Analysis and interpretation of excess molar properties of amphiphile + water systems : Part 3. Excess molar volumes of isopropoxyethanol + water and isobutoxyethanol + water

Excess molar volumes at 25°C, are reported for the systems isoPrOEtOH + water and isoBuOEtOH + water across their entire composition ranges. These data have been compared to those for their normal alkyl analogs in order to assess the effects of both - and β-chain branching.

The results are discussed in terms of the relative abilities of the amphiphiles to form structured aggregates.     

Thermal degradation of some polymers based on ethylene glycol dimethacrylate

Thermogravimetric analysis and pyrolysis in combination with gas chromatography were used to study the thermal behaviour of some cross-linked polymers of ethylene glycol dimethacrylate. The investigated polymers show a complex thermal degradation mechanism. The complexity of the reaction increases together with increase of the ethylene glycol chain in the macromolecule and with increase of the pyrolysis temperature. At low temperature, the thermal decomposition products of the analyzed polymers are mainly the constituent monomers. At high temperatures, besides the monomer, other decomposition products are formed as a result of thermal cracking reactions, i.e. secondary reactions of decomposition and recombination.

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Zusammenfassung Zur Untersuchung des thermischen Verhaltens einiger quervernetzter Polymere auf Äthylenglykoldimetacrylatbasis wurden thermogravimetrische Analyse und Pyrolyse in Zusammenhang mit der Gaschromatographie angewendet. Die untersuchten Polymere zeigten einen komplexen thermischen Zersetzungsmechanismus. Die Komplexizität der Reaktion nimmt mit Zunahme der Anzahl der Äthylenglykolketten im Makromolekül und mit Zunahme der Pyrolysentemperatur gleichermaßen zu. Bei niedrigeren Temperaturen stellen die Hauptzerfallsprodukte der analysierten Polymere hauptsächlich deren Monomere dar. Bei höheren Temperaturen werden als Ergebnis thermischer Krackreaktionen, z. B. sekundäre Zersetzungs- und Rekombinationsreaktionen, neben den Monomeren auch andere Zersetzungsprodukte gebildet.

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Effect of concentrate solution pH and mineral composition of a whey protein diluate solution on membrane fouling formation during conventional electrodialysis

The aim of this work was to study the effect of the concentrate solution pH and the composition in calcium, carbonate and protein of the diluate solution to be treated by conventional electrodialysis on the fouling of ion-exchange membranes. Conductivity, system resistance, pH of the diluate and cation migration were monitored to follow the evolution of the demineralization. Total cation migration was similar for all conditions although different forms of fouling were identified after three consecutive 100 min electrodialysis treatments. The nature of fouling and the membrane surface fouled depended on the concentrate pH value, the diluate mineral composition and the intrinsic composition of the whey isolate. Once conditions leading to membrane fouling were identified, an alternative configuration for our electrodialysis stack is proposed to prevent fouling onset.     

Comparative study of the phenolic profile,antioxidant and antimicrobial activities of leaf extracts of five Juniperus L. (Cupressaceae) taxa growing in Turkey

Abstract

The purpose of this study was to conduct a comparative evaluation of some biological properties of methanol and water extracts of leaves of five Juniperus taxa growing in Turkey: J. communis L. var. communis (Jcc), J. communis L. var. saxatilis Pall. (Jcs), J. drupacea Labill. (Jd), J. oxycedrus L. subsp. oxycedrus (Joo), J. oxycedrus L. subsp. macrocarpa (Sibth. & Sm.) Ball. (Jom). The antioxidant properties were examined in vitro; both in the DPPH and in the reducing power tests, Joo methanol extract resulted the most active (IC₅₀?=?0.09?±?0.01mg/mL and ASE/mL?=?2.56?±?0.06). In the TBA assay, Jcs methanol extract exhibited the highest activity (IC₅₀?=?4.39?±?0.47?μg/mL). The extracts displayed bacteriostatic activity against Staphylococcus aureus, and Jd methanol extract resulted the most effective (MIC?=?19.53?μg/mL); no effect on the S. aureus biofilm formation was observed. The extracts resulted non-toxic in the Artemia salina lethality bioassay. Finally, the phenolic profile of the methanol extracts was characterized by HPLC-PDA/ESI-MS.     

The enthalpies of combustion and formation of <Emphasis Type="Italic">L</Emphasis>-α-glutamic and 6-aminohexanoic acids

Summary The energies of combustion of crystalline L-α-glutamic and 6-aminohexanoic acids were measured in a static bomb adiabatic calorimeter, in pure oxygen at 3040 kPa. Corrections were made for the heats due to the ignition of sample and for the nitric acid formation. The derived enthalpies of formation for L-α -glutamic and 6-aminohexanoic acids are Δ_fH_cr⁰= -1002.6±1.1 kJ mol^-1and Δ_fH_cr⁰= -641.6±1.2 kJ mol^-1, respectively. The data of enthalpy of formation are compared with literature values and with estimated values by means of group additivity, using parameters recommended by Domalski and Hearing.     

Quantum chemical calculations and mutational analysis suggest heat shock protein 90 catalyzes trans-cis isomerization of geldanamycin

The affinity of geldanamycin (GA) for binding to heat shock protein 90 (HSP90) is 50- to 100-fold weaker than is the affinity of the structurally distinct natural product radicicol. X-ray crystallography shows that although radicicol maintains its free conformation when bound to HSP90, the conformation of GA is dramatically altered from an extended conformation with a trans amide bond to a kinked shape in which the amide group in the ansa ring has the cis configuration. We have performed ab initio quantum chemical calculations to demonstrate that the trans-cis isomeriztion of GA in solution is both kinetically and thermodynamically unfavorable. Thus, we propose that HSP90 catalyzes the isomerization of GA. We identify Ser113, a conserved residue outside the ATP binding pocket, as essential for the isomerization of GA. In support of this model, we show that radicicol binds equally well to both wild-type HSP90 and the Ser113 mutant, whereas the binding of GA to the Ser113 mutant is decreased significantly from its binding to wild-type HSP90. Based on this finding, a mechanism of keto-enol tautomerization of GA catalyzed by HSP90 is proposed. The added requirement of isomerization prior to tight binding may explain the enhanced binding affinity of GA for HSP90 in a cell extract versus in a purified form.     

New instanton and meron solutions of a generally covariant four-dimensional sigma model

We construct new solutions of the fourdimensional sigma model coupled to the metric tensor field and having an internalO invariance. Our solutions interpolate continuously between the known instanton and meron solutions depending upon a parameterf. We find that the typical domain for the instantons is 2<f≦3 while for the merons is 0≦f≦2.     

Studies towards the total synthesis of contignasterol

The (17R,20S,22S,24S) C₂₀-C₂₉ segment of contignasterol has been stereoselectively prepared in 8 steps and 40% overall yield from (S)-carvone. Synthetic studies towards contignasterol's C/D ring functionalization/isomerization are also reported.     

Calculated structures and relative stabilities of furoxan,some 1,2-dinitrosoethylenes and other isomers

The structures and relative stabilities of furoxan and some of its isomers, e.g., the 1,2-dinitrosoethylenes, have been determined by means of ab initio Hartee–Fock and Møller–Plesset calculations. Geometries were optimized at the HF/3-21G, HF/6-31G* and MP2/6-31G* levels, and subsequently used for computing MP2/6-31G*, MP3/6-31G*, and MP4/6-31G* energies. The results are markedly affected by the inclusion of electronic correlation, which renders three of the isomers unstable. It also emphasizes the importance of a zwitterionic contribution to the structure of furoxan, which promotes ring-opening through a cis 1,2-dinitrosoethylene intermediate/transition state that has an MP4/6-31G*//MP2/6-31G* energy that is 31.6 kcal/mol above furoxan.     

Diterpenoid Alkaloids of Delphinium buschianum Grossh.

From the aerial parts of Delphinium buschianum Grossh ., collected in Turkey, a new diterpenoid alkaloid 1 , named budelphine, was isolated along with the known diterpenoid alkaloids karakoline ( 2 ), 18‐hydroxy‐14‐O‐methylgadesine ( 3 ), delsoline ( 4 ), lapaconidine ( 5 ), columbianine ( 6 ), 14‐benzoylneoline ( 7 ), and hetisine ( 9 ). The structure of 1 was established on the basis of ¹H‐, ¹³C‐, DEPT, ¹H,¹H‐COSY, NOESY, HSQC, and HMBC NMR studies.