Grupno-strukturna analiza naftnih kiselina izolovanih iz srednjih uljnihkomercijalnih frakcija vojvođanske nafte „Velebit” rađena je analizom IR-,1H- i13C NMR- i ESI-MS spektara niske rezolucije. Određeno je šest klasakarboksilnih kiselina opšte molekulske formule CnH2n-ZO2. To su karboksilnekiseline u opsegu masa 240-466 sa 15-31 C atoma u molekulu koje sugrupisane u pet cikloalkil Z-serija: monociklična- (CnH2n-2O2, 14.72%),biciklična- (CnH2n-4O2, 34.63%), triciklična- (CnH2n-6O2, 25.03%), tetraciklična- (CnH2n-8O2, 10.04%), pentaciklična klasa karboksilnih kiselina (CnH2n-10O2, 4.99%) i jedna alkanska klasa kiselina sa alkil grupama otvorenog niza (CnH2nO2, 10.57%).Razdvajanjem na bazi različite kiselosti i njihove rastvorljivosti u vodi naodređenim pH vrednostima u rasponu od pH 2-10 dobijeno je devet užihfrakcija kiselina. Ekstrakcijom sa etrom u vodi nerastvornih kiselina u rasponuod po jedne pH jedinice dobijena je sledeća distribucija masa: 9.57% (pH 10),12.69% (pH 9), 5.91% (pH 8), 4.85% (pH 7), 2.44% (pH 6), 11.71% (pH 5),23.94% (pH 4), 16.76% (pH 3) i 10.12% (pH 2). Razdvajanjem kiselina na bazinjihove kiselosti oko 50% mase kiselina ekstrahovano je od pH 2-4, znači ugrupi jačih kiselina. Masenom spektrometrijom niske rezolucije ESI-MS napH 4 vidi se da su u smeši kiselina skoncentrisane kiseline sa više prstenova ualkilnom delu sa maksimumom na tricikličnim kiselinama (36.50%), dok supojedinačno najzastupljenije tetraciklične strukture kiselina C20H32O2(4.43%) iC21H34O2(4.56%). Na pH 8 biciklične- i triciklične strukture su zastupljeneukupno sa 65.02% sa maksimalno zastupljenim kiselinama sa 20-26 C atomau molekulu, a izdvajaju se C22H38O2 (5.26%)biciklične- i C24H42O2(7.01%)triciklične strukure, a od tetracikličnih struktura kiselina izdvaja se C24H40O2(4.77%). Na pH 10 najzastupljenije izolovane kiseline su aciklične, odnosnomasne kiseline zastupljene sa 25.28%, a najdominantnije su struktureC21H42O2 (4.83%), dok su ostale klase kiselina ujednačene po svom masenomudelu u odnosu na sastav u ukupnoj polaznoj smeši kiselina.Drugi deo rada obuvata derivatizaciju izolovanih prirodnih naftnih kiselina.Sintetizovani su funkcionalni kiseonični metil-, etil-, n-butil-, terc-butil- ibenzil-derivati naftnih kiselina kao i funkcionalni azotni derivati: amidi i anilidinaftnih kiselina. Sinteze navedenih estara rađene su klasičnim postupcima imodifikovanom metodom esterifikacije u kiselo-katalizovanim uslovimaupotrebom mikrotalasa kao ko-katalizatora, što je imalo za cilj skraćenjereakciong vremena i poboljšanje ekoloških sintetskih uslova.Modifikacijom sinteze metilnaftenata MT-zagrevanjem 48 puta je skraćenovreme trajanja sinteze, prinosi ni promenom reakcionih parametara (vreme,snaga MT) nisu bitno promenjeni. Strukturnom analizom ESI-MS spektrapolaznih kiselina i metilnaftenata dobijenih metilovanjem naftnih kiselinautvrđeno je da je odnos klasa u dobroj podudarnosti. Prinos estara u ovojsintezi je 95.47%. Esterifikacija naftnih kiselina etil alkoholom rađena je uuslovima kisele katalize uz konvencionalno zagrevanje (91.76%), amodifikacijom metode MT-zagrevanjem (150 W) reakciono vreme je skaćeno96 puta (92.19%). Esterifikacija naftnih kiselina n-butil alkoholom rađena je uzsumpornu kiselinu kao katalizator i uz konvencionalno zagrevanje (94.24%), au uslovima MT-zagrevanja (150 W) 72 puta je skraćeno reakciono vreme(61.15%). Sinteza terc-butilnaftenata rađena je prevođenjem naftnih kiselina uhloride a zatim reakcijom sa terc-butil alkoholom nastaju terc-butilnaftenati(80.17%). Modifikovanom metodom klasične reakcije esterifikacije naftnihkiselina terc-butil alkoholom katalizovanom sumpornom kiselinom u uslovimaMT-zagrevanja (150 W) ostvaren je prinos od 85.49% a vreme trajanja reakcijeje 5 minuta. Sinteza benzilnaftenata rađena je prevođenjem naftnih kiselina uhloride a zatim reakcijom sa benzil alkoholom nastaju benzilnaftenati(84.43%), a modifikovanom metodom klasične kiselo-katalizovaneesterifikacije naftnih kiselina benzil alkoholom u uslovima MT-zagrevanja(150 W) ostvaren je prinos od 85.49% uz reakciono vreme od 5 minuta.Sinteza amida naftnih kiselina rađena je iz hlorida reakcijom sa amonijakom.Prinos čistih amida je 65.74%, a reakcija amidacije sa amonijakom trajala je15 minuta. Strukturnom analizom ESI-MS spektra amida naftnih kiselinautvrđen je grupno-strukturni sastav amida. Među strukturama amida naftenskihkiselina takođe su dominantne biciklične- i triciklične strukture, kao i u smešislobodnih kiselina. Sinteza anilida naftnih kiselina rađena je iz hlorida reakcijom sa anilinom. Prinos čistih anilida je 96.48%, a reakcija amidacije anilinom trajala je 30 minuta. Strukturnom analizom ESI-MS spektra anilida naftnih kiselina utvrđen je grupno-strukturni sastav proizvoda, anilida. Među strukturama anilida naftenskih kiselina takođe su dominantne biciklične- i triciklične strukture kao i u smeši slobodnih kiselina.U trećem delu ovog rada ispitivana je biološka aktivnost naftnih kiselinaauksinskog i giberelinskog tipa, njihov uticaj na ožiljavanje reznica,ukorenjivanje bočnih grana i mikroizdanaka biljaka, na aktivnost biljnihhormona, kao i na usvajanje metalnih jona kod biljaka.Aktivnost naftenskih kiselina utvrđena je pomoću tri in vitro biološka testa.„Koleoptil test”, rađen je na dva supstrata, odnosno na semenu ozime pšenicenovosadske sorte Partizankai jare pšenice takođe novosadske sorte Venera.Referentna aktivnost u testu rađena je sa -naftilsirćetnom 3-indolsirćetnomkiselinom. U oba testa ustanovljen je približno isti odnos aktivnosti rastvoranaftenskih kiselina i aktivnosti standardnih biljnih hormona. „Test inhibicijeklijanja” semena rađen je sa semenom crne slačice, Brasscia nigra. Najvećiuticaj naftenskih kiselina na inhibiciju klijanja postignut je u rasponukoncentracija kiselina od 10-7-10-8mol/L (0.05-0.01 mg/L). Testovi za šest užihfrakcija dobijenih iz smeše ukupnih kiselina razdvajanjem na bazi različiterastvorljivosti pri različitim pH vrednostima pokazuju istu aktivnost kao3-indolsirćetna kiselina (0.5 mg/L), a da je frakcija izdvojena iz vodenograstvora na pH 7 takođe aktivna ali u poređenju sa 3-indolsirćetnom kiselinomto je 10 puta niža aktivnost. Hormonska aktivnost giberelenskog tipa ispitivanihkalijumovih soli naftenskih kiselina utvrđena je „Endosperm testom”, u kojem jeodređivana aktivnost amilaze spektrofotometrijskim praćenjem povećanjakoncentracije redukujućih šećera u endospermu semena tretiranog ječma ipoređena sa aktivnošću rastvora giberelinske kiseline (GA3). Rezultati ovihtestova pokazuju da delovanjem vodenih rastvora užih frakcija naftenskihkiselina u koncentraciji 1.0 mg/L (3.5 x 10-6 mol/L)frakcija izolovana pri pH 8ima aktivnost koja je približno u opsegu aktivnosti giberelina koncentracije10-2-10-3mg/L.Natrijum-naftenati u koncentraciji od 10-6do 10-8mol/L stimulišu formiranjeadventivnih korenova kod reznica suncokreta pa je broj korenova po biljci 40puta veći kod biljaka koje su bile potopljene u rastvor natrijum-naftenata uodnosu na one koje su bile potopljene u vodu, a sličan efekat utvrđen je i pritretiranju bočnih grana suncokreta.Ožiljavanje drvenastih biljaka rađeno je na reznicama bele topole (Populusalba) i reznicama američke crne topole (Populus deltoides). Uočen je jasaninhibitomi efekat na rast korenčića i izbojka u vodenom medijumu sa 10-4mol/Lnaftenskih kiselina, dok je tretman od 24 časa doprineo većem broju korenčićana donjih 5 cm reznice, kao i ukupnog broja korenčića nego kod kontrole.U testu ukorenjivanja mikroizdanaka kod hrizantema najveći broj korenovadobijen je nakon tretmana sa rastvorom koji sadrži 10 µmol/L ukupnih naftenatai tretmanom sa 50 µmol/Lfrakcijom kiselina izolovanom pri pH 7. Oba rezultatasu na nivou aktivnosti 3-indolbuterne kiseline koncentracije 10 µmol/Lšto značida u ovom slučaju frakcionacija nije neophodna.Efekti natrijum-naftenata na ukorenjivanje praćeni su merenjem nivoa totalnihperoksidaza i amilaze, kao i sadržaja redukujućih šećera i ukupnih proteina ubazalnim delovima reznica bagrema(Rozaszin-AC). Nakon 1; 3 i 6 danareznice su uzete za biohemijske analize. U svakom slučaju, aktivnostiIAA-oksidaze i amilaze su se povećavale do trećeg dana, a zatim smanjuje.Efekat je bio jače izražen posle tročasovnog tretmana sa natrijum-naftenatimau poređenju sa šestočasovnim tretmanom i kontrolom. Sadržaj rastvornihproteina je bio povećan jedan dan posle tretmana, smanjen trećeg i ponovo povećan šestog dana, osim za šestočasovni tretman natrijum-naftenatima, kada je efekat bio sasvim suprotan.Test uticaja naftnih kiselina na nivo kadmijuma u biljkama pokazuje fiziološko delovanje naftnih kiselina na snižavanje nivoa teških metala u biljci, u ovom slučaju kadmijuma. Ispitivan je efekat niske koncentracije natrijum-naftenata (10-7mol/L) na ukupan sadržaj Cd u pojedinim frakcijama interćelijskog prostora kao i unutar ćelija, kao i na neke fiziološke i biohemijske parametre kod mladih biljaka soje koje su uzgajane u prisustvu kadmijum-hlorida koncentracije 1 mmol/L. Prisustvo naftenata smanjuje sadržaj ukupnog kadmijuma kako u korenu tako i u stablu i listovima u proseku za oko 40% i ublažava štetne efekte kadmijuma na aktivnost nitrat-reduktaze kao i na sadržaje fotosintetskih pigmenata.Tretman biljaka niskim koncentracijama natrijum-naftenata utiče naakumulaciju nekih esencijalnih elemenata kod mladih biljaka soje. Prisustvonaftenata (10-7 mol/L) značajno povećava sadržaj Mn, Fe, Zn i Ni u korenu, aliu stabljici i listovima samo sadržaj Fe i Mn. U korenu, sadržaj Mn je četiri putaveći a sadržaji Fe, Zn i Ni su povećani 17%, 60% i 68%, respektivno.Ispitivanja na celeru i mrkvi su potvrdila da uticaj naftenata na mineralnuishranu zavisi od primenjenog elementa i da je način preuzimanja određenihjona različit, što ima za posledicu ili povećanje ili smanjenje sadržaja pojedinihjona u nekim delovima biljaka. Mlade biljke celera i mrkve, gajene u hranljivommedijumu, tretirane su natrijumovim solima naftenskih kiselina (10-7mol/L)folijarno ili prisustvom u hranljivom medijumu. Jedino je tretman putemprisustva naftenata u hranljivom medijumu smanjio svežu masu korena inadzemnog dela oko 20% kod obe biljke.Oba tretmana uticala su na sadržajFe, Cu, Mn, Mg i Ca kod biljaka celera i Fe, Mn, Zn i Na kod biljaka mrkve.Kod biljaka celera došlo je do smanjenja sadržaja navedenih nutrienata dok jeu korenu biljaka mrkve došlo do povećanja sadržaja Fe za 45%, Mn za 70% iZn za 37%. Kod ovih biljaka prisustvo naftenata u hranljivom medijumu dovelodo smanjenja mase korenova i nadzemnih delova, što je potpuno suprotno odrezultata dobijenih kod biljaka soje. Folijarnim tretmanom je značajnopovećana masa nadzemnog samo kod celera., Group-structural analysis of naphthenic acids isolated from middlecommercial fractions of Vojvodina oil „Velebit” was performed with theanalysis of IR-,1H- and13C NMR- and ESI-MS low resolution spectrums.Six classes of carboxylic acids of the general molecular formula CnH2n-ZO2were determined. These are carboxylic acids with mass range of 240-466with 15-31 C atoms in molecule which are grouped in five cycloalkylZ-series: monocyclic- (CnH2n-2O2, 14.72%), bicyclic- (CnH2n-4O2, 34.63%),tricyclic- (CnH2n-6O2, 25.03%), tetracyclic- (CnH2n-8O2, 10.04%), pentacyclicclass of carboxylic acids (CnH2n-10O2, 4.99%) and one alyphatic class ofacids with open chain alkyl groups (CnH2nO2, 10.57%).By fractioning on the basis of different levels of acidity and their solubility inwater with pH values ranging from pH 2-10 nine subfractions of acids wereobtained. By extraction with ether in water undissolved acids in the range ofone pH unit the following distribution of mass was performed: 9.57%(pH 10), 12.69% (pH 9), 5.91% (pH 8), 4.85% (pH 7), 2.44% (pH 6), 11.71%(pH 5), 23.94% (pH 4), 16.76% (pH 3) and 10.12% (pH 2). By fractioningacids on the basis of their acidity about 50% of acid mass was extracted atpH 2-4, i.e., in the group of stronger acids. Low resolution massspectrometry ESI-MS shows that at pH 4 acids with more rings in the alkylsection were concentrated in the mixture with maximum at tricyclic acids(36.50%), while individually tetracyclic acid structures C20H32O2 (4.43%) andC21H34O2(4.56%) were most prominent. At pH 8 bicyclic- and tricyclicstructures are represented together by 65.02% with acids with 20-26 Catoms in molecule being represented the most, and C22H38O2 (5.26%)bicyclic- and C24H42O2(7.01%) tricyclic structures stand out, while withtertacyclic acid structures C24H40O2 (4.77%) stands out. At pH 10 mostrepresented isolated acids are acyclic, i.e., fatty acids which arerepresented by 25.28%, with the most dominant C21H42O2structures(4.83%), while the other classes of acids are well balanced in their massshare in relation to the composition of the overall initial acid mixture.The second part of this work deals with derivatization of the isolated naturalnaphthenic acids. Functional oxygen methyl-, ethyl-, n-butyl-, tert-butyl andbenzyl-derivatives of naphthenic acids as well as functional nitrogenderivatives: amides and anilides of naphthenic acids were synthesized. Thesyntheses of the above mentioned esters were performed by conventionalmethods and by a modified method of esterification in acid-catalyzedconditions using microwaves as a co-catalyst with the aim of shortening thereaction time and improving the ecological synthetic conditions.By modification of methyl naphthenates synthesis using MT-heating thetime period for synthesis is reduced 48 times and the yield does notsignificantly change even after the reaction parameters (time, MT power)have been altered. Using structural analysis of ESI-MS spectrum of initialcarboxylic acids and the methyl naphthenates obtained through methylationof naphthenic acids it was establishedthat the class ratio shows greatcompatibility. The esters yield in this synthesis is 95.47%. The esterificationof naphthenic acids with ethyl alcohol done under the conditions of acidcatalysis with conventional heating (91.76%), and with the modified methodMT-heating (150 W) the reaction time is reduced 96 times (92.19%). Theesterification of naphthenic acids with n-butyl alcohol was performed usingsulphuric acid as a catalyst with conventional heating (94.24%), and underMT-heating conditions (150 W) reaction time was 72 times shorter(61.15%). The synthesis of tert-butyl naphthenates was performed byconversion of naphthenic acids into chlorides, followed by the reaction withtert-butyl alcohol which resulted in tert-butyl naphthenates (80.17%). By themodified method of conventional reaction of esterification of naphthenicacids using tert-butyl alcohol catalysed with sulphuric acid in MT-heatingconditions (150 W) the yield was 85.49% and reaction time was 5 minutes.The synthesis of benzyl naphthenates was performed by conversion ofnaphthenic acids into chlorides, followed by a reaction with benzyl alcoholwhich produces benzyl naphthenates (84.43%), whereas the modifiedmethod of conventional acid-catalysed esterification of naphthenic acidsusing benzyl alcohol under MT-heating (150 W) conditions the yield was85.49% with the reaction time of 5 minutes.The synthesis of naphthenic acid amides was done from chlorides byreaction with ammonia. The yield of pure amides was 65.74%, and thereaction of amidation with ammonia lasted for 15 minutes. The structuralanalysis of ESI-MS spectrum of naphthenic acid amides determined thegroup-structural composition of amides. With the structures of amides ofnaphthenic acids bicyclic- and tricyclic structures are also dominant, as inthe mixture of free acids. The synthesis of naphthenic acid anilides wereperformed from chloride by reacting with aniline. The yield of pure anilideswas 96.48%, and the reaction of amidatation lasted for 30 minutes. Thestructural analysis of ESI-MS spectrum of naphthenic acid anilidesdetermined the group-structural composition of anilide products. With thestructures of anilides of naphthenic acids bicyclic- and tricyclic structuresare also dominant, as in the mixture of free acids.The third part of this work tests the biological activity of naphthenic acids ofauxine and gibberellinic type, their influence on the rooting of cuttings,lateral branches and microshoots of plants, on the activity of planthormones as well as on the metal ions uptake by plants.The activity of naphthenic acids was determined using three in vitrobiological tests. „Koleoptil test”, was done on two substrates, namely theseed of winter wheat of the Partizankasort and the spring wheat of theVenerasort. The referential activity in the test was performed withα-naphthylacetic- and 3-indolacetic acid. Both tests showed approximatelythe same ratio of activity of naphthenic acid solutions and standard planthormones. „Germination Inhibition Test” of the seed was performed usingBrasscia nigraseed. The greatest influence of naphthenic acids togermination inhibition was achieved in the acid concentration ranging from10-7-10-8mol/L (0.05-0.01 mg/L). The tests for six narrow fractions obtainedfrom the overall mixture of acids through fractioning on the basis of differentsolubility at different pH values show the same activity as 3-indolacetic acid(0.5 mg/L), with the fraction isolated from the aqueous solution at pH 7 alsoactive but in comparison to 3-indolacetic acid this activity was 10 timeslower. Hormone activity of gibberellinic type of the potassium salts ofnaphthenic acids was determined using “Endosperm Test” where amylaseactivity was determined by spectrophotometric measuring of the increase ofthe concentration of reducing sugars in endosperm in the treated barleyseed which was then compared to the activity of the gibberellic acid solution(GA3). The results of these tests indicate that the activity of aqueoussolutions of narrow fractions of naphthenic acids in the concentration of1.0 mg/L (3.5 x 10-6mol/L)the fraction isolated at pH 8 has the activitywhich is approximately within the range of activities of gibberellin of theconcentration of 10-2-10-3mg/L.Sodium salts of naphthenic acids in concentrations of 10-6do 10-8mol/Lstimulated formation of adventitious roots insunflower cuttings even by afactor of 40 compared with control, the effect being also observed lateralbranches of interspecies sunflower hybrids. The obtained results suggestthe possibility of using naphthenic acids as a means for rooting of plantcuttings.Rooting of hardwood plants was investigated on the cuttings of white poplar(Populus alba) and black poplar (Populus deltoides). The distinct inhibitoryeffect on the root and shoot growth in water culture was detected in theconcentration of naphtenic acids 10-4mol/L, but 24-hour treatment raisedthe number roots on undermost 5 cm of the cutting, as well as the totalnumber of roots, comparing to the control.In the test of rooting microshoots ofchrysanthemum the highest number ofroots was achieved after the treatment with solution containing 10 µmol/L oftotal napthenates, as well as after the treatment with fraction of naphthenicacids which was isolated at pH 7 in concentration of 50 µmol/L. Both resultsare on the level of activity of 3-ndolbutyric acid in concentration of 10 µmol/Lwhich suggests that in this case ractionation is not necessary.The effects of sodium naphthenates on rooting were investigated bymeasuring the level of total peroxidases and amylase, along with thecontents of reducing sugars and total proteins in basal parts of cuttings ofblack locust (Rozaszin-AC). After 1; 3 and 6 days cuttings were taken forbiochemical analysis. In all cases, the activities of IAA-oxidase and amylaseincreased to the third day and showed a decrease afterwards. The effectwas more pronounced after the three-hour treatment with sodiumnaphthenates, compared to the six-hour treatment and control. The contentof soluble proteins increased one dayafter the treatment and decreased tothe third and again increased to the sixth day, an exception being thesix-hour treatment with sodium naphthenate, when the effect wascompletely opposite.The test of naphthenic acids influence on the level of cadmium in plantsshowed physiological activity of naphthenic acids on the decrease of thelevel of heavy metals, in this case cadmium, in the plant. The effect of lowconcentrations (10-7mol/L) of sodium naphthenate on total content of Cd inthe intercellular space and inside cells, as well as on some physiologicaland biochemical parameters of young soybean plants grown in thepresence of 1 mmol/L solution of cadmium chloride was investigated.Presence of naphthenate reduced in average by 40 % content of total andintracellular Cd in root, stem and leaves and alleviated the harmful effect ofCd on activity of nitrate reductase and content of photosynthetic pigments.Treatment of soybean plants with low concentrations of sodiumnaphthenate influenced the accumulation ofsome essential elements by theyoung plants. The presence of naphthenates (10-7mol/L) significantlyincreased content of Mn, Fe, Zn and Ni in root, but in stem and leavesincreased only contents of Fe and Mn. Inroot, the content of Mn increasedfour times while contents of Fe, Zn and Ni increased by 17%, 60% and 68%respectively compared to the control.Investigations on celery and carrot confirmed that the influence ofnaphthenates on mineral nutrition depends on the applied element and thatthe way of uptake of certain ions is different, which results in either increaseor decrease of the contents of some ions in certain parts of plants. Youngplants of celery and carrot, were grown in the nutrient medium and treatedwith sodium salts of naphthenic acids (10-7mol/L) over the leaves or with itspresence in the nutrient medium. Only the treatment based on the presenceof naphthenates in the nutrient medium resulted in the decrease of the freshmass of root and aboveground part by about 20% for both plants. Bothtreatments had influence on the content of Fe, Cu, Mn, Mg and Ca in theplants of celery and Fe, Mn, Zn and Na in the plants of carrots. In the plantsof celery the content of the mentioned nutrients was decreased, while in theroot of plants of carrot the content was increased, Fe by 45%, Mn by 70%and Zn by 37%. With these plants the presence of naphthenates in thenutrient medium caused the reducing roots and aboveground parts, which iscompletely opposite from the results obtained with soybean plants. Thetreatment by leaves significantly increased the mass of aboveground partonly with celery.