Enabling In Vivo Photocatalytic Activation of Rapid Bioorthogonal Chemistry by Repurposing Silicon-Rhodamine Fluorophores as Cytocompatible Far-Red Photocatalysts.
Enabling In Vivo Photocatalytic Activation of Rapid Bioorthogonal Chemistry by Repurposing Silicon-Rhodamine Fluorophores as Cytocompatible Far-Red Photocatalysts.
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DOI：
10.1021/jacs.1c05547
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发表时间：
2021-07-21
影响因子：
15
通讯作者：
Fox JM
中科院分区：
文献类型：
--
作者：
Wang C;Zhang H;Zhang T;Zou X;Wang H;Rosenberger JE;Vannam R;Trout WS;Grimm JB;Lavis LD;Thorpe C;Jia X;Li Z;Fox JM
在组织渗透的远红外/近红外窗口中吸收的发色团长期以来一直用作光催化剂以产生用于光动力疗法的单线态氧。然而，与单线态氧敏化相关的细胞毒性和副反应已经对使用长波长荧光素在生物环境中引发其他类型的化学反应提出了问题。在本文中，Si-罗丹明（SiR）被描述为光催化剂，用于在反式环辛烯亲二烯体的存在下使用660 nm光通过将二氢四嗪氧化成四嗪来诱导快速生物正交化学。SiR通常用作生物成像的荧光团，但尚未应用于催化化学反应。一系列的SiR衍生物进行了评估，并发现Janelia Fluor-SiR染料是特别有效的催化光氧化（通常为3%）。描述了在两种氧化态下均显示出高稳定性的二氢四嗪/四嗪对。通过反式环辛烯进行位点选择性修饰的蛋白质在暴露于660 nm光和二氢四嗪时定量缀合。相比之下，发现先前描述的亚甲蓝催化剂快速降解蛋白质。使用SiR-红光照射来交联由二氢四嗪和反式环辛烯官能化的透明质酸衍生物，使得能够进行人前列腺癌细胞的3D培养。光诱导的水凝胶形成也可以在活小鼠中通过皮下注射Cy 7标记的水凝胶前体溶液，然后短暂照射以产生稳定的水凝胶来进行。这种利用红光照射激活生物正交化学的细胞相容性方法有望在生物环境中需要时空控制的地方找到广泛的应用。
Chromophores that absorb in the tissue-penetrant far-red/near-infrared window have long served as photocatalysts to generate singlet oxygen for photodynamic therapy. However, the cytotoxicity and side-reactions associated with singlet oxygen sensitization have posed a problem for using long-wavelength photocatalysis to initiate other types of chemical reactions in biological environments. Herein, Si-Rhodamines (SiR) are described as photocatalysts for inducing rapid bioorthogonal chemistry using 660 nm light through the oxidation of a dihydrotetrazine to a tetrazine in the presence of trans-cyclooctene dienophiles. SiRs have been commonly used as fluorophores for bioimaging, but have not been applied to catalyze chemical reactions. A series of SiR derivatives were evaluated, and the Janelia Fluor-SiR dyes were found to be especially effective in catalyzing photooxidation (typically 3%). A dihydrotetrazine/tetrazine pair is described that displays high stability in both oxidation states. A protein that was site-selectively modified by trans-cyclooctene was quantitively conjugated upon exposure to 660 nm light and a dihydrotetrazine. By contrast, a previously described methylene blue catalyst was found to rapidly degrade the protein. SiR-red light photocatalysis was used to crosslink hyaluronic acid derivatives functionalized by dihydrotetrazine and trans-cyclooctenes, enabling 3D culture of human prostate cancer cells. Photoinducible hydrogel formation could also be carried out in live mice through subcutaneous injection of a Cy7-labeled hydrogel precursor solution, followed by brief irradiation to produce a stable hydrogel. This cytocompatible method for using red light photocatalysis to activate bioorthogonal chemistry is anticipated to find broad applications where spatiotemporal control is needed in biological environments.
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影响因子：
9.5
作者：
Dicker, Kevin T.;Moore, Axel C.;Jia, Xinqiao
通讯作者：
Jia, Xinqiao
DOI：
10.1002/chem.201703919
发表时间：
2018-04-03
期刊：
Chemistry (Weinheim an der Bergstrasse, Germany)
影响因子：
--
作者：
Bruins JJ;Albada B;van Delft F
通讯作者：
van Delft F
影响因子：
7
作者：
Carthew, J.;Frith, J. E.;Truong, V. X.
通讯作者：
Truong, V. X.
影响因子：
15
作者：
Carlson JCT;Mikula H;Weissleder R
通讯作者：
Weissleder R
影响因子：
18.2
作者：
Devaraj NK
通讯作者：
Devaraj NK