Font Size: a A A

Functionalization Of Ordered Porous Surfaces: Controlled Assembly Of Proteins And Asymmetric Modification Of Cells

Posted on:2016-07-20Degree:DoctorType:Dissertation
Country:ChinaCandidate:J LiangFull Text:PDF
GTID:1221330482454734Subject:Physical chemistry
Abstract/Summary:PDF Full Text Request
Surface-ordered porous polymer films have shown the great application prospect in the ?elds of optoelectronic devices, separation, bioscience, filtration and medicine. Among the various kinds of self-assembled methods, water-droplet-template approach has been widely investigated owing to its easy operation, low cost and diverse film-forming material features. At present, the experimental conditions and preparation techniques for ordered porous films by using this approach have been quite mature. Therefore, simply selecting different materials for the synthesis of ordered pore structures, has gone far unable to meet the demands of today’s science. Thus, how to apply the porous membranes becomes particularly important, but the applications of flims’ framework have been developed widely. So, transferring the target to fewer reported cavities, will bring new hopes to the research of porous membranes. If we want to use these cavity structures, realizing the selective modification of cavities is necessary. However, the decoration of cavities prepared by traditional water-droplet-template method usually requires complex steps. On the other hand, this method can not assemble diverse functional water-soluble components into the cavities in one step. Hence, developing a new strategy that the chemical modi?cation of cavity, especially the modi?er insoluble in organic solvents, can be applied into the inner of cavities in one step, is of great interest in facile chemical and biological detection purposes. In addition, after the realization of selective modification of pore structures, how to develop the new functions of the cavities, will also bring new vigor for the porous membrane fields.In the dissertation, we adopt the microemulsion droplet template(MEDT) method as a basis, and develop the new functions of holes on porous polymer film as purpose, realizing the local assembly of diverse functional water-soluble components into the cavities, and further using the components within the cavities to complete specific recognition of proteins and construction of protein microarray. In addition, we have firstly achieved glucose-responsive insulin delivery system and Janus cell construction device which both base on the porous polymer films, and further completed the preparation of various Janus cell assemblies.Firstly, we use the simple and general MEDT method for preparation of polyoxometalates(POMs) patterning polymer porous membrane. In this method, the POMs can be pre-assembled into the water phase as additives due to their water-soluble properties, and then an organic solution of polymer and an aqueous solution of POMs were mixed and emulsi?ed to prepare W/O microemulsion solution. The evaporation of solvent in the microemulsion on solid surface yields an ordered porous ?lm accompanied by the accumulation POMs on the inner surface of the cavities. By using this method, we realize the design of porous structures’ formation accompanying with the holes’ chemical modification. Comparing with other methods, it is more simple and convenient. The formation of patterned structure is proved to be independent from the type of POMs, but the size of the cavities can be adjusted to some extent by changing the concentration of surfactant and polymer, and the volume ratio of water in microemulsion solution. Further, by simply adjusting the pH value of solution and charge numbers of POMs, the locally anchored POMs can be readily applied for the construction of microarray for proteins. In addition, at a lower p H, POM pattern could prior recognize hemoglobin from its mixed solution of other proteins, generating a characteristic pattern. These experimental results demonstrate the ability of chemical composition patterning polymer porous membranes in applications of biological materials and detection.Secondly, we develop a glucose-responsive, porous polymer ?lm which can be used for controlled insulin release. The vehicle, a honeycomb-patterned polymer film, is fabricated by spreading a microemulsion. In this approach, we mix the pure water with polymer organic solution to prepare the microemulsion, after the solidification of microemulison by spreading onto a solid substrate, a porous polymer film are fabricated. Then, after the modification of cavity walls by glucose responsive and insulin captured components, the insulin aggregates prepared using a salting-out method are incorporated into the cavities by an electrostatic interaction with the modifiers. Under the stimulus of glucose, insulin aggregates are released from the cavities and further calculations demonstrate a very high release e?ciency. In contrast, in an aqueous solution without glucose, almost no insulin is released from the cavities. The controlled release behavior can be tuned by changing the glucose concentration and the release time. The porous film can be explored as a glucose-triggered insulin delivery system, in which the patterned cavities have a better ability to act as a drug reservoir in comparison to flat films. The present design demonstrates the successful accomplishment of a self-regulated insulin release system. It is envisioned that multi-component and multi-functional drugs, could also be loaded onto the vehicle in the form of a coating for the skin, so as to achieve direct drug delivery.Thirdly, we develop a novel method to prepare Janus cells in a gentle, convenient, and cheap way. The honeycomb polymer film patterned by quantum dots(QDs) is fabricated through spreading a microemulsion. In this approach, we select red fluorescent QDs as additives to incorporate into the microemulsion, after the solidification of microemulsion by spreading onto a solid substrate, a QDs patterning porous polymer film are fabricated. Then, after the decoration of cavities by applying cell-surface-recognizable phenylboronic acid(PBA) molecules, yeast cells are captured into the cavities. Due to the modified layer(red fluorescent QDs-PBA compounds) on the holes, once the yeast cells are captured into the cavities, the single-side modification process is accomplished. In addition, the exposed cell surfaces after assembly of cells into the cavities can continue to be decorated by green fluorescent QDs-PBA compounds, and then complete the double-side modification process of yeast cells. Then, the releasing of yeast from the cavities by adding NaCl to destroy the electrostatic interaction between water stabilizer and modifiers, are accompanying by the formation of single- or double-side modified Janus cells. Interestingly, various cell assemblies are realized by the interaction between the double-side modified cell surfaces and untreated cell surfaces. The porous film can be explored as a new approach to synthesize Janus cells, which also provide a selective way to construct Janus particles and life entity. Importantly, it can be envisioned that the cell assemblies fabricated by different types of cells will be in favor of investigating the cell-cell communication, cell-cell adhesion and cell therapy.In conclusion, in this dissertation, we use the general and simple MEDT approach to prepare ordered porous polymer surfaces, and successfully realize the local assembly of various kinds of functional water-soluble components into the porous cavities by one step. We apply these functional components, to successfully complete the selective recognition of proteins and preparation of protein microarrays. In addition, we use the glucose-responsive-component modifying cavities as reservoirs to store insulin, and implement the construction of glucose-responsive insulin delivery system. Further, we adopt the QDs and cell-recognition groups loading cavities to capture the yeast cells, and achieve Janus cells accompanying with the release of the cells, and prepare a variety of Janus cell assemblies in the similar steps. We believe that the developed MEDT approach in the dissertation provides a simple and easy way for preparation of functional porous structures. At the same time, the experimental results supply a new research design and application prospect for ordered porous materials as new drug loading systems and Janus particles building way.
Keywords/Search Tags:Ordered Porous Polymer Film, Microemulsion Droplet Template Method, Polyoxometalates, Yeast Cells, Proteins
PDF Full Text Request
Related items