International Journal of Biological Macromolecules 111 (2018) 498–504
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International Journal of Biological Macromolecules journal homepage: https://www.journals.elsevier.com/biomac
Development of native and modified banana starch nanoparticles as vehicles for curcumin Leonardo Acevedo-Guevara a,1, Leonardo Nieto-Suaza a,1, Leidy T. Sanchez b, Magda I. Pinzon b, Cristian C. Villa a,⁎ a b
Programa de Química, Facultad de Ciencias Básicas y Tecnologías, Universidad del Quindío, Armenia, Quindío, Colombia Programa de Ingeniería de Alimentos, Facultad de Ciencias Agroindustriales, Universidad del Quindío, Armenia, Quindío, Colombia
a r t i c l e
i n f o
Article history: Received 18 August 2017 Received in revised form 21 November 2017 Accepted 10 January 2018 Available online 11 January 2018 Keywords: Banana starch Nanoparticles Curcumin Acetylated starch
a b s t r a c t In recent years, starch nanoparticles have been of great interest for drug delivery due to their relatively easy synthesis, biocompatibility, and vast amount of botanical sources. Native and acetylated starch obtained from green bananas were used for synthesis of curcumin-loaded starch nanoparticles. Mean particle size, encapsulation efficiency, and curcumin release in simulated gastric and intestinal fluids were studied. Both nanosystems showed sizes lower than 250 nm and encapsulation efficiency above 80%, with acetylated banana starch nanoparticles having the capacity to encapsulate more curcumin molecules. Both FTIR and XRD analyses showed that starch acetylation allows stronger hydrogen bond interaction between curcumin and the starch matrix, thus, higher encapsulation efficiency. Finally, curcumin release studies showed that acetylated banana starch nanoparticles allowed more controlled release, probably due to their stronger hydrogen bond interaction with curcumin. © 2018 Published by Elsevier B.V.
1. Introduction Curcumin, Fig. 1, is a polyphenol present in the rhizomes of turmeric (Curcuma longa) that has been the subject of several studies due to its known anti-cancer, antioxidant, anti-inflammatory, antimicrobial and antiviral activities [1–6]. Nevertheless, use of curcumin is hindered by its low water solubility, fast degradation, and low bioavailability [7, 8]. In recent years, several methods have been proposed to enhance the water solubility and bioavailability of curcumin, among them nanoencapsulation seems to be preferred. Nanoparticles are small materials with high surface-to-volume ratio, which allows them to pass through biological barriers and which are made from a wide array of biocompatible materials that can be used in food and pharmaceutical industries [9–11]. Starch is a natural and biodegradable polymer used by many plants as an energy reserve. It is also the second-most abundant biomass material in nature [12]. Due to its natural abundance, biocompatibility, and relative easy structural modification through physical, enzymatic, and chemical methods [13]. A common starch modification is acetylation in which the hydrophilic native starch is converted into hydrophobic starch acetate [13]. Due to the aforementioned characteristic, starch nanoparticles have been studied as carriers for several drugs. For ⁎ Corresponding author at: Carrera 15 Calle 12 Norte, Universidad del Quindío, Armenia, Quindío, Colombia. E-mail address:
[email protected] (C.C. Villa). 1 Both authors contributed equally to this study.
https://doi.org/10.1016/j.ijbiomac.2018.01.063 0141-8130/© 2018 Published by Elsevier B.V.
instance, propyl starch nanoparticles were loaded with flufenamic acid, testosterone, and caffeine, showing enhanced effectiveness in permeation studies on human skin [14]. Xiao et al. [15] reported that dialdehyde starch nanoparticles conjugated with 5-fluorouracil (5-Fu) have enhanced breast cancer cell (MF-7) inhibition in vitro, as compared to free 5-Fu. Recently, acetylated starch nanoparticles were used as vehicles for ciprofloxacin [16]. Finally, starch nanoparticles have also been studied as curcumin carriers. Chin et al. [17], evaluated the encapsulation and release of curcumin by using sago starch nanoparticles, finding that release could take up to 10 days under physiological conditions. Additionally, Athira et al. [18], used cassava starch nanoparticles loaded with curcumin in the development of cassava starch-poly(vinyl) alcohol nanocomposites with greater anticancer activity than free curcumin. Recently, it has been reported that curcumin-loaded soluble starch nanoparticles show greater activity against Streptococcus mutans than free curcumin [8]. Green bananas (Musa paradisiaca) are an interesting source of starch. Green bananas are an important food crop extensively grown in tropical and subtropical regions around the world and have approximately 36% starch content and are easily available in local markets [19]. Banana starch is known for its higher amylose content than potato, corn, and wheat starch and for its resistance to acid hydrolysis [20–22]. It has also been reported that green banana starch is highly resistant to enzymatic hydrolysis, with up to 78% of the starch granules surviving digestion in the stomach and small intestine [22]. Those characteristics could be used in the development of nanocarriers for oral delivery of acid-sensitive drugs, like curcumin, given that they will withstand the
L. Acevedo-Guevara et al. / International Journal of Biological Macromolecules 111 (2018) 498–504
Fig. 1. Curcumin structure.
harsh conditions in the stomach with more controlled drug release in the small intestine. To our knowledge, the potential use of banana starch nanoparticles as vehicles for curcumin is still unstudied. This paper reports the synthesis and characterization of curcuminloaded native and acetylated green banana starch nanoparticles, as well as curcumin release in simulated gastric and intestinal fluids. 2. Experimental section 2.1. Materials Green bananas (Musa paradisiaca L) known in Colombian as platano guayabo were kindly provided by FEDEPLATANO from their crop in Tebaida, Colombia. Curcumin (Analytical grade) was purchased from Sigma. Pepsin, pancreatin and bile bovine were purchased from sigma. All other regents used in this studied were analytical grade and purchased from Sigma. 2.2. Green native banana starch isolation Native banana starch (NBS) was isolated according to the procedure described by Bello-Perez et al. [23], with some modifications. Green banana samples were peeled by using a kitchen knife and cut into 2-cm slices and immediately dipped in citric acid solution (2% w/v) for 5 min and blended for 2 min. The homogenate was then sieved, washed through screens (20, 40, and 60 US mesh) until the deionized wash water was free from solutes and suspended solids. The solution was left to decant during 8 h. The white starch sediments were dried in a Digitronic J.P Selecta hot air oven at 40 °C during 48 h. The solids were ground with a pestle and passed through a sieve (100 US mesh) and placed into a sealed container and stored at room temperature until required. 2.3. Synthesis of acetylated banana starch Acetylated banana starch (ABS) was obtained by using a previously reported method [24] with some modifications. In summary, NBS was dried at 60 °C during 24 h, and then 5.5 g of NBS was mixed with 45 mL of water in a 250-mL two-neck flask equipped with a condenser on a magnetic stirrer. The solution was stirred during with 15 min, until a uniform suspension was obtained. Thereafter, pH was adjusted to 8.0 using a NaOH solution (1 N) and 11.6 mL of acetic anhydride was added drop by drop with constant stirring during 30 min. Finally, pH was adjusted to 4.5 using a HCl solution (0.1 N), the ABS suspension was cooled by using an ice bath and centrifuged at 4000 rpm during 45 min. The ABS sediments were washed with cooled ethanol and centrifugated several times, until all acid residues were removed and then dried in a Digitronic J.P Selecta hot air oven at 40 °C during 48 h. The solids were ground with a pestle and passed through a sieve (100 US mesh) and placed into a sealed container and stored at room temperature until required. The ABS degree of substitution was determined according to previously reported methods [16] and calculated at 0.33. 2.4. Preparation of NBS and ABS nanoparticles The NBS nanoparticles (NBSNp) and ABS nanoparticles (ABSNp) preparation was performed by using a nanoprecipitation method
499
previously reported by Tan et al. [25], with some modifications. In brief, 4 g of NBS or ABS were mixed with 200 mL of acetone during 15 min by using a magnetic stirrer at 600 rpm. The 400 mL of water were added drop by drop (~1 mL/min) with constant stirring. All experiments were carried out at 25 °C. The resulting suspension was stirred at room temperature until acetone was completely vaporized. Finally, nanoparticles were separated by centrifugation at 4000 rpm during 40 min and dried in a Digitronic J.P Selecta hot air oven at 30 °C during 48 h. 2.5. Preparation of NBSNp and ABSNp loaded with curcumin Preparation of NBSNp and ABSNp loaded with curcumin (CurNBSNp and Cur-ABSNp) was performed as follows: 4 g NBS or ABS were mixed with a curcumin/acetone solution (40 mg curcumin/ 200 mL acetone) during 15 min by using a magnetic stirrer at 600 rpm. The 400 mL of water were added drop by drop with constant stirring. The resulting suspension was stirred at room temperature until acetone was completely vaporized. All experiments were carried out at 25 °C. Nanoparticles were separated by centrifugation at 4000 rpm during 40 min; samples were washed several times with ethanol to remove any excess of curcumin in the Cur-NBSNp and Cur-ABSNp surface. Finally, the curcumin-loaded nanoparticles were dried in hot air oven at 30 °C during 48 h. 2.6. Characterization of NBSNp and ABSNp Particle size and polydispersity index (PdI) of NBSNp and ABSNp in aqueous solution were measured by dynamic light scattering using a Mastersizer 2000 (Malvern) system. The suspensions were diluted with distilled water to a concentration of about 0.01%. The mean particle size and the polydispersity index (PdI) are reported. X-ray diffraction (XRD) spectroscopy analyses were carried out in a Bruker D8 Advance X-ray diffractometer operated at 40 kV and 100 mA with a Cu-K, radiation (λ = 1.54 Å. All samples were scanned through the 2θ range of 5–40°, with a continuous scan mode at room temperature. Fourier transform infrared (FTIR) analyses were performed by using a Prestige 21 Shimadzu FTIR spectrophotometer. All the samples were pressed as pellets with potassium bromide (KBr), dried, and put in the FTIR spectrophotometer. Transmittances were recorded at wave numbers between 4000 and 400 cm−1 at a resolution of 2 cm−1. ξ – potential measurements were performed in a zetasizer Nano ZS90 (Malvern). It determines the electrical charge at the interface of the nanoparticles dispersed in the aqueous phase. Samples were diluted prior to analysis with water (1:10). A Hewlett Packard UV–Vis spectrophotometer (HP-8453) and a Spex Fluoromax apparatus were used to obtain the absorption and emission spectra, respectively. Corrected fluorescence spectra were obtained by using the correction file provided by the manufacturer. The path length used in both experiments was 1 cm. All experimental points were measured three times with different prepared samples and the pooled standard deviation was b5%. Samples were diluted to 0.01% in water for each measurement. 2.7. Loading efficiency and loading capacity of curcumin Loading efficiency (%LE) and loading capacity (LC) of curcumin in both NBSNp and ABSNp were calculated as follows: NBSNp and ABSNp were separated from the reaction media after preparation by centrifugation at 4000 rpm during 40 min. Then, 1 mL of the supernatant was diluted to 10 mL by using distilled water and absorbance was measured at 422 nm by using a Hewlett Packard UV–Vis spectrophotometer (HP-8453), using water as a blank, curcumin concentration was calculated using a curcumin standard
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5
curve. The %LE and LC were calculated by using Eqs. (1) and (2), respectively:
Weight of Encapsulated Cur Weight of Nanoparticles
ð2Þ
2.8. In-vitro gastrointestinal release studies Curcumin release under gastrointestinal conditions was studied in two simulated fluids: simulated gastric fluid (SGF) and simulated intestinal fluid (SIF). The SGF was prepared containing NaCl (125 nM); KCl (7 mM), NHCO3 (45 mM), and pepsin (0.3%) adjusted to pH 2 with HCl [26]. While SIF was prepared as follows: bile bovine (0.3%) and pancreatin (0.1%) were dissolved in a phosphate buffer solution (pH 8) [26]. An amount of 50 mg of Cur-NBSNp were suspended in 20 mL of SSJ and incubated at 37 °C in a shaking water bath at 200 rpm. After determined amounts of times, samples were quickly cooled to 4 °C and centrifuged at 4000 rpm and 4 °C during 5 min. The supernatant was removed and the amount of curcumin released was determined. Released SGF studies were carried out at to 2 h. Then, Cur-NBSNp were re-suspended in 20 mL of SIF and incubated at 37 °C in a shaking water bath at 200 rpm. After determined amounts of time, samples were acidified to pH 2 and centrifuged at 4000 rpm and 4 °C during 5 min. The supernatant was removed and the amount of curcumin released was determined. Released SIJ studies were carried out at to 2 h. The amount of curcumin released was determined by using a Hewlett Packard UV–Vis spectrophotometer (HP-8453) at 422 nm, curcumin concentration was calculated using a curcumin standard curve. The percentage of curcumin released (%RC) was calculated by using Eq. (3): %RC ¼
Weight of Cur Released 100 Weight of Total Cur
A
4
ð1Þ
Volumen (%)
LC ¼
Weight of Encapsulated Cur 100 Total weight of Cur
3
2
1
0 0,0
0,2
0,4
0,6
0,8
1,0
Particle size (μm)
5
B
NBS ABS
4
Volumen (%)
%LE ¼
NBSNp ABSNp
3
2
1
ð3Þ 0
Unused SGF and SIF were used as blanks (targets) in each case. The same procedure was followed for Cur-ABSNp. 2.9. Statistical analysis All experiments were carried out in triplicate and results were analyzed by multifactor analysis of variance with 95% significance level, using Statgraphics®Plus 5.1. Multiple comparisons were performed through 95% least significant difference (LSD) intervals. 3. Results and discussion 3.1. Size and ξ potential characterization The particle size distribution of NBSNp and ABSNp is shown in Fig. 2A. Both nanoparticle systems presented a narrow size distribution with a mean particle size of 135.1 nm and 190.2 nm for NBSNp and ABSNp, respectively. Reports indicate that particle size and morphology of starch nanostructures heavily depends on the starch's botanic source and granule size [12, 27]. Hence, to understand the size difference between NBSNp and ABSNp, the granule size of NBS and ABS granules was studied. Fig. 2B shows the particle size distribution of NBS and ABS granules. Both starches showed a single size population with mean particle size of 33.2 μm for NBS and 52.4 μm for ABS. Several authors [22, 23, 28–31] have reported that green banana starch has a ellipsoidal morphology with sizes ranging from 0.9 to 100 μm. It is also reported that acetylation does not greatly affect the morphology of the native starch granules, but a slight aggregation of granules due to the
1
10
100
Particle size (μm) Fig. 2. Particle size distribution of A) NBSNp and ABSNp and B) NBS and ABS.
increase in the intermolecular hydrogen bonds starch granules and water can be observed [32–35]. This aggregation could lead to the size increase observed in ABS granules and ABSNp with respect of their native counterparts. Although ABSNp size is bigger than NBSNp, their polydispersity index (PdI) is smaller. A similar behavior was previously observed in the synthesis of acetylated corn starch nanospheres, where particle size augmented and PdI decreased as acetylation degree increased due to the aggregation caused by intermolecular hydrogen bonding [25]. Table 1 shows the mean particle size and PdI values of
Table 1 Mean particle size, polydispersity index (PdI), and ξ-potential of NBS, ABS, NBSNp, ABSNp, Cur-NSBNp, and Cur-ABSNp.
NBS ABS NBSNp ABSNp Cur-NBSNp Cur-ABSNp
Mean particle size (μm)
PdI
ξ-Potential (mV)
33.2 ± 5.2 52.4 ± 7.3 0.135 ± 0.011a 0.190 ± 0.014b 0.147 ± 0.012a 0.201 ± 0.009b
0.234 ± 0.025 0.321 ± 0.018 0.353 ± 0.032ª 0.233 ± 0.045c 0.391 ± 0.023a 0.275 ± 0.033c
– – −4.97 ± 0.62a −3.60 ± 0.32b −4.49 ± 0.56ab −3.67 ± 0.30b
Means with different superscripts are significantly different in their respective column (p b .05).
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A I)
Transmitance (%)
both starch nanoparticles loaded with curcumin. As shown in that table, curcumin encapsulation slightly increased particle size for both NBSNp and ABSNp to 147 and 201 nm, respectively. Nevertheless, statistical analysis did not show a significant difference (p N .05) with their unloaded counterparts. A similar behavior was observed for PdI values, given that both values slightly increased for curcumin-loaded nanoparticles, but no significant difference (p N .05) was noted with their unloaded counterparts. Finally, Table 1 shows the ξ-potential for both curcumin-loaded and unloaded NBSNp and ABSNp. All the nanoparticles studied had a negative ξ-potential greater than the generally accepted value for stable particle systems (−30 mV), a behavior previously reported for other native and modified starch nanoparticles and indicating that starch nanoparticles dispersions tend to precipitated rapidly [8, 16, 36, 37]. The slightly negative values of starch nanoparticles have been attributed to ionization of hydroxyl groups in the nanoparticle surface [16, 37]. ξ-Potential values of curcumin-loaded nanoparticles did not significantly change (p N .05) from their unloaded counterparts.
501
II)
III)
IV)
4000
3500
3000
2500
2000
1500
1000
500
-1
Wavenumber (cm )
3.2. FTIR and XRD analyses
I)
B
II)
Transmitance (%)
Fig. 3A shows the FTIR spectra of NBS, ABS, NBSNp, and ABSNp. All the FTIR spectra presented show several absorption bands attributed to the starch's molecular structure. The bands at 1160, 1082, and 1017 cm−1 can be attributed to C_O and C\\O\\C stretching; the band around 2930 cm−1 is attributed to C\\H stretching, while the broad band around 3405 cm −1 is attributed to overlapping of stretching bands of the different O\\H groups in the starch granules. The ABS and ABSNp spectra show an additional absorption band at 1731 cm−1 that corresponds to the stretching of the ester carbonyl (C_O) group, indicating acetylation of some of the starch's hydroxyl groups. To understand the possible interactions among curcumin and the native and acetylated banana starch nanoparticles, Fig. 3B presents the FTIR spectra of curcumin, Cur-NBSNp, Cur-ABSNp, and a physical mixture of curcumin and starch nanoparticles (Cur/NBSNp and Cur/ABSNp). A 2:1 curcumin:starch nanoparticles weight relation was used for physical blends. The spectra of both Cur/NBSNp and Cur/ABSNp show characteristic bands of both curcumin and the starch nanoparticles; for example, in the curcumin spectrum, the peak at 3520 cm−1 is attributed to the stretching of the O-H group in the benzene ring. That band appears in both Cur/NBSNp and Cur/ABSNp, along the broad band at 2450 cm−1 of starch hydroxyl groups. This situation is different for Cur-NBSNp and Cur-ABSNp as the peak at 3520 cm −1 and most of the peaks attributed to curcumin are completely overlapped by the spectra of starch nanoparticles. The complete overlapping of the curcumin spectrum in the CurNBSNp and Cur-ABSNp systems could indicate that no or little amount of curcumin existed as free molecules. In addition, the band at 1017 cm−1, corresponding to the vibration of C-O-C in the glucose units, increased with respect of NBSNp, ABSNp, Cur/NBSNp, and Cur/ABSNp. Other authors studying the encapsulation of curcumin in soluble starch nanoparticles observed a similar behavior, concluding that the curcumin/starch nanoparticle interaction occurs through hydrogen bonding with the hydroxyl groups of the different glucose units. Fig. 4A shows the XRD spectra of NBS, ABS, NBSNp, and ABSNP. The NBS granules exhibit the typical diffraction pattern of a C-type starch, with a small peak at 5°, sharp peaks at 15° and 17°, and a broad peak between 22° and 24°. This crystalline structure changed in ABS as the sharp peak at 15° decreased and a broadening of the peak at 17° was observed. The change in the XRD pattern is characteristic of acetylated starches with low degree of substitution (b1), as the highly ordered crystalline structure of starch formed by the intra and the new acetyl groups disrupts intermolecular hydrogen bonds of the hydroxyl groups [16]. Once the nanoparticles are formed, the crystalline structure of starch further changes. While the NBSNp X-ray diffraction pattern
III)
IV)
V)
4000
3500
3000
2500
2000
1500
1000
500
-1
Wavenumber (cm ) Fig. 3. A) FTIR spectra of I) NBS; II) ABS; III) NBSNp, and (IV) ABSNp. B) FTIR spectra of I) curcumin; II) Cur/NBSNp; III) Cur/ABSNp; IV) Cur-NBSNp; and V) Cur-ABSNp.
shows broader and less defined peaks, they completely disappear in the ABSNp diffraction pattern. Those results indicate that while NBSNp maintain certain crystalline structure, ABSNp have amorphous structures, probably related to the presence of acetyl groups in their chemical assemblies. As a way of further understanding the interaction between curcumin and the banana starch nanoparticles, the XRD patterns of Cur-NBSNp, Cur-ABSNp, Cur/NBSNp, and Cur/ABSNp were studied and are shown in Fig. 4B. The curcumin diffraction pattern showed its characteristic peaks at 8.84, 12.10, 14.39, 17.20, 23.33, 24.50, 25.52, and 28.87° attributed to its highly crystalline structure [38–40]. Most of those peaks were observed, along with the corresponding starch nanoparticles peaks, in the Cur/NBSNp and Cur/ABSNp diffraction patterns although with less intensity. This is different in the Cur-NBSNp, Cur-ABSNp diffraction patterns where those peaks disappeared. These results indicated that once encapsulated, curcumin exists in an amorphous rather than a crystalline state.
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A
Intensity
I)
II)
III) IV)
8
12
16
20
24
28
32
36
2θ
and LC values, meaning that more curcumin molecules are encapsulated. Mahmoudi Najafi et al. [16] studied the encapsulation of ciprofloxacin (CFx) in acetylated corn starch nanoparticles with different acetylation degrees. They observed that with increasing acetylation degree, LE increased because the presence of more oxygen atoms in the acetylated starch (carboxyl and hydroxyl) allows more CFx molecules interacting with the starch nanoparticles though hydrogen bonding. As previously explained, the interaction between curcumin and banana starch nanoparticles occurs mainly through hydrogen bonds; thereby, it is possible to think that as oxygen atoms increase, more curcumin molecules can be accommodated. The difference in the interaction among curcumin and NBSNp and ABSNp is also reflected in their UV–Vis and fluorescence spectra; as shown in Fig. 5A, the maximum absorption spectra of curcumin (Table 2) shifted from 429 nm in water to 424 nm in Cur-NBSNp and to 422 nm in Cur-ABSNp. A similar behavior was observed in the fluorescence emission spectra (Fig. 5B), where the emission maxima shifted from 550 nm in water to 515 and 502 nm Cur-NBSNp and Cur-ABSNp, respectively. The blue shift of both curcumin's absorption and emission spectra has been previously observed in other encapsulation studies and has been attributed to the
0,25
A
B
0,20
Absorbance
Intensity
I)
II)
0,10
0,05
III) IV)
0,00 300
V)
6
12
18
24
30
Cur Cur-NBSNp Cur-ABSNp
0,15
400
500
600
700
800
λ (nm)
36
2θ 7
1,6x10
Fig. 4. A) XRD pattern of I) NBS; II) ABS; III) NBSNp, and (IV) ABSNp. B) XRD diffraction pattern of I) curcumin; II) Cur/NBSNp; III) Cur/ABSNp; IV) Cur-NBSNp; and V) Cur-ABSNp.
B
7
1,4x10
3.3. Loading efficiency and fluorescence studies
1,2x10
The loading efficiency (LE) and loading capacity (LC) of Cur-NBSNp and Cur-ABSNp were determined and are shown in Table 2. Both nanoparticle systems showed LE and LC over 80%, indicating high affinity between curcumin and the banana starch nanoparticles. As shown in Table 2, the acetylated banana starch nanoparticles presented higher LE
1,0x10
Cur Cur-NBSNp Cur-ABSNp
Intensity (A.U)
7
7
6
8,0x10
6
6,0x10
6
4,0x10
Table 2 Loading efficiency (LE), loading capacity (LC), UV–Vis absorption maxima (λMax Abs) and fluorescence emission maxima λMax Emis (nm).
Curcumin Cur-NBSNp Cur-ABSNp
LE (%)
LC (mg/mg)
λMax Abs (nm)
λMax Emis (nm)
– 85.23 ± 2ª 90.63 ± 1.5b
– 2.031 ± 0.02a 3.205 ± 0.014b
429 424 422
550 515 502
Means with different superscripts are significantly different in their respective column (p b .05).
6
2,0x10
0,0 450
500
550
600
650
700
750
λ (nm) Fig. 5. A) UV–Vis of curcumin (Cur), Cur-NBSNp and Cur-ABSNp in water. B) Fluorescence emission spectra of UV–Vis of curcumin (Cur), Cur-NBSNp and Cur-ABSNp in water. λExc = absorption maxima.
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I
Cumulative curcumine released (%)
70
References
II
60 50
40 30
20 10 0
50
100
503
150
200
250
Time (min) Fig. 6. Curcumin release profiles of (■) Cur-ABSNp and (●) Cur-NBSNp in SGF (I) and SIF (II).
hydrogen bond interaction between curcumin and the encapsulating agent [41, 42]. So far, our results suggest that banana starch acetylation leads to more hydrogen bonding sites in the starch molecule, allowing interaction with more curcumin molecules. This seems to been confirmed as the absorption and fluorescence emission spectra of Cur-ABSNp shifted to a smaller wavelength than Cur-NBSNp, indicating that curcumin senses an environment with greater hydrogen bond acceptance. 3.4. Curcumin release studies Curcumin release in SGF and SIF was studied, as shown in Fig. 6. The Cur-ABSNp showed a lower release in SGF than Cur-NBSNp, with 15% difference after 120 min. The situation is different in SIF, given that Cur-ABSNp and Cur-NBSNp showed similar release profiles, indicating that both nanovehicles have similar interaction with the intestinal fluid. Li et al. [39] previously reported that curcumin entrapped in corn soluble starch nanoparticles have a burst release in both SGF and SIF that can be attributed to the easy degradation of soluble starch, compared to the more resistant banana starch. Incomplete curcumin release was observed in SGF and SIF, indicating that a small amount of curcumin stays trapped in the starch matrix. 4. Conclusion Nanoparticles from native and acetylated banana starch were prepared and used as nanovehicles for curcumin encapsulation and release. Acetylation probed to be a powerful chemical modification for encapsulation of hydrogen bond donor molecules, like curcumin. Given that the increasing number of hydrogen bond accepting sites allows a stronger nanoparticle-curcumin interaction which allows more curcumin molecules into the starch nanoparticles. Encapsulation did not have an effect on properties, like particle size and polydispersity index, proving that it is possible to synthetize nanoparticles from banana starch with sizes b250 nm. Finally, our results showed that ABSNp allowed a more controlled release of curcumin under gastric conditions, which could be a defining factor in their potential use in drug and nutraceutical delivery. Acknowledgement The authors want to thank Vicerrectoria de Investigaciones, Facultad de Ciencias Basicas y Tecnologias, Facultad de Ciencias Agropecuarias, Programa de Quimica, Programa de Ingenieria de Alimentos and FEDEPLATANO for their support.
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