This research was undertaken to develop a sensitive, selective, and rapid analytical method to measure ethyl glucuronide (EtG) and ethyl sulfate (EtS) in urine as urinary biomarkers of alcohol exposure. Large-volume injection (LVI) coupled with liquid chromatography / electrospray tandem mass spectrometry was used to eliminate the need for either...
A novel method for detecting the peptidase activity of clinically relevant peptidases was investigated using solid-contact electrochemical polyion sensors under chronopotentiometric control. Complete instrumental control over ion-extraction was accomplished by incorporating a lipophilic electrolyte into the ion-selective membrane; the sensors had no intrinsic ion-exchange capabilities. The sensors were used to...
Catalysis of the racemizationof optically active phenyl
benzenethiolsulfinate, (+)-I, by (a) methylthioacetic acid (II) and (b)
a -methylthio-m-toluic acid (III) has been investigated in aqueous
dioxane and anhydrous acetonitrile at 39.6°C. Added II did not cause
any increase in the rate of racemization of (+)-I in either solvent. In
aqueous...
In previous work (Blakemore et al. Org. Lett. 2005, 7, 4721; Heterocycles 2006, 70, 609), successful elaborations of the lupine alkaloids (±)-α-isosparteine (dl-2) and (±)-β-isosparteine (dl-3) were realized from a common tetraoxobispidine precursor, 3,7-diallyl -2,4,6,8-tetraoxo-3,7-diazabicyclo[3.3.1]nonane (93). Herein, the tetraoxobispidine approach to lupine alkaloids was extended to a total synthesis of...
The concentration of chlorophyll in natural bodies of water is
commonly determined as a means to rapidly estimate the phytoplankton
biomass. The literature gives numerous warnings, however, as to the
problems involved with accurately determining chlorophyll
concentrations. The author's work at Crater Lake, Oregon enticed him
to explore critically the...
Many D2d-symmetric 2,2',6,6'-tetrasubstituted biphenyls are
readily prepared via net oxidative dimerization of appropriate
1,3-disubstituted benzenes. Conversion of such proprochiral
compounds to useful C2-symmetric chiral biphenyls requires
formal replacement of two substituents on opposing aryl ring
units with alternate groups. This under exploited
desymmetrization tactic has been demonstrated for the
generation...
A sensitive, selective, rapid analytical method based on large-volume injection (LVI)
liquid chromatography/ tandem mass spectrometry was developed using
commercially-available hardware that eliminates the need for either off-line or on-line
solid phase extraction. Centrifugation followed by the direct injection of 1,800 µL
was used for the quantification of illicit drugs,...
The synthesis of 3,3'-diphenylbenzopinacol was carried out both by means of the Grignard reaction between m-diphenyl magnesium iodide and benzil, and by reduction of m-phenyl benzophenone. The pinacol was rearranged and the products analyzed. The migration aptitude of m-biphenyl was determined to be 1.5. Attempts to prepare 3,3'-diphenyl-4,4'-dimethylbenzopinacol were unsuccessful....
An intramolecular variant of the modified-Julia olefination was demonstrated by the synthesis of α,β-unsaturated lactones in a mild and (Z)-selective fashion. The lynchpin reagent (benzothiazol-2-sulfonyl) acetic acid was synthesized in a straightforward fashion in 86% overall yield from commercially available 2-mercaptobenzothiazole via conversion to ethyl (benzothiazol-2-ylthio)acetate by base mediated alkylation...