The chemical ecology of seed dispersal in monoecious and dioecious figs

In the nursery pollination system of figs (Ficus, Moraceae), flower-bearing receptacles called syconia breed pollinating wasps and are units of both pollination and seed dispersal. Pollinators and mammalian seed dispersers are attracted to syconia by volatile organic compounds (VOCs). In monoecious figs, syconia produce both wasps and seeds, while in (gyno)dioecious figs, male (gall) fig trees produce wasps and female (seed) fig trees produce seeds. VOCs were collected using dynamic headspace adsorption methods on freshly collected figs from different trees using Super Q® collection traps. VOC profiles were determined using gas chromatography–mass spectrometry (GC–MS).The VOC profile of receptive and dispersal phase figs were clearly different only in the dioecious mammal-dispersed Ficus hispida but not in dioecious bird-dispersed F. exasperata and monoecious bird-dispersed F. tsjahela. The VOC profile of dispersal phase female figs was clearly different from that of male figs only in F. hispida but not in F. exasperata, as predicted from the phenology of syconium production which only in F. hispida overlaps between male and female trees. Greater difference in VOC profile in F. hispida might ensure preferential removal of seed figs by dispersal agents when gall figs are simultaneously available.The VOC profile of only mammal-dispersed female figs of F. hispida had high levels of fatty acid derivatives such as amyl-acetates and 2-heptanone, while monoterpenes, sesquiterpenes and shikimic acid derivatives were predominant in the other syconial types. A bird- and mammal-repellent compound methyl anthranilate occurred only in gall figs of both dioecious species, as expected, since gall figs containing wasp pollinators should not be consumed by dispersal agents.

Three-dimensional hybrid networks based on aspartic acid

Three-dimensional achiral coordination polymers of the general formula M2(D, l-NHCH (COO)CH2COO)2·C4H4N2 where M = Ni and Co and pyrazine acts as the linker molecule have been prepared under hydrothermal conditions starting with [M(L-NHCH(COO)CH2COO)·3H2O] possessing a helical chain structure. A three-dimensional hybrid compound of the formula Pb2.5[N{CH(COO) CH2COO}22H2O] has also been prepared hydrothermally starting with aspartic acid and Pb(NO3)2. In this lead compound, where a secondary amine formed by the dimerisation of aspartic acid acts as the ligand, there is two-dimensional inorganic connectivity and one-dimensional organic connectivity.

One-dimensional zig-zag type coordination polymers of Ni(II) and Cu(II) containing 1,3-benzenedicarboxylate and 1,3-diaminopropane: Structural, spectral and thermal studies

Two coordination polymers [Ni(ipt)(dap)(2)](n) (1) and [Cu(ipt)(dap)H2O](n) center dot nH(2)O (2) with an overall one-dimensional arrangement and having isophthalate (ipt) as bridging moieties and chelating 1,3-diaminopropane (dap) as structure modulating units have been prepared and characterized by crystallographic, spectroscopic and thermo-analytical studies. Both have an overall one-dimensional zig-zag nature but with a distorted octahedral NiN4O2 chromophore for 1 and a distorted square pyramidal CuN2O3 chromophore for 2. Even though the ipt units are acting as bridging units through mono-dentatively coordinating carboxylate functions in both polymers, compound 1 has the carboxylate oxygen linkages at the trans positions, while in 2 the oxygen linkages occur at the cis positions leading to a different type of zig-zag arrangement. Relevant spectral and bonding parameters also could be evaluated for the compounds using UV-Vis and EPR spectra. Thermal stability and possible structural modifications on thermal treatment of the compounds were also investigated and the relevant thermodynamic and kinetic parameters evaluated from the thermal data. (C) 2007 Elsevier B.V. All rights reserved.

Synthesis, Characterization and Evaluation of Cytotoxicity of New Aminophosphonic Acid Diesters in Human Leukemia Cells

A series of novel fluoroaminophosphates 4a-4j were synthesized by one-pot method in presence of tetramethylguanidine (TMG) as a catalyst and were characterized by elemental analysis, FTIR, H-1, C-13, P-31, F-19 NMR, and mass spectra. All the title compounds were evaluated forin vitro cytotoxicity against leukemic cell line derived from T-cells of leukemia patient (CEM cells) by Trypan blue exclusion and MTT assays, and these were found to exert concentration dependent cytotoxic effects. Among them 4f, 4g & 4j possessed marked cytotoxicity. 4g (with IC50 value of 6 mu M) had emerged as lead compound.

Structural and spectral investigations on some new Ni(II) complexes of di-2-pyridyl ketone N(4)-phenylthiosemicarbazone

Ni(II)complexes(1-5)ofdi2pyridylketoneN(4)-phenylthiosemicarbazone (HL) have been synthesized and spectrochemically characterized. Elemental analyses revealed a NiL2 center dot 2H(2)O stoichiometry for compound 1. However, the single crystals isolated revealed a composition NiL, - 0.5(H,0)0.5(DMF). The compound crystallizes into a monoclinic lattice with the space group P-21/n. Complexes 2. 3 and 4 are observed to show a 1:1:1 ratio of metal: thioseicarbazone:gegenion, with the general formula NiLX center dot yH(2)O [X = NCS. Y = 2 for 2; X = Cl, Y = 3 for 3 and X = N-3, y = 4.5 for 4]. Compound 5 is a dimer with a metal:thiosemicarbazone:gegenion ratio of 2:2: 1. with the formula [Ni,L,(SO4)1 - 4H(2)O (c) 2007 Elsevier Ltd. All rights reserved.

Structural and spectral investigations on some new Ni(II) complexes of di-2-pyridyl ketone N(4)-phenylthiosemicarbazone

Ni(II) complexes (1-5) of di-2-pyridyl ketone N(4)-phenylthiosemicarbazone (HL) have been synthesized and spectrochemically characterized. Elemental analyses revealed a NiL2 center dot 2H(2)O stoichiometry for compound 1. However, the single crystals isolated revealed a composition NiL, - 0.5(H,0)0.5(DMF). The compound crystallizes into a monoclinic lattice with the space group P-21/n. Complexes 2. 3 and 4 are observed to show a 1:1:1 ratio of metal: thioseicarbazone:gegenion, with the general formula NiLX center dot yH(2)O [X = NCS. Y = 2 for 2; X = Cl, Y = 3 for 3 and X = N-3, y = 4.5 for 4]. Compound 5 is a dimer with a metal:thiosemicarbazone:gegenion ratio of 2:2: 1. with the formula [Ni,L,(SO4)1 - 4H(2)O (c) 2007 Elsevier Ltd. All rights reserved.

Metal-ion-mediated tuning of duplex DNA binding by bis(2-(2-pyridyl)-1H-benzimidazole)

Studies of double-stranded-DNA binding have been performed with three isomeric bis)2-(n-pyridyl)-1H-benzimidazole)s (n = 2, 3, 4). Like the well-known Hoechst 33258, which is a bisbenzimidazole compound, these three isomers bind to the minor groove of duplex DNA. DNA binding by the three isomers was investigated in the presence of the divalent metal ions Mg2+, Co2+, Ni2+, Cu2+, and Zn2+. Ligand-DNA interactions were probed with fluorscence and circular dichroism spectroscopy. These studies revealed that the binding of the 2-pyridyl derivative to DNA is dramatically reduced in the presence of Co2+, Ni2+, and Cu2+ ions and is abolished completely at a ligand/metal-cation ratio of 1:1. Control experiments done with the isomeric 3- and 4-pyridyl derivatives showed that their binding to DNA is unaffected by the aforementioned transition-metal ions. The ability of 2-(2-pyridyl)benzimidazole changes of the ligand associated with ion chelation probably ledto such unusual binding results for the ortho isomer. The addition of ethylenediaminetetraacetic acid (EDTA) reversed the effects completely.

1-[(2-Chloro-7-methyl-3-quinolyl)methyl]pyridin-2(1H)-one

In the title compound, C16H13ClN2O, the quinoline ring system is essentially planar, with a maximum deviation of 0.021 (2) angstrom. The pyridone ring is oriented at a dihedral angle of 85.93 (6)degrees with respect to the quinoline ring system. In the crystal structure, intermolecular C-H center dot center dot center dot O hydrogen bonds link the molecules along the b axis. Weak pi-pi stacking interactions [centroid-centroid distances = 3.7218 (9) and 3.6083 (9) angstrom] are also observed.

Ethyl 6-chloro-2-[(2-chloro-7,8-dimethylquinolin-3-yl)methoxy]-4-phenylquino line-3-carboxylate

In the title compound, C30H24Cl2N2O3, the two quinoline ring systems are almost planar [maximum deviations = 0.029 (2) and 0.018 (3) angstrom] and the dihedral angle between them is 4.17 (8)degrees. The dihedral angle between the phenyl ring and its attached quinoline ring is 69.06 (13)degrees. The packing is stabilized by C-H center dot center dot center dot O, C-H center dot center dot center dot N, weak pi-pi stacking [centroid-centroid distances = 3.7985 (16) and 3.7662(17) angstrom] and C-H center dot center dot center dot pi interactions.

1-[(2-Chloro-7,8-dimethylquinolin-3-yl)methyl]pyridin-2(1H)-one

In the title compound, C17H15ClN2O, the quinoline ring system is nearly planar, with a maximum deviation from the mean plane of 0.074 (2) angstrom, and makes a dihedral angle of 81.03 (7)degrees with the pyridone ring. The crystal packing is stabilized by pi-pi stacking interactions between the pyridone and benzene rings of the quinoline ring system [centroid-centroid distance = 3.6754 (10) angstrom]. Furthermore, weak intermolecular C-H center dot center dot center dot O hydrogen bonding links molecules into supramolecular chains along [001].

Scanning Tunneling Spectroscopy on Pr0.68Pb0.32MnO3 single crystals

Scanning tunneling microscopy/spectroscopy studies were carried out on single crystals of colossal magnetoresistive manganite Pr0. 68Pb0.32MnO3 at different temperatures in order to probe their spatial homogeneity across the metal-insulator transition temperature TM-I(similar to 255 K). A metallic behavior of the local conductance was observed for temperatures T < TM-I. Zero bias conductance (dI/dV)v=(0), which is directly proportional to the local surface density of states at the Fermi level, shows a single distribution at temperatures T < 200 K suggesting a homogeneous electronic phase at low temperatures. In a narrow temperature window of 200 K < T < TM-I, however, an inhomogeneous distribution of (dI/dV)v=(0) has been observed. This result gives evidence for phase separation in the transition region in this compound.

Chain structures in alkali metal borophosphates: synthesis and characterization of K3[BP3O9(OH)3] and Rb3[B2P3O11(OH)2]

Two new alkali metal borophosphates, K-3[BP(3)o(9)(OH)(3)] and Rb-3[B2P3O11(OH)(2)], were synthesized by applying solvothermal techniques using ethanol as solvent. The crystal structures were solved by means of single-crystal X-ray diffraction (K-3[BP3O9(OH)(3)], monoclinic, C2/c (No. 15), a = 2454.6(8) pm, b = 736.3(2) pm, c = 1406.2(4) pm, beta = 118.35(2)degrees, Z = 8; Rb-3[B2P3O11(OH)(2)], monoclinic, P2(1)/c (No. 14), a = 781.6(2) pm, b:= 667.3(2) pm, c = 2424.8(5) pm, beta = 92.88(1)degrees, Z = 4). Both crystal structures comprise borophosphate chain anions. While for the rubidium compound a loop-branched chain motif is found as common for most of the chain anions in alkali metal borophosphates, the crystal structure of the potassium phase comprises the first open-branched chain with the highest phosphate content found so far in this group of compounds. Both chain anions are Closely related to known anhydrous or hydrated phases, and the structural relations are discussed in terms of how the presence of OH groups and hydrogen bonds as well as number, charge, and size of charge balancing cations influence the 3D structural arrangement. The anionic entities are classified in terms of general principles of structural systematics for borophosphates.

Characterization of the interactions of a polycationic, amphiphilic, terminally branched oligopeptide with lipid A and lipopolysaccharide from the deep rough mutant of Salmonella minnesota

The lipid A and lipopolysaccharide (LPS) binding and neutralizing activities of a synthetic, polycationic, amphiphilic peptide were studied. The branched peptide, designed as a functional analog of polymyxin B, has a six residue hydrophobic sequence, bearing at its N-terminus a penultimate lysine residue whose alpha- and epsilon-amino groups are coupled to two terminal lysine residues. In fluorescence spectroscopic studies designed to examine relative affinities of binding to the toxin, neutralization of surface charge and fluidization of the acyl domains, the peptide was active, closely resembling the effects of polymyxin B and its nonapeptide derivative; however, the synthetic peptide does not induce phase transitions in LPS aggregates as do polymyxin B and polymyxin B nonapeptide. The peptide was also comparable with polymyxin B in its ability to inhibit LPS-mediated IL-l and IL-6 release from human peripheral blood mononuclear cells. The synthetic compound is devoid of antibacterial activities and did not induce conductance fluxes in LPS-containing asymmetric planar membranes. These results strengthen the premise that basicity and amphiphilicity are necessary and sufficient physical properties that ascribe endotoxin binding and neutralizing activities, and further suggest that antibacterial/membrane perturbant and LPS neutralizing activities are dissociable, which may be of value in designing LPS-sequestering agents of low toxicity.

Use of the liquid-liquid interface for generating ultrathin nanocrystalline films of metals, chalcogenides, and oxides

The air-water interface has traditionally been employed to prepare particle assemblies and films of metals and semiconductors. The interface between water and an organic liquid, however, has not been investigated sufficiently for possible use in preparing nanocrystals and thin films of materials. In this article, we demonstrate the use of the liquid-liquid interface as a medium for preparing ultrathin films of metals, chalcogenides and oxides. The method involves the reaction at the interface between a metal-organic compound in the organic layer and an appropriate reagent for reduction, sulfidation, etc. in the aqueous layer. Some of the materials discussed are nanocrystalline films of gold, CuS, CuSe, CuO, and Cu(OH)(2) formed at the liquid-liquid interface. The results reported in this article should demonstrate the versatility and potential of the liquid-liquid interface for preparing nanomaterials and ultrathin films and encourage further research in this area. (c) 2005 Elsevier Inc. All rights reserved.

Structural Insights into the Acyl Intermediates of the Plasmodium falciparum Fatty Acid Synthesis Pathway THE MECHANISM OF EXPANSION OF THE ACYL CARRIER PROTEIN CORE

Acyl carrier protein (ACP) plays a central role in fatty acid biosynthesis. However, the molecular machinery that mediates its function is not yet fully understood. Therefore, structural studies were carried out on the acyl-ACP intermediates of Plasmodium falciparum using NMR as a spectroscopic probe. Chemical shift perturbation studies put forth a new picture of the interaction of ACP molecule with the acyl chain, namely, the hydrophobic core can protect up to 12 carbon units, and additional carbons protrude out from the top of the hydrophobic cavity. The latter hypothesis stems from chemical shift changes observed in C-alpha and C-beta of Ser-37 in tetradecanoyl-ACP. C-13, N-15-Double-filtered nuclear Overhauser effect (NOE) spectroscopy experiments further substantiate the concept; in octanoyl (C-8)- and dodecanoyl (C-12)-ACP, a long range NOE is observed within the phosphopantetheine arm, suggesting an arch-like conformation. This NOE is nearly invisible in tetradecanoyl (C-14)-ACP, indicating a change in conformation of the prosthetic group. Furthermore, the present study provides insights into the molecular mechanism of ACP expansion, as revealed from a unique side chain-to-backbone hydrogen bond between two fairly conserved residues, Ile-55 HN and Glu-48 O. The backbone amide of Ile-55 HN reports a pK(a) value for the carboxylate, similar to 1.9 pH units higher than model compound value, suggesting strong electrostatic repulsion between helix II and helix III. Charge-charge repulsion between the helices in combination with thrust from inside due to acyl chain would energetically favor the separation of the two helices. Helix III has fewer structural restraints and, hence, undergoes major conformational change without altering the overall-fold of P. falciparum ACP.