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We describe the first determination of thiol compounds with gold nanocomposites composed of gold nanoparticles and thermoresponsive copolymers having polyamino groups. The gold nanocomposites, which are used as a chromatic sensor, reveal chromatic change from blue to red with thermal stimuli, heating followed by cooling the solution. The blue-to-red chromatic change results from disassembly of the gold nanocomposites, which arises from shrinkage of the thermoresponsive copolymers bound to the gold nanoparticle surfaces due to the phase transition induced by thermal stimuli. The disassembly is inhibited by addition of thiol compounds through displacement of the adhered thermoresponsive copolymers. The detached copolymers no longer influence morphological change of the gold nanocomposites. Corresponding with increase of concentration of the thiol compounds, a solution of the gold nanocomposites after the thermal stimuli shows chromatic change, which was quantified with the a* value in L*a*b* chromatic coordinates. A linear relationship between the a* value and concentration of cysteine, examined as a bio-important thiol, is obtained below 7x10(-6) mol dm(-3), estimating a detection limit defined as 3sigma of the blank to be 2.8x10(-7) mol dm(-3). The chromatic sensor of the gold nanocomposites is applied to the determination of cysteine in commercial supplements containing ascorbic acid, which seriously interferes with redox-based determination of cysteine. Analytical results obtained with the chromatic sensor are identical to those obtained with HPLC.

This article describes the glutathione-triggered disassembly of gold nanocomposites composed of gold cores and water-soluble copolymers [poly(N-n-isopropylacrylamide-co-acryloyldiethyletriamine)] attached to the surfaces of gold cores. The gold nanocomposites exhibit a bluish purple color because of the assembled gold cores that are conjugated with the diethylenetriamine groups incorporated into the copolymers. Glutathione added to the gold nanocomposite solution adsorbs onto the surface of the gold cores to liberate diethylenetriamine groups, resulting in spontaneous disassembly that changes the color of the solution to a reddish shade. Increasing the glutathione concentration facilitates the spontaneous disassembly of the gold nanocomposites. For the determination of glutathione, the colorimetric change of the gold nanoparticles is quantified with the a* value of the L*a*b* color coordinates defined by the CIE (Commission Internationale de l'Eclairage) chromaticity diagram. A linear relationship between the a* value and the glutathione concentration of up to 6 x 10(-6) mol/L is obtained 15 min after the addition of glutathione that has a detection limit (defined as 3sigma) of 2.9 x 10(-8) mol/L. The colorimetric assay is successfully applied to the determination of glutathione in eye drops and health supplements.

In this brief review, gold nanoparticles conjugated with functional polymers are described from the viewpoint of application to sensing materials. The optical properties of gold nanoparticles, the synthesis of polymer-functionalized gold nanoparticles, and their analytical applications are discussed. Polymer-functionalized gold nanoparticles are categorized into two classes: biopolymer-conjugated gold nanoparticles and artificial-polymer conjugated gold nanoparticles. Fluorometric and colorimetric sensing using gold nanoparticles are focused; fluorometric detection enables us to exploit sensitive assays for practical use. Furthermore, chemical amplification using gold nanoparticles is also discussed for the sensitive probing.

The growth kinetics of gold nanoparticles induced by the conformational collapse resulting from the coil−globule transition of thermoresponsive polymer was studied using small-angle X-ray scattering (SAXS) method. The growth process of aggregates and nanoparticles formed during the reaction was determined on the basis of distance distribution functions calculated from the SAXS profiles without having to approximate or simplify the actual structures. The size of aggregates and nanoparticles reached a maximum not in the final stage of the reaction but in the middle stage, indicating that shrinkage of the particles occurred in the growth process. The surface roughness increased up to the middle stage of the reaction and then significantly decreased in the final stage. Furthermore, the dependence of polymer concentration was also investigated. It was found that small particles were generated prior to the formation of main products, and size of the small particles was estimated to be ca. 7 nm in diameter. The results reveal that the formation process progresses mainly based on fusion of the small particles induced by the structural collapse of polymer. Finally, the growth mechanism is discussed in detail.

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