Tamer Karayıldırım

Liquefaction of municipal waste plastics in VGO over acidic and non-acidic catalysts

Co-processing of municipal waste plastics (MWP) with vacuum gas oil (VGO) over HZSM-5, DHC-8 (commercial silica –alumina catalyst) and cobalt loaded active carbon catalyst has been comparatively studied. Co-processing experiments were carried out under hydrogen atmosphere at temperatures between 425 and 450 8C. The composition, sulphur and chlorine amount of liquid products were determined. The product distribution and the composition of liquids were changed depending upon the temperature and the catalyst type. As expected temperature led to increase in cracking activity of catalysts. DHC-8 and HZSM-5 showed substantially different activities in coprocessing due to the difference in their acidity. HZSM-5 gave highest gas yield at all temperatures and highest liquid yield (38.3) at low temperature. Although Co-AC was a neutral catalyst, it showed the cracking activity as well as HZSM-5 and more than DHC-8. No chlorine compound was observed in liquid products. The sulphur amount in liquid products varied with the catalyst type. Although HZSM-5 showed good cracking activity at low temperatures, it gave the liquid product containing highest sulphur amount. By considering both the quantity and quality of liquid fuel obtained from co-processing, it may be concluded that Co-AC gave the best result in the co-processing of the MWP/VGO blend. To observe the effect of metal type loaded on active carbon on catalyst activity, a series of co-processing experiments was also carried out. q 2002 Published by Elsevier Science Ltd.

Oleanane glycosides from Astragalus tauricolus: Isolation and structural elucidation based on a preliminary liquid chromatography-electrospray ionization tandem mass spectrometry profiling

As a part of our ongoing research for bioactive compounds from Turkish Astragalus species, the investigation of Astragalus tauricolus has been carried out. An approach based on HPLC-ESIMS(n) experiments has been used to profile the triterpene glycosides occurring in the butanol extract of the whole plant. On the basis of the results of the online screening by HPLC-ESIMS(n), 22 oleanane-type triterpene glycosides, including ten compounds never reported before, were isolated, and their structures were established by the extensive use of 1D and 2D-NMR experiments along with ESIMS and HRMS analysis. Noteworthy, cycloartane-type triterpene glycosides, the main constituents of Astragalus spp., were not found. This peculiar feature characterizes a very limited group of Astragalus spp. The antiproliferative activity of the isolated compounds 1-12, 15, 17-19 was evaluated against a small panel of cancer cell lines. Only compound 11 showed an IC(50) of 22 μM against human leukemia cell line (U937). The other tested compounds, in a range of concentrations between 1 and 50 μM, did not cause any significant reduction of the cell number.

Conversion of plastics/HVGO mixtures to fuels by two-step processing

Abstract A blend containing 20 wt.% low density polyethylene (PE) and 5 wt.% polyvinylchloride (PVC) in heavy vacuum gas oil was pyrolyzed at 623 K (dechlorination step). This mixture was then thermally and catalytically cracked in the presence of hydrogen at 673–723 K in a batch reactor (hydrocracking step). The liquid products from hydrocracking contained no chlorine compounds although the chlorine amount in the dechlorinated mixture was 700 ppm. Experiments have shown that the dechlorination step and the temperature had great effect on the product distribution from the hydrocracking step. It was observed that the dechlorination step led to both degradation of PE and dechlorination of PVC and that PE could be completely cracked with/without a catalyst by hydrocracking even though at 673 K. The use of a catalyst decreased the gas yield and led to an increase in coke yield at 723 K. The effect of the catalyst on the boiling point range of liquid product obtained from hydrocracking depended on the reaction temperature. The chlorine compounds in dechlorinated mixture affected the catalytic activity of the catalyst especially at 723 K. 75% and 55% of the liquid products obtained at 723 K with and without a catalyst, respectively, were hydrocarbons having boiling points ranging from 323 to 473K.

Triterpene Glycosides from Astragalus angustifolius

Six new cycloartane-type (1- 6) and four new oleanane-type (7- 10) triterpene glycosides were isolated from Astragalus angustifolius Lam., together with five known triterpene glycosides. Their structures were established by the extensive use of 1D and 2D-NMR experiments along with ESIMS and HRMS analysis. Compounds 1- 3 are glycosides of cycloastragenol, while compounds 4- 6 show the C-24 epimer of cycloastragenol as aglycone, encountered for the first time in nature. All compounds were evaluated for their antiproliferative activity in Hela, H-446, HT-29, and U937 cell lines. Only compound 8 displayed a weak activity with IC (50) values of 36 and 50 µM against Hela and HT-29 cell lines, respectively.

Triterpene saponins from Cyclamen hederifolium.

Five triterpene saponins never reported before, hederifoliosides A-E, and four known triterpene saponins were isolated from the tubers of Cyclamen hederifolium. The structures of hederifoliosides A-E were determined as 3β,16α-dihydroxy-13β,28-epoxyolean-30-oic acid 3-O-{[β-D-glucopyranosyl-(1 → 2)-O]-β-D-xylopyranosyl-(1 → 2)-O-β-D-glucopyranosyl-(1 → 4)-O-α-L-arabinopyranoside}, 3β,16α-dihydroxy-13β,28-epoxyolean-30-oic acid 3-O-{[β-D-glucopyranosyl-(1 → 2)-O]-β-D-xylopyranosyl-(1 → 2)-O-[β-D-glucopyranosyl-(1 → 3)]-O-β-D-glucopyranosyl-(1 → 4)-O-α-L-arabinopyranoside}, 3β,16α-dihydroxy-13β,28-epoxyolean-30-al 3-O-{[β-D-glucopyranosyl-(1 → 2)-O]-β-D-xylopyranosyl-(1 → 2)-O-[β-D-glucopyranosyl-(1 → 3)]-O-[β-D-glucopyranosyl-(1 → 6)]-O-β-D-glucopyranosyl-(1 → 4)-O-α-L-arabinopyranoside}, 30-O-β-D-glucopyranosyl-(1 → 2)-O-β-D-glucopyranosyl-3β,16α,30-trihydroxyolean-12-en-28-al 3-O-{[β-D-glucopyranosyl-(1 → 2)-O]-β-D-xylopyranosyl-(1 → 2)-O-β-D-glucopyranosyl-(1 → 4)-O-α-L-arabinopyranoside}, 30-O-β-D-glucopyranosyl-(1 → 2)-O-β-D-glucopyranosyl-3β,16α,28,30-tetrahydroxyolean-12-en 3-O-{[β-D-glucopyranosyl-(1 → 2)-O]-β-D-xylopyranosyl-(1 → 2)-O-[β-D-glucopyranosyl-(1 → 3)]-O-β-D-glucopyranosyl-(1 → 4)-O-α-L-arabinopyranoside}, by a combination of one- and two-dimensional NMR techniques, and mass spectrometry. The cytotoxic activity of the isolated compounds was evaluated against a small panel of cancer cell lines including Hela, H-446, HT-29, and U937. None of the tested compounds, in a range of concentrations between 1 and 50 μM, caused a significant reduction of the cell number.

Synthesis of egonol derivatives and their antimicrobial activities.

Eighteen derivatives of egonol (A-R) were synthesized and evaluated for their antimicrobial activities against Staphylococcus aureus ATCC 29213, Bacillus subtilis ATCC 6633, Candida albicans ATCC 10231 and Escherichia coli ATCC 8739 microorganisms comparing with egonol. The obtained data reported that compound B exhibited improved activities against all tested bacteria than egonol, others have shown different range of activities.

Monoterpenoid glucoindole alkaloids and iridoids from Pterocephalus pinardii.

A new secondary metabolite, pterocephaline, along with the known cantleyoside, 7α‐morroniside, 3β,5α‐tetrahydrodesoxycordifoline lactam, 5S‐5‐carboxyvincoside, sweroside, and loganin have been isolated from the aerial parts of P. pinardii (Dipsacaceae). Moreover, cantleyoside‐methyl‐hemiacetal and cantleyoside‐dimethyl‐acetal were obtained as seco‐iridoid artifacts. The structures were elucidated by extensive spectroscopic methods including 1D‐(1H, 13C and TOCSY) and 2D‐NMR (DQF‐COSY, HSQC and HMBC). Monoterpenoid glucoindole alkaloids were encountered for the first time in Dipsacaceae family. Copyright

Oleanane‐Type Glycosides from Tremastelma palaestinum (L.) Janchen

Three new oleanane‐type glycosides, 1–3, were isolated from the whole plant of Tremastelma palaestinum (L.) Janchen, along with eight known triterpene glycosides. The structures of the new compounds were established as 3‐O‐[β‐d‐glucopyranosyl‐(1→3)‐α‐l‐rhamnopyranosyl‐(1→3)‐β‐d‐glucopyranosyl‐(1→3)‐α‐l‐rhamnopyranosyl‐(1→2)‐α‐l‐arabinopyranosyl]hederagenin (1), 3‐O‐[β‐d‐glucopyranosyl‐(1→3)‐α‐l‐rhamnopyranosyl‐(1→3)‐β‐d‐glucopyranosyl‐(1→3)‐α‐l‐rhamnopyranosyl‐(1→2)‐α‐l‐arabinopyranosyl]hederagenin 28‐O‐β‐d‐glucopyranosyl‐(1→6)‐β‐d‐glucopyranosyl ester (2), and 3‐O‐[α‐l‐rhamnopyranosyl‐(1→3)‐β‐d‐glucopyranosyl‐(1→3)‐α‐l‐rhamnopyranosyl‐(1→2)‐α‐l‐arabinopyranosyl]oleanolic acid 28‐O‐β‐d‐glucopyranosyl‐(1→6)‐β‐d‐glucopyranosyl ester (3) by using 1D‐ and 2D‐NMR techniques and mass spectrometry. This is the first report on the phytochemical investigation of a species belonging to Tremastelma genus.

The Knoevenagel-Doebner Reaction on 1,2-O-(2,2,2- Trichloroethylidene) Derivatives of D-Gluco- and D-Manno- furanose †

The synthesis of new α,β-unsaturated furanuronic acid derivatives of α-gluco- (3), β-gluco- (6) and β-manno-chloraloses (9) via a convenient one pot procedure using the Knoevenagel-Doebner reaction approach are described. The dialdofuranose derivatives were reacted with malonic acid under Knoevenagel-Doebner reaction conditions and (E)-α,β-unsaturated furanuronic acid derivatives were obtained.

Synthesis and antimicrobial evaluation of sulfanilamide- and carbohydrate-derived 1,4-disubstitued-1,2,3-triazoles via click chemistry

Abstract4-Sulfanilamido substitued-1,2,3-triazoles conjugated with monosaccharides (8–17) including d-glucose, d-galactose, d-mannose, and d-fructose were synthesized in good yields from azidosugars with propargyl sulfanilamides using copper catalyst 1,3-dipolar cycloaddition reaction (CuAAC). The structures of new compounds were elucidated by liquid chromatography-mass spectrometry, infrared, one-dimensional- and two-dimensional-nuclear magnetic resonance techniques. All of the new compounds were tested in vitro against Staphylococcus aureus, Bacillus subtilis, Escherichia coli, Salmonella typhimurium, Klebsiella pneumoniae, Enterococcus faecalis, Pseudomonas aeruginosa, and Candida albicans for their antibacterial and antifungal activities. Experimental results showed antimicrobial activity with minimum inhibitory concentrations values a ranging from 0.078 to 5.0 mg/mL against test microorganisms.