Hollow Microgel Based Ultrathin Thermoresponsive Membranes for Separation, Synthesis, and Catalytic Applications

Thermoresponsive core–shell microgels with degradable core are synthesized via surfactant based free radical polymerization using N,N′-(1,2-dihydroxy-ethylene)­bis­(acrylamide) (DHEA) as a cross-linker for core preparation. The 1,2-glycol bond present in DHEA is susceptible to NaIO₄ solution, and thus, the structure can be cleaved off resulting in hollow microgel. Ultrathin membranes are prepared by suction filtration of a dilute suspension of core–shell microgels over a sacrificial layer of Cd­(OH)₂ nanostrand coated on track etched membrane. After removal of the degraded cores from microgels, the membranes are cross-linked with glutaraldehyde and the nanostrands are removed by passing a 10 mM HCl solution. The prepared membranes are thoroughly characterized using scanning electron microscopy (SEM), atomic force microscopy (AFM), dynamic light scattering (DLS), and dynamic contact angle for morphology, thermoresponsive, and hydrophilic properties, respectively. The prepared membranes showed thermoresponsive permeation behavior and remarkable separation performance for low molecular weight dyes and lysozyme protein. These membranes are also used to synthesize gold nanoparticles and immobilize lactate dehydrogenase enzyme for catalytic and biocatalytic application. The results for water permeation, solute rejection, and ability to immobilize gold nanoparticles and enzymes showed its wide range of applicability. Furthermore, the synthesis of hollow microgel is simple and environmentally friendly, and the membrane preparation is easy, scalable, and other microgel systems can also be used. These responsive membranes constitute a significant contribution to advanced separation technology

Enhanced Activity of Acetyl CoA Synthetase Adsorbed on Smart Microgel: an Implication for Precursor Biosynthesis

Acetyl coenzyme A (acetyl CoA) is an essential precursor molecule for synthesis of metabolites such as the polyketide-based drugs (tetracycline, mitharamycin, Zocor, etc.) fats, lipids, and cholesterol. Acetyl CoA synthetase (Acs) is one of the enzymes that catalyzes acetyl CoA synthesis, and this enzyme is essentially employed for continuous supply of the acetyl CoA for the production of these metabolites. To achieve reusable and a more robust entity of the enzyme, we carried out the immobilization of Acs on poly­(<i>N</i>-isopropylacrylamide)-poly­(ethylenimine) (PNIPAm-PEI) microgels via adsorption. Cationic PNIPAm-PEI microgel was synthesized by one-step graft copolymerization of NIPAm and <i>N</i>,<i>N</i>-methylene bis-acrylamide (MBA) from PEI. Adsorption studies of Acs on microgel indicated high binding of enzymes, with a maximum binding capacity of 286 μg/mg of microgel for Acs was achieved. The immobilized enzymes showed improved biocatalytic efficiency over free enzymes, beside this, the reaction parameters and circular dichroism (CD) spectroscopy studies indicated no significant changes in the enzyme structure after immobilization. This thoroughly characterized enzyme bioconjugate was further immobilized on an ultrathin membrane to assess the same reaction in flow through condition. Bioconjugate was covalently immobilized on a thin layer of preformed microgel support upon polyethylene terephthalate (PET) track etched membrane. The prepared membrane was used in a dead end filtration device to monitor the bioconversion efficiency and operational stability of cross-linked bioconjugate. The membrane reactor showed consistent operational stability and maintained >70% of initial activity after 7 consecutive operation cycles