High performance near-IR-active macro- and nano-Metal-Organic-Frameworks using organic dyes

本研究旨在设计具有多种功能的纳米多孔材料。首先，这些多孔材料是由一个称为节点的无机部分和一个刚性有机单元组成的。它们一起形成各种形式和腔体尺寸的三维多孔框架。这种材料属于配位聚合物家族，更具体地说，属于金属有机框架（MOFs）。因此，由这种组装产生的空隙 * 可以被分子填充，使它们成为货物。“配位”这个词意味着金属和有机部分之间的连接是一种配位键，它比共价键弱。这种相对的脆弱性可以用来触发框架的分解，因此释放货物内部的分子（即药物输送）。第二，该提议的 * 特异性在于，有机单元是在光疗窗口（650-850 nm）中吸收和 * 发射的染料，最佳位置 * 在800 nm处，其中光最好地穿透皮肤（注意，近红外 * 区域为780-2500 nm）。简而言之，可以使用650-850 nm范围的辐射从患者体外触发药物释放。此外，来自器官内的染料的发射 * 可以在800 nm处最好地逃逸，并且可以通过近红外检测器在患者体外检测到。这个过程称为光学成像。第三，一些染料可以吸收光和热，直到MOFs分解（因为配位键的弱点）。此外，热量的增加本身也会对活细胞造成损害。这就是所谓的光热疗法。第四，氧气无处不在。这些染料还具有吸收光的能力，并通过简单的接触或碰撞将其能量传递给氧气。在能量转移时，氧变成单线态氧 *（获得能量），对活细胞非常有毒。这个过程被称为光动力疗法。有趣的是，一旦MOF被分解，染料是完整的 * 并且仍然可以具有光活性以产生单线态氧。使用合适的染料，纳米MOFs的构建（用于医疗应用，因为这种尺寸适合穿透活细胞）只需要几个步骤，并将表现出四个目标功能：成像，药物输送，光热和光动力治疗。这是一个四合一的新概念，其中三个是用来杀死癌细胞的。因为MOFs在其表面很容易修饰，* 识别受体（识别癌细胞）和近红外发射染料 * 可以锚定。

This research consists at designing nano-sized porous materials exhibiting multiple functions. First, these porous*materials are built with an inorganic part called node and a rigid organic unit. Together, they form a 3-dimensional*porous frame of various forms and cavity sizes. This material belongs to the family of coordination polymers, more specifically to*metal-organic-frameworks (MOFs). Thus, the voids*created by this assembly can be filled with molecules making them cargos. The*word coordination means that the link between the metal and organic parts is*a coordination bond, which is weaker than a covalent one. This relative*fragility can be used to trigger a breakdown of the framework, therefore a release*of the molecules inside the cargos (i.e. drug delivery). Second, the*specificity of the proposal is that the organic units are dyes absorbing and*emitting in the phototherapeutic window (650-850 nm) with an optimum position*at 800 nm where light penetrates best through skin (note that the near-IR*region is 780-2500 nm). In simple words, one can trigger a drug release from the*outside of the patient using a radiation of 650-850 nm range. Moreover, the emission*from the dye inside an organ can best escape at 800 nm and be detected outside*the patient by a near-IR detector. This process is called optical imaging.*Third, some dyes can absorb light and heat to up the point that the MOFs breaks down (because of the weakness of the coordination bond). Also the*increase in heat by itself can also cause dammage to the living cells. It is*called photothermal therapy. Fourth, oxygen is everywhere. These dyes also have*the capacity to absorb light and transfer its energy to oxygen by simple*contact or collision. Upon energy transfer, oxygen becomes singlet oxygen*(gained energy) and is very toxic to living cell. This process is called*photodynamic therapy. Interestingly, once the MOF is broken down, the dye is intact*and can still be photo-active for the generation of singlet oxygen. With the*appropriate dye or dyes, the construction of nano-MOFs (for medical*applications as this size is appropriate to penetrate the living cells) requires*only a few steps and will exhibit four target functions : imaging, drug delivery,*photothermal and photodynamic therapy. This is a new concept four in one, three of them are designed to*kill cancer cells. Because MOFs are easily modifyable at their surface,*recognition receptors (to recognize the cancer cells) and near-IR emissive dyes*can be anchored on.