Effects of formalin preservation on stable carbon and nitrogen isotope signatures in Calanoid copepods: implications for the use of Continuous Plankton Recorder Survey samples in stable isotope analyses

Preserved and archived organic material offers huge potential for the conduct of retrospective and long-term historical ecosystem reconstructions using stable isotope analyses, but because of isotopic exchange with preservatives the obtained values require validation. The Continuous Plankton Recorder (CPR) Survey is the most extensive long-term monitoring program for plankton communities worldwide and has utilised ships of opportunity to collect samples since 1931. To keep the samples intact for subsequent analysis, they are collected and preserved in formalin; however, previous studies have found that this may alter stable carbon and nitrogen isotope ratios in zooplankton. A maximum ~0.9‰ increase of δ(15) N and a time dependent maximum ~1.0‰ decrease of δ(13) C were observed when the copepod, Calanus helgolandicus, was experimentally exposed to two formalin preservatives for 12 months. Applying specific correction factors to δ(15) N and δ(13) C values for similarly preserved Calanoid species collected by the CPR Survey within 12 months of analysis may be appropriate to enable their use in stable isotope studies. The isotope values of samples stored frozen did not differ significantly from those of controls. Although the impact of formalin preservation was relatively small in this and other studies of marine zooplankton, changes in isotope signatures are not consistent across taxa, especially for δ(15) N, indicating that species-specific studies may be required.     

Cyclopropane-derived peptidomimetics. Design, synthesis, and evaluation of novel enkephalin analogues

It is known that peptide mimics containing trans-substituted cyclopropanes stabilize extended conformations of oligopeptides, and molecular modeling studies now suggest that the corresponding cis-cyclopropane dipeptide isosteres could stabilize a reverse turn. To begin to assess this possibility, a series of cis-substituted cyclopropanes were incorporated as replacements of the Gly(2)-Gly(3) and Phe(4)-Leu(5) dipeptide subunits in Leu-enkephalin (H(2)N-Tyr-Gly-Gly-Phe-Leu-OH), which is believed to bind to opiod receptors in a conformation containing a beta-turn. General methods for the synthesis of the cyclopropane-containing dipeptide isosteres -XaaPsi[COcpCO]Yaa- and -XaaPsi[NHcpNH]Yaa-were developed by a sequence that featured the enantioselective cyclization of allylic diazoacetates catalyzed by the chiral rhodium complexes Rh(2)[(5S)-MEPY](4) and Rh(2)[(5R)-MEPY](4). A useful modification of the Weinreb amidation procedure was applied to the opening of the intermediate lactones with dipeptides, and a novel method for the synthesis of substituted diaminocyclopropanes was also developed. The Leu-enkephalin analogues were tested in a panel of binding and functional assays, and although those derivatives containing cyclopropane replacements of the Gly(2)-Gly(3) exhibited low micromolar affinity for the mu-receptor, analogues containing such replacements for the Phe(4)-Leu(5) subunit did not bind with significant affinity to any of the opioid receptors. These results are discussed.     

Pyridinium chlorochromate (PCC) oxidation of bishomoallylic tertiary alcohols. A structure–reactivity study

The mechanism of the Cr(VI) oxidation of an alkene C=C is not known for certain. A particularly useful and novel example of this process is the intramolecular oxidative cyclization of bishomoallylic tertiary alcohols by pyridinium chlorochromate (PCC) to yield substituted tetrahydrofuran products via the tethered chromate ester. Several such tertiary alcohols were prepared in this study which varied in the number and position of alkyl groups attached to the C=C. The relative reactivity of these substrates toward PCC under standard conditions is dependent only on the number of R groups on the C=C, not on the degree of substitution on the most highly substituted alkene carbon. This observation suggests a symmetrical transition state in this intramolecular Cr(VI) alkene oxidation.     

Determination of metals in urine by direct injection of sample,high-performanc liquid chromatography and electrochemical or spectrophotometric detection

A method for the rapid and simultaneous determination of copper, nickel and lead in urine is described. Direct injections of freshly acidified and filtered (0.45-μm) urine samples were made onto a reverse-phase separator column with a guard column for sample clean-up. By complexing the metals with a dithiocarbamate ligand included in the mobile phase, the metal complexes could be detected electrochemically (copper and nickel) or spectrophotometrically (copper, nickel and lead). The procedure is shown to provide a convenient method for the determination of copper and nickel at normal to occupationally exposed levels of urinary output (electrochemical detection) after direct injection of samples. Spectrophotometric detection methods were insufficiently sensitive for direct determinations of copper and nickel at some of the lower levels found in urine. The spectrophotometric detection of lead is subject to interference by u.v.-absorbing constituents present in urine and is restricted to detection of lead in persons over-exposed to lead, unless additional clean-up procedures are applied.     

Synthesis of new fulvenes containing heterocyclic substituents

Four new fulvene derivatives bearing heterocyclic substituents have been prepared. Base-promoted condensation of cyclopentadiene with tetrahydropyran-4-one, tetrahydrothiopyran-4-one, and 1-methyl-4-piperidone afforded 4-(cyclopentadienylidene)tetrahydropyran 1 , 4-(cyclopentadienylidene)tetrahydrothiopyran 2 , and N-methyl-4-(cyclopentadienylidene)piperidine 3 in yields ranging from 28% to 75%. Methylation of 3 with methyl iodide gave the corresponding ammonium salt, 4 .     

A stereoselective synthesis of anti-gamma,delta-alkynyl- and -alkenyl-beta-hydroxy-alpha-amino esters from tin(II) enolates of glycinate

Condensations between the tin(II) enolate 11 of ethyl N-tosylglycinate and conjugated ynals 12 and ynones 14 are highly diastereoselective, in favour of the anti-isomers 13 and 15; similar reactions of enals and enones 17 show lower but still useful levels of anti-stereoselectivity.     

The influence of sulfur adsorption on the step structure of vicinal Mo(100): a LEED and STM study

The effect of sulfur adsorption on the step structure of vicinal Mo(100) surfaces has been studied with scanning tunneling microscopy (STM) and low energy electron diffraction (LEED). STM was used for low densities of steps on a nominally flat (100) surface. LEED was used to study the more highly and regularly stepped (910), (911), and (28,4,1) oriented surfaces. Steps and the sulfur adsorbate were found to have a strong interaction. The presence and orientation of steps on the surface governed the formation of ordered domains of sulfur, and sulfur modified the structure of the steps on the surface. Both techniques show that monatomic steps predominate on the clean surfaces. When sulfur was adsorbed on the surfaces, however, steps coalesced to form groups of steps, double atomic height steps, and multiple height steps, depending on sulfur coverage and initial step density. The results are discussed in the framework of the theory of equilibrium crystal shape and provide information on how the Mo step-step interactions are affected by sulfur adsorption.     

Heat pinches in electron-heated Tokamak plasmas: theoretical turbulence models versus experiments

Two fluid turbulence models, the drift wave based quasilinear 1.5D Weiland model and the electromagnetic global 3D nonlinear model CUTIE, have been used to account for heat pinch evidence in off-axis modulated electron cyclotron heating experiments in the Rijnhuizen Tokamak Project. Both models reproduce the main features indicating inward heat convection in mildly off-axis cases. In far-off-axis cases with hollow electron temperature profiles, the existence of outward convection was reproduced only by CUTIE. Turbulence mechanisms driving heat convection in the two models are discussed.     

Piperidines from acid-catalysed cyclisations: Pitfalls,solutions and a new ring contraction to pyrrolidines

The success of acid-catalysed cyclisations of alka-4-enylamine derivatives to piperidines depends very much on the nature of the amine protecting group: while carbamates and related amides can usually be readily and cleanly transformed, the corresponding sulfonamides react further by ring contraction leading to pyrrolidines, especially when such substrates are sterically crowded.