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71.
H Koga N Mori H Yamada Y Nishimura K Tokuda K Kato T Imoto 《Chemical & pharmaceutical bulletin》1992,40(4):965-970
Employing soluble denatured protein substrates and their derivatives, the proteolytic activity of rat cathepsin H was investigated. The enzyme showed aminopeptidase activity which sequentially released amino acid from the N-terminal of the substrate. The aminopeptidase activity did not act on N alpha-acetylated peptides and showed moderate ionic-strength dependence when methionyl-methylcoumarylamide was employed as a substrate. These results indicate that the activity essentially requires an N-terminal free amino group of the substrate and recognizes it electrostatically to some extent. On the other hand, the enzyme was also indicated to exhibit endopeptidase activity by employing appropriate N alpha-acetylated peptide substrates. In contrast to the aminopeptidase activity, the endopeptidase activity showed rather strict specificity, preferring hydrophobic residues at P2 and P3 sites. Because of the broad specificity and high efficiency of the aminopeptidase activity, it was difficult to directly observe endopeptidase activity in the digestion of large peptide substrates with a free alpha-amino terminal. Thus, this is the first experimental evidence that indicates endopeptidase activity by assigning internal peptide bonds cleaved by this activity. From this data, we proposed a model of the binding site of this enzyme. 相似文献
72.
Takegawa Y Deguchi K Ito S Yoshioka S Nakagawa H Nishimura S 《Rapid communications in mass spectrometry : RCM》2005,19(7):937-946
To investigate the possibility of structural assignment based on negative-ion MS2 spectral matching, three isomeric pairs of 2-aminopyridine (PA)-derivatized non-fucosylated, fucosylated, and sialylated oligosaccharides (complex type N-glycans) were analyzed using high-performance liquid chromatography/ion trap mass spectrometry (HPLC/ITMS) with a sonic-spray ionization (SSI) source. In the SSI negative-ion mode the deprotonated molecule [M-2H]2- becomes prominent. Negative-ion MS2 spectra derived from such ions contain many fragment types (B and Y, C and Z, A, and D) and therefore are more informative than the positive-ion MS2 spectra derived from [M+H+Na]2+ ions, which usually consist mainly of B and Y fragment ions. In particular the internal ions (D- and E-type ions) provided useful information about the alpha1-6 branching patterns and the bisecting GlcNAc residue. Spectral matching based on the correlation coefficients between negative-ion MS2 spectra was performed in a manner similar to the positive-ion MS2 spectral matching previously reported. It was demonstrated that negative-ion MS2 spectral matching is as useful and applicable to the structural assignment of relatively large non-fucosylated, fucosylated, and sialylated PA-oligosaccharide isomers as its positive-ion counterpart. 相似文献
73.
Lewis acid catalysis in supercritical carbon dioxide (CO(2)) was investigated. While solubility of most organic materials is low in scCO(2), poly(ethylene glycol) derivatives or perfluoroalkylbenzenes were found to work as surfactants to dissolve organic materials in scCO(2). In the presence of these molecules, Lewis acid catalyzed organic reactions such as aldol-, Mannich-, and Friedel-Crafts-type reactions proceeded smoothly in scCO(2). Formation of emulsions was observed in these reactions, and the systems were studied in detail. 相似文献
74.
Sigenari Suzuki Masabumi Yamaguchi Masao Onda Takesffi Sakaizumi Osamu Ohashi Ichiro Yamaguchi 《Journal of Molecular Structure》1981,73(1):41-47
Microwave spectra of thionyl chloride, SO35Cl2 and SO35Cl37Cl, in the frequency range 8–25 GHz have been analyzed. The rotational constants have been obtained from the low J transition frequencies. The rS coordinates of Cl atoms and the ro structure have been evaluated with some assumptions: r(S-O) = 1.435 ± 0.011± Å, r(S—Cl) = 2.072 0.005 Å, ∠ OSCl = 108.00 ± 0.06°, ∠ ClSCl = 97.15 ± 0.30°. Nuclear quadrupole coupling constants have been obtained for the SO35Cl2, species: xaa = ?25.02 ± 0.04 MHz, x(bb = ?0.25 ± 0.04 MHz, Xcc = 25.27 ± 0.08 MHz, and Xzz = ?96.75 MHz. The values obtained are compared with those of other workers. 相似文献
75.
Nishizawa M Kohno M Nishimura M Kitagawa A Niwano Y 《Chemical & pharmaceutical bulletin》2005,53(7):796-799
Using a new method having been developed for the purpose of quantitative determination for peroxyradicals, the presence of peroxyradicals was proved in cigarette smoke. In brief, peroxyradicals in cigarette smoke were measured by ESR spectrometry coupled to non-reductive scavenging of 1,1-diphenyl-2-picrylhydrazyl (DPPH). As a result, peroxyradicals were found to be major reactive oxygen species (ROS) since the concentration of peroxyradicals recovered from cigarette smoke was much higher than that of any of other ROS (superoxide and hydroxyl radical) and nitric oxide. Furthermore, several antioxidants (ascorbic acid, reduced glutathione, epigallocatechin gallate, shikonin) were examined for scavenging activity against peroxyradicals in the cigarette smoke. Among them shikonin alone exerted the scavenging activity, suggesting that shikonin is promising antioxidant for cigarette filters because of its effectiveness against broad range of ROS including peroxyradicals, heat resistance, nonvolatility and high affinity to the filter. 相似文献
76.
Tomoyuki Manaka Shin‐Ichiro Nagayama Wannaporn Desadee Naoki Yajima Takuya Kumamoto Toshiko Watanabe Tsutomu Ishikawa Masatoshi Kawahata Kentaro Yamaguchi 《Helvetica chimica acta》2007,90(1):128-142
Nucleophilic ring‐opening reactions of 3‐aryl‐1‐benzylaziridine‐2‐carboxylates were examined by using O‐nucleophiles and aromatic C‐nucleophiles. The stereospecificity was found to depend on substrates and conditions used. Configuration inversion at C(3) was observed with O‐nucleophiles as a major reaction path in the ring‐opening reactions of aziridines carrying an electron‐poor aromatic moiety, whereas mixtures containing preferentially the syn‐diastereoisomer were generally obtained when electron‐rich aziridines were used (Tables 1–3). In the reactions of electron‐rich aziridines with C‐nucleophiles, SN2 reactions yielding anti‐type products were observed (Table 4). Reductive ring‐opening reaction by catalytic hydrogenation of (+)‐trans‐(2S,3R)‐3‐(1,3‐benzodioxol‐5‐yl)aziridine‐2‐carboxylate (+)‐trans‐ 3c afforded the corresponding α‐amino acid derivative, which was smoothly transformed into (+)‐tert‐butyl [(1R)‐2‐(1,3‐benzodioxol‐5‐yl)‐1‐methylethyl]carbamate((+)‐ 14 ) with high retention of optical purity (Scheme 6). 相似文献
77.
Iris A. Bermejo Claudio D. Navo Jorge Castro-Lpez Ana Guerreiro Ester Jimnez-Moreno Elena M. Snchez Fernndez Fayna García-Martín Hiroshi Hinou Shin-Ichiro Nishimura Jos M. García Fernndez Carmen Ortiz Mellet Alberto Avenoza Jesús H. Busto Gonalo J. L. Bernardes Ramn Hurtado-Guerrero Jesús M. Peregrina Francisco Corzana 《Chemical science》2020,11(15):3996
The Tn antigen (GalNAc-α-1-O-Thr/Ser) is a well-known tumor-associated carbohydrate determinant. The use of glycopeptides that incorporate this structure has become a significant and promising niche of research owing to their potential use as anticancer vaccines. Herein, the conformational preferences of a glycopeptide with an unnatural Tn antigen, characterized by a threonine decorated with an sp2-iminosugar-type α-GalNAc mimic, have been studied both in solution, by combining NMR spectroscopy and molecular dynamics simulations, and in the solid state bound to an anti-mucin-1 (MUC1) antibody, by X-ray crystallography. The Tn surrogate can mimic the main conformer sampled by the natural antigen in solution and exhibits high affinity towards anti-MUC1 antibodies. Encouraged by these data, a cancer vaccine candidate based on this unnatural glycopeptide and conjugated to the carrier protein Keyhole Limpet Hemocyanin (KLH) has been prepared and tested in mice. Significantly, the experiments in vivo have proved that this vaccine elicits higher levels of specific anti-MUC1 IgG antibodies than the analog that bears the natural Tn antigen and that the elicited antibodies recognize human breast cancer cells with high selectivity. Altogether, we compile evidence to confirm that the presentation of the antigen, both in solution and in the bound state, plays a critical role in the efficacy of the designed cancer vaccines. Moreover, the outcomes derived from this vaccine prove that there is room for exploring further adjustments at the carbohydrate level that could contribute to designing more efficient cancer vaccines.An anti-cancer vaccine based on an unnatural antigen with an sp2-iminosugar fragment. 相似文献
78.
79.
Magnetic properties of three isostructural compounds BaMP2O7 (M = Co, Ni, and Cu) were investigated by dc and ac magnetization and specific heat measurements. BaCuP2O7 was shown to be an excellent quasi-one-dimensional linear-chain Heisenberg antiferromagnet with an exchange constant (J/kB) of 103.8 K (Hamiltonian H = J Sigma SiS(i+1)) and a temperature for the long-range magnetic order (TN) of 0.81 K giving the ratio kBTN/J = 0.78%. BaCoP2O7 and BaNiP2O7 exhibited long-range antiferromagnetic order at TN = 10.4 and 10.1 K, respectively. BaCoP2O7 and BaNiP2O7 showed a large contribution of the short-range correlation above TN. BaNiP2O7 remained in the antiferromagnetic state up to 90 kOe at 2 K, whereas BaCoP2O7 demonstrated two metamagnetic phase transitions at about 52 and 71 kOe at 2 K if the magnetic field was parallel to the easy direction. BaMP2O7 melted incongruently at 1323 K (M = Co), 1344 K (M = Ni), and 1338 K (M = Cu). 相似文献
80.
We synthesized Leu‐Arg‐Pro‐Val‐Ala‐Ala‐Glu, the peptide contained in lactoferrin (Lf), to identify the angiotensin converting enzyme (ACE) inhibition. In an attempt to know the structure‐activity relationship of this peptide, we replaced Pro (the third amino acid residues from N‐terminal) or Val (the fourth amino acid residues from N‐terminal) with Ala (neutral amino acid), Glu (acidic amino acid) or Lys (basic amino acid) to produce six peptides. From the in vitro ACE inhibition (IC50) of these synthesized peptides, the original peptide (Leu‐Arg‐Pro‐Val‐Ala‐Ala‐Glu) showed higher ACE inhibition than the replaced six peptides. Thus, replacement of Pro at the third amino acid residues or Val at the fourth position with Ala, Glu or Lys revealed the ACE inhibition to be lower than the original form of Leu‐Arg‐Pro‐Val‐Ala‐Ala‐Glu. Otherwise, we added one peptide at the C‐terminal of Leu‐Arg‐Pro‐Val‐Ala‐Ala‐Glu and found both products with an addition of Val (Leu‐Arg‐Pro‐Val‐Ala‐Ala‐Glu‐Val) or Ile (Leu‐Arg‐Pro‐Val‐Ala‐Ala‐Glu‐Ile) showing a lower ACE inhibition than the original one. The ACE inhibitions produced by both replaced peptides were without significance. Also, deletion of the last peptide at the C‐terminal (Leu‐Arg‐Pro‐Val‐Ala‐Ala) failed to produce a marked change of ACE inhibition as compared to the original one. These results suggest that Pro and Val are essential in the peptide for inhibition of ACE activity. 相似文献