Acrylate functionalized tetraalkylammonium salts with ionic liquid properties

Acrylate functionalized ionic liquids based on tetraalkylammonium salts with terminal acrylates- and methylacrylates were synthesized. Melting points and ionic conductivity of twenty compounds in six groups were determined. Within one group the effect of three different counterions was investigated and discussed. The groups differ in cationic structure elements because of their functional groups such as acrylate and methacrylate, alkyl residues at the nitrogen and number of quaternary ammonium atoms within the organic cation. The effect of these cationic structure elements has been examined concerning the compiled parameters with a view to qualifying them as components for solid state electrolytes. The newly synthesized ionic liquids were characterized by NMR and FTIR analysis. The exchange of halide ions like bromide as counter ions to weakly coordinating [PF?]?, [OTf]? or [TFSI]? reduces the melting points significantly and leads to an ion conductivity of about 10?? S/cm at room temperature. In the case of the dicationic ionic liquid, an ion conductivity of about 10?3 S/cm was observed.     

Epothilone Analogues with Benzimidazole and Quinoline Side Chains: Chemical Synthesis,Antiproliferative Activity,and Interactions with Tubulin

A series of epothilone B and D analogues bearing isomeric quinoline or functionalized benzimidazole side chains has been prepared by chemical synthesis in a highly convergent manner. All analogues have been found to interact with the tubulin/microtubule system and to inhibit human cancer cell proliferation in vitro, albeit with different potencies (IC₅₀ values between 1 and 150 nM ). The affinity of quinoline‐based epothilone B and D analogues for stabilized microtubules clearly depends on the position of the N‐atom in the quinoline system, while the induction of tubulin polymerization in vitro appears to be less sensitive to N‐positioning. The potent inhibition of human cancer cell growth by epothilone analogues bearing functionalized benzimidazole side chains suggests that these systems might be conjugated with tumor‐targeting moieties to form tumor‐targeted prodrugs.     

Development of a method for the determination of 93Zr and 94Nb in radioactive waste using TEVA® resin

The behaviour of ⁹⁵Zr and ⁹⁵Nb isotopes on TEVA^® resin column was studied. The influence of hydrofluoric, hydrochloric, oxalic and sulphuric acids on the separation and chemical yield of zirconium and niobium was tested. The method is suitable for the separation of ⁹³Zr and ⁹⁴Nb isotopes from hydrofluoric, hydrochloric and sulphuric acid by using different concentrations of the acid for the load or elutes solutions. Samples from reactor and fuel assemblies such as the control-rod connection rod, shielding/absorber parts of fuel rods, neutron in-core measurement channels, pressure vessel basic construction material and internal cladding, core barrel and reactor protection tube unit were analysed.     

A Structural View on Medicinal Chemistry Strategies against Drug Resistance

The natural phenomenon of drug resistance is a widespread issue that hampers the performance of drugs in many major clinical indications. Antibacterial and antifungal drugs are affected, as well as compounds for the treatment of cancer, viral infections, or parasitic diseases. Despite the very diverse set of biological targets and organisms involved in the development of drug resistance, the underlying molecular mechanisms have been identified to understand the emergence of resistance and to overcome this detrimental process. Detailed structural information on the root causes for drug resistance is nowadays frequently available, so next‐generation drugs can be designed that are anticipated to suffer less from resistance. This knowledge‐based approach is essential for fighting the inevitable occurrence of drug resistance.     

Lipophilic toxin profile in Mytilus galloprovincialis during episodes of diarrhetic shellfish poisoning (DSP) in the N.E. Adriatic Sea in 2006

Dinophysis spp. blooms and related shellfish toxicity events of diarrhetic shellfish poisoning (DSP) have been the most reported toxicity event through the Croatian National monitoring program. With the aim to characterize the DSP toxin profile in shellfish farmed in Croatia, for the first time a complete analysis of the toxin profile of Croatian mussels has been carried out using the LC-MS/MS technique. The obtained results showed okadaic acid (OA) as the main toxin contaminating Croatian mussels at that time. The maximum concentration of OA in shellfish tissue was recorded 12 days after the Dinophysis fortii bloom, thus suggesting that rapid growth of the toxin level in the shellfish occurred in the first week after the bloom while it was slower in the second week. Furthermore, the presence of only OA at concentrations which could endanger human health suggests D. fortii as the main organism responsible for the toxic event that occurred in Lim Bay. The presence of gymnodimine and spirolides in Croatian mussel has been detected for the first time, while the presence of yessotoxin and pectenotoxin-2 is confirmed.     

Highly diastereo- and enantioselective direct Barbas-List aldol reactions promoted by novel benzamidoethyl and benzamidopropyl prolinamides in water

Four novel benzamido-functionalized prolinamides have been prepared and tested as organocatalysts for enantioselective aldol reaction of aldehydes and cyclic ketones in water. In particular, prolinamide derived from achiral ethylene diamine was the best catalyst leading to anti aldols in excellent diastereomeric (up to 98/2) and enantiomeric (up to 99/1) ratios, thereby showing that lateral amide functionalities might be a key issue for facilitating "in water" chemistry. These catalysts are cheaper and easier to prepare than those previously described.     

(Perhalogenmethylthio)heterocyclen. X. Säurekatalysierte Substitutionen an (Perchlorfluormethylthio)pyrrolen und deren agrobiologische Wirkung

(Perhalomethylthio)heterocycles. X

1 IX. Mitt.: s. [1].

. Acid-catalyzed substitutions on (perchlorofluoromethylthio)pyrroles and their agro-biological activities In the presence of C₄F₉SO₃H the (perhalomethylthio)pyrroles 1a–c react with Cl_3?nF_nCSCl (n = 1–3) to give mixtures of the 2,5- and 2,4-disubstituted pyrroles 2a–f and 3a–h . 2a and 3a react with CF₃SCl (catalyst CF₃SO₃H) yielding 2,3,5-tris (trifloromethylthio)pyrrole ( 4a ), which under similar conditions reacts further to give 2,3,4,5-tetrakis (trifluoromethylthio)pyrrole ( 5 ). As a by-product during the conversion of 3a to 4a 2,3,4-tris (trifluoromethylthio)pyrrole ( 4b ) is formed. The pyrroles 2a , 4a and 5 form the mercury salts 6a–c ; compound 5 yields also a silver salt 7 . The ¹H- and ¹⁹F-NMR. spectra are discussed and the agro-biological properties of the compounds investigated.     

The fluorescence of biliverdin dimethyl ester

Freshly prepared solutions of biliverdin dimethyl ester ( 2 ) in ethanol showed fluorescence maxima at 710 and 770 nm [Φ_F = 1.1. 10^?4 (room temperature) and 5.0 10^?4 (77 K)]. The maxima of monoprotonated 2 at 77 K were shifted to 725 and 806 nm and the quantum yield was increased to 2.6. 10^?2. This acid effect was reversible by neutralization with base. When a neutral solution was kept standing in the dark at room temperature, or when an acidic solution was neutralized by base, an additional fluorescence maximum at 500 nm with a mirror image excitation spectrum with λ_max = 470 nm developed, which disappeared on addition of acid and which is attributed to a chemical change of 2 .     

Usefulness of the direct coupling headspace-mass spectrometry for sensory quality characterization of virgin olive oil samples

The applicability of the headspace coupled to mass spectrometry for evaluation of the sensory quality of virgin olive oil samples is presented. The volatiles of the oil are directly transferred from the sample vial to the detector without chromatographic separation. The mass spectrum obtained can be considered as a fingerprint of the oil sample and can be used for classification purposes. After a training step with samples previously qualified following the official method, a classification model was created using the supervised technique soft independent modeling of class analogy (SIMCA). Eight negative (rancid, winey-vinegary, muddy sediment, hay-wood, vegetable water, earthy, fusty and musty-humidity) and three principal positive attributes (fruity, bitter and pungent) have been included in this study. With them, a classification model consisting of two main classes (extra- and lampante-virgin olive oil) was constructed. In addition, the unsupervised technique cluster analysis permited the discrimination among oils with different negative attributes. The proposed procedure has been applied to the classification of commercial samples (as extra- or lampante-virgin olive oils) and the results were compared with those provided by the expert's panel with acceptable correlation.