Pharmaceuticals are regarded as emerging environmental pollutants since many of them are ubiquitous, recalcitrant and biologically active. Conventional physicochemical or biological treatment methods can only attain partial degradation while advanced oxidation processes such as UV exposure or ozonation render variable degradation yields. In this project, novel several technologies using single enzymes nanoparticles (SENs) and molecular imprinting polymers (MIPs), including magnetoactive will be developed for removal of model pharmaceuticals such as anti-inflammatory drug (diclofenac) and estrogen hormone (17 ?-estradiol) from wastewater. Thus, this project consists of two main studies on the preparation and characterization of the SENs and MIPs, including magnetoactive, for removal of two types of pharmaceuticals: anti-inflammatory and estrogenic drugs.
“Single-enzyme nanoparticles (SENs)” technology is an innovative way of enzyme stabilization under harsh conditions. This approach will consist of a 2-step procedure including surface coating and in situ aqueous polymerization to encapsulate a single enzyme in nanogel to provide robust enzymes for industrial bio-catalysis. The armor network around enzyme so thin and porous that a large mass-transfer limitation on the substrate will not take place. Single laccase and peroxidase nanoparticles will be formulated in frame of this project.
Second approach will be based on the technique of molecular imprinting for the preparation of polymer materials as specific molecular recognition receptors. Molecularly imprinted polymers (MIPs) will be prepared by copolymerization of a cross-linking agent with the complex formed from a template and polymerizable monomers that have functional groups specifically interacting with the template through covalent or non-covalent bonds. After the template is removed from resulted polymer matrices, binding sites having the size and shape complementary to the template will be generated. These molecularly imprinted polymers (MIPs) are synthesized with "tailor-made" binding sites for a template and strongly interact with the template. Humic acids and polyacrylic acids will be used as a sacrifying polymer. Combining the imprinting effects of the polymers and magnetic particles yield composite materials which are both selective to the template and magneto responsive for easy removal from aqueous solutions.
To reach the goal, the following objectives are set:
1. Synthesis, characteristics of laccase- and peroxidase based SENs systems. Degradation of ?-estradiol and diclofenac.
2. Preparation of molecularly imprinted polymers (MIPs) and evaluation the binding characteristics of non-imprinted (NIPs) and ?-estradiol/diclofenac-MIP systems.
3. Preparation and binding characteristics of magnetic MIPs for estradiol.
4. Selectivity testing of MIPs systems with similar molecular analogues.
5. Regeneration of prepared SENs and MIPs systems.
6. Estimation of toxicity of prepared SENs and MIPs systems.
Theoretical basis of the development under proposal is large-scale studies of the project participants, in particular, of studies on structure (Jorobekova, 1986; Li et al, 2014), detoxifying ability (Li, Kydralieva, 2012) and biological activity (Kydralieva et al., 2015) of humic substances. The detoxifying properties of the representative sets of humic materials in relation to the target ecotoxicants (heavy metals, atrazine) have been studied to establish a link between the chemical binding of ecotoxicants to humic substances and its environmental impact (Li, 2016), on the one hand. On the other hand, the team project has been performed for many years, investigation of binding humic acids with enzymes (Jorobekova, 1996; Jorobekova, Kydralieva, Hudaybergenova, 2004). More important in our recent research is synthesis of metal-polymer composites, including the molecularly imprinted (Dzhardimalieva, 1997; 2003; Dzhardimalieva, Kydralieva, 2016) based on magnetite and humic acids for utilization as magnetoactive sorbents for metals (Kydralieva, Zaripova, 2011; 2012, 2013, 2014a, 2014b; 2016).
Accomplishment of the Project will allow the change from SENs and MIPs theory to practice and a large-scale use of MIPs systems for removal of set of ecotoxicants. The innovation technique will be thus developed and carried to the industry. The novel techniques of production and application of SENs and MIPs can be easily adjusted for other ecotoxicants (metal ions, POPs, dioxines etc).
