Equilibrium geometries, stabilities, and electronic properties of the cationic Au n Be+ (n?=?1-8) clusters: comparison with pure gold clusters

Ab initio method based on density functional theory at PW91PW91 level has been applied in studying the geometrical structures, relative stabilities, and electronic properties of small bimetallic Au(n)Be(+) (n?=?1-8) cluster cations. The geometrical optimizations indicate that a transition point from preferentially planar (two-dimensional) to three-dimensional (3D) structures occurs at n?=?6. The relative stabilities of Au(n)Be(+) clusters for the ground-state structures are analyzed based on the averaged binding energies, fragmentation energies, and second-order difference of energies. The calculated results reveal that the AuBe(+) and Au(5)Be(+) clusters possess higher relative stability for small size Au(n)Be(+) (n?=?1-8) clusters. The HOMO-LUMO energy gaps as a function of the cluster size exhibit a pronounced even-odd alternation phenomenon. Sequently, the natural population analysis and polarizability for our systems have been analyzed and compared further.     

M?ssbauer studies of aconitase. Substrate and inhibitor binding, reaction intermediates, and hyperfine interactions of reduced 3Fe and 4Fe clusters

Active beef heart aconitase contains a [4Fe-4S] cluster. One iron of the cluster, Fea, is labile and can be removed easily by oxidation in air to yield the [3Fe-4S]1+ cluster of inactive aconitase. We have previously shown that substrate binds to Fea. We have continued our M?ssbauer studies by further investigating the active and inactive forms of the enzyme. When active aconitase, [4Fe-4S]2+, is mixed with substrate, two species (substrates or intermediates bound to Fea) labeled S1 and S2 are obtained. With the nitroanalogs of citrate and isocitrate, thought to be transition state analogs, and fluorocitrate, species S2, but not S1, is observed, suggesting that S2 represents a carbanion transition state complex. We have prepared M?ssbauer samples by rapid mix/rapid freeze techniques. Using either citrate, isocitrate or cis-aconitate, the natural substrates, we have been able to detect at 0 degree C reaction intermediates in the 5-35 ms time range and, studying enzyme substrate interactions at subzero temperatures in a water/methanol/ethylene glycol solvent, we have observed new species when substrates were added at -60 degrees C. Details of these experiments are given, although in neither case can unique interpretations be offered at this time. We have also investigated reduced active aconitase ([4Fe-4S]1+; EPR at g = 1.94) in the presence of substrate with material selectively enriched with 57Fe in either Fea or the other three cluster sites. The spectra were analyzed with a spin Hamiltonian, and the results are discussed and interpreted in terms of three inequivalent Fe sites in the cluster. Finally, we have studied enzyme containing the reduced [3Fe-4S]0 cluster. There is no indication that citrate binds to the 3Fe cluster, and since no significant activity was observed, we conclude that aconitase containing a 3Fe cluster is not active in either oxidation state.     

An insight into the structures,stabilities, and bond character of BnPt (n=1∼6) clusters

We perform a systematical investigation on the geometry, thermodynamic/kinetic stability, and bonding nature of low-lying isomers of B_nPt (n=1-6) at the CCSD(T)/[6-311+G(d)/LanL2DZ]//B3LYP/[6-311+G(d)/LanL2DZ] level. The most stable isomers of B_nPt (n=1-6) adopt planar or quasi-planar structure. B_nPt (n=2-5) clusters can be generated by capping a Pt atom on the B-B edge of pure boron clusters. However, For B₆Pt with non-planar structure, a single doped Pt atom significantly affects the shape of the host boron cluster. The dopant of the Pt atom can improve the stability of pure boron clusters. The valence molecular orbital (VMO), electron localization function (ELF), and Mayer bond order (MBO) are applied to gain insight into the bonding nature of B_nPt (n=2-6) isomers. The aromaticity for some isomers of B_nPt (n=2-6) is analyzed and discussed in terms of VMO, ELF, adaptive natural density partitioning (AdNDP), and nucleus-independent chemical shift (NICS) analyses. Results obtained from the energy and cluster decomposition analyses demonstrate that B₂Pt and B₄Pt exhibits as highly stable. Importantly, some isomers of B_nPt (n=2-5) are stable both thermodynamically and kinetically, which are observable in future experiment.     

Structure,ecology and physiology of root clusters – a review

Hairy rootlets, aggregated in longitudinal rows to form distinct clusters, are a major part of the root system in some species. These root clusters are almost universal (1600 species) in the family Proteaceae (proteoid roots), with fewer species in another seven families. There may be 10–1000 rootlets per cm length of parent root in 2–7 rows. Proteoid roots may increase the surface area by over 140× and soil volume explored by 300× that per length of an equivalent non-proteoid root. This greatly enhances exudation of carboxylates, phenolics and water, solubilisation of mineral and organic nutrients and uptake of inorganic nutrients, amino acids and water per unit root mass. Root cluster production peaks at soil nutrient levels (P, N, Fe) suboptimal for growth of the rest of the root system, and may cease when shoot mass peaks. As with other root types, root cluster production is controlled by the interplay between external and internal nutrient levels, and mediated by auxin and other hormones to which the process is particularly sensitive. Proteoid roots are concentrated in the humus-rich surface soil horizons, by 800× in Banksia scrub-heath. Compared with an equal mass of the B horizon, the A₁ horizon has much higher levels of N, P, K and Ca in soils where species with proteoid root clusters are prominent, and the concentration of root clusters in that region ensures that uptake is optimal where supply is maximal. Both proteoid and non-proteoid root growth are promoted wherever the humus-rich layer is located in the soil profile, with 4× more proteoid roots per root length in Hakea laurina. Proteoid root production near the soil surface is favoured among hakeas, even in uniform soil, but to a lesser extent, while addition of dilute N or P solutions in split-root system studies promotes non-proteoid, but inhibits proteoid, root production. Local or seasonal applications of water to hakeas initiate non-proteoid, then proteoid, root production, while waterlogging inhibits non-proteoid, but promotes proteoid, root production near the soil surface. A chemical stimulus, probably of bacterial origin, may be associated with root cluster initiation, but most experiments have alternative interpretations. It is possible that the bacterial component of soil pockets rich in organic matter, rather than their nutrient component, could be responsible for the proliferation of proteoid roots there, but much more research on root cluster microbiology is needed.     

Large gallanes and the PSEPT theory: a theoretical study of Ga n H n+2 clusters (n?=?7–9)

Do alanes Al(n)H(n+2) and gallanes Ga(n)H(n+2) satisfy the polyhedral skeletal electron pair theory (PSEPT)? Taking into account previous work on this question, this paper provides a convincing answer and proposes the reformulation of the (n + 1) electron pairs rule of Wade and Mingos (W-M) for such systems. Following recent studies of tetra-, penta-, hexa-, hepta-, octa-, and nonaalanes as well as valence-isoelectronic/related gallanes, in this paper we present an analysis of the hydrides of aluminum and gallium A(n)H(n+2) (A = Al, Ga and n = 7-9). The aim is still to examine the applicability of PSEPT, especially the W-M rule, to these clusters. Exploration of the total potential energy surfaces (PESs) of hepta-, octa-, and nonagallanes shows that the absolute minima have a nido-like polyhedron arrangement. Unlike the smaller Ga(n)H(n+2) (n = 4, 5, 6), it seems that the size of the cluster largely dictates its preferred geometry. Although none of them have closed (totally triangular) cages, these clusters exhibit significant compactness, comparable to borane double anions, B(n)H(n) (2-), which are the archetypes for the PSEPT theory.     

Ab initio investigations on planar (MgO)n clusters (n = 1–5) and their hydrogen adsorption behaviour

Ab initio calculations (B3LYP and PBE-D3) of the structures, stabilities, vibrational, electronic and hydrogen adsorption behaviour of (MgO)_n clusters are performed using 6-311+ + G(d,p) basis set. The planar (MgO)_n clusters are found to be global minima for n ≤ 3 and local minima for n = 4 and 5. In addition, we have also analysed global minimum structures of (MgO)₄ and (MgO)₅. The binding energies suggest that their stabilities increase successively. Vibrational frequencies and IR intensities further support the enhanced stability with an increase in the size of (MgO)_n clusters. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) surfaces are used to explain and discuss the electronic properties. Finally, we have demonstrated hydrogen storage capacity of (MgO)_n clusters, considering hydrogen adsorption on planar as well as global minimum (MgO)₄ and (MgO)₅ clusters. We have noticed that four and five H₂ molecules can be easily adsorbed by (MgO)₄ and (MgO)₅ clusters having adsorption energy of 0.13–0.14 eV with mass ratio of 4.76%. Thus, the present study is expected to motivate further the applications of small clusters for efficient hydrogen energy storage.     

Infecc Ón Humana PorNocardia Asteroides,En México

Summary Although the existence ofNocardia asteroides as a human pathogen in Mexico has been known for several years, up to now there are only few reports in our country concerning the isolation of this microorganism both as a saprophyte as well as human or animal pathogen. This fact is more interesting when compared with the high incidence ofN. brasiliensis, causal agent of actinomycotic mycetoma, the most frequently observed deep mycosis in Mexico.In this paper, the isolation of eigth strains ofN. asteroides from clinical specimens is reported. Five strains were isolated from sputa, one from a fistulous lesion of the scrotum, one from a brain abscess and one more from a foot mycetoma.One of the strains isolated from sputum was in a case of pulmonary nocardiasis; another of these strains was isolated from a patient with coexistent pulmonary tuberculosis and nocardiasis. With the last three strains isolated from sputa, it was not possible to establish any correlation between the isolations and the clinical and radiological findings of the patients; two of the patients had pulmonary tuberculosis and the isolation ofN. asteroides was achieved only in one occasion in each case, with scant growth, and observed in routine cultures made for tubercle bacilli. The last strain was isolated from the sputum of a patient with chronic bronchitis. Some comments are made to the possibility that these three last isolations merely represent a saprophytic phase of the fungus.Some clinical and other features are discussed concerning the other three cases of scrotal fistula, brain abscess and mycetoma produced byN. asteroides.     

Probing the electronic structures and properties of neutral and anionic ScSi n (0,−1) (n = 1–6) clusters using ccCA-TM and G4 theory

We apply molecular docking, molecular dynamics (MD) simulation, and binding free energy calculation to investigate and reveal the binding mechanism between five xanthine inhibitors and DPP-4. The electrostatic and van der Waals interactions of the five inhibitors with DPP-4 are analyzed and discussed. The computed binding free energies using MM-PBSA method are in qualitatively agreement with experimental inhibitory potency of five inhibitors. The hydrogen bonds of inhibitors with Ser630 and Asp663 can stabilize the inhibitors in binding sites. The van der Waals interactions, especially the key contacts with His740, Asn710, Trp629, and Tyr666 have larger contributions to the binding free energy and play important roles in distinguishing the variant bioactivity of five inhibitors.     

Species composition,richness, and distribution of marine bivalve molluscs in Bahía de Mazatlán,México

We describe the composition and distribution of bivalve molluscs from the sandy and rocky intertidal and the shallow subtidal environments of Bahía de Mazatlán, México. The bivalve fauna of the bay is represented by 89 living species in 28 families, including 37 new records and four range extensions: Lithophaga hastasia, Adula soleniformis, Mactrellona subalata, and Strigilla ervilia. The number of species increases from the upper (44) and lower intertidal (53) to the shallow subtidal (76), but only 11 (17%) have a wide distribution in the bay (i.e., found in all sampling sites and environments). The bivalve assemblages are composed of four main life forms: 27 epifaunal species, 26 infaunal, 16 semi-infaunal, and 20 endolithic. A taxonomic distinctness analysis identified the sampling sites and environments that contribute the most to the taxonomic diversity (species to suborder categories) of the bay. The present work increased significantly (31%) to 132 species previous inventories of bivalves of Bahía de Mazatlán. These species represent 34% of the bivalve diversity of the southern Golfo de California and approximately 15% of the Eastern Tropical Pacific region.     

Identification of FeS clusters in the glycyl-radical enzyme benzylsuccinate synthase via EPR and M?ssbauer spectroscopy

The anaerobic degradation pathway of toluene is initiated by the addition of the methyl group of toluene to the double bond of fumarate. This reaction is catalyzed by a novel glycyl-radical enzyme, (R)-benzylsuccinate synthase (BSS). The enzyme consists of three subunits, α, β, and γ, and differs from most other glycyl-radical enzymes in having additional cofactors. We have purified a Strep-tagged nonactivated BSS from recombinant Escherichia coli and identified the additional cofactors as FeS clusters by UV/vis, EPR, and M?ssbauer spectroscopy. Analysis of the metal content as well as the EPR and M?ssbauer spectra indicated that BSS contains magnetically coupled low-potential [4Fe–4S] clusters. Several enzyme preparations showed differing amounts of [3Fe–4S] clusters that could be reconstituted to [4Fe–4S] clusters, indicating that they arise from partial decay of the initial [4Fe–4S] clusters. The most likely location of these FeS clusters in the enzyme are the small β and γ subunits, which are unique for the BSS subfamily of glycyl-radical enzymes and contain conserved cysteines as potential ligands.     

Complexes of DNA bases and Watson–Crick base pairs interaction with neutral silver Agn (n = 8, 10, 12) clusters: a DFT and TDDFT study

We study the binding of the neutral Ag_n (n = 8, 10, 12) to the DNA base-adenine (A), guanine (G) and Watson–Crick –adenine-thymine, guanine-cytosine pairs. Geometries of complexes were optimized at the DFT level using the hybrid B3LYP functional. LANL2DZ effective core potential was used for silver and 6–31 + G^** was used for all other atoms. NBO charges were analyzed using the Natural population analysis. The absorption properties of Ag_n–A,G/WC complexes were also studied using time-dependent density functional theory. The absorption spectra for these complexes show wavelength in the visible region. It was revealed that silver clusters interact more strongly with WC pairs than with isolated DNA complexes. Furthermore, it was found that the electronic charge transferred from silver to isolated DNA clusters are less than the electronic charge transferred from silver to the Ag_n–WC complexes. The vertical ionization potential, vertical electron affinity, hardness, and electrophilicity index of Ag_n–DNA/WC complexes have also been discussed.     

Ethnobotany and domestication in Xoconochtli,Stenocereus stellatus (Cactaceae), in the Tehuacán Valley and La Mixteca Baja, México

Ethnobotanical information is presented on use, management, folk nomenclature and classification of the “xoconochtli” (Stenocereus stellatus) as well as on the role of this plant in subsistence of the Nahua, Mixtec and Popoloca peoples from the Tehuacán Valley and La Mixteca Baja in Central Mexico. Among all three groups, S. stellatus was used for various purposes but mainly for its edible fruits. Different variants of this species were distinguished, named and classified by indigenous people according to characteristics of the fruit; particularly size, color and flavor of the pulp, spininess and thickness of the peel. Wild plants characteristically had small red sour fruits with many spines and thick peel, while individuals selected for cultivation usually differed in one or more of these characters. Three general forms of interaction between people and this species were found: 1) gathering of useful products from the wild; 2) management of wild populations in situ which involves the sparing and enhancing of individuals with more desirable characteristics and the removal of others during clearance of the land for agriculture; and 3) cultivation, mainly in home gardens, by propagation of vegetative parts from desirable individuals. Fruit yields per individual and per population were measured and compared in wild, managed in situ and cultivated populations from the Tehuacán Valley and La Mixteca Baja. Wild and cultivated individuals from La Mixteca Baja yielded more than wild and cultivated individuals from the Tehuacán Valley. Within each region, fruit yields were similar in wild and managed in situ populations but significantly larger in cultivated populations. Forms of management of this plant species are discussed in terms of availability of products and demand for them in the local economy.     

Structures and stabilities of ScBn (n = 1–12) clusters: an ab initio investigation

The geometries, stabilities, and electronic properties of ScB_n (n?=?1–12) clusters have been systematically investigated by using density functional theory B3LYP method and coupled–cluster theory CCSD(T) method. It is found that the ground state isomers of ScB_n have planar or quasi–planar structure when n?≤?6, which can be viewed as a B atom of the corresponding B_n+1 cluster is substituted by a Sc atom. From n?≥?7, the ground state isomers favor nest–like structure, in which the Sc atom sits on a nest–like B_n cluster. The calculated second–order differences of energies manifest that the magic numbers of stability are n?=?3, 7, 8, 9 and 11 for the ScB _n clusters. Further analysis indicates that the ScB₇ cluster with C _6v symmetry represents the outstanding stable ScB_n cluster, as confirmed by its electronic structure and molecular orbitals.     

Ichthyofauna from wetlands of San Pedro, Balancán, Tabasco, México

San Pedro River's wetlands sustain trophic nets in the fluvial system, due to the high habitat availability, and space and temporal variations. In order to describe the relationship between environmental parameters and ichthyofauna, this study evaluated fish assemblages composition, distribution, abundance, density, biomass, richness species, diversity and equitability in the wetlands. Sampling considered three different sites and climatic seasons (dry, rainy and cold fronts). The physical and chemical parameters considered were dissolved oxygen, temperature, pH, water transparency and the depth. Fishes were caught with a shrimp net, after six minutes towings and were identified afterwards. A total of 1 049 organisms of 25 fish species were caught, two of which were exotic species: Oreochromis niloticus and Parachromis managuense. A total of 23 species were found at site I (with the highest density 0.23 ind./m2), 17 at site II (0.23 ind./m2) and 14 at site III (0.12 ind./m2). The dry season had the highest species number with 21 species, followed by the rainy season with 17 species, and the cold season with five species. Similarly, the highest biomass (8.30 g/m2) was found in dry season, followed by the rainy (2.16 g/m2) and the cold seasons (0.03 g/m2). Considering seasons, highest density was found during the dry (0.436 ind./m2), followed by the rainy (0.213 ind./m2) and the cold (0.023 ind./m2) seasons. The dominant density species during the study period, according to the quadrants graphic of Olmstead-Tukey were: Petenia splendida, Vieja heterospila, Vieja synspila, Dorosoma petenense and Astyanax aeneus. There were significant differences in the species richness among sites. Temperature, depth and transparency showed differences among the seasons. The canonical correspondence analysis indicated that fish distribution was governed by environmental parameters during all seasons. In terms of fish abundance and composition, environmental parameters play an important role showing spatial and temporal differences in the ecosystem, this could be explained with the fact that most of young fishes have a movement behavior to the wetlands, searching refuge and feed during the dry season. Considering the diversity indexes variation, it may be concluded that San Pedro River's wetlands correspond to a system where the ichthyofauna composition fluctuates spatial and seasonally.     

Distribution and abundance of Tillandsia spp. (Bromeliaceae) in the Zapotitlán Valley,Puebla, México

Seed germination of woody species was studied in treefall gaps in NewZealand to assess how environmental heterogeneity affects regeneration fromseed. Gaps were created in a relictual Pinus radiataplantation destined for restoration to native forest. Seeds of the nativespecies Alectryon excelsus, Macropiperexcelsum, and Fuchsia excorticata, and theinvasive alien species Cytisus scoparius andBerberis darwinii were sown in sites differing inexposure,with and without 3 cm of pine litter. Litter promoted germinationof Alectryon and Macropiper,independent of site. Without litter, percent germination ofMacropiper was negatively correlated with percent open skyoverhead. Germination of Fuchsia was significantly higherin treefall gaps than in the forest understory, with litter having littleeffect. Cytisus germinated most successfully in sitesexposed to direct solar radiation, with or without litter. Percent germinationof Berberis was high in all sites, and was consistentlypromoted by litter. Glasshouse trials for each species showed the same effectsof litter cover as found in the field. These results suggest thatmicroenvironmental heterogeneity can be an important influence on the speciescomposition of regenerating vegetation within and around treefall gaps.     

Distribution, abundance, density and morphometry of Strombus gigas (Mesogasteropoda: Strombidae) in Alacranes reef, Yucatán, México

A population of the conch Strombus gigas was sampled in 109 transects (100 x 10 m each) for an area of 109000 m2 (eight surveys in 1998 and six in 1999) in Yucatan, Mexico; S. gigas was the most abundant conch species (97% of individuals) and ocurred at depths of 0.5-18 m. Mean density was 0.0084 individuals/m2 (Standard deviation SD=0.0138, n=1910). Maximum density (0.015 individuals/m2) was at 0.5-2 m and minimal (0.001 individuals/m2) at 16-18 m. Shell length was 120-290 mm (mena=211.6, SD=26, n=1136). Shell lip thickness, measured only in adults, was 1-28 mm (mean=8.7, SD=7.5, n=1136).     

Somatic production of two species: Crassostrea virginica and Ischadium recurvum Bivalvia in Mecoacán, Tabasco, México

The Mexican oyster fishery, 90% supported by the coastal lagoons of the Gulf of Mexico, has decreased drastically in the last six years as a result of anthropogenic pollution and improper management. The mussel Ischadium recurvum has proliferated and competes with oysters for space and probably food. Crassostrea virginica and Ischadium recurvum were studied to evaluate somatic production with biometry and physiological condition indices (PCI's) during an annual cycle. A random sample of 200 organisms was taken montly for each species. Condition indices wet flesh weigth: wet shell weight ratio (WFW/WSW), dry flesh weight: wet flesh weight ratio (DFW/WFW), dry flesh wet: dry shell weight ratio (DFW/DSW), and ash free dry weight: tissue dry weight (AFDW/TDW) were calculated. In order to stablish physiological condition and temporal variability, these indices were compared between species and months. The somatic production of mussels was higher than in oysters. This enhancement in production could be explained by: 1) Mussel uses less energy for shell production, 2) a constant recruitment of mussel almost year-round, and 3) the mesohalin lagoon was more favourable to the mussel.     

Density functional study of structural and electronic properties of small binary Be n Cu m (n + m = 2∼7) clusters

The geometrical structures, electronic properties and relative stabilities of small bimetallic Be _n Cu _m (n?+?m?=?2–7) clusters have been systematically investigated by using a density functional method at the B3PW91 level. In the most stable structures of Be _n Cu _m , the Be atoms tend to gather together and construct similar configurations to those of pure Be _n clusters. Meanwhile, there is a tendency for Cu atoms to segregate toward the Be _n cluster surface. The successive binding energies, cohesive energies, second difference of energies, the highest occupied-lowest unoccupied molecular orbital energy gaps and chemical hardness of Be _n Cu _m are also investigated. All of them demonstrate that the clusters with even number of copper atoms present relatively higher stabilities. The natural population analyses on the Be _n Cu _m clusters reveal that, the charge transfers from Be to Cu when the average coordination numbers (Nc) of Be atom is less than 3, whereas the charge-transferring direction reverses when Nc(Be) increases.     

The market medicinal plants of Monterrey,Nuevo León,México

The purpose of this study is to record the popular uses of various medicinal plants collected in the market medicinal stalls of Monterrey, Nuevo León, México. One hundred and thirty-five medicinal plants were collected from 11 hierberias (stalls) of two mercados (markets) and two additional medicinal plant sources. Included is a total of 70 species in 65 genera of 38 plant families. The plant vendors of the hierberias were interviewed to determine the folk uses of these plants. Eighty-five folk uses, of both general and specific nature, are reported for the specimens collected.