ABSTRACT
Beech sawdust was treated with a ternary solvent system based on binary aqueous ethanol with partial substitution of ethanol by acetone at four different water contents (60, 50, 40, and 30%v/v). In addition to standard, i.e., noncatalyzed treatments, the application of inorganic acid in the form of 20 mm H2SO4 was evaluated. The various solvent systems were applied at 180 °C for 60 min. The obtained biomass fractions were characterized by standard biomass compositional methods, i.e., sugar monomer and oligomer contents, dehydration product contents of the aqueous product, and lignin, cellulose, and hemicellulose contents in isolated solid fractions. More advanced analyses were performed on the lignin fractions, including quantitative 13C NMR analyses, 1H-13C HSQC analysis, size exclusion chromatography, and pyrolysis-GC/MS, and the aqueous product, in the form of size exclusion chromatography and determination of total phenol contents. The picture emerging from the thorough analytical investigation performed on the lignin fractions is consistent with that resulting from the characterization of the other fractions: results point toward greater deconstruction of the lignocellulosic recalcitrance upon higher organic solvent content, replacing ethanol with acetone during the extraction, and upon addition of mineral acid. A pulp with cellulose content of 94.23 wt % and 95% delignification was obtained for the treatment employing a 55/30/15 EtOH/water/acetone mixture alongside 20 mm H2SO4. Furthermore, the results indicate the formation of two types of organosolv furan families during treatment, which differ in the substitution of their C1 and C5. While the traditional lignin aryl-ether linkages present themselves as indicators for process severity for the nonacid catalyzed systems, the distribution of these furan types can be applied as a severity indicator upon employment of H2SO4, including their presence in the isolated lignin fractions.
ABSTRACT
Organosolv lignins (OSLs) are important byproducts of the cellulose-centred biorefinery that need to be converted in high value-added products for economic viability. Yet, OSLs occasionally display characteristics that are unexpected looking at the lignin motifs present. Applying advanced NMR, GPC, and thermal analyses, isolated spruce lignins were analysed to correlate organosolv process severity to the structural details for delineating potential valorisations. Very mild conditions were found to not fractionate the biomass, causing a mix of sugars, lignin-carbohydrate complexes (LCCs), and corresponding dehydration/degradation products and including pseudo-lignins. Employing only slightly harsher conditions promote fractionation, but also formation of sugar degradation structures that covalently incorporate into the oligomeric and polymeric lignin structures, causing the isolated organosolv lignins to contain lignin-humin hybrid (HLH) structures not yet evidenced as such in organosolv lignins. These structures effortlessly explain observed unexpected solubility issues and unusual thermal responses, and their presence might have to be acknowledged in downstream lignin valorisation.
Subject(s)
Lignin , Picea , Lignin/chemistry , Cellulose , Magnetic Resonance Spectroscopy , SugarsABSTRACT
Lignocellulosic biomass is one of the most important renewable materials to replace carbon-based fossil resources. Solvent-based fractionation is a promising route for fractionation of biomass into its major components. Processing is governed by the employed solvent-systems properties. This review sheds light on the factors governing both dissolution and potential reactivities of the chemical structures present in lignocellulose, highlighting how proper understanding of the underlying mechanisms and interactions between solute and solvent help to choose proper systems for specific fractionation needs. Structural and chemical differences between the carbohydrate-based structural polymers and lignin require very different solvents capabilities in terms of causing and eventually stabilizing conformational changes and consequent activation of bonds to be cleaved by other active components in the. A consideration of potential depolymerization events during dissolution and energetic aspects of the dissolution process considering the contribution of polymer functionalities allow for a mapping of solvent suitability for biomass fractionation.
Subject(s)
Carbohydrates , Lignin , Solvents/chemistry , Biomass , Lignin/chemistry , Chemical FractionationABSTRACT
The aim of this study was to investigate the pyrolysis products of polyhydroxyalkanoates (PHAs), polyethylene terephthalate (PET), carbon fiber reinforced composite (CFRC), and block co-polymers (PS-b-P2VP and PS-b-P4VP). The studied PHA samples were produced at temperatures of 15 and 50 oC (PHA15 and PHA50), and commercially obtained from GlasPort Bio (PHAc). Initially, PHA samples were analyzed by nuclear magnetic resonance (NMR) spectroscopy and size exclusion chromatography (SEC) to determine the molecular weight, and structure of the polymers. Thermal techniques such as thermogravimetry (TG) and differential scanning calorimetry (DSC) analyses were performed for PHA, CFRC, and block co-polymers to investigate the degradation temperature range and thermal stability of samples. Fast pyrolysis (500 oC, â¼102 °C s-1) experiments were conducted for all samples in a wire mesh reactor to investigate tar products and char yields. The tar compositions were investigated by gas chromatography-mass spectrometry (GC-MS), and statistical modeling was performed. The char yields of block co-polymers and PHA samples (<2 wt. %) were unequivocally less than that of the PET sample (~10.7 wt. %). All PHA compounds contained a large fraction of ethyl cyclopropane carboxylate (~ 38-58 %), whereas PAH15 and PHA50 additionally showed a large quantity of 2-butenoic acid (~8-12 %). The PHAc sample indicated the presence of considerably high amount of methyl ester (~15 %), butyl citrate (~12.9 %), and tributyl ester (~17 %). The compositional analyses of the liquid fraction of the PET and block co-polymers have shown carcinogenic and toxic properties. Pyrolysis removed matrices in the CRFC composites which is an indication of potential recovery of the original fibers.
Subject(s)
Plastics , Pyrolysis , Esters , Recycling , TarsABSTRACT
Invited for this month's cover are Antonella Ilenia Alfano and Margherita Brindisi (University of Naples Federico II) and Heiko Lange (University of Milano Bicocca). The cover image highlights the impact of greener and more sustainable flow chemistry protocols applied to amide bond formation. The Review itself is available at 10.1002/cssc.202102708.
Subject(s)
AmidesABSTRACT
Formation of amide bonds is of immanent importance in organic and synthetic medicinal chemistry. Its presence in "traditional" small-molecule active pharmaceutical ingredients, in linear or cyclic oligo- and polypeptidic actives, including pseudopeptides, has led to the development of dedicated synthetic approaches for the formation of amide bonds starting from, if necessary, suitably protected amino acids. While the use of solid supported reagents is common in traditional peptide synthesis, similar approaches targeting amide bond formation in continuous-flow mode took off more significantly, after a first publication in 2006, only a couple of years ago. Most efforts rely upon the transition of traditional approaches in flow mode, or the combination of solid-phase peptide synthesis principles with flow chemistry, and advantages are mainly seen in improving space-time yields. This Review summarizes and compares the various approaches in terms of basic amide formation, peptide synthesis, and pseudopeptide generation, describing the technological approaches and the advantages that were generated by the specific flow approaches. A final discussion highlights potential future needs and perspectives in terms of greener and more sustainable syntheses.
Subject(s)
Amides , Solid-Phase Synthesis Techniques , Amides/chemistry , Amino Acids/chemistry , Chemistry Techniques, Synthetic/methods , Peptides/chemistry , Solid-Phase Synthesis Techniques/methodsABSTRACT
Background: Tannins have demonstrated antibacterial and antibiofilm activity, but there are still unknown aspects on how the chemical properties of tannins affect their biological properties. We are interested in understanding how to modulate the antibiofilm activity of tannins and in delineating the relationship between chemical determinants and antibiofilm activity. Materials and methods: The effect of five different naturally acquired tannins and their chemical derivatives on biofilm formation and planktonic growth of Salmonella Typhimurium, Pseudomonas aeruginosa, Escherichia coli and Staphylococcus aureus was determined in the Calgary biofilm device. Results: Most of the unmodified tannins exhibited specific antibiofilm activity against the assayed bacteria. The chemical modifications were found to alter the antibiofilm activity level and spectrum of the tannins. A positive charge introduced by derivatization with higher amounts of ammonium groups shifted the anti-biofilm spectrum toward Gram-negative bacteria, and derivatization with lower amounts of ammonium groups and acidifying derivatization shifted the spectrum toward Gram-positive bacteria. Furthermore, the quantity of phenolic OH-groups per molecule was found to have a weak impact on the anti-biofilm activity of the tannins. Conclusion: We were able to modulate the antibiofilm activity of several tannins by specific chemical modifications, providing a first approach for fine tuning of their activity and antibacterial spectrum.
ABSTRACT
The generation of peptidomimetic substructures for medicinal chemistry purposes requires effective and divergent synthetic methods. We present in this work an efficient flow process that allows quick modulation of reagents for Joullié-Ugi multicomponent reaction, using spiroindolenines as core motifs. This sterically hindered imine equivalent could successfully be diversified using various isocyanides and amino acids in generally good space-time yields. A telescoped flow process combining interrupted Fischer reaction for spiroindolenine synthesis and subsequent Joullié-Ugi-type modification resulted in product formation in very good overall yield in less than 2â hours compared to 48â hours required in batch mode. The developed protocol can be seen as a general tool for rapid and facile generation of peptidomimetic compounds. We also showcase preliminary biological assessments for the prepared compounds.
Subject(s)
Anti-Bacterial Agents/pharmacology , Peptidomimetics/pharmacology , Staphylococcus epidermidis/drug effects , Anti-Bacterial Agents/chemical synthesis , Anti-Bacterial Agents/chemistry , Biofilms/drug effects , Microbial Sensitivity Tests , Molecular Conformation , Peptidomimetics/chemical synthesis , Peptidomimetics/chemistry , StereoisomerismABSTRACT
Novel valorization routes for tannins were opened by the development of a simple, straightforward, robust, and flexible approach to the selective functionalization of condensed and hydrolyzable tannins. Irrespective of the different degrees of polymerization, different commercial tannins were efficiently functionalized by the generation of an ether linkage bound to a short linker carrying the desired functional group. Functionalizations could be realized at varying degrees of technical loadings, i.e., amounts of introduced tannin-alien functionalities per number of phenolic hydroxyl groups. The same strategy was found suitable for the synthesis of polyethylene glycol-functionalized tannin copolymers. Condensed tannins functionalized with carboxylic acid moieties could be converted into a tannin-oligopeptide hybrid.
ABSTRACT
Microcapsules of sulfited Acacia mearnsii tannin (AmST-MCs) were generated for the first time via the sonochemical method. Their stability profile was assessed and set in the general context of tannin microcapsules (TMCs) generated under the same experimental conditions. The analytical data gathered in this work indicate an excellent stability of TMCs over time as well as under high temperature and pressure, which is a major milestone toward the meaningful applications of TMCs in industrial, pharmaceutical, and biomedical applications in which sterilization of TMCs might be a prerequisite. Active release is shown to be efficiently triggered by varying pH and/or salinity, with different profiles for TMCs from sulfited and nonsulfited species. Surfactants also affect the stability of TMCs significantly, with effects eventually amplifiable by pH and the inherent kosmotropic and chaotropic characteristics of salt components in solutions.
ABSTRACT
Both condensed and hydrolysable tannins represent versatile natural polyphenolic structures exhibiting a broad range of activities that could be exploited in various fields including nutraceutics, cosmesis, consumer care, household and pharmaceutical applications. Various tannins are commercially available nowadays for use in such application fields. We have analysed a representative selection of commercially available condensed and hydrolysable tannins for structural features and purity. Using a combination of quantitative 31P NMR spectroscopy, HSQC measurements, MALDI-ToF analyses, gel permeation chromatography and wet chemical analysis, detailed structural characterisations and descriptions were possible, allowing for verification and falsification of claimed structural features.
Subject(s)
Tannins/chemistry , Hydrolyzable Tannins/chemistry , Hydrolyzable Tannins/isolation & purification , Magnetic Resonance Spectroscopy , Molecular Structure , Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization , Structure-Activity Relationship , Tannins/isolation & purificationABSTRACT
Organosolv pretreatment represents one of the most promising biomass valorization strategies for renewable carbon-based products; meanwhile, there is an overall lack of holistic approach to how extraction conditions affect the suitable end-usages. In this context, lignin extracted from silver birch (Betula pendula L.) by a novel hybrid organosolv/steam-explosion treatment at varying process conditions (EtOH %; time; catalyst %) was analyzed by quantitative NMR (1H-13C HSQC; 13C NMR; 31P NMR), gel permeation chromatography, Fourier transform infrared (FT-IR), Pyr-gas chromatography-mass spectroscopy (GC/MS), and thermogravimetric analysis, and the physicochemical characteristics of the lignins were discussed regarding their potential usages. Characteristic lignin interunit bonding motifs, such as ß-O-4', ß-ß', and ß-5', were found to dominate in the extracted lignins, with their abundance varying with treatment conditions. Low-molecular-weight lignins with fairly unaltered characteristics were generated via extraction with the highest ethanol content potentially suitable for subsequent production of free phenolics. Furthermore, ß-ß' and ß-5' structures were predominant at higher acid catalyst contents and prolonged treatment times. Higher acid catalyst content led to oxidation and ethoxylation of side-chains, with the concomitant gradual disappearance of p-hydroxycinnamyl alcohol and cinnamaldehyde. This said, the increasing application of acid generated a broad set of lignin characteristics with potential applications such as antioxidants, carbon fiber, nanoparticles, and water remediation purposes.
ABSTRACT
Lignins were fractionated in a segmented continuous flow fractionation (SCFF) approach using isocratic or gradient elution profiles of different solvent systems at various flow rates and temperatures against adjustable pressure regimes. Superior control of parameters such as temperature and pressure in combination with the possibility of freely combinable solvent gradients allowed facile fractionation and generation of industrially interesting fractions differing in molecular weight properties and/or in physicochemical properties in a process that could be fully remotely controlled for automation and performance. Scale-up of the process was possible in linear and parallel mode. Analyses of the realised fractions by standardised gel permeation chromatography and 31 Pâ NMR spectroscopy protocols showed that the SCFF of lignins delivered fractions that could be similar to conventional batch fractions, as well as novel/altered fractions available by applying overheated solvents in pressurised systems.
ABSTRACT
Thymol and the corresponding brominated derivatives constitute important biological active molecules as antibacterial, antioxidant, antifungal, and antiparasitic agents. However, their application is often limited, because their pronounced fragrance, their poor solubility in water, and their high volatility. The encapsulation of different thymol derivatives into biocompatible lignin-microcapsules is presented as a synergy-delivering remedy. The adoption of lignosulfonate as an encapsulating material possessing relevant antioxidant activity, as well as general biocompatibility allows for the development of new materials that are suitable for the application in various fields, especially cosmesis. To this purpose, lignin microcapsules containing thymol, 4-bromothymol, 2,4-dibromothymol, and the corresponding O-methylated derivatives have been efficiently prepared through a sustainable ultrasonication procedure. Actives could be efficiently encapsulated with efficiencies of up to 50%. To evaluate the applicability of such systems for topical purposes, controlled release experiments have been performed in acetate buffer at pH 5.4, to simulate skin pH: all of the capsules show a slow release of actives, which is strongly determined by their inherent lipophilicity.
Subject(s)
Anti-Infective Agents/pharmacology , Antioxidants/pharmacology , Capsules/chemistry , Delayed-Action Preparations/chemical synthesis , Lignin/analogs & derivatives , Thymol/pharmacology , Animals , Anti-Infective Agents/chemistry , Antioxidants/chemistry , Buffers , Drug Compounding/methods , Drug Liberation , Halogenation , Humans , Hydrogen-Ion Concentration , Kinetics , Lignin/chemistry , Particle Size , Solubility , Solutions , Sonication , Thymol/chemistryABSTRACT
Eucalyptus nitens wood samples were subjected to consecutive stages of hydrothermal processing for hemicellulose solubilization and delignification with an ionic liquid, i.e., either 1-butyl-3-methylimidazolium hydrogen sulfate or triethylammonium hydrogen sulfate. Delignification experiments were carried out a 170 C for 10-50 min. The solid phases from treatments, i.e., cellulose-enriched solids, were recovered by centrifugation, and lignin was separated from the ionic liquid by water precipitation. The best delignification conditions were identified on the basis of the results determined for delignification percentage, lignin recovery yield, and cellulose recovery in solid phase. The lignins obtained under selected conditions were characterized in deep by 31P-NMR, 13C-NMR, HSQC, and gel permeation chromatography. The major structural features of the lignins were discussed in comparison with the results determined for a model Ionosolv lignin.
Subject(s)
Eucalyptus/chemistry , Ionic Liquids/chemistry , Lignin/chemistry , Chromatography, Gel , Hydrolysis , Magnetic Resonance SpectroscopyABSTRACT
Two different organosolv lignins (OSLs), that is, wheat straw and corn stover OSLs, were chemically and enzymatically functionalized. Functional groups were attached via the formation of stable ether bonds exploiting the reactivity of free phenolic OH groups along the lignin backbone. The functional groups introduced a range from compact charged and chargeable building blocks for the generation of surface-active lignins to oligomeric and polymeric species used in lignin block-copolymer productions. Combination of selected functions led to novel charged or chargeable polymeric lignin-based materials. Products could be realized with different degrees of technical loadings in terms of introduced functional groups.
ABSTRACT
Stimuli-responsive behavior of lignin microcapsules (LMCs) has been investigated along with the detailed characterization of their stability profiles. The disassembly of LMCs was found to be salt species-dependent, indicating the specific relevance of inherent kosmotropic and chaotropic characteristics. For the first time, a connection between the Hofmeister series and the stability profile of lignin microscale materials is established. LMCs showed excellent stability in water and under high temperature and pressure (autoclaving conditions). Active release is efficiently triggered by pH changes and balancing chaotropic and kosmotropic effects via salinity tuning.
ABSTRACT
Phase change contrast agents for ultrasound (US) imaging consist of nanodroplets (NDs) with a perfluorocarbon (PFC) liquid core stabilized with a lipid or a polymer shell. Liquid â gas transition, occurring in the core, can be triggered by US to produce acoustically active microbubbles (MBs) in a process named acoustic droplet vaporization (ADV). MB shells containing polymerized diacetylene moiety were considered as a good trade off between the lipid MBs, showing optimal attenuation, and the polymeric ones, displaying enhanced stability. This work reports on novel perfluoropentane and perfluorobutane NDs stabilized with a monolayer of an amphiphilic fatty acid, i.e. 10,12-pentacosadiynoic acid (PCDA), cured with ultraviolet (UV) irradiation. The photopolymerization of the diacetylene groups, evidenced by the appearance of a blue color due to the conjugation of ene-yne sequences, exhibits a chromatic transition from the nonfluorescent blue color to a fluorescent red color when the NDs are heated or the pH of the suspension is basic. An estimate of the molecular weights reached by the polymerized PCDA in the shell, poly(PCDA), has been obtained using gel permeation chromatography and MALDI-TOF mass spectrometry. The poly(PCDA)/PFC NDs show good biocompatibility with fibroblast cells. ADV efficiency and acoustic properties before and after the transition were tested using a 1 MHz probe, revealing a resonance frequency between 1 and 2 MHz similar to other lipidic MBs. The surface of PCDA shelled NDs can be easily modified without influencing the stability and the acoustic performances of droplets. As a proof of concept we report on the conjugation of cyclic RGD and PEG chains of the particles to support targeting ability toward endothelial cells.
ABSTRACT
A new fractionation protocol for wheat straw organosolv lignin was developed on the basis of the dominating H-bonding orientations of its components. Acetone as H-bond accepting aprotic polar solvent and methanol as H-bond donating and accepting protic polar solvent were used in sequence. Obtained fractions were structurally and thermally analysed. The protocol allowed for the generation of purified lignin fractions and the isolation of a novel, yet unobserved lignin carbohydrate complex (LCC) fraction. This LCC fraction was found to contain exclusively phenyl glycosides and γ-esters as LCC motifs.
ABSTRACT
To liberate society from its dependence on fossil-based fuels and materials it is pivotal to explore components of renewable plant biomass in applications that benefit from their intrinsic biodegradability, safety, and sustainability. Lignin, a byproduct of the pulp and paper industry, is a plausible material for carrying various types of cargo in small- and large-scale applications. Herein, possibilities and constraints regarding the physical-chemical properties of the lignin source as well as modifications and processing required to render lignins suitable for the loading and release of pesticides, pharmaceuticals, and biological macromolecules is reviewed. In addition, the technical challenges, regulatory and toxicological aspects, and future research needed to realize some of the promises that nano- and microscaled lignin materials hold for a sustainable future are critically discussed.