A facile access to spiro furanone skeleton based on Pd(II)-mediated cyclization-carbonylation of propargylic esters

The oxidative cyclization-carbonylation of propargylic esters mediated by Pd(II) afforded cyclic orthoesters, which were hydrolyzed into γ-acetoxy-β-ketoesters. Based on the NMR experiments, it was presumed that the cyclization reaction was initiated by a nucleophilic attack of carbonyl oxygen to the alkyne carbon coordinated to palladium(II). When the γ-acetoxy-β-ketoesters were treated with a basic condition, Knoevenagel-Claisen type condensation took place, and spiro furanone derivatives were obtained in good yields. We applied these reactions to steroid derivatives, and steroid derivatives having a spiro furanone fragment were synthesized. Among them, the spiro furanone 4j had vasorelaxant and bradycardiac activities. Compounds 2i-4k had inhibitory effect on CYP3A.     

Single-vesicle estimation of ATP-binding cassette transporters in microfluidic channels

We have developed a method to analyze the substrate transport of ATP-binding cassette (ABC) transporters, which are associated with drug resistance in tumor cells. Our microfluidic method is well suited to the single-vesicle estimation of substrate transport and the rapid drug screening of ABC transporters. Using this method, we have demonstrated, for the first time, the analysis of substrate transport by a single transporter and performed drug-inhibition experiments in less than 3 h.     

Stabilization of atmospheric carbon dioxide via zero emissions-An alternative way to a stable global environment. Part 1: Examination of the traditional stabilization concept

The concept of "stabilization" of atmospheric CO2 concentration is re-examined in connection with climate-change mitigation strategies. A new "zero-emissions stabilization (Z-stabilization)" is proposed, where CO2 emissions are reduced to zero at some time and thereafter the concentration is decreased by natural removal processes, eventually reaching an equilibrated stable state. Simplified climate experiments show that, under Z-stabilization, considerably larger emissions are permissible in the near future compared with traditional stabilization, with the same constraint on temperature rise. Over longer time scales, the concentration and temperature decrease close to their equilibrium values, much lower than those under traditional stabilization. The smaller temperature rise at final state is essential to avoid longer-term risk of sea level rise, a significant concern under traditional stabilization. Because of these advantages a Z-stabilization pathway can be a candidate of practical mitigation strategies as treated in Part 2.(Contributed by Taroh MATSUNO, M.J.A.).     

Precise measurement of the CP violation parameter sin2φ1 in B0→(cc¯)K0 decays

We present a precise measurement of the CP violation parameter sin2φ1 and the direct CP violation parameter A(f) using the final data sample of 772×10(6) BB[over ˉ] pairs collected at the Υ(4S) resonance with the Belle detector at the KEKB asymmetric-energy e(+)e(-) collider. One neutral B meson is reconstructed in a J/ψK(S)(0), ψ(2S)K(S)(0), χ(c1)K(S)(0), or J/ψK(L)(0) CP eigenstate and its flavor is identified from the decay products of the accompanying B meson. From the distribution of proper-time intervals between the two B decays, we obtain the following CP violation parameters: sin2φ1=0.667±0.023(stat)±0.012(syst) and A(f)=0.006±0.016(stat)±0.012(syst).     

First observation of B(s)(0) → J/ψη and B(s)(0) → J/ψη'

We report first observations of B(s)(0) → J/ψη and B(s)(0) → J/ψη'. The results are obtained from 121.4 fb(-1) of data collected at the Υ(5S) resonance with the Belle detector at the KEKB e+ e- collider. We obtain the branching fractions B(B(s)(0) → J/ψη)=[5.10±0.50(stat)±0.25(syst)(-0.79)(+1.14)(N(B(s)(*) B(s)(*))]×10(-4), and B(B(s)(0) → J/ψη')=[3.71±0.61(stat)±0.18(syst)(-0.57)(+0.83)(N(B(s)(*) B(s)(*))]×10(-4). The ratio of the two branching fractions is measured to be (B(B(s) → J/ψη'))/(B(B(s) → J/ψη))=0.73±0.14(stat)±0.02(syst).     

Theoretical analysis of using airflow to purge residual water in an inclined pipe

ＩｎｔｒｏｄｕｃｔｉｏｎＰｕｒｇｉｎｇｒｅｓｉｄｕａｌｌｉｑｕｉｄｉｎａＵ＿ｓｈａｐｅｄｐｉｐｅｌｉｎｅｉｓｃｈａｌｌｅｎｇｅｆｏｒｃｈｅｍｉｃａｌａｎｄｔｒａｎｓｐｏｒｔａｔｉｏｎｉｎｄｕｓｔｒｙ[1].Ｍａｎｙｔｅｃｈｎｉｑｕｅｓｈａｖｅｂｅｅｎｅｍｐｌｏｙｅｄｔｏｐｕｒｇｅｏｕｔｒｅｓｉｄｕａｌｗａｔｅｒ[2 ],ｂｕｔｎｏｎｅｈａｖｅｂｅｅｎｃｏｍｐｌｅｔｅｌｙｓａｔｉｓｆａｃｔｏｒｙ .Ｏｎｅｐｏｓｓｉｂｌｅｍｅｔｈｏｄｆｏｒｄｏｉｎｇｔｈｉｓｈａｓｂｅｅｎｔｏｂｌｏｗａｇｒｅａｔｑｕａｎｔｉｔ…     

气流排除倾斜管道积水的理论分析

运用作者推导的动量积分关系式,分析了向有积水的斜置管道中分别吹入轴向气流和螺旋气流时积水的运动情况。结果表明:在大多数情况下,螺旋气流能除去斜置管道中积水;而轴向气流不能除去积水,一段时间后会出现逆流。这一结果与Horii和赵耀华等人在这个问题上所做的实验结果一致。此外,还讨论了不同的初始条件对排水情况的影响。     

Singly and Doubly Quinoxaline-Fused BIII Subporphyrins

B-Phenyl B^III subporphyrin-α-diones prepared in a three-step reaction sequence from the parent subporphyrin were condensed with 1,2-diaminobenzenes to give the corresponding quinoxaline-fused subporphyrins in variable yields. Quinoxaline-fused B-phenyl-5,10,15-triphenyl B^III subporphyrin was transformed to the corresponding subporphyrin-α-dione in the same three-step reaction sequence, which was then condensed with 1,2-diaminobenzene to give doubly quinoxaline-fused subporphyrin. These quinoxaline-fused subporphyrins exhibit redshifted absorption and fluorescence spectra compared with the parent one. A singly quinoxaline-fused subporphyrin bearing three meso-bis(4-dimethylaminophenyl)aminophenyl substituents shows blueshifted fluorescence in less polar solvent, which has been ascribed to emission associated with charge recombination of intramolecular charge transfer (CT) state.     

Fluorescence Response and Self-Assembly of a Tweezer-Type Synthetic Receptor Triggered by Complexation with Heme and Its Catabolites

There is increasing interest in the development and applications of synthetic receptors that recognize target biomolecules in aqueous media. We have developed a new tweezer-type synthetic receptor that gives a significant fluorescence response upon complexation with heme in aqueous solution at pH 7.4. The synthetic receptor consists of a tweezer-type heme recognition site and sulfo-Cy5 as a hydrophilic fluorophore. The receptor–heme complex exhibits a supramolecular amphiphilic character that facilitates the formation of self-assembled aggregates, and both the tweezer moiety and the sulfo-Cy5 moiety are important for this property. The synthetic receptor also exhibits significant fluorescence responses to biliverdin and bilirubin, but shows very weak fluorescence responses to flavin mononucleotide, folic acid, and nicotinamide adenine dinucleotide, which contain smaller π-scaffolds.     

Role of cyclic dithiocarbonate as a promoter in the reaction of epoxide and imine in the presence of water

It was demonstrated that the reaction of epoxide and imine as a latent initiator under highly humid conditions was accelerated by addition of 5‐phenoxymethyl‐1,3‐oxathiolane‐2‐thione ( 1 ). When 1 was added to a mixture of glycidyl phenyl ether and an imine, the reaction of the epoxide with an amine released from the imine became faster than was the case without 1 , that is, 1 worked as a promoter of the reaction. The curing rate and initial adhesive strength of epoxy resin increased compared with that without 1 . © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4276–4283, 2004