I.

Review of Related Literature

Nanomaterial is a material that has at least one (1) external dimension with size less

than 100 nm. Based on its morphological dimensionality, it can be classified into: zero-

dimensional (0D), e.g. fullerene, one-dimensional (1D), e.g. carbon nanotubes, two-

dimensional (2D), e.g. graphene, and three-dimensional (3D), e.g. graphite. A wide

variety of functional materials, i.e. monolithic and advanced, can be synthesized into

any of these nanostructures. [1]

There are three main approaches of synthesizing nanomaterials. These are the top-

down, bottom-up, and their combination. The top-down approach is the breakdown of

a bulk material into nano-sized components. In contrast, the bottom-up approach is the

assembly of atoms, or molecules, to form the nanomaterial through nucleation and

growth. Compared to the former, bottom-up approach is more experimentally-

controlled, and cost-efficient. [1]

Directing the focus on the bottom-up approach, this approach is subdivided further

into: (1) vapor-phase, and (2) solution-phase. Vapor-phase, which includes chemical

vapor deposition (CVD), uses a supersaturated vapor precursor, which, due to

instability, eventually, nucleates and grows to form nanostructures, [2]. This method

produces a high purity nanomaterial that has a good structural alignment. Meanwhile,

solution-phase includes a wet treatment of a precursor to form its reduced counterpart

nuclei that grow also to form a nanostructure, [2]. Compared to the former, it consumes

a lower amount of energy, and is relatively more expensive, [1]. In addition, vapor

phase is commonly used in synthesizing nanowires; while, solution phase is for

nanoparticles (NPs), [1, 3].

 In synthesizing NPs, specifically metallic ones, the solution-phase approach utilizes

a reducing agent to reduce the metallic salt precursor to form the metal ion, which acts

as the nuclei that will, eventually, grow into NPs, [4]. For silver nanoparticles (AgNPs),

commonly, these reducing agents are sodium borohydride (NaBH4), and Tollens

reagent, which, unfortunately, are both known to be toxic, [4]. Consequently, even if

there is a high demand of AgNPs due to its numerous promising properties, e.g.

antimicrobial and metal-sensors, its synthesis still poses a large health and

environmental risks, [4, 5]. Therefore, a modification on the synthesis of AgNPs is a

necessity. This leads to the development of a green synthesis approach of the AgNPs

synthesis, see Figure 1, [4].

Figure 1 Different Methods in Synthesizing Nanoparticles, [4]

In the green synthesis approach, instead of the aforementioned reducing agents

(RA), microbes, and plant extracts are used as a substitute. However, due to its high
 maintenance requirements, microbe green synthesis is not industrially feasible. This

turns the focus to the plant extracts. [4]

Figure 2 Formation of Silver Nanoparticles using Chavicol (a phenol), as the Reducing Agent, and Silver Nitrate as a Precursor, [6]

To be considered as an RA, a plant extract must contain a high amount of phenolic

acid. This is because the hydroxyl group (OH-) of phenol is oxidizable, once reacted

with a silver precursor, which is usually a silver nitrate, AgNO3, see Figure 2, [5]. But

other studies have indicated that saponins and flavonoids also help the reducing

property of a plant extract, [4, 6]. As studied by De-Hoyos et al. (2017), Camellia

sinensis (green tea) contains a large amount of epicatechin (1087.02 mg/100 g extract)

and caffeic acid (830.10 mg/100g extract), which are phenolic compounds. Using a

UV-Vis spectroscopy and TEM analysis, it was found out that a spherical, face-

centered cubic (FCC) AgNPs with a size of 3-50 nm was generated from a 3mL extract,

[5]. Swarnavalli et al. (2014) have also synthesized AgNPs, but, this time using 10-15

mL Sapindus emarginatus extract, which has a large amount of triterpenoid saponin,

[6]. Likewise, due to its high amount chavicol, which is a phenolic compound, Centella
Asiatica (Gotu-Kola), a plant abundant in the Philippines that is usually seen creeping

in water canals, has also been successful in forming a spherical, FCC AgNPs with size

of 30-50 nm, [7]. Other plant extracts used as RAs are presented in Table 1.

Table 1 Plant Extracts Utilized as Reducing Agents for the Formation of Silver Nanoparticles, [4]

As shown in the table above, the morphology of AgNPs varies with the plant extract

used as an RA. In fact, regardless of the identity of the extract, morphology does change

with varying experimental parameters. As observed by De-Hoyos et al., even at a

constant concentration of phenolics in the extract, varying amount of extract changes

 the size, distribution, and shape of AgNPs. Between 2, 3, and 4 mL of green tea extract,

the 3 mL gave a spherical and a less polydisperse AgNPs. The other two (2) setups

gave a mixture of spheroidal and triangular-shaped AgNPs with varying mean

diameter, [5]. In terms of temperature, Tippayawat, et al. (2016) had observed that at

constant reaction time (6 hrs), increasing of reaction temperature (100, 150, and 200C)

leads to a size increase, and the completion of the oxidation-reduction reaction between

the aloe vera extract and the silver precursor. The completion of the said reaction is

observed through the purity of the phase exhibited by the material, as observed in the

x-ray diffraction (XRD) analysis, [8]. For pH, Heydari et al. (2015) had observed that

the pH of the oak tree extract leads to the variation of the formation rate of AgNPs.

Using UV-Vis spectroscopy, it was shown that pH9 has served as the threshold of

increasing formation rate. Going beyond the said pH will result to a decrease of

formation rate. [9]

For Gotu Kola as the RA, a deeper understanding of the effects of the

aforementioned parameters on the morphology of AgNPs has not been explored. The

study of Rout et al. (2013) only proved the successful synthesis of AgNPs using Gotu-

Kola. No variation of any parameters was conducted. [7]

References

[1] A. Tuantranont, Applications of Nanomaterials in Sensors and Diagnostics, Springer, 2013.

[2] G. E. Fryxell and G. Cao, Environmental Applications of Nanomaterials: Synthesis,

Sorbents and Sensors, London: Imperial College Press, 2012.
[3] W. V. Prescott and . A. I. Schwartz, Nanorods, Nanotubes, and Nanomaterials Research
Progress, New York: NOVA Science Publishers, 2008.

[4] S. Ahmed, M. Ahmad, B. L. Swami and S. Ikram, "A review on plants extract mediated
synthesis of silver nanoparticles for antimicrobial applications: A green synthesis," Journal
of Advanced Research, vol. 7, pp. 17-28, 2016.

[5] L. E. Silva-De Hoyos, V. Snchez-Mendiet, A. R. Vilchis-Nestor and M. A. Camacho-

Lpez, "Biogenic Silver Nanoparticles as Sensors of Cu2+ and Pb2+ in Aqueous Solutions,"
Universal Journal of Materials Science, pp. 29-37, 2017.

[6] A. Rout, P. K. Jena, U. Parida and B. Bindhani, "Green synthesis of silver nanoparticles
using leaves extract of Centella Asiatica L. for studies against human pathogens,"
International Journal of Pharma and Bio Sciences, pp. 661-674, 2013.

[7] G. C. J. Swarnavalli, S. Dinakaran, N. Raman, R. Jegadeesh and C. Pereira, "Bio inspired

synthesis of monodispersed silver nano particles using Sapindus emarginatus pericarp
extract Study of antibacterial efficacy," Journal of Saudi Chemical Society, 2015.

[8] P. Tippayawat, N. Phromviyo, P. Boueroy and A. Chompoosor, "Green synthesis of silver

nanoparticles in aloe vera plant extract prepared by a hydrothermal method and their
synergistic antibacterial activity," PeerJ, 2016.

[9] R. Heydari and M. Rashidipour, "Green Synthesis of Silver Nanoparticles Using Extract of
Oak Fruit Hull (Jaft): Synthesis and In Vitro Cytotoxic Effect on MCF-7 Cells,"
International Journal of Breast Cancer, 2015.