Mechanistic studies of metal ion binding to water-soluble polymers using potentiometry

A method for elucidating metal ion binding mechanisms with water-soluble polymers has been developed in which the polymer is treated as a collection of monomeric units. Data obtained from potentiometric titrations are analysed by the ESTA library of programs and apparent formation constants may be calculated. From this information, predictions may be made as to metal ion separation using complexation-ultrafiltration techniques. The polymer used in this study was Polymin Water-Free and its complexation with Hg(II), Cd(II), Pb(II), Co(II) and Ni(II) was successfully modelled.     

Zero and Infinite Curvature Limits of Hyperbolic Monopoles

We show that the zero curvature limit of the space of hyperbolicmonopoles gives the Euclidean monopoles, settling a conjectureof Atiyah. We also study the infinite curvature limit of thespace of hyperbolic monopoles, and show that the associatedrational maps appear explicitly here. 1991 Mathematics SubjectClassification 81T13, 53C07.     

The Schur function realization of vertex operators

We present a realization of untwisted vertex operators in terms of operations on Schur functions. Calculations of matrix elements and traces of products of vertex operators are performed using results from the classical theory of symmetric functions. The concepts of compound, composite and supersymmetric Schur functions naturally appear in this context. Furthermore, a trace formula for a product of vertex operators turns out to be a generalization of a MacDonald identity reformulated in terms of Schur functions.     

Local internal supersymmetry of the free Maxwell theory

The free Maxwell theory is shown to possess an extended gauge invariance consisting of local internal supersymmetry transformations in addition to the usual local phase transformations. The Maxwell lagrangian is derived as a particular gauge choice in the extended theory.     

Synthesis of enantiopure substituted piperidines via an aziridinium ring expansion

Herein we report a novel methodology for the asymmetric synthesis of 3-substituted piperidines from readily available chiral building blocks. This method, which features a novel irreversible dihydropyrole-tetrahydropyridine ring expansion, allows the introduction of a large variety of substituents at the 3-position and permits substitution at the 2- and 6-position giving mono-, di-, or trisubstituted piperidines with high diastereocontrol.     

Beaked whale (Mesoplodon densirostris) passive acoustic detection in increasing ambient noise

Passive acoustic detection is being increasingly used to monitor visually cryptic cetaceans such as Blainville's beaked whales (Mesoplodon densirostris) that may be especially sensitive to underwater sound. The efficacy of passive acoustic detection is traditionally characterized by the probability of detecting the animal's sound emissions as a function of signal-to-noise ratio. The probability of detection can be predicted using accepted, but not necessarily accurate, models of the underwater acoustic environment. Recent field studies combining far-field hydrophone arrays with on-animal acoustic recording tags have yielded the location and time of each sound emission from tagged animals, enabling in-situ measurements of the probability of detection. However, tagging studies can only take place in calm seas and so do not reflect the full range of ambient noise conditions under which passive acoustic detection may be used. Increased surface-generated noise from wind and wave interaction degrades the signal-to-noise ratio of animal sound receptions at a given distance leading to a reduction in probability of detection. This paper presents a case study simulating the effect of increasing ambient noise on detection of M. densirostris foraging clicks recorded from a tagged whale swimming in the vicinity of a deep-water, bottom-mounted hydrophone array.     

A Remarkable cis‐ and trans‐Spanning Dibenzylidene Acetone Diphosphine Chelating Ligand (dbaphos)

A multidentate and flexible diolefin–diphosphine ligand, based on the dibenzylidene acetone core, namely dbaphos ( 1 ), is reported herein. The ligand adopts an array of different geometries at Pt, Pd and Rh. At Pt^II the dbaphos ligand forms cis‐ and trans‐diphosphine complexes and can be defined as a wide‐angle spanning ligand. ¹H NMR spectroscopic analysis shows that the β‐hydrogen of one olefin moiety interacts with the Pt^II centre (an anagostic interaction), which is supported by DFT calculations. At Pd⁰ and Rh^I, the dbaphos ligand exhibits both olefin and phosphine interactions with the metal centres. The Pd⁰ complex of dbaphos is dinuclear, with bridging diphosphines. The complex exhibits the coordination of one olefin moiety, which is in dynamic exchange (intramolecular) with the other “free” olefin. The Pd⁰ complex of dbaphos reacts with iodobenzene to afford trans‐[Pd^II(dbaphos)I(Ph)]. In the case of Rh^I, dbaphos coordinates to form a structure in which the phosphine and olefin moieties occupy both axial and equatorial sites, which stands in contrast to a related bidentate olefin, phosphine ligand (“Lei” ligand), in which the olefins occupy the equatorial sites and phosphines the axial sites, exclusively.     

A sensitive and selective LC-differential mobility-mass spectrometric analysis of allopregnanolone and pregnanolone in human plasma

A sensitive and selective method was developed to quantitate allopregnanolone and its 5β isomer pregnanolone in human plasma using liquid chromatography-differential mobility separation combined with MS/MS detection. The method employed a simple liquid–liquid extraction of 100 μL plasma with hexane/ethyl acetate. After extraction, the sample was derivatized using a quaternary aminooxy reagent. Separation of allopregnanolone, pregnanolone, and their 3β epimers (epiallopregnanolone and epipregnanolone) was achieved using a Phenomenex Kinetex C18 2.1?×?100-mm 2.6-μm column. A linear calibration curve was obtained over the concentration range from 10 to 25,000 pg/mL, and the inter- and intra-day accuracy of the quality control samples were between 90 and 110 % with the inter- and intra-day precision less than 10 %. The lower limit of quantitation is 50 fg (157 amol) on column for both allopregnanolone and pregnanolone which is 100-fold less than the underivatized compounds. The recovery is above 95 %, and the extracted samples are stable for at least 6 days when stored at 4 °C. Plasma samples from normal, pregnant, and postpartum women were analyzed using this method.