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Polysaccharide Chemistry—a Tool for Novel, Sustainable, and Advanced Products and Materials: A Themed Issue in Honor of Prof. Dr. Thomas Heinze

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Organic Chemistry".

Deadline for manuscript submissions: closed (31 December 2021) | Viewed by 28103

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Guest Editor
Deparment of Chemical Engineering, University of Leuven, Celestijnenlaan 200F, 3001 Leuven, Belgium
Interests: biomaterials; bionanohydrids; biomass engineering; biostructures; polysaccharides
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Polysaccharides, fascinating biopolymers and the most common organic compounds on earth, possess amazing molecular and supramolecular structures. Chemical modification, including unconventional methods for the modification of polysaccharides, has opened new avenues to the development of advanced and sustainable materials. Advanced analytical tools have been established to obtain real structure–property relationships.

This Special Issue aims to honour the outstanding contribution of Prof. Thomas Heinze to the field of polysaccharide chemistry and polysaccharide-based materials. Thomas Heinze is a Professor of Organic Chemistry at the Institute of Organic and Macromolecular Chemistry, Friedrich Schiller University of Jena, Germany. From 2010 to 2014, he also worked as a Finland Distinguished Professor at the Åbo Akademi University, Finland. Prof. Heinze has made many contributions to the research of polysaccharides at large, including concepts for polysaccharide chemistry, homogeneous phase reactions, nanostructuring of polysaccharides, and characterization by advanced analytical tools.

Prof. Dr. Pedro Fardim
Guest Editor

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Keywords

  • cellulose
  • hemicelluloses
  • nanomaterials

Published Papers (10 papers)

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Research

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13 pages, 2654 KiB  
Article
Biofabrication of Functional Pullulan by Aureobasidium pullulans under the Effect of Varying Mineral Salts and Sugar Stress Conditions
by Katia Van den Eynde, Vik Boon, Rita Caiado Gaspar and Pedro Fardim
Molecules 2023, 28(6), 2478; https://doi.org/10.3390/molecules28062478 - 08 Mar 2023
Cited by 1 | Viewed by 1652
Abstract
Pullulan is a linear exopolysaccharide, produced in the fermentation media of Aureobasidium pullulans, with a variety of applications in the food and pharmaceutical industries. Pullulan derivatives have growing potential for biomedical applications, but the high cost of pullulan biofabrication currently restricts its [...] Read more.
Pullulan is a linear exopolysaccharide, produced in the fermentation media of Aureobasidium pullulans, with a variety of applications in the food and pharmaceutical industries. Pullulan derivatives have growing potential for biomedical applications, but the high cost of pullulan biofabrication currently restricts its commercial use. Better control over pullulan yield, molecular weight and melanin production by altering fermentation conditions could improve the economics. In this study, the effects of sugar and mineral salt stresses on the pullulan production of A. pullulans ATCC 42023 were examined in batch processes. The chemical structure of the recovered pullulan was characterized by FTIR and NMR spectroscopy, and the molecular weight distribution was obtained via SEC. Pullulan yield and melanin production varied when the conditions were adjusted, and pullulans with different molar masses were obtained. Higher-yield pullulan production and a lower polydispersity index were observed when CuSO4 was added to the fermentation in comparison with the control and with the addition of sugars and other salts. Biofabrication of pullulan under stress conditions is a promising strategy to enhance biopolymer yield and to obtain pullulan with a targeted molecular weight. Full article
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14 pages, 1830 KiB  
Article
Synthesis of Polyanionic Cellulose Carbamates by Homogeneous Aminolysis in an Ionic Liquid/DMF Medium
by Cuong Viet Bui, Thomas Rosenau and Hubert Hettegger
Molecules 2022, 27(4), 1384; https://doi.org/10.3390/molecules27041384 - 18 Feb 2022
Cited by 8 | Viewed by 2488
Abstract
Polyanionic cellulose carbamates were synthesized by rapid and efficient homogeneous aminolysis of cellulose carbonate half-esters in an ionic liquid/DMF medium. Cellulose bis-2,3-O-(3,5-dimethylphenyl carbamate), as a model compound, reacted with different chloroformates to cellulose carbonates. These intermediates were subjected to aminolysis, [...] Read more.
Polyanionic cellulose carbamates were synthesized by rapid and efficient homogeneous aminolysis of cellulose carbonate half-esters in an ionic liquid/DMF medium. Cellulose bis-2,3-O-(3,5-dimethylphenyl carbamate), as a model compound, reacted with different chloroformates to cellulose carbonates. These intermediates were subjected to aminolysis, for which both the reactivity of different chloroformates towards C6-OH and the reactivity/suitability of the respective carbonate half-ester in the aminolysis were comprehensively studied. Phenyl chloroformate and 4-chlorophenyl chloroformate readily reacted with C6-OH of the model cellulose derivative, while 4-nitrophenyl chloroformate did not. The intermediate 4-chlorophenyl carbonate derivative with the highest DS (1.05) was then used to evaluate different aminolysis pathways, applying three different amines (propargyl amine, β-alanine, and taurine) as reactants. The latter two zwitterionic compounds are only sparingly soluble in pure DMF as the typical reaction medium for aminolysis; therefore, several alternative procedures were suggested, carefully evaluated, and critically compared. Solubility problems with β-alanine and taurine were overcome by the binary solvent system DMF/[EMIM]OAc (1:1, v/v), which was shown to be a promising medium for rapid and efficient homogeneous aminolysis and for the preparation of the corresponding cellulose carbamate derivatives or other compounds that are not accessible by conventional isocyanate chemistry. The zwitterionic cellulose carbamate derivatives presented in this work could be promising chiral cation exchangers for HPLC enantiomer separations. Full article
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9 pages, 2274 KiB  
Article
Lignin Quantification of Papyri by TGA—Not a Good Idea
by Florian Bausch, Dickson D. Owusu, Paul Jusner, Mario J. Rosado, Jorge Rencoret, Sabine Rosner, José C. del Río, Thomas Rosenau and Antje Potthast
Molecules 2021, 26(14), 4384; https://doi.org/10.3390/molecules26144384 - 20 Jul 2021
Cited by 10 | Viewed by 2848
Abstract
Papyri belong to the oldest writing grounds in history. Their conservation is of the highest importance in preserving our cultural heritage, which is best achieved based on an extensive knowledge of the materials’ constituents to choose a tailored conservation approach. Thermogravimetric Analysis (TGA) [...] Read more.
Papyri belong to the oldest writing grounds in history. Their conservation is of the highest importance in preserving our cultural heritage, which is best achieved based on an extensive knowledge of the materials’ constituents to choose a tailored conservation approach. Thermogravimetric Analysis (TGA) has been widely employed to quantify cellulose and lignin in papyrus sheets, yielding reported lignin contents of 25% to 40%. In this work, the TGA method conventionally used for papyrus samples was repeated and compared to other lignin determination approaches (Klason-lignin and acetyl bromide-soluble lignin). TGA can lead to a large overestimation of the lignin content of commercial papyrus sheets (~27%) compared to the other methods (~5%). A similar overestimation of the lignin content was found for the pith and rind of the native papyrus plant. We concluded that the TGA method should, therefore, not be used for lignin quantification. Full article
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13 pages, 2473 KiB  
Article
Reactive Nanoparticles Derived from Polysaccharide Phenyl Carbonates
by Martin Gericke, Katja Geitel, Cornelia Jörke, Joachim H. Clement and Thomas Heinze
Molecules 2021, 26(13), 4026; https://doi.org/10.3390/molecules26134026 - 01 Jul 2021
Cited by 2 | Viewed by 2292
Abstract
Polysaccharide (PS) based nanoparticles (NP) are of great interest for biomedical applications. A key challenge in this regard is the functionalization of these nanomaterials. The aim of the present work was the development of reactive PS-NP that can be coupled with an amino [...] Read more.
Polysaccharide (PS) based nanoparticles (NP) are of great interest for biomedical applications. A key challenge in this regard is the functionalization of these nanomaterials. The aim of the present work was the development of reactive PS-NP that can be coupled with an amino group containing compounds under mild aqueous conditions. A series of cellulose phenyl carbonates (CPC) and xylan phenyl carbonates (XPC) with variable degrees of substitution (DS) was obtained by homogeneous synthesis. The preparation of PS-NP by self-assembling of these hydrophobic derivatives was studied comprehensively. While CPC mostly formed macroscopic aggregates, XPC formed well-defined spherical NP with diameters around 100 to 200 nm that showed a pronounced long-term stability in water against both particle aggregation as well as cleavage of phenyl carbonate moieties. Using an amino group functionalized dye it was demonstrated that the novel XPC-NP are reactive towards amines. A simple coupling procedure was established that enables direct functionalization of the reactive NP in an aqueous dispersion. Finally, it was demonstrated that dye functionalized XPC-NP are non-cytotoxic and can be employed in advanced biomedical applications. Full article
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12 pages, 4350 KiB  
Article
Highly Norbornylated Cellulose and Its “Click” Modification by an Inverse-Electron Demand Diels–Alder (iEDDA) Reaction
by Christina Wappl, Viktor Schallert, Christian Slugovc, Astrid-Caroline Knall and Stefan Spirk
Molecules 2021, 26(5), 1358; https://doi.org/10.3390/molecules26051358 - 04 Mar 2021
Cited by 2 | Viewed by 2174
Abstract
A facile, catalyst-free synthesis of a norbornylated cellulosic material (NC) with a high degree of substitution (2.9) is presented by direct reaction of trimethylsilyl cellulose with norbornene acid chloride. The resulting NC is highly soluble in organic solvents and its reactive double bonds [...] Read more.
A facile, catalyst-free synthesis of a norbornylated cellulosic material (NC) with a high degree of substitution (2.9) is presented by direct reaction of trimethylsilyl cellulose with norbornene acid chloride. The resulting NC is highly soluble in organic solvents and its reactive double bonds were exploited for the copper-free inverse-electron demand Diels–Alder (iEDDA) “click” reaction with 3,6-di(pyridin-2-yl)-1,2,4,5-tetrazine. Reaction kinetics are comparable to the well-known Huisgen type 1,3-dipolar cycloaddition of azide with alkynes, while avoiding toxic catalysts. Full article
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14 pages, 5036 KiB  
Article
TEMPO-Oxidized Cellulose Beads as Potential pH-Responsive Carriers for Site-Specific Drug Delivery in the Gastrointestinal Tract
by Fan Xie, Pieter De Wever, Pedro Fardim and Guy Van den Mooter
Molecules 2021, 26(4), 1030; https://doi.org/10.3390/molecules26041030 - 15 Feb 2021
Cited by 9 | Viewed by 2479
Abstract
The development of controlled drug delivery systems based on bio-renewable materials is an emerging strategy. In this work, a controlled drug delivery system based on mesoporous oxidized cellulose beads (OCBs) was successfully developed by a facile and green method. The introduction of the [...] Read more.
The development of controlled drug delivery systems based on bio-renewable materials is an emerging strategy. In this work, a controlled drug delivery system based on mesoporous oxidized cellulose beads (OCBs) was successfully developed by a facile and green method. The introduction of the carboxyl groups mediated by the TEMPO(2,2,6,6-tetramethylpiperidine-1-oxyradical)/NaClO/NaClO2 system presents the pH-responsive ability to cellulose beads, which can retain the drug in beads at pH = 1.2 and release at pH = 7.0. The release rate can be controlled by simply adjusting the degree of oxidation to achieve drug release at different locations and periods. A higher degree of oxidation corresponds to a faster release rate, which is attributed to a higher degree of re-swelling and higher hydrophilicity of OCBs. The zero-order release kinetics of the model drugs from the OCBs suggested a constant drug release rate, which is conducive to maintaining blood drug concentration, reducing side effects and administration frequency. At the same time, the effects of different model drugs and different drug-loading solvents on the release behavior and the physical state of the drugs loaded in the beads were studied. In summary, the pH-responsive oxidized cellulose beads with good biocompatibility, low cost, and adjustable release rate have shown great potential in the field of controlled drug release. Full article
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12 pages, 2653 KiB  
Article
Cellulose Dissolution in Mixtures of Ionic Liquids and Dimethyl Sulfoxide: A Quantitative Assessment of the Relative Importance of Temperature and Composition of the Binary Solvent
by Marcella T. Dignani, Thaís A. Bioni, Thiago R. L. C. Paixão and Omar A. El Seoud
Molecules 2020, 25(24), 5975; https://doi.org/10.3390/molecules25245975 - 17 Dec 2020
Cited by 3 | Viewed by 2009
Abstract
We studied the dissolution of microcrystalline cellulose (MCC) in binary mixtures of dimethyl sulfoxide (DMSO) and the ionic liquids: allylbenzyldimethylammonium acetate; 1-(2-methoxyethyl)-3-methylimidazolium acetate; 1,8-diazabicyclo [5.4.0]undec-7-ene-8-ium acetate; tetramethylguanidinium acetate. Using chemometrics, we determined the dependence of the mass fraction (in %) of dissolved cellulose [...] Read more.
We studied the dissolution of microcrystalline cellulose (MCC) in binary mixtures of dimethyl sulfoxide (DMSO) and the ionic liquids: allylbenzyldimethylammonium acetate; 1-(2-methoxyethyl)-3-methylimidazolium acetate; 1,8-diazabicyclo [5.4.0]undec-7-ene-8-ium acetate; tetramethylguanidinium acetate. Using chemometrics, we determined the dependence of the mass fraction (in %) of dissolved cellulose (MCC-m%) on the temperature, T = 40, 60, and 80 °C, and the mole fraction of DMSO, χDMSO = 0.4, 0.6, and 0.8. We derived equations that quantified the dependence of MCC-m% on T and χDMSO. Cellulose dissolution increased as a function of increasing both variables; the contribution of χDMSO was larger than that of T in some cases. Solvent empirical polarity was qualitatively employed to rationalize the cellulose dissolution efficiency of the solvent. Using the solvatochromic probe 2,6-dichloro-4-(2,4,6-triphenylpyridinium-1-yl)phenolate (WB), we calculated the empirical polarity ET(WB) of cellobiose (a model for MCC) in ionic liquid (IL)–DMSO mixtures. The ET(WB) correlated perfectly with T (fixed χDMSO) and with χDMSO (fixed T). These results show that there is ground for using medium empirical polarity to assess cellulose dissolution efficiency. We calculated values of MCC-m% under conditions other than those employed to generate the statistical model and determined the corresponding MCC-m% experimentally. The excellent agreement between both values shows the robustness of the statistical model and the usefulness of our approach to predict cellulose dissolution, thus saving time, labor, and material. Full article
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10 pages, 1218 KiB  
Article
Possibilities for Optimization of Industrial Alkaline Steeping of Wood-Based Cellulose Fibers
by Catharina Fechter, Harald Brelid and Steffen Fischer
Molecules 2020, 25(24), 5834; https://doi.org/10.3390/molecules25245834 - 10 Dec 2020
Cited by 4 | Viewed by 1796
Abstract
Steeping of cellulosic materials in aqueous solution of NaOH is a common pre-treatment in several industrial processes for production of cellulose-based products, including viscose fibers. This study investigated whether the span of commonly applied process settings has the potential for process optimization regarding [...] Read more.
Steeping of cellulosic materials in aqueous solution of NaOH is a common pre-treatment in several industrial processes for production of cellulose-based products, including viscose fibers. This study investigated whether the span of commonly applied process settings has the potential for process optimization regarding purity, yield, and degree of transformation to alkali cellulose. A hardwood kraft dissolving pulp was extracted with 17–20 wt% aq. NaOH at 40−50 °C. The regenerated residue of the pulp was characterized regarding its chemical composition, molecular structure, and cellulose conformation. Yield was shown to be favored primarily by low temperature and secondly by high alkali concentration. Purity of xylan developed inversely. Both purity of xylan and yield varied over the applied span of settings to an extent which makes case-adapted process optimization meaningful. Decreasing the steeping temperature by 2 °C increased xylan content in the residue with 0.13%-units over the whole span of applied alkali concentrations, while yield increased by 0.15%-units when extracting with 17 wt% aq. NaOH, and by 0.20%-units when extracting with 20 wt%. Moreover, the yield-favoring conditions resulted in a narrower molecular weight distribution. The degree of transformation via alkali cellulose to cellulose II, as determined with Raman spectroscopy, was found to be high at all extraction settings applied. Full article
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14 pages, 3261 KiB  
Article
Hydration/Dehydration Behavior of Hydroxyethyl Cellulose Ether in Aqueous Solution
by Kengo Arai and Toshiyuki Shikata
Molecules 2020, 25(20), 4726; https://doi.org/10.3390/molecules25204726 - 15 Oct 2020
Cited by 13 | Viewed by 4337
Abstract
Hydroxyethyl cellulose (HeC) maintains high water solubility over a wide temperature range even in a high temperature region where other nonionic chemically modified cellulose ethers, such as methyl cellulose (MC) and hydroxypropylmethyl cellulose (HpMC), demonstrate cloud points. In order to clarify the reason [...] Read more.
Hydroxyethyl cellulose (HeC) maintains high water solubility over a wide temperature range even in a high temperature region where other nonionic chemically modified cellulose ethers, such as methyl cellulose (MC) and hydroxypropylmethyl cellulose (HpMC), demonstrate cloud points. In order to clarify the reason for the high solubility of HeC, the temperature dependence of the hydration number per glucopyranose unit, nH, for the HeC samples was examined by using extremely high frequency dielectric spectrum measuring techniques up to 50 GHz over a temperature range from 10 to 70 °C. HeC samples with a molar substitution number (MS) per glucopyranose unit by hydroxyethyl groups ranging from 1.3 to 3.6 were examined in this study. All HeC samples dissolve into water over the examined temperature range and did not show their cloud points. The value of nH for the HeC sample possessing the MS of 1.3 was 14 at 20 °C and decreased gently with increasing temperature and declined to 10 at 70 °C. The nH values of the HeC samples are substantially larger than the minimum critical nH value of ca. 5 necessary to be dissolved into water for cellulose ethers such as MC and HpMC, even in a high temperature range. Then, the HeC molecules possess water solubility over the wide temperature range. The temperature dependence of nH for the HeC samples and triethyleneglycol, which is a model compound for substitution groups of HeC, is gentle and they are similar to each other. This observation strongly suggests that the hydration/dehydration behavior of the HeC samples was essentially controlled by that of their substitution groups. Full article
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Review

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30 pages, 3518 KiB  
Review
Polysaccharide- and β-Cyclodextrin-Based Chiral Selectors for Enantiomer Resolution: Recent Developments and Applications
by Cuong Viet Bui, Thomas Rosenau and Hubert Hettegger
Molecules 2021, 26(14), 4322; https://doi.org/10.3390/molecules26144322 - 16 Jul 2021
Cited by 24 | Viewed by 4203
Abstract
Polysaccharides, oligosaccharides, and their derivatives, particularly of amylose, cellulose, chitosan, and β-cyclodextrin, are well-known chiral selectors (CSs) of chiral stationary phases (CSPs) in chromatography, because they can separate a wide range of enantiomers. Typically, such CSPs are prepared by physically coating, or chemically [...] Read more.
Polysaccharides, oligosaccharides, and their derivatives, particularly of amylose, cellulose, chitosan, and β-cyclodextrin, are well-known chiral selectors (CSs) of chiral stationary phases (CSPs) in chromatography, because they can separate a wide range of enantiomers. Typically, such CSPs are prepared by physically coating, or chemically immobilizing the polysaccharide and β-cyclodextrin derivatives onto inert silica gel carriers as chromatographic support. Over the past few years, new chiral selectors have been introduced, and progressive methods to prepare CSPs have been exploited. Also, chiral recognition mechanisms, which play a crucial role in the investigation of chiral separations, have been better elucidated. Further insights into the broad functional performance of commercially available chiral column materials and/or the respective newly developed chiral phase materials on enantiomeric separation (ES) have been gained. This review summarizes the recent developments in CSs, CSP preparation, chiral recognition mechanisms, and enantiomeric separation methods, based on polysaccharides and β-cyclodextrins as CSs, with a focus on the years 2019–2020 of this rapidly developing field. Full article
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