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Chemistry Education Study Program.
Universitas Sebelas Maret https://jurnal.
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PARTICLE SIZE MODIFICATION OF BREADFRUIT STARCH
(Artocarpus altili.
TO NANOPARTICLES USING ACID
HYDROLYSIS AND A TOP-DOWN TECHNIQUE
Asri Alfiyah Ningsih Nst 1.
Cut Fatimah Zuhra2*.
Juliati Br.
Tarigan 2 Postgraduate School.
Department of Chemistry.
Faculty of Mathematics and Natural Sciences.
University of Sumatera Utara.
Medan.
Indonesia Department of Chemistry.
Faculty of Mathematics and Natural Sciences.
University of Sumatera Utara.
Medan.
Indonesia
ARTICLE INFO
ABSTRACT
Keywords:
Breadfruit Starch (Artocarpus Nanoparticle.
Acid Hydrolysis.
Physicochemical Breadfruit (Artocarpus altili.
is a significant starch source, comprising up to 70.
25% of its composition, and holds extensive industrial However, the physicochemical properties of natural starch pose several challenges to its direct use as an industrial raw material.
These challenges include high viscosity, substantial swelling power, low solubility, significant retrogradation, limited digestibility, and poor thermal stability.
To address these issues, modification of the starch Article History:
particle size to the nanometer scale is proposed, which is anticipated to Received: 2024-02-14 enhance both functional and physicochemical properties.
This study Accepted: 2024-04-21 employs a top-down approach through 2.
2 N HCl acid hydrolysis at 38AC Published: 2024-04-25 for 24 hours.
This method offers simplicity, efficiency for scale-up in *Corresponding Author industrial applications, and relatively higher stability than alternative Email: cutfatimah@usu.
Particle size analysis using Particle Size Analysis (PSA) doi:10.
20961/jkpk.
revealed an average particle size of 215 nm.
Fourier Transform Infrared (FT-IR) spectroscopy showed characteristic bands similar to natural starch, with slight variations in peak intensity, indicating successful acid hydrolysis and structural disruption of the molecular order.
Morphological analysis revealed minimal changes in the granules' surface structure, with clumping observed due to acid hydrolysis.
The A 2024 The Authors.
This open- resultant starch nanoparticles exhibited decreased viscosity and access article is distributed swelling while solubility was enhanced.
Therefore, nanoparticle starch under a (CC-BY-SA Licens.
holds promising applications in food and non-food industries.
How to cite: A.
Ningsih Nst.
Zuhra, and J.
Tarigan, "Particle size modification of breadfruit starch (Artocarpus altili.
into nanoparticle size through top down technique using acid hydrolysis," Jurnal Kimia dan Pendidikan Kimia (JKPK), vol.
9, no.
1, pp.
xx-xx, 2024.
Available: 10.
20961/jkpk.
INTRODUCTION
as a raw material .
The composition of Starch is a renewable biopolymer breadfruit starch includes 22.
5% amylopectin that can be biodegraded naturally and is 48% amylose, offering superior abundantly available from various plant functionalities compared to wheat, rice, and sources .
, .
Artocarpus altilis, commonly cassava flours in terms of viscosity, oil and known as breadfruit, is highly productive and water binding capacities, and expandability remains underutilized despite its functional .
Currently, approximately 60% of starch properties and potential health benefits .
utilization is in the food industry, with the Indonesia, breadfruit starch is a popular remaining 40% serving non-food sectors source, comprising up to 70.
25% starch such as pharmaceuticals, chemicals, paper, content, thus presenting significant potential textiles, and cosmetics .
Ningsih Nst et.
Particle size modification of breadfruit.
Natural starch presents limitations can be executed via top-down and bottom-up that can hinder its effectiveness, particularly in the food industry, which demands raw Top-down advantageous due to their simplicity, cost- effectiveness, and efficiency at scale, making Vulnerabilities of starch include sensitivity to them suitable for industrial production.
They processing conditions such as stirring, acidic environments, high temperatures, unstable nanoparticles with consistent quality more 6-.
economically than bottom-up methods, which Therefore, starch modification is essential to require specialized precursors and complex enhance its utility.
Various methods and synthesis processes .
, .
compounds are employed to physically.
Acid hydrolysis is a prominent top- chemically, and enzymatically modify starch, down method that yields starch nanoparticles aiming to improve its structural and functional with relatively higher crystallinity and stability properties for diverse industrial applications than other methods.
This process involves .
treating starch with an acid suspension at Modification of starch to nanoparticle temperatures below its gelatinization point size can address these limitations by .
The efficacy of acid hydrolysis in reducing the particle size to nanoscale nanoparticle formation is influenced by Smaller nanoparticles enhance solubility, making them suitable for dispersion or dissolution applications.
Additionally, the increasing molecular kinetic energy.
increased surface area to volume ratio of concentration, which dictates the rate and nanoparticles improves interactions with extent of hydrolysis.
starch concentration.
functional properties.
This modification also Systematic consideration of these factors and improves stability against temperature, pH the properties of the resulting nanoparticles is changes, and retrogradation and extends Optimizing hydrolysis conditions to shelf life.
Furthermore, starch nanoparticles encapsulated substances such as drugs or experimental design, data analysis, and nutrients, thus offering enhanced biological iterative adjustments.
Therefore, this study properties not present in natural starch .
, 12, .
(Artocarpus altili.
starch nanoparticles using Nanotechnology processes produce the top-down acid hydrolysis method to starch nanoparticles that generate particles explore the characteristics and potential smaller than 1000 nm but larger than a single applications of these modified biopolymers The preparation of nanoparticles JKPK (JURNAL KIMIA DAN PENDIDIKAN KIMIA).
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METHODS
Material washed to remove any gumminess.
It was Breadfruit (Artocarpus altili.
with then chopped into small pieces and mashed, yellowed skin was sourced from Tembung, and the slurry was filtered through gauze to Deli Serdang.
North Sumatra.
Indonesia.
separate the starch.
The filtrate was left in a Chemicals used in this study include distilled beaker glass to settle, allowing the starch to water, double-distilled water, and pro-analyst This precipitate was washed repeatedly with water until the wash water Hydrochloric Acid (HC.
Sodium Hydroxide became clear.
The starch was then dried at (NaOH), and Ethanol.
45EE for 24 hoursAicare was taken to avoid Merck, gelatinization point of the starch, as this could Tools The equipment prepared for this degrade its properties.
Overly long drying study comprised Erlenmeyer flasks, beaker times were avoided to prevent excessive glasses, test tubes .
ll Pyre.
, spatulas, glass moisture loss and undesirable changes in funnels, stirring rods, mortars and pestles, starch structure and functionality.
Finally, the mesh sieves, thermometers, a pre-calibrated dried starch was pulverized, sieved, and shake incubator .
erification of incubator weighed .
, .
calibrated thermometer to ensure accurate Starch Nanoparticle Preparation 4 grams of breadfruit starch was suspended in 150 ml of 2.
2 N HCl solution.
Previous research indicates that an acid stopwatches, an analytical balance, and a concentration O 2.
2 N is optimal and does not universal indicator.
Analytical instruments produce particles smaller than 1000 nm .
, used include Fourier Transform Infrared The suspension was placed in a shake Spectroscopy (FTIR).
Scanning Electron incubator at 38EE for 24 hours.
The reaction Microscopy (SEM), and a Particle Size was neutralized with 1N NaOH to halt the acid Analyzer (PSA).
Before sample analysis, the hydrolysis process.
The resultant starch surface area of the PSA site was cleaned to suspension was filtered, washed with distilled water and ethanol, and dried at 40 EE for 24 Preparation of the PSA solution followed After drying, the material was mashed specific instructions to ensure proper dilution and sieved .
, 17, .
(Memmer.
Ostwald interference from and mixing.
Characterization Breadfruit (Artocarpus altili.
Starch Isolation Yellow-skinned peeled, and the stalk was removed.
After Following The Particle Size Analyzer Ningsih Nst et.
Particle size modification of breadfruit.
(PSA) is first employed to determine the Viscosity Measurement nanoparticle size of the treated starch.
Viscosity is measured using the Subsequent characterization involves Fourier Ostwald viscometer method .
A sample of Transform Infrared Spectroscopy (FTIR) to 5 grams of starch is dissolved in 100 ml of identify any changes in functional groups and distilled water.
This solution is transferred into to compare the intensity variations of starch nanoparticle peaks against those of natural measurements determine the precise weight.
Scanning Electron Microscopy (SEM) For viscosity testing, 10 ml of the solution is is then used to assess the differences in introduced into the Ostwald viscometer.
The solution is drawn up to the upper limit of the viscometer using a rubber bulb to ensure These analyses are crucial for accurate measurement of the time required verifying nanoparticle synthesis's success for the liquid to pass between two marked This physicochemical properties of starch, such as determining the flow properties of starch viscosity, swelling power, and solubility.
solutions, which are essential for their potential application in various industrial Swelling Power and Solubility Swelling power and solubility tests are conducted according to established RESULTS AND DISCUSSION methods .
, .
, with natural breadfruit Breadfruit (Artocarpus altili.
Starch Isolation quantity of starch is suspended in distilled water and heated in a water bath at 85EE for After temperature, the suspension is centrifuged at 5000 rpm for 15 minutes.
The supernatant is then dried in an oven at 110EE to a constant weight to measure the soluble starch, indicated by the dry weight of the residue.
The residue and the retained water postcentrifugation are weighed to evaluate the Figure 1.
Breadfruit (Artocarpus altili.
Starch swelling capacity.
Sediment Left Behind .
ycIycyceycoycoycnycuyci ycEycuycyceyc O Starch Weight .
Solubility (%) Dried Supernatant .
Starch Weight .
y 100% The starch isolated in this study was derived from breadfruit (Artocarpus altili.
with skin beginning to yellow, sourced Tembung Regency.
North Deli Sumatra Serdang Province.
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Indonesia.
This choice was influenced by the area's abundance and underutilization of encapsulated drugs or nutrients and boosts From 2 kg of breadfruit, 200 g of starch was obtained, reflecting a yield of nanoparticle stability is enhanced against The yield is contingent upon the maturity of the breadfruit.
prior studies have retrogradation, and it also extends shelf life .
, 12, .
3%, whereas ripe breadfruit Additionally.
The transformation of particles to yields about 8.
It is noted that the starch content in breadfruit varies with the fruit's conditions occurs through a two-stage acid maturity .
hydrolysis process, as illustrated in Figure 2 The efficacy of the starch isolation .
Initially, there is a rapid degradation of process is influenced by the solubility of the the starch granule's amorphous regions compounds to be extracted, adhering to the containing amylopectin, followed by a more principle of 'like dissolves like.
' Being a polar gradual breakdown of both amylose and substance, starch is extracted using waterAi amylopectin in the crystalline areas .
, .
a polar solventAiwhich has been shown to Prior to the hydrolysis of the starch enhance the yield of starch obtained.
This crystal's interior, the acidic environment aligns with findings from previous research, generates hydrogen ions that react with which indicate that using water as a solvent oxygen atoms within the glycosidic bonds of produces higher yields and proves more cost- effective and practical on a larger scale Amylose molecules, being more compared to other chemical solvents .
readily cleaved than amylopectin molecules.
This efficiency makes water an ideal choice result in a reduction of the amylose fraction and the production of shorter amylose chains availability, and environmental impact.
These bonds are with lower molecular weights, thus reducing the degree of polymerization.
The length of Breadfruit Starch (Artocarpus altili.
Nanoparticles The when used in various industries.
Specifically, nanoparticles increase solubility, which is crucial for applications that require dispersion or dissolution.
By enhancing the absorption capacity, reducing particle size increases the surface area-to-volume ratio, which in turn influences the functional properties of starch nanoparticles enhances their functionality This nanoparticles, such as the binding capacity for active ingredients when used as a matrix .
Refer to Figure 3 for a depiction of the acid hydrolysis reaction mechanism .
The process of acid hydrolysis used to produce breadfruit starch nanoparticles temperature of 33AC for 6 hours.
This procedure resulted in an average particle size of Ou1000 nm.
To optimize the reaction Ningsih Nst et.
Particle size modification of breadfruit.
conditions, the temperature was increased to or breakdown of the crystalline structure of 35AC for the same duration.
however, this the starch.
The selection of temperatures adjustment did not significantly reduce the below the gelatinization threshold is strategic, particle size.
Subsequently, the hydrolysis as acid molecules preferentially attack the time was extended to 12 hours at 35AC, which amorphous regions of the granule, leading to led to a notable reduction in particle size, a more rapid hydrolysis in these areas although the average still remained above compared to the crystalline regions .
While 1000 nm.
Therefore, to achieve the desired extending the hydrolysis time can decrease nanoparticle size, both the temperature and duration were further increased to 38AC for 24 hydrolysis may lead to the dissolution of hours, resulting in an average particle size of starch in the acidic medium, thereby reducing O1000 nm.
These reaction conditions differ the yield of starch nanoparticles .
The from those found in previous studies .
, 13, results of these adjustments are documented 16, 17, 18, .
in Table 1 and illustrated in Figure 4.
In this study, lower temperatures were employed to prevent the gelatinization Figure 2.
Scheme of Acid Hydrolysis Method Figure 3.
Mechanism of Acid Hydrolysis Reaction on Starch JKPK (JURNAL KIMIA DAN PENDIDIKAN KIMIA).
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Characterization Particle Size Analyzer (PSA) The particle size distribution was determined using a Particle Size Analyzer (PSA).
This instrument operates on the principle of dynamic light scattering, also known as photon correlation spectroscopy (PCS).
Measurements with the PSA are generally more precise than those obtained through a Scanning Electron Microscope (SEM), especially for analyzing nanometer and submicron size particles that are prone to The particle size measured represents the size of a single particle due to the dispersion of the particle into the medium.
The outcome is a distribution of particle sizes, which provides a comprehensive view of the sample's state.
Thus, this method is more techniques that use image analysis for small samples .
particle sizes analyzed with the PSA varied according to the different temperatures and durations used during the acid hydrolysis The modification of nanoparticle size through acid hydrolysis is influenced by several factors, including temperature, acid hydrolysis time, and agitation, which are crucial in achieving the desired nanoparticle size .
, .
The results are presented in Table 1 and Figure 4.
The employed in this study used 2.
2 N HCl at 38AC for 24 hours, resulting in an average particle size of 215 nm.
This outcome is superior to previous conditions, as in Table 1, where the average particle sizes did not Previous research conducted at a temperature of 35AC over 7 and 10 days yielded particle sizes ranging from 20-420 nm and 30-300 nm, respectively .
The results obtained using 2N HCl are more effective than those achieved with HCl concentrations O 2.
2 N at a temperature of 40AC for 4 hours and 24 hours, which did not produce nanoparticle sizes O1000 nm.
The optimal conditions for using HCl at a concentration of 2.
2 N have been validated by prior researchers .
, .
With an average particle size of 215 nm, these nanoparticles can significantly alter the physicochemical properties of starch to meet processing of starch nanoparticles.
The smaller particle size increases solubility, which is advantageous for applications Moreover, the increased surface area to volume ratio of nanoparticles enhances their interaction with other molecules, facilitating While process is commonly used for producing starch nanoparticles, it is also noted to be energy-intensive .
Table 1.
Average Particle Size at different reaction conditions Temperature (EE) 33EE Time (Hou.
6 hour 6 hour 12 hour 24 hour Average Particle Size 342 nm 158 nm 190 nm 215 nm Ningsih Nst et.
Particle size modification of breadfruit.
Figure 4.
PSA Characterization of Breadfruit Starch Nanoparticles under Temperature and Time conditions .
33EE.
6h, .
35EE.
36EE.
12h, and .
38EE.
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Characterization FT-IR reduction in starch crystallinity.
This reduction The FTIR spectroscopy results show structural changes in starch granules due to acid hydrolysis.
Spectra displaying occurs during the acid hydrolysis reaction, which targets starch granules' crystalline and amorphous regions.
At wavenumbers 950-1050 cm-1, a vibrational peaks in the wavenumber range of 3400-3200 cm-1 indicate the presence of hydroxyl groups (OH).
In nanoparticle starch, the stretching peak of OH groups shifts to higher wavelengths .
The absorption at wavenumbers 2923-2929 cm-1 corresponds to the stretching vibrations of the alkane C-H group (CH.
, and the absorption at presence of the CO ester group.
The absorption band at 1080 cm-1 indicates the CO glycosidic functional group .
, and the peak at 1645 cm-1 is attributed to water bonds .
The nanoparticles due to structural disruptions of the inner molecular order during acid hydrolysis, distinguishing it from natural breadfruit starch .
This structural change indicates that acid hydrolysis has reduced the amylose content, resulting in a short-chain amylose fraction with a lower molecular The length of the amylopectin chain As illustrated in Figure 5, the FTIR characteristic amorphous and crystalline within the starch granules.
nanoparticle starch display similar band characteristics, albeit with slight variations in the intensity of peaks.
The nanoparticle starch shows a decrease in the absorption ratio compared to native starch, suggesting a influences the functional properties of starch nanoparticles, such as their ability to bind active ingredients when used as a matrix.
Starch advantages for their application as functional ingredients in food, including excellent air biocompatibility .
Figure 5.
FTIR Spectra of Sukun Starch and Sukun Starch Nanoparticles Ningsih Nst et.
Particle size modification of breadfruit.
Characterization SEM SEM images, presented in Figure 6, illustrate the morphology of breadfruit starch granules both before and after acid The granules exhibit various shapesAipolyhedral, elliptical, and roundAi with sizes ranging from 3.
0 to 7.
9 AAm .
During the short-duration acid hydrolysis hydrolysis, which causes granules to adhere, forming clumps.
Such changes impact the physicochemical properties of the starch nanoparticles, including viscosity, swelling, granules undergoes minimal change.
This limited alteration is attributed to the acid's selective action on the amorphous regions of the starch.
At the same time, the crystalline areas remain intact, thus preserving the overall shape of the granules .
, .
However, the surface morphology of the starch nanoparticles appears clumpy due to the agglomeration of damaged This agglomeration results from the disruption of hydrogen bonds during acid Previous particularly suited for specific applications, such as drug delivery matrices .
The process, as depicted in the schematic in Figure 1, the morphology of the starch .
enhances their encapsulation efficiency, differing significantly from that of natural This efficiency improvement is due to resulting from the nanoparticle formation, which optimally affects particle size reduction The nanoparticle starch samples underscores their potential advantages over natural starch in pharmaceutical and other applications.
Figure 6.
Granule Morphology of .
Breadfruit Starch.
Breadfruit Starch Nanoparticles Viscosity Viscosity was measured using an and after undergoing the acid hydrolysis Ostwald viscometer, a widely utilized type viscosity of the starch nanoparticles.
Lower due to its minimal sample requirements viscosity is advantageous for encapsulation compared to other viscometers .
The viscosity of the starch samples, both before process, demonstrated a decrease in the JKPK (JURNAL KIMIA DAN PENDIDIKAN KIMIA).
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Nano starch exhibits superior The analysis of solubility and material due to its low viscosity, even at high swelling power revealed that starch subjected concentrations .
The relatively modest to the acid hydrolysis process exhibited a change in viscosity, as depicted in Figure 7, decrease in swelling power and a notable can be attributed to the limited duration of the acid hydrolysis process, which did not exceed conducted at 85AC, where the swelling 24 hours, resulting in only minor variations in behavior of starch is influenced by heat.
The viscosity values .
, .
granules absorb water if starch is heated in Viscosity .
P) performance when used as an encapsulation The excess water above 55AC.
Swelling is initially limited and reversible at the gelatinization .
round 70AC)Aihowever, swelling and eventual rupture of the starch Breadfruit Starch Nanoparticle Breadfruit Starch Figure 7.
Viscosity Bar Chart of Breadfruit Starch Breadfruit Starch Nanoparticles Swelling and Solubility granules .
Natural starch demonstrated a This enhancement in solubility is attributed to the acid-induced degradation of Swelling .
starch granules and the cleavage of starch chains into shorter chains, thus facilitating The reduced molecular weight Furthermore, as starch crystallinity Breadfruit Starch Nano Breadfruit Starch Figure 8.
Bar Diagram of Swelling Power of Breadfruit Starch and Breadfruit Starch Nanoparticles Solubility and shorter chains of starch increase its increases, the swelling power decreases.
This reduction results from forming hydrogen bonds between the external helix and water In acid-hydrolyzed starch, the dissolution of amylose and the shortening of amylopectin chains lead to a more branched structure, diminishing the swelling power .
Decreased swelling and increased Breadfruit Starch Nano Breadfruit Starch Figure 9.
Bar Diagram of Solubility of Breadfruit Starch and Breadfruit Starch Nanoparticles solubility are effects of the disruption of amylopectin side chains.
The integrity of amylopectin is crucial for starchAos ability to retain water and swell.
disrupting these Arfida et.
Increasing High School Students'.
chains prevents the formation of extensive granules due to the brief duration of acid networks, leading to solubility because the However, the surface of the starch chains can no longer effectively trap water nanoparticle granules exhibited clumping.
The high solubility of nanoparticle starch properties between natural breadfruit starch and its nanoparticle form showed a decrease in viscosity from 0.
99 cP to 0.
95 cP and materials with high solubility enhances the swelling power from 10.
659 g/g to 1.
421 g/g.
rate of absorption, bioavailability, stability.
The and bioactivity of compounds, making them increase to 85.
90% from the original 9.
This highlights the growing These changes affirm the potential for industrial demand for starch nanoparticles application according to industrial needs.
Additionally, and underscores the challenges in scaling production to meet the physicochemical ACKNOWLEDGEMEN requirements of various industries .
The author would like to thank the Ministry of Education.
Culture.
Research and CONCLUSION The Technology of the Republic of Indonesia for influenced by temperature and duration to achieve nanoparticle sizes (O1000 n.
funding this research.
DRTPM program for No.
75/UN5.
1/PPM/KP-DRTPM/B/2023.
Analysis using a particle size analyzer (PSA) under conditions of 38EE for 24 hours yielded REFERENCES