RESUMO
Recently there has been growing interest in the role of coherence in electronic dynamics. Coherent multidimensional spectroscopy has been used to reveal coherent phenomena in numerous material systems. Here we utilize a recent implementation of coherent multidimensional spectroscopy--two-dimensional photocurrent spectroscopy--in which we detect the photocurrent from a PbS quantum dot photocell resulting from its interactions with a sequence of four ultrafast laser pulses. We observe sub-picosecond evolution of two-dimensional spectra consistent with multiple exciton generation. Moreover, a comparison with two-dimensional fluorescence spectra of the quantum dots demonstrates the potential of two-dimensional photocurrent spectroscopy to elucidate detailed origins of photocurrent generating electronic state coherence pathways. Since the measurement is based on detecting the photocell current in situ, the method is well suited to study the fundamental ultrafast processes that affect the function of the device. This opens new avenues to investigate and implement coherent optimization strategies directly within devices.
RESUMO
As the number of nanoparticle-based products increase in the marketplace, there will be increased potential for human exposures to these engineered materials throughout the product life cycle. We currently lack sufficient data to understand or predict the inherent nanomaterial characteristics that drive nanomaterial-biological interactions and responses. In this study, we utilized the embryonic zebrafish (Danio rerio) model to investigate the importance of nanoparticle (NP) surface functionalization, in particular as it pertains to nanoparticle stability, on in vivo biological responses. This is a comparative study where two lead sulfide nanoparticles (PbS-NPs) with nearly identical core sizes, but functionalized with either sodium 3-mercaptopropanesulfonate (MT) or sodium 2,3-dimercaptopropanesulfonate (DT) ligand, were used. Developmental exposures and assessments revealed differential biological responses to these engineered nanoparticles. Exposures beginning at 6 h post fertilization (hpf) to MT-functionalized nanoparticles (PbS-MT) led to 100% mortality by 120 hpf while exposure to DT-functionalized nanoparticles (PbS-DT) produced less than a 5% incident in mortality at the same concentration. Exposure to the MT and DT ligands themselves did not produce adverse developmental effects when not coupled to the NP core. Following exposure, we confirmed that the embryos took up both PbS-MT and PbS-DT material using inductively coupled plasma-mass spectrometry (ICP-MS). The stability of the nanoparticles in the aqueous solution was also characterized. The nanoparticles decompose and precipitate upon exposure to air. Soluble lead ions were observed following nanoparticle precipitation and in greater concentration for the PbS-MT sample compared to the PbS-DT sample. These studies demonstrate that in vivo assessments can be effectively used to characterize the role of NP surface functionalization in predicting biological responses.
