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Alimohammadzadeh, Rana
Publications (10 of 13) Show all publications
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: 2023-09-19Bibliographically approved
Alimohammadzadeh, R., Sanhueza, I. & Cordova, A. (2023). Design and fabrication of superhydrophobic cellulose nanocrystal films by combination of self-assembly and organocatalysis. Scientific Reports, 13(1), Article ID 3157.
Open this publication in new window or tab >>Design and fabrication of superhydrophobic cellulose nanocrystal films by combination of self-assembly and organocatalysis
2023 (English)In: Scientific Reports, E-ISSN 2045-2322, Vol. 13, no 1, article id 3157Article in journal (Refereed) Published
Abstract [en]

Cellulose nanocrystals, which have unique properties of high aspect ratio, high surface area, high mechanical strength, and a liquid crystalline nature, constitute a renewable nanomaterial with great potential for several uses (e.g., composites, films and barriers). However, their intrinsic hydrophilicity results in materials that are moisture sensitive and exhibit poor water stability. This limits their use and competitiveness as a sustainable alternative against fossil-based materials/plastics in packaging, food storage, construction and materials application, which cause contamination in our oceans and environment. To make cellulose nanocrystal films superhydrophobic, toxic chemicals such as fluorocarbons are typically attached to their surfaces. Hence, there is a pressing need for environmentally friendly alternatives for their modification and acquiring this important surface property. Herein, we describe the novel creation of superhydrophobic, fluorocarbon-free and transparent cellulose nanocrystal films with functional groups by a bioinspired combination of self-assembly and organocatalytic surface modification at the nanoscale using food approved organic acid catalysts. The resulting film-surface is superhydrophobic (water contact angle > 150°) and has self-cleaning properties (the lotus effect). In addition, the superhydrophobic cellulose nanocrystal films have excellent water stability and significantly decreased oxygen permeability at high relative humidity with oxygen transmission rates better than those of commonly used plastics. 

National Category
Polymer Technologies
Identifiers
urn:nbn:se:miun:diva-47782 (URN)10.1038/s41598-023-29905-1 (DOI)000988352100025 ()36823204 (PubMedID)2-s2.0-85148799074 (Scopus ID)
Available from: 2023-03-13 Created: 2023-03-13 Last updated: 2023-06-26Bibliographically 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: 2023-02-14Bibliographically approved
Alimohammadzadeh, R., Cordova, A., Abbaszad Rafi, A., Persson, E., Marksted, K., Hilden, L. & Engstrand, P. (2022). Improving the mechanical properties of CTMP fibers by combining synergistic organocatalytic/polyelectrolyte complex surface engineering with sulfite pretreatment. In: Proceedings of the International Mechanical Pulping Conference: . Paper presented at IMPC 2022, Vancouver, BC, Canada, June 5-8, 2022 (pp. 149).
Open this publication in new window or tab >>Improving the mechanical properties of CTMP fibers by combining synergistic organocatalytic/polyelectrolyte complex surface engineering with sulfite pretreatment
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2022 (English)In: Proceedings of the International Mechanical Pulping Conference, 2022, p. 149-Conference paper, Poster (with or without abstract) (Other academic)
Abstract [en]

Fabrication of paper-based packaging materials is increasing and the challenge is developing a sustainable process to manufacture the materials that can compete with plastics. Employing stronger fiber in production of fiber-based materials improves the efficiency of fabrication process by using a reduced amount of biomass. Cationic starch is a well-known polysaccharide that has been introduced to paper and paperboard fibers to improve the mechanical properties of lignocellulosic fibers. The polyelectrolyte (PE) multilayer method has been popularized as a new and interesting technique to enhance the adsorption of cationic starch on the fiber for improving the strength properties of chemi-thermomechanical pulp (CTMP), chemical and kraft pulps. We have shown in our previous work that the synergistic combination of organocatalysis and PE complexes improved the mechanical properties of CTMP and TMP. In this work, we chose to expand this concept by integrating it with low-dose sulfite pretreatment of wood chips in preparation of CTMP. Thus, CTMP produced by initial sulfite pre-treatment was next surface engineered by synergistic combination of organocatalysis and PE complexes using organic acids as catalysts. The CTMP pulps, which contains 0.1-0.24 wt.% sulfur, produced by our novel pulp-engineering strategy shows a dramatic strength increase (Z- strength: up to 100 %) as compared to no surface engineering. While only sulfite pre-treatment and PE-complex surface engineering were able to improve the strength properties, it was only when the organic catalysts was present that the highest strength improvements were reached. Thus, a clear synergistic effect of the catalyst was observed.

National Category
Wood Science
Identifiers
urn:nbn:se:miun:diva-47689 (URN)
Conference
IMPC 2022, Vancouver, BC, Canada, June 5-8, 2022
Available from: 2023-02-27 Created: 2023-02-27 Last updated: 2023-02-27Bibliographically approved
Alimohammadzadeh, R. (2021). Eco-friendly and Catalytic Surface Engineering of Cellulose and Nanocellulose. (Doctoral dissertation). Sundsvall: Mid Sweden University
Open this publication in new window or tab >>Eco-friendly and Catalytic Surface Engineering of Cellulose and Nanocellulose
2021 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The non-stop use of petroleum-based materials such as plastics can generate significant environmental problems, including pollution of the oceans and increased CO2 levels, and cause diseases like cancer due to the starting monomers. Consequently, increased use of sustainable and non-toxic polymers and monomers is required to address these issues. Cellulose, generously supplied by Mother Nature, is the most abundant biopolymer on Earth. Nanocellulose is a sustainable polymer extracted from the cellulose inwood or produced by bacteria and algae. This biodegradable nanomaterialhas recently been receiving intense research attention, since it has great potential for use in a broad range of industrial and biomedical applications. However, it has limitations such as moisture sensitivity and incompatibility with hydrophobic materials due to its hydrophilic nature. Chemical modification is necessary for it to fulfill the requirements for applications that require high moisture resistance and water repellency. Unfortunately, several of the existing methods involve harsh and toxic conditions or reagents. In this thesis, together with my co-workers, I have employed the toolbox of organocatalysis for accomplishing eco-friendly and innovative surface modification of cellulose and nanocellulose. The organocatalysts we usedmost in our research are the naturally abundant and industrially relevantorganic acids tartaric acid and citric acid.

Direct catalytic esterification of cellulose nanocrystal (CNC) with thioglycolicacid was performed either in suspension or on solid surfaces such as films and foams. We found that the reaction was accelerated by tartaric acid but could also be autocatalytic with respect to the thioglycolic acid under certain conditions. The synthesized CNC-SH was further exploited as a heterogeneous reducing agent as well as a handle for further nanocellulose modifications. This was demonstrated by using CNC-SH as a heterogenous reducing agent of Cu(II) to Cu(I), which is essential for allowing the Cu to actas a catalyst for 2,3-dipolar cycloaddition reactions between azides andalkynes. We also showed that the thia-modified CNC could undergo further functionalizing via thiol-ene click chemistry reactions, for example, we attached fluorescent compounds such as TAMRA and quinidine.

Herein we provide a fluorine-free method to prepare superhydrophobic CNC film with excellent water-resistance properties by combining self-assemblyand organocatalysis. Self-assembly of CNC via vacuum filtration resulted in xa film with a specific roughness at the microscale. Next, the catalytic silylation with a variety of alkoxysilanes in the presence of natural organic acids such as tartaric acid and citric acid was performed. The successful implementation of our method resulted in a super-hydrophobic CNC film (water contact angleover 150°) with excellent water-resistance. Thus, the combination of the selfassembly of a rough surface with catalytic surface modification resulted in a phenomenon like the “lotus effect” as exhibited by the leaves of the lotus flower. An investigation of the oxygen permeability of the octadecyltrimethoxysilane-modified CNC film revealed that it significantly decreased at high relative humidity compared with unmodified CNC films.

In this thesis, the fabrication of hydrophobic and functionalized MTM/CNF nanocomposites using organocatalytic surface modification with a large variety of alkoxysilanes is also performed. The surface modifications are mildand the mechanical strength of the Nacre-mimetic nanocomposites is preserved. Elemental mapping analysis revealed that the silane modification occurred predominantly on the surface.

A combination of organocatalyst and biopolyelectrolyte complex was appliedfor surface engineering of chemi-thermomechanical pulp (CTMP) and bleached sulfite pulp (BSP). The reaction was performed using a synergistic combination of an organocatalyst with a polyelectrolyte (PE) complex. Using this method, the strength properties of CTMP and BSP sheets were significantly increased (up to 100% in Z-strength for CTMP). Further investigations of the distribution of the PE complex were then performed using TAMRA and quinidine labeling and confocal laser scanningmicroscopy. This revealed that an even distribution of the cationic starch component of the PE complex had occurred within the CTMP-based paper sheets, which follows its lignin distribution pattern.

Place, publisher, year, edition, pages
Sundsvall: Mid Sweden University, 2021. p. 78
Series
Mid Sweden University doctoral thesis, ISSN 1652-893X ; 339
National Category
Natural Sciences
Identifiers
urn:nbn:se:miun:diva-41889 (URN)978-91-88947-94-9 (ISBN)
Public defence
2021-05-07, C312, Holmgatan 10, Sundsvall, 10:00 (English)
Opponent
Supervisors
Note

Vid tidpunkten för disputationen var följande delarbeten opublicerade: delararbete 2 och 3 manuskript.

At the time of the doctoral defence the following papers were unpublished: paper 2 and 3 manuscripts.

Available from: 2021-04-22 Created: 2021-04-20 Last updated: 2021-04-22Bibliographically approved
Alimohammadzadeh, R., Medina, L., Deiana, L., Berglund, L. A. & Cordova, A. (2020). Mild and Versatile Functionalization of Nacre-Mimetic Cellulose Nanofibrils/Clay Nanocomposites by Organocatalytic Surface Engineering. ACS Omega, 5(31), 19363-19370
Open this publication in new window or tab >>Mild and Versatile Functionalization of Nacre-Mimetic Cellulose Nanofibrils/Clay Nanocomposites by Organocatalytic Surface Engineering
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2020 (English)In: ACS Omega, E-ISSN 2470-1343, Vol. 5, no 31, p. 19363-19370Article in journal (Refereed) Published
Abstract [en]

Development of surface-engineering strategies, which are facile, versatile, and mild, are highly desirable in tailor-made functionalization of high-performance bioinspired nanocomposites. We herein disclose for the first time a general organocatalytic strategy for the functionalization and hydrophobization of nacre-mimetic nanocomposites, which includes vide supra key aspects of surface engineering. The merging of metal-free catalysis and the design of nacre-mimetic nanocomposite materials were demonstrated by the organocatalytic surface engineering of cellulose nanofibrils/clay nanocomposites providing the corresponding bioinspired nanocomposites with good mechanical properties, hydrophobicity, and useful thia-, amino, and olefinic functionalities. 

National Category
Chemical Sciences
Identifiers
urn:nbn:se:miun:diva-39627 (URN)10.1021/acsomega.0c00978 (DOI)000562138900005 ()2-s2.0-85087717744 (Scopus ID)
Available from: 2020-08-18 Created: 2020-08-18 Last updated: 2021-04-22
Cordova, A., Afewerki, S., Alimohammadzadeh, R., Sanhueza, I., Tai, C.-W., Osong, S. H., . . . Ibrahem, I. (2019). A sustainable strategy for production and functionalization of nanocelluloses. Pure and Applied Chemistry, 91(5), 865-874
Open this publication in new window or tab >>A sustainable strategy for production and functionalization of nanocelluloses
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2019 (English)In: Pure and Applied Chemistry, ISSN 0033-4545, E-ISSN 1365-3075, Vol. 91, no 5, p. 865-874Article in journal (Refereed) Published
Abstract [en]

A sustainable strategy for the neat production and surface functionalization of nanocellulose from wood pulp is disclosed. It is based on the combination of organocatalysis and click chemistry ("organoclick" chemistry) and starts with nanocellulose production by organic acid catalyzed hydrolysis and esterification of the pulp under neat conditions followed by homogenization. This nanocellulose fabrication route is scalable, reduces energy consumption and the organic acid can be efficiently recycled. Next, the surface is catalytically engineered by "organoclick" chemistry, which allows for selective and versatile attachment of different organic molecules (e.g. fluorescent probes, catalyst and pharmaceuticals). It also enables binding of metal ions and nanoparticles. This was exemplified by the fabrication of a heterogeneous nanocellulose-palladium nanoparticle catalyst, which is used for Suzuki cross-coupling transformations in water. The disclosed surface functionalization methodology is broad in scope and applicable to different nanocelluloses and cellulose based materials as well.

Keywords
click chemistry, cross-coupling reaction, heterogeneous catalysis, nanocellulose, NICE-2016, organocatalysis, surface engineering
National Category
Chemical Engineering
Identifiers
urn:nbn:se:miun:diva-35142 (URN)10.1515/pac-2018-0204 (DOI)000466859500008 ()2-s2.0-85056591870 (Scopus ID)
Available from: 2018-12-10 Created: 2018-12-10 Last updated: 2020-01-21Bibliographically approved
Alimohammadzadeh, R., Osong, S. H., Abbaszad Rafi, A., Dahlström, C. & Cordova, A. (2019). Cellulosic Materials: Sustainable Surface Engineering of Lignocellulose and Cellulose by Synergistic Combination of Metal-Free Catalysis and Polyelectrolyte Complexes. Global Challenges, 3(7), Article ID 1970071.
Open this publication in new window or tab >>Cellulosic Materials: Sustainable Surface Engineering of Lignocellulose and Cellulose by Synergistic Combination of Metal-Free Catalysis and Polyelectrolyte Complexes
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2019 (English)In: Global Challenges, E-ISSN 2056-6646, Vol. 3, no 7, article id 1970071Article in journal (Refereed) Published
Abstract [en]

In article number 1900018 by Armando Cordova and co‐workers, the novel combination of metal‐free catalysis and renewable polyelectrolyte complexes leads to synergistic surface engineering of lignocellulose and cellulose fibers derived from wood. This sustainable strategy allows for improvement and introduction of important properties such as strength (up to 100% in Z‐strength), water resistance, and fluorescence to the renewable fibers and cellulosic materials under eco‐friendly conditions.

National Category
Chemical Engineering
Identifiers
urn:nbn:se:miun:diva-37903 (URN)10.1002/gch2.201970071 (DOI)
Available from: 2019-12-06 Created: 2019-12-06 Last updated: 2020-11-18Bibliographically approved
Alimohammadzadeh, R., Osong, S. H., Abbaszad Rafi, A., Dahlström, C. & Cordova, A. (2019). Sustainable Surface Engineering of Lignocellulose and Cellulose by Synergistic Combination of Metal‐Free Catalysis and Polyelectrolyte Complexes. Global Challenges, 3, Article ID 1900018.
Open this publication in new window or tab >>Sustainable Surface Engineering of Lignocellulose and Cellulose by Synergistic Combination of Metal‐Free Catalysis and Polyelectrolyte Complexes
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2019 (English)In: Global Challenges, E-ISSN 2056-6646, Vol. 3, article id 1900018Article in journal (Refereed) Published
Abstract [en]

A sustainable strategy for synergistic surface engineering of lignocellulose and cellulose fibers derived from wood by synergistic combination of metal‐free catalysis and renewable polyelectrolyte (PE) complexes is disclosed. The strategy allows for improvement and introduction of important properties such as strength, water resistance, and fluorescence to the renewable fibers and cellulosic materials. For example, the “green” surface engineering significantly increases the strength properties (up to 100% in Z‐strength) of chemi‐thermomechanical pulp (CTMP) and bleached sulphite pulp (BSP)‐derived sheets. Next, performing an organocatalytic silylation with a nontoxic organic acid makes the corresponding lignocellulose and cellulose sheets hydrophobic. A selective color modification of polysaccharides is developed by combining metal‐free catalysis and thiol‐ene click chemistry. Next, fluorescent PE complexes based on cationic starch (CS) and carboxymethylcellulose (CMC) are prepared and used for modification of CTMP or BSP in the presence of a metal‐free catalyst. Laser‐scanning confocal microscopy reveals that the PE‐strength additive is evenly distributed on the CTMP and heterogeneously on the BSP. The fluorescent CS distribution on the CTMP follows the lignin distribution of the lignocellulosic fibers.

Keywords
click chemistry, lignocellulose, metal‐free catalysis, selective fluorescent labeling, sustainable polyelectrolyte complex, synergistic surface engineering, water repellent
National Category
Materials Chemistry Organic Chemistry Paper, Pulp and Fiber Technology
Identifiers
urn:nbn:se:miun:diva-37905 (URN)10.1002/gch2.201900018 (DOI)000518818400001 ()
Available from: 2019-12-06 Created: 2019-12-06 Last updated: 2021-04-22Bibliographically approved
Alimohammadzadeh, R., Osong, S. H., Dahlström, C. & Cordova, A. (2018). Scalable Improvement of the Strength Properties of Chemimechanical Pulp Fibers by Eco-Friendly Catalysis. In: IMPC 2018: . Paper presented at International Mechanical Pulping Conference (IMPC) 2018, May 27-30, 2018, Trondheim, Norway. Trondheim, Norway
Open this publication in new window or tab >>Scalable Improvement of the Strength Properties of Chemimechanical Pulp Fibers by Eco-Friendly Catalysis
2018 (English)In: IMPC 2018, Trondheim, Norway, 2018Conference paper, Published paper (Refereed)
Abstract [en]

The sustainable improvement of the strength properties of chemimechanical pulp by eco-friendlycatalysis is disclosed. Significant research activities have been performed on the use of cationic starchand polyelectrolyte complexes for improving the strength properties of cellulose-based materials. Herewe apply an eco-friendly strategy based on catalysis for significantly improving the strength propertiesof sheets made from chemimechanical pulp (CTMP) and bleeched sulphite pulp (BSP) using sustainablepolyelectrolyte complexes as the strength additives and organocatalysis. This surface engineeringstrategy significantly increased the strength properties of the assembled sheets (up to 100% in the caseof Z-strength). We also developed a catalytic selective colour marking of the cationic potato starch (CS)and carboxymethylcellulose (CMC) in order to elucidated how the specific strength additives aredistributed on the sheets. It revealed that the strength additives were more evenly distributed on thesheets made from CTMP as compared to BSP sheets. This is most likely attributed to the presence oflignin in the former lignocellulosic material. It also contributes to the increase in strength (up to 100%,Z-strength) for the CTMP derived sheets. The selective colour marking method also revealed that morestrength additives had been bound to the pulps in the presence of the catalyst.

Place, publisher, year, edition, pages
Trondheim, Norway: , 2018
National Category
Paper, Pulp and Fiber Technology
Identifiers
urn:nbn:se:miun:diva-34682 (URN)
Conference
International Mechanical Pulping Conference (IMPC) 2018, May 27-30, 2018, Trondheim, Norway
Available from: 2018-10-08 Created: 2018-10-08 Last updated: 2018-10-08Bibliographically approved
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