Putrescine, spermidine from

Species of Pseudomonas can utilize the a,(i)-diamines putrescine, spermidine, and spermine as sources of carbon and nitrogen, and putrescine can be produced from the secondary amine spermidine together with 1,3-diaminopropane (Dasu et al. 2006). Putrescine (1,4-diaminobutane) is an intermediate in the arginine decarboxylase (ADC) pathway of L-arginine degradation, which is described later, and can be degraded, by two pathways ... 

At physiological pH, polyamines are fully protonated and polycationic. It is possible that the amino group of amines prevents SAM from reacting with ACS by interfering with the prosthetic groups of the enzyme. Polyamines such as putrescine, spermidine, and spermine, and methionine cycle intermediates such as MTA and KMB have been shown to have an inhibitory effect on ACS activity. ... 

The naturally occurring di- and polyamine alkaloids are listed in the tables of Section V. At present, nearly 100 compounds have been reported. They were isolated from 56 genera in 30 plant and animal families. Some of the plants contain all three kinds of alkaloids (putrescine, spermidine, and spermine), e.g., Ananas comosus Merill. (Bromeliaceae). Intensive investigations of alkaloids were performed in some genera, e.g., Aphelandra, Chaenorhinum, Equisetum, Maytenus. The reasons were commercial availability and pharmacological interest (Maytenus). 

Figure 21.10 depicts synthesis of putrescine, spermidine, and spermine from ornithine. Putrescine is synthesized by decarboxylation of ornithine and it derives its name from the fact it was originally isolated from rotting meat. Putrescine is a precursor to spermidine, then to spermine through the AdoMet-mediated transfer of active propylamino groups... 

Figure 21.10 depicts synthesis of putrescine, spermidine, and spermine from ornithine.The "H3N ... 

Figure 21.10 depicts depicts synthesis of putrescine, spermidine, and spermine from ornithine.. The polyamines are polycationic substances that stabilize intracellular conformations of negatively charged nucleic acids. Poly amines bind to phosphates on both strands of a duplex nucleic acid, thereby stabilizing double-stranded DNA or a duplex region of RNA. 

Abdel-Monem and Ohno, 1975). Shalaby (1995) described the use of TLC with a multiple development technique to resolve the dansyl derivatives of histamine, cadaverine, putrescine, phenylethylamine, tyramine, tryptamine, spermine, and spermidine from fish, cheese, and meat samples. The procedure allowed for the detection in 14 samples of as little as 5 or 10 ng of the dansyl derivatives of the amines within 2 hr. 

The enzymatic decarboxylation of AdoMet to produce thej -methyladenosyl-homocysteamine (decarboxylated AdoMet) that is required for Eqs. (13) and (14) has been demonstrated in extracts of a number of plants (Coppoc et al., 1971 Baxter and Coscia, 1973 Suresh and Adiga, 1977). Enzymatic synthesis of spermidine from putrescine and 5-methyladenosylhomocyste-amine [Eq. (13)] has been demonstrated in crude extracts of Vinca rosea seedlings (Baxter and Coscia, 1973). Spermine synthesis appears not to have been studied in plants, but is assumed to proceed by Eq. (14), catalyzed by spermine synthase, as has been established in mammals (Hannonen et al., 1972). 

Two Cig columns and a guard column were used for separation. The mobile phase was methanol/water (65 35 v/v). The benzoylated putrescine, 1,6-hexanediamine, spermidine and spermine were separated in 10 min. Detection was at the absorption maximum of 229 nm (instead of 254 nm) with a detection limit of 1 pmol. The linear range was up to 100 nmol of polyamine and the recoveries for putrescine, spermidine and spermine were 104.7 + 3.4%, 97.3 + 3.7% and 88.8 5.5% respectively. Considerably lower spermidine and putrescine concentrations were found in tumour tissues obtained from animals treated with DL-a-difluoromethylomithine for seven days compared with untreated controls. 

Biologically active polyamines putrescine, spermidine and spermine, differ from the traditional group of biogenic amines. Spermidine and spermine arise under specific conditions and they also have different biological effects in comparison with the classical biogenic amines, which are mainly histamine, tyramine, 2-phenylethylamine, putrescine, cadaverine, tryptamine and agmatine. 

Global wanning has become a major issue, and there is a move away from fossil resources toward recyclable resources, not only as energy sources but also as chemical feedstocks. Polyamines are used as intermediate materials in the production of synthetic fibers and fabrics. At present, they are mainly produced from petroleum by industrial chemical processes, but putrescine, spermidine, and cadaverine can all be synthesized biologically from arginine, ornithine, and lysine. These amino acids are produced industrially by fermentation. To obtain a higher polyamine yield and industrialize the process, we await a more detailed understanding of polyamine metabolism in bacteria. 

The main subcellular PA-binding sites are probably (I) RNA, both ribosomal and transfer, (2) DNA, both nuclear and oiganellar, (3) cell wall, and (4) membranes (Bachrach, 1970). It is well known that PAs, like Mg, bind to ribosomes and facilitate the association of ribosomal subunits (see reviews in Tabor and Tabor, 1976,1984). Polyamines can bind to specific sites on tRNA molecules (Pochon and Cohen, 1972 Sakai and Cohen, 1973). In plants, bound putrescine, spermidine, and spermine have been found in ribosomes (Cocucci and Bagni, 1968), as well as in complexes with rRNA and tRNA (Bagni et ai, 1973 Serafini-Fracassini et ai, 1984). On the other hand, numerous studies have shown the interaction and stabilization of DNA by PAs as well as their binding to this macromolecule (see reviews in Bachrach, 1970 Cohen and McCormick, 1979 Tabor and Tabor, 1984). In plants the information is scarce, but the occurrence of spermidine and spermine in chromatin isolated from com has been reported. Most of the spermine is probably chromatin bound in vivo (Hirasawa and Suzuki, 1985). However, the localization of PAs in the nucleus, in vivo, still remains somewhat uncertain (Tabor and Tabor, 1984). 

Putrescine, apart from being a precursor of the higher PAs spermidine and spermine, is also a precursor in the biosynthesis of the pyrrolidine alkaloids... 

Figure 31-4. Conversion of spermidine to spermine. Spermidine formed from putrescine (decarboxylated L-ornithine) by transfer of a propylamine moiety from...

The polyamines putrescine, cadaverine, spermidine, and spermine, which are seen at elevated levels in some victims of cancer, were separated on a Technicon (The Technicon Company Chauncey, NY) TSM Amino Acid Analyzer packed with an 8% divinylbenzene-co-polystyrene sulfonated resin with post-column ninhydrin detection.111 Amines such as ethanolamine, noradrenaline, hexamethylene diamine, methoxytryptamine, spermine, and spermidine were separated from amino acids on a DC-4A cation exchange resin.112 A similar approach, using a Beckman Model 121M amino acid analyzer equipped with an AA-20 column, was also successful.113 A Polyamin-pak strong cation exchange column (JASCO) was eluted with a citrate buffer for the detection of putrescene, spermine, cadaverine, and 1,5-diaminohex-ane from rat thymus.114 A post-column o-phthaldehyde detection system was used. 

Although no experiment has yet been reported to support the idea, it seems clear that a majority of the pyrrolidine alkaloids arise from the ornithine, pu-trescine, and proline pool. This could be the case for ficine (61) and isoficine (62), vochysine (63), and phyllospadine (64) but also of the Darlingia alkaloids, which share common features with hygrine this assertion probably also holds for the ruspolinone (25) and odorine-roxburghlin (59) families. Peripentadenine, isolated from a plant of the family Elaeocarpaceae, bears resemblance to other alkaloids of the elaeocarpus type such as isoelaeocarpicine (124) (161). It cannot be excluded, however, that spermidine may be a biosynthetic intermediate instead of putrescine. The question of the origin of ant alkaloid substances remains so far without an obvious answer. 

As you might guess from their names, these molecules have notably unpleasant odors. They were initially identified as degradation products of the action of bacteria on animal tissue. Cadaverine is also notably toxic. Putrescine is found in most cell types and is a precursor to spermidine. Note that both molecules have two amino groups. 

Three acyclic amines, dimethylamine (109), putrescine (111), and spermidine (110), have been isolated from the accessary sexual glands of the mature male desert locust, Schistocerca gregaria (Table VIII). In addition, A -pyrroline (12i) has been identified as a volatile emanating from the mature male locust colony (Table II). It is an oxidation product of putrescine and probably could be responsible for the maturation-accelerating effect observed to be specific to the mature male insect 106). 

Dimethylamine (109), putrescine (111), and spermidine (110), isolated from various insects (Table VIII), were obtained as p,p -nitrophenylazobenzoyl, p-phenylazobenzenesulfonyl, and I-dimethylaminonaphthalene-5-sulfonyl (dan-syl) derivatives and picrates or were detected by high-performance liquid chromatography (HPLC) using the ion-exchange resin (106,343). V,V-Dimethyl-3-phenylethylamine (131) from spiders of the genus Sclerobunus (Table VIII) has been identified by mass spectral comparison with a synthetic sample (117). 

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