Kraft Lignin: A Valuable, Sustainable Resource, Opportunities and Challenges.

Kraft lignin, a by-product from the production of pulp, is currently incinerated in the recovery boiler during the chemical recovery cycle, generating valuable bioenergy and recycling inorganic chemicals to the pulping process operation. Removing lignin from the black liquor or its gasification lowers the recovery boiler load enabling increased pulp production. During the past ten years, lignin separation technologies have emerged and the interest of the research community to valorize this underutilized resource has been invigorated. The aim of this Review is to give (1) a dedicated overview of the kraft process with a focus on the lignin, (2) an overview of applications that are being developed, and (3) a techno-economic and life cycle asseeements of value chains from black liquor to different products. Overall, it is anticipated that this effort will inspire further work for developing and using kraft lignin as a commodity raw material for new applications undeniably promoting pivotal global sustainability concerns.

Novel and Integrated Process for the Valorization of Kraft Lignin to Produce Lignin-Containing Vitrimers.

The valorization of lignin into value-added products by oxidative conversion is a widely studied strategy. However, in many cases, this approach has limited scope for integration into industrial processes. The objective of our work is to maximize overall lignin utilization to produce diverse value-added products with a focus on integration in the existing industrial pulp and paper processes. The utilization of the sequential oxidation strategy using oxygen and ozone resulted in kraft lignin with a marked improvement in carboxyl content and also allowed the formation of vanillin and vanillic acid in the oxygen stage. The sequentially oxidized lignin (OxL-COOH) was then cured with poly(ethylene glycol) diglycidyl ether (PEG-epoxy) to form high-lignin-content (>48 wt %) vitrimers with high thermal stability, fast relaxation, swelling, and self-healing due to the presence of bond-exchangeable cross-linked networks. Overall, this study provides a novel approach for the multidimensional valorization of lignin and demonstrates an integrated approach for kraft lignin valorization in the pulp and paper industry.

Copolymers of starch, a sustainable template for biomedical applications: A review.

The outstanding versatility of starch offers a source of inspiration for the development of high-performance-value-added biomaterials for the biomedical field, including drug delivery, tissue engineering and diagnostic imaging. This is because starch-based materials can be tailored to specific applications via facile grafting or other chemistries, introducing specific substituents, with starch being effectively the "template" used in all the chemical transformations discussed in this review. A considerable effort has been carried out to obtain specific tailored starch-based grafted polymers, taking advantage of its biocompatibility and biodegradability with appealing sustainability considerations. The aim of this review is to critically explore the latest research that use grafting chemistries on starch for the synthesis of products for biomedical applications. An effort is made in reviewing the literature that proposes synthetic "greener" approaches, the use of enzymes and their immobilized analogues and alternative solvent systems, including water emulsions, ionic liquids and supercritical CO2.

Quantitative 31P NMR Analysis of Lignins and Tannins.

The development of sustainable biorefinery products is confronted, among others, with the challenge of lignin and tannin valorization. These abundant, renewable aromatic biopolymers have not been widely exploited due to their inherent structural complexity and high degrees of variability and species diversity. The lack of a defined primary structure for these polyphenols is further compounded with complex chemical alterations induced during processing, eventually imparting a large variety of structural features of extreme significance for any further utilization efforts. Consequently, a protocol for the rapid, simple, and unequivocal identification and quantification of the various functional groups present in natural polyphenols, is a fundamental prerequisite for understanding and accordingly tailor their reactivity and eventual utility. Quantitative 31P NMR offers the opportunity to rapidly and reliably identify unsubstituted, o-mono substituted, and o-disubstituted phenols, aliphatic OHs, and carboxylic acid moieties in lignins and tannins with broad application potential. The methodology consists of an in situ quantitative lignin or tannin labeling procedure using a suitable 31P containing probe, followed by the acquisition of a quantitative 31P NMR spectrum in the presence of an internal standard. The high natural abundance of the 31P nucleus allows for small amounts of the sample (~30 mg) and short NMR acquisition times (~30-120 min) with well-resolved 31P signals that are highly dependent on the surrounding chemical environment of the labeled OH groups.

Computer Assisted Structure Elucidation (CASE): Current and future perspectives.

The first efforts for the development of methods for Computer-Assisted Structure Elucidation (CASE) were published more than 50 years ago. CASE expert systems based on one-dimensional (1D) and two-dimensional (2D) Nuclear Magnetic Resonance (NMR) data have matured considerably by now. The structures of a great number of complex natural products have been elucidated and/or revised using such programs. In this article, we discuss the most likely directions in which CASE will evolve. We act on the premise that a synergistic interaction exists between CASE, new NMR experiments, and methods of computational chemistry, which are continuously being improved. The new developments in NMR experiments (long-range correlation experiments, pure-shift methods, coupling constants measurement and prediction, residual dipolar couplings [RDCs]), and residual chemical shift anisotropies [RCSAs], evolution of density functional theory (DFT), and machine learning algorithms will have an influence on CASE systems and vice versa. This is true also for new techniques for chemical analysis (Atomic Force Microscopy [AFM], "crystalline sponge" X-ray analysis, and micro-Electron Diffraction [micro-ED]), which will be used in combination with expert systems. We foresee that CASE will be utilized widely and become a routine tool for NMR spectroscopists and analysts in academic and industrial laboratories. We believe that the "golden age" of CASE is still in the future.

Chlorines Are Not Evenly Substituted in Chlorinated Paraffins: A Predicted NMR Pattern Matching Framework for Isomeric Discrimination in Complex Contaminant Mixtures.

Chlorinated paraffins (CPs) can be mixtures of nearly a half-million possible isomers. Despite the extensive use of CPs, their isomer composition and effects on the environment remain poorly understood. Here, we reveal the isomeric distributions of nine CP mixtures with single-chain lengths (C14/15) and varying degrees of chlorination. The molar distribution of C n H2n+2-m Cl m in each mixture was determined using high-resolution mass spectrometry (MS). Next, the mixtures were analyzed by applying both one-dimensional 1H, 13C and two-dimensional nuclear magnetic resonance (NMR) spectroscopy. Due to substantially overlapping signals in the experimental NMR spectra, direct assignment of individual isomers was not possible. As such, a new NMR spectral matching approach that used massive NMR databases predicted by a neural network algorithm to provide the top 100 most likely structural matches was developed. The top 100 isomers appear to be an adequate representation of the overall mixture. Their modeled physicochemical and toxicity parameters agree with previous experimental results. Chlorines are not evenly distributed in any of the CP mixtures and show a general preference at the third carbon. The approach described here can play a key role in understanding of complex isomeric mixtures such as CPs that cannot be resolved by MS alone.

3D Photoinduced Spatiotemporal Resolution of Cellulose-Based Hydrogels for Fabrication of Biomedical Devices.

Rational spatiotemporal irradiation of cellulose-based hydrogels (carboxymethylcellulose (CMC), citric acid, and riboflavin) using a laser diode stereolithography 3D printer obtained architectures referred to as photodegradation addressable hydrogels (PAHs). Under irradiation, these PAHs engage in an unprecedented spatially resolved zonal swelling illustrating marked but controllable changes in swelling and thickness while concomitantly obtaining improved oxygen transmission rate values by 5 times. XPS, carboxyl content, and swelling data comparisons of hydrogel formulations show that photodegradation and ablation of the material occur, where hydroxyl sites of CMC are converted to aldehydes and ketones. XRD data show that the total number of crystalline aggregates in the material are lowered after photoablation. The spatially tuned (photoablated) hydrogel films can thus be shaped into a lens form. The energy required for the lens tuning process can be lowered up to 30 times by incorporation of riboflavin in the films. The method demonstrated here enables the processing of a material that is difficult to be machined or cast by popular contact lens making methods.

Determination of hydroxyl groups in biorefinery resources via quantitative 31P NMR spectroscopy.

The analysis of chemical structural characteristics of biorefinery product streams (such as lignin and tannin) has advanced substantially over the past decade, with traditional wet-chemical techniques being replaced or supplemented by NMR methodologies. Quantitative 31P NMR spectroscopy is a promising technique for the analysis of hydroxyl groups because of its unique characterization capability and broad potential applicability across the biorefinery research community. This protocol describes procedures for (i) the preparation/solubilization of lignin and tannin, (ii) the phosphitylation of their hydroxyl groups, (iii) NMR acquisition details, and (iv) the ensuing data analyses and means to precisely calculate the content of the different types of hydroxyl groups. Compared with traditional wet-chemical techniques, the technique of quantitative 31P NMR spectroscopy offers unique advantages in measuring hydroxyl groups in a single spectrum with high signal resolution. The method provides complete quantitative information about the hydroxyl groups with small amounts of sample (~30 mg) within a relatively short experimental time (~30-120 min).

Synthesis and characterization of nano fibrillated cellulose/Cu2O films; micro and nano particle nucleation effects.

Cubic, truncated cubic and spherical nano and micro particles of Cu2O, can be selectively deposited onto nano fibrilated cellulose gels by the modulated alkaline reduction of Cu2+ ions aided by the cellulose's reducing end groups. The role of the cellulose's reducing end groups and that of externally added carbohydrate reducing agents, towards inducing various Cu2O morphologies, is discussed with respect to the detailed nucleation effects leading to micro and nano Cu2O particle deposition on NFC. When the reducing end groups are provided only by the cellulose's chain ends, supersaturation effects seem to be affecting the Cu2O nucleation mechanism. However, the Cu2O nucleation considerations were altered when mobile reducing end groups were provided by adding dextrose in the system, promoting additional particle nucleation sites. Furthermore, the effort offered the possibility to quantitatively determine the number of accessible reducing end groups (-CHO) present in NFC, expressed in mmol/g. The optical properties of the created NFC/Cu2O films were examined by UV-vis absorption measurements, revealing band gaps ranging between 2.02-2.25 eV. The accumulated understanding expands the utility window and opens new directions for the novel utilization of nano-fibrillated cellulose, and more specifically toward semiconductor applications.

NMReDATA, a standard to report the NMR assignment and parameters of organic compounds.

Even though NMR has found countless applications in the field of small molecule characterization, there is no standard file format available for the NMR data relevant to structure characterization of small molecules. A new format is therefore introduced to associate the NMR parameters extracted from 1D and 2D spectra of organic compounds to the proposed chemical structure. These NMR parameters, which we shall call NMReDATA (for nuclear magnetic resonance extracted data), include chemical shift values, signal integrals, intensities, multiplicities, scalar coupling constants, lists of 2D correlations, relaxation times, and diffusion rates. The file format is an extension of the existing Structure Data Format, which is compatible with the commonly used MOL format. The association of an NMReDATA file with the raw and spectral data from which it originates constitutes an NMR record. This format is easily readable by humans and computers and provides a simple and efficient way for disseminating results of structural chemistry investigations, allowing automatic verification of published results, and for assisting the constitution of highly needed open-source structural databases.

Ultrasound assisted polyacrylamide grafting on nano-fibrillated cellulose.

Polyacrylamide has been grafted onto nanofibrillated cellulose (NFC-g-PAM) under mild conditions. This was accomplished by developing and optimizing an ultrasound assisted protocol in the presence of potassium persulfate initiator. The synthesis was optimized on the basis of maximizing grafting percentage and grafting efficiency by varying the initiator and monomer concentration. The data shows that ultrasound has a profound effect in promoting the grafting of PAM onto NFC. The intended grafting was confirmed and the properties of the new co-polymers were examined by elemental analyses, Fourier transform infrared spectroscopy, thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). Intrinsic viscosity determinations in 0.1M cupriethylenediamine solutions for the NFC-g-PAM copolymers and the starting NFC and PAM homopolymer revealed that grafting of PAM onto nanofibrillated cellulose has a profound effect on the hydrodynamic characteristics of the graft polymers.

Stable Organic Radicals in Lignin: A Review.

Lignin and the quest for the origin of stable organic radicals in it have seen numerous developments. Although there have been various speculations over the years on the formation of these stable radicals, researchers have not been able to arrive at a solid, unequivocal hypothesis that applies to all treatments and types of lignin. The extreme complexity of lignin and its highly aromatic, cross-linked, branched, and rigid structure has made such efforts rather cumbersome. Since the early 1950s, researchers in this field have dedicated their efforts to the establishment of methods for the detection and determination of spin content, theoretical simulations, and reactions on model compounds and spin-trapping studies. Although a significant amount of published research is available on lignin or its model compounds and the reactive intermediates involved during various chemical treatments (pulping, bleaching, extractions, chemical modifications, etc.), the literature provides a limited view on the origin, nature, and stability of such radicals. Consequently, this review is focused on examining the origin of such species in lignin, factors affecting their presence, reactions involved in their formation, and methods for their detection.

Ionic Liquid Character of Zinc Chloride Hydrates Define Solvent Characteristics that Afford the Solubility of Cellulose.

The recently described ionic liquid structure of the three equivalent hydrate of zinc chloride (ZnCl2·R H2O, R = 3, existing as [Zn(OH2)6][ZnCl4]) explains the solubility of cellulose in this medium. Only hydrate compositions in the narrow range of 3 - x < R < 3 + x with x ≈ 1 dissolve cellulose. Once dissolved, the cellulose remains in solution up to the R = 9 hydrate. Neutron diffraction and differential pair distribution function analysis of cellulose and model compound solutions (1 wt % cellulose in the R = 3 hydrate and 1 wt % ethanol in the R = 3 hydrate and the ZnCl2·3 ethanol liquid) coupled with detailed solubility measurements suggest that cellulose solubility occurs via coordination of the primary OH to the hydrated zinc cation with ring hydroxyls forming part of a second coordination shell around the cation of the ionic liquid.

Wood Extractives Promote Cellulase Activity on Cellulosic Substrates.

Deposition of hydrophobic wood extractives and representative model compounds, on the surface of cellulose prior to enzymatic hydrolysis was found to either enhance or inhibit the action of cellulase enzymes. The effect of these compounds was correlated with their chemical structure, which may in part explain the differential effects observed between softwood and hardwood extractives. Specifically, the addition of sterol, enhanced enzymatic hydrolysis of microcrystalline cellulose by 54%, whereas the addition of a triglyceride could inhibit the hydrolysis by 49%. The effects of the different extractives' could be explained by considering their Hansen solubility parameters. The amphiphilic and/or hydrophobic character of model extractives was found to be the variable that affected the deposition of extractives on cellulose surfaces and the eventual adsorption of cellulolytic enzymes on it. The observed beneficial effects of extractives are likely related to a reduction in the irreversible binding of the enzymes on the cellulose surface.

Synthesis, Characterization, and Antimicrobial Efficacy of Photomicrobicidal Cellulose Paper.

Toward our goal of scalable, antimicrobial materials based on photodynamic inactivation, paper sheets comprised of photosensitizer-conjugated cellulose fibers were prepared using porphyrin and BODIPY photosensitizers, and characterized by spectroscopic (infrared, UV-vis diffuse reflectance, inductively coupled plasma optical emission) and physical (gel permeation chromatography, elemental, and thermal gravimetric analyses) methods. Antibacterial efficacy was evaluated against Staphylococcus aureus (ATCC-2913), vancomycin-resistant Enterococcus faecium (ATCC-2320), Acinetobacter baumannii (ATCC-19606), Pseudomonas aeruginosa (ATCC-9027), and Klebsiella pneumoniae (ATCC-2146). Our best results were achieved with a cationic porphyrin-paper conjugate, Por((+))-paper, with inactivation upon illumination (30 min, 65 ± 5 mW/cm(2), 400-700 nm) of all bacterial strains studied by 99.99+% (4 log units), regardless of taxonomic classification. Por((+))-paper also inactivated dengue-1 virus (>99.995%), influenza A (∼ 99.5%), and human adenovirus-5 (∼ 99%). These results demonstrate the potential of cellulose materials to serve as scalable scaffolds for anti-infective or self-sterilizing materials against both bacteria and viruses when employing a photodynamic inactivation mode of action.

Determination of molecular weight distributions in native and pretreated wood.

The analysis of native wood components by size-exclusion chromatography (SEC) is challenging. Isolation, derivatization and solubilization of wood polymers is required prior to the analysis. The present approach allowed the determination of molecular weight distributions of the carbohydrates and of lignin in native and processed woods, without preparative component isolation steps. For the first time a component selective SEC analysis of sawdust preparations was made possible by the combination of two selective derivatization methods, namely; ionic liquid assisted benzoylation of the carbohydrate fraction and acetobromination of the lignin in acetic acid media. These were optimized for wood samples. The developed method was thus used to examine changes in softwood samples after degradative mechanical and/or chemical treatments, such as ball milling, steam explosion, green liquor pulping, and chemical oxidation with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ). The methodology can also be applied to examine changes in molecular weight and lignin-carbohydrate linkages that occur during wood-based biorefinery operations, such as pretreatments, and enzymatic saccharification.