HPLC-NMR of fatty alcohol ethoxylates

The application of HPLC-NMR for the analysis of a mixture of fatty alcohol ethoxylates (FAEs) is described. The use of the new generation, cryogenically cooled probes is investigated in respect of the sensitivity advantage that they provide. The FAE mixture is separated using liquid chromatography at the critical point of adsorption. The ability of the method to differentiate between the different end groups and the degree of polymerization of the mixture constituents is investigated. Both on-flow and stop-flow HPLC-NMR techniques were used together with two-dimensional NMR spectroscopy. The results are compared with those obtained by using an evaporative light scattering detector for the HPLC.     

On the interaction of UV screens with the lignocellulosic matrix

In this report, we describe our attempt to understand the photochemical interactions that occur between dihydroxybenzophenone (DHB)-based UV screens and lignin when high-yield pulps are treated with such materials. Milled wood lignin (MWL) and filter paper were used as models, and various irradiation protocols were carried out in the presence and absence of UV screens. After irradiation, the lignin and the UV screen were extracted and the products analyzed. These experiments showed that upon irradiation, fragments of MWL-containing chromophores were linked to cellulose via an acid-labile linkage. In the presence of UV screens, these reactions were minimized. Molecular weight measurements of the extracted lignin showed that the MWL is degraded upon solid-state irradiation. The samples that contained UV screens showed a reduced tendency to degrade. Using quantitative 31P NMR, it was possible to probe further the detailed structural changes that occurred in MWL during irradiation. In general, DHB-based UV screens and derivatives were found to interact actively with MWL when irradiated.     

1,3-Dipolar cycloaddition reactions of 2-phenyl-4-arylidene-5(4H)-oxazolones with nitrile oxides

Stable nitrile oxides are added stereospecifically and regioselectively to the carbon carbon double bond of 2-phenyl-4-arylidene-5(4H)-oxazolones resulting spiro-derivatives 3, 5 . The spectral properties of the reaction products are discussed. The cycloadducts give several substituted isoxazolines via an opening of the oxazolone ring with nucleophilic reagents.     

Photochemically Induced Solid-State Degradation, Condensation, and Rearrangement Reactions in Lignin Model Compounds and Milled Wood Lignin

Abstract— Milled wood lignin produced from alkaline hydrogen peroxide-bleached softwood thermomechanical pulp (TMP) fibers was adsorbed on pure cellulose and irradiated for variable periods of time under oxygen and/or nitrogen. The absolute amounts of β-O-4 ethers, phenolic hydroxyl groups, carboxylic acids and various condensed phenolic units were quantified, nondestructively, using ³¹P NMR spectroscopy. Photoirradiation was found to severely cleave the β-O-4 ethers present in lignin with the concomitant formation of new phenolic units. The rate of this cleavage was found to be faster under oxygen than under nitrogen. The catalytic role of oxygen can be rationalized by invoking the formation of peroxy free radicals that may initiate new sites of radical generation ( e.g. ketyl radicals) within the lignin causing the subsequent breakdown of the β-O-4 linkage. The photoirradiation was found to cause a net increase of the C₅-related condensed phenolic units in lignin. Among these, C_α-C₅ and/ or C_β-C₅ phenolic moieties were found to predominate. Similar irradiation of a binary mixture of model compounds resembling structures present in softwood lignin resulted in 18 products that were identified and quantified using gas chromatography coupled to mass spectrometry. The photochemical products obtained supported the phenacyl and ketyl mechanistic pathways to pho-toyellowing, whereas the detection of β-5 coupling products (common in both the model compound and milled wood lignin studies) may point a new avenue toward the formation of light-induced products that has not been previously considered in the solid state.     

Proton spin-lattice relaxation time measurements of solid wood and its constituents as a function of pH: part II

The proton spin-lattice relaxation times (T1H) for isolated cuoxam lignin and fully bleached cellulose were measured as a function of pH in the solid-state. These experiments provided the opportunity to examine for possible macromolecular connectivities that may be present between lignin and carbohydrates within softwood. These studies have shown that the molecular mobilities of the isolated polymeric constituents of wood are affected by the ionization of their functional groups at different pHs. The shapes of the plots of T1H as a function of pH for the two isolated polymers were dramatically different, while those for softwood were similar. This fact provides evidence supporting the notion that in wood, lignin and carbohydrates are intimately associated with each other.     

Bandwidth evaluation of dispersive transformation electromagnetics based devices

In this paper, the transient responses of some devices which are based on transformation electromagnetics are studied, such as invisible cloaks and concentrators, by using the Finite-Difference Time-Domain (FDTD) numerical technique. In particular, effects of the inherent losses as well as the coating size of the ideal cylindrical cloak on its bandwidth and cloaking performance are examined. In addition, it is demonstrated that the performance of transformation electromagnetics based devices is affected by the material parameters in the design, although they may behave nicely under monochromatic plane wave illuminations. The obtained results are of interest for the future practical implementation of these structures.     

The study of hydronium NASICON conductivity with deuterium

The ionic conductivity of the bulk phase of bonded hydronium NASICON (Hyceram^TM) was measured at equilibrium with an H₂O/N₂ and then a D₂O/N₂ atmosphere, each at 100% relative humidity and 75% relative humidity over the temperature range 25°C to 50°C. At 100% relative humidity and 25°C, the protonic system had a bulk conductivity of 5.0×10⁻⁴ S/cm and an activation energy of 17.3kJ/mole; the same sample, when deuterated, had a bulk conductivity of 2.2×10⁻⁴ S/cm and an activation energy of 19.3kJ/mole. At 75% relative humidity and 25°C, the conductivity of the protonated system decreased to 1.4×10⁻⁴S/cm with an activation energy of 24.1 kJ/mole. The deuterated sample at 75% relative humidity had a bulk conductivity of 5.4×10⁻⁵ S/cm with an activation energy of 26.0 kJ/mole. The isotope effect suggested a proton hopping (Grotthus) mechanism as the means by which the protons pass through the lattice.     

1,3-Dipolar cycloaddition reactions of 4-arylidene-2-phenyl-1,4-dihydroimidazol-5-ones with nitrile oxides

Stable nitrile oxides add regioselectively to the carbon-carbon double bond of 4-arylidene-2-phenyl-1,4-dihydroimidazol-5-ones to afford spiro isoxazolines 3 . Compounds 3 are further hydrolysed to isoxazole derivatives.     

Synthesis of 1,3,4-oxadiazaspiro[4.4]nona-2,6,8-trienes via 1,3-dipolar cycloadditions of diphenylnitrilimine with cyclopentadienones. Crystal and molecular structure of a cycloadduct

The cycloaddition of diphenylnitrilimine with substituted cyclopentadienones leads to the formation of the title spirooxadiazoline derivatives 2 , in good yields. The reaction is examined on the basis of the frontier molecular orbitals of the reacting reagents. An X-ray crystallographic analysis of the product 2b is made.     

Effect of Pr-Ca substitution on the transport and magnetic behavior of LaMnO3 perovskite

The effect of simultaneous substitution of a fluctuating cation and a divalent cation in LaMnO₃ perovskite modifies the properties of the material to exhibit large valence colossal magnetoresistance (CMR) effect. A good example of these properties is (La_1−2x Pr _x Ca _x )MnO₃ (LPCMO) type CMR material. In this communication it is reported that, with the increase in x (for x=0.1, 0.15, 0.2), the T _c varies between 100 and 120 K with improvisation in metal-insulator transition. Interestingly, resistance increases with x from few hundred ohms to few kilo ohms with corresponding decrease in the unit cell volume. The results of the studies using X-ray diffraction (XRD), electrical resistivity, magnetoresistance and ac susceptibility measurements on LPCMO samples for understanding the structural, transport and magnetic properties are discussed in detail.