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Abbaszad Rafi, Abdolrahim
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Publications (10 of 17) Show all publications
Abbaszad Rafi, A. (2025). Sustainable Engineering, Click Chemistry and Catalysis: Modification, Fabrication and Application of Cellulosic Materials. (Doctoral dissertation). Sundsvall: Mid Sweden University
Open this publication in new window or tab >>Sustainable Engineering, Click Chemistry and Catalysis: Modification, Fabrication and Application of Cellulosic Materials
2025 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Due to challenges such as sustainability and increasing carbon footprint, there is a growing demand to replace fossil-based materials with green sustainable alternatives like cellulosic materials. However, unmodified cellulosic materials often encounter issues like high wettability and low mechanical strength that limit their applicability. To overcome these drawbacks, functionalization and modification are crucial and inevitable. Reported methods often involve toxic/harsh conditions or reagents, and multi-step processes. The focus of this thesis is on the fabrication, functionalization, and modification of cellulosic materials through facile and eco-friendly approaches to enhance their properties and broaden their potential applications.

We started with immobilizing copper nanoparticles on controlled pore glass substrate and used it as a recyclable heterogenous catalyst for the copper-catalyzed alkyne-azide cycloaddition (CuAAC). Focusing on sustainability, we also employed cellulosic materials as catalyst supports. First, cellulose was functionalized using a mild organocatalytic approach. Then, copper or palladium nanoparticles were immobilized onto the functionalized cellulose and used as effective recyclable heterogeneous catalysts in different reactions.

Direct esterification of CNC materials with thioglycolic acid was performed enabling us to introduce thiol groups onto CNC materials. The reaction occurred under mild conditions using natural nontoxic organic acid as an organocatalyst. The method was applied on different CNC materials, producing the corresponding thiol-functionalized CNC materials. The thiol-functionalized CNC was used as a heterogeneous recyclable reducing agent to reduce Cu(II) to Cu(I), which is the active form of copper in CuAAC. The prepared thiol-functionalized CNC materials further functionalized with attaching UV active molecules via thiol-ene click chemistry.

Lactic acid (LA) functionalized CNFs were prepared by using an ecofriendly one-step reaction method in high yields. This was achieved by converting pulp fibers into nanofibrillated cellulose lactate under mild conditions, using LA as both reaction media and catalyst. The process was concurrent and involved an autocatalytic esterification reaction without using metal-based or harsh acid catalysts. Moreover, the LA media were recycled and reused in multiple reaction cycles. 

In the fourth study, strong hydrophobic cellulosic materials were prepared via a facile, scalable and eco-friendly method. The method involves a betulin treatment and hot-pressing processes. First, a water-based betulin formulation was developed and used for the treatment of cellulosic materials. The betulin-treated samples were then hot-pressed. Hot-pressing altered the morphologies and led to dense structures. Moreover, it caused a polymorphic transformation of the betulin particles. Water contact angle and tensile tests revealed that the applied betulin/hot-pressing treatment method noticeably enhanced the samples’ hydrophobicities as well as their tensile strengths. Furthermore, a synergistic effect was noticed between the hot-pressing, betulin treatment, and sulfonation during the pulping process.

Densified and strong large veneers were fabricated via a facile and scalable method. The method involves a combination of chemical modifications of aspen veneers followed by hot-pressing. The study showed that hot-pressing enhanced the tensile strengths. The chemical modifications further improved the efficiency of the hot-pressing, resulting in higher tensile strengths. The chemical modifications changed the wood’s composition promoting wood softening and increasing the bonding. Since the method uses convenient and mild treatments combined with continuous hot-pressing, it enables the processing of large samples. It can also lower time/energy consumption, production costs and the environmental impact.

Place, publisher, year, edition, pages
Sundsvall: Mid Sweden University, 2025. p. 112
Series
Mid Sweden University doctoral thesis, ISSN 1652-893X ; 416
National Category
Chemical Engineering Materials Engineering Chemical Sciences Materials Chemistry Organic Chemistry
Identifiers
urn:nbn:se:miun:diva-53250 (URN)978-91-89786-87-5 (ISBN)
Public defence
2025-01-23, C312, Holmgatan 10, Sundsvall, 10:00 (English)
Opponent
Supervisors
Note

Vid tidpunkten för disputationen var följande delarbete opublicerat: delarbete 5 (manuskript).

At the time of the doctoral defence the following paper was unpublished: paper 5 (manuscript).

Available from: 2024-12-10 Created: 2024-12-05 Last updated: 2024-12-05Bibliographically approved
Abbaszad Rafi, A., Deiana, L., Alimohammadzadeh, R., Engstrand, P., Granfeldt, T., Nyström, S. K. & Cordova, A. (2024). Birch-Bark-Inspired Synergistic Fabrication of High-Performance Cellulosic Materials. ACS Sustainable Resource Management, 1(12), 2554-2563
Open this publication in new window or tab >>Birch-Bark-Inspired Synergistic Fabrication of High-Performance Cellulosic Materials
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2024 (English)In: ACS Sustainable Resource Management, ISSN 2837-1445, Vol. 1, no 12, p. 2554-2563Article in journal (Refereed) Published
Abstract [en]

There is a growing demand for the utilization of sustainable materials, such as cellulose-based alternatives, over fossil-based materials. However, the inherent drawbacks of cellulosic materials, such as extremely low wet strength and resistance to moisture, need significant improvements. Moreover, several of the commercially available wet-strength chemicals and hydrophobic agents for cellulosic material treatment are toxic or fossil-based (e.g., epichlorohydrin and fluorocarbons). Herein, we present an eco-friendly, high-yield, industrially relevant, and scalable method inspired by birch bark for fabricating hydrophobic and strong cellulosic materials. This was accomplished by combining simple surface modification of cellulosic fibers in water using colloidal particles of betulin, an abundant triterpene extracted from birch bark, with sustainable chemical engineering (e.g., lignin modification and hot-pressing). This led to a transformative process that not only altered the morphology of the cellulosic materials into a more dense and compact structure but also made them hydrophobic (contact angles of up to >130°) with the betulin particles undergoing polymorphic transformations from prismatic crystals (betulin III) to orthorhombic whiskers (betulin I). Significant synergistic effects are observed, resulting in a remarkable increase in wet strength (>1400%) of the produced hydrophobic cellulosic materials.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2024
National Category
Chemical Sciences Materials Chemistry Chemical Engineering Materials Engineering
Identifiers
urn:nbn:se:miun:diva-53239 (URN)10.1021/acssusresmgt.4c00266 (DOI)
Funder
Swedish Research CouncilEuropean CommissionMid Sweden UniversityKnowledge Foundation
Available from: 2024-12-04 Created: 2024-12-04 Last updated: 2025-01-07Bibliographically approved
Deiana, L., Avella, A., Abbaszad Rafi, A., Mincheva, R., De Winter, J., Lo Re, G. & Cordova, A. (2024). In Situ Enzymatic Polymerization of Ethylene Brassylate Mediated by Artificial Plant Cell Walls in Reactive Extrusion. ACS APPLIED POLYMER MATERIALS, 6(17), 10414-10422
Open this publication in new window or tab >>In Situ Enzymatic Polymerization of Ethylene Brassylate Mediated by Artificial Plant Cell Walls in Reactive Extrusion
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2024 (English)In: ACS APPLIED POLYMER MATERIALS, ISSN 2637-6105, Vol. 6, no 17, p. 10414-10422Article in journal (Refereed) Published
Abstract [en]

Herein, we describe a solvent-free bioinspired approach for the polymerization of ethylene brassylate. Artificial plant cell walls (APCWs) with an integrated enzyme were fabricated by self-assembly, using microcrystalline cellulose as the main structural component. The resulting APCW catalysts were tested in bulk reactions and reactive extrusion, leading to high monomer conversion and a molar mass of around 4 kDa. In addition, we discovered that APCW catalyzes the formation of large ethylene brassylate macrocycles. The enzymatic stability and efficiency of the APCW were investigated by recycling the catalyst both in bulk and reactive extrusion. The obtained poly(ethylene brassylate) was applied as a biobased and biodegradable hydrophobic paper coating.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2024
Keywords
poly(ethylene brassylate), artificial plant cell wall, macrocycles, ring-opening polymerization, reactiveextrusion, solvent-free, ethylene brassylate, metal-free catalysis
National Category
Chemical Sciences
Identifiers
urn:nbn:se:miun:diva-52320 (URN)10.1021/acsapm.4c01568 (DOI)001293294600001 ()2-s2.0-85202187961 (Scopus ID)
Available from: 2024-08-30 Created: 2024-08-30 Last updated: 2024-09-16
Avella, A., Rafi, A., Deiana, L., Mincheva, R., Cordova, A. & Lo Re, G. (2024). Organo-Mediated Ring-Opening Polymerization of Ethylene Brassylate from Cellulose Nanofibrils in Reactive Extrusion. ACS Sustainable Chemistry and Engineering, 12(29), 10727-10738
Open this publication in new window or tab >>Organo-Mediated Ring-Opening Polymerization of Ethylene Brassylate from Cellulose Nanofibrils in Reactive Extrusion
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2024 (English)In: ACS Sustainable Chemistry and Engineering, E-ISSN 2168-0485, Vol. 12, no 29, p. 10727-10738Article in journal (Refereed) Published
Abstract [en]

Ethylene brassylate is a renewable macrolactone from castor oil that can be polymerized via ring-opening polymerization (ROP) to obtain a fully biosourced biodegradable polyester. ROP mediated by organometallic catalysts leads to high molar mass poly(ethylene brassylate) (PEB). However, the use of metal-free organocatalysis has several advantages, such as the reduction of toxic and expensive metals. In this work, a novel cellulose nanofibril (CNF)/PEB nanocomposite fabrication process by organocatalysis and reactive extrusion (REx) is disclosed. Here, ROP was carried out via solvent-free REx in the presence of CNFs using organic 1,5,7-triazabicyclo[4.4.0]dec-5-ene as a catalyst. Neat or lactate-esterified CNFs (LACNF) were used as initiators to investigate the effect of surface topochemistry on the in situ polymerization and the properties of the nanocomposites. A molar mass of 9 kDa was achieved in the presence of both unmodified and LACNFs with high monomer conversion (>98%) after 30 min reaction in a microcompounder at 130 °C. Tensile analysis showed that both nanofibril types reinforce the matrix and increase its elasticity due to the efficient dispersion obtained through the grafting from polymerization achieved during the REx. Mechanical recycling of the neat polymer and the nanocomposites was proven as a circular solution for the materials’ end-of-life and showed that lactate moieties induced some degradation. 

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2024
Keywords
cellulose nanofibrils, ethylene brassylate, grafting, organic catalyst, reactive extrusion, ring-opening polymerization
National Category
Polymer Chemistry
Identifiers
urn:nbn:se:miun:diva-52064 (URN)10.1021/acssuschemeng.4c01309 (DOI)001267427400001 ()2-s2.0-85198510360 (Scopus ID)
Available from: 2024-08-08 Created: 2024-08-08 Last updated: 2024-08-08
Abbaszad Rafi, A., Alimohammadzadeh, R., Avella, A., Mõistlik, T., Jűrisoo, M., Kaaver, A., . . . Cordova, A. (2023). A facile route for concurrent fabrication and surface selective functionalization of cellulose nanofibers by lactic acid mediated catalysis. Scientific Reports, 13(1), Article ID 14730.
Open this publication in new window or tab >>A facile route for concurrent fabrication and surface selective functionalization of cellulose nanofibers by lactic acid mediated catalysis
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2023 (English)In: Scientific Reports, E-ISSN 2045-2322, Vol. 13, no 1, article id 14730Article in journal (Refereed) Published
Abstract [en]

Celulose nanofibers are lightweight, recycable, biodegradable, and renewable. Hence, there is a great interest of using them instead of fossil-based components in new materials and biocomposites. In this study, we disclose an environmentally benign (green) one-step reaction approach to fabricate lactic acid ester functionalized cellulose nanofibrils from wood-derived pulp fibers in high yields. This was accomplished by converting wood-derived pulp fibers to nanofibrillated “cellulose lactate” under mild conditions using lactic acid as both the reaction media and catalyst. Thus, in parallel to the cellulose nanofibril production, concurrent lactic acid-catalyzed esterification of lactic acid to the cellulose nanofibers surface occured. The direct lactic acid esterification, which is a surface selective functionalization and reversible (de-attaching the ester groups by cleavage of the ester bonds), of the cellulose nanofibrils was confirmed by low numbers of degree of substitution, and FT-IR analyses. Thus, autocatalytic esterification and cellulose hydrolysis occurred without the need of metal based or a harsh mineral acid catalysts, which has disadvantages such as acid corrosiveness and high recovery cost of acid. Moreover, adding a mineral acid as a co-catalyst significantly decreased the yield of the nanocellulose. The lactic acid media is successfully recycled in multiple reaction cycles producing the corresponding nanocellulose fibers in high yields. The disclosed green cellulose nanofibril production route is industrial relevant and gives direct access to nanocellulose for use in variety of applications such as sustainable filaments, composites, packaging and strengthening of recycled fibers. 

Place, publisher, year, edition, pages
Springer Nature, 2023
National Category
Paper, Pulp and Fiber Technology
Identifiers
urn:nbn:se:miun:diva-49330 (URN)10.1038/s41598-023-41989-3 (DOI)37679445 (PubMedID)2-s2.0-85170181889 (Scopus ID)
Available from: 2023-09-19 Created: 2023-09-19 Last updated: 2024-12-05Bibliographically approved
Deiana, L., Abbaszad Rafi, A., Tai, C.-W., Bäckvall, J.-E. & Cordova, A. (2023). Artificial Arthropod Exoskeletons/Fungi Cell Walls Integrating Metal and Biocatalysts for Heterogeneous Synergistic Catalysis of Asymmetric Cascade Transformations. ChemCatChem, 15(15)
Open this publication in new window or tab >>Artificial Arthropod Exoskeletons/Fungi Cell Walls Integrating Metal and Biocatalysts for Heterogeneous Synergistic Catalysis of Asymmetric Cascade Transformations
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2023 (English)In: ChemCatChem, ISSN 1867-3880, E-ISSN 1867-3899, Vol. 15, no 15Article in journal (Refereed) Published
Abstract [en]

A novel and sustainable tandem-catalysis system for asymmetric synthesis is disclosed, which is fabricated by bio-inspired self-assembly of artificial arthropod exoskeletons (AAEs) or artificial fungi cell walls (AFCWs) containing two different types of catalysts (enzyme and metal nanoparticles). The heterogeneous integrated enzyme/metal nanoparticle AAE/AFCW systems, which contain chitosan as the main structural component, co-catalyze dynamic kinetic resolution of primary amines via a tandem racemization/enantioselective amidation reaction process to give the corresponding amides in high yields and excellent ee. The heterogeneous AAE/AFCW systems display successful heterogeneous synergistic catalysis at the surfaces since they can catalyze multiple reaction cycles without metal leaching. The use of natural-based and biocompatible structural components makes the AAE/AFCW systems fully biodegradable and renewable, thus fulfilling important green chemistry requirements.

Place, publisher, year, edition, pages
John Wiley & Sons, 2023
Keywords
asymmetric tandem catalysis, chiral amines, chitosan, dynamic kinetic resolution, heterogeneous hybrid catalyst
National Category
Organic Chemistry
Identifiers
urn:nbn:se:miun:diva-49019 (URN)10.1002/cctc.202300250 (DOI)001022816700001 ()2-s2.0-85164018579 (Scopus ID)
Available from: 2023-08-15 Created: 2023-08-15 Last updated: 2023-08-15Bibliographically approved
Deiana, L., Badali, E., Abbaszad Rafi, A., Tai, C.-W., Bäckvall, J.-E. & Cordova, A. (2023). Cellulose-Supported Heterogeneous Gold-Catalyzed Cycloisomerization Reactions of Alkynoic Acids and Allenynamides. ACS Catalysis, 13(15), 10418-10424
Open this publication in new window or tab >>Cellulose-Supported Heterogeneous Gold-Catalyzed Cycloisomerization Reactions of Alkynoic Acids and Allenynamides
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2023 (English)In: ACS Catalysis, E-ISSN 2155-5435, Vol. 13, no 15, p. 10418-10424Article in journal (Refereed) Published
Abstract [en]

Herein, we describe efficient nanogold-catalyzed cycloisomerization reactions of alkynoic acids and allenynamides to enol lactones and dihydropyrroles, respectively (the latter via an Alder-ene reaction). The gold nanoparticles were immobilized on thiol-functionalized microcrystalline cellulose and characterized by electron microscopy (HAADF-STEM) and by XPS. The thiol-stabilized gold nanoparticles (Au-0) were obtained in the size range 1.5-6 nm at the cellulose surface. The robust and sustainable cellulose-supported gold nanocatalyst can be recycled for multiple cycles without losing activity.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2023
Keywords
cellulose-supported nanogold catalysis, C-C bondformation, heterogeneous catalysis, cycloisomerization, heterocycles, Alder-ene reaction
National Category
Organic Chemistry
Identifiers
urn:nbn:se:miun:diva-49539 (URN)10.1021/acscatal.3c02722 (DOI)001066876500001 ()37560186 (PubMedID)2-s2.0-85167895594 (Scopus ID)
Available from: 2023-10-13 Created: 2023-10-13 Last updated: 2024-07-04Bibliographically approved
Veluru, R. N., Abbaszad Rafi, A., Tai, C.-W., Bäckvall, J.-E. & Cordova, A. (2023). Regio- and Stereoselective Carbon-Boron Bond Formation via Heterogeneous Palladium-Catalyzed Hydroboration of Enallenes. Chemistry - A European Journal
Open this publication in new window or tab >>Regio- and Stereoselective Carbon-Boron Bond Formation via Heterogeneous Palladium-Catalyzed Hydroboration of Enallenes
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2023 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765Article in journal (Refereed) Published
Abstract [en]

A highly efficient regio- and stereoselective heterogeneous palladium-catalyzed hydroboration reaction of enallenes was developed. Nanopalladium immobilized on microcrystalline cellulose (MCC) was successfully employed as an efficient catalyst for the enallene hydroboration reaction. The nanopalladium particles were shown by HAADF-STEM to have an average size of 2.4 nm. The cellulose-supported palladium catalyst exhibits high stability and provides vinyl boron products in good to high isolated yields (up to 90 %). The nanopalladium catalyst can be efficiently recycled and it was demonstrated that the catalyst can be used in 7 runs with a maintained high yield (>80 %). The vinylboron compounds prepared from enallenes are important synthetic intermediates that can be used in various organic synthetic transformations. 

Keywords
cellulose, enallenes, heterogeneous catalysis, palladium, regio- and stereoselective hydroboration
National Category
Organic Chemistry
Identifiers
urn:nbn:se:miun:diva-48009 (URN)10.1002/chem.202203950 (DOI)000953617500001 ()2-s2.0-85150410152 (Scopus ID)
Available from: 2023-03-28 Created: 2023-03-28 Last updated: 2023-04-27Bibliographically approved
Deiana, L., Abbaszad Rafi, A., Bäckvall, J.-E. & Cordova, A. (2023). Subtilisin integrated artificial plant cell walls as heterogeneous catalysts for asymmetric synthesis of (S)-amides. RSC Advances, 13(29), 19975-19980
Open this publication in new window or tab >>Subtilisin integrated artificial plant cell walls as heterogeneous catalysts for asymmetric synthesis of (S)-amides
2023 (English)In: RSC Advances, E-ISSN 2046-2069, Vol. 13, no 29, p. 19975-19980Article in journal (Refereed) Published
Abstract [en]

Subtilisin integrated artificial plant-cell walls (APCWs) were fabricated by self-assembly using cellulose or nanocellulose as the main component. The resulting APCW catalysts are excellent heterogeneous catalysts for the asymmetric synthesis of (S)-amides. This was demonstrated by the APCW-catalyzed kinetic resolution of several racemic primary amines to give the corresponding (S)-amides in high yields with excellent enantioselectivity. The APCW catalyst can be recycled for multiple reaction cycles without loss of enantioselectivity. The assembled APCW catalyst was also able to cooperate with a homogeneous organoruthenium complex, which allowed for the co-catalytic dynamic kinetic resolution (DKR) of a racemic primary amine to give the corresponding (S)-amide in high yield. The APCW/Ru co-catalysis constitutes the first examples of DKR of chiral primary amines when subtilisin is used as a co-catalyst.

Place, publisher, year, edition, pages
Royal Society of Chemistry (RSC), 2023
National Category
Organic Chemistry
Identifiers
urn:nbn:se:miun:diva-49034 (URN)10.1039/d3ra02193a (DOI)001022295400001 ()37404321 (PubMedID)2-s2.0-85165532562 (Scopus ID)
Available from: 2023-08-15 Created: 2023-08-15 Last updated: 2023-08-15Bibliographically approved
Alimohammadzadeh, R., Abbaszad Rafi, A., Goclik, L., Tai, C.-W. & Cordova, A. (2022). Direct Organocatalytic Thioglycolic Acid Esterification of Cellulose Nanocrystals: A simple entry to click chemistry on the surface of nanocellulose. Carbohydrate Polymer Technologies and Applications, 3, Article ID 100205.
Open this publication in new window or tab >>Direct Organocatalytic Thioglycolic Acid Esterification of Cellulose Nanocrystals: A simple entry to click chemistry on the surface of nanocellulose
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2022 (English)In: Carbohydrate Polymer Technologies and Applications, ISSN 2666-8939, Vol. 3, article id 100205Article in journal (Refereed) Published
Abstract [en]

The mild and simple direct organocatalytic esterification of cellulose nanocrystals (CNC) and nanocellulose-based materials (e.g. foams and films) with thioglycolic acid (TGA) is disclosed. The transformation gives the corresponding thiol group (-SH) functionalized crystalline nanocellulose (CNC-SH) using simple, naturally occurring, and non-toxic organic acids (e.g. tartaric acid) as catalysts. We also discovered that the direct esterification of cellulose with TGA is autocatalytic (i.e. the TGA is catalyzing its own esterification). The introduction of the -SH functionality at the nanocellulose surface opens up for further selective applications. This was demonstrated by attaching organic catalysts and fluorescent molecules, which are useful as sensors, to the CNC-SH surface by thiol-ene click chemistry. Another application is to use the CNC-SH-based foam as a heterogeneous biomimetic reducing agent, which is stable during multiple recycles, for the copper-catalyzed alkyne-azide 1,3-dipolar cycloaddition (“click” reaction).

Keywords
Cellulose nanocrystals, Thiol-functionalized nanocellulose, Organocatalysis, Heterogeneous catalysis, Direct esterification, Click chemistry
National Category
Natural Sciences Bio Materials
Identifiers
urn:nbn:se:miun:diva-41923 (URN)10.1016/j.carpta.2022.100205 (DOI)000821577600041 ()2-s2.0-85129227500 (Scopus ID)
Available from: 2023-01-01 Created: 2021-04-22 Last updated: 2024-12-05Bibliographically approved
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