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Sustainable Chemistry and Pharmacy 4 (2016) 3239

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Sustainable Chemistry and Pharmacy


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

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


soaps prepared from plant-based renewable sources would key
Everyone desires beautiful hair and skin. Therefore, since into the United Nation 17 sustainable development goals to protect
maintaining a beautiful skin and hair is a daily affair for many the planet, have good health, sustainable community, clean energy
people all over the world, the application of appropriate and safe and make life on land and in water safer (UNDP-SDG, 2000).
cosmetic is inevitable. Cosmetics from natural sources containing Cosmetics made from natural sources possess the ability of
bioactive phytochemical compounds offer great deal of beauty and improving psychological, social and clinical impulses on users.
Many articial and synthetic constituents of cosmetics for skin and
pharmacological effect with less toxicity to users and the
hair usually results in damaged skin, dry skin, brittle hair,
browning of hair, itching among other things (Joshi and Pawal,
n
Corresponding author at: Department of Chemistry, University of Ilorin, Ilorin,
2015). For instance, butylated hydroxyanisole (BHA), butylated
Nigeria. hydroxytoluene (BHT) and parabens used as antioxidant and/or
E-mail address: tolanvent@yahoo.com (O. Atolani). 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 33

O O and others (Fathima et al., 2011; Kapoor, 2005; Joshi and Pawal,
CH2O-C-R1 CH2OH R1-C-O-Na+ 2015).
NaOH
O + H2O O Increased attention has been given to the use of natural anti-
Saponification
CH2O-CH-R 2 CH2OH + R2-C-O-Na+ oxidants for prevention of diseases caused by oxidative damage in
O O human body and/or by lipid peroxidation in food (Teow et al.,
CH2O-C-R3 CH2OH R3-C-O-Na+ 2007). The traditional medical practice in Nigeria utilises many
Triglyceride Glycerol Sodium salts of fatty acids seed oils or medicinal plant extracts, which are cheaply sourced
(oil/fat) (Soap)
for skin and hair care products due to their abilities to rejuvenate,
moisten and enhance strong skin and hair.
O
CH2OH The seeds produced from plants usually contain lipids, fatty
R1-C-O-Me acids, amines, proteins and esters which are essential for main-
O
KOH/MeOH
CH2OH taining body skin function. In Nigeria, many valuable seeds that
R2-C-O-Me
Transesterification are oil-rich are allowed to perish each year because they belong to
O
CH2OH non-conventional oil seeds.
R3-C-O-Me
Daniellia oliveri (Rolfe) Hutch & Dalziel of the family Caesalpi-
Glycerol 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
Fig. 1. Saponication and transesterication of lipid (xed oils) from plant seeds.
known as emi ya in south west Nigeria. It is a grossly under-
utilized tropical tree with many potential economic and health
in human skins and are have been classied as potential carcino- values. The plant is used as ornamental tree in many parts of south
gen by the international agency for research on cancer (Joshi and western Nigeria and it grows widely in the forest region. The tree
Pawal, 2015; Suzuki, 2010; IARC, 1978). exudate has been applied as a component of cosmetics and its
Soap is the major product of chemical reaction between tri- potential as anti-wrinkle agent has been patented (Lamy et al.,
glyceride (xed oil from seed) and lye solution (Gunstone, 2004; 2010). Polyalthic acid, a furano-terpene has been isolated from the
Scrimgeour, 2005). The process is termed saponication (Fig. 1). exudate from the plant (Atolani and Olatunji, 2014), while the
The soap comes in solid moulded form, termed bars or in liquid chemical composition of the resin have been examined (Atolani
usually termed liquid soap kept in dispenser now widespread in and Olatunji, 2016). Other seeded plants which include Shea
many public washrooms. In order to characterise the triglyceride butter tree (Vitellaria paradoxa) of the family Sapotaceae and
composition of the oils from seeds, the lipid is usually transes- Moringa oleifera of the family Moringaceae are widely reported in
teried (Fig. 1). Previous research effort has been directed to ex- literature for various biological activities. The leaves, fruits, ow-
hibit the potential of seed oils such as shea butter, neem seed oil ers, roots, seeds, bark and pods of Moringa oleifera have been re-
and palm kernel oil for the production of soap of varied char- ported to possess analgesic, antitumour, cardiac and blood circu-
acteristics (Alander, 2004; Aliyu et al., 2012; Ameh et al., 2013; lation stimulatory activities (Makonnen et al., 1997; Sutar et al.,
Getradeghana, 2000; Maranz et al., 2004; Warra et al., 2011). 2008), antipyretic, antiepileptic, anti-inammatory and antiulcer
The production of soaps with unique properties needs a careful properties (Pal et al., 1995). Elaeis guineensis (family) is a well
selection of oil type. The criteria for the selection of oil for in- useful plant whose seed oil, known as palm kernel oil (PKO) is
dustrial or domestic application in soap-making includes the grossly applied for formulations of different cosmetic product
presence of natural characteristic aroma, clarity, natural colour, especially, soap (Amira et al., 2014; Traitler and Dieffenbacher,
low moisture content and absence of at and rancid (unpleasant) 1985). The plant is readily available in Nigeria where its serves
odour (Okoye et al., 1999; Manji et al., 2013). Values that major economic purpose for the local users. Ocimum basilicum
determine the quality of bar soaps include the hardness, cleansing (family) is an important medicinal plant with varied application
power, conditioning, lathering potential and antiseptic nature. across tribes and regions (Grayer et al., 2004; Lawrence, 1988;
These qualities are attained by reacting various combinations of Politeo et al., 2007). This present study aimed at producing herbal
oils or fat in different proportion with lye (Manji et al., 2013). soaps with antiseptic properties that will possess the capacity of
While many of the synthetic antiseptic soaps seems expensive and improving the natural beauty, attractiveness and appearance of
unaffordable especially in developing countries, herbal cosmetics African skin and hair from underutilised tropical seeds by adopting
offers an affordable and sustainable cheap means with compara- the principle of green chemistry in order to attain a pollution free
tive health and safety benets (Joshi and Pawal, 2015; Sharma environment.
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 2. Materials and methods
products (Ekor, 2014; Joshi and Pawal, 2015; WHO, 2002). In fact,
the global market for herbal medicines was over $60 billion per 2.1. Collection of plant materials
annum with an estimate of 6.4% increase average annual growth
rate. This is apparently due to the contribution of the signicant The seed of Daniellia oliveri (Rolfe), Ocimum basilicum and Vi-
health and economic values of herbal products (Inamdar et al., tellaria paradoxa (Shea butter nut) were collected during the
2008; Sharma et al., 2008; WHO, 2002). fruiting season from the premises of the University of Ilorin, Ilorin,
Herbal cosmetics contain antioxidant, anticancer and anti- Nigeria while Moringa oleifera leaves and seeds were collected
microbial agents that could help in the management of various from the fruiting tree within Ilorin metropolis, Nigeria. The plant
skin and hair conditions. The presence of phytochemicals such as materials were identied and authenticated at the Herbarium of
vitamins, proteins, tannins, terpenoids and other bioactive in- the Department of Plant Biology, University of Ilorin, Ilorin, Nigeria
gredients rejuvenate, freshen and protect the hair and skin from where voucher specimen numbers UIH 964, UILH/001/961 and
various skin and hair conditions such as psoriasis, eczema, skin UILH/002/1008 were obtained for Daniellia oliveri, Vitellaria para-
dryness, skin cancers, sun burn, skin dryness, boil, solar keratosis, doxa and Moringa oleifera respectively.
dermatitis, impetigo, candidiasis, athlete's foot, chicken pox, car- The seeds were dried at ambient temperature, de-shelled and
buncles, staph infections, cyst, abscess, cracking, dandruff, aking 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- were expressed in mMol/Kg. The peroxide value was calculated
mum basilicum were collected and used fresh when needed in using the formula
order to preserve the fragrance content. All pulverised plant ma- ( Vs Vb) molarity of titrant 103 g / Kg
Peroxide value= WEIGHT OF SAMPLE ( g )
= meq/kg
terials were kept in a cool dark place for further work.
where Vb titre for blank; Vs titre for sample; MMolarity.

2.2. Solvents and reagents


2.5. Transesterication of the oil
Potassium hydroxide (KOH) and hydrochloric acid (HCl) used
were analytical grade. n-Hexane and methanol were re-distilled The oils were subjected to transesterication by treating 2 g of
before use when necessary while palm kernel seed oil (PKO) and each oil with 0.2 M methanolic HCl. 2 g of the oil was poured into a
honey were obtained from reliable commercial local retailers in beaker containing 10 mL of the prepared methanolic HCl. The
Ilorin metropolis. mixture was reuxed for an hour and allowed to settle into layers
in a separating funnel. The layers were separated and the aqueous
2.3. Extraction of seed oils layer was re-washed with hexane before discarding it. The organic
phase was also washed with water and then concentrated to afford
The pulverised Daniellia oliveri seed (388.5 g) was subjected to the fatty acid methyl esters (FAMES) which was dried over anhy-
soxhlet extraction using n-hexane as the extracting solvent at drous magnesium sulphate and stored for GCMS analysis. The
60 C for approximately 3 h. The extract was concentrated via yield of the transesteried oil was determined using the formula:
distillation to obtain the oil. The oil yield was 59.15 g. A similar
weight of trans esterified oil
procedure was adopted for 235.9 g of the pulverised Vitellaria Percentage Yield= 100
weight of lipid
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.

2.6. GC/GCMS analyses


2.4. Determination of the physicochemical parameter of the oils
The fatty acid composition of the transesteried oils were
The physicochemical parameters of the oils were determined
analyzed using Agilent 19091S-433HP-5MS equipped with pH
using standard procedures with slight modication where ap-
column of 30 m  250 mm  0.25 mm. The column was packed with
plicable (Gerpen, 2005; Ibeto et al., 2012). Odour, colour, and
5% Phenyl Methyl Silox. The column temperature was initially held
physical state were determined by sensory evaluation.
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
2.4.1. Saponication value
1 g of each oil was weighed into a conical ask containing time of 62 min at a split mode of ratio 50:1. The heater was set at
25 mL of methanolic KOH and mixed together. The mixture was 300 C, whereas the detector (mass spectrophotometer) tem-
warmed in a water bath for 5 min, 3 drops of phenolphthalein perature was maintained at 250 C. Carrier gas, helium was at an
were added to it and the content titrated against 0.5 M HCl until average velocity of 44.3 cm/s and pressure of 11.604 psi. Ionisation
the pink colour disappeared. The discolouration indicates the end mode was electron impact at a voltage of 70 eV. The identication
point. of the chemical components was by matching mass spectral with
Saponication value was then calculated using the equation: those of NIST library.

mLOF ( S B) M 56. 1 g /mol


SV= = mgKOH/g 2.7. Lye preparation
WEIGHT OF SAMPLE( g )

where B blank titre value (mL); S sample titre value (mL); The wood ash was collected from the University's restaurant
M Molarity of KOH. was soaked in hot water for a day and then ltered using Wattman
Molecular weight of KOH was taken to be 56.1 g/mol. lter paper to obtain the lye, a brown coloured solution.

2.4.2. Acid value 2.8. Conductivity and turbidity tests


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 The conductivity of the lye solutions was determined using an
mixture was warmed in a water bath for 5 min and titrated against
EC 214 Conductivity Meter while the turbidity was determined
0.1 M KOH until the pink colour appeared which indicates the end
using 2100N Turbidity Meter.
point.
Acid value was calculated using the equation:
2.9. Saponication of oils
mLOFKOH N 56. 1 g /mol
AV= = mgKOH/g
WEIGHT OF SAMPLE( g ) The various oils were saponied using hot process since the
where AV Acid value; M Molarity of KOH. 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-
2.4.3. Peroxide value warmed lye solution was added to the boiling oil with constant
0.5 g of each oil sample was weighed into a conical ask con- stirring. A thick dark-brown coloured semi-solid mass of soap was
taining 1 g potassium iodide. The mixture of glacial acetic acid observed immediately. Where applicable, honey was added and
(13.5 mL) and chloroform (6.5 mL) was added to it. The conical the semi-solid mass was further stirred for about 10 min before it
ask was placed in a water bath for one minute after which 20 mL was allowed to cool and set for some weeks (Warra et al., 2011;
of 5% potassium iodide and 25 mL of water was added to it. The Ogunsuyi and Akinnawo, 2012). In order to obtain soap of varied
whole content was titrated against sodium thiosulphate solution properties, the components, Palm kernel oil, D. oliveri oil, Moringa
(0.002 M) to colourless using starch as an indicator. The results oleifera leaf extract and honey were mixed at different ratios.
O. Atolani et al. / Sustainable Chemistry and Pharmacy 4 (2016) 3239 35

2.10. Inclusion of natural additives for bacteria and fungi respectively. The zone of inhibition was
measure using a ruler.
Additives which include 1 mL of aqueous moringa extract and
0.2 mL of honey were added after the saponication to the semi- 2.17. Cost analysis of the soaps
solid matter and stirred together. For the scent, approximately
0.5 g of the fresh leaves of Ocimum basilicum was inserted to the The production cost analysis of the soaps was carried out by
semi-solid matter to impart scent and antibacterial properties to estimating the amount of each reagent which includes the lye, oils
the soap. The leaf was removed after few minutes before allowing and additives used for each soap. The cost was compared to that of
the soap to set. commercial soaps.

2.11. Soap characterisations


3. Results and discussion
All the prepared soaps were characterised by their pH, foaming
ability, solubility and hardness whilst comparing their values with Biodegradable antiseptic herbal soaps have been produced
commercial soap samples using standard procedure (Ameh et al., from natural renewable sources in line with the principles of green
2013). Commercial bathing soaps which include Dettol soap, Lux chemistry. The use of auxiliary raw materials such as sodium hy-
soap and Dudu osun were used as standards for comparison. droxide, sodium silicate, sodium sulphate and articial perfumes,
colourants, preservatives and synthetic antimicrobial agents were
2.12. Determination of pH of soaps avoided. Sodium hydroxide has been linked to the cause of skin
irritation and cancer. They strip the skin of oil, and sometimes
The pH values of the soaps were determined using a pH meter raise the pH beyond tolerable limit of the skin's microora (Tarun
(Inolab, WTW, Germany, pH 7310). 1 g of the soaps was weighed et al., 2014; IARC, 1978). The soaps were made from natural re-
and dissolved in 10 mL distilled water and made up to 100 mL newable and sustainable raw materials such as oils from under-
mark to afford 1% (w/v) homogeneous soap solution. The electrode utilised tropical seeds, wood ash which is a huge waste of the
of the pH meter was inserted into the solution and the value re- baking and cooking industries. Ashes of plants contain potassium
corded. The steps were repeated for all the soaps as well as the carbonate (K2CO3) and sodium carbonate (Na2CO3). The carbonate
commercial soaps used as standards. ion present in both of these compounds reacted with water to
form an alkaline solution. Natural scent was incorporated directly
2.13. Foaming ability tests from plant source i.e. leaves of Ocimum basilicum.
Many modern commercial antiseptic soaps contain synthetic
0.2 g each of the soap sample was put into a 100 mL measuring chemicals such as triclosan, trichlorocarbanilide and chlorox-
cylinder containing only 10 mL distilled water. The mixture was ylenol, most of which are known to be carcinogenic, mutagenic
shaken vigorously so as to generate foams. After shaking for 2 min, and able to generate allergic reactions (Ameh et al., 2013). As a
the cylinder was allowed to stand for about 10 min and the height result, many of the modern soaps could cause increased bacterial
of the foam was then measured and recorded. The steps were resistance and also introduce or cause the release of metabolism
repeated for the other prepared soap as well as the commercial hazardous compounds such as endocrine disruptors to the en-
soaps. vironment. Many cosmetic preservatives such as parabens are now
considered as emerging contaminants because of their ability to
2.14. Solubility tests disrupt the endocrine systems (Gore et al., 2015; Joshi and Pawal,
2015). Natural antiseptic soaps produced in this study are expected
0.2 g of each soap was added to a 100 mL measuring cylinder to be environmentally benign with less or no interference with
containing 10 mL of distilled water. The duration of the dissolution hormone functions. Many of the herbal plant used in cosmetics
of the soap after continuous shaking was recorded. have natural benecial effects which could be of tremendous im-
portance to human. Olive oil used in lotions and shampoos con-
2.15. Hardness tests tains beta-sitosterol and tocopherol which acts as antioxidants
(Rabasco and Gonzalez, 2000), Aloe vera contains leucine and sa-
The hardness of the soap was determined by inserting a regular ponin glycosides that provides vitamins, antioxidant and moist-
hand-sewing needle (4.2 cm in length and 0.5 mm in diameter) to urising activities (Basmatekar et al., 2011) while neem seed (Aza-
the soap. The needle was loaded at top with a weight of 370 g on dirachta indica) contains phytochemicals that produces antifungal,
lever system. The lever was raised and allowed to gently penetrate antibacterial, pain-relieving, wound healing and anti-dandruff ef-
the soap within 30 s. The process was repeated three times and fects (Anand et al., 2010).
the average depth of the penetration of the needle was measured
and recorded (Ameh et al., 2013). 3.1. Physicochemical characteristics of the oils

2.16. Determination of soap sensitivity to microbes 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
The antimicrobial sensitivity potential of the soap samples was D. oliveri oil had higher saponication value and yield of transes-
studied using selected bacteria: Streptococcus aureus, Klebsiella teried product compared to that of shea butter. The D. oliveri oil
granulomatis, and a fungus: Aspergillus niger. Agar diffusion had saponication value of 280.5 (mgKOH/g), peroxide value of
method was adopted (Ameh et al., 2013). Media were autoclaved 7.025 (meq/kg) and acid value of 1.12 (mgKOH/g). The analytical
and 20 mL of the prepared sterilised Sabouraud Dextrose Agar was values obtained for the physicochemical properties were sig-
poured into sterile petri-dishes. The microorganisms of interest nicantly in favour of the utilisation of the oil from the indigenous
were inoculated following serial dilution of 1  106 CFU/mL. After seeds of Daniellia oliveri and shea nut for soap production on
the agar solidies, 1 mL of 100 mg/mL of the sample solution commercial scale.
prepared in water was pipetted into each hole in the petri dish The physicochemical parameters of the oil/fat are shown in
bored aseptically. They were incubated at 37 C for 48 h and 96 h 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 seeds. The adoption of these techniques and natural resources for
Estimated production cost analysis of prepared soaps. the preparation of herbal soaps would save the environment of the
daily introduction of many hazardous chemical products which
Soap sample Cost (USD) per 1 g
results from the utilisation of commercial synthetic soaps. The
A1 0.0025 soaps prepared avoided the inclusion of auxiliary raw materials
A2 0.0023 such as sodium silicate, sodium sulphate, sodium silicate and ar-
A3 0.0020 ticial perfumes, colourants, preservatives and synthetic anti-
B1 0.0030
B2 0.0025
microbial agents. Soap made from Daniellia oliveri seed oil, which
B3 0.0023 is usually an undervalued stock in the environment had the best
PKO only 0.0018 properties in terms of hardness, forming ability, texture, colour,
Dudu Osun 0.0040 antimicrobial activity and commercial rating. The adopted method
Lux 0.0050
helps in the conversion of agro waste products in the environment
Dettol 0.0085
to commercial utility products thereby improving the economic
where USD means United State Dollars; A1: PKO D. status of the community.
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.
Conict of interest

Authors declared that there is no conict of interest.


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 Acknowledgement
drugs like ampicillin and tetracycline. The antimicrobial result
indicates that the soap produced from the natural underutilised Authors gratefully acknowledges TWAS research grant: 15-244
product has potential of inhibiting related microbial infections. RG/CHE/AF/AC_G FR3240287031 which supports this work.
Other seed oils such as neem oil (Azadirachta indica) has been
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