Cubic and spirocyclic radicals containing a tetraimidophosphate dianion [P(NR)3(NR')]*2-

The reaction of Cl(3)PNSiMe(3) with 3 equiv of LiHNR (R = (i)Pr, Cy, (t)Bu, Ad) in diethyl ether produces the corresponding tris(amino)(imino)phosphoranes (RNH)(3)PNSiMe(3) (1a, R = (i)Pr; 1b, R = Cy; 1c, R = (t)Bu; 1d, R = Ad); subsequent reactions of 1b-d with (n)BuLi yield the trilithiated tetraimidophosphates {Li(3)[P(NR)(3)(NSiMe(3))]} (2a, R = Cy; 2b, R = (t)Bu; 2c, R = Ad). The reaction of [((t)BuNH)(4)P]Cl with 1 equiv of (n)BuLi results in the isolation of ((t)BuNH)(3)PN(t)Bu (1e); treatment of 1e with additional (n)BuLi generates the symmetrical tetraimidophosphate {Li(3)[P(N(t)Bu)(4)]} (2d). Compounds 1 and 2 have been characterized by multinuclear ((1)H, (13)C, and (31)P) NMR spectroscopy; X-ray structures of 1b,c were also obtained. Oxidations of 2a-c with iodine, bromine, or sulfuryl chloride produces transient radicals in the case of 2a or stable radicals of the formula {Li(2)[P(NR)(3)(NSiMe(3))]LiX.3THF}* (X = Cl, Br, I; R = (t)Bu, Ad). The stable radicals exhibit C(3) symmetry and are thought to exist in a cubic arrangement, with the monomeric LiX unit bonded to the neutral radical {Li(2)[P(NR)(3)(NSiMe(3))]}* to complete the Li(3)N(3)PX cube. Reactions of solvent-separated ion pair {[Li(THF)(4)]{Li(THF)(2)[(mu-N(t)Bu)(2)P(mu-N(t)Bu)(2)]Li(THF)(2)} (6) with I(2) or SO(2)Cl(2) produce the persistent spirocyclic radical {(THF)(2)Li(mu-N(t)Bu)(2)P(mu-N(t)Bu)Li(THF)(2)}* (10a); all radicals have been characterized by a combination of variable concentration EPR experiments and DFT calculations.     

N-heterocyclic carbenes with inorganic backbones: electronic structures and ligand properties

The electronic structures of known N-heterocyclic carbenes (NHCs) with boron, nitrogen, and phosphorus backbones are examined using quantum chemical methods and compared to the experimental results and to the computational data obtained for a classical carbon analogue, imidazol-2-ylidene. The sigma-donor and pi-acceptor abilities of the studied NHCs in selected transition-metal complexes are evaluated using a variety of approaches such as energy and charge decomposition analysis, as well as calculated acidity constants and carbonyl stretching frequencies. The study shows that the introduction of selected heteroatoms into the NHC backbone generally leads to stronger metal-carbene bonds and therefore improves the ligand properties of these systems. The backdonation of pi-electron density from the metal to the ligand is found to be strong in complexes of the studied NHCs with group 11 metals, where it constitutes up to nearly 35% of the total orbital interaction energy. The ligand properties of the aluminum analogues of some of the reported NHCs with boron backbones are also assessed.     

Simulations of lesion detection using a combined phased array LHMI-technique

Ultrasound based elasticity imaging techniques have been developed during the past decades. Some of these techniques are based on an internal radiation force stimulation in which a transient or dynamic radiation force is produced by using a single or dual-frequency sonication. In addition, sonication and data acquisition can be implemented using combined or separate transducers. In this simulation study of lesion detection using localized harmonic motion imaging (LHMI), we used a combined phased array designed for simultaneous thermal ablation and lesion detection. In the sonication mode, a focused single-frequency amplitude-modulated sonication is used to induce harmonic motion and in the tracking mode, some of the array elements are used for pulse-echo tracking of the induced displacements. The results showed that the size of the lesion affected the induced displacement around the sonication point. The displacement tracking simulations demonstrated that these changes in the displacement distributions can be detected using only a few of the array elements in the tracking mode but the exact size of the lesion can not be detected accurately. The simulations also showed that two lesions having the radius of 2.5mm can be distinguished if distance between these lesions is at least 2.5mm.     

Electron microscopy studies on the coil-to-globule transition of a polyelectrolyte in a water–acetone mixture

A high molar mass polycation poly(methacryloylethyl trimethylammonium methylsulphate), PMETMMS, dissolved in mixtures of water and acetone, was studied using light scattering during the reversible coil-to-globule transition. When the mass fraction of acetone in the solvent mixture, γ, is higher than 0.80, PMETMMS adopts a globular state but does not aggregate. The collapse of PMETMMS can also be induced by the dilution of the polymer solution, if 0.70 ≤ γ < 0.80, and the solvent composition is kept constant. The results obtained by light scattering have been confirmed using a transmission electron microscope with which the collapse of PMETMMS has been observed. At high polymer concentration and 0.70 ≤ γ < 0.80, a transient network is formed: coils strongly interact with each other via dipole–dipole interactions in a thermodynamically poor solvent. At low concentration regime when 0.70 ≤ γ < 0.80, or in solutions with the mass fraction of acetone higher than 0.80, all the PMETMMS molecules are collapsed. In the intermediate region, the collapse of PMETMMS is gradual and coils, globules, as well as fragments of the network coexist in the solution. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 3337–3343, 1999     

Adsorption of polymeric additives and their effect on the deposition of wood materials in paper production

The objective of this study is to understand how adsorbed synthetic polymers affect deposition kinetics of dissolved and colloidal wood materials. The synthetic polymers were characterised by means of static and dynamic light scattering, and their adsorption on silica was studied by means of optical reflectometry. Deposition kinetics of colloidal wood resin, compounds in model process water, as well as adsorption of anionic carbohydrates was then studied on the surface layers formed by synthetic polymers. It was found that neither wood resin nor anionic carbohydrates have affinity for adsorbed polyethylene oxide. However, wood resin deposited readily on adsorbed cationic polyacryl amides. Both polyethylene oxide and cationic polyacryl amides formed multilayers with compounds in the model process water.     

Fragmentation of protonated O,O-dimethyl O-aryl phosphorothionates in tandem mass spectral analysis

A study was carried out on the fragmentation of 12 protonated O,O-dimethyl O-aryl phosphorothionates by tandem quadrupole mass spectrometry. Some of the studied compounds are used in agriculture as pesticides. Energy-resolved and pressure-resolved experiments were performed on the [M + H]⁺ ions to investigate the dissociation behavior of the ions with various amounts of internal energy. On collisionally activated dissociation, the [M + H]⁺ ions decompose to yield the [M + H ? CH₃OH]⁺, (CH₃O)₂PS⁺ (m/z 125), and (CH₃O)₂PO⁺ (m/z 109) ions as major fragments. The ions [M + H ? CH₃OH]⁺ and (CH₃O)₂PS⁺ probably arise from the [M + H]⁺ ions of the O,O-dimethyl O-aryl phosphorothionates with the proton on the sulfur or on the oxygen of the phenoxy group. The origin of the hydroxy proton of the methanol fragment was in many cases, surprisingly, the phenyl group and not the reagent gas. This was confirmed by using deuterated isobutane, C₄D₁₀, as reagent gas in Cl. The fragment ions (CH₃O)₂PO⁺ and [ZPhS]⁺ are the results of thiono-thiolo rearrangement reaction. The precursor ion for the ion (CH₃O)₂PO⁺ arises from most compounds upon chemical ionization, whereas the precursor ion for the ion [ZPhS]⁺ arises only from a few compounds upon chemical ionization. The observed fragments imply that several sites carry the extra proton and that these sites get the proton usually upon ionization. The stability order and some characteristics of three protomers of O,O-dimethyl O-phenyl phosphorothionate were investigated by ab initio calculations at the RHF/3-21G* level of theory.     

Interaction of Maleic Acid Copolymers with Collagen

One of the present trends to increase the efficiency of the chrome tanning process is the use of chemicals which change the affinity and induce a better binding of the chromium ions in the hides. Recently, some anionic polyelectrolytes based on poly(acrylic acid) or maleic acid copolymers were developed as additives in the chrome tanning. The effect of polyelectrolytes could be explained by their interaction with the collagen from hide. In our work four maleic acid copolymer/collagen systems were investigated by turbidimetric, conductometric and potentiometric titrations. The interaction between the two macromolecular compounds was clearly evidenced, and its dependence on the chemical structure of the maleic acid copolymer and on the amount of added chromium ions was studied. Homogeneous systems or turbid dispersions were observed depending on the hydrophilic or hydrophobic character of the maleic copolymer, on the [CH]/[MP] ratio, and on the concentration of the chromium ions.     

Partially fluorinated thermally responsive latices of linear and crosslinked copolymers

A series of thermally responsive copolymers of N-isopropylacrylamide (NIPAAM) with a fluorinated hydrophobic comonomer, either hexafluoroisopropylmethacrylate (HFIPMA) or 2,2,3,3,4,4-hexafluorobutylmethacrylate (HFBMA) and a hydrophilic comonomer, methacrylic acid (MAA), were synthesized by emulsion polymerization. The chemical structures of the copolymers were studied by the IR technique. Dynamic light scattering (DLS) showed that aqueous latices of the copolymers exhibited swelling–deswelling changes typical to PNIPAAM; the degree of swelling as well as the temperature at which the polymers collapse depended on the chemical structure of the comonomers. Endotherms related to the contraction of the polymers were studied by differential scanning calorimetry (DSC). A combination of DLS and DSC results revealed that the hydrophobic and hydrophilic units in the copolymers strongly affected the swelling behavior, as well as the local environment of the PNIPAAM chains. The comonomer HFIPMA increased the hydrophobicity of NIPAAM, reduced the swelling, and caused coagulation of the copolymer of NIPAAM and HFIPMA at temperatures above the critical temperature. Hydrophobicity of HFIPMA also affected the rheological properties of the latex. The HFBMA comonomer increased the swelling of the latex particles. Methacrylic acid added into the associating copolymers made the copolymers to show polyelectrolyte behavior with an increase of swelling and a decrease of the enthalpy change upon the collapse. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2141–2152, 1998     

Thermal,electric and spin transport in superconductor/ferromagnetic-insulator structures

A ferromagnetic insulator (FI) attached to a conventional superconductor (S) changes drastically the properties of the latter. Specifically, the exchange field at the FI/S interface leads to a splitting of the superconducting density of states. If S is a superconducting film, thinner than the superconducting coherence length, the modification of the density of states occurs over the whole sample. The coexistence of the exchange splitting and superconducting correlations in S/FI structures leads to striking transport phenomena that are of interest for applications in thermoelectricity, superconducting spintronics and radiation sensors. Here we review the most recent progress in understanding the transport properties of FI/S structures by presenting a complete theoretical framework based on the quasiclassical kinetic equations. We discuss the coupling between the electronic degrees of freedom, charge, spin and energy, under non-equilibrium conditions and its manifestation in thermoelectricity and spin-dependent transport.