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91.
E Hayakawa M Nakakura Y Kato Y Okubo T Hosokawa 《Chemical & pharmaceutical bulletin》1991,39(3):773-776
When doxorubicin was encapsulated into liposomes by freeze-thawing, the percentage of encapsulated doxorubicin (EN%) was found to vary according to the type of buffer solution used. The reason for this was investigated in the present report. Drug-free liposomes prepared by hydration were mixed with doxorubicin dissolved in a certain type of buffer solution that shows a pH decrease on freezing, and this mixture was subjected to freeze-thawing. Doxorubicin was encapsulated by the liposomes due to the difference in pH between freezing and thawing. EN% depended on the pH of the buffer solution before freezing and increased significantly at over pH 7. About 60% of doxorubicin was encapsulated into liposomes after the Ist freeze-thawing cycle, and EN% was increased gradually with the number of freeze-thawing cycles. The addition of sugar to the experimental system was seen to affect doxorubicin encapsulation and the particle size of liposomes. 相似文献
92.
A reversed-phase liquid chromatographic method for the determination of trace amounts of vanadium is described. Metal ions are converted into 2-(8-quinolylazo)-5-N,N-diethylaminophenol chelates in an off-line system. The chelates are injected onto a Zorbax CN column and separated with an aqueous acetonitrile mobile phase containing no chromogenic reagent. Unter these conditions, only vanadium(V) is spectrophotometrically detected at 540 nm among the metal ions Al(III), Ba(II), Ca(II), Cd(II), Co(II), Cr(III), Cu(II), Fe(III), Ga(III), Hg(II), Mg(II), Mn(II), Ni(II), Pb(II), V(V) and Zn(II). Amounts of 8.0–200 pg of vanadium(V) in 100-μl injections can be determined without interference from 10-fold molar excesses of many cations. At 0.001 a.u.f.s., the detection limit (twice the peak-to-peak noise) for vanadium(V) is 8.0 pg in 100 μl of injected solution and the relative standard deviation at 120 pg of vanadium(V) in a 100-μl injection is 3.5%. The proposed method is applied to the determination of vanadium in rain water and airborne particulates. 相似文献
93.
Yamada K Yagishita S Tanaka H Tohyama K Adachi K Kaizaki S Kumagai H Inoue K Kitaura R Chang HC Kitagawa S Kawata S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(11):2647-2660
Novel metal-complex assemblies constructed from the flexible hinge-like ligand H(2)bhnq (H(2)bhnq=2,2'-bi(3-hydroxy-1,4-naphthoquinone)) have been synthesized. The X-ray crystal structures of these compounds reveal that four types of architectures are accessible by variation of the metal ions. In copper(II) compounds 1-3, the chelating bhnq(2-) ions bridge copper(II) centers to form one-dimensional zigzag chains. The chains of 1-3 are arranged by hydrogen-bonding interactions and stacking interactions to produce porous structures. Cobalt(II) and zinc(II) compounds 4 and 5 form one-dimensional helical chains. In 4 and 5, the crystal packing induces spontaneous resolution of the helical chains with chiral cavities formed perpendicular to the helices. Nickel(II) compounds 6 and 7 form cyclic tetramers. The fourth architecture, a dimer (compound 8), is obtained by the reaction of zinc(II) and bhnq(2-) in MeOH. In these compounds, changes of the dihedral angles and the metal-coordination mode of the bhnq(2-) ion induce the structural versatility. The assemblies of the zigzag chains of the copper(II) compounds exhibit reversible vapochromic behavior. UV/Vis, powder X-ray diffraction, EPR, and adsorption isotherm measurements indicate that this vapochromic behavior is based on the hinge-like flexibility of the bhnq(2-) ion. 相似文献
94.
Kamoda S Nomura C Kinoshita M Nishiura S Ishikawa R Kakehi K Kawasaki N Hayakawa T 《Journal of chromatography. A》2004,1050(2):211-216
Carbohydrate chains in glycoprotein pharmaceuticals have important roles for the expression of their biological activities. Therefore, development of an assessment method for the carbohydrate chains is an important parameter for quality control of glycoprotein pharmaceuticals such as newly developed therapeutic antibodies. In this report, we applied capillary electrophoresis with laser-induced fluorescence detection to the analysis of carbohydrate chains after releasing with glycoamidase followed by derivatization with 3-aminobenzoic acid. We found that four major oligosaccharides present in antibody pharmaceuticals were successfully separated with good resolution. The present method showed good precision in both migration times and relative peak areas, and gave comparable accuracy with that using a derivatization method with 8-aminopyrene-1,3,6-trisulfonate. 相似文献
95.
Photochemie von tricyclischen β, γ-γ′, δ′-ungesättigten Ketonen. 50. Mitteilung über Photoreaktionen
Photochemistry of tricyclic β, γ-γ′, δ′-unsaturated ketones The easily available tricyclic ketone 1 (cf. Scheme 1) with a homotwistane skeleton yielded upon direct irradiation the cyclobutanone derivative 3 by a 1,3-acyl shift. Further irradiation converted 3 into the tricyclic hydrocarbon 4 . However, acetone sensitized irradiation of 1 gave the tetracyclic ketone 5 by an oxa-di-π-methane rearrangement. Again with acetone as a sensitizer the ketone 5 was quantitatively converted to the pentacyclic ketone 6 . The conversion 5 → 6 represents a novel photochemical 1,4-acyl shift. The possible mechanisms are discussed (see Scheme 7). The tricyclic ketone 2 underwent similar types of photoreactions as 1 (Scheme 2). Unlike 5 the tetracyclic ketone 9 did not undergo a photochemical 1,4-acyl shift. The epoxides 10 and 14 derived from the ketones 1 and 2 , respectively, underwent a 1,3-acyl shift upon irradiation followed by decarbonylation, and the oxa-di-π-methane rearrangement (Schemes 3 and 4). The diketone 18 derived from 1 behaved in the same way (Scheme 5). The tetracyclic diketone 21 cyclized very easily to the internal aldol product 22 under the influence of traces of base (Scheme 5). Upon irradiation the γ, δ-unsaturated ketone 24 underwent only the Norrish type I cleavage to yield the aldehyde 25 (Scheme 6). 相似文献
96.
A convenient synthesis of peripherally substituted or unsubstituted phthalocyanines having a variety of metals is described. Phthalocyanines can be obtained by heating phthalimides or phthalic anhydride with metal salts, hexamethyldisilazane, a catalytic amount of p-TsOH, and DMF at 150 degrees C. 相似文献
97.
Hitoshi Miyasaka Yuko YoshinoTomohiko Ishii Ryo KanehamaToshio Manabe Masahiro YamashitaHiroyuki Nishikawa Isao IkemotoHideo Kishida Hiroyuki MatsuzakiHiroshi Okamoto 《Journal of solid state chemistry》2002,168(2):418-426
An assembled compound (BEDT-TTF)2[Mn2Cl5(EtOH)] (1) consisting of two structural lattices of Mn(II)-Cl one-dimensional (1-D) chains and bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) stacking layers was synthesized by electrochemical crystallization. Compound 1 crystallized in triclinic space group P-1 (#2) with a=13.1628(5) Å, b=20.3985(9) Å, c=7.4966(3) Å, α=98.3498(8)°, β=104.980(1)°, γ=74.602(2)°, V=1868.3(1) Å3, and Z=2. The 1-D chains and the stacking layers are aligned along the c-axis of the unit cell. The 1-D chain is described as [Mn2Cl5(EtOH)]∞− in which two Mn(II) ions and four Cl− ions form a ladder-like chain with Kagomé (cuboidal) sublattices, and the remaining Cl− ion and an ethanol molecule cap the edge-positioned Mn(II) ions of the chains. The BEDT-TTF molecules are packed between the Mn-Cl chains (ac-plane), the intermolecular S·S contacts of which are approximately found in the range 3.440(2)-3.599(2) Å. The packing feature of BEDT-TTF molecules is very similar to that of (BEDT-TTF)2ClO4(TCE)0.5 (TCE=1,1,2-trichloroethane) (J. Am. Chem. Soc., 105, 297 (1983)). Regarding the electronic state of each BEDT-TTF molecule, Raman spectroscopic analysis and ESR study revealed the presence of half-valence BEDT-TTF molecules (charge delocalization) in 1. Magnetic measurements clearly demonstrated that the paramagnetic spins on the 1-D chain [Mn2Cl5(EtOH)]∞− arrange antiferromagnetically in the low-temperature region. Additionally, 1 exhibits metallic conductivity in the temperature range 2.0-300 K (σ=21 S cm−1 at 300 K and 1719 S cm−1 at 2.0 K), due to the contribution of the stacked BEDT-TTFs. Consequently, these peculiarities that correspond to antiferromagnetic/metallic conductivity demonstrate the “bi-functionality” of 1. 相似文献
98.
A simple and sensitive method is described for the determination of biogenic indole compounds adsorbed on cellulose or alumina plates for thin-layer chromatography by room-temperature phosphorimetry. The optimum conditions were investigated for 5-hydroxyindole-3-acetic acid and indole-3-acetic acid. The compounds are spotted on the plates, which are then sprayed successively with sodium citrate or sodium acetate, and sodiu iodide solutions. The plates are dried completely under a stream of dry nitrogen, and immediately dipped in molten paraffin. The phosphorescence is stable for at least 3 h even in moist air. The limits of detection for nine biogenic indole compounds tested are between 2 and 300 pmol per sample spot. 相似文献
99.
Takashi Tozawa Dr. Hitoshi Nagao Yoshinobu Yamane Teruaki Mukaiyama Prof. Dr. 《化学:亚洲杂志》2007,2(1):123-134
Chiral quaternary ammonium phenoxides were readily prepared from commercially available cinchona alkaloids and proved to be useful new asymmetric organocatalysts. Among various chiral quaternary ammonium phenoxides, a cinchonidine‐derived catalyst that bears both a sterically hindered N1‐9‐anthracenylmethyl group and a strongly electron withdrawing 9‐O‐3,5‐bis(trifluoromethyl)benzyl group were found to be highly effective for the Michael addition of ketene silyl acetals (derived from phenyl carboxylates) and α,β‐unsaturated ketones followed by lactonization. Optically active 3,4‐dihydropyran‐2‐one derivatives were obtained in high yields with excellent control of enantio‐ and diastereoselectivity. This catalyst can be handled in air and stored at room temperature in a sealed bottle without decomposition for at least one month. 相似文献
100.
Tsuneyuki Sato Shukei Inui Hitoshi Tanaka Tadatoshi Ota Mikiharu Kamachi Kohji Tanaka 《Journal of polymer science. Part A, Polymer chemistry》1987,25(2):637-652
The polymerization of di-n-butyl itaconate (DBI) intiated with AIBN was kinetically investigated in benezene. The polymerization rate (Rp) was expressed by: Rp = k[AIBN]0.5[DBI]1.7. The polymerization showed a considerably low overall activation energy of 15.3 kcal/mol. The initiator efficiency of AIBN in this system decreased with increasing DBI concentration, ranging from 0.34 to 0.55°C, which is ascribable to viscosity effect due to the monomer. From an ESR study, the polymerization system was found to involve two kinds of persistent radicals, namely, primary propagating ( III ) and propagating ( I ) radicals. The relative concentration of III to I increased with decreasing monomer concentration. Azo-nitrile initiators such as AVN and ACN similarly produced two persistent radicals, while MAIB, DBPO, and PBO yielded only propagating radical I as persistent. The MAIB-initiated polymerization of DBI was also performed in benzene. Similar kinetic features were observed, that is, a higher dependence of Rp on the DBI concentration and a low overall activation energy (14.4 kcal/mol). The following rate equation was obtained at 50°C:Rp = k[MAIB]0.5[DBI]1.6. The initiator efficiency of MAIB decreased with increasing DBI concentration, ranging from 0.32 to 0.53 at 50°C. The concentration of propagating radical I was determined by ESR at 50 and 61°C, from which kp and kt were estimated. The kp value increased with increasing monomer concentration, while the kt one decreased with the DBI concentration. These values are much lower compared with those of MMA. 相似文献