Engineering thermoresponsive materials via supracolloidal assembly in polymer-stabilised emulsions.

通过聚合物稳定乳液中的超胶体组装来工程热响应材料。

• 批准号: EP/T00813X/1
• 负责人: Michael Cook
• 金额: $ 18.99万
• 依托单位: University of Hertfordshire
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2020
• 资助国家: 英国
• 起止时间: 2020 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FT00813X%2F1
• 关键词: Engineering; thermoresponsive; materials; via; supracolloidal

Stimuli-responsive materials have become very important in scientific research, allowing for "smart" control over material properties when triggered by external signals, such as changes in temperature or pH. This control has enabled ground-breaking scientific advances in fields such as tissue engineering, soft robotics, healthcare and diagnostics. One reported class of smart materials are "engineered emulsions", which use branched copolymer surfactants (BCSs) to stabilise emulsion droplets. These emulsions respond to changes in pH by solidifying into gels due to a change in the interactions between copolymers on adjacent emulsion droplets becoming attractive, leading to the self-assembly of the droplets into a hierarchical network structure. These "smart" materials are highly attractive, displaying stimulus-responsiveness combined with the availability of large hydrophobic and aqueous domains, which could be used as a reservoir or solubilisation locus for large payloads, released on demand. While the use of pH may be of interest for specific applications, temperature as a trigger offers wider applicability, particularly in biomaterials and food.We have recently demonstrated that engineered emulsions stabilised by poly(ethylene glycol) - poly(N-isopropyl acrylamide) BCSs exhibit "thermothickening" behaviour, in other words, they respond to temperature as a stimulus and their viscosity dramatically increases upon warming. These new materials have many potential applications in advanced therapeutics, tissue engineering, and in emerging fields such as 3D printing. However, poly(N-isopropyl acrylamide), which is the most widely used polymers for thermothickening applications, is cytotoxic against some cell types, so a more biocompatible alternative must be found. In this project, candidate temperature-responsive materials with promising safety profiles have been identified, namely poly(N-vinylcaprolactam), poly(2-dimethylaminoethylmethacrylate), and poly(N,N-diethyl acrylamide), which could replace poly(N-isopropylacrylamide). In addition, the relationship between polymer block composition and thermothickening behaviour must be established to inform the design of future smart gelling materials. Finally, a better understanding of the mechanisms behind the thickening need to be achieved. This project hypothesises that BCSs containing PEGMA and a temperature-responsive component may be used to engineer emulsions which thicken upon warming to body temperature, leading to the design of advanced functional materials. This project will explore the relationship between BCS structure and supracolloidal assembly in BCS-stabilised emulsions, to generate optimised materials with smart thermoresponsive thickening. Cutting-edge neutron scattering and reflectometry techniques will be used to understand morphology at the nanoscale relates to the gelling properties of the hierarchical assemblies, informing the design of future advanced materials.Once developed, thermothickening BCS-stabilised emulsions have numerous potential applications, enhancing existing technologies and providing a platform for future advanced materials. Thermothickening materials could be used in mucosal drug delivery to sites such as the eye, vagina, and rectum, where a fluid containing drug may pass through an applicator, before forming a viscous gel at the site of administration, enhancing retention at sites where rapid clearance leads to poor therapeutic effect and low patient compliance. In tissue engineering, cellular medicines may be administered within a thickening material which forms a scaffold in situ in which the cells may grow and either replace damaged tissue or act as bioreactors. In 3D printing, these materials could be solidified using heat as a stimulus, creating scaffolds with microscale patterning. The temperature-responsive BCSs could also be impactful in areas such as cosmetics, chemically-enhanced oil recovery, and as flocculants.

刺激响应材料在科学研究中变得非常重要，在由外部信号触发时，例如温度或pH的变化，可以“智能”控制材料特性。这种控制已使组织工程，软机器人技术，医疗保健和诊断等领域的开创性科学进步。据报道，智能材料类别是“工程乳液”，使用分支共聚物表面活性剂（BCSS）稳定乳液液滴。由于相邻乳液液滴上的共聚物之间的相互作用变化，这些乳液通过凝固成凝胶的变化来反应pH的变化，从而导致液滴的自组装成层次结构。这些“智能”材料具有很高的吸引力，表现出刺激反应性，结合了大型疏水和水域的可用性，可以用作大型有效载荷的储层或溶解基因座，并按需发布。虽然对特定应用的使用可能引起了pH的使用，但温度作为触发剂具有更广泛的适用性，尤其是在生物材料和食物中。我们最近证明，通过聚（乙二醇）稳定的工程乳液 - 聚（N-异丙基丙烯酰胺）BCS BCS BCS bcs在其他语言上表现出“热态性”，它们响应于刺激性的范围，他们的访问量会增加，他们的刺激性却是刺激性的。这些新材料在晚期治疗，组织工程以及3D打印等新兴领域具有许多潜在的应用。然而，对于某些细胞类型的聚合物，聚合物最广泛使用的聚合物是细胞毒性的，因此必须找到一种更具生物相容性的替代方法。在该项目中，已经鉴定出具有有前途的安全剖面的候选温度响应材料，即聚（N-乙烯基caprolactam），聚（2-二甲基氨基甲基丙烯酸酯）和聚（N，N，N-二乙基丙烯酰胺），可以取代聚（N-异丙基酰基酰胺）。此外，必须建立聚合物块组成与热疗行为之间的关系，以告知未来智能胶凝材料的设计。最后，需要更好地理解增厚背后的机制。该项目假设含有PEGMA的BCSS和温度响应组件可用于设计乳液，这些乳液在变暖到体温时会增稠，从而导致高级功能材料的设计。该项目将探讨BCS结构与BCS稳定乳液中的BCS结构与上固体组件之间的关系，以生成具有智能热响应增厚的优化材料。尖端的中子散射和反射仪技术将用于理解纳米级的形态学与层次组件的凝胶特性有关，告知未来的先进材料的设计。开发的，耐热性BCS稳定的乳液具有许多潜在的应用，并为未来的先进材料提供了一个潜在的现有技术，并为未来的先进材料提供了一个平台。热疗材料可用于粘膜药物传递到诸如眼睛，阴道和直肠的部位，其中含有药物的液体可能会通过涂药器，然后在给药部位形成粘性凝胶，从而增强了在快速清除导致治疗效应不良和患者依从性较低的部位的保留率。在组织工程中，可以在增厚材料中施用细胞药物，该材料形成脚手架，在该材料的原位可能生长并替代受损的组织或充当生物反应器。在3D打印中，可以使用热量作为刺激来巩固这些材料，从而形成微观图案。温度响应的BCSS在化妆品，化学增强的油回收和絮凝剂等区域也可能影响。

项目成果

Thermoresponsive Triblock-Copolymers of Polyethylene Oxide and Polymethacrylates: Linking Chemistry, Nanoscale Morphology, and Rheological Properties

• DOI: 10.1002/adfm.202109010
• 发表时间: 2021-11-23
• 期刊: ADVANCED FUNCTIONAL MATERIALS
• 影响因子: 19
• 作者: da Silva, Marcelo Alves;Haddow, Peter;Cook, Michael T.
• 通讯作者: Cook, Michael T.

Polymer Architecture Effects on Poly(N,N-Diethyl Acrylamide)-b-Poly(Ethylene Glycol)-b-Poly(N,N-Diethyl Acrylamide) Thermoreversible Gels and Their Evaluation as a Healthcare Material.

聚合物结构对聚（N,N-二乙基丙烯酰胺）-b-聚（乙二醇）-b-聚（N,N-二乙基丙烯酰胺）热可逆凝胶的影响及其作为保健材料的评估。

• DOI: 10.1002/mabi.202100432
• 发表时间: 2022
• 期刊: Macromolecular bioscience
• 影响因子: 4.6
• 作者: Haddow PJ

Polymer architecture dictates thermoreversible gelation in engineered emulsions stabilised with branched copolymer surfactants

• DOI: 10.1039/d2py00876a
• 发表时间: 2022
• 期刊: Polymer Chemistry
• 影响因子: 4.6
• 作者: A. Rajbanshi;M. A. da Silva;D. Murnane;L. Porcar;C. A. Dreiss;M. Cook

Thermoresponsive poly(di(ethylene glycol) methyl ether methacrylate)-ran-(polyethylene glycol methacrylate) graft copolymers exhibiting temperature-dependent rheology and self-assembly

• DOI: 10.1016/j.molliq.2021.117906
• 发表时间: 2022-01-08
• 期刊: JOURNAL OF MOLECULAR LIQUIDS
• 影响因子: 6
• 作者: da Silva, Jessica Bassi;Haddow, Peter;Cook, Michael Thomas
• 通讯作者: Cook, Michael Thomas

Branched Copolymer Surfactants as Versatile Templates for Responsive Emulsifiers with Bespoke Temperature-Triggered Emulsion-Breaking or Gelation

支化共聚物表面活性剂作为响应乳化剂的通用模板，具有定制的温度触发破乳或凝胶作用

• DOI: 10.1002/admi.202300755
• 发表时间: 2023
• 期刊: Advanced Materials Interfaces
• 影响因子: 5.4
• 作者: Rajbanshi A