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International Journal of Biological Macromolecules 93 (2016) 476–482

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International Journal of Biological Macromolecules


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

Assessment of physical and structural characteristics of almond gum


Mudasir Bashir, Sundaramoorthy Haripriya ∗
Department of Food Science and Technology, Pondicherry Central University, Pondicherry 605014, India

a r t i c l e i n f o a b s t r a c t

Article history: Almond gum was investigated for its physical and structural characteristics in comparison to gum arabic.
Received 2 March 2016 Among physical properties, bulk density was found to be 0.600 ± 0.12 g/mL and 0.502 ± 0.20 g/mL for
Received in revised form 2 September 2016 almond and gum arabic respectively. Almond gum (0.820 ± 0.13 g/mL) displayed the maximum value for
Accepted 4 September 2016
tapped density. Compressibility index of exudate gum powders varied from 26.79 ± 1.47 to 37.46 ± 0.50%
Available online 5 September 2016
and follow the order gum arabic > almond gum. Almond gum demonstrated good flow characteristics
when compared to gum arabic. True density showed significant difference (p < 0.05) among the exudate
Keywords:
samples and it was recorded higher for gum arabic. The maximum value of porosity recorded in case of
Almond gum
Gum arabic
gum arabic indicates the presence of large number of interstitial spaces among its particles. Almond gum
Flow properties had fair flow character while good for the other exudate gum powder. Almond gum had relatively higher
X-ray diffractogram mineral content than gum arabic. The oil holding capacity of exudate gums varied from 0.87 ± 0.05 to
0.92 ± 0.02 g/g. Exudate powder samples were found to lie in the first quadrant of the hue angle (0–90◦ )
corresponding to the range of reddish–purple to yellow. The absence of peaks in the X-ray diffractograms
of exudate samples reflects their amorphous nature. SEM micrographs revealed a lot of variability in shape
and size of the exudate particles.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction and limited moisture [3]. Yields can be increased by making inci-
sions in the bark or stripping it from the tree or shrub [4]. Vilela and
A large number of plant gum exudates have been discovered in Ravetta [5] reported increased exudation from the wounded trees
the last few decades. The typical examples of this category include of genus Prosopis (P. chilensisand P. nigra) during late summers. It is
gum arabic, gum ghatti, gum karaya and tragacanth gum. These evident from earlier studies that exudate gums are safe for human
natural gums, secreted by trees and shrubs, solidify upon expo- consumption as being used as pharmaceutical substances or as
sure to air and heat of the sun which hardens them into different food additives in addition to other industrial uses [6–8]. They vary
shapes including tears, semisolid nodules and lumps. Phenomenon in their physicochemical and functional properties to a great deal
of exudation does not happen in normal trees. However, it is an which is due to source specificity and most importantly governed
absolute response against the stimuli of changing external environ- by discrepancy of agro-climatic conditions.
ment. Exudate gums are produced in response to biotic and abiotic Physical properties like bulk density, tapped density, porosity,
stressors like infection, insect attack, and mechanical or chemical wettability, particle size and their distribution are the indicators
injury and such phenomena of exudation are known as gummosis that determine the quality of powders [9]. These also affect their
[1]. These exudates are therefore produced as a result of defence functionality. Reducing food substances to desirable particle sizes
to seal wounds, site of infection or injury of a tree. Gum yield is are primarily important for mixing two different food ingredi-
influenced by various controlling factors such as tapping intensity, ents for formulating a uniformly blended finished food product.
rainfall, and temperature. Ballal et al. [2] found positive correla- Any difference in the particle size of ingredients may result in
tion of yield with tapping intensity, rainfall and the minimum and their improper mixing due to weight discrepancy leading to non-
maximum temperatures at tapping time, and negative correlation uniform (defective) finished product. Therefore, the knowledge of
with tapping time and the minimum and maximum temperatures density and its related properties will be instrumental in the suc-
at gum collection. Gum production increases at high temperatures cessful development of food formulations involving exudate gums
as ingredients.
Almond (Prunus dulcis), native to central Asia (Iran, India and
Pakistan), belongs to rosaceae family [3]. In India, it is usu-
∗ Corresponding author. ally cultivated for its nut production or as an ornamental plant.
E-mail address: shprieya@gmail.com (S. Haripriya).

http://dx.doi.org/10.1016/j.ijbiomac.2016.09.009
0141-8130/© 2016 Elsevier B.V. All rights reserved.
M. Bashir, S. Haripriya / International Journal of Biological Macromolecules 93 (2016) 476–482 477

It is commonly known as Badam in Indian subcontinent and base and a pile was formed at the base. The angle of repose was
spatially distributed in the states of Jammu and Kashmir and then calculated as follows:
Himachal Pradesh. Natural polysaccharides are known to possess
h
anti-cancerous [10,11], antioxidant and anti-inflammatory prop- Angle of repose() = Tan −1 ( ) (1)
r
erties [12–14]. Therefore, a growing quest is developing among
food scientists for new sources of biopolymers to be used in food where h and r are the height and radius of the pile, respectively.
industry. In this direction, almond gum has been identified as a
novel gum, an exudate collected from trunk, branches and fruits 2.3.2. Compressibility index
of almond tree that could be utilized in food and allied industries The compressibility index of exudate gum was determined
on a large scale. Ethylene or ethylene-releasing compounds such as according to Carr’s Index after determining bulk and tapped den-
ethephon (2-chloroethyl-dioxido-oxophosphorane) stimulate gum sities. 20 g of the dried gum was taken into 50 mL graduated
formation [15] in trees and fruits of stone-fruit species of the measuring cylinder and the initial volume (V0 ) was recorded. The
Rosaceae family, such as almonds [16]. Almond gum has received cylinder was then tapped 100 times using bulk density apparatus
less attention in India, resulting in total wastage of this exudate. (ACM-157, Acmus Technocracy, New Delhi) to achieve a final vol-
The state can produce sizeable quantities of this gum which could ume (Vf ). The bulk density was calculated from the initial volume
accomplish to broaden the spectrum of its use in food products. and tapped density from the final volume after hundred tappings.
This natural polysachharide is almost colourless, odourless and Carr’s Index was then determined by the following equation [22].
non-toxic which may qualify it as an additive in wide variety of
Tapped density − Bulk density
food systems. Almond gum is a natural polymer composed, on dry carr  s index = × 100 (2)
weight basis, of proteins (2.45%), fats (0.85%) and carbohydrates Tapped density
(92.36%). Carbohydrates comprise of arabinose (46.83%), galactose
(35.49%) and uronic acid (5.97%) with traces of rhamnose, mannose 2.3.3. Hausner ratio
and glucose [6]. The gum exudate is also a rich source of various Hausner ratio measures cohesiveness of the exudate gum pow-
minerals including sodium, potassium, magnesium, calcium and der. It was calculated using the measured values of bulk density
iron [17]. It is a better emulsifier than gum arabic [18] and a proven and tapped density as per the following equation.
antioxidant and antimicrobial source capable of enhancing biolog- Tapped density
ical and functional properties in diverse food formulations [19]. Hausner ratio = (3)
Bulk density
Growing demand for exudate gums has prompted us towards the
discovery of new exudate gums that could substitute the major exu-
2.3.4. True density
dates in diverse food applications with better functional properties
True density of exudate samples was measured using the
than the existing ones. The selection of an exudate gum as a food
method as suggested by Santhalakshmy et al. [23]. Briefly, 1 g of
additive will be determined by its physicochemical characteristics
dried powder sample was transferred into a 10 mL measuring cylin-
and interaction with water [20,21]. To our knowledge there is no
der with a glass stopper. A total of 5 mL of petroleum ether was then
such report available on exudate from almond tree. Therefore, the
added to this sample and shaken for some time so that all the par-
aim of the present study was to evaluate the physical and struc-
ticles were suspended. Finally, the wall of the cylinder was rinsed
tural characteristics of almond gum exudate in comparison to gum
with 1 mL of petroleum ether and the total volume of the petroleum
arabic.
ether and suspended particles were read. The powder density was
calculated as follows:
2. Materials and methods

Weight of the powder (g)


2.1. Materials True density =
Total volume of petroleum ether and suspended particles (mL) − 6
(4)
Almond gum nodules were collected afresh by hand-picking
from different almond trees (Prunus dulcis) in Budgam, Jammu and
Kashmir, India during the month of August 2015. Gum arabic (Aca-
cia senegal) was obtained from Himedia Mumbai, India. 2.3.5. Porosity
Porosity was determined from the measured values of true den-
2.2. Sample preparation
sity and tapped density as given by the following formula.

The exudate gums were dried in hot air oven at 65 ◦ C. The True density − Tapped density
Porosity (%) = × 100 (5)
dried gum was milled to fine powder. The powdered gum exu- True density
date (almond or arabic) was mixed with deionized water and gently
stirred overnight on a magnetic stirrer for complete hydration of the 2.3.6. Moisture content
gum. Insoluble mass including hydrogel obtained post hydration Moisture content was expressed as percentage weight loss on
was separated by filtration using Whatman No.1 filter paper and drying (% LOD). 2 g of ground gum sample was weighed and oven
the filtrate was oven dried at 65 ◦ C. The dried gum was milled and dried at 105 ◦ C for 5 h to a constant weight. The experiment was
passed through sieve no. 100 and stored in dessicator for further done in triplicate. The percent loss on drying was then calculated
analysis. as follows Rankell et al. [24]:

2.3. Physicochemical properties weight of water in sample


% loss on drying = × 100 (6)
total weight o f dried sample
2.3.1. Determination of angle of repose
Angle of repose (␪) was measured using a fixed height funnel 2.3.7. Determination of protein, fat and carbohydrate
fitted at the height of 10 cm from the base (the funnel is 60◦ , 10 cm in The protein and fat content was analysed for exudate gums
diameter, 0.7 cm internal stem diameter with 9.6 cm stem length). using AOAC standard methods [25]. Carbohydrate was calculated
20 g of the powder was allowed to flow through the funnel into the by difference as given by Balaghi et al. [26].
478 M. Bashir, S. Haripriya / International Journal of Biological Macromolecules 93 (2016) 476–482

Table 1 2.4. Fourier transform infrared spectroscopy


Physico-chemical characteristics of exudate gums.

Parameter Almond gum Gum arabic Fourier transform infrared spectroscopy (FT-IR) spectra of exu-
Bulk density (g/mL) 0.600 ± 0.12 0.502 ± 0.20 date gum samples were recorded on an FTIR Spectrophotometer
Tapped density (g/mL) 0.820 ± 0.13 0.803 ± 0.25 (Thermo Nicolet Model: 6700, UK) at room temperature. The exu-
True density (g/mL) 1.037 ± 0.24 1.060 ± 0.32 date gum samples were mixed with KBr and made into pellets
Porosity (%) 42.06 ± 0.97 52.65 ± 0.19 before measurement. Standardization of instrument was carried
Hausner ratio 1.37 ± 0.03 1.60 ± 0.01
out using KBr pellet as blank and the spectra were recorded in the
Compressibility index (%) 26.79 ± 1.47 37.46 ± 0.50
Angle of repose (◦ ) 36.98 ± 0.93 34.75 ± 0.23 range of 400–4000 cm−1 .
Moisture content (%) 12.23 ± 0.12 10.77 ± 0.20
Carbohydrate (g/100 g) 82.26 ± 0.08 84.21 ± 0.18
2.5. X-ray diffraction
Protein (g/100 g) 1.41 ± 0.12 1.75 ± 0.19
Fat (g/100 g) 0.23 ± 0.06 0.37 ± 0.1
Ash (g/100 g) 3.86 ± 0.08 2.9 ± 0.07 X-ray diffraction analysis of samples was performed using X-
OHC (g/g) 0.92 ± 0.02 0.87 ± 0.05 ray diffractometer (Shimadzu, XRD 7000) operated at 30 mA (tube
Chromaticity 14.54 ± 0.09 12.10 ± 0.067
current) and 40 kV (target voltage) with Cu K␣ filtered radiation.
Hue Angle (◦ ) 80.18 ± 0.06 73.73 ± 0.08
aw 0.48 ± 0.00 0.39 ± 0.00
The scanning range for 2␪ values was set from 10◦ to 75◦ to cover
L* 82.90 ± 0.15 84.68 ± 0.20 all significant diffraction peaks of sample crystallites with a scan
a* 2.48 ± 0.00 3.39 ± 0.00 speed of 2◦ /min.
b* 14.29 ± 0.04 11.62 ± 0.06

All data were means of triplicates ± standard deviation 2.6. Scanning electron microscopy

Morphology of the exudate gum samples was analyzed by scan-


2.3.8. Determination of ash ning electronic microscopy (Hitachi, S-3400N, and Tokyo, Japan).
The ash content was determined by following the method of The samples were mounted on aluminium stubs using double sided
Yebeyen et al. [27]. 2 g of the exudate gum was first heated on a adhesive tape to which the samples were fixed and afterwards were
burner in air to remove its smoke. Then it was burned in a muffle coated with a thin layer of gold. An acceleration potential of 15 kV
furnace at 550 ◦ C. The ash content was expressed as a percentage was used during micrography.
ratio of the weight of the ash to the oven dry weight of the powdered
gum. 2.7. Statistical analysis

2.3.9. Oil holding capacity The data were analyzed statistically using package SPSS 20.0
Oil holding capacity (OHC) was determined according to the (SPSS Inc. Chicago, USA). One way ANOVA was performed with sig-
modified method described by Mirhosseini and Amid [9]. 0.5 g of nificance at p < 0.05. All the data are presented as the mean of three
exudate powder sample was added to 10 mL of mustard oil in a determinations with the standard deviation.
centrifuge tube. The resulting suspension was stirred for 2 min fol-
lowed by centrifugation at 1600 × g for 10 min. The supernatant 3. Results and discussion
was decanted and the gain in weight was expressed as oil holding
capacity. It was then calculated by the following formula. 3.1. Physicochemical properties
g  weight of wet sediment − weight of sample
OHC = (7) 3.1.1. Bulk and tapped densities
g weight of sample The bulk density values of exudate gums are depicted in Table 1.
The values for bulk density (g/mL) were found to be 0.600 ± 0.1, and
2.3.10. Water activity 0.502 ± 0.2 for almond gum and gum arabic exudates respectively.
Water activity of the powders was measured using an elec- It is reported to be influenced by various factors such as prepara-
tronic dew point water activity meter (Aqualab Series 4TE, Decagon tion, treatment, storage, particle size and moisture content. The
Devices, Inc., Pullman, Washington, USA). bulk density of the exudate gums was comparable with that of
reported for badam (Terminalia catappa) gum (0.721 ± 0.16 g/mL),
mangifera gum (0.74 g/mL), gum tragacanth (0.640 ± 0.00 g/mL)
2.3.11. Tristumilus color values and dioclea gum (0.564 ± 0.05) [22,28,29,30]. Tapped density is the
The color of the sample powder was measured using Color- maximum compaction a powder can undergo under the impact of
flex (Hunter Associates Laboratory Inc., Reston, VA, USA). The CIE external force. The interstitial spaces are very less when compared
L* (light d/ ark), a* (red g/ reen) and b* (yellow b/ lue) values were to bulk volume. Upon comparing tapped density values of gum
obtained. Color intensity in terms of chroma (C*) was calculated by exudates, almond gum (0.820 ± 0.013 g/mL) displayed the higher
the formula, C* = (a*2 + b*2 )1/2 , whereas hue angle (H◦ ) was calcu- value for tapped density. Results obtained for tapped density of
lated by the formula H◦ = tan−1 (b*/a*). exudate gums were found similar to those reported for gum arabic

Table 2
Positions of FT-IR bands and their respective assignments in exudate gums.

Characteristic group Almond gum (cm−1 ) Gum arabic (cm−1 )

O H stretching vibration 3523.41 3526.35


C H stretching of CH2 group 2909.39 2910.87
COOH stretching 1625.4, 1436.91 1627.4, 1437.2
(1–4), (1–6) linkage of galactose and mannose 772.13 779.2
Uronic acid (COOH) 1436.91 1437.2
Galactose and mannose 884.6 844
M. Bashir, S. Haripriya / International Journal of Biological Macromolecules 93 (2016) 476–482 479

Fig 1. FT-IR spectra of almond gum and gum arabic.

(0.86 g/mL), tragacanth gum (0.740 ± 0.01 g/mL) and Dioclea gum predicted by knowing the compressibility index [32]. Powders with
(0.706 ± 0.01 g/mL) [29,31]. the least compressibility indices therefore, exhibit excellent flow
characteristics [7,9]. Compressibility index value greater than 26
3.1.2. Compressibility index and hausner ratio indicates poor flowability. Hausner ratio is the manifestation of
Compressibility index and Hausner ratio are the relative mea- cohesion among the particles of gum powder. The powders hav-
sures computed from the knowledge of bulk and tapped densities ing Hausner values between 1.35 and 1.45 exhibit poor flow index
that reflect powder’s ability to settle down or interparticulate inter- [33]. The Hausner ratio recorded for almond gum and gum arabic
actions that interfere with powder flow. Compressibility index of was 1.37 ± 0.03 and 1.60 ± 0.01 respectively. Almond gum demon-
exudate gum powders varied from 26.79 ± 1.47 to 37.46 ± 0.50 % strated good flow characteristics when compared to gum arabic.
and follow the order gum arabic > almond gum. The compressibil- Hausner ratio for don gum (Prunus cerasoides) was reported as
ity is expressed as Carr’s index. The flowability of powders can be 1.33 ± 0.24 which was lower than the almond gum exudate [12].
480 M. Bashir, S. Haripriya / International Journal of Biological Macromolecules 93 (2016) 476–482

Fig. 2. X- ray diffractogram of almond gum and gum arabic.

3.1.3. True density, porosity and angle of repose


True density (g/mL) showed significant difference among the
exudate samples. It ranged between 1.037 ± 0.24 and 1.060 ± 0.32
(Table 1). The values of true density, reported for don gum
(1.67 ± 0.23 g/mL) and air dried grewia gum (2.0 ± 0.01 g/mL) were
comparatively higher than our exudate gums under study [12,34].
True density was comparatively higher for gum arabic. Poros-
ity is the fraction of total volume occupied by interstices found
among the particles of the exudate gum powder. It varied signifi-
cantly between the exudate samples and the values calculated were
42.06 ± 0.97 and 52.65 ± 0.19 % for almond gum and gum arabic
exudates respectively. The maximum value of porosity recorded in
case of gum arabic indicates the presence of large number of inter-
stitial spaces among its particles. Samples with higher values of
porosity are more prone to oxidative reactions than the ones with
lower values of the same attribute. In the current study, exudate
samples exhibited different angle of repose (Table 1). It measures
the powder resistance offered by frictional forces emanating from
the surface properties of granules [35]. Almond gum had fair flow
character while good for the other exudate gum powder [33]. It Fig. 3. Scanning electron micrographs of almond gum and gum arabic.
may also be influenced by drying procedure employed [9].

3.1.4. Chemical composition and type of hydrophobic fraction present in the composition of
Chemical composition of exudate gums is shown in Table 1. The food material decides its extent of oil absorption [37]. The non-
moisture content was determined as percent (%) loss on drying. polar groups present in the component constituents are lipophilic
This intrinsic property affects the quality as well as shelf stability in nature binding more and more lipid (oil) molecules. The dif-
of a powder sample. There was significant difference in moisture ference in porosity and proportion of biopolymers like proteins
content between the two exudate gums. Almond gum had the and fats of exudate samples may therefore reflect their variable
higher moisture content when compared to gum arabic. Protein oil holding capacities.
found in both the exudate samples was very less as their composi-
tion is predominantly comprised of carbohydrate. Protein content 3.1.6. Water activity
was found to vary significantly with sample. This moiety, although Water activity (aw ), an intrinsic property, measures free water
less in amount, play an important role in lending emulsification available in a food system. Based on its values the shelf life of a
and foaming potential to the exudate gums. The ash content of particular food system is determined. Limited water activity of a
exudate samples represents their mineral content. The ash con- food article makes it resistant to microbial growth and deteriorative
tent for almond gum and gum arabic was 3.86 ± 0.08 g/100 g, biochemical reactions while higher water activity reduces its shelf
and 2.9 ± 0.07 g/100 g respectively. Bouaziz et al. [36] reported life. In the current study, there is variability in the values of water
3.28 ± 0.04 % of ash for the almond gum found in Tunisia. activity of different exudate gum samples (Table 1). The water activ-
ity (aw ) values of exudate gum powders ranged from 0.39 to 0.48.
3.1.5. Oil holding capacity Lower water activity recorded for the gum powders reiterates their
The oil holding capacity (OHC) of exudate gums is their ability longer shelf stability. Bouaziz et al. [38] obtained higher aw for gum
to absorb or hold oil. The oil holding capacity of gums vary sig- arabic (0.53 ± 0.01) and almond gum (0.55 ± 0.03).
nificantly as depicted in Table 1.The imbibed oil may include both
physically entrapped oil occupying the interstices of powder bed 3.1.7. Tristumilus color values
and chemically engaged oil which might be credited to the pres- Color of the exudate gum samples were read as L*, a* and b* and
ence of protein and fat moieties of the exudate gums. The content from their knowledge the derived color properties like chromatic-
M. Bashir, S. Haripriya / International Journal of Biological Macromolecules 93 (2016) 476–482 481

ity and hue were calculated. The color properties are presented in ability in terms of their shape and size. The gum samples were
Table 1. Gum arabic exhibited the highest value for lightness (L*) viewed at 500× magnification (scale bar 100 ␮m). The shapes of
followed by almond gum whilst a* (redness) and b* (yellowness) the particles were irregular and diverse in their forms. Gum ara-
varied significantly from 2.48 ± 0.00 to 3.39 ± 0.00 and 11.62 ± 0.06 bic had the smallest sized particles as observed after comparing
to 14.29 ± 0.04 respectively. Similarly lightness of zedo gum (Amyg- the micrographs of all the samples. Acetyl groups are essential for
dalus scoparia) exudate was highest followed by yellowness and maintaining the structural integrity of exudate gum for its particu-
redness [39]. Chromaticity parameter was measured as Chroma late nature [45]. Earlier studies reported the diversity in shape and
(C*) which denotes the saturation of color. Almond gum was found size of exudate particles [7,12]. However, the particles of almond
to exhibit the highest chromaticity. Hue angle represents the per- gum manifested irregular as well as smooth surfaces. Bouaziz et al.
ception of color. From the results, exudate powder samples were [46] reported pores on the rough surface of almond gum particles.
found to lie in the first quadrant of the hue angle (0–90◦ ) corre- Particle size may influence the dissolution rate of the gum powders
sponding to the range of reddish-purple to yellow. besides other factors.

3.2. IR-spectroscopy
4. Conclusion
Fourier transform infrared (FTIR) spectroscopy is used to
identify different organic functional groups present in natural Comparative analysis of almond gum with gum arabic was con-
substances. FT-IR spectra recorded for different exudate gum sam- sidered with a view to exploit the nature of this novel exudate in
ples presented complex vibrational modes at low wavenumbers order to specify its use as an additive in food systems. In this study,
(Fig. 1). The spectral bands falling between 3000–3600 cm−1 and almond gum exhibited better physical properties when compared
2800–3000 cm−1 correspond to O H and C H stretching modes to gum arabic. Low compressibility for almond gum reflects its bet-
respectively. Peaks observed at 3523.41 cm−1 (almond gum), and ter flowability than gum arabic which is a desirable property in
3526.35 cm−1 (gum arabic) in the spectra are therefore due to packaging of food powders. Use of almond gum could also be appre-
the presence of O H groups only. While the major IR-bands at ciated in wake of its high mineral content in foods. FT-IR of both
2909.39 cm−1 and 2910.87 cm−1 observed for almond gum and the exudates presented characteristic spectra of polysaccharides.
gum arabic, were assigned to the vibrational modes of C H XRD diffraction analysis reiterated the amorphous nature of the
group. Peaks present in the spectra at 1625.4 cm−1 1627.4 cm−1 , two exudates.
1437.2 cm−1 and 1436.91 cm−1 correspond to the presence of
COOH (carboxylic group). Carboxylic acids show characteristic
Acknowledgement
O H in-plane bending band at 1430 cm−1 [40]. Peaks centered
at 1436.9 cm−1 (almond gum), and 1437.2 cm−1 (gum arabic)
This project is financially supported by the Department of Food
wavenumbers may be due to the symmetrical stretching of car-
Science and Technology, Pondicherry Central University, India.
boxylic groups of uronic acid residues of gum polysaccharides
(Table 2). However, these wavenumbers of exudate samples dif-
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