Three protected tetrapeptides

The structures of three protected tetrapeptides, containing the Boc-Gly-Gly-Phe-X-OMe chain, tert-butoxycarbonyl-glycy-glycl-phenylalanine-leucine methyl ester dihydrate, Boc-Gly-Gly-L-Phe-D-Leu-OMe, C25H38N4O7·2H2O, tert-butoxycarbonyl-glycy-glycl-phenylalanine-methionine methyl ester dihydrate, Boc-Gly Gly-L-Phe-D-Met-OMe, C24H36N4O7S.2H2O and tert-butoxycarbonyl-glycy-glycl-phenylalanine-norleucine methyl ester dihydrate, Boc-Gly-Gly-D-Phe-L-Nle-OMe, C25H38N4O7.2H2O, are described. The three molecules have the same conformation of the Boc-Gly Gly Phe-X-OMe tetrapeptide chain and display the same packing, consisting of couples of molecules linked head-to-tail by two hydrogen (N-HO) bonds; other hydrogen bonds, also involving two water molecules of crystallization, link these couples together, and give rise to a planar structure

Functional poly(2-oxazoline)s by direct amidation of methyl ester side chains

Poly(2-alkyl/aryl-2-oxazoline)s (PAOx) are biocompatible pseudopolypeptides that have received significant interest for biomedical applications in recent years. The growing popularity of PAOx in recent years is driven by its much higher chemical versatility compared with the gold standard in this field, poly(ethylene glycol) (PEG), while having similar beneficial properties, such as stealth behavior and biocompatibility. We further expand the PAOx chemical toolbox by demonstrating a novel straightforward and highly versatile postpolymerization modification platform for the introduction of side-chain functionalities. PAOx having side chain methyl ester functionalities is demonstrated to undergo facile uncatalyzed amidation reactions with a wide range of amines, yielding the corresponding PAOx with side-chain secondary amide groups containing short aliphatic linkers as well as a range of side-chain functionalities including acid, amine, alcohol, hydrazide, and propargyl groups. The PAOx with side-chain methyl ester groups can be prepared by either partial hydrolysis of a PAOx followed by the introduction of the methyl ester via modification of the secondary amine groups with methyl succinyl chloride or by the direct copolymerization of a nonfunctional 2-oxazoline monomer with a 2-methoxycarbonylethyl-2-oxazoline. Thus, this novel synthetic platform enables direct access to a wide range of side-chain functionalities from the same methyl-ester-functionalized poly(2-oxazoline) scaffold

On the ordeal of quinolone preparation via cyclisation of aryl-enamines; synthesis and structure of ethyl 6-methyl-7-iodo-4-(3-iodo-4-methylphenoxy)-quinoline-3-carboxylate

Recent studies directed to the design of compounds targeting the bc(1) protein complex of Plasmodium falciparum, the parasite responsible for most lethal cases of malaria, identified quinolones (4-oxo-quinolines) with low nanomolar inhibitory activity against both the enzyme and infected erythrocytes. The 4-oxo-quinoline 3-ester chemotype emerged as a possible source of potent bc(1) inhibitors, prompting us to expand the library of available analogs for SAR studies and subsequent lead optimization. We now report the synthesis and structural characterization of unexpected ethyl 6-methyl-7-iodo-4-(3-iodo-4-methylphenoxy)quinoline-3-carboxylate, a 4-aryloxy-quinoline 3-ester formed during attempted preparation of 6-methyl-7-iodo-4-oxo-quinoline-3-carboxylate (4-oxo-quinoline 3-ester). We propose that the 4-aryloxy-quinoline 3-ester derives from 6-methyl-7-iodo-4-hydroxy-quinoline-3-carboxylate (4-hydroxy-quinoline 3-ester), the enol form of 6-methyl-7-iodo-4-oxo-quinoline-3-carboxylate. Formation of the 4-aryloxy-quinoline 3-ester confirms the impact of quinolone/hydroxyquinoline tautomerism, both on the efficiency of synthetic routes to quinolones and on pharmacologic profiles. Tautomers exhibit different cLogP values and interact differently with the enzyme active site. A structural investigation of 6-methyl-7-iodo-4-oxo-quinoline-3-carboxylate and 6-methyl-7-iodo-4-hydroxy-quinoline-3-carboxylate, using matrix isolation coupled to FTIR spectroscopy and theoretical calculations, revealed that the lowest energy conformers of 6-methyl-7-iodo-4-hydroxy-quinoline-3-carboxylate, lower in energy than their most stable 4-oxo-quinoline tautomer by about 27 kJ mol(-1), are solely present in the matrix, while the most stable 4-oxo-quinoline tautomer is solely present in the crystalline phase.Fundacao para a Ciencia e Tecnologia (FCT - Portugal) [UID/Multi/04326/2013]; QREN-COMPETE-UE; CCMAR; FCT [SFRH/BD/81821/2011, RECI/BBB-BQB/0230/2012, UI0313/QUI/2013, UID/FIS/04564/2016]; FEDER/COMPETE-UE; [PTDC/QEQ-QFI/3284/2014 - POCI-01-0145-FEDER-016617]info:eu-repo/semantics/publishedVersio

l-Leucine Methyl Ester: The Female-Produced Sex Pheromone of the Scarab Beetle, Phyllophaga lanceolata

The female-produced sex pheromone of the scarab beetle Phyllophaga lanceolata was identified as the methyl ester of an essential amino acid, l-leucine. During field testing, 239 male P. lanceolata were caught in traps baited with l-leucine methyl ester. l-Isoleucine and l-valine methyl esters, similar in structure to l-leucine methyl ester and previously identified as female-produced sex pheromone compounds employed by other Phyllophaga species, were also tested. Addition of l-valine or l-isoleucine methyl esters to the l-leucine methyl ester in 1:1 ratios completely inhibited attraction of P. lanceolata males. Males of P. squamipilosa were also captured using l-leucine methyl ester. This is the first record of P. squamipilosa from Kansa

Evaluation of the Effect of Tocopherols on the Stability of Biodiesel

End of Project ReportA comprehensive study was carried out on the effects of naturally occurring tocopherols and carotenoids on the stability of biodiesel-grade methyl esters. Commercially available tocopherols and carotenoids, α-, γ- and δ-tocopherol, carotene and asthaxanthin, were added to destabilised methyl esters and the solutions were exposed to air at 65oC. The stabilising effect of the added tocopherols and carotenoids was determined from the number of days needed to reach the same increase of viscosity as destabilised methyl ester without tocopherols after 1 day. All three tocopherols stabilised methyl esters; γ- being the most effective and α- the least. The stabilising effect of tocopherols increased with concentration up to an optimum level. Concentrations above this level did not improve stability significantly. The stabilising effect of the tocopherols also depended on the composition of the methyl ester; they were most effective in tallow methyl ester, and had the least effect on sunflower methyl ester. Carotene and asthaxanthin had no effect on the stability of the methyl esters. However an unidentified carotenoid in rape methyl ester changed the oxidation pattern by reducing rates of peroxide and viscosity increase, without affecting overall stability

UPLC-MS/MS analysis of ochratoxin A metabolites produced by Caco-2 and HepG2 cells in a co-culture system

Ochatoxin A (OTA) is one of the most important mycotoxins based on its toxicity. The oral route is the main gateway of entry of OTA into the human body, and specialized epithelial cells constitute the first barrier. The present study investigated the in vitro cytotoxic effect of OTA (5, 15 and 45 μM) and production of OTA metabolities in Caco-2 and HepG2 cells using a co-culture Transwell System to mimic the passage through the intestinal epithelium and hepatic metabolism. The results derived from MTS cell viability assays and transepithelial electrical resistance measurements showed that OTA was slightly cytotoxic at the lowest concentration at 3 h, but significant toxicity was observed at all concentrations at 24 h. OTA metabolites generated in this co-culture were ochratoxin B (OTB), OTA methyl ester, OTA ethyl ester and the OTA glutathione conjugate (OTA-GSH). OTA methyl ester was the major metabolite found in both Caco-2 and HepG2 cells after all treatments. Our results showed that OTA can cause cell damage through several mechanisms and that the OTA exposure time is more important that the dosage in in vitro studies. OTA methyl ester is proposed as an OTA exposure biomarker, although future studies should be conducted.The authors are grateful to the Spanish (Project AGL2011-24862) and Catalonian (XaRTA-Reference Network on Food Technology) Governments for their financial support. C.A. González-Arias thanks the Secretaria de Universitats i Recerca del Departament de Economia i Coneixement of the Generalitat de Catalunya for the pre-doctoral grant

Synthesis and structural characterization of 6-(N-Methyl-pyridin-2-ylcarbamoyl)-pyridine-2-carboxylic acid methyl ester isomers

A series of monoamide isomers have been successfully synthesised and characterised using combination of common spectroscopic techniques such Fourier Transform Infrared (FT-IR), 1H and 13C Nuclear Magnetic Resonance (NMR) and Ultraviolet-visible (UV-vis). The monoamide compounds namely 6-(3-methyl-pyridin-2-ylcarbamoyl)-pyridine-2-carboxylic acid methyl ester (L1), 6-(4-methyl-pyridin-2-ylcarbamoyl)-pyridine-2-carboxylic acid methyl ester (L2), 6-(5-methyl-pyridin-2-ylcarbamoyl)-pyridine-2-carboxylic acid methyl ester (L3) and 6-(6-methyl-pyridin-2-ylcarbamoyl)-pyridine-2-carboxylic acid methyl ester (L4) were prepared from reaction between 6-(methoxycarbonyl)pyridine-2-carboxylic acid with 2-amino-N-methylpyridine (where N = 3, 4, 5 and 6) by using acyl chloride reaction. In this present studies, the synthesis and characterization of these compounds are discussed along with the inductive effects contributed by methyl substituted groups at the pyridine ring

Synthesis of perfluoroalkylene aromatic diamines

Analogues of methylene dianilines were synthesized, in which the methylene group between the two aromatic nuclei was replaced by various perfluoroalkylene linkage. The hydrolytic thermal, and thermal oxidative stabilities of PMR Polyimides derived from these diamines were determined. Three types of PMR Polyimide discs were fabricated from the dimethyl ester of 3,3', 4,4'-benzophenonetetracarboxylic acid, the methyl ester of 5-norbornene-2,3-dicarboxylic acid, and one of the following three diamines: methyl dianiline, 1,3-bis(4-aminophenyl)hexafluoropropane, and 2,2-bis(4-aminophenyl)hexafluoropropane. The polyimide based on 2,2-bis(4-aminophenyl)hexafluoropropane exhibited the best hydrolytic, thermal, and thermal oxidative stability as determined by moisture uptake and thermogravimetric analysis

Quenching of fluorescence of aromatic molecules by graphene due to electron transfer

Investigations on the fluorescence quenching of graphene have been carried out with two organic donor molecules, pyrene butanaoic acid succinimidyl ester (PyBS, I) and oligo(p-phenylenevinylene) methyl ester (OPV-ester, II). Absorption and photoluminescence spectra of I and II recorded in mixture with increasing the concentrations of graphene showed no change in the former, but remarkable quenching of fluorescence. The property of graphene to quench fluorescence of these aromatic molecules is shown to be associated with photo-induced electron transfer, on the basis of fluorescence decay and time-resolved transient absorption spectroscopic measurements.Comment: 18 pages, 6 figure

Biodiesel Fuel from Differently Sourced Local Seed Oils: Characterization, Effects of Catalysts, Total Glycerol Content and Flow Rates

The recently observed depletion in the petroleum resources, which also mainly constituted carbon dioxide emission and global warming problems call for renewable and sustainable alternative fuels. Oils were extracted from various seeds: Jatropha curcas (Botuje), Pentaclethra macrophylla (Apara) and soybean, using petroleum ether (40-60℃). Alkali catalyzed transesterification of the oils (biodiesel pro-duction) in the presence of different kinds of alcohol (methanol, ethanol and propanol) were carried out using sodium hydroxide as catalyst. In the case of Jatropha oil, potassium hydroxide served as catalyst. Effect of catalysts to obtain optimum biofuel was established. In the case of soybean oil, fatty acid methyl ester, FAME, (96%), fatty acid ethyl ester, FAEE, (84%) and fatty acid propyl ester, FAPE, (37.50%) were pro-duced. In waste palm kernel oil, methyl ester (72.92%) and ethyl ester (46.25%) were obtained. In refined palm kernel oil, methyl ester (70.83%), ethyl ester (66.67%) and (14.17%) propyl ester were produced. However, only methyl ester conversion (20.83%) was possible in Pen-taclethra macrophylla oil. In Jatropha curcas using KOH catalyst, only methyl ester (80%) formation was possible. Moreover, yields were af-fected as the alcohol alkyl became bulkier giving relatively lower value of biodiesel. Sulphur content (0.01) obtained for each of the biofuel was satisfactory when compared with ASTM standard (0.05 maximum). The cetane value of soybean oil (45.5), refined palm kernel oil (46) and used oil (44.6) were quite reasonable compared with the special standard (47). The combustion energy of the fuels from refined palm kernel oil, waste palm kernel oil and soybean are 39, 36 and 45.5 respectively. The total glycerol content (Gc) of the methyl and ethyl esters emanat-ed from soybean are quite reasonable and fell within standard. Keywords: biodiesel, flow rates, local seed oils, total glycerol content, transesterificatio