Photocontrolled Reversible Amyloid Fibril Formation of Parathyroid Hormone-Derived Peptides.

Peptide fibrillization is crucial in biological processes such as amyloid-related diseases and hormone storage, involving complex transitions between folded, unfolded, and aggregated states. We here employ light to induce reversible transitions between aggregated and nonaggregated states of a peptide, linked to the parathyroid hormone (PTH). The artificial light-switch 3-{[(4-aminomethyl)phenyl]diazenyl}benzoic acid (AMPB) is embedded into a segment of PTH, the peptide PTH25-37, to control aggregation, revealing position-dependent effects. Through in silico design, synthesis, and experimental validation of 11 novel PTH25-37-derived peptides, we predict and confirm the amyloid-forming capabilities of the AMPB-containing peptides. Quantum-chemical studies shed light on the photoswitching mechanism. Solid-state NMR studies suggest that ß-strands are aligned parallel in fibrils of PTH25-37, while in one of the AMPB-containing peptides, ß-strands are antiparallel. Simulations further highlight the significance of π-π interactions in the latter. This multifaceted approach enabled the identification of a peptide that can undergo repeated phototriggered transitions between fibrillated and defibrillated states, as demonstrated by different spectroscopic techniques. With this strategy, we unlock the potential to manipulate PTH to reversibly switch between active and inactive aggregated states, representing the first observation of a photostimulus-responsive hormone.

A CASSCF/MRCI trajectory surface hopping simulation of the photochemical dynamics and the gas phase ultrafast electron diffraction patterns of cyclobutanone.

We present the simulation of the photochemical dynamics of cyclobutanone induced by the excitation of the 3 s Rydberg state. For this purpose, we apply the complete active space self-consistent field method together with the spin-orbit multireference configuration interaction singles treatment, combined with the trajectory surface hopping for the inclusion of nonadiabatic effects. The simulations were performed in the spin-adiabatic representation, including nine electronic states derived from three singlet and two triplet spin-diabatic states. Our simulations reproduce the two previously observed primary dissociation channels: the C2 pathway yielding C2H4 + CH2CO and the C3 pathway producing c-C3H6 + CO. In addition, two secondary products, CH2 + CO from the C2 pathway and C3H6 from the C3 pathway, both of them previously reported, are also observed in our simulation. We determine the ratio of the C3:C2 products to be about 2.8. Our findings show that most of the trajectories reach their electronic ground state within 200 fs, with dissociation events finished after 300 fs. We also identify the minimum energy conical intersections that are responsible for the relaxation and provide an analysis of the photochemical reaction mechanism based on multidimensional scaling. Furthermore, we demonstrate a minimal impact of triplet states on the photodissociation mechanism within the observed timescale. In order to provide a direct link to experiments, we simulate the gas phase ultrafast electron diffraction patterns and connect their features to the underlying structural dynamics.

Enhanced Gain in Organic Photodetectors Using the Polymer with Singlet Open-Shell Ground State.

Photodetectors are critical components in intelligent optoelectronic systems, and photomultiplication-capable devices are essential for detecting weak optical signals. Despite significant advances, developing photomultiplication-type organic photodetectors with high gain and low noise current simultaneously remains challenging. In this work, a new conjugated polymer PDN with singlet open-shell ground state is introduced in active layers for electron capture, and the corresponding PDN-based photodetectors exhibited an enhanced photoelectric gain and decreased dark current density at a low forward bias. At 1.5 V, the PDN-based ternary photodetector has the external quantum efficiency (EQE) up to 2552.3 % and the specific detectivity of 1.4×1014  Jones at 710 nm calculated by the measured noise current, with the gain 22 times higher than that of the control group. This study provides an approach for exploiting polymers with singlet open-shell ground state to enhance the gain of organic photodetectors.

The investigation of precipitation behavior of titanium compounds for high titanium steel based on in situ observation.

The effects of cooling rate, Ti content, and casting temperature on titanium compounds for high titanium steel were investigated. In-situ observation of high titanium steel during remelting and solidification was carried out by using a High Temperature Confocal Scanning Laser Microscope (HTCSLM), and the observed results were in good agreement with the thermodynamic and kinetic calculations. The observation and calculation results both show that the inclusions in high titanium steel first precipitate in the form of TiN, followed by TiC precipitates as temperature decreases, eventually forming TiCxN1-x type inclusions at room temperature. The initial precipitation temperature of the inclusions increases with the increase of Ti content in molten steel, whereas casting temperature has little effect on the initial precipitation temperature of inclusions. In addition, the size of TiN inclusions increases with the increase of Ti content in steel but decreases with the increase in cooling rate.

Ultrafast Ring Closure Reaction of Gaseous cis-Stilbene from S1(ππ*).

cis-Stilbene (cis-St) is a well-known benchmark system for cis-trans photoisomerization. cis-St also produces 4a,4b-dihydrophenanthrene (DHP) in solution with a quantum yield of less than 0.19. The ring closure reaction, however, has never been identified for gaseous cis-St, and a recent computational simulation predicted the quantum yield of DHP to be only 0.04. In the present study, we identified an ultrafast ring closure reaction of gaseous cis-St for the first time using extreme ultraviolet time-resolved photoelectron spectroscopy. Surface hopping trajectory calculations at the SA3-XMS-CASPT2(2,2) level of theory reproduce the features of the observed time-resolved photoelectron spectra and predict the cis-St:DHP:trans-St branching ratio to be 0.55:0.41:0.04, in contrast with previous estimates. The results indicate that photoexcited cis-St favors ring closure over cis-trans isomerization under the isolated condition.

Stacking Is Favored over Hydrogen Bonding in Azaphenanthrene Dimers.

N-Doped polycyclic aromatic hydrocarbons have recently emerged as potential organic electronic materials. The function of such materials is determined not only by the intrinsic electronic properties of individual molecules but also by their supramolecular interactions in the solid state. Therefore, a proper characterization of the interactions between the individual units is of interest to materials science since they ultimately govern properties such as excitons and charge transfer. Here, we report a joint experimental and computational study of two azaphenanthrene dimers to determine the structure and the nature of supramolecular interactions in the aggregates. IR/UV double-resonance experiments were carried out using far- and mid-infrared free-electron laser radiation. The experimental spectra are compared with quantum chemical calculations for the lowest-energy π-stacked and hydrogen-bonded structures. The data reveal a preference of the π-stacked structure for the benzo[f]quinoline and the phenanthridine dimer.

Excimer formation dynamics in the isolated tetracene dimer.

The understanding of excimer formation and its interplay with the singlet-correlated triplet pair state 1(TT) is of high significance for the development of efficient organic electronics. Here, we study the photoinduced dynamics of the tetracene dimer in the gas phase by time-resolved photoionisation and photoion imaging experiments as well as nonadiabatic dynamics simulations in order to obtain mechanistic insight into the excimer formation dynamics. The experiments are performed using a picosecond laser system for excitation into the S2 state and reveal a biexponential time dependence. The time constants, obtained as a function of excess energy, lie in the range between ≈10 ps and 100 ps and are assigned to the relaxation of the excimer on the S1 surface and to its deactivation to the ground state. Simulations of the quantum-classical photodynamics are carried out in the frame of the semi-empirical CISD and TD-lc-DFTB methods. Both theoretical approaches reveal a dominating relaxation pathway that is characterised by the formation of a perfectly stacked excimer. TD-lc-DFTB simulations have also uncovered a second relaxation channel into a less stable dimer conformation in the S1 state. Both methods have consistently shown that the electronic and geometric relaxation to the excimer state is completed in less than 10 ps. The inclusion of doubly excited states in the CISD dynamics and their diabatisation further allowed to observe a transient population of the 1(TT) state, which, however, gets depopulated on a timescale of 8 ps, leading finally to the trapping in the excimer minimum.

Effect of varying the TD-lc-DFTB range-separation parameter on charge and energy transfer in a model pentacene/buckminsterfullerene heterojunction.

Atomistic modeling of energy and charge transfer at the heterojunction of organic solar cells is an active field with many remaining outstanding questions owing, in part, to the difficulties in performing reliable photodynamics calculations on very large systems. One approach to being able to overcome these difficulties is to design and apply an appropriate simplified method. Density-functional tight binding (DFTB) has become a popular form of approximate density-functional theory based on a minimal valence basis set and neglect of all but two center integrals. We report the results of our tests of a recent long-range correction (lc) [A. Humeniuk and R. Mitric, J. Chem. Phys. 143, 134120 (2015)] for time-dependent (TD) lc-DFTB by carrying out TD-lc-DFTB fewest switches surface hopping calculations of energy and charge transfer times using the relatively new DFTBABY [A. Humeniuk and R. Mitric, Comput. Phys. Commun. 221, 174 (2017)] program. An advantage of this method is the ability to run enough trajectories to get meaningful ensemble averages. Our interest in the present work is less in determining exact energy and charge transfer rates than in understanding how the results of these calculations vary with the value of the range-separation parameter (Rlc = 1/µ) for a model organic solar cell heterojunction consisting of a gas-phase van der Waals complex P/F made up of a single pentacene (P) molecule together with a single buckminsterfullerene (F) molecule. The default value of Rlc = 3.03 a0 is found to be much too small as neither energy nor charge transfer is observed until Rlc ≈ 10 a0. Tests at a single geometry show that the best agreement with high-quality ab initio spectra is obtained in the limit of no lc (i.e., very large Rlc). A plot of energy and charge transfer rates as a function of Rlc is provided, which suggests that a value of Rlc ≈ 15 a0 yields the typical literature (condensed-phase) charge transfer time of about 100 fs. However, energy and charge transfer times become as high as ∼300 fs for Rlc ≈ 25 a0. A closer examination of the charge transfer process P*/F → P+/F- shows that the initial electron transfer is accompanied by a partial delocalization of the P hole onto F, which then relocalizes back onto P, consistent with a polaron-like picture in which the nuclei relax to stabilize the resultant redistribution of charges.

Properties and effects of remaining carbon from waste plastics gasifying on iron scale reduction.

The carbonous activities of three kinds of carbon-bearing materials gasified from plastics were tested with coal coke as reference. The results showed that the carbonous activities of these remaining carbon-bearing materials were higher than that of coal-coke. Besides, the fractal analyses showed that the porosities of remaining carbon-bearing materials were higher than that of coal-coke. It revealed that these kinds of remaining carbon-bearing materials are conducive to improve the kinetics conditions of gas-solid phase reaction in iron scale reduction.

Reduction experiment of iron scale by adding waste plastics.

The special features of waste plastics in China are huge in total amount, various in type and dispersive in deposition. Therefore, it is necessary to try some new ways that are fit to Chinese situation for disposing waste plastics as metallurgical raw materials more effectively and flexibly. Owing to its high ferrous content and less impurity, the iron scale became ideal raw material to produce pure iron powder. One of the methods to produce pure iron powder is Hoganas Method, by which, after one or multistage of reduction steps, the iron scale can be reduced pure iron powder. However, combining utilization of waste plastics and iron powder production, a series of reduction experiments were arranged and investigated, which is hoped to take use of both thermal and chemical energy contained in waste plastics as well as to improve the reducing condition of iron scale, and hence to develop a new metallurgical way of disposing waste plastics. The results show that under these experimental conditions, the thermal-decomposition of water plastics can conduce to an increase of porosity in the reduction systems. Moreover, better thermodynamics and kinetics conditions for the reduction of scale can be reached. As a result, the reduction rate is increased.