| Citation: |
WANG Chuanhao, WANG Mingye, LIU Ying, et al. Preparation and research of Diatomite@PNIPAm-stabilized Pickering emulsion with temperature responsiveness[J]. Acta Materiae Compositae Sinica, 2024, 41(12): 6589-6598. DOI: 10.13801/j.cnki.fhclxb.20240314.001
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Aiming at the shortcomings of the emulsion stabilized by surfactant due to toxicity and non-environmental protection, modified diatomite particles (DE), the temperature-responsive Pickering emulsion was studied. Due to the advantages of superior biocompatibility, DE have application potential in the field of cosmetics and pharmaceuticals. First, the Diatomite@MPS was obtained by silane coupling agent (MPS) hydrophobic modified DE. Then, modified DE (Diatomite@PNIPAm) with temperature responsiveness was synthesized successfully by grafting the temperature-responsive polymer poly N-isopropylacrylamide (PNIPAm). According to the characterization results of FTIR testing and water contact angle testing, the diatomaceous earth was modified successfully. The TGA results showed that the optimal molar ratio of the Diatomite@PNIPAm prepared from MPS to NIPAm was 1∶1. Subsequently, oil-in-water (O/W) Pickering emulsions were prepared with Diatomite@PNIPAm as an emulsifier at different concentrations, and 3.0wt% was determined as the optimal concentration. In addition, the emulsion was prepared with different oil-water volume ratios from 1∶9 to 9∶1 after determining the Diatomite@PNIPAm concentration, and the results showed that the oil-water volume ratio was 7∶3 as the best. The characterization results of differential scanning calorimeter (DSC) testing showed that the lower critical solution temperature (LCST) of the Pickering emulsion was 40℃. The emulsion can undergo at least 6 demulsification-reemulsification cycles, and possesses excellent demulsification-reemulsification cycle performance.
With the development of traditional emulsions with surfactants as stabilizers, the problem of environmental pollution has become more and more serious, which endangers people's health greatly.The preparation of Pickering emulsions from biocompatible solid particles as stabilizer can effectively solve the shortcomings of traditional emulsions. However, the currently reported Pickering emulsions are too stable to achieve phase transition, resulting in a narrow range of applications. In recent years, Pickering emulsions with stimulus responsiveness have become a new research trend. Among them, the temperature-responsive Pickering emulsions have crucial research significance and application value because it has no chemical additives, can recover emulsification after demulsification, and can be recycled and reused, which is in line with the concept of environmental protection.
Diatomite (DE) was modified with a hydrophobic DE with silane coupling agent (MPS), and then a ring-opening reaction with a temperature-responsive material N-isopropylacrylamide (NIPAm) was performed by MPS, and NIPAm was successfully grafted onto the surface of DE to synthesize a modified DE particle with core-shell structure (Diatomite@PNIPAm). The synthesized Diatomite@PNIPAm possesses temperature-responsive performance, and so does the Pickering emulsion using it as a stabilizer.
The Diatomite@PNIPAm was characterized by FTIR spectroscopy, and the results showed that PNIPAm was successfully grafted onto the DE surface. The size and morphology of DE and Diatomite@PNIPAm were observed by scanning electron microscopy, and the results showed that the Diatomite@PNIPAm still remain the porous structure of DE. Furthermore, the results of the contact angle measuring instrument showed that Diatomite@PNIPAm was amphiphilic. The effects of different Diatomite@PNIPAm as stabilizers, different oil-water volume ratios and different solid particle concentrations on the stability of Pickering emulsions was compared. The results showed that the Diatomite@PNIPAm prepared by MPS and NIPAm with a molar ratio of 1:1 could obtain the Pickering emulsion with the best stability at a concentration of 3.0 wt% and an oil-water volume ratio of 7:3. The results of differential scanning calorimetry showed that the Pickering emulsion stabilized by the Diatomite@PNIPAm had a lower critical solution temperature (LCST) of 40 C, indicating that the Pickering emulsion was equipped with temperature responsive property. By repeatedly adjusting the temperature range of the Pickering emulsion from room temperature to LCST and then back to room temperature, the prepared Pickering emulsion could break the emulsion and reemulsify 6 times, and had the performance of the demulsification-reemulsification cycle. By comparing the permeability of the droplets of pure white oil and Pickering emulsion, it could be seen that Pickering emulsion improved the permeability of white oil. Therefore, this study proposes a protocol for drug delivery by using temperature-responsive Pickering emulsion as a drug carrier.Conclusions: Diatomite@PNIPAm was synthesized by NIPAm-modified DE. O/W Pickering emulsion was prepared with Diatomite@PNIPAm as a stabilizer. (1) A series of Diatomite@PNIPAm was prepared via changing the molar ratio of MPS to NIPAm. Different oil-water volume ratios and Diatomite@PNIPAm concentrations were selected to explore the influencing factors of the stability of Pickering emulsion. (2) According to the testing results, the prepared Pickering emulsion possessed excellent stability, and could still be stably emulsified after 2 months, and the droplet morphology and diameter of the emulsion remain basically unchanged. (3) The prepared Pickering emulsion possessed temperature-responsive property: On the one hand, the solution would undergo phase separation when the ambient temperature was higher than the LCST; on the other hand, the solution could resume emulsification when reduced the ambient temperature to within the LCST. (4) Since the prepared Pickering emulsion could switch back and forth between the demulsification state and the emulsification state for 6 times, indicating that the emulsion possessed the performance of demulsification-reemulsification cycle. (5) Osmosis experiments showed that the permeability of Pickering emulsions to propose the possibility of a new drug delivery protocol. The use of temperature-responsive Pickering emulsions for drug delivery enables precise dosing, avoiding problems such as over-medication or frequent dressing changes for patients.
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