Nano ordered polyacrylonitrile-grafted chitosan as a robust biopolymeric catalyst for efficient synthesis of highly substituted pyrrole derivatives

Nano ordered polyacrylonitrile-grafted chitosan as a robust biopolymeric catalyst for efficient synthesis of highly substituted pyrrole derivatives | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article Nano ordered polyacrylonitrile-grafted chitosan as a robust biopolymeric catalyst for efficient synthesis of highly substituted pyrrole derivatives Mahsa Zohrevand, Mohammad G. Dekamin, Niloufar Nashibi, Afshin Sarvary This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-5782484/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 01 Jul, 2025 Read the published version in Scientific Reports → Version 1 posted 14 You are reading this latest preprint version Abstract A novel heterogeneous nanocatalyst was developed using chitosan, as a natural polysaccharide derived from crustacean shells, and its in-situ grafting by polyacrylonitrile to afford nano ordered polyacrylonitrile-modified chitosan (CS-g-PAN). The obtained CS-g-PAN nanomaterial was thoroughly analyzed using several appropriate spectroscopic, microscopic or analytical techniques, including EDS and FTIR spectroscopy, EDS elemental mapping, FESEM imaging, XRD spectroscopy, TGA and DTA, and N 2 adsorption-desorption isotherm. The catalytic activity of multifunctional CS-g-PAN nanomaterial, as an organocatalyst, was evaluated in the green synthesis of highly substituted pyrrole derivatives through multi-component reactions strategy from corresponding α-haloketones, β-dicarbonyl compounds, and primary amines. This method offers several advantages, including high efficiency, short reaction times, ease of catalyst separation and recovery as well as recyclability for at least five cycles without significant loss of its activity. The catalyst's eco-friendly nature, lack of toxic transition metals, and mild reaction conditions make it a promising sustainable alternative for the Hantzsch synthesis of different pyrrole derivatives. Biological sciences/Biochemistry/Carbohydrates Biological sciences/Biochemistry/Chemical modification Earth and environmental sciences/Environmental sciences/Environmental chemistry Physical sciences/Chemistry/Catalysis Physical sciences/Chemistry/Chemical safety Physical sciences/Chemistry/Environmental chemistry Physical sciences/Chemistry/Green chemistry Physical sciences/Chemistry/Materials chemistry Physical sciences/Chemistry/Organic chemistry Physical sciences/Chemistry/Polymer chemistry Physical sciences/Chemistry/Supramolecular chemistry Physical sciences/Chemistry/Surface chemistry Physical sciences/Chemistry/Synthesis Biological sciences/Cancer Biological sciences/Drug discovery Physical sciences/Chemistry Physical sciences/Materials science Physical sciences/Materials science/Biomaterials Physical sciences/Materials science/Materials for devices Physical sciences/Materials science/Materials for energy and catalysis Physical sciences/Materials science/Nanoscale materials Physical sciences/Materials science/Techniques and instrumentation Modified chitosan Heterogenous organocatlyst Multi-Component reactions (MCRs) Nano ordered copolymers Heterocycles Pyrrole derivatives Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 Figure 10 Figure 11 Introduction Nanocatalytic systems have emerged as a bridge between homogeneous and heterogeneous catalytic systems, exhibiting numerous advantages such as enhanced activity, stability, and selectivity compared to traditional catalytic systems. Different supports such as silica, alumina, graphene oxide (GO) and its reduced form (rGO), biopolymers, natural asphalt, etc have been used in preparation of heterogeneous catalytic systems. The use of these supports provides high surface area, tunable functional groups, and remarkable stability under harsh reaction conditions to make them highly suitable for a broad spectrum of organic transformations 1 – 6 . The incorporation of carbon-based materials such as GO and rGO, biopolymers and natural asphalt as supports in nanocatalytic systems represents a promising strategy for the development of high-performance catalysts. The unique properties and adaptability of these materials make them highly attractive for various industrial and scientific applications, with the potential to significantly enhance catalytic process efficiency, selectivity, and sustainability 7 – 13 . Hence, the development of a heterogeneous catalytic system that represents the principles of green chemistry, while also offering a cost-effective solution, is a highly desirable goal 14 – 16 . Such a catalyst should exhibit enhanced reaction efficiency, and be well-suited for the synthesis of organic compounds including heterocyclic derivatives, especially pyrroles, facilitate effortless product isolation, thereby addressing a significant progress in the field of organic chemistry. While previous studies have employed a variety of homogenous and heterogeneous catalysts to enhance reaction conditions and efficiency for the Hantzsch pyrrole synthesis, these approaches often show drawbacks such as low to moderate efficiency, prolonged reaction times, challenges in product separation, the need for hazardous organic solvents, catalyst toxicity, high costs, and the inability to reuse homogenous catalysts 14 , 17 – 21 . Green chemistry provides a framework for chemists to adopt more sustainable practices, integrating principles such as minimizing hazards in synthesis, maximizing atom economy, utilizing renewable resources, designing for product degradation, and improving energy efficiency in the design of more efficient and safer chemical processes. Sustainable chemistry combines this foundation by broadening the scope to encompass the wider impacts of chemistry, including global resource consumption, human and environmental health, engagement with communities affected by chemical product life cycles, and social needs. This expanded vision for the future of chemistry demands a larger investor view across business value and supply chains 22 . Along these lines, natural biopolymers including cellulose, starch, chitin, chitosan, alginate and carrageenan have been widely employed in nanocatalytic systems because of their numerous advantages 8 , 23 – 27 . These include their abundance in nature, biocompatibility, low toxicity, and biodegradability, which make them attractive for a variety of applications 28 . These biopolymers have certain features such as the presence of hydroxymethyl groups in cellulose, starch and chitosan as well as the acetyl, amino, carboxyl and sulfonate groups in in chitin, chitosan, alginate and carrageenan, respectively. This remarkable diversity in the peripheral groups of polysaccharides enables a broad spectrum of physical and chemical modifications to afford a wide range of bio-based materials with versatile applications 29 – 31 . Tailoring the properties of biopolymers can significantly enhance their compatibility and performance in various applications. The obtained modified biopolymers have been successfully utilized in diverse fields, including biomedical applications, pharmaceuticals, agricultural and food industry, environmental remediation such as wastewater treatment, sensors and catalytic systems, highlighting their potential for driving sustainable technological innovations 32 – 35 . Among these biopolymers, chitosan stands out as a multifunctional polysaccharide derived from the alkaline deacetylation of chitin, which is a naturally abundant biomaterial found in the outer shells of shrimp, lobster and crab, as well as the cell walls of some bacteria and fungi 36 – 38 . Its biodegradable and biocompatible nature makes it an ideal candidate for academic and industrial applications across multiple disciplines 39 – 43 . Chitosan's unique molecular structure, containing amino and hydroxyl functional groups with high reactivity as well as appropriate geometry, make it an attractive material for various applications, either in its pristine form or after chemical modification 44 – 50 . The ability of pristine chitosan or its modified versions to form hydrogen bonds or metal-ligand interactions as well as undergoing chemical modifications with diverse components of composites, metal cations or reagents enables their use in organic reactions as heterogeneous organo- or metal-chelated catalytic systems 51 – 58 . Along these lines, polysaccharide modification through co-polymerization with synthetic polymers offers a useful approach to enhance their useful properties for catalytic applications. Radical copolymerization of chitosan using various alkene monomers enables the creation of copolymers with improved thermal and mechanical stability, as well as increased surface area, the crucial factors for designing efficient heterogeneous catalysts. Among of them, copolymers comprising of in-situ grafting of acrylonitrile monomer to the chitosan backbone can be readily prepared and be used. The obtained polyacrylonitrile-modified chitosan (CS-g-PAN) contains both chitosan’s functional groups and significant numbers of the nitrile (‒C ≡ N) functional group for further modifications through rich chemistry of the ‒OH, NH 2 , NH and ‒C ≡ N functional groups to produce new bio-based materials with tailored properties for specific catalytic applications 59 – 62 . In recent years, multi-component reactions (MCRs) have emerged as a powerful and sustainable approach in organic synthesis, offering a fascinating alternative to the traditional multi-steps reactions 63 . By enabling the simultaneous synthesis of complex scaffolds through enhanced selectivity, efficiency, and atom efficiency in a one-pot reaction, MCRs significantly reduce the number of reaction steps and isolation procedures 24 , 50 , 64 – 66 . These advantages will result in preventing the formation of byproducts and excessive the use of solvents, mild reaction conditions and lower energy consumption. The MCR strategy also provides cost-effective and versatility in product design through various substrates with high reaction efficiency. Notably, MCRs have significantly facilitated the synthesis of complex heterocyclic compounds, especially pyrrole derivatives, demonstrating their vast potential in modern organic chemistry 17 , 67 – 70 . Pyrrole moiety is biologically active and found in natural compounds such as chlorophyll, vitamin B 12 , Bile pigments such as Bilirubin, porphyrins, and others 17 , 71 , 72 . Furthermore, Lamelarin, Hulitolin, and Marinopyrrole are other natural marine compounds containing the pyrrole ring, which are particularly important due to their high activity against methicillin-resistant bacteria. Pyrrole derivatives also have anti-HIV and anti-tumor activities 73 , 74 . For instance, research have shown that the obtained Hulitolitans from the extract of the Haliclona tulearensis sponge has cytotoxic activity, and also exhibits antitumor activity 74 – 76 . On the other hand, the diverse biological activities of synthetic pyrrole derivatives including lowering cholesterol, anti-inflammatory, anti-cancer, analgesics, and sedatives have led to the production of medicines such as atorvastatin, ketorolac, tolmetin and sunitinib, which are used worldwide today 18 , 77 – 81 . Some other derivatives of pyrrole have been used in semiconductor materials 82 , laser and chemical sensors 83 that show strong absorption in the ultraviolet region and emit strong fluorescence 84 . Furthermore, its use in the food industry and the production of tea and coffee are other applications of pyrrole in the industry 85 , 86 . For example, phycocyanin is another derivative of pyrrole-containing compounds used as a blue pigment in the food industry 86 , 87 (Fig. 1 ). The significance of pyrrole derivatives in various fields including pharmaceuticals and materials science has received significant research interest for the development of diverse efficient methodologies targeting their synthesis. Pyrrole derivatives are commonly synthesized using the Paal–Knorr or Hantzsch methods, with the Hantzsch method being more widely used due to its inherent simplicity and direct access to highly substituted pyrroles, and flexibility in terms of solvent, temperature, and catalyst. The Hantzsch pyrrole synthesis, a classic and well-established route for constructing the pyrrole moiety, involves the three-component reaction of α-haloketones, β-dicarbonyl compounds, and primary amines 85 , 88 – 96 . Various catalytic systems have been explored to promote the synthesis of pyrrole derivatives using the benefits of homogeneous or heterogeneous catalytic systems 97 . Moreover, the incorporation of new energy inputs, such as microwave irradiation sonication or ball-milling, has emerged as a promising strategy to enhance the reaction efficiency, reduce reaction times, and minimize environmental impact 17 , 98 – 100 . Some notable examples of these advancements include the use of β-cyclodextrin 101 , urea/choline chloride 102 , squaric acid 103 , p -chloropyridine hydrochloride 104 , p -toluenesulphonic acid 105 , Yb(OTf) 3 39 , DABCO 89 , polystyrene sulfonate under microwaves irradiation 106 CAN–silver nitrate system or I 2 under high-speed vibration milling conditions 19 , 107 , and ZnO under ultrasound conditions 108 , which have contributed to the expansion of the Hantzsch pyrrole derivative synthetic pathway. As research in this area improves, the development of novel, sustainable, and efficient methodologies for the synthesis of pyrrole derivatives is in high demand. To address the challenges during development of different protocols for the synthesis of pyrrole scaffold and in continuation of our ongoing research to develop chitosan-based nanomaterials modified by different methods and reagents 12 , 13 , 24 , 25 , 50 , 66 , 109 – 112 , we wish herein to report the Hantzsch pyrrole synthesis catalyzed by in-situ grafted polyacrylonitrile (PAN) onto the chitosan backbone (CS-g-PAN) nanomaterial. Acetyl acetone and different phenacyl bromide derivatives and amine components were smoothly involved in the presence of CS-g-PAN nano ordered organocatalyst to afford the corresponding pyrrole derivatives in good to excellent yields and short reaction times ( Fig. 2 ). Experimental Materials and methods Chitosan with medium molecular weight (180–300 kDa) and a 75–85% deacetylation degree, purchased from Merck, was used without further processing. Other chemicals and solvents, including AcOH, acrylonitrile, ammonium persulfate, acetyl acetone, aliphatic or aromatic amines, phenacyl bromide derivatives, toluene, EtOAc, n-hexane, and EtOH (96%), were also supplied by Merck, Sigma Aldrich and local companies. The chemicals and solvents were used as received without further purification. Fourier transform infrared spectroscopy (FTIR) spectra were recorded using KBr pellets on a 1720-X Perkin Elmer (USA) spectrometer. Energy-dispersive X-ray (EDS) spectra and X-ray powder diffraction (XRD) patterns were obtained using Bruker EDS (Germany) and D8 ADVANCE diffractometer (Germany) with Cu Ka radiation (λ = 1.54050 Å) instruments, respectively. Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) of the samples were measured using a BAHR-STA 504 device. Field emission scanning electron microscope (FESEM) images were obtained using a FESEM-ZEISS (Germany) instrument. Thin-layer chromatography (TLC) was performed on the Merck F256 silica gel plates to monitor the reaction progress. Melting points were measured using an Electrothermal 9200 instrument and are uncorrected. 1 H NMR spectra were recorded in DMSO- d 6 solvent at ambient temperature using a Bruker Avance 400 MHz NMR spectrometer. Synthesis of the CS-g-PAN (1) For the preparation of polyacrylonitrile grafted onto the chitosan backbone (CS-g-PAN) nanomaterial, chitosan (CS, 1.0 g) was dissolved in an aqueous AcOH solution (5%, V:V ; 100.0 ml) and heated to 50°C. The obtained mixture was stirred continuously until it was changed to a clear, colorless solution. Notably, repeating of prior studies by employing an aqueous AcOH solution (1%, V/V) afforded hydrogels unsuitable for the catalytic applications in our hands. However, increasing the AcOH concentration to 10% from 5% restored its suitability for the catalytic purposes. The solution was then degassed for at least 15 min. using N 2 gas. After that, an aqueous solution of ammonium persulfate (NH 4 ) 2 S 2 O 8 , 2.0 M) was added dropwise within 30 min. Subsequently, after an additional 45 min., acrylonitrile (AN, 6.0 ml) was gradually added to the mixture at 55°C and stirred for 40 min to facilitate polymerization. The reaction was maintained at 55°C for 15 h. The obtained mixture was mixed with EtOH (96%, 200 ml), which gave rise to precipitating of the CS-g-PAN nano ordered hydrogel. Finally, after 4 h, the hydrogel was collected and washed sequentially with acetone and deionized H 2 O until it turns into a white precipitate. The precipitates are filtered off and then dried at room temperature for 2 h. The results of FTIR, EDS, XRD, TGA and FESEM characterization data proved successful preparation of the CS-g-PAN catalyst (Fig. 3 ). General procedure for the preparation of pyrrole derivatives catalyzed by CS-g-PAN nanomaterial (1) A mixture of acetylacetone ( 2 , 1.0 mmol), amine derivatives ( 3 , 1.5 mmol), phenacyl bromide derivatives ( 4 , 1.0 mmol) and CS-g-PAN catalyst ( 1 , 15.0 mg) in toluene (2.5 ml) was stirred for 30 min at 30–35 ℃ and then heated at 100–110 ℃ for 8–12 h as indicated in Table 2 . The progress of reaction was monitored using TLC (n-hexane, EtOAc; 3:1 V/V). Upon completion of the reaction, EtOH (96%, 5.0 ml) was added to the reaction mixture and it was heated to dissolve the product. The CS-g-PAN catalyst ( 1 ) was then separated by filtration and kept for next runs after activation. The filtrate was cooled to ambient temperature, and the product was separated by silica gel plate chromatography. The obtained products were characterized based on their melting points, as well as FTIR and 1 H NMR spectral data. The results are summarized in Table 2 . Selected spectral data for pyrrole derivatives: Results and discussion Characterization of the CS-g-PAN nanomaterial (1) The prepared CS-g-PAN nanomaterial was characterized utilizing a range of spectroscopic, microscopic and analytical techniques. Elemental composition and their distribution was analyzed through energy-dispersive X-ray spectroscopy (EDS) and and EDS elemental mapping, while the functional groups present in the structure of the CS-g-PAN was determined using Fourier transform infrared (FTIR) spectroscopy. Additionally, its surface morphology was investigated using field-emission scanning electron microscopy (FESEM ). The crystallinity of the CS-g-PAN nanomaterial was determined using powder X-ray diffraction (XRD). The thermal stability as well as porosimetery of the CS-g-PAN sample was determined using thermogravimetric analysis (TGA), differential thermal analysis (DTA) and N 2 adsorption-desorption analysis. These combined spectroscopic, microscopic, and analytical techniques provided a detailed characterization of the prepared CS-g-PAN catalyst, highlighting its structural and thermal features relevant to its catalytic performance. To determine the chemical composition and percentage of different atoms, present in the structure of CS-g-PAN ( 1 ), both energy-dispersive X-ray spectroscopy (EDS, Fig. 4a ) and EDS elemental mapping were used ( Fig. 4b ). According to the obtained data for EDS spectra of the CS-g-PAN nanomaterial, the atomic percentage of carbon, oxygen and nitrogen in its structure was 79.78%, 6.06% and 14.17%, respectively. Indeed, the structures of chitosan biopolymer and polyacrylonitrile contain only C, N and O atoms. This means that impurities were not observed inside of the structure of CS-g-PAN nanomaterial. Due to the presence of nitrile functional group having N in the polyacrylonitrile structure, its grafting onto the chitosan backbone also increases the percentage of nitrogen atoms in the CS-g-PAN nanomaterial structure compared to the pristine chitosan. The FTIR spectrum of CS-g-PAN copolymer ( 1 ), presented in Fig. 5 ., reveals several characteristic absorption bands. It shows a combination of peaks characteristic of both chitosan and PAN. The broad band ranging 3700–3300 shows O‒H and N‒H stretching vibrations of the CS moiety in the CS-g-PAN structure. Furthermore, the absorption band at 2960 cm − 1 corresponds to C‒H stretching vibrations, which are present in both chitosan and PAN. The stretching vibration of C ≡ N group at 2194 cm⁻¹ is a strong indicator of PAN's presence in the grafted CS-g-PAN material. The signals at 1400 − 1200 cm⁻¹ region show N‒H bending modes, typical of chitosan in its pristine or Cs-g-PAN modified forms. Additionally, the signal observed at 1100 cm⁻¹ can be attributed to the C‒O stretching vibration, characteristic of the glycosidic bonds in chitosan 113 . This analysis provides strong evidences for the successful preparation of the desired grafted CS-g-PAN material. The morphological characteristics of the CS-g-PAN nanomaterial ( 1 ) were examined through field-emission scanning electron microscopy (FESEM) imaging. The FESEM micrographs of CS-g-PAN catalyst, captured at magnifications corresponding to 1 µm, 200 nm, and 100 nm scales, revealed a swollen spherical morphology uniformly dispersed across the nanomaterial ( Fig. 6 ). The observed structure demonstrates the successful cross-linking and copolymerization processes involving acrylonitrile units grafted onto the planar pristine chitosan backbone to improve its surface area and porosity, making it suitable for catalytic applications. The thermogravimetric analysis (TGA) of CS-g-PAN nanomaterial ( 1 ) demonstrates an initial weight loss of approximately 8% from 50 to 220°C, which can be attributed to the evaporation of residual moisture or used solvents during its preparation (Fig. 7 ). A subsequent stage of decomposition was observed between 220 and 375°C, corresponding to the primary thermal degradation of the chitosan chains and grafted PAN. The cumulative weight loss reached approximately 40% within the temperature range of 50–500°C, indicating that the CS-g-PAN nanomaterial exhibits notable thermal stability suitable for various applications. Complementary differential thermal analysis (DTA) further confirmed that the exothermic weight loss occurred at around 250°C, aligning with the observed TGA profile 35 . These findings underscore the robust thermal properties of CS-g-PAN nanomaterial, highlighting its potential for use in thermally demanding environments. The powder XRD pattern of CS-g-PAN nanomaterial has been shown in Fig. 8 . The first sharp peak at 2θ = 16.87° is attributed to the overlap of characteristic peaks of crystalline phase of PAN at 2θ = 17.03 and chitosan at 2θ = 20.10°. Notably, intensity of the peak at 20.10° was significantly reduced in the CS-g-PAN grafted copolymer, indicating a decrease in the chitosan crystallinity upon modification with PAN. The significant reduction in diffraction intensity at 2θ = 20.10° suggests a decrease in chitosan crystallinity, which can be attributed to the graft copolymerization process. This process disrupts the intrinsic crystalline arrangement of chitosan while simultaneously facilitating the formation of new ordered crystalline regions within the nanomaterial structure. Furthermore, the retaining of certain crystalline diffraction reflections confirms that the incorporation of PAN does not severely disrupt the crystalline order, but rather signifies a successful polymer blending process and compatibility between the two polymers. The XRD analysis also verifies the favorable molecular-scale interaction between chitosan and PAN, leading to the formation of a stable nanomaterial with modified crystallinity. Furthermore, an amorphous region centered at 2θ = 25.80° was developed in the structure of CS-g-PAN nanomaterial. This suggests that the graft copolymerization of PAN onto the chitosan backbone enabled the development of both ordered crystalline and amorphous regions, leading to a stable structure. The observed diffraction pattern demonstrates the compatibility of the two polymers and the absence of significant disruptions to the crystal structure, indicating a successful blending process. Overall, these findings support the formation of a stable CS-g-PAN nanomaterial with a modified crystal structure. The Brunauer-Emmett-Teller (BET) surface area analysis, employing N 2 adsorption-desorption isotherm, was employed to quantify the specific surface area and average pore width size of the synthesized CS-g-PAN nanomaterial ( 1 ), as illustrated in Fig. 9 . Interestingly, the nitrogen adsorption-desorption isotherm for the CS-g-PAN nanomaterial displayed characteristics consistent with a Type III isotherm. Analysis of the BET data revealed that the specific surface area and average pore width size of the CS-g-PAN nanomaterial were found to be approximately 2.9 m²·g⁻¹ and 5.80 nm, respectively. Interestingly, grafting of PAN onto the chitosan backbone has an appropriate impact on it to increase specific surface area, which is a very important factor for the heterogeneous catalytic systems. Catalytic activity evaluation of the CS-g-PAN nanomaterial for the synthesis of pyrrole derivatives To show the efficiency of CS-g-PAN nanomaterial ( 1 ) and determine the optimized conditions, the three-component reaction of acetyl acetone ( 2 ), benzyl amine ( 3a , 1.50 mmol) and phenacyl bromide ( 4a , 1.0 mmol) for the synthesis of 1-(1-benzyl-2-methyl-4-phenyl- 1H -pyrrol-3-yl) ethenone ( 5a ) was studied as the model reaction. The optimized conditions for this reaction were determined through a systematic study for experiments evaluating different parameters, including catalyst loading, solvent type, and reaction temperature. The results are summarized in Table 1 . Initially, the reaction was performed in toluene without any catalyst, which resulted in a prolonged reaction time of 43 h and very low yield (entry 1). When pristine chitosan, as a catalyst, was used a moderate yield of 58% for the desired product 5a was obtained (entry 2). Interestingly, the use of the CS-g-PAN nanomaterial ( 1 ), as a heterogenous catalyst, in toluene demonstrated superior efficiency compared to other solvents such as THF, MeCN, EtOH, and DMF under the same catalyst loading of 10.0 mg (entries 3–7). Therefore, toluene was used as the most effective solvent for the three-component Hantzsch pyrrole synthesis catalyzed by the CS-g-PAN nanocatalyst in the next experiments. In the course of our experiments to optimize the model reaction conditions, prolonged reaction times were explored to optimize the yield of the desired product 5a . Notably, the model reaction afforded 81% of the desired product 5a , demonstrating a favorable yield after 10 h. However, extending the reaction time to 14 h resulted in a yield of 67%, and further extension to 24 h led to a significant yield decrease to 22% (entries 8–10). These trends can be attributed to the equilibrium-driven nature of pyrrole formation from its substrates and the simultaneous susceptibility of the intermediates and product to hydrolysis. The hydrolysis process is expected to be catalyzed by the HBr byproduct, which is absorbed on the basic sites of the CS-g-PAN nanocatalyst ( 1 , Fig. 10 ). On the other hand, reducing the catalyst loading to 5.0 mg resulted in a diminished product yield compared to higher loadings, indicating a dependency of the reaction on catalyst loading. Importantly, the model reaction employing 15.0 mg catalyst loading afforded the highest efficiency, reaching a 91% yield after 8 h (entries 11–12). In contrast, when the model reaction was run by using 15.0 mg CS-g-PAN catalyst ( 1 ) loading, 69% and 72% of the desired pyrrole derivative 5a were obtained after 6 and 12 h, respectively (entries 13, 14). In addition, by examining of lower temperatures, the model reaction afforded lower yields of the product 5a under 15.0 mg catalyst loading in toluene and after 8 h (entries 15–17). However, a further increase in the amount of loaded catalyst ( 1 , 20.0 mg) in toluene at 100–110 ℃ did not significantly affect the yield and reaction time (entry 18). All of these findings imply that catalyst loading, reaction times and temperature must be optimized to achieve the most efficient catalytic activity. This observed behavior emphasizes the balance between the appropriate amount of loaded catalyst, enough reaction time, higher product yield, and lower side reactions, providing critical insights into the reaction kinetics and required precautions for the yield improvement. In the next step of our study, the optimized reaction conditions (15.0 mg CS-g-PAN loading in toluene at 100–110 ℃) were developed to other amines 3b-l as well as phenacyl bromide derivatives 4b-c . The results are summarized in Table 2 . All studied amine or phenacyl bromide substrates survived well under the optimized reaction conditions to afford the corresponding pyrrole derivatives 5a-n in good to excellent yields. Under the optimized conditions, a wide range of pyrrole derivatives 5a-n were synthesized, demonstrating the versatility and high efficiency of CS-g-PAN nanocatalyst ( 1 ). These findings underscore the potential of CS-g-PAN nanomaterial, as an effective heterogeneous catalyst, for the multicomponent Hantzsch pyrrole synthesis, particularly in enhancing reaction rates and product yields. According to the data provided in Table 2 , the presence of electron-donating groups (EDGs, entries 1, 3–5,7,8) on the amino moiety generally has a pronounced effect on the reaction efficiency and time compared to the electron-withdrawing groups (EWGs, entries 9, 12–14) to form the corresponding imine and enamine intermediate ( II’ , Fig. 10 ). Hence, the steric hindrance in aliphatic amines (entry 2) or resonance in the aromatic ones (entry 6) retards the three-component Hantzsch pyrrole synthesis to afford lower yields of the corresponding products. Furthermore, the introduction of electron-withdrawing groups such as halogen substituents in the structure of phenacyl bromide component causes an increase in the reaction yield. This demonstrates the importance of EWGs in the structure of phenacyl bromide component to facilitate the S N 2 reaction of enamine intermediate ( II ) with them to form corresponding more complicated imine and enamine intermediates ( III ). The obtained results prove that the presence of EWGs can significantly accelerate the nucleophilic attack of the amine component 3a-l on the carbonyl group of phenacyl bromide 4a-c , thereby promoting the reaction. These data provide valuable insights into the role of electronic effects or steric hindrance to control the reactivity of amines and phenacyl bromide and offer a useful guide for the optimization of similar reactions. All these data support the mechanism depicted in Fig. 10 . Proposed mechanism for the synthesis of pyrrole derivatives 5a-o catalyzed by the CS-g-PAN nanomaterial (1) A plausible mechanism for the Hantzsch pyrrole synthesis c atalyzed by the multifunctional CS-g-PAN nanomaterial ( 1 ) has been proposed in Fig. 10 . The catalyst 1 can activate different reaction components by its acidic and basic centers. Indeed, the carbonyl functional groups as well as S N 2 electrophilic site in both acetylacetone ( 2 ) and phenacyl bromide ( 4 ) components are more activated via hydrogen bonding to react with the nucleophilic sites of the amine component ( 3 ) or β-enamine intermediates (II’ and III’). Therefore, acetylacetone ( 2 ) reacts with amines 3a-l to form the corresponding imines ( II ) by losing a water molecule. The produced imine ( II ) is then equilibrated to the tautomeric β-enamine intermediates (II’) in the presence of CS-g-PAN nanocatalyst ( 1 ). The more nucleophilic β-enamine ( II’ ) then reacts with the activated phenacyl bromide 4a-c to form α,γ-ketoimine intermediate ( III ). Interestingly, HBr byproduct can be absorbed by the basic amine sites in the structure of the catalyst 1 . Hence, the protonated form of the catalyst 1 can be in exchange with the intermediates ( III ), ( III’ ) and IV to facilitate formation of products 5a-o . The produced α,γ-ketoimines ( III ) in this step is again equilibrated to the tautomeric γ-enamine intermediates ( III’ ) in the presence of CS-g-PAN nanocatalyst ( 1 ) or its protonated form. Subsequent activation of the carbonyl group in the intermediate ( III’ ) by the catalyst ( 1 ) or its protonated form affords the cyclic intermediate ( IV ). This intermediate then loses water to afford the aromatic desired pyrrole products 5a-o . Notably, the catalyst 1 , having the hygroscopic chitosan moiety, can adsorb water molecules liberated during the products formation and promote the reaction more efficiently. 24 , 50 , 111 , 114 – 116 Reusability of the catalyst 1 for the synthesis of pyrrole derivative 5a Recyclability and reuse of the CS-g-PAN nanocatalyst ( 1 ) in the synthesis of pyrrole derivative 5a was also investigated as a part of our study. The relevant results are summarized in Fig. 11 . After completion of the reaction in each run, monitored by TLC, the catalyst 1 was separated from the reaction mixture and washed with EtOH twice and dried in an oven at 70 ℃ for 3 h. The dried catalyst was used in the next run of the model reaction with similar conditions. The catalyst was used five times and there were no significant changes in its efficiency. The results of XRD analysis for the recycled CS-g-PAN nanocatalyst ( 1 ) after first, third and fifth runs have also been presented in Fig. S12 . The obtained XRD patterns clearly demonstrate that the structure of the CS-g-PAN catalyst ( 1 ) remains stable and without any substantial changes under optimized conditions after fifth run. Furthermore, all of these findings approve the heterogenous nature of the CS-g-PAN nanocatalyst ( 1 ). To demonstrate the catalytic activity of CS-g-PAN nanomaterial ( 1 ) for the synthesis of pyrrole derivatives under the optimized conditions, the obtained results for the synthesis of 5a have been compared with the previous methods reported in the literature. The results are summarized in Table 3 . Data provided in Table 3 clearly show the superior efficiency of catalyst 1 for the three-component Hantzsch pyrrole synthesis in terms sustainability, catalyst loading, the use of solvent with lower toxicity, temperature and required time compared to many of them. Table 3 Comparison of the catalytic efficiency of CS-g-PAN ( 1 ) with some previously reported catalytic systems for the synthesis of pyrrole derivatives. Entry Catalyst Catalyst loading Conditions Yield (%) 1 Yb(OTf) 3 0.1 mol% CH 3 CN/ 80–85 \(\:\:℃\) 72 39 2 DABCO 10 mol% H 2 O/ \(\:\:60\:℃\) 70 89 3 KO t Bu 1.1 equiv THF/ 24 h 88 92 4 NaOMe 15 mg MeOH/ THF/ 24 h 80 94 5 AgOAc 2 mol% PhCl/ 130 ℃, 24 h 61 95 6 Hf/SBA-15 140 mg DMF/150°C/ 6h 84 117 7 Cu@imine/Fe 3 O 4 MNPs 0.36 mol% MeCN/ Reflux/ 80 ℃ 91 118 8 CS-g-PAN 15 mg Toluene/ reflux/ 8 h 91 (This work) Conclusion In brief, polyacrylonitrile grafted onto the renewable, biocompatible and bio-degradable chitosan (CS-g-PAN) nanomaterial was developed as an efficient multifunctional organocatalyst for the three-component Hantzsch pyrrole synthesis. The efficiency of this new nanomaterial for the atom efficient synthesis of a wide range of pyrrole derivatives was assessed through one-pot reaction in toluene and short reaction times. The heterogeneous CS-g-PAN nanocatalyst showed very high activity compared to previously reported methods in the literature. Other advantages of this methodology are avoiding the use of toxic transition metals and mild reaction conditions, which make it a promising alternative for sustainable Hantzsch pyrrole synthesis. In addition, the catalyst was easily recovered and reused at least five times without significantly loss of its activity. Further studies on the catalytic activity of CS-g-PAN for different organic transformations and its composites with other nanomaterials are in progress in our lab and would be published in due course. Declarations Conflict of interest The authors declare that there are no conflicts of interest regarding the publication of this manuscript. Author Contribution 1) M.Z. worked on the topic, as her MSc thesis, and prepared the initial draft of the manuscript. 2) Prof. M.G.D. is the supervisor of M.Z. and N.N. as his MSc and PhD students, respectively. Also, he edited and revised the manuscript completely. 3) N. N. worked closely with M.Z. for doing experiments, interpreting of the characterization and preparation of the initial draft of the manuscript. 4) Dr. A.S. is the supervisor of M.Z. as his MSc student. Also, he helped to prepare the initial draft and revised version of the manuscript by M.Z. and N.N. Acknowledgements We are grateful for the financial support from The Research Council of Iran University of Science and Technology (IUST), Tehran, Iran (Grant No 160/24293) as well as the support of the Iran Nanotechnology Initiative Council (INIC), Iran. The partial financial support from The Research Council of Babol Noshirvani University of Technology, Babol, Iran is highly appreciated. Data Availability All data generated or analyzed during this study are included in this published article [and its supplementary information files. References Mohammadi, M. & Soleiman-Beigi, M. 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D., Wang, F. & L.-C. & N-aryl pyrrole synthesis from biomass-derived furans and arylamine over Lewis acidic Hf-doped mesoporous SBA-15 catalyst. ACS Sustain. Chem. Eng. 8 , 12161–12167 (2020). Thwin, M., Mahmoudi, B., Ivaschuk, O. A. & Yousif, Q. A. An efficient and recyclable nanocatalyst for the green and rapid synthesis of biologically active polysubstituted pyrroles and 1, 2, 4, 5-tetrasubstituted imidazole derivatives. RSC Adv. 9 , 15966–15975 (2019). Tables Tables 1 and 2 are available in the Supplementary Files section. Additional Declarations No competing interests reported. Supplementary Files ElectronicSupplemntaryInformation32ec493f96a24dfc8b5d72007f50a5bdR1.pdf Tables.docx Cite Share Download PDF Status: Published Journal Publication published 01 Jul, 2025 Read the published version in Scientific Reports → Version 1 posted Editorial decision: Revision requested 02 May, 2025 Reviews received at journal 02 May, 2025 Reviews received at journal 23 Apr, 2025 Reviews received at journal 15 Apr, 2025 Reviewers agreed at journal 15 Apr, 2025 Reviews received at journal 13 Apr, 2025 Reviewers agreed at journal 13 Apr, 2025 Reviewers agreed at journal 13 Apr, 2025 Reviews received at journal 13 Apr, 2025 Reviewers agreed at journal 12 Apr, 2025 Reviewers agreed at journal 12 Apr, 2025 Reviewers invited by journal 12 Apr, 2025 Submission checks completed at journal 11 Apr, 2025 First submitted to journal 28 Mar, 2025 You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-5782484","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":442408034,"identity":"16300058-f36c-4337-b3e1-7ce4c6afbb53","order_by":0,"name":"Mahsa Zohrevand","email":"","orcid":"","institution":"Babol Noshirvani University of Technology","correspondingAuthor":false,"prefix":"","firstName":"Mahsa","middleName":"","lastName":"Zohrevand","suffix":""},{"id":442408035,"identity":"6f5e1199-5d21-4b66-b0c4-f2c20ab47c9c","order_by":1,"name":"Mohammad G. Dekamin","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA0klEQVRIiWNgGAWjYFCCBGYgIcHAzwwTYMajGEWLZDOQOkCCFgYGgwMwLYSAbnvyYYOfORZ5xsd5jD9/YLCTZ2DnfYBXi9mZZ8mJvdskis0O85hJHGBINmxgZjfAr+VGjvEB3m0SiduAWoAOY05gYGbD7zCzG/mfD/4FatnczGP84QBDPTFacpiTQbZsYOYxADrsMBFazjwzNpYFaplxmK1M4ozBccM2glqOJz+WfLutLrG///DmDxUV1fL8/Mfwa0EDwLAiYMcoGAWjYBSMAmIAANa9PfaH67ynAAAAAElFTkSuQmCC","orcid":"","institution":"Iran University of Science and Technology","correspondingAuthor":true,"prefix":"","firstName":"Mohammad","middleName":"G.","lastName":"Dekamin","suffix":""},{"id":442408037,"identity":"c78c1fdc-f958-4283-8b3b-72233d8266aa","order_by":2,"name":"Niloufar Nashibi","email":"","orcid":"","institution":"Iran University of Science and Technology","correspondingAuthor":false,"prefix":"","firstName":"Niloufar","middleName":"","lastName":"Nashibi","suffix":""},{"id":442408038,"identity":"03b0f956-2ea4-4c52-a577-2e3ab732b64f","order_by":3,"name":"Afshin Sarvary","email":"","orcid":"","institution":"Babol Noshirvani University of Technology","correspondingAuthor":false,"prefix":"","firstName":"Afshin","middleName":"","lastName":"Sarvary","suffix":""}],"badges":[],"createdAt":"2025-01-07 15:08:08","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-5782484/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-5782484/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1038/s41598-025-05504-0","type":"published","date":"2025-07-01T15:58:11+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":80785618,"identity":"d94b757a-12ee-4a1b-931e-05027cf67896","added_by":"auto","created_at":"2025-04-17 05:41:33","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":41420,"visible":true,"origin":"","legend":"\u003cp\u003eThe chemic al structure of selected examples of pharmacologically-active pyrrole derivatives.\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-5782484/v1/bd2b464813ccc6fd5b49223f.png"},{"id":80785629,"identity":"5ade30cc-c574-491b-80e9-e71b4b938ea3","added_by":"auto","created_at":"2025-04-17 05:41:35","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":14846,"visible":true,"origin":"","legend":"\u003cp\u003eOne-pot three-component reaction of acetyl acetone, phenacyl bromide and amine derivatives catalyzed by the CS-g-PAN for synthesis of pyrrole derivatives.\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-5782484/v1/5fc55cc1b776687ea8780f09.png"},{"id":80785624,"identity":"a448d117-25c1-4102-9340-dd4c130994f3","added_by":"auto","created_at":"2025-04-17 05:41:34","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":75868,"visible":true,"origin":"","legend":"\u003cp\u003eSchematic representation for the preparation of CS-g-PAN nanomaterial (\u003cstrong\u003e1\u003c/strong\u003e).\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-5782484/v1/54486d381e352d35ae5a293b.png"},{"id":80787251,"identity":"d5f911de-91d4-4eaf-9f34-461ee6a397b3","added_by":"auto","created_at":"2025-04-17 06:06:50","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":195622,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003e(a)\u003c/strong\u003e Eenergy-dispersive X-ray spectrum and \u003cstrong\u003e(b)\u003c/strong\u003e EDS elemental mapping of CS-g-PAN nanomaterial (\u003cstrong\u003e1\u003c/strong\u003e) for the distribution of C, N, and O atoms.\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-5782484/v1/f7b79680c63788ada6805f85.png"},{"id":80787320,"identity":"06e18cd9-c59d-4d8e-aaad-c5a242fb23e5","added_by":"auto","created_at":"2025-04-17 06:07:53","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":122858,"visible":true,"origin":"","legend":"\u003cp\u003eFTIR spectra of the CS-g-PAN (\u003cstrong\u003e1\u003c/strong\u003e), CS, AN and PAN.\u003c/p\u003e","description":"","filename":"5.png","url":"https://assets-eu.researchsquare.com/files/rs-5782484/v1/72c4068dd4363a1ab14c1f74.png"},{"id":80785646,"identity":"fd7b23e9-e19e-42f2-85ee-20f63c6ea9d5","added_by":"auto","created_at":"2025-04-17 05:41:37","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":306088,"visible":true,"origin":"","legend":"\u003cp\u003eFESEM images of CS-g-PAN nanomaterial (\u003cstrong\u003e1\u003c/strong\u003e) (scale bars: 1 μm, and 200 and 100 nm).\u003c/p\u003e","description":"","filename":"6.png","url":"https://assets-eu.researchsquare.com/files/rs-5782484/v1/fe9226bb676e77b8c127c374.png"},{"id":80785649,"identity":"5cfcde0e-3948-49cd-b9fa-6343d3acfbf9","added_by":"auto","created_at":"2025-04-17 05:41:37","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":163263,"visible":true,"origin":"","legend":"\u003cp\u003e(\u003cstrong\u003ea\u003c/strong\u003e)\u003cstrong\u003e \u003c/strong\u003eTGA and (\u003cstrong\u003eb\u003c/strong\u003e)\u003cstrong\u003e \u003c/strong\u003eDTA curves of the CS-g-PAN nanomaterial (\u003cstrong\u003e1\u003c/strong\u003e).\u003c/p\u003e","description":"","filename":"7.png","url":"https://assets-eu.researchsquare.com/files/rs-5782484/v1/b3adb5d10674dbb6fafe55f2.png"},{"id":80787249,"identity":"b11aeb4c-0ffe-4a1b-b896-2b43d9c6b754","added_by":"auto","created_at":"2025-04-17 06:06:26","extension":"png","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":62413,"visible":true,"origin":"","legend":"\u003cp\u003eThe XRD analysis of the CS-g-PAN nanomaterial (\u003cstrong\u003e1\u003c/strong\u003e).\u003c/p\u003e","description":"","filename":"8.png","url":"https://assets-eu.researchsquare.com/files/rs-5782484/v1/07b9ef582194bdbbfc77e583.png"},{"id":80785642,"identity":"3688c7cd-6f86-4dfb-a512-44fe9c48f712","added_by":"auto","created_at":"2025-04-17 05:41:37","extension":"png","order_by":9,"title":"Figure 9","display":"","copyAsset":false,"role":"figure","size":117131,"visible":true,"origin":"","legend":"\u003cp\u003eBET analysis of the CS-g-PAN nanomaterial(\u003cstrong\u003e1\u003c/strong\u003e).\u003c/p\u003e","description":"","filename":"9.png","url":"https://assets-eu.researchsquare.com/files/rs-5782484/v1/c255a3602f5bf9bf18885041.png"},{"id":80785635,"identity":"633f60ae-ddac-40d6-a586-8f4d01e06578","added_by":"auto","created_at":"2025-04-17 05:41:36","extension":"png","order_by":10,"title":"Figure 10","display":"","copyAsset":false,"role":"figure","size":142557,"visible":true,"origin":"","legend":"\u003cp\u003eProposed mechanism for the synthesis of pyrrole derivatives \u003cstrong\u003e5a-o\u003c/strong\u003e catalyzed by the CS-g-PAN (\u003cstrong\u003e1\u003c/strong\u003e).\u003c/p\u003e","description":"","filename":"10.png","url":"https://assets-eu.researchsquare.com/files/rs-5782484/v1/f0b85ff119a13e6dc3a57183.png"},{"id":80785620,"identity":"9c366977-e030-4ce5-8a03-8e48dbaddb5f","added_by":"auto","created_at":"2025-04-17 05:41:34","extension":"png","order_by":11,"title":"Figure 11","display":"","copyAsset":false,"role":"figure","size":56114,"visible":true,"origin":"","legend":"\u003cp\u003eReusability of the recycled CS-g-PAN catalyst (\u003cstrong\u003e1\u003c/strong\u003e) for the synthesis of pyrrole derivative \u003cstrong\u003e5a\u003c/strong\u003e.\u003c/p\u003e","description":"","filename":"11.png","url":"https://assets-eu.researchsquare.com/files/rs-5782484/v1/4640abad5a0d1ffa7006ece2.png"},{"id":86180303,"identity":"d5e08170-4ba7-464b-b9cb-2d2ac30e8766","added_by":"auto","created_at":"2025-07-07 16:22:09","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":2464762,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-5782484/v1/ee32f96a-75e2-4e19-bf6b-e12081f663c0.pdf"},{"id":80785652,"identity":"94a24cc7-0d98-4e39-8297-2bc0ee2ce9f4","added_by":"auto","created_at":"2025-04-17 05:41:37","extension":"pdf","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":1558727,"visible":true,"origin":"","legend":"","description":"","filename":"ElectronicSupplemntaryInformation32ec493f96a24dfc8b5d72007f50a5bdR1.pdf","url":"https://assets-eu.researchsquare.com/files/rs-5782484/v1/3f613cdb36bff2b558fe7fa9.pdf"},{"id":80785616,"identity":"d6b7cbc8-e9d8-48df-a280-d2184bb9e46f","added_by":"auto","created_at":"2025-04-17 05:41:33","extension":"docx","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":270042,"visible":true,"origin":"","legend":"","description":"","filename":"Tables.docx","url":"https://assets-eu.researchsquare.com/files/rs-5782484/v1/2975f7d68dab85de15686208.docx"}],"financialInterests":"No competing interests reported.","formattedTitle":"Nano ordered polyacrylonitrile-grafted chitosan as a robust biopolymeric catalyst for efficient synthesis of highly substituted pyrrole derivatives","fulltext":[{"header":"Introduction","content":"\u003cp\u003eNanocatalytic systems have emerged as a bridge between homogeneous and heterogeneous catalytic systems, exhibiting numerous advantages such as enhanced activity, stability, and selectivity compared to traditional catalytic systems. Different supports such as silica, alumina, graphene oxide (GO) and its reduced form (rGO), biopolymers, natural asphalt, etc have been used in preparation of heterogeneous catalytic systems. The use of these supports provides high surface area, tunable functional groups, and remarkable stability under harsh reaction conditions to make them highly suitable for a broad spectrum of organic transformations\u003csup\u003e\u003cspan additionalcitationids=\"CR2 CR3 CR4 CR5\" citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e\u003c/sup\u003e. The incorporation of carbon-based materials such as GO and rGO, biopolymers and natural asphalt as supports in nanocatalytic systems represents a promising strategy for the development of high-performance catalysts. The unique properties and adaptability of these materials make them highly attractive for various industrial and scientific applications, with the potential to significantly enhance catalytic process efficiency, selectivity, and sustainability \u003csup\u003e\u003cspan additionalcitationids=\"CR8 CR9 CR10 CR11 CR12\" citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e\u003c/sup\u003e. Hence, the development of a heterogeneous catalytic system that represents the principles of green chemistry, while also offering a cost-effective solution, is a highly desirable goal\u003csup\u003e\u003cspan additionalcitationids=\"CR15\" citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e\u003c/sup\u003e. Such a catalyst should exhibit enhanced reaction efficiency, and be well-suited for the synthesis of organic compounds including heterocyclic derivatives, especially pyrroles, facilitate effortless product isolation, thereby addressing a significant progress in the field of organic chemistry. While previous studies have employed a variety of homogenous and heterogeneous catalysts to enhance reaction conditions and efficiency for the Hantzsch pyrrole synthesis, these approaches often show drawbacks such as low to moderate efficiency, prolonged reaction times, challenges in product separation, the need for hazardous organic solvents, catalyst toxicity, high costs, and the inability to reuse homogenous catalysts\u003csup\u003e\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e,\u003cspan additionalcitationids=\"CR18 CR19 CR20\" citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eGreen chemistry provides a framework for chemists to adopt more sustainable practices, integrating principles such as minimizing hazards in synthesis, maximizing atom economy, utilizing renewable resources, designing for product degradation, and improving energy efficiency in the design of more efficient and safer chemical processes. Sustainable chemistry combines this foundation by broadening the scope to encompass the wider impacts of chemistry, including global resource consumption, human and environmental health, engagement with communities affected by chemical product life cycles, and social needs. This expanded vision for the future of chemistry demands a larger investor view across business value and supply chains\u003csup\u003e\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e\u003c/sup\u003e. Along these lines, natural biopolymers including cellulose, starch, chitin, chitosan, alginate and carrageenan have been widely employed in nanocatalytic systems because of their numerous advantages\u003csup\u003e\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e,\u003cspan additionalcitationids=\"CR24 CR25 CR26\" citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e\u003c/sup\u003e. These include their abundance in nature, biocompatibility, low toxicity, and biodegradability, which make them attractive for a variety of applications\u003csup\u003e\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e\u003c/sup\u003e. These biopolymers have certain features such as the presence of hydroxymethyl groups in cellulose, starch and chitosan as well as the acetyl, amino, carboxyl and sulfonate groups in in chitin, chitosan, alginate and carrageenan, respectively. This remarkable diversity in the peripheral groups of polysaccharides enables a broad spectrum of physical and chemical modifications to afford a wide range of bio-based materials with versatile applications\u003csup\u003e\u003cspan additionalcitationids=\"CR30\" citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e\u003c/sup\u003e. Tailoring the properties of biopolymers can significantly enhance their compatibility and performance in various applications. The obtained modified biopolymers have been successfully utilized in diverse fields, including biomedical applications, pharmaceuticals, agricultural and food industry, environmental remediation such as wastewater treatment, sensors and catalytic systems, highlighting their potential for driving sustainable technological innovations\u003csup\u003e\u003cspan additionalcitationids=\"CR33 CR34\" citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e35\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eAmong these biopolymers, chitosan stands out as a multifunctional polysaccharide derived from the alkaline deacetylation of chitin, which is a naturally abundant biomaterial found in the outer shells of shrimp, lobster and crab, as well as the cell walls of some bacteria and fungi\u003csup\u003e\u003cspan additionalcitationids=\"CR37\" citationid=\"CR36\" class=\"CitationRef\"\u003e36\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e38\u003c/span\u003e\u003c/sup\u003e. Its biodegradable and biocompatible nature makes it an ideal candidate for academic and industrial applications across multiple disciplines\u003csup\u003e\u003cspan additionalcitationids=\"CR40 CR41 CR42\" citationid=\"CR39\" class=\"CitationRef\"\u003e39\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR43\" class=\"CitationRef\"\u003e43\u003c/span\u003e\u003c/sup\u003e. Chitosan's unique molecular structure, containing amino and hydroxyl functional groups with high reactivity as well as appropriate geometry, make it an attractive material for various applications, either in its pristine form or after chemical modification\u003csup\u003e\u003cspan additionalcitationids=\"CR45 CR46 CR47 CR48 CR49\" citationid=\"CR44\" class=\"CitationRef\"\u003e44\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR50\" class=\"CitationRef\"\u003e50\u003c/span\u003e\u003c/sup\u003e. The ability of pristine chitosan or its modified versions to form hydrogen bonds or metal-ligand interactions as well as undergoing chemical modifications with diverse components of composites, metal cations or reagents enables their use in organic reactions as heterogeneous organo- or metal-chelated catalytic systems\u003csup\u003e\u003cspan additionalcitationids=\"CR52 CR53 CR54 CR55 CR56 CR57\" citationid=\"CR51\" class=\"CitationRef\"\u003e51\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR58\" class=\"CitationRef\"\u003e58\u003c/span\u003e\u003c/sup\u003e. Along these lines, polysaccharide modification through co-polymerization with synthetic polymers offers a useful approach to enhance their useful properties for catalytic applications. Radical copolymerization of chitosan using various alkene monomers enables the creation of copolymers with improved thermal and mechanical stability, as well as increased surface area, the crucial factors for designing efficient heterogeneous catalysts. Among of them, copolymers comprising of in-situ grafting of acrylonitrile monomer to the chitosan backbone can be readily prepared and be used. The obtained polyacrylonitrile-modified chitosan (CS-g-PAN) contains both chitosan\u0026rsquo;s functional groups and significant numbers of the nitrile (‒C\u0026thinsp;\u0026equiv;\u0026thinsp;N) functional group for further modifications through rich chemistry of the ‒OH, NH\u003csub\u003e2\u003c/sub\u003e, NH and ‒C\u0026thinsp;\u0026equiv;\u0026thinsp;N functional groups to produce new bio-based materials with tailored properties for specific catalytic applications\u003csup\u003e\u003cspan additionalcitationids=\"CR60 CR61\" citationid=\"CR59\" class=\"CitationRef\"\u003e59\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR62\" class=\"CitationRef\"\u003e62\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eIn recent years, multi-component reactions (MCRs) have emerged as a powerful and sustainable approach in organic synthesis, offering a fascinating alternative to the traditional multi-steps reactions\u003csup\u003e\u003cspan citationid=\"CR63\" class=\"CitationRef\"\u003e63\u003c/span\u003e\u003c/sup\u003e. By enabling the simultaneous synthesis of complex scaffolds through enhanced selectivity, efficiency, and atom efficiency in a one-pot reaction, MCRs significantly reduce the number of reaction steps and isolation procedures\u003csup\u003e\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e,\u003cspan citationid=\"CR50\" class=\"CitationRef\"\u003e50\u003c/span\u003e,\u003cspan additionalcitationids=\"CR65\" citationid=\"CR64\" class=\"CitationRef\"\u003e64\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR66\" class=\"CitationRef\"\u003e66\u003c/span\u003e\u003c/sup\u003e. These advantages will result in preventing the formation of byproducts and excessive the use of solvents, mild reaction conditions and lower energy consumption. The MCR strategy also provides cost-effective and versatility in product design through various substrates with high reaction efficiency. Notably, MCRs have significantly facilitated the synthesis of complex heterocyclic compounds, especially pyrrole derivatives, demonstrating their vast potential in modern organic chemistry\u003csup\u003e\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e,\u003cspan additionalcitationids=\"CR68 CR69\" citationid=\"CR67\" class=\"CitationRef\"\u003e67\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR70\" class=\"CitationRef\"\u003e70\u003c/span\u003e\u003c/sup\u003e. Pyrrole moiety is biologically active and found in natural compounds such as chlorophyll, vitamin B\u003csub\u003e12\u003c/sub\u003e, Bile pigments such as Bilirubin, porphyrins, and others\u003csup\u003e\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e,\u003cspan citationid=\"CR71\" class=\"CitationRef\"\u003e71\u003c/span\u003e,\u003cspan citationid=\"CR72\" class=\"CitationRef\"\u003e72\u003c/span\u003e\u003c/sup\u003e. Furthermore, Lamelarin, Hulitolin, and Marinopyrrole are other natural marine compounds containing the pyrrole ring, which are particularly important due to their high activity against methicillin-resistant bacteria. Pyrrole derivatives also have anti-HIV and anti-tumor activities \u003csup\u003e\u003cspan citationid=\"CR73\" class=\"CitationRef\"\u003e73\u003c/span\u003e,\u003cspan citationid=\"CR74\" class=\"CitationRef\"\u003e74\u003c/span\u003e\u003c/sup\u003e. For instance, research have shown that the obtained Hulitolitans from the extract of the Haliclona tulearensis sponge has cytotoxic activity, and also exhibits antitumor activity\u003csup\u003e\u003cspan additionalcitationids=\"CR75\" citationid=\"CR74\" class=\"CitationRef\"\u003e74\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR76\" class=\"CitationRef\"\u003e76\u003c/span\u003e\u003c/sup\u003e. On the other hand, the diverse biological activities of synthetic pyrrole derivatives including lowering cholesterol, anti-inflammatory, anti-cancer, analgesics, and sedatives have led to the production of medicines such as atorvastatin, ketorolac, tolmetin and sunitinib, which are used worldwide today\u003csup\u003e\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e,\u003cspan additionalcitationids=\"CR78 CR79 CR80\" citationid=\"CR77\" class=\"CitationRef\"\u003e77\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR81\" class=\"CitationRef\"\u003e81\u003c/span\u003e\u003c/sup\u003e. Some other derivatives of pyrrole have been used in semiconductor materials\u003csup\u003e\u003cspan citationid=\"CR82\" class=\"CitationRef\"\u003e82\u003c/span\u003e\u003c/sup\u003e, laser and chemical sensors\u003csup\u003e\u003cspan citationid=\"CR83\" class=\"CitationRef\"\u003e83\u003c/span\u003e\u003c/sup\u003e that show strong absorption in the ultraviolet region and emit strong fluorescence \u003csup\u003e\u003cspan citationid=\"CR84\" class=\"CitationRef\"\u003e84\u003c/span\u003e\u003c/sup\u003e. Furthermore, its use in the food industry and the production of tea and coffee are other applications of pyrrole in the industry\u003csup\u003e\u003cspan citationid=\"CR85\" class=\"CitationRef\"\u003e85\u003c/span\u003e,\u003cspan citationid=\"CR86\" class=\"CitationRef\"\u003e86\u003c/span\u003e\u003c/sup\u003e. For example, phycocyanin is another derivative of pyrrole-containing compounds used as a blue pigment in the food industry\u003csup\u003e\u003cspan citationid=\"CR86\" class=\"CitationRef\"\u003e86\u003c/span\u003e,\u003cspan citationid=\"CR87\" class=\"CitationRef\"\u003e87\u003c/span\u003e\u003c/sup\u003e (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e).\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe significance of pyrrole derivatives in various fields including pharmaceuticals and materials science has received significant research interest for the development of diverse efficient methodologies targeting their synthesis. Pyrrole derivatives are commonly synthesized using the Paal\u0026ndash;Knorr or Hantzsch methods, with the Hantzsch method being more widely used due to its inherent simplicity and direct access to highly substituted pyrroles, and flexibility in terms of solvent, temperature, and catalyst. The Hantzsch pyrrole synthesis, a classic and well-established route for constructing the pyrrole moiety, involves the three-component reaction of α-haloketones, β-dicarbonyl compounds, and primary amines\u003csup\u003e\u003cspan citationid=\"CR85\" class=\"CitationRef\"\u003e85\u003c/span\u003e,\u003cspan additionalcitationids=\"CR89 CR90 CR91 CR92 CR93 CR94 CR95\" citationid=\"CR88\" class=\"CitationRef\"\u003e88\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR96\" class=\"CitationRef\"\u003e96\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eVarious catalytic systems have been explored to promote the synthesis of pyrrole derivatives using the benefits of homogeneous or heterogeneous catalytic systems\u003csup\u003e\u003cspan citationid=\"CR97\" class=\"CitationRef\"\u003e97\u003c/span\u003e\u003c/sup\u003e. Moreover, the incorporation of new energy inputs, such as microwave irradiation sonication or ball-milling, has emerged as a promising strategy to enhance the reaction efficiency, reduce reaction times, and minimize environmental impact\u003csup\u003e\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e,\u003cspan additionalcitationids=\"CR99\" citationid=\"CR98\" class=\"CitationRef\"\u003e98\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR100\" class=\"CitationRef\"\u003e100\u003c/span\u003e\u003c/sup\u003e. Some notable examples of these advancements include the use of β-cyclodextrin\u003csup\u003e\u003cspan citationid=\"CR101\" class=\"CitationRef\"\u003e101\u003c/span\u003e\u003c/sup\u003e, urea/choline chloride\u003csup\u003e\u003cspan citationid=\"CR102\" class=\"CitationRef\"\u003e102\u003c/span\u003e\u003c/sup\u003e, squaric acid\u003csup\u003e\u003cspan citationid=\"CR103\" class=\"CitationRef\"\u003e103\u003c/span\u003e\u003c/sup\u003e, \u003cem\u003ep\u003c/em\u003e-chloropyridine hydrochloride\u003csup\u003e\u003cspan citationid=\"CR104\" class=\"CitationRef\"\u003e104\u003c/span\u003e\u003c/sup\u003e, \u003cem\u003ep\u003c/em\u003e-toluenesulphonic acid\u003csup\u003e\u003cspan citationid=\"CR105\" class=\"CitationRef\"\u003e105\u003c/span\u003e\u003c/sup\u003e, Yb(OTf)\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e39\u003c/sup\u003e, DABCO\u003csup\u003e\u003cspan citationid=\"CR89\" class=\"CitationRef\"\u003e89\u003c/span\u003e\u003c/sup\u003e, polystyrene sulfonate under microwaves irradiation\u003csup\u003e\u003cspan citationid=\"CR106\" class=\"CitationRef\"\u003e106\u003c/span\u003e\u003c/sup\u003e CAN\u0026ndash;silver nitrate system or I\u003csub\u003e2\u003c/sub\u003e under high-speed vibration milling conditions\u003csup\u003e\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e,\u003cspan citationid=\"CR107\" class=\"CitationRef\"\u003e107\u003c/span\u003e\u003c/sup\u003e, and ZnO under ultrasound conditions\u003csup\u003e\u003cspan citationid=\"CR108\" class=\"CitationRef\"\u003e108\u003c/span\u003e\u003c/sup\u003e, which have contributed to the expansion of the Hantzsch pyrrole derivative synthetic pathway. As research in this area improves, the development of novel, sustainable, and efficient methodologies for the synthesis of pyrrole derivatives is in high demand. To address the challenges during development of different protocols for the synthesis of pyrrole scaffold and in continuation of our ongoing research to develop chitosan-based nanomaterials modified by different methods and reagents\u003csup\u003e\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e,\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e,\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e,\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e,\u003cspan citationid=\"CR50\" class=\"CitationRef\"\u003e50\u003c/span\u003e,\u003cspan citationid=\"CR66\" class=\"CitationRef\"\u003e66\u003c/span\u003e,\u003cspan additionalcitationids=\"CR110 CR111\" citationid=\"CR109\" class=\"CitationRef\"\u003e109\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR112\" class=\"CitationRef\"\u003e112\u003c/span\u003e\u003c/sup\u003e, we wish herein to report the Hantzsch pyrrole synthesis catalyzed by in-situ grafted polyacrylonitrile (PAN) onto the chitosan backbone (CS-g-PAN) nanomaterial. Acetyl acetone and different phenacyl bromide derivatives and amine components were smoothly involved in the presence of CS-g-PAN nano ordered organocatalyst to afford the corresponding pyrrole derivatives in good to excellent yields and short reaction times \u003cb\u003e(\u003c/b\u003eFig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e\u003cb\u003e).\u003c/b\u003e\u003c/p\u003e \u003cp\u003e \u003c/p\u003e"},{"header":"Experimental","content":"\u003ch3\u003eMaterials and methods\u003c/h3\u003e\n\u003cp\u003eChitosan with medium molecular weight (180\u0026ndash;300 kDa) and a 75\u0026ndash;85% deacetylation degree, purchased from Merck, was used without further processing. Other chemicals and solvents, including AcOH, acrylonitrile, ammonium persulfate, acetyl acetone, aliphatic or aromatic amines, phenacyl bromide derivatives, toluene, EtOAc, n-hexane, and EtOH (96%), were also supplied by Merck, Sigma Aldrich and local companies. The chemicals and solvents were used as received without further purification. Fourier transform infrared spectroscopy (FTIR) spectra were recorded using KBr pellets on a 1720-X Perkin Elmer (USA) spectrometer. Energy-dispersive X-ray (EDS) spectra and X-ray powder diffraction (XRD) patterns were obtained using Bruker EDS (Germany) and D8 ADVANCE diffractometer (Germany) with Cu Ka radiation (\u0026lambda;\u0026thinsp;=\u0026thinsp;1.54050 \u0026Aring;) instruments, respectively. Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) of the samples were measured using a BAHR-STA 504 device. Field emission scanning electron microscope (FESEM) images were obtained using a FESEM-ZEISS (Germany) instrument. Thin-layer chromatography (TLC) was performed on the Merck F256 silica gel plates to monitor the reaction progress. Melting points were measured using an Electrothermal 9200 instrument and are uncorrected. \u003csup\u003e\u003cspan class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003eH NMR spectra were recorded in DMSO-\u003cem\u003ed\u003c/em\u003e\u003csub\u003e6\u003c/sub\u003e solvent at ambient temperature using a Bruker Avance 400 MHz NMR spectrometer.\u003c/p\u003e\n\u003ch3\u003eSynthesis of the CS-g-PAN (1)\u003c/h3\u003e\n\u003cp\u003eFor the preparation of polyacrylonitrile grafted onto the chitosan backbone (CS-g-PAN) nanomaterial, chitosan (CS, 1.0 g) was dissolved in an aqueous AcOH solution (5%, V:V ; 100.0 ml) and heated to 50\u0026deg;C. The obtained mixture was stirred continuously until it was changed to a clear, colorless solution. Notably, repeating of prior studies by employing an aqueous AcOH solution (1%, V/V) afforded hydrogels unsuitable for the catalytic applications in our hands. However, increasing the AcOH concentration to 10% from 5% restored its suitability for the catalytic purposes. The solution was then degassed for at least 15 min. using N\u003csub\u003e2\u003c/sub\u003e gas. After that, an aqueous solution of ammonium persulfate (NH\u003csub\u003e4\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e8\u003c/sub\u003e, 2.0 M) was added dropwise within 30 min. Subsequently, after an additional 45 min., acrylonitrile (AN, 6.0 ml) was gradually added to the mixture at 55\u0026deg;C and stirred for 40 min to facilitate polymerization. The reaction was maintained at 55\u0026deg;C for 15 h. The obtained mixture was mixed with EtOH (96%, 200 ml), which gave rise to precipitating of the CS-g-PAN nano ordered hydrogel. Finally, after 4 h, the hydrogel was collected and washed sequentially with acetone and deionized H\u003csub\u003e2\u003c/sub\u003eO until it turns into a white precipitate. The precipitates are filtered off and then dried at room temperature for 2 h. The results of FTIR, EDS, XRD, TGA and FESEM characterization data proved successful preparation of the CS-g-PAN catalyst (Fig. \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003e).\u003c/p\u003e\n\u003ch3\u003eGeneral procedure for the preparation of pyrrole derivatives catalyzed by CS-g-PAN nanomaterial (1)\u003c/h3\u003e\n\u003cp\u003eA mixture of acetylacetone (\u003cstrong\u003e2\u003c/strong\u003e, 1.0 mmol), amine derivatives (\u003cstrong\u003e3\u003c/strong\u003e, 1.5 mmol), phenacyl bromide derivatives (\u003cstrong\u003e4\u003c/strong\u003e, 1.0 mmol) and CS-g-PAN catalyst (\u003cstrong\u003e1\u003c/strong\u003e, 15.0 mg) in toluene (2.5 ml) was stirred for 30 min at 30\u0026ndash;35 ℃ and then heated at 100\u0026ndash;110 ℃ for 8\u0026ndash;12 h as indicated in Table\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003e. The progress of reaction was monitored using TLC (n-hexane, EtOAc; 3:1 V/V). Upon completion of the reaction, EtOH (96%, 5.0 ml) was added to the reaction mixture and it was heated to dissolve the product. The CS-g-PAN catalyst (\u003cstrong\u003e1\u003c/strong\u003e) was then separated by filtration and kept for next runs after activation. The filtrate was cooled to ambient temperature, and the product was separated by silica gel plate chromatography. The obtained products were characterized based on their melting points, as well as FTIR and \u003csup\u003e\u003cspan class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003eH NMR spectral data. The results are summarized in Table\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003e.\u003c/p\u003e\n\u003ch3\u003eSelected spectral data for pyrrole derivatives:\u003c/h3\u003e\n\u003cp\u003e\u003cimg 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\" height=\"231\" width=\"584\"\u003e\u003c/p\u003e"},{"header":"Results and discussion","content":"\u003cdiv id=\"Sec8\" class=\"Section2\"\u003e\n \u003ch2\u003eCharacterization of the CS-g-PAN nanomaterial (1)\u003c/h2\u003e\n \u003cp\u003eThe prepared CS-g-PAN nanomaterial was characterized utilizing a range of spectroscopic, microscopic and analytical techniques. Elemental composition and their distribution was analyzed through energy-dispersive X-ray spectroscopy (EDS) and and EDS elemental mapping, while the functional groups present in the structure of the CS-g-PAN was determined using Fourier transform infrared (FTIR) spectroscopy. Additionally, its surface morphology was investigated using field-emission scanning electron microscopy (FESEM ). The crystallinity of the CS-g-PAN nanomaterial was determined using powder X-ray diffraction (XRD). The thermal stability as well as porosimetery of the CS-g-PAN sample was determined using thermogravimetric analysis (TGA), differential thermal analysis (DTA) and N\u003csub\u003e2\u003c/sub\u003e adsorption-desorption analysis. These combined spectroscopic, microscopic, and analytical techniques provided a detailed characterization of the prepared CS-g-PAN catalyst, highlighting its structural and thermal features relevant to its catalytic performance.\u003c/p\u003e\n \u003cp\u003eTo determine the chemical composition and percentage of different atoms, present in the structure of CS-g-PAN (\u003cstrong\u003e1\u003c/strong\u003e), both energy-dispersive X-ray spectroscopy (EDS, \u003cstrong\u003eFig.\u0026nbsp;4a\u003c/strong\u003e) and EDS elemental mapping were used (\u003cstrong\u003eFig.\u0026nbsp;4b\u003c/strong\u003e). According to the obtained data for EDS spectra of the CS-g-PAN nanomaterial, the atomic percentage of carbon, oxygen and nitrogen in its structure was 79.78%, 6.06% and 14.17%, respectively. Indeed, the structures of chitosan biopolymer and polyacrylonitrile contain only C, N and O atoms. This means that impurities were not observed inside of the structure of CS-g-PAN nanomaterial. Due to the presence of nitrile functional group having N in the polyacrylonitrile structure, its grafting onto the chitosan backbone also increases the percentage of nitrogen atoms in the CS-g-PAN nanomaterial structure compared to the pristine chitosan.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec10\" class=\"Section2\"\u003e\n \u003cp\u003eThe FTIR spectrum of CS-g-PAN copolymer (\u003cstrong\u003e1\u003c/strong\u003e), presented in Fig. \u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003e., reveals several characteristic absorption bands. It shows a combination of peaks characteristic of both chitosan and PAN. The broad band ranging 3700\u0026ndash;3300 shows O‒H and N‒H stretching vibrations of the CS moiety in the CS-g-PAN structure. Furthermore, the absorption band at 2960 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e corresponds to C‒H stretching vibrations, which are present in both chitosan and PAN. The stretching vibration of C\u0026thinsp;\u0026equiv;\u0026thinsp;N group at 2194 cm⁻\u0026sup1; is a strong indicator of PAN\u0026apos;s presence in the grafted CS-g-PAN material. The signals at 1400\u0026thinsp;\u0026minus;\u0026thinsp;1200 cm⁻\u0026sup1; region show N‒H bending modes, typical of chitosan in its pristine or Cs-g-PAN modified forms. Additionally, the signal observed at 1100 cm⁻\u0026sup1; can be attributed to the C‒O stretching vibration, characteristic of the glycosidic bonds in chitosan\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e113\u003c/span\u003e\u003c/sup\u003e. This analysis provides strong evidences for the successful preparation of the desired grafted CS-g-PAN material.\u003c/p\u003e\n \u003cp\u003eThe morphological characteristics of the CS-g-PAN nanomaterial (\u003cstrong\u003e1\u003c/strong\u003e) were examined through field-emission scanning electron microscopy (FESEM) imaging. The FESEM micrographs of CS-g-PAN catalyst, captured at magnifications corresponding to 1 \u0026micro;m, 200 nm, and 100 nm scales, revealed a swollen spherical morphology uniformly dispersed across the nanomaterial (\u003cstrong\u003eFig.\u0026nbsp;6\u003c/strong\u003e). The observed structure demonstrates the successful cross-linking and copolymerization processes involving acrylonitrile units grafted onto the planar pristine chitosan backbone to improve its surface area and porosity, making it suitable for catalytic applications.\u003c/p\u003e\n \u003cp\u003eThe thermogravimetric analysis (TGA) of CS-g-PAN nanomaterial (\u003cstrong\u003e1\u003c/strong\u003e) demonstrates an initial weight loss of approximately 8% from 50 to 220\u0026deg;C, which can be attributed to the evaporation of residual moisture or used solvents during its preparation (Fig. \u003cspan class=\"InternalRef\"\u003e7\u003c/span\u003e). A subsequent stage of decomposition was observed between 220 and 375\u0026deg;C, corresponding to the primary thermal degradation of the chitosan chains and grafted PAN. The cumulative weight loss reached approximately 40% within the temperature range of 50\u0026ndash;500\u0026deg;C, indicating that the CS-g-PAN nanomaterial exhibits notable thermal stability suitable for various applications. Complementary differential thermal analysis (DTA) further confirmed that the exothermic weight loss occurred at around 250\u0026deg;C, aligning with the observed TGA profile\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e35\u003c/span\u003e\u003c/sup\u003e. These findings underscore the robust thermal properties of CS-g-PAN nanomaterial, highlighting its potential for use in thermally demanding environments.\u003c/p\u003e\n \u003cp\u003eThe powder XRD pattern of CS-g-PAN nanomaterial has been shown in Fig. \u003cspan class=\"InternalRef\"\u003e8\u003c/span\u003e. The first sharp peak at 2\u0026theta;\u0026thinsp;=\u0026thinsp;16.87\u0026deg; is attributed to the overlap of characteristic peaks of crystalline phase of PAN at 2\u0026theta;\u0026thinsp;=\u0026thinsp;17.03 and chitosan at 2\u0026theta;\u0026thinsp;=\u0026thinsp;20.10\u0026deg;. Notably, intensity of the peak at 20.10\u0026deg; was significantly reduced in the CS-g-PAN grafted copolymer, indicating a decrease in the chitosan crystallinity upon modification with PAN. The significant reduction in diffraction intensity at 2\u0026theta;\u0026thinsp;=\u0026thinsp;20.10\u0026deg; suggests a decrease in chitosan crystallinity, which can be attributed to the graft copolymerization process. This process disrupts the intrinsic crystalline arrangement of chitosan while simultaneously facilitating the formation of new ordered crystalline regions within the nanomaterial structure. Furthermore, the retaining of certain crystalline diffraction reflections confirms that the incorporation of PAN does not severely disrupt the crystalline order, but rather signifies a successful polymer blending process and compatibility between the two polymers. The XRD analysis also verifies the favorable molecular-scale interaction between chitosan and PAN, leading to the formation of a stable nanomaterial with modified crystallinity. Furthermore, an amorphous region centered at 2\u0026theta;\u0026thinsp;=\u0026thinsp;25.80\u0026deg; was developed in the structure of CS-g-PAN nanomaterial. This suggests that the graft copolymerization of PAN onto the chitosan backbone enabled the development of both ordered crystalline and amorphous regions, leading to a stable structure. The observed diffraction pattern demonstrates the compatibility of the two polymers and the absence of significant disruptions to the crystal structure, indicating a successful blending process. Overall, these findings support the formation of a stable CS-g-PAN nanomaterial with a modified crystal structure.\u003c/p\u003e\n \u003cp\u003eThe Brunauer-Emmett-Teller (BET) surface area analysis, employing N\u003csub\u003e2\u003c/sub\u003e adsorption-desorption isotherm, was employed to quantify the specific surface area and average pore width size of the synthesized CS-g-PAN nanomaterial (\u003cstrong\u003e1\u003c/strong\u003e), as illustrated in Fig. \u003cspan class=\"InternalRef\"\u003e9\u003c/span\u003e. Interestingly, the nitrogen adsorption-desorption isotherm for the CS-g-PAN nanomaterial displayed characteristics consistent with a Type III isotherm. Analysis of the BET data revealed that the specific surface area and average pore width size of the CS-g-PAN nanomaterial were found to be approximately 2.9 m\u0026sup2;\u0026middot;g⁻\u0026sup1; and 5.80 nm, respectively. Interestingly, grafting of PAN onto the chitosan backbone has an appropriate impact on it to increase specific surface area, which is a very important factor for the heterogeneous catalytic systems.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec11\" class=\"Section2\"\u003e\n \u003ch2\u003eCatalytic activity evaluation of the CS-g-PAN nanomaterial for the synthesis of pyrrole derivatives\u003c/h2\u003e\n \u003cp\u003eTo show the efficiency of CS-g-PAN nanomaterial (\u003cstrong\u003e1\u003c/strong\u003e) and determine the optimized conditions, the three-component reaction of acetyl acetone (\u003cstrong\u003e2\u003c/strong\u003e), benzyl amine (\u003cstrong\u003e3a\u003c/strong\u003e, 1.50 mmol) and phenacyl bromide (\u003cstrong\u003e4a\u003c/strong\u003e, 1.0 mmol) for the synthesis of 1-(1-benzyl-2-methyl-4-phenyl-\u003cem\u003e1H\u003c/em\u003e-pyrrol-3-yl) ethenone (\u003cstrong\u003e5a\u003c/strong\u003e) was studied as the model reaction. The optimized conditions for this reaction were determined through a systematic study for experiments evaluating different parameters, including catalyst loading, solvent type, and reaction temperature. The results are summarized in Table \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e. Initially, the reaction was performed in toluene without any catalyst, which resulted in a prolonged reaction time of 43 h and very low yield (entry 1). When pristine chitosan, as a catalyst, was used a moderate yield of 58% for the desired product \u003cstrong\u003e5a\u003c/strong\u003e was obtained (entry 2). Interestingly, the use of the CS-g-PAN nanomaterial (\u003cstrong\u003e1\u003c/strong\u003e), as a heterogenous catalyst, in toluene demonstrated superior efficiency compared to other solvents such as THF, MeCN, EtOH, and DMF under the same catalyst loading of 10.0 mg (entries 3\u0026ndash;7). Therefore, toluene was used as the most effective solvent for the three-component Hantzsch pyrrole synthesis catalyzed by the CS-g-PAN nanocatalyst in the next experiments.\u003c/p\u003e\n \u003cp\u003eIn the course of our experiments to optimize the model reaction conditions, prolonged reaction times were explored to optimize the yield of the desired product \u003cstrong\u003e5a\u003c/strong\u003e. Notably, the model reaction afforded 81% of the desired product \u003cstrong\u003e5a\u003c/strong\u003e, demonstrating a favorable yield after 10 h. However, extending the reaction time to 14 h resulted in a yield of 67%, and further extension to 24 h led to a significant yield decrease to 22% (entries 8\u0026ndash;10). These trends can be attributed to the equilibrium-driven nature of pyrrole formation from its substrates and the simultaneous susceptibility of the intermediates and product to hydrolysis. The hydrolysis process is expected to be catalyzed by the HBr byproduct, which is absorbed on the basic sites of the CS-g-PAN nanocatalyst (\u003cstrong\u003e1\u003c/strong\u003e, Fig. \u003cspan class=\"InternalRef\"\u003e10\u003c/span\u003e). On the other hand, reducing the catalyst loading to 5.0 mg resulted in a diminished product yield compared to higher loadings, indicating a dependency of the reaction on catalyst loading. Importantly, the model reaction employing 15.0 mg catalyst loading afforded the highest efficiency, reaching a 91% yield after 8 h (entries 11\u0026ndash;12). In contrast, when the model reaction was run by using 15.0 mg CS-g-PAN catalyst (\u003cstrong\u003e1\u003c/strong\u003e) loading, 69% and 72% of the desired pyrrole derivative \u003cstrong\u003e5a\u003c/strong\u003e were obtained after 6 and 12 h, respectively (entries 13, 14). In addition, by examining of lower temperatures, the model reaction afforded lower yields of the product \u003cstrong\u003e5a\u003c/strong\u003e under 15.0 mg catalyst loading in toluene and after 8 h (entries 15\u0026ndash;17). However, a further increase in the amount of loaded catalyst (\u003cstrong\u003e1\u003c/strong\u003e, 20.0 mg) in toluene at 100\u0026ndash;110 ℃ did not significantly affect the yield and reaction time (entry 18). All of these findings imply that catalyst loading, reaction times and temperature must be optimized to achieve the most efficient catalytic activity. This observed behavior emphasizes the balance between the appropriate amount of loaded catalyst, enough reaction time, higher product yield, and lower side reactions, providing critical insights into the reaction kinetics and required precautions for the yield improvement.\u003c/p\u003e\n \u003cp\u003eIn the next step of our study, the optimized reaction conditions (15.0 mg CS-g-PAN loading in toluene at 100\u0026ndash;110 ℃) were developed to other amines \u003cstrong\u003e3b-l\u003c/strong\u003e as well as phenacyl bromide derivatives \u003cstrong\u003e4b-c\u003c/strong\u003e. The results are summarized in Table \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003e. All studied amine or phenacyl bromide substrates survived well under the optimized reaction conditions to afford the corresponding pyrrole derivatives \u003cstrong\u003e5a-n\u003c/strong\u003e in good to excellent yields. Under the optimized conditions, a wide range of pyrrole derivatives \u003cstrong\u003e5a-n\u003c/strong\u003e were synthesized, demonstrating the versatility and high efficiency of CS-g-PAN nanocatalyst (\u003cstrong\u003e1\u003c/strong\u003e). These findings underscore the potential of CS-g-PAN nanomaterial, as an effective heterogeneous catalyst, for the multicomponent Hantzsch pyrrole synthesis, particularly in enhancing reaction rates and product yields.\u003c/p\u003e\n \u003cp\u003eAccording to the data provided in Table \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003e, the presence of electron-donating groups (EDGs, entries 1, 3\u0026ndash;5,7,8) on the amino moiety generally has a pronounced effect on the reaction efficiency and time compared to the electron-withdrawing groups (EWGs, entries 9, 12\u0026ndash;14) to form the corresponding imine and enamine intermediate (\u003cstrong\u003eII\u0026rsquo;\u003c/strong\u003e, Fig. \u003cspan class=\"InternalRef\"\u003e10\u003c/span\u003e). Hence, the steric hindrance in aliphatic amines (entry 2) or resonance in the aromatic ones (entry 6) retards the three-component Hantzsch pyrrole synthesis to afford lower yields of the corresponding products. Furthermore, the introduction of electron-withdrawing groups such as halogen substituents in the structure of phenacyl bromide component causes an increase in the reaction yield. This demonstrates the importance of EWGs in the structure of phenacyl bromide component to facilitate the S\u003csub\u003e\u003cem\u003eN\u003c/em\u003e\u003c/sub\u003e2 reaction of enamine intermediate (\u003cstrong\u003eII\u003c/strong\u003e) with them to form corresponding more complicated imine and enamine intermediates (\u003cstrong\u003eIII\u003c/strong\u003e). The obtained results prove that the presence of EWGs can significantly accelerate the nucleophilic attack of the amine component \u003cstrong\u003e3a-l\u003c/strong\u003e on the carbonyl group of phenacyl bromide \u003cstrong\u003e4a-c\u003c/strong\u003e, thereby promoting the reaction. These data provide valuable insights into the role of electronic effects or steric hindrance to control the reactivity of amines and phenacyl bromide and offer a useful guide for the optimization of similar reactions. All these data support the mechanism depicted in Fig. \u003cspan class=\"InternalRef\"\u003e10\u003c/span\u003e.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec12\" class=\"Section2\"\u003e\n \u003ch2\u003eProposed mechanism for the synthesis of pyrrole derivatives 5a-o catalyzed by the CS-g-PAN nanomaterial (1)\u003c/h2\u003e\n \u003cp\u003eA plausible mechanism for the Hantzsch pyrrole synthesis \u003cstrong\u003ec\u003c/strong\u003eatalyzed by the multifunctional CS-g-PAN nanomaterial (\u003cstrong\u003e1\u003c/strong\u003e) has been proposed in Fig. \u003cspan class=\"InternalRef\"\u003e10\u003c/span\u003e. The catalyst \u003cstrong\u003e1\u003c/strong\u003e can activate different reaction components by its acidic and basic centers. Indeed, the carbonyl functional groups as well as S\u003csub\u003eN\u003c/sub\u003e2 electrophilic site in both acetylacetone (\u003cstrong\u003e2\u003c/strong\u003e) and phenacyl bromide (\u003cstrong\u003e4\u003c/strong\u003e) components are more activated via hydrogen bonding to react with the nucleophilic sites of the amine component (\u003cstrong\u003e3\u003c/strong\u003e) or \u0026beta;-enamine intermediates (II\u0026rsquo; and III\u0026rsquo;). Therefore, acetylacetone (\u003cstrong\u003e2\u003c/strong\u003e) reacts with amines \u003cstrong\u003e3a-l\u003c/strong\u003e to form the corresponding imines (\u003cstrong\u003eII\u003c/strong\u003e) by losing a water molecule. The produced imine (\u003cstrong\u003eII\u003c/strong\u003e) is then equilibrated to the tautomeric \u0026beta;-enamine intermediates (II\u0026rsquo;) in the presence of CS-g-PAN nanocatalyst (\u003cstrong\u003e1\u003c/strong\u003e). The more nucleophilic \u0026beta;-enamine (\u003cstrong\u003eII\u0026rsquo;\u003c/strong\u003e) then reacts with the activated phenacyl bromide \u003cstrong\u003e4a-c\u003c/strong\u003e to form \u0026alpha;,\u0026gamma;-ketoimine intermediate (\u003cstrong\u003eIII\u003c/strong\u003e). Interestingly, HBr byproduct can be absorbed by the basic amine sites in the structure of the catalyst \u003cstrong\u003e1\u003c/strong\u003e. Hence, the protonated form of the catalyst \u003cstrong\u003e1\u003c/strong\u003e can be in exchange with the intermediates (\u003cstrong\u003eIII\u003c/strong\u003e), (\u003cstrong\u003eIII\u0026rsquo;\u003c/strong\u003e) and \u003cstrong\u003eIV\u003c/strong\u003e to facilitate formation of products \u003cstrong\u003e5a-o\u003c/strong\u003e. The produced \u0026alpha;,\u0026gamma;-ketoimines (\u003cstrong\u003eIII\u003c/strong\u003e) in this step is again equilibrated to the tautomeric \u0026gamma;-enamine intermediates (\u003cstrong\u003eIII\u0026rsquo;\u003c/strong\u003e) in the presence of CS-g-PAN nanocatalyst (\u003cstrong\u003e1\u003c/strong\u003e) or its protonated form. Subsequent activation of the carbonyl group in the intermediate (\u003cstrong\u003eIII\u0026rsquo;\u003c/strong\u003e) by the catalyst (\u003cstrong\u003e1\u003c/strong\u003e) or its protonated form affords the cyclic intermediate (\u003cstrong\u003eIV\u003c/strong\u003e). This intermediate then loses water to afford the aromatic desired pyrrole products \u003cstrong\u003e5a-o\u003c/strong\u003e. Notably, the catalyst \u003cstrong\u003e1\u003c/strong\u003e, having the hygroscopic chitosan moiety, can adsorb water molecules liberated during the products formation and promote the reaction more efficiently.\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e24\u003c/span\u003e,\u003cspan class=\"CitationRef\"\u003e50\u003c/span\u003e,\u003cspan class=\"CitationRef\"\u003e111\u003c/span\u003e,\u003cspan class=\"CitationRef\"\u003e114\u003c/span\u003e\u0026ndash;\u003cspan class=\"CitationRef\"\u003e116\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec13\" class=\"Section2\"\u003e\n \u003ch2\u003eReusability of the catalyst 1 for the synthesis of pyrrole derivative 5a\u003c/h2\u003e\n \u003cp\u003eRecyclability and reuse of the CS-g-PAN nanocatalyst (\u003cstrong\u003e1\u003c/strong\u003e) in the synthesis of pyrrole derivative \u003cstrong\u003e5a\u003c/strong\u003e was also investigated as a part of our study. The relevant results are summarized in Fig. \u003cspan class=\"InternalRef\"\u003e11\u003c/span\u003e. After completion of the reaction in each run, monitored by TLC, the catalyst \u003cstrong\u003e1\u003c/strong\u003e was separated from the reaction mixture and washed with EtOH twice and dried in an oven at 70 ℃ for 3 h. The dried catalyst was used in the next run of the model reaction with similar conditions. The catalyst was used five times and there were no significant changes in its efficiency. The results of XRD analysis for the recycled CS-g-PAN nanocatalyst (\u003cstrong\u003e1\u003c/strong\u003e) after first, third and fifth runs have also been presented in \u003cstrong\u003eFig. S12\u003c/strong\u003e. The obtained XRD patterns clearly demonstrate that the structure of the CS-g-PAN catalyst (\u003cstrong\u003e1\u003c/strong\u003e) remains stable and without any substantial changes under optimized conditions after fifth run. Furthermore, all of these findings approve the heterogenous nature of the CS-g-PAN nanocatalyst (\u003cstrong\u003e1\u003c/strong\u003e).\u003c/p\u003e\n \u003cp\u003eTo demonstrate the catalytic activity of CS-g-PAN nanomaterial (\u003cstrong\u003e1\u003c/strong\u003e) for the synthesis of pyrrole derivatives under the optimized conditions, the obtained results for the synthesis of \u003cstrong\u003e5a\u003c/strong\u003e have been compared with the previous methods reported in the literature. The results are summarized in Table \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003e. Data provided in Table \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003e clearly show the superior efficiency of catalyst \u003cstrong\u003e1\u003c/strong\u003e for the three-component Hantzsch pyrrole synthesis in terms sustainability, catalyst loading, the use of solvent with lower toxicity, temperature and required time compared to many of them.\u0026nbsp;\u003c/p\u003e\n \u003ctable id=\"Tab3\" border=\"1\"\u003e\n \u003ccaption language=\"En\"\u003e\n \u003cdiv class=\"CaptionNumber\"\u003eTable 3\u003c/div\u003e\n \u003cdiv class=\"CaptionContent\"\u003e\n \u003cp\u003eComparison of the catalytic efficiency of CS-g-PAN (\u003cstrong\u003e1\u003c/strong\u003e) with some previously reported catalytic systems for the synthesis of pyrrole derivatives.\u003c/p\u003e\n \u003c/div\u003e\n \u003c/caption\u003e\n \u003cthead\u003e\n \u003ctr\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eEntry\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eCatalyst\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eCatalyst loading\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eConditions\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eYield (%)\u003c/p\u003e\n \u003c/th\u003e\n \u003c/tr\u003e\n \u003c/thead\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eYb(OTf)\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e0.1 mol%\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCH\u003csub\u003e3\u003c/sub\u003eCN/ 80\u0026ndash;85\u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:\\:℃\\)\u003c/span\u003e\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e72\u003csup\u003e39\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eDABCO\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e10 mol%\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eH\u003csub\u003e2\u003c/sub\u003eO/\u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:\\:60\\:℃\\)\u003c/span\u003e\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e70\u003csup\u003e89\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eKO\u003csup\u003et\u003c/sup\u003eBu\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e1.1 equiv\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eTHF/ 24 h\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e88\u003csup\u003e92\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eNaOMe\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e15 mg\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eMeOH/ THF/ 24 h\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e80\u003csup\u003e94\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eAgOAc\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e2 mol%\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003ePhCl/ 130 ℃, 24 h\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e61\u003csup\u003e95\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e6\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eHf/SBA-15\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e140 mg\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eDMF/150\u0026deg;C/ 6h\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e84\u003csup\u003e117\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e7\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCu@imine/Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e MNPs\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e0.36 mol%\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eMeCN/ Reflux/ 80 ℃\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e91\u003csup\u003e118\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e8\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCS-g-PAN\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e15 mg\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eToluene/ reflux/ 8 h\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e91 (This work)\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n \u003c/table\u003e\n\u003c/div\u003e"},{"header":"Conclusion","content":"\u003cp\u003eIn brief, polyacrylonitrile grafted onto the renewable, biocompatible and bio-degradable chitosan (CS-g-PAN) nanomaterial was developed as an efficient multifunctional organocatalyst for the three-component Hantzsch pyrrole synthesis. The efficiency of this new nanomaterial for the atom efficient synthesis of a wide range of pyrrole derivatives was assessed through one-pot reaction in toluene and short reaction times. The heterogeneous CS-g-PAN nanocatalyst showed very high activity compared to previously reported methods in the literature. Other advantages of this methodology are avoiding the use of toxic transition metals and mild reaction conditions, which make it a promising alternative for sustainable Hantzsch pyrrole synthesis. In addition, the catalyst was easily recovered and reused at least five times without significantly loss of its activity. Further studies on the catalytic activity of CS-g-PAN for different organic transformations and its composites with other nanomaterials are in progress in our lab and would be published in due course.\u003c/p\u003e "},{"header":"Declarations","content":"\u003ch2\u003eConflict of interest\u003c/h2\u003e \u003cp\u003eThe authors declare that there are no conflicts of interest regarding the publication of this manuscript.\u003c/p\u003e\u003ch2\u003eAuthor Contribution\u003c/h2\u003e\u003cp\u003e1) M.Z. worked on the topic, as her MSc thesis, and prepared the initial draft of the manuscript. 2) Prof. M.G.D. is the supervisor of M.Z. and N.N. as his MSc and PhD students, respectively. Also, he edited and revised the manuscript completely. 3) N. N. worked closely with M.Z. for doing experiments, interpreting of the characterization and preparation of the initial draft of the manuscript. 4) Dr. A.S. is the supervisor of M.Z. as his MSc student. Also, he helped to prepare the initial draft and revised version of the manuscript by M.Z. and N.N.\u003c/p\u003e\u003ch2\u003eAcknowledgements\u003c/h2\u003e \u003cp\u003eWe are grateful for the financial support from The Research Council of Iran University of Science and Technology (IUST), Tehran, Iran (Grant No 160/24293) as well as the support of the Iran Nanotechnology Initiative Council (INIC), Iran. The partial financial support from The Research Council of Babol Noshirvani University of Technology, Babol, Iran is highly appreciated.\u003c/p\u003e\u003ch2\u003eData Availability\u003c/h2\u003e\u003cp\u003eAll data generated or analyzed during this study are included in this published article [and its supplementary information files.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eMohammadi, M. \u0026amp; Soleiman-Beigi, M. 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An efficient and recyclable nanocatalyst for the green and rapid synthesis of biologically active polysubstituted pyrroles and 1, 2, 4, 5-tetrasubstituted imidazole derivatives. \u003cem\u003eRSC Adv.\u003c/em\u003e \u003cb\u003e9\u003c/b\u003e, 15966\u0026ndash;15975 (2019).\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"},{"header":"Tables","content":"\u003cp\u003eTables 1 and 2 are available in the Supplementary Files section.\u003c/p\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"scientific-reports","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"scirep","sideBox":"Learn more about [Scientific Reports](http://www.nature.com/srep/)","snPcode":"","submissionUrl":"","title":"Scientific Reports","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Scientific Reports","inReviewEnabled":true,"inReviewRevisionsEnabled":true},"keywords":"Modified chitosan, Heterogenous organocatlyst, Multi-Component reactions (MCRs), Nano ordered copolymers, Heterocycles, Pyrrole derivatives","lastPublishedDoi":"10.21203/rs.3.rs-5782484/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-5782484/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eA novel heterogeneous nanocatalyst was developed using chitosan, as a natural polysaccharide derived from crustacean shells, and its in-situ grafting by polyacrylonitrile to afford nano ordered polyacrylonitrile-modified chitosan (CS-g-PAN). The obtained CS-g-PAN nanomaterial was thoroughly analyzed using several appropriate spectroscopic, microscopic or analytical techniques, including EDS and FTIR spectroscopy, EDS elemental mapping, FESEM imaging, XRD spectroscopy, TGA and DTA, and N\u003csub\u003e2\u003c/sub\u003e adsorption-desorption isotherm. The catalytic activity of multifunctional CS-g-PAN nanomaterial, as an organocatalyst, was evaluated in the green synthesis of highly substituted pyrrole derivatives through multi-component reactions strategy from corresponding α-haloketones, β-dicarbonyl compounds, and primary amines. This method offers several advantages, including high efficiency, short reaction times, ease of catalyst separation and recovery as well as recyclability for at least five cycles without significant loss of its activity. The catalyst's eco-friendly nature, lack of toxic transition metals, and mild reaction conditions make it a promising sustainable alternative for the Hantzsch synthesis of different pyrrole derivatives.\u003c/p\u003e","manuscriptTitle":"Nano ordered polyacrylonitrile-grafted chitosan as a robust biopolymeric catalyst for efficient synthesis of highly substituted pyrrole derivatives","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-04-17 05:41:25","doi":"10.21203/rs.3.rs-5782484/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision 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