Capillary flooding of wood with microemulsions from Winsor I systems

A new approach based on microemulsions formulated with at least 85% water and minority components consisting of oil (limonene) and surfactant (anionic and nonionic) is demonstrated for the first time to be effective for flooding wood's complex capillary structure. The formulation of the microemulsion was based on phase behavior scans of Surfactant-Oil-Water systems (SOWs) and the construction of pseudo-ternary diagrams to localize thermodynamically stable one-phase emulsion systems with different composition, salinity and water-to-oil ratios. Wicking and fluid penetration isotherms followed different kinetic regimes and indicated enhanced performance relative to that of the base fluids (water, oil or surfactant solutions). The key properties of microemulsions to effectively penetrate the solid structure are discussed; microemulsion formulation and resultant viscosity are found to have a determining effect in the extent of fluid uptake. The solubilization of cell wall components is observed after microemulsion impregnation. Thus, the microemulsion can be tuned not only to effectively penetrate the void spaces but also to solubilize hydrophobic and hydrophilic components. The concept proposed in this research is expected to open opportunities in fluid sorption in fiber systems for biomass pretreatment, and delivery of hydrophilic or lipophilic moieties in porous, lignocellulosics.     

Hydridosilazanes hydrolysis-condensation reactions studied by <Superscript>1</Superscript>H and <Superscript>29</Superscript>Si liquid NMR spectroscopy

Hydridosilazane compounds containing Si–N and Si–H bonds can be used as precursors of SiO_x materials. The hydrolysis-condensation reactions of tetramethyldisilazane, as a polyhydridosilazane model compound, were investigated by ¹H and ²⁹Si liquid NMR spectroscopy. These reactions were carried out at room temperature for up to 120 min in presence of water. The identified products are short linear siloxane species (hydride terminated polydimethylsiloxanes M^HD_xM^H) and cyclosiloxanes. Silicon hydride persistence in the reactional mixture suggested that silazane group is more sensitive to hydrolysis reaction than silicon hydride group. Moreover, additional experiments evidenced that the low steric hindrance of the silicon hydride influences the silazane hydrolysis kinetic. Hence the presence of ammonia released during silazane hydrolysis reaction was demonstrated to be a catalyst of the silicon hydride hydrolysis reaction.     

Fast counter-electroosmotic capillary electrophoresis–time-of-flight mass spectrometry of hyaluronan oligosaccharides

Fast capillary electrophoresis–mass spectrometry measurements under counter-electroosmotic analyte migration conditions are presented. Efficient separations of a homologous series of six hyaluronan oligosaccharides (comprising 1–6 hyalobiuronic acid moieties) could be completed in 65 s. Separations were achieved in short-length fused silica capillaries under high electric field strengths of up to 1.25 kV·cm⁻¹. Capillary inner diameters ranging from 5 to 50 μm were investigated, resulting in an optimal value of 15 μm. The influence of capillary dimensions and buffer composition on separation efficiency and sensitivity are discussed. Optimal separations were achieved using a 28 cm × 15 μm capillary, a separation high voltage of 35 kV, a background electrolyte of 25 mM ammonium acetate adjusted to pH 8.5, and negative ionization mode. The optimized method was successfully applied to a bovine testicular hyaluronidase digest of hyaluronan. Only minimal sample pretreatment for protein-containing samples is required. The simple manual injection procedure and fast separations allow for a sample throughput of 35 samples per hour.     

Energy gap of alternant carbon nanotubes

The energy spectra of two types of non-helical carbon nanotubes are investigated theoretically. It is shown that either the topological or the correlational contributions determine the width of the band gap. In some cases (for nanotubes with diameter < 1 nm) the electron correlation changes qualitatively the results for the width of the energy gap ΔE: if in the one-electron approximation the band width ΔE = 0, the contribution of the electron correlation becomes dominant and increases the band gap ΔE > 0. At small diameter of the nanotubes (D > 1 nm) the ground state of the tubes corresponds to semiconductors with moderate or narrow energy gap, while at D > 1 nm ΔE decreases monotonously. The energy spectra of the planar ribbon polymers are compared with those of the iso-electronic nanotubes.     

Synthesis and Complexation Studies of a Convex Bis-porphyrin Tweezer—A Molecular Capsule Precursor

The synthesis and spectroscopic studies of a convex bis-porphyrin based molecular tweezer are reported. The complexation of small bidentate ligands by metallated derivatives of the bis-porphyrin host were monitored through UV–visible and ¹H NMR spectroscopy and yielded large association constants.     

Synthesis of Highly Functionalized Fluorinated Porphyrins

Highly functionalized fluorinated porphyrins were synthesized by a convergent strategy. Nucleophilic substitution using fluorinated branched unit and 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin afforded highly functionalized fluorinated porphyrin 8 containing 24 fluorinated chains in the peripheral region.     

Multinuclear NMR Studies of the Substitlent Effects in N-Phenyl-P,P,P-Triarylphospha-λ5-Azenes,Triaryl-Phosphines and Triarylphosphine Oxides

Abstract

A series of N-phenyl-P,P,P-triarylphospha-λ⁵-azenes (1) as well as their ^l5N labeled analogs was synthesized. The ¹³C, ³¹P, and ¹⁵N NMR spectra of this series and those of two other series of related compounds, namely triarylphosphines (2) and triarylphosphine oxides (3), were measured and are reported. Many satisfactory correlations using the mono-substituent parameter (MSP) and the Taft dual-substituent parameter (DSP) treatments with the ¹³C substituent chemical shifts (SCS), ³¹P SCS, ¹⁵N SCS and the one bond P-N, P-C and C-N coupling constants were observed and will be discussed. Thus, for example, the ³¹P and ¹⁵N chemical shifts in 1 correlated with [sgrave]^?with negative slopes while the ³¹P chemical shifts in 3 correlated with those in 1 with a slope of 2.0. The ¹³C chemical shifts in 1 correlated excellently with the corresponding ones in 3 with slopes very close to unity. The substituent effects on the chemical shifts of the various nuclei were shown to be mainly due to changes in the charge distribution on those nuclei. In 1 the one bond P-N and P-C coupling constants correlated with [sgrave]_p and [sgrave]_R respectively. The one bond P-C coupling constants of 1 correlated quite well with those of 3 with a slope of 0.93 while the corresponding correlation of 1 with 2 was quite poor. Taft DSP treatment of ¹J_PCin 1 and 3 were quite similar, ρI and ρR were both negative and ρR was much larger than ρI. Series 2 showed behavior which was different from that shown by 1 and 3 but similar to that shown by other systems with a lone electron pair on the atom bound to the phenyl ring. The substituent effects on the one bond P-N, P-C and C-N coupling constants will be discussed in terms of bonding and hybridization changes between the directly bonded nuclei.     

Synthesis and Study of a Sulfur Heterocycle Fused p-Phenylene Vinylene Conducting Polymer

Abstract

Poly(benzo[1,2-b:4,5-b′]dithiophene-4,8-diyl vinylene) (1) has been prepared by the pyrolysis of the precursor polymer 2 and studied. Quantum mechanical calculations on the aromatic and quinoid monomers, oligomers and polymers indicate that 1 is a planar aromatic polymer.     

Metal-Rich Phosphanediyl-and Arsanediyl-Clusters

Abstract

The reactions of primary silylphosphanes and -arsanes 1 with BuLi yield the three-dimensional M₂ER-aggregates 2 (E = P, As). We observed that the double lithiation of 1 in the presence of Li₂O results in the formation of the aggregates 3 and 4.     

Preparation and properties of polyurethane networks based on α,ω-difunctional poly(hexafluoropropylene oxide)

Poly(hexafluoropropylene oxide), poly(HFPO), networks were prepared from functional polymers by end linking via urethane groups. The prepolymers were characterized by NMR spectroscopy and GPC. The networks were characterized by determination of the number of network chains from the shear modulus, and were snown to contain both trifunctional crosslinks and difunctional links. The properties of the networks were investigated by a range of techniques. Compared with fully-fluorinated networks formed via triazine cross-links, investigated previously, the urethane-linked networks were more readily prepared but were poorer elastomers, were less thermally stable, and were less resistant to swelling by common polar solvents. © 1995 John Wiley & Sons, Inc.