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101.
The synthesis of new D-seco-C-nor-taxane derivatives in which the D-ring has been deleted and the C-ring has been transformed into a new pentatomic ring, i.e., the polyfunctionalized tetrahydrofuranosyl and cyclopentenyl or cyclopentyl ring, was performed starting from baccatin III derivatives. The synthetic strategy adopted took advantage of the oxetane ring opening and disconnection of the C4-C5 bond, followed by an intramolecular condensation. The formation of furanosyl or cyclopentyl rings is strictly dependent on the presence of unprotected or protected oxygen at C-7 in the starting material. The reactions proceeded with good diastereoselectivity with control of the stereochemistry of one or two stereocenters.  相似文献   
102.
103.
The fluorescent dye thioflavin T (ThT) is commonly used for in situ amyloid fibril detection. In this work, we focused on the spectroscopic properties and chemical stability of ThT in aqueous solution as a function of pH, temperature, and dye concentration. A reversible hydroxylation process occurs in alkaline solutions, which was characterized using a combination of UV-vis absorption spectroscopy, proton NMR, and density functional theory (DFT). On the basis of these studies, we propose a chemical structure for the hydroxylated form. Finally, by means of fluorescence spectroscopy, ThT hydroxylation effects on in situ amyloid detection have been investigated, providing new insights on the efficiency of the ThT assay for quantitative fibril evaluation at basic pH.  相似文献   
104.
Proton nuclear magnetic resonance (1H NMR) experiments have been performed to measure the spin-lattice, T1, and spin-spin, T2, relaxation times of the three functional groups in water/methanol mixtures at different methanol molar fractions (XMeOH=0, 0.04, 0.1, 0.24, 0.5, 1) as a function of temperature in the range 205 K相似文献   
105.
106.
    
Because of the emergence of multi-drug resistance bacteria and fungi, alternatives to conventional antimicrobial therapy are needed. This study aims to evaluate in vitro the antimicrobial activity of: Mirtus communis, Coriandrum sativum, Pelargonium capitatum, Cuminum cyminum, Ocimum basilicum, Citrus aurantium amara, Cymbopogon. winterianus, Cymbopogon martini, Salvia sclarea, Melaleuca alternifolia and Mentha suaveolens essential oils on bacteria and fungi, in relation to their chemical composition. The potential interaction of M. alternifolia (TTO), C. sativum (CDO) and M. suaveolens (EOMS) essential oils when used in combination with gentamicin and fluconazole has been evaluated. The results obtained showed a synergic effect on some bacteria and fungi, with FICI values ≤5. The cytotoxicity of TTO, CDO and EOMS was investigated towards HeLa cells. Only EOMS did not result cytotoxic at the active concentrations on micro-organisms. Further studies are necessary to obtain optimal ratios and dosing regimens for higher therapeutic efficacy and to decrease toxicological profiles.  相似文献   
107.
    
Like many other bacterial cell surfaces, the cell wall of Clostridium difficile is also encapsulated by a proteinaceous paracrystalline layer, the surface (S)-layer. In many bacterial species, the S-layer proteins (SLPs) have been shown to be glycosylated, whereas in other species glycosylation is absent. Unusually, the S-layer of C. difficile is composed of two distinct proteins, the high-molecular weight (HMW) and low-molecular-weight (LMW) SLPs. Previous investigations have reported that one or both of these SLPs are glycosylated, though no definitive study has been conducted. We have used a variety of mass spectrometric approaches to analyse SLPs from a number of strains of C. difficile for the presence of associated glycans. Analysis of intact SLPs by matrix assisted laser desorption/ionisation time of flight (MALDI-ToF) mass spectrometry demonstrated that the observed molecular masses matched the predicted masses of the LMW and HMW SLPs. Furthermore, analysis of Cyanogen bromide (CNBr) and tryptic peptides displayed no evidence of post-translational modification. In the first in-depth study of its kind, we unequivocally demonstrate that the S-layer proteins from the C. difficile strains investigated are not glycosylated.  相似文献   
108.
109.
    
The structure of trans‐[Cr(Me2tn)2Cl2]2ZnCl4 (Me2tn = 2,2‐dimethylpropane‐1,3‐diamine) was determined by a single‐crystal X‐ray diffraction study at 173 K. The analysis reveals that there are three crystallographically independent chromium(III) complex cations in the title compound. The chromium(III) atoms are coordinated by four nitrogen atoms of Me2tn and two chlorine atoms in a trans arrangement, displaying a distorted octahedral geometry. The two six‐membered chelate rings in three complex cations are oriented in an anti chair–chair conformation with respect to each other. The Cr–N and Cr–Cl bond lengths average 2.0862(2) and 2.3112(6) Å, respectively. The ZnCl42– have slightly distorted tetrahedral arrangement with Zn–Cl lengths and the Cl–Zn–Cl angles are influenced by hydrogen bonding. The resolved absorption maxima in the electronic d–d spectrum were fitted with a secular determinant for a quartet energy state of the d3 configuration in a tetragonal field. It is confirmed that the nitrogen atoms of the Me2tn ligand are strong σ donors, but the chloro ligands have weak σ‐ and π donor properties toward the chromium(III) ion.  相似文献   
110.
    
(E)‐1,3‐Pentadiene (EP) and (E)‐2‐methyl‐1,3‐pentadiene (2MP) were polymerized to cis‐1,4 polymers with homogeneous and heterogeneous neodymium catalysts to examine the influence of the physical state of the catalyst on the polymerization stereoselectivity. Data on the polymerization of (E)‐1,3‐hexadiene (EH) are also reported. EP and EH gave cis‐1,4 isotactic polymers both with the homogeneous and with the heterogeneous system, whereas 2MP gave an isotactic cis‐1,4 polymer with the heterogeneous catalyst and a syndiotactic cis‐1,4 polymer, never reported earlier, with the homogeneous one. For comparison, the results obtained with the soluble CpTiCl3‐based catalyst (Cp = cyclopentadienyl), which gives cis‐1,4 isotactic poly(2MP), are examined. A tentative interpretation is given for the mechanism of the formation of the stereoregular polymers obtained and a complete NMR characterization of the cis‐1,4‐syndiotactic poly(2MP) is reported. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3227–3232  相似文献   
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