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541.
Ohyama K Fujimoto E Wada M Kishikawa N Ohba Y Akiyama S Nakashima K Kuroda N 《Journal of separation science》2005,28(8):767-773
Capillary electrochromatography (CEC) with a novel stationary phase, 3-(4-sulfo-1,8-naphthalimido)propyl-modified silyl silica gel (SNAIP), proved useful for the separation of nucleosides and nucleic acid bases. The application scope of SNAIP, which is a relatively polar reversed-phase (RP)-type stationary phase, was successfully expanded to include the CEC separation of polar compounds although the combination of non-polar RP phase with highly aqueous mobile phase is often inadequate. Due to the permanently charged sulfonic acid groups and the naphthalimidopropyl moiety, the retention of charged and relatively polar nucleosides as well as bases on the SNAIP stationary phase was effected by electrostatic and hydrophobic interactions. This yielded a unique selectivity on SNAIP toward nucleosides and bases. The characteristic EOF on SNAIP, which was stronger at higher aqueous content in the mobile phase, proved suitable for the separation of polar compounds in reversed-phase mode with highly aqueous mobile phase. In addition, when a double stepwise gradient was employed to accelerate the latest peak (adenine), the elution time was shortened to less than half its original duration. 相似文献
542.
An anti-selective catalytic asymmetric Michael-type vinylogous addition of β,γ-butenolides to chromones was developed. The catalyst system developed herein is characterized by tuning of the steric and electronic effects using a proper Biphep-type chiral ligand to invert the diastereoselection, and improvement of the catalyst turnover by a coordinative phenolic additive. The catalytic protocol renders potentially biologically active natural product analogs accessible in good yield with moderate diastereoselectivity and high enantiomeric purity, mostly greater than 99% ee.An anti-selective catalytic asymmetric Michael-type vinylogous addition of β,γ-butenolides to chromones was developed. 相似文献
543.
Hattori T Shimazumi Y Goto H Yamabe O Morohashi N Kawai W Miyano S 《The Journal of organic chemistry》2003,68(6):2099-2108
A naturally occurring 1,1'-biphenanthrene, blestriarene C (1), was prepared in 13 steps and 30% overall yield. The key steps are the ester-mediated nucleophilic aromatic substitution on 2,6-di-tert-butyl-4-methoxyphenyl 5-isopropoxy-2-methoxybenzoate (4) by 2-methoxy-4-methoxymethoxy-6-methylphenylmagnesium bromide (5) and a novel intramolecular cyclization of the resulting 4-isopropoxy-2'-methoxy-4'-methoxymethoxy-6'-methylbiphenyl-2-carboxylic ester 14 to 7-isopropoxy-4-methoxy-2-(methoxymethoxy)phenanthren-9-ol (15). The racemic blestriarene C was optically resolved by chiral HPLC on a preparative scale to give several 10-mg yields of both the enantiomers in up to 95% ee. The absolute stereochemistry was determined to be S(a)-(-) by the axial chirality recognition method, which was based on the stereospecific formation of a 12-membered cyclic diester containing two biaryl-o,o'-diyl unites joined by ester -CO(2)- linkages. The validity of the method was confirmed by an X-ray crystallographic analysis and ab initio conformational analyses of such 12-membered cyclic diesters. It was found that blestriarene C and its 7,7'-diisopropyl ether 2 underwent rapid photoracemization even under ambient light exposure. 相似文献
544.
Microbial column flotation usingThiobacillus ferrooxidans was applied for desulfurization of Pittsburgh coal of CWM (Coal-Water Mixture) size between 38 μm and 75 μm. The coal contained
ferrous ion which would interfere separation of pyrite from coal by microbial flotation. The wash-out of ferrous ion with
0.5N HC1 solution enabled pyrite removal from coal. The coal was divided into two parts, the small-size coal between 38 μm
and 53 μm, and the large-size coal between 53 μm and 75 μm. The pyritic sulfur content was decreased from 2.88% of the feed
coal to 0.98% of the product coal for the largesize coal and from 2.77% of the feed coal to 1.12% of the product coal for
the small-size coal by microbial flotation. The decrease was based on removal of liberated pyrite particles (between 20 μm
and 70 μm). However, the fine particles (less than 20 μm) could not be removed even though the pyrite particles were liberated
from coal particles. The microbial column flotation was more effective for desulfurization of the large liberated pyrite particle
than that of the small. It was not effective for desulfurization of the locked pyrite particles that were buried in coal particles.
Both the pyrite liberation from coal and its particle size are important factors for the pyrite removal by microbial column
flotation. 相似文献
545.
Noriaki Dokoshi Shunroku Tohyama Saburo Fujita Masaru Kurihara Naoya Yoda 《Journal of polymer science. Part A, Polymer chemistry》1970,8(8):2197-2217
Fully aromatic poly(heterocyclic imides) of high molecular weight were prepared by the cyclopolycondensation reactions of aromatic diamines with new monomer adducts prepared by condensing orthodisubstituted aromatic diamines with chloroformyl phthalic anhydrides. The low-temperature solution polymerization techniques yielded tractable poly(amic acid), which was converted to poly(heterocyclic imides) by heat treatment to effect cyclodehydration at 250–400°C under reduced pressure. In this way, the polyaromatic imideheterocycles such as poly(benzoxazinone imides), poly(benzoxazole imides), poly(benzimidazole imides) and poly(benzothiazole imides) were prepared, which have excellent processability and thermal stability both in nitrogen and in air. The poly(amic acids) are soluble in such organic polar solvents as N,N-dimethyl-acetamide, N-methylpyrrolidone, and dimethyl sulfoxide, and the films can be cast from the polymer solution of poly(amic acids) (ηinh = 0.8–1.8). The film is made tough by being heated in nitrogen or under reduced pressure to effect cyclodehydration at 300–400°C. The polymerization was carried out by first isolating the monomer adducts, followed by polymerization with aromatic diamines. On subsequently being heated, the open-chain precursor, poly(amic acid), undergoes cyclodehydration along the polymer chain, giving the thermally stable ordered copolymers of the corresponding heterocyclic imide structure. 相似文献
546.
Yoshida N Ishizuka T Osuka A Jeong DH Cho HS Kim D Matsuzaki Y Nogami A Tanaka K 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(1):58-75
A series of meso-meso-linked diporphyrins S(n) strapped with a dioxymethylene group of various length were synthesized by intramolecular Ag(I)-promoted coupling of dioxymethylene-bridged diporphyrins B(n), for n=10, 8, 6, 5, 4, 3, 2, and 1. Shortening of the strap length causes a gradual decrease in the dihedral angle between the porphyrins and increasing distortion of porphyrin ring, as suggested by MM2 calculations and (1)H NMR studies. This trend has been also suggested by X-ray crystallographic studies on the corresponding Cu(II) complexes of nonstrapped diporphyrin 2 Cu, and strapped diporphyrins S(8)Cu, S(4)Cu, and S(2)Cu. The absorption spectrum of relatively unconstrained diporphyrins S(10) strapped with a long chain exhibits split Soret bands at 414 and 447 nm and weak Q(0,0)- and prominent Q(1,0)-bands, both of which are similar to those of nonstrapped diporphyrin 2. Shortening of the strap length causes systematic changes in the absorption spectra, in which the intensities of the split Soret bands decrease, the absorption bands at about 400 nm and > 460 nm increase in intensity, and a prominent one-band feature of a Q-band is changed to a distinct two-band feature with concurrent progressive red-shifts of the lowest Q(0,0)-band. The fluorescence spectra also exhibit systematic changes, roughly reflecting the changes of the absorption spectra. The strapped diporphyrins S(n) are all chiral and have been separated into enantiomers over a chiral column. The CD spectra of the optically active S(n) display two Cotton effects at 430-450 and at about 400 nm with the opposite signs. The latter effect can be explained in terms of oblique arrangement of m( perpendicular 1) and m( perpendicular 2) dipole moments, while the former effect cannot be accounted for within a framework of the excition coupling theory. The resonance Raman (RR) spectra taken for excitation at 457.9 nm are variable among S(n), while the RR spectra taken for excitation at 488.0 nm are constant throughout the S(n) series. These photophysical properties can be explained in terms of INDO/S-SCI calculations, which have revealed charge transfer (CT) transitions accidentally located close in energy to the excitonic Soret transitions. This feature arises from a close proximity of the two porphyrins in meso-meso-linked diporphyrins. In addition to the gradual red-shift of the exciton split Soret band, the calculations predict that the high-energy absorption band at about 400 nm, the lower energy Cotton effect, and the RR spectra taken for excitation at 457.9 nm are due to the CT states which are intensified upon a decrease in the dihedral angle. 相似文献
547.
Naoya Uchida 《Optical and Quantum Electronics》1977,9(1):1-13
Electro-optic waveguide modulators utilizing phase retardation of two orthogonally polarized optical modes in LiNbO3 and LiTaO3 waveguides have been designed taking into consideration the optical field distribution in the waveguides and the electrical properties of the electrodes. The analysis has revealed that a driving-voltage to frequency-bandwidth ratio of 1 V/GHz is attainable at the wavelength of 1.05 m using presently available embedded and ridge waveguides. Improvement in waveguide fabrication techniques may reduce the ratio by at least a half. Thus, LiNbO3 and LiTaO3 waveguide modulators are considered to be promising candidates for practical application to single-mode optical-fibre transmission systems of higher than 1 Gbit/s. 相似文献
548.
Natsumi Suko Hideki Itamoto Yoshinori Okayasu Naoya Okura Junpei Yuasa 《Chemical science》2021,12(25):8746
Long-range chirality recognition between the two chiral guest ligands can be tuned based on the helix distances (dLn–Ln = 11.5 and 14.0 Å) of bis-diketonate bridged dinuclear lanthanide complexes (2Th and 3Th, respectively) used as mediators. Both 2Th and 3Th form one-dimensional (1D) helical structures upon terminal binding of two chiral guest co-ligands (LR or LS). Long-range chiral self-recognition is achieved in self-assembly of 2Th with LR and LS to preferentially form homochiral assemblies, 2Th-LR·LR and 2Th-LS·LS, whereas there is no direct molecular interaction between the two guest ligands at the terminal edges. X-ray crystal structure analysis and density functional theory studies reveal that long-range chiral recognition is achieved by terminal ligand-to-ligand interactions between the bis-diketonate ligands and chiral guest co-ligands. Conversely, in self-assembly of 3Th with a longer helix length, statistical binding of LR and LS occurs, forming heterochiral (3Th-LR·LS) and homochiral (3Th-LR·LR and 3Th-LS·LS) assemblies in an almost 1 : 1 ratio. When phenyl side arms of the chiral guest co-ligands are replaced by isopropyl groups (L′R and L′S), chiral self-recognition is also achieved in the self-assembly process of 3Th with the longer helix length to generate homochiral (3Th-L′R·L′R and 3Th-L′S·L′S) assemblies as the favored products. Thus, subtle modification of the chiral guests is capable of achieving over 1.4 nm-range chirality recognition.Long-range chirality recognition between the two chiral guest ligands can be tuned based on the helix distances (dLn–Ln = 11.5 and 14.0 Å) of bis-diketonate bridged dinuclear lanthanide complexes (2Th and 3Th, respectively). 相似文献
549.
Mouri E Matsumoto K Matsuoka H Torikai N 《Langmuir : the ACS journal of surfaces and colloids》2005,21(5):1840-1847
The "carpet"/brush double layer structure in the polyelectrolyte layer in the amphiphilic diblock copolymer monolayer at the air-water interface was quantitatively studied by in situ neutron reflectometry in addition to X-ray reflectivity measurements. As a result of the higher contrast between polyelectrolyte [poly(methacrylic acid)] and solvent (D(2)O) for the neutron, the brush structure could be estimated more accurately as a function of surface pressure, that is, brush density. The thickness of the carpet layer, which is thought to be formed to reduce the interfacial free energy between water and the hydrophobic layer, was almost constant at 10-20 A at any surface pressure studied. Growth was clearly observed in the whole brush length with increasing surface pressure, and it was estimated to be almost 60% of the full-stretch length of the ionic polymer chain. Furthermore, by the comparison of density profiles by neutron and X-ray reflectometry, an anomalous hydration was suggested. 相似文献
550.
Ohyama K Shirasawa Y Wada M Kishikawa N Ohba Y Nakashima K Kuroda N 《Journal of chromatography. A》2004,1042(1-2):189-195
A novel packing material, 3-(4-sulfo-1,8-naphthalimido)propyl-modified silyl silica gel (SNAIP), was prepared for the use as a stationary phase of capillary electrochromatography (CEC). The sulfonic acid groups on SNAIP stationary phase contributed to the generation of electroosmotic flow (EOF) at low pH and served as a strong cation-exchanger. In CEC with SNAIP, a mixed-mode separation was predicted, comprising hydrophobic and electrostatic interactions as well as electrophoretic migration process. In order to understand the retention mechanism on SNAIP, effects of buffer pH, concentration, and mobile phase composition on EOF mobility and the retention factors of barbiturates and benzodiazepines were systematically investigated. Moreover, the retention behavior of barbiturates on SNAIP was investigated and compared with those on octadecyl silica (ODS), phenyl-bonded silica, and 3-(1,8-naphthalimido)propyl-modified silyl silica gel to confirm the presence of pi-pi interaction on its retention mechanism. It was observed that a column efficiency was more than 85,000 N/m for retained compounds and the relative standard deviations for the retention times of EOF marker, thiourea, and five barbiturates were below 2.5% (n = 4). Under an applied voltage of 20 kV and a mobile phase consisted of 5 mM phosphate (pH 3.8) and 40% methanol, the baseline separation of five barbiturates was achieved within 3 min. 相似文献