Method for the determination of gamma-L-glutamyl-L-dihydroxyphenylalanine and its major metabolites L-dihydroxyphenylalanine, dopamine and 3,4-dihydroxyphenylacetic acid by high-performance liquid chromatography with electrochemical detection

A high-performance liquid chromatographic method for the analysis of gamma-L-glutamyl-L-dihydroxyphenylalanine (gludopa) and its major metabolites L-dihydroxyphenylalanine (L-DOPA), dopamine and 3,4-dihydroxyphenylacetic acid (DOPAC) is described. High sensitivity is achieved with a multi-cell coulometric detector utilising the specific electrochemical properties of gludopa (limit of detection 10 pg on-column). The retention time of gludopa was both pH-dependent and sensitive to negatively charged ion-pairing agents. An alumina-based solid-phase sample preparation technique with dihydroxybenzylamine as internal standard is described for plasma and urine (limit of detection 40 pg/ml) and an ultrafiltration technique is described for tissues (limit of detection 1-10 ng/g). After treatment with 50 mg/kg gludopa, in excess of twenty separate catecholic metabolic peaks can be detected in rat urine, whereas in humans after 9 mg/kg the only catechols detected were L-DOPA, dopamine and DOPAC.     

Phosphinoboration of Diazobenzene: Intramolecular FLP Synthon for PN2B-Derived Heterocycles

Phosphinoboration of diazobenzene with Ph₂PBR′₂ cleanly affords products of the form Ph₂P(PhNNPh)BR′₂ ( 2 : R′₂=catechol, cat; 4 : R′₂=phenanthrenediol, quin) and shows evidence of Ph₂P(PhNNPh)Bpin 7 (pin: pinacol). The mechanism of these reactions was probed computationally and shown to proceed via intermediates involving a diazobenzene-adduct of the boron center of the PB reagent. The resulting PNNB species 2 and 4 are shown to be frustrated Lewis pairs (FLPs). Despite the presence of weakly Lewis acidic boron centers, these species react with diazobenzene. Additionally, the FLP reactivity of 2 was further probed with 4-phenyl-1,2,4-triazole-3,5-dione, 1,10-phenanthroline-5,6-dione, and benzyl azide to give unique five-, six-, and eight-membered heterocyclic rings. Thus, phosphinoboration provides a new avenue to FLPs in which donor and acceptor sites are linked by nitrogen atoms.     

An asymmetric solar wind termination shock

Voyager 2 crossed the solar wind termination shock at 83.7 au in the southern hemisphere, approximately 10 au closer to the Sun than found by Voyager 1 in the north. This asymmetry could indicate an asymmetric pressure from an interstellar magnetic field, from transient-induced shock motion, or from the solar wind dynamic pressure. Here we report that the intensity of 4-5 MeV protons accelerated by the shock near Voyager 2 was three times that observed concurrently by Voyager 1, indicating differences in the shock at the two locations. (Companion papers report on the plasma, magnetic field, plasma-wave and lower energy particle observations at the shock.) Voyager 2 did not find the source of anomalous cosmic rays at the shock, suggesting that the source is elsewhere on the shock or in the heliosheath. The small intensity gradient of Galactic cosmic ray helium indicates that either the gradient is further out in the heliosheath or the local interstellar Galactic cosmic ray intensity is lower than expected.     

Equation of state and liquid-vapor equilibria of one- and two-Yukawa hard-sphere chain fluids: theory and simulation

The accuracy of several theories for the thermodynamic properties of the Yukawa hard-sphere chain fluid are studied. In particular, we consider the polymer mean spherical approximation (PMSA), the dimer version of thermodynamic perturbation theory (TPTD), and the statistical associating fluid theory for potentials of variable attractive range (SAFT-VR). Since the original version of SAFT-VR for Yukawa fluids is restricted to the case of one-Yukawa tail, we have extended SAFT-VR to treat chain fluids with two-Yukawa tails. The predictions of these theories are compared with Monte Carlo (MC) simulation data for the pressure and phase behavior of the chain fluid of different length with one- and two-Yukawa tails. We find that overall the PMSA and TPTD give more accurate predictions than SAFT-VR, and that the PMSA is slightly more accurate than TPTD.     

Sound transmission at low frequencies through the walls of distorted circular ducts

A theoretical treatment of sound transmission through the walls of distorted circular ducts is given, for plane mode transmission within the duct. The transmission mechanism is essentially that of “mode coupling”, whereby higher structural modes in the duct walls are excited, because of the wall distortion, by the internal sound field. The theory is in two parts: an approximate analytical model for the structural response of the walls to the internal sound field, and a structural radiation model. Computed results, based on the theory, are compared to measurements on “long-seam” air conditioning ducts. Where the duct geometry can be reliably specified, reasonably good agreement is obtained between theoretical and experimental data. It is concluded that mode coupling effects serve to account for the discrepancies between ideal and observed behaviour in sound transmission through duct walls.     

Crystal and molecular structure of rubidium azidotrimethylaluminate,Rb[Al(CH3)3N3]

The crystal structure of rubidium azidotrimethylaluminate has been determined from three-dimensional counter data, and refined by full-matrix least-squares techniques. The crystals belong to the monoclinic space groupP2₁/n, witha= 10.003(5),b=7.497(4),c= 11.806(5) Å, = 108.70(3) °, andD _c= 1.58 g cm⁼³ forZ=4. The finalR factor for 922 observed reflections is 0.049. The compound is not isostructural with its cesium analog. The aluminum atom is coordinated in a tetrahedral fashion, and the Al-N bond length is 1.944(8) Å.     

Gallic acid-functionalized magnetic nanoparticles: a convenient and green approach for synthesis of α-aminonitriles under solvent-free conditions

Research on Chemical Intermediates - Gallic acid-coated magnetic nanoparticles were efficiently prepared, characterized by Fourier transform infrared spectroscopy, X-ray diffraction, vibrating...     

Singular cardinals and strong extenders

We investigate the circumstances under which there exist a singular cardinal µ and a short (κ,µ)-extender E witnessing “κ is µ-strong”, such that µ is singular in Ult(V, E).