Spermine determination

Kamei et al. [45] separated spermine, spermidine, putrescine, and cadav-erine in an ion-pair reversed-phase LC system and detected the hydrogen peroxide formed in the reaction catalyzed by the enzymes putrescine oxidase and polyamine oxidase with POCL. The same analytes were determined in a later study [46], together with the acetyl derivatives. The sensitive determination of uric acid, selectively converted to hydrogen peroxide by uricase, has been investigated by several authors [37, 47],... 

Experiments utilizing D,L-a-difluoromethylornithine (DFMO), an irreversible inhibitor of ornithine decatboxylase, to determine its effect on mitogen- or al-loantigen-induced lymphocyte proliferation and CTL induction have certain similarities to the inhibition seen in N=0-induced inhibition of lymphocyte function. Stimulation of both mouse and human T cells in the presence of DFMO results in partial inhibition of proliferation which can be reversed by addition of the polyamines putrescine, spermidine, and spermine (Bowlin et al., 1987 McCarthy et al., 1990). lL-2 levels in these lymphocyte cultute supernatants as well... 

A systematic analysis to determine the biophysical characteristics of some cationic lipid/DNA complexes from this series was undertaken (Eastman et al., 1997). Product 1 (Figure 15.7) is currently being used in clinical trials as a carrier of CFTR gene in cystic fibrosis. The synthesis of these cholesteryl derivatives is similar to that of DC-Chol cholesteryl chloroformate is reacted with spermine or spermidine as polycation (Lee et al., 1996). 

The alkaloid chaenorhine (C31H40O5N4 mp 263-268° dec. [a]D + 46.7°) proved to be maerocyclic containing a spermine moiety. The entire gamut of spectral studies was involved to determine its structure (60). Of special interest is the observation that the hydrogenolysis of the alkaloid with sodium in liquid ammonia occurred at the ether linkage and generated 61 with concomitant reduction of the cyclic double bond. Hydrolysis, some chemical degradation, and further spectral studies served to elucidate the entire structure (31). 

Sugiura, T., Hayashi, T., Kawai, S., and Ohno, T., High speed liquid chromatographic determination of putrescine, spermidine and spermine, J. Chromatogr., 110, 385, 1975. 

In a reinvestigation of the minor alkaloids of A. quebrachoblanco, whose presence had already been indicated by Hesse (59) in 1882 (Vol. II), Biemann et al. (28, 51a) were able to isolate by a combination of alumina and gas chromatography about twenty compounds. The identification or structure determination of fifteen of these by mass spectrometry was described. Six belonged to the aspidospermine group and four of these were the known compounds, aspidospermine (II), deacetylaspido-spermine (VI), V.,-methyldeacetylaspidospermine (XLI), and (— )-pyri-folidine (XLVI). The three last-named had not previously been encountered in nature, VI and XLI having been prepared from aspidospermine (II) and vallesine (XXXVIII) (38, 39, 25). (— )-Pyrifolidine is identical with O-methylaspidocarpine (XLVI) which has been prepared... 

Cells treated with 5-FU undergo cell cycle arrest or apoptosis by inhibition of DNA synthesis. When human oral squamous cell carcinomas (HSC-2, HSC-3, HSC-4) were treated with 5-FU, viable cell numbers declined dose-dependently (CC50 determined after 24 hours treatment 3.4,6.9 and 1.7 p,M, respectively). The intracellular putrescine concentration slightly declined (Table 2) [29]. The combination treatment of 5-FU with N(l),N(ll)-diethylnorspermine (DEN-SPM), which is an inducer of spermidine/spermine N(l)-acetyltransferase (SSAT) that depletes polyamine, has been reported to augment the cytotoxic activity of 5-FU, suggesting possible clinical application [30]. 

Another difficulty is the determination of the homogenity of the isolated alkaloids. To illustrate this two extreme examples are given. By different chromatographic methods and because of its spectral properties (NMR, IR, MS), the natural, approximate 1 1 mixture of the spermidine alkaloids inandenin-12-one and inandenin-13-one appeared to be a pure compound. This was supported by the sharp melting point of its hydrochloride (150- 151°C). Only after chemical degradation was the nature of the mixture determined by mass spectrometry. On the other hand, the behavior of the pure crystalline spermine alkaloid aphelandrine was that of a mixture. At least two criteria were in favor of a mixture. In the H-NMR spectrum... 

P NMR study of the chiral configuration of the unsymmetrical substituted cyclophosphazenes (146) and (147), prepared from (136) via (144) and (145), has shown these compounds to be diastereoisomeric each consisting of two different racemic mixtures. The spermine-bridged cyclophosphazenes (148) appear to exist in meso and racemic forms, which for the gfem-diphenyl derivative were separated by column chromatography and investigated by NMR spectroscopy and X-ray structure determinations. ... 

Aminopropylation The transfer of decarboxylated SAMe is crucial to the synthesis of polyamines (spermine, spermidine, putresdne). Together with ornithine decarboxylase, SAMe determines the synthesis rate of polyamines, which are essential for cell regeneration. At 30 — 60 minutes, the half-fife of SAMe decarboxylase is very short and thus readily adaptable to various metabolic situations. 

Another labelling agent suitable for determination by HPLC of histamine, tyramine, phenylethylamine, tryptamine, cadaverine, putrescine, spermidine and spermine in wines is 4-(4-dimethyl-aminophenylazo)benzenesulfonyl (dabsyl) chloride (see Figure 4.14) (Bockhardt et al., 1996 Romero et al., 2000). 

R3. Raina, A., Studies on the determination of spermidine and spermine and their metabolism in the developing chick embryo. Acta Physiol. Scand. 60, Suppl. 218, 7-81 (1963). 

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