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101.
The synthesis of a variety of organotin compounds with 1H, 1H, 2H, 2H‐perfluorooctyl groups is reported, together with an improved method for the corresponding distannoxane. Unique properties of this compound are disclosed in terms of fluorophilicity and activity as a Lewis acid catalyst in comparison with other mono‐nuclear derivatives. A new criterion for obtaining high solubility in fluorocarbon solvents is presented. Copyright © 2003 John Wiley & Sons, Ltd.  相似文献   
102.
We show a descent method for submodular function minimization based on an oracle for membership in base polyhedra. We assume that for any submodular function f: ?→R on a distributive lattice ?⊆2 V with ?,V∈? and f(?)=0 and for any vector xR V where V is a finite nonempty set, the membership oracle answers whether x belongs to the base polyhedron associated with f and that if the answer is NO, it also gives us a set Z∈? such that x(Z)>f(Z). Given a submodular function f, by invoking the membership oracle O(|V|2) times, the descent method finds a sequence of subsets Z 1,Z 2,···,Z k of V such that f(Z 1)>f(Z 2)>···>f(Z k )=min{f(Y) | Y∈?}, where k is O(|V|2). The method furnishes an alternative framework for submodular function minimization if combined with possible efficient membership algorithms. Received: September 9, 2001 / Accepted: October 15, 2001?Published online December 6, 2001  相似文献   
103.
The effects of the homogeneity of precursor non-crystalline Pb---Ti---O gels on their transformation to crystalline PbTiO3 were studied. Hydrous gels were prepared via two different routes, i.e., (i) mixing two unitary sols (MS), and (ii) co-precipitation (CP). Mechanical pretreatment was also carried out, primarily for the purpose of homogenization. The local homogeneity was evaluated by elementary microanalysis using a transmission electron microscope. The process of ball-milling the MS gel for 3 h improved its homogeneity only slightly. However, the homogeneity of the ball-milled MS gel suddenly increased to that of the CP gel on subsequent heating to a temperature as low as 483 K. This type of thermal homogenization was not observed for the unground MS gel. The evaporation of lead monoxide on further heating to 1023 K was also suppressed by preliminary ball-milling. All these results suggest that the ionic migration and the formation of Pb---O---Ti bonds in the gels take place during the mechanical activation with the aid of OH groups.  相似文献   
104.
Treatment of antiaromatic nickel(II) norcorrole with potassium cyanide provided nickel(II) 3‐cyanonorcorrole with perfect regioselectivity without the help of a catalyst. The reaction of the nickel(II) norcorrole with phenol or thiophenol in the presence of a base also yielded substitution products. The antiaromatic 16π conjugation system in the norcorrole core was preserved in the functionalized products. Introduction of phenylthio groups significantly decreased the HOMO–LUMO gap and enhanced the near IR absorption property.  相似文献   
105.
The total synthesis of (?)‐isoschizogamine was accomplished, featuring the construction of the quaternary carbon center by the modified Johnson–Claisen rearrangement in basic media and the facile assembly of the key tetracyclic quinolone intermediate through a cascade cyclization. The characteristic cyclic aminal was constructed by late‐stage C?H functionalization at the position adjacent to the lactam nitrogen using a combination of CrO3 and nBu4NIO4 and subsequent Bi(OTf)3‐mediated cyclization.  相似文献   
106.
Ito T  Kaneko S  Suzuki K 《Talanta》2011,85(1):707-712
We proposed a low cost fabrication procedure of a poly(methylmethacrylate) (PMMA) column chip. 3D microchannel structure consisting of four columns in a chip for a mother die was fabricated using dry film photoresist and photolithography technique. Electroforming was applied to the mother die in order to obtain a Ni mold, then, the pattern was transferred to PMMA by hot press. The column had a dam structure to keep enzyme-immobilized microbeads with volume of 640 nL. The column chip was applied for a micro flow injection analysis (μFIA) system. For a demonstration, we measured lactose using two columns in series. One column was set on upper stream and filled with chitosan microbeads immobilized with β-galactosidase, the other was on downstream and filled with the beads immobilized with glucose oxidase. The lactose detection was accomplished less than 90s after the sample injection. The biosensing system also showed a high performance for lactose detection in wide range of 1 μM to 1mM. These results show that the column chip and our microfluidic biosensing system have the potential to assist minuaturization with small sample volume and short determination time for a sequential analysis.  相似文献   
107.
In this study, mono- and pentacyclic C(35) terpenes from Bacillus subtilis were biosynthesized via the cyclization of C(35) isoprenoid using purified enzymes, including the first identified new terpene cyclase that shows no sequence homology to any of the known terpene cyclases. On the basis of these findings, we propose that these C(35) terpenes should be called the new family of "sesquarterpenes."  相似文献   
108.
Copper(II) complexes 1a and 1b, supported by tridentate ligand bpa [bis(2-pyridylmethyl)amine] and tetradentate ligand tpa [tris(2-pyridylmethyl)amine], respectively, react with cumene hydroperoxide (CmOOH) in the presence of triethylamine in CH(3)CN to provide the corresponding copper(II) cumylperoxo complexes 2a and 2b, the formation of which has been confirmed by resonance Raman and ESI-MS analyses using (18)O-labeled CmOOH. UV-vis and ESR spectra as well as DFT calculations indicate that 2a has a 5-coordinate square-pyramidal structure involving CmOO(-) at an equatorial position and one solvent molecule at an axial position at low temperature (-90 °C), whereas a 4-coordinate square-planar structure that has lost the axial solvent ligand is predominant at higher temperatures (above 0 °C). Complex 2b, on the other hand, has a typical trigonal bipyramidal structure with the tripodal tetradentate tpa ligand, where the cumylperoxo ligand occupies an axial position. Both cumylperoxo copper(II) complexes 2a and 2b are fairly stable at ambient temperature, but decompose at a higher temperature (60 °C) in CH(3)CN. Detailed product analyses and DFT studies indicate that the self-decomposition involves O-O bond homolytic cleavage of the peroxo moiety; concomitant hydrogen-atom abstraction from the solvent is partially involved. In the presence of 1,4-cyclohexadiene (CHD), the cumylperoxo complexes react smoothly at 30 °C to give benzene as one product. Detailed product analyses and DFT studies indicate that reaction with CHD involves concerted O-O bond homolytic cleavage and hydrogen-atom abstraction from the substrate, with the oxygen atom directly bonded to the copper(II) ion (proximal oxygen) involved in the C-H bond activation step.  相似文献   
109.
Nickel complexes having acetylated glucopyranosyl group incorporated N-heterocyclic carbene (NHC) ligands with methyl or benzyl groups as an N-substituent exhibit two kinds of dynamic behaviours in solution (1)H NMR spectroscopy. One of the dynamic behaviours is attributed to the anti- and syn-rotamers, which occur by the rotation of the unsymmetrical NHC ligands around the axes of the Ni-C bonds. The other is attributed to the diastereomers of the syn-rotamers, which occur by opposite rotation of the imidazolylidene rings and the chiral carbohydrate group incorporated into the NHC ligands. Crystallographic analysis of the nickel complex having the NHC ligand with acetylated glucopyranosyl and benzyl groups as N-substituents showed CH-π interaction between the glucopyranosyl unit of each NHC ligand and the phenyl ring of the other NHC ligand in the complex in the solid state.  相似文献   
110.
Treatment of perylene bisimides (PBIs) with bis(pinacolato)diboron in the presence of an iridium catalyst provides tetraborylated PBIs at 2,5,8,11-positions in good yields with perfect regioselectivity. The planar structure of the perylene core has been confirmed by X-ray diffraction analysis. Oxidation of tetraborylated PBI with hydroxylamine hydrochloride affords tetrahydroxy PBI in excellent yield, which exhibits a substantially blue-shifted absorption spectrum due to an intramolecular hydrogenbonding interaction between carbonyl and hydroxy groups.  相似文献   
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