ABSTRACT
The biological effects of terahertz (THz) radiation have been observed across multiple levels of biological organization, however the sub-cellular mechanisms underlying the phenotypic changes remain to be elucidated. Filamentous protein complexes such as microtubules are essential cytoskeletal structures that regulate diverse biological functions, and these may be an important target for THz interactions underlying THz-induced effects observed at the cellular or tissue level. Here, we show disassembly of microtubules within minutes of exposure to extended trains of intense, picosecond-duration THz pulses. Further, the rate of disassembly depends on THz intensity and spectral content. As inhibition of microtubule dynamics is a mechanism of clinically-utilized anti-cancer agents, disruption of microtubule networks may indicate a potential therapeutic mechanism of intense THz pulses.
ABSTRACT
We present a potential solution to the problem of extraction of photogenerated holes from CdS nanocrystals and nanowires. The nanosheet form of C3N5 is a low-band-gap (Eg = 2.03 eV), azo-linked graphenic carbon nitride framework formed by the polymerization of melem hydrazine (MHP). C3N5 nanosheets were either wrapped around CdS nanorods (NRs) following the synthesis of pristine chalcogenide or intercalated among them by an in situ synthesis protocol to form two kinds of heterostructures, CdS-MHP and CdS-MHPINS, respectively. CdS-MHP improved the photocatalytic degradation rate of 4-nitrophenol by nearly an order of magnitude in comparison to bare CdS NRs. CdS-MHP also enhanced the sunlight-driven photocatalytic activity of bare CdS NWs for the decolorization of rhodamine B (RhB) by a remarkable 300% through the improved extraction and utilization of photogenerated holes due to surface passivation. More interestingly, CdS-MHP provided reaction pathway control over RhB degradation. In the absence of scavengers, CdS-MHP degraded RhB through the N-deethylation pathway. When either hole scavenger or electron scavenger was added to the RhB solution, the photocatalytic activity of CdS-MHP remained mostly unchanged, while the degradation mechanism shifted to the chromophore cleavage (cycloreversion) pathway. We investigated the optoelectronic properties of CdS-C3N5 heterojunctions using density functional theory (DFT) simulations, finite difference time domain (FDTD) simulations, time-resolved terahertz spectroscopy (TRTS), and photoconductivity measurements. TRTS indicated high carrier mobilities >450 cm2 V-1 s-1 and carrier relaxation times >60 ps for CdS-MHP, while CdS-MHPINS exhibited much lower mobilities <150 cm2 V-1 s-1 and short carrier relaxation times <20 ps. Hysteresis in the photoconductive J-V characteristics of CdS NWs disappeared in CdS-MHP, confirming surface passivation. Dispersion-corrected DFT simulations indicated a delocalized HOMO and a LUMO localized on C3N5 in CdS-MHP. C3N5, with its extended π-conjugation and low band gap, can function as a shuttle to extract carriers and excitons in nanostructured heterojunctions, and enhance performance in optoelectronic devices. Our results demonstrate how carrier dynamics in core-shell heterostructures can be manipulated to achieve control over the reaction mechanism in photocatalysis.
ABSTRACT
Tin iodide phosphide (SnIP), an inorganic double-helix material, is a quasi-1D van der Waals semiconductor that shows promise in photocatalysis and flexible electronics. However, the understanding of the fundamental photophysics and charge transport dynamics of this new material is limited. Here, time-resolved terahertz (THz) spectroscopy is used to probe the transient photoconductivity of SnIP nanowire films and measure the carrier mobility. With insight into the highly anisotropic electronic structure from quantum chemical calculations, an electron mobility as high as 280 cm2 V-1 s-1 along the double-helix axis and a hole mobility of 238 cm2 V-1 s-1 perpendicular to the double-helix axis are detected. Additionally, infrared-active (IR-active) THz vibrational modes are measured, which shows excellent agreement with first-principles calculations, and an ultrafast photoexcitation-induced charge redistribution is observed that reduces the amplitude of a twisting mode of the outer SnI helix on picosecond timescales. Finally, it is shown that the carrier lifetime and mobility are limited by a trap density greater than 1018 cm-3 . The results provide insight into the optical excitation and relaxation pathways of SnIP and demonstrate a remarkably high carrier mobility for such a soft and flexible material, suggesting that it could be ideally suited for flexible electronics applications.
