YANG Ying, GAO Baojiao, WANG Jian. ADSORPTION OF DINITROBENZOATE-MODIFIED HEMA/NVP MICROSPHERE FOR CREATININE AND THE MECHANISM OF CHEMISORPTION. [J]. Acta Polymerica Sinica (6):587-593(2008)
DOI:
YANG Ying, GAO Baojiao, WANG Jian. ADSORPTION OF DINITROBENZOATE-MODIFIED HEMA/NVP MICROSPHERE FOR CREATININE AND THE MECHANISM OF CHEMISORPTION. [J]. Acta Polymerica Sinica (6):587-593(2008) DOI: 10.3724/SP.J.1105.2008.00587.
ADSORPTION OF DINITROBENZOATE-MODIFIED HEMA/NVP MICROSPHERE FOR CREATININE AND THE MECHANISM OF CHEMISORPTION
A kind of new functional polymeric microspheres with strong adsorption ability for creatinine was prepared
and the adsorption mechanism was studied in depth. First of all
the crosslinked copolymer microspheres of 2-hydroxyethyl methacrylate (HEMA) and N-vinylpyrrolidone (NVP) with an average diameter of 180 μm were prepared by suspension copolymerization and denoted as HEMA/NVP
which has biocompatibility. In the suspension copolymerization system
N
N′-methylene biscrylamide (MBA) was used as crosslinking agent
α
α′-azoisobisbutyronitrile (AIBN) was used as initiator
and Span-60 (Sorbitan monooleate) was used as suspension stabilizer. Subsequently
the microspheres HEMA/NVP were chemically modified with 3
5-dinitrobenzoyl chloride (DNBC)
and the functional microspheres DNBZ-HEMA/NVP
on which a number of 3
5-dinitrobenzoate (DNBZ) groups were bonded
were obtained. In the modification reaction
triethylamine was used as the agent to capture acid
and reaction could be carried out favourably. The chemical structure and composition of the functional microspheres were characterized with FTIR and chemical analytical method. The adsorption characteristics of DNBZ-HEMA/NVP for creatinine were studied
and the effects of various factors on the adsorption properties of the functional microspheres were investigated. Static adsorption experiments show that the functional microspheres DNBZ-HEMA/NVP have strong adsorption property for creatinine due to the chemical reaction analogous to Jaffe′ reaction between 3
5-dinitrobenzoate on the surface of the microspheres and creatinine. In the aqueous solution
creatinine has two kinds of tautomers
the keto form and the enol form. The tautomer with enol form is easy to loss a proton and produces a negative oxyanion. The negative oxyanions are attracted by the nitrogen atoms with positive electricity on the nitro groups of DNBZ. Finally
a complex reaction takes place and a complex of 1∶1σ is formed between DNBZ of the microspheres and the creatinine molecule. Obviously
the adsorption of the functional microsphere DNBZ-HEMA/NVP for creatinine is attributed to chemical adsorption
furthermore
it is a chemical adsorption driven by electrostatic interaction. The adsorption capacity of DNBZ-HEMA/NVP is enhanced 20 times as compared with that of the unmodified microsphere HEMA/NVP
and the saturated adsorption amount reaches 21 mg/g. Both pH value and salinity influence the adsorption capacity greatly. As pH value of the medium is lower
creatinine exists mainly as keto form
and there are few negative oxyanions
so there is weak electrostatic interaction between the microsphere DNBZ-HEMA/NVP and the creatinine molecule resulting in the poor adsorption ability of the microsphere DNBZ-HEMA/NVP for creatinine and lower adsorption capacity. With the increase of pH value
the equilibrium between the two tautomers of creatinine moves to enol form
and more negative oxyanions will be produced. So the electrostatic interaction is strengthened
resulting in the stronger adsorption ability of the microsphere DNBZ-HEMA/NVP for creatinine and higher adsorption capacity. However
the too high pH value is also disadvantageous to the electrostatic interaction. The experimental results show that as pH=8.5
there is the strongest electrostatic interaction between the microsphere DNBZ-HEMA/NVP and the creatinine molecule
resulting in a maximum adsorption capacity. The ionic strength weakens the lectrostatic interaction
so greater salinity leads to decreasing the adsorption ability of the microsphere DNBZ-HEMA/NVP for creatinine.