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101.
Anthramycin is a benzodiazepine alkaloid with potent antitumor and antibiotic activity produced by the thermophilic actinomycete Streptomyces refuineus sbsp. thermotolerans. In this study, the complete 32.5 kb gene cluster for the biosynthesis of anthramycin was identified by using a genome-scanning approach, and cluster boundaries were estimated via comparative genomics. A lambda-RED-mediated gene-replacement system was developed to provide supporting evidence for critical biosynthetic genes and to validate the boundaries of the proposed anthramycin gene cluster. Sequence analysis reveals that the 25 open reading frame anthramycin cluster contains genes consistent with the biosynthesis of the two halves of anthramycin: 4 methyl-3-hydroxyanthranilic acid and a "dehydroproline acrylamide" moiety. These nonproteinogenic amino acid precursors are condensed by a two-module nonribosomal peptide synthetase (NRPS) terminated by a reductase domain, consistent with the final hemiaminal oxidation state of anthramycin. 相似文献
102.
103.
Mangelings D Tanret I Meert V Eeltink S Schoenmakers PJ Kok WT Vander Heyden Y 《Journal of chromatographic science》2007,45(9):578-586
Polymeric methacrylate-based monoliths are evaluated in capillary electrochromatography (CEC) and pressurized capillary electrochromatography (p-CEC) for their potential in pharmaceutical analysis. Using a given polymerization mixture as a basis for the monolith synthesis, different mobile phase pH at constant organic modifier concentrations are tested in both CEC and p-CEC. The test set consists of basic, acidic, amphoteric, and neutral compounds, which are mainly pharmaceuticals. Because of the mainly hydrophobic character of the stationary phase, the interactions are largest when the compounds appear in an uncharged state, but some ion-exchange phenomena with negatively charged compounds can also be observed. In CEC, acidic substances are most retained at low pH. For amphoteric and neutral compounds, no preference regarding analyzing pH can be derived from these experiments. For basics, a high pH is chosen, but a reduced solvent strength is needed to enhance the retention of these compounds. The retention mechanism in p-CEC can also be assigned to both hydrophobic and ionic interactions. For acidic, amphoteric, and neutral compounds, acceptable retention is seen. For the basic compounds, the retention with a mobile phase containing 50% organic modifier is low, as in CEC. However, when the organic modifier content in the mobile phase is decreased, retention increases and the selectivity of the stationary phase is more pronounced. This mode of operation presents a possibility for separating some test mixtures, thus some potential for pharmaceutical analysis is seen. More efforts are needed to obtain higher efficiencies and better peak shapes, which might be solved by a further optimization of both the stationary phase synthesis and the mobile phase composition. 相似文献
104.
Soares VA Severino D Junqueira HC Tersariol IL Shida CS Baptista MS Nascimento OR Nantes IL 《Photochemistry and photobiology》2007,83(5):1254-1262
In this work, the regeneration of native horseradish peroxidase (HRP), following the consecutive reduction of oxo-ferryl pi-cation (compound I) and oxo-ferryl (compound II) forms, was observed by UV-visible spectrometry and electron paramagnetic resonance (EPR) in the presence of methylene (MB+), in the dark and under irradiation. In the dark, MB+ did not affect the rate of HRP compound I and II reduction, compatible with hydrogen peroxide as the solely reducing species. Under irradiation, the dye promoted a significant increase in the native HRP regeneration rate in a pH-dependent manner. Flash photolysis measurements revealed significant redshift of the MB+ triplet absorbance spectrum in the presence of native HRP. This result is compatible with the dye binding on the enzyme structure leading to the increase in the photogenerated MB* yield. In the presence of HRP compound II, the lifetime of the dye at 520 nm decreased approximately 75% relative to the presence of native HRP that suggests MB* as the heme iron photochemical reducing agent. In argon and in air-saturated media, photoactivated MB+ led to native HRP regeneration in a time- and concentration-dependent manner. The apparent rate constant for photoactivated MB+-promoted native HRP regeneration, in argon and in air-saturated medium and measured as a function of MB+ concentration, exhibited saturation that is suggestive of dye binding on the HRP structure. The dissociation constant (KMB) observed for the binding of dye to HRP was 5.4+/-0.6 microM and 0.57+/-0.05 microM in argon and air-saturated media, respectively. In argon-saturated medium, the rate of the conversion of HRP compound II to native HRP was significantly higher, k2argon=(2.1+/-0.1)x10(-2) s(-1), than that obtained in air-equilibrated medium, k2air=(0.73+/-0.02)x10(-2) s(-1). Under these conditions the efficiency of photoactivated MB(+)-promoted native HRP regeneration was determined in argon and air-equilibrated media as being, respectively: k2/KMB=3.9x10(3) and 12.8x10(3) M(-1) s(-1). 相似文献
105.
Giacomelli C Schmidt V Borsali R 《Langmuir : the ACS journal of surfaces and colloids》2007,23(13):6947-6955
Block copolymer micelles find application in many fields as nanocarriers, especially in drug delivery. We report herein that specific interactions between hydrophobic guest molecules and core-forming segments can significantly improve the loading capacity of polymeric micelles. High loading capacities (>100% weight/weight of polymer (w/wp)) were systematically observed for the encapsulation of probes containing weak carboxylic acid groups by micellar nanoparticles having poly[2-(dialkylamino)ethyl methacrylate] cores (i.e., particles whose cargo space exhibits antagonist weak base functions), as demonstrated by the incorporation of indomethacin (IND), ibuprofen (IBPF), and trans-3,5-bis(trifluoromethyl)cinnamic acid (F-CIN) into either poly(ethylene oxide)-b-poly[2-(diisopropylamino)ethyl methacrylate] (PEO-b-PDPA) or poly(glycerol monomethacrylate)-b-PDPA (PG2MA-b-PDPA) micelles. The esterification of IND yielding to a nonionizable IND ethyl ester derivative (IND-Et) caused an abrupt decrease in the micellar loading capacity down to 10-15% w/wp. Similar results were also obtained when IND was combined with nonionizable block copolymers such as PEO-b-polycaprolactone (PEO-b-PCL) and PEO-b-poly(glycidyl methacrylate) (PEO-b-PGMA). The existence of acid-base interactions between the solubilizate and the weak polybase block forming the micelle core was confirmed by 1H NMR measurements. However, the incorporation of high numbers of hydrophobic guest molecules inside polymeric micelles can provoke not only an increase in the hydrodynamic size (2RH) of the objects but also a substantial change in the morphology (transition from spheres to cylinders). The application of the Higuchi model showed that the probe release followed a diffusion-controlled mechanism, and diffusion coefficients (D) on the order of 10-18-10-17 cm2/s were determined for IND release from 1.0 mg/mL PEO113-b-PDPA50 + 100% w/wp IND. Probe release from micelles with weak polybase-based cores can also be triggered by changes in the solution pH. 相似文献
106.
王黑龙 Vanessa J. Murray 钱敏 Donna J. Minton 董爱义 刘建德 武博涵 车丽 Timothy K. Minton 《化学物理学报》2019,32(5):543-552
本文采用激光爆破法高能原子氧束源研究了纳米粘土增强环氧树脂复合材料的抗原子氧性能. 研究了四种样品:纯环氧树脂,纳米粘土含量为1 wt%,2 wt%和4 wt%的纳米粘土增强环氧树脂复合材料,结果表明腐蚀深度随着纳米粘土含量的增加而降低,当掺杂纳米粘土含量为4 wt%时,腐蚀深度为纯环氧树脂腐蚀深度的28%∽37%;X射线光电子能谱(XPS)分析表明原子氧轰击后,材料表面C-C/C-H键比例减少,C-O键、酮类比例增加,表面氧化程度增加,掺杂纳米粘土的材料表面生成了新的碳酸盐,掺杂4 wt%纳米粘土的复合材料表面氧化程度增加最小;扫描电子显微镜(SEM)结果显示含有纳米粘土的复合材料表面被原子氧轰击后在纳米粘土团簇处形成了“块状”物质,掺杂4 wt%纳米粘土的复合材料,“块状”物质尺寸和分布密度最大;综合腐蚀深度,XPS,以及SEM结果表明,虽然所有表面都一定程度地被原子氧腐蚀和氧化,但掺杂纳米粘土的复合材料表面由于生成了“块状”物质,阻挡了原子氧进一步腐蚀其下的材料,提高了抗原子氧性能. 相似文献
107.
Sabine Devautour‐Vinot Eriyakkadan S. Sanil Amine Geneste Vanessa Ortiz Pascal G. Yot Jong‐San Chang Guillaume Maurin 《化学:亚洲杂志》2019,14(20):3561-3565
Post‐synthesis modification of MIL‐101(Cr)‐NO2 was explored in order to decorate the organic backbone by propyl‐sulfonic groups, with the aim to incorporate mobile and acidic protons for solid‐state proton electrolyte applications. The resulting solid switched from insulating towards proton superconductive behavior under humidity, while the conductivity recorded at 363 K and 95 % relative humidity reached 4.8×10?3 S cm?1. Propitiously, the impregnation of the material by strong acidic molecules (H2SO4) further boosted the proton conductivity performances up to the remarkable σ value of 1.3×10?1 S cm?1 at 363 K/95 % RH, which reaches the performances of the best proton conductive MOF reported so far. 相似文献
108.
Manfredo Hrner Vanessa S. Carratu Jairo Bordinhao Angela Silva Elke Niquet 《Acta Crystallographica. Section C, Structural Chemistry》2004,60(3):m140-m142
In the title compound, [Cd(C12H8F2N3)2(C5H5N)2], the Cd atom lies on a crystallographic twofold axis in space group Iba2. The coordination geometry about the CdII ion corresponds to a rhombically distorted octahedron, with two deprotonated 1,3‐bis(2‐fluorophenyl)triazenide ions, viz. FC6H4NNNC6H4F−, acting as bidentate ligands (four‐electron donors). Two neutral pyridine (py) molecules complete the coordination sphere in positions cis with respect to one another. The triazenide ligand is not planar (r.m.s. deviation = 0.204 Å), the dihedral angle between the phenyl rings of the terminal 2‐fluorophenyl substituents being 24.6 (1)°. The triazenide and pyridine Cd—N distances are 2.3757 (18)/2.3800 (19) and 2.3461 (19) Å, respectively. Intermolecular C—H⋯F interactions generate sheets of molecules in the (010) plane. 相似文献
109.
Goverdhan Mehta Gagliardini Vanessa Kabirul Islam Kailasam Venkatesan 《Acta Crystallographica. Section C, Structural Chemistry》2004,60(1):o90-o93
The cis,syn,cis‐tricyclic [2+2]‐dimer of cyclooctatetraene, C16H16, crystallizes in space group Pca21 with two molecules in the asymmetric unit. An extensive network of weak C—H⋯π(Czdbnd;C) interactions between the two independent molecules, A and B, as well as A⋯A and B⋯B interactions, are observed in the supramolecular assembly. The C—H groups point more towards one C atom than to the centre of the Czdbnd;C bond. Notable among the interactions are bifurcated (cyclobutane)C—H⋯Czdbnd;C contacts that span transannularly the eight‐membered ring. 相似文献
110.
Vanessa Gisele Pasqualotto Severino Cristiane de Melo CazalMoacir Rossi Forim Maria Fátima das Graças Fernandes da SilvaEdson Rodrigues-Filho João Batista FernandesPaulo Cezar Vieira 《Journal of chromatography. A》2009,1216(19):4275-4281
High-speed counter-current chromatography (HSCCC) with a two-phase solvent system (hexane–ethanol–acetonitrile–water 10:8:1:1, v/v) was applied to examine the leaves of Hortia oreadica, which afforded the known limonoid guyanin (1), the alkaloids rutaecarpin (2) and dictamnine (6), the dihydrocinnamic acid derivatives methyl 5,7-dimethoxy-2,2-dimethyl-2H-1-benzopyran-6-propanoate (3), 5,8-dimethoxy-2,2-dimethyl-2H-1-benzopyran-6-propanoic acid (4), together with the new E-3,4-dimethoxy-α(3-hydroxy-4-carbomethoxyphenyl)cinnamic acid (5). The recovery of compounds 1–6 was determined by comparison with LC-atmospheric pressure chemical ionization MS/MS data: 66.2%, 93.1%, 102.5%, 101.2%, 99.0% and 84.9%, respectively. Compound 3 showed IC50 of 23.6 μM against Plasmodium falciparum and 15.6 μM against Trypanosoma brucei rhodesienses and was not toxic to KB cells (IC50 > 100 μM). 相似文献