Formation Of Ether Bonds Research Articles

Tailoring the Structure and Physico-Chemical Features of Cellulose-Based Hydrogels Using Multi-Epoxy Crosslinking Agents.

Hydrogel features can be designed and optimized using different crosslinking agents to meet specific requirements. In this regard, the present work investigates the physico-chemical features of cellulose-based hydrogels, designed by using different epoxy crosslinkers from the same glycidyl family, namely epichlorohydrin (ECH), 1,4-butanediol diglycidyl ether (BDDE), and trimethylolpropane triglycidyl ether (TMPTGE). The effect of the crosslinker's structure (from simple to branched) and functionality (mono-, bi- and tri-epoxy groups) on the hydrogels' features was studied. The performances of the hydrogels were investigated through the gel fraction, as well as by ATR-FTIR, DVS, SEM, DSC, and TG analyses. Also, the swelling and rheological behaviors of the hydrogels were examined. The advantages and limitations of each approach were discussed and a strong correlation between the crosslinker structure and the hydrogel properties was established. The formation of new ether bonds was evidenced by ATR-FTIR spectroscopy. It was emphasized that the pore size is directly influenced by the crosslinker type, namely, it decreases with the increasing number of epoxy groups from the crosslinker molecule, i.e., from 46 ± 11.1 µm (hydrogel CE, with ECH) to 12.3 ± 2.5 µm (hydrogel CB, with BDDE) and 6.7 ± 1.5 µm (hydrogel CT, with TMPTGE). The rheological behavior is consistent with the swelling data and hydrogel morphology, such as CE with the highest Qmax and the largest pore size being relatively more elastic than CB and CT. Instead, the denser matrices obtained by using crosslinkers with more complex structures have better thermal stability. The experimental results highlight the possibility of using a specific crosslinking agent, with a defined structure and functionality, in order to establish the main characteristics of hydrogels and, implicitly, to design them for a certain field of application.

Chemical Transformation of B- to A-type Proanthocyanidins and 3D Structural Implications.

In nature, proanthocyanidins (PACs) with A-type linkages are relatively rare, likely due to biosynthetic constraints in the formation of additional ether bonds to be introduced into the more common B-type precursors. However, A-type linkages confer greater structural rigidity on PACs than do B-type linkages. Prior investigations into the structure-activity relationships (SAR) describing how plant-derived PACs with B- and complex AB-type linkages affect their capacity for dentin biomodification indicate that a higher ratio of double linkages leads to a greater interaction with dentin type I collagen. Thus, A-type PACs emerge as particularly intriguing candidates for interventional functional biomaterials. This study employed a free-radical-mediated oxidation using DPPH to transform trimeric and tetrameric B-type PACs, 2 and 4, respectively, into their exclusively A-type linked analogues, 3 and 5, respectively. The structures and absolute configurations of the semisynthetic products, including the new all-A-type tetramer 5, were determined by comprehensive spectroscopic analysis. Additionally, molecular modeling investigated the conformational characteristics of all trimers and tetramers, 1-5. Our findings suggest that the specific interflavan linkages significantly impact the flexibility and low-energy conformations of the connected monomeric units, which conversely can affect the bioactive conformations relevant for dentin biomodification.

Ether Bond Formation in Waste Biomass–Derived, Value-Added Technical Hardwood Kraft Lignin Using Glycolic Acid

Ether bond formation in technical hardwood kraft lignin (THKL) by crosslinking using glycolic acid was investigated for bio-adhesive applications. Industrial hardwood kraft black liquor was used to extract the THKL utilized by acidification. Chemical and thermal properties of the THKL with and without crosslinking were analyzed by Fourier transform infrared (FTIR) spectroscopy, solid-state 13C cross-polarization/magic angle spinning nuclear magnetic resonance (13C CP/MAS NMR) spectroscopy, X-ray photoelectron spectroscopy (XPS), gel permeation chromatography (GPC), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). FTIR results revealed a new peak corresponding to the ether bond and hemiacetal formation due to crosslinking at 1075 cm-1 and 1324 cm-1. 13C CP/MAS NMR spectra revealed the presence of a higher number of ether bonds due to the reduced aromatic and aliphatic hydroxyl groups in THKL and new bonds formed at 62-64 ppm and 168-191 ppm due to crosslinking. XPS results revealed that new bonds were formed between glycolic acid and THKL, leading to increased atomic oxygen percentage and carbon–oxygen bonds in crosslinked THKL detected by peak intensity changes at 287.7 and 288.8 related to O–C–O and O–C=O. Also, the oxygen content increased from 14.88% to 31.76% due to bond formation. GPC confirmed a higher molecular weight and broader molecular-weight distribution of THKL. DSC and TGA curves of crosslinked THKL revealed exothermic behavior, high thermal stability, and low thermal degradation rate. Owing to a significant amount of kraft black liquor being generated by wood pulp industries and attractive chemical properties of THKL, THKL demonstrates promise as a raw material to produce green, sustainable bio-adhesives via the crosslinking of its different hydroxyl groups using glycolic acid.

Characterization of the depsidone gene cluster reveals etherification, decarboxylation and multiple halogenations as tailoring steps in depsidone assembly.

Depsides and depsidones have attracted attention for biosynthetic studies due to their broad biological activities and structural diversity. Previous structure‒activity relationships indicated that triple halogenated depsidones display the best anti-pathogenic activity. However, the gene cluster and the tailoring steps responsible for halogenated depsidone nornidulin (3) remain enigmatic. In this study, we disclosed the complete biosynthetic pathway of the halogenated depsidone through invivo gene disruption, heterologous expression and invitro biochemical experiments. We demonstrated an unusual depside skeleton biosynthesis process mediated by both highly-reducing polyketide synthase and non-reducing polyketide synthase, which is distinct from the common depside skeleton biosynthesis. This skeleton was subsequently modified by two in-cluster enzymes DepG and DepF for the ether bond formation and decarboxylation, respectively. In addition, the decarboxylase DepF exhibited substrate promiscuity for different scaffold substrates. Finally, and interestingly, we discovered a halogenase encoded remotely from the biosynthetic gene cluster, which catalyzes triple-halogenation to produce the active end product nornidulin (3). These discoveries provide new insights for further understanding the biosynthesis of depsidones and their derivatives.

ELABORATION OF CHEMICAL SENSOR SENSITIVE TO BORON BENZILATE

Over the last decades, the development of simple and selective methods for the determination of organic analytes has been getting attention from analytical chemists. Particularly, the same applies to biologically active substances of natural and artificial origin, precursors, and metabolites of pharmaceuticals[1]. An example of such substance is benzylic acid (2, 2-diphenyl-2-hydroxyacetic acid) (BA), gravimetric reagent for zirconium [2], a product of hydrolysis and a metabolite of the antispasmodic and sedative drugs Pipoxolan, Benactyzine, or Metacin [3]. The complexes of BA have been proposed as corrosion inhibitors for some steels and aluminum alloys [4]. Its derivatives are being studied as new analgesics [5], anticancer drugs [6], and also as deep eutectic solvents [7]. The BA was used in the synthesis of the psychotropic combatant substance 3-quinuclidinyl benzilate (BZ), which causes mental slowing, and hydrolyzes to form BC [8-11]. For BA determination high-performance liquid chromatography and chromatography-mass spectrometry [12-15] are mostly used, hence the development of simple methods for determining benzylic acid is pertinent and relevant.
 Boric acid is known to form compounds with diols, α-hydroxy acids, dicarboxylic acids, and α-diketones [16] and that was used in developing potentiometric sensors for the determination of mandelic acid and vitamin C [17, 18]. As BA also forms complexes with boric acid and various metals [19, 20] the H3BO3 has been used in the present study as a reagent for obtaining boric acid benzilate ester - the analytical form of BA, as well as the ionic associate of its anion with tetraoctylammonium(TOA) as the active substance of a potentiometric PVC plasticized sensor sensitive to the mentioned above analytical form. The complex formation has been confirmed using IR spectroscopy. On the IR spectrum of BA, the absorption bands in the region of 3393. 69 cm-1 and 1715. 77 cm-1, which correspond to the vibrations of –ОН and >С=О groups, respectively have been detected [23]. At the same time, in the IR spectrum of the complex, the absorption band of –ОН groups in the region of 3300 - 3400 cm-1 was absent, that indicates their participation in the formation of ether bonds, additionally, the intensive bands of >C=O in the region of 1723. 41 cm-1 and 1742. 05 cm-1 has appeared. The ion pair of tetraoctylammonium cation with synthesized complex ion [B(Benz)2]- has been used as an active substance of the potentiometric sensor. The metrological and operational characteristics of the sensor and the optimal conditions of the analytical form obtaining have been systematically studied. The optimized composition of the sensitive PVC membrane was 0. 1% of IP, 33. 0% of PVC and 66. 9% of o-NFOE. For high yield [B(Benz)(ОН)2]--analytical form preparation the boiling of BA for 15 minutes in the medium of a buffer solution that consists of H3BO3 (sat.) - 0. 1 M NaOH - 0. 1 M H3PO4 with a pH of 5. 5 is needed. In optimal conditions, the slope of the sensor developed is close to the theoretical value of 55. 2 mV/pС, has a detection limit pCmin= 4. 9, and the linearity range 10-2 – 10-4mol/l. The response time of a sensor ranges from 5 to 30 seconds depending on the added quantity. High selectivity of the sensor to metal cations, anions of organic and inorganic acids, as well as polyatomic alcohols that are able to form complex compounds with BA or H3BO3 has been shown. The sensor developed was used for benzylic acid analysis in "Difenin", which can be formed during the synthesis of this drug [27].
 It has been shown that the use of potentiometry in combination with the conversion of the analyte into an active form using a cheap reagent - boric acid allows to develop simple methods of the organic analytes determination for which the use of potentiometry is not common. Preparation of the complex boronate ester of benzylic acid in the sample provides the selectivity of the technique to the target analyte.
 Keywords: benzylic acid; boron benzilate; potentiometric sensor; ion pair.

Synthesis of Prepolymers of Poly(glycerol-co-diacids) Based on Sebacic and Succinic Acid Mixtures.

In this study, poly(glycerol-co-diacids) prepolymers were produced using different ratios of glycerol (G), sebacic acid (S), and succinic acid (Su) (molar ratios: GS 1:1, GSSu 1:0.9:0.1, GSSu 1:0.8:0.2, GSSu 1:0.5:0.5, GSSu 1:0.2:0.8, GSSu 1:0.1:0.9, GSu 1:1). All polycondensation reactions were performed at 150 °C until reaching a degree of polymerization of ≈55%, inferred by the water volume collected from a reactor. We concluded that the reaction time is correlated with the ratio of diacids used, that is, the increase in succinic acid is proportional to a decrease in the duration of the reaction. In fact, the reaction of poly(glycerol sebacate) (PGS 1:1) is twice as slow as the reaction of poly(glycerol succinate) (PGSu 1:1). The obtained prepolymers were analyzed by electrospray ionization mass spectrometry (ESI-MS) and 1H and 13C nuclear magnetic resonance (NMR). Besides its catalytic influence in poly(glycerol)/ether bond formation, the presence of succinic acid also contributes to a mass growth of ester oligomers, the formation of cyclic structures, a greater number of oligomers detected, and a difference in mass distribution. When compared with PGS (1:1), and even at lower ratios, the prepolymers produced with succinic acid presented mass peak characteristics of oligomer species with a glycerol unit as its end group in higher abundance. Generally, the most abundant oligomers have molecular weights between 400 and 800 g/mol.

Synthesis of biologically derived poly(pyrogallol) nanofibers for antibacterial applications.

Herein, we present the facile synthesis of poly(pyrogallol) biopolymers and their application as antibacterial agents. Pyrogallol is a class of phenolic compounds that can be found in various plants. Polymerization was performed by the auto-oxidation of pyrogallol under a hydrated condition. The microscopic image of poly(pyrogallol) shows a highly homogenous nanofibrous structure with a diameter of 100.3 ± 16.3 nm. Spectroscopic analysis by FT-IR spectroscopy, Raman spectroscopy, and XPS corroborated the formation of ether (C-O-C) bonds between the hydroxyl group and adjacent carbons of pyrogallol during polymerization. The FT-IR and XPS spectra also revealed redox-active gallol functional groups on poly(pyrogallol) nanofibers, which can be used to release free electrons and protons during oxidation followed by the generation of reactive oxygen species (ROS). The generated ROS from poly(pyrogallol) was used to inhibit the growth of bacteria, Escherichia coli, at a inhibition rates of 56.3 ± 9.7% and 95.5 ± 2.0% within 0.5 and 2 h, respectively. This finding suggests that poly(pyrogallol) can be used as a naturally occurring antibacterial agent for various biomedical and environmental applications.

Disentangling the lipid divide: Identification of key enzymes for the biosynthesis of membrane-spanning and ether lipids in Bacteria

Bacterial membranes are composed of fatty acids (FAs) ester-linked to glycerol-3-phosphate, while archaea have membranes made of isoprenoid chains ether-linked to glycerol-1-phosphate. Many archaeal species organize their membrane as a monolayer of membrane-spanning lipids (MSLs). Exceptions to this "lipid divide" are the production by some bacterial species of (ether-bound) MSLs, formed by tail-to-tail condensation of FAs resulting in the formation of (iso) diabolic acids (DAs), which are the likely precursors of paleoclimatological relevant branched glycerol dialkyl glycerol tetraether molecules. However, the enzymes responsible for their production are unknown. Here, we report the discovery of bacterial enzymes responsible for the condensation reaction of FAs and for ether bond formation and confirm that the building blocks of iso-DA are branched iso-FAs. Phylogenomic analyses of the key biosynthetic genes reveal a much wider diversity of potential MSL (ether)-producing bacteria than previously thought, with importantt implications for our understanding of the evolution of lipid membranes.

Structural, antioxidant, antibacterial and biodegradation properties of rice straw xylan (native and modified) based biofilms

SummaryThe present study involved valorisation of rice straw by conversion of its constituent polymer xylan and chemically modified xylans into biofilms. Hemicellulosic xylan (19.94%) extracted with 10% NaOH (85 °C, 2.6 h) was chemically modified to acetylated (AX) and carboxymethylated xylan (CMX). Biofilms were prepared by reaction of xylan/modified xylan (1% and 2%) with polyvinyl alcohol using eco‐friendly and cheap cross‐linker citric acid and glycerol as plasticiser. 2% xylan biofilms showed maximum inhibition (94.25%) of DPPH at 4 mg mL−1 which was due to large number of free ‐OH groups (highest intensity of ‐OH absorption bands in FT‐IR spectra). 2% CMX biofilms exhibited maximum antibacterial effectiveness with diameter of zone of inhibition 33.5 and 30.5 mm against Bacillus subtilis and Pseudomonas sp., respectively. This may be due to large number of undissociated COO− ions (citric acid) in CMX biofilms which was evident from lesser cross‐linking observed in their SEM images. 2% CMX biofilms also showed the highest biodegradation (86.5%) which may be attributed to formation of ether bonds along with ester bonds leading to their fast degradation. Owing to good bioactive properties of prepared biofilms, it was concluded that these can be appropriate material for food packaging by replacing synthetic plastics.

Plasmalogens and Photooxidative Stress Signaling in Myxobacteria, and How it Unmasked CarF/TMEM189 as the Δ1'-Desaturase PEDS1 for Human Plasmalogen Biosynthesis.

Plasmalogens are glycerophospholipids with a hallmark sn-1 vinyl ether bond that endows them with unique physical-chemical properties. They have proposed biological roles in membrane organization, fluidity, signaling, and antioxidative functions, and abnormal plasmalogen levels correlate with various human pathologies, including cancer and Alzheimer’s disease. The presence of plasmalogens in animals and in anaerobic bacteria, but not in plants and fungi, is well-documented. However, their occurrence in the obligately aerobic myxobacteria, exceptional among aerobic bacteria, is often overlooked. Tellingly, discovery of the key desaturase indispensable for vinyl ether bond formation, and therefore fundamental in plasmalogen biogenesis, emerged from delving into how the soil myxobacterium Myxococcus xanthus responds to light. A recent pioneering study unmasked myxobacterial CarF and its human ortholog TMEM189 as the long-sought plasmanylethanolamine desaturase (PEDS1), thus opening a crucial door to study plasmalogen biogenesis, functions, and roles in disease. The findings demonstrated the broad evolutionary sweep of the enzyme and also firmly established a specific signaling role for plasmalogens in a photooxidative stress response. Here, we will recount our take on this fascinating story and its implications, and review the current state of knowledge on plasmalogens, their biosynthesis and functions in the aerobic myxobacteria.

Identification of a poly-cyclopropylglycine–containing peptide via bioinformatic mapping of radical S-adenosylmethionine enzymes

Peptide-derived natural products are a large class of bioactive molecules that often contain chemically challenging modifications. In the biosynthesis of ribosomally synthesized and posttranslationally modified peptides (RiPPs), radical-SAM (rSAM) enzymes have been shown to catalyze the formation of ether, thioether, and carbon-carbon bonds on the precursor peptide. The installation of these bonds typically establishes the skeleton of the mature RiPP. To facilitate the search for unexplored rSAM-dependent RiPPs for the community, we employed a bioinformatic strategy to screen a subfamily of peptide-modifying rSAM enzymes which are known to bind up to three [4Fe-4S] clusters. A sequence similarity network was used to partition related families of rSAM enzymes into >250 clusters. Using representative sequences, genome neighborhood diagrams were generated using the Genome Neighborhood Tool. Manual inspection of bacterial genomes yielded numerous putative rSAM-dependent RiPP pathways with unique features. From this analysis, we identified and experimentally characterized the rSAM enzyme, TvgB, from the tvg gene cluster from Halomonas anticariensis. In the tvg gene cluster, the precursor peptide, TvgA, is comprised of a repeating TVGG motif. Structural characterization of the TvgB product revealed the repeated formation of cyclopropylglycine, where a new bond is formed between the γ-carbons on the precursor valine. This novel RiPP modification broadens the functional potential of rSAM enzymes and validates the proposed bioinformatic approach as a practical broad search tool for the discovery of new RiPP topologies.

FeIII/TBHP mediated remote C–O bond construction of 8-aminoquinolines: access to methoxylation and cyanomethoxylation

The C5 regioselective methoxylation and cyanomethoxylation of 8-aminoquinolines were achieved under FeIII/TBHP system by tuning the temperature and solvent. TBHP was investigated as an “oxygen” source in the ether bond formation for the first time.

Acid catalyzed cross‐linking of polyvinyl alcohol for humidifier membranes

AbstractPolyvinyl alcohol (PVA) is a hydrophilic polymer well known for good film forming properties, high water vapor permeance JW, and low nitrogen permeance. However, depending on molar mass and temperature, PVA swells strongly in water until complete dissolution. This behavior affects the usability of PVA in aqueous environments and makes cross‐linking necessary if higher structural integrity is envisaged. In this work, PVA networks are formed by thermal cross‐linking in the presence of p‐toluenesulfonic acid (TSA) and investigated in a design of experiments approach. Experimental parameters are the cross‐linking period tc, temperature ϑ and the TSA mass fraction wTSA. Cross‐linking is found to proceed via ether bond formation at all reaction conditions. Degradation is promoted especially by a combination of high wTSA, tc and ϑ. Thermal stability of the networks after preparation is strongly improved by neutralizing residual TSA. Humidification membranes with a JW of 6423 ± 63.0 gas permeation units (GPU) are fabricated by coating PVA on polyvinyliden fluoride hollow fibers and cross‐linking with TSA. Summarizing, the present study contributes to a clearer insight into the cross‐linking of PVA in presence of TSA, the thermal stability of the resulting networks and the applicability as selective membrane layers for water vapor transfer.

Chemoselective, Scalable Nickel-Electrocatalytic O-Arylation of Alcohols.

The formation of aryl-alkyl ether bonds through cross coupling of alcohols with aryl halides represents a useful strategic departure from classical SN 2 methods. Numerous tactics relying on Pd-, Cu-, and Ni-based catalytic systems have emerged over the past several years. Herein we disclose a Ni-catalyzed electrochemically driven protocol to achieve this useful transformation with a broad substrate scope in an operationally simple way. This electrochemical method does not require strong base, exogenous expensive transition metal catalysts (e.g., Ir, Ru), and can easily be scaled up in either a batch or flow setting. Interestingly, e-etherification exhibits an enhanced substrate scope over the mechanistically related photochemical variant as it tolerates tertiary amine functional groups in the alcohol nucleophile.

Polyhydroxybutyrate Bioresins with High Thermal Stability by Cross-linking with Resorcinol Diglycidyl Ether.

The development of sustainable materials by employing natural and nontoxic resources has been attracting much attention over the previous years. In this work, we discuss for the first time the chemical combination between resorcinol diglycidyl ether (RDGE), an aromatic biobased thermosetting monomer, and polyhydroxybutyrate (PHB), a bioderived and biodegradable thermoplastic polyester. By this combination, we aimed to associate the high thermal stability of RDGE with a toughening effect by the aliphatic chains of PHB. The investigations on the mechanism of the cross-linking reaction and on the structural connectivity between the two components were realized by Fourier transform infrared (FTIR) and NMR spectroscopies. We found that the epoxide polymerization catalyzed by tertiary amines triggers the formation of crotonyl species by polyhydroxybutyrate cleavage. Two-dimensional NMR experiments show that polyhydroxybutyrate fragments covalently bind as side chains to the rigid aromatic network of the epoxide frame. The cross-linking between the two systems entails the formation of new ester and ether bonds. The obtained structures show a network homogeneity confirmed by a single Tg, from 85 to 47 °C, as a function of the formulation, and tan δ values from 87 to 53 °C. The combination of the two comonomers showed a positive effect. The PHB increased the toughness of RDGE-based thermosets, improving the material elasticity by increasing the chain length between the cross-links. An important result of this study is the high thermal stability of RDGE/PHB bioresins, with the T5% varying between 330 and 310 °C as a function of the PHB ratio.

Cross-linking of poly (vinyl alcohol) films under acidic and thermal stress

Poly (vinyl alcohol), PVA, a commonly used excipient to coat tablets, forms insoluble films in the presence of acids and thermal stress. This may lead to drug products failing to meet dissolution specifications over time. Studies were conducted to understand the effect of acid strength, processing conditions, and storage stress on the mechanism of insoluble film formation using PVA and OpadryⓇ II as model systems. Aqueous cast films, prepared by incorporating hydrochloric acid (HCl) into the coating solutions or exposing pre-cast “as is” films to HCl vapors, were used as surrogates to develop analytical methods. To understand effect of acid and processing on coatings, acidified OpadryⓇ II was spray coated onto inert cores under “wet” or “dry” conditions. Samples stored at 50-60 °C were analyzed for film disintegration to understand physical/chemical changes in the polymer. Rate and extent of insoluble films formation was dependent on the acid concentration and thermal stress. Analysis of the films indicated significant de-acetylation and ether bond formation in insoluble aqueous cast films. In contrast, acidified coated films showed only ether bond formation, which increased on stress, forming insoluble films. The reduction in the time to form insoluble films for “wet” versus “dry” coated films was rationalized by considering effect of coating, drying, and storage on the microstructure of acidified PVA and ether bond propagation. The results highlight the need to develop an in-depth understanding of the design space for PVA coated products and storage conditions in presence of acids.

Crystal structure and Hirshfeld surface analysis of diethyl 5-(2-cyanophenoxy)isophthalate

The title compound, C19H17NO5, obtained by ether bond formation between the reagents, crystallizes in the monoclinic space group P21/c. The compound is non-planar, subtending a dihedral angle of 82.38 (4)° between the plane of hy-droxy isophthalate-based ester and that of the benzo-nitrile moiety. The mol-ecule is bent at the ether linkage, with a Car-yl-O-Car-yl bond angle of 116.74 (11)°. In the crystal, mol-ecules are linked by C-H⋯O hydrogen bonds and other weak inter-actions forming a supra-molecular framework. A Hirshfeld surface analysis was performed to generate two-dimensional fingerprint plots, which reveal the type of inter-actions occurring in the vicinity of the mol-ecule.

Synthesis and Study of Properties of Organic and Carbon Xerogels from Abies Bark Tannins

Methods of organic and carbon xerogels synthesis based on the use of condensed tannins isolated from abies bark were developed. Organic gels were synthesized by sol-gel condensation of tannins with formaldehyde in a solution of ethanol in the presence of catalysts (NaOH or HCl). The final gelation products were dried by alternating low (-18 – -40 °C) and room temperature to obtain tanninformaldehyde (TF) xerogels. FTIR study indicates that the formation of xerogels was accompanied by crosslinking reactions mainly due to the formation of carbon-carbon and alkyl ether bonds. Using the method of thermogravimetry, it was found that organic TF xerogels are thermally stable up to a temperature of 295 °C and they are resistant to ignition in air at temperatures up to 600 °C and can be used as thermo- and fire-retardant materials. Carbon tannin-formaldehyde xerogels were obtained by carbonization of organic xerogels at 800 °C in an argon atmosphere. The porous structure and surface morphology of organic and carbon xerogels was studied by BET- and SEM–methods. A significant development of the specific surface area (to 483–524 m2/g)as a result of the organic xerogels carbonization was established. Using SEM, it was shown that in carbon gels a spatially cross-linked structure of polymer chains consisting of 5-10 nmsized globule particles forming nanometer-sized pores is retained

Functionalized Organosolv Lignins Suitable for Modifications of Hard Surfaces.

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.

Laccase-catalyzed oxidative modification of lignosulfonates from acidic sulfite pulping of eucalyptus wood

Abstract Lignosulfonates (LS) from acidic magnesium-based sulfite cooking of Eucalyptus globulus wood were modified via laccase-catalyzed oxidative treatment with the aim to improve their performance as plasticizing additives in concrete formulations. The target parameters were the increment of molecular weight (Mw) and the amount of oxidized groups. The laccase-assisted oxidation under optimized conditions (40°C, pH 4.5, enzyme loads of 83–500 U g−1 for 90 min) allowed Mw increment up to 11-fold and almost doubled the amount of carbonyl and carboxyl groups without using any mediators. Modified LS maintained their solubility in water and possessed a zeta- potential close to that of initial LS. The characterization of modified LS has been carried out by ultraviolet-visible (UV-Vis), Fourier transform infrared-attenuated total reflectance (FTIR-ATR) and quantitative 13C nuclear magnetic resonance (NMR) spectroscopy, and the sulfonic and phenolic groups were assessed by conductometric titration. It was concluded that LS polymerization occurred mostly via the formation of new aryl ether bonds (two thirds of the modification) and biphenyl bonds (the remaining third). However, part of the newly formed bonds of unknown origin are temperature labile and cleaved during the concentration of LS at pH 4 and 80°C under vacuum, which led to the reduction of the Mw of the modified lignin to almost one third.