RESUMEN
The development of robust and thin CO2 separation membranes that allow fast and selective permeation of CO2 will be crucial for rebalancing the global carbon cycle. Hydrogels are attractive membrane materials because of their tunable chemical properties and exceptionally high diffusion coefficients for solutes. However, their fragility prevents the fabrication of thin defect-free membranes suitable for gas separation. Here, we report the assembly of defect-free hydrogel nanomembranes for CO2 separation. Such membranes can be prepared by coating an aqueous suspension of colloidal hydrogel microparticles (microgels) onto a flat, rough, or micropatterned porous support as long as the pores are hydrophilic and the pore size is smaller than the diameter of the microgels. The deformability of the microgel particles enables the autonomous assembly of defect-free 30-50 nm-thick membrane layers from deformed â¼15 nm-thick discoidal particles. Microscopic analysis established that the penetration of water into the pores driven by capillary force assists the assembly of a defect-free dense hydrogel layer on the pores. Although the dried films did not show significant CO2 permeance even in the presence of amine groups, the permeance dramatically increased when the membranes are adequately hydrated to form a hydrogel. This result indicated the importance of free water in the membranes to achieve fast diffusion of bicarbonate ions. The hydrogel nanomembranes consisting of amine-containing microgel particles show selective CO2 permeation (850 GPU, αCO2/N2 = 25) against post-combustion gases. Acid-containing microgel membranes doped with amines show highly selective CO2 permeation against post-combustion gases (1010 GPU, αCO2/N2 = 216) and direct air capture (1270 GPU, αCO2/N2 = 2380). The membrane formation mechanism reported in this paper will provide insights into the self-assembly of soft matters. Furthermore, the versatile strategy of fabricating hydrogel nanomembranes by the autonomous assembly of deformable microgels will enable the large-scale manufacturing of high-performance separation membranes, allowing low-cost carbon capture from post-combustion gases and atmospheric air.
RESUMEN
The availability of metal mesh device sensors has been investigated using surface-modified nickel mesh. Biotin was immobilized on the sensor surfaces consisting of silicon and nickel via a thiol-ene click reaction, known as the Michael addition reaction. Biotinylation on the maleimidated surface was confirmed by X-ray photoelectron spectroscopy. The binding of streptavidin to the biotinylated surfaces was evaluated using a quartz crystal microbalance and a metal mesh device sensor, with both techniques providing similar binding constant value. The recognition ability of the biotin immobilized using the thiol-maleimide method for streptavidin was comparable to that of biotin immobilized via several other methods. The adsorption of a biotin conjugate onto the streptavidin-immobilized surface via the biotin-streptavidin-biotin sandwich method was evaluated using a fluorescent microarray, with the results demonstrating that the biological activity of the streptavidin remained.
Asunto(s)
Técnicas Biosensibles/métodos , Biotinilación , Níquel/química , Silicio/química , Estreptavidina/análisis , Adsorción , Biotina/química , Oro/química , Proteínas Inmovilizadas/química , Maleimidas/química , Nanoestructuras/análisis , Estreptavidina/química , Propiedades de SuperficieRESUMEN
A novel surface modification method was investigated. The surface of siliceous materials was modified using polystyrene, poly(acrylic acid), poly(N-isopropylacrylamide), and poly(p-acrylamidophenyl-α-mannoside) synthesized by reversible addition-fragmentation chain transfer polymerization. Thiol-terminated polymers were obtained by reduction of the thiocarbonate group using sodium borohydride. The polymers were immobilized on the surface via the thiol-ene click reaction, known as the Michael addition reaction. Immobilization of the polymers on the maleimidated surface was confirmed by X-ray photoelectron spectroscopy, infrared spectroscopy, and contact angle measurements. The polymer-immobilized surfaces were observed by atomic force microscopy, and the thickness of the polymer layers was determined by ellipsometry. The thickness of the polymer immobilized by the maleimide-thiol reaction was less than that formed by spin coating, except for polystyrene. Moreover, the polymer-immobilized surfaces were relatively smooth with a roughness of less than 1 nm. The amounts of amine, maleimide, and polymer immobilized on the surface were determined by quartz crystal microbalance measurements. The area occupied by the amine-containing silane coupling reagent was significantly less than the theoretical value, suggesting that a multilayer of the silane coupling reagent was formed on the surface. The polymer with low molecular weight had the tendency to efficiently immobilize on the maleimidated surface. When poly(p-acrylamidophenyl-α-mannoside)-immobilized surfaces were used as a platform for protein microarrays, strong interactions were detected with the mannose-binding lectin concanavalin A. The specificity of poly(p-acrylamidophenyl-α-mannoside)-immobilized surfaces for concanavalin A was compared with poly-l-lysine-coated surfaces. The poly-l-lysine-coated surfaces nonspecifically adsorbed both concanavalin A and bovine serum albumin, while the poly(p-acrylamidophenyl-α-mannoside)-immobilized surface preferentially adsorbed concanavalin A. Moreover, the poly(p-acrylamidophenyl-α-mannoside)-immobilized surface was applied to micropatterning with photolithography. When the micropattern was formed on the poly(p-acrylamidophenyl-α-mannoside)-spin-coated surface by irradiation with ultraviolet light, the pattern of the masking design was not observed on the surface adsorbed with fluorophore-labeled concanavalin A using a fluorescent microscope because of elution of poly(p-acrylamidophenyl-α-mannoside) from the surface. In contrast, fluorophore-labeled concanavalin A was only adsorbed on the shaded region of the poly(p-acrylamidophenyl-α-mannoside)-immobilized surface, resulting in a distinctive fluorescent pattern. The surface modification method using maleimidation and reversible addition-fragmentation chain transfer polymerization can be used for preparing platforms for microarrays and micropatterning of proteins.