Isolation, characterization and biological activity of jatrophane diterpens from Euphorbia dendroides L.

Rod Euphorbia, sa više od 2.000 vrsta jednogodišnjih, dvogodišnjih ili višegodišnjih cvetnica koje su članovi familije Euphorbiaceae, jedan je od najvećih i najraznovrsnijih rodova ne samo u svojoj familiji, već u celom biljnom carstvu. Biljke ovog roda koriste se u tradicionalnoj medicini još od antičkih vremena. Dosadašnja fitohemijska proučavanja pokazala su da vrste roda Euphorbia proizvode veoma raznovrsne sekundarne metabolite, uključujući različite terpene (seskviterpeni, diterpeni i triterpeni), steroide, cerebrozide, glicerole i fenolna jedinjenja (floracetofenoni, flavonoidi, tanini, kumarini). Mnoga od ovih jedinjenja pokazuju biološke aktivnosti, a najvažnije su reverzija višestruke rezistencije na lekove, antimitotsko, antiproliferativno, citotoksično, antivirusno, antimikrobno, antitumorsko, antiinflamatorno, tumor promotorsko i proinflamatorno dejstvo. Vrste iz roda Euphorbia su bogat izvor jatrofana, makrocikličnih diterpena osnovne trans-biciklo[10.3.0]pentadekanske strukture, za koje je karakteristično postojanje veoma fleksibilnog dvanaestočlanog prstena. To su veoma funkcionalizovana, različito oksigenovana jedinjenja; u biljkama se obično nalaze u obliku polihidroksilovanih diterpena esterifikovanih različitim kiselinama (acetil, propanoil, nbutanoil, izobutanoil, izovaleril, angeloil, tigloil, benzoil, nikotinoil derivati, itd.), zbog čega su poznati i pod nazivom jatrofanski poliestri. U okviru ove disertacije ispitivani su jatrofanski diterpeni iz vrste Euphorbia dendroides L. poreklom iz Crne Gore koja do sada nije fitohemijski proučavana. Proučavanje je obuhvatalo dve celine: nadzemni deo i mlečni lateks. Iz nadzemnog dela E. dendroides izolovano je i okarakterisano šest novih jatrofana, koji su nazvani eufodendrofani A – F (1 – 5, 16), a iz mlečnog lateksa E. dendroides izolovano je i okarakterisano trinaest novih jatrofana, eufodendrofani G – S (6 – 15, 17 – 19), kao i tri jatrofana izolovana iz nadzemnih delova (1, 2, 16). Izolovani jatrofani imaju vrlo slične strukture. Jatrofani 1 – 15 se međusobno razlikuju samo po vrsti, broju i položaju supstituenata, dok se jatrofani 16 – 19 od njih razlikuju po tome što sadrže endocikličnu (Δ5) umesto egzociklične (Δ6(17)) dvostruke veze. Jedinjenja 1 – 14 su penta- ili heksaesterifikovani jatrofanski polioli koji sadrže keto grupu u položaju C-14, jednu endocikličnu 11 E– i jednu egzocikličnu C-6(17) dvostruku vezu...Genus Euphorbia, with more than 2,000 species of annual, biennial or perennial flowering plants belonging to the family Euphorbiaceae, is one of the largest and most diverse genera not only in the spurge family but in the entire plant kingdom. Plants of this genus are used in traditional medicine since ancient times. Phytochemical studies up to now have shown that the species of the genus Euphorbia produce a variety of secondary metabolites, including various terpenes (sesquiterpenes, diterpenes and triterpenes), steroids, cerebrosides, glycerols and phenolic compounds (phloracetophenones, flavonoids, tannins, coumarins). These compounds perform many different activities, including modulability of multidrug resistance, microtubuleinteracting activity, antiproliferative, cytotoxic, antiviral, antimicrobial, anticancer, antiinflammatory, tumor promoting and proinflammatory effects. Genus Euphorbia is a rich source of jatrophanes, macrocyclic diterpenes with basic trans-bicyclo[10.3.0]pentadecane structure, which are characterized by the existence of a flexible twelve membered ring. These are very functionalized compounds with various oxygenation stages; in plants are usually found in the form of polyhydroxylated diterpenes esterified with various acids (acetyl, propanoil, n-butanoyl, isobutanoyl, isovaleryl, angeloyl, tigloyl, benzoyl, nicotinoyl derivatives, etc...), and are sometimes called jatrophane polyesters. In this dissertation, jatrophane diterpenes from Euphorbia dendroides L. originating from Montenegro were investigated. The study comprises investigation of the aerial parts and of the milky latex. From the aerial parts of E. dendroides six new jatrophanes, namely euphodendrophanes A F (1 5, and 16), were isolated and characterized. From the milky latex of E. dendroides, in addition to 1, 2, and 16, the constituents of the aerial parts, thirteen new jatrophanes, euphodendrophanes G S (6 15, and 17 19), were isolated and characterized..

New Pseudoguaiane Derivatives from Inula aschersoniana Janka var. aschersoniana

The aerial parts of Inula aschersoniana Janka var. aschersoniana afforded parthenolide, diepoxycostunolide, inusoniolide, chrysosplenol C and four new pseudoguaiane-type sesquiterpenoids. Their structures were determined using spectral methods and relative stereochemistry by NOESY correlations

New insights into sesquiterpene lactones composition of Western Balkan’s genus Amphoricarpos revealed by rapid resolution liquid chromatography coupled with quadrupole time-of-flight mass spectrometry

This study revealed results from reinvestigation of sesquiterpene lactones composition in the crude and leaf surface extracts of Amphoricarpos plants by rapid resolution liquid chromatography (RRLC) coupled with quadrupole time-of-flight mass spectrometry (QToF MS) and the tentative identification of undescribed sesquiterpene lactones is presented.11th Conference on Medicinal and Aromatic Plants of Southeast European Countries, (11th CMAPSEEC), Ohrid, North Macedonia, 6–10 October 202

Supplementary data for article: Čukanović, J.; Tešević, V.; Jadranin, M.; Ljubojević, M.; Mladenović, E.; Kostić, S. Horse Chestnut (Aesculus Hippocastanum L.) Seed Fatty Acids, Flavonoids and Heavy Metals Plasticity to Different Urban Environments. Biochemical Systematics and Ecology 2020, 89. https://doi.org/10.1016/j.bse.2019.103980

Supplementary material for: [https://doi.org/10.1016/j.bse.2019.103980]Related to published version: [http://cherry.chem.bg.ac.rs/handle/123456789/3806

Tetraciklični triterpenoidi iz vrste Euphorbia nicaeensis All

In this study, three tetracyclic triterpenes: (3S,24S)-tirucall-7-ene-3,24,25-triol (1), (3S,24R)-tirucall-7-ene-3,24,25-triol (2) and inoterpene C (3), were isolated from the milkweed Euphorbia nicaeensis All. using dry-column flash silica gel chromatography and semipreparative normal-phase HPLC. Their structures were determined on the basis of 1D and 2D NMR spectra and literature review. Although these three compounds have previously been isolated from other plant species, this is the first time that they have been isolated from E. nicaeensis.U ovom radu, tri tetraciklična triterpena: (3S,24S)-tirukal-7-en-3,24,25-triol (1), (3S,24R)-tirukal-7-en-3,24,25-triol (2) i inoterpen C (3) su izolovana iz mlečike Euphorbia nicaeensis All. koristeći brzu hromatografiju na suvom stubu silika gela i semipreparativnu normalno-faznu HPLC. Strukture su određene na osnovu 1D i 2D NMR spektara i poređenjem sa literaturom. Iako su ova tri jedinjenja ranije izolovana iz drugih biljnih vrsta, ovo je prvi put da su izolovana iz E. nicaeensis

Supplementary data for article: Čukanović, J.; Tešević, V.; Jadranin, M.; Ljubojević, M.; Mladenović, E.; Kostić, S. Horse Chestnut (Aesculus Hippocastanum L.) Seed Fatty Acids, Flavonoids and Heavy Metals Plasticity to Different Urban Environments. Biochemical Systematics and Ecology 2020, 89. https://doi.org/10.1016/j.bse.2019.103980

Supplementary material for: [https://doi.org/10.1016/j.bse.2019.103980]Related to published version: [http://cherry.chem.bg.ac.rs/handle/123456789/3806

Extraction Kinetic of Some Phenolic Compounds During Cabernet Sauvignon Alcoholic Fermentation and Antioxidant Properties of Derived Wines

In this study, we estimated the usage of Cabernet Sauvignon in microvinifications, obtaining wines with increased phenolic compound content. Kinetic extraction of phenolic compounds during alcoholic fermentation was affected by maceration time (3, 5, 7, 14 and 21 days) and the addition and kinetics of enzyme preparations (EP). The highest extraction rates were observed for catechin (EXV EP – EXV en-zyme preparation and CP EP – Color plus enzyme preparation) and p-hydroxybenzoic acid (Car EP - Ca-ractere enzyme preparation). According to extraction time of the analyzed phenolic compounds, maximal values (ellagic acid, ferulic acid, chlorogenic acid, caffeic acid, naringenin, p-hydroxybenzoic acid, p-coumaric acid, protocatechuic acid, trans-resveratrol, syringic acid, vanillin, and vanillic acid) were ob-tained on day 15 of maceration with addition of CP EP, with exceptions of gallic acid, catechin, and my-ricetin. Prolonged maceration times, up to 21 days, showed the most potent DPPH free radical scavenging activity with Car EP and the highest Ferric Reducing Ability of Plasma (FRAP) values with CP EP

Anti-melanoma effects of ingenanes isolated from Euphorbia species

In this research, from two species, E. palustris and E. lucida, four ingenane derivatives were isolated. Their anticancer effects were evaluated in the human melanoma – 518A2 cell line and compared with the effects of ingenolmebutate. Selectivity towards human melanoma cells was determined using normal human keratinocytes – HaCaT.11th Conference on Medicinal and Aromatic Plants of Southeast European Countries, (11th CMAPSEEC), Ohrid, North Macedonia, 6–10 October 202

Фитохемијско истраживање биљног рода Amphoricarpos

Phytochemistry deals with the study of secondary metabolites pro­duced by plants that synthesize these compounds for many reasons, including their own protection against attack of herbivores and plant diseases. Secondary metabolites are believed to represent plant adaptation to various environmental factors and that they enabled the survival of the species. Secondary metabolites of plants can have curative or toxic effects in humans and animals. Herbal medicine has a long tradition in folk medicine and until the early 20th century, when synthetic organic chemistry began to develop, plants were the main source of medicines. The two basic goals of our phytochemical research are: isolation and identification of new (biologically active) compounds – potential drugs, and chemotaxonomy (chemo­systematics). In the following text through one selected example, the genus Amphoricarpos Vis., our phytochemical res­earch is shown on both aspects.Фитохемија се бави изучавањем секундарних метаболита кoje биљке синтетишу из много разлога, укључујући сопствену заштиту од напада биљоједа и од биљних болести. Сматра се да секундарни метаболити представљају адаптацију биљака на различите факторе околине и да су управо они омогућили опстанак врста. Секундарни метаболити биљака могу испољити лековито или токсично дејство на људе и животиње. Лечење биљем има дугу традицију у народној медицини и све до почетка 20. века, када је почела да се развија синтетичка органска хемија, биљке су биле главни извор лекова. Основни циљеви наших фитохемијских истраживања обухватају: изоловање и идентификацију нових (биолошки активних) једињења – потенцијалних лекова, и хемотаксономију (хемосистематика). У тексту су кроз један одабран пример – род Amphoricarpos Vis. – приказана оба наведена аспекта наших фитохемијских истраживања.Part of the theme issue honoring Professor Emeritus Slobodan Milosavljevićs 80th birthday

Електрохемијска стабилност метформина у воденим растворима NaHCO3 И Na2SO4 на Au, GC и IrOx електродама

In this study the electrochemical behavior of metformin (MET), oral antihyperglycaemic agent, was assayed at three different electrodes. The drug standard was investigated by cyclic voltammetry (CV) and square wave volta-mmetry (SWV) via its electrooxidation at Au and glassy carbon (GC) electrode in 0.05 M NaHCO3. Under these conditions transformation of MET to corresponding N-carbonyl guanidine via oxime intermediate is suggested. The stability of MET was tested under directed stress conditions using IrOx elec-trode with sodium sulphate as an electrolyte and cyclic 4-amino-2-imino-1-me-thyl-1,2-dihydro-1,3,5-triazine (4,2,1-AIMT) appeared as the main end-product. The courses of the electrochemical processes at three electrodes are followed by UV spectroscopy and evaluated by total organic carbon (TOC) analysis.У оквиру рада изучавано је електрохемијско понашање метформина, лека са антихипергликемијским дејством, на три различите електроде. Стандард лека испитан је цикличном волтаметријом и волтаметријом са правоугаоним импулсима у 0,05 М раствору NaHCO3 на елекроди од злата и електроди од стакластог угљеника. Под овим условима, предложена је трансформација лека до одговарајућег N-карбонил гуанидина преко оксима као интермедијера. Стабилност метформина тестирана је и под условима електрохемијске оксидације на IrOx електроди у присуству натријум сулфата као електолита. У овом случају, предложено је настајање цикличног 4-амино-2-имино-1- метил-1,2-дихидро-1,3,5-триазина као главног производа. Ток електрохемијских процеса на све три електроде праћен је УВ спектроскопијом. Степен минерализације утврђен је анализом укупног органског угљеника.This is the peer-reviewed version of the article: Lović Jelena, Lađarević Jelena, Mijin Dušan, Jadranin Milka, Petrović Slobodan D., Avramov-Ivić Milka, Electrochemical stability of metformin in NaHCO3 and Na2SO4 water solution at Au, GC and IrOx electrodes, Journal of the Serbian Chemical Society 2019 Volume 84, Issue 11, Pages: 1319-1327 [https://doi.org/10.2298/JSC190731091L]The published version: [http://cer.ihtm.bg.ac.rs/handle/123456789/3383