A single chemosensor for multiple analytes: fluorogenic and ratiometric absorbance detection of Zn²⁺, Mg²⁺ and F⁻, and its cell imaging

A simple coumarin based sensor 1 has been synthesized from the condensation reaction of 7-hydroxycoumarin and ethylenediamine via the intermediate 7-hydroxy-8-aldehyde-coumarin. As a multiple analysis sensor, 1 can monitor Zn²⁺ with the fluorescence enhanced at 457 nm, and ratiometric detection at 290 nm, 350 nm and 420 nm in DMF/H₂O (1/4, v/v) medium. Sensor 1 can also monitor Mg²⁺ with the fluorescence enhanced at 430 nm, and ratiometric detection at 290 nm, 370 nm and 430 nm in DMF medium through the interaction of chelation enhance fluorescence (CHEF) with metal ions. Furthermore, 1 also can monitor F⁻ with the fluorescence enhanced at 460 nm, and ratiometric detection at 290 nm and 390 nm in DMF medium simultaneously via hydrogen bonding and deprotonation with F− anion. Spectral titration, isothermal titration calorimetry and mass spectrometry revealed that the sensor formed a 1:1 complex with Mg²⁺, Zn²⁺ or F⁻, with stability constants of 4.5 × 10⁶, 3.4 × 10⁶, 8.0 × 10⁴ M⁻1 respectively. The complexation of the ions by 1 was an exothermic reaction driven by entropy processes. Furthermore, the sensor exhibits good membrane-permeability and was capable of monitoring at the intracellular Zn²⁺ level in living cells

Visualizing metal ions in cells: An overview of analytical techniques, approaches, and probes

AbstractQuantifying the amount and defining the location of metal ions in cells and organisms are critical steps in understanding metal homeostasis and how dyshomeostasis causes or is a consequence of disease. A number of recent advances have been made in the development and application of analytical methods to visualize metal ions in biological specimens. Here, we briefly summarize these advances before focusing in more depth on probes for examining transition metals in living cells with high spatial and temporal resolution using fluorescence microscopy. This article is part of a Special Issue entitled: Cell Biology of Metals

Imaging mobile zinc in biology

Trafficking and regulation of mobile zinc pools influence cellular functions and pathological conditions in multiple organs, including brain, pancreas, and prostate. The quest for a dynamic description of zinc distribution and mobilization in live cells fuels the development of increasingly sophisticated probes. Detection systems that respond to zinc binding with changes of their fluorescence emission properties have provided sensitive tools for mobile zinc imaging, and fluorescence microscopy experiments have afforded depictions of zinc distribution within live cells and tissues. Both small-molecule and protein-based fluorescent probes can address complex imaging challenges, such as analyte quantification, site-specific sensor localization, and real-time detection.National Institute of General Medical Sciences (U.S.) (grant GM065519

Biochemistry of mobile zinc and nitric oxide revealed by fluorescent sensors

Biological mobile zinc and nitric oxide (NO) are two prominent examples of inorganic compounds involved in numerous signaling pathways in living systems. In the past decade, a synergy of regulation, signaling, and translocation of these two species has emerged in several areas of human physiology, providing additional incentive for developing adequate detection systems for Zn(II) ions and NO in biological specimens. Fluorescent probes for both of these bioinorganic analytes provide excellent tools for their detection, with high spatial and temporal resolution. We review the most widely used fluorescent sensors for biological zinc and nitric oxide, together with promising new developments and unmet needs of contemporary Zn(II) and NO biological imaging. The interplay between zinc and nitric oxide in the nervous, cardiovascular, and immune systems is highlighted to illustrate the contributions of selective fluorescent probes to the study of these two important bioinorganic analytes.National Science Foundation (Grant Number CHE-0907905)National Institutes of Health (U.S.) (Grant Number GM065519)National Institutes of Health (U.S.) (Grant Number K99GM092970

Supramolecular Luminescent Sensors

There is great need for stand-alone luminescence-based chemosensors that exemplify selectivity, sensitivity, and applicability and that overcome the challenges that arise from complex, real-world media. Discussed herein are recent developments toward these goals in the field of supramolecular luminescent chemosensors, including macrocycles, polymers, and nanomaterials. Specific focus is placed on the development of new macrocycle hosts since 2010, coupled with considerations of the underlying principles of supramolecular chemistry as well as analytes of interest and common luminophores. State-of-the-art developments in the fields of polymer and nanomaterial sensors are also examined, and some remaining unsolved challenges in the area of chemosensors are discussed

Optical nanoparticle sensors for quantitative intracellular imaging

Real-time measurements of biological/chemical/physical processes, with no interferences, are an ultimate goal for in vivo intracellular studies. To construct intracellular biosensors that meet such a goal, nanoparticle (NP) platforms seem to be most promising, because of their small size and excellent engineerability. This review describes the development of NP-based opical sensors and their intracellular applications. The sensor designs are classified into two types, based on the sensor structures regarding analyte receptor and signal transducer. Type 1 sensors, with a single component for both receptor and transducer, work by mechanisms similar to those of ‘molecular probes’. Type 2 sensors, with a separate component for receptor and transducer, work by different mechanisms that require the presence of specific NPs. A synergistic increase in optical signal or selectivity has been reported for these second type of NP sensors. With ongoing rapid advances in nanotechnology and instrumentation, these NP systems will soon be capable of sensing at the single-molecule level, at the point of interest within the living cell, and capable of simultaneously detecting multiple analytes and physical parameters. Copyright © 2008 John Wiley & Sons, Inc.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/61310/1/2_ftp.pd