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181.
A method incorporating high-performance liquid chromatography (HPLC) with electrospray ionization and tandem mass spectrometry, with parallel analysis by HPLC with UV detection using a diode-array detector, was developed for the qualitative characterization of flavonoids in D. odorifera. Twenty-three flavonoids, including six isoflavones, six neoflavones, four isoflavanones, three flavanones, two chalcones, one isoflavanonol and one pterocarpan, were unambiguously identified by comparing their retention times, UV and MS spectra with those of authentic compounds. Furthermore, the collision-induced dissociations of the [M-H]- ions were studied to clarify the MS behavior of the different types of flavonoids. In negative ion ESI-MS all the flavonoids yielded prominent [M-H]- ions in the first order mass spectra. Fragments involving losses of CH3*, H2O, CO, C2H2O, and CO2 were observed in the MS/MS spectra. Each of the seven types of flavonoid showed characteristic MS/MS fragmentation patterns. The isoflavanones, flavanones and chalcones were observed to undergo retro-Diels-Alder fragmentations. The spectra of almost all the neoflavonoids unexpectedly exhibited only [M-H-CH3]-* radical anions as base peaks without any further fragmentation. Substitution positions also remarkably influenced the fragmentation behavior, which could assist in distinction among the flavonoid isomers. The fragmentation rules deduced here could aid in the characterization of other flavonoids of these types. 相似文献
182.
Hansen KT 《Chaos (Woodbury, N.Y.)》1992,2(1):71-75
It is shown that for the four-disk system and the hyperbola billiard it is possible to construct a new symbolic plane preserving the orientation existing in the dynamical space. Physical orbits are mapped into the topological well-ordered plane and it is shown that the forbidden and allowed orbits are separated by a monotone pruning front. 相似文献
183.
Eker F Griebenow K Schweitzer-Stenner R 《Journal of the American Chemical Society》2003,125(27):8178-8185
Determination of the precise solution structure of peptides is of utmost importance to the understanding of protein folding and peptide drugs. Herein, we have measured the UV circular dichroism (UVCD) spectra of tri-alanine dissolved in D(2)O, H(2)O, and glycerol. The results clearly show the coexistence of a polyproline II or 3(1)-helix and a somewhat disordered flat beta-strand conformation, in complete agreement with recent predictions from spectroscopic data (Eker et al. J. Am. Chem. Soc. 2002, 124, 14 330-14 341). A thermodynamic analysis revealed that enthalpic contributions of about 11 and 17 kJ/mol stabilize polyproline II in D(2)O and H(2)O, respectively, but at room temperature they are counterbalanced by entropic contributions, which clearly favor the more disordered beta-strand conformation. It is hypothesized that this delicate balance is the reason for the variety of structural propensities of amino acid residues in the absence of nonlocal interactions. The isotope effect yielding a higher occupation of polyproline II in H(2)O with respect to D(2)O strongly suggests that a hydrogen-bonding network involving the peptide and water molecules in the hydration shell plays a major role in stabilizing this conformation. The equilibrium between polyproline II and beta-strand is practically maintained in glycerol, which suggests that glycerol can substitute water as stabilizing solvent for the polyproline II conformation. We also measured the UVCD spectra of tri-valine and tri-lysine (both at acidic pD) in D(2)O and found them to adopt a flat beta-strand and left-handed turn structure, respectively, in accordance with recent analyses of vibrational spectroscopy data. Generally, the present study adds substantial evidence to the notion that the so-called random coil state of peptides is much more structured than generally assumed. 相似文献
184.
A pre-column fluorescence derivatization method is described for the high-performance liquid chromatographic determination of tyrosine-containing peptides. A tyrosyl residue in the peptide is first formylated in an alkaline medium in the presence of chloroform, and the resulting aldehyde is then converted into a fluorescent derivative by reaction with 1,2-diamino-4,5-dimethoxybenzene. The derivative is separated on a reversed-phase column (LiChrosorb RP-18) by isocratic elution with an aqueous acetonitrile-containing potassium chloride-hydrochloric acid buffer (pH 2.2) and sodium 1-hexanesulphonate. The method is selective and fairly sensitive; the lower limits of detection for the tyrosine-containing peptides tested are in the range 3.4-26.2 pmol in a 100-microliter injection volume. 相似文献
185.
Duanjun Xu Kunio Miki Yasushi Kai Nobutami Kasai Masanori Wada 《Journal of organometallic chemistry》1985,287(2):265-273
The structure of a nickel(II) complex, trans-[Ni(C6Cl5)(PMe2Ph)2{C(OMe)Me}]BF4, containing the simplest alkyl(alkoxy)carbene ligand has been determined by X-ray crystallography (R = 0.091). The geometry around the nickel atom is square-planar. The comparatively short NiC(1) bond length of 1.843(10) Å showed the presence of π-bonding in the nickel-carbene bond. 相似文献
186.
Huang WL Cui SH Liang KM Gu SR Yuan ZF 《Journal of colloid and interface science》2002,246(1):129-134
Silica xerogels were prepared by thermal drying wet gels in an electric oven (70 degrees C) after certain duration of ambient drying, and the relevant effect is investigated on the mesopore structures and surface fractal dimensions of the resultant xerogels. The silica gels were derived from a hydrochloric acid-catalyzed TEOS (tetraethylorthaosilicate) system, and both magnetic stirring and ultrasonic vibration were adopted during sol preparation. The percentage mesoporosity and surface fractal dimensions are evaluated using image analysis methods, based on FE-SEM (field emission gun-scanning electron microscopy) images. The results show that the mesoporosity of the resultant xerogels decreases with the duration of ambient drying for samples prepared using magnetic stirring and low-intensity ultrasonic vibration, while samples subjected to high-intensity ultrasound show a somewhat reverse trend. Samples prepared with magnetic stirring have almost constant surface fractal dimensions (nearly 3), irrespective of the ambient drying before thermal drying. The surface fractal dimensions of samples prepared using ultrasound increase with the duration of ambient drying. 相似文献
187.
苯并菲盘状液晶的合成、亲氟效应及分子对称性对介晶性的影响 总被引:3,自引:0,他引:3
New symmetrical and asymmetrical triphenylene-containing discotic liquid crystals with two different peripheral alkyl chains, known as sym-TP(OC6H13)3(OR)3 and asym-TP(OC6H13)3(OR)3, were synthesized. Their thermotropic liquid crystal properties were investigated through polarizing optical microscopy (POM), differential scanning calorimetry (DSC) and X-ray diffraction (XRD) analyses. The asyrranetdcal discogens are 2,6,11-rialkoxy-3,7,10-trihexyloxytriphenylenes, with the alkyl chain carbon numbers varying from 3-10, 12, and 14, while the symmetrical compounds are 2,6,10-trialkyloxy-3,7,11-trihexyloxytriphenylene. Two fluoroalkoxy substituted triphenylene discogens, 2,6,10-td(4,4,4-trifluorobutoxy)-3,7,11-trihexyloxytriphenylene and its asymmetrical isomer 2,6,11-tri(4,4,4-trifluorobutoxy)-3,7,10-trihexyloxytdphenylene were prepared. These two compounds show higher melting and clearing points than their alkoxy analogs, which implies that fluorophilic effect exists in the formation and stabilization of discotic columnar mesophase. The triphenylene derivatives TP(OC6H13)3(OR)3 with two different peripheral chains, symmetrically or asymmetrically attached on triphenylene cores, have lower melting points and clearing points than those of the higher symmetrical compounds TP(OR)6 with the same total chain carbon numbers. The mixed-chain-triphenylenes with longer alkoxy chains (n=9,10,12,14) show columnarmesophase at room temperature. 相似文献
188.
Jian Zhang Zhao‐Ji Li Yi‐Hang Wen Yao Kang Jian‐Kai Cheng Yuan‐Gen Yao 《无机化学与普通化学杂志》2004,630(15):2731-2735
Two new metal succinates modified by rigid bipyridines, Cd(4, 4′‐bpy)(C4H4O4)·1/4H2O ( 1 ) and Cu(2, 2′‐bpy)(C4H4O4)0.5(NO3)(H2O) ( 2 ) (bpy = bipyridine), have been synthesized by hydrothermal reactions and structurally determined. Complex 1 crystallizes in the orthorhombic space group Cmca with the cell parameters a = 11.696(2), b = 15.554(2), c = 15.874(3) Å, α = β = γ = 90.00°, V = 2888(3) Å3, Z = 8. Complex 2 crystallizes in the triclinic space group with a = 7.077(1), b = 9.838(2), c = 10.461(2) Å, α = 71.941(3)°, β = 73.078(3)°, γ = 74.502(3)°, V = 649.8(2) Å3, Z = 2. In complex 1 , a 2‐D network was formed by Cd‐succinato bonding. The 2‐D networks are pillared by 4, 4′‐bpy ligands, forming a 3‐D grid framework. The 2‐fold interpenetration of the resulting 3‐D frameworks completes the molecular structure. In complex 2 , the CuII atom adopts a distorted octahedral in which the CuII atoms are bridged by two H2O molecules into an infinite zigzag chain, [Cu2(H2O)2(C4H4O4)]n. The neighboring chains are further linked by π‐π stacking interactions into a 2‐D network, and the interlayer hydrogen bonds lead to the final 3‐D crystal structure. 相似文献
189.
A new activation method has been developed for electroless copper plating on silicon wafer based on palladium chemisorption on SAMs of APTS without SnCl2 sensitization and roughening condition.A closely packed electroless copper film with strong adhesion is successfully formed by AFM observation.XPS study indicates that palladium chemisorption occurred via palladium chloride bonding to the pendant amino group of the SAMs. 相似文献
190.
Quality-of-service provisioning and efficient resource utilization in CDMA cellular communications 总被引:1,自引:0,他引:1
Hai Jiang Weihua Zhuang Xuemin Shen Qi Bi 《Selected Areas in Communications, IEEE Journal on》2006,24(1):4-15
One of the major challenges in supporting multimedia services over Internet protocol (IP)-based code-division multiple-access (CDMA) wireless networks is the quality-of-service (QoS) provisioning with efficient resource utilization. Compared with the circuit-switched voice service in the second-generation CDMA systems (i.e., IS-95), heterogeneous multimedia applications in future IP-based CDMA networks require more complex QoS provisioning and more sophisticated management of the scarce radio resources. This paper provides an overview of the CDMA-related QoS provisioning techniques in the avenues of packet scheduling, power allocation, and network coordination, summarizes state-of-the-art research results, and identifies further research issues. 相似文献