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Hp-β-Cyclodextrin assisted ozonation
Wang Tao1a,Peng Daoping1a, Li Yunzhen2b, Bai Yang1a,Huang Tao1a
1Faculty of Geosciences and Environmental Engineering,Southwest Jiaotong University,Chengdu
611756, China;
b
Sichuan Academy of Environmantal Science, No.18 Section 4, Renmin South Road, Chengdu,
China;
a Email:wangtao19830410@163.com
Keywords: Ozone, Hp-β-cyclodextrin, ozonation, ABTS, spectra,inclusion complex
Abstract. The purpose of this paper is to introduce
hydroxypropyl-β-cyclodextrin(Hp-β-cyclodextrin) into ozonation, and investigate the oxidation
properties of Hp-β-cyclodextrin after ozonation. In this study, Potassium indigo trisulfonate, (Indigo)
and 2.2’-azino-bis (3-ethylbenzothiazoline-6-sulfonate, (ABTS) were used as indicative
contaminants. During our observation, the oxidizing ability of Hp-β-cyclodextrin solution increased
significantly after ozonation. The kinetic curves of ABTS and ozone/Hp-β-cyclodextrin inclusion
complex solution shows that the reaction between two compounds are mixed reactions with
muti-steps. On the basis of these results, it appears that ozone/Hp-β-cyclodextrin inclusion complex
solution may be useful as a combination with ozoantion or applied after ozonation for sustained
oxidation.
Introduction
Cyclodextrins(CDs) are supramoleculars which extract from starch, and comprised of
glucopyranose units[1]. The typical feature of CDs is to combine some molecules to form a
coordination compound or accommodate one or more molecules to form a inclusion complex[2].
2-hydroxypropyl-β-cyclodextrin (Hp-β-CD)is the most important cyclodextrin derivative due to its
high water solubility. Hp-β-CD has been employed in the enhanced fenton degradation of
hydrophobic organic compounds(HOC) by forming ternary HOC-CD-iron inclusion complexes[3,4].
The ternary structure HOCs-CD-iron has been assessed and observed with NMR and fluorescence
detection[5,6]. In this study, we tried to introduce 2-hydroxypropyl-β-cyclodextrin in ozonation and
analysis its oxidatizing performance.
Experimental materials and procedures
All chemical reagents were purchased from Sigma Aldrich Co, with high purity.Ozone/CD
inclusion complex solution are prepared by bubbling ozone gas through a 1 liter volume glass
reactor with a diffuser cover. In our study, various Hp-β-CD solutions were used for studying the
kinetics of ABTS decay, the transferred ozone dose were calculated by the integrated difference of
the absorbance of ozone gas from inlet and outlet of the reactor, recorded by two UV-vis
spectrophotometer, respectively. the spectra of the indicators change will be measured by an UV-vis
spectrophotometer with time and then the changes will be plotted.
International Conference on Civil, Transportation and Environment (ICCTE 2016)
© 2016. The authors - Published by Atlantis Press
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Results and discussing
Fig. 1 Comparison of indigo decay rate in different solutions
Fig. 2 Comparison of the Spectra among pure CD, ozone and ozone/CD solution
As seen in Fig.1, the flask added ozone/CD solution is the only one that indigo color decrease
obviously,the only reason for the degradation of indigo is the addition of ozone/CD solution, which
means the ozone/CD solution is able to oxidize indigo for more than one week. .During the contrast
experiment, the flask added ozone/CD solution is the only one that indigo color decrease obviously,
which means Milli-Q water, Hp-β-CD solution, and buffer solution do not affect the indigo
degradation much. The only reason for the degradation of indigo is the addition of ozone/CD
solution. In figure 1, the absorbance of the flasks added with various reagents at 600 nm were
presented. After 72 hrs, the absorbance of the Indigo stock with the addition of Milli-Q water, pure
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Hp-β-CD solution and buffer solution almost had no changes, while the flask added with ozone/CD
solution decrease at a slow rate[4,5].
From the comparison of spectra of ozone, ozone/CD and pure CD solution, we know that the
pure CD solution has no obvious absorbance at 190-400 nm, however, after ozonation, the spectra
of ozone/CD solution has a significant increase in 190-400 nm. This phenomenon confirms the
formation of ozone/CD inclusion complex in another aspect[6]
Fig. 3 ABTS decay curves with respect to the addition of various dose of ozone/CD solution
Fig. 4 The transferred ozone dose with the ozonation of Hp-β-CD solution in one hour
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The kinetics of various concentration of ozone/CD solution with ABTS are neither fit for first
order reaction rate nor for the second order reaction rate, there, we consider it a mixed reaction.
The kinetic curves shown in fig. 3 was clearly give a mixed reaction rate combined by a fast
raction and slow reaction. The CSR(chemical stochiomtric ration) numberis a parameter used in
calculating of the ratio of guest and host molecule in cyclodextrin chemistry. Based on the theory of
cyclodextrin, one host molecule generally able to include one guest molecule. In view of the
molecule size of ozone, the most possible form of ozone/CD inclusion complex is one ozone
molecule accommodated in one cyclodextrin. In fig. 4 the relationship between transferred ozone
dose and CD dose a generally give a CSR number of 1:1 of ozone and CD[7-10].
Conclusions
A new material based on the ozonation of cyclodextrin was presented. This ozone/CD solution as
proved to be a powerful and sustainable oxidant, and this new oxidant could be used in contaminant
remediation in many fields.
Acknowledgements
This work was supported by China scholarship council (file NO: 201207000022).
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