Libyan Date Syrup (Rub Al-Tamr)
MOSTAFA A. MOHAMED and AHMED ASHOUR AHMED
ABSTRACT
Representative samples of date syrup were obtained from the local
market and analysed. The chemical composition and some char-
acteristics of these samples were investigated. The reducing sugarsof
the syrup comprised about 95% of its total sugars content. The
major sugars present were glucose-48.70%, fructose-45.21%,
and sucrose-6.09%. Furthermore, the coloring matters of date
syrup were isolated, separated and further investigated. It was con-
cluded that the color groups, degradation products of reducing
sugars, melanoidines, and iron-polyphenolic complexes, contributed
to the color of date syrup. The melanoidine-type compounds,
which comprised the major part of syrup colorants, showed a low
selective adsorption tendency on both charcoal and anion resins.
An efficient clarification of date syrup has been achieved by the
use of calcium phosphate precipitation. The results obtained may be
of help in devising industrial processes for the utilization of dates,
abundantly grown in Libya, in the production of “Total invert
liquid sugar” with multiple commercial uses of its own.
INTRODUCTION
SINCE ANCIENT TIMES, dates have been considered one
of the most important fruits in the desert regions. There are
about 90 million palm trees all over the world, which yield
about 1.25 million tons of dates annually (Dowson, 1962;
Popenoe, 1974). They are distributed in 22 countries,
mostly in the desert regions of North Africa and South
Western Asia.
According to the Ministry of Agriculture in Libyan
Jamahiriya, there are more than 4 million palm trees in
Libya which yield around 87,000 tons of dates. The present
Libyan production represents about 5% of the total world
production There are many varieties of dates grown lo-
cally, but Bikrari, Khadhrai, and Taasfirt constitute the
main varieties grown in Libya (Dowson, 1962). No statis-
tical data are available concerning the individual production
of each variety.
Date. syrup, locally known as Rub Al-Tamr, is a popular
‘food commodity produced by small plants from Bikrari
dates. Moreover, considerable amounts of date syrup are
produced at home from some local date varieties.
Owing to the absence -of a sugar industry in Libya,
large quantities are imported annually for domestic con-
sumption. SimultaneousIy, there are some food industries
in Libya that consume considerable quantities of sugar
which is considered a subsidized commodity. Consequently,
the abundance of dates grown in Libya and their high sugar
content should justify their use as a source of liquid
sugar suited to many food industries. However, the large
amount of coloring matter found in date syrup may present
a deterrent to its direct use for this purpose.
The production of liquid sugar from dates has been
investigated by many workers (Alegedi and Beshkov, 1976;
Author Mohamed, formerly with the Food Technology
Faculty of Agriculture, Assiut Univ., Assiut, Egypt, is now with
the Food Science Dept., FacuIty of Agriculture, Univ. of Al-Fareh,
Tripoli, S.P.L.A.J. Author Ahmed is with the affiliation Food Sci-
ence Dept., Faculty of Agriculture, Univ. of Al-Fateh,
P.O. Box 13271, Libya.
1162-JOURNAL OF FOOD SCIENCE-Volume 46 (1981)
Ehrenberg, 1977; Nakahara and Telsujiro, 19:77; Nowatzyk,
1976; Wolf et al., 1976). Ehrenberg (1977) reported that
treating the date extract with lime followed by purification
with cation and anion exchangers yielded a syrup with a
purity of 99.26%. Nakahara and Tetsujiro (1977) reported
on the use of an ultrafiltration membrane with 20,000
molecular weight to obtain a clear date syrup which can be
used as a flavoring agent for processed foods. According to
Nowatzyk (1976) an excellent liquid sugar could be ob-
tamed from date extract by clarification with lime at pH
10.6 followed by desalting by ion exchangers and concen-
trating in vacuum. Wolf et al. (1976) studied the effect of
different types of ion-exchange resins on the decolorization
of date juices. They concluded that the use of sulfonated
divinylbenzenestyrene copolymer considerably improved
the decolorization of date juice.
The aims of the experiments run in the present investi-
gation are :
(1) To evaluate the gross composition and study the
principal physicochemical properties of date syrup pro-
duced in Libya. Such analyses would be of help in estab-
lishing standards and general specifications of the Libyan
date syrup known as “Rub Al-Tamr.”
(2) To obtain relevant information on properties and
structure of the color components of date syrup.
(3) To study the possibility of decolorizing date syrup
to produce a liquid sugar from it.
MATERIALS & METHODS
TWENTY KILOGRAMS of date-syrup samples (5OOg each) were
obtained at random from the local market. These samples were
thoroughly mixed together and a representative portion taken and
analyzed.
Methods of analysis
The following determinations were run in triplicate, and results
are reported as a mean of the three runs. The physicochemical prop-
erties measured for the date-syrup were: viscosity, refractive index,
polarization, color, pH, and the indicator property. The UV-absorp-
tion spectra were obtained from aqueous solutions of the original
date syrup and its colorants. Infra-red analysis was carried out for
the coloring matters isolated from date syrup. Total soluble solids,
acidity, total ash, potassium, sodium, calcium, and iron content
were also determined. Ammo acids of the date syrup proteins were
qualitatively determined by paper chromatograph!y using Whatman
peper No. 1 in a descending system. The preparation of the hydro-
lysate, the solvent system employed, and the development of the
chromatograms were done as described by Peswk and Shields
(1968).
Date-syrup samples were analyzed for total sugars and reducing
sugars using the “Lane-Eynon” volumetric method. The sucrose
content was determined using three different techniques, namely,
polarimetric, “Lane-Eynon” volumetric method .before and after
inversion, and thin-layer chromatography (TLC) All the above
mentioned determinations were carried out according to the
methods described by Berger and Borodkm (1967); Creswell et al.
Dept., (1972); DeWhalley (1964); Pearson (1970, 19’73); Pecsok and
Shields (1968) employing Abbe refractometer; pH-meter, Bekman
Chem-Mat; viscosimeter, Rheomat 15 T; polarimeter, Karl Kolb,
model 14.220; flamephotometer,Carl Zeiss-pf 5; spectrophotometer,
Tripoli, double beam, Colemanl24;and infrared spectrophotometer, Perkin-
Elmer-567.
The individual sugars, glucose, fructose and sucrose, were qual-
 LIBYAN DATE SYRUP (RUB AL-TAMR) ...

itatively and quantitatively determined using a combination of 1977; Nakahara and Tetsujiro, 1977; Mowatzyk, 1976).
chromatographic and micro-calorimetric procedures (Berger and Data also conformed with that mentioned in the Libyan
Borodkin, 1967; Hodge and Hofreiter, 1962) with some modifica- standard specifications for local date syrup (Anon., 1974).
tions to suit the material analyzed. The technique employed may be The only exception was that the date syrup samples had a
summarized as follows: thin-layer chromatography (TLC) on plates higher total ash content than that reported in the Libyan
containing “cellulose DF” was applied to separate the sugars. Sam-
standard specifications.
ples consisting of 800 micrograms in solutions were spotted. The
plates were then multiple developed according to the method The sugar analysis of date syrup was accomplished em-
described by Berger and Borodkin (1967). Pure sugarswere chroma- ploying the above mentioned three different techniques.
tographed along with the date-syrup samples in order to identify The data obtained are reported in Tables 1 and 2. Figure 2
the sugars present. The quantitative determination of the separated
individual sugars was carried out as described by Hodge and Hof- Table l-Physicochemical properties and average composition of
reiter (1962). the date syrup

Isolation of the coloring matter from date syrup Characteristic measured

The date syrup, after dilution, was centrifuged at 5000 rpm for Constant direct polarization at 20°C (angular degree) - 5.92O
15 min. The coIoring matter was then adsorbed on a mixture of Invert polarization at 20°C (angular degree) - 6.75’
equal parts of animal charcoal and activated vegetable carbon. After Colora 10.00
filtration, the charcoal bed was washed with hot distilled water Viscosity at 20°C (P) 17.17
following by another wash with ethyl alcohol. Then the adsorbed PH 3.80
colorants were extracted from charcoal using 70% pyridine. The Refractive index at 20°C 1.4788
pyridine was evaporated under vacuum at 55’C. The moistened Degree of acidityb 8.90
coloring matter remaining after evaporation was dried further in a Total soluble solids % (by refractometer) 75.80
desiccator over HzS04. After recording the weight of the dried Total sugars % ’ 70.81
coloring matter, it was ground to powder and stored for the follow- Purity o/ad 93.42
ing analysis. Protein % (N x 6.25) 1.02
Total ash % 2.03
Ionexchange chromatography Na (mg/lOOg) 70.40
The coloring matter was adsorbed from date syrup on an anion- Ca (mg/lOOg) 37.70
exchange resin (amberlite IRA-401CI- form). For this purpose a K hs/lOOg) 217.00
column (4x45 cm) was prepared by the usual procedure (Pecsok and Fe (mg/lOOg) 9.30
Shields, 1968). A diluted solution of date syrup containing 15% Total coloring matters % 4.08
refractometer solids was first centrifuged at 5000 rpm for 15 min, Coloring matters adsorbed on charcoal % 1.86
then 20 ml of the supematant were applied into the column. Chrom- Coloring matters not adsorbed on charcoal % 2.22
atography was carried out with stepwise elution using HzO, 0.3M
L Determined as attenuation Index (DeWhalley, 1964)
NaCl, 0.5M HCl, 0.5M NaOH, and 2M NaCl. The flow rate was Calculated as milliliters of O.lN NaOH required to neutralize
about 1 ml/mm Column effluents were collected in 10 ml portions. 10 9 of the date syrup
The optical density was measured for each portion at 560 nm. UV- z Calculated as invert sugar
absorption spectra were obtained for the fractions separated by Calculated as (total sugar/total soluble solids) x 100
column chromatography.
Decolorization of date syrup
A diluted solution of date syrup (20% T.S.) was heated to about
70°C, then treated with milk of lime (1%) and H,P04 to a pH value
of 7.5. The defecated solution was left for 3 hr to settle. The heavy
precipitate yielded by this treatment was separated by decantation
and filtration. The clarified date extract was then boiled for 10 m m
with a mixture of vegetable and animal charcoal (0.3%) to remove
the reamining coloring matter. After filtration, the purified date
extract was used for further analysis.

RESULTS & DISCUSSION

Date-syrup characteristics and composition

Dates are considered a good source for calories, minerals
and amino acids (Dowson, 1962; El-Shurafa, 1978; Hulme,
1970; Popenoe, 1974). Data concerning the average com-
position and principal characteristics of Libyan date syrup
are presented in Table 1. The date syrup studied was levoro-
tatory and it exhibited a slight difference in the polariza-
tion value after and before inversion. This may indicate
the low sucrose content. The relatively high viscosity of the
syrup, 17P, was undoubtedly affected by the presence of
nonsugar materials present, such as proteins, pectins, and
dextrins. The acids present in the syrup contributed to its
flavor complex. The high level of acidity (pH 3.8) contrib-
uted to its stability against microorganisms. Figure 1 illus-
trates the amino acids chromatogram of the Libyan date
syrup. The following amino acids could be identified:
Argenin, glutamic acid, methionine, histidine, alanine, ly-
sine, and glycine. However, the presence of other amino
acids was not examined. The analytical results obtained
fig. l-Amino-acids content of “Rub Al-Tamr.” l--a&nine; 2-
agreed with those recorded for date syrup produced in
glutamic acid; 3-methionine; 4-histidine; Galanine; 6-lysine;
other countries (Aligedi and Beshkov, 1976; Ehrenberg, 7-glycine; S 1 and S2- two original samples.

Volume 46 (1981IJOlJRNAL OF FOOD SCIENCE- 1163

 illustrates the sugar chromatogram of the Libyan date syr-
up. It was observed that date-syrup sugars developed on the
cellulose plate were resolved into discrete spots. Glucose,
fructose, and sucrose were identified. These findings agreed
with the results reported by other investigators (Al-Dawody
et al., 1976; El-Shurafa, 1978; Hulme, 1970; Nowatzyk,
1976). The data in Tables 1 and 2 indicated that reducing
sugars comprised about 95% of the total sugars. The glucose
concentration slightly exceeded that of fructose. The
purity of the date syrup produced in Libya reached 93.42%.
Such characteristics enable date syrup to be used as a less
expensive substitute for glucose syrup in those countries
having a ready supply of dates. However, the high color,
reported in Table 1, necessitates clarification of date syrup
before using it as liquid invert sugar.
Isolation, separation, and characterization
of the coloring matter of date syrup
The method used for isolation of the colored compo-
nents from date syrup did not affect their chemical struc-
ture. It has to be mentioned that the charcoal mixture
adsorbed only a part of the date syrup colorants, 45.6%,
while the remaining part was precipitated after treatment of
the charcoal-bed filtrate with ethyl alcohol. The alcohol
precipitated colorants comprised about 54.4% of the total
coloring substances of date syrup. The powder of the color-
ing matter adsorbed on charcoal had a brownish-grey color
Table 2-Sugar analysis of the date syrup
Sucrose Glucose
Method of analysis % %
and an odor characteristic of dates. It was easily soluble in
water at room temperature. The alcohol precipitated
colroants were darker in color, odorless, and insoluble in
water. Generally, date syrup contained total coloring
matter as high as 4.08% (see Table 1).
Figure 3 illustrates UV-absorption spectra for an original
sample of date syrup and for the filtrates after treatment
with charcoal and alcohol, respectively. ‘The extinction
curve of the original syrup, curve A, exhibited minimum
absorption at 26.5 nm and a maximum absorption at 275
nm. The extinction curve of the adsorbed-on-charcoal
colorants (curve C) showed a sharp absorption peak at 295
nm, while the filtrates after treatment with charcoal and al-
cohol (curves B and D, respectively) exhibited an intensive
absorption at the range 290-295 nm. This could be attrib-
uted to the existence of different groups o:f chromophores
and auxochromes, which have intensive absorption in the
preceding wavelength range of spectra (Creswell et al,
1972; Pecsok and Shields, 1968). The wavelength range
270-275 nm,,for example, may be associated with com-
pounds of the type, ,
R-CH=C (OH)-CHO
which could be detected among the degmdation products
of reducing sugars. The UV-absorption band in the region
285-295 nm has been recognized as ,an indication of
amino-carbonyl products known as melanoidines (Cres-
well et al., 1972; Farber et al., 1971; Fleming et al., 1971).
Moreover, phenolic compounds present in ripe dates
(about 0.5%) may form iron-polyphenolic colored com-
plexes not adsorbed on charcoal with characteristic absorb-
ance at 272-273 nm (Farber et al., 1971; Fleming, 1971;
Reducing Hulme, 1970; Mohamed, 1979). This may be an indication
Fructose sugars
% %

T.L.C. 3.97 33.32 30.93 68.42a

Lane-Eynon
volumetric
Polarimetric
method
method 3.62

2.98
-

-
-

-
67.01
E
1.6
I IIAI I
Isd (0.05) 1.08
Isd (0.01) 1.79 1.4
a Calculated as equivalent total invert sugar

1.2

1.0

0.8

0.6

0.4

0.2

0.0
220 40 60 80 300 20nr
Fig. 3-U V-absorp tion spec tre of: (AI The original samples of “Rub
Al-Tamr;” IS) The filtrate after treatment with charcoal; (Cl The
Fig. P-Sugar’s chromatogram of “Rub Al-Tamr:” l-fructose; 2- coloring matters adsorbed on charcoal; and (0) The filtrate after
glucose; d-sucrose. treatment with alcohol.

1164-JOURNAL OF FOOD SCIENCE-Volume 46 (1981)

 LIBYAN DATE SYRUP (RUB AL-TAMR) ...

that the coloring groups, degradation products of reducing
sugars, melanoidines, and iron-polyphenolic complexes,
contributed to the color of date syrup. However, the condi-
tions prevailing during the processing of date syrup, i.e.
prolonged heating of solutions of reducing sugars in the
presence of amino acids, phenolic compounds, and metals,
are considered favorable to the formation and accumulation
of such type of coloring compounds. It should be pointed
out that a minor part of the charcoal-nonadsorbed color-
ants, probably of melanoidines type, was not precipitated
with alcohol and appeared in the final filtreate giving it a
very weak grey hue (curve D in Fig. 3).
Figure 4 illustrates changes in the optical density de-
pending upon pH values for the coloring matters under
study. Noticeable differences could be seen in configuration
and extreme points between curve A and curve B. This
could be regarded as an indication of the difference in the
nature of the two types of colorants shown in this figure.
The infrared spectra of the coloring matters isolated
from date syrup are illustrated in Figure 5. The patterns of
these colorants displayed at least 16 significant bands for
both of the groups of colorants. The identification of the
functional groups assigned to these bands is shown in Table
3.
Figure 6 illustrates UV-absorption spectra of the color
fractions of date syrup separated by column chromatog-
raphy. The date-syrup colorants were separated into two
fractions: Water fraction of brownish-red hue, and the 2M
NaCl fraction of light yellowish-brown hue. The water
fraction had an absorption peak at 295 nm, while the NaCl
fraction exhibited an intensive absorbance in the wave-
length range 305-3 15 nm. The latter band has usually been
assigned to the absorption of melanoidine-type compounds
resulting from amino-carbonyl reaction with the contri-
bution of various ammo acids (Farber et al., 1971; Fleming
et al., 1971; Gross, 1967; Mohamed, 1979; Pecsok and
Shields, 1968). Regarding configuration and extreme
points, a kind of similarity can be noticed between curve e
(Fig. 6) and the curves B, C, D (Fig. 5). This may be due to
the fact that the melanoidine-type compounds which
comprise the major part of date-syrup colorants have a
quite low selective adsorption tendency on both charcoal
and anion resins. Only melanoidines of highly complex
structure, NaCl fraction, exhibited noticeable selective
E
1.6
1.4
1.2

1.0

0.8

0.6
1.1
0.4

0.2
0.0
220 40 60 80 300 20 nm
0 2 4 6 8 10 pH x
Fig. I-indicator property of the coloring matters of “Rub Al- Fig. 6-lJV-absorption spectra of: (Al The original sample of “Rub
Tamri;” IA) Coloring matters adsorbed on charcoal; IS) Coloring Al-Tamr;” fel The H20-fraction from ion-exchange column; and
matters nor adsorbed on charcoal. /Fl NaCI-fraction from ion-exchange column.

0 I I
alo 3600 x00 2600 2WO lKU l600 1400 1MB lOOIl B(w) 600 400 200

Fig. 5-Infrared specrra of: (1) Coloring matters of “Rub Al-Tamr”not adsorbed on charcoal; (2) Coloring marrers of “Rub Al-Tamr”adsorbed
on charcoal.

Volume 46 (19811-JOURNAL OF FOOD SCIENCE-l 165

 Table d-identification of the functional groups of the date-syrup colorantsa
I
Absorption Colorant
Number band CM-l Characterization of band Corresponding functional group groupb
I
1 3400 Very strong, very broad = N-H, > C-H, HN = C(O-R), A and B
2 2950 Medium, sharp -CH,-K=O)-CH, - fC=N) A and B
2380 Weak, sharp B

i
I 6
a
2340
2320
2020
Weak, sharp
Weak, sharp
Weak, broad
1 -CcN

= (-J=
B
A
A

1
) 7 1730 Weak, broad -CH2-CO-O-R, 0 = C (O-R), B
8 1725 Weak, sharp
9 1710 Weak, sharp CH2--CO-O-R A
10 1625 Medium, broad -NH,, phenyl ring B
11 1610 Medium, borad Phenyl ring A
12 1580 Weak, very sharp A
13
14
1570
1560
Weak, very sharp
Weak, very sharp 1 O=N=O(Nitro) A
A
15
16
1430
1425
Weak, broad
Weak, broad 1 Ionized carboxyl, alkene group B
17
18
1060
1050
Very strong, sharp
Very strong, Very broad 1 0-H. C)- *,b
B
A
19
20
21
925
910
870
Weak, sharp
Very weak, sharp
Weak, sharp
1 RCH = CH,
R.-j3 = CH,, 6
B
B
B
22 820. Medium, sharp >C = CH-, -O-C-O, 0 *co’ A and B
II

23 780 Very weak, sharp 1

1
(Ior
a
Al kane group
24 775 Medium, sharp
25 700 Very weak, sharp

1
26 630 Very weak, sharp
27 620 Very weak, sharp Acetate or Acetyl
28 610 Very weak, sharp
29 430 Medium, sharp ,oni2”i;zic sulfate
30 400 Medium, sharp

a Identification was Performed according to Creswell et al. (1972) and Pecsok and Shields (1968).
b A-Colorants not adsorbed on charcoal; B-Colorants adsorbed on charcoal.

adsorption property on anion resins. The data obtained conformed with the Libyan standard specifications with the
could confirm the complexity of the chemical nature of exception of the high total ash content.
date-syrup colorants. Such data could be of help in devising (2) The reducing sugars of Libyan date syrup comprised
processes for their reduction or elimination as an industrial about 95% of its total sugars content. The major sugars
scale. present were glucose 48.70%, fructose 4.5.21%, and sucrose
6.09% of the equivalent total invert sugars.
Decolorization of date syrup (3) The Libyan syrup contained total coloring matter as
Besides sugars, date extract contains different amounts of high as 4.08%, only 45.6% of which could be adsorbed
pectins, proteins, minerals, and hemicellulose substances directly on charcoal. The remaining part has to be elimi-
(Aligedi and Beshkov, 1976; Popenoe, 1974). Pectins, nated by an appropriate chemical treatment.
(4) The ultraviolet spectroscopic examinations indi-
which are considered hydrophilic colloidal substances,
cated that each of the coloring groups, degradation prod-
cause remarkable increases in date-syrup viscosity. Their
presence retards the rate of filtration and renders clarifi- ucts of reducing sugars, melanoidins, and iron-polyphenolic
cation of the date extract quite difficult. Proteins have complexes, contributed to the color complex of date syrup.
‘the same effect. It has been generally agreed by most (5) The melanoidine-type compounds, which comprise
investigators that the elimination of proteins and pectins the major part of date-syrup colorants showed a low
need specific materials having the ability to adsorb such selective adsorption tendency on both, charcoal and anion
colloidal matters (Ehrenberg, 1977; Hoynak and Bollen- resins. Only melanoidines of highly complex structure
back, 1966; Nakahara and Tetsujiro, 1977; Nowatzyk, exhibited noticeable selective adsorption property on anion
1976). In the present study an attempt was made to clarify resins.
date syrup using calcium phosphate precipitation. The de- (6) An efficient clarification of date: syrup has been
colorizing efficiency was about 98%, the loss in soluble achieved by the use of calcium phosphate precipitation.
solids amounted to 2.7%, and a decrease of 1.9% in ash The results obtained may be of help in setting some
content had been achieved along with decolorization. After practical basis for utilizing the dates grown in Libya in the
decolorization, the purity of date extract increased to production of “total invert liquid sugar,” which has numer-
‘99.3%. The data obtained may furnish a verified basis for ous uses in the food industry.
the use of dates grown in Libya in the production of a type
of liquid sugar known as “total invert liquid sugar” having REFERENCES
important uses in food industries. Anonymous. 1974. Libyan Standard Specifications No. 44. for the
The results obtained in the present work lead to the production of “Rub Al-Tamr.” Ministry of Industry and Minerals,
S.P.L.A.J.
following conclusions: Al-Dawody. A., Al-Ani, M., and Al-Jawad, L. 19176. Paper chromato-
(1) The analytical data of date syrup produced in Libya graphic separation of free sugars of three varieties of Iraq dates of
-Continued on page I174
1166-JOURNAL OF FOOD SCIENCE-Volume’46 (1981)