scholarly journals Building Quantitative Relationships between Ligand Structure and Its Reactivity with Organic Radical Species

2020 ◽  
Author(s):  
Stephen Mezyk ◽  
◽  
Gregory Horne ◽  
Travis Grimes ◽  
Peter Zalupski ◽  
...  
Molecules ◽  
2019 ◽  
Vol 24 (4) ◽  
pp. 665 ◽  
Author(s):  
Takashi Kubo

Recently, long-lived, organic radical species have attracted much attention from chemists and material scientists because of their unique electronic properties derived from their magnetic spin and singly occupied molecular orbitals. Most stable and persistent organic radicals are heteroatom-centered radicals, whereas carbon-centered radicals are generally very reactive and therefore have had limited applications. Because the physical properties of carbon-centered radicals depend predominantly on the topology of the π-electron array, the development of new carbon-centered radicals is key to new basic molecular skeletons that promise novel and diverse applications of spin materials. This account summarizes our recent studies on the development of novel carbon-centered radicals, including phenalenyl, fluorenyl, and triarylmethyl radicals.


2006 ◽  
Vol 11-12 ◽  
pp. 281-284 ◽  
Author(s):  
Nayumi Ohata ◽  
Yurie Ito ◽  
Daisuke Gomibuchi ◽  
Hideki Kitamura ◽  
Yasuhiro Funahashi ◽  
...  

Nickel(II) phthalocyanine complexes encapsulated in X-type Zeolite were constructed by the ‘Ship-in-bottle’ synthesis, whose characterizations were performed by fluorescent X-ray, UV-vis, reflectance, and ESR spectroscopic methods. UV-vis and Reflectance spectra of NiPc-Na+-X suggested that the Pc ring was synthesized. Solid state ESR spectrum of NiPc-Na+-X gave characteristic pattern for organic radical species. Catalytic oxidation reactivity of the NiPc-Na+-X in homogeneous reaction have been studied for organic substrate in the presence of H2O2.


2020 ◽  
Vol 7 (1) ◽  
Author(s):  
Peter C. St. John ◽  
Yanfei Guan ◽  
Yeonjoon Kim ◽  
Brian D. Etz ◽  
Seonah Kim ◽  
...  

Author(s):  
M. Bertrand ◽  
E. Besson ◽  
S. Gastaldi

AbstractMost organic radical species are transient and were long considered to be beyond control. Tremendous progress in the knowledge and understanding of their reactivity has enabled their use as standard intermediates in organic synthesis. In this review, strategies implemented to increase radical lifetimes, without modifying fundamentally their structural features, are presented. A wide array of systems has been designed that allow modulation of the level of confinement constraints. The ability of these systems to increase radical lifetime has now reached the point where a transient radical can become persistent, which opens up many new prospects for future applications.


2009 ◽  
Vol 11 (7) ◽  
pp. 1369-1372 ◽  
Author(s):  
Hugo A. López-Peña ◽  
Lindsay S. Hernández-Muñoz ◽  
Judith Cardoso ◽  
Felipe J. González ◽  
Ignacio González ◽  
...  

1996 ◽  
Vol 61 (15) ◽  
pp. 5190-5190
Author(s):  
Donald J. Gallagher ◽  
Shengde Wu ◽  
Nikola A. Nikolic ◽  
Peter Beak

2004 ◽  
Vol 114 ◽  
pp. 533-535 ◽  
Author(s):  
H.-J. Lee ◽  
H.-B. Cui ◽  
H. Fujiwara ◽  
H. Kobayashi ◽  
E. Fujiwara ◽  
...  

2018 ◽  
Author(s):  
Madushani Dharmarwardana ◽  
André F. Martins ◽  
Zhuo Chen ◽  
Philip M. Palacios ◽  
Chance M. Nowak ◽  
...  

Superoxide overproduction is known to occur in multiple disease states requiring critical care yet non-invasive detection of superoxide in deep tissue remains a challenge. Herein, we report a metal-free magnetic resonance imaging (MRI) and electron paramagnetic resonance (EPR) active contrast agent prepared by “click conjugating” paramagnetic organic radical contrast agents (ORCAs) to the surface of tobacco mosaic virus (TMV). While ORCAs are known to be reduced <i>in vivo</i> to an MRI/EPR silent state, their oxidation is facilitated specifically by reactive oxygen species—in particular superoxide—and are largely unaffected by peroxides and molecular oxygen. Unfortunately, single molecule ORCAs typically offer weak MRI contrast. In contrast, our data confirm that the macromolecular ORCA-TMV conjugates show marked enhancement for <i>T<sub>1</sub></i> contrast at low field (<3.0 T), and <i>T<sub>2</sub></i> contrast at high field (9.4 T). Additionally, we demonstrated that the unique topology of TMV allows for “quenchless fluorescent” bimodal probe for concurrent fluorescence and MRI/EPR imaging, which was made possible by exploiting the unique inner and outer surface of the TMV nanoparticle. <a>Finally, we show TMV-ORCAs do not respond to normal cellular respiration, minimizing the likelihood for background, yet still respond to enzymatically produced superoxide in complicated biological fluids like serum.</a>


2019 ◽  
Author(s):  
Hamilton Lee ◽  
Jenica Lumata ◽  
Michael A. Luzuriaga ◽  
Candace Benjamin ◽  
Olivia Brohlin ◽  
...  

<div><div><div><p>Many contrast agents for magnetic resonance imaging are based on gadolinium, however side effects limit their use in some patients. Organic radical contrast agents (ORCAs) are potential alternatives, but are reduced rapidly in physiological conditions and have low relaxivities as single molecule contrast agents. Herein, we use a supramolecular strategy where cucurbit[8]uril binds with nanomolar affinities to ORCAs and protects them against biological reductants to create a stable radical in vivo. We further over came the weak contrast by conjugating this complex on the surface of a self-assembled biomacromolecule derived from the tobacco mosaic virus.</p></div></div></div>


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