Simplex optimization of the separation of phospholipids by high-pressure liquid chromatography

A simplex procedure is shown to be an efficient approach for solving separation problems. The best solvent ratio for the separation of phosphatidylcholine and sphingomyelin has been found by means of a two-dimensional simplex capable of expansion and contraction. A successful high-pressure liquid chromatography separation of lysophosphatidylcholine, phoaphatidylethanolamine, phosphatidylinositol, phosphatidylserine, phosphatidylcholine, sphingomyelin and phosphatidic acid was achieved with a 180-cm column packed with Corasil II and a solvent mixture of chloroform—methanol—ammonia (50.0:35.9:7.0, v/v/v).     

The amperometric detection of thyroid hormones following reverse-phase high-performance liquid chromatography

The principle of an assay of the major thyroid hormones by an electrochemical technique is demonstrated. The separation of 3,3',5-triiodothyronine, 3,3',5'-triiodothyronine, and thyroxine, by reverse-phase high-performance liquid chromatography is followed by their electrochemical oxidation in a thin-layer electrochemical detection cell with a low-temperature isotropic carbon working electrode. The limits of detection found were in the subnanogram range with linear response in the ranges 0–125 ng for T₃ and 0–500 ng for T₄. The approach makes the simultaneous assay of total serum thyroid hormones feasible.     

Liquid chromatographic separation of the thyroid hormones

The liquid Chromatographic separation of 3,3',5-triiodothyronine, 3,3',5'-triiodothyronine, and thyroxine with a nonpolar stationary phase was studied as a function of pH, temperature, organic content of the mobile phase, and ionic strength using aqueous phosphate—acetonitrile, aqueous phosphate—methanol, and aqueous phosphate— n-propanol mobile phase systems. It was demonstrated that the quality of the thyroid hormone separations, as determined by normalized peak capacity values, was unchanged with temperature, remained relatively constant with increasing ionic strength, and was affected to the greatest extent by changes in pH and organic modifier content of the mobile phase. Chromatographic behavior of the compounds studied as a function of these variables was found to be consistent with existing Chromatographic theory and/or empirical observations. Recommended conditions are aqueous phosphate—methanol mobile phase, pH 2–5 (aqueous portion), and high temperature (60–70°C).     

Evaluation of a Novel Dechlorination Reaction as an Analytically Useful Derivatization Reaction Part 1. Stoichiometry,Mechanism and Yield Optimization

Abstract

A novel reaction for the dechlorination of polychlorinated biphenyls (PCBs) as well as most other chlorinated aromatic and aliphatic compounds is evaluated and discussed in terms of its potential for analytical purposes. The active dechlorinating agent is prepared through the reaction of molten sodium or potassium with polyethylene glycols (MW >200), in the absence of oxygen, to form the corresponding alkali metal glycolate, a powerful nucleophilic agent. Special emphasis is given to the mechanistic aspects of the reaction and their importance in terms of achieving high and reproducible yields with analytical quantities of substrate, in short periods of time. The contribution of the techniques: ESR, NMR, IR, UV, MS, GC-ECD, LC-EC, CIDNP-NMR, conductimetry and chloride analysis (amperometric) in elucidating the reaction mechanism and providing valuable kinetic data is illustrated. This reaction can potentially be applied to the determination of PCBs in waste oils.     

Structural polymorphism of the actin-espin system: a prototypical system of filaments and linkers in stereocilia

We examine the interaction between cytoskeletal F-actin and espin 3A, a prototypical actin bundling protein found in sensory cell microvilli, including ear cell stereocilia. Espin induces twist distortions in F-actin as well as facilitates bundle formation. Mutations in one of the two F-actin binding sites of espin, which have been implicated in deafness, can tune espin-actin interactions and radically transform the system's phase behavior. These results are compared to recent theoretical work on the general phase behavior linker-rod systems.     

Electrothermal atomic absorption spectrometric techniques for the determination of zinc and copper in microliter and submicroliter volumes of aqueous and serum matrices

Two electrothermal atomic absorption techniques which provide linear working functions over wide concentration ranges, and are suitable for the determination of zinc and copper in aqueous and 10-fold diluted blood serum matrices are evaluated. The first technique is based on modification of the furnace tube to provide a significant decrease of the atomic absorption signal when microliter and larger volumes of sample are injected. The second technique involves a delivery system capable of dispensing micro- and submicroliter sample volumes to the furnace tube. The precision of the two techniques is about 98%.     

Nematic phase transitions in mixtures of thin and thick colloidal rods

We report experimental measurements of the phase behavior of mixtures of thin (charged semiflexible fd virus) and thick (fd-PEG, fd virus covalently coated with polyethylene glycol) rods with diameter ratio varying from 3.7 to 1.1. The phase diagrams of the rod mixtures reveal isotropic-nematic, isotropic-nematic-nematic, and nematic-nematic coexisting phases with increasing concentration. In stark contrast to predictions from earlier theoretical work, we observe a nematic-nematic coexistence region bound by a lower critical point. Moreover, we show that a rescaled Onsager-type theory for binary hard-rod mixtures qualitatively describes the observed phase behavior.     

Frequency specificity of the human auditory brainstem and middle latency responses using notched noise masking

This study investigated the frequency specificity of the auditory brainstem and middle latency responses to 80 and 90 dB ppe SPL 500-Hz and 90 dB ppe SPL 2000-Hz tonebursts. The stimuli were brief (2-1-2 cycle) linear-gated tonebursts. ABR/MLRs were recorded using two electrode montages: (1) Cz-nape of neck and (2) Cz-ipsilateral earlobe. Cochlear contributions to ABR wave V-Na and MLR waves Na-Pa and Pa-Nb were assessed by plotting notched noise tuning curves which showed amplitudes and latencies as a function of center frequency of the noise masker [Abdala and Folsom, J. Acoust. Soc. Am. 97, 2394 (1995); ibid. 98, 921 (1995)]. Maxima in the response amplitude profiles for the ABR and MLR to 80 dB ppe SPL tonebursts occurred within one-half octave of the nominal stimulus frequency, with minimal contributions to the responses from frequencies greater than one octave away. At 90 dB ppe SPL, contributions came from a slightly broader frequency region for both stimulus frequencies. Thus, the ABR/MLR to 80 dB ppe SPL tonebursts shows good frequency specificity which decreases at 90 dB ppe SPL. No significant differences exist in frequency specificity of: (1) ABR wave V-Na versus MLR waves Na-Pa and Pa-Nb at either stimulus frequency or intensity; and (2) ABR/MLRs recorded using the two electrode montages.     

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