Richard S. Reiner

A new environmentally benign technology for transforming wood pulp into paper. Engineering polyoxometalates as catalysts for multiple processes

A new environmentally benign technology, based on the use of polyoxometalate (POM) salts and oxygen, is being developed to bleach wood pulps for use in the manufacture of paper. Details of POM chemistry relating to the unit operations of an effluent-free bleaching process are reported. These include anaerobic delignification of wood pulp, aerobic reoxidation of reduced POMs for their cyclic reuse and POM catalyzed and initiated aerobic mineralization (wet oxidation) of lignin fragments removed from pulp during bleaching. The results of bleaching trials using a series of isostructural POM complexes of the Keggin family are reported. Key structural components of the POMs are varied to determine the effects of these changes on POM performance. Homogeneous reactions of lignin-model compounds with select POMs are used to help interpret kinetic data obtained in the heterogeneous reaction of POM solutions with pulp fibers. Finally, new directions in catalyst design that promise to expand the potential of the technology are discussed.

Selective transition-metal catalysis of oxygen delignification using water-soluble salts of polyoxometalate (POM) anions. part II. Reactions of α-[SiVW11O40]5- with phenolic lignin-model compounds

When heated under anaerobic conditions, aqueous solutions of the polyoxometalate anion α-(SiVW 11 O 40 ] 5- (POM ox , 1), supplied as the salt K 5 [SiVW 11 O 40 ].12H 2 O, selectively delignify unbleached mixed-pine kraft pulps. During delignification, 1 is reduced hy residual lignin to α-[SiVW 11 O 40 ] 6- (POM red 2) : α-[SiVW 11 O 40 ] 5- + 1e- → α-[SiVW 11 O 40 ]6-, E o = +0.69V vs. NHE. Model studies suggest that phenolic (hydroxylated phenyl) groups present in residual lignin are substrates for the reduction of 1. Reactions of 1 with phenolic arylglycerol β-aryl ethers and other phenolic lignin models suggest that anaerobic POM degradation of residual lignin may occur via sequential single-electron oxidation reactions of phenolic substructures, first to cyclohexadienyl radicals and subsequently to cyclohexadienyl cations. Hydrolysis of these cationic intermediates results in alkyl-side-chain cleavage, a likely route to polymer degradation.

Selective transition-metal catalysis of oxygen delignification using water-soluble salts of polyoxometalate (POM) anions. part I. Chemical principles and process concepts

Polymeric metal-oxide anion complexes (polyoxometalates) may provide a means for using transition metals and oxygen (O 2 ) to selectively delignify wood or wood pulp in effluent-free (closed) mills. The development of this chemistry. and associated process concepts, evolved from the observation that certain fungi use transition metals (Cu. Fe and Mn) to selectively transfer electrons from lignin to oxygen. Chemical, physicochemical and engineering issues pertaining to the development of aqueous transition-metal systems for selective delignification, and for mill closure, are outlined in this brief introduction to the title technology.

Highly Transparent and Toughened Poly(methyl methacrylate) Nanocomposite Films Containing Networks of Cellulose Nanofibrils

Cellulose nanofibrils (CNFs) are a class of cellulosic nanomaterials with high aspect ratios that can be extracted from various natural sources. Their highly crystalline structures provide the nanofibrils with excellent mechanical and thermal properties. The main challenges of CNFs in nanocomposite applications are associated with their high hydrophilicity, which makes CNFs incompatible with hydrophobic polymers. In this study, highly transparent and toughened poly(methyl methacrylate) (PMMA) nanocomposite films were prepared using various percentages of CNFs covered with surface carboxylic acid groups (CNF-COOH). The surface groups make the CNFs interfacial interaction with PMMA favorable, which facilitate the homogeneous dispersion of the hydrophilic nanofibrils in the hydrophobic polymer and the formation of a percolated network of nanofibrils. The controlled dispersion results in high transparency of the nanocomposites. Mechanical analysis of the resulting films demonstrated that a low percentage loading of CNF-COOH worked as effective reinforcing agents, yielding more ductile and therefore tougher films than the neat PMMA film. Toughening mechanisms were investigated through coarse-grained simulations, where the results demonstrated that a favorable polymer-nanofibril interface together with percolation of the nanofibrils, both facilitated through hydrogen bonding interactions, contributed to the toughness improvement in these nanocomposites.

Polyoxometalates in Oxidative Delignification of Chemical Pulps: Effect on Lignin

Chemical pulps are produced by chemical delignification of lignocelluloses such as wood or annual non-woody plants. After pulping (e.g., kraft pulping), the remaining lignin is removed by bleaching to produce a high quality, bright paper. The goal of bleaching is to remove lignin from the pulp without a negative effect on the cellulose; for this reason, delignification should be performed in a highly selective manner. New environmentally-friendly alternatives to conventional chlorine-based bleaching technologies (e.g., oxygen, ozone, or peroxide bleaching) have been suggested or implemented. In an attempt to find inorganic agents that mimic the action of highly selective lignin-degrading enzymes and that can be applicable in industrial conditions, the researchers have focused on polyoxometalates (POMs), used either as regenerable redox reagents (in anaerobic conditions) or as catalysts (in aerobic conditions) of oxidative delignification. The aim of this paper is to review the basic concepts of POM delignification in these two processes.

Polyoxometalate Delignification of Birch Kraft Pulp and Effect on Residual Lignin

Abstract To advance the understanding of delignification with polyoxometalates (POMs) that have been explored for use in bleaching of chemical pulps, the transformation of lignin during anaerobic treatment of birch kraft pulp with an equilibrated POM mixture composed of Na5(+2)[SiV1(-0.1)MoW10(+0.1)O40] was investigated. The conversion factor between the Klason lignin and the kappa number corrected for the hexenuronic acid (HexA) contribution gradually increased, indicating loss of lignin oxidizability. Comparative analysis of residual lignins isolated from pulps of decreasing kappa number showed that lignin undergoes changes that include a sharp reduction in the content of PhOH groups, a gradual demethylation, and a high increase in carbonyl groups. The results indicated that the POM treatment of kraft pulps leads to the loss of aromaticity, most likely caused by the conversion of aromatic rings to quinone moieties. The 2D NMR studies revealed the disappearance of the correlations assigned to stilbene structures formed during kraft pulping, and the weakening of those assigned to the native lignin bonds. The GPC studies showed a gradual lignin depolymerization.

Pulmonary exposure to cellulose nanocrystals caused deleterious effects to reproductive system in male mice.

ABSTRACT Over the past several years there has been an increased number of applications of cellulosic materials in many sectors, including the food industry, cosmetics, and pharmaceuticals. However, to date, there are few studies investigating the potential adverse effects of cellulose nanocrystals (CNC). The objective of this study was to determine long-term outcomes on the male reproductive system of mice upon repeated pharyngeal aspiration exposure to CNC. To achieve this, cauda epididymal sperm samples were analyzed for sperm concentration, motility, morphological abnormalities, and DNA damage. Testicular and epididymal oxidative damage was evaluated, as well as histopathology examination of testes. In addition, changes in levels of testosterone in testes and serum and of luteinizing hormone (LH) in serum were determined. Three months after the last administration, CNC exposure significantly altered sperm concentration, motility, cell morphology, and sperm DNA integrity. These parameters correlated with elevated proinflammatory cytokines levels and myeloperoxidase (MPO) activity in testes, as well as oxidative stress in both testes and epididymis. Exposure to CNC also produced damage to testicular structure, as evidenced by presence of interstitial edema, frequent dystrophic seminiferous tubules with arrested spermatogenesis and degenerating spermatocytes, and imbalance in levels of testosterone and LH. Taken together, these results demonstrate that pulmonary exposure to CNC induces sustained adverse effects in spermatocytes/spermatozoa, suggesting male reproductive toxicity.

Lignin modification in the initial phase of softwood kraft pulp delignification with polyoxometalates (POMs)

Abstract Commercial softwood kraft pulp with kappa number 30.5 (KP30.5) was delignified with polyoxometalates (POM, Na5(+2)[SiV1(-0.1)MoW10(+0.1)O40]), and POM-treated kraft pulp of kappa number 23.6 was obtained (KPPOM,23.6). Residual lignin from pulps was isolated by mild acid hydrolysis and characterized by analytical and spectral methods to gain insight into lignin reactions taking place during the initial delignification phase. Lignin from POM-delignified pulp was isolated in lower yield. Comparative analysis of residual lignins (RL-KP30.5, RL-KPPOM,23.6) showed that POM leads to products enriched in carbonyl/carboxyl groups and carbohydrates. POM lignins have a lower molecular mass and a lower content of phenolic hydroxyl and methoxyl groups. Based on these results and FTIR spectra, we suggest that aromatic ring cleavage and quinone formation occur during POM delignification. The degree of lignin-cellulose association increases after POM delignification. Lignin-cellulose association was found to be partially unstable under mild alkaline conditions, as residual lignin isolated after alkaline extraction of KPPOM,23.6 pulp (RL-KPPOM/NaOH) exhibited lower glucose content, higher Klason lignin content, and less extraneous material.

Nanofibrillated Cellulose from Appalachian Hardwoods Logging Residues as Template for Antimicrobial Copper

TEMPO nanofibrillated cellulose (TNFC) from two underutilized Appalachian hardwoods, Northern red oak (Quercus rubra) and yellow poplar (Liriodendron tulipifera), was prepared to determine its feasibility to be used as template for antimicrobial metallic copper particles. In addition, a comparison of the TNFC from the two species in terms of their morphological, chemical, thermal, and mechanical properties was also performed. The woody biomass was provided in the form of logging residue from Preston County, West Virginia. A traditional kraft process was used to produce the pulp followed by a five-stage bleaching. Bleached pulps were then subjected to a TEMPO oxidation process using the TEMPO/NaBr/NaClO system to facilitate the final mechanical fibrillation process and surface incorporation of metallic copper. The final TNFC diameters for red oak and yellow poplar presented similar dimensions,  nm and  nm, respectively. The TNFC films fabricated from both species exhibited no statistical differences in both Young’s modulus and the final strength properties. Likely, after the TEMPO oxidation process both species exhibited similar carboxyl group content, of approximately 0.8 mmol/g, and both species demonstrated excellent capability to incorporate antimicrobial copper on their surfaces.