Unexpected Isolation of 4‐Isothiocyanatomethylene‐4H‐pyridine‐1‐carboxylic Acid Ethyl Ester as Potential Template in Organic Synthesis

The synthesis of 4‐isothiocyanatomethyl‐pyridine 4 in 36% yield by Hasegawa and Kotani (Japanese patent 49088878, 1974) has spurred us to investigate this preparation in detail. In addition to this compound, 4‐isothiocyanatomethylene‐4H‐pyridine‐1‐carboxylic acid ethyl ester 3 can be isolated. The synthesis of both compounds 3 and 4 were optimized to 75% and 50% yield respectively. Reaction of compound 3 with methylamine gave thiourea derivatives 5, the same product obtained on reacting 4‐isothiocyanatomethyl‐pyridine 4 with methylamine. We succeed in adjusting the reaction conditions to obtain high yield either from compound 3 or isothiocyanate derivatives 4.     

Development and validation of an LC–MS/MS method for the quantification of artificial sweeteners in human matrices

Artificial sweeteners are widely used as substitutes for sugar. The sweeteners are generally considered safe, however their whereabouts during pregnancy and lactation and the effect on child development are poorly explored. There is a need for new tools to measure these substances during pregnancy and lactation. Here, we describe the development and validation of a sensitive liquid chromatography–tandem mass spectrometry method for the simultaneous quantification of acesulfame, cyclamate, saccharin and sucralose in human plasma, umbilical cord blood, amniotic fluid and breast milk. The samples were prepared by protein precipitation and separated on a Luna Omega Polar C₁₈ column (2.1 × 50 mm, 1.6 μm). Electrospray ionization in negative mode and multiple reaction monitoring were used to monitor the ion transitions. The validated concentration ranges were from 1 to 500 ng/ml (10–500 ng/ml for sucralose). Interassay precisions were all ≤15% and the accuracies were within ±15%. Stability, linearity, dilution integrity, carryover and recovery were also examined and satisfied the validation criteria. Finally, this analytical method was successfully applied on spiked samples of plasma, umbilical cord blood, amniotic fluid and breast milk, proving its suitability for use in clinical studies on artificial sweeteners, including during pregnancy and lactation.     

Monitoring the Transition from Spherical to Polymer‐like Surfactant Micelles Using Small‐Angle X‐Ray Scattering

Despite over a century of modern surfactant science, the kinetic pathways of morphological transitions in micellar systems are still not well understood. This is mainly as a result of the lack of sufficiently fast methods that can capture the structural changes of such transitions. Herein, a simple surfactant system consisting of sodium dodecyl sulfate (SDS) in aqueous NaCl solutions is investigated. Combining synchrotron radiation small‐angle X‐ray scattering (SAXS) with fast stopped‐flow mixing schemes allows monitoring the process where polymer‐like micelles are formed from globular micelles when the salt concentration is suddenly increased. The results show that “worm‐like” micelles are formed by fusion of globular micelles and short cylinders in a fashion that bears similarities to a step‐like polymerization process.     

Confinement of nonneutral plasmas on magnetic surfaces

The confinement of a nonneutral plasma in a magnetic-surface, or stellarator, configuration is explored. The fluid equilibrium equations are derived and are found to be fundamentally different from previous results. Diocotron modes are predicted to be stable. The collisional confinement time can be very long. Possible applications include positron trapping and confinement of positron-electron plasmas. The basic physics can be addressed experimentally in the simple tabletop stellarator planned for construction at Columbia University.     

Critical slowing down of space-charge field relaxation in photorefractive sillenites

We propose a theoretical model for the recently reported anomalously long decay of a space-charge field that was resonantly excited in a photorefractive sillenite crystal [Phys. Rev. Lett. 79, 67 (1997)]. The model is based on the conventional concept of charge transfer and does not require excessively large values of the quality factor for space-charge waves. The effect in question is qualified as a critical slowing of the relaxation process as the threshold of optical oscillation is approached.     

Relationship between the properties of radical cations and the rate constants and the substitution patterns in electrophilic aromatic substitution

By a charge transfer mechanism for electrophilic aromatic substitution the logarithmic plot of overall rate constants for substitution against ionization potentials is correctly predicted. Also, orientation of substitution is found to be correlated with the hyperfine coupling constants of the aromatic radical cation. The presence of radical cations under the conditions of electrophilic substitution is discussed.