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Zhao 2010
a r t i c l e i n f o a b s t r a c t
Article history: The surface composition of five types of ginger powders with the particle sizes of 300, 149, 74, 37 and
Received 24 December 2009 8.34 m was investigated by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy
Received in revised form 5 May 2010 (SEM) and various types of physical–chemical characteristics regarding material particle size distribu-
Accepted 5 May 2010
tions, discoloration and chemical composition. The results show that the color differences are greater
Available online 13 May 2010
for superfine ground ginger than for conventional comminuted ones; the values of crude fibre, neu-
tral detergent fiber (NDF) and acid detergent fiber (ADF) decrease with decreasing ginger particle size.
Keywords:
However, no relationship with the surface fat, crude protein, ash and total solids exists. With superfine
Ginger
Superfine grinding
grinding the XPS O/C ratios of the five ginger powders were similar since the surfaces were not oxidized.
XPS Correlations were observed between the XPS N/C ratios and the high resolution XPS N 1s spectra. SEM
SEM observations revealed that the surface of ginger powder with a particle size of 300 m is rougher, while
Physical and chemical characterization superfine ground powders with particle sizes of 149, 74, 37 and 8.34 m are similar to each other. This
roughness difference between these surfaces correlates with the differences in their O/C ratios and the
surface morphology of five ginger powders.
© 2010 Elsevier B.V. All rights reserved.
0927-7765/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.colsurfb.2010.05.019
X. Zhao et al. / Colloids and Surfaces B: Biointerfaces 79 (2010) 494–500 495
hydrolyzed part. However, the surface of the powders is expected Each color difference reported in this paper is the average of three
to play an essential role in the bio-material process and should cer- measurements.
tainly not be neglected. The physical properties and/or the bulk
composition of superfine ground ginger powder in relation to its 2.2.1.2. Chemical analysis. The chemical composition of the ginger
chemical properties have been investigated [16]. While very lim- powders was analyzed using AOAC [24] method. The water content
ited information is available on the effect of the superfine grinding was determined by weight loss after drying 1 g of samples of pow-
on the surface composition of ginger powder. der at 105 ◦ C for 6 h. Total protein was determined by the Kjeldhal
The application of X-ray photoelectron spectroscopy (XPS) to method for quantification of nitrogen and using a conversion fac-
biopolymers has been recently extensively developed as many tor of 6.25. Ash was measured after incineration at 550 ◦ C for 6 h.
properties of polymer materials are strongly related to surface com- Crude fiber was determined by de-fatting the samples, separating
position [17,18]. XPS has been successfully applied to investigate the residue by filtration and measuring the mass loss by burning.
the surface composition of dairy powders at an elemental level Neutral detergent fiber (NDF) and acid detergent fiber (ADF) frac-
[19–21]. However, few works concern the surface composition of tions were determined sequentially by using the filter bag system
ginger powders observed by XPS. (Ankom Technology, New York). Total solid content was deter-
The surface composition of ginger powders was investigated by mined by drying the samples at 105 ◦ C up to a constant weight.
XPS and scanning electron microscopy (SEM) in conjunction with Determinations were carried out in triplicate and the results are
physical characterization measurements in order to get a better expressed in wt.%.
understanding of superfine grinding behavior.
2.2.2. X-ray photoelectron analysis
2. Materials and methods XPS was performed in a PerkinElmer PHI Quantera SXM using
monochromated radiation equipped with Al K␣ (1486.6 eV). The
2.1. Source of ginger and milling equipment had a hemispheric analyzer/detector (CHA). The X-ray
source was run at 2.0 kV and 20 mA. Samples were placed in a vac-
Fresh ginger was purchased from in the market of Laiwu, China, uum chamber (5.0 × 10−10 Torr) with photoelectron collection at an
were sorted, cleaned, cut into small pieces, and dried at 40 ◦ C. angle of 45◦ to the sample film surface at room temperature. Each
Excess water was drained off being placed in a mechanical drier spectrum was obtained under the following conditions: Ar+ scan,
till the water content reached less than 9%. The dried materials 1 × 1 mm2 analyzed area, 3 M CPS sensitivity, 20 nm/min sputtering
were subjected to coarse milling using a disc-mill, and screened speed, 0.05 eV resolution. All core-level spectra were referenced to
through different sized sieves; finally the uniform coarse parti- the C 1s neutral carbon peak at 284.8 eV [17]. Atomic concentra-
cles were ground in an HMB-701 type micronizer (Huanyatianyuan tions were calculated from photoelectron peak areas subtracting
Machinery Company, Beijing, China). The planetary rubbing mill the Shirley background [25] and taking into account sensitivity
(power 0.75 kW) was a vertical batch type mill. Three rubbing rings factors provided by the spectrometer manufacturer (PHI) [26].
were vertically equipped with pot holders on the turntable. The
inner volume and diameter of the cylindrical shape pot were 300 ml 2.2.3. Scanning electron microscopy (SEM)
and 400 mm, respectively. The pot was made of wear-resistant zir- Morphological characterization of ginger particles was per-
conia, and the rubbing rings with diameter of 300 mm were also formed on images acquired using a scanning electron microscope
made of the same material. The sample was mainly ground with (SEM), Quanta 200FEG-SEM (FEI Co. Netherlands) at 150 kV accel-
pressure, collision and abrasion between rubbing rings and inner erated voltage and 10–15 mm working distance. The samples were
bottom of pot. The revolution speed of turntable was unfixed at coated with platinum of 10 nm thicknesses to make the samples
2500–2800 rpm/min. conductive.
Table 1
Characteristic parameters of ginger particle distributions with different sizes.
300 8.21 ± 0.01 44.96 ± 0.01 150.49 ± 0.03 311.79 ± 0.02 107.51 ± 0.01 18.11 ± 0.01
150 6.02 ± 0.02 18.89 ± 0.01 52.48 ± 0.01 144.70 ± 0.03 35.29 ± 0.01 10.39 ± 0.02
74 5.35 ± 0.01 13.59 ± 0.02 22.90 ± 0.01 73.48 ± 0.01 20.46 ± 0.02 8.22 ± 0.02
37 3.16 ± 0.01 10.25 ± 0.01 18.13 ± 0.02 40.19 ± 0.01 18.35 ± 0.01 6.30 ± 0.01
8.34 2.91 ± 0.01 9.77 ± 0.01 13.15 ± 0.01 8.34 ± 0.02 6.48 ± 0.01 4.56 ± 0.01
a
Values are mean ± standard deviation, n = 3.
b
The particle of the equivalent diameter accounts for 10% of the total examined particle.
c
The particle of the equivalent diameter accounts for 50% of the total examined particle.
d
The particle of the equivalent diameter accounts for 75% of the total examined particle.
e
The particle of the equivalent diameter accounts for 90% of the total examined particle.
f
Mean value of examined particle volume.
g
Mean value of examined particle specific surface area.
Table 2
Color coordinates and color differences corresponding to ginger particles with different sizes.
L* b 81.20 ± 0.71 83.15 ± 0.65 84.31 ± 0.63 85.06 ± 0.62 85.53 ± 0.63
a* c 0.49 ± 0.04 0.49 ± 0.10 0.58 ± 0.10 1.38 ± 0.06 1.51 ± 0.10
b* d 24.04 ± 0.26 22.26 ± 0.26 21.74 ± 0.33 20.54 ± 0.23 19.22 ± 0.26
E* e 0 2.6 3.8 5.3 6.5
a
Values are mean ± standard deviation, n = 3.
b
L* : the lightness coordinate.
c
a* : chromaticity coordinate in the red–green axis.
d
b* : chromaticity coordinate the yellow–blue axis.
e
E* : total color differences.
included. Table 2 reveals that the color differences of superfine nificant difference between the particle size of 300 and 8.34 m
ground ginger are greater than conventional comminuted ones. It (P < 0.05) (Table 3), suggesting that the superfine grinding treat-
is obtained that the superfine grinding can influence on the L* , a* ment can lead to the degradation of ginger fiber. However, the fiber
and b* of ginger powders. The aberration of the grinding-treated content is not significantly different for over the particle sizes of
samples increases with decreasing ginger particle size. 150 m (P > 0.05). The NDF content of ginger with particle sizes
The chemical composition and physical properties of the pow- of 300 and 150 m is not significantly different (P > 0.05). Similar
ders are reported in Table 3. The fat, water, protein, ash and total significant reduction in the NDF contents with the particle sizes
solid contents are almost constant for the five ginger powders. The of 150 and 74 m is noticed (P < 0.05). The content of ADF (19.88%)
values of crude fiber, NDF and ADF decrease with decreasing ginger was higher (P < 0.05) in a particle size of 300 m as compared to the
particle size. In comparison with a particle size of 300 m, gin- particle sizes of 150, 74, 37 and 8.34 m. The results indicate that
ger powder with a particle size of 8.34 m is consequently poorer the superfine grinding can lead to the change of cell wall constitu-
in the crude fiber, NDF and ADF. The results clearly show a sig- tion of ginger rhizome. In comparison with coarse ginger powders,
Table 3
Chemical composition of ginger particles with different sizes.
(1) Values are mean ± standard deviation, n = 3. (2–5) Means with different superscripts in each line are significantly different from each other (P ≤ 0.05).
X. Zhao et al. / Colloids and Surfaces B: Biointerfaces 79 (2010) 494–500 497
Fig. 1. XPS survey spectra obtained from ginger particles with different sizes (a: Fig. 2. XPS C 1s features obtained from ginger particles with different sizes (a:
300 m; b: 149 m; c: 74 m; d: 37 m; e: 8.34 m;). 300 m; b: 149 m; c: 74 m; d: 37 m; e: 8.34 m;).
the amounts of the crude fiber, NDF and ADF in ultra-fine ginger they represent an average over the outermost 45 Å with the lay-
powders are relatively lower, which implicate the disintegration of ers nearer the surface contributing more to the signal. Although
the cellulose–hemicelluose network of ginger [15]. Regarding frac- inhomogeneous elemental distributions can have a large effect on
tion characterization, the variations of chemical composition are the calculated composition [28], methods are not available yet for
attributed to fast separation of different botanical constituents of calculating compositions for inhomogeneous elemental distribu-
the ginger [27]. tions on rough surfaces. Table 4 shows that the carbon percentage
decreases with decreasing powder size, while the oxygen and nitro-
3.2. X-ray photoelectron characteristics of ginger powder surface gen percentage increases.
As the grinding parameters were different for the powders with
An XPS survey spectrum obtained from ginger particles with different sizes, we could suppose some differences in porosity or
different sizes is shown in Fig. 1. The two predominant features are specific surface area of powders. The reason is that the surface prop-
the C 1s and O 1s peaks. Very small peaks of N and S are also present erties of superfine powders have changed after superfine milling,
in the survey spectra, but their combined concentration is under which causes marked differences in chemical composition separa-
3 at.% for all of the samples examined in this study. The content tion of the granulometric fractions [29].
of S element was found below 1% for the five powders (Table 4). The O/C atom ratios are of particular interest. This ratio is 0.29
Consequently, the S element other than C, O and N was neglected. for ginger powders with the particle sizes of 37 and 8.34 m, 0.28
Table 4 shows the peak area ratios observed for ginger powder for ginger powders with the particle sizes of 150 and 74 m. Gin-
surface with different sizes. The ratio of the peak area of O 1s, N 1s ger powder with a particle size of 300 m has a value of 0.26. No
and C 1s, O/C and N/C, roughly reflects the ratio of the concentration significant differences are found among the O/C ratios of the pow-
of these atoms in the ginger power surface. The compositions cal- ders with different sizes. The increase of the O/C ratio from 0.26 to
culated using the XPS data obtained from the samples examined in 0.29 indicated that the surface of superfine ground powders was
this study (an average of three different data points collected from slightly oxidized [18]. The N/C atom ratios increase with decreas-
three different areas) are presented in Table 4. These compositions ing ginger particle size. It is interesting to note that the N/C ratio
were calculated using the homogeneous assumption. Therefore, of superfine powder with a particle size of 8.34 m is higher than
Table 4
Compositional information obtained using X-ray photoelectron spectroscopy.
Ginger particle size (m) Ca (at.%) Ob (at.%) Nc (at.%) Sd (at.%) N/Ce O/Cf
Fig. 3. XPS O 1s features obtained from ginger particles with different sizes (a:
Fig. 4. XPS N 1s features obtained from ginger particles with different sizes (a:
300 m; b: 149 m; c: 74 m; d: 37 m; e: 8.34 m).
300 m; b: 149 m; c: 74 m; d: 37 m; e: 8.34 m).
powders with the particle sizes of 300, 150, 74 and 37 m. These
facts indicate that the surface of ultra-fine ginger powders has more powers could be slightly oxidized in the process of preparation,
amino groups exposed [30]. The slight increase of O/C and N/C ratios resulting in the increase of oxygen content. Generally, the O 1s
on the samples indicates that mechanical force plays a major role spectra do not provide useful chemical-state information because
in the process of superfine grinding. so many O-containing species are present which are not resolvable
The XPS C 1s features of the five samples are shown in Fig. 2. by XPS due to their closely spaced BEs [17].
The C 1s spectra obtained from ginger particles with different sizes In contrast, ginger powders with different sizes show clear N 1s
(Fig. 2) are quite similar to that reported in literatures [18,19]. The peaks around 399.8 ± 0.1 eV. The N 1s peak shape of five samples
peak shape similarity of C 1s among Fig. 2a–e indicates that the was similar. But the N 1s area increases with decreasing ginger
similar distribution of oxygen is present on the powder samples particle size (Table 4). As compared to superfine ground ginger
with the particle sizes of 300, 150, 74, 37 and 8.34 m. The C 1s powders (Fig. 4c–e), the N 1s spectra shown in Fig. 4a and b obtained
line for ginger powders with different sizes is characterized by a from the coarse ginger powders are narrower. The broadening in
narrow peak with binding energy (BE) = 284.7 ± 0.1 V, and its line the ultra-fine powders may be due to exposure of amino groups
form and position in the spectrometer chambers does not change [30]. The reasons might be that the structure of superfine ground
after superfine grinding (Fig. 2). By comparison with the powders ginger particles is broken down, which results in enhanced expo-
with the particle sizes of 74, 37 and 8.34 m (Fig. 2c–e), the C 1s sure of amino groups. In conclusion, superfine milling favors the
spectra of the coarse ginger powders with the particle sizes of 300 appearance of proteins at the surface of the particles. We assume
and 150 m (Fig. 2a and b) are narrower. The spectra shown in that superfine powders would give a higher surface content than
Fig. 2 indicate that the superfine milling can result in gaining of coarse powders.
oxygenated organic species since the predominant peak becomes
broader. This is consistent with the increase observed of the O/C
ratio from 0.26 to 0.29 (Table 4). The broadening of C 1s spectra in 3.3. Microphotographs of ginger powder
the ultra-fine powders may be attributed to formation of hydro-
carbons [18]. Because the O 1s peak shapes described below do SEM micrographs obtained from the surfaces examined in this
not exhibit a similar broadness, the chemical-state or charging of study are shown in Fig. 5. The ginger powders with the particle
surface for superfine ground ginger powders maybe change. Hydro- sizes of 149, 74, 37 and 8.34 m present a smooth surface. As far as
carbon formation is probable through bond scission in the course we can observe, the four powders appear to have a rather similar
of superfine grinding. Most oxygen-containing organic compounds surface by SEM. The SEM micrographs obtained from the surface
including alcohols, ketones and ethers have binding energies (BEs) of superfine ground powders with particle sizes of 149, 74, 37 and
between 284 and 285 eV [17]. Due to the similar BEs and the large 8.34 m are similar to each other as expected based on their simi-
variety of species, it is not possible to be specific about which lar O/C ratios of 0.28 and 0.29, but the surface of powders with the
oxygen-containing species form during superfine grinding. particle sizes 149 and 74 m is somewhat rough (Fig. 5b and c). The
The O 1s features corresponding to the C 1s features in Fig. 2 surface of ginger powder with a particle size of 300 m (Fig. 5a) are
are shown in Fig. 3. It contains one contribution with BEs of rougher than other particles (Fig. 5b–e). This roughness difference
532.7 ± 0.1 eV. The O 1s features in Fig. 3 have similar shapes and among these surfaces correlates with the differences of their O/C
BEs, indicating that the oxygen-containing species on all the sam- ratios. This fact suggests that the superfine pulverized treatment is
ples are similar. This similarity is consistent with the C 1s peak effective to change the original structure of the ginger powder sur-
shape similarity for all samples. The O percentage of ultra-fine face. The morphology after milling is changed considerably, which
powders is slightly higher than coarse powders. Ultra-fine ginger can have a significant impact on physical–chemical properties [16].
X. Zhao et al. / Colloids and Surfaces B: Biointerfaces 79 (2010) 494–500 499
Fig. 5. SEM micrographs obtained from ginger particles with different sizes (a: 300 m; b: 149 m; c: 74 m; d: 37 m; e: 8.34 m).
superfine grinding, the more amino groups on the near-surface [8] J. Bidlack, M. Malone, R. Benson, Proceedings of Oklahoma Academy of Sciences
ginger powders is exposed through bond breakage, which results 72 (1992) 51–56.
[9] Plant physiology and plant cells, in: F.B. Salisbury, C.W. Ross (Eds.), Plant phys-
in the increase of the surface nitrogen percentage of superfine iology, Wadsworth Inc., Belmont, CA, 1992 (Chapter 1).
ground powders. Improving ginger powder properties by superfine [10] K. Tkacova, N. Stevulova, Freiberger Forsclungshefte A (Partikeltechnologie)
grinding can be one way to extend the application of these high A841 (1998) 14–25.
[11] H. Yoshizawa, E. Hiroshi, Diamond slurry or paste for superfine grinding, patent
protein content powder and low fiber. Superfine ground powders B22F001-00, JP, 1991.
appear here that random variations of surface composition may [12] L.L. Song, B.Y. Fan, S.Z. Jiang, Journal of Chinese Materia Medica 27 (1) (2002)
be meaningful themselves, reflecting either actual variations of the 12–15.
[13] N.N. Win, W.F. Stevens, Applied Microbiology and Biotechnology 57 (3) (2001)
composition of the coarse powder surface induced by reorganiza- 334–341.
tion of powder surface polymers upon superfine grinding. The novel [14] S.Y. Jin, H.Z. Chen, Biochemical Engineering Journal 30 (2006) 225–230.
process allows the relatively complete exploitation of the ginger [15] R. Rajkhowa, L.J. Wang, X.G. Wang, Powder Technology 185 (2008) 87–95.
[16] X.Y. Zhao, Z.B. Yang, G.S. Gai, Y.F. Yang, Journal of Food Engineering 91 (2009)
rhizome.
217–222.
[17] G. Beamson, D. Briggs, High Resolution XPS of Organic Polymers: The Scienta
Acknowledgments ESCA300 Database, John Wiley & Sons, Chichester, 1992.
[18] G.N. Salaita, F.M.S. Ma, T.C. Parker, B. Gar, G.B. Hoflund, Applied Surface Science
254 (2008) 3925–3934.
Financial support of this work by Fund of Post-doctor Sci- [19] C. Gaiani, J.J. Ehrhardt, J. Scher, J. Hardy, S. Desobry, S. Banon, Colloids and
ence (Project 20080440388), National Natural Science Foundation Surfaces B: Biointerfaces 49 (2006) 71–78.
of China (grant no. 40701173) and Project of Agriculture Scien- [20] C. Gaiani, P. Schuck, J. Scher, J.J. Ehrhardt, E. Arab-Tehrany, M. Jacquot, S. Banon,
Journal of Food Engineering 94 (2009) 130–134.
tific and Technological Achievement Transfer of China (grant no. [21] C. Gaiani, M. Morand, C. Sanchez, E. Arab Tehrany, M. Jacquot, P. Schuck, R.
2009GB2C600198). Jeantet, J. Scher, Colloids and Surfaces B: Biointerfaces 75 (2010) 377–384.
[22] AFNOR Standard X11-666, Analyse granulométrique des poudres, Méthode par
diffraction, Paris-La-Défense, 1984, Chapter 1.
References [23] M.U. de la Orden, M.C. Matías, J.M. Martínez Urreaga, Polymer Degradation and
Stability 85 (2004) 697–703.
[1] V.N. Dedov, V.H. Tran, C.C. Duke, M. Connor, M.J. Christie, S. Mandadi, B.D. [24] AOAC, Official Methods of Analysis, 17th ed., Association of Official Analytical
Roufogalis, British Journal of Pharmacology 137 (6) (2002) 793–798. Chemists, Arlington, VA, 2000.
[2] W.H. Wang, Z.M. Wang, Journal of China Chinese Medicine 30 (2005) [25] D.A. Shirley, Physical Review B 5 (1972) 4709–4714.
1569–1573. [26] J.F. Moulder, W.F. Stickle, P.E. Sobol, K.D. Bomben, in: J. Chastain (Ed.), Handook
[3] L.C. Tapsell, I. Hemphill, L. Cobiac, C.S. Patch, D.R. Sullivan, M. Fenech, S. Rooden- of X-ray Photoelectron Spectroscopy, 2nd ed., PHI, Eden Prairie, MV, 1992.
rys, J.B. Keogh, P.M. Clifton, P.G. Williams, V.A. Fazio, K.E. Inge, Medical Journal [27] N. Kobayashi, P. Guilin, J. Kobayashi, S. Hatano, Y. Itaya, S. Mori, Powder Tech-
of Australia 185 (2006) S4–S24. nology 180 (2008) 272–283.
[4] S.D. Jolad, R.C. Lantz, A.M. Solyon, G.J. Chen, R.B. Bates, B.N. Timmermann, Phy- [28] G.B. Hoflund, in: J.C. Rivière, S. Myhra (Eds.), Handbook of Surface and Interface
tochemistry 65 (2004) 1937–1954. Analysis: Methods in Problem-Solving, Marcel Dekker, Inc., New York, NY, 1998
[5] S.D. Jolad, R.C. Lantz, G.J. Chen, R.B. Bates, B.N. Timmermann, Phytochemistry (Chapter 4).
66 (2005) 1614–1635. [29] C. Maarou, J.P. Melcion, F.B. de Monredon, D. Giboulot, M.P. Guibert, Le Guen,
[6] B.M. Naveena, S.K. Mendiratta, British Poultry Science 42 (2001) 344–349. Animal Feed Science and Technology 85 (2000) 61–78.
[7] H.X. Wang, T.B. Ng, Biochemical and Biophysical Research Communications 336 [30] S. Suzuki, B. Ying, H. Yamane, H. Tachi, K. Shimahashi, K. Ogawa, S. Kitamura,
(2005) 100–104. Carbohydrate Research 342 (2007) 2490–2493.