Collagen-Coated Superparamagnetic Iron Oxide Nanoparticles as a Sustainable Catalyst for Spirooxindole Synthesis

doi:10.21203/rs.3.rs-509159/v1

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Collagen-Coated Superparamagnetic Iron Oxide Nanoparticles as a Sustainable Catalyst for Spirooxindole Synthesis

https://doi.org/10.21203/rs.3.rs-509159/v1

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In this work, a novel magnetic organic-inorganic hybrid catalyst was fabricated by encapsulating [email protected] ([email protected]) nanoparticles with Isinglass protein collagen (IGPC) using epichlorohydrin (ECH) as crosslinking agent. Characterization studies of the prepared particles were accomplished by various analytical techniques specifically, Fourier transform infrared (FTIR) analysis, scanning electron microscopy (SEM), transmission electron microscopy (TEM), vibrating sample magnetometry (VSM), energy dispersive X-ray (EDX), X-ray diffraction (XRD), and Brunauer−Emmett−Teller (BET) analysis. The XRD results showed a crystalline and amorphous phase which contribute to magnetite and isinglass respectively. Moreover, the formation of the core/shell structure had been confirmed by TEM images. The synthesized [email protected]/ECH/IG was applied as bifunctional heterogeneous catalyst in the synthesis of spirooxindole derivatives demonstrating excellent catalytic properties, stability and recyclability.

Physical Chemistry

Catalysis

catalysis

nanoparticles

catalytic properties

Nowadays, the use of bifunctional catalysts has become a new field to promote chemical reactions in green, and environmentally friendly pathways and processes. In order to develop new approaches that are more respectful of the environment, catalyst development strategies are now oriented towards polymers of natural origin such as polysaccharides or proteins which come from renewable resources, often biocompatible and also more biodegradable than their synthetic counterparts. Bio-based heterogeneous catalysts, prepared from renewable natural polymers, have received significant attention in recent years due to their substantial advantages such as biodegradability, stability, and recyclability. The combination of nanoparticles and biodegradable polymers can result in nano-biocomposites, which have the potential for various catalytic and environmental applications^1-5.

Plentiful supports have been commonly used for the immobilization of natural polymers such as silica, resins, silica composites, and magnetic materials among others. Magnetic nanoparticles based on metals such as Cu, Co, Fe, and Ni provide a potent solid support system to immobilize proteins^6-10, among them, magnetite nanoparticles (Fe₃O₄) have remarkable properties such as superparamagnetism, low toxicity, high specific surface area, biocompatibility and easy separation which makes them more interesting for researchers.

One of the most commonly used techniques for the immobilization of proteins is cross-linking. For collagen materials, many crosslinkers such as glutaraldehyde, isocyanates, glyoxal, and carbodiimides, were used¹¹.

Natural polymers such as polysaccharides (cellulose, chitosan, chitin, alginate, carrageenan, lignin, fucoidan, etc.) and proteins have been used as catalysts in chemical transformations^12-18. Coating magnetic particles with natural polymers allows them to use their functional groups for promoting chemical reactions and also easy separation^19,20.

Based on our interest for turning agricultural and marine waste into value added materials, [^21-23] we have used Isinglass (IG), a natural polymer derived from swim bladder of fish with high content of collagen protein, for encapsulating Fe₃O₄@SiO₂ nanoparticles using epichlorohydrin (ECH) as crosslinking agent. The prepared hybrid material named Fe₃O₄@SiO₂/ECH/IG was applied as bifunctional heterogeneous catalyst in the synthesis of spirooxindole derivatives. Such hybrid material based on natural polymer IG with both acidic and basic groups has been shown to be a very effective catalyst in a variety of chemical transformation, including the synthesis of, triazoles²⁴, 4H-pyran derivatives²⁵, and Suzuki coupling²⁶. IG contains many amino acids whom their properties and catalytic performances have been demonstrated for many years^27,28.

Defined as processes allowing at least three reagents to react in a single pot, all of which participate in the structure of the final product, multicomponent reactions make it possible to synthesize highly functionalized compounds. In addition, multicomponent reactions offer rapid access to a wide variety of potential active ingredients. In the same way that a 4-digit code offers 10,000 possibilities, the possible variations for each reagent give access to an impressive number of related compounds. Very useful in combinatorial chemistry, MCRs make it possible to constitute chemical libraries for high throughput screening in the pharmaceutical industry. Several evocative tags are commonly involved in MCRs such as the atomic economy, easy to implement, using very mild reaction conditions, and without recourse to toxic metals, these reactions represent a definite step forward to ideal synthesis^{29, 30}.

Heterocyclic compounds represent more than 90% of the active ingredients possessing a wide range of applications in pharmaceutical industry, veterinary medicine and phytochemistry³¹. Indoles, oxindoles, and spirooxindoles are important heterocyclic compounds, and ubiquitous motifs in naturally and unnaturally occurring biologically active pharmaceutical ingredients²⁹^2, ^30,31⁴. Some biologically active indoles, oxindoles and spirooxindoles are presented in figure 1.

So far, various methods and catalysts have been used for the synthesis of these compounds, including the reaction between isatin, malononitrile and dimedone with different catalysts such as α-amylase³², CoFe₂O₄@SiO₂@SO₃H³³, [email protected]³⁴, magnetic sulfonated chitosan³⁵, magnetic poly ethyleneimine³⁶, etc.

Here, we have developed a new collagen-coated superparamagnetic iron oxide nanoparticle as a sustainable bio-based catalyst for the direct synthesis of spirooxindole (Figure 2).

Synthesis pathway of Fe₃O₄@SiO₂/ECH/IG is illustrated in figure 2. Fe₃O₄ NPs were prepared by co-precipitation method by dissolving divalent and trivalent iron salts into distilled water, followed by precipitation with NH₄OH Afterward, TEOS was hydrolyzed to form silica oligomers, which were coated on the surface of Fe₃O₄ nanoparticles to obtain Fe₃O₄@SiO₂ nanoparticles. Subsequently, ECH was cross-linked on the surface of Fe₃O₄/SiO₂. Fe₃O₄@SiO₂/ECH/IG was obtained by nucleophilic addition of IG to as-prepared magnetic nanoparticles. (figure 2)

Characterization of the Fe₃O₄@SiO₂/ECH/IG

After preparation of the nanocatalyst, its composition, structure, morphology and textural properties was properly characterized by different methods and techniques. The FT-IR spectra of the Fe₃O₄@SiO₂/ECH/IG, Fe₃O₄@SiO₂, and Fe₃O₄ are compared in Figure S1(see supporting information). The three curves show variation in the intensity of the bands in different regions. The FTIR spectrum of Fe₃O₄ indicates the characteristic band of Fe–O at 596 cm^-1. The peak identified at 3426 cm⁻¹ which was assigned to the O–H stretching vibrations was shifted from 3426 to 3276 cm^-1 in Fe₃O₄@SiO₂/ECH/IG with a net diminution of intensity indicating the involvement of isinglass in the synthesis of final composite. The characteristic bands appeared at 1400, 1385 and 1220 cm^-1 were attributed to C–O (carboxyl), C–OH (secondary) and C–O groups. Finally, this FT-IR spectrum can be clearly shown that the Fe₃O₄@SiO₂/ECH/IG was successfully prepared.

The morphology and the structure of the Fe₃O₄@SiO₂/ECH/IG was characterized by SEM and TEM analysis (figure 3a and b). The average particle size was estimated to be 58 nm. Moreover, the well-ordered structure of the catalyst and its almost uniform distribution are clearly observable (Fig. 3a). The core-shell structure of the magnetic particles was proofed with the black centres and the brightest areas as Fe₃O₄cores and SiO₂ shells respectively. These images also approve that the particles are nanometric in size (Fig. 3b).

Furthermore, the presence of carbon, oxygen, nitrogen, iron and Si elements were confirmed by energy dispersive X-ray (EDX) analysis which was showed in Figure 4a and b.

The magnetic features of Fe₃O₄, Fe₃O₄@SiO₂ and Fe₃O₄@SiO₂/ECH/IG were investigated using VSM analysis. Magnetic hysteresis loop measurements of Fe₃[email protected]₂/ECH/IG indicate that its saturation magnetization value (17.162 emus. g^-1) is less than Fe₃O₄ (63.9 emus. g^-1). This value demonstrated the incorporation of IG on the surface of Fe₃O₄ (Figure 5).

In addition, in XRD pattern (figure 6) the peaks in 35, 57, and 62 were assigned to the presence of Fe₃O₄ in structure. The broad peak at 10-20 attributed to the amorphous structure of isinglass. The patterns were compared in X’pert software and correspond with 00-001-1111, 00-002-0459 reference card numbers. (The individual reference card numbers were collected from the X'pert HighScore Plus version 1.0d software developed by the PANalytical B.V.)

According to the results of BET analysis shown in figure S2 (see supporting information), the special surface area 8.6115 m² g⁻¹ and the volume of P/P° is 0.298949197 cm³ g⁻¹. Also, the volume of the single-point adsorption cavity and the single-point cavity desorption volume is 0.051635 cm³/g and 0.045370 cm³/g respectively.

Investigation the catalytic activities of Fe₃O₄@SiO₂/ECH/IG for the synthesis of spirooxindole derivatives 4a-t

The catalytic behavior of Fe₃O₄@SiO₂/ECH/IG was investigated for the synthesis of spirooxindole derivatives via a three- component reaction between CH-acids, malononitrile, and isatin derivatives under different conditions. To find the optimal reaction conditions, various factors such as catalyst loading, solvent, time and reaction temperature were scrutinized in a model reaction including dimedone (1a), malononitrile (2a), and isatin (3a) to estimate the proper catalytic loading and time (figure 7). Amid different solvents, the mixture of EtOH/H₂O (1:1) was completed in a shorter time and gave a better yield (Table S1).

For further optimization, the effect of temperature, type of catalyst, and the amount of catalyst were also investigated and tabulated in Table S2 and S3 (See supporting information).

The results revealed the high performance of Fe₃O₄@SiO₂/ECH/IG due to synergistic effects and improved number of active sites on surface. The highest conversion of 94% was attained at a catalyst loading of 10 mg and reaction temperature 60 °C.

To generalize the optimum conditions, different spirooxindole derivatives from 4a-t were prepared through a one pot reaction of isatin derivatives 1, malononitrile 2 and 1,3 dicarbonyl derivatives 3a-3e in the presence of Fe₃O₄@SiO₂/ECH/IG. (figure 7). The results are summarized in table 1.

Table 1 Synthesis of spirooxindole derivatives in the presence of Fe₃O₄@SiO₂/ECH/IG

Entry	R₁	R₂	1,3-dicarbonyl compound	Time (min)	Yield (%)	m.p. °C (reported)	Product
1	H	H	3a	10	94	301-303 (302-306)⁴⁰	4a
2	H	H	3b	10	88	282-284 (278-280)⁴¹	4b
3	H	H	3c	20	81	267-268 (268-270)⁴¹	4c
4	H	H	3d	15	85	230-232 (240-241)³⁷²	4d
5	H	H	3e	25	80	301-303 (290-292)²¹	4e
6	H	NO₂	3a	10	89	>300 (302-304)³⁸³	4f
7	H	NO₂	3b	5	85	>300 (306-307)³⁹⁴	4g
8	H	NO₂	3c	5	93	286-288 (288-289)⁴⁰⁵	4h
9	H	NO₂	3d	10	98	240-242 (253-255)⁴¹⁶	4i
10	H	NO₂	3e	30	82	297-299 (294-296)⁴²⁷	4j
11	H	Cl	3c	20	70	234-236 (240-242)⁴³	4k
12	H	Cl	3e	30	79	>300 (300-302)⁴³	4l
13	Bn	H	3a	10	86	284-286 (281-282)⁴⁴	4m
14	Bn	H	3b	5	92	282-284 (282-284)⁴⁵	4n
15	Bn	H	3e	30	88	273-275 (280-282)⁴⁶	4o
16	Me	H	3a	10	80	260-262 (255-258)⁴⁷	4p
17	Me	H	3b	10	83	244-246 (243-245)⁴⁸	4q
18	Me	H	3c	35	94	279-281 (285-286)⁴⁹	4r
19	Me	H	3d	15	92	274-276 (280-282)⁵⁰	4s
20	Me	H	3e	30	83	281-283 (283-285)⁵¹	4t

*Reaction condition: Isatin 1 (1 mmol), 2 (1 mmol), 1,3-dicarbonyl 3 (1 mmol), 10 mg catalyst, and 3 ml solvent at 60 °C

Catalyst Recyclability

The easy separation of Fe₃O₄@SiO₂/ECH/IG heterogenious catalyst was mentioned further. In this regard, the recyclability of the nanocatalyst in the model reaction was investigated. At the end of the reaction, Fe₃O₄@SiO₂/ECH/IG was collected by an external magnetic field and washed with ethanol and water. The dried magnetic nanocatalyst was successively used for four times in the model reaction with a yield as 89%. According to the results displayed in Figure S3(see supporting information), there is no significant reduction in the catalytic efficiency of Fe₃O₄@SiO₂/ECH/IG. FTIR spectra of the recycled catalyst were recorded after multiple cycles and compared with the fresh catalyst (Figure S1). It is clear that the used catalyst has not endure any structural changes.

In order to demonstrate the efficacy of the prepared Fe₃O₄@SiO₂/ECH/IG catalyst, the catalytic activity in the preparation of spirooxindole derivatives was compared with the previous reports. It has several advantages over the reported studies which can be seen in table 2.

Table 2. Comparison of the present catalyst for the synthesis of spirooxindole derivatives with reported studies

Entry	Catalyst	Conditions	Time(min)	Yield(%)	References
1	[Bmim]OH	Solvent free/R.T.	600	98	52
2	Tris-hydroxymethyl aminomethane	Ethanol/R.T.	240	94	53
3	Trisodium citrate dihydrate	EtOH:Water/R.T.	120	96	54
4	Fe₃O₄@SiO₂/ECH/IG	EtOH:Water/60°C	10	94	This work

Reagents and Apparatus

All reagents and materials were purchased from commercial sources and used without purification. All of them were analytical grade. The commercially swim bladders, isinglass, were purchased from grocery store. All methods were carried out in accordance with relevant guidelines and regulations. The known products were identified by comparison of their melting points. Melting points were determined in open capillaries using an Electrothermal 9100 instrument. Infrared (IR) spectra were acquired on a Shimadzu FT-IR-8400S spectrometer with spectroscopic grade KBr. The ¹HNMR (500 MHz) were obtained on a Bruker Avance DPX-300 instrument. The spectra were obtained in DMSO-d6 relative to TMS as internal standard. Scanning electron microscopy (SEM) was recorded on a VEG2/TESCAN 30kv with gold coating, and energy dispersive X-ray spectroscopy (EDX) was recorded on a VEG//TESCAN-XMU.

General procedure for the preparation of the Fe₃O₄ NPs

The superparamagnetic iron oxide nanoparticles (SPIONs) were synthesized using a co-precipitation method described before^55,56. In a brief, FeCl₃·6H₂O (1.215 g) and FeCl₂·4H₂O (0.637 g) (Fe²⁺/Fe³⁺ = 1:2) were dissolved in deionized water (20 mL) under an inert atmosphere to get a homogenous solution. Chemical precipitation was carried out by the slow addition of NaOH solution (25%), stirring vigorously at 80 °C for 60 min, until the pH= 10 was attained. The obtained magnetic particles were separated by an external magnetic field, washed three times with deionized water and ethanol (25 mL), and dried in a 65 °C oven for 24 h.

General procedure for the preparation of Fe₃O₄@SiO₂.

Initially, Fe₃O₄ (1 g) and DI water (50 mL) were for 30 min. Then, ammonia (5 ml) and 50 ml ethanol were added to the flask followed by adding 1.5 ml TEOS. The mixture was stirred for 24 h in room temperature. The prepared Fe₃O₄@SiO₂ was magnetically separated, washed sequentially with water and ethanol and dried in a vacuum oven at 50 °C.

General procedure for the preparation of Fe₃O₄@SiO₂/ECH

Fe₃O₄@SiO₂(1g) was mixed with 1 ml ECH and 3 ml of ethanol and stirred for 5h at 60 °C. The resulted precipitate was then washed and dried in a vacuum oven at 50 °C.

General procedure for the preparation of Fe₃O₄@SiO₂/ECH/IG

0.1 g of the dried precipitate was dissolved in 20 ml ethanol and mixed with 0.2 g isinglass. The mixture was sonicated for 30 min and then stirred for 1 h. As before the obtained precipitate was washed and dried.

General experimental procedure for the synthesis of benzimidazoles derivatives catalysed by Fe₃O₄@SiO₂/ECH/IG

A mixture of isatin (1 mmol), malononitrile (1 mmol), various 1,3 dicarbonyls (1 mmol), and Fe₃O₄@SiO₂/ECH/IG (0.02 g) in EtOH/water (1:1) had been stirred for an appropriate period of time. After completion of the reaction as indicated by TLC, the reaction mixture had been dissolved in hot ethanol and the catalyst was recovered by external magnet, washed, dried and then reused in successive reaction. The reaction mixture had been recrystallized with ethanol to afford pure desired substituted benzimidazoles.

In summary, we devised a novel collagen-coated superparamagnetic organic-inorganic hybrid catalyst, Fe₃O₄@SiO₂/ECH/IG, which exhibited radically enhanced catalytic activity in the synthesis of a wide range of substituted spirooxindole derivatives through a one pot atom economical process. This bifunctional heterogeneous catalyst efficiency is achieved in several aspects, such as high product yields under mild conditions, stability, recyclability, and high reaction rate.

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No competing interests reported.

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Collagen-Coated Superparamagnetic Iron Oxide Nanoparticles as a Sustainable Catalyst for Spirooxindole Synthesis

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