This study describes the modulation of interparticle distances in aggregates of gold nanoparticles by light irradiation. Stable aggregates of a series of imidazolium-presenting gold nanoparticles were obtained via a photo-responsive mono-carboxylate linker. In the first step, the mono-carboxylate linker attracted the gold nanoparticles to form water-dispersive aggregates of gold nanoparticles with hydrophobic surface properties. By irradiating the aggregates with ultraviolet, the photo-responsive linker was transformed, leading to the generation of another carboxyl group. As a result, the gold nanoparticles were tightly bound via the dicarboxylate linkers. These changes decreased the interparticle distances in the aggregates, as verified by microscopic observations, and can induce significant changes in their optical characteristics. To the best of our knowledge, this is the first example of a light-driven manipulation system for the distribution of nanoparticles in an aggregate.
INTRODUCTIONThe physical properties of metal nanoparticles strongly depend on their assembled states. It is known that an assembly of gold nanoparticles has different light-absorption properties to that of single particles. 1,2 Based on this phenomenon, a wide variety of biomedical applications has been accomplished. 3,4 In addition, by manipulating the hybridization process involved in anchoring DNA to the surface of particles, cluster formation and morphology can be precisely controlled. 5-7 These manipulation methods for the nanoparticle assembly are versatile and can be used to construct biosensors with good response to stimuli. 8,9 Furthermore, additional functions have been derived from the specific distribution of nanoparticles in an assembly. For instance, a class of unique optical functional materials involving metamaterials has been manufactured with a well-ordered assembly of gold nanoparticles. 10-13 Therefore, precisely controlling the morphology and relative positions of nanoparticles in an assembly is critically important to obtain superior or unexpected functions. [14][15][16][17][18][19][20] Structural manipulation with light has various advantages. A rapid, time-sensitive, and site-sensitive response can be achieved without additives. In previous reports, the photoisomerizations of azobenzene 21-26 and stilbene derivatives 27-29 tethered to the surface of nanoparticles have been investigated. Based on the structural changes triggered by the light irradiation, the dispersion states were controlled. The aggregation/dispersion of gold nanoparticles can also be modulated reversibly by the photo-triggered dimerization of thymine and the splitting of the thymine dimer. 30 Although the formation of aggregates can be controlled with various methods, as mentioned here, modulating the morphology of the aggregates is less well established.