The Tausk Controversy on the Foundations of Quantum Mechanics: Physics, Philosophy, and Politics

In 1966 the Brazilian physicist Klaus Tausk (b. 1927) circulated a preprint from the International Centre for Theoretical Physics in Trieste, Italy, criticizing Adriana Daneri,Angelo Loinger,and Giovanni Maria Prosperi’s theory of 1962 on the measurement problem in quantum mechanics. A heated controversy ensued between two opposing camps within the orthodox interpretation of quantum theory, represented by Léon Rosenfeld and Eugene P.Wigner. The controversy went well beyond the strictly scientific issues, however, reflecting philosophical and political commitments within the context of the Cold War, the relationship between science in developed and Third World countries, the importance of social skills, and personal idiosyncrasies.     

Enantioselectivity in Ni(II) Schiff-base complexes derived from amino-acids and (S)-o-N-(N-benzylprolyl)aminobenzophenone: molecular structure of several chiral Ni(II) Schiff-base complexes, circular dichroism and molecular mechanics studies

Several Ni(II) complexes derived from (S)-o-N-(N-benzylprolyl)aminobenzophenone ((S)-BBP) and amino acids of general formula [Ni((S)-BBP-L-(or D-)-aa)] were prepared. The crystal and molecular structures of [Ni((S)-BBP-Gly)], [Ni((S)-BBP-L-Ser)] and [Ni((S)-BBP-L-aaIm)](aaIm =L-2-amino-3-(imidazol-1-yl)propanoate were determined by X-ray diffraction analysis. In the three complexes the nickel atoms display a square-planar coordination and the overall structure around the metal indicates that the entire Schiff-base ligands form quite rigid frameworks. Molecular mechanics calculations were carried out for complexes [Ni((S)-BBP-Gly)], [Ni((S)-BBP-Ser)] and [Ni((S)-BBP-aaIm)] containing either the L- or D-amino acid forms, and the factors controlling the stereoselectivity are discussed. Several other [Ni((S)-BBP-L-aa)] complexes are also prepared and their circular dichroism spectra in solution and of the solids dispersed in KBr disks are measured and discussed. In agreement with other studies in solution with similar [Ni((S)-BBP-aa)] complexes, the Cotton effects for the bands with lambda(max) at 520--530 nm are positive when the amino acids have the L-configuration at the alpha-carbon. The same is observed in this work for the solid-state CD spectra of all compounds.     

Automation of a Mass Flow Controller for Application in Time‐Multiplex SF6+CH4 Plasma Etching of Silicon

In this work is proposed the automation of a gas injection (mass flow) system in order to generate timemultiplex SF₆/CH₄ radiofrequency plasma applied for silicon (Si) etching process. The control of the gas injection system is important in order to better control the process anisotropy, i.e., the high‐aspect‐ratio of mask pattern transfer to substrate surface. In other words, this control allows the attainment of deep Si etching process. Here, the automation of the gas injection system was realized through the interface between a computer and a data acquisition board. The automation software developed allows controlling the gas flow rate switching it on and off during whole process through the use of a square waveform routine, intermittent flow, beyond the conventional condition of a fixed value for gas flow rate, continuous flow. In order to investigate the time‐multiplex SF₆/CH₄ plasma etching of Si, the residual gas analysis was performed. The investigations were made keeping the following process parameters: flow of SF₆: 10 sccm, flow of CH₄: 6 sccm, 100 W rf power, wave period: 20 sec. It were monitored the partial pressure of SF⁺ ₅ (parent neutral specie: SF₆), CH⁺₄ (CH4) and SiF+ ₃ (SiF4) species as a function of time for different gas flow switching and duty cycle. The results showed that with the generation of plasma occurs a drastic change in behavior of partial pressures of SF⁺ ₅ and CH⁺₄ species. Moreover, it is evidenced that the interactions between the SF₆ and CH₄ fragments promotes a high production rate of HF molecule and consequently a decrease of atomic fluorine, mainly when plasma is on. Finally, the behavior of partial pressure of SiF⁺ ₃ specie for alternatively intermittent SF₆ and CH₄ flow operation shows us that both the etching processes and the deposition of a polymer passivation layer are occurring alternatively, a desirable feature for multi‐step etching process (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Experimental and theoretical investigation of the micellar-assisted solubilization of ibuprofen in aqueous media

Surfactants can be used to increase the solubility of poorly soluble drugs in water and to increase drug bioavailability. In this article, the aqueous solubilization of the nonsteroidal, antiinflammatory drug ibuprofen is studied experimentally and theoretically in micellar solutions of anionic (sodium dodecyl sulfate, SDS), cationic (dodecyltrimethylammonium bromide, DTAB), and nonionic (dodecyl octa(ethylene oxide), C12E8) surfactants possessing the same hydrocarbon "tail" length but differing in their hydrophilic headgroups. We find that, for these three surfactants, the aqueous solubility of ibuprofen increases linearly with increasing surfactant concentration. In particular, we observed a 16-fold increase in the solubility of ibuprofen relative to that in the aqueous buffer upon the addition of 80 mM DTAB and 80 mM C12E8 but only a 5.5-fold solubility increase upon the addition of 80 mM SDS. The highest value of the molar solubilization capacity (chi) was obtained for DTAB (chi = 0.97), followed by C12E8 (chi = 0.72) and finally by SDS (chi = 0.23). A recently developed computer simulation/molecular-thermodynamic modeling approach was extended to predict theoretically the solubilization behavior of the three ibuprofen/surfactant mixtures considered. In this modeling approach, molecular-dynamics (MD) simulations were used to identify which portions of ibuprofen are exposed to water (hydrated) in a micellar environment by simulating a single ibuprofen molecule at an oil/water interface (modeling the micelle core/water interface). On the basis of this input, molecular-thermodynamic modeling was then implemented to predict (i) the micellar composition as a function of surfactant concentration, (ii) the aqueous solubility of ibuprofen as a function of surfactant concentration, and (iii) the molar solubilization capacity (chi). Our theoretical results on the solubility of ibuprofen in aqueous SDS and C12E8 surfactant solutions are in good agreement with the experimental data. The ibuprofen solubility in aqueous DTAB solutions was somewhat overpredicted because of challenges associated with accurately modeling the strong electrostatic interactions between the anionic ibuprofen and the cationic DTAB. Our results indicate that computer simulations of ibuprofen at a flat oil/water interface can be used to obtain accurate information about the hydrated and the unhydrated portions of ibuprofen in a micellar environment. This information can then be used as input to a molecular-thermodynamic model of self-assembly to successfully predict the aqueous solubilization behavior of ibuprofen in the three surfactant systems studied.     

Prediction of vapor–liquid and liquid–liquid equilibria for polymer systems: Comparison of activity coefficient models

A large number of equations of state and activity coefficient models capable of describing phase equilibria in polymer solutions are available today, but only a few of these models have been applied to different systems. It is therefore useful to investigate the performance of existing thermodynamic models for complex polymer solutions which have not yet been widely studied. The present work studies the application of several activity coefficient models [P.J. Flory, Principles of Polymer Chemistry, Cornell University Press, New York, NY, 1953; T. Oishi, J.M. Prausnitz, Estimation of solvent activities in polymer solutions using a group-contribution method, Ind. Eng. Chem. Process Design Dev. 17 (1978) 333; H.S. Elbro, A. Fredenslund, P. Rasmussen, A new simple equation for the prediction of solvent activities in polymer solutions, Macromolecules 23 (1990) 4707; G.M. Kontogeorgis, A. Fredenslund, D. Tassios, Simple activity coefficient model for the prediction of solvent activities in polymer solutions, Ind. Eng. Chem. Res. 32 (1993) 362; C. Chen, A segment-based local composition model for the Gibbs energy of polymer solutions, Fluid Phase Equilib. 83 (1993) 301; A. Vetere, Rules for predicting vapor–liquid equilibria of amorphous polymer solutions using a modified Flory–Huggins equation, Fluid Phase Equilib. 97 (1994) 43; C. Qian, S.J. Mumby, B.E. Eichinger, Phase diagrams of binary polymer solutions and blends, Macromolecules 24 (1991) 1655; Y.C. Bae, J.J. Shim, D.S. Soane, J.M. Prausnitz, Representation of vapor–liquid and liquid–liquid equilibria for binary systems containing polymers: applicability of an extended Flory–Huggins equation, J. Appl. Polym. Sci. 47 (1993) 1193; G. Bogdanic, J. Vidal, A segmental interaction model for liquid–liquid equilibrium calculations for polymer solutions, Fluid Phase Equilibria 173 (2000) 241] and activity coefficient from equations of state [F. Chen, A. Fredenslund, P. Rasmussen, Group-contribution Flory equation of state for vapor–liquid equilibria en mixtures with polymers, Ind. Eng. Chem. Res. 29 (1990) 875; M.S. High, R.P. Danner, Application of the group contribution lattice—fluids EOS to polymer solutions, AIChE J. 36 (1990) 1625]. The evaluation of these models was carried out both at infinite dilution and at finite concentrations and the results compared to experimental data. Furthermore, liquid–liquid equilibrium predictions for binary polymer solutions using six activity coefficient models are compared in this work. The parameters were estimated for all the models to achieve the best possible representation of the reported experimental equilibrium behavior.     

Robust branch-cut-and-price for the Capacitated Minimum Spanning Tree problem over a large extended formulation

This paper presents a robust branch-cut-and-price algorithm for the Capacitated Minimum Spanning Tree Problem (CMST). The variables are associated to q-arbs, a structure that arises from a relaxation of the capacitated prize-collecting arborescence problem in order to make it solvable in pseudo-polynomial time. Traditional inequalities over the arc formulation, like Capacity Cuts, are also used. Moreover, a novel feature is introduced in such kind of algorithms: powerful new cuts expressed over a very large set of variables are added, without increasing the complexity of the pricing subproblem or the size of the LPs that are actually solved. Computational results on benchmark instances from the OR-Library show very significant improvements over previous algorithms. Several open instances could be solved to optimality.     

Vanadium complexes immobilized on solid supports and their use as catalysts for oxidation and functionalization of alkanes and alkenes

This review mainly discusses the immobilization strategies that have been used for vanadium complexes, typically mesoporous material, zeolites and polymers, the characterization procedures for the obtained materials, and their catalytic applications. The retention of the active metal compound within the catalyst may be based on (i) adsorption, (ii) the formation of covalent bonds between metal ligand and support, (iii) ion exchange, (iv) encapsulation, or (v) entrapment. The heterogenized complexes are used as catalysts for oxidations and functionalization of alkanes, alkenes and other substrates, and an account of the various applications reported is given.     

The speciation of vanadium in human serum

A knowledge of the speciation of vanadium in human serum is essential for an understanding of the biotransformation of antidiabetic vanadium complexes in human blood and of how vanadium is transported to the target cells. Such information may be acquired by two completely different approaches: separation techniques and modeling calculations. This review focuses on the latter.The two major metal ion binders in human serum are apotransferrin (apoTf) and human serum albumin (HSA), the interactions of which with V^IVO and V^V are discussed in detail. A partially new model for HSA–V^IVO interactions is introduced, in which the two binding sites (one for two and one for one metal ion) compete not only with each other, but also with hydrolysis of the metal ion.Focus is also placed on the possibility and importance of ternary complex formation between V^IVO, serum proteins and drug candidate ligands (maltol (mal), 1,2-dimethyl-3-hydroxy-4(1H)-pyridinone (dhp), acetylacetone (acac) and picolinic acid, (pic)): the structures and formation constants of different ternary complexes reported by the different research groups are critically reviewed.The serum speciations for V^IVO and V^V are calculated through use of the most recent stability constants; at biologically relevant concentrations (～1 μM, but definitely <10 μM) the apoTf complexes predominate for both metal ions. This has the consequences that the primary role of the drug candidate ligands of the original complexes is a carrier function until the vanadium is taken up into the serum, and the vanadium ion itself is the active metabolite responsible for the antidiabetic effect.     

On lévy measure and integrability of the norm in C[0, 1]

We prove that integrability of the norm is the best sufficient condition in terms of integrability of functions of the norm for a positive measure to be a Lévy Measure in C[0, 1].