We demonstrate using single molecule spectroscopy that inorganic CsPbI3 perovskite quantum dots (PQDs) undergo an irreversible, photoaccelerated reaction with water that results in a blue-shift of the photoluminescence (PL) and ultimately to complete quenching of the emission. We find that decomposition does not take place in the presence of oxygen alone but that it requires light and water. We also analyze the blinking for some stable PQDs and find a continuous distribution of emission states with a linear correlation between intensity and lifetime. We postulate that, in addition to charging and discharging processes, blinking arises from the activation and deactivation of nonradiative recombination centers in the PQDs.

Selectivity and enhanced sensitivity for SERS measurements are highly desirable for environmental and analytical applications. Interaction of a target molecule with SERS substrate plays a pivotal role in determining the magnitude of enhancement and spectral profile of the SERS signal. A reduced graphene oxide−Ag nanoparticle (RGO-Ag NP) composite has been designed to boost SERRS sensitivity of a porphyrin derivative. Complexation between 5,10,15,20-tetrakis(1-methyl-4-pyridinio)porphyrin tetra(p-toluenesulfonate) (TMPyP) porphyrin and the RGO-Ag NP composite is evidenced by a red-shifted porphyrin absorption band. Results indicate complexation is influential in improved surfaceenhanced resonance Raman (SERRS) signal for TMPyP and thus offers an advantage for target molecule detection at low concentration levels. The combined effects of RGO and Ag NPs in the enhancement of SERS signal of TMPyP are discussed.

Highly photoactive porphyrin is shown to form charge-transfer complex with silver nanoparticles. Complexation of tetra(4-aminophenyl) porphyrin (TAPP) with Ag nanoparticles is confirmed by ground-state absorption and Raman spectroscopy. Strong Raman enhancement indicates both electromagnetic and chemical enhancement. Evidence of chemical enhancement includes a selective enhancement of porphyrin Raman bands. Fast charge separation in the complex is indicated by ultrafast transient absorption and fluorescence upconversion measurements. The charge-separated state is shown to have a lifetime of 116 ± 6 ps. Porphyrin substituents are shown to play a role in the formation of charge-transfer complex.

Single- to few-layer graphene oxide (GO) sheets have been successfully anchored onto TiO2 films using electrophoretic deposition. Upon UV illumination of TiO2-GO films, photogenerated electrons from TiO2 are captured by GO. These electrons are initially used in GO's reduction, while additional electron transfer results in storage across its sp(2) network. In the presence of silver ions, deposition of silver nanoparticles (NPs) is accomplished on the GO surface opposite the TiO2, thus confirming the ability of GO to transport electrons through its plane. Illumination-controlled reduction of silver ions allows for simple selection of particle size and loading, making these semiconductor-graphene-metal (SGM) films ideal for custom catalysis and sensor applications. Initial testing of SGM films as surface-enhanced resonance Raman (SERRS) sensors produced significant target molecule signal enhancements, enabling detection of nanomolar concentrations.

Hydrophobic forces play a key role in the processes of collapse and reswelling of thermoresponsive polymers. However, little is known about the dynamics of these processes. Here, thermoresponsive poly(N-isopropylacrylamide)-encapsulated gold nanoparticles (Au-PNIPAM) are heated via nanosecond laser flash photolysis. Photothermal heating via excitation of the localized surface plasmon resonance of the Au nanoparticle cores results in rapid PNIPAM shell collapse within the 10 ns pulse width of the laser. Remarkably, reswelling of the polymer shell takes place in less than 100 ns. A clear pump fluence threshold for the collapse of the PNIPAM shell is demonstrated, below which collapse is not observed. Reswelling takes longer at higher laser intensities.