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.     

Solubility Switching of Metallophthalocyanines and Their Larger Derivatives upon Encapsulation

Metallophthalocyanines (MPcs) are very useful pigments but scarcely soluble without appropriate functional groups in common solvents. Herein, we report that bent polyaromatic amphiphiles act as excellent solubilizing reagents for nonfunctionalized MPcs and larger MPc derivatives (e.g., CuPc, perhalogenated CuPcs, Cu‐naphthalocyanine, CuPc polymers, and double‐decker MPcs) in neutral water upon encapsulation. The resultant MPc nanocomposites display high stability towards heat and pH change. More importantly, the encapsulated MPcs can be released by simple protocols under mild conditions both into a bulk solvent and onto glass or polymer plates.     

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.     

QUANTUM EFFICIENCY FOR THE PHOTOCONVERSION OF BACTERIORHODOPSIN AT VERY LOW TEMPERATURES

Abstract— Quantum efficiencies for photoconversion of bacteriorhodopsin (trans-bR) to a bathochromic product (batho-bR^t) and its photoreversion in purple membrane at 77 and 9 K were investigated with low temperature spectrophotometry. The kinetics of the photoconversion and its photoreversion cannot be expressed by a single exponential curve. The photoconversions at 77 and 9 K showed the same slope in the early stage. The kinetics of the photoreversions were identical at the two temperatures. These results indicate that the quantum efficiencies for the conversion of trans-bR to batho-bR^t or for its photoreversion are identical at the two temperatures.
The fact that the photoreversion cannot be expressed by a single exponential curve suggests the existence of several conformational states of batho-bR^t due to the trimer structure of the purple membrane.     

AND/OR bimolecular recognition

cis-Decalin (2) and perylene (3) are co-enclathrated by a self-assembled M6L4-coordination cage (1) to give 1 superset(2.3) although each of them is not enclathrated. This phenomenon is termed as AND bimolecular recognition because enclathration occurs only if 2 and 3 coexist. Cage 1 also coenclathrates azulene (8) and 1,4-naphthoquinone (9) to give 1 superset(8.9). In this case, 1 superset(8)2 and 1 superset(9)2 are formed by treating 1 with 8 and 9 individually. This case is termed as OR bimolecular recognition because enclathration occurs if 8 or 9 exists. Accordingly, we have shown that the self-assembled cage 1 experiences both AND and OR bimolecular recognition.     

Oxygen triggering reversible modulation of Vibrio fischeri strain Y1 bioluminescence in vivo

Yellow-emitting Vibrio fischeri Y1 modulates its bioluminescence (BL) depending on the dissolved O2 concentration. On supplying O2 to the cells under anaerobiosis, the cells begin to emit striking yellow BL peaking around 535 nm. The enhanced yellow emission reverts reversibly to the original level after O2 is consumed. Moreover, the reversible rise and fall of the yellow emission occurs repeatedly in accord with the repeating cycles of aeration on and off. This indicates that an increase in the cellular amount of yellow fluorescent protein (YFP) is not an immediate cause of the yellow emission enhancement. One suggested explanation is that the activity of YFP originating from its highly fluorescent property is altered by redox interaction with the respiratory components, including the soluble cytochrome c. Under the O2-limited conditions, the cellular YFP molecules, in part, seem to lose the fluorescent property possibly because of being reduced via redox interaction with some respiratory components in reduced form. On stimulating aerobic respiration with O2 supply, the reduced YFP seems to retrieve its fluorescent property via oxidation possibly with both O2, diffused across the cell membrane, and ferricytochrome c, generated during the respiratory turnover. The suggested redox interactions seem primarily to cause the reversible BL modulation.