Calorimetric analysis of the ethanolysis of 1,2-epoxybutane

Polyethers, which are produced by alcoholysis of oxiranes, are often used as solvents in chemical plants. The spectra of the products can be influenced by the choice of the catalyst (acid or base). The results of the base-catalyzed ethanolysis of 1,2-epoxybutane are displayed. The reaction was investigated calorimetrically by varying the molar ratio between ethanol and 1,2-epoxybutane, the starting temperature and the concentration of the catalyst sodium hydroxide. Additionally, the influence of the used alcohol will be shown in one example. To determine the activation parameters, the experiments were evaluated by the nonlinear software package TA-kin v3.3.     

CO laser stabilization using the optogalvanic Lamb-dip

Frequency stabilization of the CO laser using a CO lamb-dip is achieved in the range from 5.0–6.3 m. The CO saturation signal is obtained from a low-pressure discharge in absorption and is detected using optogalvanic, detection. The frequency stability and reproducibility has been verified to be better than 100 kHz; this is an improvement of more than one order of magnitude compared with locking techniques using CO laser gain profiles.Alexander von Humboldt Awardee from National Bureau of Standards, Boulder, Colorado, USA     

Development and prevalidation of a method for phenol determination by solid-phase spectrophotometry

A simple, sensitive and rapid solid-phase spectrophotometric procedure was developed for the determination of traces of phenol with 4-aminoantipyrine as a reagent (AAP-SPS), and the optimal experimental conditions were established. This method was performed by sorption and direct absorbance measurements of the product phenol-AAP sorbed on the anion-exchanger Dowex 1-X4 (0.2 g) at 495 nm (absorption maximum) and 700 nm (non-absorption wavelength). The sensitivity offered by the AAP-SPS procedure was higher by a factor of 40 compared with the respective conventional spectrophotometric method. Metrological characteristics were established using a prevalidation strategy. The AAP-SPS procedure is characterized by a linear calibration function in the working range of 0.05–0.50 μmol, low standard deviation of procedure (±0.012), low limit of determination (0.021 μmol), and favorable random (±0.85 to ±11.27%) and systematic deviations (−4.55 to +11.50%). Moreover, the accuracy of the system investigated by the recovery test is acceptable (99–102%). Favorable working and performance characteristics make the new SPS method ideal for phenol monitoring in pharmaceutical preparations as well as other matrices.     

A liquid chromatography-mass spectrometry method for the quantification of both etoricoxib and valdecoxib in human plasma

A practicable and selective liquid chromatography-mass spectrometry assay for the determination of two cyclooxygenase-2 inhibitors, etoricoxib and valdecoxib, in human plasma is presented. The analytical technique is based on reversed-phase high-performance liquid chromatography (HPLC) coupled to atmospheric pressure chemical ionisation (APCI) mass spectrometry (Finnigan Mat LCQ ion trap). Mass analysis was performed in the positive ion mode. The ion trap was operated in the tandem MS mode (MS2) and the transitions of etoricoxib (m/z 359.2 --> 280.3) and valdecoxib (m/z 315.1 --> 235.1) were followed by selected reaction monitoring. Retention times of etoricoxib and valdecoxib were 1.05 and 1.08 min, respectively. The method was validated over a linear range 10-2500 and 5-1000 microg/L using the other substrate as internal standard. After validation, the method was used to study the pharmacokinetic pro fi le of etoricoxib or valdecoxib in a healthy volunteer after administration of a single oral dose (valdecoxib, 20 mg; etoricoxib, 90 mg). The presented method was suf fi cient to cover more than 90% of the area under the plasma concentration time curve.     

A synthesis, including asymmetric synthesis, of α-quaternary α-amino aldehydes from ketones and chloromethyl p-tolyl sulfoxide via sulfinylaziridines

Treatment of 1-chlorovinyl p-tolyl sulfoxides, prepared from ketones and chloromethyl p-tolyl sulfoxide, with N-lithio arylamines resulted in the formation of sulfinylaziridines in good to high yields. The sulfinylaziridines were treated with N-lithio aniline or N-lithio p-chloroaniline to afford α-quaternary α-amino aldehydes in good yields. From α-quaternary α-amino aldehydes, α-quaternary α-amino acid esters and β-quaternary β-amino alcohols were obtained. When optically active chloromethyl p-tolyl sulfoxide was used in this procedure, a method for the synthesis of optically active α-quaternary α-amino aldehydes was realized. The reaction mechanism, including asymmetric induction, for the formation of the sulfinylaziridines is described.     

Heterodyne measurements of hot bands and isotopic transitions of N2O near 7.8 µm

Heterodyne frequency measurements are reported for absorption transitions of N₂O in the frequency range from 1257 to 1335 cm^?1. The measurements use a CO laser as a transfer oscillator whose frequency is measured directly against combinations of frequencies of two stabilized CO₂ lasers whose frequencies are well known. A tunable diode laser is locked to the N₂O absorption feature and the frequency difference is measured between the diode laser and the CO laser. Thev ₃ fundamental bands of the¹⁵N¹⁴N¹⁶O and¹⁴N¹⁵N¹⁶O isotopes are reported. Measurements are also given for the 00⁰2–00⁰1, 02⁰1–02⁰0, and 02²1–02²0 vibrational transitions of N₂O. A table of frequencies is given for the 00⁰2–00⁰0 band near 2560 cm^?1 based on these and earlier measurements.     

Character sums and primitive roots in algebraic number fields

Let ν denote a totally positive integer of an algebraic number fieldK such that ν is a least primitive root modulo a prime ideal \(\mathfrak{p}\) ofK, least in the sense that its normNν is minimal. One of the simplest questions that presents itself is that of the order of magnitude ofNν in comparison toN \(\mathfrak{p}\) . In the present paper the following bound is shown: $$N_\nu<< N\mathfrak{p}^{{1 \mathord{\left/ {\vphantom {1 4}} \right. \kern-\nulldelimiterspace} 4} + a} for fixed a > 0.$$ The proof of this result is based on deep estimates for certain character sums inK.     

Microcolumns with self-assembled particle frits for proteomics

LC-MS-MS experiments in proteomics are usually performed with packed microcolumns employing frits or outlets smaller than the particle diameter to retain the packing material. We have developed packed microcolumns using self-assembled particles (SAPs) as frits that are smaller than the size of the outlet. A five to one ratio of outlet size to particle diameter appears to be the upper maximum. In these situations the particles assembled into an arch over the outlet like the stones in a stone bridge. When 3 microm particles were packed into a tapered column with an 8 microm outlet, two particles bridged the outlet with 0.3 pl dead volume and perfect success rate. In peptide analysis by LC-MS, the peak width at half height was normally less than 6 s, compared to 12 s without SAPs. The LC-MS-MS system provided 37% sequence coverage (21 matched peptides) for a tryptically-digested sample of 10 fmol bovine serum albumin. We also describe application of the SAP principle to make disposable pipette tip columns with short pieces of fused-silica capillary as the outlet.     

Simultaneous determination of oxycodone and its major metabolite, noroxycodone, in human plasma by high-performance liquid chromatography

Oxycodone (14-hydroxy-7,8-dihydrocodeinone) is a potent opioid receptor agonist. In the present study, a liquid-liquid extraction-based reversed-phase HPLC method with UV detection was validated and applied for the analysis of oxycodone and its major metabolite, noroxycodone, in human plasma. The analytes were separated using a mobile phase, consisting of acetonitrile and phosphate buffer (8:92, v/v) at a flow rate of 1 mL/min, and UV detection at 205 nm. The retention times for oxycodone, noroxycodone and codein (internal standard) were 14.7, 13.8 and 10.2 min, respectively. The validated quantitation range of the method was 2-100 ng/mL for oxycodone and 10-100 ng/mL for noroxycodone. The developed procedure was applied to assess the pharmacokinetics of oxycodone and its metabolite following administration of a single 20 mg oral dose of oxycodone hydrochloride to one healthy male volunteer.