One step preparation of stable gold nanoparticle using red cabbage extracts under UV light and its catalytic activity

Journal Pre-proof One step preparation of stable gold nanoparticle using red cabbage extracts under UV light and its catalytic activity

Ilay Sema Unal, Ayse Demirbas, Irem Onal, Nilay Ildiz, Ismail Ocsoy PII:

S1011-1344(19)31003-6

DOI:

https://doi.org/10.1016/j.jphotobiol.2020.111800

Reference:

JPB 111800

To appear in:

Journal of Photochemistry & Photobiology, B: Biology

Received date:

2 August 2019

Revised date:

15 January 2020

Accepted date:

18 January 2020

Please cite this article as: I.S. Unal, A. Demirbas, I. Onal, et al., One step preparation of stable gold nanoparticle using red cabbage extracts under UV light and its catalytic activity, Journal of Photochemistry & Photobiology, B: Biology(2020), https://doi.org/ 10.1016/j.jphotobiol.2020.111800

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© 2020 Published by Elsevier.

Journal Pre-proof

One step preparation of stable gold nanoparticle using red cabbage extracts under UV Light and its catalytic activity

Ilay Sema Unal 1,§, Ayse Demirbas2,§, Irem Onal 3,§, Nilay Ildiz3 and Ismail Ocsoy1* 1

Department of Analytical Chemistry, Faculty of Pharmacy, Erciyes University, 38039 Kayseri, Turkey

Recep Tayyip Erdogan University, Faculty of Fisheries and Aquatic Sciences, 53100 Rize, Turkey

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Department of Pharmaceutical Microbiology, Faculty of Pharmacy, Erciyes University, Kayseri,

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38039 Turkey

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Abstract Herein, we have reported the synthesis, characterization and catalytic activity of highly stable gold nanoparticles (Au NPs) using red cabbage extract (RCE) under UV irradiation. The anthocyanin groups predominantly existing in RCE play an essential role for biosynthesis of stable Au NPs. The reasons for using anthocyanins: 1) they act as chelating agents for preferentially reacting with gold ions (Au3+) to form Au3+- anthocyanin complexes, 2) as lightactive reductants for reduction of Au 3+ to zero valent Au0 under UV irradiation and 3) as stabilizing agent for preventing Au NPs from aggregation in high salt concentration owing to their unique salt tolerance property . We also demonstrate that how reaction time, concentration of RCE, pH value of reaction solutions and using one more reducing agent affected formation of the Au NPs. The stability of RCE Au NPs was comparatively studied with commercial (citrate stabilized) Au NPs against 100 mM salt (NaCl) solution. The RCE-Au NP showed reduction ability for conversion of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP). UV-vis spectrometry, transmission electron microscopy (TEM), dynamic light scattering (DLS) and zeta potential (ZT) methods were utilized to characterize the Au NPs. We demonstrated that how whole RCE (anthocyanins molecules are major component) can be used as photo-active reducing and stabilizing agents to form Au NPs in a short time under UV irradiation and strong reducing agent without additional agents. Keywords: anthocyanin, Au nanoparticle, photo-reduction, salt tolerance and catalytic activity

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1. Introduction A variety of biomolecules such as DNA, enzyme, protein and plant extracts have been actively used to provide various water-soluble and biocompatible nanoparticles (NPs) [1-17]. Among biomolecules, plant extracts have been considered by researchers as a remedy for overcoming drawbacks of chemical methods in NP synthesis owing to their easy availability,

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stability against environmental conditions, biocompatibility and cost-effectiveness. Despite

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those advantages of plant extracts, presence of several different components including

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polyphenols, flavonoids, terpenoids, sugars and enzymes in plant extracts may result in lack of

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control on size and morphology of NPs and less stable NP in aqueous solutions [15-21].

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Turkevich and coworkers developed first work for synthesis of colloidal gold nanoparticles (Au NPs) in aqueous solution using sodium citrate salt as functioned reducing and

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stabilizing agent [22]. The sodium citrate was also used with various concentrations to form different sizes of Au NPs at high temperature through thermal reduction process [23-25].

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However, previous reports showed that although thermal reduction process acted as driving

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force for synthesis of monodispersed and colloidal Au NPs, temperature is invasive and cannot be immediately reached to targeted position in Au NP synthesis. In contrast to that, photoactive agents were successfully benefited for synthesis of monodispersed and colloidal Au NPs in targeted position owing to noninvasive and immediate acting features of light [26-29]. In this work, we present synthesis, characterization and catalytic activity of highly stable and colloidal Au NPs using red cabbage extract (RCE) in aqueous solution. The essential components in RCE are anthocyanins groups, which give stable gold ions (Au 3+)-anthocyanin complexes via hydroxyl groups of anthocyanin molecules and produce Au NPs at room

Journal Pre-proof temperature (RT: 20°C) [30-33]. Phytochemical compositions of various cabbages including Brassica oleracea L. var. capitata were well documented with their antioxidant activities [34, 35]. Additionally, the salt tolerance property of the RCE inspired us to utilize the anthocyanins as photo-active reducing and stabilizing agents to form stable Au NPs in a short time under UV irradiation [36]. The effects of experimental conditions such as reaction time, concentration of RCE, pH value of reaction solutions and using an extra reducing and/or stabilizing agent were

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systematically examined on formation of the Au NPs. The RCE Au NPs exhibited unique stability

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in the high concentration of NaCl solution (100 mM) compared to commercial or lab-synthesized

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citrate capped Au NPs. The RCE Au NPs also efficiently reduced 4-nitrophenol (4-NP) to 4aminophenol (4-AP). We also characterized the Au NPs using UV-vis spectrometry, transmission

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electron microscopy (SEM), dynamic light scattering (DLS) and zeta potential (ZT)

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instrumentations.

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2. Experimental

2.1. Chemicals and instrumentation

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Gold (III) chloride trihydrate (HAuCl4.3H2O), sodium chloride (NaCl), 4-nitrophenol,

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ascorbic acid, sodium, hydroxide (NaOH) and hydrochloric acid (HCl) were purchased from Sigma-Aldrich and all chemical used as received. Deionized water with 18.2 M Ω (Millipore Co., USA) was used in all experiments. For photoreductive synthesis, 6 W power UV fluorescein Blacklight blue lamp (BLB) was used. UV-vis spectrometer, scanning electron microscope (SEM), dynamic light scattering (DLS) and zeta potential (ZT) instrumentations were employed to characterize the Au NPs. 2.2. Red cabbage (Brassica oleracea) extract preparation The red cabbages extract (RCE) was prepared using a previous reported method [17]. Briefly, red cabbage (Brassica oleracea var. capitata f. rubra) were obtained from local market

Journal Pre-proof and cut into small pieces. 100 mL distilled water was added to 500 mL glass beaker containing approximately 100 gram (gr) red cabbage and the beaker was placed into microwave oven (using 900 W power) for 2 minutes (min.). After microwave, aqueous extract was collected using vacuum filter and stored at -20C for further use. The concentration of obtained RCE solution is adjusted via addition of distilled water.

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2.3. Synthesis and Characterization of gold nanoparticles (Au NPs)

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1mL of 1 mM Au3+ solution and 1 mL 5% w/w RCE were mixed in 5 mL glass vial and

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exposed to UV irradiation for different time periods under the mild stirring. The formation of Au NPs was observed based on appearance of their characteristic Localized Surface plasmon

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resonance (LSPR) absorption peaks. After the Au NP synthesis was completed, the reaction

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mixture was centrifugation at 12.000 rpm for 15 min to collect the Au NPs and to remove excess of RCE and Au3+ ions. The synthesized Au NPs were stored in aqueous solution at 4 °C for

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further use and characterization. Additionally, formation of the Au NPs was also systematically

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documented based upon reaction time, concentration of RCE, pH value of reaction solutions and

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using ascorbic acid as an extra reducing agent. UV-vis spectrometry was used for recording LSPR peaks of the Au NPs and conversion of 4-NP to 4-AP. For TEM operation, a few drops of concentrated RCE Au NP solutions was deposited on carbon film coated copper grids and they were left overnight for dry to monitor the size and morphology of the Au NPs with clear images. The effective size and charge density of the Au NPs were determined via DLS and ZT methods, respectively.

2.4. Catalytic Activity of Au NPs

Journal Pre-proof The reduction of 4-NP to 4-AP was accomplished by following modified methods [3742]. 2 mL of 0.2 mM 4-NP solution was mixed with 0.015 M sodium borohydride (NaBH4) at room temperature (RT: 25 °C), then 0.5 mL of 0.2 µM RCE Au NP solution was added to resulting mixture. The reduction catalysis of 4-NP to 4-AP was successfully monitored with absorption peak of 4-AP appeared at 300 nm for every 1 min.

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3. Results and Discussions

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3.1. Synthesis and characterization of RCE Au NPs

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Anthocyanins knowns as natural pigments and secondary metabolites are major components of RCE. Molecular structure of anthocyanins is affected by pH values (pHs) and they

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give pH dependent colors. For instance, anthocyanins in neutral form in between pH 5-7

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including physical condition (pH 7,4); give purple color; when they are positively charged at acidic solution (pH 3 and below), pink-red color is appeared; blue and green colors are obtained

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when anthocyanins are basic and hold negative charges (at pH 8 and above). Scheme 1

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illustrated that synthesis of RCE Au NPs was accomplished at various pHs and charge densities

pHs.

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on the surface of the Au NPs which influence the stability of the Au NPs were varied based on

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Scheme. 1. Illustration of pH dependent RCE Au NP under UV irradiation. Color of RCE solutions, electronic structure of anthocyanin and charge density on the surface of RCE Au NPs are directly dependent upon reaction pHs.

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In synthesis of RCE Au NPs, 1 mL of 1 mM Au3+ solution and 1 mL 5% w/w RCE were mixed in 5 mL glass vial and exposed to UV irradiation for different time periods under the mild stirring. The potential reaction between anthocyanin and Au3+ and Au NP formation were demonstrated step by step in Figure 1. Firstly, the catecholamine group of anthocyanins preferentially bind to Au 3+ to make anthocyanins-Au3+ complexes, hydrogen (H+) and chloride (Cl) ions (eq 1). With application of UV irradiation, charge transfer from anthocyanins to Au 3+ as ligand-to-metal was occurred and Au +Cl2− species and quinone derivatives were produced (eq 2). As a final step, preparation of stable zero valent Au NPs was successfully completed (eq 3). We

Journal Pre-proof claim that anthocyanins exhibited great ability to form strong anthocyanins-Au3+ complexes and

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acted as efficient photo-reductant comparted to other reductants.

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Figure 1. A) Proposed mechanism for formation of RCE Au NPs via photoreductive synthesis process comprising three steps: 1) formation of anthocyanins-Au3+ complexes at RT in dark, 2) charge transfer from anthocyanin to Au 3+ to form Au+Cl 2− species and quinone derivatives and completion of synthesis of the colloidal Au NPs.

Figure 2 shows the characterization of RCE Au NPs formed at pH 7.4. Time dependent Au formation with its characteristic LSPR absorption peak was determined based on UV-Vis spectra (Figure 2A). The first and broad absorption peak appeared between 521 and 565 nm in 10 min of the reaction, which can be considered as initial formation of the Au NP. However, the sharp absorption peak was seen at 532 nm after 20 min photoirradiation, which indicates the synthesis of the spherical and colloidal Au NP. Although the reaction for synthesis of Au NPs was continued under photoirradiation for 50 min, no remarkable shift was observed compared to 20

Journal Pre-proof min photoirradiation. Figure 2B presented dramatic increases in the characteristic absorption peak of the Au NPs formed at 25°C and pH 7 after photoreduction of Au 3+ with 254 nm wavelength UV light. In Figure 2C, TEM images presented that RCE Au NPs have quite spherical shapes with diameter of ∼25 nm in size. The effective size of the Au NPs was determined as ∼40 nm via DLS (Figure 2D). Both TEM and DLS proved that the Au NPs synthesized via photoreductive synthesis procedure are well colloidal and have narrow size distribution.

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Additionally, the charge type and density on surface of the Au NPs were analyzed with ZT

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measurements. The RCE Au NPs formed at pH 7 were negatively charged with -23 mV, which

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makes contribution to stability of the Au NP by preventing them from aggregation.

Fig. 2. Characterization of RCE Au NPs formed using 1 mM Au 3+ solution and 5% w/w RCE extract at pH 7. A) Time dependent UV-Vis spectra of Au NPs, B) Time dependent increase in LSPR peak

Journal Pre-proof (532 nm) of Au NP formed under 254 nm UV irradiation, C) SEM images of the Au NPS and D) measurement of effective diameter and size distribution of the Au NPs with DLS method.

As a further study, we examined the effects of RCE extract concentrations on the formation of the Au NPs. Although ideal Au NPs with a ruby-red colour and 532 nm LSPR peak were obtained using 5% w/w RCE extract as mentioned above, the Au NPs were formed when the concentration of RCE extract was decreased until 1% w/w (data not shown). In contrast to

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that, when RCE extract was used with concentrations of 0.5 % w/w, 0.2 % w/w and 0.1 % w/w,

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no intrinsic color (ruby-red) and no LSPR absorption peak, as indication of the Au NP formation,

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were observed (Figure 3). We assume that the concentration of RCE extract was unable to

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reduce enough Au 3+ to Au0 for initiating the nucleation and seed formation processes. Most

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possibly, very less amount of seed formation was occurred, and it cannot be reached to energy

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barrier for the initiation of nucleation and further growth phases.

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Fig. 3. A) RCE concentration dependent UV-Vis spectra of the Au NPs formation. No color change was observed during the 60 min photoirradiation as photos of reaction solution given inset of Figure 3.

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For additional study, effects of pHs on formation of RCE Au NPs were evaluated in Figure 4. The Au NP formation were implemented in acidic (pH 2.5) and basic (pH 11). It is well known that electronic structure of anthocyanins found as major component in RCE is prone to change with positive or negative charges based on pH. Although the Au NPs were synthesized at both pHs, much stable and colloidal Au NPs were obtained at pH 11 compared to pH 2.5. Figure 4A shows that the Au NPs formed at pH 2.5 posed a very broad LSPR peak between 535-585 nm (maxima around 560 nm) with low intensity (black line) and intrinsic ruby red color and optical transparency of Au NP solution were also not seen (i). In contrast, quite narrow and intense LSPR peaks (red line) at ~521 nm and a typical ruby red color (ii) were captured when synthesis

Journal Pre-proof of Au NPs was completed at pH 11. We demonstrated that the TEM image in Figure 4B and DLS result in Figure 4C are consistent each other in terms of stability and uniformity of the Au NPs formed at pH11. For instance, while size of the Au NP formed at pH 11 in range of between was 18–30 nm (Figure 4B), effective size measured with DLS was determined as around 70 nm (Figure 4C). The surface charge density of the Au NPs was recorded to be -28 mV owing to negatively charging of anthocyanin molecules as shown in inset of Figure 4C. In contrast to that,

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the Au NPs synthesized at pH 2.5 resulted in larger size distribution, aggregative growth and less

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stable Au NPs compared ones at pH 11. The TEM image in Figure 4D showed sizes of the Au NPs

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ranging from 5 nm to 70 nm. Owing to aggregative growth and rapid aggregation, effective diameters were measured in range of between ~696 nm and ~1200 nm (Figure 4E). The

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anthocyanins hold a positive charge at pH 2.5 (inset of Figure 4D) and gave -2.7 mV zeta

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potential on the surface of the Au NPs. We assume that low charge density may trigger to aggregative growth during the Au NP synthesis and reasoned the production of less stable Au

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NPs owing to attractive van-der-Waals interactions between the Au NPs. It is also worthy to

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mention that further or heterogenous nucleation gave large size distribution as shown in Figure

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4D with TEM image and aggregative growth resulted in rapid agglomeration of the Au NPs as presented in Figure 4E with DLS data.

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Fig. 4. Characterization of pH dependent RCE Au NPs. A) UV-Vis spectra of the Au NPs formed at pH 2.5 (black line) and pH 11 (red line). Inset in Figure A: Photos showing color of the Au NPs solutions at pH 2.5 (i) and pH 11 (ii). B) SEM image of the Au NP formed at pH 11. Inset in Figure B: The molecular structure of negatively charged anthocyanin. C) Size distribution of the Au NP formed at pH 11. The same characterization for Au NPs formed at pH 2.5. D) SEM image of the Au NPs. Inset in Figure D: The molecular structure of positively charged anthocyanin. E) Size distribution of the Au NPs.

As a further evaluation on formation of the Au NP, we demonstrated how using single or more reducing or stabilizing agent influence the formation of Au NPs. Although several reports on photoreductive synthesis of Au NPs have been previously published, most of them used reducing both and stabilizing agents separately [25-27]. In this study, anthocyanin used as a reagent acted both reducing and stabilizing agent and gave the response to UV light as an efficient photoreductant (Figure 5). Additionally, we also used ascorbic acid as an extra reducing agent before or after addition of RCE (anthocyanin) (Figure 5). UV-Vis spectra in Figure 5A

Journal Pre-proof showed that using only RCE resulted in uniform Au NP with absorption peak of 537 nm (blue line). Introduction of ascorbic acid into Au3+ solution lead to red shift on the LSPR of Au NPs to 559 nm (red line) and 547 nm (black line) before and after addition of RCE, respectively. TEM image in Figure 5B and DLS in Figure 5C demonstrated size and effective diameter of the Au NPs formed using RCE as a single reducing agent to be 27 nm and 70 nm, respectively. While addition of RCE into mixture of Au3+ and ascorbic acid gave the NPs with ranging between 18 and

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53 nm as shown in TEM image (Figure 5D) and 185 nm effective diameter as shown in DLS

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spectra (Figure 5E). However, TEM image and DLS spectra demonstrated that addition of

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ascorbic acid into mixture of Au 3+ and RCE produce the Au NPs with sizes of between 21 and 35

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nm and effective diameter of 90 nm, respectively.

Figure 5. Characterization of reducing agent dependent RCE Au NPs. A) UV-Vis spectra of the Au NPs formed at pH 2.5 (black line) and pH 11 (red line). Inset in Figure A: Photos showing color of

Journal Pre-proof the Au NPs solutions at pH 2.5 (i) and pH 11 (ii). B) SEM image of the Au NP formed at pH 11. Inset in Figure B: The molecular structure of negatively charged anthocyanin. C) Size distribution of the Au NP formed at pH 11. The same characterization for Au NPs formed at pH 2.5. D) SEM image of the Au NPs. Inset in Figure D: The molecular structure of positively charged anthocyanin. E) Size distribution of the Au NPs.

As a final examination, colloidal stability of the Au NPs were systematically investigated in different concentrations of NaCl solutions. Aggregation of nanoparticles may reduce their intrinsic properties and hinder their efficient uses in various scientific applications [34-36].

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Especially for biological applications, fully dispersibility of the NPs in aqueous solution play a

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vital role. For instance, if the NPs are rapidly aggregated when applied to cell solution or living

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organisms, aggregated NPs cannot reach and internalize to targeted cells for in vitro experiment

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and may clogs blood vessels and prevents blood circulation for in vivo experiment. Herein, we

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offered that RCE Au NPs exhibited much enhanced stability or dispersibility even in high concentration of NaCl solution without any additional surfactant and stabilizing agent compared

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to commercial (citrate capped) Au NPs (Figure 6). The citrate capped Au NPs was dispersed in 20 mM NaCl but above that point the aggregation of the Au NPs was initiated. While the citrate

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capped Au NP synthesized in water gave a sharp LSPR peak at around 521 nm (blue line) with

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wine red color solution (inset of Figure 6A), addition of 100 mM NaCl solution to the Au NP solution induced a very broad and shifted LSPR peak at around 680 (red line) and turned the Au NP solution from red to blue color (Figure 6A). However, RCE Au NPs showed long term and extraordinary dispersibility both in water and in 100 mM NaCl solution without any changes in their LSPR peaks (532 nm) and original solution color (ruby red) (Figure 6B). RCE Au NPs also remained stable without aggregation even in 400 mM NaCl solution (data now shown). We believe that RCE Au NPs can avoid from opsonization when used in biomedical applications owing to their excellent colloidal stability in aqueous solutions.

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Figure 6. Colloidal stability of commercial (citrate capped) and RCE Au NPs. A) UV-Vis spectra of citrate capped Au NPs before (blue line) and after (red line) treated with 100 mM NaCl. Inset: Color of citrate capped Au NP solutions before (wine red color) and after (blue color) treated with 100 mM NaCl. B) A) UV-Vis spectra of RCE Au NPs before (blue line) and after (red line) treated with 100 mM NaCl. Inset: Color of RCE Au NP solutions before (ruby red color) and after (ruby color) treated with 100 mM NaCl.

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Various metallic NPs have been employed for designing promising catalysts for many

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catalytic reactions [34-45]. For instance, Wang and co-workers reported synthesis several

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platinum (Pt) and palladium (Pd) integrated hybrid nanoparticle with their catalytic performance for 4-nitrophenol reduction. We also showed that the RCE Au NP acted as an efficient homogeneous catalyst for reduction 4-NP to 4-AP owing to their long term stability. In typical catalytic experiment, RCE Au NP solution was added into glass vial containing 4-NP and sodium borohydride (NaBH4). The RCE Au NPs showed excellent catalysis performance by reducing 4-NP to 4-AP. During the catalytic reaction, characteristic absoroption peaks at around 300 nm for 4AP were appeared and minimizing of the 400 nm peaks for 4-NP were observed on UV-Vis spectra (Figure 7A). The catalytic reaction for reduction of 4-NP to 4-AP was illustrated in Figure 7B.

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Figure 7. Conversion of 4 NP to 4 AP catalyzed by RCE NPs. A) UV-Vis spectra of catalytic reaction and B) Reaction for reduction of 4 NP and formation of 4AP.

4. Conclusion We developed a novel, one step and rapid strategy for synthesis of biocompatible and colloidal Au NPs. The anthocyanin groups which are major components in RCE acted as efficient reducing and stabilizing agents under UV irradiation. The rational combination of complexation ability of anthocyanins with Au3+ and photo-reductive function of anthocyanins provided rapid Au NPs formation at room condition with narrow size distribution and spherical shape. Although characteristic LSPR peak of Au NP which can be indication of Au NP formation silighly appeared

Journal Pre-proof in first 10 min of reaction, a sharp and intense LSPR peak proving complete Au NP formation was appreatly and clearly observed with 20 min photoreduction. The effect of experimental parameters incluing reaction time, concentration of RCE, pH value of reaction solutions and using extra reducing agent on size and morphology of Au NPs were systematically investigated. Additionally, RCE Au NP exhibited much enhanced colloidal stability in concentrated NaCl solution compared to citrate capped Au NPs. The efficient catalysis performance of RCE Au NPs for conversion of 4-NP to 4-AP was demonstrated. Finally, we propose that based on our results, the ability of metal–anthocyanin complexes can be utilized for further designing a novel

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synthesis methods or nanoparticles via photoreduction process. Author Contributions

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The project was conveyed and designed by I.O. as a corresponding author. I.S.U., A.D., and I.U.

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run all the experiments as Co-first authors. N.I made contributions on experimental section. N.I. and I.O. guided in all the experiments. A.D. N.I. and I.O. wrote the manuscript.

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§: S.U., A.D., and I.U. contributed equally. Notes

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The authors declare no competing financial interest. Acknowledgment

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We appreciate Berkay Saraymen at the Erciyes University Nanotechnology Research Center for assistance with DLS and Zeta measurements. This work was supported by grants from the

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Erciyes University Scientific Research Office numbered FCD-2018-8242 and numbered TCD-

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2019-8016.

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Journal Pre-proof Highlights

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Photoreductive synthesis of colloidal gold nanoparticles Anthocyanin rich red cabbage extract (Brassica oleracea). pH dependent synthesis of colloidal gold nanoparticles Salt tolerance property of gold nanoparticles Catalytic activity

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