Polyamine Composition Research Articles

Alkaline Stress Causes Changes in Polyamine Biosynthesis in Thermus thermophilus.

An extreme thermophile, Thermus thermophilus, produces 16 different polyamines including long-chain and branched-chain polyamines. The composition and content of polyamines in the thermophile cells change not only with growth temperature but also with pH changes. In particular, cell growth decreased greatly at alkaline medium together with significant changes in the composition and content of polyamines. The amounts of tetraamines (spermine and its homologs) markedly decreased at alkaline pH. Thus, we knocked out the speE gene, which is involved in the biosynthesis of tetraamines, and changes of composition of polyamines with pH changes in the mutant cells were studied. Cell growth in the ΔspeE strain was decreased compared with that of the wild-type strain for all pHs, suggesting that tetraamines are important for cell proliferation. Interestingly, the amount of spermidine decreased and that of putrescine increased in wild-type cells at elevated pH, although T. thermophilus lacks a putrescine synthesizing pathway. In addition, polyamines possessing a diaminobutane moiety, such as spermine, decreased greatly at high pH. We assessed whether the speB gene encoding aminopropylagmatine ureohydrolase (TtSpeB) is directly involved in the synthesis of putrescine. The catalytic assay of the purified enzyme indicated that TtSpeB accepts agmatine as its substrate and produces putrescine due to the change in substrate specificity at high pH. These results suggest that pH stress was exacerbated upon intracellular depletion of polyamines possessing a diaminobutane moiety induced by unusual changes in polyamine biosynthesis under high pH conditions.

Heterologous Expression and Characterization of Tea (Camellia sinensis) Polyamine Oxidase Homologs and Their Involvement in Stresses.

Polyamine oxidase (PAO) is a key enzyme maintaining polyamine homeostasis, which affects plant physiological activities. Until now, the gene members and function of PAOs in tea (Camellia sinenesis) have not been fully identified. Here, through the expression in Escherichia coli and Nicotiana benthamiana, we identified six genes annotated as CsPAO in tea genome and transcriptome and determined their enzyme reaction modes and gene expression profiles in tea cultivar 'Yinghong 9'. We found that CsPAO1,2,3 could catalyze spermine, thermospermine, and norspermidine, and CsPAO2,3 could catalyze spermidine in the back-conversion mode, which indicated that the precursor of γ-aminobutyric acid might originate from the oxidation of putrescin but not spermidine. We further investigated the changes of CsPAO activity with temperature and pH and their stability. Kinetic parameters suggested that CsPAO2 was the major PAO modifying polyamine composition in tea, and it could be inactivated by β-hydroxyethylhydrazine and aminoguanidine. Putrescine content and CsPAO2 expression were high in tea flowers. CsPAO2 responded to wound, drought, and salt stress; CsPAO1 might be the main member responding to cold stress; anoxia induced CsPAO3. We conclude that in terms of phylogenetic tree, enzyme characteristics, and expression profile, CsPAO2 might be the dominant CsPAO in the polyamine degradation pathway.

Polyamines produced by an extreme thermophile are essential for cell growth at high temperature.

An extreme thermophile, Thermus thermophilus grows at an optimum temperature of around 70°C and produces 16 different polyamines including long-chain and branched-chain polyamines. We found that the composition of polyamines in the thermophile cells changes with culture temperature. Long-chain and branched-chain polyamines (unusual polyamines) were increased in the cells grown at high temperature such as 80°C, but they were minor components in the cells grown at relatively lower temperature such as 60°C. The effects of polyamines on cell growth were studied using T. thermophilus HB8 ΔspeA deficient in arginine decarboxylase. Cell growth of this mutant strain was significantly decreased at 70°C. This mutant strain cannot produce polyamines and grows poorly at 75°C. It was also determined whether polyamines are directly involved in protecting DNA from DNA double-strand breaks (DSBs) induced by heat. Polyamines protected DNA against double-strand breaks. Therefore, polyamines play essential roles in cell growth at extremely high temperature through maintaining a functional conformation of DNA against DSBs and depurination.

Genotype and Maturity Stage Affect the Content and Composition of Polyamines in Tomato—Possible Relations to Plant and Human Health

Polyamines (PAs) are molecules affecting several physiological characteristics in all living organisms with cell protective effects, thereby impacting plant and human health. Here, we used HPLC-DAD-ESI-MS to evaluate the content and composition of PAs in eight tomato genotypes over their maturation period, and related the content and composition to other quality traits and possible implications for plant and human health. The tomato genotype, maturity stage and their interactions, significantly affected the content and composition of PAs. Two of the genotypes, ‘Huichol’ and ‘Rio Grande’ showed consistently lower levels of PAs than the other evaluated genotypes. The variation in content and composition of PAs among genotypes was found to vary inconsistently over the maturation period. Putrescine content in the different genotypes either did not vary significantly, increased, or showed the lowest level in the middle of the maturation period, while spermidine content decreased or did not show significant variation. The genotypes ‘HT36’ and ‘HT25’ showed high levels of PAs during red and green maturity stages, respectively, and can thereby be seen as suitable health promoting red and green candidate tomatoes. Depiction of variation of the PAs creates opportunities for breeding and production of health promoting tomato as a food or food additive.

Composition of polyamines and amino acids in plant-source foods for human consumption.

Dietary polyamines and amino acids (AAs)are crucial for human growth, development, reproduction, and health. However, the scientific literature shows large variations in polyamine and AA concentrations among major staple foods of plant origin, and there is a scarcity of information regarding their complete composition of AAs. To provide a much-needed database, we quantified polyamines, agmatine, and AAs in select plant-source foods. On the dry matter basis, total polyamines were most abundant in corn grains, followed by soybeans, sweet potatoes, pistachio nuts, potatoes, peanuts, wheat flour and white rice in descending order. Glutamine was the most abundant AA in pistachio nuts, wheat flour and white rice, arginine in peanuts, leucine in corn grains, glutamate in soybeans, and asparagine in potatoes and sweet potatoes. Glutamine was the second most abundant AA in corn grains, peanuts, potatoes, and soybeans, arginine in pistachio nuts, proline in wheat flour, and glutamate in sweet potatoes andwhite rice. Free AAs represented ≤ 3.1% of total AAs in corn grains, peanuts, pistachio nuts, soybeans, wheat flour and white rice, but 34.4% and 28.5% in potatoes and sweet potatoes, respectively. Asparagine accounted for 32.3%, 17.5%, and 19.4%of total free AAs in potatoes, sweet potatoes,and white rice, respectively. The content of histidine, glycine, lysine, tryptophan, methionine, cysteine, and threonine was relatively low in corn grains, potatoes, sweet potatoes, and white rice. All of the analyzed plant-source foods lacked taurine, creatine, carnosine and anserine(antioxidants that are abundant in meats and also present in milk), and contained little 4-hydroxyproline. Proper proportions of plant- and animal-source products are likely most desirable for optimizing human nutrition and health.

New Heterogeneous Rh-Containing Catalysts Immobilized on a Hybrid Organic-Inorganic Surface for Hydroformylation of Unsaturated Compounds.

Anchoring Rh complexes to the surface of a silica polyamine composite, which has a poly(allylamine) covalently grafted to the surface of amorphous silica gel, yielded a material that proved to be an effective and novel heterogeneous catalyst for hydroformylation of unsaturated compounds. Surface amino groups of the material were modified with phosphines by covalent and ionic coupling. The modified materials were then treated with Rh(acac)(CO)2, giving the catalysts K-1 and K-2. Catalysts were characterized by solid-state NMR spectroscopy, IR spectroscopy, XPS, TEM, and elemental analysis. The activity and stability of K-1 and K-2 were then studied for the hydroformylation of selected unsaturated compounds. Hydroformylation of terminal double bonds occurred selectively in the presence of internal double bonds. Characterization of the catalysts and the problems encountered with the supported catalysts are discussed. Catalyst K-1 is reusable and can be applied to the hydroformylation of linear olefins, styrene, 4-vinylcyclohexene, and dienes, as well as representative terpenes and other unsaturated hydrocarbons in a batch reactor.

The association of maternal diet and polyamines in human milk: a study among malay ethnic mothers in kuantan, malaysia

Human milk contains a lot of nutrient and it offers advantages to infant age less than six months. Polyamines in milk accelerate the infants’ gut maturation and protect babies from the harsh environment. Maternal diet is a factor which can affect the polyamines variability in milk. To date, no research on local diet and the composition of human milk has been investigated. This study aimed to identify an association between Malaysian maternal diet and composition of polyamines in human milk. Seventy nursing mothers were recruited in Pahang and each mother recorded their 24-hours food consumption within a week. Maternal diets were recorded in Nutritionist Pro-software and the macronutrients were calculated. Milk samples were collected from each mother after24 h of food diary. Polyamines in milk were extracted using 0.4 M Perchloric acid, dansylated and quantified using HPLC. The mean age of the respondent was 30.13 years [SD= 3.145].Nursing mothers consumed high carbohydrate [41.4%] compared to fat [23.1%] and protein [13.7%].Spermidine [49.1%] was the highest polyamines in the breast milk samples. A significant correlation were shown between putrescine and dietary carbohydrate [p=0.027] and putrescine and dietary protein [p=0.031].The maternal education levels has no association with maternal diet pattern and breastfeeding practice in this study [p=0.657]. It is suggested that polyamines composition in human milk may be modulated by carbohydrate and protein intake among maternal mother

Estamos vivendo uma epidemia de alergia alimentar?

Estamos vivendo uma epidemia de alergia alimentar?

Dehydrogenative coupling of alcohols to esters on a silica polyamine composite by immobilized PNN and PONOP pincer complexes of ruthenium

Heterogenization of catalytically important homogeneous catalysts on solid supports has become an expanding area of research. PNN and PONOP ruthenium pincer complexes were immobilized on a silica poly(allylamine) composite, BP-1 by a two-step Mannich reaction. The complexes on BP-1 were characterized by solid state NMR, FT-IR, elemental analysis, and metal digestion studies. Model solution experiments were carried out to determine the site of electrophilic substitution on the pyridine ring of the pincer complexes and revealed substitution in both the meta- and para-position. The catalytic reactivity of immobilized (PNN)RuH(Cl)(CO) and (PONOP)RuH(Cl)(CO) on BP-1 was studied for the dehydrogenative coupling of alcohols to esters with the liberation of H2. Moderate to good ester yields were realized with both immobilized systems without using the base required for the homogeneous reaction and also in the presence of KOH. The homogeneous model reactions required a base for ester formation. The amine functionality on BP-1 served as the base to generate the active pincer catalyst on the BP-1 surface. Both immobilized catalysts were recycled for multiple alcohol reaction cycles. Four-step control experiments were carried out using an alcohol and both immobilized systems. The results revealed the heterogeneity of the alcohol catalysis by both BP-1-Ru-PNN and BP-1-Ru-PONOP systems. This study has opened a new catalytic methodology for reactions where base is required for catalyst activation, by using a solid support with basic functionality.

Luminescence Quenching and Enhancement by Adsorbed Metal Ions with Ruthenium Diimine Complexes Immobilized on Silica Polyamine Composites.

Luminescent ruthenium diimine complexes have been covalently bound to the surface of a silica polyamine composite (SPC) using peptide coupling agents. The loading of the complexes using this route is quite low (~0.01-0.04 mmol/g) leaving sufficient surface amines to coordinate added metal ions. When the composite particles containing the Ru complexes are exposed to solutions of Cu2+, Ni2+ or Zn2+, luminescence is quenched with efficiencies that follow concentration dependence and the relative binding affinities of the ions. When heavy metal ions such as mercury or lead are adsorbed onto the same surface, luminescence is enhanced by a factor of ~3.5. When the complexes are exposed to these metals in solution, no quenching or enhancement is observed. Both phenomena were shown to be the result of adsorption of the cations onto the polyamine surface by using the Stern-Volmer relationship. The mechanism of both quenching and enhancement is discussed and the options for further development of this novel metal sensing technique are presented.

Acrylic‐based epoxy resin damping systems: Synthesis, characterization, and properties

ABSTRACTAcrylate‐based epoxy resin (AE)/low molecular weight polyamine (LPA) composites were developed. The chemical structure, curing behavior, fracture morphology, damping properties, and mechanical properties were evaluated by Fourier transform infrared (FTIR), 1H‐nuclear magnetic resonance (1H‐NMR), gel permeation chromatography (GPC), Differential scanning calorimeter (DSC), scanning electron microscope (SEM), Dynamic mechanical thermal analysis (DMTA), and electro mechanical machine. Transmission electron microscope (TEM) and SEM pictures exhibited nanoscale micro‐phase separation between epoxy and acrylic segmers. DMTA results indicated that the loss factor of cured AE/LPA system could reach 1.84 and temperature range of tan δ > 0.5 was about 84 °C. Tensile strength and elongation at break of the cured AE samples can reach 6.5 MPa and 185%, respectively. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43654.

A methods study of immobilization of PONOP pincer transition metal complexes on silica polyamine composites (SPC)

Immobilization of catalytically active transition metal complexes on silica polyamine composite (SPC) surfaces offers many advantages for applications in catalysis particularly for catalyst recovery and reuse. We report here the immobilization of PONOP pincer complexes of Ru, Rh, Ni and Pd on the poly(allylamine) SPC, BP-1 using the Mannich reaction. Three different methods have been investigated for synthesizing the PONOP pincer transition metal complexes on BP-1: 1) direct reaction of the preformed pincer complexes using a two step Mannich reaction; 2) immobilization of the PONOP ligand using the Mannich reaction followed by the addition of a transition metal compound of a given metal; 3) the stepwise construction of PONOP on BP-1 followed by addition of a transition metal compound. The immobilized complexes on BP-1 were characterized by FT-IR, solid-state CPMAS 13C and 31P NMR, as well as elemental analysis. Anchoring of the complexes on BP-1 was also evaluated by the metal loading data obtained from the digestion of the loaded composites followed by Atomic Absorption Spectroscopy (AAS) or Inductively Coupled Plasma Atomic Emission Spectroscopy (ICPAES). The results showed that method 1 works better for the loading of pincer complexes on the SPC than methods 2 and 3. In the case of the Ru and Ni pincer complexes reasonable agreement with the phosphorous analysis was realized, while for the Pd complex values were high relative to the loading predicted from the phosphorus analysis, indicating the formation of the Pd nanoparticles on the surface during immobilization. For the Rh and Ru immobilized complexes with methods 2 & 3, metal loading was lower than the phosphorous analysis and this is attributed to entrained triphenylphosphine from the starting rhodium and ruthenium complexes based on the 13C and 31P CPMAS NMR data. Solution experiments using the PONOP pincer ligand and the Ru(PONOP) complex with n-butyl amine were conducted to model the site of electrophilic aromatic substitution on the pyridine ring. It was found that substitution both meta- and para-to the nitrogen takes place and this helped in the interpretation of the solid-state data.

In the Lab: Uranium Capture From High Sulfate and Nitrate Waste Streams with Modified Silica Polyamine Composites

In the Lab: Uranium Capture From High Sulfate and Nitrate Waste Streams with Modified Silica Polyamine Composites

Alkyne hydrogenation using Pd–Ag hybrid nanocatalysts in surface‐immobilized dendrimers

A series of Pd–Ag mixed‐metal nanocatalysts were prepared by reduction of Pd–Ag salts in the presence of poly(propylene imine) dendrimers, which were covalently bound to the surface of a silica polyamine composite, BP‐1 (polyallylamine covalently bound to a silanized amorphous silica gel). Three different Pd‐to‐Ag ratios were evaluated (50:50, catalyst 1; 40:60, catalyst 2; 60:40, catalyst 3) with the goal of determining how the amount of Ag effects selectivity, rate and conversion in the selective reduction of alkynes, such as phenylacetylene and 1‐ or 4‐octyne, to the corresponding alkenes. Conditions for the catalysis are reported where there is improved selectivity without a serious reduction in rate when compared with the analogous Pd‐only catalysts. Catalyst 2 worked best for phenylacetylene and catalyst 3 worked best for the octynes. The catalysts could be reused seven times without loss of activity. Copyright © 2015 John Wiley & Sons, Ltd.

Polyamine metabolism in flax in response to treatment with pathogenic and non-pathogenic Fusarium strains.

Flax crop yield is limited by various environmental stress factors, but the largest crop losses worldwide are caused by Fusarium infection. Polyamines are one of the many plant metabolites possibly involved in the plant response to infection. However, in flax plants the polyamine composition, genes involved in polyamine synthesis, and in particular their regulation, were previously unknown. The aim of this study was to investigate the polyamine synthesis pathway in flax and its involvement in response to pathogen infection. It is well established that polyamines are essential for the growth and development of both plants and fungi, but their role in pathogen infection still remains unknown. In our study we correlated the expression of genes involved in polyamine metabolism with the polyamine levels in plant tissues and compared the results for flax seedlings treated with two pathogenic and one non-pathogenic strains of Fusarium. We observed an increase in the expression of genes participating in polyamine synthesis after fungal infection, and it was reflected in an increase of polyamine content in the plant tissues. The highest level of mRNA was characteristic for ornithine decarboxylase during infection with all tested, pathogenic and non-pathogenic, Fusarium strains and the arginine decarboxylase gene during infection with the pathogenic strain of Fusarium culmorum. The main polyamine identified in the flax seedlings was putrescine, and its level changed the most during infection. Moreover, the considerable increase in the contents of cell wall-bound polyamines compared to the levels of free and conjugated polyamines may indicate that their main role during pathogen infection lies in strengthening of the cell wall. In vitro experiments showed that the polyamines inhibit Fusarium growth, which suggests that they play an important role in plant defense mechanisms. Furthermore, changes in metabolism and content of polyamines indicate different defense mechanisms activated in flax in response to infection by pathogenic and non-pathogenic Fusarium strains.

Evolution de la composition en polyamines des baies de raisin au cours du processus d'infection par Botrytis cinerea

Evolution of polyamine composition in grape berries during infection with Botrytis cinerea Polyamines are growth regulators occurring naturally in grapevine( Vitis vinifera L.) and pathogenic fungi, e.g. Botrytis cinerea . Investigation of polyamines of in vitro -grown Botrytis cinerea mycelium and infected berries has shown modifications in the metabolism of the berries which are directly related to the development of the fungi in the berries. The abnormal polyamine concentrations in infected berries appear to be of fungal origin for free polyamines and of plant origin for conjugated polyamines. The specific role of each type of polyamine is discussed with regard to the host-parasite relation.

Investigations on the surface structure and properties of silica‐polyamine composites on the nanoscales and microscales

ABSTRACTThe structure and properties of silica polyamine composites (SPC) made from microparticles of amorphous silica gel (300–600 microns) and silica nanoparticles (10–20 nm) modified with aminopropyltrimethoxysilane (APTMS), poly(allylamine) (PAA) or poly(ethyleneimine) (PEI) have been studied. The APTMS nano‐hybrids showed batch capacities for copper equal to or better than the corresponding polymer‐based micro‐hybrids. Loading of the PEI on the nanoparticles was independent of molecular weight of the polymer. Dynamic light scattering measurements showed that the SiO2 nanoparticles and the composites made from them aggregate in water and the degree of aggregation is dependent on the surface modification. All of the amine‐modified materials were catalysts for the Knoevenagel reaction but interestingly, the microparticles modified with APTMS were better catalysts than the corresponding nanoparticles or the polyamine modified composites. Solid‐state 19Si NMR has been used to elucidate the surface structure of the various composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42271.

Surface-Bound Ruthenium Diimine Organometallic Complexes: Excited-State Properties.

Ruthenium complexes of the general formula [Ru(CO)(H)(L2)(L′2)][PF6] (L2 = trans-2PPh3, L′ = η2-4,4′-dicarboxybipyridine (1); L2 =trans-2Ph2PCH2CH2COOH, L′2 = bipyridine (2); L2 = Ph2PCHCHPPh2, L′ = η2-5-amino-1,10-phenanthroline (3); L2 = trans-2PPh3, L′2 = η2-4-carboxaldehyde-4′-methylbipyridine (4)) have been shown to have longer emission lifetimes and higher quantum yields in solution compared with more symmetrical molecules such as [Ru(bpy)3][Cl]2. Compound 4 is obtained as a mixture with the corresponding acetal, 4′. These less symmetrical complexes have been covalently immobilized on the surface of silica polyamine composites, and their photophysical properties have been studied. The surface-bound complexes have been characterized by solid-state CPMAS 13C, 31P, and 29Si NMR, UV–vis, and FT-IR spectroscopies. Excited-state lifetime studies revealed that, in general, the lifetimes of the immobilized complexes are 1.4 to 8 times longer than in solution and are dependent on particle size (300–500 μm versus 10–20 nm average diameter silica gels), polymer structure (linear poly(allylamine) versus branched poly(ethylenimine)), and the type of surface tether. One exception to this trend is the previously reported complex [Ru(bpy)2(5-amino-1,10-phenanthroline)][PF6]2 (5), where only a slight increase in lifetime is observed. Only minor changes in emission wavelength are observed for all the complexes. This opens up the possibility for enhanced heterogeneous electron transfer in photocatalytic reactions.

Putrescine, a fast-acting switch for tolerance against osmotic stress

During the last decade we showed clearly that abiotic stress changes the cellular composition of polyamines, which in turn regulate the photochemical and non-photochemical quenching of the received light energy in the photosynthetic apparatus and that modulate substantially the level of plant tolerance. In the present contribution, we tried to change the bioenergetics of the leaf discs before the exposure to osmotic stress only by exogenously supplied putrescine, in order to enhance quickly the tolerance against the abiotic stress. Tobacco leaf discs treated with polyethylene-glycol reduced their water content about 24% within 1h. This relatively mild osmotic stress increased endogenous putrescine about 83% and decreased maximum photosystem II photochemical efficiency about 14%. In line with this, here we show that treatment with 1mM exogenous putrescine 1h before polyethylene-glycol addition protects the photochemical capacity and inhibits loss of water, confirming the key role of putrescine in the modulation of plant tolerance against osmotic stress. Furthermore, our recent works indicate that putrescine is accumulated in lumen during light reactions and may act as a permeable buffer and an osmolyte.

Kinetic, equilibrium and thermodynamic modelling of the sorption of metals from aqueous solution by a silica polyamine composite

Batch sorption studies were conducted to assess the potential of a phosphonated silica polyamine composite (BPAP) to remove metals (Co, Cu, Fe, Mg, Mn, Ni, U and Zn) from mine waters. The metal adsorption showed a good Langmuir isotherm fit. Ni and Mn fitted both the Freundlich and Langmuir isotherms. The activation energies (Ea) of Co, Mg and Ni ranged between 5 and 40 kJ∙moℓ-1, signifying physisorption while U showed a chemisorption type of adsorption (with Ea > 50 kJ∙moℓ-1). Cu and Fe on the other hand gave negative Ea values, indicating their preference to bind to low-energy sites. The pseudo-second-order kinetic model provided the best correlation of the experimental data, except for Mg and Ni for which the pseudo-first-order model and the Elovich model gave a better fit, respectively. Adsorption was almost constant over a wide pH regime and increased with time. Adsorption increased with concentration of the metals with the exception of Co, Fe and Ni which displayed about a 40% drop at a concentration of 200 mg∙ℓ-1. Desorption experimental data gave poor results except for U which showed 99.9% desorption.Keywords: silica polyamine composite, sorption, kinetics, isotherms, desorption