosphatidylcholine species can be used to calculate the vesicle/mixed micelle partitioning of total phosphatidylcholine only after it has been established that the radioactive species reaches the same partitioning as total phosphatidylcholine.

Bile↗

PubMed1999

Species-specific responses to metals in organically enriched river water, with emphasis on effects of humic acids.

Invertebrate communities in polluted rivers are often exposed to a wide variety of compounds. Due to complex interactions, 'pollution tolerant' species are not necessarily the most tolerant species to toxicants tested under standard laboratory conditions. It was hypothesized that the distribution of species in polluted rivers is not only dependent on the tolerance of species to toxicants, but also on species-specific capacities to modify or compensate for negative effects of toxicants. To test this hypothesis, species-specific responses to metals in organically enriched river water were studied under controlled conditions. The zebra mussel Dreissena polymorpha and the midge Chironomus riparius were exposed to metal-polluted water from the River Dommel. Additionally, the (interactive) effects of metals and humic acids (HA) on both species were evaluated. In spite of a lower tolerance of Chironomus riparius to metals in laboratory studies, the midge was the most tolerant of the two test species to metal-polluted site water. The results indicated that the sensitivities of the two test species determined in laboratory tests were inversely related to their sensitivities to polluted river water. In accordance with these results, midge larvae were protected from copper (Cu) toxicity by HA, while metal toxicity was not reduced (Cu) or even amplified (cadmium) by HA for the zebra mussel. Thus, the presence of (naturally occurring) HA in site water may partly account for discrepancies between responses of species to bioassays and toxicity tests. It is suggested that these differences in responses to metals in site water are strongly influenced by species-specific preferences for organic compounds (like HA). It is concluded that the response to organic compounds present in site water largely determines whether a species is classified as 'pollution tolerant' or 'pollution sensitive'.

Journal Article↗

PubMed2001

Determination of diffusion coefficients of electroactive species in time-of-flight experiments using a microdispenser and microelectrodes.

Two novel methods for the determination of diffusion coefficients of redox species combining the special properties of microdispensing devices and microelectrodes are presented. Both are based on the local application of tiny volumes of the redox-active species by means of a dispenser nozzle at a defined distance from the surface of a microelectrode. The microelectrode, which is inserted through the bottom into an electrochemical cell, is held at a constant potential sufficient to oxidize or reduce the electro-active species under diffusional control. The dispenser, which is filled with the electro-active species, can be positioned by means of micrometer screws over the microelectrode. After dispensing a defined number of droplets near the microelectrode surface, the current through the microelectrode is recorded, usually yielding a peak-shaped curve having a defined time delay between the shooting of the droplets and the maximum current. The time that is necessary to attain maximum current, together with the known distance between two dispensing points, can be used to determine the diffusion coefficient of the electroactive species without knowledge of any system parameters, such as concentration of the redox species, diameter of the electroactive surface or number of transferred electrons. A similar method for the determination of diffusion coefficient of redox species involves a second redox species for calibration purposes. A mixture of both species is shot close to the microelectrode surface. Due to the different formal potentials of the redox species that are used, they can be distinguished in sequential experiments by variation of the potentials that are applied to the microelectrode, and it is thus possible to determine the individual transit times of the redox species independently. The difference in the transit times, together with the known diffusion coefficient of one of the redox species, can be used to calculate the unknown diffusion coefficient of the second one.

Journal Article↗

PubMed1997

Characterization of the interaction of Ca2+ with hydroxy and non-hydroxy fatty acid species of cerebroside sulfate by Fourier transform infrared spectroscopy and molecular modeling.

Ca2+-mediated interactions between the carbohydrate groups of glycolipids, including that of cerebroside sulfate (galactosylceramide I3-sulfate), have recently been implicated as a basis of cell recognition and adhesion. Hydroxylation of the fatty acid of this lipid has an effect on these interactions. Therefore, FT-IR spectroscopy was used to study the interaction of Ca2+ with semisynthetic hydroxy (HFA) and non-hydroxy fatty acid (NFA) species of cerebroside sulfate (CBS). Ca2+ caused partial dehydration of the sulfate group and reduced hydrogen bonding of the sugar hydroxyls of both species. The amide I and II bands of the lipids in the absence of Ca2+ (NH4+ salt forms) suggested that the N-H of the HFA species is involved in a bent intramolecular hydrogen bond, probably with the fatty acid hydroxyl group and the glycosidic oxygen, while that of the NFA species is involved in a linear intermolecular hydrogen bond with the C=O and/or other oxygens. Ca2+ caused a rearrangement of the hydrogen-bonding network in the interfacial region of the HFA species involving the amide group. The results suggested increased hydrogen bonding of the C=O and a shift in hydrogen bonding of the N-H of the Ca2+ salt form of the HFA species from a bent intramolecular hydrogen bond to a linear intermolecular hydrogen bond, probably with the C=O of neighboring molecules, similar to the NFA species. The involvement of the fatty acid alpha-hydroxyl group in the rearranged network was indicated by a reduction in mobility of the alpha-CH group of the HFA species, in contrast to that of the NFA species. Participation of the alpha-OH group in hydrogen-bonding networks in the interfacial region of both the NH4+ and Ca2+ salt forms caused a significant increase in the interchain packing, as evident from correlation field splitting of the HFA-CBS methylene scissoring mode, while this did not occur for the NFA species. The absence of intramolecular hydrogen bonding of the N-H with the glycosidic oxygen for both salt forms of the NFA species and for the Ca2+ salt form of the HFA species may destabilize the "bent shovel", bilayer planar conformation of the sugar and cause it to be in the extended, bilayer perpendicular conformation. Calculations of the three-dimensional interaction energy of Ca2+ with CBS showed strong binding around the sulfate and the surface of galactose facing the bilayer in the bent shovel conformation. Ca2+ binding at this surface would disrupt intra- and intermolecular hydrogen-bonding interactions of the head group, thus accounting for its effect in inducing a transition to the extended conformation.

Binding Sites↗

PubMed2000

Solution equilibria of tetrakis(ethyisocyanide)platinum(II) with tetracyanoplatinate(II): equilibria and thermodynamics of the formation of di-, tri-, and tetraplatinum species.

In aqueous solution, the tetrakis(ethylisocyanide)platinum(II) cation, Pt(CNC2H5)4(2+), reacts with tetracyanoplatinate(II), Pt(CN)4(2-), to form four multinuclear species. These species are the diplatinum(II) compound [Pt(CNC2H5)4(2+)][Pt(CN)4(2-)], two triplatinum compounds, [Pt(CNC2H5)4(2+)]2[Pt(CN)4(2-)]2+ and [Pt(CNC2H5)4(2+)][Pt(CN)4(2-)]2(2-), and the tetraplatinum species [Pt(CNC2H5)4(2+)]2[Pt(CN)4(2-)]2. The interactions leading to the stability of these species are not simply ionic. The interactions result in major differences in the electronic absorption spectra, and the oligomers are not disrupted by the addition of other salts. The formation constant for each of the oligomers was determined at several temperatures, and the enthalpies and entropies of formation were measured. Species with even numbers of platinum ions have more negative stepwise enthalpies of formation than do the species with odd numbers of platinum ions. Entropies of formation are negative as well; however, the values are significantly more positive for the species with odd numbers of platinum ions than for those with an even number. These thermodynamic trends can be rationalized by recognizing that the species with even numbers of platinum ions are dipolar and organize the solvent better than the species with odd numbers of platinum ions, which are not dipolar. Thus, the more negative enthalpies of formation of the species with even numbers of platinum ions are a consequence of better solvation than species with odd numbers of platinum ions. Accordingly, the entropies of formation of the species with even numbers of platinum ions are more negative because they organize solvent to a greater extent. Exclusive of solvent effects, the anion-cation interaction is about 30 kJ/mol.

Journal Article↗

PubMed2006

On the reactivity of surface methoxy species in acidic zeolites.

The in situ preparation and isolation of surface methoxy species on acidic zeolites are followed by further investigations of their reactivity in heterogeneously catalyzed reactions. For the first time, the following solid-state NMR evidence for the high reactivity of surface methoxy species has been obtained: (i) Surface methoxy species react readily with ammonia on acidic zeolites at room temperature, by which methylamines and methylammonium cations are formed. (ii) The transformation of surface methoxy species to other alkoxy species can be achieved by the reaction of surface methoxy species and corresponding alkyl halides on acidic zeolites. (iii) Surface methoxy species react readily with hydrochloride, giving methyl chloride as the sole product. (iv) The classic Koch carbonylation reaction and Ritter reaction in solution can be performed with surface methoxy species on acidic zeolites. (v) Carbon monoxide and carbon dioxide are produced by the oxidation of surface methoxy species in the presence of oxygen. The stability and reactivity of surface methoxy species are discussed in comparison with other surface alkoxy species (> C(1) species).

Journal Article↗