A biocompatible chitosan-ionic liquid hybrid catalyst for regioselective synthesis of 1,2,3-triazols

International Journal of Biological Macromolecules 140 (2019) 939–948

Contents lists available at ScienceDirect

International Journal of Biological Macromolecules journal homepage: http://www.elsevier.com/locate/ijbiomac

A biocompatible chitosan-ionic liquid hybrid catalyst for regioselective synthesis of 1,2,3-triazols Mansoureh Daraie, Majid M. Heravi ⁎ Department of Chemistry, School of Science, Alzahra University, PO Box 1993891176, Vanak, Tehran, Iran

a r t i c l e

i n f o

Article history: Received 2 June 2019 Received in revised form 15 August 2019 Accepted 18 August 2019 Available online 19 August 2019 Keywords: Biopolymer Cu (I) nanoparticles Chitosan SMA Ionic liquid Click reaction 1,2,3-Triazoles

a b s t r a c t A new type of quadruple hybrid system was prepared containing chitosan (CS), folic acid (FA), Poly(styrene-comaleic anhydride) [SMA] and ionic liquid (IL). This nanocatalyst was synthesized by the functionalization of SMA with folic acid and then polymerization with chitosan in the presence of DCC and NHS. CuI was immobilized onto this support to provide Cu@SMA-FA-CS-IL. The catalyst was fully characterized by using different characterization techniques such as FTIR, 1H NMR, ICP, SEM, EDX, TGA, and XRD. This Cu (I) heterogeneous species was successfully applied in the reaction of sodium azide, terminal alkynes, and alkyl halides or α-haloketones in water to afford 1,4-disubstituted-1,2,3-triazoles within relatively short reaction times. Moreover, the catalyst is recyclable for five reaction cycles with minor CuI leaching and slight drop of the catalytic activity. © 2019 Published by Elsevier B.V.

1. Introduction In recent decades, observance of “Green Chemistry concepts” has gained enormous attention. Green Chemistry proposes those synthetic methods that lead to the reduction or elimination of the hazardous substances [1]. Green polymer chemistry is developed along with the rules of green chemistry for the polymer science and engineering [2]. In recent times, biodegradable polymer and biomaterials have become worthy due to a wide range of their applications in different fields of gene delivery, cosmetics, optical, antimicrobial, and tissue engineering, and biotechnology [3–5]. Development of functional biomaterials led to the improved scaffolds and new polymeric systems [6–8]. Among them, chitosan based materials play an important role since chitosan (CS) is known as an eco-friendly, biocompatible and biodegradable compound [6]. It is obtained from deacetylation of chitin that is the second most abundant natural polymer found in the exoskeletons of crustaceans, insects, and in the cell walls of fungi. CS provides some of the most favorite properties such as good adsorption, non-toxicity, biocompatibility, and bio-degradability [7]. The presence of NH2 groups in the structure of CS provides much greater potential compared to that of chitin for using in different applications [8]. For instances, ⁎ Corresponding author. E-mail address: [email protected] (M.M. Heravi).

https://doi.org/10.1016/j.ijbiomac.2019.08.162 0141-8130/© 2019 Published by Elsevier B.V.

chitosan was extensively investigated in chemical synthesis [9,10], electrolyte-based fuel cells studies [11] and metal extraction [12,13]. Owing to the presence of both active hydroxyl and amino groups in the structure of CS, its surface can be modified with specific chemical compounds, such as various ligands or functional molecules [14–16]. Attractive CS-based composites have also been produced and widely employed in different applicable areas because of their improved thermal, mechanical or adsorption properties [17,18]. CS could be also easily functionalized with active targeting agents like folic acid (FA) via its amino groups improving the capability of the system for bonding to metal salts. Folic acid (FA) is a stable water soluble vitamin. A robust surface engineering approach is described using FA–CS conjugates for the surface modification of nanocatalyst [19,20]. FA is an inexpensive compound with active chemical sites such as acid and amine, which is capable to make chemical bonds with different types of molecules and nanoparticles, thus it is widely employed as a ligand [21]. Worthy to mention that FA can be easily subjected to the self-condensation and self-assemblage (Scheme 1). The commercially available copolymer Poly(styrene-co-maleic anhydride) [SMA] contains reactive anhydride groups, which can be treated with various nucleophiles, providing a reactive support for the preparation of effective catalysts [22,23]. Najera et al. [24] treated SMA with di(2-pyridyl)methylamine to obtain a support for palladiumbased catalyst, although employing of this polymer as catalyst was essentially overlooked [25].

940

M. Daraie, M.M. Heravi / International Journal of Biological Macromolecules 140 (2019) 939–948

was 10 °C min−1. X-ray diffraction pattern of Cu@CS-Fa-SMA-IL was obtained by using a Powder X-Ray Diffractometer Bruker AXS-D8 Advance. 2.2. Synthesis of SMA-FA

Scheme 1. Folic acid structure

SMA-FA was synthesized in two steps according to the procedure previously reported by Lee et al. [42]. In a 100 ml glass reactor a suspension of SMA (2.00 g) in dry DMF (15 ml) and Folic acid (3.54 g, 8 mmol) was heated at 35 °C for 3 h under N2 atmosphere. After that, triethylamine (0.6 ml), acetic anhydride (1.2 ml) and sodium acetate (0.66 g), were added into the reactor. The temperature was raised to 80 °C, and then the mixture was heated at 80 °C for 7 h. The reaction mixture was then cooled and poured drop wise into vigorously stirring methanol (300 ml). The fiber-like precipitated polymer was collected by filtration, washed with methanol, and dried at 70 °C. 2.3. Synthesis of SMA-FA-CS

The FA molecule is composed of a pterin moiety with active NH2 group, which can bind to the anhydride group of SMA. The glutamic acid moiety is considered to be the key in the polymerization with chitosan. So, folic acid was trapped between to polymer (SMA and Chitosan) and these prevents from self-condensation of folic acid. During recent years, ionic liquids (ILs) have attracted attention of synthesis designers due to their application as catalysts and solvents [26]. ILs provide unique properties involving brilliant conductivity, high thermal and chemical stability, and small vapor pressure [27]. Currently, heterogenized ILs by incorporating ILs onto a heterogeneous support have become a hot research area because of the broad advantages including low cost, easy recyclability, operational simplicity, and recovery [28]. Hence, nano-solid supports show more benefits than the conventional supports since they represent higher ILs loading capacity, higher activity and selectivity, and good dispersion [29–32]. Remarkably, the use of Cu (I) as catalyst has quickly increased in organic syntheses, owing to its low cost, high selectivity and reactivity, availability, and some other properties [33,34]. Following our research on development of CS-based supports for immobilizing catalytic active species [35,36] and creating new types of heterogeneous catalysts [37–41], in this article, a novel quadruple hybrid system, a composition of CS, FA, SMA and IL, was prepared and used as support for immobilizing Cu (I) nanoparticles. 2. Experimental 2.1. Materials and instruments The catalyst was synthesized using the following chemicals: SMA [Poly(styrene-co-maleic anhydride)] with average Mn~1600 by GPC, Chitosan (CS) [medium molecular weight] With about 75–85% deacetylation, Folic acid (FA), DMF, TEA, toluene, MeOH, (3chloropropyl)trimethoxysilane, 1-methylimidazole and CuI. All purchased from Sigma-Aldrich and used without any purification. For the synthesis of triazole derivatives, terminal alkynes, sodium azide and α- haloketones or alkyl halides, were used. These compounds were obtained from Sigma -Aldrich on analytical grade. The progress of click reaction was monitored by TLC silica gel 60 F254, using ultraviolet light. To characterize Cu@CS-Fa-SMA-IL, NMR, SEM, EDX, XRD, TGA, FTIR, and ICP-AES were employed. FTIR spectra of each hybrid component of catalyst was recorded using KBr disks on FTIR spectrometer Bruker Tensor 27 in the 400–4000 cm−1 region. Scanning electron micrographs of the catalyst surface were performed by a TESCAN, VEGA 3 SEM instrument. Thermo gravimetric analyses (TGA) were carried out with a NETZSCH TG 209 F1 Iris thermo gravimetric analysis apparatus. This analysis was achieved under N2 atmosphere, in the temperature range of 35 to 750 °C, and the heating rate

The process of conjugation of folic acid to chitosan molecules is described as follows [43]: A solution of FA + SMA (1 g), DDC (0.5 g) and NHS (0.5 g) were dissolved in 3 ml of dimethylsulfoxide (DMSO) and stirred at room temperature until DDC and folic acid were welldissolved and mixed. Cs (200 mg) was then added into the reaction mixture and temperature was raised to 70 °C for 24 h. The NPs of CSFA-SMA were washed repeatedly and dried at 60 °C under a vacuum for 24 h. Folic acid-chitosan conjugates were formed at selected amino groups of chitosan to folic acid. 2.4. Synthesis of 1-methyl-3-(trimethoxysilylpropyl)imidazolium chloride 1-methyl-3-(trimethoxysilylpropyl)imidazolium chloride was synthesized by solvent-free reaction of N-methylimidazole (1 mol) and (3-chloropropyl)trimethoxysilane (1 mol) in reflux conditions at 95 °C overnight [44,45]. After the end of the reaction, the mixture was cooled to room temperature. The pure [pmim]Cl was obtained after washing with diethyl ether (3*10 ml) and dried at 40 °C. 2.5. Synthesis of SMA-FA-CS-IL In this step, SMA-FA-CS (2 g) was dispersed in dry toluene with ultrasonic irradiation for 30 min. Then, [pmim] ionic liquid (6 g) and a catalytic amount of Et3N (1 ml) was introduced and the obtained suspension stirred at room temperature for 36 h. At the end of the reaction, the resulting product was filtrated, washed three times with methanol and dried at 80 °C for 12 h. 2.6. Immobilization of CuI nanoparticles: synthesis of Cu@SMA-FA-CS-IL To immobilize CuI on the surface of SMA-FA-CS-IL, initially CuI (0.247 g) was dissolved in acetonitrile (2 ml) under ultrasonic irradiation to give a transparent pale yellow solution [25]. After that SMAFA-CS-IL (1 g) was added, and the mixture was magnetically stirred at reflux temperature for 6 h under a nitrogen atmosphere. After completion of the process, the precipitate was filtered off and washed with acetonitrile and dried under vacuum at 60 °C overnight (Scheme 2). 2.7. General procedure for the synthesis of 1,4-disubstituded 1,2,3-triazoles To a mixture of α-haloketone (1 mmol) or alkyl halide (1 mmol), sodium azide (1.2 mmol), and terminal alkyne (1 mmol) in water (15 ml), Cu@SMA-FA-CS-IL (0.01 g) as a catalyst was added and the resulting mixture was ultrasound at ambient temperature for an appropriate reaction time with power of 100 W. At the end of the reaction (monitored by TLC), the solid was filtered off and recrystallized in EtOH. Cu@SMA-

M. Daraie, M.M. Heravi / International Journal of Biological Macromolecules 140 (2019) 939–948

941

Scheme 2. The schematic route for the preparation of Cu@SMA-FA-CS-IL catalyst.

FA-CS can be recovered and reused with a simple washing up, at least in five consecutive runs without appreciable loss of activity (Scheme 3).

3. Result and discussion 3.1. Catalyst characterization Initially, the morphology of Cu@SMA-FA-CS-IL was studied using SEM. It can be seen in Fig. 1 that catalyst particles exhibited aggregated morphology.

The Cu@SMA-FA-CS-IL catalyst was also studied using EDX analysis (Fig. 2). The presence of Si signal in the EDX analysis indicates the presence of IL. Finally, the CuI signal shows the immobilization of CuI nanoparticles. The good treatment of the maleic anhydride groups in SMA with amine to give maleimide moieties was proved by FT-IR and 1 H NMR analyses. In the 1 H NMR spectrum (Fig. 3), the peaks of SMA-FA were similar to those obtained from SMA [25], while the estimated aromatic and aliphatic protons of the folate moieties were also observed, as follows: [1.10 (m, 2H), 1.53 (q, 2H), 1.82 (t, 2H), 2.10 (t, 1H), 2.32 (m, 2H), 2.75 (t,

942

M. Daraie, M.M. Heravi / International Journal of Biological Macromolecules 140 (2019) 939–948

Scheme 3. Synthesis of 1,4-disubstituted 1,2,3-triazoles.

Fig. 1. SEM images of Cu@SMA-FA-CS-IL.

2H), 4.00 (s, 1H, NH), 4.41 (s, 1H), 4.60 (s, 1H), 6.69 (2H, Ar-H), 6.98–7.31 (5H, Ar-H), 7.44 (2H, Ar-H)], 7.93 (s, 1H, NH), 8.49 (s, 1H, NH), 8.98 (s, 1H), 10.94 (s, 1H, OH)].

Fig. 4 displays the differences and similarities in the FT-IR pattern of SMA, SMA-FA, SMA-FA-CS and Cu@SMA-FA-CS-IL. As is clear, the absorption bands at 1871 and 1787 cm−1 belong to the

Fig. 2. EDX analysis of Cu@SMA-FA-CS-IL.

M. Daraie, M.M. Heravi / International Journal of Biological Macromolecules 140 (2019) 939–948

Fig. 3. 1H NMR analysis of SMA-FA.

Fig. 4. The FTIR spectra of SMA (a), SMA-FA (b), SMA-FA-CS (c), and Cu@SMA-FA-CS-IL (d).

Fig. 5. The TGA analysis of SMA-FA (S1), SMA-FA-CS (S2), and Cu@SMA-FA-CS-IL (S3).

943

944

M. Daraie, M.M. Heravi / International Journal of Biological Macromolecules 140 (2019) 939–948

Fig. 6. The XRD patterns of Cu@SMA-FA-CS-IL.

characteristic doublet of anhydride units. The formed imide band through the reaction of SMA with folic acid, is observed at 1689–1783 cm−1. The broadband at 3300–3500 is representative of hydroxyl groups that overlap with NH groups at 3251–3405 cm−1. The FT-IR spectrum of SMA-FA-CS demonstrates the characteristic absorption bands of CS-FA as reported in literature [47]. The characteristic bands observed at 1682, 1651, 1468, 1349, 1128, 1053, 874 cm−1. The absorption bands of Cu@SMA-FA-CS-IL are approximately similar to those observed in SMA-FA-CS spectrum, except that the removal of OH bands. Remarkably, the absorption bands of the C_N band of the imidazole ring (at 1651 cm −1 ) overlapped with that of CS (Fig. 4). To further characterize the Cu@SMA-FA-CS-IL, ICP-AES analysis was used in order to measure the Cu content. To prepare samples for analysis, the catalyst was digested in a concentrated solution of HCl and HNO3. After filtration, the ICP-AES analysis was performed. The Cu content was calculated to be 5.15 wt%. The thermal stability of SMA-FA, SMA-FA-CS and Cu@SMA-FACS-IL was investigated using TGA curves (Fig. 5). According to the literature [58], the two weight losses observed for SMA-FA at 120–205 °C can be due to the loss of H2O and the physical absorbed solvent. The second weight drop in thermogram, which was observed at the range of 270–350 °C (54.06%), can also be attributed to the thermal decomposition of organic groups. The thermogram of SMA-FA-CS is very similar to that of SMA-FA. The weight loss (4.92%) at temperatures below 200 °C can be due to the loss of adsorbed water. Thermal decomposition of the pendant groups of catalyst caused the other weight loss, in the range of 260–320 °C (57.86%). Cu@SMA-FA-CS-IL exhibited two weight losses: the first one, around 110 °C, is as a result of losing water and the second one, around 280–320 °C (49.94%), is due to the decomposition of the organic ligands. A comparison of the thermograms of SMA-FACS and Cu@SMA-FA-CS-IL showed that incorporation of CuI can alter the thermogram. To approve the structure the catalyst, its X-ray diffraction (XRD) pattern was compared with literature (Fig. 6). The XRD pattern of the prepared CuI nanoparticles is in agreement with the standard pattern.

According to the obtained reflection peaks in Fig. 6, it can be concluded that this is a cubic phase of CuI with space group F43 m. (JCPDS 82–2111). Moreover, the sharp peaks at 2θ = 25.557, 49.884 & 67.528 indicate a high crystallinity of CuI NPs. 3.2. Catalytic activity In the next step of this research, the catalytic activity of Cu@SMA-FACS-IL was investigated. For this aim, synthesis of 1,4-disubstituded 1,2,3-triazoles was selected as a model reaction. To design an ecofriendly method, ultrasonic-assisted reaction was chosen. Primarily, a model reaction of phenacylbromide, phenylacetylene and sodium azide was selected to optimize the catalyst amount, solvent, and the reaction condition. Next, to approve the efficiency of ultrasonic irradiation, this model reaction was accomplished under reflux condition accompany by stirring and the yield of product was compared with that obtained by ultrasonic irradiation. Satisfyingly, the ultrasonic

Table 1 Optimization of the reaction conditions. Entry Reaction condition

Temp. (°C)

Solvent US power

1 2 3 4 5 6

Stirrer reflux US US US US

r.t. 96 r.t. r.t. r.t. r.t.

H2O H2O H2O EtOH CH3CN H2O

– – 80 80 80 100

7 8 9

US US US

50 70 50

H2O H2O H2O

100 100 100

10

US

50

H2O

100

11

US

50

H2O

100

Catalyst amount

Time (min)

Yield (%)

0.01 0.01 0.01 0.01 0.01 0.01 (0.81 mol%) 0.01 0.01 0.005 (0.40 mol%) 0.02 (1.6 mol%) 0.04 (3.2 mol%)

60 35 17 20 20 10

85 80 89 87 85 97

12 12 20

91 89 87

18

89

12

94

M. Daraie, M.M. Heravi / International Journal of Biological Macromolecules 140 (2019) 939–948

945

Table 2 Synthesis of 1,2,3-triazole derivatives in the presence of Cu@SMA-FA-CS-IL.

Entry

M. P. Obs. 169–171

M. P. Rep

1

Yield (%) 97

170–171 [41]

120/719

2

14

92

158–160

157–159 [41]

113/487

3

11

94

109–110

108–110 [41]

116/633

4

12

94

115–118

116–118 [41]

116/580

5

15

92

188–190

189–190 [41]

113/454

6

12

96

125–128

126–128 [41]

118/592

7

15

91

148–150

147–149 [42]

112/449

8

15

90

104–107

104–106 [42]

111/444

9

17

92

144–146

143–146 [42]

113/401

10

10

94

126–128

125–128 [41]

116/696

11

12

92

145–148

147–1492 [42]

113/567

12

15

90

105–107

104–106 [42]

111/444

13

17

89

152–155

153–156 [42]

110/388

20

88

122–125

123–126 [41]

108/326

CH3I

Alkyne

TON/TOF (h−1)

Time (min) 10

14

Phenacyl bromide/alkylhalide

gained the product in higher yield and shorter reaction time compared to the conventional methods. According to the published theories [49,50], ultrasound irradiation leads to the formation, growing and collapse of the cavities in the reaction mixture. This is identified as cavitation effect. This phenomenon increases the local temperature and pressure through high energy. Consequently, the reaction variables, including the reaction temperature, the employed power of ultrasonic irradiation, the catalyst amount, and solvent, should be optimized. Water showed the most favorable results among other tested solvents, EtOH and CH3CN (Table 1, entries 1–5). Besides, the best results were found in the presence of 0.01 g of the catalyst. The ultrasonic power and reaction temperature were also optimized as 100 W and ambient temperature, respectively (Table 1). The generality of this condition was then investigated by employing different starting materials to produce various 1,2,3triazoles. The results approved that SMA-FA can catalyze the Click reaction of all applied substrates to give the corresponding 1,2,3-triazole compounds in high efficiencies within short reaction times. The results also demonstrated that α-haloketones may decrease slightly the yields and increase the reaction times compared to alkyl halides. All compounds are known and their physical data were compared with those of authentic samples and found to be identical [51,52] (Table 2). The efficiency of Cu@SMA-FA-CS-IL as catalyst in the Click reaction is compared with some previously reported catalysts. As the results shown in Table 3, it can be said that employing SMA-FA as

catalyst leads to higher or comparable efficiency of the favorable product within short reaction time. In addition, of the catalyst recyclability, aqueous media of the reaction mixture, and low reaction temperature makes this protocol as an eco-friendly methodology (Table 3). 3.3. Reaction mechanism Based on the previous reports [58], a plausible mechanistic pathway is suggested for the three-component click reaction catalyzed by Cu@

Table 3 The comparison of the catalytic activity of Cu@SMA-FA-CS-IL with previously reported catalysts. Entry

catalyst

1

Cu@SMA-FA-CS-IL

2 3 4 5 6 7 8

Cu@SMI Cu@KIT-5 Fe3O4@TiO2/Cu2O MNP@PILCu CuI-MMT Au-TiO2 GO-CO-NH-IA-Cu (I)

Solvent

Condition

Time (min)

Yield (%)

H2O

US

10

97

H2O H2O H2O H2O H2O H2O H2O/EtOH

Reflux Reflux Reflux 50 °C r.t. r.t. 90 °C

20 20 20 180 60 30 120

90 85 89 95 98 91 89

Ref. This work [53] [54] [52] [55] [56] [57] [39]

946

M. Daraie, M.M. Heravi / International Journal of Biological Macromolecules 140 (2019) 939–948

Scheme 4. Possible mechanism for click reaction

SMA-FA-CS-IL as shown in Scheme 4. Firstly, the azide ion is acted as a nucleophile group to add to benzyl halide. Simultaneously, the catalyst activates the terminal alkyne tolerating homocoupling reaction to gain

a diyne. Finally, the desired product 1,2,3-triazole is formed through CuI-catalyzed cycloaddition reaction (Scheme 4). 3.4. Catalyst recyclability

Fig. 7. Reusability of the Cu@SMA-FA-CS-IL.

Lastly, the recyclability and recoverability of Cu@SMA-FA-CS-IL was investigated. In this regard, the product yield in the model product was studied for 5 8cycles in the presence of fresh and recycled Cu@SMA-FA-CS-IL. The results were compared in Fig. 7 and it was found that Cu@SMA-FA-CS-IL can be recycled for eight reaction runs while its catalytic activity was not changed but slightly.The ICP-AES analysis was employed to prove the minor leaching of the copper species (Fig. 7). To investigate the heterogeneity of the catalyst, the leaching of CuI species after recycling was studied. ICP-AES analysis showed that after each recovery, copper leaching is negligible (0.05 wt%) . Next, to investigate the effect of recycling on the morphology of Cu@ SMA-FA-CS-IL, the recycled catalyst was characterized by using SEM image (Fig. 8). The SEM images of the recycled and fresh catalyst are similar and no significant agglomeration was observed. To further study, the FTIR spectrum of the recycled catalyst was recorded after five reaction runs and compared with the fresh Cu@ SMA-FA-CS-IL, Fig. 9. The comparison of two spectra indicates that the FTIR spectrum of the recycled catalyst exhibited the characteristic bands of the catalyst, indicating the stability of the catalyst after recycling. The EDX analysis indicates that the recycling of the catalyst did not induce any significant change in the structure (Fig. 10). 4. Conclusions

Fig. 8. SEM image of the recycled catalyst.

In summary, a new hybrid catalyst, Cu@SMA-FA-CS-IL, was designed and produced by treating functionalized SMA with ionic liquid-modified chitosan, followed by immobilizing the Cu (I) nanoparticles on its surface. The obtained Cu@SMA-FA-CS-IL catalyzed successfully the Click reactions of terminal alkyne, αhaloketone or alkyl halide, and sodium azide in water as solvent under mild reaction conditions to give 1,2,3-triazoles. Remarkably, the results of repeating the model reaction in the presence of recovered catalyst confirmed that Cu@SMA-FA-CS-IL is a completely recoverable catalyst with low leaching of CuI species onto the reaction solution. Moreover, the recycled catalyst characterization

M. Daraie, M.M. Heravi / International Journal of Biological Macromolecules 140 (2019) 939–948

947

Fig. 9. FT-IR spectra of (a) fresh Cu@SMA-FA-CS-IL and (b) after five uses.

Fig. 10. EDX analysis of the recycled catalyst.

proved the preservation of its morphology and structure upon recycling. Acknowledgments The authors are grateful to Alzahra University Research Council for partial financial support. Appendix A. Supplementary data Supplementary data to this article can be found online at https://doi. org/10.1016/j.ijbiomac.2019.08.162. References [1] D. Çelik, M. Yıldız, Investigation of hydrogen production methods in accordance with green chemistry principles, Int. J. Hydrog. Energy 42 (2017) 23395–23401. [2] I.T. Horváth, P.T. Anastas, Innovations and green chemistry, Chem. Rev. 107 (2007) 2169–2173. [3] R. Jayakumar, D. Menon, K. Manzoor, S.V. Nair, H. Tamura, Biomedical applications of chitin and chitosan based nanomaterials-a short review, Carbohyd. Polym. 82 (2010) 227–232. [4] R.A. Muzzarelli, F. Greco, A. Busilacchi, V. Sollazzo, A. Gigante, Chitosan, hyaluronan and chondroitin sulfate in tissue engineering for cartilage regeneration: a review, Carbohyd. Polym. 89 (2012) 723–739. [5] S. Kumar, J. Koh, Synthesis, physiochemical and optical properties of chitosan based dye containing naphthalimide group, Carbohyd. Polym. 94 (2013) 221–228.

[6] Y. Zhang, Y. Wang, B. Shi, X. Cheng, A platelet-derived growth factor releasing chitosan/coral composite scaffold for periodontal tissue engineering, Biomaterials 28 (2007) 1515–1522. [7] S. Kumar, M. Kumari, P.K. Dutta, J. Koh, Chitosan biopolymer Schiff Base: preparation, characterization, optical, and antibacterial activity, Int. J. Polym. Mat. Polym. Biomat. 63 (2014) 173–177. [8] A. Ayati, M.M. Heravi, M. Daraie, B. Tanhaei, F.F. Bamoharram, M. Sillanpaa, H3PMo12O40 immobilized chitosan/Fe3O4 as a novel efficient, green and recyclable nanocatalyst in the synthesis of pyrano-pyrazole derivatives, J. Iran. Chem. Soc. 13 (2016) 2301–2308. [9] J. Zhou, Z. Dong, H. Yang, Z. Shi, X. Zhou, R. Li, Pd immobilized on magnetic chitosan as a heterogeneous catalyst for acetalization and hydrogenation reactions, Appl. Surf. Sci. 279 (2013) 360–366. [10] P.K. Sahu, P.K. Sahu, S.K. Gupta, D.D. Agarwal, Chitosan: an efficient, reusable, and biodegradable catalyst for green synthesis of heterocycles, Ind. Eng. Chem. Res. 53 (2014) 2085–2091. [11] J. Ma, Y. Sahai, Chitosan biopolymer for fuel cell applications, Carbohyd. Polym. 92 (2013) 955–975. [12] V. Mohanasrinivasan, M. Mishra, S. Singh, E. Selvarajan, V. Suganthi, C.S. Devi, Studies on heavy metal removal efficiency and antibacterial activity of chitosan prepared from shrimp shell waste, Biotech 4 (2014) 167–175. [13] M.A. Barakat, New trends in removing heavy metals from industrial wastewater, Arab. J. Chem. 4 (2011) 361–377. [14] M. Lee, B.-Y. Chen, W. Den, Chitosan as a natural polymer for heterogeneous catalysts support: a short review on its applications, Appl. Sci. 5 (2015) 1272–1283. [15] E. Guibal, Heterogeneous catalysis on chitosan-based materials: a review, Prog. Polym. Sci. 30 (2005) 71–109. [16] K.R. Reddy, K. Rajgopal, C.U. Maheswari, M.L. Kantam, Chitosan hydrogel: a green and recyclable biopolymer catalyst for aldol and Knoevenagel reactions, New J. Chem. 30 (2006) 1549. [17] Á. Molnár, The use of chitosan-based metal catalysts in organic transformations, Coord. Chem. Rev. 388 (2019) 126–171.

948

M. Daraie, M.M. Heravi / International Journal of Biological Macromolecules 140 (2019) 939–948

[18] P.K. Sahu, P.K. Sahu, S.K. Gupta, D.D. Agarwal, Chitosan: an efficient, reusable, and biodegradable catalyst for green synthesis of heterocycles, Ind. Eng. Chem. Res. 53 (2014) 2085–2091. [19] N.J. Wald, J.K. Morris, C. Blakemore, Public health failure in the prevention of neural tube defects: time to abandon the tolerable upper intake level of folate, Public Health Rev. 39 (2018) 2. [20] L. Cai, R. Yu, X. Hao, X. Ding, Folate receptor-targeted bioflavonoid genistein-loaded chitosan nanoparticles for enhanced anticancer effect in cervical cancers, Nanoscale Res. Lett. 12 (2017) 509–516. [21] H.F. Li, L.D. Wang, S.Y. Qu, Phytoestrogen genistein decreases contractile response of aortic artery in vitro and arterial blood pressure in vivo, Acta Pharmacol. Sin. 25 (2004) 313–318. [22] R. Chinchilla, D.J. Dodsworth, C. Nájera, J.M. Soriano, Polymer-bound Nhydroxysuccinimide as a solid-supported additive for DCC-mediated peptide synthesis, Tetrahedron Lett. 42 (2001) 4487–4489. [23] R. Chinchilla, D.J. Dodsworth, C. Nájera, J.M. Soriano, 2,7-Di-tert-butyl-Fmoc-P-OSu: a new polymer-supported reagent for the protection of the amino group, Bioorg. Med. Chem. Lett. 12 (2002) 1817–1820. [24] J. Gil-Moltó, S. Karlström, C. Nájera, Di (2-pyridyl) methylamine–palladium dichloride complex covalently anchored to a styrene-maleic anhydride copolymer as recoverable catalyst for C–C cross-coupling reactions in water, Tetrahedron 61 (2005) 12168–12176. [25] E. Hashemi, Y.S. Beheshtiha, S. Ahmadi, M.M. Heravi, In situ prepared CuI nanoparticles on modified poly (styrene-co-maleic anhydride): an efficient and recyclable catalyst for the azide–alkyne click reaction in water, Trans. Met. Chem. 39 (2014) 593–601. [26] S.A. Forsyth, J.M. Pringle, D.R. MacFarlane, Ionic liquids: an overview, Aust. J. Chem. 57 (2004) 113–119. [27] S. Keskin, D. Kayrak-Talay, U. Akman, Ö. Hortaçsu, A review of ionic liquids towards supercritical fluid applications, J. Supercrit. Fluids 43 (2007) 150–180. [28] V.V. Singh, A.K. Nigam, A. Batra, M. Boopathi, B. Singh, R. Vijayaraghavan, Applications of ionic liquids in electrochemical sensors and biosensors, Int. J. Electrochem. 2012 (2012) 1–19. [29] I. Khan, K. Saeed, I. Khan, Nanoparticles: properties, applications and toxicities, Arab. J. Chem. (2017) https://doi.org/10.1016/j.arabjc.2017.05.011. [30] J. Jeevanandam, A. Barhoum, Y.S. Chan, A. Dufresne, M.K. Danquah, Review on nanoparticles and nanostructured materials: history, sources, toxicity and regulations, Beilstein J. Nanotechnol. 9 (2018) 1050–1074. [31] A. Maleki, R. Taheri-Ledari, M. Soroushnejad, Surface functionalization of magnetic nanoparticles via palladium-catalyzed Diels-Alder approach, Chem. Select 3 (2018) 13057–13062. [32] R. Firouzi-Haji, A. Maleki, L-Proline-functionalized Fe3O4 nanoparticles as an efficient nanomagnetic organocatalyst for highly stereoselective one-pot two-step tandem synthesis of substituted cyclopropanes, Chem. Select 4 (2019) 853–857. [33] D. Nainamalai, S. Palaniswamy, Copper-catalyzed oxidative coupling of arylboronic acids with aryl carboxylic acids: Cu3 (BTC) 2 MOF as a sustainable catalyst to access aryl esters, Org. Chem. Front. 5 (2018) 2322–2331. [34] M.B. Gawande, A. Goswami, F.X. Felpin, T. Asefa, X. Huang, R. Silva, R.S. Varma, Cu and cu-based nanoparticles: synthesis and applications in catalysis, Chem. Rev. 116 (2016) 3722–3811. [35] S. Sadjadi, M.M. Heravi, S.S. Kazemi, Ionic liquid decorated chitosan hybridized with clay: a novel support for immobilizing Pd nanoparticles, Carbohyd. Polym. 200 (2018) 183–190. [36] S. Sadjadi, M.M. Heravi, M. Raja, Composite of ionic liquid decorated cyclodextrin nanosponge, graphene oxide and chitosan: a novel catalyst support, Int. J. Biol. Macromol. 122 (2019) 228–237. [37] S. Sadjadi, M.M. Heravi, M. Daraie, A novel hybrid catalytic system based on immobilization of phosphomolybdic acid on ionic liquid decorated cyclodextrinnanosponges: efficient catalyst for the green synthesis of benzochromenopyrazole through cascade reaction: triply green, J. Mol. Liquids 231 (2017) 98–105. [38] S. Sadjadi, M.M. Heravi, M. Daraie, Cyclodextrin nanosponges: a potential catalyst and catalyst support for synthesis of xanthenes, Res. Chem. Intermed. 43 (2017) 843–857.

[39] M. Daraie, M.M. Heravi, S.S. Kazemi, Pd@GO/Fe3O4/PAA/DCA: a novel magnetic heterogeneous catalyst for promoting the Sonogashira cross-coupling reaction, J. Coord. Chem. (2019) https://doi.org/10.1080/00958972.2019.1640360. [40] M. Daraie, M.M. Heravi, M. Mirzaei, N. Lotfian, Synthesis of Pyrazolo-[4́,3́:5,6]pyrido [2,3-d]pyrimidine-diones catalyzed by a nano-sized surface-grafted neodymium complex of the Tungstosilicate via multicomponent reaction, Appl Organometal Chem. (2019) e5058. [41] M. Daraie, R. Mirsafaei, M.M. Heravi, Acid-functionalized mesoporous silicate (KIT5-Pr-SO3H) synthesized as an efficient and Nanocatalyst for green multicomponent, Curr. Org. Synth. 16 (2019) 145–153. [42] S.S. Lee, T.O. Ahn, Direct polymer reaction of poly (styrene-co-maleic anhydride): polymeric imidization, J. Appl. Poly. Sci. 71 (1999) 1187–1196. [43] S. Mansouri, Y. Cuie, F. Winnik, Q. Shi, P. Lavigne, M. Benderdour, J.C. Fernandes, Characterization of folate-chitosan-DNA nanoparticles for gene therapy, Biomaterials 27 (2006) 2060–2065. [44] J. Xiong, W. Zhu, W. Ding, L. Yang, Y. Chao, H. Li, H. Li, Phosphotungstic acid immobilized on ionic liquid-modified SBA-15: efficient hydrophobic heterogeneous catalyst for oxidative desulfurization in fuel, Ind. Eng. Chem. Res. 53 (2014) 19895–19904. [45] S. Sadjadi, M.M. Heravi, M. Malmir, Green bio-based synthesis of Fe2O3@ SiO2-IL/Ag hollow spheres and their catalytic utility for ultrasonic-assisted synthesis of propargylamines and benzo [b] furans, Appl. Organomet. Chem. 32 (2018), e4029. [47] P. Chanphai, V. Konka, H.A. Tajmir-Riahi, Folic acid–chitosan conjugation: a new drug delivery tool, J. Mol. Liquids 238 (2017) 155–159. [49] H. Naeimi, R. Shaabani, Ultrasound promoted facile one pot synthesis of triazole derivatives catalyzed by functionalized graphene oxide Cu (I) complex under mild conditions, Ultrason. Sonochem. 34 (2017) 246–254. [50] S. Sadjadi, M. Eskandari, Ultrasonic assisted synthesis of imidazo [1, 2-a] azine catalyzed by ZnO nanorods, Ultrason. Sonochem. 20 (2013) 640–643. [51] T. Hossiennejad, M. Daraie, M.M. Heravi, N.N. Tajoddin, Computational and experimental investigation of immobilization of CuI nanoparticles on 3-aminopyridine modified poly (styrene-co-maleic anhydride) and its catalytic application in regioselective synthesis of 1,2,3-Triazoles, J. Inorg. Organometal. Polym. Mat. 27 (2017) 861–870. [52] F. Nemati, M.M. Heravi, A. Elhampour, Magnetically nano-Fe3O4@TiO2/Cu2O coreshell composite: an efficient novel catalyst for the regio-selective synthesis of 1,2,3-triazoles: a click reaction, RSC Adv. 5 (2015) 45775–45784. [53] T. Baie Lashaki, H.A. Oskooie, T. Hosseinnejad, M.M. Heravi, CuI nanoparticles on modified poly (styrene-co-maleic anhydride) as an effective catalyst in regioselective synthesis of 1,2,3-triazoles via click reaction: a joint experimental and computational study, J. Coord. Chem. 70 (2017) 1815–1834. [54] R. Mirsafaei, M.M. Heravi, S. Ahmadi, M.H. Moslemin, T. Hosseinnejad, In situ prepared copper nanoparticles on modified KIT-5 as an efficient recyclable catalyst and its applications in click reactions in water, J. Mol. Catal. A Chem. 402 (2015) 100–108. [55] A. Pourjavadi, S.H. Hosseini, N. Zohreh, C. Bennett, Magnetic nanoparticles entrapped in the cross-linked poly (imidazole/imidazolium) immobilized Cu (II): an effective heterogeneous copper catalyst, RSC Adv. 4 (2014) 46418–46426. [56] M.E.M. Mekhzoum, H. Benzeid, A.E.K. Qaiss, E.M. Essassi, R. Bouhfid, Copper (I) confined in interlayer space of montmorillonite: a highly efficient and recyclable catalyst for click reaction, Catal. Lett. 146 (2016) 136–143. [57] M. Boominathan, N. Pugazhenthiran, M. Nagaraj, S. Muthusubramanian, S. Murugesan, N. Bhuvanesh, Nanoporous titania-supported gold nanoparticlecatalyzed green synthesis of 1,2,3-triazoles in aqueous medium, ACS Sustain. Chem. Eng. 1 (2013) 1405–1411. [58] P.V. Chavan, K.S. Pandit, U.V. Desai, M.A. Kulkarni, P.P. Wadgaonkar, Cellulose supported cuprous iodide nanoparticles (cell-CuI NPs): a new heterogeneous and recyclable catalyst for the one pot synthesis of 1, 4-disubstituted–1,2,3-triazoles in water, RSC Adv. 4 (2014) 42137–42146.