Metal‐Catalyzed Sequential Formation of Distant Bonds in Organic Molecules: Palladium‐Catalyzed Hydrosilylation/Cyclization of 1,n‐Dienes by Chain Walking

Sequential formation of distant bonds in organic molecules was achieved for the palladium‐catalyzed hydrosilylation/cyclization of various 1,n‐dienes by chain walking of the metal catalyst. The reaction was applicable to various 1,n‐dienes, including a 1,13‐diene, to form a cyclopentane ring as well as a carbon–silicon bond at a remote site. The use of “nondissociative” chain walking provides a fascinating strategy in organic synthesis to functionalize distant parts of organic molecules, in a particular order, within a catalytic cycle by effectively moving the reactive center from a remote position.     

Carbon Dioxide to Methanol: The Aqueous Catalytic Way at Room Temperature

Carbon dioxide may constitute a source of chemicals and fuels if efficient and renewable processes are developed that directly utilize it as feedstock. Two of its reduction products are formic acid and methanol, which have also been proposed as liquid organic chemical carriers in sustainable hydrogen storage. Here we report that both the hydrogenation of carbon dioxide to formic acid and the disproportionation of formic acid into methanol can be realized at ambient temperature and in aqueous, acidic solution, with an iridium catalyst. The formic acid yield is maximized in water without additives, while acidification results in complete (98 %) and selective (96 %) formic acid disproportionation into methanol. These promising features in combination with the low reaction temperatures and the absence of organic solvents and additives are relevant for a sustainable hydrogen/methanol economy.     

Practical Route to the Left Wing of CTX1B and Total Syntheses of CTX1B and 54‐deoxyCTX1B

Ciguatoxins, the principal causative agents of ciguatera seafood poisoning, are extremely large polycyclic ethers. We report herein a reliable route for constructing the left wing of CTX1B, which possesses the acid/base/oxidant‐sensitive bisallylic ether moiety, by a 6‐exo radical cyclization/ring‐closing metathesis strategy. This new route enabled us to achieve the second‐generation total synthesis of CTX1B and the first synthesis of 54‐deoxyCTX1B.     

Turbulence Characteristics in Flows Over Solid and Porous Square Ribs Mounted on Porous Walls

PIV measurements have been performed for turbulent flows in a rib-mounted channel whose bottom wall is made of a porous layer. The ratio of the rib and channel heights is fixed at 0.5. The effects of the wall and rib permeability are investigated focusing on the separating and reattaching flows at the bulk Reynolds number of 10³???10⁴. Three kinds of foamed ceramics are employed as the porous media. They have the same porosity of 0.8 but each permeability is different from the others. Its normalized values by the rib height are 0.89 × 10^???4, 1.47 × 10^???4 and 3.87 × 10^???4. Two kinds of square cylinder ribs: an impermeable smooth solid rib or a permeable porous rib which is made of the same porous medium as that for the bottom wall are used. The obtained turbulent velocity fields of the solid rib flows indicate that the turbulent intensity behind the rib becomes weak and the recirculation bubble in the clear channel tends to vanish as the the wall permeability increases. In the porous rib flow, the recirculation and the reattachment point shift downstream and turbulence becomes weaker due to the bleeding flow through the rib. In the higher permeability cases, the recirculation bubble hardly exists due to the flows through not only the bottom wall but also the porous rib. From the measurements, it is suggested that in the solid rib flows, a reverse flow region exists inside the porous wall whereas in porous rib flows, such reverse flow does not exist at higher permeability.     

二氧化钛薄膜上三氯乙烯光催化氧化反应机理

 研究了二氧化钛薄膜上三氯乙烯(TCE)气相光催化氧化的反应机理. 结果表明,TCE气相光催化氧化反应生成的氯气可引发TCE的连锁反应. 当添加氯气的浓度相同时TCE表面光催化反应的初速率约为光化学反应初速率的2倍,说明连锁反应主要发生在催化剂表面. 氯可吸附在催化剂表面,作为电子的接受体抑制空穴与电子复合,提高TiO2光催化剂的活性. 除了TCE与吸附在催化剂表面的·OH的相互作用及反应产物/中间产物二氯乙酰氯的光催化分解可生成氯气以外,光气在与氯气共存时的光分解也有利于氯的生成.     

Organic Ligand Binding by a Hydrophobic Cavity in a Designed Tetrameric Coiled‐Coil Protein

The design and characterization of a hydrophobic cavity in de novo designed proteins provides a wide range of information about the functions of de novo proteins. We designed a de novo tetrameric coiled‐coil protein with a hydrophobic pocketlike cavity. Tetrameric coiled coils with hydrophobic cavities have previously been reported. By replacing one Leu residue at the a position with Ala, hydrophobic cavities that did not flatten out due to loose peptide chains were reliably created. To perform a detailed examination of the ligand‐binding characteristics of the cavities, we originally designed two other coiled‐coil proteins: AM2, with eight Ala substitutions at the adjacent a and d positions at the center of a bundled structure, and AM2W, with one Trp and seven Ala substitutions at the same positions. To increase the association of the helical peptides, each helical peptide was connected with flexible linkers, which resulted in a single peptide chain. These proteins exhibited CD spectra corresponding to superhelical structures, despite weakened hydrophobic packing. AM2W exhibited binding affinity for size‐complementary organic compounds. The dissociation constants, K_d, of AM2W were 220 nM for adamantane, 81 μM for 1‐adamantanol, and 294 μM for 1‐adamantaneacetic acid, as measured by fluorescence titration analyses. Although it was contrary to expectations, AM2 did not exhibit any binding affinity, probably due to structural defects around the designed hydrophobic cavity. Interestingly, AM2W exhibited incremental structure stability through ligand binding. Plugging of structural defects with organic ligands would be expected to facilitate protein folding.     

Credibilistic Markov decision processes: The average case

Using a concept of random fuzzy variables in credibility theory, we formulate a credibilistic model for unichain Markov decision processes under average criteria. And a credibilistically optimal policy is defined and obtained by solving the corresponding non-linear mathematical programming. Also we give a computational example to illustrate the effectiveness of our new model.     

Approximation algorithms for the single allocation problem in hub-and-spoke networks and related metric labeling problems

This paper deals with a single allocation problem in hub-and-spoke networks. We present a simple deterministic 3-approximation algorithm and randomized 2-approximation algorithm based on a linear relaxation problem and a randomized rounding procedure. We handle the case where the number of hubs is three, which is known to be NP-hard, and present a (5/4)-approximation algorithm.The single allocation problem includes a special class of the metric labeling problem, defined by introducing an assumption that both objects and labels are embedded in a common metric space. Under this assumption, we can apply our algorithms to the metric labeling problem without losing theoretical approximation ratios. As a byproduct, we also obtain a (4/3)-approximation algorithm for an ordinary metric labeling problem with three labels.