Aggregation of two different sizes of semiconductor quantum dots is successfully applied to a novel ratiometric fluorescent sensor, in which Förster type energy transfer between quantum dots is induced by the interaction with 2,4,6-trinitrotoluene (TNT) as a binder of quantum dots. The detection limit for TNT achieved is 5 pM, and the system shows relatively high sensitivity against TNT in comparison to 2,4-dinitrotoluene and 2-nitrotoluene at 5 pM500 nM range.Nanoparticles designed for semiconductors and metals are gathering a great deal of interests because of their fascinating nature characterized by quantum confinement of electrons or surface plasmon oscillation.1 In particular, assemblies of nanoparticles are expected to be novel versatile tools in various fields including sensors, optoelectronics, and catalysts.2 As a unique sensing application, Mirkin et al. employed aggregation of gold nanoparticles featuring a change in the color from surface plasmon resonance and succeeded in detection of hybridization with DNA.3 However, aggregation of semiconductor quantum dots (QDs) has scarcely been applied for detecting analytes.QDs are promising nanomaterials with characteristic emission depending on the particle size; the smaller the size is, the shorter the wavelength emission becomes. Recently, a few fundamental research papers about energy transfer between QDs appeared, which demonstrated that when the sizes are different, the energy of excited small QDs is transmitted to large QDs with lower exciton energy. 4 It thus occurred to us that aggregationinduced energy transfer between size-different QDs can be utilized for detection of organic analytes that feature ³³, donoracceptor, and hydrogen-bonding interactions. Another interesting characteristic of QDs is that size-different QDs can be excited concurrently at a single wavelength band expanding from ultraviolet to visible wavelengths. These advantages will enable us to apply QDs to a ratiometric fluorescent detection method that utilizes the fluorescence intensity ratio of two emission bands. Conventional detection methods using a single wavelength emission band are prone to cause errors of detected signals, especially in weak signal response. In the ratiometric sensing, on the other hand, emission spectra are changed by added analytes and allow us to achieve not only accuracy enhancement but also visually detectable response.
5As a detection target we chose an explosive compound. Detecting explosives like 2,4,6-trinitrotoluene (TNT) is an important public safety issue. In particular, sensitive detection of trace analytes is of great important. So far, several TNT sensors have been fabricated on the basis of fluorescence, colorimetric, and electrochemical techniques. 6,7 As examples of fluorescence systems, small molecule fluorophores, 6 conjugated polymers, 6,8 and semiconductor quantum dots (QDs) 9 have been used as reporter materials, but examples using QDs are limited either to fluorescence quenching or recovery sensors or to Förster resonance energy-...