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Study on electrochemical fi ngerprints of different Chrysanthemums by using B Z oscillation system Wang Xing Cheng Jia Chen Cheng Wu Fang De Ling Wu School of Pharmacy Anhui University of Traditional Chinese Medicine Anhui Key Laboratory of Modern Traditional Chinese Medicine Hefei 230031 China Received 14 October 2010 Abstract A sensitive and convenient method for the study of electrochemical fi ngerprints of Chrysanthemums from different regions is studied by Belousov Zhabotinskii B Z oscillation system with malonate as a dissipative material The results indicated that the electrochemical fi ngerprints ofChrysanthemums from different regionsshowsignifi cantly different characteristics and can beused to identify the regions of Chrysanthemums 2011 Wang Xing Cheng Published by Elsevier B V on behalf of Chinese Chemical Society All rights reserved Keywords Chrysanthemum Electrochemical fi ngerprint B Z oscillation Different regions Identify Chrysanthemum fl owers the dry capitulum of Chrysanthemum morifolium Ramat can be divided into Qi ju Gong ju Bo ju and Hang ju according to different growing regions Chrysanthemum is a popular traditional Chinesemedicinewith markedeffects on treating common cold of wind heat headache dizzinessand dimsighted 1 The modern pharmacological research indicates that Chrysanthemum extract has a certain function on cholesterol metabolism anti bacterial anti virus anti infl ammatory anti mutagenic and anti neoplastic 2 But the source of Chrysanthemums is very complicated involving different species and adulteration Even the kindred plants may have different chemical constituents and contents owning to various reasons such as the regions gathering times processing conditions and storage conditions At present Fourier transform infrared spectroscopy FT IR 3 intersimple sequence repeat ISSR 4 5 random amplifi ed polymorphic DNAs RAPDs 6 10 methods were mainly used for identifying the regions These methods have high sensitivity and good selectivity but the pre treatment of sample is not only very diffi cult but also time and energy consuming However the B Z oscillation system will be stable compared with unvaried medicine materials It shows that the B Z oscillation system is objective and has good repeatability The application of oscillation system for the identifi cation of traditional Chinese medicine has gained interest from some scientists 11 14 As is known the chemical constituents in the medicinal materials are the substantial foundation of curative effect So it is necessary to establish a reliable and convenient analytical method to distinguish Chrysanthemums of different regions In this work little of Chrysanthemum powder added into oscillation system causes a change of E t curve The Available online at Chinese Chemical Letters 22 2011 729 732 Corresponding author E mail address chengwangxing W X Cheng 1001 8417 see front matter 2011 Wang Xing Cheng Published by Elsevier B V on behalf of Chinese Chemical Society All rights reserved doi 10 1016 j cclet 2010 12 047 reason is that Chrysanthemum samples of different regions have different chemical constituents and contents for climate conditions and soil regimes So the E t curve is correlated with the different regions and it can be used to identify the regions of Chrysanthemum 1 Experimental All chemicals used were of analytical reagent grade Solutions of 0 2 mol L KBrO3 0 4 mol L HOOCCH2COOH 3 0 mol L H2SO4 and 0 005 mol L Ce SO4 4 NH4 4 2H2O were made immediately before the experiment Double distilled water was used throughout Oscillating experiments were performed in a glass container with a Model CJJ78 1 magnetic stirrer Jiangsu China regulatedbyaModelHH 501thermostatat37 0 05 8C Jiangsu China Changesinpotentialwerefollowed by a Model 213 platinum electrode Shanghai China as a working electrode and a Model 217 saturated calomel electrode Shanghai China as a reference electrode Potentials E of the electrode as a function of time t were recorded by LK2005A electrochemical instrument Tianjin China to record kinetic curves E t of the oscillation reaction 1 1 Samples All the Chrysanthemum samples of different regions Table 1 were provided and identifi ed by Jianli Zhou Anhui College of Traditional Chinese Medicine Three batches of Chrysanthemum samples were collected for each region 1 2 Oscillating experiment procedure Thefollowingprocedurewasusedinallexperimentsforgettingelectrochemicalfi ngerprint A12 mLof3 0 mol L H2SO4 6 mL of 0 4 M HOOCCH2COOH and 3 mL of 0 005 mol L Ce SO4 4 NH4 4 2H2O along with a certain amountofChrysanthemummedicinalmaterialsgroundedintopowderwithover100screenmesh Thentheplatinum electrode and reference electrode were immersed in the reaction mixture the mixture was homogenized by continuous magnetic stirring at 500 rpm and kept constant at 37 0 05 8C Finally 3 mL of 0 2 mol L KBrO3was injected to the reaction and oscillations began immediately and at the same time E t curve of the reaction was recorded To obtain a stable electrochemical fi ngerprint for identifying Chrysanthemums of different regions the effects of various variables for the oscillation system were tested in the study The effect of H2SO4concentration was studied within the range of 0 5 5 0 mol L with increasing the H2SO4concentration the oscillation life and oscillation amplitudewould be decreased and eventually disappeared If the malonate concentrations were changed from 0 1 to 0 6 mol L the oscillation lifewould be lengthened The concentrationof potassium bromate and cerium ammonium sulfate had strong effect on the oscillation reaction in which the oscillation life increased with increasing of potassium bromate concentration from 0 05 to 0 5 mol L or cerium ammonium sulfate concentration from 0 002 to 0 008 mol L The oscillation parameters including the amplitude the period the induction period oscillation life decreased with increasing temperature and Chrysanthemum powder amount from 300 K to 350 K 0 2 g to 0 6 g respectively Finally 3 mol L sulfuric acid 0 4 mol L malonate 0 2 mol L potassium bromate 0 005 mol L cerium ammoniumsulfate 310 Ktemperatureand0 4 gofChrysanthemumpowderwerechosenastheoptimalexperimental condition W X Cheng et al Chinese Chemical Letters 22 2011 729 732730 Table 1 Descriptions of the Chrysanthemum samples No NameSource Sample aQi juAnguo county Hebei province China Sample bGong juShe county Anhui province China Sample cBo juBozhou city Anhui province China Sample dHang juTongxiang county Zhejiang province China 2 Results and discussion Fig 1 shows the electrochemical fi ngerprint of Chrysanthemums obtained in the KBrO3 H2SO4 HOOCCH2 COOH Ce SO4 4 NH4 4 2H2O system under the optimum conditions The E t curve changed while an amount of Chrysanthemum powder was added into the B Z system Employing E t curve in B Z oscillation system tested the response to the perturbation of Chrysanthemum powder of different regions so the electrochemical fi ngerprints obtained by E t curve were corresponding to Chrysanthemum of different regions Fig 1 shows the electrochemical fi ngerprint of samples a b c and d respectively It is very clear that Chrysanthemums of different regions has its own W X Cheng et al Chinese Chemical Letters 22 2011 729 732731 TD FIG 180016001400120010008006004002000 0 3 0 4 0 5 0 6 0 7 0 8 0 9 1 0a E V t s 120010008006004002000 0 45 0 50 0 55 0 60 0 65 0 70 0 75 0 80 0 85 0 90b E V t s 10008006004002000 0 65 0 70 0 75 0 80 0 85 0 90 E V t s c 180016001400120010008006004002000 0 3 0 4 0 5 0 6 0 7 0 8 0 9 d E V t s Fig 1 The electrochemical fi ngerprints of Chrysanthemums from different regions TD FIG 120010008006004002000 0 3 0 4 0 5 0 6 0 7 0 8 0 9 E V t s 0 4013g 0 4010g 0 4009g 0 4007g 0 4006g Fig 2 The repeatability of electrochemical fi ngerprints of sample c electrochemical fi ngerprint the oscillation parameters including the life the period the induction period and the amplitude are signifi cantly different from each other Underthe optimum conditions astable regularoscillating profi lewas obtainedfromthe samesample c Fig 2 the oscillation parameters are almost the same for fi ve times so the electrochemical fi ngerprints have good repeatability 3 Conclusions TheB Z oscillation system has been used toanalyze andcompare the different regionsof Chrysanthemum samples and demonstrated higher characteristic features Furthermore the herb powder guarantees the stabilities of the chemical constituents and contents in herb medicines so its E t curve shows better repeatability and comparability TheanalysisandcomparisonoftheE tcurveofthesamplesshowsthattheherbmedicinesfromdifferentregionshave its own electrochemical fi ngerprint We can identify the different regions of Chrysanthemums by adopting the electrochemical fi ngerprint characters Using B Z oscillation system as an analytical method to distinguish the herb medicines is more objective reliable and effective Acknowledgme
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