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731.
This review focuses on the discovery of cyclotides in the Violaceae, their isolation and their anti-cancer effects. These macrocyclic plant peptides consist of about 30 amino acids, including three conserved disulfide bonds in a cystine knotted arrangement, which renders them a remarkable stability. Their unique structure, combined with a wide array of biological activities, makes them of great interest as possible leads in drug development or as carriers of grafted peptide sequences. Here we describe the work conducted in our laboratory, which started with the overall aim of identifying peptides and small proteins of the size 10-50 amino acid residues in plants with novel chemical structures and biological profiles with a potential for drug development or for use as pharmacological tools. Thus we developed a fractionation protocol to directly address major challenges encountered when dealing with plant material, such as removal of chlorophyll, polyphenols, and low molecular compounds omnipresent in plants. Using this protocol, we then discovered a suite of cyclotides, the varv peptides, from the plant Viola arvensis (Violaceae). Following this, separation methods directly targeting cyclotides were developed, e.g. by adsorption, ion exchange chromatography and solvent-solvent partitioning, which then were used in the isolation of additional cyclotides. To structurally examine cyclotides we have also developed methods based on mass spectrometry for cyclotide sequencing and mapping of disulfide bonds. Finally, to assess structure-activity relationships, regarding their anti-cancer and cytotoxic effects that we focus upon, we have also characterized the three dimensional structure of cyclotides by homology modeling techniques. 相似文献
732.
Lattová E Snovida S Perreault H Krokhin O 《Journal of the American Society for Mass Spectrometry》2005,16(5):683-696
The ionization and fragmentation behaviors of carbohydrate derivatives prepared by reaction with 2-aminobenzamide (AB), 1-phenyl-3-methyl-5-pyrazolone (PMP), and phenylhydrazine (PHN) were compared under identical mass spectrometric conditions. It has been shown that the intensities of signals in MS spectra depend on the kind of saccharides investigated and reducing end labels used. PMP sialyllactose, when ionized by ESI/MALDI, produced a mixture of [M + H]+, [M + Na]+, [M - H + 2Na]+ ions in the positive mode and [M - H]-, [M + Na - 2H]- ions in the negative mode. The AB and PHN derivatives formed abundant [M + H]+ and [M - H]- ions in ESI, and by matrix-assisted laser desorption/ionization (MALDI) produced abundant [M + Na]+ ions. PMP- and reduced AB-sialyllactose produced only Y-type fragment ions under both MS/MS sources. In the electrospray ionization (ESI)-MS/MS spectrum of PHN-sialyllactose, abundant ions corresponded to B, Z cleavages and in its MALDI-MS/MS spectrum, the abundant ions were consistent with Y glycosidic cleavages with the concurrence of B, C, and cross-ring fragment ions. In the MALDI-MS spectra of oligosaccharides acquired immediately after derivatization, it was possible to detect only PHN derivatives. After purification, spectra of all three types of derivatives showed high signal-to-noise ratios with the most abundant ions observed for AB reduced saccharides. [M + Na]+ ions were the dominant products and their fragmentation patterns were influenced by the type of the labeling and the kind of oligosaccharide considered. In the MALDI-PSD and -MS/MS spectra of AB-derivatized glycans, higher m/z fragment ions corresponded to B and Y cleavages and the loss of bisecting GlcNAc appeared as a weak signal or was not detected at all. Fragmentation patterns observed in the spectra of hybrid/complex PHN and PMP glycans were more comparable-higher m/z fragments corresponded to B and C glycosidic cleavages. For PHN glycans, the abundance of ions resulting from the loss of bisecting GlcNAc depended on the number of residues linked to the 6-positioned mannose. Also, PHN and PMP derivatives produced cross-ring cleavages with abundances higher than observed in the spectra of AB derivatized oligosaccharides. For high-mannose glycans, the most informative cleavages were provided by AB and PHN type of labeling. Here, PMP produced dominant Y-cleavages from the chitobiose while other ions produced weak signals. 相似文献
733.
Erika?Kozma Ioan?Cristea Norbert?MüllerEmail author 《Monatshefte für Chemie / Chemical Monthly》2004,135(1):35-40
Summary. Pure (1S,2R,4S)-1,2-epoxy-p-menthan-4-ol and (1R,2S,4R)-1,2-epoxy-p-menthan-4-ol (trans-epoxides of (4S)-terpinen-4-ol and (4R)-terpinen-4-ol) were prepared and certain reactions of these compounds with nucleophilic reagents were studied. It was shown that the Fürst-Plattner rule regarding the trans-diaxial opening of cyclohexene epoxides predicts the predominant products in all cases studied. 相似文献
734.
735.
R. Vergaz J. M. S. Pena D. Barrios I. Pérez J. C. Torres 《Opto-Electronics Review》2007,15(3):154-158
A suspended particle device is made by electrophoretic rod-shape particles suspended in an organic gel. These particles can
twist and order with an applied voltage. The light crossing the material suffers more or less scattering according to that
voltage. A commercial device is analyzed in this work. Several electrical models are tested, being the best one a series configuration
including a shunt double layer capacitance and a Warburg element. Main parameter errors are below 2%, showing the quality
of this new electrical model for this kind of devices. A quick method to improve the manufacturing process on-line is also
proposed. Impedance measurements will be fitted to the selected electrical model, in order to check physical aspects such
as charge diffusion lengths and response times. An electronic driver to obtain several levels of device transmission has been
also developed, being its linearity demonstrated too. Colour changes are negligible for the main part of the bleaching process.
All these features allow the use of this set in domotics application. 相似文献
736.
Kenshi Takahashi Erika Iwasaki Tomoki Nakayama Yutaka Matsumi Timothy J. Wallington 《国际化学动力学杂志》2007,39(6):328-332
Pulsed laser photolysis/vacuum ultraviolet laser‐induced fluorescence techniques were used to measure rate coefficients for Cl atom reactions with a series of fluoroalkenes (CxF2x+1CH?CH2, x = 1,2,4,6,8) in 6–10 Torr of CF4 diluent at 295 ± 2 K. Rate coefficients (units of 10?11 cm3 molecule?1s?1) of 4.49 ± 0.64, 6.58 ± 0.59, 8.91 ± 0.58, 9.27 ± 0.64, and 9.00 ± 0.87 were determined for CxF2x+1CH?CH2 with x = 1,2,4,6, and 8, respectively. In 6–10 Torr of CF4 diluent, the kinetics of the title reactions are at, or near, the high‐pressure limit for x = 4, 6, and 8, approximately 30% below the high‐pressure limit for x = 2, and approximately 50% below the high‐pressure limit for x = 1. © 2007 Wiley Periodicals, Inc. Int J Chem Kinet 39: 328–332, 2007 相似文献
737.
Intermolecular additive free microwave (MW) promoted and cobalt octacarbonyl mediated Pauson-Khand reaction (PKR) performance was improved for estrone ring extension. The reaction development with norbornene and cyclopentene produced cyclopentenones in yields of comparable levels with those previously obtained with the aid of chemical additives as promoters. The PKRs with norbornene demonstrated that a low cobalt complex concentration increases yields, especially for the aliphatic alkynes. Furthermore, a boost for the MW PKR could be obtained by a gradual cobalt complex addition. These expedients combined with the use of an excess of free and cobalt complexed alkyne led to successful estrone ring system extension with various alkynes. 相似文献
738.
739.
We consider the solutions of general three term recurrence relations whose coefficients are analytic functions in a prescribed region. We study the ratio asymptotic of such solutions under the assumption that the coefficients are asymptotically periodic, and their strong asymptotic under more restrictive conditions. 相似文献
740.
Daichi Koseki Erika Aoto Toshitaka Shoji Kazuma Watanabe Yasuko In Yasuyuki Kita Toshifumi Dohi 《Tetrahedron letters》2019,60(18):1281-1286
It was determined that diaryliodonium(III) triflates bearing a trimethoxybenzene (TMP) auxiliary are more reactive than the reported selective aryl-transfer iodonium salts in the N-arylation of benzimidazoles and other types of azole compounds under catalytic conditions. The TMP-iodonium(III) salts can thus effectively facilitate the reaction at 50?°C or below, producing the corresponding N-arylated biaryls without the formation of TMP-derived coupling byproducts. Utilization of this TMP reagent under mild conditions would prevent the underlying problem of participation of the auxiliary group in the coupling reactions, which is observed while using the iodonium(III) salts that require elevated temperatures. 相似文献