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Polyamines are essential analytes due to their critical role in various biological processes and human health in general. Due to their role as regulators for cell growth and proliferation (putrescine and spermine), as neuroprotectors, gero-, and cardiovascular protectors (spermidine), and as bacterial growth indicators (cadaverine), rapid, simple, and cost-effective methods for polyamine detection in biofluids are in demand. The present study focuses on the development and investigation of self-assembled and fluorescent host⋅dye chemo-sensors based on sulfonated pillar[5]arene for the specific detection of polyamines. Binding studies, as well as stability and functionality assessments of the turn-on chemosensors for selective polyamine detection in saline and biologically relevant media, are shown. Furthermore, the practical applicability of the developed chemo-sensors is demonstrated in biofluids such as human urine and saliva., (© 2024 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Developing synthetic materials, with enzyme-like molecular recognition capabilities, as functional receptors in electronic or electrochemical devices for the timely diagnosis of major diseases is a great challenge. Herein, we present the development of Fe/MIPpy nanozymes, characterized as enzyme-like artificial receptors, for the precise and non-invasive monitoring of cancer biomarkers in aqueous solutions and human saliva. Through the integration of PVA-stabilized FeFe 2 O 4 nanocrystals in a molecularly imprinted conducting polypyrrole matrix, the Fe/MIPpy nanozymes demonstrate 424 nA cm -2 nM -1 sensitivity and 220 pM detection limit. Charge-transfer mechanisms, Fe/MIPpy-spermine interactions, and the principle of spermine recognition are investigated by electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The disposable Fe/MIPpy sensor operates wirelessly and offers rapid and remote quantification of spermine, making it a promising material for the development of cost-effective tools for non-invasive cancer diagnosis and prognosis.

Small fruits such as strawberries, are a good source of natural antioxidants. In recent decades, many efforts have been made to increase the shelf life of strawberries and maintain its nutritional value in post-harvest conditions. In the present study, the effects of spermine (Spm) and spermidine (Spd) (0, 1.0 and 1.5 mM) on the post-harvest life and quality of strawberry fruits during the 3rd, 6th, and 12th days of storage, were investigated. Applications of Spm and Spd decreased the rate of weight loss, fruit decay, soluble solids content, fruit juice pH and taste index during the storage period in compared to the control. However, titratable acids and vitamin C contents, tissue stiffness, phenolic compounds and antioxidant activity increased in compared to the control. These growth regulators prevented the aging and loss of bioactive compounds of the fruit by increasing the antioxidant activity and preventing the destruction of the fruit tissue. Among the studied treatments, applications of 1.5 mM of Spm and Spd were the most effective treatments to enhance the storage life and quality characters of strawberry fruits.

(1) Background: Spermidine is a biogenic polyamine that plays a crucial role in mammalian metabolism. As spermidine levels decline with age, spermidine supplementation is suggested to prevent or delay age-related diseases. However, valid pharmacokinetic data regarding spermidine remains lacking. Therefore, for the first time, the present study investigated the pharmacokinetics of oral spermidine supplementation. (2) Methods: This study was designed as a randomized, placebo-controlled, triple-blinded, two-armed crossover trial with two 5-day intervention phases separated by a washout phase of 9 days. In 12 healthy volunteers, 15 mg/d of spermidine was administered orally, and blood and saliva samples were taken. Spermidine, spermine, and putrescine were quantified by liquid chromatography-mass spectrometry (LC-MS/MS). The plasma metabolome was investigated using nuclear magnetic resonance (NMR) metabolomics. (3) Results: Compared with a placebo, spermidine supplementation significantly increased spermine levels in the plasma, but it did not affect spermidine or putrescine levels. No effect on salivary polyamine concentrations was observed. (4) Conclusions: This study's results suggest that dietary spermidine is presystemically converted into spermine, which then enters systemic circulation. Presumably, the in vitro and clinical effects of spermidine are at least in part attributable to its metabolite, spermine. It is rather unlikely that spermidine supplements with doses <15 mg/d exert any short-term effects.

The evaluation of the biogenic amines (BAs) profile of different types of craft beers is herein presented. A previously developed and validated analytical method based on ion-pair chromatography coupled with potentiometric detection was used to determine the presence of 10 BAs. Good analytical features were obtained for all amines regarding linearity (R 2 values from 0.9873 ± 0.0015 to 0.9973 ± 0.0015), intra- and inter-day precision (RSD lower than 6.9% and 9.7% for beer samples, respectively), and accuracy (recovery between 83.2-108.9%). Detection and quantification limits range from 9.3 to 60.5 and from 31.1 to 202.3 µg L -1 , respectively. The validated method was applied to the analysis of four ale beers and one lager craft beer. Ethylamine, spermidine, spermine, and tyramine were detected in all analyzed samples while methylamine and phenylethylamine were not detected. Overall, pale ale beers had a significantly higher total content of BAs than those found in wheat pale and dark samples. A general least square regression model showed a good correlation between the total content of BAs and the brewing process, especially for Plato degree, mashing, and fermentation temperatures. Knowledge about the type of ingredients and manufacturing processes that contribute to higher concentrations of these compounds is crucial to ensuring consumer safety.

A method for the determination of 8 biogenic amines in aquatic products and their derived products was established by HPLC-MS/MS without derivatization. The samples were extracted by 5% perchloric acid solution. N-hexane was used to clean the extract. The analytes were separated by a column of ACQUITY UPLC HSS T3 (100 mm × 2.1 mm, 1.8 µm), and gradient eluted with a mixed solution of (0.5% formic acid) and acetonitrile. Good linearity was obtained with correlation coefficients (R 2 ) >0.99. This method achieved higher sensitivity (from 0.1 mg/kg for tyramine, 2-phenylethylamine and tryptamine to 1.0 mg/kg for spermidine, spermine, cadaverin, histamine and putrescine). The average recoveries were demonstrated in the range of 70.9%-113.1%, with relative standard deviations (RSDs) from 0.33% to 10.81%. This method was suitable for the detection of BAs in aquatic products and their products., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

The polyamine content of human breast milk, which is the first exogenous source of polyamines for the newborn, can be affected by several factors associated with the mother, the infant, or breastfeeding itself. The aim of this study was to evaluate the influence of different breastfeeding factors on the polyamines found in human milk. For this study, a cohort of 83 mothers was considered for up to 4 months, and a subgroup of 33 mothers were followed during the first six months of breastfeeding. Two breast milk samples were collected at each sampling point (foremilk and hindmilk) and the polyamine content was determined by UHPLC-FL. Polyamine levels varied considerably between the mothers and tended to decrease over time. Putrescine was the minor polyamine, whereas spermidine and spermine contents were very similar. The concentrations of the three polyamines were significantly higher in hindmilk than foremilk ( p < 0.001). Spermidine and spermine levels decreased significantly through the lactation progress ( p < 0.05). Finally, slightly higher levels of polyamines were observed in the milk of mothers providing partial, rather than full, breastfeeding, although the differences were not significant. The polyamine content in human milk was found to change during a single feed (foremilk versus hindmilk) and as lactation progressed, mainly in response to the specific circumstances of the newborn.

We developed a facile detection method of spermine based on the fluorescence (FL) quenching of the ciprofloxacin-Tb3+ complex, which shows astrong green emission. Ciprofloxacin (CP) makes efficient bondings to Tb3+ ion as a linker molecule through carboxylic and ketone groups to form a kind of lanthanide coordination polymer. The addition of spermine that competes with Tb3+ ions for the interaction with CP due to its positive charge brings about weakened coordination linkage of CP and Tb3+. The probe exhibited high sensitivity, selectivity, and good linearity in the range of 2-180 μM with a low limit of detection of 0.17 μM. Moreover, we applied this method on the paper strip test (PST), along with the integration of a smartphone and Arduino-based device. The practical reliability of the developed probe was evaluated on human serum samples with acceptable analytical results., Competing Interests: The authors have declared that no competing interests exist.

Aim: To assess the applicability of the novel technique based on the detection of spermine in solutions by spectrocolorimetric method using gold and silver colloidal nanoparticles., Materials and Methods: Colloidal solution of gold nanoparticles were synthesized by chemical reduction of tetrachlorauric acid with trisodium citrate. Colloidal solution of silver nanoparticles was obtained by chemical reduction of silver nitrate with tryptophan. The absorption spectra of gold/silver metal colloids and their mixtures with polyamines were recorded., Results: The increase of spermine concentration in solution caused the change in the intensity of the band of localized surface plasmon resonance that was not affected by the excess of spermidine. The color shift in colloidal gold due to its aggregation with spermine was registered spectrophotometrically., Conclusion: The principal possibility of selective quantification of spermine in the presence of spermidine in extremely high concentration using colloidal gold has been shown. This method can be used to assay selectively spermine in biological fluids.

During maize production, drought throughout the flowering stage usually induces seed abortion and yield losses. The influence of postpollination drought stress on seed abortion and its underlying mechanisms are not well characterized. By intervening in the competition for assimilates between kernel siblings under different degrees of postpollination drought stresses accompanied by synchronous pollination (SP) and incomplete pollination (ICP) approaches, the mechanisms of postpollination abortion were investigated at physiological and molecular levels. Upon SP treatment, up to 15% of the fertilized apical kernels were aborted in the drought-exacerbated competition for assimilates. The aborted kernels exhibited weak sucrose hydrolysis and starch synthesis but promoted the synthesis of trehalose-6-phosphate and ethylene. In ICP where basal pollination was prevented, apical kernel growth was restored with reinstated sucrose metabolism and starch synthesis and promoted sucrose and hexose levels under drought stress. In addition, the equilibrium between ethylene and polyamine in response to the drought and pollination treatments was associated with the abortion process. We conclude that competition for assimilates drives postpollination kernel abortion, whereas differences in sugar metabolism and the equilibrium between ethylene and polyamines may be relevant to the "live or die" choice of kernel siblings during this competition., (© 2019 John Wiley & Sons Ltd.)

Background: Nitric oxide (NO) and abscisic acid (ABA) are important regulators of plant response to cold stress, and they interact in response to cold signals. The primary goal of this study was to determine the roles of exogenous NO and ABA on the synthesis of endogenous NO and ABA in cold-stored peach fruit., Results: Exogenous NO and ABA maintained a relatively high content of NO, increased nitrate reductase (NR) activity, and inhibited the activity of NO synthase (NOS)-like and the levels of polyamine biosynthesis in peaches during cold storage. Treatments of potassium 2-(4-carboxyphenyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide (c-PTIO), NO, N-nitro-l-Arg-methyl ester ( L -NAME), and sodium tungstate did not influence ABA content. Exogenous ABA increased the content of carotenoids and the activities of aldehyde oxidase (AO), 9-cis-epoxycarotenoid dioxygenase (NCED), and zeaxanthin epoxidase (ZEP) of ABA synthesis in peaches during cold storage, and upregulated the gene expression of PpAO1, PpNCED1, PpNCED2, and PpZEP. The production of endogenous NO was differentially inhibited by NO scavengers, ABA inhibitors, and NR inhibitors, but not affected by NOS-like inhibitors during cold storage., Conclusion: Exogenous NO and ABA can induce endogenous NO synthesis in cold-stored peaches by the nitrate reductase pathway, and ABA can mediate endogenous ABA synthesis by the autocatalytic reaction. NO does not regulate ABA synthesis. © 2019 Society of Chemical Industry., (© 2019 Society of Chemical Industry.)

The sustainable development of point-of-care testing (POCT) for spermine detection is important to check for food spoilage, early diagnosis of various malignancies and diminished anticonvulsant drug carbamazepine response in chronic epilepsy. Herein, the synthesis, characterization and spectroscopic properties of perylene diimide EA-PDI∩Cu 2+ complex based nanoparticles towards spermine were studied in detail. This EA-PDI∩Cu 2+ complex can be used for the ultrasensitive detection of spermine as low as 86.3 nM (UV-vis) and 90 pM (fluorescence) in aqueous medium, in urine and blood serum samples (recovery 99 ± 3) and in the solid state (0.1 μg L -1 ), and EA-PDI shows minimal cytotoxicity to cells and can easily enter into Human Osteosarcoma MG-63 cells for bio-imaging of Cu 2+ and spermine. This EA-PDI∩Cu 2+ complex can be established as a cost-effective method to develop a diagnostic kit for POCT of spermine in terms of a solution-based test kit for real time detection of spermine in vapor and solution form released from fermented food samples.

Aim: To analyze the performance of biosensor based on nanoparticles of zinc oxide for the detection of spermine and spermidine in solution and in cell culture., Materials and Methods: Zinc oxide nanoparticles were used for preparing biosensor containing antibodies to spermine and spermidine. Polyamine concentration is solutions of spermine and spermidine as well as in lyophilisate of MCF-7 cells was measured by luminescence of the samples excited by laser beam at 380 nm., Results: The minimum concentration for the detection of polyamines in model solutions is 10 ng/ml, and maximum one is 100 ng/ml. A higher level of luminescence intensity of nanoparticles was found during analysis the polyamines in MCF-7 lyophilisate allowing for detecting polyamines at concentrations from 100 cells/ml to 100,000 cells/ml., Conclusions: The proposed biosensor system for determining the level of biogenic polyamines in cell lyophilisate using the optical properties of zinc oxide nanoparticles is promising for further improvement of the methodology and its implementation for detection and measurement of polyamines in biological systems.

Bioactive amines are found in food and can be relevant for the assessment of fruits shelf life and nutritional quality. The pulp and peel of 20 banana and plantain were analyzed and the bioactive amine content varied according to the genotype, ripening stage, fruit tissue and thermal processing. In most of the analyzed genotypes, tyramine, histamine, dopamine, serotonin, spermidine, and spermine were decreased during the ripening process in the pulps. By contrast, there was an increase in putrescine level. In many genotypes of plantains, the serotonin and dopamine contents in pulp decreased until stage 5 and increased at stage 7. Peels contain higher levels of serotonin, dopamine, histamine and tyramine than pulps. Additionally, thermal processing affects the content of amines present in fruit. Boiling with the peel should be preferred in domestic preparations, regardless of the genotype used., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Spermine contamination ranks as one of the food safety issues, it will cause some adverse reactions if the intake of spermine is excessive in human body. So it is of great significance to establish fast and efficient analysis method to detect spermine in foods. In this study, the spermine aptamers with high affinity and specificity were obtained by the capture systematic evolution of ligands by exponential enrichment (Capture-SELEX) technique. Forty-one aptamer sequences were obtained by cloning and sequencing, and were divided into eight families based on homology and secondary structure analysis. The affinity and specificity of candidate aptamers was analyzed by isothermal titration calorimetry (ITC) and fluorescence assay. The aptamers named APJ-6 was picked out as the optimal aptamer that recognizes spermine specifically with the Kd value of 9.648 ± 0.896 nM. In order to verify the practicability of the selected aptamers, the sensitive aptamer-based fluorescene assay was designed. Under optimized conditions, this aptasensor exhibited a low detection limit of 0.052 nM, as well as a linear within the range of 0.1-20 nM. Besides, it has been further applied for the determination of spermine in pork samples and the recoveries ranged from 86.45% to 98.15%, showing its great potential for sensitive analysis in food safety control., (Copyright © 2019. Published by Elsevier B.V.)

Non-covalent interaction in the binary systems of polyamines (putrescine, spermidine, spermine) with citric acid and complex formation in the binary as well as ternary systems of lanthanide(III) ions, citric acid and polyamine have been investigated. The studies were performed in aqueous solution. The overall stability constants of the complexes were determined using the potentiometric method with computer analysis of the data. Only mononuclear type of complexes were found in the ternary systems and polyamines were located in the outer as well as inner coordination sphere. Non-covalent interaction between biogenic amines and citric acid in the binary and ternary systems were confirmed on the basis of the equilibrium constants analysis and spectroscopic studies., (Copyright © 2019 Elsevier Inc. All rights reserved.)

Twenty-two compounds belonging to several classes of polyamine analogs have been examined for their ability to inhibit the growth of the human malaria parasite Plasmodium falciparum in vitro and in vivo . Four lead compounds from the thiourea sub-series and one compound from the urea-based analogs were found to be potent inhibitors of both chloroquine-resistant (Dd2) and chloroquine-sensitive (3D7) strains of Plasmodium with IC 50 values ranging from 150 to 460 nM. In addition, the compound RHW, N 1, N 7-bis (3-(cyclohexylmethylamino) propyl) heptane-1,7-diamine tetrabromide was found to inhibit Dd2 with an IC 50 of 200 nM. When RHW was administered to P. yoelii -infected mice at 35 mg/kg for 4 days, it significantly reduced parasitemia. RHW was also assayed in combination with the ornithine decarboxylase inhibitor difluoromethylornithine, and the two drugs were found not to have synergistic antimalarial activity. Furthermore, these inhibitors led to decreased cellular spermidine and spermine levels in P. falciparum , suggesting that they exert their antimalarial activities by inhibition of spermidine synthase.

Shuidouchi is a traditional Chinese fermented soybean product and its quality is largely affected by the microbes involved in the fermentation. In this study, eleven Shuidouchi samples were collected from southwest China and the microbial diversity and its correlations with chemical characteristics were investigated. Bacterial community was detected using 16S rRNA sequencing, along with bacterial and fungal viable plate counts. Biogenic amines and other chemical characteristics were determined by HPLC and corresponding chemical reaction methods. Among eleven Shuidouchi samples, 21 phyla and 356 genera were identified. Firmicutes, Bacteroidetes and Proteobacteria were the predominant phyla while Bacillus, Bacteroides and Lactobacillus were the main genera. The average cell number of bacteria, lactic acid bacteria and fungi were 1.6 × 10 6 , 5.9 × 10 4 and 7.6 × 10 3  CFU/g, respectively. HPLC results showed that the mean concentration of tryptamine, β-phenylethylamine, putrescine, cadaverine, histamine, tyramine, spermidine and spermine were 23.11, 3.66, 12.21, 7.12, 8.13, 22.98, 24.72, and 39.00 mg/kg, respectively. The average content of other characteristics including amino acid nitrogen, titratable acidity, and reducing sugar were 2.08, 3.44, and 25.78 g/kg, respectively. Shuidouchi samples were slightly acidic or neutral. Fibrinolytic enzyme activity was detected only in one sample. Among top 52 identified genera, 9 genera showed positive correlations with the chemical characteristics of Shuidouchi while 15 genera were negatively associated. Our results indicated that Shuidouchi contained rich microbial resources and were edible safety based on the tested indexes. The associations identified between microbes and chemical characteristics could be further utilized in the food fermentation industry., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

A new method for determination of underivatized biogenic amines in cheese based on ion exchange chromatography coupled with tandem mass spectrometric detection was proposed. The method was applied to the analysis of 10 biogenic amines (trimethylamine, putrescine, cadaverine, histamine, 2-phenylethylamine, spermine, spermidine, tryptamine, agmatine, and tyramine) in different types of cheese. The amines were extracted only with water without any additional derivatization step or sample cleanup. This is a great advantage in terms of simplicity of sample pretreatment procedure compared with other currently existing methods in the literature. Biogenic amines were separated using cation exchange column, under gradient elution conditions by mixing formic acid (1.00 M) and deionized water. Detection was achieved using tandem MS/MS, with the instrument set into multiple reaction monitoring mode to ensure high specificity. The detection and quantification limits were in the ranges of 12-46 μg/L and 40-153 μg/L, respectively. The exceptions were spermidine and spermine, with detection limits of 0.8 and 5.4 mg/L, respectively. The linearity for most of the biogenic amines was from 10 μg/L up to 10 mg/L. The best recoveries were observed for trimethylamine, tyramine, and cadaverine, and were 89, 94, and 102%, respectively. The results showed that this method can be used for routine determination of biogenic amines in different types of cheeses as well other food matrices. It must be stressed that the proposed method is capable of determining 10 biogenic amines, including tyramine, which is reported to cause food intoxication commonly associated with cheeses.

We developed a competitive fluorescent molecularly imprinted polymer (MIP) assay to detect biogenic amines in fish samples. MIPs synthesized by precipitation polymerization using histamine as template were used in a batch binding assay analogous to competitive fluoroimmunoassays. Introducing a complex sample matrix, such as fish extract, into the assay changes the environment and the binding conditions, therefore the importance of the sample preparation is extensively discussed. Several extraction and purification methods for fish were comprehensively studied, and an optimal clean-up procedure for fish samples using liquid-liquid extraction was developed. The feasibility of the competitive MIP assay was shown in the purified fish extract over a broad histamine range (1 - 430µM). The MIP had the highest affinity towards histamine, but recognized also the structurally similar biogenic amines tyramine and tryptamine, as well as spermine and spermidine, providing simultaneous analysis and assessment of the total amount of biogenic amines., (Copyright © 2018 Elsevier B.V. All rights reserved.)

No expression and distribution patterns of polyamines (PAs), spermine, spermidine, and their precursor putrescine in mammalian hair follicle are available, although polyamines are known to correlate well with hair growth and epidermal tumor genesis. Immunohistochemistry (IHC) using our original two monoclonal antibodies (mAbs) ASPM-29 specific for spermine or spermidine, and APUT-32 specific for putrescine allowed us to detect immunoreactivity for polyamines in hair follicles from normal adult rats. A wide range of immunoreactivity for the total spermine and spermidine was observed in the compartments of hair follicle: The highest degree of immunoreactivity for polyamines was observed in the matrix, in the Huxley's layer, in the deeper Henle's layer, and in the cuticle of the inner root sheath/the hair cuticle, while moderate immunoreactivity existed in the lower-to-mid cortex and the companion layer, followed by lower immunoreactivity in the outer root sheath, including the bulge region and in the deeper medulla, in which the immunoreactivity was also evident in their nuclei. In addition, somewhat surprisingly, with IHC by APUT-32 mAb, we detected significant levels of putrescine in the compartments, in which the immunostaining pattern was the closely similar to that of the total spermine and spermidine. Thus, among these compartments, the cell types of the matrix, the Huxley's layer, the deeper Henle's layer, and the cuticle of the inner root sheath/the hair cuticle seem to have the biologically higher potential in compartments of anagen hair follicle, maybe suggesting that they are involved more critically in the biological event of hair growth. In addition, we noted sharp differences of immunostaining by IHCs between ASPM-29 mAb and APUT-32 mAb in the epidermis cells and fibroblast. ASPM-29 mAb resulted in strong staining in both the cell types, but APUT-32 mAb showed only very light staining in both types. Consequently, the use of the two IHCs could be extremely useful in further studies on hair cycle and epidermal tumor genesis experimentally or clinically.

In this work a detailed description of the development of amine oxidase-based electrochemical biosensors for the selective determination of the biogenic amines is presented. The enzymes required for this operation are Polyamine Oxidase (PAO) and Spermine Oxidase (SMO) which are physically entrapped in poly(vinyl alcohol) bearing styrylpyridinium groups (PVA-SbQ), a photo-cross-linkable gel, onto screen printed electrode (SPE) surface. The developed biosensors are deeply characterized in the analysis of biogenic amines by using flow injection amperometric (FIA) technique. The enzymatic electrodes are characterized by good sensitivity, long-term stability, and reproducibility. To test the feasibility of the developed biosensors in the analysis of real matrices, they are used for the analysis of blood samples. The results obtained are in good agreement with those obtained with the GC-MS reference method.

Thermospermine, a structural isomer of spermine, is widely spread in the plant kingdom and has recently been shown to play a key role in the repression of xylem differentiation in vascular plants. However, a standard high-performance liquid chromatography (HPLC) protocol for detecting polyamines as their dansyl derivative cannot distinguish themospermine from spermine. These isomers become separated from each other after benzoylation. In this chapter, we describe a simple protocol for extraction, benzoylation, and HPLC detection of thermospermine and spermine with other polyamines from plant material.

The mucopolysaccharidoses (MPS) are rare genetic disorders marked by severe somatic and neurological symptoms. Development of treatments for the neurological manifestations of MPS has been hindered by the lack of objective measures of central nervous system disease burden. Identification of biomarkers for central nervous system disease in MPS patients would facilitate the evaluation of new agents in clinical trials. High throughput metabolite screening of cerebrospinal fluid (CSF) samples from a canine model of MPS I revealed a marked elevation of the polyamine, spermine, in affected animals, and gene therapy studies demonstrated that reduction of CSF spermine reflects correction of brain lesions in these animals. In humans, CSF spermine was elevated in neuropathic subtypes of MPS (MPS I, II, IIIA, IIIB), but not in subtypes in which cognitive function is preserved (MPS IVA, VI). In MPS I patients, elevated CSF spermine was restricted to patients with genotypes associated with CNS disease and was reduced following hematopoietic stem cell transplantation, which is the only therapy currently capable of improving cognitive outcomes. Additional studies in cultured neurons from MPS I mice showed that elevated spermine was essential for the abnormal neurite overgrowth exhibited by MPS neurons. These findings offer new insights into the pathogenesis of CNS disease in MPS patients, and support the use of spermine as a new biomarker to facilitate the development of next generation therapeutics for MPS., (© The Author 2017. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.)

The detection and quantification of spermine in clinical practice is important for early diagnosis of many diseases. Chromatographic and immunoassay-based methods are commonly used. However, a fluorescence-based assay could provide real-time detection. Herein, the synthesis and aggregation properties of a dicationic perylene probe (N 1 -dodecyl-N 3 -(4-phenyl)benzimidazolium-functionalized perylenediimide (DAB-PDI)) used to develop a fluorescent "turn-on" ensemble for the detection of spermine are discussed. The fluorescence of DAB-PDI (10 μm, Φ=0.55) is efficiently quenched by negatively charged sodium dodecylsulfate (SDS) through the formation of ionic self-assembled aggregates (charge ratio of negative (N) in SDS to positive (P) in DAB-PDI (N/P)=9). This negatively charged ionic self-assembly between DAB-PDI and SDS has been characterized by using photophysical, microscopic, dynamic light scattering, isothermal titration calorimetry, and HRMS techniques. The addition of spermine to this ensemble solution results in the breakdown of the DAB-PDI-SDS ensemble owing to strong binding of spermine with SDS and, as a result, the fluorescence of DAB-PDI is recovered. This ensemble exhibits high sensitivity and selectivity for spermine detection in water, urine, and blood serum. The lowest limit of detection is 27.5 nm, which is at least about 36 times lower than that required for early diagnosis of cancer (1 to 10 μm for urinary spermine)., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Objective: The effects of aging, magnetic field and the voxel localization on measured concentrations of citrate (Cit), creatine (Cr), cholines (Cho) and polyamines (PA) in a healthy prostate were evaluated., Materials and Methods: 36 examinations at both 1.5T and 3T imagers of 52 healthy subjects aged 19-71 years were performed with PRESS 3D-CSI sequences (TE = 120 and 145 ms). Concentrations in laboratory units and their ratios to citrate were calculated using the LCModel technique. Absolute concentrations were also obtained after the application of correction coefficients. Statistical analysis was performed using a robust linear mixed effects model., Results: Significant effects of aging, the magnetic field strength and the voxel position in central (CZ) or peripheral (PZ) zones on all measured metabolites were found. The concentrations (mmol/kg wet tissue) including prediction intervals in a range of 20-70 years were found: Cit: 7.9-17.2; Cho: 1.4-1.7; Cr: 2.8-2.5; PA (as spermine): 0.6-2.1 at 3T in CZ. In PZ, the concentrations were higher by about 10 % as compared to CZ., Conclusion: Increasing citrate and spermine concentrations with age are significant and correlate well with a recently described increase of zinc in the prostate. These findings should be considered in decision-making if the values obtained from a subject are in the range of control values.

Relationships between endogenous levels of polyamines by thin layer chromatography (TLC) and gas chromatography (GC), nitrate and response to the application of ethylene were established between organic and conventional vegetables (broccoli, collard greens, carrots and beets), both raw and cooked. Responses to ethylene showed that organic plants were less responsive to the growth regulator. The levels of free polyamines obtained by TLC were higher in organic vegetables. Organic broccoli showed higher levels of putrescine (Put), and cooking resulted in lowering the overall content of these amines. Conventional collard green showed the highest level of putrescine in the leaves compared with organic. Tubers of carrots and beets contain the highest levels of Put. These plants also contain high levels of spermine. GC analysis showed the highest polyamines contents compared with those obtained by TLC. Cooking process decreased putrescine and cadaverine content, both in conventionally and organically grown vegetables. Organic beets contain lower NO3(-) compared with its conventional counterpart., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Since amine compounds have been widespread pollutants in nature and they are extensively used in pharmaceutical industries and dye manufacturing, it is highly desirable to develop simple, effective and naked-eye available analytical methods for such aliphatic diamines determination. Calixarenes as macrocycles have drawn intensive interests for fields such as biomedicine, supramolecular chemistry and smart materials. Here, instead of the normal complicated modification strategy, a facile and efficient method for one-pot synthesis of calix[4]arene crown ether (CCE4) capped gold nanoparticles (AuNPs) is proposed. The as-prepared CCE4-AuNPs are not only high water dispersity and stability even after storage for 3 months, but also capable of host-guest recognition of diamines in aqueous systems. Size-selective encapsulation of amine group between CCE4 and diamines carry out the aggregation of CCE4-AuNPs. The determination of diamines such as hexamethylenediamine or spermine can be realized by the UV-vis absorbance change and visual color difference., (Copyright © 2015 Elsevier B.V. All rights reserved.)

A novel complexation between kukoamines and dihydrogen phosphate ions (DPI) during CZE was discovered to improve the UV signal of kukoamine by around 30-fold. This complexation formed by electric current was attributed to the hydrogen bonding of hydroxyl and amino (or amide) groups between the analyte and electrolyte anions. The established CZE method is low-cost, easy to operate, and eco-friendly, and it was shown to be superior to HPLC in terms of separation capability, efficiency, specificity, and sensitivity. We believe that our CZE method can be applied as an alternative to HPLC for kukoamine assay. The approach described here can be also extended for analyzing other compounds with similar functional groups., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The influence of somatic cells counts (SCC) in milk on bioactive amines in Mozzarella cheese was investigated. High SCC milk had lower lactose and higher pH compared to low and medium SCC. Low spermine levels were found in milk irrespective of SCC. The cheeses had similar characteristics, but the extension and depth of proteolysis increased with SCC. Cheese from all SCC categories contained spermine; whereas tyramine and tryptamine were only detected in cheese from high SCC milk. During 60-days refrigerated storage, significant positive effects were observed between SCC and proteolysis, storage time and pH and storage time and proteolysis. There was a significant positive effect of storage time on spermine and serotonin levels. Only cheese from high SCC milk showed significantly higher serotonin levels. Tyramine and tryptamine were found in cheese from high SCC milk., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Eight biogenic amines (spermine, spermidine, putrescine, histamine, tyramine, phenylethylamine, cadaverine and serotonin) were determined by LC-UV after derivatization with dansyl-chloride in both ground coffee and coffee beverages obtained by different methods. In ground coffee, the most relevant amine was PUT, followed by SPD, HIS, TYR, CAD, SPM, PHE, and SER, with the total BAs content decreasing as the roasting degree increased. In coffee brews, the order was PUT, SPM, TYR, CAD, SPD, PHE, HIS, and SER, but at a very low level in comparison with the amount of BAs determined in roasted ground coffee. Beverages prepared by espresso, capsule, and pod machines had the lowest BAs contents, as a result of the thermal and physical stress imposed on ground coffee by these methods, while mocha contained the highest BAs amounts owing to lower pressure and longer brewing time., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

The objective of this study was to monitor the post-partum variation of polyamine content, in ovine and caprine milk, from indigenous Greek breeds. Twenty samples of ewe and 20 samples of goat colostrum and milk were collected at the 1st, 2nd, 3rd, 4th, 5th and 15th day post-partum. Putrescine, spermidine and spermine were measured as dansylated derivatives by high-performance liquid chromatography. Putrescine was the least concentrated of these substances in both milk types. Spermidine was the prevailing polyamine in caprine samples, reaching levels up to 4.41 μmol/l on the 3rd day post-partum. In ovine milk, the profile of the mean concentrations showed greater levels of spermine than spermidine, except for the 5th day post-partum. These data suggest that goat colostrum and ewe milk (15th day) could be considered as good natural sources for these bioactive growth factors, and may become useful raw materials for designing tailored dairy products for specific population groups., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

The present work describes the development and optimization of electrochemical biosensors for specific determination of the biogenic polyamine spermine (Spm) and spermidine (Spmd) whose assessment represents a novel important analytical tool in food analysis and human diagnostics. These biosensors have been prepared using novel engineered enzymes: polyamine oxidase (PAO) endowed with selectivity towards Spm and Spmd and spermine oxidase (SMO) characterized by strict specificity towards Spm. The current design entails biosensors in which the enzymes were entrapped in poly(vinyl alcohol) bearing styrylpyridinium groups (PVA-SbQ), a photocrosslinkable gel, onto an electrode surface. Screen-printed electrodes (SPEs) were used as electrochemical transducers for enzymatically produced hydrogen peroxide, operating at different potential vs Ag/AgCl according to the material of the working electrode (WE): +700 mV for graphite (GP) or -100 mV for Prussian blue (PB)-modified SPE, respectively. Biosensor performances were evaluated by means of flow injection amperometric (FIA) measurements. The modified electrodes showed good sensitivity, long-term stability and reproducibility. Under optimal conditions, the PAO biosensor showed a linear range 0.003-0.3 mM for Spm and 0.01-0.4 mM for Spmd, while with the SMO biosensor, a linear range of 0.004-0.5 mM for Spm has been obtained. The main kinetic parameters apparent Michaelis constant (K M), turnover number (K cat) and steady-state current (I max) were determined. The proposed device was then applied to the determination of biogenic amines in blood samples. The results obtained were in good agreement with those obtained with the GC-MS reference method.

Spermine and spermidine are multiple-nitrogen compounds found in many foods. Both compounds are essential for cell growth and human health. This study established a simple and fast method of detecting spermine and spermidine in food samples by matrix-assisted laser desorption/ionization combined with time-of-flight mass spectrometry (MALDI-TOF MS). After a simple sample preparation procedure, spermine and spermidine were directly detected by MALDI-TOF MS with no additional purification procedure. The calibration curves for spermine and spermidine ranged from 0.1 to 10 μg/mL. In intra- and inter-batch assays of three different concentrations of spermine and spermidine, all relative standard deviations and relative errors were below 18.9%. These experimental results confirmed the practicability and effectiveness of the proposed MALDI-TOF MS method for fast determination of spermine and spermidine in food samples. Furthermore, since spermine and spermidine have important roles in apoptosis, up-regulation and down-regulation of spermine and spermidine during apoptosis were analyzed. After treating NRK-52E cells with spermine and spermidine, the cells were lysed, and cell proteins were collected, and digested. Apoptosis-related proteins were then identified by tandem MS., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Polyamines (PAs) in plant foods are relevant due to the association of these bioactive nutrients with health and disease. The scope of the present study was to monitor the content of free, conjugated, and total (free + conjugated) putrescine (Put), spermidine (Spd), and spermine (Spm) at five stages of lettuce growth in three different greenhouses. The daily intake of PAs from lettuce consumption was estimated since its consumption represents about 7.2% of vegetables intake. Results showed that the content of free Put, Spd, and Spm decreased during plant growth, while the content of conjugated Put, Spd, and Spm increased. Nevertheless, the total PA content remained fairly constant. Significant differences were observed in the PAs content in lettuces grown in different greenhouses. The conjugated fraction of PAs in mature lettuces has an important contribution to the total PAs and will certainly influence the bioavailability and/or bioactivity of dietary polyamines.

Polyamines (PAs) are low molecular weight aliphatic compounds that have been shown to be an important part of plant responses to salt stress. For that reason in this work we have investigated the involvement of PAs in the response to salt stress in root nodules of Phaseolus vulgaris in symbiosis with Rhizobium tropici. The level and variety of PAs was higher in nodules, compared to leaves and roots, and in addition to the common PAs (putrescine, spermidine and spermine) we found homospermidine (Homspd) as the most abundant polyamine in nodules. UPLC-mass spectrometry analysis revealed the presence of 4-aminobutylcadaverine (4-ABcad), only described in nodules of Vigna angularis before. Indeed, the analysis of different nodular fractions revealed higher level of 4-ABcad, as well as Homspd, in bacteroids which indicate the production of these PAs by the bacteria in symbiosis. The genes involved in PAs biosynthesis in nodules displayed an induction under salt stress conditions which was not consistent with the decline of free PAs levels, probably due to the nitrogen limitations provoked by the nitrogenase activity depletion and/or the conversion of free PAs to theirs soluble conjugated forms, that seems to be one of the mechanisms involved in the regulation of PAs levels. On the contrary, cadaverine (Cad) and 4-ABcad concentrations augmented by the salinity, which might be due to their involvement in the response of bacteroids to hyper-osmotic conditions. In conclusion, the results shown in this work suggest the alteration of the bacteroidal metabolism towards the production of uncommon PAs such as 4-ABcad in the response to salt stress in legume root nodules., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Plants which have been traditionally eaten by alpine populations may provide new opportunities of agricultural development for mountain regions. In this context we investigated the chemical composition of Cirsium spinosissimum (Asteraceae), a perennial thistle. Its receptacles were eaten by shepherds in Valais (Switzerland). Extracts of aerial parts were subjected to a comprehensive metabolite profiling, using a dereplication platform, combining HPLC-PDA-MS and offline microprobe NMR analysis. Twenty compounds, including various phenolic glycosides, a monoterpene lactone, a spermine derivative, and fatty acids, could be identified online, or after targeted isolation. The total phenolic content was determined, and the major flavonoids were quantitatively assessed in fresh receptacles by HPLC-PDA analysis. In addition, substances relevant for nutrition, such as β-carotene, fatty acids, ascorbic acid, and minerals, were quantified. The ethanolic extract of the receptacles showed no sign of cytotoxicity when tested in Caco-2 cells., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Background: Polyamine intake from milk is considered essential for post-natal maturation of the immune system and small intestine. The present study aimed to determine polyamine content in human milk after preterm delivery and the association with mothers' dietary intake. In comparison, the polyamine levels were compared with those in term breast milk and some corresponding formulas., Methods: Transitional breast milk was collected from 40 mothers delivering after 24-36 weeks of gestation, and from 12 mothers delivering after full term. Food intake was assessed in mothers delivering preterm babies using a 3-day diary. Polyamines were analysed by high-performance liquid chromatography., Results: The dietary intake of polyamines was significantly associated with breast milk content but weaker for spermine than for spermidine and putrescine. Total polyamine level was higher in preterm than term milk and lower in the corresponding formulas. Putrescine, spermidine and spermine contents [mean (SEM)] in preterm milk were 165.6 (25), 615.5 (80) and 167.7 (16) nmol dL⁻¹, respectively, with the levels of putrescine and spermidine being 50% and 25% higher than in term milk. The content of spermine did not differ., Conclusions: Dietary intake of polyamines has an impact on the content in breast milk. The difference between human milk after preterm and term delivery might be considered when using donor human milk for preterm infants. The corresponding formulas had lower contents. Further studies are important for determining the relationship between tissue growth and maturation and optimal intake., (© 2013 The British Dietetic Association Ltd.)

Electromembrane extraction (EME) as a novel sample preparation technique was firstly applied for the purification and enrichment of four polyamines mainly present in saliva samples. These four target analytes, putrescine, cadaverine, spermidine, and spermine, were directly determined by CZE with capacitively coupled contactless conductivity detection (CZE-C(4)D) after EME procedure. Several factors affecting extraction efficiency, electrophoretic separation, and detection were investigated. Under the optimum conditions, four polyamines were baseline separated within 22 min, exhibiting a linear calibration over three orders of magnitude (r>0.999); the highest enrichment factor could reach 106-fold (for spermidine), and the LODs were in the range of 1.4-7.0 ng mL(-1). The proposed EME/CZE-C(4)D method has been successfully applied to analyze human saliva samples with recoveries in the range of 78-97%., (Copyright © 2014 Elsevier B.V. All rights reserved.)

The effect of methyl jasmonate (MeJA) on changes in polyamines content and energy status and their relation to disease resistance was investigated. Freshly harvested loquat fruit were treated with 10 μmol l(-1) MeJA and wound inoculated with Colletotrichum acutatum spore suspension (1.0 × 10(5) spores ml(-1)) after 24h, and then stored at 20 °C for 6 days. MeJA treatment significantly reduced decay incidence. MeJA treated fruit manifested higher contents of polyamines (putrescine, spermidine and spermine) compared with the control fruit, during storage. MeJA treatment also maintained higher levels of adenosine triphosphate, and suppressed an increase in adenosine monophosphate content in loquat fruit. These results suggest that MeJA treatment may inhibit anthracnose rot by increasing polyamine content and maintaining the energy status., (Copyright © 2013. Published by Elsevier Ltd.)

A rapid and sensitive ultraperformance liquid chromatography coupled with electrospray ionization tandem mass spectrometry (UPLC-ESI-MS/MS) method has been developed and validated for quantitatively determining diacetylpolyamines in the human fingernail. N(1),N(8)-diacetylspermidine (DiAct-Spd), N(1),N(12)- diacetylspermine (DiAct-Spm) and 1,6-diaminohexane (DAH) the [internal standard (IS)] were extracted from human fingernail samples by MeOH: 5 M HCl solution, followed by 4-(N,N-dimethylaminosulfonyl)-7-fluoro- 2,1,3-benzoxadiazole (DBD-F) derivatization, and then separated on an ACQUITY BEH C18 column with a gradient elution of acetonitrile and water containing 0.1% formic acid. The derivatives of the diacetylpolyamines were fully separated within a short run time (3.0 min). The triple quadrupole mass spectrometric detection was performed in the multiple reactions monitoring (MRM) mode by the UPLC-ESI- MS/MS system in the positive ionization mode. MRM using the fragmentation transitions of m/z 455.20→ 100.07, 737.25 → 100.07 and 567.10 → 479.07 in the positive ESI mode was performed to quantify DiAct-Spd, DiAct-Spm and IS, respectively. The calibration curve is between 0.04 ng mL(-1) for DiAct-Spd and DiAct-Spm. The detection limits (signal to noise ratio of five) were 5-10 pg mL(-1). A good linearity was achieved from the calibration curves (r(2) >0.9999), and the intra-day and inter-day assay precisions were less than 7.06%. Furthermore, the recoveries (%) of the diacetylpolyamines spiked in the human fingernails were 79.18-97.11. The present method proved that the high sensitivity is characterized by the specificity and feasibility of the sample analysis. Consequently, the proposed method was used to analyze human fingernail samples from 15 lung- cancer patients and 22 healthy volunteers. Diacetylpolyamines were detected from the fingernails of the lung- cancer patients for the first time. The concentration of DiAct-Spd in the lung-cancer patient group tended to be higher than those in the healthy volunteers.

This study assessed proof-of-concept for use of polyamine inhibitor 2-diluoromethylornithine (DFMO) as a treatment for oral squamous cell carcinoma (SCC) in client-owned cats. Polyamine levels in tumor tissue and normal oral mucosa were quantified before and after treatment. DFMO was administered orally to 14 client-owned cats with histologically confirmed oral SCC. Patients were monitored for gastrointestinal, dermatologic, auditory, hematological, and biochemical abnormalities. Total polyamine levels in tumor tissue decreased after treatment, as did the specific polyamine putrescine in both tumor tissue and normal mucosa. Ototoxicity was observed in 5 of 6 cats receiving pre- and post-treatment brainstem auditory evoked potential tests. Subclinical thrombocytopenia was observed in 6 of 14 cats. One cat showed mild post-anesthetic tremors that resolved without treatment. Oral administration of DFMO at doses used in this study resulted in significantly decreased tumor polyamine levels without life-threatening clinical or hematological toxicities. Further studies are warranted to explore pathophysiology of polyamine biochemistry and use of polyamine inhibitors in treatment of cats with oral SCC.

Maternal milk is the first source of exogenous polyamines for the newborn. Polyamines modulate gut maturation in neonates, but no studies are available on polyamine concentration in human milk of preterm babies, even though they could be important for their immature gut. The present study aimed to determine polyamine concentration in human breast milk of mothers with preterm or term infants during the first month of lactation. Human milk samples were obtained during the first month of lactation from twenty-seven mothers with preterm babies and twelve mothers with babies born at term. The polyamine concentration in human milk was quantified by HPLC. During the first month of lactation, the total polyamine concentration was significantly higher in preterm milk than in term milk samples (7590 (SD 4990) v. 4660 (SD 4830) nmol/l, respectively (P ¼ 0·034)), as well as individual polyamine concentrations. Polyamine concentration in mature milk for preterm babies was significantly higher than that in mature milk for babies at term, and a similar trend was observed in colostrum and transition human milk. The spermidine/spermine ratio was higher in transition milk in preterm v. term samples, while in mature milk, the ratio was significantly lower in preterm than in term babies. In conclusion, the polyamine concentration was significantly higher in human milk for preterm than for term infants. This and the different spermidine/spermine ratios could influence the gut development of premature babies.

MR metabolic profiling of the prostate is promising as an additional diagnostic approach to separate indolent from aggressive prostate cancer. The objective of this study was to assess the relationship between the Gleason score and the metabolic biomarker (choline + creatine + spermine)/citrate (CCS/C) measured by ex vivo high-resolution magic angle spinning MRS (HR-MAS MRS) and in vivo MRSI, and to evaluate the correlation between in vivo- and ex vivo-measured metabolite ratios from spatially matched prostate regions. Patients (n = 13) underwent in vivo MRSI prior to radical prostatectomy. A prostate tissue slice was snap-frozen shortly after surgery and the locations of tissue samples (n = 40) collected for ex vivo HR-MAS were matched to in vivo MRSI voxels (n = 40). In vivo MRSI was performed on a 3T clinical MR system and ex vivo HR-MAS on a 14.1T magnet. Relative metabolite concentrations were calculated by LCModel fitting of in vivo spectra and by peak integration of ex vivo spectra. Spearman's rank correlations (ρ) between CCS/C from in vivo and ex vivo MR spectra, and with their corresponding Gleason score, were calculated. There was a strong positive correlation between the Gleason score and CCS/C measured both in vivo and ex vivo (ρ = 0.77 and ρ = 0.69, respectively; p < 0.001), and between in vivo and ex vivo metabolite ratios from spatially matched regions (ρ = 0.67, p < 0.001). Our data indicate that MR metabolic profiling is a potentially useful tool for the assessment of cancer aggressiveness. Moreover, the good correlation between in vivo- and ex vivo-measured CCS/C demonstrates that our method is able to bridge MRSI and HR-MAS molecular analysis., (Copyright © 2012 John Wiley & Sons, Ltd.)

It is a challenge to detect molecules lacking a chromophore, such as polyamines, by optical methods since they are insensitive to light. In order to detect the optical signals, it is compulsory to derive these molecules with optical labels, which, however, is complicated, time-consuming and may be expensive. In this work, a highly specific strategy for spermine detection is developed on the basis of the iodide-induced conformational change of polythiophene. By using the triplex complex of negatively charged double-stranded calf thymus DNA (ctDNA)-stabilized cationic polythiophene as a fluorescent probe, the highly specific detection of spermine could be realized since polythiophene, which will be released from the triplex complex owing to the condensation and aggregation of ctDNA with spermine, undergoes a conformational change from the random-coiled non-planar state to the highly conjugated planar form in the presence of iodide, resulting in a yellow-to-red color conversion and fluorescence quenching. The quenched fluorescence was found to be proportional to the spermine concentrations in the range of 1.2-50 μM with the limit of detection (LOD) being 0.5 μM (3σ/k).

Polyamine (PA) metabolism was studied in liquid cultures of Scots pine (Pinus sylvestris L.) embryogenic cells. The focus of the study was on the metabolic changes at the interphase between the initial lag phase and the exponential growth phase. PA concentrations fluctuated in the liquid cultures as follows. Putrescine (Put) concentrations increased, whereas spermidine (Spd) concentrations decreased in both free and soluble conjugated PA fractions. The concentrations of free and soluble conjugated spermine (Spm) remained low, and small amounts of excreted PAs were also found in the culture medium. The minor production of secondary metabolites reflected the undifferentiated stage of the embryogenic cell culture. Put was produced via the arginine decarboxylase (ADC) pathway. Futhermore, the gene expression data suggested that the accumulation of Put was caused neither by an increase in Put biosynthesis nor by a decrease in Put catabolism, but resulted mainly from the decrease in the biosynthesis of Spd and Spm. Put seemed to play an important role in cell proliferation in Scots pine embryogenic cells, but the low pH of the culture medium could also, at least partially, be the reason for the accumulation of endogenous Put. High Spd concentrations at the initiation of the culture, when cells were exposed to stress and cell death, suggested that Spd may act not only as a protector against stress but also as a growth suppressor, when proliferative growth is not promoted. All in all, Scots pine embryogenic cell culture was proved to be a favourable experimental platform to study PA metabolism and, furthermore, the developed system may also be beneficial in experiments where, e.g., the effect of specific stressors on PA metabolism is addressed.

A charge-frustrated amphiphile composed of a pyrene-1,3,6-trisulfonate head group and an eicosane side chain can be used as a fluorescence chemosensor for spermine. The sensor allows the detection of spermine down to the nanomolar concentration range with good selectivity over closely related biogenic amines such as spermidine.

Although a potential role for polyamines and transglutaminases (TGs) in memory mechanisms have been proposed, hippocampal spermine (SPM) and spermidine (SPD) levels as well as transamidating activity of TG in spatial memory have not been addressed yet. It was therefore the aim of the study to assess hippocampal polyamines and TG activity at the probe trial in a spatial memory paradigm. C57BL/6J mice (20 animals per group) were used for the experiments and divided into a trained and a yoked (untrained) group. The Morris water maze (MWM) was selected as the memory test, animals were sacrificed within 5 min following the probe trial and hippocampi were taken for biochemical analysis. SPD and SPM levels were assessed by an analytical procedure according to Gismondi et al. Transamidating activity of TG was determined following the method described by Chung and Folk using [14C] methylamine as substrate. γ-(Glutamyl)-polyamine levels were evaluated by ion exchange chromatography according to Folk et al. Animals learned the task in the MWM as latencies and pathlengths were significantly reduced. At the probe trial mice showed significantly higher preference for the target quadrant. Free SPD and SPM levels were manifold decreased in the trained as compared to the yoked group. Transamidating activity of TG was fourfold increased in trained as compared to yoked controls. γ-(Glutamyl)-SPD was comparable while γ-(glutamyl)-SPM was significantly higher in the trained group. The findings show a potential role for polyamines, their derivative γ-(glutamyl)-SPM and transamidating activity of TG at memory retrieval or formation. Results from this study are extending and knowledge on polyamines and report for the first time involvement of γ-(glutamyl)-SPM and transamidating activity of TG that may form the basis for future neurochemical and pharmacological studies and indeed, modulation of polyamine and TG activity has been already proposed as a tentative therapeutical concept., (Copyright © 2012 Wiley Periodicals, Inc.)

The concentration of putrescine (PUT), spermidine (SPD) and spermine (SPM) was determined in chilled meat and kidneys of 18 rabbits and in liver of 12 animals 24h after slaughter. Very low PUT concentrations were detected only in kidneys. Mean SPD levels were 2.2, 2.2, 61.7 and 32.7mgkg(-1) in saddle, leg, liver and kidneys, respectively. The respective SPM concentrations were 14.7, 8.0, 115 and 88.4mgkg(-1). SPD and SPM losses of about one third of the initial levels were apparent in saddles stored at -18°C for 8months. Losses of both polyamines of about 15-20% of the initial concentrations were found in saddles stored aerobically at +2°C for up to 9days. Stewing of saddles caused significant SPD and SPM losses of about 20-25%, while upon roasting and pan-roasting without oil a decrease of about 50% of the initial concentration was observed., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

Alterations in temperature adaptation processes and changes in the content of stress-related compounds, polyamines and salicylic acid were evaluated in Atnoa1 (NO-associated 1) Arabidopsis mutant. The F(v)/F(m) chlorophyll-a fluorescence induction parameter and the actual quantum yield were significantly lower in the Atnoa1 mutant than in the wild-type. In the wild-type Col-0, the fastest increase in the non-photochemical quenching (NPQ) occurred in plants pre-treated at low temperature (4 °C), while the slowest was in those adapted to 30 °C. The NPQ showed not only a substantially increased level in the light-adapted state, but also more rapid light induction after the dark-adapted state in the Atnoa1 mutant than in the wild-type. The results of freezing tests indicated that both the wild-type and the mutant had better freezing tolerance after cold hardening, since no significant differences were found between the genotypes. The level of putrescine increased substantially, while that of spermine decreased by the end of the cold-hardening (4°C, 4d) period. The quantity of spermidine in Atnoa1 was significantly higher than in Col-0, at both control and cold-hardening temperatures. A similar trend was observed for spermine, but only under control conditions. The mutant plants showed substantially higher salicylic acid (SA) contents for both the free and bound forms. This difference was significant not only in the control, but also in the cold-hardened plants. These results suggest that there is a compensation mechanism in Atnoa1 mutant Arabidopsis plants to reduce the negative effects of the mutation. These adaptation processes include the stimulation of photoprotection and alterations in the SA and polyamine compositions., (Copyright © 2011 Elsevier GmbH. All rights reserved.)