Solution behavior of a surfactant aldehyde–the oxidation product of an alcohol ethoxylate

It has previously been shown that alcohol ethoxylates readily undergo autoxidation and that one of the major oxidation products is the surfactant aldehyde, i.e. an ethoxylate carrying a –CH₂CHO group at the terminal end of the polyoxyethylene chain. In this work the cloud point, phase behavior and aggregation characteristics of the surfactant aldehyde produced by oxidation of C₁₂H₂₅(OCH₂CH₂)₅OH (C₁₂E₅) are determined and compared with the values obtained with the parent surfactant. It was found that the physico–chemical behavior of the two species was very similar, which indicates that a considerable portion of the aldehyde group is in hydrated state, i.e. the surfactant aldehyde consists of a mixture of aldehyde in carbonyl form and the corresponding geminal diol. The cloud point of the surfactant aldehyde decreased rapidly with time, even when it was stored at low temperature. Also the parent surfactant and its homologue C₁₂E₆ exhibited a decrease in cloud point during storage. For instance, a 1% aqueous solution of C₁₂E₆ showed a cloud point decrease from 62 to 32°C after 4 months storage at 40°C. Such a change in solution behavior can have important practical implications.     

Numerical calculation of an asymmetric supply function equilibrium with capacity constraints

Producers submit offer curves to a procurement auction, e.g. an electricity auction, before uncertain demand has been realised. In the supply function equilibrium (SFE), every firm commits to the offer curve that maximises its expected profit, given the offer curves of competitors. The equilibrium is given by a system of differential equations. In practice, it has been very difficult to find valid SFE, i.e. non-decreasing solutions, from this system, especially for asymmetric producers. This paper shows that valid SFE can be calculated by means of a shooting algorithm that combines numerical integration with an optimisation procedure that searches for an end-condition. Multiple/parallel shooting is used for ill-conditioned cases.     

Aldehyde

Ohne Zusammenfassung     

Pionic Fusion Study of the halo analogue state6Li

The isobaric analogue state of the ground state of the halo nucleus⁶He,⁶Li* has been studied in a pionic fusion experiment at the CELSIUS storage ring facility in Uppsala, Sweden. This was the first of two proposed experiments with the aim to study the high momentum part of the wave functions of the halo nuclei⁶He and⁶Li (0⁺, T=1). The Li nuclei were produced in inverse kinematics reactions with alpha particles incident on a deuterium cluster jet target. The⁶Li ions were detected in a zero-degree spectrometer situated in the fourth quadrant of the CELSIUS ring. The measurement was done for three different beam energies corresponding to 5.4, 2.2 and 1.5 MeV above threshold in the c.m. The cross-sections slowly increase with beam energy from 95 nb at the lowest energy to about 250 nb at 5.4 MeV above threshold.     

Enzymes immobilized in mesoporous silica: A physical–chemical perspective

Mesoporous materials as support for immobilized enzymes have been explored extensively during the last two decades, primarily not only for biocatalysis applications, but also for biosensing, biofuels and enzyme-controlled drug delivery. The activity of the immobilized enzymes inside the pores is often different compared to that of the free enzymes, and an important challenge is to understand how the immobilization affects the enzymes in order to design immobilization conditions that lead to optimal enzyme activity. This review summarizes methods that can be used to understand how material properties can be linked to changes in enzyme activity. Real-time monitoring of the immobilization process and techniques that demonstrate that the enzymes are located inside the pores is discussed by contrasting them to the common practice of indirectly measuring the depletion of the protein concentration or enzyme activity in the surrounding bulk phase. We propose that pore filling (pore volume fraction occupied by proteins) is the best standard for comparing the amount of immobilized enzymes at the molecular level, and present equations to calculate pore filling from the more commonly reported immobilized mass. Methods to detect changes in enzyme structure upon immobilization and to study the microenvironment inside the pores are discussed in detail. Combining the knowledge generated from these methodologies should aid in rationally designing biocatalyst based on enzymes immobilized in mesoporous materials.     

On the convergence of cross decomposition

Cross decomposition is a recent method for mixed integer programming problems, exploiting simultaneously both the primal and the dual structure of the problem, thus combining the advantages of Dantzig—Wolfe decomposition and Benders decomposition. Finite convergence of the algorithm equipped with some simple convergence tests has been proved. Stronger convergence tests have been proposed, but not shown to yield finite convergence.In this paper cross decomposition is generalized and applied to linear programming problems, mixed integer programming problems and nonlinear programming problems (with and without linear parts). Using the stronger convergence tests finite exact convergence is shown in the first cases. Unbounded cases are discussed and also included in the convergence tests. The behaviour of the algorithm when parts of the constraint matrix are zero is also discussed. The cross decomposition procedure is generalized (by using generalized Benders decomposition) in order to enable the solution of nonlinear programming problems.     

Improved description of the Van der Waals interaction in physisorption

The attractive interaction between an atom and a metal surface is calculated, taking into account the d-electron contribution to the metal response, together with an atomic polarizability going beyond the dipole approximation. A numerical calculation is presented for helium on noble metals, giving a slightly deeper physiosorption well compared to the “standard” treatment.     

Levels and transitions in126Te

The decay of¹²⁶Sb to¹²⁶Te is studied by use of Ge(Li) detectors in singles and coincidence arrangements. The gamma-gamma directional correlations of six cascades are measured. A level scheme is constructed where all transitions observed are located. The characteristics of several of the levels are assigned, on basis of the logft values deduced and the directional correlation results. Mixing ratios are deduced for three transitions. From the comparison of the relative intensities ofE1 andE2 transitions depopulating the same levels, threeE1 transitions are concluded to be strongly retarded.     

Nonisotropic L-conversion-electron — X-ray directional correlations in160Dy

The directional correlations betweenL-conversion electrons andL x-rays have been measured. The electrons were emitted in the 86.78keV 2⁺→0⁺ transition in¹⁶⁰Dy, in the decay of¹⁶⁰Tb. The experimental results areA ₂₂(e _L -x _Li )=0.085 (22),A ₂₂(e _L -x _Lα )=0.0066 (29),A ₂₂(e _L -x _Lβ )=0.0000 (27), andA ₂₂(e _L -x _Lγ )=0.0096 78). These results are in disagreement with published theoretical values. It is suggested that the discrepancy is due to a phase inconsistency in the internal conversion matrix elements and there is good agreement withA ₂₂ values calculated in this work.     

Core-electron spectroscopy of alkaline-earth and transition-metal ions in solution

Core-electron spectra of alkaline-earth and transition-metal ions in solution have been recorded. Solvation energies for the core-ionized species are derived using thermodynamic cycles which involve the free-ion to dissolved-ion binding energy shifts. The distinction between “soft” and “hard” ion behaviour is discussed in relation to the solvation energies and multi-line features in the transition-metal core spectra.