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Microencapsulation of Zanthoxylum Limonella Oil (ZLO) Genipin Crosslinked Chitosan-Gelatin Complex For Mosquito Repellent Application
Microencapsulation of Zanthoxylum Limonella Oil (ZLO) Genipin Crosslinked Chitosan-Gelatin Complex For Mosquito Repellent Application
.
Genipin Crosslinked Chitosan-Gelatin Complex for
Mosquito Repellent Application
ABSTRACT: Essential oil containmg chitosan gelatin com- improved with the mcrease in the amOlmt of chitosan in chi-
plex microcapsules crosslmked with gem pin were prepared tosan-gel,'tin matrix as revealed by thermogravimetric anal-
by complex coacervation process. The effects of various pa- YSIS. FT-IR spectroscopy and differenlial scanmng
rameters such as oil loading, ratio of chltosan to gelatin, calorimetry study indicated that there was no significant
degree of crosslinking on oil content, encapsulation effi- interaction between chitosan-gelatin complex and oil. 02008
ciency, and the release rate of the essential oil were studied. WIley' Periodicals, Inc J Appl Polym Sci Ill. 779-785,2009
Scanning electron nucroscopy study indicated that the sur-
face of the microcapsules were more irregular as the amount Key words: chitosan; gelatin; essential oil; microencap-
of oil loading Increased. Thermal stability of microcapsules sulation; genipin; mosquito repellent
Taiwan), and silicone oil (Ranbaxy Fine Chemical,s, range 0.005 to 0.1 gilOO mL, a sharp peak at 256 nm
Delhi, India) were used as such received.: TJ;1e core was noticed. 'The absorbance values at 256 run
material, essential oil from ZLO, was extracted in ,obtained "yith the respective concentrations were
our laboratory. DOl (double-dIstilled deionized) recorded and plotted. From the calibration curve,
water was used throughout the study. Other the unknown concentration of ZLO was obtained by
reagents used were of analytical grade. knowing the absorbance value
TABLE I
Effect of Variation of Oil Loading, Chitosan to Gelatin Ratio, and Genipin
Concentration on the Behavior of Microcapsules
Sample parhculars
Chitosan (gm) : Genipin Oil load Oil content EncapsulJ tion
Gelatm (gm) (mmol) ZLO (mL) (%) (%) efflciency (%).
0.25·1 O.OS 4 308.75 26.45 == 1.20 3414 ± 1.74
066· 1 005 4 30875 25.15 :!: 057 32.47 ± 1.07
2.1 0.05 4 30875 3065 ± 0.54 3956 ± 1.74
4.1 005 4 30875 37.65 ± 075 48.60 ± 1.14
1.1 D.D5 1 77.20 22.32 ± D.l5 48.31 ± 0.84
1: I 0.05 2 154.37 23.68 ± 051 44.3 ± 0.35
1:1 0.05 3 231.56 28.0 ± 0.12 32.87 ± 0.96
1:1. 0.10 4 280.27 42.0 ± 0.45 54.22 ± 1.12
1:1 0.20 4 236.60 4534 ± 087 58.53 ± 1.36
1: I 050 4 161.26 46.50 ± 0.64 60.05 ± 0.89
Total polymer = 1 g; genipin == (0.05-0.5 mmol/gm of polymer; oil == (1-4 mL); water
= 100 mL; Temperature = (40 ± 1)"C.
10 100
SO
GO
III
i7'O
:EO
.Ja
~«>
=
~010
~30
20 L~~~de
10 II) ~
O~~---r--~--r-~---r--'---~~---'
0
0 10 20 110 ~ 60 110 10 110 110 100
o ro ~ ~ ~ ~ R 10 U ~ 100
TirIuo.h nn•. h
Figure 1 Effect of variation of oil loadmg on release pro- Figure 2 Effect of variation of chitosan to gelatin ratio on
file. (a) Polymer 1.0 gm, crosslinker 0.05 mmol, ZLO 1.0 mL; release profile. Total polymer 1.0 gm, ratio of chitosan to
(b) polymer 1.0 gm, crossJinker 0.05 mmol, ZLO 2.0 mL; gelatin m (a) 0.25 . 1; (b) 0.66 : 1; (c) 2 : 1; (d) 4 : 1, ZLO
(c) polymer 1.0 gm, crosslinker 0 05 nunol, ZLO 3.0 mL 40 mL; crosslmker 0.05 mmol.
of microcapsule wall. Besides this, the amount of during the study of the release behavior of triclosan
. chitosan-gelatin mixture might not be sufficient to encapsulated within chitosan-gelatin microcapsules .
encapsulate all the oil droplets. Some oil droplets Both oil content (%) and encapsulation efficiency
might present without encapsulation. These oil were also found to increase with the increase in the
droplets might get exhausted during recovery of chitosan concentration. As explained earlier, the
microcapsules. As wall thickness decreased, the dif- increase in viscosity of the medium resulted in
fusional path for the oil became short27,2~ which the formation of large oil droplets. These large oil
resulted in an increase of release rate. droplets had a tendency to coalesce at higher oil
Again oil content (%) was found to increase with load to form further large oil droplets and therefore
the increase in the % of oil load. At low oil load, more oil could be encapsulated with the same
many of the microcapsules probably contained few amount of encapsulating material.
oil droplets indicating that there was an abundance
of encapsulating polymer for the oil present. As oil
load ('Yo) increased, the number of oil droplets in the Effect of variation of concentration of genipin on
release rate
microcapsules increased which resulted in an
increase in oil content. Results showing the oil load (%), oil content (%) and
encapsulation efficiency are shown in Table I. The
release profile of the oil is shown in Figure 3. The
Effect of variation of chitosan/ gelatin ratio on trend shown by both oil loading and oil content was
release rate as per expectation. Encapsulation efficiency increased
The effect of variation of chitosan-gelatin ratio on oil 71
loading, encapsulation efficiency and release rate are
shown in Table I and Figure 2. The release rate of oil 6.
was governed by the o,{, of chitosan present in the chito-
san-gelatin mixture. With the increase 10 the concentra-
tion of chitosan in chitosan-gelatin mixture, the release
f'..
~
FIgure 4 Scam-ung electron rruClogIaph~ of mICrocapsules prepared '\lth Oll load ('Yo) (a) 15437, (b) 30875, (c) 61702,
(d) 15437 (after 011 rdea~e)
wIth the ll1Crea6e m gempm concentratIOn The con- of 011 The burface of the mlcrocap~ule6 con tamed a
centratIOn of gempm was vaned from a 1 to 050 'ilgnlficant numbel of pm holes (arrow marked)
mmol/g of polymer mIxture The mClea::.ed effICIency These pm holes might be formed due to the release of
was due to the hIgher 011 retentIon capacIty of the 011 by dlffu'iIOn Moreover, on phYSical venficatJOn,
mIcrocapsules caused by the formatIOn of crosshnk- the mICrocapsules prepared at higher Oil loadmg
mg The cros~lmkmg reachon took place between appeared OIly and agglomerated where as tho::.e pre-
gempm, gelatm, and chltoc;an The release rate of 011 pared at low OIlloadmg appeared dry and powdery
was found to decrease as the % of gempm mCl eased
The mIcrocapsule wall became compact a::. degree of
crosslmkmg mcrea'ied ThIS re'iulted m the decrease ThermogravImetric analYSIS
of dIffuSIOn rate through the mIcrocapsule ,·vall Simi- Table II showb the mlhal decompositIOn tempelature
lar fmdmgs were cIted m the hterature 1030 (T,) and residual weIght (RW, %) of vlrgm polymer,;
(chltosan and gelatm), ZLO and ZLO contammg
Scarming electron microscopy study TABLE II
Scannmg electron mlcrobcopy (SEM) mlcrograph~ of Thermal Analyhcal Data for Vlfgm Polymer and OIl
Contammg MIcrocapsules
gempm crosshnked dutosan-gelatm microcapsules
havmg dIfferent percentage of 011 content ale ~hown SamplE' palhcu!ar:,
m FIgure 4 At low Oliloadmg [FIg 4(a)], the burface Gelatm (gm) 011 RW(%)
of the microcapsules appeared smooth compaled Chltosan (gm) (mL) T,CC) ilt 600 "C
With those of microcapsules prepared at hIgher all J 0 236 875
loadmg [FIg 4(b,c)] At hIgher OIlloadmg, a burstmg 1 05 40 175 933
look was observed due to the presence of large per- ! 1 40 190 2306
centage of 011 Sirrular observatIons were reported In 0 1 273 3774
Olla
the hterature 10 14 The burface of the mlcrocapbule6
became more megular as the percentage of 011 load- T" Imtlal d€'compo<;ltlOn temperature, RW, lesldua!
mg mcreabed Figure 4(d) bhow::. the microgiaph of \\ eIght
the microcapsule,; after release of 'iubc;tanhal amount 1 Stal ted decompo'img flom the vely begmnmg
TABLE III
Temperature of Decomposition (TD) at Different Weight Loss (%) of Virgin Polymer and
Oil Containing Microcapsules
Temperature of decomposition (To) (0C)
Sample particulars at dIfferent welght loss (%)
Gelatin (gm) : Chitosan (gm) Oli (mL) 20 40 60 70 80
1:0 286 331 394 438 529
1 : 0.5 4 236 300 354 370 446
1'1 4 200 302 366 448
0:1 294 320 543
Oil 90 115 155 228
microcapsules. Both the Ti (0C) and RW ('Yo) were tosan. The reaction rate of chitosan and genipin was
found to increase with the increase in chitosan con- reported more compared with that of gelatin?l So
centration in the chitosan-gelatin mixture. The chitosan could form more crosslink bridges com-
decomposition of ZLO started at an early stage and pared with that of gelatin and thereby would lead to
there was no residue at 600°C. more thermally stable microcapsules.
Temperature of decomposition (To) values of The difference in T, values for vClrious samples
ZLO/chitosan/gelatin microcapsules, chitosan, gela- could be explained on the baSIS of their difference in
tin and oil at different weight loss (%) are shown in rate of decomposition. The crosslinking reaction of
Table III. T D values for the microcapsules increased . genipin with chitosan was higher compared with
with the increase in the % of chitosan in the micro- that of gelatin as per explanation given above. More-
capsules. This observed high values might be due to over oil decomposed at fast rate. Both of these influ-
the decreasing chance of elimination of small mole- enced the rate of decomposition and were
cules like NH 3, CO 2, etc. with the formation of cross- responsible for different T, values.
linking by genipin. Gelatin contains lower 01<. of
lysine and arginine residues as primary amll1e
groups. Chitosan contains gluco~amine unit in larger FTlR study
percentage. Genipin could react with the pnmClry
amine group of gelatin and glucosar11ine unit of chi- FTIR spectra of chltosan, gelatin, ZLO, and chi to-
san/gelatin microcapsules containing ZLO were
recorded and presented in Figure 5. The spectrum of
chitosan displayed a strong amide characteristic
peak at 1632 cm- 1 . Similarly gelatin spectrum also
J;
..
==
1
3alO ~ 2500 2000 1eoo 1000 SIO 100.00 200.00 300.00 COO.IO
WU\'C number (ern ') Tempertturc(C)-
Figure 5 FTTR spectra of (a) geJatlll B, (b) ehitosan, (e) Figure 6 DSC thermograms of (a) chitosan, (b) gelatin B,
oli, (d) oil contaIning microcapsules. (c) oil, (d) oil containi.ng microcapsules.
showed an ammo band at 1547 cm- l and carbonyl to decrease as the concentration of chltosan m the dl1-
peak at 1624 cm- l In ZLO, the peaks appeared tosan-gelatm mixture mcreases SEM study show1>
between 1638 and 1720 cm- 1 were due to carbonyl that the surface of the mIcrocapsules became Irregular
stretchmg band Besides thiS, the other notable peaks due to presence of Oil Thermal stabIlIty has been
appeared at 1457 cm- 1 and 1378 cm- l were due to found to be 1l1l.proved WIth the mcrea5e m the per-
CH 2 asymmetnc deformation and ,CH 2 symmetrIc centage of chltosan lli the chltosan/gelatIn matnx A
deformation In the mlcrocapsules, the carbonyl low compatibility lli thermal properties lli the I elation
band &hlfted to 1641 cm- 1 mdICatmg an mterachon between 011, gelahn, and chltosan eXIsts as revealed
between chltosan and gelatm complex The posItion by DSC study FTIR .,tudy shows that there IS no
of these peaks remamed almost unchanged when remarkable lliteractlon between polymer and 011
compared wIth that of &pectrum of ZLO The POSI-
tion of other peaks which were due to CH 2 asym- References
metnc deformatIOn was also remamed unchanged
Thl<; suggested that there was no slgmfICant mterac- 1 ['>man, M B Pe~hc Outlook 1999, 10, 68
2 Peterson, C J, Coats, J R Pe,tIc Outlook 2001, 8, 154
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4 Omolo, M 0, Okmyo, D, Ndlege, I 0, Lwande, W , Ha,~a
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another bload peak havmg average peak tempera- Borne DJ' 2003, 40, 49
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another tvvo peaks (m shoulder fmm) havmg avel-
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17, 757
phYSICal mixture of chltosan/ gelatm/ Oil at 95°C was
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CONCLUSIONS 25 Chen H, Ouyang, W , LauduYI, B, M"rtol1l, C, Praka~h, S
J BIOInt'd Mater Res A 2005 75, 917
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hnker The release rate of 011 depends on 011 content, 28 l\ladan, P L J Phann Su 1988, 70,430
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crosshnkmg den<y, polyme\ concentratIOn, etc The
1\1 J J 01, ScI Technol 2006, 22, 591
release rate Increases With the 1I1crease 111 the 011 load- 10 Dma] "and, R, Mahmood], S, Faruoud, E, Saleh], M, Artyabl,
mg The higher the percentage of gempl11, the lower I~ FActa Pharm 2005, 55, 57
the release rate The release rate ha& also been found 31 MI, F L BlOmacromolccl1le~ 2005, 6, 975