Development and validation of a high-throughput double solid phase extraction-liquid chromatography-tandem mass spectrometry method for the determination of tetrodotoxin in human urine and plasma

A sensitive analytical method for the determination of tetrodotoxin (TTX) in urine and plasma matrices was developed using double solid phase extraction (C18 and hydrophilic interaction liquid chromatography) and subsequent analysis by HPLC coupled with tandem mass spectrometry. The double SPE sample cleanup efficiently reduced matrix and ion suppression effects. Together with the use of ion pair reagent in the mobile phase, isocratic elution became possible which enabled a shorter analysis time of 5.5 min per sample. The assay results were linear up to 500 ng mL⁻¹ for urine and 20 ng mL⁻¹ for plasma. The limit of detection and limit of quantification were 0.13 ng mL⁻¹ and 2.5 ng mL⁻¹, respectively, for both biological matrices. Recoveries were in the range of 75-81%. To eliminate the effect of dehydration and variations in urinary output, urinary creatinine-adjustment was made. TTX was quantified in eight urine samples and seven plasma samples from eight patients suspected of having TTX poisoning. TTX was detected in all urine samples, with concentrations ranging from 17.6 to 460.5 ng mL⁻¹, but was not detected in any of the plasma samples. The creatinine-adjusted TTX concentration in urine (ranging from 7.4 to 41.1 ng μmol⁻¹ creatinine) correlated well with the degree of poisoning as observed from clinical symptoms.     

Iron-catalyzed cross-coupling reactions between a bicyclic alkenyl triflate and Grignard reagents

Fe-catalyzed cross-coupling reactions between a bicyclic alkenyl triflate and Grignard reagents were investigated. Under the optimized reaction conditions, various 2-substituted bicyclic alkenes were synthesized in moderate to excellent yields (52-93%). This method provided an efficient route for the synthesis of 2-substituted bicyclic alkenes with secondary alkyl groups which cannot be synthesized using previous methods such as Pd-catalyzed coupling reactions and lithium-halide exchange reactions.     

The Organocatalytic Asymmetric Prins Cyclization

We describe here the design and development of an organocatalytic Prins cyclization. In the presence of a confined chiral imidodiphosphoric acid catalyst, salicylaldehydes react with 3‐methyl‐3‐buten‐1‐ol to afford highly functionalized 4‐methylenetetrahydropyrans in excellent regio‐ and enantioselectivity. The extreme steric demand of the acid catalyst is key for the success of this transformation.     

Intervalley gap anomaly of two-dimensional electrons in silicon

We report here a systematic study of the energy gaps at the odd-integer quantum Hall states nu = 3 and 5 under tilted magnetic (B) fields in a high quality Si two-dimensional electron system. Out of the coincidence region, the valley splitting is independent of the in-plane fields. However, the nu = 3 valley gap differs by about a factor of 3 (Deltav approximately 0.4 vs 1.2 K) on different sides of the coincidence. More surprisingly, instead of reducing to zero, the energy gaps at nu = 3 and 5 rise rapidly when approaching the coincidence angles. We believe that such an anomaly is related to strong couplings of the nearly degenerate Landau levels.     

Quantum Hall ferromagnetism in a two-valley strained Si quantum well

Tilted field magnetotransport study was performed in a two-valley strained Si quantum well and hysteretic diagonal resistance spikes were observed near the coincidence angles. The spike around filling factor ν=3 develops into a giant feature when it moves to the high-field edge of the quantum Hall (QH) state and quenches for higher tilt angles. When the spike is most prominent, its peak resistance is temperature independent from T20 mK up to 0.3 K, which is different from the critical behavior previously reported near the Curie temperature of the QH ferromagnet in AlAs quantum wells. Our data suggest a strong interplay between spins and valleys near the coincidence.     

A Practical Route to Chiral Phenylalanine via the Condensation of Keto Acids with Amides and Asymmetric Hydrogenation

The condensation of β-phenylpyruvic acid with amides gave olefinic intermediates in good yields (75-80%). The asymmetric catalytic hydrogenation of α-acetamidocinnamic acid with high enantioselectivity is described.     

Effect of C60 molecular rotation on nanotribology

The effect of C60 molecular rotation on the nanotribological properties of C60 single crystal surfaces has been studied by atomic/frictional force microscopy. The orientational order-disorder phase transition, in which the high temperature C60 free rotation is reduced to a low temperature hindered rotation, is shown to give rise to an abrupt change in friction and adhesion. This change in frictional force is quantitatively consistent with the observed change in adhesion. The similar slopes of the friction versus load curves in both phases indicate that the friction coefficient in the two phases remains about the same. Hence the C60 rotation does not provide an additional energy dissipation channel in the friction process.     

Frequency dependence of cyclotron resonance in si inversion layers in the region of activated conductivity

Cyclotron resonance of electrons in a Si MOSFET has been studied at a number of far infrared laser frequencies and at surface electron densities down to 3 × 10 cm^?2 in the activated conductivity regime. The scattering rate exhibits $\text{B}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ behavior for ωτ > 2 as in the metallic regime. Effective masses obtained from the fits are found to increase with decreasing density at frequencies $\text{V}\text{?}\text{? 25}\text{cm}{}^{\mathrm{?1}}$. It is possible that this continued evidence of metallic-like behavior is due to the fact that the photon energy is larger than the DC activation energy at these densities.