Sustainable Chemistry and Pharmacy 4 (2016) 3239

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Sustainable Chemistry and Pharmacy

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Green synthesis and characterisation of natural antiseptic soaps from

the oils of underutilised tropical seed
Olubunmi Atolani a,b,n, Elizabeth Temitope Olabiyi a, Abdullateef Abiodun Issa a,
Hidiat Taiwo Azeez a, Ehi Gift Onoja b, Sulyman Olalekan Ibrahim c,
Marili Funmilayo Zubair c, Olubunmi Stephen Oguntoye a, Gabriel Ademola Olatunji c
a
Department of Chemistry, University of Ilorin, P.M.B. 1515, Ilorin, Nigeria
b
Department of Chemical Sciences, Redeemer's University, Ede, Nigeria
c
Department of Industrial Chemistry, University of Ilorin, P.M.B. 1515, Ilorin, Nigeria

art ic l e i nf o a b s t r a c t

Article history: The maintenance of beautiful skin and hair is the desire of many people all over the world, thus, the
Received 30 March 2016 application of safe cosmetic products is inevitable. Natural cosmetics containing bioactive phytochemical
Received in revised form compounds offer great deal of beauty and pharmacological effect with less toxicity to users and the
22 July 2016
environment. The principle of green chemistry was adopted for the preparation of herbal antiseptic soaps
Accepted 24 July 2016
which were plant-based, biodegradable and free of articial colourings/preservatives. Underutilised
Available online 11 August 2016
tropical seeds of Daniellia oliveri, Elaeis guineensis and Vitellaria paradoxa (Shea butter) were used as
Keywords: sources of oil or fat for the saponication processes while Moringa oleifera seed oil and leave extract
Daniellia oliveri served as sources of antimicrobial agents. Ocimum basilicum also served as source of fragrance as well as
Moringa oleifera
antiseptic agent. The oils were mixed at different ratio to obtain soaps with different properties. Phy-
Elaeis guineensis
sicochemical parameters which include colour, acid value, free fatty acid values, saponication values,
Vitellaria paradoxa Saponication
Transesterication hardness, pH, colour and foaming ability of the oil and soaps were determined as applicable. The fatty
acids methyl esters of the oils were prepared via transesterication and subjected to GCMS analysis to
obtain the fatty acid composition of the oils. Daniellia oliveri oil contains 57% linolelaidic acid as the major
fatty acid, while oleic acid (46%) and lauric acid (44%) were the most prominent in Shea butter and palm
kernel oil respectively. The antimicrobial activity of the soaps determined using agar diffusion method
indicated that the soaps made from the oil of Daniellia oliveri and Shea butter inhibited the growth
Streptococcus aureus, Klebsiella granulomatis and Aspergillus niger. Shea butter soap has the highest ac-
tivity against Klebsiella granulomatis (42 mm), while soaps made from blend of palm kernel oil and Shea
butter had highest activity against Aspergillus niger (7.0). The production was highly cost effective when
compared to selected commercial soaps. Therefore, the adoption of these natural resources for the
preparation of eco-friendly herbal soaps would save the environment of the daily introduction of many
hazardous synthetic chemical products whilst also nding utility for non-conventional seed oils and at
the same time improving the economic status of the community.
& 2016 Elsevier B.V. All rights reserved.

1. Introduction environment. Following the principle of green chemistry, herbal

Everyone desires beautiful hair and skin. Therefore, since
maintaining a beautiful skin and hair is a daily affair for many
people all over the world, the application of appropriate and safe
cosmetic is inevitable. Cosmetics from natural sources containing
bioactive phytochemical compounds offer great deal of beauty and
pharmacological effect with less toxicity to users and the
n
Corresponding author at: Department of Chemistry, University of Ilorin, Ilorin,
Nigeria.
E-mail address: tolanvent@yahoo.com (O. Atolani).
soaps prepared from plant-based renewable sources would key
into the United Nation 17 sustainable development goals to protect
the planet, have good health, sustainable community, clean energy
and make life on land and in water safer (UNDP-SDG, 2000).
Cosmetics made from natural sources possess the ability of
improving psychological, social and clinical impulses on users.
Many articial and synthetic constituents of cosmetics for skin and
hair usually results in damaged skin, dry skin, brittle hair,
browning of hair, itching among other things (Joshi and Pawal,
2015). For instance, butylated hydroxyanisole (BHA), butylated
hydroxytoluene (BHT) and parabens used as antioxidant and/or
preservatives in cosmetics are known to induce allergic reactions

http://dx.doi.org/10.1016/j.scp.2016.07.006
2352-5541/& 2016 Elsevier B.V. All rights reserved.
 O. Atolani et al. / Sustainable Chemistry and Pharmacy 4 (2016) 3239
O O
CH2O-C-R1 CH2OH
NaOH
O + H2O
Saponification
CH2O-CH-R 2 CH2OH
O O
CH2O-C-R3 CH2OH
Triglyceride Glycerol
(oil/fat)
CH2OH
KOH/MeOH
CH2OH
Transesterification
CH2OH
Glycerol
Fig. 1. Saponication and transesterication of lipid (xed oils) from plant seeds.
in human skins and are have been classied as potential carcino-
gen by the international agency for research on cancer (Joshi and
Pawal, 2015; Suzuki, 2010; IARC, 1978).
Soap is the major product of chemical reaction between tri-
glyceride (xed oil from seed) and lye solution (Gunstone, 2004;
Scrimgeour, 2005). The process is termed saponication (Fig. 1).
The soap comes in solid moulded form, termed bars or in liquid
usually termed liquid soap kept in dispenser now widespread in
many public washrooms. In order to characterise the triglyceride
composition of the oils from seeds, the lipid is usually transes-
teried (Fig. 1). Previous research effort has been directed to ex-
hibit the potential of seed oils such as shea butter, neem seed oil
and palm kernel oil for the production of soap of varied char-
acteristics (Alander, 2004; Aliyu et al., 2012; Ameh et al., 2013;
Getradeghana, 2000; Maranz et al., 2004; Warra et al., 2011).
The production of soaps with unique properties needs a careful
selection of oil type. The criteria for the selection of oil for in-
dustrial or domestic application in soap-making includes the
presence of natural characteristic aroma, clarity, natural colour,
low moisture content and absence of at and rancid (unpleasant)
odour (Okoye et al., 1999; Manji et al., 2013). Values that
determine the quality of bar soaps include the hardness, cleansing
power, conditioning, lathering potential and antiseptic nature.
These qualities are attained by reacting various combinations of
oils or fat in different proportion with lye (Manji et al., 2013).
While many of the synthetic antiseptic soaps seems expensive and
unaffordable especially in developing countries, herbal cosmetics
offers an affordable and sustainable cheap means with compara-
tive health and safety benets (Joshi and Pawal, 2015; Sharma
et al., 2008). The global dependence on herbal products seems to
be on the increase. WHO estimated that about 80% of African
population depend directly or indirectly on herbal or natural
products (Ekor, 2014; Joshi and Pawal, 2015; WHO, 2002). In fact,
the global market for herbal medicines was over $60 billion per
annum with an estimate of 6.4% increase average annual growth
rate. This is apparently due to the contribution of the signicant
health and economic values of herbal products (Inamdar et al.,
2008; Sharma et al., 2008; WHO, 2002).
Herbal cosmetics contain antioxidant, anticancer and anti-
microbial agents that could help in the management of various
skin and hair conditions. The presence of phytochemicals such as
vitamins, proteins, tannins, terpenoids and other bioactive in-
gredients rejuvenate, freshen and protect the hair and skin from
various skin and hair conditions such as psoriasis, eczema, skin
dryness, skin cancers, sun burn, skin dryness, boil, solar keratosis,
dermatitis, impetigo, candidiasis, athlete's foot, chicken pox, car-
buncles, staph infections, cyst, abscess, cracking, dandruff, aking
33
and others (Fathima et al., 2011; Kapoor, 2005; Joshi and Pawal,
R1-C-O-Na+ 2015).
O Increased attention has been given to the use of natural anti-
+ R2-C-O-Na+ oxidants for prevention of diseases caused by oxidative damage in
human body and/or by lipid peroxidation in food (Teow et al.,
R3-C-O-Na+ 2007). The traditional medical practice in Nigeria utilises many
Sodium salts of fatty acids seed oils or medicinal plant extracts, which are cheaply sourced
(Soap)
for skin and hair care products due to their abilities to rejuvenate,
moisten and enhance strong skin and hair.
O
The seeds produced from plants usually contain lipids, fatty
R1-C-O-Me acids, amines, proteins and esters which are essential for main-
O
taining body skin function. In Nigeria, many valuable seeds that
R2-C-O-Me
are oil-rich are allowed to perish each year because they belong to
O
non-conventional oil seeds.
R3-C-O-Me
Daniellia oliveri (Rolfe) Hutch & Dalziel of the family Caesalpi-
Fatty acid methyl esters
(FAMEs) niaceae is a well-known plant in Africa and the Amazon region
(Langenhein, 1983; Atolani and Olatunji, 2016). The plant is locally
known as emi ya in south west Nigeria. It is a grossly under-
utilized tropical tree with many potential economic and health
values. The plant is used as ornamental tree in many parts of south
western Nigeria and it grows widely in the forest region. The tree
exudate has been applied as a component of cosmetics and its
potential as anti-wrinkle agent has been patented (Lamy et al.,
2010). Polyalthic acid, a furano-terpene has been isolated from the
exudate from the plant (Atolani and Olatunji, 2014), while the
chemical composition of the resin have been examined (Atolani
and Olatunji, 2016). Other seeded plants which include Shea
butter tree (Vitellaria paradoxa) of the family Sapotaceae and
Moringa oleifera of the family Moringaceae are widely reported in
literature for various biological activities. The leaves, fruits, ow-
ers, roots, seeds, bark and pods of Moringa oleifera have been re-
ported to possess analgesic, antitumour, cardiac and blood circu-
lation stimulatory activities (Makonnen et al., 1997; Sutar et al.,
2008), antipyretic, antiepileptic, anti-inammatory and antiulcer
properties (Pal et al., 1995). Elaeis guineensis (family) is a well
useful plant whose seed oil, known as palm kernel oil (PKO) is
grossly applied for formulations of different cosmetic product
especially, soap (Amira et al., 2014; Traitler and Dieffenbacher,
1985). The plant is readily available in Nigeria where its serves
major economic purpose for the local users. Ocimum basilicum
(family) is an important medicinal plant with varied application
across tribes and regions (Grayer et al., 2004; Lawrence, 1988;
Politeo et al., 2007). This present study aimed at producing herbal
soaps with antiseptic properties that will possess the capacity of
improving the natural beauty, attractiveness and appearance of
African skin and hair from underutilised tropical seeds by adopting
the principle of green chemistry in order to attain a pollution free
environment.
2. Materials and methods
2.1. Collection of plant materials
The seed of Daniellia oliveri (Rolfe), Ocimum basilicum and Vi-
tellaria paradoxa (Shea butter nut) were collected during the
fruiting season from the premises of the University of Ilorin, Ilorin,
Nigeria while Moringa oleifera leaves and seeds were collected
from the fruiting tree within Ilorin metropolis, Nigeria. The plant
materials were identied and authenticated at the Herbarium of
the Department of Plant Biology, University of Ilorin, Ilorin, Nigeria
where voucher specimen numbers UIH 964, UILH/001/961 and
UILH/002/1008 were obtained for Daniellia oliveri, Vitellaria para-
doxa and Moringa oleifera respectively.
The seeds were dried at ambient temperature, de-shelled and
pulverised. The leaves of Moringa oleifera were also collected, dried
34 O. Atolani et al. / Sustainable Chemistry and Pharmacy 4 (2016) 3239
at ambient temperature and pulverised while the leaves of Oci-
mum basilicum were collected and used fresh when needed in
order to preserve the fragrance content. All pulverised plant ma-
terials were kept in a cool dark place for further work.
2.2. Solvents and reagents
Potassium hydroxide (KOH) and hydrochloric acid (HCl) used
were analytical grade. n-Hexane and methanol were re-distilled
before use when necessary while palm kernel seed oil (PKO) and
honey were obtained from reliable commercial local retailers in
Ilorin metropolis.
2.3. Extraction of seed oils
The pulverised Daniellia oliveri seed (388.5 g) was subjected to
soxhlet extraction using n-hexane as the extracting solvent at
60 C for approximately 3 h. The extract was concentrated via
distillation to obtain the oil. The oil yield was 59.15 g. A similar
procedure was adopted for 235.9 g of the pulverised Vitellaria
paradoxa seed to obtain 61.30 g shea butter while 180.4 g of the
pulverised Moringa oleifera seed yielded 69.48 g of oil.
2.4. Determination of the physicochemical parameter of the oils
The physicochemical parameters of the oils were determined
using standard procedures with slight modication where ap-
plicable (Gerpen, 2005; Ibeto et al., 2012). Odour, colour, and
physical state were determined by sensory evaluation.
2.4.1. Saponication value
1 g of each oil was weighed into a conical ask containing
25 mL of methanolic KOH and mixed together. The mixture was
warmed in a water bath for 5 min, 3 drops of phenolphthalein
were added to it and the content titrated against 0.5 M HCl until
the pink colour disappeared. The discolouration indicates the end
point.
Saponication value was then calculated using the equation:
mLOF ( S B) M 56. 1 g /mol
SV= = mgKOH/g
WEIGHT OF SAMPLE( g )
where B blank titre value (mL); S sample titre value (mL);
M Molarity of KOH.
Molecular weight of KOH was taken to be 56.1 g/mol.
2.4.2. Acid value
1 g of each oil was weighed into a ask with 25 mL of methanol
and 3 drops of phenolphthalein indicator was added to it. The
mixture was warmed in a water bath for 5 min and titrated against
0.1 M KOH until the pink colour appeared which indicates the end
point.
Acid value was calculated using the equation:
mLOFKOH N 56. 1 g /mol
AV= = mgKOH/g
WEIGHT OF SAMPLE( g )
where AV Acid value; M Molarity of KOH.
2.4.3. Peroxide value
0.5 g of each oil sample was weighed into a conical ask con-
taining 1 g potassium iodide. The mixture of glacial acetic acid
(13.5 mL) and chloroform (6.5 mL) was added to it. The conical
ask was placed in a water bath for one minute after which 20 mL
of 5% potassium iodide and 25 mL of water was added to it. The
whole content was titrated against sodium thiosulphate solution
(0.002 M) to colourless using starch as an indicator. The results
were expressed in mMol/Kg. The peroxide value was calculated
using the formula
( Vs Vb) molarity of titrant 103 g / Kg
Peroxide value= WEIGHT OF SAMPLE ( g )
= meq/kg
where Vb titre for blank; Vs titre for sample; MMolarity.
2.5. Transesterication of the oil
The oils were subjected to transesterication by treating 2 g of
each oil with 0.2 M methanolic HCl. 2 g of the oil was poured into a
beaker containing 10 mL of the prepared methanolic HCl. The
mixture was reuxed for an hour and allowed to settle into layers
in a separating funnel. The layers were separated and the aqueous
layer was re-washed with hexane before discarding it. The organic
phase was also washed with water and then concentrated to afford
the fatty acid methyl esters (FAMES) which was dried over anhy-
drous magnesium sulphate and stored for GCMS analysis. The
yield of the transesteried oil was determined using the formula:
weight of trans esterified oil
Percentage Yield= 100
weight of lipid
2.6. GC/GCMS analyses
The fatty acid composition of the transesteried oils were
analyzed using Agilent 19091S-433HP-5MS equipped with pH
column of 30 m  250 mm  0.25 mm. The column was packed with
5% Phenyl Methyl Silox. The column temperature was initially held
at 35 C for 3 min with injection volume of 0.2 L and then pro-
grammed to rise at the rate of 5 C/min to 280 C over a total run
time of 62 min at a split mode of ratio 50:1. The heater was set at
300 C, whereas the detector (mass spectrophotometer) tem-
perature was maintained at 250 C. Carrier gas, helium was at an
average velocity of 44.3 cm/s and pressure of 11.604 psi. Ionisation
mode was electron impact at a voltage of 70 eV. The identication
of the chemical components was by matching mass spectral with
those of NIST library.
2.7. Lye preparation
The wood ash was collected from the University's restaurant
was soaked in hot water for a day and then ltered using Wattman
lter paper to obtain the lye, a brown coloured solution.
2.8. Conductivity and turbidity tests
The conductivity of the lye solutions was determined using an
EC 214 Conductivity Meter while the turbidity was determined
using 2100N Turbidity Meter.
2.9. Saponication of oils
The various oils were saponied using hot process since the
cold process produced no instant saponication. 10 mL of the Palm
kernel oil was heated to boiling in a beaker and 10 mL of pre-
warmed lye solution was added to the boiling oil with constant
stirring. A thick dark-brown coloured semi-solid mass of soap was
observed immediately. Where applicable, honey was added and
the semi-solid mass was further stirred for about 10 min before it
was allowed to cool and set for some weeks (Warra et al., 2011;
Ogunsuyi and Akinnawo, 2012). In order to obtain soap of varied
properties, the components, Palm kernel oil, D. oliveri oil, Moringa
oleifera leaf extract and honey were mixed at different ratios.
 O. Atolani et al. / Sustainable Chemistry and Pharmacy 4 (2016) 3239
2.10. Inclusion of natural additives
Additives which include 1 mL of aqueous moringa extract and
0.2 mL of honey were added after the saponication to the semi-
solid matter and stirred together. For the scent, approximately
0.5 g of the fresh leaves of Ocimum basilicum was inserted to the
semi-solid matter to impart scent and antibacterial properties to
the soap. The leaf was removed after few minutes before allowing
the soap to set.
2.11. Soap characterisations
All the prepared soaps were characterised by their pH, foaming
ability, solubility and hardness whilst comparing their values with
commercial soap samples using standard procedure (Ameh et al.,
2013). Commercial bathing soaps which include Dettol soap, Lux
soap and Dudu osun were used as standards for comparison.
2.12. Determination of pH of soaps
The pH values of the soaps were determined using a pH meter
(Inolab, WTW, Germany, pH 7310). 1 g of the soaps was weighed
and dissolved in 10 mL distilled water and made up to 100 mL
mark to afford 1% (w/v) homogeneous soap solution. The electrode
of the pH meter was inserted into the solution and the value re-
corded. The steps were repeated for all the soaps as well as the
commercial soaps used as standards.
2.13. Foaming ability tests
0.2 g each of the soap sample was put into a 100 mL measuring
cylinder containing only 10 mL distilled water. The mixture was
shaken vigorously so as to generate foams. After shaking for 2 min,
the cylinder was allowed to stand for about 10 min and the height
of the foam was then measured and recorded. The steps were
repeated for the other prepared soap as well as the commercial
soaps.
2.14. Solubility tests
0.2 g of each soap was added to a 100 mL measuring cylinder
containing 10 mL of distilled water. The duration of the dissolution
of the soap after continuous shaking was recorded.
2.15. Hardness tests
The hardness of the soap was determined by inserting a regular
hand-sewing needle (4.2 cm in length and 0.5 mm in diameter) to
the soap. The needle was loaded at top with a weight of 370 g on
lever system. The lever was raised and allowed to gently penetrate
the soap within 30 s. The process was repeated three times and
the average depth of the penetration of the needle was measured
and recorded (Ameh et al., 2013).
2.16. Determination of soap sensitivity to microbes
The antimicrobial sensitivity potential of the soap samples was
studied using selected bacteria: Streptococcus aureus, Klebsiella
granulomatis, and a fungus: Aspergillus niger. Agar diffusion
method was adopted (Ameh et al., 2013). Media were autoclaved
and 20 mL of the prepared sterilised Sabouraud Dextrose Agar was
poured into sterile petri-dishes. The microorganisms of interest
were inoculated following serial dilution of 1  106 CFU/mL. After
the agar solidies, 1 mL of 100 mg/mL of the sample solution
prepared in water was pipetted into each hole in the petri dish
bored aseptically. They were incubated at 37 C for 48 h and 96 h
35
for bacteria and fungi respectively. The zone of inhibition was
measure using a ruler.
2.17. Cost analysis of the soaps
The production cost analysis of the soaps was carried out by
estimating the amount of each reagent which includes the lye, oils
and additives used for each soap. The cost was compared to that of
commercial soaps.
3. Results and discussion
Biodegradable antiseptic herbal soaps have been produced
from natural renewable sources in line with the principles of green
chemistry. The use of auxiliary raw materials such as sodium hy-
droxide, sodium silicate, sodium sulphate and articial perfumes,
colourants, preservatives and synthetic antimicrobial agents were
avoided. Sodium hydroxide has been linked to the cause of skin
irritation and cancer. They strip the skin of oil, and sometimes
raise the pH beyond tolerable limit of the skin's microora (Tarun
et al., 2014; IARC, 1978). The soaps were made from natural re-
newable and sustainable raw materials such as oils from under-
utilised tropical seeds, wood ash which is a huge waste of the
baking and cooking industries. Ashes of plants contain potassium
carbonate (K2CO3) and sodium carbonate (Na2CO3). The carbonate
ion present in both of these compounds reacted with water to
form an alkaline solution. Natural scent was incorporated directly
from plant source i.e. leaves of Ocimum basilicum.
Many modern commercial antiseptic soaps contain synthetic
chemicals such as triclosan, trichlorocarbanilide and chlorox-
ylenol, most of which are known to be carcinogenic, mutagenic
and able to generate allergic reactions (Ameh et al., 2013). As a
result, many of the modern soaps could cause increased bacterial
resistance and also introduce or cause the release of metabolism
hazardous compounds such as endocrine disruptors to the en-
vironment. Many cosmetic preservatives such as parabens are now
considered as emerging contaminants because of their ability to
disrupt the endocrine systems (Gore et al., 2015; Joshi and Pawal,
2015). Natural antiseptic soaps produced in this study are expected
to be environmentally benign with less or no interference with
hormone functions. Many of the herbal plant used in cosmetics
have natural benecial effects which could be of tremendous im-
portance to human. Olive oil used in lotions and shampoos con-
tains beta-sitosterol and tocopherol which acts as antioxidants
(Rabasco and Gonzalez, 2000), Aloe vera contains leucine and sa-
ponin glycosides that provides vitamins, antioxidant and moist-
urising activities (Basmatekar et al., 2011) while neem seed (Aza-
dirachta indica) contains phytochemicals that produces antifungal,
antibacterial, pain-relieving, wound healing and anti-dandruff ef-
fects (Anand et al., 2010).
3.1. Physicochemical characteristics of the oils
The D. oliveri had a lower yield (18.44%) compared to the oil
obtained from the shea butter nuts (62.9%) (Table 1). However, the
D. oliveri oil had higher saponication value and yield of transes-
teried product compared to that of shea butter. The D. oliveri oil
had saponication value of 280.5 (mgKOH/g), peroxide value of
7.025 (meq/kg) and acid value of 1.12 (mgKOH/g). The analytical
values obtained for the physicochemical properties were sig-
nicantly in favour of the utilisation of the oil from the indigenous
seeds of Daniellia oliveri and shea nut for soap production on
commercial scale.
The physicochemical parameters of the oil/fat are shown in
Table 1.
36 O. Atolani et al. / Sustainable Chemistry and Pharmacy 4 (2016) 3239

Table 1 saturated fatty acid was high in the palm kernel oil. Only palm
Physicochemical characteristics of the oils. kernel oil had lauric and myristic acids in the oil as they were not
within detectable limit in both the D. oliveri oil and shea butter.
Parameter D.oliveri Palm kernel oil Shea butter
Both D. oliveri oil and shea butter had above 90% unsaturation
%Yield of oil from seed 18.44 62.9 while Palm kernel oil had only 20.73% unsaturation. The high
Saponication value (mgKOH/g) 280.5 152 percentage of the saturated C-12 and C-14 fatty acids in the palm
Acid value (mgKOH/g) 1.122 22.44 kernel oil and the low concentration of the unsaturated fatty acids
% Free fatty acid 91 11.24
Peroxide value (meq/kg) 7.025
might be responsible for the observed low quality (washing ef-
Physical state at room Liquid Liquid Solid ciency, forming ability) of the soap produced from palm kernel oil.
temperature The linolelaidic acid which was the major constituent of the D.
Colour Light Brownish Yellow Pale yellow oliveri oil has also been reported to be
Yellow
%Yield of the transesteried oil 75 91 62.9
3.4. Oil mixing ratio for soap production

Table 2 The saponied products were obtained by using different

Conductivity and turbidity test of lye (wood ash). proportion of the oils in order to determine the various properties
of oils. The mixing ratios, soap colour and washing efciency of the
Parameter Wood Ash lye
soap are shown in Table 4. The soap made from the D. oliveri was
Conductivity (mS) 0.2 pale brown while that of shea butter was cream colour. The soaps
Turbidity (NTU) 185 with the highest washing efciency based on physical observation
were the ones produced solely of D. oliveri oil and shea butter,
without mixing with any oil. The incorporation of Palm kernel oil
to form oil blends for the soap preparation lower the washing
3.2. Conductivity and turbidity
efciency.
The conductivity and turbidity results of lye solution are shown
3.5. The physicochemical characteristics of the soaps
in Table 2 below.

The pH values (Table 5) of the soaps were determined at two

3.3. Fatty acids composition of the oils
different stages which include the day the oils were saponied and
after the soaps had cured (after about three months). All the pH
The fatty acids compositions of D. oliveri seed oil, Palm kernel
values of the cured soaps fell within acceptable range (910) that
oil and shea butter used in preparation of the soaps were de-
is permitted by a regulating authority especially in Nigeria except
termined by subjecting the transesteried oils to GC/GCMS ana-
the soap made from palm kernel oil only which had pH slightly
lyses. The results (Table 3) indicated that the predominant fatty
above 10 (Oyedele, 2002). The pH values obtained are also in
acid in the D. oliveri oil is linolelaidic acid, an omega-6 trans-fatty
agreement with literature results (Ogunsuyi and Akinnawo, 2012;
acid (TFA). The D. oliveri contains 57% linolelaidic acid as the major
Vivian et al., 2014). The obtained pH values indicate that the soaps
fatty acid, while oleic acid (46%) and lauric acid (44.60%) were the
would be less corrosive and is expected to produce less skin re-
most prominent in Shea butter and Palm kernel oil respectively.
action when used. High pH values are usually obtained (most often
Stearic acid a, monounsaturated fatty acid was also prominent
when industrial sodium or potassium hydroxides are used) as a
(40.10%) in the shea butter while palmitic acid (17.94%), a C-16
result of incomplete hydrolysis which results from saponication
process. The high alkalinity is overcome by the addition of excess
Table 3
Fatty acid compositions of D. oliveri oil, shea butter and Palm kernel oil. fat or oil or any other super fatting agent to reduce the harshness
of soap (Warra et al., 2011). The alkalinity favours detergency
Peak no. Fatty acids Saturation % RA % RA of % RA of (Kaoru, 1998). More so, The use of high alkaline soaps can neu-
of D. Palm Shea tralise the body's protective acid mantle that acts as a barrier
oliveri kernel butter
oil
against bacteria and viruses since a healthy human skin has a pH
range of 5.45.9 (Mak-Mensah and Firempong, 2011). The use of
1 Lauric acid 12:0 44.60 soap with high pH value causes an increase in skin pH, which
2 Myristic acid 14:0 17.94 results into an increase in dehydration, irritation and destruction
3 Palmitic acid 16:0 3.43 11.70 4.32
of the bacterial ora (Tarun et al., 2014). The application of wood
4 Methyl 16- 18:0 3.50
methylheptadecanoate ash as the source of alkali in this work produced less alkaline soaps
5 Linolelaidic acid 18:2 56.57 which would be more body-friendly.
6 Stearic acid, 18:1 8.11 40.10 Soaps A3 and B3 which are soaps made from only D. oliveri oil
7 cis-Oleic acid 18:1 19.67 46.33 and Shea butter respectively had the highest foaming ability
8 Linoleic acid 18:2 7.70
9 Methyl 9-cis,11-trans- 18:2 1.86
(Fig. 2). Their foaming abilities were superior to the commercial
octadecadienoate soaps namely; dudu osun, lux and Dettol soaps. The two, A3 and
10 Eicosanoic acid 20:0 0.88 1.55 B3 also had moderate solubilities (Fig. 3) and higher hardness
11 Heneicosanoic acid 21:1 2.97 properties (Fig. 4) compared to the commercial soaps and other
12 Monoolein 21:1 15.90
soaps with mixtures of oils. The solubility and hardness of the
13 Docosanoic acid 22:0 5.1 1.53
14 Tetracosenoic acid 24:1 6.24 soaps is an indication of the ability of the soaps to last longer when
Total Saturate 9.41 79.27 5.87 used due to its ability to slowly dissolve in water. Shea butter had
Total Unsaturate 90.59 20.73 94.13 been reported to contain some unsaponiables that do not react
Monounsaturate 34.02 18.87 86.43 with lye which thus remain in soap to nourish the skin. Shea
Polyunsaturate 56.57 1.86 7.70
butter gives soap with hardness, conditioning, stable lather, and a
%RA indicates percentage relative abundance (peak area relative to the total peak silky feel. Shea butter is known to help in removing skin blem-
area). ishes, dry skin, and wrinkles (Manji et al., 2013). The high
 O. Atolani et al. / Sustainable Chemistry and Pharmacy 4 (2016) 3239 37

Table 4
Mixing ratio of the oils/fat used for the saponication.

Samples Oils/fat and additives mixing ratio Mixing ratios Soap colour Washing efciency

A1 PKOD. oliveri oil Moringa leaf extract Honey 0.89:0.05:0.05:0.01 Dark brown Good
A2 PKOD. oliveri oil 0.95:0.5 Dark brown Good
A3 D. oliveri oil 1 Pale brown Very good
B1 PKOShea butter Moringa leaf extractHoney 0.89:0.05:0.05:0.01 Dark brown Good
B2 PKOShea butter 0.95:0.5 Dark brown Good
B3 Shea butter 1 Cream Very good

where A1: PKOD. oliveri oil M. oleifera leaf extract Honey; A2: PKO D. oliveri oil; A3: D. oliveri oil; B1: PKO Shea butter M. oleifera leaf extract Honey; B2:
PKOShea butter; B3: Shea butter.

Table 5 2.5

Hardness (cm)
The physical characteristics of the Soap samples. 2

1.5
Soap pH pH Foam Solubility Hardness Texture
sample before after height (sec) (cm) 1

curing curing (cm3) 0.5

0
A1 9.99 8.75 3.11 420 1.55 Hard A1 A2 A3 B1 B2 B3 PKO only Dudu Lux Dettol
A2 10.13 8.52 2.53 420 0.35 Very hard Osun
A3 8.72 4.50 420 0.30 Very hard Soap samples
B1 10.11 9.48 2.53 620 2.30 Soft
B2 9.46 8.64 2.77 600 1.30 Hard Fig. 4. Hardness of the soaps. Where A1: PKO D. oliveri oil M. oleifera leaf ex-
B3 9.78 5.00 540 0.20 Very hard tract Honey; A2: PKOD. oliveri oil; A3: D. oliveri oil; B1: PKOShea butter M.
PKO 10.91 10.10 2.29 300 1.40 Hard oleifera leaf extract Honey; B2: PKOShea butter; B3: Shea butter.
only
Dudu 9.17 3.61 360 2.20 Soft concentration of the short chain saturated C-12 and C-14 fatty
Osun
acids in the PKO is suspected to have led to the production of less
Lux 9.73 3.69 780 1.30 Hard
Dettol 9.08 3.48 600 1.30 Hard quality soaps when compared to the D. oliveri oil and Shea butter
soaps. Fatty acids with only 10 or fewer carbons are not the fa-
where A1: PKOD. oliveri oil M. oleifera leaf extract Honey; A2: PKO D. oliveri vourite in soaps making because they produces soaps that pos-
oil; A3: D. oliveri oil; B1: PKO Shea butter M. oleifera leaf extractHoney; B2:
sesses obnoxious odours and also irritates the skin (Chalmers and
PKOShea butter; B3: Shea butter.
Bathe, 1978; Vivian et al., 2014). The chemical nature of the lipo-
philic part of soap plays the largest role in determining the per-
6
formance of nished soap (Viorica et al., 2011). The physico-
chemical characteristic of soap which includes moisture content,
5
total fat matter (TFM), pH, free caustic alkalinity depends largely
Foaming height (cm)

4 on several factors such as the strength and purity of alkali, the type
of oil used, degree of saponication, constituent of the oil and
3
many others (Roila et al., 2001; Vivian et al., 2014).
2

1 3.6. Result of antimicrobial sensitivity tests

0
A1 A2 A3 B1 B2 B3 PKO Dudu Lux Dettol All the prepared soaps showed appreciable level of microbial
only Osun
activity (Table 6) against some of tested organisms. A broad ac-
Soap samples tivity was recorded in sample A3, that is, the soap prepared from
Fig. 2. Foaming ability of the soaps. Where A1: PKO D. oliveri oil M. oleifera leaf D. oliveri oil only. It showed sensitivity against three organisms;
extract Honey; A2: PKOD. oliveri oil; A3: D. oliveri oil; B1: PKO Shea butter M. Streptococcus aureus, Klebsiella granulomatis, Aspergillus niger and a
oleifera leaf extract Honey; B2: PKO Shea butter; B3: Shea butter.

Table 6
Sensitivity of microorganisms to the prepared soaps.
900
800 Sample code ZI ofStreptococcus ZI ofKlebsiella ZIAspergillus
700 aureus (mm) granulomatis niger (mm)
Solubility

600 (mm)
500
400 A1 NI 31 NI
300 A2 NI 42 NI
200 A3 1.0 29 3.0
100 B1 NI 3.0 7.0
0 B2 5.0 NI 1.0
A1 A2 A3 B1 B2 B3 PKO Dudu Lux Dettol B3 4.0 42 NI
only Osun Ampicillin 14 40 3.0
Soap samples Tetracycline 9.0 25 11

Fig. 3. Solubilities of the soaps. Where A1: PKO D. oliveri oil M. oleifera leaf where ZI: Zone of Inhibition; NI: No inhibition; A1: PKO D. oliveri oil M. oleifera
extract Honey; A2: PKOD. oliveri oil; A3: D. oliveri oil; B1: PKO Shea butter M. leaf extractHoney; A2: PKOD. oliveri oil; A3: D. oliveri oil; B1: PKO Shea
oleifera leaf extract Honey; B2: PKO Shea butter; B3: Shea butter. butter M. oleifera leaf extract Honey; B2: PKO Shea butter; B3: Shea butter.
38 O. Atolani et al. / Sustainable Chemistry and Pharmacy 4 (2016) 3239
Table 7
Estimated production cost analysis of prepared soaps.
Soap sample Cost (USD) per 1 g
A1 0.0025
A2 0.0023
A3 0.0020
B1 0.0030
B2 0.0025
B3 0.0023
PKO only 0.0018
Dudu Osun 0.0040
Lux 0.0050
Dettol 0.0085
where USD means United State Dollars; A1: PKO D.
oliveri oil M. oleifera leaf extract Honey; A2:
PKO D. oliveri oil; A3: D. oliveri oil; B1: PKO Shea
butter M. oleifera leaf extract Honey; B2: PKO-
Shea butter; B3: Shea butter.
lower activity recorded against Klebsiella granulomatis. B3, Shear
butter showed complete inhibition of the Klebsiella granulomatis
bacteria which was comparable to the inhibition using standard
drugs like ampicillin and tetracycline. The antimicrobial result
indicates that the soap produced from the natural underutilised
product has potential of inhibiting related microbial infections.
Other seed oils such as neem oil (Azadirachta indica) has been
reported to show broad spectrum antimicrobial activity (Sairam
et al., 2000). However, a wider range of anti-microbial tests would
be necessary to ascertain the potential of the soaps to inhibit a
broad spectrum of organisms.
The use of the soaps may help in the prevention of skin in-
fections and communicable diseases. The application of antiseptic
or medicated soaps for washing the body is the rst line of defense
against bacteria and other pathogens that can cause colds, the u,
skin infections and even deadly communicable diseases (Larson,
1988; Mwambete and Lyombe, 2011). However, the inoculum sizes
of both pathogenic and non-pathogenic microorganisms would be
reduced by the use of medicated soaps (Nester et al., 2002).
Although, it has been highlighted that overuse of antiseptic soaps
can have the negative effect by making users vulnerable to op-
portunistic skin infection and thereby spreading diseases instead
of preventing them. Synthetic antimicrobial agent such as triclosan
in soaps has been linked to the incidences of induced clinical an-
timicrobial resistance (Russell, 1998; Chuanchen et al., 2001; Levy,
2001; White and McDermott, 2001; Poole, 2002). Hence, the
adoption of benign natural antimicrobial agents in soaps and
cosmetics may assist in reversing the trend.
3.7. Production cost analysis of prepared herbal soaps
Table 7 shows the cost of production of the prepared herbal
soaps from the selected natural sources. The cost per gram of the
soap was estimated and compared to the market cost of com-
mercial soaps. All materials used were given a relative value and
the cost of production thus calculated. The cost analysis was based
on cost of raw materials vis--vis the relative yield of the soaps.
The D. oliveri oil-made soap and the Shea butter-made soap had
lower cost of production when compared to others that have other
additives such as honey and Moringa oleifera seed oil.
4. Conclusion
Following the principles of green chemistry, herbal antiseptic
eco-friendly soaps have been prepared from underutilized oil
seeds. The adoption of these techniques and natural resources for
the preparation of herbal soaps would save the environment of the
daily introduction of many hazardous chemical products which
results from the utilisation of commercial synthetic soaps. The
soaps prepared avoided the inclusion of auxiliary raw materials
such as sodium silicate, sodium sulphate, sodium silicate and ar-
ticial perfumes, colourants, preservatives and synthetic anti-
microbial agents. Soap made from Daniellia oliveri seed oil, which
is usually an undervalued stock in the environment had the best
properties in terms of hardness, forming ability, texture, colour,
antimicrobial activity and commercial rating. The adopted method
helps in the conversion of agro waste products in the environment
to commercial utility products thereby improving the economic
status of the community.
Conict of interest
Authors declared that there is no conict of interest.
Acknowledgement
Authors gratefully acknowledges TWAS research grant: 15-244
RG/CHE/AF/AC_G FR3240287031 which supports this work.
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