| 1. |
- Abbaszad Rafi, Abdolrahim, et al.
(författare)
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A facile route for concurrent fabrication and surface selective functionalization of cellulose nanofibers by lactic acid mediated catalysis
- 2023
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Ingår i: Scientific Reports. - : Springer Nature. - 2045-2322 .- 2045-2322. ; 13:1
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Tidskriftsartikel (refereegranskat)abstract
- 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.
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| 2. |
- Abbaszad Rafi, Abdolrahim, et al.
(författare)
-
Copper nanoparticles on controlled pore glass (CPG) as highly efficient heterogeneous catalysts for “click reactions”
- 2020
-
Ingår i: Scientific Reports. - : Springer Science and Business Media LLC. - 2045-2322. ; 10:1
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Tidskriftsartikel (refereegranskat)abstract
- We herein report that supported copper nanoparticles (CuNPs) on commercially available controlled pore glass (CPG), which exhibit high mechanical, thermal and chemical stability as compared to other silica-based materials, serve as a useful heterogeneous catalyst system for 1,3-dipolar cycloadditions (“click” reactions) between terminal alkynes and organic azides under green chemistry conditions. The supported CuNPs-CPG catalyst exhibited a broad substrate scope and gave the corresponding triazole products in high yields. The CuNPs-CPG catalyst exhibit recyclability and could be reuced multiple times without contaminating the products with Cu.
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| 3. |
- Afewerki, Samson, 1985-, et al.
(författare)
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Cooperative Lewis Acids and Aminocatalysis
- 2017
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Ingår i: Chiral Lewis Acids in Organic Synthesis. - Weinheim, Germany : Wiley-Blackwell. ; , s. 345-374
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Bokkapitel (refereegranskat)abstract
- This chapter describes the cooperative strategy of combining metal catalyst activation with aminocatalysis, with a focus on the metal acting as a Lewis acid catalyst. It gives examples where the metal catalyst promotes the reactivity of different substrates by the formation of reactive intermediates. These intermediates can act either as electrophiles or nucleophiles, which in turn can couple with nucleophilic enamine or electrophilic iminium intermediates formed between the carbonyl compounds and aminocatalyst. The chemical transformation ensues via the merging of the enamine and π‐allyl‐Pd complex via asymmetric counteranion‐direct catalysis (ACDC). Subsequently, several groups reported different co‐catalytic systems and chemical strategies for the α‐allylic alkylation of aldehydes and ketones. Cordova and coworkers reported the first example where iminium activation catalysis is combined with metal catalyst activation cooperatively. The stratagem was demonstrated for the catalytic enantioselective conjugate silyl addition to α,β‐unsaturated aldehydes.
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| 4. |
- Afewerki, Samson, 1985-, et al.
(författare)
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Efficient Heterogeneous Palladium-Catalyzed Transfer Hydrogenolysis of Benzylic Alcohols by Formic Acid
- 2020
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Ingår i: Synthesis (Stuttgart). - : Georg Thieme Verlag KG. - 0039-7881 .- 1437-210X. ; 52:16, s. 2330-2336
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Tidskriftsartikel (refereegranskat)abstract
- An efficient heterogeneous palladium-catalyzed transfer hydrogenolysis of primary, secondary, and tertiary benzylic alcohols using formic acid as hydrogen source has been developed. The resulting hydrocarbon products were obtained in excellent yields. Moreover, the system exhibits high chemoselectivity, reacting only with the hydroxy groups in the presence of other functional groups, and excellent recyclability.
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| 5. |
- Afewerki, Samson, 1985-, et al.
(författare)
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Enamine/Transition Metal Combined Catalysis : Catalytic Transformations Involving Organometallic Electrophilic Intermediates
- 2019
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Ingår i: Topics in current chemistry. - : Springer Science and Business Media LLC. - 0340-1022 .- 1436-5049 .- 2365-0869 .- 2364-8961. ; 377:6
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Tidskriftsartikel (refereegranskat)abstract
- The concept of merging enamine activation catalysis with transition metal catalysis is an important strategy, which allows for selective chemical transformations not accessible without this combination. The amine catalyst activates the carbonyl compounds through the formation of a reactive nucleophilic enamine intermediate and, in parallel, the transition metal activates a wide range of functionalities such as allylic substrates through the formation of reactive electrophilic π-allyl-metal complex. Since the first report of this strategy in 2006, considerable effort has been devoted to the successful advancement of this technology. In this chapter, these findings are highlighted and discussed.
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| 6. |
- Afewerki, Samson, 1985-, et al.
(författare)
-
Sustainable and recyclable heterogenous palladium catalysts from rice husk-derived biosilicates for Suzuki-Miyaura cross-couplings, aerobic oxidations and stereoselective cascade carbocyclizations
- 2020
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Ingår i: Scientific Reports. - : Springer Science and Business Media LLC. - 2045-2322. ; 10
-
Tidskriftsartikel (refereegranskat)abstract
- A new eco-friendly approach for the preparation of sustainable heterogeneous palladium catalysts from rice husk-derived biogenic silica (RHP-Si and RHU-Si). The designed heterogeneously supported palladium species (RHP-Si-NH2-Pd and RHU-Si-NH2-Pd) were fully characterized and successfully employed as catalysts for various chemical transformations (C–C bond-forming reactions, aerobic oxidations and carbocyclizations). Suzuki-Miyaura transformations were highly efficient in a green solvent system (H2O:EtOH (1:1) with excellent recyclability, providing the cross-coupling products with a wide range of functionalities in high isolated yields (up to 99%). Palladium species (Pd(0)-nanoparticles or Pd(II)) were also efficient catalysts in the green aerobic oxidation of an allylic alcohol and a co-catalytic stereoselective cascade carbocyclization transformation. In the latter case, a quaternary stereocenter was formed with excellent stereoselectivity (up to 27:1 dr).
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| 7. |
- Afewerki, Samson, 1985-, et al.
(författare)
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Sustainable Design for the Direct Fabrication and Highly Versatile Functionalization of Nanocelluloses
- 2017
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Ingår i: Global Challenges. - Weinheim : Wiley. - 2056-6646. ; 1:7
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Tidskriftsartikel (refereegranskat)abstract
- This study describes a novel sustainable concept for the scalable direct fabrication and functionalization of nanocellulose from wood pulp with reduced energy consumption. A central concept is the use of metal-free small organic molecules as mediators and catalysts for the production and subsequent versatile surface engineering of the cellulosic nanomaterials via organocatalysis and click chemistry. Here, organoclick chemistry enables the selective functionalization of nanocelluloses with different organic molecules as well as the binding of palladium ions or nanoparticles. The nanocellulosic material is also shown to function as a sustainable support for heterogeneous catalysis in modern organic synthesis (e.g., Suzuki cross-coupling transformations in water). The reported strategy not only addresses obstacles and challenges for the future utilization of nanocellulose (e.g., low moisture resistance, the need for green chemistry, and energy-intensive production) but also enables new applications for nanocellulosic materials in different areas.
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| 8. |
- Afewerki, Samson, 1985-, et al.
(författare)
-
Synthesis of amides and amines from aldehydes or ketones by heterogeneous metal catalysis
- 2019
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Patent (populärvet., debatt m.m.)abstract
- A mild and efficient synthesis of primary amines and amides from aldehydes or ketones using a heterogeneous metal catalyst and amine donor is disclosed. The initial heterogeneous metal-catalyzed reaction between the carbonyl and the amine donor components is followed by the addition of a suitable acylating agent component in one-pot, thus providing a catalytic one-pot three-component synthesis of amides. Integration of enzyme catalysis allows for eco-friendly one-pot co-catalytic synthesis of amides from aldehyde and ketone substrates, respectively. The process can be applied to asymmetric synthesis or to the co-catalytic one-pot three-component synthesis of capsaicin and its analogues from vanillin or vanillyl alcohol. A co-catalytic reductive amination/dynamic kinetic resolution (dkr) relay sequence for the asymmetric synthesis of optically active amides from ketones is disclosed. Implementation of a catalytic reductive amination/kinetic resolution (kr) relay sequence produces the corresponding optically active amide product and optical active primary amine product with the opposite stereochemistry from the starting ketones.
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| 9. |
- Afewerki, Samson, 1985-, et al.
(författare)
-
The Chemical Synthesis and Applications of Tropane Alkaloids
- 2019
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Ingår i: Alkaloids: Chemistry and Biology. - : Elsevier. - 1099-4831. ; 81, s. 151-233
-
Tidskriftsartikel (refereegranskat)abstract
- Tropanes are an important class of alkaloid natural products that are found in plants all over the world. These compounds can exhibit significant biological activity and are among the oldest known medicines. In the early 19th century, tropanes were isolated, characterized, and synthesized by notable chemical researchers. Their significant biological activities have inspired tremendous research efforts toward their synthesis and the elucidation of their pharmacological activity both in academia and in industry. In this chapter, which addresses the developments in this field since 1994, the focus is on the synthesis of these compounds, and several examples of sophisticated synthetic protocols involving both asymmetric and catalytic approaches are described. In addition, the structures of more than 100 new alkaloids are included as well as the applications and pharmacological properties of some tropane alkaloids.
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| 10. |
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| 11. |
- Alimohammadzadeh, Rana, et al.
(författare)
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Design and fabrication of superhydrophobic cellulose nanocrystal films by combination of self-assembly and organocatalysis
- 2023
-
Ingår i: Scientific Reports. - : Springer Science and Business Media LLC. - 2045-2322. ; 13:1
-
Tidskriftsartikel (refereegranskat)abstract
- 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.
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| 12. |
- Alimohammadzadeh, Rana, et al.
(författare)
-
Direct Organocatalytic Thioglycolic Acid Esterification of Cellulose Nanocrystals : A simple entry to click chemistry on the surface of nanocellulose
- 2022
-
Ingår i: Carbohydrate Polymer Technologies and Applications. - : Elsevier BV. - 2666-8939. ; 3
-
Tidskriftsartikel (refereegranskat)abstract
- 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).
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| 13. |
- Alimohammadzadeh, Rana
(författare)
-
Eco-friendly and Catalytic Surface Engineering of Cellulose and Nanocellulose
- 2021
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- 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.
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| 14. |
- Alimohammadzadeh, Rana, et al.
(författare)
-
Improving the mechanical properties of CTMP fibers by combining synergistic organocatalytic/polyelectrolyte complex surface engineering with sulfite pretreatment
- 2022
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Ingår i: Proceedings of the International Mechanical Pulping Conference. ; , s. 149-
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Konferensbidrag (övrigt vetenskapligt/konstnärligt)abstract
- 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.
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| 15. |
- Alimohammadzadeh, Rana, et al.
(författare)
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Mild and Versatile Functionalization of Nacre-Mimetic Cellulose Nanofibrils/Clay Nanocomposites by Organocatalytic Surface Engineering
- 2020
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Ingår i: ACS Omega. - : American Chemical Society (ACS). - 2470-1343. ; 5:31, s. 19363-19370
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Tidskriftsartikel (refereegranskat)abstract
- 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.
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| 16. |
- Alimohammadzadeh, Rana, et al.
(författare)
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Scalable Improvement of the Strength Properties of Chemimechanical Pulp Fibers by Eco-Friendly Catalysis
- 2018
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Ingår i: IMPC 2018. - Trondheim, Norway.
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Konferensbidrag (refereegranskat)abstract
- 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.
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| 17. |
- Alimohammadzadeh, Rana, et al.
(författare)
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Sustainable Surface Engineering of Lignocellulose and Cellulose by Synergistic Combination of Metal‐Free Catalysis and Polyelectrolyte Complexes
- 2019
-
Ingår i: Global Challenges. - : Wiley. - 2056-6646. ; 3
-
Tidskriftsartikel (refereegranskat)abstract
- 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.
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| 18. |
- Carmo, C., et al.
(författare)
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Exploring the impact of meso-position fluorination on BODIPYs : Synthesis, electrochemical Insights, and potential therapeutic applications in breast cancer
- 2024
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Ingår i: Dyes and pigments. - : Elsevier BV. - 0143-7208 .- 1873-3743. ; 229
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Tidskriftsartikel (refereegranskat)abstract
- Three boron dipyrromethane molecules (BODIPYs) were synthesized in this study with different quantities of fluorine in the meso position. The samples were characterized by NMR spectroscopy, absorption, mass spectrometry, and cyclic voltammetry, which was utilized to electrochemically measure the energy gaps between the HOMO (highest-energy occupied molecular orbital) and LUMO (lowest-energy unoccupied molecular orbital). The MTT and SRB assays were used to assess the viability of these dyes in breast cancer cells (MCF-7 and HCC-1806) and African green monkey kidney cells (Vero). The newly synthesized BODIPY tris(perfluorophenoxy)phenyl (1) compound has exhibited remarkable stability and lacks photocytotoxicity in this investigation, thus rendering it a promising candidate for application in bioimaging. At defined concentrations, the BODIPYs bearing perfluorophenyl (2) and hydroxyphenyl (3) moieties have been identified as prospective candidates for photosensitization in photodynamic therapy for breast cancer. Their notable phototoxic properties upon irradiation and the absence of significant metabolic activity reduction in normal VERO cells after 24 h of exposure suggest their potential efficacy in this therapeutic approach.
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| 19. |
- Cordova, Armando, 1970-, et al.
(författare)
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A sustainable strategy for production and functionalization of nanocelluloses
- 2019
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Ingår i: Pure and Applied Chemistry. - : Walter de Gruyter GmbH. - 0033-4545 .- 1365-3075. ; 91:5, s. 865-874
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Tidskriftsartikel (refereegranskat)abstract
- 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.
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| 20. |
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| 21. |
- Cordova, Armando, 1970-, et al.
(författare)
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Efficient synthesis of amines and amides from alcohols and aldehydes by using cascade catalysis
- 2019
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Patent (populärvet., debatt m.m.)abstract
- The present invention relates generally to an eco-friendly methodology for the conversion of alcohols and aldehydes to amines and amides using an integrated enzyme cascade system with metal-and organocatalysis. More specifically, the present invention relates to synthesis of capsaicinoids starting from vanillin alcohol and using a combination of an enzyme cascade system and catalysts. Furthermore, the method also relates to synthesis of capsaicinoids derivatives starting from vanillin alcohol derivatives and using a combination of an enzyme cascade system and catalysts.
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| 22. |
- Cordova, Armando, 1970-, et al.
(författare)
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Heterogeneous Thiol-ene Click Modifications Of Solid Polysaccharide-based Materials
- 2016
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Patent (populärvet., debatt m.m.)abstract
- This invention concerns the first environmentally benign heterogeneous modification of polysaccharide-based material in native solid state by thiol-ene “click chemistry”. The direct reaction of a thiol with an un-activated double or triple bond by thiol-ene and thiol-enyne click modification is thermally or photochemically catalyzed and is completely metal-free and allows for a highly modular approach to modifications of fibers and fiber-based materials.
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| 23. |
- Cordova, Armando, 1970-, et al.
(författare)
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Mild Catalytic Reduction Of C—o Bonds And C═o Bonds Using A Recyclable Catalyst System
- 2019
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Patent (populärvet., debatt m.m.)abstract
- A method of reducing a C--O bond to the corresponding C--H bond in a substrate, which could be a benzylic alcohol, allylic alcohol, ester or an ether bond beta to a hydroxyl group or alpha to a carbonyl group using a recyclable metal catalyst system. The recyclable catalyst system is also applicable to reducing a C.dbd.O bond to the corresponding C--OH bond and then C--H bond. These methodologies can be linked in one-pot to selective oxidation and depolymerizations of aromatic polyols such as lignin.
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| 24. |
- Cordova, Armando, 1970-, et al.
(författare)
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Organocatalytic Dynamic Kinetic Asymmetric Transformations
- 2023
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Ingår i: Dynamic Kinetic Resolution (DKR) and Dynamic Kinetic Asymmetric Transformations (DYKAT). - : Georg Thieme Verlag KG. - 9783132453777 - 9783132453791
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Bokkapitel (refereegranskat)abstract
- Dynamic kinetic asymmetric transformations (DYKAT) are an important way of converting simple organic molecules into complex small molecules as single diastereo- and enantiomers. Herein we describe selected examples that are catalyzed by small organic molecules, which utilize activation mechanisms similar to enzymes for accomplishing the high stereoselectivity. The research area of DYKAT is growing and remarkable examples for producing important organic molecules and pharmaceuticals are demonstrated. In this context, organocatalysis will play an important role.
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| 25. |
- Deiana, Luca, et al.
(författare)
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Artificial Arthropod Exoskeletons/Fungi Cell Walls Integrating Metal and Biocatalysts for Heterogeneous Synergistic Catalysis of Asymmetric Cascade Transformations
- 2023
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Ingår i: ChemCatChem. - : John Wiley & Sons. - 1867-3880 .- 1867-3899. ; 15:15
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Tidskriftsartikel (refereegranskat)abstract
- 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.
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| 26. |
- Deiana, Luca, et al.
(författare)
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Artificial plant cell walls as multi-catalyst systems for enzymatic cooperative asymmetric catalysis in non-aqueous media
- 2021
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Ingår i: Chemical Communications. - : Royal Society of Chemistry (RSC). - 1359-7345 .- 1364-548X. ; 57:70, s. 8814-8817
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Tidskriftsartikel (refereegranskat)abstract
- The assembly of cellulose-based artificial plant cell wall (APCW) structures that contain different types of catalysts is a powerful strategy for the development of cascade reactions. Here we disclose an APCW catalytic system containing a lipase enzyme and nanopalladium particles that transform a racemic amine into the corresponding enantiomerically pure amide in high yield via a dynamic kinetic resolution.
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| 27. |
- Deiana, Luca, et al.
(författare)
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Cellulose-Supported Heterogeneous Gold-Catalyzed Cycloisomerization Reactions of Alkynoic Acids and Allenynamides
- 2023
-
Ingår i: ACS Catalysis. - : American Chemical Society (ACS). - 2155-5435. ; 13:15, s. 10418-10424
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Tidskriftsartikel (refereegranskat)abstract
- 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.
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| 28. |
- Deiana, Luca, et al.
(författare)
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Subtilisin integrated artificial plant cell walls as heterogeneous catalysts for asymmetric synthesis of (S)-amides
- 2023
-
Ingår i: RSC Advances. - : Royal Society of Chemistry (RSC). - 2046-2069. ; 13:29, s. 19975-19980
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Tidskriftsartikel (refereegranskat)abstract
- 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.
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| 29. |
- Guangning, Ma, et al.
(författare)
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Accelerating Amine-Catalyzed Asymmetric Reactions by Intermolecular Cooperative Thiourea/Oxime Hydrogen-Bond Catalysis
- 2021
-
Ingår i: European Journal of Organic Chemistry. - : Wiley. - 1434-193X .- 1099-0690. ; 2021:21, s. 3043-3049
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Tidskriftsartikel (refereegranskat)abstract
- The ability of intermolecular cooperative thiourea/oxime hydrogen-bond catalysis for improving and accelerating asymmetric aminocatalysis is presented. The two readily available hydrogen-bond-donating catalysts operates in synergy with a chiral amine catalyst to accomplish highly stereoselective transformations. The synergistic catalyst systems simultaneously activate both electrophiles and nucleophiles, and make the transformations more chemo- and stereoselective. This was exemplified by performing co-catalytic enantioselective direct intermolecular α-alkylation reactions of aldehydes, direct aldol reactions, and asymmetric conjugate reactions, which gave the corresponding products in high yields and enantiomeric ratios.
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| 30. |
- Hafrén, Jonas, et al.
(författare)
-
Organoclick : Applied Eco-Friendly and Metal-Free Catalysis for Wood and Fiber Modifications
- 2016
-
Ingår i: Industrial Biorenewables: A Practical Viewpoint. - Hoboken, NJ, USA : John Wiley & Sons. - 9781118843796 - 9781118843727 ; , s. 437-450
-
Bokkapitel (övrigt vetenskapligt/konstnärligt)abstract
- This chapter provides a brief background to the research area of organocatalysis with respect to wood and fiber modification. It focuses on some of the examples of industrially produced materials from the chemical company OrganoClick AB, which employ organocatalytic reactions for modification, and to add new or improved functionalities to wood and natural fiber materials. The biomimetic activation of organic compounds via fundamental activation mechanisms is key in our efforts to create new functionally modified wood or fiber materials. There has been extensive research on the cross-linking of polysaccharides. The most common methods apply inorganic acids as catalysts for the cross-linking of the polysaccharide chains with low-molecular cross-linking agents, which are actually not eco-friendly. The novel materials could be of interest for the printing- or cellulose-based packaging industries. The OrganoWood process is based on mimicking the natural fossilization process in which wood is slowly transformed into mineral.
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| 31. |
- Kaiheng, Zhang
(författare)
-
Highly enantioselective synthesis of lactam and sugar derivatives by chiral aminocatalysis and merging with transition metal catalysis
- 2023
-
Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- This thesis presented novel methodologies for enantioselectivesynthesis of highly functionalized lactam and sugar derivatives.Asymmetric organocatalysis, cooperative dual catalysis and one-pot multicomponent reaction strategies were applied for the construction of continuous and quaternary stereogenic center.In Chapter I, an unique strategy for enantioselective synthesis of bicyclic lactam N,S-acetals scaffolds was developed. The reaction intiates from an aminocatalyzed transformation. Next, the addition of thiol amine leads to the construction of bicyclic lactams via aimine/N,S-acetal formation/lactamization cascade sequence.Chapter II focuses on a stereodivergent synthesis of fluorinated lactams bearing two vicinal stereogenic centers by multicomponent reaction. The reaction proceeds via enantioselective Michael addition/imine formation/lactamization cascade process. The reaction solventused in the lactamizarion step gives switchable diastereoselectivity to the fluorinated quaternary stereocenter. DFT calculation revealed a mechanistic insight into the unexpected diastereoselectivity. The usefulness of fluorinated lactams was demonstrated in fluorinated drug analogue synthesis.Chapter III illustrates a new enantioselective allylic alkylation of acetonide protected trioses and furanosides by merging enamine catalysis with transition metal catalysis. An intrinsic sugar-assistedkinetic resolution mechanism between aldehyde and aminocatalystwas proposed and monitored in NMR studies.Chapter IV is about a new chiral amine-catalyzed C4’ α-aminomethylaction of furanoside and nucleoside derived C5’ aldehydes. The C4’ aminomethyl functionalized furanoside precursors have potentials fornew nucleoside analogue synthesis.
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| 32. |
- Li, Man-Bo, et al.
(författare)
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Silver-Triggered Activity of a Heterogeneous Palladium Catalyst in Oxidative Carbonylation Reactions
- 2020
-
Ingår i: Angewandte Chemie International Edition. - : Wiley. - 1433-7851 .- 1521-3773. ; 59:26, s. 10391-10395
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Tidskriftsartikel (refereegranskat)abstract
- A silver-triggered heterogeneous Pd-catalyzed oxidative carbonylation has been developed. This heterogeneous process exhibits high efficiency and good recyclability, and was utilized for the one-pot construction of polycyclic compounds with multiple chiral centers. AgOTf was used to remove chloride ions in the heterogeneous catalyst Pd-AmP-CNC, thereby generating highly active Pd-II, which results in high efficiency of the heterogeneous catalytic system.
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| 33. |
- Rahman, Hafizur, Research Engineer, 1978-
(författare)
-
Aspects of optimizing pulp fibre properties for tissue and packaging materials
- 2021
-
Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- To improve the competitive advantages of pulp fibre-based materials for tissue and packaging over fossil-based products, it is essential to increase knowledge of the selectivity of the cooking and the chemimechanical processes by optimizing the unit operations of impregnation, cooking and refining. A general goal in pulping processes is to achieve as efficient and even fibre separation as possible. A key to achieving this is to improve impregnation uniformity. In the case of chemical pulping, we need to study how a more even distribution of lignin at the fibre level via easily impregnated wood chips can be achieved using classic measures such as equalized hydroxide ion concentration, increased initial sulphide ion concentration, low sodium ion concentration and a low cooking temperature combined with an oxidative and reductive environment. In the case of chemithermomechanical pulp (CTMP) manufacturing, we need to achieve as even a degree of sulphonation as possible at the level of the individual fibres by means of improved sulphite ion distribution within the wood chips before they are pre-heated prior to entering the refiner. Firstly, we have studied selective cooking systems for sulphate pulp manufacturing in oxidative (polysulfide) and reductive (sodium borohydride) environments. The yield increased from 48% to a maximum of 53%, which resulted in faster dewatering when mimicking a tissue papermaking process. This could explain how the advantage of the increased yield (fewer fibres and a more open sheet structure) outweighs the negative effects of the higher hemicellulose content on the dewatering properties. Moreover, the increased proportion of hemicellulose in the fibre walls resulted in improved bonding and increased tensile index at a certain refining energy. Secondly, we have studied the uniformity of impregnation at the fibre level by developing an accurate way of measuring sulphur and sodium content in measuring points that are 5-10 µm in diameter with miniaturized X-ray-based technology. This technology is considered cheap and efficient enough to be introduced in industrial labs and/or in online equipment. Our newly built miniaturized energy dispersive X-ray fluorescence (ED-XRF) demonstrates the capability of imaging sulphur and possibly sodium distribution in wood chip fibres or individual fibres on a micro scale. In parallel, to the above research we have studied a new catalytic lignin-selective cooking method where a substantial portion of the dissolved lignin can be extracted as vanillin, creating significant value and opportunities for new cost-efficient wood biorefinery systems.
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| 34. |
- Veluru, Ramesh Naidu, et al.
(författare)
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Regio- and Stereoselective Carbon-Boron Bond Formation via Heterogeneous Palladium-Catalyzed Hydroboration of Enallenes
- 2023
-
Ingår i: Chemistry - A European Journal. - : Wiley. - 0947-6539 .- 1521-3765. ; 29:24
-
Tidskriftsartikel (refereegranskat)abstract
- 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.
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| 35. |
- Wu, Haibo, 1989-, et al.
(författare)
-
Heterogeneous Copper-Catalyzed Cross-Coupling for Sustainable Synthesis of Chiral Allenes : Application to the Synthesis of Allenic Natural Products
- 2023
-
Ingår i: Angewandte Chemie International Edition. - : Wiley. - 1433-7851 .- 1521-3773. ; 62:50
-
Tidskriftsartikel (refereegranskat)abstract
- Classical Crabbé type SN2' substitutions of propargylic substrates has served as one of the standard methods for the synthesis of allenes. However, the stereospecific version of this transformation often requires either stoichiometric amounts of organocopper reagents or special functional groups on the substrates, and the chirality transfer efficiency is also capricious. Herein, we report a sustainable methodology for the synthesis of diverse 1,3-di and tri-substituted allenes by using a simple and cheap cellulose supported heterogeneous nanocopper catalyst (MCC-Amp-Cu(I/II)). This approach represents the first example of heterogeneous catalysis for the synthesis of chiral allenes. High yields and excellent enantiospecificity (up to 97 % yield, 99 % ee) were achieved for a wide range of di- and tri-substituted allenes bearing various functional groups. It is worth noting that the applied heterogeneous catalyst could be recycled at least 5 times without any reduced reactivity. To demonstrate the synthetic utility of the developed protocol, we have applied it to the total synthesis of several chiral allenic natural products.
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| 36. |
- Xu, Chao, et al.
(författare)
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Cyclopalladated Azo-linked Porous Polymers in C-C Bond Forming Reactions
- 2016
-
Ingår i: CHEMISTRYSELECT. - : Wiley. - 2365-6549. ; 1:18, s. 5801-5804
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Tidskriftsartikel (refereegranskat)abstract
- We designed a new cyclopalladated porous polymer (cyclo-Pd (II)/PP-2) with up to 20.7 wt% of Pd and investigated it as a heterogeneous catalyst for C-C bond-forming transformations. It was also shown to be an effective scavenger for Pd2+ in solution. The palladacycles formed along the backbone of the azo-linked porous polymer (PP-2) with (Pd-N) and (Pd-C) bonds as were confirmed by a combination of spectroscopies. The cyclo-Pd(II)/PP-2 decomposed when used for Suzuki and Heck cross-coupling reactions, and acyclic-Pd/PP-2 formed with Pd nanoparticles (NPs) bound to the PP-2. The Suzuki couplings were highly efficient in water and exhibited excellent recyclability. The cyclo-Pd(II)/PP-2 was also an effective heterogeneous Lewis-acid catalyst for stereoselective carbocyclization reactions.
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| 37. |
- Zhang, Keihang, et al.
(författare)
-
Catalytic Enantioselective Synthesis of Bicyclic Lactam N,S-Acetals in One Pot by Cascade Transformations
- 2019
-
Ingår i: European Journal of Organic Chemistry. - : Wiley. - 1434-193X .- 1099-0690. ; :29, s. 4649-4657
-
Tidskriftsartikel (refereegranskat)abstract
- A versatile strategy for the enantioselective synthesis of bicyclic lactam N,S-acetals by one-pot cascade transformations is disclosed. The transformation of readily available substrates is promoted by chiral amines and creates bicyclic or tricyclic lactam N,S-acetals with high chemo- and stereoselectivity (up to > 99.5:0.5 dr and > 99 % ee) in one-pot operations.
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| 38. |
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| 39. |
- Zhang, Kaiheng, et al.
(författare)
-
Solvent Dependency in Stereoselective δ-Lactam Formation of Chiral α-Fluoromalonate Derivatives : Stereodivergent Synthesis of Heterocycles with Fluorine Containing Stereocenters Adjacent to Tertiary Stereocenters
- 2022
-
Ingår i: Advanced Synthesis and Catalysis. - : Wiley. - 1615-4150 .- 1615-4169. ; 364:5, s. 958-965
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Tidskriftsartikel (refereegranskat)abstract
- The discovery and investigation of solvent dependency in stereoselective intramolecular amidation of chiral 5-aminofunctionalized-2-fluoromalonate ester derivatives, which gives access to highly functionalized δ-lactams with a quaternary fluorine-containing stereocenter, is disclosed. Experimental work together with density functional theory calculations led to understanding of how to direct and switch the stereochemical outcome of the stereoselective δ-lactam formation. The merging of this solvent-dependent stereoselective switch with asymmetric catalysis and cascade reactions gives access to an unprecedented strategy for stereodivergent synthesis of all possible stereoisomers of fluorine-containing stereocenters adjacent to tertiary stereocenters of a wide range of heterocyclic compounds with 95->99% ee in one-pot. It is also useful for application in total synthesis of fluorine-containing pharmaceuticals.
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| 40. |
- Zhang, Kaiheng, et al.
(författare)
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Sugar-Assisted Kinetic Resolutions in Metal/Chiral Amine Co-Catalyzed α-Allylations and [4+2] Cycloadditions : Highly Enantioselective Synthesis of Sugar and Chromane Derivatives
- 2023
-
Ingår i: Chemistry - A European Journal. - : Wiley. - 0947-6539 .- 1521-3765. ; 29:53
-
Tidskriftsartikel (refereegranskat)abstract
- Functionalized triose-, furanose and chromane-derivatives were synthesized by the titled reactions. The sugar-assisted kinetic resolution/C−C bond-forming cascade processes generate a functionalized sugar derivative with a quaternary stereocenter in a highly enantioselective fashion (up to >99 % ee) by using a simple combination of metal and chiral amine co-catalysts. Notably, the interplay between the chiral sugar substrate and the chiral amino acid derivative allowed for the construction of a functionalized sugar product with high enantioselectivity (up to 99 %) also when using a combination of racemic amine catalyst (0 % ee) and metal catalyst.
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| 41. |
- Zheng, Zhiyao, et al.
(författare)
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Efficient Heterogeneous Copper-Catalyzed Alder-Ene Reaction of Allenynamides to Pyrrolines
- 2022
-
Ingår i: ACS Catalysis. - : American Chemical Society (ACS). - 2155-5435. ; 12:3, s. 1791-1796
-
Tidskriftsartikel (refereegranskat)abstract
- Herein, we describe an efficient nanocopper-catalyzed Alder-ene reaction of allenynamides. The copper nanoparticles were immobilized on amino-functionalized microcrystalline cellulose. A solvent-controlled chemoselectivity of the reaction was observed, leading to the chemodivergent synthesis of pyrrolines (2,5-dihydropyrroles) and pyrroles. The heterogeneous copper catalyst exhibits high efficiency and good recyclability in the Alder-ene reaction, constituting a highly attractive catalytic system from an economical and environmental point of view.
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