Trace element speciation in largemouth bass ( Micropterus salmoides) from a fly ash settling basin by liquid chromatography-ICP-MS

Analytical techniques used to examine the chemical speciation of multiple trace elements are important for the investigation of biological systems. Size exclusion chromatography (SEC) coupled to ICP-MS was used to investigate the speciation of Se, As, Cu, Cd and Zn in tissue extracts from a largemouth bass (Micropterus salmoides) collected from a coal fly ash basin and results were compared to a largemouth bass collected at a reference site. Using a Biosil SEC column, with an effective separation range of 100-7 KDa, Cu, Zn and Cd were shown to be bound to metallothionein (MT) in the liver, gill and, to a lesser extent, gonad tissue extract. In liver, muscle and gill of the ash basin bass, Se was predominantly present as low molecular weight species. Only in the gonad extract was the major fraction of Se associated with high molecular weight species. For the liver and gill extracts, further SEC-ICP-MS on a column with an effective separation range of 7000-500 Da was performed, but Se species still eluted near the total volume of the column suggesting a low molecular weight organic or inorganic species. Ion chromatography (IC)-ICP-MS using an AS7 column and HNO(3) gradient elution indicated that the Se and As species in the liver and gill extracts had similar retention times but these retention times did not correspond to retention times for As(III), As(V), dimethylarsenate, arsenobetaine, Se(IV), Se(VI), seleno-methionine, or seleno-cystine.     

New Molecular Receptors with Cyclophosphazene Subunits: Synthesis, Reactivity, and Structure-Property Relationships

A series of hydrophopic ( 2 and 3) and new hydrophilic ( 4– 7) molecular receptors of the PNP-lariat ether with tetra-substituted cyclotriphosphazene subunits have been prepared by the complete nucleophilic substitution of chlorine atoms in the reactive PNP-crown precursor 1 with the respective sodium cation-paired oxyanions (phenoxy 2, -naphthoxy 3, and methoxytrioxyethylenoxy 4) and aliphatic amines (n-propylamine 5 aziridine 6, and pyrrolidine 7). Their structures were established by MS and ³¹P NMR spectroscopy and their metal ion complexing properties tested by a TLC method. Comparison of the complexation behaviour for ligands 1– 7 shows that the affinity for particular cations is strongly substituent-dependent and, in general, is significantly enhanced by cooperation of the side arm donor atoms (O or N) with the parent PNP-crown structure in the binding process. The remarkable affinity of some ligands for selected cations, in particular lithium, cesium, and silver ions, is interpreted in terms of structure-property relationships.     

A magnetostatic-coupling based remote query sensor for environmental monitoring

A new type of in situ, remotely monitored magnetism-based sensor is presented that is comprised of an array of magnetically soft, magnetostatically-coupled ferromagnetic thin-film elements or particles combined with a chemically responsive material that swells or shrinks in response to the analyte of interest. As the chemically responsive material changes size the distance between the ferromagnetic elements changes, altering the inter-element magnetostatic coupling. This in turn changes the coercive force of the sensor, the amplitude of the voltage spikes detected in nearby pick-up coils upon magnetization reversal and the number of higher-order harmonics generated by the flux reversal. Since the sensor is monitored through changes in magnetic flux, no physical connections such as wires or cables are needed to obtain sensor information, nor is line of sight alignment required as with laser telemetry; the sensors can be detected from within sealed, opaque or thin metallic enclosures.     

Magnetic moments of composite fermions

There have been a considerable number of papers proposing composite models for leptons and quarks. Recently, Glück and Lipkin have stated that reproducing the observed magnetic moments of these fermions presents a serious difficulty for these composite models. We show for a renormalizable theory that, in contrast to Glück's and Lipkin's nonrelativistic arguments, a deeply bound system (with heavy constituent particle masses m_c) of (total) spin $\text{1}\text{2}$, charge e and mass m has the magnetic moment $\text{(e/2m) [1 +}\text{“usual” (QED + QCD + weak) corrections +O}\text{(m/m}{}_{\mathrm{<mtext>c</mtext>}}\text{)}\text{“new” bindng corrections]}$. Although there remains the considerable dynamical problem of obtaining “light” bound fermions from heavy constituents, there is no separate, additional magnetic moment difficulty.     

The application of neutron activation analysis to the determination of trace elements in pollen and sporopollenins

Neutron activation analysis has been used to assay the trace elements Co, Fe, Sc, Rb and Zn in pollen and derived sporopollenins. The method is capable of high precision and avoids the necessity for sample ashing and the introduction of reagent contamination. Rubidium was completely removed during the chemical isolation of sporopollenins and the remaining elements which survived chemical treatment were found in reduced amounts. The ratio of Sc: Fe in pollen and in several derived sporopollenins was found to be approximately constant. Results are discussed with reference to the possibilities of anomalous chemical behaviour of the elements resulting from irradiation.     

Radiation-driven hydrodynamics of high- hohlraums on the national ignition facility

The first hohlraum experiments on the National Ignition Facility (NIF) using the initial four laser beams tested radiation temperature limits imposed by plasma filling. For a variety of hohlraum sizes and pulse lengths, the measured x-ray flux shows signatures of filling that coincide with hard x-ray emission from plasma streaming out of the hohlraum. These observations agree with hydrodynamic simulations and with an analytical model that includes hydrodynamic and coronal radiative losses. The modeling predicts radiation temperature limits with full NIF (1.8 MJ), greater, and of longer duration than required for ignition hohlraums.     

Retention of configuration in the nucleophilic substitution reactions of some nine-membered ansa derivatives of cyclotriphosphazatriene

X-ray crystallographic evidence shows that nucleophilic substitution reactions of two different types of cyclophosphazene derivatives with relatively rigid nine-membered ansa rings leads to the first demonstration of retention of configuration in these molecular systems.     

Gas-liquid and gas-liquid-solid catalysis in a mesh microreactor

A microstructured mesh contactor that can offer residence time of more than minutes is used for gas-liquid-solid hydrogenations and gas-liquid asymmetric hydrogenations. Applications for catalyst/chiral inductor screening and for kinetic data acquisition are demonstrated.     

Small-core As-Se fiber for Raman amplification

We have demonstrated Raman small-core As-Se fiber. More than 20-dB of gain was observed in a 1.1-m length of fiber pumped by a nanosecond pulse of approximately 10.8-W peak power at 1.50 microm. The peak of the Raman gain occurred at a shift of approximately 240 cm(-1). The Raman gain coefficient is estimated to be approximately 2.3 x 10(-11) m/W, which is more than 300 times greater than that of silica. The large Raman gain coefficient coupled with the large IR transparency window of these fibers shows promise for development of As-Se Raman fiber lasers and amplifiers in the near-, mid-, and long-IR spectral regions.     

A new copper acetate-bis(oxazoline)-catalyzed, enantioselective Henry reaction

A highly enantioselective, nitroaldol reaction catalyzed by a chiral Cu(II) bis(oxazoline) complex has been developed. The reaction scope includes both aromatic and aliphatic aldehydes (15 examples) affording products in good yields and enantioselectivities (87-94% ee). An X-ray structure of the catalyst has been provided along with a rationalization of the sense of asymmetric induction.