Magnetically aligned phospholipid bilayers with large q ratios stabilize magnetic alignment with high order in the gel and L(alpha) phases

The magnetic alignment behavior ofbicelles (magnetically alignable phospholipid bilayered membranes) as a function of the q ratio (1,2-dihexanoyl-sn-glycerol phosphatidylcholine/1,2-dimyristoyl-sn-glycerol phosphatidylcholine mole ratio) and temperature was studied by spin-labeled X-band electron paramagnetic resonance (EPR) spectroscopy and solid-state 2H and 31P NMR spectroscopy. Well-aligned bicelle samples were obtained at 45 degrees C for q ratios between 2.5 and 9.5 in both the EPR and NMR spectroscopic studies. The molecular order of the system, S(mol), increased as the q ratio increased and as the temperature decreased. For higher q ratios (> or = 5.5), bicelles maintained magnetic alignment when cooled below the main phase transition temperature (approximately 30 degrees C when in the presence of lanthanide cations), which is the first time, to our knowledge, that bicelles were magnetically aligned in the gel phase. For the 9.5 q ratio sample at 25 degrees C, S(mol) was calculated to be 0.83 (from 2H NMR spectra, utilizing the isotopic label perdeuterated 1,2-dimyristoyl-sn-glycerol phosphatidylcholine) and 0.911 (from EPR spectra utilizing the spin probe 3beta-doxyl-5alpha-cholestane). The molecular ordering of the high q ratio bicelles is comparable to literature values of S(mol) for both multilamellar vesicles and macroscopically aligned phospholipid bilayers on glass plates. The order parameter S(bicelle) revealed that the greatest degree of bicelle alignment was found at higher temperatures and larger q ratios (S(bicelle) = -0.92 for q ratio 8.5 at 50 degrees C).     

Effect of environmental factors and carbohydrate on gellan gum production

Submerged culture fermentation studies were carried out in batch mode for optimizing the environmental parameters and carbon source requirement by Pseudomonas elodea for the production of gellan gum. The maximum production of gellan gum was obtained with 16-h-old culture and 8% inoculum at 30°C and pH 7.0 after 52 h of incubation (6.0 g/L). Of the various carbon sources tested, 2% sucrose, glucose, and soluble starch yielded considerably high amounts of gellan. Studies on the concentration of various carbohydrates on gellan gum production indicated that the optimum concentration of glucose and starch was 3%, whereas for sucrose it was 4%. The addition of glucose in the medium above 3% had a detrimental effect on gellan yield. The investigation of intermediate two-step addition of glucose under identical conditions of fermentation showed an enhanced production of gellan (8.12 g/L) as compared with the control (6.0 g/L). To optimize the recovery of gellan from fermented broth, different solvents were tested for precipitation of gellan gum. Among the various solvents tested, tetrahydrofuran gave better recovery of gellan (82%) as compared with the conventional solvent isopropanol (49%).     

Study of Densities, Viscosities and Ultrasonic Speeds of Binary Mixtures Containing 1,2-Dimethoxyethane and an Alkan-l-ol at 298.15 K

The viscosity deviation (Δη), the excess molar volume (V ^E) and the ultrasonic speed (u) have been investigated from viscosity (η) and density (ρ ) measurements of binary liquid mixtures of 1,2-dimethyoxyethane with methanol, ethanol, propan-1-ol, butan-1-ol, pentan-1-ol, hexan-1-ol or octan-1-ol over the entire range of composition at 298.15 K. The excess volumes are negative over the entire range of composition for all of the mixtures with the exception of hexan-1-ol and octan-1-ol. The excess isentropic compressibilities (K _S ^E) and viscosity deviations are negative for all of the mixtures. The magnitudes of the negative values of V ^E decrease with the number of carbon atoms of the alkan-1-ol. The trend of increasing K _S ^E values with the chain length of the alkanol is similar to that observed in the case of V ^E. Graphs of V ^E, Δ η, K _S ^E, Δ u, L _f ^E and Z ^E against composition are presented as a basis for a qualitative discussion of the results.     

Aquation of α-cis-chloroaquoethylenediamine-N,N'-diacetatocobalt(III) in aqueous and in mixed solvents: A mechanistic study

Summary The displacement of chloride ligands from -cis-chloro-aquoethylenediamine-N,N-diacetatocobalt(III) in nonacidic aqueous solutions was followed conductimetrically at 30–45° and the products of aquation were characterised by conductance, spectral and ion-exchange techniques. The rate constants for aquation in aqueous media and in 1 : 4 v : v mixed solvents at 25° are: 4.0 × 10^–5 s^–1 in H₂O, 2.71 × 10^–5 s^–1 in MeOH : H₂O, 2.74 × 10^–5 s^–1 in EtOH: H₂,O and 2.58 × 10^–5 s^–1 n in Me₂CO : H₂O. The corresponding H* and S* values have also been evaluated. Solvent polarity has a marked influence on the rate of chloride ion release. The aquation rate constants and the activation parameters have been correlated with solvent parameters,e.g. D, Y-values, Dimroth's E_T and Kosower's Z-values and, based on these correlations, a dissociative interchange (I_d) mechanism is proposed rather than dissociative as observed for some other cobalt(III) complexes.Senior author.     

Polymerization of methyl methacrylate using isatoic anhydride–bromine donor–acceptor complex as the photoinitiator

Isatoic anhydride (IA) alone did not initiate photopolymerization of methyl metacrylate (MMA) at 40°C when exposed to visible light for about 180 min. But IA, when used in combination with bromine (Br₂) as the initiator, initiated the photopolymerization of MMA readily under the same conditions. This behavior was explained by the formation of a donor-acceptor type of complex between IA and Br₂ in the presence of MMA. The polymerization was found to proceed via a free radical mechanism and the radical generation process was considered to follow an initial complexation reaction between the initiator components and monomer. The complex initiator showed nonideal kinetics for the present system (initiator exponent < 0.5) and was analyzed. The monomer exponents varied from 0.83 to 1.15 normally depending on the nature of solvent used. Initiator-dependent chain termination was significant as well as the bimolecular mode of chain termination. © 1993 John Wiley & Sons, Inc.     

A Sensitive Spectrophotometric Determination of Nitrite in Water and Soil

A highly sensitive spectrophotometric method for the determination of nitrite in water and soil has been developed. The reaction of nitrite with acidified potassium iodide to liberate iodine which oxidizes leuco‐crystal violet (LCV) to form crystal violet having absorption maxima at 590 nm forms the bases of this method. In aqueous medium the system obeys Beer's law in the range of 0.1 to 1.0 μg per 25 mL (0.004–0.04 ppm), while in an extractive system the range is 0.025–0.25 μg in 100 mL (0.00025–0.0025 ppm). The molar absorptivity and Sandell's sensitivity were found to be 1.54 × 10⁶ 1 mol^?1 cm^?1 and 44 pg cm^?2, respectively.     

Kinetics of oxidation of ethyldigol by vanadium(V) in aqueous acidic medium

The kinetics of oxidation of ethyldigol by vanadium(V) in aqueous acidic medium has been carried out. The reaction is first order with respect to vanadium(V) and the substrate and is acid catalysed.Hammett acidity function (H ₀) andBunnett hypothesis have been applied. The formation of free radicals during the course of the reaction has been indicated. A probable reaction mechanism is proposed.

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Die Kinetik der Oxidation von Ethyldigol mit Vanadium(V) in wäßrigem saurem Medium

Zusammenfassung Es wurde die Kinetik der Oxidation von Ethyldigol mittels Vanadium(V) in wäßriger saurer Lösung untersucht. Die Reaktion ist erster Ordnung bezüglich Vanadium(V) und Substrat und ist säurekatalysiert. Es wurden dieHammett-Aciditätsfunktion (H ₀) und dieBunnett-Hypothese angewandt. Die Bildung von freien Radikalen während der Reaktion konnte bestätigt werden. Es wird ein Reaktionsmechanismus vorgeschlagen.

     

Studies in inorganic polyelectrolytes — Part II

Viscosity behaviour of several samples ofGraham's salt with varying molecular weight has been studied. Reduced viscosity (η _sp /c) versus concentration curves were found to be characteristic of polyelectrolytes. They are dependent on the molecular weight and can be reduced to straight lines by plotting the reciprocal of the reduced viscosity against the square root of concentration. The intrinsic viscosities obtained by extrapolation were found to be proportional to the square of molecular weights. The value of reduced viscosity at any particular concentration in the concentration range between 0.25% and 4.0% was linearly related to the molecular weight. Reduced viscosities were found to decrease considerably on addition of electrolytes. Reduced viscosity versus added salt concentration curves were remarkably molecular weight dependent. The p_H of the medium seemed to have no effect at all. Bivalent salts reduce the viscosity to a much greater extent than monovalent ones. By keeping the concentration of the added salt constant and varying that ofGraham's salt, curves showing hump which disappeared at higher concentration of the added salt, were obtained. In the action of electrolytes the more important factor is the valency of cation rather than the ionic strength of the medium. Most observations confirm the already well-establishedFolding-Chain Theory of polyelectrolytes developed byKatchalsky, Fuoss and others.