Reactivity of Aliphatic and Phenolic Hydroxyl Groups in Kraft Lignin towards 4,4′ MDI

Several efforts have been dedicated to the development of lignin-based polyurethanes (PU) in recent years. The low and heterogeneous reactivity of lignin hydroxyl groups towards diisocyanates, arising from their highly complex chemical structure, limits the application of this biopolymer in PU synthesis. Besides the well-known differences in the reactivity of aliphatic and aromatic hydroxyl groups, experimental work in which the reactivity of both types of hydroxyl, especially the aromatic ones present in syringyl (S-unit), guaiacyl (G-unit), and p-hydroxyphenyl (H-unit) building units are considered and compared, is still lacking in the literature. In this work, the hydroxyl reactivity of two kraft lignin grades towards 4,4′-diphenylmethane diisocyanate (MDI) was investigated. ³¹P NMR allowed the monitoring of the reactivity of each hydroxyl group in the lignin structure. FTIR spectra revealed the evolution of peaks related to hydroxyl consumption and urethane formation. These results might support new PU developments, including the use of unmodified lignin and the synthesis of MDI-functionalized biopolymers or prepolymers.     

Duality in reconstruction systems

We consider reconstruction systems (RS’s), which are G-frames in a finite dimensional setting, and that includes the fusion frames as projective RS’s. We describe the spectral picture of the set of RS operators for the projective systems with fixed weights. We also introduce a functional defined on dual pairs of RS’s, called the joint potential, and study the structure of the minimizers of this functional. In the case of irreducible RS’s the minimizers are characterize as the tight systems. In the general case we give spectral and geometric characterizations of the minimizers of the joint potential. At the end of the paper we show several examples that illustrate our results.     

Quantitative analysis of thin samples by differential absorption imaging using a laser-plasma soft X-ray source

We consider the application of the differential absorption imaging technique in the soft X-ray region. The surface-density maps of test samples containing bromine, resulting from the application of the differential absorption imaging technique, are presented. Images of the samples were obtained in an X-ray monochromatic projection imaging scheme based on a spherically bent crystal using line emission close to the $L_2$ edge of bromine from a microplasma produced by focusing a nanosecond laser on the surface of an aluminum target.     

Spectral Shorted Operators

If $$\mathcal{H}$$ is a Hilbert space, $$\mathcal{S}$$ is a closed subspace of $$\mathcal{H},$$ and A is a positive bounded linear operator on $$\mathcal{H},$$ the spectral shorted operator $$\rho \left( {\mathcal{S},\mathcal{A}} \right)$$ is defined as the infimum of the sequence $$\sum (\mathcal{S},A^n )^{1/n} ,$$ where denotes $$\sum \left( {\mathcal{S},B} \right)$$ the shorted operator of B to $$\mathcal{S}.$$ We characterize the left spectral resolution of $$\rho \left( {\mathcal{S},\mathcal{A}} \right)$$ and show several properties of this operator, particularly in the case that dim $${\mathcal{S} = 1.}$$ We use these results to generalize the concept of Kolmogorov complexity for the infinite dimensional case and for non invertible operators.     

Chemometric approaches in environmental problems concerning PCDD and PCDF. Data interpretation and source correlation. Mechanisms of formation and destruction in MSW combustion process

Summary The role of multivariate analysis methods in evaluating, rationalizing, and working out complex environmental problems is discussed. The discussion is organized in two sections; a literature analysis of the application of chemometric methods to PCDD/PCDF data interpretation and source correlation and a review of the role of chemometric methods in analysing the results obtained by the Authors studying PCDD/PCDF formation and destruction mechanisms in MSW combustion processes.     

Use of solid-phase microextraction-capillary-gas chromatography (SPME-CGC) for the varietal characterization of wines by means of chemometrical methods

The extraction of wine aroma compounds was studied by direct-SPME (DI/SPME), headspace-SPME (HS/SPME) and multiple-headspace-extraction-SPME (MHE/SPME). The aromagrams obtained by HS/SPME-CGC were evaluated with chemometrical methods for the varietal classification of wines. Received: 25 July 1997 / Revised: 24 September 1997 / Accepted: 7 October 1997     

Speciation of phytate ion in aqueous solution. Cadmium(II) interactions in aqueous NaCl at different ionic strengths

Interactions between myo-inositol 1,2,3,4,5,6-hexakis(dihydrogen phosphate) (phytic acid) and cadmium(II) were studied by using potentiometry (at 25 °C with the ISE-H⁺ glass electrode) in different metal to ligand (Phy) ratios (1:1≤Cd²⁺:Phy≤4:1) in NaCl_aq at different ionic strengths (0.1≤I/mol L⁻¹≤1). Nine Cd_iH_jPhy^{(12−2i−j)−} species are formed with i=1 and 2 and 4≤j≤7; and trinuclear Cd₃H₄Phy²⁻. Dependence of complex formation constants on ionic strength was modeled by using Specific ion Interaction Theory (SIT) equations. Phytate and cadmium speciation are also dependent on the metal to ligand ratio. Stability of Cd_iH_jPhy^{(12−2i−j)−} species was modeled as a function of both the ligand protonation step (j) and the number of metal cations bound to phytate (i), and relationships found were used for the prediction of species other than those experimentally determined (mainly di- and tri-protonated complexes), allowing the possibility of modeling Phy and Cd(II) behavior in natural waters and biological fluids. A critical evaluation of phytate sequestering ability toward cadmium(II) has been made under several experimental conditions, and the determination of an empirical parameter has been proposed for an objective “quantification” of this ability. A thorough analysis of literature data on phytate–cadmium(II) complexes has been performed. Previous contributions to this series: [1–8]     

Formation and stability of phytate complexes in solution

1,2,3,4,5,6 hexakis (di-hydrogen phosphate) myo-inositol, best known as phytic acid, is a very important molecule from a biological, environmental and technological point of view. For a thorough understanding of phytate properties and the mechanisms involving this ligand, a careful study of its acid–base behavior and of the formation and stability of its complexes in solution is necessary. Unfortunately, regarding the thermodynamic data on phytate complexes in solution, some are lacking, while some others exhibit large discrepancies between different authors. This motivated a detailed evaluation of the literature on this topic, aimed at identifying the most accurate data on phytate coordination chemistry in solution. This review presents the results of this, reporting and analyzing the most significant thermodynamic parameters published for both phytate protonation and complex formation with several metal and organometal cations, as well as polyammonium ligands.     

Jensen's inequality for spectral order and submajorization

Let A be a C^∗-algebra and be a positive unital map. Then, for a convex function defined on some open interval and a self-adjoint element a∈A whose spectrum lies in I, we obtain a Jensen's-type inequality f(?(a))??(f(a)) where ? denotes an operator preorder (usual order, spectral preorder, majorization) and depends on the class of convex functions considered, i.e., monotone convex or arbitrary convex functions. Some extensions of Jensen's-type inequalities to the multi-variable case are considered.     

A unified characterization of reproducing systems generated by a finite family

This article presents a general result from the study of shift-invariant spaces that characterizes tight frame and dual frame generators for shift-invariant subspaces of L²(ℝⁿ). A number of applications of this general result are then obtained, among which are the characterization of tight frames and dual frames for Gabor and wavelet systems.