Reference materials for marine science

Summary The second edition of the catalog of reference materials suited for use in marine science, originally compiled in 1986 for NOAA, IOC and UNEP, has been recently completed. The catalog lists more than 900 reference materials from thirteen producers and contains information about their proper use, sources, availability, and analyte concentrations. The reference material matrices include ashes, airborne particulate matter, gases, oils, rocks and sediments, sludges, tissues and waters. Reference materials used for the evaluation of instruments and the determination of sample physical properties are also included. Indices are available for elements, isotopes and organic compounds, as are cross references to CAS registry numbers, and alternate names and chemical structures of selected organic compounds.     

Stability studies of transition-metal linkage isomers using quantum mechanical methods. Groups 11 and 12 transition metals

Several hypotheses to elucidate the linkage isomer preference of the thiocyanate (SCN(-)) ion have been offered. For complexes with small coordination numbers (i.e., 1 and 2) and groups 11 (Cu-triad) and 12 (Zn-triad) metals, different levels of theory and a variety of basis sets have been employed to study linkage isomerism. Similar results are obtained for all density functionals tested, pure and hybrid. Overall, good agreement, vis-à-vis experimentally identified linkage isomers, is achieved for ab initio techniques, whereas semiempirical quantum mechanical methods show a bias toward S-ligated isomers. Despite the seeming ease for the a priori prediction of the most stable thiocyanate isomers using acid/base principles, this research highlights the sensitivity of quantitative calculations of transition-metal linkage isomerism to the choice of basis set and electron correlation, particularly with post-Hartree-Fock treatments.     

Preparation and characterization of chelating resins loaded with 2-(5-bromo-2-pyridylazo)-5-(diethylamino)phenol for preconcentration of rare earth elements

 Chelating resins prepared by sorption of 2-(5-bromo-2-pyridylazo)-5-(diethylamino)phenol (5-BrPADAP) on macroporous resins (Amberlite XAD-4 and XAD-7) were characterized. The adsorption properties (amount of chelating agent adsorbed per gram of resin, sorption kinetics, retention capacity, etc.) and the thermodynamic quantities of each adsorption process were determined. The retention of some rare earth elements (e.g. Er, Yb and Lu) on these chelating resins was studied in order to preconcentrate them for their determination by X-Ray fluorescence spectrometry. Received: 7 September 1995/Revised: 2 January 1996/Accepted: 10 January 1996     

Isomerisation of ω-hydroxyalkenes under hydroxycarbonylation conditions in palladium catalysed aqueous phase systems

The ω-hydroxyolefins 3-buten-1-ol, 3-buten-1-methyl-1-ol and 4-penten-1-ol were subjected to hydroxycarbonylation conditions in water in the presence of PdCl₂(PhCN)₂ and 4-8 equiv. of water soluble tris(3-sodiumsulfonatophenyl)phosphine (TPPTS), or N-bis(N′,N′-diethyl-2-aminoethyl)-4-aminomethylphenyl-diphenylphosphine (N3P). Under conditions of high conversion, the olefins primarily undergo isomerisation through a chain walking mechanism with selectivities for aldehyde ranging from 65% to 98%, with the lower values for longer chain alcohols. The lactones formed as the minor product are almost exclusively branched, indicating that in the first step 2,1-insertion is strongly favoured over 1,2-insertion. In the N3P system also linear lactone is produced at lower conversion. Running the reaction in D₂O produces multiple deuterium incorporation in all positions of the carbon chain. A mechanism is discussed.     

Impact of the Cooking Process on Metabolite Profiling of Acanthocereus tetragonus,a Plant Traditionally Consumed in Mexico

Acanthocereus tetragonus (L.) Hummelinck is used as an alternative food source in some Mexican communities. It has been shown that the young stems of A. tetragonus provide crude protein, fiber, and essential minerals for humans. In this work, we analyzed the phytochemical profile, the total phenolic content (TPC), and the antioxidant activity of cooked and crude samples of A. tetragonus to assess its functional metabolite contribution to humans. The phytochemical profile was analyzed using Ultra-High-Performance Liquid Chromatography coupled to High-Resolution Mass Spectrometry (UHPLC-PDA-HESI-Orbitrap-MS/MS). Under the proposed conditions, 35 metabolites were separated and tentatively identified. Of the separated metabolites, 16 occurred exclusively in cooked samples, 6 in crude samples, and 9 in both crude and cooked samples. Among the detected compounds, carboxylic acids, such as threonic, citric, and malic acids, phenolic acids, and glycosylated flavonoids (luteolin-O-rutinoside) were detected. The TPC and antioxidant activity were analyzed using the Folin–Ciocalteu method and the 2,2-diphenyl-1-picrylhydrazyl (DPPH) free radical inhibition method, respectively. The TPC and antioxidant activity were significantly reduced in the cooked samples. We found that some metabolites remained intact after the cooking process, suggesting that A. tetragonus represents a source of functional metabolites for people who consume this plant species.     

Coiling, entrainment, and hydrodynamic coupling of decelerated fluid jets

From algal suspensions to magma upwellings, one finds jets which exhibit complex symmetry-breaking instabilities as they are decelerated by their surroundings. We consider here a model system--a saline jet descending through a salinity gradient--which produces dynamics unlike those of standard momentum jets or plumes. The jet coils like a corkscrew within a conduit of viscously entrained fluid, whose upward recirculation braids the jet, and nearly confines transverse mixing to the narrow conduit. We show that the underlying jet structure and certain scaling relations follow from similarity solutions to the fluid equations and the physics of Kelvin-Helmholtz instabilities.     

The far infrared spectrum of trans-formic acid: An extension up to 175 cm−1

The far infrared spectrum of HCOOH was recorded at a high resolution (0.0009 cm^?1) and long path length (72 m) at the far-infrared beamline, Canadian Light Source. Spectra were recorded in the region 62–300 cm^?1, showing transitions from the trans-isomer.Ground state rotational transitions with K_a up to 30, were identified up to 175 cm^?1, extending the observation reported in the literature. A total of 3321 transitions were assigned and fitted together with previous (4149) published data. An improved set of rotational parameters was obtained adopting the symmetric top (A) reduction of the rotational Hamiltonian in the I^r representation. The newly measured far infrared transitions allowed the determination of all diagonal and off diagonal 8th order parameters L and of some of the diagonal 10th order parameters P.     

Robust D-wave pairing correlations in a hole-doped spin-fermion model

Pairing correlations are studied numerically in a hole-doped spin-fermion model. Simulations performed on up to 12 x 12 clusters provide indications of D-wave superconductivity away from half-filling comparable to those of the 2D t-J model. The pairing correlations are the strongest in the direction perpendicular to the dynamic stripes that appear in the ground state at some densities. An optimal doping, where correlations are maximized, was observed at approximately 25% doping with an estimated T(c) approximately 100-200 K, in qualitative agreement with high-T(c) cuprates' phenomenology, while pairing correlations are suppressed by static stripe inhomogeneities.