High-performance liquid chromatographic determination of morphine and its 3- and 6-glucuronide metabolites: improvements to the method and application to stability studies

Improvements to previously reported methods for the determination of morphine, morphine-3-glucuronide (M3G) and morphine-6-glucuronide (M6G) in human plasma are described. The improved methods involve the use of a solid-phase extraction cartridge and a chromatographic system which uses paired-ion reversed-phase high-performance liquid chromatography with a radially compressed column. Only one cartridge is used to prepare each sample for chromatography and each cartridge may be used for at least fourteen 1-ml plasma samples. The recovery is greater than 85%. The improvements to the method of sample pretreatment and in the chromatographic conditions have allowed determination of morphine, M3G and M6G in human plasma down to 13.3 nmol/l (coefficient of variation = 9.3%), 108 nmol/l (6.6%) and 41 nmol/l (6.7%), respectively, using ultraviolet detection alone. It was shown that all three compounds were stable in plasma for up to 101 weeks when stored at -20 degrees C.     

Self-assembly of a linear mesoscale tetramer with electrical connectivity

Capillary interaction-based self-assembly of block-shaped mesoscale components into an electrically interconnected 1-D tetramer is reported. Low melting point solder droplets, selectively patterned on the faces of the blocks, were employed to drive the sequential alignment, registration, linking and electrical interconnection of each block. The solder patterns were designed so that successful assembly would only occur when the solder patterns on one block face were correctly aligned with those on the face of an adjacent block. For assembly, the blocks were agitated in a flask containing KBr solution. At 60 °C the solder was molten, and collisions between blocks enabled the solder menisci to easily interact. To minimize interfacial free energy, the menisci coalesced and quickly drove the interacting blocks to form a stable, registered and aligned assembly. When agitation was terminated and the solution cooled, the self-aligned, linear tetrameric arrangement of blocks was permanently captured by solder solidification, a process that provided good mechanical bonding and electrical interconnection between each block. PACS 81.16.Dn; 68.03.Cd; 85.40.-e     

The polarographic determination of indium in zinc-base alloys : The determination of indium in zinc and in zinc alloys of low aluminium content

Studies of the application of an 8-hydroxyquinoline extraction and of a zinc oxide “collection” procedure for the separation of trace amounts of indium from zinc alloys are described and discussed. A combination of radio-chemical and polarographic determination were employed for this work. A polarographic method for the determination of indium in zinc and in zinc alloys of low aluminium content is presented     

Δ4,4' -4-chalcogenapyranyl-4h-chalcogenapyrans : Synthesis,electrochemical oxidation,and esr investigations of radical-cation states

The O-, S-, Se- and Te-containing Δ^4,4' -2,2?,6,6'-tetramethyl-, -tetra-t-butyl- and -tetraphenyl-4-(chalcogenapyranyl)-4H-chalcogenapyrans were prepared from the corresponding chalcogenapyran-4-ones. The thia-, selena- and tellurapyran-4-ones were prepared by sodium borohydride reduction of the appropriate chalcogen and addition of the disodium chalcogenide to a 1,4-diyn-3-one. The comparative electrochemistry of all three series was examined by cyclic voltammetry. Within each scries the first oxidation (E₁) became more difficult with increasing chalcogen size. The radical-cation states of the tetra-t-butyl analogues were examined by ESR. The O and S analogues gave well-defined five-line spectra, but the Se and Te analogues gave broad single lines. The g value increased with increasing size of the heteroatom. A linear correlation exists between g value and spin-orbit coupling constants λ for the chalcogens, suggesting that the electron densities on the heteroatoms are similar in each heteroatom analogue.     

Effect of varying counterions on the sensitivity of electrohydrodynamic and fast atom bombardment mass spectrometry

The abundance of ion pairs (CA⁺) relative to that of doubly charged ions (C²⁺) in electrohydrodynamic (EH) mass spectra of a series of anions with a common dication in glycerol was found to increase in the order acetate < nitrite < chloride < bromide ≈ nitrate < iodide < perchlorate. Correlation with enthalpies of hydration for the anions suggests that this trend reflects the solution chemistry of ion association. These spectra also reveal that solvation rather than interactions with the extracting field is more important in determining the overall EH mass spectrometric sensitivity to doubly charged ions. Therefore, the use of anions that promote more extensive ion pairing enhances the overall sensitivity to multiply charged ions that otherwise interact strongly with the solvent, but reduces sensitivity to singly charged ions. These observations hold in fast atom bombardment mass spectrometry, surviving the invasive effects of the primary beam.     

Characterization of inclusion complexes of betamethasone-related steroids with cyclodextrins using high-performance liquid chromatography

HPLC was used to study the inclusion complexes formed between various beta- and gamma-cyclodextrins and a series of corticosteroids related to betamethasone. Apparent association constants were measured in acetonitrile-water for a set of 13 steroids. An increase in the stability of the steroid-cyclodextrin complex is observed at lower concentrations of acetonitrile. The effects of the nature of the halide at the 9-position, the location of a double bond within the C-ring, substitution at the 9- and 11-positions, and modification of the D-ring of the steroid backbone were studied. The 11- and 17-positions were found to be critically involved in the inclusion process. Larger apparent association constants were obtained with gamma-cyclodextrin (gamma-CD) than with beta-cyclodextrin (beta-CD) due to the increased diameter of the gamma-CD cavity. Van't Hoff plots were constructed to examine the thermodynamic properties of the inclusion process. Plots constructed using retention factors were found to be nonlinear when gamma-CD was present in the mobile phase. This is due to an increase in the strength of the inclusion complex as temperature decreases. Plots constructed using apparent association constants were linear, indicating that the mechanism of inclusion does not change over the range of temperatures studied (10 to 80 degrees C). Enthalpy-entropy compensation was observed for 11 of the 13 steroids studied. The usefulness of cyclodextrins to achieve the separation of steroids in HPLC is discussed and a practical application for the analysis of a steroid and three potential impurities is described.