Netto Caterina G C Marques, Bell Sarah, Castro Caio B, Machado Pedro Henrique, Purohit Vatsal, Davis Katherine M, Batista Ana Paula L, Dyer R Brian
Departamento de Quimica, Universidade Federal de São Carlos, Rod. Washington Luiz, Km 235, s/n, São Carlos, SP, 13565-905, Brazil.
Department of Chemistry, Emory University, 1515 Dickey Drive, Atlanta, GA, 30030, USA.
Angew Chem Int Ed Engl. 2025 Sep 1;64(36):e202504332. doi: 10.1002/anie.202504332. Epub 2025 Jul 25.
Caged compounds are a valuable tool to photocontrol the release of enzymatic substrates in a reaction. For example, caged urea molecules were proposed to control urea delivery to urease reactions and aid the determination of the catalytic mechanism of this enzyme. Owing to the success of several caged compounds based on ruthenium complexes, we synthesized a new inorganic caged urea (RuBpy-urea) and monitored the release of free urea by infrared spectroscopy upon irradiation. Transient infrared absorption (TRIR) indicates diffusion-controlled release of urea, and kinetics studies after photolysis demonstrate the functionality of the new caged molecule for photocontrolled delivery of urea to urease. Coupling photocontrolled delivery of urea to cryo-FTIR (fourier transform infrared spectroscopy) revealed that inhibition of urease results in different FTIR spectrum than the one observed for the noninhibited urease.
笼形化合物是光控反应中酶底物释放的一种有价值的工具。例如，有人提出用笼形尿素分子来控制尿素向脲酶反应的递送，并有助于确定该酶的催化机制。由于几种基于钌配合物的笼形化合物取得了成功，我们合成了一种新型无机笼形尿素（RuBpy-尿素），并通过辐照后的红外光谱监测游离尿素的释放。瞬态红外吸收（TRIR）表明尿素的释放受扩散控制，光解后的动力学研究证明了这种新型笼形分子用于光控尿素向脲酶递送的功能。将尿素的光控递送与低温傅里叶变换红外光谱（cryo-FTIR）相结合，发现脲酶的抑制导致的傅里叶变换红外光谱与未抑制的脲酶所观察到的不同。
