Glucosinolates potential role in plant defence

Glukozinolati su složena klasa spojeva tioglukozidne strukture svojstvena biljkama porodice Cruciferae, u koju ubrajamo značajne kulture kao što su uljana repica, kupus, cvjetača, brokula, koraba, kelj, hren, gorušica. Sve biljke koje sadrže glukozinolate sadrže i endogeni enzim hidrolize - mirozinazu (β-tioglukozid-glukohidrolaza, EC 3.2.1.1) u odijeljenim dijelovima biljke. Oštećenjem tkiva oni dolaze u kontakt s enzimom mirozinazom te ovisno o strukturi glukozinolata nastaju različiti biološki aktivni produkti razgradnje, koji imaju čitav niz bioloških svojstava, od toksičnih do antikarcinogenih. Udio i sastav glukozinolata razlikuje se između biljnih vrsta te izmedu sorata istih vrsta te se mogu razlikovati unutar biljne jedinke ovisno o stupnju razvoja i vrsti organa. Različiti uvjeti okoliša u kojima se biljka nalazi, kao što su svjetlo, nutritivni status biljke, mehaničko oštećenje, infekcija fitopatogenima i oštećenja uzrokovana napadom insekata, mogu uzrokovati značajne promjene u sastavu i udjelu glukozinolata. Stoga postoji niz teorija o potencijalonoj ulozi glukozinolata u biljci, iako se njihova uloga u obrani biljke od insekata i fitopatogena smatra primarnom.Glucosinolates are sulfur- and nitrogen-containing plant secondary metabolites common in the Brassicaceae and related plant families. In the plant, they coexist with an endogenous β-thioglucosidase (EC 3.2.3.1) called myrosinase and upon plant tissue disruption, glucosinolates are released at the damage site and become hydrolyzed by myrosinase. The chemical nature of the hydrolysis products depends on the structure of the glucosinolate side chain, plant species and reaction conditions. Glucosinolate pattern differs between species and ecotype as well as between and even within individual plants, depending on developmental stage, tissue and photoperiod. A number of environmental conditions such as light plant, nutritional status, fungal infection, wounding and insect damage can alter the glucosinolate pattern significantly. The change of the glucosinolate profile by several environmental factors has brought forward different theories regarding their potential roles in the plant. However, the most accepted theory is that the glucosinolate-myrosinase system is involved in defense against herbivores and pathogens

Stability of glucosinolates during processing

Glukozinolati su sekundarni biljni metaboliti ß-tioglukozidne strukture koji hrani biljnog podrijetla daju aromu, miris i okus. Smatraju se fitokemikalijama što znači da mogu predstavljati prevenciju ljudskom organizmu od različitih bolesti, a naročito kod pojave karcinoma. Glavni izvor glukozinolata u ljudskoj prehrani su biljke iz porodice Brassicaceae u koju pripadaju kupus, brokula, cvjetača, repa, kelj, hren. Glukozinolati su fiziološki neaktivni i kemijski stabilni i tek njihovom razgradnjom djelovanjem enzima mirozinaze dolazi do oslobađanja raznovrsnih hlapljivih spojeva (izotiocijanata, tiocijanata, nitrila). U radu će biti opisana struktura, biodostupnost glukozinolata kao i njihov sadržaj u biljkama, njihovo oslobađanje enzimskom ili neenzimskom razgradnjom, stabilnost tijekom procesiranja te pozitivno djelovanje na ljudsko zdravlje. Osim što njihov unos ima pozitivan učinak na ljudski organizam, glukozinolati i njihovi razgradni spojevi mogu imati i antinutritivno djelovanje.Glucosinolates are plant secondary metabolites of ß-thioglucoside structure that are responsible for flavor, aroma and taste of foods of plant origin. They are considered phytochemicals which means that they can protect the human body from various diseases, especially with the onset of cancer. The main sources of glucosinolates in the human diet are plants from the family Brassicaceae, like cabbage, broccoli, cauliflower, beets, savoy cabbage, horseradish. Glucosinolates are physiologically inert and chemically stable. Activation of the enzyme myrosinase leads to the formation of various volatile compounds (isothiocyanates, thiocyanate, nitrile). This paper deals with structure, bioavailability of glucosinolates and their content in plants, their release by enzymatic or non-enzymatic degradation, stability during processing and positive effect on human health. Next to positive effect on the human body, glucosinolates and their degradation compounds may have antinutritive activity

Isolation and identification of volatile sulphur compounds from selected Brassicaceae family plants : diploma thesis

Hlapljivi sumporovi spojevi čine veliku grupu različitih vrsta koje su pronađene u čak 43 biljne porodice i 173 biljna roda, među kojima je najvažnija porodica Brassicaceae. Glukozinolati, β-tioglukozidni-N-hidroksisulfati s varijabilnim bočnim lancem su sekundarni metaboliti identificirani u preko 16 različitih biljnih porodica. Ovim spojevima posebno obiluju biljke porodice Brassicaceae među kojima se ističe rod Brassica. Glukozinolati su kemijski i biološki neaktivni, dok su komponente koje nastaju razgradnjom istih poznate po brojnim antikancerogenim, antimikrobnim i antioksidacijskim djelovanjima. Izolacija razgradnih produkata glukozinolata vrši se destilacijom i ekstrakcijom. Identifikacija glukozinolata se provodi indirektnom metodom, kojom se GC-MS analizom utvrđuje prisustvo produkata njihove razgradnje djelovanjem enzima mirozinaze. U ovom radu obrađene su dvije vrste spomenutog roda, Brassica rupestris Raf. ssp. gongyloides L.(koraba) i Bunias erucago L. (čunjasti repušac). Rezultati analize Brassica rupestris Raf. ssp. gongyloides L. pokazali su prisutnost sinigrina, glukotropeolina, glukolimnantina, glukoerucina, glukonasturcina, ali i S-metil- L -cistein sulfoksida karakterističnog za Allium vrste. Uzorci Bunias erucago L. su prikupljeni s dva lokaliteta; Marjan u Splitu i otok Brač (Škrip). Analizom Bunias erucago L. s otoka Brača ustanovljena je prisutnost samo dvije vrste glukozinolata: glukotropeolina i glukodehidroerucina dok je u biljnom materijalu Bunias erucago L. s Marjana prisutno pet vrsta glukozinolata: glukonapin, glukotropeolin, heptil glukozinolat, glukodehidroerucin te glukoerucin.Volatile sulphur compounds make up a large group of different species found in a 43 plant families and 173 plant genera, including the most important family, Brassicaceae. Glucosinolates, β-thioglucoside-N- hydroxysulfates with variable side chains are secondary metabolites identified in over 16 different plant families. These compounds are found particularly in the Brassicaceae family, among which Brassica stands out. Isolation of the degraded glucosinolate products is performed by distillation and extraction. The glucosinolate identification is carried out by an indirect method by which is determinated the presence of degradation products by the action of the myosinase enzyme using GC-MS method. In this paper two different species of Brassica genus are processed, Brassica rupestris Raf. ssp. gongyloides L. (kohlrabi) and Bunias erucago L. (crested warty cabbage). Glucosinolates are chemically and biologically inactive, while components that are formed by their degradation are known by numerous anticancer, antimicrobial and antioxidant activities. Analysis results of Brassica rupestris Raf. ssp. gongyloides L. showed the presence of sinigrin, glucotropaeolin, glucolimnantin, glucoerucin, gluconasturitiin, but also S-methyl- L -cysteine sulfoxide characteristic for the Allium species. Samples of Bunias erucago L. are collected from two different locations; Marjan in Split and island Brač (Škrip). Analysis results of Bunias erucago L. from island Brač had shown the presence of glucotropaeoline and glucodehydroerucin while in the same plant taken from Marjan had been identified five types of glucosinolates: gluconapin, glucotropaeolin, heptyl glucosinolate, glucodehydroerucin and glucoerucin

Glucosinolates concentration and yield of broccoli cultivars in different growing periods

Potrošnja brokule u Hrvatskoj porasla je tijekom posljednjih desetak godina zbog njezine izuzetne nutritivne vrijednosti koja ovisi o genetskim, abiotskim i agrotehničkim čimbenicima. Zbog genotipa, sorte brokule se razlikuju u koncentraciji bioaktivnih spojeva, odnosno, učinku na ljudsko zdravlje. Promjenjiv sastav i koncentracija fitotvari glavni su problem pri proizvodnji povrća kao funkcionalne hrane, od koje se očekuje ujednačena razina zdravstvene vrijednosti. Budući da je na tržištu prisutan raznolik sortiment, postavljeno je istraživanje s ciljem odabira perspektivnih sorata brokule, za uzgoj u uvjetima sjeverozapadne Hrvatske, odgovarajućeg prinosa i koncentracije pojedinačnih te ukupnih glukozinolata u različitim rokovima uzgoja. Najveći prinos tržnog vršnog cvata ostvarila je sorta Parthenon (13,3 t/ha) u proljetno-ljetnom roku, odnosno sorta Montop (15,0 t/ha) u ljetno-jesenskom roku uzgoja. Testirane sorte brokule statistički su se značajno razlikovale u koncentraciji ukupnih glukozinolata. Tijekom proljetno-ljetnog roka uzgoja u vršnom cvatu sorata brokule utvrđene su značajno veće vrijednosti ukupnih glukozinolata (12 do 22,5 μmol/g suhe tvari), nego u ljetno-jesenskom uzgojnom roku (5,4 do 15,5 μmol/g suhe tvari).In recent decades, broccoli consumption in Croatia increased due to its exceptional nutritive value, which depends on genetic, abiotic factors and agronomic factors. Because of the genotype, there are significant variation in the concentration of bioactive compounds among broccoli cultivars which affects on the human health. Variations in concentration of phytochemicals is the major problem in the production of vegetables as functional food, while uniform level of health is expected.As numerous broccoli cultivars are available at the market, research with the aim to select promising hybrid broccoli cultivars for growing in agroecological conditions of northwestern Croatia, with high values of yield and concentration of individual and total glucosinolates in different growing periods. The highest values of top inflorescence yield were achieved by ‘Parthenon’ (13.3 t/ha) in spring-summer growing period and ‘Montop’ (15.0 t/ha) in summer-autumn growing period. There were significant differences among broccoli cultivars in total glucosinolates concentration. The values of total glucosinolates in broccoli top inflorescence were significantly higher during spring-summer growing period (12 to 22.5 μmol/g dry weight) than in summer-autumn growing period (5.4 to 15.5 μmol/g dry weight)

GLUCOSINOLATES: BIOAVAILABILITY AND INFLUENCE ON HUMAN HEALTH

Glukozinolati su jedinstvena i važna skupina sekundarnih metabolita u nekim vrstama biljaka. Ubrajaju se u specifičnu skupinu kemijskih spojeva tzv. \u27fitokemikalija\u27 koja je zastupljena u 16 botaničkih porodica reda Capparales. Za prehranu ljudi najznačajnija je porodica Brassicaceae u koju se ubrajaju kupus, brokula, cvjetača, prokulice, roktvica, repa, gorušica. U ovom radu obuhvatiti će se svi parametri koji vladaju u različitim stadijima od uzgoja do prerade povrća iz porodice Brassicaceae, na biodostupnost glukozinolata i njihovih razgradnih produkata, i na zdravlje ljudi. Glukozinolati su kemijski stabilni sve dok ne dođu u kontakt s enzimom mirozinazom (β-tioglukozid glukohidrolaza; EC 3.2.1.147). Hidroliziraju se u niz biološki aktivnih tvari (izoticijanati, indol-3-karbinol). Osim što se konzumira svježe, povrće se vrlo često procesira, te ovisno o uvjetima prerade, prisutni glukozinolati se mogu razgraditi što može imati za posljedicu promjenu njihove biološke aktivnosti. Mnogobrojna epidemiološka istraživanja dokazala su i potvrdila pozitivan učinak konzumiranja povrća iz porodice Brassicaceae, a time i unosa glukozinolata u ljudski organizam. U radu će biti obrađen mehanizam njihovog pozitivnog djelovanja (antifungalno, antibakterijsko, antioksidativno, antimutageno, antikancerogeno djelovanje). Osim što imaju pozitivan učinak u ljudskom organizmu, glukozinolati i njihovi razgradni produkti mogu imati i antinutritivni učinak, što je također potrebno uzeti u obzir, međutim, potrebno je provesti još istraživanja u tom smjeru.Glucosinolates are unique group of secondary plant metabolites. They are specific chemical compounds i.e. phytochemicals occurring in about 16 botanical families of the order Capparales. For the human diet, the most important are representatives of the Brassicaceae like cabbage, Brussels sprouts, broccoli, cauliflower, radish, mustard. In this review, we will elaborate all the relevant steps in the food supply chain of Brassica vegetables and their influence on intake and bioavailability of glucosinolates and bioactive breakdown products in relation to human health. Plants possessing glucosinolates also contain an enzyme, myrosinase (β-thioglucoside glucohydrolase; EC 3.2.3.1). When glucosinolates and myrosinase come in contact with each other in the presence of water, the enzyme immediately causes the hydrolysis of the glucosinolates. Those breakdown products of glucosinolates are also biologically active. Except consuming fresh, vegetables are often processed. Depending on conditions during processing, degradation of glucosinolates can occur resulting in change of their bioavailability and biological activity. Numerous epidemiological studies have proven positive influence of consumption of Brassica vegetables on human health. Glucosinolates and their enzymatic hydrolysis products have the potentially beneficial activities as antioxidants, antifungal, antibacterial, bioherbicidal, biopesticidal, antimutagenic and anticarcinogenic agents. Next to their positive effect on human health, the antinutritional effects and the possible toxicity of glucosinolates were also observed. Those effects should also be taken in account and there is a need for further investigation of these effects

Bioactive compounds glucosinolates and polyphenols in florets, leaves and stems of broccoli (Brassica oleracea var. italica L.)

Brokula (Brassica oleracea var. italica L.) je povrće koje se smatra izvornim oblikom cvjetače, a uzgaja se zbog zelenih cvjetnih izdanaka smještenih na razgranatoj mekanoj stabljici. Brokula je bogata bioaktivnim spojevima, glukozinolatima i polifenolima te se uvelike istražuje radi njihova korisnog djelovanja na ljudsko zdravlje. U literaturi je mnogo više radova o sastavu i udjelima bioaktivnih spojeva u cvatu nego u listovima i stabljici biljke. U ovom radu analizirani su ukupni i pojedinačni glukozinolati, ukupni polifenolni spojevi te njihov antioksidacijski kapacitet u svim jestivim dijelovima brokule (cvat, listovi, stabiljka). Utvrđeno je da je količina glukozinolata najveća u listu brokule pri čemu udio indolnih prevladava nad alifatskim spojevima što vrijedi i za cvat. U stabljici je veći udio alifatskih spojeva. Udio polifenolnih spojeva u uzorcima u rasponu je od 9,70-16,11 mg GE g-1 s. tv. u stabljici, od 17,65-31,08 mg GE g-1 s. tv. u cvatu i od 22,27-34,02 mg GE g-1 s.tv. u listu brokule. Veću antioksidacijsku aktivnost pokazuju uzorci s većom koncentracijom polifenola. Ti rezultati upućuju da ne samo cvat brokule već i ostali dijelovi biljke mogu biti vrijedan izvor bioaktivnih spojeva te ih se preporuča također koristiti u prehrani. Nadalje, nusproizvodi nakon berbe, stabiljke i listovi mogli bi se koristiti kao sirovina za njihovu izolaciju te eventualnu uporabu kao dodataka prehrani.Broccoli is rich in bioactive compounds, polyphenols and glucosinolates, and as such considered as functional food and great experimental material. Previous scientific attention had mostly been focussed on composition and amounts of phytochemicals in florets rather than leaves and stem. In this research, content of total and individual glucosinolates, total polyphenols and antioxidative capacity were studied in broccoli florets, leaves and stems. Leaves showed to be the most abundant in glucosinolates with indolyl predominating aliphatic as was also the case in florets. In contrast, stem contained more aliphatic than indolyl glucosinolates. Polyphenol quantity ranged from 9.70-16.11 mg GE g-1 DW in stems, from 17.65-31.08 mg GE g-1 DW in florets and from 22.27-34.02 mg GE g-1 DW in leaves and was the highest in leaves irrespective of extraction method. It was determined that samples containing the highest amounts of polyphenols also had the highest antioxidant activity

Antiestrogenic effects of indoles from green leafy vegetables

Zeleno lisnato povrće skupina je biljaka koja pripada porodici Brassicaceaea. Bogato je indolima, koji su produkt hidrolize glukozinolata. U potencijalno korisne aktivnosti glukozinolata i proizvoda njihove enzimatske hidrolize ubrajaju se antifungalna, antibakterijska, bioherbicidna, biopesticidna, antioksidativna, antimutagena iantikancerogena aktivnost. Indol 3-karbinol i i diindolilmetan (DIM) su ključne bioaktivne molekule zelenog lisnatog povrća. Djeluju kao antiestrogeni, odnosno antagonisti receptora estrogena, na način da blokiraju ili ometaju receptor za estrogen. Induciraju enzim koji pretvara estron u 2-OHE na trošak 16 -OHE, a povećanje omjera 2:16 -hidroksiestrona povezano je sa smanjenjem rizika od raka dojke.Green leafy vegetables are a group of plant families Brassicaceaea. They are richin indoles, which are products of hydrolysis of glucosinolates. Potentially useful activities of glucosinolates and products of their enzymatic hydrolysis includes antifungal, antibacterial,bioherbicidal, biopesticidal, antioxidant, anticancer and antimutagenic activity. Indole 3-carbinol and the diindolilmetan (DIM) are a key bioactive molecules of green leafy vegetables. They act as anti estrogens or estrogen receptor antagonists, by blocking orcounteract estrogen receptor.They induce an enzyme that converts estrone in 2 -OHE to cost16 -OHE , and an increase in the ratio of 2:16 -hidroksiestron associated with reduced riskof breast cancer

Antiestrogenic effects of indoles from green leafy vegetables

Zeleno lisnato povrće skupina je biljaka koja pripada porodici Brassicaceaea. Bogato je indolima, koji su produkt hidrolize glukozinolata. U potencijalno korisne aktivnosti glukozinolata i proizvoda njihove enzimatske hidrolize ubrajaju se antifungalna, antibakterijska, bioherbicidna, biopesticidna, antioksidativna, antimutagena iantikancerogena aktivnost. Indol 3-karbinol i i diindolilmetan (DIM) su ključne bioaktivne molekule zelenog lisnatog povrća. Djeluju kao antiestrogeni, odnosno antagonisti receptora estrogena, na način da blokiraju ili ometaju receptor za estrogen. Induciraju enzim koji pretvara estron u 2-OHE na trošak 16 -OHE, a povećanje omjera 2:16 -hidroksiestrona povezano je sa smanjenjem rizika od raka dojke.Green leafy vegetables are a group of plant families Brassicaceaea. They are richin indoles, which are products of hydrolysis of glucosinolates. Potentially useful activities of glucosinolates and products of their enzymatic hydrolysis includes antifungal, antibacterial,bioherbicidal, biopesticidal, antioxidant, anticancer and antimutagenic activity. Indole 3-carbinol and the diindolilmetan (DIM) are a key bioactive molecules of green leafy vegetables. They act as anti estrogens or estrogen receptor antagonists, by blocking orcounteract estrogen receptor.They induce an enzyme that converts estrone in 2 -OHE to cost16 -OHE , and an increase in the ratio of 2:16 -hidroksiestron associated with reduced riskof breast cancer

Antinutrients and plant toxins

Kultivirane biljke čine osnovu moderne ljudske civilizacije jer se iskorištavaju kao hrana, gradivni materijal ili izvor raznih korisnih kemijskih spojeva. Tijekom domestifikacije su izvorne vrste značajno promijenjene. Kod onih koje se koriste za hranu, odabir je bio u smjeru povećanja prinosa, olakšavanja sakupljanja ili poboljšanja okusa i probavljivosti. Poboljšanje u okusu i probavljivosti je u mnogo slučajeva bilo posljedica uklanjanja neke tvari otrovnog ili antinutrijentskog djelovanja. Također su se razvili razni načini pripreme koji su uklanjali ili neutralizirali nepoželjne tvari iz biljaka. Antinutrijetni se nalaze u svim kuluturama koje se u svijetu svakodnevno konzumiraju. U pšenici se nalazi fitinska kiselina koja veže katione metala i ometa njihovu apsorpciju, grah sadrži lektine koji mogu izazvati hemolizu, soja stvara inhibitore proteaza čime onemogućava probavu proteina, krumpir ima glikoalkaloide koji su otrovni za ljude, a krstašice stvaraju glukozinolate koji štetno djeluju na štitnjaču. Iako se te tvari općenito smatraju nepoželjnima, imaju i neka poželjna svojstva, bilo da su odgovorne za karakterističan okus i aromu, štite zube, usporavaju rast šećera u krvi nakon obroka i sl. Kada se govori o otrovima važno je prisjetiti se da doza čini otrov.Cultivated plants are the foundations of the modern human civilization because they are used as food, building material and source of great number of useful chemical compounds. Original species have been greatly transformed during domstification. Those used for food, selected traits were amount of yield, ease of harvest or taste and digestibility improvement. Better taste and digestibility were, in most cases, the result of removal of some toxic compound or antinutrient. Also, lots of food preparation techniques were developed to displace or neutralize unwanted chemicals form plants. Antinutrents are found in every plant species eaten every day around the world. Wheat contains phytic acid which binds metal cations and hinders their apsorption, beans has lectins which are able to cause haemolysis, soy sinthesises protease inhibitors to impede protein digestion, potato has glycoalkaloids which are poisonous to humans and plants from Brassicaceae fammily contain glucosinolates which have detrimental effect on thyroid gland. Even though those chemicals are generally recognised as unwanted, they also have desirable properties. They are responsible for caracteristic taste and aroma of some foods, they can protect teeth or blunt blood glucose spikes after meal. When disussing poisons, it is useful to have in mind that the dose makes the poison

Contribution to the Research of Glucosinolates (2005–2020): Structural Diversity, Degradation, and Biological Potential

U radu je prikazan doprinos istraživanju glukozinolata u razdoblju 2005. – 2020. koji je ostvaren radom na Kemijsko-tehnološkom fakultetu, Sveučilišta u Splitu. Pregledom sveoubuhvatne dokumentacije utvrđeno je da znatnom broju predloženih struktura nedostaju važne strukturne informacije koje bi osigurala NMR i MS spektroskopija, pa je danas broj glukozinolata još uvijek varijabilan. U najnovijem istraživanju, u rodu Hesperis, identificiran je 4-O-D-apiozilglukomatronalin, čime ukupni broj glukozinolata danas broji između 89 i 136 struktura. U svrhu identificiranja izvora specifičnih glukozinolata koji bi mogli djelovati kao prekursori biološki aktivnih izotiocijanata, istraživan je sadržaj glukozinolata u biljkama. Istraživanja uključuju i razgradnju glukozinolata (enzimska, termička i kemijska) kao i biološku aktivnost (citotoksična, antimikrobna, protuupalna i dr.). Ovo djelo je dano na korištenje pod licencom Creative Commons Imenovanje 4.0 međunarodna.This review paper presents a contribution to the research of glucosinolates over the period 2005–2020, which was obtained during work at the Faculty of Chemical Technology, University of Split. After review of the comprehensive documentation, it was determined that a significant number of proposed structures lack important structural information that would be provided by NMR and MS spectroscopy, and today the number of glucosinolates is still variable. In the recent study of Hesperis genus, 4-O-D-apiosylglucomatronalin was identified, which gives the total number of glucosinolates today ranging from 89 to 136 structures. In order to identify the sources of specific glucosinolates that could act as precursors of biologically active isothiocyanates, the content of glucosinolates in plants was investigated. The study also includes the degradation of glucosinolates (enzymatic, thermal, and chemical), as well as biological activity (cytotoxic, antimicrobial, anti-inflammatory, etc.). This work is licensed under a Creative Commons Attribution 4.0 International License