Wednesday, 14 September 2016

Fingerprint chemotaxonomic GC–TOFMS profile of wood and bark of mangrove tree Sonneratia caseolaris (L.) Engl.

Published Date
July 2011, Vol.15(3):229237doi:10.1016/j.jscs.2010.09.003
Open Access, Creative Commons license, Funding information
ORIGINAL ARTICLE

Title 

Fingerprint chemotaxonomic GC–TOFMS profile of wood and bark of mangrove tree Sonneratia caseolaris (L.) Engl.

  • Author 
  • Raza Murad Ghalib a,,
  • Rokiah Hashim a
  • Othman Sulaiman a
  • Mohd Fahmi B. Awalludin a
  • Sayed Hasan Mehdi a
  • Fumio Kawamura b
  • aSchool of Industrial Technology, USM, 11800 Pinang, Malaysia
  • bDepartment of Biomass Chemistry, Forestry and Forest Products, Research Institute, Tsukuba, Ibaraki 305-8687, Japan
Sonneratia caseolaris (L.) Engl. is commonly known as Berembangpedada nasiperangatperepat merah or perepat lautlamphuam’-pielop outapootamoo or bogem (Mastaller, 1997). It grows wildly from Sri Lanka to Malay Peninsula and northern Australia. This species can also be found in Sumatra, Java, Borneo, Celebes, Philippines, Moluccas, Timor, New Guinea, Solomon Islands, and New Hebrides (Little, 1983). Berembang tree is a hard wood species (800 kg/m3). The sour taste of its young fruits can be used for vinegar, Oriental chutneys and curries. The ripe fruits are like cheese in taste and can be eaten raw or cooked. A clear jelly can be prepared from the pectinaceous fruits. Previously fatty acids, hydrocarbons, steroids, pectin, and sugars have been isolated from S. caseolaris (L.) Engl. (Hogg and Gillan, 1984Xu et al., 1981 and Bandaranayake, 2002). Recently (−)-(R)-nyasol, (−)-(R)-4′-O-methylnyasol, 3,8-dihydroxy-6H-benzo[b,d]pyran-6-one, 3-hydroxy-6H-benzo[b,d]pyran-6-one, oleanolic acid, maslinic acid, Luteolin, luteolin 7-O-β-glucoside, and benzyl-O-β-glucopyranoside have been isolated from the dried and powdered fruits of S. caseolaris. All these isolated compounds were screened against a rat glioma C-6 cell line using the MTT assay method; only compounds (−)-(R)-nyasol, (−)-(R)-4′-O-methylnyasol and maslinic acid were found to show moderate cytotoxic activity (Wu et al., 2009). Sadhu et al. (2006) reported the isolation and identification of two flavonoids luteolin and luteolin 7-O-β-glucoside from the leaves of S. caseolaris and tested their antioxidant activity using 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging effect on a thin-layer chromatography. Both the compounds were found to possess antioxidant activity. Minqing et al. (2009) isolated twenty-four compounds including eight steroids, nine triterpenoids, three flavonoids and four benzenecarboxylic derivatives from stems and twigs of S. caseolaris. In the in vitro cytotoxic assay of these constituents against SMMC-7721 human hepatoma cells, compound 3′,4′,5,7-tetrahydroxyflavone exhibited significant activity with IC50 2.8 μg/mL, while oleanolic acid, 3,3′-di-O-methyl ether ellagic acid, and 3,3′,4-tri-O-methyl ether ellagic acid showed weak activity.
The fishermen use the pneumatophores of Berembang tree as corks or floats for fishing nets while the pulp of Berembang tree is suitable for Kraft paper production. The flowers of Berembang contain abundant honey (Backer and van Steenis, 1951). The Berembang tree is reported to be hemostat. The crabapple mangrove is a folk remedy for sprains, swellings, and worms (Duke and Wain, 1981). It is also used in poultices for cuts, bruises, sprains and swellings. The Malays use the old Berembang's fruit walls to expel intestinal parasites (Mastaller, 1997). The half-ripe fruits are good to cure coughs and the pounded leaves are good for hematuria and smallpox (Perry, 1980). In Eastern Africa the leaves are used as camel fodder (Field, 1995). Berembang is also used as firewood as it produces a lot of heat, ash and salts. The heavy timber is resistant to shipworm and pests; so it is used for building boats, piling and posts for bridges and houses. The wood of Berembang corrodes metal because of the timber's high mineral content (Mastaller, 1997). Berembang is among the mangroves to protect coastlines (Peter and Sivasothi, 1999). In this present study thirty-two compounds from bark and twenty-eight compounds from wood of S. caseolaris (L.) Engl. have been identified.

2 Experimental

2.1 General

The analyses and identification process of extractives were carried out by Mr. Noramin Mohd Noor, a Chemist Executive from Kedah BioResources Corporation Sdn. Bhd. Analytical results were generated with a LECO Pegasus time-of-flight mass spectrometer (TOFMS). The Pegasus GC–TOFMS instrument was equipped with an Agilent 6890 N gas chromatograph and an auto sampler. A HP-5, 30 m × 0.32 mm ID × 0.25 μm film thickness, capillary column was used for the chromatographic separation. The GC was operated with helium carrier gas at a corrected constant flow of 1.2 ml/min. The LECO ChromaTOF software was used for all acquisition control and data processing. The GC temperature program was set to an initial oven temperature of 80 °C for 5 min, followed by a temperature ramp of 5 °C/min, to a final temperature of 280 °C. The GC method injection port temperature was set at 250 °C and 1.0 μL of sample was injected in a splitless way. The MS transfer line temperature was set at 250 °C. The MS mass range was set at 39–550 amu with an acquisition rate of 15 spectra per second.

2.2 Plant material

The Bark and wood of S. caseolaris (L.) were collected from the Malay Peninsula and identified by Prof. Wazahat Hussain, Taxonomist, Department of Botany AMU Aligarh and Mrs. Siti Nurdijati Baharuddin, Taxonomist and lecturer, School of Biological sciences, USM, Malaysia. The sample voucher specimens of Bark and wood have been preserved in the School of Industrial Technology, Division Bioresources and Wood Technology, Laboratory No. 320, USM, Malaysia under voucher specimen numbers BSC/2012010, WSC/2112010.

2.3 Extraction and isolation

This paper also presents a comparative analysis of chemicals of bark (Fig. 1) and wood (Fig. 2) of S. caseolaris (L.) Engl.; air dried wood (30 g) and bark (30 g) of S. caseolaris (L.) Engl. were chipped into small pieces by using a chisel. Both the samples were milled using a grinder (Dietz-motoren GmbH & Co., KG) to make sawdust (to a size about 1–5 mm). Special care was taken during the grinding process to avoid over heating to the sample. The ground bark (5 g) and wood (5 g) of Berembang were separately extracted with hexane for three times successively for 1, 2 and 3 h. Both the hexane soluble parts of bark and wood were separately dried on the BÜCHI Rotavapor R-210 to give the solid mass of bark extract (23.0 mg) and wood extract (9.1 mg).
Figures 1 and 2. Bark sample Figure, wood sample Figure of Sonneratia caseolaris (L. Engl.).

3 Results and discussion

The comparative analysis of GC–TOFMS chromatograms of bark and wood of Berembang revealed some different peak patterns (Figure 3 and Figure 4). These results indicated the presence of some different chemical constituents in both bark and wood extracts. Both the extracts of Berembang tree show the presence of organic compounds, such as alkanes, alkenes, aromatic compounds, alcohols, phenols, carboxylic acids, amides and also amines (Tables 1 and 2). Overall 32 compounds from bark and 28 compounds from wood have been detected. Sixteen constituents have been found to be common in both the extracts which are (E)-2-octenal, nonanal, piperonal, 2-undecenal, 2,4-bis(1,1-dimethylethyl)-phenol, 1-hexadecene, hexadecanal, 1,2-benzenedicarboxylic acid bis(2-methylpropyl) ester, 7,9-di-tert-butyl-1-oxaspiro(4,5)deca-6,9-diene-2,8-dione, dodecanamide, 1-docosene, octacosane, ethaneperoxoic acid 1-cyano-1-[2-(2-phenyl-1,3-dioxolan-2-yl)ethyl]pentyl ester, pentadecane, (E,E)-2,4-decadienal, (Z)-2-decenal and hentriacontane. There are 16 different compounds in bark extract and 12 different compounds in wood extract. This is the first report of the presence of these components in the bark (Table 1) and wood (Table 1) of S. caseolaris L., respectively. The chemical profile of bark and wood extract identified by the GC–TOFMS analysis may be a finger print chemotaxonomic marker (Ge et al., 2008) for S. caseolaris (L.) Engl. Although more than 100 compounds could be detected in the analyzed extracts, only those with a similarity higher than 900 are presented in the chemical profile (Figure 5 and Figure 6).
Figure 3. Chromatograms of bark extract of Berembang.
Figure 4. Chromatograms of wood extract of Berembang.
Table 1. Components of Berembang bark extract.
PeakNo.NameAreaR.T. (s)WeightFormulaSimilarity
81Propiolactone506,387,26701:17.472C3H4O2936
142Isobutane683,305,19001:25.258C4H10909
193Hexane, 3-methyl-61,133,25801:42.7100C7H16910
3742-Heptenal, (Z)-174,447,01502:32.8112C7H12O906
6152-Octenal, (E)-42,688,39103:46.1126C8H14O911
776Nonanal99,299,04404:29.0142C9H18O926
9572-Nonenal, (E)-24,285,45605:29.0140C9H16O915
1008Octanoic acid76,758,47405:46.9144C8H16O2915
1079Decanal8,392,96806:23.3156C10H20O909
131102,4-Decadienal, (E,E)-148,264,54608:49.3152C10H16O952
13811Piperonal10,788,90409:14.4150C8H6O3945
147122-Undecenal96,774,60409:54.3168C11H20O913
16013Vanillin21,409,93910:45.4152C8H8O3942
19814Pentadecane10,783,43013:03.3212C15H32948
20415Phenol, 2,4-bis(1,1-dimethylethyl)-15,118,82113:21.7206C14H22O928
235161-Hexadecene9,160,33115:09.1224C16H32953
23717Diethyl phthalate472,35415:13.7222C12H14O4960
27718Eicosane7,202,86017:30.5282C20H42915
33419Hexadecanal16,673,88219:56.7240C16H32O929
358201,2-Benzenedicarboxylic acid, bis(2-methylpropyl) ester9,693,00120:59.7278C16H22O4903
381217,9-Di-tert-butyl-1-oxaspiro(4,5)deca-6,9-diene-2,8-dione7,786,52021:59.8276C17H24O3921
38822Oxacyclotetradecane-2,11-dione, 13-methyl-9,228,33622:12.7240C14H24O3905
40623Ethaneperoxoic acid, 1-cyano-1-[2-(2-phenyl-1,3-dioxolan-2-yl)ethyl]pentyl ester27,963,56822:49.9347C19H25NO5926
43024Octadecanal55,867,52123:56.5268C18H36O935
46525Oxacycloheptadec-8-en-2-one141,977,40026:11.3252C16H28O2940
48126Dodecanamide52,785,31327:01.2199C12H25NO943
585271-Docosene5,793,87431:59.9308C22H44940
58728Octacosane81,413,53832:04.9394C28H58953
600291,2-Benzenedicarboxylic acid, mono(2-ethylhexyl) ester332,356,11532:49.9278C16H22O4914
64830Hentriacontane91,613,72035:02.7436C31H64948
70831Heptacosane, 1-chloro-115,551,39037:49.5414C27H55Cl907
7513217-Pentatriacontene292,673,54540:30.9490C35H70917
Table 2. Components of Berembang wood extract.
PeakNo.NameAreaR.T. (s)WeightFormulaSimilarity
6212-Octenal, (E)-19,637,57703:46.2126C8H14O905
792Nonanal62,437,83304:29.2142C9H18O932
13332-Decenal, (Z)-610,496,57807:36.0154C10H18O934
14742,4-Decadienal, (E,E)-140,107,98408:49.6152C10H16O951
1505Pentadecane10,156,62409:02.5212C15H32904
1526Piperonal31,780,62309:13.8150C8H6O3953
16272-Undecenal71,108,49709:54.3168C11H20O906
2098Heptadecane4,780,61112:58.1240C17H36902
2189Phenol, 2,4-bis(1,1-dimethylethyl)-23,401,29913:21.9206C14H22O934
258101H-Cycloprop[e]azulen-4-ol, decahydro-1,1,4,7-tetramethyl-, [1ar (1aà,4á,4aá,7à,7aá,7bà)]-170,497,85915:11.2222C15H26O908
28511Nonadecane, 2-methyl-2,703,18716:42.9282C20H42925
30312Trimethylamine8,180,48517:29.759C3H9N904
31213Hexadecanal8,170,44617:49.1240C16H32O905
355141-Hexadecene3,331,10619:28.1224C16H32938
380151,2-Benzenedicarboxylic acid, bis(2-methylpropyl) ester11,867,45220:59.8278C16H22O4903
38416Hexadecen-1-ol, trans-9-8,999,87721:14.5240C16H32O908
397177,9-Di-tert-butyl-1-oxaspiro(4,5)deca-6,9-diene-2,8-dione1,886,88421:59.8276C17H24O3903
41518Ethaneperoxoic acid, 1-cyano-1-[2-(2-phenyl-1,3-dioxolan-2-yl)ethyl]pentyl ester21,055,12122:49.9347C19H25NO5922
43519Octadecane5,250,20023:33.2254C18H38903
44820Tetradecanal17,170,59623:56.3212C14H28O923
51921Dodecanamide20,434,81127:00.8199C12H25NO965
52322Tetracosane15,948,53627:10.6338C24H50934
55923Heptacosane32,977,88928:52.7380C27H56920
578244,8,12,16-Tetramethylheptadecan-4-olide17,672,83229:44.2324C21H40O2941
63925Octacosane22,234,70532:04.3394C28H58951
658261,2-Benzenedicarboxylic acid, diisooctyl ester251,155,78132:49.5390C24H38O4919
70727Hentriacontane13,558,28335:02.5436C31H64964
830281-Docosene73,767,86940:30.8308C22H44922
Figure 5. Chemical profile of Berembang (bark).
Figure 6. Chemical profile of Berembang (wood).

4 Conclusion

In conclusion it may be said that a particular plant can be identified on the basis of its GC–TOFMS chemical profile of different extracts. The GC–TOFMS of a particular plant may be a significant fingerprint chemotaxonomic marker for the identity.

Acknowledgments

We would like to acknowledge Universiti Sains Malaysia (USM) for the University Grant 1001/PTEKIND/8140152.

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