Kraft pulping is interpreted in chemical terms on the basis of results from extensive qualitative and quantitative model experiments. In essence, the behavior of lignin is explained as a competition between degradation reactions, mainly involving aryl ether cleavage with participation of neighboring groups, and condensation reactions, comprising conjugate addition of carbanions to quinone methide intermediates. The initial phase of technical delignification is tentatively ascribed to the cleavage of α- and β-aryl ether bonds in phenolic lignin units, whereas the cleavage of β-aryl ether bonds in non-phenolic lignin units is considered to be the rate-determining reaction of the bulk phase. The residual phase may possibly be attributed to the rupture of C-C linkages and to aryl ether cleavage without neighboring group participation. Experimental support for these correlations is provided. The interplay of the various lignin reactions, illustrated in a summarizing scheme, explains some known observations in kraft pulping. Attention is drawn to analogies between reactions involved in the degradation of carbohydrates and those reponsible for the degradation of lignin. From the chemical standpoint, therefore, the selectivity of delignification is due to differences in the reactivity of the wood polymers, rather than to differences in the mechanisms of the degradation reactions. This fact explains the limitations of selective delignification.

Chemical aspects of kraft pulping

In various biological systems, 1,2-epoxides are able to cause biological effects with genetic mechanisms: point mutations, deletions, chromosomal aberrations, gene conversion, crossing-over, cancer and virus (prophage) induction. Dose—response curves are linear, or should be interpreted to have a linear component that predominates at low doses or concentrations. In forward mutation systems the effectiveness is related to the dose in the target cells and to the chemical reactivity. By applying experimentally determined correction factors for difunctionality (in the case of diepoxides or monoepoxides with a reactive substituent such as a carbonyl group), genetic risks may be estimated by a unitary approach, valid for epoxides in general, if not for all alkylating agents. The use of this approach, to calculate type-II errors in negative carcinogenicity tests, indicates that no data presently available support a conclusion that certain epoxides are non-mutagenic or non-carcinogenic, i.e. are less effective than expected from reactivity data. Determination of the rad-equivalence of genetic risks, i.e. the use of corresponding risks from a unit dose of ionizing radiation as a standard, indicates that the risks associated with Threshold Limit Values for epoxides in work environments in Western countries are 1–2 orders of magnitude higher than permissible risks for radiological workers.

Genetic toxicity of some important epoxides

In this paper we present a local coupled cluster approach based on a dynamical screening scheme, in which amplitudes are either calculated at the coupled cluster level (in this case CCSD) or at the level of perturbation theory, employing a threshold driven procedure based on MP2 energy increments. This way, controllable accuracy and smooth convergence towards the exact result are obtained in the framework of an a posteriori approximation scheme. For the representation of the occupied space a new set of local orbitals is presented with the size of a minimal basis set. This set is atom centered, is nonorthogonal, and has shapes which are fairly independent of the details of the molecular system of interest. Two slightly different versions of combined local coupled cluster and perturbation theory equations are considered. In the limit both converge to the untruncated CCSD result. Benchmark calculations for four systems (heptane, serine, water hexamer, and oxadiazole-2-oxide) are carried out, and decay of the amplitudes, truncation error, and convergence towards the exact CCSD result are analyzed.

Dynamically screened local correlation method using enveloping localized orbitals.

Density functional theory calculations at the B3LYP/6-31G* level on the dimerization reactions of acetonitrile oxide and para-chlorobenzonitrile oxide to form furoxans indicate that these processes are stepwise involving dinitrosoalkene intermediates that have considerable diradical character. The rate-determining steps for these two reactions correspond to C-C bond formation. The retardation of dimerization in aromatic nitrile oxides arises from the interruption of conjugation between the nitrile oxide and aryl groups in the C-C bond formation step. The present study also suggests that the isomerization of single-ring furoxans occurs via a diradical intermediate mechanism.

Dimerizations of nitrile oxides to furoxans are stepwise via dinitrosoalkene diradicals: a density functional theory study.

The reactions of lignins during lignin-degrading bleaching are more difficult to survey than those taking place during pulping for the following tow reasons: 1) The structural features of the actual Substrate, in most cases residual lignins in pulps, are essentially unknown and 2) Standard bleaching sequences include a variety of electrophilic and nucleophilic bleaching reagents which may operate simultaneously or successively.

The Chemistry of Delignification - A General Concept - Part II

The tautomerism of furoxan (1,2,5-oxadiazole-2-oxide) has been investigated by different computational methods comprising modern density functionals as well as single-reference and multi-reference ab initio methods. The ring-opening process to 1,2-dinitrosoethylene is the most critical step of the reaction and cannot be treated reliably by low-level computations. The existence of cis-cis-trans-1,2-dinitrosoethylene as a stable intermediate is advocated by perturbational methods, but high-level coupled-cluster calculations identify this as an artifact. In contrast to the analogous reaction in benzofuroxans, cis-cis-cis-1,2-dinitrosoethylene was found to be a transition state rather than a local minimum. Model potentials were used to explain the occurrence and the disappearing of transition states and local minima relative to the reaction of benzofuroxan. Low-lying triplet states that can be accessed due to spin-orbit coupling were investigated as taking part in alternative routes to a proposed singlet pathway. Barriers for rotations of the nitroso groups on the S(0) and T(1) surfaces are reported.

John Ed Stevens

Papers

Toward an understanding of the furoxan-dinitrosoethylene equilibrium.

Kinetics of the Reaction between Ethylene Chlorohydrin and Hydroxyl or Alkoxyl Ions in Mixed Solvents1,2