Temperature-dependent structural change of D-penicillamine-capped chiral gold nanoparticles investigated by infrared spectroscopy.

The structure and stability of D-penicillamine-capped gold nanoparticles (d-Pen Au NPs) were studied using spectroscopic tools. The synthesis of d-Pen Au NPs was examined using high-resolution transmission electron microscopy (HR-TEM), UV-vis absorption spectroscopy, and circular dichroism (CD). Temperature-dependent reversible structural changes of d-Pen Au NPs were observed using infrared spectroscopic tools. The three thiol, carboxyl, and amino binding groups of d-Pen were presumed to interact with Au NP surfaces on the basis of the infrared spectral features. d-Pen appeared to form quite a stable structure and desorb at a high temperature above 453 K on Au NPs. Our deconvolution analysis indicated the ν(s)(COO(-)) and ν(as)(COO(-)) carboxylate bands at ∼1,392 and ∼1,560 cm(-1) appeared to be weakened, whereas the amino band at ∼1,595 cm(-1) remained strong in increasing the temperature from 293 to 373 K. On the other hand, the intensities of the zwitter ionic bands at ∼999, ∼1,117, and ∼1,631 cm(-1) for NH(3)(+) appeared to decrease presumably due to the deprotonation process at 373 K. Our infrared spectroscopic study suggests that the deprotonated amino groups bind stronger, whereas the intra-carboxylate bonds become weaker as the temperature increase. Such structural changes of d-Pen Au NPs appeared to be reversible between 293 and 373 K.