Responsive polymeric nanoreactors

响应性聚合物纳米反应器

• 批准号: EP/G004897/1
• 负责人: Rachel O'Reilly
• 金额: $ 110.63万
• 依托单位: University of Warwick
• 依托单位国家: 英国
• 项目类别: Fellowship
• 财政年份: 2009
• 资助国家: 英国
• 起止时间: 2009 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FG004897%2F1
• 关键词: Responsive; polymeric; nanoreactors

The overall goal of the project is to create and control the properties and local environment of catalysts and reagents by tethering or encapsulating them to new 'smart' nanoscale polymeric scaffolds. These small discrete molecules or nanoparticles (10-150 nanometers in diameter) when constructed, will be functionalised in a 'bottom-up' strategy by the introduction of reactive groups in their shell, core or surface domain, to allow for the specific examination of the effect of surrounding environment on their reactivity. Such a 'bottom up' strategy for the synthesis of these materials will allow for the introduction of the functional groups and specific responsive properties early in the synthesis helping to ensure that the functionality is maintained throughout the process, to afford well-defined functionalised nanomaterials. Investigation of these nanoparticles as nanosized carrier/recovery vehicles that respond to external triggers/stimuli to release or sequester a specific moiety is proposed to enable packaging of reactive functionality, that is incompatible with the surrounding media or other reagents, within the nanoparticle and enable selective and controlled release when required. The nanoparticles are made up from many polymer 'arms', which in turn possess hydrophilic (water liking) and hydrophobic (water repelling) parts; such polymers are called amphiphilic copolymers. Due to the different solvent affinity of the hydrophobic and hydrophilic parts, these polymers arrange themselves into sphere-like structures, called micelles, with a core and shell structure. For example, the structure of a micelle in water (or any incompatible solvent for the core domain) consists of the micelle's outer shell which is made up of hydrophilic polymer segments in direct contact with water and the hydrophobic polymer segments are hidden inside the micelle core, minimising unfavourable interactions with the solvent (and vice versa in organic media). These micelles are inherently unstable to concentration changes but they can be stabilised using covalent bonding or crosslinking chemistries selectively in the shell layer, to afford robust nanoparticles. The degree of crosslinking must be carefully considered to ensure a robust nanoparticle is formed, but this chemistry should not significantly affect the permeability of the shell layer and still allow for the diffusion of small molecules through this layer to the functionality which is located within the core domain. The unique core-shell morphology of these nanoparticles imparts novel properties including the ability to behave as hosts or vessels to carry or sequester cargo and also the ability to embed reactive functionality within the nanoparticle whilst protecting it from the surrounding media. As a result these nanoparticles can be envisaged as 3-dimensional modifiable supports to provide unique environments in which the selective reaction, encapsulation or transformation of small molecules can occur. The chemistry proposed in this Fellowship application will explore these two aspects of these polymeric materials. The first will develop new water soluble and responsive polymeric scaffolds that contain distinct domains in which selective catalysis can occur to allow for the development of greener industrial methodologies, by reducing the amount of costly and environmentally damaging organic solvents required. The mediation of reactions within the specific environments within or on the surface of the nanoparticles is also proposed to lead to control over the composition and nature of products. The second approach will utilise responsive polymers to allow for the triggered release of reagents or catalysts into the surrounding media for applications in controlled sequential reactions. These methodologies are proposed to enable the development of novel 'smart' nanoreactors for catalysis and multi-step organic reactions.

该项目的总体目标是通过将催化剂和试剂捆绑或封装到新的“智能”纳米级聚合物支架上，来创造和控制催化剂和试剂的特性和局部环境。这些小的离散分子或纳米颗粒（直径10-150纳米）在构建时，将以“自下而上”的策略通过在其外壳，核心或表面域引入反应基团来实现功能化，从而允许对周围环境对其反应性的影响进行具体检查。这种“自下而上”的合成策略将允许在合成的早期引入官能团和特定的响应特性，这有助于确保在整个过程中保持功能，从而提供定义良好的功能化纳米材料。研究这些纳米颗粒作为纳米级载体/回收载体，对外部触发/刺激做出反应，释放或隔离特定的片段，以实现与周围介质或其他试剂不相容的反应性功能包装，并在需要时实现选择性和控制释放。纳米颗粒由许多聚合物“臂”组成，这些聚合物“臂”又具有亲水性（喜水）和疏水性（拒水）部分；这种聚合物被称为两亲性共聚物。由于疏水部分和亲水部分对溶剂的亲和力不同，这些聚合物将自己排列成球状结构，称为胶束，具有核壳结构。例如，胶束在水中（或任何不相容的溶剂）的结构由胶束的外壳组成，胶束的外壳由与水直接接触的亲水性聚合物片段组成，疏水性聚合物片段隐藏在胶束核心内部，最大限度地减少与溶剂的不利相互作用（在有机介质中反之亦然）。这些胶束对浓度变化本身是不稳定的，但它们可以通过在壳层中选择性地使用共价键或交联化学来稳定，从而提供坚固的纳米颗粒。必须仔细考虑交联的程度，以确保形成坚固的纳米颗粒，但这种化学反应不应显着影响壳层的渗透性，并且仍然允许小分子通过这一层扩散到位于核心区域内的功能。这些纳米颗粒独特的核壳形态赋予了其新的特性，包括作为宿主或容器携带或隔离货物的能力，以及在纳米颗粒内嵌入反应功能的能力，同时保护其免受周围介质的影响。因此，这些纳米颗粒可以被设想为三维可修改的载体，以提供独特的环境，在这种环境中，小分子的选择性反应、封装或转化可以发生。本奖学金申请中提出的化学将探讨这些聚合物材料的这两个方面。第一个项目将开发新的水溶性和反应性聚合物支架，这些支架包含不同的区域，其中可以发生选择性催化，通过减少所需的昂贵和对环境有害的有机溶剂的数量，从而允许开发更环保的工业方法。在纳米颗粒内部或表面的特定环境中调解反应也被提议导致对产品的组成和性质的控制。第二种方法将利用反应性聚合物，允许试剂或催化剂被触发释放到周围介质中，用于受控的顺序反应。提出这些方法是为了开发用于催化和多步有机反应的新型“智能”纳米反应器。

项目成果

Fabrication of crystals from single metal atoms.

• DOI: 10.1038/ncomms4851
• 发表时间: 2014-05-27
• 期刊: NATURE COMMUNICATIONS
• 影响因子: 16.6
• 作者: Barry, Nicolas P. E.;Pitto-Barry, Anais;Sanchez, Ana M.;Dove, Andrew P.;Procter, Richard J.;Soldevila-Barreda, Joan J.;Kirby, Nigel;Hands-Portman, Ian;Smith, Corinne J.;O'Reilly, Rachel K.;Beanland, Richard;Sadler, Peter J.
• 通讯作者: Sadler, Peter J.

Osmium Atoms and Os2 Molecules Move Faster on Selenium-Doped Compared to Sulfur-Doped Boronic Graphenic Surfaces.

与掺杂硫磺的硼酸硼石墨烯表面相比，在硒掺杂的硒原子和OS2分子上移动的速度更快。

• DOI: 10.1021/acs.chemmater.5b01853
• 发表时间: 2015-07-28
• 期刊: Chemistry of materials : a publication of the American Chemical Society
• 作者: Barry NP;Pitto-Barry A;Tran J;Spencer SE;Johansen AM;Sanchez AM;Dove AP;O'Reilly RK;Deeth RJ;Beanland R;Sadler PJ
• 通讯作者: Sadler PJ

A comparative study of the stimuli-responsive properties of DMAEA and DMAEMA containing polymers

• DOI: 10.1002/pola.26730
• 发表时间: 2013-08-15
• 期刊: JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY
• 作者: Cotanda, Pepa;Wright, Daniel B.;O'Reilly, Rachel K.
• 通讯作者: O'Reilly, Rachel K.

Hybrid inorganic-organic composite nanoparticles from crosslinkable polyfluorenes

由可交联聚芴制成的杂化无机-有机复合纳米粒子

• DOI: 10.1039/c3tc30266k
• 发表时间: 2013
• 期刊: Journal of Materials Chemistry C
• 影响因子: 6.4
• 作者: Behrendt J

Fluorescent nanoparticles from PEGylated polyfluorenes

• DOI: 10.1039/c3py21068e
• 发表时间: 2013-02
• 期刊: Polymer Chemistry
• 影响因子: 4.6
• 作者: Jonathan M. Behrendt;Yun Wang;H. Willcock;Laura Wall;M. Mccairn;R. O’Reilly;M. Turner