Yuming Yang,†,§ Qiang Zhao,‡,§ Wei Feng,† and Fuyou Li*,† †Department of Chemistry and State Key Laboratory of Molecular Engineering of Polymers and Institutes of Biomedical Sciences, Fudan University, Shanghai 200433, P. R. China ‡Key Laboratory for Organic Electronics and Information Displays (KLOEID) and Institute of Advanced Materials (IAM), Nanjing University of Posts and Telecommunications, Nanjing 210046, P. R. China.

Luminescent chemodosimeters for bioimaging.

Fluorescent Chemosensors Based on Spiroring-Opening of Xanthenes and Related Derivatives Xiaoqiang Chen, Tuhin Pradhan, Fang Wang, Jong Seung Kim,* and Juyoung Yoon* Departments of Chemistry and Nano Science and of Bioinspired Science (WCU), Ewha Womans University, Seoul 120-750, Korea State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemistry and Chemical Engineering, Nanjing University of Technology, Nanjing 210009, China Department of Chemistry, Korea University, Seoul 136-701, Korea

Fluorescent chemosensors based on spiroring-opening of xanthenes and related derivatives.

Heavy metal ions are of great concern, not only among the scientific community, especially chemists, biologists, and environmentalists, but increasingly among the general population, who are aware of the some of the disadvantages associated with them. In spite of the fact that some heavy metal ions play important roles in living systems, they are very toxic and hence capable of causing serious environmental and health problems.1-6 Some heavy metal ions, such as Fe(III), Zn(II), Cu(II), Co(II), Mn(II), and Mo(VI), are essential for the maintenance of human metabolism. However, high concentrations of these ions can lead to many adverse health effects.1,2,7-20 It is also a fact that others such as Hg(II), Cd(II), Pb(II), and As(III) are among the most toxic ions known that lack any vital or beneficial effects. Accumulation of these over time in the bodies of humans and animals can lead to serious debilitating illnesses.2,21-30 Therefore, the development of increasingly selective and sensitive methods for the determination of heavy metal ions is currently receiving considerable attention.7,23,31-36 Several methods, including atomic absorption spectroscopy, inductively coupled plasma atomic emission spectrometry, electrochemical sensoring, and the use of piezoelectric quartz crystals make it possible to detect low limits.37-40 However, these methods require expensive equipment and involve time-consuming and laborious procedures that can be carried out only by trained professionals. Alternatively, analytical techniques based on fluorescence detection are very popular because fluorescence measurements are usually very sensitive (parts per billion/trillion), easy to perform, and inexpensive.23,37,41-45 Furthermore, the photophysical properties of a fluorophore can be easily tuned using a range of routes: charge transfer, electron transfer, energy transfer, the influence of the heavy metal ions, and the destabilization of nonemissive n-π* excited states.5 Consequently, a large number of papers involving fluorescent chemosensors (see definition in section 2) have been published. In general to date, fluorescent chemosensors for anions and cations have proven popular, but those for many heavy metal ions such as Hg(II), Pb(II), Cu(II), Fe(III), and Ag(I) present challenges because these ions often act as fluorescence quenchers. Cu(II) is a typical ion that causes the chemosensor to decrease fluorescent emissions due to quenching of the fluorescence by mechanisms inherent to the paramagnetic species.46-48 Such decreased emissions are impractical for analytical purposes because of their low signal outputs upon complexation. In addition, temporal separation of spectrally similar complexes by time-resolved fluorimetry is subsequently prevented.49 Compared to the relatively well-developed fluorescent chemosensors, fluorescent chemodosimeters (see definition in section 2) have recently emerged as a research area of * Corresponding author. E-mail: jongskim@korea.ac.kr. † Hue University. ‡ Korea University. Duong Tuan Quang was born in 1970 in Thanhhoa, Vietnam, and graduated from Hue University in 1992, where he obtained his M.S. degree two years later and began his career as a lecturer in Chemistry soon afterwards. He received his Ph.D. degree in 2003 from Institute of Chemistry, Vietnamese Academy of Science and Technology. In 2006, he worked as a postdoctoral fellow in Professor Jong Seung Kim’s laboratory, Dankook University, Seoul, Korea. He was promoted as an associate professor in 2009 and went to Korea University as a research professor in 2010. His main task involved the development of chromogenic and fluorogenic molecular sensors to detect specific cations and anions. Chem. Rev. 2010, 110, 6280–6301 6280

Fluoro- and Chromogenic Chemodosimeters for Heavy Metal Ion Detection in Solution and Biospecimens

Rhodamine dyes are widely used as fluorescent probes owing to their high absorption coefficient and broad fluorescence in the visible region of electromagnetic spectrum, high fluorescence quantum yield and photostability. A great interest in the development of new synthetic procedures for preparation of Rhodamine derivatives has arisen in recent years because for most applications the probe must be covalently linked to another (bio)molecule or surface. In this critical review the strategies for modification of Rhodamine dyes and a discussion on the variety of applications of these new derivatives as fluorescent probes are given (108 references).

Synthesis and applications of Rhodamine derivatives as fluorescent probes

Recently, the use of phosphorescent heavy-metal complexes as chemosensors has attracted increasing interest due to their advantageous photophysical properties. This critical review focuses on the design principles and the recent development of phosphorescent chemosensors for metal cations, anions, pH, oxygen, volatile organic compounds and biomolecules based on some heavy-metal complexes (such as Pt(II)-, Ru(II)-, Re(I)-, Ir(III)-, Cu(I)-, Au(I)- and Os(II)-based complexes), in which the variation in phosphorescence signals induced by the interaction between heavy-metal complexes and analytes is utilized (217 references).

Phosphorescent chemosensors based on heavy-metal complexes

A rhodamine B derivative 4 containing a highly electron-rich S atom has been synthesized as a fluorescence turn-on chemodosimeter for Cu(2+). Following Cu(2+)-promoted ring-opening, redox and hydrolysis reactions, comparable amplifications of absorption and fluorescence signals were observed upon addition of Cu(2+); this suggests that chemodosimeter 4 effectively avoided the fluorescence quenching caused by the paramagnetic nature of Cu(2+). Importantly, 4 can selectively recognize Cu(2+) in aqueous media in the presence of other trace metal ions in organisms (such as Fe(3+), Fe(2+), Cu(+), Zn(2+), Cr(3+), Mn(2+), Co(2+), and Ni(2+)), abundant cellular cations (such as Na(+), K(+), Mg(2+), and Ca(2+)), and the prevalent toxic metal ions in the environment (such as Pb(2+) and Cd(2+)) with high sensitivity (detection limit < or =10 ppb) and a rapid response time (< or =1 min). Moreover, by virtue of the chemodosimeter as fluorescent probe for Cu(2+), confocal and two-photon microscopy experiments revealed a significant increase of intracellular Cu(2+) concentration and the subcellular distribution of Cu(2+), which was internalized into the living HeLa cells upon incubation in growth medium supplemented with 50 muM CuCl(2) for 20 h.

Jia Xu

Papers

Highly sensitive and fast responsive fluorescence turn-on chemodosimeter for Cu2+ and its application in live cell imaging.

Modulation of the photochromic property in an organoboron-based diarylethene by a fluoride ion.

A highly selective ratiometric chemosensor for Hg2+ based on the anthraquinone derivative with urea groups