Ultrasound-Assisted Green Synthesis of 1,4-Disubstituted 1,2,3-Triazoles Using Natural Polymer Supports

Ultrasound-Assisted Green Synthesis of 1,4-Disubstituted 1,2,3-Triazoles Using Natural Polymer Supports | 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 Ultrasound-Assisted Green Synthesis of 1,4-Disubstituted 1,2,3-Triazoles Using Natural Polymer Supports Khatereh Haseli, Maryam Esmkhani, Shahrzad Javanshir This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-6868863/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 05 Aug, 2025 Read the published version in Scientific Reports → Version 1 posted 10 You are reading this latest preprint version Abstract The advent of click chemistry has significantly accelerated the synthesis of 1,2,3-triazoles, key structures found in numerous biologically active and pharmaceutical compounds. Click reactions can be notably enhanced by employing ultrasonic irradiation and supported catalysts. In this study, we report the development of an eco-friendly catalyst based on natural biopolymers, chitosan and shilajit, designed to facilitate an improved click chemistry protocol under ultrasonic conditions at room temperature. The catalyst was thoroughly characterized using Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), energy-dispersive X-ray spectroscopy (EDX), and scanning electron microscopy (SEM). The results confirm the successful immobilization of copper species onto the polymer supports. This method offers several advantages, including the use of water as a green solvent, elimination of reducing agents, high catalytic efficiency, short reaction times, cost-effectiveness, and excellent catalyst recyclability. Physical sciences/Chemistry Physical sciences/Nanoscience and technology Click Reaction Sonochemistry Polysaccharide 1 2 3-Triazole Biopolymer Chitosan Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 1. Introduction In recent years, scientific advancements have increasingly emphasized the utilization of sustainable and eco-friendly resources. Green chemistry, a crucial field in this movement, aims to minimize or eliminate the use and generation of hazardous substances during chemical production, thereby promoting safer and more environmentally sustainable manufacturing practices 1 , 2 . Among natural resources, polysaccharides derived from algae, plants, and microbial biomass have gained considerable attention. Biopolymers obtained from these sources offer several advantages, including non-toxicity, excellent physicochemical properties, ease of functionalization, abundance, and biocompatibility. Consequently, biopolymers are increasingly recognized as promising materials for diverse applications 3 – 6 . Supported metal catalysts are becoming increasingly popular in the preparation of compounds for fine chemicals and pharmaceuticals, in response to growing environmental awareness 7 , 8 . To improve their stability and prevent the agglomeration of metals, metal nanoparticles have been incorporated into different types of matrices, thus allowing the separation of the metal from the solution and the recycling of the catalyst. Activated carbon 9 , metal oxides 10 – 12 , zeolites 13 , 14 , clays 15 , and natural polymers have all been used as supports for this purpose. There has been a significant increase in the use of natural polymers as ideal materials for developing a variety of catalysts. These natural polymers have proven to be effective stabilizing and reducing agents for various reactions. Polysaccharides, such as cellulose, pectin, alginate, starch, gum, chitin, and chitosan, are a significant category of natural polymers that can be employed as efficient bases for these objectives 16 . Chitosan (CS), a naturally occurring polysaccharide, has been extensively utilized for the preparation of bio-based catalysts owing to its non-toxic nature and functional versatility. However, its practical applications are sometimes limited by its low solubility in water. Chemical modifications targeting the amino (-NH₂) and hydroxyl (-OH) groups of the chitosan backbone can significantly improve its solubility and biological activity, thereby broadening its functional scope. These functional groups also provide reactive sites for further chemical derivatization to enhance catalytic performance. Shilajit, a natural exudate obtained from mountainous rocks, is a complex material rich in humic and fulvic acids. Comprising 60–80% fulvic acid among its bioactive components, Shilajit also contains benzoic acid, hippuric acid, fatty acids, ichthyol, ellagic acid, resins, waxes, gums, albuminoids, triterpenes, sterols, aromatic carboxylic acids, 3,4-benzocoumarins, amino acids, and phenolic lipids 17 . Owing to its rich functional groups and complex organic composition, Shilajit has been explored as a cost-effective, natural catalyst 18 , and serves as a versatile platform for the development of catalysts and adsorbents. Among transition metals, copper stands out due to its abundance, affordability, low toxicity, and its capacity to catalyze a wide range of chemical transformations 19 . Catalysts, fundamental to the advancement of green chemistry, not only enable more sustainable chemical processes but also support cleaner technologies and the synthesis of value-added products with minimized environmental impact 20 – 22 . Key advantages of catalysts include their reusability and environmentally benign nature 23 . In particular, heterogeneous catalysis is highly valued for its operational simplicity, high efficiency, product selectivity, and ease of catalyst recovery and recycling 24 – 26 . Utilizing heterogeneous catalysts has provided significant advantages in synthesis, as these robust materials offer multiple benefits over conventional homogeneous catalysts. They can be easily restored using filtration or centrifugation, and this allows them to be reused instead of turning into chemical waste 27 , 28 . Chitosan is an important polysaccharide used in various biomedical and engineering applications. In this context, chitosan and its modified analogs are commonly used as supports for the immobilization of transition metals in catalysis 29 – 31 . So far, Huisgen’s copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) is a well-known reaction known for its ability to quickly, efficiently, and consistently produce a wide range of five-membered heterocycles 1 , 32 , 33 . Nevertheless, the traditional conditions of the Huisgen reaction demand high temperatures, and extended reaction times, resulting in a blend of 1,4- and 1,5-triazole isomers. (Fig. 1) Following up on our earlier research in this area, we created a new, highly efficient bio-based catalyst and tested how well it works in a click reaction. The chitosan-shilajit@Cu catalyst was synthesized through a simple, cost-effective approach and successfully applied in click reaction. The reaction yielded products rapidly and in high quantities. The removed catalyst was successfully recycled and reused for four additional cycles with high efficiency. 2. Experimental 2.1. Materials and instruments: All the reactants such as copper iodide, sodium acetate, acetic acid (Merck Germany), phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, dimethyl sulfoxide (DMSO), 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC), sodium hydroxide, n-Hydroxy succinimide (NHS), phenylacetylene, benzyl bromide, sodium azide, 1-phenyl, 2-propene, 1-ol were purchased from Merck Chemical Company. Chitosan with 75–85% deacetylation was purchased from Sigma Aldrich. Shilajit was acquired from the grocery store. The melting points were used to confirm the identity of the products. The melting points were measured with the Electrothermal 9100 instrument. Infrared (IR) spectra were recorded on a Bruker VERTEX 70 model spectrometer with spectroscopic grade KBr. Scanning electron microscopy (SEM) was performed via a VEG2/TESCAN 30kv with gold coating, and energy dispersive X-ray spectroscopy (EDX) was recorded on a VEG//TESCAN-XMU. We indicated the X-ray diffraction (XRD) of the catalyst with a Rigaku-Dmax 2500 diffractometer with nickel-filtered Cu Kα radiation ( λ = 1.5418 Å, 40 kV) 2.1.1. Preparation of chitosan-shilajit (Cs-Sh) composite Firstly, 1-ethyl-3-(3-dimethyl aminopropyl) carbodiimide (EDC) with shilajit, dimethylsulfoxide (DMSO) and N-hydroxy succinimide (NHS) were poured into a round bottom flask, and stirred at room temperature for one hour until the components mixed well. Then, the mixture was added to a 1% solution of chitosan in buffer acetate (pH = 4.7). The mixture was vigorously stirred in the dark under an argon atmosphere for 16 hrs. After that, the pH was set to 9 by adding 1M NaOH. The final product was dialyzed against buffer phosphate (pH = 7.4) and distilled water for another 3 days. At last, the brown viscous product was poured into a Petri dish and freeze-dried. The scheme of the steps is shown in Fig. 2 . 2.1.2. Immobilization of copper For incorporating Cu on the prepared Cs-Sh, 0.09 gr of CuI was completely dissolved in 1 mL of acetonitrile in an ultrasonic bath. Then 0.03 gr of Cs-Sh was added to the CuI yellow solution and subjected to an argon atmosphere for 6 hours at reflux temperature. The precipitate was rinsed with acetonitrile and acetone and vacuum-dried at 60°C overnight. 2.1.3. General procedure for preparation of triazole derivatives A blend of phenylacetylene derivatives ( 1.2 mmol), benzyl halide ( 1.0 mmol), and NaN 3 ( 1.2 mmol) in water ( 3 ml) was sonicated for an adequate time. The reaction progress was monitored using thin-layer chromatography. When the reaction was finished, we filtered the catalyst and removed the solvent. An ethanol/water solution can be used to further purify the product. 3. Results and discussion The FT-IR spectra of the CS-Sh@Cu, Cs-Sh, and Shilajit are investigated in Figure S1 (see supporting information). The FT-IR spectrum of shilajit indicates characteristics peaks at 3316 cm − 1 and 1624 cm − 1 attributed to OH stretching vibration and C = O vibrational groups respectively. The peak at 1091 cm − 1 is related to C-O vibration which indicates the presence of polysaccharide. The incorporation of chitosan and shilajit was also determined by the FTIR spectrum. According to the literature 34 , 35 , the peak observed at 3378 – 3680 cm − 1 showed the stretching vibration of the N-H amide group of the second type, and since the intensity of the peak is reduced, it can be evidence of the formation of chitosan and shilajit combination. The peak that appeared at 1655 − 1626 cm − 1 can also be related to the C = O group formed through the combination of chitosan and shilajit 36 , 37 . By comparing the above spectrum and the corresponding spectrum of the final catalyst, it can be concluded that the corresponding peaks at low frequencies of 563 Cm − 1 are related to the presence of copper 18 (Figure S1 ). EDS analysis confirms the presence of carbon, oxygen, nitrogen, and copper in the final composition of the catalyst with ratios of 35.64: 52.99: 7.30: 4.08 wt%, respectively. It can also confirm that the copper immobilization was performed successfully (Fig. 3 ). Moreover, the copper concentration was determined by inductively coupled plasma optical emission spectrometry (ICP-OES). ICP analysis revealed a decrease in metal loading upon catalyst reuse, dropping from 1.6 wt% in the fresh catalyst to 1.1 wt% after reuse. This reduction could be attributed to metal leaching during the reaction, partial loss of active sites, or structural modifications affecting metal retention. These findings highlight the necessity of further investigation into the stability and recyclability of the catalyst. The XRD profile in the 2θ range of ( 5 to 80 °) was measured. The wide peaks with some sharp peaks at 2θ = 28.33, and 46.54 are attributed to shilajit, implying its non-crystalline nature 18 . The peaks at 2θ = 25.997, 41.024, 50.221 corresponded to the (111), (220), and (311) reflection crystal plans of CuI respectively 38 (JCPDS card no. 01-075-0832). The defining peak at about 2θ = 20º linked to the chitosan’s mild crystalline structure 39 . (Figure S2-a (see supporting information)) The amount of weight change of Cs-Sh@Cu catalyst was measured as a function of temperature (from 50 °C to 700 °C) in the argon atmosphere using Thermal Gravimetric Analysis (TGA) shown in Fig. 4 . The results revealed a weight loss of 28 % equal to ~ 1 mg. The initial weight gain observed before reaching a temperature of 100°C can be attributed to the buoyancy effect, where the sample absorbs moisture or gases from the surrounding environment, causing an apparent increase in weight. This phenomenon occurs because the displaced air exerts an upward buoyant force on the sample, leading to an overestimation of its weight during measurements. This is a common occurrence in thermogravimetric analysis (TGA)t 40 . In the following, the loss of weight near 100°C relates to the physically adsorbed moisture or organic solvents on the surface of the catalyst. The mass decrease around ~ 300°C is attributed to thermal decomposition of chitosan 41 . In SEM scanning electron images shown in Fig. 5 , the copper particles are almost uniformly dispersed on the substrate. At a magnification of 200 nm, both the substrate and the nanoparticles can be seen. To calculate the surface area and pore diameter of the prepared catalyst, the Brunauer–Emmett–Teller (BET) method was utilized. According to the results demonstrated in Figure S3 (See supporting information), the adsorption-desorption isotherm displays an IV isotherm with the H3 hysteresis loop type which is typically observed in mesoporous materials. Moreover, the surface area is 4.14 m 2 /g for Cs-Sh@Cu catalyst. 4. Evaluation of the catalytic activity of Cs-Sh@Cu in the synthesis of 1,2,3-triazole derivatives The efficiency of Cs-Sh@Cu was evaluated in the preparation of derivatives based on triazole under different situations. Several parameters such as catalyst dosage, solvent type, duration, and temperature conditions were examined using a model three-component reaction involving phenylacetylene, benzyl bromide, and sodium azide shown in Table S1 (see supporting information). As is obvious, the best results were obtained in the presence of water and under ultrasonic irradiation. It should be noted that ultrasonic irradiation enhances reaction efficiency by generating localized high temperatures and pressures through acoustic cavitation. This phenomenon accelerates reaction rates, improves mass transfer, and facilitates catalyst activation, leading to higher yields and shorter reaction times. Additionally, ultrasound promotes cleaner reactions by reducing the need for harsh conditions, making it an environmentally friendly approach in green chemistry. Additionally, under sonication, the presence of hydrogen radicals (H•) acts as an in situ reducing agent, promoting the reduction of Cu(II) to the active Cu(I) species. This dual role of ultrasound enhancing reaction conditions and facilitating catalyst activation further improves the process's efficiency and environmental friendliness. Importantly, this approach eliminates the need for additional reducing agents, making the overall system more environmentally benign. 42 , 43 The catalyst dosage is another important factor that can affect the reaction rate and yield due to the increment of the active sites. Table S1 shows that the increase in catalyst dosage was not favorable and with a 10 mg catalyst loading, a 93 % conversion was obtained. Further optimization was carried out to find the synergetic effect of the catalyst components. The results were tabulated in Table S2(see supporting information). As it was predictable, the reaction did not occur without copper. Generalizing the optimum conditions was carried out using a one-pot reaction involving acetylene derivatives, sodium azide, and benzyl halide derivatives to prepare different 1,2,3-triazoles by using Cs-Sh@Cu and the results are presented in Table 1 . As expected, the reaction rate and yield increased in the presence of electron-withdrawing groups, whereas both parameters declined with electron-donating groups. 4.1. Hot filtration The hot filtration test was conducted under the optimized reaction conditions to assess the heterogeneity of the Cs-Sh@Cu catalyst in the synthesis of 1,2,3-triazole derivatives. After 15 minutes of reaction, the mixture was hot-filtered to remove the catalyst, and the reaction continued without the catalyst in the filtrate. The progress of the reaction was monitored, and negligible product formation after catalyst removal indicated that no active copper species leached into the solution. These results strongly suggest that the catalytic activity primarily stems from the heterogeneous Cs-Sh@Cu catalyst and that the leaching of active metal into the reaction medium is minimal. Therefore, the catalyst can be considered truly heterogeneous, which is beneficial for catalyst recyclability and the environment sustainability. 4.2. Catalyst recyclability Heterogeneous catalysts should be investigated from the recyclability point of view. After the modal reaction was complete, the used Cs-Sh@Cu catalyst was gathered and rinsed with ethanol and water to eliminate impurities and unreacted compounds. The dried catalyst was successfully reused for four reaction cycles, with negligible loss in yield or performance, as shown in Fig. 6 . Moreover, FT-IR analysis and the XRD pattern of the reused catalyst (Figure S1 and S2-b, see supporting information) further confirm that the catalyst retained its structural integrity after multiple cycles of use. To evaluate the catalyst’s efficiency, the produced Cs-Sh@Cu was compared with reported catalysts, additionally the results are summarized in Table 2 . The synthesized catalyst exhibits several advantages, making it a promising candidate for further applications. Table 2 A comparison of performance of Cs-Sh@Cu with catalysts reported in previous studies. Entry Catalyst Conditions Yield (%) References 1 Cu(I)-AMPS Water/R.T/60 min 82% 39 2 Cu@KIT-5 Water/20min/ 85% 51 3 Cu@SMI Water/reflux/20 min 90% 52 4 CuFe 2 O 4 @SiO 2 @l-arginine@Cu(I) EtOH: Water/60°C/35 min 89% 53 5 Ag@Fe 3 O 4 -g-C 3 N 4 -Arg-CG Water/50°C/35 min 90% 54 6 Cs-Sh@Cu Water/ultrasonic/25min 93% This work Conclusion In a nutshell, a new bio-based catalyst was created by immobilizing copper onto chitosan-shilajit. Various analytical techniques were used to characterize the catalyst, confirming its successful preparation. The catalyst demonstrated its catalytic efficiency in producing 1,2,3-triazole derivatives using a one-pot, three-component reaction involving sodium azide, acetylene, and benzyl halide derivatives under ultrasonic irradiation in water, a sustainable solvent. The reaction was efficiently mediated by ultrasonic irradiation, demonstrating its effectiveness in promoting the reaction. The heterogeneity of the catalyst was verified via a hot filtration analysis. Its benefits, such as recyclability, high yield, short reaction time, and ease of production, position it as a promising option for future applications in other synthetic pathways. Our results illustrate an improved version of ultrasonic click chemistry to produce 1,2,3-triazoles at low temperatures. Declarations Conflicts of interest There are no conflicts to declare. Data Availability Data is provided within the manuscript or supplementary information files. Funding No funding to declare References Kolewe, K. W., Peyton, S. 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Technology","correspondingAuthor":false,"prefix":"","firstName":"Maryam","middleName":"","lastName":"Esmkhani","suffix":""},{"id":473078554,"identity":"4584b2e2-56dc-4ca2-98e8-daa7e8008bbd","order_by":2,"name":"Shahrzad Javanshir","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA1ElEQVRIie2PsQrCMBCGr0tcgnNEaF+hxcWpz3IlYBZ9gw6Z6iKdC75MIdBn6NChLro4VISCSzEVRBA0GQXzLXcc/wf/ATgcvwgDHIdPngfyMfqmLHTSk7bKg0Q+FSPBXh6uNG1EzsSphTSG6bz8roRNyee0Om4yto4kVBzIFA0KQ5wVRI2KLkZKINRUrEB+KwYlCBMHCYOFAjWu2CVTSBhG0ssslFAry0uuooyeoyLJObUotuY19ioItqLtuj72g52pGFB87Xo1fqKZlBYhh8Ph+GvuGT49rv+MuDgAAAAASUVORK5CYII=","orcid":"","institution":"Iran University of Science and Technology","correspondingAuthor":true,"prefix":"","firstName":"Shahrzad","middleName":"","lastName":"Javanshir","suffix":""}],"badges":[],"createdAt":"2025-06-11 07:23:12","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-6868863/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-6868863/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1038/s41598-025-13114-z","type":"published","date":"2025-08-05T15:58:03+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":84983975,"identity":"8f3f806c-5bda-4101-a4a5-036846aaa0bd","added_by":"auto","created_at":"2025-06-19 13:58:15","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":200436,"visible":true,"origin":"","legend":"\u003cp\u003eThe Huisgen 1,3-Dipolar cycloaddition between azide/alkyne\u003c/p\u003e","description":"","filename":"floatimage2.png","url":"https://assets-eu.researchsquare.com/files/rs-6868863/v1/3cfb4e0cd78e16c7f8a146ee.png"},{"id":84982826,"identity":"bbedf3c8-2eac-4938-91c2-dbcb2982577d","added_by":"auto","created_at":"2025-06-19 13:50:15","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":167172,"visible":true,"origin":"","legend":"\u003cp\u003eSchematic representation of the catalyst preparation.\u003c/p\u003e","description":"","filename":"floatimage3.png","url":"https://assets-eu.researchsquare.com/files/rs-6868863/v1/02dcc6822a3ec751227f9f72.png"},{"id":84982829,"identity":"7a5e6d06-a6b4-4dda-9783-8e60144e3108","added_by":"auto","created_at":"2025-06-19 13:50:15","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":647381,"visible":true,"origin":"","legend":"\u003cp\u003eEDS analysis of catalyst\u003c/p\u003e","description":"","filename":"floatimage4.png","url":"https://assets-eu.researchsquare.com/files/rs-6868863/v1/430ec256471f5ca1fe088db2.png"},{"id":84983977,"identity":"493fcd57-2e83-4854-ab54-354afd5d0754","added_by":"auto","created_at":"2025-06-19 13:58:15","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":74966,"visible":true,"origin":"","legend":"\u003cp\u003eTGA analysis of Cs-Sh@Cu.\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-6868863/v1/5d61c8a08f1532b8175fc1e5.png"},{"id":84983979,"identity":"a080a39c-99f0-416d-b1be-ba4baf028927","added_by":"auto","created_at":"2025-06-19 13:58:15","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":441556,"visible":true,"origin":"","legend":"\u003cp\u003eSEM of Cs-Sh@Cu.\u003c/p\u003e","description":"","filename":"floatimage6.png","url":"https://assets-eu.researchsquare.com/files/rs-6868863/v1/d06f3bb529c5acbf26fa62c7.png"},{"id":84982832,"identity":"18e1e1d6-f39b-4d90-8b04-5580c0775abf","added_by":"auto","created_at":"2025-06-19 13:50:15","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":33386,"visible":true,"origin":"","legend":"\u003cp\u003eReusability of the Cs-Sh@Cu\u003c/p\u003e","description":"","filename":"6.png","url":"https://assets-eu.researchsquare.com/files/rs-6868863/v1/49d6ff38b3efc7ec8fcad4a8.png"},{"id":88814957,"identity":"c1993f5d-ce9b-4b06-8491-0d115ce3657b","added_by":"auto","created_at":"2025-08-11 16:10:20","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":2274233,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-6868863/v1/a141a7ca-7aa1-4396-88b3-95bb52fea45b.pdf"},{"id":84984328,"identity":"fbecca82-a76e-47d5-8991-7ef95896135c","added_by":"auto","created_at":"2025-06-19 14:06:15","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":132019,"visible":true,"origin":"","legend":"","description":"","filename":"SUPPORTINGINFORMATIONedited.docx","url":"https://assets-eu.researchsquare.com/files/rs-6868863/v1/572316b32650546a0ecd034f.docx"},{"id":84982830,"identity":"93fc30c8-acf8-4cf3-8b7c-b9d086ced0a8","added_by":"auto","created_at":"2025-06-19 13:50:15","extension":"jpeg","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":533309,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eGraphical abstract\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"floatimage1.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-6868863/v1/1a762e2db73bbb550a9e5ce7.jpeg"},{"id":84982822,"identity":"a00b22df-9622-4842-9a8a-e812d471f6c3","added_by":"auto","created_at":"2025-06-19 13:50:15","extension":"docx","order_by":3,"title":"","display":"","copyAsset":false,"role":"supplement","size":35981,"visible":true,"origin":"","legend":"","description":"","filename":"Table1.docx","url":"https://assets-eu.researchsquare.com/files/rs-6868863/v1/e3b96628b55d8de1a78c8388.docx"}],"financialInterests":"No competing interests reported.","formattedTitle":"Ultrasound-Assisted Green Synthesis of 1,4-Disubstituted 1,2,3-Triazoles Using Natural Polymer Supports","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003eIn recent years, scientific advancements have increasingly emphasized the utilization of sustainable and eco-friendly resources. Green chemistry, a crucial field in this movement, aims to minimize or eliminate the use and generation of hazardous substances during chemical production, thereby promoting safer and more environmentally sustainable manufacturing practices\u003csup\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e,\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e\u003c/sup\u003e. Among natural resources, polysaccharides derived from algae, plants, and microbial biomass have gained considerable attention. Biopolymers obtained from these sources offer several advantages, including non-toxicity, excellent physicochemical properties, ease of functionalization, abundance, and biocompatibility. Consequently, biopolymers are increasingly recognized as promising materials for diverse applications\u003csup\u003e\u003cspan additionalcitationids=\"CR4 CR5\" citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eSupported metal catalysts are becoming increasingly popular in the preparation of compounds for fine chemicals and pharmaceuticals, in response to growing environmental awareness\u003csup\u003e\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e,\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e\u003c/sup\u003e. To improve their stability and prevent the agglomeration of metals, metal nanoparticles have been incorporated into different types of matrices, thus allowing the separation of the metal from the solution and the recycling of the catalyst. Activated carbon\u003csup\u003e\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e\u003c/sup\u003e, metal oxides\u003csup\u003e\u003cspan additionalcitationids=\"CR11\" citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e\u003c/sup\u003e, zeolites\u003csup\u003e\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e,\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e\u003c/sup\u003e, clays\u003csup\u003e\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e\u003c/sup\u003e, and natural polymers have all been used as supports for this purpose. There has been a significant increase in the use of natural polymers as ideal materials for developing a variety of catalysts. These natural polymers have proven to be effective stabilizing and reducing agents for various reactions. Polysaccharides, such as cellulose, pectin, alginate, starch, gum, chitin, and chitosan, are a significant category of natural polymers that can be employed as efficient bases for these objectives\u003csup\u003e\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e\u003c/sup\u003e. Chitosan (CS), a naturally occurring polysaccharide, has been extensively utilized for the preparation of bio-based catalysts owing to its non-toxic nature and functional versatility. However, its practical applications are sometimes limited by its low solubility in water. Chemical modifications targeting the amino (-NH₂) and hydroxyl (-OH) groups of the chitosan backbone can significantly improve its solubility and biological activity, thereby broadening its functional scope. These functional groups also provide reactive sites for further chemical derivatization to enhance catalytic performance.\u003c/p\u003e \u003cp\u003eShilajit, a natural exudate obtained from mountainous rocks, is a complex material rich in humic and fulvic acids. Comprising 60\u0026ndash;80% fulvic acid among its bioactive components, Shilajit also contains benzoic acid, hippuric acid, fatty acids, ichthyol, ellagic acid, resins, waxes, gums, albuminoids, triterpenes, sterols, aromatic carboxylic acids, 3,4-benzocoumarins, amino acids, and phenolic lipids \u003csup\u003e\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e\u003c/sup\u003e. Owing to its rich functional groups and complex organic composition, Shilajit has been explored as a cost-effective, natural catalyst \u003csup\u003e\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e\u003c/sup\u003e, and serves as a versatile platform for the development of catalysts and adsorbents.\u003c/p\u003e \u003cp\u003eAmong transition metals, copper stands out due to its abundance, affordability, low toxicity, and its capacity to catalyze a wide range of chemical transformations \u003csup\u003e\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eCatalysts, fundamental to the advancement of green chemistry, not only enable more sustainable chemical processes but also support cleaner technologies and the synthesis of value-added products with minimized environmental impact \u003csup\u003e\u003cspan additionalcitationids=\"CR21\" citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e\u003c/sup\u003e. Key advantages of catalysts include their reusability and environmentally benign nature \u003csup\u003e\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e\u003c/sup\u003e. In particular, heterogeneous catalysis is highly valued for its operational simplicity, high efficiency, product selectivity, and ease of catalyst recovery and recycling \u003csup\u003e\u003cspan additionalcitationids=\"CR25\" citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e\u003c/sup\u003e. Utilizing heterogeneous catalysts has provided significant advantages in synthesis, as these robust materials offer multiple benefits over conventional homogeneous catalysts. They can be easily restored using filtration or centrifugation, and this allows them to be reused instead of turning into chemical waste \u003csup\u003e\u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e,\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e\u003c/sup\u003e. Chitosan is an important polysaccharide used in various biomedical and engineering applications. In this context, chitosan and its modified analogs are commonly used as supports for the immobilization of transition metals in catalysis \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.\u003c/p\u003e \u003cp\u003eSo far, Huisgen\u0026rsquo;s copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) is a well-known reaction known for its ability to quickly, efficiently, and consistently produce a wide range of five-membered heterocycles \u003csup\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e,\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e,\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e\u003c/sup\u003e. Nevertheless, the traditional conditions of the Huisgen reaction demand high temperatures, and extended reaction times, resulting in a blend of 1,4- and 1,5-triazole isomers. (Fig.\u0026nbsp;1)\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eFollowing up on our earlier research in this area, we created a new, highly efficient bio-based catalyst and tested how well it works in a click reaction. The chitosan-shilajit@Cu catalyst was synthesized through a simple, cost-effective approach and successfully applied in click reaction. The reaction yielded products rapidly and in high quantities. The removed catalyst was successfully recycled and reused for four additional cycles with high efficiency.\u003c/p\u003e"},{"header":"2. Experimental","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003e2.1. Materials and instruments:\u003c/h2\u003e \u003cp\u003eAll the reactants such as copper iodide, sodium acetate, acetic acid (Merck Germany), phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, dimethyl sulfoxide (DMSO), 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC), sodium hydroxide, n-Hydroxy succinimide (NHS), phenylacetylene, benzyl bromide, sodium azide, 1-phenyl, 2-propene, 1-ol were purchased from Merck Chemical Company. Chitosan with 75\u0026ndash;85% deacetylation was purchased from Sigma Aldrich. Shilajit was acquired from the grocery store.\u003c/p\u003e \u003cp\u003eThe melting points were used to confirm the identity of the products. The melting points were measured with the Electrothermal 9100 instrument. Infrared (IR) spectra were recorded on a Bruker VERTEX 70 model spectrometer with spectroscopic grade KBr. Scanning electron microscopy (SEM) was performed via a VEG2/TESCAN 30kv with gold coating, and energy dispersive X-ray spectroscopy (EDX) was recorded on a VEG//TESCAN-XMU. We indicated the X-ray diffraction (XRD) of the catalyst with a Rigaku-Dmax 2500 diffractometer with nickel-filtered Cu Kα radiation (\u003cem\u003eλ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;1.5418 \u0026Aring;, 40 kV)\u003c/p\u003e \u003cdiv id=\"Sec4\" class=\"Section3\"\u003e \u003ch2\u003e2.1.1. Preparation of chitosan-shilajit (Cs-Sh) composite\u003c/h2\u003e \u003cp\u003eFirstly, 1-ethyl-3-(3-dimethyl aminopropyl) carbodiimide (EDC) with shilajit, dimethylsulfoxide (DMSO) and N-hydroxy succinimide (NHS) were poured into a round bottom flask, and stirred at room temperature for one hour until the components mixed well. Then, the mixture was added to a 1% solution of chitosan in buffer acetate (pH\u0026thinsp;=\u0026thinsp;4.7). The mixture was vigorously stirred in the dark under an argon atmosphere for 16 hrs. After that, the pH was set to 9 by adding 1M NaOH. The final product was dialyzed against buffer phosphate (pH\u0026thinsp;=\u0026thinsp;7.4) and distilled water for another 3 days. At last, the brown viscous product was poured into a Petri dish and freeze-dried. The scheme of the steps is shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e2\u003c/span\u003e.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec5\" class=\"Section3\"\u003e \u003ch2\u003e2.1.2. Immobilization of copper\u003c/h2\u003e \u003cp\u003eFor incorporating Cu on the prepared Cs-Sh, \u003cem\u003e0.09\u003c/em\u003e gr of CuI was completely dissolved in \u003cem\u003e1\u003c/em\u003e mL of acetonitrile in an ultrasonic bath. Then \u003cem\u003e0.03\u003c/em\u003e gr of Cs-Sh was added to the CuI yellow solution and subjected to an argon atmosphere for 6 hours at reflux temperature. The precipitate was rinsed with acetonitrile and acetone and vacuum-dried at 60\u0026deg;C overnight.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec6\" class=\"Section3\"\u003e \u003ch2\u003e2.1.3. General procedure for preparation of triazole derivatives\u003c/h2\u003e \u003cp\u003eA blend of phenylacetylene derivatives (\u003cem\u003e1.2\u003c/em\u003e mmol), benzyl halide (\u003cem\u003e1.0\u003c/em\u003e mmol), and NaN\u003csub\u003e3\u003c/sub\u003e (\u003cem\u003e1.2\u003c/em\u003e mmol) in water (\u003cem\u003e3\u003c/em\u003e ml) was sonicated for an adequate time. The reaction progress was monitored using thin-layer chromatography. When the reaction was finished, we filtered the catalyst and removed the solvent. An ethanol/water solution can be used to further purify the product.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003c/div\u003e"},{"header":"3. Results and discussion","content":"\u003cp\u003eThe FT-IR spectra of the CS-Sh@Cu, Cs-Sh, and Shilajit are investigated in Figure \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e (see supporting information). The FT-IR spectrum of shilajit indicates characteristics peaks at \u003cem\u003e3316\u003c/em\u003e cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and \u003cem\u003e1624\u003c/em\u003e cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e attributed to OH stretching vibration and C\u0026thinsp;=\u0026thinsp;O vibrational groups respectively. The peak at \u003cem\u003e1091\u003c/em\u003e cm\u003csup\u003e\u0026minus;\u0026thinsp;1 is\u003c/sup\u003e related to C-O vibration which indicates the presence of polysaccharide. The incorporation of chitosan and shilajit was also determined by the FTIR spectrum. According to the literature \u003csup\u003e\u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e,\u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e35\u003c/span\u003e\u003c/sup\u003e, the peak observed at \u003cem\u003e3378\u003c/em\u003e\u0026ndash;\u003cem\u003e3680\u003c/em\u003e cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e showed the stretching vibration of the N-H amide group of the second type, and since the intensity of the peak is reduced, it can be evidence of the formation of chitosan and shilajit combination. The peak that appeared at \u003cem\u003e1655\u003c/em\u003e\u0026thinsp;\u0026minus;\u0026thinsp;\u003cem\u003e1626\u003c/em\u003e cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e can also be related to the C\u0026thinsp;=\u0026thinsp;O group formed through the combination of chitosan and shilajit \u003csup\u003e\u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e36\u003c/span\u003e,\u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e37\u003c/span\u003e\u003c/sup\u003e. By comparing the above spectrum and the corresponding spectrum of the final catalyst, it can be concluded that the corresponding peaks at low frequencies of \u003cem\u003e563\u003c/em\u003e Cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e are related to the presence of copper \u003csup\u003e\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e\u003c/sup\u003e (Figure \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eEDS analysis confirms the presence of carbon, oxygen, nitrogen, and copper in the final composition of the catalyst with ratios of \u003cem\u003e35.64: 52.99: 7.30: 4.08\u003c/em\u003e wt%, respectively. It can also confirm that the copper immobilization was performed successfully (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e3\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eMoreover, the copper concentration was determined by inductively coupled plasma optical emission spectrometry (ICP-OES). ICP analysis revealed a decrease in metal loading upon catalyst reuse, dropping from \u003cem\u003e1.6\u003c/em\u003e wt% in the fresh catalyst to \u003cem\u003e1.1\u003c/em\u003e wt% after reuse. This reduction could be attributed to metal leaching during the reaction, partial loss of active sites, or structural modifications affecting metal retention. These findings highlight the necessity of further investigation into the stability and recyclability of the catalyst.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe XRD profile in the 2θ range of (\u003cem\u003e5\u003c/em\u003e to \u003cem\u003e80\u003c/em\u003e\u0026deg;) was measured. The wide peaks with some sharp peaks at 2θ\u0026thinsp;=\u0026thinsp;\u003cem\u003e28.33, and 46.54\u003c/em\u003e are attributed to shilajit, implying its non-crystalline nature\u003csup\u003e\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e\u003c/sup\u003e. The peaks at 2θ\u0026thinsp;=\u0026thinsp;\u003cem\u003e25.997, 41.024, 50.221\u003c/em\u003e corresponded to the (111), (220), and (311) reflection crystal plans of CuI respectively\u003csup\u003e\u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e38\u003c/span\u003e\u003c/sup\u003e (JCPDS card no. 01-075-0832). The defining peak at about 2θ\u0026thinsp;=\u0026thinsp;\u003cem\u003e20\u0026ordm;\u003c/em\u003e linked to the chitosan\u0026rsquo;s mild crystalline structure \u003csup\u003e\u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e39\u003c/span\u003e\u003c/sup\u003e. (Figure S2-a (see supporting information))\u003c/p\u003e \u003cp\u003eThe amount of weight change of Cs-Sh@Cu catalyst was measured as a function of temperature (from \u003cem\u003e50\u003c/em\u003e\u0026deg;C to \u003cem\u003e700\u003c/em\u003e\u0026deg;C) in the argon atmosphere using Thermal Gravimetric Analysis (TGA) shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e4\u003c/span\u003e. The results revealed a weight loss of \u003cem\u003e28\u003c/em\u003e% equal to ~\u0026thinsp;\u003cem\u003e1\u003c/em\u003e mg. The initial weight gain observed before reaching a temperature of 100\u0026deg;C can be attributed to the buoyancy effect, where the sample absorbs moisture or gases from the surrounding environment, causing an apparent increase in weight. This phenomenon occurs because the displaced air exerts an upward buoyant force on the sample, leading to an overestimation of its weight during measurements. This is a common occurrence in thermogravimetric analysis (TGA)t\u003csup\u003e\u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e40\u003c/span\u003e\u003c/sup\u003e. In the following, the loss of weight near \u003cem\u003e100\u0026deg;C\u003c/em\u003e relates to the physically adsorbed moisture or organic solvents on the surface of the catalyst. The mass decrease around ~\u0026thinsp;\u003cem\u003e300\u0026deg;C\u003c/em\u003e is attributed to thermal decomposition of chitosan \u003csup\u003e\u003cspan citationid=\"CR41\" class=\"CitationRef\"\u003e41\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eIn SEM scanning electron images shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e5\u003c/span\u003e, the copper particles are almost uniformly dispersed on the substrate. At a magnification of \u003cem\u003e200\u003c/em\u003e nm, both the substrate and the nanoparticles can be seen.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eTo calculate the surface area and pore diameter of the prepared catalyst, the Brunauer\u0026ndash;Emmett\u0026ndash;Teller (BET) method was utilized. According to the results demonstrated in Figure S3 (See supporting information), the adsorption-desorption isotherm displays an IV isotherm with the H3 hysteresis loop type which is typically observed in mesoporous materials. Moreover, the surface area is 4.14 m\u003csup\u003e2\u003c/sup\u003e/g for Cs-Sh@Cu catalyst.\u003c/p\u003e"},{"header":"4. Evaluation of the catalytic activity of Cs-Sh@Cu in the synthesis of 1,2,3-triazole derivatives","content":"\u003cp\u003eThe efficiency of Cs-Sh@Cu was evaluated in the preparation of derivatives based on triazole under different situations. Several parameters such as catalyst dosage, solvent type, duration, and temperature conditions were examined using a model three-component reaction involving phenylacetylene, benzyl bromide, and sodium azide shown in Table \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e (see supporting information). As is obvious, the best results were obtained in the presence of water and under ultrasonic irradiation. It should be noted that ultrasonic irradiation enhances reaction efficiency by generating localized high temperatures and pressures through acoustic cavitation. This phenomenon accelerates reaction rates, improves mass transfer, and facilitates catalyst activation, leading to higher yields and shorter reaction times. Additionally, ultrasound promotes cleaner reactions by reducing the need for harsh conditions, making it an environmentally friendly approach in green chemistry. Additionally, under sonication, the presence of hydrogen radicals (H•) acts as an in situ reducing agent, promoting the reduction of Cu(II) to the active Cu(I) species. This dual role of ultrasound enhancing reaction conditions and facilitating catalyst activation further improves the process's efficiency and environmental friendliness. Importantly, this approach eliminates the need for additional reducing agents, making the overall system more environmentally benign.\u003csup\u003e\u003cspan citationid=\"CR42\" class=\"CitationRef\"\u003e42\u003c/span\u003e,\u003cspan citationid=\"CR43\" class=\"CitationRef\"\u003e43\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e \u003cp\u003eThe catalyst dosage is another important factor that can affect the reaction rate and yield due to the increment of the active sites. Table \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e shows that the increase in catalyst dosage was not favorable and with a 10 mg catalyst loading, a \u003cem\u003e93\u003c/em\u003e% conversion was obtained.\u003c/p\u003e \u003cp\u003eFurther optimization was carried out to find the synergetic effect of the catalyst components. The results were tabulated in Table S2(see supporting information). As it was predictable, the reaction did not occur without copper.\u003c/p\u003e \u003cp\u003eGeneralizing the optimum conditions was carried out using a one-pot reaction involving acetylene derivatives, sodium azide, and benzyl halide derivatives to prepare different 1,2,3-triazoles by using Cs-Sh@Cu and the results are presented in Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e. As expected, the reaction rate and yield increased in the presence of electron-withdrawing groups, whereas both parameters declined with electron-donating groups.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\n\u003ch2\u003e4.1. Hot filtration\u003c/h2\u003e\n\u003cp\u003eThe hot filtration test was conducted under the optimized reaction conditions to assess the heterogeneity of the Cs-Sh@Cu catalyst in the synthesis of 1,2,3-triazole derivatives. After 15 minutes of reaction, the mixture was hot-filtered to remove the catalyst, and the reaction continued without the catalyst in the filtrate. The progress of the reaction was monitored, and negligible product formation after catalyst removal indicated that no active copper species leached into the solution. These results strongly suggest that the catalytic activity primarily stems from the heterogeneous Cs-Sh@Cu catalyst and that the leaching of active metal into the reaction medium is minimal. Therefore, the catalyst can be considered truly heterogeneous, which is beneficial for catalyst recyclability and the environment sustainability.\u003c/p\u003e\n\u003cp\u003e\u003c/p\u003e\n\u003cdiv id=\"Sec10\" class=\"Section2\"\u003e\n \u003ch2\u003e4.2. Catalyst recyclability\u003c/h2\u003e\n \u003cp\u003eHeterogeneous catalysts should be investigated from the recyclability point of view. After the modal reaction was complete, the used Cs-Sh@Cu catalyst was gathered and rinsed with ethanol and water to eliminate impurities and unreacted compounds. The dried catalyst was successfully reused for four reaction cycles, with negligible loss in yield or performance, as shown in Fig. \u003cspan class=\"InternalRef\"\u003e6\u003c/span\u003e.\u003c/p\u003e\n \u003cp\u003eMoreover, FT-IR analysis and the XRD pattern of the reused catalyst (Figure \u003cspan class=\"InternalRef\"\u003eS1\u003c/span\u003e and S2-b, see supporting information) further confirm that the catalyst retained its structural integrity after multiple cycles of use.\u003c/p\u003e\n \u003cp\u003eTo evaluate the catalyst’s efficiency, the produced Cs-Sh@Cu was compared with reported catalysts, additionally the results are summarized in Table \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003e. The synthesized catalyst exhibits several advantages, making it a promising candidate for further applications.\u003c/p\u003e\u003ctable id=\"Tab2\" border=\"1\"\u003e\u003ccaption language=\"En\"\u003e\n \u003cdiv class=\"CaptionNumber\"\u003eTable 2\u003c/div\u003e\n \u003cdiv class=\"CaptionContent\"\u003e\n \u003cp\u003eA comparison of performance of Cs-Sh@Cu with catalysts reported in previous studies.\u003c/p\u003e\n \u003c/div\u003e\n \u003c/caption\u003e\u003cthead\u003e\u003ctr\u003e\u003cth align=\"left\"\u003e\n \u003cp\u003eEntry\u003c/p\u003e\n \u003c/th\u003e\u003cth align=\"left\"\u003e\n \u003cp\u003eCatalyst\u003c/p\u003e\n \u003c/th\u003e\u003cth align=\"left\"\u003e\n \u003cp\u003eConditions\u003c/p\u003e\n \u003c/th\u003e\u003cth align=\"left\"\u003e\n \u003cp\u003eYield (%)\u003c/p\u003e\n \u003c/th\u003e\u003cth align=\"left\"\u003e\n \u003cp\u003eReferences\u003c/p\u003e\n \u003c/th\u003e\u003c/tr\u003e\u003c/thead\u003e\u003ctbody\u003e\u003ctr\u003e\u003ctd align=\"left\"\u003e\n \u003cp\u003e1\u003c/p\u003e\n \u003c/td\u003e\u003ctd align=\"left\"\u003e\n \u003cp\u003eCu(I)-AMPS\u003c/p\u003e\n \u003c/td\u003e\u003ctd align=\"left\"\u003e\n \u003cp\u003eWater/R.T/60 min\u003c/p\u003e\n \u003c/td\u003e\u003ctd align=\"left\"\u003e\n \u003cp\u003e82%\u003c/p\u003e\n \u003c/td\u003e\u003ctd align=\"left\"\u003e\n \u003cp\u003e\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e39\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\"\u003e\n \u003cp\u003e2\u003c/p\u003e\n \u003c/td\u003e\u003ctd align=\"left\"\u003e\n \u003cp\u003eCu@KIT-5\u003c/p\u003e\n \u003c/td\u003e\u003ctd align=\"left\"\u003e\n \u003cp\u003eWater/20min/\u003c/p\u003e\n \u003c/td\u003e\u003ctd align=\"left\"\u003e\n \u003cp\u003e85%\u003c/p\u003e\n \u003c/td\u003e\u003ctd align=\"left\"\u003e\n \u003cp\u003e\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e51\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\"\u003e\n \u003cp\u003e3\u003c/p\u003e\n \u003c/td\u003e\u003ctd align=\"left\"\u003e\n \u003cp\u003eCu@SMI\u003c/p\u003e\n \u003c/td\u003e\u003ctd align=\"left\"\u003e\n \u003cp\u003eWater/reflux/20 min\u003c/p\u003e\n \u003c/td\u003e\u003ctd align=\"left\"\u003e\n \u003cp\u003e90%\u003c/p\u003e\n \u003c/td\u003e\u003ctd align=\"left\"\u003e\n \u003cp\u003e\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e52\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\"\u003e\n \u003cp\u003e4\u003c/p\u003e\n \u003c/td\u003e\u003ctd align=\"left\"\u003e\n \u003cp\u003eCuFe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@SiO\u003csub\u003e2\u003c/sub\u003e@l-arginine@Cu(I)\u003c/p\u003e\n \u003c/td\u003e\u003ctd align=\"left\"\u003e\n \u003cp\u003eEtOH: Water/60°C/35 min\u003c/p\u003e\n \u003c/td\u003e\u003ctd align=\"left\"\u003e\n \u003cp\u003e89%\u003c/p\u003e\n \u003c/td\u003e\u003ctd align=\"left\"\u003e\n \u003cp\u003e\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e53\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\"\u003e\n \u003cp\u003e5\u003c/p\u003e\n \u003c/td\u003e\u003ctd align=\"left\"\u003e\n \u003cp\u003eAg@Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e-Arg-CG\u003c/p\u003e\n \u003c/td\u003e\u003ctd align=\"left\"\u003e\n \u003cp\u003eWater/50°C/35 min\u003c/p\u003e\n \u003c/td\u003e\u003ctd align=\"left\"\u003e\n \u003cp\u003e90%\u003c/p\u003e\n \u003c/td\u003e\u003ctd align=\"left\"\u003e\n \u003cp\u003e\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e54\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\"\u003e\n \u003cp\u003e6\u003c/p\u003e\n \u003c/td\u003e\u003ctd align=\"left\"\u003e\n \u003cp\u003eCs-Sh@Cu\u003c/p\u003e\n \u003c/td\u003e\u003ctd align=\"left\"\u003e\n \u003cp\u003eWater/ultrasonic/25min\u003c/p\u003e\n \u003c/td\u003e\u003ctd align=\"left\"\u003e\n \u003cp\u003e93%\u003c/p\u003e\n \u003c/td\u003e\u003ctd align=\"left\"\u003e\n \u003cp\u003eThis work\u003c/p\u003e\n \u003c/td\u003e\u003c/tr\u003e\u003c/tbody\u003e\u003c/table\u003e\n \u003cp\u003e\u003c/p\u003e\n \n \n\u003c/div\u003e"},{"header":"Conclusion","content":"\u003cp\u003eIn a nutshell, a new bio-based catalyst was created by immobilizing copper onto chitosan-shilajit. Various analytical techniques were used to characterize the catalyst, confirming its successful preparation. The catalyst demonstrated its catalytic efficiency in producing 1,2,3-triazole derivatives using a one-pot, three-component reaction involving sodium azide, acetylene, and benzyl halide derivatives under ultrasonic irradiation in water, a sustainable solvent. The reaction was efficiently mediated by ultrasonic irradiation, demonstrating its effectiveness in promoting the reaction. The heterogeneity of the catalyst was verified via a hot filtration analysis. Its benefits, such as recyclability, high yield, short reaction time, and ease of production, position it as a promising option for future applications in other synthetic pathways. Our results illustrate an improved version of ultrasonic click chemistry to produce 1,2,3-triazoles at low temperatures.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eConflicts\u0026nbsp;of interest\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThere are no conflicts to declare.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eData Availability\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eData is provided within the manuscript or supplementary information files.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eFunding\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eNo funding to declare\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eKolewe, K. W., Peyton, S. R. \u0026amp; Schiffman, J. D. 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Ag nanoparticles on arginine-cyanoguanidine functionalized magnetic g-C3N4: A catalyst for nitroaromatic hydrogenation and regioselective click reactions. \u003cem\u003eHeliyon\u003c/em\u003e \u003cstrong\u003e10\u003c/strong\u003e (2024).\u003c/li\u003e\n\u003c/ol\u003e"},{"header":"Table 1","content":"\u003cp\u003eTable 1 is 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":"Click Reaction, Sonochemistry, Polysaccharide, 1,2,3-Triazole, Biopolymer, Chitosan","lastPublishedDoi":"10.21203/rs.3.rs-6868863/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-6868863/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"The advent of click chemistry has significantly accelerated the synthesis of 1,2,3-triazoles, key structures found in numerous biologically active and pharmaceutical compounds. Click reactions can be notably enhanced by employing ultrasonic irradiation and supported catalysts. In this study, we report the development of an eco-friendly catalyst based on natural biopolymers, chitosan and shilajit, designed to facilitate an improved click chemistry protocol under ultrasonic conditions at room temperature. The catalyst was thoroughly characterized using Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), energy-dispersive X-ray spectroscopy (EDX), and scanning electron microscopy (SEM). The results confirm the successful immobilization of copper species onto the polymer supports. This method offers several advantages, including the use of water as a green solvent, elimination of reducing agents, high catalytic efficiency, short reaction times, cost-effectiveness, and excellent catalyst recyclability.","manuscriptTitle":"Ultrasound-Assisted Green Synthesis of 1,4-Disubstituted 1,2,3-Triazoles Using Natural Polymer Supports","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-06-19 13:50:10","doi":"10.21203/rs.3.rs-6868863/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2025-06-24T06:31:28+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-06-23T12:55:40+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-06-18T11:44:03+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"243043718912328533991162267536130250425","date":"2025-06-18T11:16:28+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"138720807346842439288015965927160996956","date":"2025-06-17T17:15:15+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2025-06-17T16:51:57+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2025-06-12T09:01:19+00:00","index":"","fulltext":""},{"type":"editorInvited","content":"","date":"2025-06-12T08:34:37+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2025-06-11T08:52:04+00:00","index":"","fulltext":""},{"type":"submitted","content":"Scientific Reports","date":"2025-06-11T07:09:03+00:00","index":"","fulltext":""}],"status":"published","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}}],"origin":"","ownerIdentity":"d5e3a579-c5eb-4372-84a1-9922cfda2dcc","owner":[],"postedDate":"June 19th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[{"id":50240753,"name":"Physical sciences/Chemistry"},{"id":50240754,"name":"Physical sciences/Nanoscience and technology"}],"tags":[],"updatedAt":"2025-08-11T16:09:27+00:00","versionOfRecord":{"articleIdentity":"rs-6868863","link":"https://doi.org/10.1038/s41598-025-13114-z","journal":{"identity":"scientific-reports","isVorOnly":false,"title":"Scientific Reports"},"publishedOn":"2025-08-05 15:58:03","publishedOnDateReadable":"August 5th, 2025"},"versionCreatedAt":"2025-06-19 13:50:10","video":"","vorDoi":"10.1038/s41598-025-13114-z","vorDoiUrl":"https://doi.org/10.1038/s41598-025-13114-z","workflowStages":[]},"version":"v1","identity":"rs-6868863","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-6868863","identity":"rs-6868863","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}