The stannylation of carbonyl-stabilised phosphorus ylids,and tin-assisted elimination reactions

The interaction of organotin halides with lithium salts of mono-substituted phosphorus ylids and also with disubstituted ylids is described.     

Wurster's crowns: a comparative study of ortho- and para-phenylenediamine-containing macrocyclic receptors

Two series of isomeric, redox-responsive azacrown ethers based on ortho- and para-phenylenediamine (Wurster's crowns) have been synthesized and their properties explored through 13C NMR spectroscopy, electrospray ionization mass spectrometry, cyclic voltammetry, and X-ray crystallography. These crowns display strong affinity for alkali metal cations while maintaining comparable selectivity profiles to the parent crown ethers from which they are derived. Like Wurster's reagent (N,N,N',N'-tetramethyl-p-phenylenediamine or para-TMPD), the para-Wurster's crowns undergo two reversible one-electron oxidations. The integrity of the alkali metal ion complexes is maintained in the neutral and singly oxidized ligand states but not after removal of two electrons. In contrast, the oxidation of ortho-Wurster's crowns is scan rate dependent, occurring at potentials substantially higher than their para counterparts, with their complexes oxidizing irreversibly. X-ray crystal structures of representative complexes show, in all cases, participation of the redox-active phenylenediamine subunits in complex formation via direct bonding to the guest cation.     

Detector technologies for comprehensive two-dimensional gas chromatography

The detector is an integral and important part of any chromatographic system. The chromatographic peak profiles (i.e. peak separation) should, ideally, be unaffected by the detector--it should only provide the sensing capacity required at the end of a column separation process. The relatively new technique of comprehensive 2-D GC (GC x GC) extends the performance of GC manyfold, but comes at a price--existing GC systems may not be adequately designed with the requirements of GC x GC in mind. This is primarily the need for precise measurement of very fast peaks entering the detector (e.g. as fast as 50 ms basewidth in some instances). The capacity of the detector to closely track a rapidly changing chromatographic peak profile depends on a number of factors, such as design of flow paths and make-up gas introduction, type of detector response mechanism, and the chemistry of the response. These factors are discussed here as a means to appreciate the technical demands of detection in GC x GC. The MS detector will not be included in this review.     

Aromaticity and Möbius antiaromaticity in monocyclic [11]annulenium cations

Monocyclic [11]annulenium cations, which are experimentally unknown, have been studied primarily via DFT methods but also with some CCSD(T) validation. We have located six minima: two doubly trans (26, 27), one triply trans (28), one singly trans (29), one quintuply trans (trannulene-type, 33), and one all-cis (31). The first three are aromatic, 33 is modestly aromatic, 29 is nonaromatic, and the last is a M?bius antiaromatic species. We also investigated the fusion of various numbers of three-membered rings (3MRs) to the central 11-membered ring (11MR). We found several planar, all-cis-[11]annulenium ion derivatives as well as another M?bius antiaromatic species (52b); for comparison, we also found planar, antiaromatic all-cis-[12]annulene (60) and [15]annulenium cation (61) derivatives. The (anti)aromatic characterization of these compounds is based mainly on calculated magnetic data for the ground singlet and vertical triplet states, although aromatic stabilization energies (ASE) are also considered. Data for optimized triplets, several of which are M?bius aromatic systems (31t, 52t, 63t, 64t), are also included. Several of these cations are reasonable synthetic targets.     

Radium-224 in natural waters measured by γ-ray spectrometry

A method based on Ge(Li) γ-ray spectrométry is applied to the determination of ²²⁴Ra (t_{$\text{1}\text{2}$}= 3.64 days) in natural waters. The ²²⁴Ra is first removed from several hundred liters of water by preconcentration onto manganese dioxide-impregnated acrylic fibers. The fibers are leached, radium is coprecipitated with barium sulfate, and the γ-ray activity is counted so that activity ratios among ²²⁴Ra, ²²⁵Ra and ²²⁶Ra can be calculated. Concentrations are determined by using the ²²⁶Ra concentration determined on a small separate sample. Results from samples collected from ground water, estuarine, and continental shelf environments are presented.     

Structural studies in main group chemistry : XIX. Organotin(IV) derivatives of tetracyanoethylene, 7,7,8,8-tetracyanoquinodimethane and 2,3,5,6-tetrachlorobenzoquinone. The isolation of stable organotin-substituted radicals

The reaction of organotin chlorides with the lithium salt of 7,7,8,8-tetracyanoquinodimethane (TCNQ) or hexaalkylditins with TCNQ yield stable organotin-substituted free radicals of the types R₃SnTCNQ^. (R = Me, n-Pr, n-Bu) and Me₂Sn(TCNQ^.)₂. The reaction of hexaphenylditin with TCNQ yields a (σ → π) charge transfer complex of stoichiometry (Ph₃SnSnPh₃)·TCNQ, whilst [Me₂SnCl(terpyridyl)⁺](TCNQ^-·) was isolated from the reaction of [Me₂SnCl(terpyridlyl)⁺][Me₂SnCl₃^-] and LiTCNQ. The oxidation of hexaalkylditins by tetracyanoethylene (TCNE) yields stable free radicals of the type R₃SnTCNE·, but treatment with 2,3,5,6-tetrachlorobenzoquinone yields either R₃SnOC₆Cl₄O·-p (R = Me) or R₃SnOC₆Cl₄OSnR₃-p (R = n-Bu, Ph). Tin-119 Mössbauer spectroscopy shows that the derivatives R₃SnTCNQ· and R₃TCNE· have trigonally-bipyramidally coordinated tin with planar [SnC₃] skeletons and bridging [TCNQ·] and [TCNE·] groups forming infinite one-dimensional chain structures. Me₃SnOC₆Cl₄O·-p was inferred to possess a similar structure but with oxy bridges forming chains with a Sn---O---Sn---O backbone. Me₂Sn(TCNQ·)₂ has a structure intermediate between tetrahedral and octahedral with a non-linear MeSnMe unit and anisobidentate chelation by two TCNQ groups. The TCNQ derivatives were of two types: (i) “green” or “brown”, indicative of delocalisation of the Ione electron over the cyanoquinone ligand, and (ii) a “blue” form in which spin-pairing of the Ione electron between adjacent organic groups takes place. Me₃SnTCNQ· may exist in both forms depending upon the mode of preparation.     

A short synthetic route to the calystegine alkaloids

An efficient strategy is described for the synthesis of enantiopure calystegine alkaloids. The key step employs a zinc-mediated fragmentation of benzyl-protected methyl 6-iodo-glycosides followed by in situ formation of the benzyl imine and Barbier-type allylation with zinc, magnesium, or indium metal. Stereochemistry in the pivotal allylation is controlled by the choice of the metal. The functionalized 1,8-nonadienes, thus formed, are converted into cycloheptenes by ring-closing olefin metathesis. Regioselective hydroboration and oxidation give the corresponding cycloheptanones, which are deprotected to afford the desired calystegines. Hereby, calystegine B(2), B(3), and B(4) are prepared from D-glucose, D-galactose, and D-mannose, respectively. This route constitutes the shortest synthesis of calystegine B(2) and gives rise to the first total syntheses of calystegine B(3) and B(4).     

Inversion of particle-stabilized emulsions of partially miscible liquids by mild drying of modified silica particles

Using a system of modified silica particles and mixtures of water and 2,6-lutidine to form particle-stabilized emulsions, we show that subtle alterations to the hydration of the particle surface can cause major shifts in emulsion structure. We use fluorescence confocal microscopy, solid state nuclear magnetic resonance (NMR) and thermo-gravimetric analysis (TGA) to explore this sensitivity, along with other shifts caused by modifications to the silica surface chemistry. The silica particles are prepared by a variant of the St?ber procedure and are modified by the inclusion of 3-(aminopropyl)triethoxysilane and the dye fluorescein isothiocyanate. Treatment prior to emulsification consists of gently drying the particles under carefully controlled conditions. In mixtures of water and 2,6-lutidine of critical composition, the particles stabilize droplet emulsions and bijels. Decreasing particle hydration yields an inversion of the emulsions from lutidine-in-water (L/W) to water-in-lutidine (W/L), with bijels forming around inversion. So dependent is the emulsion behavior on particle hydration that microscopic differences in drying within a particle sample can cause differences in the wetting behavior of that sample, which helps to stabilize multiple emulsions. The formation of bijels at emulsion inversion is also crucially dependent on the surface modification of the silica.     

Antibody properties for chemically reversible biosensor applications

A recently reported fiber-optic sensor based on a homogeneous fluorescence energy-transfer immunoassay operates in a continuous, reversible manner to quantify the anticonvulsant drug phenytoin (5,5-diphenylhydantoin). The chemical kinetics of the two simultaneous antibody-hapten (analyte) and antibody-hapten (labeled indicator) reactions in the sensor are now modeled mathematically. Simulation shows that the chemical response time is controlled by the dissociation rate constant and is independent of the association rate constant, and that an equalibrium chemical response can be achieved in minutes. The sensitivity and dynamic range of the analyte concentration which can be measured depends on the ratio of dissociation rate constants for the labeled and unlabeled hapten reactions, and on the total concentration of reactants in the sensor. The relative concentration ratios of antibody to labeled hapten has little impact on the sensitivity or dynamic range of the system, but can be optimized to provide the maximum amount of labeled hapten availble for instrumental measurement.     

A molecular orbital study of the rotation about the C-C bond in 1,3-butadiene

The geometry and energy of 1,3-butadiene have been calculated using the 6-311G** basis set as a function of the CCCC dihedral angle-0 ° (trans), 30 °, 60 °, 75 °, 90 °, 120 °, 135 °, 150 °, 165 ° and 180 ° (cis)-assuming that the vinyl groups remain planar. Potential minima are located at 0 ° and 141.4 °, with the trans structure more stable than the gauche by 13.2 kJ mol^–1. Potential maxima are located at 76.7 °, giving a barrier height of 25.4 kJ mol^–1 relative to the trans structure, and at 180 ° giving a barrier height of 3.0 kJ mol^–1 relative to the 141.4 °-gauche structure. Using the 6-31G* basis set the inclusion of electron correlation, accounting for about 52% of the correlation energy, was found to produce no significant change in the shape of the potential energy curve. The magnitude of the expectation energy differences is such that both barriers with respect to the 14l.4 °-gauche maximum structure can be categorized unequivocally as attractive-dominant, whereas the values for the energy barrier with respect to the trans structure, although characteristic of a repulsive-dominant barrier at the 6–311G** level, are sufficiently small that higher level calculations might give the opposite result. Analysis of V _nn for the conversion reactions cis 150 °-gauche, trans 60 °-gauche, and trans 90 °-gauche in terms of the individual contributions from the various internuclear interactions shows that nonbonded interactions are important, not only in initiating the destabilization of the crowded cis structure, but also through-out the entire range of CCCC dihedral angles, 0 ° to 180 °.