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.

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.

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.

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.

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.

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.

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 (C) and varying degrees of chlorination.

Determination of hydroxyl groups in biorefinery resources via quantitative P 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 P 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.

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

Cubic, truncated cubic and spherical nano and micro particles of CuO, can be selectively deposited onto nano fibrilated cellulose gels by the modulated alkaline reduction of Cu 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 CuO morphologies, is discussed with respect to the detailed nucleation effects leading to micro and nano CuO 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 CuO nucleation mechanism.

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.

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.

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.

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.

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%.

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.

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.

Quantitative 31P NMR analysis of solid wood offers an insight into the acetylation of its components.

As a solid substrate, wood and its components are almost invariably examined via spectroscopic or indirect methods of analysis. Unlike earlier approaches, in this effort we dissolve pulverized wood in ionic liquid and then directly derive its functional group contents by quantitative (31)P NMR. As such, this novel analytical methodology is thoroughly examined and an insight into the detailed way acetylation proceeds on solid wood and its components is provided as a function of wood density and within its various anatomical features.

Kraft lignin chain extension chemistry via propargylation, oxidative coupling, and Claisen rearrangement.

Despite its aromatic and polymeric nature, the heterogeneous, stochastic, and reactive characteristics of softwood kraft lignin seriously limit its potential for thermoplastic applications. Our continuing efforts toward creating thermoplastic lignin polymers are now focused at exploring propargylation derivatization chemistry and its potential as a versatile novel route for the eventual utilization of technical lignins with a significant amount of molecular control. To do this, we initially report the systematic propargylation of softwood kraft lignin.

Efficient one-pot synthesis of 5-chloromethylfurfural (CMF) from carbohydrates in mild biphasic systems.

5-Halomethylfurfurals can be considered as platform chemicals of high reactivity making them useful for the preparation of a variety of important compounds. In this study, a one-pot route for the conversion of carbohydrates into 5-chloromethylfurfural (CMF) in a simple and efficient (HCl-H3PO4/CHCl3) biphasic system has been investigated. Monosaccharides such as D-fructose, D-glucose and sorbose, disaccharides such as sucrose and cellobiose and polysaccharides such as cellulose were successfully converted into CMF in satisfactory yields under mild conditions.

Accurate and reproducible determination of lignin molar mass by acetobromination.

The accurate and reproducible determination of lignin molar mass by using size exclusion chromatography (SEC) is challenging. The lignin association effects, known to dominate underivatized lignins, have been thoroughly addressed by reaction with acetyl bromide in an excess of glacial acetic acid. The combination of a concerted acetylation with the introduction of bromine within the lignin alkyl side chains is thought to be responsible for the observed excellent solubilization characteristics acetobromination imparts to a variety of lignin samples.