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Principles Of Fluorescence Spectroscopy

Switches, and Actuators Masahiro Irie,*,† Tuyoshi Fukaminato,‡ Kenji Matsuda, and Seiya Kobatake †Research Center for Smart Molecules, Rikkyo University, Nishi-Ikebukuro 3-34-1, Toshima-ku, Tokyo 171-8501, Japan ‡Research Institute for Electronic Science, Hokkaido University, N20, W10, Kita-ku, Sapporo 001-0020, Japan Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510, Japan Department of Applied Chemistry, Graduate School of Engineering, Osaka City University, Sugimoto 3-3-138, Sumiyoshi-ku, Osaka 558-8585, Japan

Photochromism of Diarylethene Molecules and Crystals: Memories, Switches, and Actuators

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

Because of its fundamental importance in many branches of science, hydrogen bonding is a subject of intense contemporary research interest. The physical and chemical properties of hydrogen bonds in the ground state have been widely studied both experimentally and theoretically by chemists, physicists, and biologists. However, hydrogen bonding in the electronic excited state, which plays an important role in many photophysical processes and photochemical reactions, has scarcely been investigated.Upon electronic excitation of hydrogen-bonded systems by light, the hydrogen donor and acceptor molecules must reorganize in the electronic excited state because of the significant charge distribution difference between the different electronic states. The electronic excited-state hydrogen-bonding dynamics, which are predominantly determined by the vibrational motions of the hydrogen donor and acceptor groups, generally occur on ultrafast time scales of hundreds of femtoseconds. As a result, state-of-the-art femtos...

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Hydrogen Bonding in the Electronic Excited State

Detection Ying Zhou,†,‡ Jun Feng Zhang, and Juyoung Yoon*,† †Department of Chemistry and Nano Science, Ewha Womans University, Seoul 120-750, Korea ‡Key Laboratory of Medicinal Chemistry for Natural Resource, School of Chemical Science and Technology, Yunnan University, Kunming, 650091, P. R. China College of Chemistry and Chemical Engineering, Yunnan Normal University, Kunming 650500, P. R. China

Fluorescence and colorimetric chemosensors for fluoride-ion detection.

Synthesis, structures and fluorescence of nickel, zinc and cadmium complexes with the N,N,O-tridentate Schiff base N-2-pyridylmethylidene-2-hydroxy-phenylamine

Interaction of 3-acetyl-4-oxo-6,7-dihydro-12H indolo-[2,3-a] quinolizine (AODIQ), a biologically active molecule, with model transport proteins, bovine serum albumin (BSA) and human serum albumin (HSA) have been studied using steady state and picosecond time-resolved fluorescence and fluorescence anisotropy. The polarity dependent intramolecular charge transfer (ICT) process is responsible for the remarkable sensitivity of this biological fluorophore to the protein environments. The CT fluorescence exhibits appreciable hypsochromic shift along with an enhancement in the fluorescence yield, fluorescence anisotropy (r) and fluorescence lifetime upon binding with the proteins. The reduction in the rate of ICT within the hydrophobic interior of albumins leads to an increase in the fluorescence yield and lifetime. Marked increase in the fluorescence anisotropy indicates that the probe molecule is located in a motionally constrained environment within the proteins. Micropolarities in the two proteinous environments have been determined following the polarity sensitivity of the CT emission. Addition of urea to the protein-bound systems leads to a reduction in the fluorescence anisotropy indicating the denaturation of the proteins. Polarity measurements and fluorescence resonance energy transfer (FRET) studies throw light in assessing the location of the fluorophore within the two proteinous media.

Spectroscopic investigation on the interaction of ICT probe 3-acetyl-4-oxo-6,7-dihydro-12H Indolo-[2,3-a] quinolizine with serum albumins.

Binding interaction of a biological photosensitizer with serum albumins : A biophysical study

Tuning of the sensory capability of a potentially bioactive indoloquinolizine system, namely, 3-acetyl-4-oxo-6,7-dihydro-12H-indolo-[2,3-a]-quinolizine (AODIQ), is described in a biomimicking micellar nanocage. It has been shown that surfactant concentration dictates the sensing behavior of the fluorophore toward physiologically essential trace metals, such as Cu2+. This is a simple, efficient, and general technique that allows one to utilize the sensor to its maximum efficiency.

Surfactant-induced modulation of fluorosensor activity: a simple way to maximize the sensor efficiency.

The title compound, a new coumarin based fluorophore having a piperazine moiety as the photoinduced electron transfer (PET) switch was prepared and its photophysical properties studied in various solvents and under different pH. Solvatochromic shift in the fluorescence spectrum revealed an increase in the dipole moment in the lowest excited singlet state compared to that in the ground state. The compound also showed an interesting intramolecular photoinduced proton transfer phenomenon in the excited state under neutral pH. It was effectively utilized as a new Chelation-enhanced fluorescence (CHEF) based chemosensor for zinc and nickel ions in water.

Photophysical studies of 7-hydroxy-4-methyl-8-(4′-methylpiperazin-1′-yl) methylcoumarin: A new fluorescent chemosensor for zinc and nickel ions in water

Arabinda Mallick

Papers

Synthesis, structures and fluorescence of nickel, zinc and cadmium complexes with the N,N,O-tridentate Schiff base N-2-pyridylmethylidene-2-hydroxy-phenylamine

Spectroscopic investigation on the interaction of ICT probe 3-acetyl-4-oxo-6,7-dihydro-12H Indolo-[2,3-a] quinolizine with serum albumins.

Binding interaction of a biological photosensitizer with serum albumins : A biophysical study

Surfactant-induced modulation of fluorosensor activity: a simple way to maximize the sensor efficiency.

Photophysical studies of 7-hydroxy-4-methyl-8-(4′-methylpiperazin-1′-yl) methylcoumarin: A new fluorescent chemosensor for zinc and nickel ions in water