Disassembly of microtubules by intense terahertz pulses.

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.

Photocatalytic Mechanism Control and Study of Carrier Dynamics in CdS@C3N5 Core-Shell Nanowires.

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.

Ultrafast Photoconductivity and Terahertz Vibrational Dynamics in Double-Helix SnIP Nanowires.

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.

Terahertz Excitonics in Carbon Nanotubes: Exciton Autoionization and Multiplication.

Excitons play major roles in optical processes in modern semiconductors, such as single-wall carbon nanotubes (CNTs), transition metal dichalcogenides, and 2D perovskite quantum wells. They possess extremely large binding energies (>100 meV), dominating absorption and emission spectra even at high temperatures. The large binding energies imply that they are stable, that is, hard to ionize, rendering them seemingly unsuited for optoelectronic devices that require mobile charge carriers, especially terahertz emitters and solar cells. Here, we have conducted terahertz emission and photocurrent studies on films of aligned single-chirality semiconducting CNTs and find that excitons autoionize, i.e., spontaneously dissociate into electrons and holes. This process naturally occurs ultrafast (<1 ps) while conserving energy and momentum. The created carriers can then be accelerated to emit a burst of terahertz radiation when a dc bias is applied, with promising efficiency in comparison to standard GaAs-based emitters. Furthermore, at high bias, the accelerated carriers acquire high enough kinetic energy to create secondary excitons through impact exciton generation, again in a fully energy and momentum conserving fashion. This exciton multiplication process leads to a nonlinear photocurrent increase as a function of bias. Our theoretical simulations based on nonequilibrium Boltzmann transport equations, taking into account all possible scattering pathways and a realistic band structure, reproduce all of our experimental data semiquantitatively. These results not only elucidate the momentum-dependent ultrafast dynamics of excitons and carriers in CNTs but also suggest promising routes toward terahertz excitonics despite the orders-of-magnitude mismatch between the exciton binding energies and the terahertz photon energies.

Dynamical Control over Terahertz Electromagnetic Interference Shielding with 2D Ti3C2Ty MXene by Ultrafast Optical Pulses.

High electrical conductivity and strong absorption of electromagnetic radiation in the terahertz (THz) frequency range by metallic 2D MXene Ti3C2Ty make it a promising material for electromagnetic interference shielding, THz detectors, and transparent conducting electrodes. Here, we demonstrate that ultrafast optical pulses with wavelengths straddling the visible range (400 and 800 nm) induce transient broad-band THz transparency in the MXene that persists for nanoseconds. We demonstrate that optically induced transient THz transparency is independent of temperature from 95 to 290 K. This discovery opens new possibilities for development of switchable electromagnetic interference shielding materials and devices that can be rendered partially transparent on demand for transmitting THz signals, or for designing new THz devices such as sensitive optically gated detectors.

Understanding the Origin of Phosphorescence in Bismoles: A Synthetic and Computational Study.

A series of bismuth heterocycles, termed bismoles, were synthesized via the efficient metallacycle transfer (Bi/Zr exchange) involving readily accessible zirconacycles. The luminescence properties of three structurally distinct bismoles were explored in detail via time-integrated and time-resolved photoluminescence spectroscopy using ultrafast laser excitation. Moreover, time-dependent density functional theory computations were used to interpret the nature of fluorescence versus phosphorescence in these bismuth-containing heterocycles and to guide the future preparation of luminescent materials containing heavy inorganic elements. Specifically, orbital character at bismuth within excited states is an important factor for achieving enhanced spin-orbit coupling and to promote phosphorescence. The low aromaticity of the bismole rings was demonstrated by formation of a CuCl π-complex, and the nature of the alkene-CuCl interaction was probed by real-space bonding indicators derived from Atoms-In-Molecules, the Electron Localizability Indicator, and the Non-Covalent Interaction index; such tools are of great value in interpreting nonstandard bonding environments within inorganic compounds.

Synthesis and Surface Functionalization of Hydride-Terminated Ge Nanocrystals Obtained from the Thermal Treatment of Ge(OH)2.

The synthesis of germanium nanocrystals (GeNCs) with well-defined surface chemistry is of considerable interest because of their potential applications in the optoelectronic, battery, and semiconductor industries. Modifying and tailoring GeNC surface chemistry provides an avenue by which reactivity, environmental compatibility (e.g., solubility, resistance to oxidation), and electronic properties may be tailored. Hydride-terminated GeNCs (H-GeNCs) are of particular interest because the reactivity of surface Ge-H bonds toward alkenes and alkynes via hydrogermylation affords the potential for convenient modification; however, these reactions and their scope have not been widely explored. This report describes a straightforward route for preparing a GeNC/GeO2 composite via disproportionation of heretofore-unexplored Ge(II) oxide-based precursor from which the H-GeNCs were freed by subsequently chemical etching. The H-GeNCs were derivatized using a series of hydrogermylation approaches (i.e., thermally activated, radical-initiated, and borane-catalyzed). The presented findings indicate surface functionalization occurs under all conditions investigated; however the nature of surface species (i.e., monolayers vs multilayers) and surface coverage varies depending upon the conditions employed.

Charge transfer state emission dynamics in blue-emitting functionalized silicon nanocrystals.

We explore the dynamics of blue emission from dodecylamine and ammonia functionalized silicon nanocrystals (Si NCs) with average diameters of ∼3 and ∼6 nm using time-resolved photoluminescence (TRPL) spectroscopy. The Si NCs exhibit nanosecond PL decay dynamics that is independent of NC size and uniform across the emission spectrum. The TRPL measurements reveal complete quenching of core state emission by a charge transfer state that is responsible for the blue PL with a radiative recombination rate of ∼5 × 10(7) s(-1). A detailed picture of the charge transfer state emission dynamics in these functionalized Si NCs is proposed.

Generation of terahertz radiation by optical excitation of aligned carbon nanotubes.

We have generated coherent pulses of terahertz radiation from macroscopic arrays of aligned single-wall carbon nanotubes (SWCNTs) excited by femtosecond optical pulses without externally applied bias. The generated terahertz radiation is polarized along the SWCNT alignment direction. We propose that top-bottom asymmetry in the SWCNT arrays produces a built-in electric field in semiconducting SWCNTs, which enables generation of polarized terahertz radiation by a transient photocurrent surge directed along the nanotube axis.

Ultrafast imaging of terahertz Cherenkov waves and transition-like radiation in LiNbO3.

We use ultrafast phase-contrast imaging to directly observethe cone-like terahertz (THz) Cherenkov wave generated by optical rectification of femtosecond laser pulses focused into bulk lithium niobate (LiNbO3) single crystals. The transverse imaging geometry allows the Cherenkov angle, THz wave velocity, and optical pump pulse group velocity to be measured. Furthermore, transition-like THz radiation generated by the femtosecond laser pulse at the air-crystal boundary is observed. The effect of optical pump pulse polarization on the generation of THz Cherenkov waves and transition-like radiation in LiNbO3 is also investigated.

One-pot synthesis of functionalized germanium nanocrystals from a single source precursor.

One-pot syntheses of surface functionalized germanium nanocrystals (GeNCs) based upon traditional hot injection and microwave-assisted heating of a Ge(II) dihydride single source precursor have been developed. The reported procedures offer in situ hydrogermylation-based covalent attachment of alkene/alkyne derived surface moieties that give access to hydrophobic or hydrophilic GeNCs.

Size vs surface: tuning the photoluminescence of freestanding silicon nanocrystals across the visible spectrum via surface groups.

The syntheses of colloidal silicon nanocrystals (Si-NCs) with dimensions in the 3-4 nm size regime as well as effective methodologies for their functionalization with alkyl, amine, phosphine, and acetal functional groups are reported. Through rational variation in the surface moieties we demonstrate that the photoluminescence of Si-NCs can be effectively tuned across the entire visible spectral region without changing particle size. The surface-state dependent emission exhibited short-lived excited-states and higher relative photoluminescence quantum yields compared to Si-NCs of equivalent size exhibiting emission originating from the band gap transition. The Si-NCs were exhaustively characterized using transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and Fourier transformed infrared spectroscopy (FTIR), and their optical properties were thoroughly investigated using fluorescence spectroscopy, excited-state lifetime measurements, photobleaching experiments, and solvatochromism studies.

Intense THz pulses down-regulate genes associated with skin cancer and psoriasis: a new therapeutic avenue?

Terahertz (THz) radiation lies between the infrared and microwave regions of the electromagnetic spectrum and is non-ionizing. We show that exposure of artificial human skin tissue to intense, picosecond-duration THz pulses affects expression levels of numerous genes associated with non-melanoma skin cancers, psoriasis and atopic dermatitis. Genes affected by intense THz pulses include nearly half of the epidermal differentiation complex (EDC) members. EDC genes, which are mapped to the chromosomal human region 1q21, encode for proteins that partake in epidermal differentiation and are often overexpressed in conditions such as psoriasis and skin cancer. In nearly all the genes differentially expressed by exposure to intense THz pulses, the induced changes in transcription levels are opposite to disease-related changes. The ability of intense THz pulses to cause concerted favorable changes in the expression of multiple genes implicated in inflammatory skin diseases and skin cancers suggests potential therapeutic applications of intense THz pulses.

Intense THz pulses cause H2AX phosphorylation and activate DNA damage response in human skin tissue.

Recent emergence and growing use of terahertz (THz) radiation for medical imaging and public security screening raise questions on reasonable levels of exposure and health consequences of this form of electromagnetic radiation. In particular, picosecond-duration THz pulses have shown promise for novel diagnostic imaging techniques. However, the effects of THz pulses on human cells and tissues thus far remain largely unknown. We report on the investigation of the biological effects of pulsed THz radiation on artificial human skin tissues. We observe that exposure to intense THz pulses for ten minutes leads to a significant induction of H2AX phosphorylation, indicating that THz pulse irradiation may cause DNA damage in exposed skin tissue. At the same time, we find a THz-pulse-induced increase in the levels of several proteins responsible for cell-cycle regulation and tumor suppression, suggesting that DNA damage repair mechanisms are quickly activated. Furthermore, we find that the cellular response to pulsed THz radiation is significantly different from that induced by exposure to UVA (400 nm).

Two-photon absorption properties of two-dimensional π-conjugated chromophores: combined experimental and theoretical study.

The two-photon absorption (TPA) properties of four TPEB [tetrakis(phenylethynyl)benzene] derivatives (TD, para, ortho, and meta) with different donor/acceptor substitution patterns have been investigated experimentally by the femtosecond open-aperture Z-scan method and theoretically by the time-dependent density-functional theory (TDDFT) method. The four compounds show relatively large TPA cross sections, and the all-donor substituted species (TD) displays the largest TPA cross-section σ(2) = 520 ± 30 GM. On the basis of the calculated electronic structure, TD shows no TPA band in the lower energy region of the spectrum because the transition density is concentrated on particular transitions due to the high symmetry of the molecular structure. The centrosymmetric donor-acceptor TPEB para shows excitations resulting from transitions centered on D-π-D and A-π-A moieties, as well as transition between the D-π-D and A-π-A moieties; this accounts for the broad nature of the TPA bands for this compound. Calculations for two noncentrosymmetric TPEBs (ortho and meta) reveal that the diminished TPA intensities of higher-energy bands result from destructive interference between the dipolar and three-state terms. The molecular orbitals (MOs) of the TPEBs are derivable with linear combinations of the MOs of the two crossing BPEB [bis(phenylethynyl)benzene] derivatives. Overall, the characteristics of the experimental spectra are well-described based on the theoretical analysis.

Pentacene-based dendrimers: synthesis and thin film photoconductivity measurements of branched pentacene oligomers.

The synthesis of pentacene-based dendrimers has been achieved via esterification of 1,3,5-benzenetricarboxylic acid and unsymmetrical pentacene 4 possessing a hydroxy group. Dendrimers 1 (C(183)H(204)O(9)Si(9), 2800 g mol(-1)) and 2 (C(540)H(570)O(30)Si(24), 8214 g mol(-1)) are characterized by (1)H and (13)C NMR, IR, UV-vis, and fluorescence spectroscopy, as well as mass spectrometry. These branched oligomeric materials are benchtop stable and soluble in common organic solvents, allowing for solution cast formation of thin films. Photocurrent and photocurrent yield measurements of these films reveal improved efficiency in photogenerated conduction for dendrimers in comparison to linearly connected pentacene-based polymers.

Synthesis and electronic properties of conjugated pentacene dimers.

Conjugated pentacene dimers 1-3 were synthesized in two steps from readily available precursors. Noteworthy is the initial step, which assembles five independent fragments to form the carbon-rich molecular framework. Solution-cast films of these materials are air stable. Photocurrent measurements for solution-deposited thin films show that dimer 3 exhibits photoconductive gain >10.

Two-photon absorption in two-dimensional conjugated quadrupolar chromophores.

We present ultrafast z-scan measurements of the two-photon absorption (TPA) spectra of a pair of two-dimensionally conjugated quadrupolar donor/acceptor (D/A) chromophores. The all-donor substituted species displays a peak TPA cross section [sigma(2)=520+/-30 GM] that is more than twice that of the D-A species [sigma(2)=240+/-20 GM]. Unlike previous structure-property studies that have evaluated TPA behavior for D/A molecules through the comparison of dipolar and quadrupolar compounds, both molecules investigated herein are quadrupolar, ultimately providing a more consistent evaluation of the effects of donor and/or acceptor substitution on the TPA of conjugated chromophores.

Synthesis, spectroscopic and nonlinear optical properties of multiple [60]fullerene-oligo(p-phenylene ethynylene) hybrids.

A series of multiple [60]fullerene terminated oligo(p-phenylene ethynylene) (OPE) hybrid compounds has been synthesized through a newly developed in situ ethynylation method. Structural and magnetic shielding properties of the highly unsaturated carbon-rich C(60) and OPE scaffolds were characterized by 1D and 2D NMR spectroscopic analyses. Electronic interactions between the [60]fullerenes and the OPE backbones were investigated by UV/Vis spectroscopic and cyclic voltammetry (CV) experiments. Our studies clearly show that although the multiple [60]fullerene groups are connected via pi-conjugated OPE frameworks, they present diminutive electronic interactions in the ground state, and the electronic behavior of the [60]fullerene cages are only affected by the OPE backbones through modest inductive effects. Interestingly, sizable third-order nonlinear optical (NLO) responses (gamma) and enhanced two-photon absorption (TPA) cross-sections (sigma((2))) were determined for the multifullerene-OPE hybrid 31 relative to its OPE precursor from differential optical Kerr effect (DOKE) experiments. Such enhanced NLO performance is presumably due to the occurrence of periconjugation and/or charge transfer effects in the excited state. In addition, comparatively strong excited-state absorption was observed and characterized for OPE pentamer 12. Thus, the use of such fullerene-derivatized conjugated oligomers aids the quest for molecules with large third-order NLO and TPA properties.

Polyynes as a model for carbyne: synthesis, physical properties, and nonlinear optical response.

With the Fritsch-Buttenberg-Wiechell rearrangement as a primary synthetic route, a series of conjugated, triisopropylsilyl end-capped polyynes containing 2-10 acetylene units has been assembled. In a few steps, significant quantities of the polyynes are made available, which allow for a thorough analysis of their structural, physical, and optical properties. Molecules in the series have been characterized in detail using (13)C NMR spectroscopy, differential scanning calorimetry, mass spectrometry, and, for four derivatives including octayne 6, X-ray crystallography. UV-vis spectroscopy of the polyynes 1-7 shows a consistent lowering of the HOMO-LUMO gap (E(g)) as a function of the number of acetylene units (n), fitting a power-law relationship of E(g) approximately n(-)(0.379)(+/-)(0.002). The third-order nonlinear optical (NLO) properties of the polyyne series have been examined, and the nonresonant molecular second hyperpolarizabilities (gamma) increase as a function of length according to the power-law gamma approximately n(4.28)(+/-)(0.13). This result exhibits an exponent that is larger than theoretically predicted for polyynes and higher than is observed for polyenes and polyenynes. The combined linear and nonlinear optical results confirm recent theoretical studies that suggest polyynes as model 1-D conjugated systems. On the basis of UV-vis spectroscopic analysis, the effective conjugation length for this series of polyynes is estimated to be ca. n = 32, providing insight into characteristics of carbyne.