不同形态的氧氟沙星在凹凸棒土上的吸附特征

doi:10.7503/cjcu20160773

摘要/Abstract

摘要：

通过控制反应体系的pH值, 探究了阳离子、兼性和阴离子形态的氧氟沙星(OFL, 3种形态分别记为OFL⁺, OFL^±和OFL^-)在凹凸棒土(ATP)上的吸附特征. 实验结果表明, OFL⁺主要通过与ATP表面的Ca²⁺, Mg²⁺进行阳离子交换吸附于ATP上, 当其吸附量较高时, 会存在少量的氢键; OFL^±和OFL^-可与ATP表面的铁氧化物、铝氧化物进行表面络合, 也可与溶液中从ATP中溶解出的Ca²⁺和Mg²⁺形成络合物, 再通过静电作用吸附于ATP上. 在中性至微碱性(pH=7.10~7.70)条件下, 由于Ca的电负性小于Mg, [Ca²⁺-OFL]⁺不能稳定地存在于溶液中, 使得OFL^±与Ca²⁺进行阳离子交换而与Mg²⁺形成络合物, 再通过静电作用吸附于ATP上. 当OFL主要以OFL^-形态存在于溶液中时(pH=9.00~10.00), Ca²⁺和Mg²⁺均可与OFL^-形成络合物, 再通过静电作用吸附于ATP上.

关键词: 氧氟沙星, 凹凸棒土, 阳离子交换, 表面络合, 静电作用

Abstract:

By controlling the pH of reaction system, the adsorption characteristics of different forms of ofloxacin(i. e., OFL^±, OFL⁺, and OFL^-) to attapulgite(ATP) were investigated. The experimental results showed that exchanging with Ca²⁺ and Mg²⁺on the surface of ATP was the main sorption mechanism for OFL⁺. When OFL⁺ adsorption quantity increased, there will be little amount of hydrogen bonding between OFL⁺ and ATP surface. OFL^± and OFL^- can form surface complexation with iron/aluminum oxide on the surface of ATP. Meanwhile, both OFL^± and OFL^- can form complexes with cations(Ca²⁺, Mg²⁺) dissolved from ATP and then adsorbed on ATP by electrostatic attraction. Because of the lower electronegativity of Ca than Mg, [Ca²⁺-OFL]⁺ cannot exist stably in neutral to weakly alkaline(e. g., pH=7.10—7.70) solution, which results in the situation that OFL^± exchange with Ca²⁺but form complexes with Mg²⁺ then adsorbed to ATP by electrostatic attraction. When OFL^- was the main form in solution(pH=9.00—10.00), both Ca²⁺ and Mg²⁺ can form complexes with OFL^- and then adsorbed to ATP by electrostatic attraction.

Key words: Ofloxacin, Attapulgite, Cation exchange, Surface complex, Electrostatic interaction

中图分类号:

O647

TrendMD:

全瑶, 毕二平. 不同形态的氧氟沙星在凹凸棒土上的吸附特征. 高等学校化学学报, 2017, 38(4): 622.

QUAN Yao, BI Erping. Adsorption Characteristics of Different Forms of Ofloxacin to Attapulgite^†. Chem. J. Chinese Universities, 2017, 38(4): 622.

图/表 9

Fig.1 Speciation of OFL as a function of pH

Fig.2 Effects of time on OFL adsorption onto ATP(A) and the variation of pH(B)

Fig.3 Adsorption isotherm of OFL on ATP under different pH conditions

Table 1 Langmuir isotherm parameters of the adsorption of OFL by ATP with different pH values

pH	S_m/(mmol·kg^-1)	K_L/(L·mol^-1)	R²
1.88—2.16	214.60	26.85	0.96
7.10—7.70	281.16	9.72	0.99
9.00—10.00	200.87	3.85	0.98

Fig.4 Effects of initial pH value on OFL adsorption onto ATP

Fig.5 Desorption of Ca2+, Mg2+, K+ and Na+ accompanying OFL adsorption to ATP(A) and comparison of the total desorbed Ca2+ and Mg2+ with the adsorbed OFL(B)

Fig.6 Relationship between OFL+(A), OFL±(B) and OFL-(C) adsorbed, cations desorbed and cations in solution at pH=7.10—7.70(D) and pH=9.00—10.00(E)

Fig.7 ATR-FTIR spectra of OFL, ATPs and different forms of OFL adsorbed to ATPa. OFL powder(purity 98%); b. OFL-+ATP(pH=9.00—10.00), Cs=143.56 mmol/kg; c. OFL±+ATP(pH=7.10—7.70), Cs=212.16 mmol/kg; d. OFL++ATP(pH=1.65—1.88), Cs=180.87 mmol/kg; e. ATP used for OFL+ experiments; f. ATP used for OFL± experiments; g. ATP used for OFL- experiments.

Fig.8 Conceptual model of adsorption of ATP for OFL+(A), OFL±(B) and OFL-(C)

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