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31.
Mitsuo Takayama 《Journal of mass spectrometry : JMS》1993,28(8):878-882
The collision-induced dissociation (CID) spectra of glycoside–alkali metal adduct ions [M + C]+ (C = Li, Na, K and Rb) produced under fast atom bombardment (FAB) conditions are reported. The results obtained suggested that the CID spectra of the [M + C]+ ions of some flavonoid glycosides reflect the coordination structures because the CID patterns generally changed with the metal cation size. In diglycosides, the CID spectra showed that the relatively small cations Li+ and Na+ rather bind to the sugar moiety, whereas the large cations K+ and Rb+ rather bind to the aglycone moiety. In monoglycosides, the cations C+ rather bind to the aglycone moiety. It was concluded that the CID technique combined with FAB is useful for the structural elucidation of [M + C]+ ions and, in principle, the CID spectra reflect the coordination structures in the gas phase. 相似文献
32.
Hiroji Fukui Mitsuo Sawamoto Toshinobu Higashimura 《Journal of polymer science. Part A, Polymer chemistry》1994,32(14):2699-2708
Telechelic ( 8 ) and end-functionalized four-arm star polymers ( 9 ) were synthesized through the coupling reactions of end-functionalized living poly(isobutyl vinyl ether) ( 5; DP n ~ 10) with the bi-and tetrafunctional silyl enol ethers, H4-nC? [CH2OC6H4C(OSiMe3) = CH2]n ( 3: n = 2; 4: n = 4). The precursor polymers 5 were prepared by living cationic polymerization with functionalized initiators, CH3CH(Cl)OCH2CH2X(6), in conjunction with zinc chloride in methylene chloride at ?15°C. The initiators 6 were obtained by the addition of hydrogen chloride gas to vinyl ethers bearing pendant functional groups X , including acetoxy [? OC(O)CH3], styryl (? OCH2C6H4-p-CH = CH2), and methacryloyl [? OC(O)C(CH3) = CH2]. The coupling reactions with 3 and 4 in methylene chloride at ?15°C for 24 h afforded the end-functionalized multiarmed polymers ( 8 and 9 ) in high yield (>91%), where those with styryl or methacryloyl groups are new multifunctional macromonomers. © 1994 John Wiley & Sons, Inc. 相似文献
33.
Mitsuo Takayama Michiko Iwamura Shohaku Fuchibe 《Journal of mass spectrometry : JMS》1994,29(11):601-606
The formation of molecular ions, M+., under fast atom bombardment (FAB) conditions using a liquid matrix was examined by using a new type of synthesized compounds in which preferential M+. peaks appear in their FAB spectra. The FAB spectra were compared with the corresponding mass spectra obtained by the electron impact (EI) ionization, chemical ionization (CI) and charge-exchange ionization (CEI) methods. All of the spectra showed preferential peaks of M+. ion and a characteristic intense fragment ion peak originating from a β-fission. The FAB spectra were similar in the fragment ions appearing in the EI spectra and were very similar in the fragmentation pattern to the CEI spectra using Ar+. and Xe+. as the reagent ions. Further, the FAB spectra did not show any doubly charged ion peaks, while the 70 eV EI spectra showed the peaks of doubly charged molecular and/or fragment ions. The isobutane CI spectra of the synthesized compounds suggested that the formation of M+. ions occurred through the CE reaction with isobutane ion, C4H10+., and the CI spectra showed a marked intense fragment ion peak originating from the β-fission which seemed to occur characteristically in CEI processes. The results obtained suggested that the formation of M+. ions under matrix FAB conditions occurred mainly by CE reactions between the analytes M and matrix molecular ions B+. and/or fragment ions b+.. 相似文献
34.
Horiyama S Suwa K Yamaki M Kataoka H Katagi T Takayama M Takeuchi T 《Chemical & pharmaceutical bulletin》2002,50(7):996-1000
Hydroxylamines gradually undergo oxidation to their oximes on being dissolved in organic solvent (e.g. methanol). This phenomenon was followed by (1)H-NMR and liquid chromatography-mass spectrometry (LC-MS). The oxidation rate was estimated from the peak area observed on the mass chromatogram at the protonated molecule or fragment ion on LC-atmospheric pressure chemical ionization (APCI)-MS. The results showed that the oxidation rate of hydroxylamines depended on the solvent type. 相似文献
35.
Shokyoku Kanaoka Masahiko Minoda Mitsuo Sawamoto Toshinobu Higashimura 《Journal of polymer science. Part A, Polymer chemistry》1990,28(5):1127-1136
Amphiphilic block polymers of vinyl ethers (VEs). $\rlap{--} [{\rm CH}_{\rm 2} {\rm CH}\left( {{\rm OCH}_{\rm 2} {\rm CH}_{\rm 2} {\rm NH}_{\rm 2} } \right)\rlap{--} ]_m \rlap{--} [{\rm CH}_{\rm 2} {\rm CH}\left( {{\rm OR}} \right)\rlap{--} ]_n \left( {{\rm R: }n{\rm - C}_{{\rm 16}} {\rm H}_{{\rm 33}} ,{\rm }n{\rm - C}_{\rm 4} {\rm H}_{\rm 9} ;m \simeq 40,{\rm n} = 1 - 10} \right)$ were prepared, each of which consists of a hydrophilic segment with pendant primary amino groups and a hydrophobic poly(alkyl VE) segment. Their precursors were obtained by the HI/I2-initiated sequential living cationic polymerization of an alkyl VE and a VE with a phthalimide pendant (CH2 = CHOCH2CH2Im; Im; phthalimide group), where the segment molecular weights and compositions (m/n ratio) could be controlled by regulating the feed ratio of two monomers and the concentration of hydrogen iodide. Hydrazinolysis of the imide functions gave the target polymers which were readily soluble in water under neutral conditions at room temperature. These amphiphilic block polymers lowered the surface tension of their aqueous solutions (0.1 wt%, 25°C) to a minimum ? 30 dyn/cm when the hydrophobic pendant R was n-C4H9 (n = 4–9). The polymers with n-C4H9 pendants in the hydrophobic segment exhibited a higher surface activity than those with n-C16 H33 pendants. The surface activity of the polymers also depended on the pH of the polymer solutions; the surface activity increased in more basic solutions where the ionization of the amino group (? NH2)2? NH3⊕) is suppressed. 相似文献
36.
Kon Y Ogasawara J Sakamoto K Kabuto C Kira M 《Journal of the American Chemical Society》2003,125(31):9310-9311
A silicon-containing fused bicyclic compound with a highly strained bridgehead double bond, 2,3,6,7-tetra-tert-butyl-4-(tert-butyldimethylsilyl)-5-(tert-butyldimethylsiloxy)-5-silabicyclo[3.2.0]hepta-1,3,6-triene (2), was synthesized quantitatively by the reaction of 1,2-bis-tert-butyl-4,4-bis(tert-butyldimethylsilyl)-4-silatriafulvene (3) with di-tert-butylcyclopropenone (4) at 80 degrees C. An X-ray crystallographic analysis for 2 not only confirmed a bicyclic structure having a silacyclopentadiene (silole) ring fused with a silacyclobutene ring but also the remarkable deformation around the double bonds; the sum of the bond angles around the unsaturated bridgehead carbon was 333 degrees . The strain energy of a model 5-silabicyclo[3.2.0]hepta-1,3,6-triene was calculated at the MP2/6-31+G(d,p)//B3LYP/6-31+G(d) level (30.2 kcal/mol) to be comparable to that for parent bicyclo[3.2.0]hepta-1,3,6-triene (30.7 kcal/mol). Despite the high steric strain, 2 was stable enough to be kept intact for several months in the air. The high stability is ascribed to the effective steric protection of the ring system by the bulky substituents. 相似文献
37.
Perphenylcyclopolysilanes [Si(C6H5)2]n (n = 4, 5) are reduced by potassium to radical anions. Their simple ESR spectra demonstrate, that the extra electron is confined to the inner SinC2n skeleton of the uncleaved and presumably planarized cyclopolysilanes. 相似文献
38.
Oligonucleotides containing 2-thiouridine (s2U) in place of uridine form stable RNA duplexes with complementary RNAs. Particularly, this modified nucleoside has proved to recognize highly selectively adenosine, the genuine partner, without formation of a mismatched base pair with the guanosine counterpart. In this paper, we describe new methods for the synthesis of 2-thiouridine and various 2'-O-alkyl-2-thiouridine derivatives. Oligoribonucleotides having these modified nucleoside derivatives were synthesized, and their hybridization and structural properties were studied in detail by the 1H NMR analysis of these modified nucleosides and Tm experiments of RNA duplexes with their complementary RNA strands. 相似文献
39.
Chromal blue G in the presence of cetyltrimethylammonium chloride is proposed for the spectrophotometric determination of microgram amounts of beryllium. The sensitivity of color reaction between beryllium and chromai blue G has been greatly increased by the sensitizing action of cetyltrimethylammonium chloride (626nm = 93,000). Beer's law is obeyed over the range 0.012–0.12 ppm of beryllium. Full color development occurs in 20 min at pH 5.5 and at 626 nm. The mole ratio of beryllium and chromai blue G in the complex is estimated to be 1:2. The proposed method is very sensitive and selective for determination of beryllium when EDTA is used as a masking agent. 相似文献
40.
The relaxation time of a polymer chain in an elongational flow field was investigated for hydroxypropylcellulose (HPC) semidilute solution systems by two methods: phenomenological analysis of elongational flow-induced birefringence, and dynamic light scattering (DLS) and rheological measurements. To understand the relaxation time of an entangled semiflexible polymer solution in an elongational flow field, scaling analysis of the elongational flow-induced birefringence curve was performed. The results of both temperature and concentration scaling analyses showed that birefringence curves at different temperatures and at several HPC concentrations were described well by a universal birefringence–strain rate curve. This scaling behavior was compared with the "fuzzy cylinder" model. The critical strain rate corresponded to the correlation time of the slow relaxation mode determined by DLS measurement and the relaxation spectrum obtained by dynamic viscoelasticity measurement. The elongational flow-induced birefringence observed in an HPC semidilute solution was concluded to be attributed to the orientation of the HPC segment in the entangled molecular system, because the dominant relaxation mode is found to be the concentration fluctuation of an entangled molecular cluster in a quiescent state. 相似文献