The effect of Cu(I)-doping on the photoinduced electron transfer from aqueous CdS quantum dots.

The doping of CdS quantum dots (QDs) with Cu(I) disrupts electron-hole correlation due to hole trapping by the dopant ion, post-photoexcitation. The present paper examines the effect of such disruption on the rate of photoinduced electron transfer (PET) from the QDs to methyl viologen (MV2+), with implications in their photocatalytic activity. A significantly greater efficiency of PL quenching by MV2+ is observed for the doped QDs than for the undoped ones. Interestingly, the Stern-Volmer plots constructed using PL intensities exhibit an upward curvature for both the cases, while the PL lifetimes remain unaffected. This observation is rationalized by considering the adsorption of the quencher on the surface of the QDs and ultrafast PET post-photoexcitation. Ultrafast transient absorption experiments confirm a faster electron transfer for the doped QDs. It is also realized that the transient absorption experiment yields a more accurate estimate of the binding constant of the quencher with the QDs, than the PL experiment.

Role of Solvent in Electron-Phonon Relaxation Dynamics in Core-Shell Au-SiO2 Nanoparticles.

Relaxation dynamics of plasmons in Au-SiO2 core-shell nanoparticles have been followed by femtosecond pump-probe technique. The effect of excitation pump energy and surrounding medium on the time constants associated with the hot electron relaxation has been elucidated. A gradual increase in the electron-phonon relaxation time with pump energy is observed and can be attributed to the higher perturbation of the electron distribution in AuNPs at higher pump energy. Variation in time constants for the electron-phonon relaxation in different solvents is rationalized on the basis of their thermal conductivities, which govern the rate of dissipation of heat of photoexcited electrons in the nanoparticles. On the other hand, phonon-phonon relaxation is found to be much less effective than electron-phonon relaxation for the dissipation of energy of the excited electron and the time constants associated with it remain unaffected by thermal conductivity of the solvent.

Design and Expeditious Synthesis of Quinoline-Pyrene-Based Ratiometric Fluorescent Probes for Targeting Lysosomal pH.

Intracellular pH plays a significant role in many pathological and physiological processes. A series of quinoline-pyrene probes were synthesized in one-step fashion through an oxonium-ion-triggered alkyne carboamination sequence involving C-C, C-O and C-N bond formation for intracellular pH sensing. The quinoline-pyrenes showed significant red shifts at low pH. Fluorescence lifetime decay measurements of the probes showed decreases in lifetime at pH 4. The probes showed excellent selectivity in the presence of various potential interfering agents such as amino acids and cations/anions. Furthermore, the probes were found to show completely reversible emission behaviour in the window between pH 4 and 7. A morpholine-substituted quinoline-pyrene probe efficiently stained lysosomes with high Pearson correlation coefficients (0.86) with Lysotracker Deep Red DND-99 as a reference. A co-localization study of the probe with Lysotracker DND-99 showed selective intracellular targeting and a shift in fluorescence emission due to acidic lysosomal pH.

Enhancement of the band edge emission of CdSe nano-tetrapods by suppression of surface trapping.

Preparation of CdSe nano-tetrapods in a controlled environment, using a glove box for the preparation of the Se precursor, was found to eliminate radiative surface trap emission to a large extent. This manifested in an increase in the band edge photoluminescence quantum yield by a factor of 20 and a concomitant decrease in the surface trap emission by a factor of 8. Interestingly, the time for recovery of ground state bleaching was more or less the same in the two kinds of nano-tetrapods, even though the photoluminescence dynamics are significantly slower in the more emissive ones. In single emissive nano-tetrapods, the kinetic traces for ground state bleaching recovery became gradually faster upon increasing the pump power. This is likely to be due to the effect of multiexciton relaxation and nonradiative Auger recombination.

Single particle level dynamics of photoactivation and suppression of Auger recombination in aqueous Cu-doped CdS quantum dots.

Cu-doped CdS quantum dots (QDs) have been synthesized in water using 3-mercaptopropionic acid (3-MPA) as the capping agent. They exhibit intense photoluminescence and excellent color tunability, unlike most of the QDs synthesized/dispersed in water so far. Complete characterization of these aqueous doped CdS QDs has been performed for the first time, along with a single particle level elucidation of their exciton dynamics using fluorescence correlation spectroscopy. Photoactivation via dim/dark to bright particle conversion is observed at higher excitation powers. Dispersive blinking kinetics in undoped QDs reflects the involvement of a broad distribution of trap states. A lesser extent of dispersity is observed for doped QDs, in which hole-capture by Cu-defect states predominates. Excitation fluence dependence of the blinking rate highlights the role of Auger recombination in undoped QDs, which is suppressed significantly upon doping, due to disruption of the electron-hole correlation.

Intense photoluminescence from Cu-doped CdSe nanotetrapods triggered by ultrafast hole capture.

Brightly photoluminescent Cu-doped CdSe nanotetrapods (NTPs) have been prepared by a modified hot injection method. Their photoluminescence (PL) has a quantum yield of 38% and decays slowly over a few microseconds, while the PL in undoped NTPs has a rather small quantum yield of 1.7% and decays predominantly in tens of picoseconds, with a minor component in the nanosecond time regime. PL spectra of doped NTPs are significantly Stokes shifted compared to the band edge (BE). Efficient PL quenching by a hole scavenger confirms the oxidation state of +I for the dopant ion and establishes hole capture by this ion to be the primary event that leads to the Stokes shifted PL. A fast decay of the photoinduced absorption band, along with a similar decay in PL, observed in a femtosecond optical gating experiment, yields a time constant of about a picosecond for the hole capture from the valence band (VB) by Cu+. The remarkably long PL lifetime in the doped NTPs is ascribed to the decrease in the overlap between the wavefunctions of the photogenerated electrons and the captured hole. Hot carrier relaxation processes, triggered by excitation at energies greater than the band gap, leave their signature in a rise time of few hundreds of femtoseconds, in the ground state bleach recovery kinetics. Hence, a complete picture of exciton dynamics in the doped NTPs has been obtained using ultrafast spectroscopic techniques working in tandem.