Triggered Metal Ion Release and Oxidation: Ferrocene as a Mechanophore in Polymers

被引:100
作者
Di Giannantonio, Michela [1 ]
Ayer, Mathieu A. [2 ]
Verde-Sesto, Ester [2 ,3 ]
Lattuada, Marco [1 ,2 ]
Weder, Christoph [2 ]
Fromm, Katharina M. [1 ]
机构
[1] Univ Fribourg, Dept Chem, Chemin Musee 9, CH-1700 Fribourg, Switzerland
[2] Univ Fribourg, Adolphe Merkle Inst, Chemin Verdiers 4, CH-1700 Fribourg, Switzerland
[3] Univ Basque Country UPV EHU, Joxe Mari Korta Ctr, Polymat, Acda Tolosa 72, Donostia San Sebastian 20018, Spain
基金
欧洲研究理事会; 瑞士国家科学基金会;
关键词
mechanophores; organometallic chemistry; polymers; stimuli-responsive polymers; MECHANOCHEMICAL ACTIVATION; INDUCED CHEMILUMINESCENCE; ULTRASONIC DEGRADATION; COORDINATION POLYMERS; MECHANICAL FORCE; DRUG-DELIVERY; COMPLEXES; POLYMERIZATION; TRANSITION; CATALYSTS;
D O I
10.1002/anie.201803524
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The introduction of mechanophores into polymers makes it possible to transduce mechanical forces into chemical reactions that can be used to impart functions such as self-healing, catalytic activity, and mechanochromic response. Here, an example of mechanically induced metal ion release from a polymer is reported. Ferrocene (Fc) was incorporated as an iron ion releasing mechanophore into poly(methyl acrylate)s (PMAs) and polyurethanes (PUs). Sonication triggered the preferential cleavage of the polymers at the Fc units over other bonds, as shown by a kinetic study of the molar mass distribution of the cleaved Fc-containing and Fc-free reference polymers. The released and oxidized iron ions can be detected with KSCN to generate the red-colored [Fe(SCN)(n)(H2O)(6-n))]((3-n)+) complex or reacted with K-4[Fe(CN)(6)] to afford Prussian blue.
引用
收藏
页码:11445 / 11450
页数:6
相关论文
共 75 条
[1]  
[Anonymous], 2006, Angew. Chem
[2]   Recent applications of chiral ferrocene ligands in asymmetric catalysis [J].
Arrayas, Ramon Gomez ;
Adrio, Javier ;
Carretero, Juan Carlos .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2006, 45 (46) :7674-7715
[3]  
Ayer M. A., 2018, THESIS
[4]   Azo-Containing Polymers with Degradation On-Demand Feature [J].
Ayer, Mathieu A. ;
Simon, Yoan C. ;
Weder, Christoph .
MACROMOLECULES, 2016, 49 (08) :2917-2927
[5]  
Azzaroni O., 2006, ANGEW CHEM, V118, P7600
[6]   Mechanically induced generation of counterions inside surface-grafted charged macromolecular films: Towards enhanced mechanotransduction in artificial systems [J].
Azzaroni, Omar ;
Trappmann, Britta ;
van Rijn, Patrick ;
Zhou, Feng ;
Kong, Bokyung ;
Huck, Wilhelm T. S. .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2006, 45 (44) :7440-7443
[7]   Mechanochemistry with Metallosupramolecular Polymers [J].
Balkenende, Diederik W. R. ;
Coulibaly, Souleymane ;
Balog, Sandor ;
Simon, Yoan C. ;
Fiore, Gina L. ;
Weder, Christoph .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2014, 136 (29) :10493-10498
[8]   Multistimuli, multiresponsive metallo-supramolecular polymers [J].
Beck, JB ;
Rowan, SJ .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (46) :13922-13923
[9]   KINETICS OF THE FORMATION OF THE FERRIC THIOCYANATE COMPLEX [J].
BELOW, JF ;
CONNICK, RE ;
COPPEL, CP .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1958, 80 (12) :2961-2967
[10]   Ultrasound-induced site-specific cleavage of azo-functionalized poly(ethylene glycol) [J].
Berkowski, KL ;
Potisek, SL ;
Hickenboth, CR ;
Moore, JS .
MACROMOLECULES, 2005, 38 (22) :8975-8978