Physicochemical studies on hydrophobic PEO‐PPO‐PEO triblock copolymer micelles in SDS micellar environment

The shape, size, aggregation, hydration, and correlation times of water insoluble PEO‐PPO‐PEO triblock copolymer micelles with sodium dodecylsulfate (SDS) micelles were investigated using transport studies and dynamic light scattering technique. From the conductance of micellar solutions of the polymer in 25 mM SDS and 5 mM NaCl, the hydration of polymer micelles were determined using the principle of obstruction of electrolyte migration by the polymer. The asymmetry of the micellar particles of polymer and polymer‐SDS mixed micellar systems in 5 mM NaCl and their average axial ratios were calculated using intrinsic viscosity and hydration data obeying Simha–Einstein equation. Hydration number and micellar sizes were variable with temperature. The shape of the polymer micelles has been ellipsoidal rather than spherical. The micellar volume, hydrodynamic radius, radius of gyration, diffusional coefficients as well as translational, rotational and effective correlation times have been calculated from the absolute values of the axes. The partial molal volume of polymer micelles has also been determined and its comparison with the molar volume of pure polymer suggested a volume contraction due to immobilization of the water phase by the hydrophilic head groups of the polymer. The thermodynamic activation parameters for viscous flow favor a more ordered water structure around polymer micelles at higher temperatures. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2410–2420, 2007     

Water wave radiation by a sphere submerged in water with an ice-cover

Using the multipoles method, we formulate the problems of radiation (both heave and sway) of water waves by a submerged sphere in deep as well as in uniform finite depth water with an ice-cover, with the ice-cover being modelled as an elastic plate of very small thickness. In each case this leads to an infinite system of linear equations which are solved numerically by standard techniques. The added-mass and damping coefficients for a heaving and swaying sphere are obtained and depicted graphically against the wave number for various values of the radius of the submerged sphere and flexural rigidity of the ice-cover to show the effect of the presence of ice-cover on these quantities. When the flexural rigidity is taken to be zero, the numerical results for the added-mass and damping coefficient for water with a free surface are recovered.     

Chain-transfer constant of fluoroalcohols

Chain transfer constants of some fluoroalcohols [HCF₂(CF₂)_n?1CH₂OH, n = 2, 4, 6] in the catalyzed polymerization of vinyl acetate, styrene, acrylonitrile, and methyl methacrylate at 60°C have been evaluated by a method based on degree of polymerization. Since fluoroalcohols are normally nonsolvents for polymers, a homogeneous reaction phase is maintained by carrying out the polymerization in benzene (except in case of acrylonitrile, where no solvent was used). The transfer constants vary, depending on the reactivity as well as the polarity of the radicals, in the following order: vinyl acetate > styrene > methyl methacrylate > acrylonitrile. Of the three fluoroalcohols studied, the transfer constants increase with the increasing value of n. The results have been interpreted in terms of polar structure contribution in the transition state of the transfer reactions.     

Anomalies in the asymmetric hydroboration of olefins with the 11 adduct of (+)-α-pinene and BH3 · THF

The hydroboration of cis-2-butene and cis-3-hexene with pure diisopinocampheylborane (IPC₂BH) and monoisopinocampheylborane (IPCBH₂), both prepared from (+)-α-pinene, were studied. In contrast to IPC₂BH, which yielded R-(?)-2-butanol and R-(?)-3-hexanol in 98.4 and 94.5% optical purities, IPCBH₂ yielded S-(+)-2-butanol and S-(+)-3-hexanol in 23.6 and 19.7% optical purifies respectively. PMR examination of the methanolyzed products were utilized to establish the species present in the freshly prepared and aged $\text{1}\text{1}$ adduct from (+)-α-pinene and BH₃ · THF. The results confirm the interpretation previously advanced for the major differences realized in asymmetric hydroboration with the fresh and aged $\text{1}\text{1}$ adducts.     

Synthesis and molecular structure of a substituted 8-oxa-10-azatricyclo [7.3.1.0]tridecatetraene

10,11-Dimethyl-9-(coumarin-3 -yl)-12-ethoxycarbonyl-8-oxa-10-azatricyclo[7,3,1.0^2.7]trideca-2,4,6-11-tetraene was isolated from the mixture of products from the condensation of salicyl aldehyde with acetoacetic ester and methylamine. Its molecular structure has been established by x-ray crystallography.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 259–264, February, 1996.     

Mechanism and kinetics of thermal decomposition of precipitates of the zinc oxide-aluminium oxide system from non-isothermal tg curves

Kinetics of decomposition of the precipitates of the ZnO&2sbndAl₂O₃ system, prepared by coprecipitation and mechanical mixing of the individual precipitates, have been studied. The decomposition of zinc basic carbonate is a first order rate process with an activation energy of 34.5 kcal/mole (Coats and Redfern equation). The decomposition of aluminium hydroxide is also best described as a first order rate process with one break in the Coats and Redfern plot corresponding to activation energies of 29.4 and 8.3 kcal/mole respectively. The entire course of decomposition of coprecipitated as well as mechanically mixed samples cannot be described by any one of the many rate equations available. Consequently, the Coats and Redfern equation has been employed. The plots indicate one or two breaks and thus two to three values of activation energy are reported. From the results it is to be concluded that decomposition of these precipitates is a heterogeneous process. The first step is definitely the decomposition of zinc basic carbonate followed by decomposition of aluminium hydroxide and/or interaction of the two precipitates resulting in the formation of “precursor” to spinel. The results of our earlier investigation on the same system (especially the formation of precursors) are well supported by the results reported in this investigation. p]A new equation (a modified form of the Elovich equation) has been proposed for such heterogeneous decomposition processes. The proposed equation also appears to be the general form of the equations where diffusion is the rate controlling process.     

Vinylation and polymerization with trivinylaluminum. I. Vinylation of organic halides as a model for termination in cationic polymerization leading to vinyl end groups

An improved synthesis of trivinylaluminum (V₃Al) is described. The proton magnetic resonance (PMR) spectrum of V₃Al was recorded and analyzed. A new vinylation method involving the use of V₃Al as the vinylating agent has been developed, and the vinylation of organic halides by V₃Al was studied at ?30, ?50 and ?70°C. Primary alkyl chlorides, such as methyl and methylene chloride, do not react with V₃Al and were used as solvents. Secondary chlorides such as 2-chloropropane also do not react. t-Butyl chloride gives rise to t-butylethylene (70–98%), depending on reaction conditions, and the allylic chlorides, 3-chloro-1-butene, and 3-chloro-3-methyl-1-butene, yield the expected vinylated products and their isomers (～90%). Allyl and benzyl chloride do not react under the conditions tried. The reaction between V₃Al and the ditertiary dichloride 2,6-dichloro-2,6-dimethylheptane yields several isomeric C₁₃H₂₄ and C₁₁H₂₀ hydrocarbons; however, surprisingly, C₉H₁₆ does not form. The C₁₃ hydrocarbons arise by divinylation at the termini of the dichloride, while the C₁₁ hydrocarbons are formed by vinylation at one and proton elimination at the other terminus of the dichloride. The presence of unsaturated C₁₃H₂₄ and C₁₁H₂₀ isomers is most likely due to proton induced isomerization. These results are explained by a proximity effect involving vinylation at one end of the dichloride by V₃Al followed by rapid reaction of the second chlorine (mostly) by V₂AlCl generated in situ during the first vinylation in the proximity of the chloride. At the other chlorine terminus V₂AlCl causes either a second vinylation (leading to C₁₃ hydrocarbons) or a proton elimination (leading to C₁₁ hydrocarbons). The absence of C₉H₁₆ among the reaction products indicates that V₃Al exclusively effects vinylation. The RCl + V₃Al ← RV + V₂AlCl reaction may be regarded as a model for initiation followed by immediate termination in cationic olefin polymerization, a process leading to vinyl-ended polymers.     

Absorption and fluorescence behavior of cytosine irradiated at different pH and in the presence of Cu(II) ions at neutral pH

Dilute aqueous solutions of cytosine were irradiated with⁶⁰Co -rays under N₂O saturated conditions at different pH and in the presence of Cu(II) ions at neutral pH. The base degradation decreased from neutral to acidic and basic conditions. In the presence of metal ions at neutral pH conditions there was a significant increase in the base degradation compared to that in the absence of metal ions under similar conditions. From the difference absorption spectra and fluorescence behavior of the irradiated solutions it was observed that the major radiolytic products of cytosine under different conditions are cytosine glycols, 5-hydroxycytosine, hydroxy-hydrocytosine and cytosine dimers. The yields of dimers is maximum in neutral conditions and it decreased from basic to acidic conditions. However, in the presence of Cu(II) ions formation of cytosine dimers is completely restricted and there is an increase in the yields of cytosine glycol, hydroxy-hydrocytosine and 5-hydroxycytosine. From the post-radiolytic changes in absorption and fluorescence behavior of irradiated solutions, it is revealed that some of the radiolytic products, namely cytosine glycol and hydroxy-hydrocytosine decompose to 5-hydroxycytosine and cytosine, respectively.     

Construction and studies of a new class of reciprocal trees: interknitting of the Pascal's triangle

A method of construction of a new class of trees with reciprocal pairs of eigenvalues (λ, 1/λ) has been developed. They are derived from star graphs and can be symbolized as K _{1, n ?1} + n(p) + mK ₂ (1 ≤ m ≤ n ? 1 except for n = 1). The trees are minimally Kekulenoid and hence contain reciprocal pairs of eigenvalues in their eigenspectra. The characteristic polynomial coefficients of these trees with given values of n and m are shown to be obtainable by appropriate use of the Pascal's triangle. A general formula for this purpose has been developed. An analytical formula for the Wiener indices of such trees in terms of m and n has been derived and some consequences of this formula are presented. The relevance of these trees to real molecular structures is discussed. The trees have been shown to be useful in observing the subspectrallity of two series of IPR fullerenes of formulae C_{50+10 n} and C_{60+12 n} (n is a positive integer).