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91.
Kano K Kitagishi H Tamura S Yamada A 《Journal of the American Chemical Society》2004,126(46):15202-15210
5,10,15,20-Tetrakis(4-sulfonatophenyl)porphinato iron(III) (Fe(III)TPPS) forms a very stable 1:2 complex with heptakis(2,3,6-tri-O-methyl)-beta-cyclodextrin (TMe-beta-CD), whose iron(III) center is located at a hydrophobic cleft formed by two face-to-face TMe-beta-CD molecules. Various inorganic anions (X(-)) such as F(-), Cl(-), Br(-), I(-), N(3)(-), and SCN(-) coordinate to Fe(III)TPPS(TMe-beta-CD)(2) to form five-coordinate high-spin Fe(III)TPPS(X)(TMe-beta-CD)(2), while no coordination occurs with ClO(4)(-), H(2)PO(4)(-), NO(3)(-), and HSO(4)(-). Except for F(-), none of the anions investigated coordinate to Fe(III)TPPS in the absence of TMe-beta-CD due to extensive hydration to the anions as well as to Fe(III)TPPS. The present system shows a high selectivity toward the N(3)(-) anion. The thermodynamics suggests that Lewis basicity, hydrophilicity, and shape of an X(-) anion are the main factors to determine the stability of the Fe(III)TPPS(X)(TMe-beta-CD)(2) complex. 相似文献
92.
The asymmetric hydroformylation of 2‐ and 3‐vinylfurans ( 2a and 2b , resp.) was investigated by using [Rh{(R,S)‐binaphos}] complexes as catalysts ((R,S)‐binaphos = (11bS)‐4‐{[1R)‐2′‐phosphino[1,1′‐binaphthalen]‐2‐yl]oxy}dinaphtho[2,1‐d:1′,2′‐f][1,3,2]dioxaphosphepin; 1 ). Hydroformylation of 2 gave isoaldehydes 3 in high regio‐ and enantioselectivities (Scheme 2 and Table). Reduction of the aldehydes 3 with NaBH4 successfully afforded the corresponding alcohols 5 without loss of enantiomeric purity (Scheme 3). 相似文献
93.
Ikehata J Shinomiya K Kobayashi K Ohshima H Kitanaka S Ito Y 《Journal of chromatography. A》2004,1025(2):169-175
The effect of Coriolis force on the counter-current chromatographic separation was studied using centrifugal partition chromatography (CPC) with four different two-phase solvent systems including n-hexane-acetonitrile (ACN); tert-butyl methyl ether (MtBE)-aqueous 0.1% trifluoroacetic acid (TFA) (1:1); MtBE-ACN-aqueous 0.1% TFA (2:2:3); and 12.5% (w/w) polyethylene glycol (PEG) 1000-12.5% (w/w) dibasic potassium phosphate. Each separation was performed by eluting either the upper phase in the ascending mode or the lower phase in the descending mode, each in clockwise (CW) and counterclockwise column rotation. Better partition efficiencies were attained by the CW rotation in both mobile phases in all the two-phase solvent systems examined. The mathematical analysis also revealed the Coriolis force works favorably under the CW column rotation for both mobile phases. The overall results demonstrated that the Coriolis force produces substantial effects on CPC separation in both organic-aqueous and aqueous-aqueous two-phase systems. 相似文献
94.
Tachibana Y Otsuka K Terabe S Arai A Suzuki K Nakamura S 《Journal of chromatography. A》2003,1011(1-2):181-192
A robust and simple interface for microchip electrophoresis-mass spectrometry (MCE-MS) was developed using a spray nozzle connected to the exit of the separation channel of the microchip. The spray nozzle was attached to the microchip using a polyether ether ketone screw without adhesive, thus allowing easy replaced. Sample injection and electrophoretic separation was performed by control of the voltage only. The analysis of a few basic drugs was performed using the optimized MCE-MS system. The separation was improved by using a high-viscosity separation buffer and a spray nozzle with a small bore size. This system was also applied to the separation of peptides and protein-trypsin digests. Sample adsorption was minimized by adding acetonitrile to the separation buffer when using a quartz microchip. 相似文献
95.
A mononuclear five-coordinate molybdenum(IV) monosulfide complex, (Et4N)2[MoS(L)2] (L = cyclohexene-1,2-dithiolate) (1), was obtained and characterized by IR, UV-vis spectroscopic methods, and X-ray crystallography. 1 was oxidized by an equivalent ferrocenium cation to give the corresponding mononuclear molybdenum(V) complex, (Et4N)[MoS(L)2] (2), which was stable for a few minutes under a lower concentration than 0.3 mM and then further dimerized to (Et4N)2[Mo(L)2]2(mu-S)2 (3). 相似文献
96.
Nakamura K Suzuki T Hasegawa M Kato Y Sasaki H Inouye K 《Journal of chromatography. A》2003,1009(1-2):133-139
An affinity sorbent, hydrophilic polymer-based carrier of different pore size (Toyopearl) with immobilized p-aminobenzamidine (ABA), has been prepared. Its basic properties and some applications for protein purification were studied. ABA, which is a synthetic inhibitor for trypsin-like proteases, was covalently immobilized to Toyopearl by reductive amination. The ligand density and binding capacity for porcine trypsin varied depending on the pore size of Toyopearl. The maximum binding capacity of the immobilized p-aminobenzamidine Toyopearl (ABA-Toyopearl) for trypsin was more than 40 mg/ml gel. ABA-Toyopearl thus obtained was very stable below pH 8 and was successfully used for high-performance affinity chromatography of trypsin-like proteases such as trypsin, thrombin, tissue-type plasminogen activator or urokinase in a single step at 25 degrees C. 相似文献
97.
By using an oligopeptide chain as a functional linker and introducing coumarin 2 and coumarin 343 at the chain ends, an effective photo-induced energy transfer system was constructed and energy transfer from coumarin 2 to coumarin 343 was switched on and off by a solvent-induced helix-coil secondary transition of the oligopeptide chain. 相似文献
98.
Kodera M Shimakoshi H Nishimura M Okawa H Iijima S Kano K 《Inorganic chemistry》1996,35(17):4967-4973
A mononucleating tripyridine ligand, 2-(bis(2-pyridyl)methyl)-6-methylpyridine (L(1)), and a dinucleating hexapyridine ligand, 1,2-bis[2-(bis(2-pyridyl)methyl)-6-pyridyl]ethane (L(2)), have been prepared. The reaction of a carbanion of 2,6-lutidine with 2-bromopyridine affords L(1) which is converted to L(2) quantitatively by treating with tert-butyllithium and 1,2-dibromoethane. (&mgr;-Oxo)bis(&mgr;-acetato)diiron(III) complexes [Fe(2)(O)(OAc)(2)(L(1))(2)](ClO(4))(2) (1) and [Fe(2)(O)(OAc)(2)L(2)](ClO(4))(2) (2) have been synthesized and characterized by means of infrared, UV/vis, mass, and M?ssbauer spectroscopies and by measuring magnetic susceptibility and cyclic voltammograms. All the spectral data are consistent with the (&mgr;-oxo)bis(&mgr;-acetato)diiron(III) core structure in both 1 and 2. A relatively strong molecular ion peak at m/z 865 corresponding to [{Fe(2)O(OAc)(2)L(2)}(ClO(4))](+) in a FAB mass spectrum of 2 suggests the stabilization of the (&mgr;-oxo)bis(&mgr;-acetato)diiron(III) core structure by L(2) in a solution state. The compound 2.DMF.2-PrOH.H(2)O, chemical formula C(44)Cl(2)Fe(2)H(51)N(7)O(16), crystallizes in the monoclinic space group C2/c with a = 22.034(6) ?, b = 12.595(5) ?, c = 20.651(7) ?, beta = 121.49(2) degrees, and Z = 4. The cation has 2-fold symmetry with the bridging oxygen atom on the 2-fold axis: Fe-(&mgr;-O) = 1.782(5) ?, Fe-O-Fe = 123.6(6) degrees, and Fe.Fe = 3.142(3) ?. The diiron(III) core structure of 2 seems to be stabilized by encapsulation of the ligand. Compound 2 is the first example of a discrete (&mgr;-oxo)bis(&mgr;-acetato)diiron(III) complex with a dinucleating ligand. 相似文献
99.
[reaction: see text] Allylzirconium reagents are effective for radical allylation of alpha-halo carbonyl compounds. The key steps would be homolytic cleavage of the zirconium-carbon bond and halogen abstraction by the resulting Cp(2)ZrCl(III). Zirconocene-olefin complex can be also utilized for the allylation of alpha-halo compounds. 相似文献
100.
Hiroshi Tanaka Tsuyoshi Hasegawa Narumi Kita Hiroko Nakahara Takahiro Shibata Sho Oe Makoto Ojika Koji Uchida Takashi Takahashi 《化学:亚洲杂志》2006,1(5):669-677
An efficient solution‐phase synthesis of rac‐15‐deoxy‐Δ12,14‐PGJ2 (15dPGJ2) derivatives that contain variable α and ω chains based on a polymer‐assisted strategy and their neurite‐outgrowth‐promoting activity are described. The strategy for the synthesis of PGJ2 derivatives involves the use of a vinyl iodide bearing cyclopentenone as a key intermediate, which undergoes Suzuki–Miyaura coupling and subsequent Lewis acid catalyzed aldol condensation for incorporation of the ω and α chains, respectively. For easy access to the PGJ2 derivatives, a polymer‐supported catalyst and scavengers were adapted for use in these four diverse steps, in which workup and purification can be performed by simple filtration of the solid‐supported reagents. By using this methodology, we succeeded in the synthesis of 16 PGJ2 derivatives with four alkyl boranes and four aldehydes. The neurite‐outgrowth‐promoting activity of the 16 synthetic compounds in PC12 cells revealed that the side‐chains play a major role in modulating their biological activity. The carboxylic acid on the α chain improved the biological activity, although it was not absolutely required. Furthermore, a PGJ2 derivative with a phenyl moiety on the ω chain was found to exhibit an activity comparable to that of natural 15dPGJ2. 相似文献