Prediction of the cloud point of polyethoxylated surfactants and their mixtures by the thermodynamic model of Flory-Huggins-Rupert

The cloud point curves of polyethoxylated surfactants are established experimentally. These experimental data are preliminary to the development of the cloud point extraction process, which appears as an interesting alternative to the usual solvent extraction unit operation. Starting from the thermodynamic model developed by Flory and Huggins for phase separation of polymer aqueous solutions, this paper aims at the prediction of cloud point curves. In this work, Rupert’s approach is extended to commercial nonionic surfactants, mixtures of homologous species, namely a few alkylphenol and alcohol ethoxylates. The limit of such an approach is clearly demonstrated, provided that a fitting parameter is finally required for a successful model application to pilot-plant manufactured surfactants, like C₈ΦE_n (n?=?7.5, 10, 12), C₉ΦE_n (n?=?8, 10, 12), C₁₂E₄, C₁₂E₆ and commercial Tergitol 15-S-7 (linear C₁₂-C₁₄ secondary alcohol with an average of 7 ethylene oxide units).GRAPHICAL ABSTRACT     

Dipole-dipole plasmon interactions in gold-on-polystyrene composites

Red-shifting of the optical absorption spectra of aggregates of gold nanoparticles by dipole-dipole interactions is of considerable interest, both for theoretical reasons and because the phenomenon can be potentially exploited in various applications. A convenient and practical way to control the effect is to assemble the aggregated ensemble of n gold nanoparticles on the outer surface of larger dielectric spheres. Here, we show by experiment and calculation how the spectra of these structures can be systematically morphed from that of isolated gold particles, through the regime of broad absorption dominated by particle-particle interactions, and finally to the limiting case of a continuous nanoshell. The experimental data were produced using the process of deposition-precipitation, which provides a facile method to decorate polystyrene microspheres with gold nanoparticles. There is no need for prior functionalization of the microsphere surface in our method of deposition-precipitation. Calculations were carried out using a code based on the discrete dipole approximation (DDA). The spectra were dominated by three effects. These were a peak absorption at about 540 nm produced by the conventional plasmon resonance of spherical gold nanoparticles, a broad absorption in the range 600-900 nm caused by diverse dipole-dipole interactions between particles, which strengthened as the number of attached gold particles increased and finally, when n was large, an absorption peak due to the onset of nanoshell-like resonances. The experimental spectra could be successfully fitted by spectra calculated using combinations of these effects.     

Fluorination of poly(p-phenylene) using TbF4 as fluorinating agent

The fluorination using TbF₄ as fluorinating agent was successfully performed on poly(p-phenylene). The method allows the fluorine content of the polymer to be controlled and the formation of structural defects, such as dangling bonds, to be significantly decreased by comparison with the direct fluorination using pure F₂ gas. The aromatic character of the phenyl ring is partly maintained through the fluorination contrary to the direct fluorination (using pure F₂ gas), for which a quasi-perfluorination and a partial decomposition of the polymer occur. Complementary analytical techniques have been used, such as ¹⁹F and ¹³C solid state NMR, FT-IR and EPR to compare the samples as a function of the reaction conditions.     

Second-Harmonic-generation studies of inclined thin films

The nonlinear surface susceptibility _S ⁽²⁾ is generally referred to the system of Cartesian coordinates of thesample. However, since actual measurements take place with respect to thelaboratory system of coordinates, appropriate transformation of _S ⁽²⁾ is necessary to deduce the underlying susceptibility-components. We demonstrate this by analyzing the second-harmonic signal generated by an inclined sample upon rotation around thes-axis of the laboratory system of coordinates. The sample consists of two Langmuir-Blodgett-type monolayers of rotational symmetry around the sample normal, the two layers being separated by a plane-parallel flat of 1 mm thickness. The occurrence of a symmetry-forbiddenI _SS ² -signal is discussed in detail.     

Catalytic transfer hydrogenation with terdentate CNN ruthenium complexes: the influence of the base

The catalytic activity of the terdentate complex [RuCl(CNN)(dppb)] (A) [dppb=Ph(2)P(CH(2))(4)PPh(2); HCNN=6-(4'-methylphenyl)-2-pyridylmethylamine] in the transfer hydrogenation of acetophenone (S) with 2-propanol has been found to be dependent on the base concentration. The limit rate has been observed when NaOiPr is used in high excess (A/base molar ratio > 10). The amino-isopropoxide species [Ru(OiPr)(CNN)(dppb)] (B), which forms by reaction of A with sodium isopropoxide via displacement of the chloride, is catalytically active. The rate of conversion of acetophenone obeys second-order kinetics v=k[S][B] with the rate constants in the range 218+/-8 (40 degrees C) to 3000+/-70 M(-1) s(-1) (80 degrees C). The activation parameters, evaluated from the Eyring equation are DeltaH(++)=14.0+/-0.2 kcal mol(-1) and DeltaS(++)=-3.2 +/-0.5 eu. In a pre-equilibrium reaction with 2-propanol complex B gives the cationic species [Ru(CNN)(dppb)(HOiPr)](+)[OiPr](-) (C) with K approximately 2x10(-5) M. The hydride species [RuH(CNN)(dppb)] (H), which forms from B via beta-hydrogen elimination process, catalyzes the reduction of S and, importantly, its activity increases by addition of base. The catalytic behavior of the hydride H has been compared to that of the system A/NaOiPr (1:1 molar ratio) and indicates that the two systems are equivalent.     

Density functional restricted-unrestricted approach for nonlinear properties: application to electron paramagnetic resonance parameters of square planar copper complexes

The density functional restricted-unrestricted approach for treatments of spin polarization effects in molecular properties using spin restricted Kohn-Sham theory has been extended from linear to nonlinear properties. It is shown that the spin polarization contribution to a nonlinear property has the form of a quadratic response function that includes the zero-order Kohn-Sham operator, in analogy to the lower order case where the spin polarization correction to an expectation value has the form of a linear response function. The developed approach is used to formulate new schemes for computation of electronic g-tensors and hyperfine coupling constants, which include spin polarization effects within the framework of spin restricted Kohn-Sham theory. The proposed computational schemes are in the present work employed to study the spin polarization effects on electron paramagnetic resonance spin Hamiltonian parameters of square planar copper complexes. The obtained results indicate that spin polarization gives rise to sizable contributions to the hyperfine coupling tensor of copper in all investigated complexes, while the electronic g-tensors of these complexes are only marginally affected by spin polarization and other factors, such as choice of exchange-correlation functional or molecular structures, will have more pronounced impact on the accuracy of the results.     

How Crystal Symmetry Dictates Non-Local Vibrational Circular Dichroism in the Solid State

Solid-State Vibrational Circular Dichroism (VCD) can be used to determine the absolute structure of chiral crystals, but its interpretation remains a challenge in modern spectroscopy. In this work, we investigate the effect of a twofold screw axis on the solid-state VCD spectrum in a combined experimental and theoretical analysis of P2₁ crystals of (S)-(+)-1-indanol. Even though the space group is achiral, a single proper symmetry operation has an important impact on the VCD spectrum, which reflects the supramolecular chirality of the crystal. Distinguishing between contributions originating from molecular chirality and from chiral crystal packing, we find that while IR absorption hardly depends on the symmetry of the space group, the situation is different for VCD, where completely new non-local patterns emerge. Understanding the two underlying mechanisms, namely gauge transport and direct coupling, will help to use VCD to distinguish polymorphic forms.     

Mechanically tunable phononic band gaps in three-dimensional periodic elastomeric structures

Three-dimensional periodic structures have many applications in acoustics and their properties are strongly related to structural details. Here we demonstrate through simulations the ability to tune the phononic band gaps of 3D periodic elastomeric structures using deformation. The elastomeric nature of the material makes the transformation of the band gaps a reversible and repeatable process, providing avenues for the design of tunable 3D phononic crystals such as sonic switches.     

Characterization and catalytic activity of iron(III) mono(4-N-methyl pyridyl)-tris(halophenyl) porphyrins in homogeneous and heterogeneous systems

The synthesis, characterization and catalytic activity of the cationic iron porphyrins Fe[M(4-N-MePy)TDCPP]Cl₂ and Fe[M(4-N-MePy)TFPP]Cl₂ in the epoxidation of (Z)-cyclooctene by PhIO in homogeneous solution and supported on silica gel (SG), imidazole propyl gel (IPG) or SG modified with 2-(4-sulfonatophenyl)ethyl groups (SiSO₃) have been accomplished. When supported on IPG, both cationic FeP bind to the support via Fe–imidazole coordination. Fe[M(4-N-MePy)TDCPP]IPG contains a mixture of low-spin bis-coordinated Fe^IIIP and high-spin mono-coordinated Fe^IIIP species, whereas Fe[M(4-N-MePy)TFPP]IPG only contains high-spin mono-coordinated Fe^IIIP. These FePIPG catalysts also contain Fe^IIP species, whose presence was confirmed by EPR spectroscopy using NO as a paramagnetic probe. Both cationic FePs coordinate to SG through Fe–O ligation and they are present as high-spin Fe^IIIP species. The cationic FePs supported on SiSO₃⁻ are also high-spin Fe^IIIP species and they bind to the support via electrostatic interaction between the 4-N-methylpyridyl groups and the SO₃⁻ groups present on the matrix. In homogeneous solution, both Fe[M(4-N-MePy)TDCPP]Cl₂ and Fe[M(4-N-MePy)TFPP]Cl₂ have similar catalytic activity to Fe(TDCPP)Cl and Fe(TFPP)Cl, leading to cis-epoxycyclooctane yields of 92%. When supported on inorganic matrices, both FePs lead to epoxide yields comparable to their homogeneous analogues and their anchoring enables catalyst recovery and re-use. Recycling of Fe[M(4-N-MePy)TDCPP]SiSO₃⁻ shows that this FeP maintains its activity in a second reaction.