Hot Branching Dynamics in a Light‐Harvesting Iron Carbene Complex Revealed by Ultrafast X‐ray Emission Spectroscopy

Iron N‐heterocyclic carbene (NHC) complexes have received a great deal of attention recently because of their growing potential as light sensitizers or photocatalysts. We present a sub‐ps X‐ray spectroscopy study of an Fe^IINHC complex that identifies and quantifies the states involved in the deactivation cascade after light absorption. Excited molecules relax back to the ground state along two pathways: After population of a hot ³MLCT state, from the initially excited ¹MLCT state, 30 % of the molecules undergo ultrafast (150 fs) relaxation to the ³MC state, in competition with vibrational relaxation and cooling to the relaxed ³MLCT state. The relaxed ³MLCT state then decays much more slowly (7.6 ps) to the ³MC state. The ³MC state is rapidly (2.2 ps) deactivated to the ground state. The ⁵MC state is not involved in the deactivation pathway. The ultrafast partial deactivation of the ³MLCT state constitutes a loss channel from the point of view of photochemical efficiency and highlights the necessity to screen transition‐metal complexes for similar ultrafast decays to optimize photochemical performance.     

Fusion of Different Crosslinked Polymers Based on Dynamic Disulfide Exchange

Crosslinked polymers (CLPs) exhibit exceptional mechanical properties as well as good chemical and solvent resistance. However, their reprocessing, recycling, and modification remain difficult. One promising approach to overcome this limitation is to introduce dynamic covalent bonds that enable chain‐exchange reactions and network‐structure rearrangements in identical polymer networks (A–A fusion), resulting in self‐healing and reprocessing properties. Reported here is the fusion of two distinct polymer networks (A–B fusion) by the dynamic behavior of bis(2,2,6,6‐tetramethylpiperidin‐1‐yl)disulfide (BiTEMPS) at the interface between different CLPs. The appearance, swelling behavior, and mechanical properties of the fused samples indicate exchange reactions of the BiTEMPS units and the formation of topological bonds at the interface, commensurate with the generation of a CLP that exhibits tunable properties.     

Biosynthesis of Indole Diterpene Lolitrems: Radical‐Induced Cyclization of an Epoxyalcohol Affording a Characteristic Lolitremane Skeleton

Lolitrems are tremorgenic indole diterpenes that exhibit a unique 5/6 bicyclic system of the indole moiety. Although genetic analysis has indicated that the prenyltransferase LtmE and the cytochrome P450 LtmJ are involved in the construction of this unique structure, the detailed mechanism remains to be elucidated. Herein, we report the reconstitution of the biosynthetic pathway for lolitrems employing a recently established genome‐editing technique for the expression host Aspergillus oryzae. Heterologous expression and bioconversion of the various intermediates revealed that LtmJ catalyzes multistep oxidation to furnish the lolitrem core. We also isolated the key reaction intermediate with an epoxyalcohol moiety. This observation allowed us to establish the mechanism of radical‐induced cyclization, which was firmly supported by density functional theory calculations and a model experiment with a synthetic analogue.     

Morphological studies of a hydrogen-bonded LC polymer obtained by photopolymerization in LC solvents

Anisotropic morphologies and the phase behaviour of a hydrogen-bonded LC polymer obtained by photopolymerization in two kinds of LC solvent are discussed. The hydrogen-bonded LC monomer, 4-(6-acryloyloxyhexyloxy) benzoic acid (A6OBA), was photopolymerized in 4-cyano-4′-hexyloxybiphenyl (6OCB) and in 4-cyano-4′-undecyloxybiphenyl (11OCB), which show a nematic phase and a smectic A phase, respectively. After photo-polymerization, the LC media were removed by extraction and the pure polymer was observed by scanning electron microscopy. SEM images showed that the polymer possessed fibrous morphology with a fibre diameter of a few micrometers, based on polymerization-induced phase separation. The overall geometries reflected typical LC characteristics such as schlieren and focal-conic fan textures. It was found that the hydrogen bond between benzoic acid groups in the monomer was rigid enough to fix the anisotropic phase-separated structure forming during the early stage of phase separation; however, it could not permanently maintain the fibre structure due to dissociation at elevated temperature. X-ray measurements revealed that a well developed layer structure of the hydrogen-bonded mesogen existed in the polymer obtained from the smectic phase of 11OCB, whereas a polymer layer structure could develop only partially from the nematic phase of 6OCB.     

Study of reduction processes over cerium oxide surfaces with atomic hydrogen using ultra accelerated quantum chemical molecular dynamics

Ceria plays an important role in catalysis, due to its ability to store and release oxygen depending on the condition present in the catalyst environment. To analyze the role of ceria in catalytic reactions, it is necessary to know the details of the interaction of ceria surface with environmentally sensitive molecules. This study was conducted using ultra accelerated quantum chemical molecular dynamics. Its purpose was to investigate the reduction process of the (1 1 1) and (1 1 0) surfaces of ceria with atomic hydrogen as well as water desorption mechanisms from the surfaces. This simulation demonstrated that when a high-energy colliding hydrogen atoms are adsorbed on the ceria, it pulls up an O atom from the ceria surfaces and results in the formation of a H₂O molecule. This is the first dynamics simulation related to such reduction processes based on quantum chemistry.     

From

Let be a space of finite type. Set as usual, and define the mod support of by for 0.$"> Call sparse if there is no with

Then we show the relation for any finite type space with being sparse.

As a special case, we have and the main theorem of Ravenel, Wilson and Yagita is also generalized in terms of the mod support.

     

Ruthenium(II)-catalyzed [2 + 2 + 2] cycloaddition of 1,6-diynes with tricarbonyl compounds

In the presence of catalytic amounts of Cp*Ru(cod)Cl, unsymmetrical 1,6-diynes possessing a variety of functional groups reacted with electron-deficient tricarbonyl compounds at the ketone C=O double bonds to selectively afford dienones via electrocyclic ring opening of the expected alpha-pyrans. The intramolecular Michael addition of the cycloadducts having an acetyl and an alkylidenemalonate moiety gave bicyclo[3.3.0]octenone derivatives.     

Broad-spectrum frequency comb generation and carrier-envelope offset frequency measurement by second-harmonic generation of a mode-locked fiber laser

A frequency comb spanning more than one octave has been achieved by injecting the second-harmonic generation (780 nm) of a mode-locked fiber laser (1.56 microm) into a photonic crystal fiber. We propose and realize a novel interferometric scheme for observing the carrier-envelope offset frequency of the frequency comb. Frequency noise has been observed on the measured carrier-envelope offset frequency, which has been confirmed to be generated in the photonic crystal fiber by comparing the measured beat frequencies between cw lasers and frequency combs before and after the photonic crystal fiber. The mode-locked fiber laser is considered to be an important candidate for the light source used in realizing a compact optical frequency measurement system including applications in the telecommunication bands.     

Synthesis and evaluation of 6-nitro-7-(1-piperazino)quinazolines: dual-acting compounds with inhibitory activities toward both tumor necrosis factor-alpha (TNF-alpha) production and T cell proliferation

We investigated the chemical modifications of the nitroquinazoline derivative (1) through the replacement of the NH group at the C(4)-position with several N-alkyl groups to increase the lipophilicity at the C(4)-position. Among them, we found that the N-methyl analogue (5a) showed a 2-fold loss in the inhibitory activity toward tumor necrosis factor-alpha (TNF-alpha) production in vitro as compared with the NH analogue (1); however, 5a exhibited an oral inhibitory activity on TNF-alpha production with an ED50 value of 26 mg/kg, whereas 1 did not. Moreover, the oral bioavailability of 5a was higher than that of 1 (1, F=1%; 5a, F=21%), and the calculated ClogP value for 5a was higher than that for 1. These results suggest that the improved lipophilicity of 5a compared with that of 1 reflects its greater inhibitory activity on TNF-alpha production in vivo as well as oral bioavailability.     

Reduction of ion thermal diffusivity associated with the transition of the radial electric field in neutral-beam-heated plasmas in the large helical device

Recent large helical device experiments revealed that the transition from ion root to electron root occurred for the first time in neutral-beam-heated discharges, where no nonthermal electrons exist. The measured values of the radial electric field were found to be in qualitative agreement with those estimated by neoclassical theory. A clear reduction of ion thermal diffusivity was observed after the mode transition from ion root to electron root as predicted by neoclassical theory when the neoclassical ion loss is more dominant than the anomalous ion loss.