Quantifying the Fast Dynamics of HClO in Living Cells by a Fluorescence Probe Capable of Responding to Oxidation and Reduction Events within the Time Scale of Milliseconds.

The biological roles of reactive oxygen species (ROS) depend highly on their dynamics. However, it has been challenging for measuring the dynamics of ROS in cells. In this study, we address a core challenge in developing fluorescence probes for monitoring ROS dynamics by designing a redox couple that can respond rapidly to both oxidation and reduction events. We show that such molecules can be designed by taking advantage of the steric effects of electron-donating groups at the ortho position relative to the selenium center. We demonstrate this design in a new fluorescence probe named Fl-Se. Results reveal that Fl-Se and its oxidized product Fl-SeO rapidly respond to HClO, an important member of the ROS family, and glutathione (GSH), with t1/2 = 2.7 ms at [HClO] = 1 µM; t1/2 = 61 ms at [GSH] = 1 mM. When applied in cells, Fl-Se satisfactorily tracks the dynamics of intracellular HClO in H2O2-stimulated HL-60 cells, as well as the different dynamic behaviors of HClO fluctuations involved in the phorbol 12-myristate-13-acetate-activated immune response of RAW264.7 cells and the 3-deazaneplanocin A-induced apoptosis of HL 60 cells.

Self-Assembled Framework Enhances Electronic Communication of Ultrasmall-Sized Nanoparticles for Exceptional Solar Hydrogen Evolution.

Colloidal quantum dots (QDs) have demonstrated great promise in artificial photosynthesis. However, the ultrasmall size hinders its controllable and effective interaction with cocatalysts. To improve the poor interparticle electronic communication between free QD and cocatalyst, we design here a self-assembled architecture of nanoparticles, QDs and Pt nanoparticles, simply jointed together by molecular polyacrylate to greatly enhance the rate and efficiency of interfacial electron transfer (ET). The enhanced interparticle electronic communication is confirmed by femtosecond transient absorption spectroscopy and X-ray transient absorption. Taking advantage of the enhanced interparticle ET with a time scale of ∼65 ps, 5.0 mL of assembled CdSe/CdS QDs/cocatalysts solution produces 94 ± 1.5 mL (4183 ± 67 µmol) of molecular H2 in 8 h, giving rise to an internal quantum yield of ∼65% in the first 30 min and a total turnover number of >1.64â€¯× 107 per Pt nanoparticle. This study demonstrates that self-assembly is a promising way to improve the sluggish kinetics of the interparticle ET process, which is the key step for advanced H2 photosynthesis.

Side-chain effects on the solution-phase conformations and charge photogeneration dynamics of low-bandgap copolymers.

Solution-phase conformations and charge photogeneration dynamics of a pair of low-bandgap copolymers based on benzo[1,2-b:4,5-b(')]dithiophene (BDT) and thieno[3,4-b]thiophene (TT), differed by the respective carbonyl (-C) and ester (-E) substituents at the TT units, were comparatively investigated by using near-infrared time-resolved absorption (TA) spectroscopy at 25 °C and 120 °C. Steady-state and TA spectroscopic results corroborated by quantum chemical analyses prove that both PBDTTT-C and PBDTTT-E in chlorobenzene solutions are self-aggregated; however, the former bears a relatively higher packing order. Specifically, PBDTTT-C aggregates with more π-π stacked domains, whereas PBDTTT-E does with more random coils interacting strongly at the chain intersections. At 25 °C, the copolymers exhibit comparable exciton lifetimes (~1 ns) and fluorescence quantum yields (~2%), but distinctly different charge photogeneration dynamics: PBDTTT-C on photoexcitation gives rise to a branching ratio of charge separated (CS) over charge transfer (CT) states more than 20% higher than PBDTTT-E does, correlating with their photovoltaic performance. Temperature and excitation-wavelength dependent exciton∕charge dynamics suggest that the CT states localize at the chain intersections that are survivable up to 120 °C, and that the excitons and the CS states inhabit the stretched strands and the also thermally robust orderly stacked domains. The stable self-aggregation structures and the associated primary charge dynamics of the PBDTTT copolymers in solutions are suggested to impact intimately on the morphologies and the charge photogeneration efficiency of the solid-state photoactive layers.

Charge Carrier Recombination Dynamics in MAPb(BrxCl1-x)3 Single Crystals.

Understanding carrier recombination processes in MAPb(BrxCl1-x)3 crystals is essential for their photoelectrical applications. In this work, carrier recombination dynamics in MAPb(BrxCl1-x)3 single crystals were studied by steady-state photoluminescence (PL), time-resolved photoluminescence (TRPL), and time-resolved microwave photoconductivity (TRMC). By comparing TRPL and TRMC, we find TRPL of MAPb(BrxCl1-x)3 (x < 0.98) single crystals is dominated by a hole trapping process while the long-lived component of TRMC is dominated by an electron trapping process. We also find both electron and hole trapping rates of MAPb(BrxCl1-x)3 (x < 0.98) crystals decrease with an increase in Br content. A temperature-dependent PL study shows there are shallow trap states besides the deep level trap states in the MAPb(Br0.82Cl0.18)3 crystal. The activation energy for holes in shallow trap states detrapped into the valence band is ∼0.1 eV, while the activation energy for free holes to be trapped into deep trap states is ∼0.4 eV. This work provides insight into carrier recombination processes in MAPb(BrxCl1-x)3 single crystals.

Solution-grown BiI/BiI3 van der Waals heterostructures for sensitive X-ray detection.

X-ray detectors must be operated at minimal doses to reduce radiation health risks during X-ray security examination or medical inspection, therefore requiring high sensitivity and low detection limits. Although organolead trihalide perovskites have rapidly emerged as promising candidates for X-ray detection due to their low cost and remarkable performance, these materials threaten the safety of the human body and environment due to the presence of lead. Here we present the realization of highly sensitive X-ray detectors based on an environmentally friendly solution-grown thick BiI/BiI3/BiI (BixIy) van der Waals heterostructure. The devices exhibit anisotropic X-ray detection response with a sensitivity up to 4.3 × 104 µC Gy-1 cm-2 and a detection limit as low as 34 nGy s-1. At the same time, our BixIy detectors demonstrate high environmental and hard radiation stabilities. Our work motivates the search for new van der Waals heterostructure classes to realize high-performance X-ray detectors and other optoelectronic devices without employing toxic elements.

Subnanosecond charge recombination dynamics in P3HT/PC61BM films.

Ultrafast near-infrared absorption spectroscopy was used to investigate the influence of film morphology and excitation photon energy on the charge recombination (CR) dynamics in the initial nanosecond timescale in the P3HT/PC(61)BM blend films. With reference to the CS(2)-cast films, the solvent vapor annealed (SVA) ones show 2­3-fold improvement in hole mobility and more than 5-fold reduction in the polymer-localized trap states of holes. At Dt = 70 ps, the hole mobility (m(h)) and the bimolecular CR rate (γ(bi)) of the SVA films are µ(h) = 8.7 × 10(−4) cm2 × s(−1) × V(−1) and γ(bi) = 4.5 × 10(−10) cm3 × s(−1), whereas at Δt = 1 ns they drop to 8.7 × 10(−5) cm2 × s(−1) × V(−1) and 4.6 × 10(−11) cm3 × s(−1), respectively. In addition, upon increasing the hole concentration, the hole mobility increases substantially faster under the above-gap photoexcitation than it does under the band-gap photoexcitation, irrespective of the film morphologies. The results point to the importance of utilizing the photogenerated free charges in the early timescales.

Photoinduced Polaron Formation in a Polymerized Electron-Acceptor Semiconductor.

Polymerized small molecular acceptor (PSMA) based all-polymer solar cells (all-PSC) have achieved power conversion efficiencies (PCE) over 16%, and the PSMA is considered to hold great promise for further improving the performance of all-PSC. Yet, in comparison with that of the polymer donor, the photophysics of a polymerized acceptor remains poorly understood. Herein, the excited state dynamics in a polymerized acceptor PZT810 was comprehensively investigated under various pump intensities and photon energies. The excess excitation energy was found to play a key role in excitons dissociation into free polarons for neat PSMA films, while free polarons cannot be generated from the polaron pairs in neat acceptor films. This work reveals an in-depth understanding of relaxation dynamics for PSMAs and that the underlying photophysical origin of PSMA can be mediated by excitation energies and intensities. These results would benefit the realization of the working mechanism for all-PSC and the designing of new PSMAs.

TDDFT study on recognition mechanism for the oxygen sensing of the cyclometalated platinum (II) complex.

The influence of oxygen molecule on the luminescent properties of a cyclometalated Pt(II) complex Lxp1, was investigated using density functional theory (DFT) and time-dependent density functional theory (TDDFT) methods. Analysis of frontier molecular orbitals and electronic configuration indicated that the highest-occupied molecular orbital of the Lxp1 has a significant mixture of metal Pt (d) as well as 2-phenylpyridine and acetyl acetone(π). The lowest-unoccupied orbital of the Lxp1 primarily locates on π* of 2-phenylpyridineligands. The emission mechanism of the cyclometalated Pt(II) complex Lxp1 is assigned to the mixing of ligand-to-metal charge transfer and ligand-to-ligand charge transfer. The emission mechanism of the Lxp1-O2 complex can be attributed to the charge transfer from the oxygen molecule to the luminescent material Lxp1. Our study showed that intermolecular hydrogen bonding between the Lxp1 and oxygen molecule was strengthened by the calculation of electronic excitation, leading to a luminescence-decreasing phenomenon. The calculation of the radiative and non-radiative decay rate constants of the Lxp1 and the Lxp1-O2 complex demonstrates that the phosphorescence from T1-S0 of the Lxp1 would alter to the internal conversion from T1-T0 of the Lxp1-O2 complex. This alteration further explains the luminescence quenching phenomenon of the cyclometalated Pt(II) complex Lxp1 after interacting with oxygen molecule.

A femtosecond transient absorption study of charge photogeneration and recombination dynamics in photovoltaic polymers with different side-chain linkages.

A pair of 9-arylidene-9H-fluorene and benzothiadiazole based, low-bandgap copolymers differing merely in the para or meta substitution of alkoxy groups to the arylidene linkages, i.e. p-PAFDTBT and m-PAFDTBT respectively, were comparatively investigated by using morphological characterization, ultrafast spectroscopy and quantum chemical calculations. Despite the subtle difference in the alkoxy substitution patterns, p-PAFDTBT molecules in photoactive films were shown to have a higher degree of crystallinity owing to the relatively less rotational torsion of the arylidene linkages. As a result, in either neat or fullerene-blended films, p-PAFDTBT compared to m-PAFDTBT gave rise to a substantially higher charge yield and much slower charge recombination. This work demonstrates that the alkoxy substitution pattern and the arylidene linkage are highly influencing on the morphology of the photoactive layers and thereby on the photovoltaic performance of the semiconducting copolymers.

Dependence of Excited-State Properties of a Low-Bandgap Photovoltaic Copolymer on Side-Chain Substitution and Solvent.

The excited-state properties and chain conformations of a new low-bandgap copolymer based on benzo[1,2-b:4,5-b']dithiophene (BDT) and thieno[3,4-b]thiophene with meta-alkoxyphenyl-substituted side chains in solution were investigated comprehensively. Time-resolved spectroscopy suggested that the excited-state properties were sensitive to the conformations of the copolymer in solution. In addition, excited-state dynamics analyses revealed the photogeneration of triplet excited states by intersystem crossing (ISC) at a rate constant of ∼0.4×10(9)  s(-1) as a result of direct meta-alkoxyphenyl connection to the donor unit BDT irrespective to the macromolecular conformations. According to El-Sayed's rule, the fast ISC herein is correlated with the change of orbital types between singlet and triplet excited states as also shown by quantum chemical calculations. Our studies may shed light on the structure-property relationships of photovoltaic materials.

Controlled Growth of Well-Defined Conjugated Polymers from the Surfaces of Multiwalled Carbon Nanotubes: Photoresponse Enhancement via Charge Separation.

The installation of heterojunctions on the surfaces of carbon nanotubes (CNTs) is an effective method for promoting the charge separation processes needed for CNT-based electronics and optoelectronics applications. Conjugated polymers are proven state-of-the-art candidates for modifying the surfaces of CNTs. However, all previous attempts to incorporate conjugated polymers to CNTs resulted in unordered interfaces. Herein we show that well-defined chains of regioregular poly(3-hexylthiophene) (P3HT) were successfully grown from the surfaces of multiwalled CNTs (MWNTs) using surface-initiated Kumada catalyst-transfer polycondensation. The polymerization was found to proceed in a controlled manner as chains of tunable lengths were prepared through variation of the initial monomer-to-initiator ratio. Moreover, it was determined that large-diameter MWNTs afforded highly ordered P3HT aggregates, which exhibited a markedly bathochromically shifted optical absorption due to a high grafting density induced planarization of the polymer chains. Using ultrafast spectroscopy, the heterojunctions formed between the MWNTs and P3HT were shown to effectively overcome the binding energy of excitons, leading to photoinduced electron transfer from P3HT to MWNTs. Finally, when used as prototype devices, the individual MWNT-g-P3HT core-shell structures exhibited excellent photoresponses under a low illumination density.

Thermal Adaptability of the Light-Harvesting Complex 2 from Thermochromatium tepidum: Temperature-Dependent Excitation Transfer Dynamics.

The photosynthetic purple bacterium Thermochromatium (Tch.) tepidum is a thermophile that grows at an optimal temperature of ∼50 °C. We have investigated, by means of steady-state and time-resolved optical spectroscopies, the effects of temperature on the near-infrared light absorption and the excitation energy transfer (EET) dynamics of its light-harvesting complex 2 (LH2), for which the mesophilic counterpart of Rhodobacter (Rba.) sphaeroides 2.4.1 (∼30 °C) was examined in comparison. In a limited range around the physiological temperature (10-55 °C), the B800-to-B850 EET process of the Tch. tepidum LH2, but not the Rba. sphaeroides LH2, was found to be characteristically temperature-dependent, mainly because of a temperature-tunable spectral overlap. At 55 °C, the LH2 complex from Tch. tepidum maintained efficient near-infrared light harvesting and B800-to-B850 EET dynamics, whereas this EET process was disrupted in the case of Rba. sphaeroides 2.4.1 owing to the structural distortion of the LH2 complex. Our results reveal a remarkable thermal adaptability of the light-harvesting function of Tch. tepidum, which could enhance our understanding of the survival strategy of this thermophile in response to environmental challenges.