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Polymers
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Carbohydrate Polymers—Current Trends and Future Perspectives in Extraction, Characterization and...
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Carbohydrate Polymers—Current Trends and Future Perspectives in Extraction, Characterization and Applications

A special issue of Polymers (ISSN 2073-4360). This special issue belongs to the section "Biomacromolecules, Biobased and Biodegradable Polymers".

Deadline for manuscript submissions: closed (31 July 2022) | Viewed by 22795

Special Issue Editors

Dr. Adrian C. Puiţel

E-Mail Website1 Website2
Guest Editor
Department of Natural and Synthetic Polymers, Faculty of Chemical Engineering and Environmental Protection, "Gheorghe Asachi" Technical University, Iasi, Romania
Interests: Biomass fractionation; hemicellulose extaction and characterisation; pulping; papermaking; environmental friendly materials; liquid chromatography
Dr. Dan Belosinschi

E-Mail Website
Guest Editor
Département de Chimie-Biologie/Biologie Medicale, Université du Québec à Trois-Rivières, Quebec, Canada
Interests: Lignocellulosic materials; chemical modifications; nanomaterials; pulp and paper additives
Dr. Bogdan Marian Tofanica

E-Mail Website
Guest Editor
Departmenf of Natural Resources, EngMat Ltd, Galway, Ireland
Interests: Cellulose, Lignin, Wood Chemistry, Lignocellulosic Chemistry; Lignocellulosic Materials; Pulp and Paper; Biomass; Fibre; Fibre Processing

Special Issue Information

Naturally occurring carbohydrate polymers (polysaccharides) represent a huge portion of our planet’s biomass. They are formed by chains of monomers of the same type or by a combination of different sugar residues, characterized by complex secondary structures performing several roles in algae, bacteria, fungi, plants and animals. Because of their renewability, versatility, biodegradability, they have been used since the dawn of civilization for food, energy, pharmaceuticals, paper, packaging and construction. Their structural complexity, heterogeneity and diversity are source-dependent and generally include several types of residues, providing them with different physicochemical properties and applications. In recent years, their skillful use, both as a renewable class of polymeric materials and as a source for new chemical routes, has gained significant attention from researchers. Their complex structure renders unique properties which could be of great use in niche applications such as nanomaterials, medical devices, targeted drug delivery, tissue engineering, conductive materials, etc. The aim of this Special Issue is to highlight carbohydrate polymers such as starch, cellulose, hemicelluloses, gums, agars, chitin, chitosan, xanthan, pullulan and others, in both current trends and future perspectives, regarding extraction from new sources and methods, characterization and developments in emergent application.

Dr. Adrian C. Puiţel
Dr. Dan Belosinschi
Dr. Bogdan Marian Tofanica
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Polymers is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • biomass
  • polysaccharides
  • renewability
  • structural complexity
  • biodegradability
  • versatility

Published Papers (7 papers)

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Research

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25 pages, 4723 KiB  
Article
Characterization and Bioactivity of Polysaccharides Separated through a (Sequential) Biorefinery Process from Fucus spiralis Brown Macroalgae
by Cătălina Filote, Elhafnaoui Lanez, Valentin I. Popa, Touhami Lanez and Irina Volf
Polymers 2022, 14(19), 4106; https://doi.org/10.3390/polym14194106 - 30 Sep 2022
Cited by 3 | Viewed by 1533
Abstract
Marine macroalgae biomass is a valuable renewable resource that can be used for the development of bioeconomy through the valorisation of valuable compounds. The aim of the current study is separate macroalgal polysaccharides with bioactive properties from brown macroalgae Fucus spiralis based on [...] Read more.
Marine macroalgae biomass is a valuable renewable resource that can be used for the development of bioeconomy through the valorisation of valuable compounds. The aim of the current study is separate macroalgal polysaccharides with bioactive properties from brown macroalgae Fucus spiralis based on a designed biocascading biorefinery approach. Thus, we applied an integrated processing method for the separation of fucoidan and alginate, in addition to characterization through IR spectroscopy and 1H NMR. The bioactivity potential (antioxidant activity using superoxide anion and DPPH radical scavenging analysis) of the two polysaccharides was evaluated, together with DNA binding studies performed though voltametric techniques and electronic spectroscopy titration. In terms of results, functional groups S=O (1226 cm−1), N=S=O (1136 cm−1) and C-O-SO3 (1024 cm−1), which are characteristic of fucoidan, were identified in the first polysaccharidic extract, whereas guluronic units (G) (1017 cm−1) and mannuronic units (M) (872 and 812 cm−1) confirmed the separation of alginate. The DNA binding studies of the isolated polysaccharides revealed an electrostatic and an intercalation interaction of DNA with fucoidan and alginate, respectively. Both antioxidant activity assays revealed improved antioxidant activity for both fucoidan and alginate compared to the standard α-tocopherol. Full article
(This article belongs to the Special Issue Carbohydrate Polymers—Current Trends and Future Perspectives in Extraction, Characterization and Applications)
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19 pages, 5288 KiB  
Article
Cluster Size of Amylopectin and Nanosized Amylopectin Fragments Characterized by Pyrene Excimer Formation
by Damin Kim and Jean Duhamel
Polymers 2022, 14(16), 3418; https://doi.org/10.3390/polym14163418 - 21 Aug 2022
Cited by 2 | Viewed by 1501
Abstract
Amylopectin from waxy corn and the three nanosized amylopectin fragments (NAFs)—NAF(56), NAF(20), and NAF(8)—from waxy corn starch with a hydrodynamic diameter of 227, 56, 20, and 8 nm, respectively, were randomly labeled with 1-pyrenebutyric acid. The efficiency of these pyrene-labeled amylopectin-based polysaccharides (Py-A [...] Read more.
Amylopectin from waxy corn and the three nanosized amylopectin fragments (NAFs)—NAF(56), NAF(20), and NAF(8)—from waxy corn starch with a hydrodynamic diameter of 227, 56, 20, and 8 nm, respectively, were randomly labeled with 1-pyrenebutyric acid. The efficiency of these pyrene-labeled amylopectin-based polysaccharides (Py-AbPS) for pyrene excimer formation (PEF) upon diffusive encounter between an excited and a ground-state pyrene increased with increasing concentration of unlabeled NAF(56) in Py-AbPS dispersions in DMSO. Fluorescence decay analysis of the Py-AbPS dispersions in DMSO prepared with increasing [NAF(56)] yielded the maximum number (Nblobexp) of anhydroglucose units (AGUs) separating two pyrene-labeled AGUs while still allowing PEF. Comparison of Nblobexp with Nblobtheo, obtained by conducting molecular mechanics optimizations on helical oligosaccharide constructs with HyperChem, led to a relationship between the interhelical distance (dh-h) in a cluster of oligosaccharide helices, [NAF(56)], and the number of helices in a cluster. It was found that the AbPSs were composed of building blocks made of 3.5 (±0.9) helices that self-assembled into increasingly larger clusters with increasing [NAF(56)]. The ability of PEF-based experiments to yield the cluster size of AbPSs provides a new experimental means to probe the interior of AbPSs at the molecular level. Full article
(This article belongs to the Special Issue Carbohydrate Polymers—Current Trends and Future Perspectives in Extraction, Characterization and Applications)
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17 pages, 3730 KiB  
Article
An Experimental Study on the Hot Alkali Extraction of Xylan-Based Hemicelluloses from Wheat Straw and Corn Stalks and Optimization Methods
by Adrian Cătălin Puițel, Gabriel Dan Suditu, Maricel Danu, Gabriela-Liliana Ailiesei and Mircea Teodor Nechita
Polymers 2022, 14(9), 1662; https://doi.org/10.3390/polym14091662 - 20 Apr 2022
Cited by 18 | Viewed by 2096
Abstract
In this paper, we describe an experimental study on the hot alkali extraction of hemicelluloses from wheat straw and corn stalks, two of the most common lignocellulosic biomass constituents in Romania. The chemical compositions of the raw materials were determined analytically, and the [...] Read more.
In this paper, we describe an experimental study on the hot alkali extraction of hemicelluloses from wheat straw and corn stalks, two of the most common lignocellulosic biomass constituents in Romania. The chemical compositions of the raw materials were determined analytically, and the relevant chemical components were cellulose, hemicelluloses, lignin, and ash. Using the response surface methodology, the optimum values of the hot alkaline extraction parameters, i.e., time, temperature, and NaOH concentration, were identified and experimentally validated. The physicochemical characterization of the isolated hemicelluloses was performed using HPLC, FTIR, TG, DTG, and 1H-NMR spectroscopy. The main hemicellulose components identified experimentally were xylan, arabinan, and glucan. The study emphasizes that both corn stalks and wheat straw are suitable as raw materials for hemicellulose extraction, highlighting the advantages of alkaline pretreatments and showing that optimization methods can further improve the process efficiency. Full article
(This article belongs to the Special Issue Carbohydrate Polymers—Current Trends and Future Perspectives in Extraction, Characterization and Applications)
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23 pages, 6975 KiB  
Article
Cyclodextrin-Oligocaprolactone Derivatives—Synthesis and Advanced Structural Characterization by MALDI Mass Spectrometry
by Cristian Peptu, Diana-Andreea Blaj, Mihaela Balan-Porcarasu and Joanna Rydz
Polymers 2022, 14(7), 1436; https://doi.org/10.3390/polym14071436 - 31 Mar 2022
Cited by 8 | Viewed by 2233
Abstract
Cyclodextrins have previously been proven to be active in the catalysis of cyclic ester ring-opening reactions, hypothetically in a similar way to lipase-catalyzed reactions. However, the way they act remains unclear. Here, we focus on β-cyclodextrin’s involvement in the synthesis and characterization of [...] Read more.
Cyclodextrins have previously been proven to be active in the catalysis of cyclic ester ring-opening reactions, hypothetically in a similar way to lipase-catalyzed reactions. However, the way they act remains unclear. Here, we focus on β-cyclodextrin’s involvement in the synthesis and characterization of β-cyclodextrin-oligocaprolactone (CDCL) products obtained via the organo-catalyzed ring-opening of ε-caprolactone. Previously, bulk or supercritical carbon dioxide polymerizations has led to inhomogeneous products. Our approach consists of solution polymerization (dimethyl sulfoxide and dimethylformamide) to obtain homogeneous CDCL derivatives with four monomer units on average. Oligomerization kinetics, performed by a matrix-assisted laser desorption ionization mass spectrometry (MALDI MS) optimized method in tandem with 1H NMR, revealed that monomer conversion occurs in two stages: first, the monomer is rapidly attached to the secondary OH groups of β-cyclodextrin and, secondly, the monomer conversion is slower with attachment to the primary OH groups. MALDI MS was further employed for the measurement of the ring-opening kinetics to establish the influence of the solvents as well as the effect of organocatalysts (4-dimethylaminopyridine and (–)-sparteine). Additionally, the mass spectrometry structural evaluation was further enhanced by fragmentation studies which confirmed the attachment of oligoesters to the cyclodextrin and the cleavage of dimethylformamide amide bonds during the ring-opening process. Full article
(This article belongs to the Special Issue Carbohydrate Polymers—Current Trends and Future Perspectives in Extraction, Characterization and Applications)
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20 pages, 2298 KiB  
Article
Polysaccharides Used in Biosorbents Preparation for Organic Dyes Retaining from Aqueous Media
by Daniela Suteu, Alexandra Cristina Blaga, Carmen Zaharia, Ramona Cimpoesu, Adrian Cătălin Puițel, Ramona-Elena Tataru-Farmus and Alexandra Maria Tanasă
Polymers 2022, 14(3), 588; https://doi.org/10.3390/polym14030588 - 31 Jan 2022
Cited by 6 | Viewed by 2411
Abstract
Natural polymers can themselves be efficient as materials with biosorptive properties but can also be used to transform microbial biomass into an easy-to-handle form, respectively, into biosorbents, through immobilization. The article aims to study biosorbents based on residual microbial biomass (Saccharomyces pastorianus [...] Read more.
Natural polymers can themselves be efficient as materials with biosorptive properties but can also be used to transform microbial biomass into an easy-to-handle form, respectively, into biosorbents, through immobilization. The article aims to study biosorbents based on residual microbial biomass (Saccharomyces pastorianus yeast, separated after the brewing process by centrifugation and dried at 80 °C) immobilized in sodium alginate. The biosorptive properties of this type of biosorbent (spherical particles 2 and 4 mm in diameter) were studied for removal of reactive dye Brilliant Red HE-3B (with concentration in range of 16.88–174.08 mg/L) from aqueous media. The paper aims at three aspects: (i) the physico-chemical characterization of the biosorbent (Scanning Electron Microscopy (SEM), Energy-dispersive X-ray spectroscopy (EDX) and Fourier Transform Infrared (FTIR) spectra); (ii) the modeling of biosorption data in order to calculate the quantitative characteristic parameters using three equilibrium isotherms (Langmuir, Freundlich, and Dubinin–Radushkevich—DR); and (iii) the evaluation of thermal effect and the possible mechanism of action. The results of the study showed that biosorption capacity evaluated by Langmuir (I) model is 222.22 mg/g (ϕ = 2 mm) and 151.51 mg/g (ϕ = 4 mm) at 30 °C, and the free energy of biosorption (E) is in the range of 8.45–13.608 KJ/mol (from the DR equation). The values of thermodynamic parameters suggested an exothermic process due the negative value of free Gibbs energy (ΔG0 = −9.031 kJ/mol till −3.776 kJ/mol) and enthalpy (about ΔH0 = −87.795 KJ/mol). The obtained results underline our finding that the immobilization in sodium alginate of the residual microbial biomass of Saccharomyces pastorianus led to an efficient biosorbent useful in static operating system in the case of effluents with moderate concentrations of organic dyes. Full article
(This article belongs to the Special Issue Carbohydrate Polymers—Current Trends and Future Perspectives in Extraction, Characterization and Applications)
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16 pages, 2338 KiB  
Article
Hydrogels Based on Alginates and Carboxymethyl Cellulose with Modulated Drug Release—An Experimental and Theoretical Study
by Cătălina Anișoara Peptu, Elena Simona Băcăiță, Corina-Lenuta Savin (Logigan), Marian Luțcanu and Maricel Agop
Polymers 2021, 13(24), 4461; https://doi.org/10.3390/polym13244461 - 20 Dec 2021
Cited by 7 | Viewed by 2587
Abstract
New hydrogels films crosslinked with epichlorohydrin were prepared based on alginates and carboxymethyl cellulose with properties that recommend them as potential drug delivery systems (e.g., biocompatibility, low toxicity, non-immunogenicity, hemostatic activity and the ability to absorb large amounts of water). The characterization of [...] Read more.
New hydrogels films crosslinked with epichlorohydrin were prepared based on alginates and carboxymethyl cellulose with properties that recommend them as potential drug delivery systems (e.g., biocompatibility, low toxicity, non-immunogenicity, hemostatic activity and the ability to absorb large amounts of water). The characterization of their structural, morphological, swelling capacity, loading/release and drug efficiency traits proved that these new hydrogels are promising materials for controlled drug delivery systems. Further, a new theoretical model, in the framework of Scale Relativity Theory, was built with to offer insights on the release process at the microscopic level and to simplify the analysis of the release process. Full article
(This article belongs to the Special Issue Carbohydrate Polymers—Current Trends and Future Perspectives in Extraction, Characterization and Applications)
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Review

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23 pages, 2937 KiB  
Review
Overview on Foam Forming Cellulose Materials for Cushioning Packaging Applications
by Petronela Nechita and Silviu Marian Năstac
Polymers 2022, 14(10), 1963; https://doi.org/10.3390/polym14101963 - 11 May 2022
Cited by 29 | Viewed by 7469
Abstract
Wet foam can be used as a carrier in the manufacturing of lightweight materials based on natural and man-made fibers and specific additives. Using a foam forming method and cellulose fibers, it is possible to produce the porous materials with large area of [...] Read more.
Wet foam can be used as a carrier in the manufacturing of lightweight materials based on natural and man-made fibers and specific additives. Using a foam forming method and cellulose fibers, it is possible to produce the porous materials with large area of end-using such as protective and cushioning packaging, filtering, hydroponic, thermal and sound absorption insulation, or other building materials. In comparison with the water-forming used for conventional paper products, foam-forming method provides many advantages. In particular, since fibers inside the foam are mostly trapped between the foam bubbles, the formed materials have an excellent homogeneity. This allows for using long fibers and a high consistency in head box without significant fiber flocking. As result, important savings in water and energy consumptions for dewatering and drying of the foam formed materials are obtained. In cushioning packaging, foam-formed cellulose materials have their specific advantages comparing to other biodegradable packaging (corrugated board, molded pulp) and can be a sustainable alternative to existing synthetic foams (i.e., expanded polystyrene or polyurethane foams). This review discusses the technical parameters to be controlled during foam forming of cellulose materials to ensure their performances as cushioning and protective packaging. The focus was on the identification of practical solutions to compensate the strength decreasing caused by reduced density and low resistance to water of foam formed cellulose materials. Full article
(This article belongs to the Special Issue Carbohydrate Polymers—Current Trends and Future Perspectives in Extraction, Characterization and Applications)
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