Basketing nanopalladium into calix[4]pyrrole as an efficient catalyst for Mizoroki-Heck reaction

Anita Kongor; Manthan Panchal; Viren Mehta; Keyur Bhatt; Dehin Bhagat; Devayani Tipre; Vinod K. Jain

doi:10.1016/j.arabjc.2016.06.019

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Original article

10 (

); 1125-1135

doi:

10.1016/j.arabjc.2016.06.019

Basketing nanopalladium into calix[4]pyrrole as an efficient catalyst for Mizoroki-Heck reaction

Anita Kongor^{^a}, Manthan Panchal^{^a}, Viren Mehta^{^a}, Keyur Bhatt^{^b}, Dehin Bhagat^{^c}, Devayani Tipre^{^c}, Vinod K. Jain^{^a,⁎}

a Department of Chemistry, School of Sciences, Gujarat University, Ahmedabad 380009, Gujarat, India

b Department of Chemistry, C.U. Shah University, Wadhwan 363030, Gujarat, India

c Department of Microbiology, School of Sciences, Gujarat University, Ahmedabad 380009, Gujarat, India

⁎Corresponding author. Fax: +91 079 26303263. drvkjain@hotmail.com (Vinod K. Jain)

Received: 2016-3-10, Accepted: 2016-6-25, Published: 2016-12-01

Disclaimer:
This article was originally published by Elsevier and was migrated to Scientific Scholar after the change of Publisher.

Peer review under responsibility of King Saud University.

Abstract

Abstract

An approach to synthesize calix[4]pyrrole protected palladium nanoparticles (PdNPs) employed for catalytic Mizoroki-Heck C-C coupling reaction is reported. The nanoparticles are synthesized in water using novel calix[4]pyrrole tetrahydrazide (CPTH) as a reducing as well as stabilizing agent which is a proficient “one-pot” synthesis discouraging the need of an external stabilizer. CPTH-PdNPs have been characterized and studied by UV–Vis spectroscopy, Fourier transform infrared, transmission electron microscopy, energy‐dispersive X‐ray and powder X‐ray diffraction. The synthesized palladium nanoparticles with a size range of 5–9 nm show an efficient catalytic activity for Heck cross-coupling reactions giving good yields within short reaction time in comparison with conventional palladium catalyst. Also, a good degree of recyclability is shown by the nanocatalyst with five consecutive catalytic cycles. CPTH-PdNPs also exhibit a potential antimicrobial activity against gram-negative bacteria which shows the biological applicability of the synthesized CPTH-PdNPs.

Keywords

Calix[4]pyrrole tetrahydrazide

Palladium nanoparticles

Nanocatalyst

Mizoroki-Heck reaction

Recyclability

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1 Introduction

A growing interest in the field of nanotechnology with adorable signature in medicine, optics, genomics, sensors and catalysis is seen (Narayanan and El-Sayed, 2005; Rosi and Mirkin, 2005; Zhang et al., 2008; Sathyavathi et al., 2010; Vyas et al., 2012 ). Due to the beguiling properties of nanoparticles, extreme small size (less than 10 nm) and high surface area to volume ratio compared to the bulk metal or ion, metal nanoparticles have gained wide utility in the field of synthetic organic chemistry as catalyst. Mostly transition metal nanoparticles such as palladium, ruthenium, gold, silver and platinum have been studied and utilized for different catalytic applications (Mandal et al., 2004; Joo et al., 2010; Gangula et al., 2011 ).

Palladium nanoparticles (PdNPs) as catalyst are particularly appealing as they have attracted many researchers for different organic processes, for example, Suzuki-Miyaura, Mizoroki-Heck, Sonogashira, Stille, Hiyama and Tsuji-Trost reactions (Choudary et al., 2002; Astruc, 2007; Srimani et al., 2007; Yin and Liebscher, 2007; Lamblin et al., 2010; Le Bras and Muzart, 2011 ). Mizoroki-Heck reaction was discovered independently by Heck and Mizoroki in the early 1970s and was awarded nobel prize for the same in 2010 (Wu et al., 2010). Heck reaction holds a potential place for carbon-carbon cross coupling reaction between aryl, vinyl, benzyl/allyl halide, acetates/triflates and olefins. The wide varieties of end products synthesized have applications in many areas such as pharmaceutical drugs (Ripin et al., 2005), fine chemicals and agrochemicals (De Vries, 2001; Torborg and Beller, 2009). The general requirement for Heck reactions includes bulky phosphine ligand and palladium complex/palladium salt. The use of phosphine ligand will arise certain problems such as instability at high temperature, air-sensitivity, expensive and unavailability which precludes the end product from industrial applications (Grigg and York, 2000; Rahim et al., 2001; Mino et al., 2006 ). Also, the reaction process requires large amount of catalyst for acceptable conversion and recyclable ability is thus lessened (Zhao et al., 2002). Phosphine ligands are also susceptible to get converted into phosphine oxide species which can cause poisoning and decomposition of the palladium catalyst thus lowering its reusability (Park and Alper, 2003). Hence, a phosphine-free catalytic system is required for the Mizoroki-Heck reaction.

The synthesis of palladium nanoparticles mostly involves chemical reduction method where hydrogen (Ding and Gin, 2000), hydrazine (Papp et al., 2001) and sodium borohydride (Pittelkow et al., 2003) are used as reducing agents. However the nanoparticles so formed need to be prevented from aggregation in the process of its synthesis. To overcome such aggregation, palladium nanoparticles are prepared by stabilizing them with different ligands such as polymers or some organic surfactants. The consequence of utilizing such stabilizers may lessen the catalytic activity by the strong adsorption to the surface of nanoparticles (Guo and Li, 2004). There is also possibility of leaching when concerned with palladium nanoparticles as catalyst; thus, a perfect stabilizer is needed to overcome this problem and generates nanoparticles of suitable size to prove as a highly active catalyst (Balanta et al., 2011).

Calixarenes (Gutsche, 1983) are cone shaped molecules with inherent hollow cavity to encapsulate nano-sized metals in its preorganized structure (Wei, 2006). Huc et al. have reported the use of thioester functionalized calix[4]arene derivative for synthesis of palladium nanoparticles (Huc and Pelzer, 2008). Other calix systems used for the synthesis of palladium nanoparticles with different diametric sizes are also reported (Kongor et al., 2016). Different calix based compounds acting as both reducing and stabilizing agents have been explored by our group for the preparation of nano-gold (Vyas et al., 2012; Bhatt et al., 2014; Mishra et al., 2015 ), nano-silver (Makwana et al., 2015a,b; Bhatt et al., 2016 ) and nano-palladium (Panchal et al., 2016). Calix[4]pyrrole with four pyrrole groups in the place of phenolic units is placed under hetero-calixarene class. To our knowledge, no reports of using calix[4]pyrrole to synthesize PdNPs are found in the literature. Here in this work, we report a novel tetrahydrazide derivative of calix[4]pyrrole, CPTH to synthesize PdNPs and have showed them as an efficient and recyclable nanocatalyst for Mizoroki-Heck cross coupling reactions. The present study also addresses the antibacterial activity of CPTH-PdNPs against gram-negative bacteria using micro-broth dilution method. Thus the nanocatalyst also suggests favorable utility in biological field.

CPTH can be considered as an electron rich ligand with an excellent capacity to reduce the metal ions and encapsulate nanoparticles so formed due to two reasons: (a) four pyrrole groups which are responsible for non-covalent hydrogen bonding, (b) electrons on amino groups of hydrazide functional group present on the ligand. Therefore we propose that the web-like capping of our calix system on palladium is stronger compared to simple hydrazine or other reducing agents due to the presence of electron withdrawing amino groups all over the periphery of PdNPs. CPTH-PdNPs are both air and water stable. Thus, CPTH proves to be conventional, easy, facile and low-cost alternative to prepare stable colloidal PdNPs. Moreover, we can say that the stabilization of PdNPs using CPTH plays a crucial role as the nature of the stabilizing agent not only determines the longevity of nanoparticles but also increases its activity and selectivity. This prompts us to declare that the combination of physical properties of nano-structured palladium and the powerful chemical capping of CPTH brings up a promising application of Heck cross coupling reaction with high catalytic activity.

2 Materials and methods

2.1

2.1 Materials

All chemicals of best grade materials were purchased from commercial sources and used without further purification. Palladium acetate, 1-Methyl-2-pyrrolidinone (NMP) and all aryl halides were purchased from Sigma‐Aldrich. TLC fluorescence active plates (F‐2009) were procured from Merck. Water with a resistivity of 18 MΩ cm@25 °C was used in the experiment from Millipore water system.

2.2

2.2 Synthesis of meso-tetra(methyl) meso-tetra(4-hydoxyphenyl) calix[4]pyrrole (CP)

CP was synthesized using modification in general procedure mentioned in the literature methods (Anzenbacher et al., 1999; Bonomo et al., 1999). To 30 mL of methanol as solvent, a mixture of 4-hydroxyacetophenone (2.0 gm, 14.7 mmol) and freshly distilled pyrrole (1.0 mL, 14.7 mmol) was added under vigorous stirring at ambient temperature. To the above solution, 2.0 mL of BF₃.Et₂O was added dropwise to the solution over a time period of 15 min. The reaction mixture was kept for 8 h and thereafter the dark brown mixture was quenched in 500 mL of cold distilled water. The acidic solution was neutralized using triethylamine (TEA). The orange colored precipitate was then filtered and made soluble in diethyl ether, dried over Na₂SO₄ and concentrated under reduced pressure to get solid residue that was further separated and purified by column chromatography to get light brown solid compound, CP with 68% yield (Scheme 1).

Synthesis of compounds: CP, HAECP and CPTH.

¹H NMR (400 MHz, DMSO): δ = 1.72 (12H, s, CH₃), 5.94 (d, 8H, pyrr.CH); 6.66 (m, 16H, ArH); 9.29 (s, 4H, OH); 9.45 (s, 4H, NH); ¹³C NMR (100 MHz, DMSO): δ = 154.73, 136.29, 139.28, 126.74, 113.69, 103.03, 42.18, 30.43; ESI‐Mass: 741.5 [M + 1]⁺; M.P. 179 °C (Supporting information Figs. S1–S3).

2.3

2.3 Synthesis of meso-tetra (methyl) meso-tetra (4-hydroxy phenoxy acetate) calix[4]pyrrole (HAECP)

HAECP was also prepared using a slight modification of referred literature method (Camiolo and Gale, 2000). To 100 mL of dry acetone, CP (2.00 gm, 2.7 mmol) and anhydrous potassium carbonate (1.19 gm, 8.6 mmol) were dissolved and stirred for 2 h. Ethyl bromoacetate (1.44 gm, 8.6 mmol) was then added and the suspension was kept under reflux conditions for 5 days. K₂CO₃ was removed by filtration and dry acetone was removed in vacuum. Brown colored oil was obtained and dissolved in dichloromethane and washed with water after neutralization. The organic phase was separated and then dried with Na₂SO₄. The solvent was removed in vacuum affording oil which was triturated with methanol. A whitish color powder was obtained which was collected by filtration and dried under vacuum to obtain HAECP with 74% yield.

¹H NMR (400 MHz, CDCl₃): δ = 1.30 (12H, t, CH₃), 1.55 (12H, s, CCH3), 4.27 (8H, s, OCH₂), 4. 59 (8H, s, OCH₂CO), 5.71 (8H, s, pyrr.CH), 6.77, 7.02 (16H, d, ArH), 7.61 (4H, s, NH); ¹³C NMR (100 MHz in CDCl₃): δ = 168.64, 156.28, 142.78, 137.25, 127.82, 114.12, 104.40, 64.32, 60.65, 13.99; ¹³C DEPT (100 MHz, DMSO) δ = 60.65, 64.30; ESI–MS m/z: 1107.7 [M + Na]⁺; M.P.120 °C (Figs. S4–S7).

2.4

2.4 Synthesis of Calix[4]pyrrole tetra-hydrazide (CPTH)

HAECP (2.00 gm, 1.8 mmol) was dissolved in fresh distilled methanol:toluene solvent (50:50) and stirred under reflux condition. After 2 h, hydrazine hydrate (1.47 gm, 29.4 mmol) was added and the suspension was refluxed for 72 h. The solvent was removed in vacuum and the white solid was suspended in dichloromethane (50 mL). The suspension was filtered and washed with DCM (3 × 20 mL). The crude compound was recrystallized in hot water to give pure white solid compound CPTH, with 48% yield.

¹H NMR (400 MHz, DMSO): δ = 1.73(12H, s, CH₃), 4.43 (8H, s, OCH₂), 2.51 (8H, d, NH₂), 5.94(8H, s, pyrr. CH), 6.77,6.84 (16H, d, ArH), 9.42 (4H, s, NH), 9.29 (4H, s, CONH); ¹³C NMR (100 MHz, DMSO) δ = 166.74, 156.57, 142.79, 137.28, 127.81, 114.32, 104.44, 66.16, 43.42, 31.23; ¹³C DEPT (100 MHz, DMSO) δ = 66.15; ESI–MS: 1029.5[M + 1]⁺; M.P. 157 °C (Figs. S8–S11).

2.5

2.5 Synthesis of calix[4]pyrrole tetrahydrazide-palladium nanoparticles(CPTH-PdNPs)

Heat 100 mL of CPTH (0.102 g) ligand solution in water at 50 °C and then add to it Pd(OAc)₂ (0.022 g) dissolved in 100 mL of distilled water. Keep the reaction mixture under vigorous stirring for 1 h, after which the brownish yellow color of the solution changed to colloidal black. The black color formation and UV–Vis spectroscopy (UV–Vis) confirmed the successful formation of CPTH-PdNPs. CPTH-PdNPs were collected by centrifugation with a yield of 113.5 mg and used as recyclable nanocatalyst. The content of water soluble, CPTH in CPTH-PdNPs is 102.9 mg and the Pd loading in CPTH-PdNPs is 10.6 mg. Therefore, a simple one-pot chemical reduction process is shown (Scheme 2) using CPTH as both reducing and capping agent in environmentally benign solvent i.e., water.

Schematic representation depicting the preparation of CPTH-PdNPs.

2.6

2.6 General procedure for Heck coupling reaction

In a round bottom flask containing 10 ml of NMP and water (1:1) mixture as solvent, aryl halide (1 mmol), olefinic compound (2 mmol), Na₂CO₃ (2 mmol) and CPTH-PdNPs (0.0086 mmol) were added. The reaction mixture was stirred under reflux conditions at 80 °C for aryl iodides and 100 °C for aryl bromides. After cooling to room temperature, the reaction mixture was extracted with ethyl acetate (3 × 15 mL) and washed with water (50 mL) and then the organic phase was dried over Na₂SO₄, filtered, and concentrated in vacuum. The coupling products were purified by column chromatography using hexane or ethyl acetate (2–4%)/hexane solvent system. The recovered CPTH-PdNPs nanocatalyst was thoroughly washed with ethyl acetate and dried under vacuum and consequently reused. The nanocatalyst was separated by centrifugation at 3000 rpm for 15 min and then washed thoroughly with acetone, water and NMP successively, then after reused efficiently for five consecutive catalytic cycles. A summary of reactions performed is given in Table 2. The products have been characterized by ¹H NMR and ESI-MS (Characterization data are provided in Supplementary information).

2.7

2.7 Characterization

Melting points (uncorrected) were measured in a single capillary tube using VEEGO (Model No: VMP-DS) melting point apparatus (Mumbai, India). The colloidal solutions were centrifuged using a Remi, Model No. C-24BL laboratory centrifuge. All ¹H NMR and ¹³C NMR spectra were obtained on a Bruker AV‐(III)‐400 and 100 MHz spectrometer respectively using a BBFO probe. Mass spectra were recorded on a Micromass Q‐TOF micro mass spectrometer with a capillary voltage of 3000 V and a source temperature of 120 °C. FT-IR spectra were recorded on Bruker, tensor 27 Infrared spectrometer with samples prepared as KBr pellets. The ultraviolet absorption spectra are studied in the range 200–800 nm using Jasco V-570 UV–Vis recording spectrophotometer (Tokyo, Japan). Transmission electron microscopy (TEM) micrographs were recorded on a JEOL JEM 2100 microscope using an accelerated voltage of 200 kV. Powder X‐ray diffraction (XRD) was recorded on a PANalytical Empyrean powder diffractometer using Cu Kα. Zeta potential and particle size were measured using a Malvern Zetasizer ZEN3600 without dilution.

3 Results and discussion

3.1

3.1 Characterization of CPTH-PdNPs

Amphiphilic calix[4]pyrrole based small and stable solid lipid nanoparticles were reported by Helttunen et al. (2016). Calix[4]pyrrole hydrazide was used by our research group to synthesize both gold and silver nanoparticles. To our knowledge none have reported the use of calix[4]pyrrole tetrahydrazide (CPTH) as both reducing and stabilizing agents to synthesize nanoparticles, in particular, PdNPs. Herein, we have prepared PdNPs using palladium acetate and novel calix[4]pyrrole tetrahydrazide (CPTH) in water without the use of any external reducing or stabilizing agent. Thus, water-dispersible CPTH-PdNPs were formed by one-pot chemical reduction method. The nanoparticles morphology so formed was investigated by UV–Vis spectroscopy, TEM, energy‐dispersive X‐ray spectroscopy (EDX) and powder XRD.

The addition of palladium acetate to the hot CPTH solution shows a color change from brownish yellow to black color after one hour which preliminarily confirms the formation of colloidal CPTH-PdNPs (inset of Fig. 1). UV–Visible spectrum was taken to monitor and verify the so formed CPTH-PdNPs. Palladium acetate solution gives a broad absorption band around 400 nm which refers to the presence of Pd(II) (Ahmadian Namini et al., 2007). The disappearance of band at 400 nm was found due to the reduction of Pd(II) to Pd(0) oxidation state confirming formation of PdNPs (Fig. 1).

UV–Vis analysis of CPTH-PdNPs with inset showing the photograph of palladium nanoparticles.

The black colloidal nanoparticles were imaged to characterize their size using Transmission electron microscopy (TEM). Fig. 2a shows TEM images which visualize the presence of roughly spherical shaped CPTH-PdNPs of an average size range of 5–9 nm. High-resolution TEM (HRTEM) image as shown in Fig. 2b, reveals atomic lattice fringe, demonstrating the crystalline nature of the nanoparticles. Energy dispersive X‐ray spectroscopy (EDX) analysis spectrum giving the elemental composition of CPTH-PdNPs was collected from TEM data. Strong signals from Pd atoms while weaker signals from Si and Cu atoms were observed (Fig. 2c). The invariable presence of copper signals in the EDX spectra is due to copper in the TEM grid. The selected area electron diffraction (SAED) pattern given in Fig. 2d shows concentric rings, composed of discrete diffraction spots, which can be indexed to the (1 1 1), (2 0 0), (2 2 0) and (3 1 1) planes of face centered cubic (fcc) Pd (Rajakumar et al., 2015). The SAED pattern of CPTH-PdNPs thus shows to be crystalline in nature. The size distribution diagram of the CPTH-PdNPs is shown in Fig. 2e and the average hydrodynamic diameter using particle size analyzer was found to be 14.2 nm. The particle size extends the observed core size due to organic layer of stabilizing ligand (CPTH) on the surface of PdNPs depending on the density of surface coverage (Shevchenko et al., 2006).

(a and b) TEM micrographs of CPTH‐PdNPs; (c) EDX spectroscopy analysis showing the presence of Pd and (d) SAED of CPTH-PdNPs showing the rings. (e) Histogram showing particle size distribution.

The CPTH‐PdNPs could be isolated in the solid state for Powder X‐ray diffraction (PXRD) analysis. The PdNPs were confirmed to be metallic giving the expected fcc Pd pattern. The PXRD pattern of CPTH-PdNPs exhibited well-defined peaks at 40.25°, 46.84°, 67.92°, and 82.14°, which can be attributed to the distinctive (1 1 1), (2 0 0), (2 2 0), and (3 1 1) crystalline planes for a face-centered-cubic fcc palladium (0) lattice, respectively (Fig. 3) (Yang et al., 2012). According to Debye–Scherrer equation (Goudarzi et al., 2009), the average size of CPTH-PdNPs calculated from Pd(1 1 1) peak was 6.4 nm which falls in line with the TEM observations.

Zeta-potential of nanoparticles is measured to explore the stability of nanoparticles. The overall surface charge associated with the particles is also governed by zeta potential measurements (Bagwe et al., 2006). The zeta potential recorded for CPTH-PdNPs was −28.6 mV (Fig. 4) which indicates better stability and negative charge of the ligand, CPTH on the surface of the PdNPs.

Zeta potential distribution graph of CPTH‐PdNPs.

Fourier transform infrared (FT-IR) was employed to investigate the existence of stabilizing ligand (CPTH) on surface of the PdNPs. Fig. 5 depicts FT-IR bands for (a) CPTH and (b) CPTH-PdNPs, the bands at 3320 cm⁻¹ and 1675 cm⁻¹ were found for –NH and –CONH groups respectively. It was observed that there was no direct bonding between CPTH and PdNPs but some chemical interactions could be possible due to the broadening of band around 1675 cm⁻¹ (Cao et al., 2010).

FT-IR spectra of (a) CPTH and (b) CPTH-PdNPs.

3.2

3.2 Catalytic activity

In principle, the catalytic activity of metal nanoparticles depends on its smaller size with large surface area to volume ratio which produces excellent results in terms of yield and reaction time. Palladium nanoparticles are found to be sensitive for many carbon-carbon coupling reactions (Chen et al., 2008). Therefore, CPTH-PdNPs of size range 5–9 nm were thought to catalyze carbon-carbon coupling Heck reaction.

The potential catalytic activity of CPTH-PdNPs was optimized for the Mizoroki-Heck coupling reaction using iodobenzene (a) and styrene (b) as model starting compounds and the results are summarized in Table 1. To show the clarity of CPTH-PdNPs as an efficient catalyst for the coupling reaction, the reaction was first carried out in the absence of palladium nanocatalyst at 80 °C in (Dimethyl formamide) DMF and Na₂CO₃ as base, where no reaction product was obtained (Table 1, entry 1). As thought of, a yield with 75% of the coupling product was obtained in the presence of palladium nanocatalyst in DMF which interprets the catalytic utility of PdNPs (Table 1 entry 2). Also, to further justify the catalytic efficiency, the reaction was carried out with conventional catalyst, Pd(OAc)₂ instead of palladium nanocatalyst, where 46% yield of the product was observed after 24 h (Table 1, entry 3). The reaction was then performed in various solvents such as dimethyl sulfoxide (DMSO), water, methanol, ethanol, 1-Methyl-2-pyrrolidinone (NMP) and acetonitrile (MeCN) where nearly 50–60% yield of (c) was obtained (Table 1, entry 4–9). But with NMP as polar aprotic solvent, the reaction proceeded in a better fashion with 89% yield (Table 1, entry 8). Also, the use of a mixture of solvents such as NMP–water (1:1) was even worthier with 96% yield of (c) (Table 1, entry 10). Since the nature and concentration of base matters a lot in Mizoroki-Heck coupling reactions, the optimization was done using different bases such as triethylamine (TEA), potassium carbonate (K₂CO₃), potassium hydroxide (KOH) and sodium acetate (CH₃COONa) (Table 1 entries 11–15) where only Na₂CO₃ (entry 10) gave excellent results. In the absence of base, the reaction failed to proceed without any desired conversion and when the amount of base was reduced to 1 mmol the yield of products also decreased (Table 1 entry 16–17). Parameters such as temperature, reaction time and amount of catalyst were also further taken into consideration. At room temperature the reaction had no completion and at below 80 °C, the yield of the coupling product decreased, whereas a rise in temperature conditions (Table 1, entries 18–20) showed no noticeable change in the overall yield. The amount of catalyst for the optimized reaction was also studied. An amount of 0.0086 mmol of CPTH-PdNPs was found to be optimum. It was worth noting that a decrease in the amount of nanocatalyst below the optimum value greatly reduced the yield but an increase in its amount had no positive effect on the overall yield of product (Table 1, Entries 10, 21 and 22). A slight variation in optimization parameter was observed for aryl bromides, i.e., a temperature of 100 °C yielded better results and rest all the other optimized conditions were same as for aryl iodides. Thus, the overall optimized results declare the use of CPTH-PdNPs (0.0086 mmol) as nanocatalyst in NMP-water (1:1) as solvent and Na₂CO₃ as base for Mizoroki-Heck cross coupling reactions (entry 10). Thus, cross coupling reactions of different aryl halides and alkenes with good to excellent yields are as shown in Table 2. Thus precisely, CPTH-PdNPs prove to be an efficient nanocatalyst and are unrestrictive to any external additives (Ren et al., 2010) and inert atmospheric conditions (Meier et al., 2006).

3.3

3.3 Recycling of the CPTH-PdNPs as nanocatalyst

The recovery of catalyst for an organic chemical reaction is very important from industrial and economic point of view. Therefore, after completion of the model optimized Mizoroki-Heck reaction, the recyclability of the nanocatalyst was assessed. The nanocatalyst was reused for five catalytic cycles without appreciable loss of its catalytic activity (Fig. 6). The catalytic stability and change in morphology were confirmed by TEM micrographs (Fig. 7a) after the second run of recyclability. The recycling potential of the nanocatalyst was maintained. Furthermore, after the sixth run of recyclability of the nanocatalyst the decrease in the catalytic activity was tested by the TEM micrographs as shown in Fig. 7b which showed sign of aggregation. Thus, CPTH-PdNPs prove to be an efficient nanocatalyst for Mizoroki-Heck cross coupling reaction for over five cycles.

TEM micrographs of CPTH‐PdNPs (a) after the second cycle of Mizoroki-Heck reaction (b) after the sixth cycle of Mizoroki-Heck reaction.

3.4

3.4 Antibacterial activity

Development of different nanoparticles as potent antibacterial agent is reported in the literature (Zhang et al., 2010; Hajipour et al., 2012). Palladium nanoparticles have flagged its importance in the field of catalysis and have also explored its usefulness in biological field as anti-malarial agent (Rajakumar et al., 2015), antioxidant agent (Kora and Rastogi, 2015) and antimicrobial agent (Adams et al., 2014; Panchal et al., 2016). It has been noted that the antibacterial activity of nanoparticles increases with the reduction of the particle size (Martinez-Castanon et al., 2008; Nair et al., 2009).

The resistance of bacteria against CPTH-PdNPs was tested using the micro-broth dilution method (Wiegand et al., 2008). The bacteria tested were Escherichia coli and Bacillus subtilis as gram negative and gram-positive bacteria respectively. The minimum inhibitory concentration of CPTH-PdNPs was determined and comparison was done using Ampicillin as a standard drug (Fig. 8). A good anti-bacterial activity was found against E.coli in comparison with palladium acetate and CPTH ligand. Thus, CPTH-PdNPs can be formulated as a chemotherapeutic drug for the treatment of some entero-pathogenic E-coli infections.

4 Conclusion

A simple one-pot chemical reduction method using novel, tetrahydrazide derivative of calix[4]pyrrole (CPTH) for the preparation of small sized palladium nanoparticles is described in this work. The effective reduction of palladium acetate to nano-palladium could be possible by reducing nature of hydrazide groups crafted on the calix system which also stabilizes the nanoparticles. This novel nanocatalyst showed high catalytic performance for Mizoroki-Heck coupling reactions and could be reused five times without considerable loss in its catalytic activity. Thus, CPTH-PdNPs can be used to develop practical synthesis of fine chemical products in the future in comparison with other conventional palladium catalysts. Also, the antibacterial nature of the nanoparticles suggests its utility in biological fields. We are further looking forward to explore this nanocatalyst in different reactions and their environmental applications.

Acknowledgment

The authors gratefully acknowledge the financial assistance provided by Department of Science & Technology (DST) - Innovation in Science Pursuit for Inspired Research (INSPIRE), (New Delhi) and DRDO (Defence Research and Development Organisation), New Delhi, India. The authors also acknowledge Central Salt & Marine Chemicals Research Institute (Bhavnagar), Sophisticated Analytical Instrument Facility (Panjab University), Gujarat Forensic Sciences University (Gandhinagar) for providing instrumental facilities and UGC Infonet & Information and Library Network (INFLIBNET) (Ahmedabad) for e-journals.

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Gangula A., Podila R., Karanam L., Janardhana C., Rao A.M., . Catalytic reduction of 4-nitrophenol using biogenic gold and silver nanoparticles derived from Breynia rhamnoides. Langmuir. 2011;27:15268-15274.
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Srimani D., Sawoo S., Sarkar A., . Convenient synthesis of palladium nanoparticles and catalysis of Hiyama coupling reaction in water. Organ. Lett.. 2007;9:3639-3642.
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Torborg C., Beller M., . Recent applications of palladium-catalyzed coupling reactions in the pharmaceutical, agrochemical, and fine chemical industries. Adv. Synth. Catal.. 2009;351:3027-3043.
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Vyas D.J., Makwana B.A., Gupte H.S., Bhatt K.D., Jain V.K., . An efficient one pot synthesis of water-dispersible calix [4] arene polyhydrazide protected gold nanoparticles-A “turn off” fluorescent sensor for Hg [II] ions. J. Nanosci. Nanotechnol.. 2012;12:3781-3787.
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Zhao F., Shirai M., Ikushima Y., Arai M., . The leaching and re-deposition of metal species from and onto conventional supported palladium catalysts in the Heck reaction of iodobenzene and methyl acrylate in N-methylpyrrolidone. J. Mol. Catal. A: Chem.. 2002;180:211-219.
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Appendix A

Supplementary material

Supplementary data associated with this article can be found, in the online version, at https://doi.org/10.1016/j.arabjc.2016.06.019.

Appendix A

Supplementary material

Supplementary data 1

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[56] Yin L., Liebscher J., . Carbon-carbon coupling reactions catalyzed by heterogeneous palladium catalysts. Chem. Rev.. 2007;107:133-173.
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[57] Zhang L., Gu F., Chan J., Wang A., Langer R., Farokhzad O., . Nanoparticles in medicine: therapeutic applications and developments. Clin. Pharmacol. Ther.. 2008;83:761-769.
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[58] Zhang L., Pornpattananangkul D., Hu C.-M., Huang C.-M., . Development of nanoparticles for antimicrobial drug delivery. Curr. Med. Chem.. 2010;17:585-594.
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[59] Zhao F., Shirai M., Ikushima Y., Arai M., . The leaching and re-deposition of metal species from and onto conventional supported palladium catalysts in the Heck reaction of iodobenzene and methyl acrylate in N-methylpyrrolidone. J. Mol. Catal. A: Chem.. 2002;180:211-219.
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Entry	Time	^aYield (%)
1	2 h	95
2	2 h	90
3	2 h	96
4	2 h	93
5	2 h	96
6	2.5 h	92
7	3 h	95
8	2.5 h	95
9	3 h	93
10	3 h	95

Basketing nanopalladium into calix[4]pyrrole as an efficient catalyst for Mizoroki-Heck reaction

Abstract

Abstract

Keywords

Calix[4]pyrrole tetrahydrazide

Palladium nanoparticles

Nanocatalyst

Mizoroki-Heck reaction

Recyclability

1 Introduction

2 Materials and methods

2.1 Materials

2.2 Synthesis of meso-tetra(methyl) meso-tetra(4-hydoxyphenyl) calix[4]pyrrole (CP)

2.3 Synthesis of meso-tetra (methyl) meso-tetra (4-hydroxy phenoxy acetate) calix[4]pyrrole (HAECP)

2.4 Synthesis of Calix[4]pyrrole tetra-hydrazide (CPTH)

2.5 Synthesis of calix[4]pyrrole tetrahydrazide-palladium nanoparticles(CPTH-PdNPs)

2.6 General procedure for Heck coupling reaction

2.7 Characterization

3 Results and discussion

3.1 Characterization of CPTH-PdNPs

3.2 Catalytic activity

3.3 Recycling of the CPTH-PdNPs as nanocatalyst

3.4 Antibacterial activity

4 Conclusion

Acknowledgment

References

Appendix A

Supplementary material

Appendix A

Supplementary material

Supplementary data 1

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