Identification of defensive substances from selected species of myriapod classes Diplopoda and Chilopoda (Arthropoda, Myriapoda)

Субфилум Myriapoda представља веома значајну групу земљишних зглавкара која се састоји од четири класе: Chilopoda, Diplopoda, Pauropoda и Symphyla. Досадашња испитивања одбрамбених супстанци код стонога поглавито су била везана са представнике класе Diplopoda, као наjбројнијих стонога, док су подаци за остале класe Myriapoda веома oскудни. Генерално, досадашњи резултати су показали велику разноврсност одбрамбених једињења која могу бити гасовите супстанце, попут цијановодоника, али и ароматична једињења, алкалоиди, па чак и протеини. У оквиру ове дисертације испитиван је састав одбрамбених секрета петнаест врста Diplopoda и шест врста Chilopoda уз помоћ савремених инструменталних метода, међу којима су GC‒MS, LC–MS, LC–MS–MS i NMR (1H и 13C NMR, COSY, NOESY, DOSY, HSQC, HMBC, 15N HSQC и 15N HMBC). Протеински део секрета је анализиран електрофорезом. Анализиране диплоподне врсте припадају редовима Callipodida, Polydesmida, Polyzoniida, Julida и Glomerida. Из реда Callipodida анализиране су две врсте Apfelbeckia insculpta и Callipodella fasciata. Обе врсте припадају фамилији Schizopetalidae и у одбрамбеном секрету садрже пара–крезол (D2) као главно одбрамбено једињење, а фенол (D1) и пара–етил фенол (D3) у траговима. Из реда Polydesmida анализиран је одбрамбени секрет четири врсте: Polydesmus complanatus, Brachydesmus avalae, B. dadayii и B. troglobius и идентификовано је 9 одбрамбених једњења (D4–D12). Све четири врсте припадају фамилији Polydesmidaе. Из реда Polyzoniida анализирани је одбрамбени секрет врсте Polyzonium germanicum чији ареал обухвата и простор Балканског полуострва. Са хемоеколошког аспекта ова врста је интересантна јер као одбрамбена једињења производи неколико алкалоида. Главно одбрамбено једињење је полизонимин (D13), док су у секрету регистровани и спиропиролизидин O–метилоксим (D14), нитрополизонамин (D15), као и ново једињење, 7–ацетокси–нитрополизонамин (D16). Из реда Julida испитивано је укупно шест врста које припадају фамилији Julidae: Julus terrestris, Cylindroiulus boleti, Leptoiulus trilineatus, Megaphyllum bosniense, M. austriacum и M. unilineatum. Укупно је идентификовано тринаест бензохинонских деривата D17–29. Поред хинонских деривата у одбрамбеним секретима испитиваних врста јулида пронађене су и нехинонске компоненте као што су бутил– и хексил–естри масних киселина...The aims of this dissertation were to the identify the chemical composition of the defensive fluids in some representatives of the classes Diplopoda and Chilopoda (Myriapoda); to compare the results with those of previously analyzed relatives; to test possibly interspecific and intergeneric differences in composition of defensive secretion in millipedes and centipedes; and to analyze protein part of secretions. This dissertation contains eight additinal chapters: Uvod (Introduction), Opšti deo (General prat), Naši radovi (Results and Discussion), Eksperimentalni deo (Experimental Part), Zaključak (Concusions), Literatura (References), Indeks pojmova (Index), and Biografija (Biography). The dissertation is written in Serbian with exception of this chapter, but with quite a few of chemical formulas, spectra, and Latin names that could be also understandable for non Balkan chemists and ecologists. General part includes the most important defensive chemicals in phylum Arthropoda sorted by functional groups and classes (cyanogenetic compounds, organic acids and related compounds, quinones and hydroquinones, terpens and steroids, alkaloids and related compounds). Modern instrumental methods such as GC‒MS, LC–MS, LC–MS–MS and NMR (1H and 13C NMR, COSY, NOESY, DOSY, HSQC, HMBC, 15N HSQC and 15N HMBC) were used to identify defensive compounds from 15 millipedes and 6 centipedes species. Protein part of secretions was analysed by electrophoresis. The analysed Diplopoda species belong to orders Callipodida, Polydesmida, Polyzoniida, Julida, and Glomerida. Defensive secretions from two Callipodida species (Apfelbeckia insculpta and Callipodella fasciata) were analysed. Both species belong to family Schizopetalidae and contain p–cresol (D2) as main defensive compound, phenol (D1) and p–ethylphenol (D3) in traces. Defensive secretions from four Polydesmida species (Polydesmus complanatus, Brachydesmus avalae, B. dadayi, and B. troglobius) were analysed. All species belong to family Polydesmidaе and contain cyanogenic compouds as defence, i. e. hydrogen cyanide (D12), benzaldehyde (D4), benzyl alcohol (D5), benzoyl nitrile (D6), benzoic acid (D8), mandelonitrile (D10), and mandelonitrile benzoate (D11). Becides these compounds there were two aromatic ketones D7 and D9

An Insight into Fatty Acid Composition of Calliergonella cuspidata

The fatty acid composition of the moss Calliergonella cuspidata (Hedw.) Loeske (Amblystegiaccae) was preliminary analyzed by gas chromatography (GC FID) and gas chromatography-mass spectrometry (GC-MS). Six fatty acids were identified in its chloroform-methanol extract 1/1: palmitic acid (66.83 %), stearic acid (11.73%), oleic acid (8.21 %), linolenic acid (6.01 %), alpha-linolenic acid (3.95 %) and arachidic acid (3.26 %). Arachidonic acid and cis-5,8,11,14,17-eicosapentaenoic acid, typical long-chain polyunsaturated fatty acids for many mosses, were not detected in Calliergonella cuspidata

Chemical weapons in university curricula - A way to safer society

Chemistry has been used as a tool of war for thousands of years. The earliest tools were poisoned arrows, Greek fire, water poisoning by hellebore plant extracts, etc. Apart from the chemicals used in the early wars, the modern chemical weapons (CW) were created during WWI and took more than one hundred thousand lives and caused around million casualties. Today CW have been regulated/prohibited by the Chemical Weapons Convention (OPCW, 2005) signed by 192 state parties. The implementing body for CWC is the Organisation for the Prohibition of Chemical Weapons (OPCW). Nowadays, when fear of terrorism is bigger than ever, society needs a better insight into CW, safety and widely used industrial chemicals with terrible potential. In the current curriculum CW is studied mostly from military point of view and the focus is more on the weapons than on chemistry. Authors suggest that the development of chemical weapon related courses in a chemistry curriculum could be a way to achieve safer society. CW courses could cover different topics, e.g. ethics in science, history of chemistry, safety in chemistry and chemical industry, organic and bioorganic chemistry, biochemistry, analytical chemistry, environmental and industrial chemistry, multiple usage chemicals, green chemistry as an alternative to widely used CW related chemicals, etc. Development of a CW syllabus could be supported by various internet-based resources used for education for peace (www.opcw.org/specialsections/education, http://multiple.kcvs.ca, www.thefiresproject.com). Diversity of chemicals covered by CWC in combination with multi-disciplinary approach is a great foundation for development of different student skills: science ethics, problemsolving skills, safety skills, 21st century searching skills, team skills… The authors created a new graduate course called Chemical weapons at Faculty of Chemistry, University of Belgrade in 2016/17. The syllabus of CW can be seen on the internet (www.chem.bg.ac.rs/predmeti/279H1-en.html). In conclusion, the chemistry behind chemical weapons is quite diverse and the authors suggest that undergraduate or graduate course Chemical weapons could be very interesting and beneficial for both chemistry major/minor students

Hemija masnih kiselina Atrichum undulatum i Hypnum andoi

The fatty acid compositions of the moss species Atrichum undulatum (Hedw.) P. Beauv. (Polytrichaceae) and Hypnum andoi A.J.E. Sm. (Hypnaceae) collected in winter time were analysed by gas chromatography (GC) and gas chromatography mass spectrometry (GC-MS) as a contribution to their chemistry. Eight fatty acids were identified in the chloroform/methanol extract 1:1 of A. undulatum (linoleic acid, 26.80%, palmitic acid, 22.17%, alpha-linolenic acid, 20.50%, oleic acid, 18.49%, arachidonic acid, 6.21%, stearic acid, 3.34%, cis-5,8,11,14,17-eicosapentaenoic acid, 1.52% and behenic acid, 1.01%), while six fatty acids were found in the same type of extract of H. andoi (palmitic acid, 63.48%, erucic acid, 12.38%, stearic acid, 8.08%, behenic acid, 6.26%, lignoceric acid, 5.16% and arachidic acid, 4.64%). According to this study, the moss A. undulatum can be considered as a good source of both essential fatty acids for humans (linoleic acid and alpha-linolenic acid) during the winter.Kao doprinos izučavanju njihovog hemijskog sastava, u ovom radu GC i GC-MS analizom ispitivane su masne kiseline mahovina Atrichum undulatum (Hedw.) P. Beauv. (Polytrichaceae) i Hypnum andoi A.J.E. Sm. (Hypnaceae) sakupljene za vreme zimskog doba. U ekstraktu hloroform/metanol 1:1 vrste A. undulatum identifikovano je osam viših masnih kiselina (linolna kiselina, 26,80%, palmitinska kiselina, 22,17%, α-linolenska kiselina, 20,50%, oleinska kiselina, 18,49%, arahidonska kiselina, 6,21%, stearinska kiselina, 3,34%, cis-5,8,11,14,17-eikosapentaenska kiselina, 1,52% i behenska kiselina, 1,01%), dok je u istom ekstraktu vrste H. andoi nađeno šest viših masnih kiselina (palmitinska kiselina, 63,48%, erukinska kiselina, 12,38%, stearinska kiselina, 8,08%, behenska kiselina, 6,26%, lignocerinska kiselina, 5,16% i arahidinska kiselina, 4,64%). Dobijeni rezultati ukazuju da u ispitivanom vremenskom periodu mahovina A. undulatum predstavlja dobar izvor linolne i α-linolenske kiseline, esencijalnih masnih kiselina za ljude

Osvrt na hemiju masnih kiselina Rhytididelphus squarrosus (Hedw.) Warnst

The fatty acid composition of the moss Rhytididelphus squarrosus (Hedw.) Warnst. (Hylocomiaceae) collected in Germany during winter time was analyzed by gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS). Nine fatty acids were identifi ed in its chloroform:methanol extract 1:1: arachidonic acid (30.7%), α-linolenic acid (19.1%), linoleic acid (15.1%), cis-5,8,11,14,17-eicosapentaenoic acid (14.4%), palmitic acid (11.9%), cis-8,11,14- eicosatrienoic acid (4.1%), oleic acid (2.3%), γ-linolenic acid (1.4%) and stearic acid (1.0%). Th e results indicate that this plant species can be a good source of arachidonic acid collected during the winter.Sastav viših masnih kiselina mahovine Rhytididelphus squarrosus (Hedw.) Warnst. (Hylocomiaceae), sakupljene u Nemačkoj za vreme zimskog doba, preliminarno je ispitivan GC i GC-MS analizom. U njenom ekstraktu hloroform: metanol 1:1 identifikovano je devet viših masnih kiselina: arahidonska kiselina (30.7%), α-linolenska kiselina (19.1%), linolna kiselina (15.1%), cis-5,8,11,14,17-eikosapentaenska kiselina (14.4%), palmitinska kiselina (11.9%), cis-8,11,14-eikosatrienska kiselina (4.1%), oleinska kiselina (2.3%), γ-linolna kiselina (1.4%) i stearinska kiselina (1.0%). Dobijeni rezultati ukazuju da je ova biljna vrsta dobar izvor arahidonske kiseline u ispitivanom vremenskom periodu

Preliminarna analiza hemije masnih kiselina vrsta Kindbergia praelonga i Kindbergia stokesii (Brachytheciaceae)

Moss species of the family Brachytheciaceae, Kindbergia praelonga (Hedw.) Ochyra and Kindbergia stokesii (Turn.) Ochyra, were preliminarily analysed for their fatty acid composition with the aim of studying the chemical relationship of these two entities. Fatty acid methyl esters were examined by GC and GC MS in their methanol extracts. Thirteen fatty acids were identified. It is likely that the mosses are chemically distinguishable and should be treated as separate entities. However, additional chemical constituents of various moss samples, such as phenolic acids, their derivatives and flavonoids, must be also analyzed in order to support the re-examination of the relationship between these two species.Preliminarno je ispitivan sastav viših masnih kiselina dve mahovine iz familije Brachytheciaceae, Kindbergia praelonga (Hedw.) Ochyra i Kindbergia stokesii (Turn.) Ochyra, sa hemotaksonomskim ciljem. Ukupno je identifikovano 13 viših masnih kiselina GC i GC-MS analizom. Na osnovu dobijenih eksperimentalnih rezultata se može zaključiti da se navedene biljne vrste značajno hemijski razlikuju i da bi se mogle smatrati zasebnim entitetima ukoliko se to potvrdi i dodatnim analizama

Editorial: Chemical ecology of arthropods, plants, and fungi: bioactivity and importance of natural products

Bioactivity and Importance of Natural Products" was intended to be a collection of The authors declare that the research was conducted in the absence of any commercial 100 or financial relationships that could be construed as a potential conflict of interest.Publisher's note 103 104 All claims expressed in this article are solely those of the authors and do not 105 necessarily represent those of their affiliated organizations, or those of the publisher, the 106 editors and the reviewers. Any product that may be evaluated in this article, or claim that may 107 be made by its manufacturer, is not guaranteed or endorsed by the publisher

Volatile Components from Old Plum Brandies

Gas chromatography and GC/MS methods were used to detect volatile components of three home-made natural old plum brandy samples and one sample of industrially-produced plum brandy. Gas chromatography and gas chromatography-mass spectrometric analysis of this extracts led to the identification of 99 components, including 46 esters, 7 hydrocarbons (alkanes and alkenes), 3 aldehydes, 9 alcohols, 1 lactone, 1 ketone, 8 acetals, 14 terpenes, 8 acids and 2 phenols. Ethyl esters of C8–C18 acids were the most abundant in all samples. In addition, the content of methanol, ethanol and higher alcohols C3–C5 was determined

Fitohemijsko ispitivanje biljne vrste Anthemis cotula

The investigation of roots of Anthemis cotula (Asteraceae) from cast Serbia revealed, in addition to polyacetylenes previously isolated from the same species, three prenylated 4-hydroxyacetophenones, detected for the first time in any Anthemis species. It is possible that they act as phytoalexins in the plant. From the aerial parts, six linear sesquiterpene lactones (four known and two new ones), as well as two known flavones, apigenin and hispidulin, were isolated.Novo ispitivanje korena biljke A. cotula (Asteraceae) pokazalo je, pored četiri već izolovana poliacetilena, i prisustvo tri prenilovana 4-hidroksiacetofenona koji do sada nisu bili izolovani iz ovog roda. Iz nadzemnog dela biljke izolovano je šest linearnih seskviterpenskih laktona, od koji su dva nova, dok su preostali ranije nađeni u istoj biljci. Takođe su u nadzemnom delu identifikovana dva poznata flavona, apigenin i hispidulin

Volatile Components from Old Plum Brandies

Gas chromatography and GC/MS methods were used to detect volatile components of three home-made natural old plum brandy samples and one sample of industrially-produced plum brandy. Gas chromatography and gas chromatography-mass spectrometric analysis of this extracts led to the identification of 99 components, including 46 esters, 7 hydrocarbons (alkanes and alkenes), 3 aldehydes, 9 alcohols, 1 lactone, 1 ketone, 8 acetals, 14 terpenes, 8 acids and 2 phenols. Ethyl esters of C8–C18 acids were the most abundant in all samples. In addition, the content of methanol, ethanol and higher alcohols C3–C5 was determined