Chemical defense and self-defense: Biochemical transformations of contact insecticides produced by soldier termites

Soldiers of the advanced genera of rhinotermitids (Isoptera: Rhinotermitidae) produce lipophilic contact insecticides formally derived from fatty acids. Each of these defense substances possesses a reactive electrophilic center (vinyl ketone, nitroalkene, or β-ketoaldehyde) responsible for toxicity. We describe the synthesis of radioactively-labelled defense secretions of two of these species and their use in studying the substrate-selective detoxication by worker termites. Preliminary studies on biosynthesis of defense secretions by termite soldiers are also discussed.     

Crystal and molecular structure of the smectogenic compound di-n-propyl-p-terphenyl-4,4″-carboxylate

An X-ray crystallographic study of di-n-propyl-p-terphenyl-4,4-carboxylate (DPTC) showed that the crystals belong to the triclinic system with space groupP¯1,a=22.191(14),b=5.960(1),c=10.951(4) Å, =129.651(16), =102.560(51), and =83.103(39) ° with two molecules per unit cell. The crystal structure was solved by Patterson synthesis, Fourier, and difference Fourier calculations. It was refined by block-diagonal and full-matrix least-squares methods to a finalR factor of 0.17. The molecules form a herringbone type of packing in tilted layers. Each of the two molecules is nonplanar in itself and shows highly anisotropic behavior of the end groups.     

Studies in organometallic rearrangements IV—proton and carbon nuclear magnetic resonance spectra of group IVA substituted indenes and indenyl anions

The proton and carbon NMR spectra for a series of substituted indenes [C₉H₇R, R = H, CH₃, Si(CH₃)₃] are reported. The proton and carbon resonances for the 5-membered ring exhibit pronounced changes as a function of the substituents.     

Elephant albumin: a multipurpose pheromone shuttle

(Z)-7-dodecenyl acetate (Z7-12:Ac) is present in the urine of female Asian elephants (Elephas maximus) approaching ovulation and functions as a female-to-male sex pheromone. Here we show that a significant fraction of the pheromone in the urine is bound to a protein, elephant serum albumin (ESA), and provide evidence for key physiological functions of urinary ESA. Our biochemical and behavioral experiments suggest a three-fold role of ESA in pheromone signaling: (1) transporting Z7-12:Ac from serum into urine; (2) extending the presence of the pheromone in the environment without hampering detection; and (3) targeting pheromone delivery to chemosensory organs through localized release of the ligand induced by a pH change. The exploitation of albumin in pheromone transport clearly distinguishes the elephant from other mammals studied, and complements the uniqueness of elephant anatomy, physiology, and behavior.     

Constraining the topology of the universe

The first year data from the Wilkinson Microwave Anisotropy Probe are used to place stringent constraints on the topology of the Universe. We search for pairs of circles on the sky with similar temperature patterns along each circle. We restrict the search to back-to-back circle pairs, and to nearly back-to-back circle pairs, as this covers the majority of the topologies that one might hope to detect in a nearly flat universe. We do not find any matched circles with radius greater than 25 degrees. For a wide class of models, the nondetection rules out the possibility that we live in a universe with topology scale smaller than 24 Gpc.     

Entanglement formation and violation of Bell's inequality with a semiconductor single photon source

We report the generation of polarization-entangled photons, using a quantum dot single photon source, linear optics, and photodetectors. Two photons created independently are observed to violate Bell's inequality. The density matrix describing the polarization state of the postselected photon pairs is reconstructed and agrees well with a simple model predicting the quality of entanglement from the known parameters of the single photon source. Our scheme provides a method to create no more than one entangled photon pair per cycle after postselection, a feature useful to enhance quantum cryptography protocols based on shared entanglement.     

Silsesquioxane models for silica surface silanol sites with adjacent siloxide functionalites and olefin polymerization catalysts thereof

Incompletely condensed silsesquioxanes of the type R7Si7O9(O[SiR'2O]n)OH (R = c-C5H9, c-C6H11; R' = Me, Ph; n = 1-4), containing a siloxane ring of variable size and rigidity and a remaining silanol, are described. Compared with a truly isolated silanol [R7Si8O12(OH)], solution and solid state FT-IR spectra of these compounds show a nu(OH) shift of approximately 150 cm(-1) to lower frequency, which suggests hydrogen bonding of the silanol with the internal siloxane ring. In agreement with this, the relative ion pair acidities of the silanols in THF, determined by UV/Vis, were lowered by 0.8-1.2 compared with a truly isolated silanol. Density functional theory (DFT) calculations on these systems confirm the presence of intramolecular hydrogen bonding. Possible interaction of the silyl ether functionalities with Lewis acidic metal sites was studied for the neutral gallium-substituted systems and cationic titanium silsesquioxane complexes, models for an immobilized titanium olefin polymerization catalyst. The electron donating capability of the siloxide functionalities in 1, 6, and 7 is not sufficient to satisfy the electron deficiency of the corresponding gallium silsesquioxane species, which form dimeric structures with a bridging siloxide unit rather than Lewis base adducts with coordinated siloxide functionalities. Metallation of 1 and 4 with [Cp"Ti(CH2Ph)3] (Cp" = eta5-1,3-C5H3(SiMe3)2) in a 1:1 ratio afforded monomeric titanasilsesquioxanes. To probe the effect of the neighboring siloxane ring on the highly Lewis acidic titanium center, the catalytic activities of the corresponding cationic half-sandwich complexes were tested in 1-hexene polymerization. Compared with the catalyst system based on the isolated silanol [(c-C5H9)7Si8O12OH], the presence of a neighboring siloxane ring causes considerable retardation of the polymerization process but also improves the stability of the catalyst.     

Trapping an elusive intermediate in manganese-oxo cubane chemistry

A new member of the Mn-oxo cubane core complex family [Mn2III,2IV4O4L6] (1), where L = (p-MeOPh)2PO2-, has been synthesized and characterized. Compound 1 possesses structurally inequivalent MnIII and MnIV with clear valence electron localization in the crystal phase, quite unlike the structurally equivalent sites, tetrahedral core symmetry, and delocalized valence of its analogue where L = Ph2PO2-. Compound 1 exhibits appreciable positive shifts (0.1-0.3 V) of both the oxidation and reduction electrochemical potentials, attributable to the remote electron donating p-MeO groups. Reduction of 1 by methanol yields a novel core complex [MnIII4O2(OMe)2(MeOH)[(p-MeOPh)2PO2]6] (2). Each MnIII of 2 is tetragonally distorted due to the Jahn-Teller effect with elongated Mn-O bonds that are directed at the two micro3-MeO bridges and neither of the two micro3-oxos. These electronically driven distortions provide a structural rationale for the greater basicity of the former sites and explain why 2 of the 4 corner oxos are preferentially reduced to water molecules.     

Diastereomer assignment of an olefin-linked bis-paracyclophane by ion mobility mass spectrometry

trans-1,2-Bis([2.2]paracyclophanyl)ethene (1) exists as a pair of diastereomers whose conformations, and thus effective collision cross sections, are quite different. The two forms can be obtained by different transition metal-catalyzed reactions. To assign meso and racemic structures, a novel method is reported in which experimental gas-phase ion mobility data are compared with theoretical structures obtained from molecular mechanics calculations.