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Journal of Photochemistry & Photobiology, B: Biology 205 (2020) 111837

Contents lists available at ScienceDirect

Journal of Photochemistry & Photobiology, B: Biology


journal homepage: www.elsevier.com/locate/jphotobiol

Sunscreen protection factor enhancement through supplementation with T


Rambutan (Nephelium lappaceum L) ethanolic extract
Milleno Dantas Motaa,b, Airana Nascimento da Boa Mortea,
Lidércia Cavalcanti Ribeiro Cerqueira e Silvac, Fábio Alexandre Chinaliac,

a
Department of Life Sciences, State University of Bahia, Silveira Martins Street, 2555, Cabula, Zip code 41150-000, Salvador, Bahia, Brazil
b
Department of Medicine, Faculty of Pharmacy, Federal University of Bahia, Barão do Jeremoabo Street, 147, Ondina, Zip code 40170-115 Salvador, Bahia, Brazil
c
Postgraduate Program in Biotechnology, Health Sciences Institute, Federal University of Bahia, Principal Miguel Calmon Avenue, Canela Valley, Zip code 40110-100
Salvador, Bahia, Brazil

ARTICLE INFO ABSTRACT

Keywords: The use of plant bioactives in cosmetic formulations are increasing due to the search for new sustainable sources
Cosmetics of raw materials, greater concern for safety and possible social impacts caused by the incorrect use of natural
Sun protection factor resources. Plant extracts have been the subject of several studies in several industrial areas. However, the po-
Photoprotection tential use of tropical fruits extracts in cosmetic formulations remains largely unexplored. Considering the im-
Nephelium lappaceum L
pact on public health and the possibility of using wastes from fruit processing, the aim of this work is to identify,
evaluate and develop a sunscreen based on rambutan peel extracts (Nephelium lappaceum L) as a natural additive
for enhancing the final product sun protection factor (SPF). The phytochemical screening revealed the presence
of tannins and flavonoids and the absence of coumarins. Even presenting a low sunscreen factor when used alone
(SPF value 0.4), rambutan extract at 1.00% FTP concentration improved the photoprotective result (11.2) of the
formulation containing 7.5% of ethylhexyl metoxycinnamate (EHMC) by 134%. The addition of rambutan ex-
tract in the formulation shows the potential to reduce the use of synthetic photoprotectors by about 64% of the
total synthetic organic filters used to achieve the SPF value of 26.3. In addition, the sunscreen formulation
supplemented with rambutan extract containing 1.00% RTP shows the potential to minimize the risk of synthetic
agent toxicity and a 45% reduction in the cost of sunscreen production.

1. Introduction intracellular DNA. The production of reactive oxygen species (ROS)


promotes oxidative stress that can cause skin photo aging. Therefore,
The ultraviolet (UV) radiation is only approximately 5% of the total the development of skin cancers as carcinomas and malignant mela-
solar radiation reaching the earth's surface. On the other hand, the noma are the principal long-term adverse effect of skin exposition to UV
Global Cancer Observatory (GCO) platform reports that, in 2019 alone, radiation [2].
more than 287,723 cases of malignant melanoma (MM) were associated In the list of most prevalent cancers, MM and NMSC occupy the 20th
to UV radiation with 21% mortality ratio. Furthermore, in the same and 5th positions respectively. Of the estimated total cases of skin
period it was reported 1,042,056 cases of non-melanoma skin cancer cancers (MM and NMSC) caused by exposure to UV radiation, the
(NMSC) with 6% mortality ratio [1]. Photoprotectors sunscreens are majority are concentrated in North America (42.3%), followed by
therefore used to minimize exposure to this radiation. This product can Europe (34.8%), Asia (7.5%), Oceania (6.6%), Africa (2.3%) and Latin
prevent severe debilitating sunburn, solar urticarial, suppression of the America/Caribbean (6.5%). Europe and Asia are the continents with
immune system and other health problems caused by damage to the highest estimated total deaths from the disease (32.5% and 30.6%,

Abbreviations: UV, ultraviolet; GCO, Global Cancer Observatory; MM, malignant melanoma; NMSC, non-melanoma skin cancer; ROS, reactive oxygen species; FDA,
Food and Drug Administration; EC, European Commission; CAGR, compound annual growth rate; RLE, Rambutan Liquid Extract; RCCE, rambutan concentrated
crude extract; EqGA, equivalents of gallic acid; SPF, sun protection factor; O/A, oil-in-water; EHMC, ethylhexyl methoxycinnamate; HMS, homomenthyl salicylate;
RTP, rambutan total phenolic; CF, correction factor; EE, erythematogenic effect; I, radiation intensity; EHS, ethylhexyl salicylate; BMDBM, butyl methoxydibenzoyl
methane; OCR, octocrylene; BP3, benzophenone-3; CAPES, Brazilian Coordination for the Improvement of Higher Education Personnel; PPGBiotec, Postgraduate
Program in Biotechnology.

Corresponding author.
E-mail address: chinalia@hotmail.com (F.A. Chinalia).

https://doi.org/10.1016/j.jphotobiol.2020.111837
Received 25 November 2019; Received in revised form 20 January 2020; Accepted 20 February 2020
Available online 21 February 2020
1011-1344/ © 2020 Elsevier B.V. All rights reserved.
M.D. Mota, et al. Journal of Photochemistry & Photobiology, B: Biology 205 (2020) 111837

respectively) [1]. It is also estimated that UV radiation exposure will be


responsible for 177,579 new cases of MM, and 931,411 new cases of
NMSC worldwide by 2040 [3]. These data demonstrate the importance
of UV protection for human health and well-being.
The wavelengths of UV radiation are distributed in the range from
100 to 400 nm. This radiation is subdivided into UV-C (100 to 280 nm),
UV-B (280 to 315 nm) and UV-A (315 to 400 nm). UV radiation from
the sun that reaches the earth's surface in the midday period is about
95% UV-A and 5% UV-B. The stratospheric ozone layer absorbs the
remaining UV-B radiation and all UV-C, but the depletion of the ozone
layer in the past has increased the amount of UV-B that reaches the
earth's surface [4,5]. UV-A radiation is responsible for immediate skin
pigmentation. This radiation has the ability to penetrate to deeper
layers of the skin and can reach the dermis, being responsible for skin
changes related to photo aging. UV-B can induce late pigmentation and,
due to its higher energy, is the leading cause of immediate skin damage
(erythema and sunburn). It is also related with changes in cellular DNA
and has the potential to induce skin cancer [6].
To prevent and minimize the damaging effects of UV radiation, it is
recommended to wear clothes, accessories, sunscreens or by avoiding Fig. 1. Diagram with the description of the methodology applied in this re-
sun exposure. The first sunscreen became commercially available in the search. Six different samples (S1, S2, S3, S4, S5 and S6) of cosmetic formulation
USA market in 1928. However, it was only in the late 1970s that natural were tested according to the different concentrations of rambutan fruit peel
organics with UV-A and UV-B protective properties were incorporated extract and synthetic organic filter. Three controls were used (C1, C2 and C3)
in sunscreen formulations [7]. In the USA and Europe, the Food and for the experiment.
Drug Administration (FDA) and the European Commission (EC) are the
agencies responsible for ensuring that the sunscreen product is effective Considering the impact of the use of sunscreens on public health and
and safe. These agencies often determine the minimum and maximum the possibility of upcycling wastes from fruit processing, the aim of this
of such UV protective substances [8,9]. The global market of sun care work is to identify, evaluate and develop a sunscreen based on etha-
products amounted to about 9.23 billion US dollars in 2018, and it is nolic rambutan fruit peel extract as a natural additive for SPF cosmetic
projected to reach 10.4 billion dollars by 2024. It represents an annual products.
growth rate (CAGR) of 2.15% [10].
Sunscreens can protect the skin from UV radiation through the as-
sistance of different organic and inorganic filters. Inorganic filters are 2. Materials and Methods
commonly particulate oxides reflecting or scattering UV radiation.
Organic filters are aromatic compounds that have groups capable of The methodology used in this research is described in the diagram
absorbing high-energy photons from the UV radiation. By absorbing presented in Fig. 1. In the scheme, it can be observed that the fruits
energy, the molecules are excited and when it returns to its ground were acquired and then dried by lyophilization and submitted to sub-
state, this energy is released in the form of heat or light in a non- sequent extraction with ethanol. The extract was used for the phyto-
harmful wavelength. Both organic and inorganic filters are often asso- chemical screening tests followed by concentration and standardization
ciated in commercial sunscreens to increase product efficiency [11,12]. prior to sunscreen formulation. This was followed by the preparation of
With the pursuit of more skin-compatible cosmetic actives, espe- cosmetic products, which had their sun protection factor then de-
cially for people with sensitive or allergic skin, a novel wide range of termined.
hypoallergenic cosmetics have also been developed in recent years.
Several new plant-based products cause less skin irritation. These
2.1. Plant Material
bioactive molecules are often obtained from parts of the fruits. For in-
stance, Vitellaria paradoxa fruit extract, known as shea butter, contains
The red rambutan fruits were purchased at a free market in down-
a mixture of fatty acids that are commercially used as sunscreen cos-
town Salvador, Bahia, Brazil. Healthy red fruits with intact peel and no
metic. Punica granatum fruit extract is also effective against UV radia-
signs of contamination were selected for the research. Confirmation of
tion [13–15]. In addition to UV protection, some fruit extract exhibit
botanical identity was performed by comparison with information and
also an antioxidant effect. For instance, passion fruit seed oil (Passiflora
characteristics described in specialized literature. After the fruits were
edulis) has been added to cosmetic formulations due to its antioxidant
washed quickly with drinking water, the pulp and seeds were separated
and UV-protective properties [16]. An UK company, REN, produces the
from the peel. The peels were then stored at −40 °C for preparation for
Clean Screen Mineral SPF 30, a mattifying face sunscreen with broad
extraction.
spectrum UV-A and UV-B protection. This product contains the yellow
passion fruit seed extract [17]. Mishrar et al. described other herbal
cosmeceuticals products based on fruits extracts from tomato, apple, 2.2. Liquid Extract Preparation and Concentration
lemon and bitter orange [18].
Rambutan (Nephelium lappaceum L) is a tropical plant commonly Frozen peels were lyophilized until reach a constant weight.
found in the Northeast Brazil and Southeast Asia. The peel (exocarp) of Rambutan liquid extract (RLE) was carried out using ethanol. Three
the fruits contain high concentration of substances with photo- maceration cycles of 48 h each were applied and the extract was filtered
protective potential and are discarded after pulp extraction [19–21]. before use [24]. At the end of the cycles, the three RLEs obtained were
Global rambutan production was approximately 2.5 million tons in combined and a sample (30.0 mL) was separated for phytochemical
2018, and commercialization is expected to grow at a CAGR of 3.2% by screening. Rambutan concentrated crude extract (RCCE) was obtained
2026 [22]. The estimated market of fresh rambutan in Asia is of ap- with assistance of a rotary evaporator at 40 °C and under vacuum.
proximately € 4 million [23]. Standardization was monitored by total phenolic content.

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M.D. Mota, et al. Journal of Photochemistry & Photobiology, B: Biology 205 (2020) 111837

2.3. Phytochemical Screening and Total Phenolic Content Determination (Table 1), they were separately heated to 75 °C (phase 1) and 80 °C
(phase 2). After reaching working temperatures, both phases were
For presence identification of flavonoids, tannins and coumarins, combined under mechanical agitation. Stirring was maintained at a
the RLE was chemically screened according to the methodology pro- constant rate of 1500 rpm until the emulsion was cooled to about 40 °C,
posed by Matos in 1997 and Simões et al. in 2017 [25,26]. previous to the addition of the remaining components of the different
For extract standardization, the determination of the total phenolic formulations (phase 3, Table 1).
content present in the RCCE was performed by visible region spectro- The estimated SPF values were calculated using Eq. (1) according to
scopy using the Folin-Ciocalteu method adapted from the methodology methodology developed and proposed by Mansur et al. in 1986 [30],
developed by Slinkard & Singleton in 1977, using gallic acid as re- and used in various studies of this nature [31,32]. This is a simple and
ference [27]. For the construction of the analytical curve, standard reliable methodology that shows significant correlation with the data
solutions of gallic acid at concentrations of 25.0 μg mL−1, obtained in in vivo SPF studies [33,34]. Controls (C1, C2 and C3) and
50.0 μg mL−1, 100.0 μg mL−1, 150.0 μg mL−1 and 500.0 μg mL−1 were samples (S1, S2, S3, S4, S5 and S6) were diluted in ethanol to final
used. concentration of 0.20 mg mL−1. Triplicates of these solutions were
A 0.5 g sample of the RCCE was weighed and then diluted to subjected to absorbance scanning in the range between 290 and
10.0 mL with distilled water. From this diluted extract, a 0.5 mL aliquot 320 nm, at 5 nm intervals in a Biochrom, Libra S50UV scanning spec-
was taken for sample preparation by adding 7.9 mL distilled water and trophotometer. The correction factor (CF) was determined using stan-
0.5 mL Folin-Ciocalteu reagent (phosphomolybdate and phosphotung- dardized control sample containing 8% (w/w) of HMS, which, in such
state) at 0.2 M. The mixture was allowed to stand for 4 min protected conditions, is known to provide a SPF of 4 (C3, Table 1). The absor-
from light. Then 2.25 mL of 7.5% (w/v) sodium carbonate solution was bances obtained for the working samples were then applied to the Eq.
added to the reaction mixture while stirring. The solution was kept for (1) in order to estimate the in vitro SPF.
20 min at 50 °C in a heated bath. Standard gallic acid solutions were 320
submitted to the same sample preparation process in triplicate. The SPF = CF x EE( ) x I( ) x ABS( )
absorbance readings were taken on a spectrophotometer (Bel, SP 2000 290 (1)
UV) at 765 nm and the results of standard gallic acid solutions were where: SPF is the Solar Protection Factor; CF is the correction factor (=
computed on a graph correlating the absorbance of the solution with its 10,24), estimated from the control containing 8% HMS corresponding
concentration [28]. From the calibration curve and line equation ob- to SPF 4; EE(λ) is the erythematogenic effect of radiation with wave-
tained, it was possible to determine the concentration of total phenolic length λ; I(λ) is the intensity of sunlight radiation with wavelength λ;
in RCCE, expressed in milligrams equivalents of gallic acid per gram of ABS(λ) = absorbance of the controls and samples containing the organic
RCCE (mg EqGA g−1). filters and extract at the wavelength λ.
In a previous study (1979) that compared the in vivo and in vitro
2.4. In vitro Solar Protection Factor (SPF) Determination efficacy of sunscreens, Sayre et al. determined the EE x I constant values
[35,36], as described in Table 2.
Three different controls (C1, C2 and C3) and six different samples
(S1, S2, S3, S4, S5 and S6) were used for the in vitro SPF determination 3. Results and Discussion
(cream emulsion), as it is shown in Fig. 1 and Table 1. The negative
control corresponds to the results obtained with a cream oil-in-water 3.1. Phytochemical Screening and Total Phenolic Content Determination
(O/A) emulsion (C1). This base was prepared according to the nonionic
lotion II formula described in the Brazilian Pharmacopoeia National Chemical characterization showed that rambutan fruit peel extract
Protocol [29], with the modifications shown in Table 1. Controls C2 is rich in substances related to a photoprotective action such as flavo-
and C3 corresponded to the cream emulsion in which was added the noids and tannins (Table 3). Furthermore, the extract shows the ab-
organic filters ethylhexyl methoxycinnamate (EHMC) and homo- sence of coumarins, which are harmful for the skin. Because of their
menthyl salicylate (HMS), respectively (Fig. 1 and Table 1). Experi- chemical structure, they absorb UV radiation and are photosensitizing,
mental samples consisted of cream emulsion added with RCCE and which justifies their use in photochemotherapy. Due to this feature,
three distinct concentrations of rambutan total phenolic (RTP) (S1, S2 their presence in photoprotective formulations should be avoided
and S3, Fig. 1 and Table 1); and the cream emulsion added with EHMC [37,38]. Many factors affect the chemical composition of the fruits,
and RCCE in three distinct concentrations of RTP (S4, S5 and S6, Fig. 1 such as climate, harvest, soil and extractive process (method, tem-
and Table 1). Biological and chemical preservatives, fragrances and perature and solvent employed). Fila et al. analyzed rambutan fruits
pigments, were not used in the formulations. from Nigeria and reported that peels contain tannins at concentration of
Cream base emulsion (C1) was produced according to the general 1.35 mg 100 g−1, which is significantly higher than what is found in
hot emulsification method [29]. After weighing phases 1 and 2 seed (0.15 mg 100 g−1) and pulp (0.12 mg 100 g−1) [39]. Likewise,

Table 1
Compositions of the cosmetics formulations. ⁎INCI, International Nomenclature of Cosmetic Ingredients, −, raw material not added.
Components (INCI)⁎ Concentration (%, w/w)

C1 C2 C3 S1 S2 S3 S4 S5 S6

Phase 1
Disodium EDTA 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10
Purified water 88.90 81.40 80.90 88.65 88.40 87.90 81.15 80.90 80.40
Phase 2
Nonionic self-emulsifying wax (cetostearyl alcohol, ethoxylated sorbitan monostearate) 9.00 9.00 9.00 9.00 9.00 9.00 9.00 9.00 9.00
Decyl oleate 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00
Phase 3
Rambutan total phenolics - - - 0.25 0.50 1.00 0.25 0.50 1.00
Ethylhexyl methoxycinnamate - 7.50 - - - - 7.50 7.50 7.50
Homomenthyl salicylate - - 8.00 - - - - - -

3
M.D. Mota, et al. Journal of Photochemistry & Photobiology, B: Biology 205 (2020) 111837

Table 2
Relationship between the erythematogenic effect (EE)
and the intensity of the radiation (I) at each wavelength
[35].
Wavelenght (λ nm) EE(λ) x I(λ)

290 0.0150
295 0.0817
300 0.2874
305 0.3278
310 0.1864
315 0.0839
320 0.0180
Total 1.0000

Fig. 2. Absortion spectrum of rambutan fruit peel extract and ethylhexyl


methoxycinnamate.
Table 3
Phytochemical screening in the ethanolic extract of N. lappaceum L.
3.2. In vitro SPF Determination
Metabolites Results Estimated concentration (mg 100 g−1) References

Flavonoids Positive 69.36 to 88.84 [39][40] The synthetic photoprotector EHMC showed significant absorption
Tannins Positive 1.35 [39] efficient in both UV-B and UV-A ranges (Fig. 2). The RCCE showed a
Coumarins Negative Not reported –
maximum absorption range between the UV-B region (315-280 nm),
which is lower than that observed for EHMC alone. Although the ab-
sorption of RCCE in the UV-B range was lower, it is possible to observe a
tannins are also present at a higher concentration in the peels
positive synergistic interaction in the UV absorption range when both
(88.84 mg 100 g−1) than in seed (16.00 mg 100 g−1) or the pulp
are combined in the designed cosmetic formulations (Fig. 3). This in-
(7.64 mg 100 g−1). Working with ethanolic extract, Yunusa et al. re-
teraction results in an increase of SPF value (Fig. 4).
ported that flavonoid in the peels reach a concentration of 69.36 mg
The main compounds that can be associated to SPF improvements
100 g−1 [40]. Phenolic substances such as tannins and flavonoids are
when using rambutan extract are ellagic acid (Fig. 5), corilagin, ger-
directly related to photoprotective action against UV radiation [41,42].
aniin, apigenin, quercetin, catechin and anthocyanins (Table 4)
They are often related to plant defense mechanisms but, in cosmetic
[45–47]. These substances have conjugated bonds and chemical groups
formulations, these substances are antioxidant, anti-inflammatory and
responsible for absorbing UV radiation at different wavelengths
anti-aging [43,44]. The RCCE showed a total phenolic content of
(Fig. 5). For instance, quercetin and anthocyanins directly absorb UV
151.00 mg g−1.
radiation, inhibiting skin damage promoted by UV-B radiation [43].
According to research developed by Thitilertdecha et al. (2010), the
Furthermore, the ellagitannins and cathechin are also considered potent
main phenolic compounds found in the methanolic extract of rambutan
antioxidants capable of minimizing the effect of free radical damage
peels are the ellagitannins such as ellagic acid, geraniin and corilagin;
that is associated to UV radiation exposure. Several studies have de-
which account for about 69% of the substances present in such extract
monstrated the protective effect of apigenin in the prevention of skin
[45]. Hernández et al. (2017) and Zhuang et al. (2017) reported the
carcinogenesis induced by UV radiation [43]. The antioxidant proper-
same ellagitannins and derivatives as the main phenolic compounds
ties of these metabolites may also contribute to stabilize the organic
present in rambutan peel methanolic extracts. In addition, the authors
synthetic UV filters, such as EHMC. Therefore, their presence minimize
have also identified the presence of hydroxycinnamic and hydro-
the EHMC photodegradation improving the UV protection effect
xybenzoic acids derivatives, flavones, anthocyanins, flavonols and fla-
[48,49]. In other words, although some natural substances do not show
vanols (Table 4) [46,47].
photoprotective activity, they may enhance the synthetic filter protec-
tion by stabilizing or rejuvenate its chemical characteristics during UV
exposure.
The control containing only the base lotion (C1) or the sample
Table 4 containing only 0.25% of RTP (S1, Fig. 4) showed a SPF value of zero.
Phytochemical compounds in N. lappaceum L fruit peel extracts. The main
components (ellagic acid, corilagin and geraniin) correspond to a range of
69.3% to 74.6% of the extracts, with geraniin being the major component
among all identified (56.8% to 61.4%) [46,47].
Major Compound Class References

Pelargonidin Anthocyanins [46]


Vitisin A [46]
Brevifolin carboxylic acid Ellagitannins [46]
Castalagin/Vescalagin [46]
Casuarinin [46]
Corilagin [45–47]
Ellagic acid and derivatives [45–47]
Geraniin [45–47]
Catechin Flavanols [47]
Procyanidins [47]
Apigenin Flavones [46]
Apigenin arabinoside-glucoside [46]
Rutin [47] Fig. 3. Comparison of the absorption spectrum of the control containing EHM
Kaempferol derivatives Flavonols [47]
and samples containing EHM (C2) and total phenolic of rambutan in different
Quercetin derivatives [47]
concentrations (S4, S5 and S6).

4
M.D. Mota, et al. Journal of Photochemistry & Photobiology, B: Biology 205 (2020) 111837

points to the alternative of reducing the concentration of the inorganic


filter when associated with the natural bioactive in the formulation.
Such a reduction is positive for it can mitigate costs and potential toxic
effect of the synthetic compound.
In order to achieve higher SPF values, the cosmetic industry uses the
combination of many other organic filters in the same formulation.
Compounds such as ethylhexyl salicylate (EHS) and butyl methox-
ydibenzoyl methane (BMDBM) are commonly used in commercial
photoprotective products. When in combination, their maximum al-
lowable concentrations are of 5 and 3% w/w, respectively. This com-
bination can increase the EHMC-based SPF value in about 63%. The SPF
augmentation that was achieved by the addition of natural RTP in the
formulation (134% promoted by S6), is only similarly achieved with the
Fig. 4. In vitro SPF determined by spectrophotometry of controls and samples. addition of other two synthetic filters such as octocrylene (OCR) and
benzophenone-3 (BP3). They would be required at concentrations of
The other two samples containing only RTP at concentrations of 0.50 0.15 and 5%, respectively. Thus, 1% augmentation with natural RTP
and 1.00% (S2 and S3, Fig. 4) showed SPF value of 0.1 and 0.4, re- (S6, Fig. 4) reduces the total amount of synthetic sunscreens by almost
spectively. According to the FDA [9] the final product must provide a 64%. It is a significant achievement that can affect risk of skin irritation
minimum SPF of 2 to be approved as sunscreen. These results indicate and toxicity. This can also reduce costs in about 45%.
that in order to obtain the expected photoprotection, RTP must be used In recent years, several studies were carried out in order to evaluate
at very high concentrations in the cosmetic product. the photoprotective potential of plant extracts. Fruit extracts such as
The results showed that control containing only 7.5% of EHMC (C2, Carica papaya L., Passiflora edulis, Musa accuminata L., Psidium guajava
Fig. 4) provides a SPF value of 11.2. This is the maximum concentration L. and Pyrus communis L. were used in different concentrations, either
allowed by the FDA to use this active ingredient in sunscreen for- alone or in combination with organic and inorganic filters, in the de-
mulations. At this concentration, and depending on the cosmetic for- velopment of cosmetic formulations, and had their photoprotective
mulation used and the amount of product applied to the skin, the activities evaluated [16,51–53]. The SPF values obtained for formula-
product may provide an estimated SPF in the range of 6.4 to 13.3 [50]. tions containing the extracts of C. papaya and P. guajava alone, and a
The synergistic effect of rambutan extract with EHMC is clear when combination of M. accuminata, P. guajava and P. communis, varied from
analyzing the results shown for samples containing organic sunscreen 1.0 to 3.9 [51–53], demonstrating the low activity of the isolated ex-
and RTP at three different concentrations (S4, S5 and S6, Fig. 4). The tracts. Studies using the combination of P. edulis fruit extract with in-
addition of rambutan phenolics at concentrations of 0.25%, 0.50% and organic titanium dioxide sunscreen [16], and the combination of P.
1.00% resulted in an increase of SPF values of 23.5, 49.6 and 134.9% guajava fruit extract with EHMC [53], obtained SPF values in the range
(with values of 13.8, 16.8 and 26.3, Fig. 4), respectively. This result of 9.7 to 18.9. In these two studies, the extracts tested showed the

Fig. 5. Mechanism of action of organic synthetic


filter ethylhexyl methoxycinnamate (EHM), based on
the mechanism of p-aminobenzoic acid (Adapted
from Shaath [49]), and ellagic acid (phenolic com-
pound found on rambutan fruits peel). The scheme
represents the electron delocalization in the mole-
cules of (a) EHMC and (b) ellagic acid. Energy ab-
sorbed by lone pairs of electrons and double bonds of
molecules is released by fluorescence or photo-
chemical reactions as non-aggressive energy to the
skin when it returns to the ground state.

5
M.D. Mota, et al. Journal of Photochemistry & Photobiology, B: Biology 205 (2020) 111837

ability to improve SPF of inorganic and organic sunscreen formulations mono100D-6.pdf, (2012).
by up to 66% and 133%, respectively. Thus demonstrating the sy- [5] A. Modenese, L. Korpinen, F. Gobba, Solar radiation exposure and outdoor work: an
underestimated occupational risk, Int. J. Environ. Res. Public Health 15 (2018)
nergistic effect of the extracts with the synthetic filters used in the 2063, https://doi.org/10.3390/ijerph15102063.
formulation, with the most significant result achieved with P. guajava [6] E.B. Manaia, R.C.K. Kaminski, M.A. Corrêa, L.A. Chiavacci, Inorganic UV filters,
extract. Brazilian J. Pharm. Sci. 49 (2013) 201–209, https://doi.org/10.1590/S1984-
82502013000200002.
In spite of the reported advantages, sunscreens commercial for- [7] S. Schalka, V.M.S. dos Reis, Sun protection factor: meaning and controversies, An.
mulation using herbal or plant extracts is still limited to a few species. It Bras. Dermatol. 86 (2011) 507–515, https://doi.org/10.1590/s0365-
is important to highlight that in the development of this research no 05962011000300013.
[8] European Commission, Regulation (EC) No 1223/2009. Establishes rules to be
sunscreen products or patent registrations containing rambutan fruit complied with by any cosmetic product made available on the market, in order to
extract were found in the market. Diversification of cosmetic formula- ensure the functioning of the internal market and a high level of protection of
tions can significantly contribute to the socio-economic development of human health, European Union, https://ec.europa.eu/health/sites/health/files/
endocrine_disruptors/docs/cosmetic_1223_2009_regulation_en.pdf, (2009).
small regional farmers as well as reduce the dependency of synthetic
[9] Food and Drugs Administration, Electronic Code of Federal Regulations, Federal
substances. Sunscreen augmentation with fruit extract has the potential Register of May 21, 1999 (64 FR 27666), Title 21: Food and Drugs. Part 352 -
for increasing the quality of the commercially available products. Sunscreen Drug Products For Over-The-Counter Human Use [Stayed Indefinitely].
Subpart B - Active Ingredients. §352.10 Sunscreen ac, USA, https://www.ecfr.gov/
cgi-bin/text-idx?SID=3ebe6e78b2fd53705d632ea124784d03&mc=true&node=
4. Conclusions se21.5.352_110&rgn=div8, (1999).
[10] Mordor Intelligence, Global Sun Care Products Market - Growth, Trends and
Like EHMC and other photoprotective active substances, the Forecasts (2019–2024), Hyderabad, India, https://research.mordorintelligence.
com/reports/sun-care-products-market, (2018).
Nephelium lappaceum L. extract used in this research was able to absorb [11] M. Latha, J. Martis, V. Shobha, R.S. Shinde, S. Bangera, B. Krishnankutty, S. Bellary,
UV radiation in the UV-B range, between the ranges of 290 to 320 nm. S. Varughese, P. Rao, B.N. Kumar, Sunscreening agents: a review, J. Clin. Aesthet.
The association of EHMC with RTP resulted in a significant increase in Dermatol. 6 (2013) 16–26.
[12] S.E. Mancebo, J.Y. Hu, S.Q. Wang, Sunscreens: a review of health benefits, reg-
the SPF values, even at the lowest concentration. This increase is due to ulations, and controversies, Dermatol. Clin. 32 (2014) 427–438, https://doi.org/10.
the synergistic effect between the phenolic substances present in the 1016/j.det.2014.03.011.
rambutan fruits peels and the EHMC. This indicate a significant po- [13] L. Araújo, S. Curty, A. Moreira, A. Rossi, N. Raposo, U. Vaz, H. Polonini,
Development of broad-spectrum natural sunscreens using combinations of five
tential for the reduction of synthetic filter in the formulation. plant species, J. Young Pharm. 8 (2016) 144–148, https://doi.org/10.5530/jyp.
Coumarins were not detected in the fruit extract. This research shows 2016.2.17.
several possibilities for composing new innovative cosmetic formula- [14] L. Montenegro, L. Santagati, Use of vegetable oils to improve the Sun protection
factor of sunscreen formulations, Cosmetics. 6 (2019) 25, https://doi.org/10.3390/
tions such as the development of rambutan based sunscreen. The pro-
cosmetics6020025.
duction of cosmetics from natural substances with these activities will [15] P. Goswami, M. Samant, R. Srivastava, Natural sunscreen agents: a review, Sch.
be of great importance to the cosmetic industry and may reduce the cost Acad. J. Pharm. 2 (2013) 458–463.
of production, which represents a major scientific and economic im- [16] N. Lourith, M. Kanlayavattanakul, J. Chingunpitak, Development of sunscreen
products containing passion fruit seed extract, Brazilian J. Pharm. Sci. 53 (2017),
pact. Further allergenic, toxicological and stability testing of these https://doi.org/10.1590/s2175-97902017000116116.
products is still required. This research also points to new technologies [17] REN Clean Skincare, Clean Screen Mineral SPF 30, https://www.renskincare.com/
for the recovery and purification of photoprotective bioactive from products/clean-screen-mineral-spf-30-mattifying-face-sunscreen, (2019) , Accessed
date: 21 October 2019.
these natural derivatives, as well as suggesting the synergistic interac- [18] A. Mishra, A. Mishra, P. Chattopadhyay, Herbal cosmeceuticals for photoprotection
tion between the extracts with other synthetic filters. The global ram- from ultraviolet b radiation: a review, Trop. J. Pharm. Res. 10 (2011), https://doi.
butan fruit market is likely to grow further with the development of org/10.4314/tjpr.v10i3.7.
[19] R.A. de Andrade, E.G.M. de Lemos, A.B.G. Martins, R.C. de Paula, J.L. Pitta Junior,
new products such as described in this research. Once this research was Caracterização morfológica e química de frutos de rambutan, Rev. Bras. Frutic. 30
based in the upcycling of fruit wastes, a potential new product is (2008) 958–963, https://doi.org/10.1590/S0100-29452008000400020.
complementary to de food and drink marked associated to this fruit. [20] A.D.F. Santos Junior, L.C. Oliveira, A.D.S. Guedes, M.D. Mota, H.I.F. Magalhaes,
Atividade antioxidante e tóxica de extratos de cascas do fruto de Nephelium
Lappaceum L. (Sapindaceae), comercializados em Salvador, Bahia, Brasil, Infarma -
Declaration of Competing Interest Ciências Farm. 28 (2016) 173, https://doi.org/10.14450/2318-9312.v28.e3.a2016.
pp173–178.
[21] S. Riyanto, A. Rohman, Antioxidant activities of Rambutan (Nephelium lappaceum L)
The authors declare that they have no known competing financial
peel in vitro, Food Res. 2 (2017) 119–123, https://doi.org/10.26656/fr.2017.2(1).
interests or personal relationships that could have appeared to influ- 150.
ence the work reported in this paper. [22] Global Market Monitor, Global Rambutan Market Professional Research Report
2014-2026, Segmented by Players, Types, End-Users in Major 40 Countries or
Regions, (2019).
Acknowledgements [23] Centre for the Promotion of Imports from developing countries (CBI), Exporting
rambutan to Europe, Minist. Foreign Aff, 19 (2019) https://www.cbi.eu/market-
The authors are grateful to the Pharmaceutical Compounding information/fresh-fruit-vegetables/rambutan/.
[24] N.N. Azwanida, A review on the extraction methods use in medicinal plants,
Laboratory and the Instrumental Multipurpose Laboratory of the principle, strength and limitation, Med. Aromat. Plants. 04 (2015), https://doi.org/
Faculty of Pharmacy, Federal University of Bahia, for providing the 10.4172/2167-0412.1000196.
necessary equipment for the study. The authors also thank the Brazilian [25] F.J. Matos, Introdução à fitoquímica experimental, second ed., Edições UFC,
Fortaleza, 1997.
Coordination for the Improvement of Higher Education Personnel [26] L.A.P.P. Simões, C.M.O. Schenkel, E.P. Gosmann, G. Mello, J.C.P. Mentz,
Council (CAPES). Farmacognosia: Do Produto Natural ao Medicamento, 1st ed, (2017) Artmed, Porto
Alegre.
[27] K. Slinkard, V.L. Singleton, Total phenol analysis: automation and comparison with
References
manual methods, Am. J. Enol. Vitic. 28 (1977) 49–55.
[28] F.-L. Song, R.-Y. Gan, Y. Zhang, Q. Xiao, L. Kuang, H.-B. Li, Total phenolic contents
[1] World Health Organization, International Agency for Research on Cancer, Global and antioxidant capacities of selected Chinese medicinal plants, Int. J. Mol. Sci. 11
Cancer Observatory, Cancer Today, https://gco.iarc.fr/today/home, (2019). (2010) 2362–2372, https://doi.org/10.3390/ijms11062362.
[2] World Health Organization, International travel and health: situation as on 1 [29] Brazil. Ministry of Health. Brazilian Health Surveillance Agency (ANVISA),
January 2012, (2012), p. 274 https://www.who.int/ith/ITH_EN_2012_WEB_1.2. Brazilian Pharmacopeia National Form, ANVISA, Brasília, Brazil, (2012).
pdf?ua=1. [30] J.S. Mansur, M.N.R. Breder, M.C.D. Mansur, R.D. Azulay, Determinação do fator de
[3] World Health Organization, International Agency for Research on Cancer, Global proteção solar por espectrofotometria, An. Bras. Dermatol. 61 (1986) 121–124.
Cancer Observatory, Cancer Tomorrow, https://gco.iarc.fr/tomorrow/home, [31] M.A. Khan, Sun protection factor determination studies of some sunscreen for-
(2019). mulations used in cosmetics for their selection, J. Drug Deliv. Ther. 8 (2018)
[4] World Health Organization, International Agency for Research on Cancer, Solar and 149–151, https://doi.org/10.22270/jddt.v8i5-s.1924.
Ultraviolet Radiation, https://monographs.iarc.fr/wp-content/uploads/2018/06/ [32] S.N. Naik, S. Desai, Estimation and comparison of hydro-alcoholic and water extract

6
M.D. Mota, et al. Journal of Photochemistry & Photobiology, B: Biology 205 (2020) 111837

for Sun protection factor activity from naturally available resources, Int. J. Env. Sci. V.O. Consiglieri, T.M. Kaneko, C. Rosado, J. Mota, M.V.R. Velasco, A.R. Baby,
Nat. Res. 21 (2019) 15–20. Functional photostability and cutaneous compatibility of bioactive UVA sun care
[33] E.P. Santos, Z.M. Freitas, K.R. Souza, S. Garcia, A. Vergnanini, In Vitro and In Vivo products, J. Photochem. Photobiol. B Biol. 148 (2015) 154–159, https://doi.org/10.
determinations of sun protection factors of sunscreen lotions with 1016/j.jphotobiol.2015.04.007.
Octylmethoxycinnamate, Int. J. Cosmet. Sci. 21 (1999) 1–5, https://doi.org/10. [45] N. Thitilertdecha, A. Teerawutgulrag, J.D. Kilburn, N. Rakariyatham, Identification
1046/j.1467-2494.1999.181658.x. of major phenolic compounds from Nephelium lappaceum L. and their antioxidant
[34] S.I. Yang, S. Liu, G.J. Brooks, Y. Lanctot, J.V. Gruber, Reliable and simple spec- activities, Molecules 15 (2010) 1453–1465, https://doi.org/10.3390/
trophotometric determination of sun protection factor: a case study using organic molecules15031453.
UV filter-based sunscreen products, J. Cosmet. Dermatol. 17 (2018) 518–522, [46] C. Hernández, J. Ascacio-Valdés, H. De la Garza, J. Wong-Paz, C.N. Aguilar,
https://doi.org/10.1111/jocd.12390. G.C. Martínez-Ávila, C. Castro-López, A. Aguilera-Carbó, Polyphenolic content, in
[35] R.M. Sayre, P.P. Agin, G.J. LeVee, E. Marlowe, A comparison of in vivo and in vitro vitro antioxidant activity and chemical composition of extract from Nephelium
testing of sunscreening formulas, Photochem. Photobiol. 29 (1979) 559–566, lappaceum L. (Mexican rambutan) husk, Asian Pac, J. Trop. Med. 10 (2017)
https://doi.org/10.1111/j.1751-1097.1979.tb07090.x. 1201–1205, https://doi.org/10.1016/j.apjtm.2017.10.030.
[36] R.M. Sayre, P.P. Agin, D.L. Desrochers, E. Marlowe, Sunscreen testing methods : In [47] Y. Zhuang, Q. Ma, Y. Guo, L. Sun, Protective effects of rambutan (Nephelium lap-
vitro predictions of effectiveness, J. Soc. Cosmet. Chem. 31 (1980) 133–143. paceum) peel phenolics on H 2 O 2 -induced oxidative damages in HepG2 cells and d
[37] R. Dubakiene, M. Kupriene, Scientific problems of photosensitivity, Medicina -galactose-induced aging mice, Food Chem. Toxicol. 108 (2017) 554–562, https://
(Kaunas). 42 (2006) 619–624. doi.org/10.1016/j.fct.2017.01.022.
[38] M.J. Matos, L. Santana, E. Uriarte, O.A. Abreu, E. Molina, E.G. Yordi, Coumarins - [48] A. Hubner, F. Sobreira, A. Vetore Neto, C.A.S.O. de Pinto, M.F. Dario, I.E.C. Díaz,
an important class of phytochemicals, Phytochem. - Isol. Characterisation Role F.R. Lourenço, C. Rosado, A.R. Baby, E.M. Bacchi, The synergistic behavior of an-
Hum. Heal., InTech, 2015, https://doi.org/10.5772/59982. tioxidant phenolic compounds obtained from winemaking Waste’s valorization,
[39] W.O. Fila, J.T. Johnson, P.N. Edem, M.O. Odey, V.S. Ekam, U.P. Ujong, O.E. Eteng, increased the efficacy of a sunscreen system, Antioxidants 8 (2019) 530, https://
Comparative anti-nutrients assessment of pulp, seed and rind of rambutan doi.org/10.3390/antiox8110530.
(Nephelium lappaceum), Ann. Biol. Res. 3 (2012) 5151–5156. [49] N.A. Shaath, Ultraviolet filters, Photochem. Photobiol. Sci. 9 (2010) 464–469,
[40] A.K. Yunusa, N. Abdullahi, A. Rilwan, A.R. Abdulkadir, A. Dandago, U. Sultan, https://doi.org/10.1039/b9pp00174c.
Z. Abidin, B. Campus, T. Wudil, DPPH radical scavenging activitiy and total phe- [50] BASF, Sunscreen Simulator, Web, https://www.sunscreensimulator.basf.com/
nolic content of rambutan (Nephelium lappaceum) peel and seed, Ann. Food Sci. Sunscreen_Simulator, (2019) , Accessed date: 15 June 2019.
Technol. 19 (2018) 774–779. [51] P.N. Shenekar, P.S. Ukirade, S.D. Salunkhe, S.T. Sutar, C.S. Magdum, S.K. Mohite,
[41] D. Lin, M. Xiao, J. Zhao, Z. Li, B. Xing, X. Li, M. Kong, L. Li, Q. Zhang, Y. Liu, S.G. Lokapure, S.M. Metri, vitro evaluation of sun protection factor of fruit extract of
H. Chen, W. Qin, H. Wu, S. Chen, An overview of plant phenolic compounds and Carica papaya L. as a lotion formulation, Eur. J. Exp. Biol. 4 (2014) 44–47.
their importance in human nutrition and Management of Type 2 diabetes, [52] S. Imam, I. Azhar, Z.A. Mahmood, In-vitro evaluation of sun protection factor of a
Molecules. 21 (2016) 1374, https://doi.org/10.3390/molecules21101374. cream formulation prepared from extracts of Musa accuminata (L.), Psidium gujava
[42] S. Aryal, M.K. Baniya, K. Danekhu, P. Kunwar, R. Gurung, N. Koirala, Total phenolic (L.) and Pyrus communis (L.), Asian J. Pharm. Clin. Res. 8 (2015) 234–237.
content, flavonoid content and antioxidant potential of wild vegetables from [53] M.D. Mota, R.Y.S. Costa, A. aa S. Guedes, L.C.R.C. e Silva, F.A. Chinalia, Guava-fruit
Western Nepal, Plants. 8 (2019) 96, https://doi.org/10.3390/plants8040096. extract can improve the UV-protection efficiency of synthetic filters in sun cream
[43] N. Saewan, A. Jimtaisong, Photoprotection of natural flavonoids, J. Appl. Pharm. formulations, J. Photochem. Photobiol. B Biol. 201 (2019) 111639, https://doi.org/
Sci. 3 (2013) 129–141, https://doi.org/10.7324/JAPS.2013.3923. 10.1016/j.jphotobiol.2019.111639.
[44] C.A. de Oliveira, D.D. Peres, C.M. Rugno, M. Kojima, C.A.S.O. de Pinto,

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