Hydrophobic guar gum derivatives prepared by controlled grafting processes–Part II: rheological and degradation properties toward fracturing fluids applications

Introduction of polyalkoxyalkyleneamide grafts to guar gum produces new water soluble guar derivatives as described in an earlier publication. 10 In this paper, the rhelogical behavior of these products was explored in more detail at 25 and 65°C. In addition, the viscosity was measured at high temperatures (90 and 120°C) and pressure (150 psi) to partially simulate the down hole conditions of oil wells. Upon treatment with zirconium lactate, the cross‐linked hydrophobically‐modified CMG derivatives exhibited better high‐temperature stability and higher gel viscosities than the corresponding CMHPG derivatives. The cross‐linked gel viscosities indicate that gels will be capable of supporting a high proppant carrying capacity. To facilitate removal of the gels from the formation, the hydrophobically modified derivatives were treated with an enzyme breaker system which produced fragments capable of producing stable emulsions when extracted with toluene. Thus, the clean up process will be enhanced by emulsification of the gel fragments produced by the gel hydrolysis. The low viscosities of the linear derivatives, the rapid formation of high viscosity gels upon cross‐linking and generation of emulsifiers during the gel removal suggest that these new derivatives are good candidates for fracturing fluid applications. Copyright © 2007 John Wiley & Sons, Ltd.     

Chromium-salen-mediated alkene epoxidation: a theoretical and experimental study indicates the importance of spin-surface crossing and the presence of a discrete intermediate

The mechanism of alkene epoxidation by chromium(v) oxo salen complexes has been studied by DFT and experimental methods. The reaction is compared to the closely related Mn-catalyzed process in an attempt to understand the dramatic difference in selectivity between the two systems. Overall, the studies show that the reactions have many similarities, but also a few critical differences. In agreement with experiment, the chromium system requires a change from low- to high-spin in the catalytic cycle, whereas the manganese system can proceed either with spin inversion or entirely on the high-spin surface. The low-spin addition of metal oxo species to an alkene leads to an intermediate which forms epoxide either with a barrier on the low-spin surface or without a barrier after spin inversion. Supporting evidence for this intermediate was obtained by using vinylcyclopropane traps. The chromium(v) oxo complexes can adopt a stepped shape or form a more concave surface, analogous to previous results on manganese salen complexes.     

Application of Bender's salts to the synthesis of S-vinyl-O-tert-alkylthiocarbonates

Three thermally labile Bender's salts were synthesized and utilized to effect quantitative S_N2 displacement of primary halides to form tert-alkylthiocarbonate derivatives. Selective displacement of bromide from 1,2-bromochloroethane by either VI or VII followed by dehydrohalogenation with potassium tert-butoxide yielded S-vinyl-O-tert-butylthiocarbonate (I) and S-vinyl-O-tert-amylthiocarbonate (X), two excellent vinyl monomer precursors for polymercaptan, in 62 and 51% yield, respectively. Reaction of VI with vinylbenzyl chloride yielded S-(vinylbenzyl)-O-tert-butylthiocarbonate which polymerized in the presence of free radical initiators to produce a poly(vinylbenzyl mercaptan) precursor. Dilatometric studies of the homopolymerization of I demonstrated that the polymerization rate was proportional to [I]^0.765 and [M]^1.7, respectively; the monomer exhibited a high chain transfer constant (C_M = 3.9 × 10^?3).     

Multiple periodic solutions for a nonlinear suspension bridge equation

We investigate nonlinear oscillations in a fourth-order partialdifferential equation which models a suspension bridge. Previouswork establishes multiple periodic solutions when a parameterexceeds a certain eigenvalue. In this paper, we use Leray-Schauderdegree theory to prove that if the parameter is increased further,beyond a second eigenvalue, then additional solutions are created.     

Hörmander multipliers on two-dimensional dyadic Hardy spaces

In this paper we are interested in conditions on the coefficients of a two-dimensional Walsh multiplier operator that imply the operator is bounded on certain of the Hardy type spaces Hp, 0<p<∞. We consider the classical coefficient conditions, the Marcinkiewicz-Hörmander-Mihlin conditions. They are known to be sufficient for the trigonometric system in the one and two-dimensional cases for the spaces Lp, 1<p<∞. This can be found in the original papers of Marcinkiewicz [J. Marcinkiewicz, Sur les multiplicateurs des series de Fourier, Studia Math. 8 (1939) 78-91], Hörmander [L. Hörmander, Estimates for translation invariant operators in Lp spaces, Acta Math. 104 (1960) 93-140], and Mihlin [S.G. Mihlin, On the multipliers of Fourier integrals, Dokl. Akad. Nauk SSSR 109 (1956) 701-703; S.G. Mihlin, Multidimensional Singular Integrals and Integral Equations, Pergamon Press, 1965]. In this paper we extend these results to the two-dimensional dyadic Hardy spaces.     

The structure of the side chain of the frog alkaloid pumiliotoxin B

The E configuration at the double bond and $\text{threo}$ relation for diol moiety of the pumiliotoxin B side chain were defined, respectively, through nuclear- Overhauser effects and comparison with model $\text{threo}$- and $\text{erythro}$- diol compounds.     

High-yield catalytic metathesis of alkenyl tosylates with applications in organic synthesis

Alkenyl tosylates of the type RCHCH(CH₂)_nOTs [RH, n=9; RH, n=7; and RCH₃(CH₂)₇, n=8] undergo metathesis using a WCl₆-Me₃SnCl catalyst system, producing difunctionalised alkenes of the type TsO(CH₂)_nCHCH(CH₂)_nOTs (n=7,8, and 9); examples of the use of these products in synthesis are presented.     

Effects of the detection window on the determination of organic copper speciation in estuarine waters

The complexation of copper by natural organic ligands in sea water was measured by cathodic stripping voltammetry with ligand (catechol and quinolin-8-ol) competition. Two methods to determine copper complexation in estuarine waters were compared, one based on a complete titration of the complexing capacity of the sample and the other on measurement of the labile and total dissolved metal concentrations only. Values for log α_CuL (ihe α-coefficient for complexation of Cu²⁺ by natural organic ligands) ranging from 3.2 to 7.7 and from 3.3 to 7.8 could be detected by varying long α_CuAL (the α-coefficient for complexation of Cu²⁺ by the added competing ligand) from 3.4 to 8.9 in samples from the Tamar estuary and from the Channel. The two methods gave comparable results and showed that the type of sites detected depends on the detection window of the technique. This effect is due to the sea and estuarine water samples containing a series of complexing ligands forming complexes of greatly varying strength, thus causing a rnage of complex stabilities to be measured as a function of the detection window of each technique. A comparison showed that lower values for α_CuL are obtained by anodic stripping voltammetry as a result of that technique having a lower detection window. A detailed study of the Tamar estuary revealed a decrease in log α_CuL from 10.8 to 8.3 with increasing salinity, demonstrating that major cations compete with copper for the complexing sites. The free Cu²⁺ concentrations were very low throughout the estuary (16.2 < pCu²⁺ < 18.2) even though the total measurements to establish potential toxic effects of copper in natural waters.