Putrescine

{{Short description|Foul-smelling organic chemical compound}}

{{Chembox

| Verifiedfields = changed

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| verifiedrevid = 408973251

| ImageFile1 = Diaminobutane.svg

| ImageFile1_Ref = {{chemboximage|correct|??}}

| ImageSize1 = 160

| ImageName1 = Skeletal formula of putrescine

| ImageCaption1 = Skeletal formula

| ImageFile2 = Putrescine-3D-balls.png

| ImageFile2_Ref = {{chemboximage|correct|??}}

| ImageSize2 = 160

| ImageName2 = Ball and stick model of putrescine

| ImageCaption2 = Ball-and-stick model{{ Cite journal | url = https://dx.doi.org/10.5517/cc4g850 | title = CSD Entry: QATWAJ : 1,4-Butanediamine | website = Cambridge Structural Database: Access Structures | year = 2001 | publisher = Cambridge Crystallographic Data Centre | doi = 10.5517/cc4g850 |access-date = 2021-11-07 | last1 = Thalladi | first1 = V.R. | last2 = Boese | first2 = R. | last3 = Weiss | first3 = H.-C. }}{{ cite journal | title = The Melting Point Alternation in α,ω-Alkanediols and α,ω-Alkanediamines: Interplay between Hydrogen Bonding and Hydrophobic Interactions | first1 = V. R. | last1 = Thalladi | first2 = R. | last2 = Boese | first3 = H.-C. | last3 = Weiss | journal = Angew. Chem. Int. Ed. | year = 2000 | volume = 39 | issue = 5 | pages = 918–922 | doi = 10.1002/(SICI)1521-3773(20000303)39:5<918::AID-ANIE918>3.0.CO;2-E | pmid = 10760893 }}

| PIN = Butane-1,4-diamine

| OtherNames = 1,4-Diaminobutane, 1,4-Butanediamine

| Section1 = {{Chembox Identifiers

|CASNo = 110-60-1

|CASNo_Ref = {{cascite|correct|CAS}}

|UNII_Ref = {{fdacite|correct|FDA}}

|UNII = V10TVZ52E4

|PubChem = 1045

|ChemSpiderID = 13837702

|ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}

|EINECS = 203-782-3

|UNNumber = 2928

|DrugBank = DB01917

|DrugBank_Ref = {{drugbankcite|changed|drugbank}}

|KEGG = C00134

|KEGG_Ref = {{keggcite|correct|kegg}}

|MeSHName = Putrescine

|ChEBI = 17148

|ChEBI_Ref = {{ebicite|changed|EBI}}

|ChEMBL = 46257

|ChEMBL_Ref = {{ebicite|correct|EBI}}

|IUPHAR_ligand = 2388

|RTECS = EJ6800000

|Beilstein = 605282

|Gmelin = 1715

|3DMet = B00037

|SMILES = NCCCCN

|StdInChI = 1S/C4H12N2/c5-3-1-2-4-6/h1-6H2

|StdInChI_Ref = {{stdinchicite|correct|chemspider}}

|StdInChIKey = KIDHWZJUCRJVML-UHFFFAOYSA-N

|StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}

}}

| Section2 = {{Chembox Properties

|C=4 | H=12 | N=2

|Appearance = Colourless crystals

|Odor = very unpleasant; putrid, fishy-ammoniacal

|Density = 0.877 g/mL

|MeltingPtC = 27.5

|BoilingPtK = 431.7

|Solubility = Miscible

|LogP = −0.466

|VaporPressure = 2.33 mm Hg at 25 deg C (est)

|HenryConstant = 3.54x10−10 atm-cu m/mol at 25 deg C (est)

|RefractIndex = 1.457

}}

| Section3 = {{Chembox Hazards

|GHSPictograms = {{GHS flame}} {{GHS corrosion}} {{GHS skull and crossbones}}

|GHSSignalWord = DANGER

|HPhrases = {{H-phrases|228|302|312|314|331}}

|PPhrases = {{P-phrases|210|261|280|305+351+338|310}}

|FlashPtC = 51

|ExploLimits = 0.98–9.08%

|LD50 = {{Unbulleted list|463 mg kg−1 (oral, rat)|1.576 g kg−1 (dermal, rabbit)}}

}}

| Section4 = {{Chembox Related

|OtherFunction_label = alkanamines

|OtherFunction = {{Unbulleted list|Propylamine|Isopropylamine|1,2-Diaminopropane|1,3-Diaminopropane|Isobutylamine|tert-Butylamine|n-Butylamine|sec-Butylamine|1-Aminopentane|Cadaverine}}

|OtherCompounds = {{Unbulleted list|2-Methyl-2-nitrosopropane|Nylon 46 }}

}}

}}

Putrescine is an organic compound with the formula (CH2)4(NH2)2. It is a colorless solid that melts near room temperature. It is classified as a diamine.{{Ullmann|doi=10.1002/14356007.a02_001|title=Amines, Aliphatic|year=2000|last1=Eller|first1=Karsten|last2=Henkes|first2=Erhard|last3=Rossbacher|first3=Roland|last4=Höke|first4=Hartmut|isbn=3527306730}} Together with cadaverine, it is largely responsible for the foul odor of putrefying flesh, but also contributes to other unpleasant odors.

Production

Putrescine is produced on an industrial scale by the hydrogenation of succinonitrile.

Biotechnological production of putrescine from a renewable feedstock has been investigated. A metabolically engineered strain of Escherichia coli that produces putrescine at high concentrations in glucose mineral salts medium has been described.{{cite journal| title = Metabolic Engineering of Escherichia coli for the Production of Putrescine: A Four Carbon Diamine| doi = 10.1002/bit.22502

| year = 2009| journal = Biotechnology and Bioengineering | last1 = Qian | first1 = Zhi-Gang | last2 = Xia | first2 = Xiao-Xia | last3 = Yup Lee | first3 = Sang| volume = 104| issue = 4| pages = 651–662| pmid = 19714672| doi-access = free}}

Biochemistry

File:Polyamine synthesis.svg

Spermidine synthase uses putrescine and S-adenosylmethioninamine (decarboxylated S-adenosyl methionine) to produce spermidine. Spermidine in turn is combined with another S-adenosylmethioninamine and gets converted to spermine.

Putrescine is synthesized in small quantities by healthy living cells by the action of ornithine decarboxylase.

Putrescine is synthesized biologically via two different pathways, both starting from arginine.

  • In one pathway, arginine is converted into agmatine. The conversion is catalyzed by the enzyme arginine decarboxylase (ADC). Agmatine is transformed into N-carbamoylputrescine by agmatine imino hydroxylase (AIH). Finally, N-carbamoylputrescine is hydrolyzed to give putrescine.{{cite journal|pmid=6895223|title=Enzymic conversion of agmatine to putrescine in Lathyrus sativus seedlings. Purification and properties of a multifunctional enzyme (putrescine synthase). | volume=256 | issue=18|date=September 1981|pages=9532–41|author=Srivenugopal KS, Adiga PR|journal=J. Biol. Chem.|doi=10.1016/S0021-9258(19)68795-8 |doi-access=free}}
  • In the second pathway, arginine is converted into ornithine and then ornithine is converted into putrescine by ornithine decarboxylase (ODC).

Putrescine, via metabolic intermediates including N-acetylputrescine, γ-aminobutyraldehyde (GABAL), N-acetyl-γ-aminobutyric acid (N-acetyl-GABAL), and N-acetyl-γ-aminobutyric acid (N-acetyl-GABA), biotransformations mediated by diamine oxidase (DAO), monoamine oxidase B (MAO-B), aminobutyraldehyde dehydrogenase (ABALDH), and other enzymes, can act as a minor biological precursor of γ-aminobutyric acid (GABA) in the brain and elsewhere.{{cite book | last1=Rashmi | first1=Deo | last2=Zanan | first2=Rahul | last3=John | first3=Sheeba | last4=Khandagale | first4=Kiran | last5=Nadaf | first5=Altafhusain | title=Studies in Natural Products Chemistry | chapter=γ-Aminobutyric Acid (GABA): Biosynthesis, Role, Commercial Production, and Applications | publisher=Elsevier | volume=57 | date=2018 | isbn=978-0-444-64057-4 | doi=10.1016/b978-0-444-64057-4.00013-2 | pages=413–452 | url=https://www.researchgate.net/publication/324580560 | quote=Alternate pathways of GABA synthesis from putrescine and other polyamines have also been reported [207–211]. Here, γ-aminobutyraldehyde, an intermediate from polyamine degradation reaction via combined activities of diamine oxidase (DAO, E.C. 1.4.3.6) and 4-aminobutyraldehyde dehydrogenase (ABALDH), leads to the synthesis of GABA [205,212,213]. In response to abiotic stresses, GABA is also reported to be synthesized from proline via D1-pyrroline intermediate formation [47,205,214] and also by a nonenzymatic reaction [214]. However, GABA synthesis from polyamine pathways is minor in the brain, [215] although they play a significant role in the developing brain [216] and retina [217]. But GABA can be formed from putrescine in the mammalian brain [218].}}{{cite journal | vauthors = Shelp BJ, Bozzo GG, Trobacher CP, Zarei A, Deyman KL, Brikis CJ | title = Hypothesis/review: contribution of putrescine to 4-aminobutyrate (GABA) production in response to abiotic stress | journal = Plant Sci | volume = 193-194 | issue = | pages = 130–135 | date = September 2012 | pmid = 22794926 | doi = 10.1016/j.plantsci.2012.06.001 | bibcode = 2012PlnSc.193..130S | url = }}{{cite journal | vauthors = Benedetti MS, Dostert P | title = Contribution of amine oxidases to the metabolism of xenobiotics | journal = Drug Metab Rev | volume = 26 | issue = 3 | pages = 507–535 | date = 1994 | pmid = 7924902 | doi = 10.3109/03602539408998316 | url = | quote = MAO also catalyses the deamination of a natural brain constituent, monoacetyl-putrescine, producing y-acetylaminobutyraldehyde, which in turn participates in the formation of brain GABA [13].}}{{cite book | vauthors = Watanabe M, Maemura K, Kanbara K, Tamayama T, Hayasaki H | title = A Survey of Cell Biology | chapter = GABA and GABA Receptors in the Central Nervous System and Other Organs | series = International Review of Cytology | volume = 213 | pages = 1–47 | date = 2002 | pmid = 11837891 | doi = 10.1016/s0074-7696(02)13011-7 | isbn = 978-0-12-364617-0 | url = }}{{cite journal | vauthors = Seiler N | title = Catabolism of polyamines | journal = Amino Acids | volume = 26 | issue = 3 | pages = 217–233 | date = June 2004 | pmid = 15221502| doi = 10.1007/s00726-004-0070-z | url = }}{{cite journal | vauthors = Cho HU, Kim S, Sim J, Yang S, An H, Nam MH, Jang DP, Lee CJ | title = Redefining differential roles of MAO-A in dopamine degradation and MAO-B in tonic GABA synthesis | journal = Exp Mol Med | volume = 53 | issue = 7 | pages = 1148–1158 | date = July 2021 | pmid = 34244591 | pmc = 8333267 | doi = 10.1038/s12276-021-00646-3 | url = }} In 2021, it was discovered that MAO-B does not mediate dopamine catabolism in the rodent striatum but instead participates in striatal GABA synthesis and that synthesized GABA in turn inhibits dopaminergic neurons in this brain area.{{cite journal | vauthors = Nam MH, Sa M, Ju YH, Park MG, Lee CJ | title = Revisiting the Role of Astrocytic MAOB in Parkinson's Disease | journal = Int J Mol Sci | volume = 23 | issue = 8 | date = April 2022 | page = 4453 | pmid = 35457272 | pmc = 9028367 | doi = 10.3390/ijms23084453 | doi-access = free | url = }} It has been found that MAO-B, via the putrescine pathway, importantly mediates GABA synthesis in astrocytes in various brain areas, including in the hippocampus, cerebellum, striatum, cerebral cortex, and substantia nigra pars compacta (SNpc).

Occurrence

Putrescine is found in all organisms.{{Cite journal |last1=Cui |first1=Jing |last2=Pottosin |first2=Igor |last3=Lamade |first3=Emmanuelle |last4=Tcherkez |first4=Guillaume |date=June 2020 |title=What is the role of putrescine accumulated under potassium deficiency? |url=https://onlinelibrary.wiley.com/doi/10.1111/pce.13740 |journal=Plant, Cell & Environment |language=en |volume=43 |issue=6 |pages=1331–1347 |doi=10.1111/pce.13740 |pmid=32017122 |s2cid=211023002 |issn=0140-7791}} Putrescine is widely found in plant tissues, often being the most common polyamine present within the organism. Its role in development is well documented, but recent studies have suggested that putrescine also plays a role in stress responses in plants, both to biotic and abiotic stressors.{{Cite journal |last1=González-Hernández |first1=Ana Isabel |last2=Scalschi |first2=Loredana |last3=Vicedo |first3=Begonya |last4=Marcos-Barbero |first4=Emilio Luis |last5=Morcuende |first5=Rosa |last6=Camañes |first6=Gemma |date=January 2022 |title=Putrescine: A Key Metabolite Involved in Plant Development, Tolerance and Resistance Responses to Stress |journal=International Journal of Molecular Sciences |language=en |volume=23 |issue=6 |pages=2971 |doi=10.3390/ijms23062971 |issn=1422-0067 |pmc=8955586 |pmid=35328394|doi-access=free}} The absence of putrescine in plants is associated with an increase in both parasite and fungal population in plants.

Putrescine serves an important role in a multitude of ways, which include: a cation substitute, an osmolyte, or a transport protein. It also serves as an important regulator in a variety of surface proteins, both on the cell surface and on organelles, such as the mitochondria and chloroplasts. A recorded increase of ATP production has been found in mitochondria and ATP synthesis by chloroplasts with an increase in mitochondrial and chloroplastic putrescine, but putrescine has also been shown to function as a developmental inhibitor in some plants, which can be seen as dwarfism and late flowering in Arabiadopsis plants.

Putrescine production in plants can also be promoted by fungi in the soil.{{Cite journal |last=Copeland |first=Charles |date=2022-04-01 |title=The feeling is mutual: Increased host putrescine biosynthesis promotes both plant and endophyte growth |url=https://doi.org/10.1093/plphys/kiac001 |journal=Plant Physiology |volume=188 |issue=4 |pages=1939–1941 |doi=10.1093/plphys/kiac001 |issn=0032-0889 |pmc=8968283 |pmid=35355052}} Piriformospora indica (P. indica) is one such fungus, found to promote putrescine production in Arabidopsis and common garden tomato plants. In a 2022 study it was shown that the presence of this fungus had a promotional effect on the growth of the root structure of plants. After gas chromatography testing, putrescine was found in higher amounts in these root structures.{{Cite journal |last1=Ioannidis |first1=Nikolaos E. |last2=Cruz |first2=Jeffrey A. |last3=Kotzabasis |first3=Kiriakos |last4=Kramer |first4=David M. |date=2012-01-12 |title=Evidence That Putrescine Modulates the Higher Plant Photosynthetic Proton Circuit |journal=PLOS ONE |language=en |volume=7 |issue=1 |pages=e29864 |doi=10.1371/journal.pone.0029864 |issn=1932-6203 |pmc=3257247 |pmid=22253808|bibcode=2012PLoSO...729864I |doi-access=free }}

Plants that had been inoculated with P. indica had presented an excess of arginine decarboxylase. This is used in the process of making putrescine in plant cells. One of the downstream effects of putrescine in root cells is the production of auxin. That same study found that putrescine added as a fertilizer showed the same results as if it was inoculated with the fungus, which was also shown in Arabidopsis and barley. The evolutionary foundations of this connection and putrescine are still unclear.

Putrescine is a component of bad breath and bacterial vaginosis.{{cite journal|author1=Yeoman, CJ |author2=Thomas, SM |author3=Miller, ME |author4=Ulanov, AV |author5=Torralba, M |author6=Lucas, S |author7=Gillis, M |author8=Cregger, M |author9=Gomez, A |author10=Ho, M |author11=Leigh, SR |author12=Stumpf, R |author13=Creedon, DJ |author14=Smith, MA |author15=Weisbaum, JS |author16=Nelson, KE |author17=Wilson, BA |author18=White, BA |title=A multi-omic systems-based approach reveals metabolic markers of bacterial vaginosis and insight into the disease.|journal=PLOS ONE|year=2013|volume=8|issue=2|pages=e56111|doi=10.1371/journal.pone.0056111|pmid=23405259|pmc=3566083|bibcode=2013PLoSO...856111Y|doi-access=free}} It is also found in semen and some microalgae, together with spermine and spermidine.

Uses

Putrescine reacts with adipic acid to yield the polyamide nylon 46, which is marketed by Envalior (formerly DSM) under the trade name Stanyl.{{cite web |url=http://www.dsm.com/products/stanyl/en_US/home.html|archive-url=https://web.archive.org/web/20170925055608/http://www.dsm.com/products/stanyl/en_US/home.html |title=Stanyl® |publisher=DSM |archive-date= 25 September 2017}}{{cite web |url=https://www.envalior.com/en-us/products/stanyl.html |title=PA46 - Stanyl® |publisher=Envalior |access-date= 28 August 2024}}

Application of putrescine, along with other polyamines, can be used to extend the shelf life of fruits by delaying the ripening process.{{Cite journal|last1=Abbasi|first1=Nadeem Akhtar|last2=Ali|first2=Irfan|last3=Hafiz|first3=Ishfaq Ahmad|last4=Alenazi|first4=Mekhled M.|last5=Shafiq|first5=Muhammad|date=January 2019|title=Effects of Putrescine Application on Peach Fruit during Storage|journal=Sustainability|language=en|volume=11|issue=7|pages=2013|doi=10.3390/su11072013|doi-access=free}} Pre-harvest application of putrescine has been shown to increase plant resistance to high temperatures and drought.{{Cite journal|last1=Todorov|first1=D.|last2=Alexieva|first2=V.|last3=Karanov|first3=E.|date=1998-12-01|title=Effect of Putrescine, 4-PU-30, and Abscisic Acid on Maize Plants Grown under Normal, Drought, and Rewatering Conditions|url=https://doi.org/10.1007/PL00007035|journal=Journal of Plant Growth Regulation|language=en|volume=17|issue=4|pages=197–203|doi=10.1007/PL00007035|pmid=9892742|s2cid=20062811|issn=1435-8107}} Both of these effects seem to result from lowered ethylene production following exogenous putrescine exposure.{{Cite journal|last1=Khan|first1=A.S.|last2=Z. Singh|title=Influence of Pre and Postharvest Applications of Putrescine on Ethylene Production, Storage Life and Quality of 'Angelino' Plum|date=May 2008|url=https://www.actahort.org/books/768/768_14.htm|journal=Acta Horticulturae|issue=768|pages=125–133|doi=10.17660/ActaHortic.2008.768.14|issn=0567-7572}}

Due to its role in putrification, putrescine has also been proposed as a biochemical marker for determining how long a corpse has been decomposing.{{Cite journal|last1=Pelletti|first1=Guido|last2=Garagnani|first2=Marco|last3=Barone|first3=Rossella|last4=Boscolo-Berto|first4=Rafael|last5=Rossi|first5=Francesca|last6=Morotti|first6=Annalisa|last7=Roffi|first7=Raffaella|last8=Fais|first8=Paolo|last9=Pelotti|first9=Susi|date=2019-04-01|title=Validation and preliminary application of a GC–MS method for the determination of putrescine and cadaverine in the human brain: a promising technique for PMI estimation|url=https://www.sciencedirect.com/science/article/pii/S0379073819300283|journal=Forensic Science International|language=en|volume=297|pages=221–227|doi=10.1016/j.forsciint.2019.01.025|pmid=30831414|s2cid=73461335|issn=0379-0738}}

Putrescine together with chitosan has been successfully used in postharvest physiology as a natural fruit coating.{{cite journal |first1= R |last1= Bahmani | first2= F |last2= Razavi | first3= S|last3= Mortazavi | first4= A |last4= Juárez-Maldonado | first5= G |last5= Gohari | title = Chitosan–putrescine nanoparticle coating attenuates postharvest decay and maintains ROS scavenging system activity of strawberry cv. 'Camarosa' during cold storage | journal = Folia Horticulturae | volume = 36 | issue = 1 | pages = 149–160 | date = February 2024 | pmid = | doi = 10.2478/fhort-2024-0009 | publisher = Polish Society of Horticultural Science | s2cid = 19887643 | doi-access = free }} Putrescine with chitosan treated fruits had higher antioxidant capacity and enzyme activities than untreated fruits. Fresh strawberries coated have lower decay percentage, higher tissue firmness, contents of total soluble solids. Nanoparticles of putrescine with chitosan are effective in preserving the nutritional quality and prolonging the post-harvest life of strawberries during storage up to 12 days.

History

Putrescine and cadaverine were first described in 1885 by the Berlin physician Ludwig Brieger (1849–1919).Brief biography of [http://www.sammlungen.hu-berlin.de/dokumente/14948/ Ludwig Brieger] {{Webarchive|url=https://web.archive.org/web/20111003041704/http://www.sammlungen.hu-berlin.de/dokumente/14948/ |date=2011-10-03}} (in German). Biography of [http://jewishencyclopedia.com/articles/3708-brieger-ludwig Ludwig Brieger] in English.Ludwig Brieger, "Weitere Untersuchungen über Ptomaine" [Further investigations into ptomaines] (Berlin, Germany: August Hirschwald, 1885), [https://archive.org/details/weitereuntersuc00briegoog/page/n49 page 43]. From page 43: Ich nenne dasselbe Putrescin, von putresco, faul werden, vermodern, verwesen. (I call this [compound] "putrescine", from [the Latin word] putresco, to become rotten, decay, rot.)Ludwig Brieger, "Weitere Untersuchungen über Ptomaine" [Further investigations into ptomaines] (Berlin, Germany: August Hirschwald, 1885), [https://archive.org/details/weitereuntersuc00briegoog/page/n45 page 39].

Toxicity

In rats, putrescine has a low acute oral toxicity of 2000 mg/kg body weight, with no-observed-adverse-effect level of 2000 ppm (180 mg/kg body weight/day).{{cite journal |last1=Til|first1=H.P.|last2=Falke|first2=H.E.|last3=Prinsen|first3=M.K.|last4=Willems|first4=M.I.|title=Acute and subacute toxicity of tyramine, spermidine, spermine, putrescine and cadaverine in rats|journal=Food and Chemical Toxicology |volume=35|issue=3–4|year=1997|pages=337–348|issn=0278-6915|doi=10.1016/S0278-6915(97)00121-X|pmid=9207896}}

Further reading

  • {{cite book | last =Haglund | first =William | title =Forensic taphonomy: The Postmortem Fate of Human Remains | publisher =CRC Press | year =1996 | isbn =0-8493-9434-1 | pages =[https://archive.org/details/forensictaphonom0000unse/page/100 100] | url-access =registration | url =https://archive.org/details/forensictaphonom0000unse/page/100}}

References

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