Simultaneous determination of all-trans, 9-cis, 13-cis retinoic acid and retinol in rat prostate using liquid chromatography-mass spectrometry

Since retinoic acid (RA) and RA receptors are key developmental regulators during organogenesis, they might participate in the abnormal development of the prostate caused by early estrogen exposure. In order to test this assumption, a sensitive analytical method that can differentiate 9-cis, 13-cis, and all-trans RA in small tissue samples ( approximately 8 mg) is required. Since retinol is the metabolic precursor to RA, simultaneous quantification of retinol would also provide valuable information. Here, we report a liquid chromatography-mass spectrometry method for simultaneous determination of retinol and 9-cis, 13-cis, and all-trans RA in rat prostate. Mass spectrometric signal responses for RA were compared using positive ion atmospheric-pressure chemical ionization (APCI) and electrospray, as well as positive ion and negative ion APCI. Positive ion APCI was selected for all subsequent analysis for its better sensitivity, and to provide simultaneous determination of retinol and RA. Ventral prostate tissue samples were homogenized and extracted following simple protein precipitation without derivatization. Baseline separation of 9-cis, 13-cis, and all-trans RA standards was obtained by using a non-porous silica C18 column. Selected ion monitoring of the ions m/z 301 and m/z 269 was carried out for mass spectrometric quantitative analysis. The ion of m/z 301 corresponded to the protonated molecule of RA, whereas the ion of m/z 269 corresponded to loss of water or acetic acid from the protonated molecule of retinol or the internal standard retinyl acetate respectively. The method has a linear response over a concentration range of at least three orders of magnitude. The limit of quantitation was determined to be 702 fmol all-trans RA injected on-column. The method showed excellent intra- and inter-assay reproducibility and good recovery, and is suitable for analyzing RA and retinol in small tissue samples (approximately 8 mg).     

Amorphous-amorphous transition in glassy polymers subjected to cold rolling studied by means of positron annihilation lifetime spectroscopy

In this study, polycarbonate (PC) and polystyrene (PS) are subjected to plastic deformation by means of cold rolling and the resulting variation of the free volume and its subsequent time evolution after rolling is investigated by means of positron annihilation lifetime spectroscopy (PALS). The value of the long lifetime component that is attributed to the decay of ortho-positronium (tau(o-Ps)) and its intensity (I(o-Ps)) are used to characterize, respectively, the size and the concentration of the free-volume holes. In addition to the PALS experiments, the effect of plastic deformation on the dynamic tensile modulus is investigated. The PALS results show that both for well-aged PC and PS an increase of tau(o-Ps) and a decrease of I(o-Ps) occur upon plastic deformation. During the subsequent aging, tau(o-Ps) tends to return to the value assumed before plastic deformation, while I(o-Ps) remains constant with time. These results corroborate the idea of an amorphous-amorphous transition, rather than that of a "mechanical rejuvenation" as proposed in the past to explain the ability of plastic deformation to reinitiate physical aging. Finally, a linear relation between the size of the free-volume holes and the dynamic tensile modulus is found, which suggests that the stiffness of amorphous glassy polymers is fully determined by their nanoscopic structure.     

Anisotropic muon Knight shift in the HCP single crystals of Cd,Zn and Be

In single crystal samples of Zn, Cd and Be (hcp structure) stroboscopicSR measurements successfully revealed anisotropies in the muon Knight shift (K). An anisotropic K can provide information on the amount of non s-electrons screening the charge of the muon implanted in these metals as a light hydrogen isotope. In Cd, the anisotropic part depends strongly on the temperature and shows a change in sign at roughly 110 K. In Zn, the anisotropic part below 10 K turns out to comprise 4th order contributions in the direction cosines of the external field. This can be understood on the basis of an anisotropicg-factor of the conduction electrons or spin-orbit coupling, respectively.     

Direct determination of the enantiomeric purity of oxyphenonium using chiral HPLC with post-column extraction detection

Summary A method is described for the determination of the enantiomeric purity (enantiomeric excess) of the anticholinergic drug oxyphenonium. The method for this quaternary ammonium compound is based on the direct HPLC analysis with a chiral stationary phase. Two kinds of 1-acid glycoprotein-bonded phases were used.For the detection a post-column extraction with fluorescence detection of the ion-pair counter ion dimethoxyantracene sulphonate was used.     

Isolation and synthesis of vobparicine,a novel type dimeric indole alkaloid

From the rootbark of Tabernaemontana chippii a novel antimicrobially active dimeric indole alkaloid was isolated which was assigned structure $\text{1}$ on the basis of spectroscopic evidence and its synthesis.     

Generalized kinetic equations

We study the abstract differential equation on a Hilbert space H, which represents a variety of different kinetic equations. T is assumed bounded and self-adjoint on H, and A (unbounded) positive self-adjoint and Fredholm. For partial range boundary conditions and 0x<, we prove existence and (non-) uniqueness theorems and give representations of the solution. Various examples from neutron transport, radiative transfer of polarized and unpolarized light, and electron transport are given.This paper is dedicated to K.M. Case on the occasion of his sixtieth birthday     

Photometrische Titration der Carboxylendgruppen in Poly?thylenterephthalat

Zusammenfassung Es wird eine schnelle Methode zur Bestimmung von Carboxylendgruppen in Polyäthylenterephthalat beschrieben; sie beruht auf der Messung der Farbänderung von Bromphenolblauindicator während der Titration einer Lösung des Polymeren in o-Kresol/Chloroform mit alkoholischer Lauge.Resultate von Bestimmungen an einer organischen Säure und an Polymerproben werden gegeben. Die Resultate von Bestimmungen an Polymeren wurden mit denen nach der von Pohl beschriebenen visuellen, nach der von Maurice beschriebenen potentiometrischen Methode und nach der von Ward beschriebenen Infrarotmethode verglichen und gleiche Resultate erhalten. Die photometrische Methode wird aus verschiedenen Gründen bevorzugt.

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Photometric titration of carboxyl end groups in polyethylene terephthalate

The method is based on the continuous measurement of the changes in absorbance of bromophenol blue indicator during titration of a solution of the polymer in o-cresol/chloroform with standard alcoholic potassium hydroxide solution.Results are given of tests with an organic acid and polymers amples. The results obtained with the polymer samples are compared with those obtained by the visual titration method of Pohl, the potentiometric titration method of Maurice and the infrared method of Ward. The four methods yield the same results. For several reasons the photometric method is preferred.

     

The signal vs. concentration relationships in fluorimetry

Formulae for the fluorescence signal are derived which take into account some factors hitherto neglected. From these formulae conditions are deduced, for which a linear relationship exists between the concentration of the fluorescent components and the intensity of the fluorescence. In some cases of practical interest the fulfilment of these conditions cause too low a sensitivity. For such cases a method of optimization is outlined, by means of which the conditions are found which lead to the least deviation from linearity at the required sensitivity.     

Mössbauer effect study of Y(Fe0.022 Co0.978)2 at temperatures between 0.15 and 4.2k

A³He-⁴He dilution refrigerator was constructed to perform Mössbauer measurements well below 4.2K. Results are reported here on the pseudobinary Laves-Phase system Y (Fe_1-x Co_x)₂ for x=0.978. We found that at low temperatures, the Fe ions undergo a disordered magnetic phase transition, with a Curie temperature of approximately 4K and a saturation field of 96K0e. The easy axis of magnetization appears to be the [111] direction. This study is an extension to very low temperatures of previous work on the system with 0X0.978.Supported by the NSF Grant No. DMR 73-07665 AO 3     

SCF—CI calculations and the assignment of the absorption spectrum of the excimer of 1-methyl naphthalene; relation to 1,1′-binaphthyl

An SCF MO calculation followed by extensive configuration interaction between all singly-excited singlet states has been performed for the excimer of naphthalene in a perfect and in some distorted sandwich structures. With these results an assignment is given for the bonds in the absorption spectrum of the excimer of 1-methyl naphthalene. It is further shown that the similarity between the optical properties of the 1-methyl naphthalene excimer and those of 1,1′-binaphthyl in fluid solution, is also reflected by the calculations.