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41.
Sonnenschein RN Farias JJ Tenney K Mooberry SL Lobkovsky E Clardy J Crews P 《Organic letters》2004,6(5):779-782
A reinvestigation of Auletta sp. yielded the novel compound milnamide C (3) plus the known compounds milnamide A (1), milnamide B (hemiasterlin) (2), jasplakinolide (5), and geodiamolides A (6), D (7), E (8), and G (9). The isolation work was guided by cytoskeletal bioactivity data. Compounds 2 and 3 were shown to cause microtubule depolymerization, and 6-9 were shown to cause microfilament disruption. This biological activity and the structural elucidation of 3, including X-ray analysis, are reported here. [structure: see text] 相似文献
42.
Dynamics of Fluorescent Dyes Attached to G‐Quadruplex DNA and their Effect on FRET Experiments 下载免费PDF全文
Siri Søndergaard Dr. Mikayel Aznauryan Emil K. Haustrup Prof. Birgit Schiøtt Prof. Victoria Birkedal Prof. Ben Corry 《Chemphyschem》2015,16(12):2562-2570
FRET spectroscopy is a promising approach for investigating the dynamics of G‐quadruplex DNA folds and improving the targeting of G‐quadruplexes by potential anticancer compounds. To better interpret such experiments, classical and replica‐exchange molecular dynamics simulations and fluorescence‐lifetime measurements are used to understand the behavior of a range of Cy3‐based dyes attached to the 3′ end of G‐quadruplex DNA. The simulations revealed that the dyes interact extensively with the G‐quadruplex. Identification of preferred dye positions relative to the G‐quadruplex in the simulations allows the impact of dye–DNA interactions on FRET results to be determined. All the dyes show significant deviations from the common approximation of being freely rotating and not interacting with the host, but one of the Cy3 dye analogues is slightly closer to this case. 相似文献
43.
Emil Pop Stanislaw Rachwal Marcus E. Brewster 《International journal of quantum chemistry》1996,60(8):1829-1834
The allylic rearrangement of trans-pinocarveol esters ( I ) to myrtenol esters ( II ), a reaction of interest in the chemistry of terpenes and cannabinoids, has been theoretically investigated. The intramolecular, cyclization-induced rearrangement results in equilibrium mixtures of the starting compounds and the products with the ratio of I vs. II in the equilibrium mixture being determined by their thermodynamic stabilities. The relative thermodynamic stabilities as reflected by calculated AM1 heats of formations (ΔHf) were determined for various I-II ester pairs. The study, in agreement with available experimental evidence, indicates that generally I , which contain an endocyclic double bond, are more stable and thus predominantly form following rearrangements. In two cases (acetate and pivalate) the stability is reversed. Calculations performed for similar structures, esters of 2-methylene cyclohexane-1-ol ( IV ) and 1-cyclohexene-1-methanol ( V ) gave similar results. Structural and electronic factors which might influence the stability of these compounds were examined. Interestingly, a correlation between thermodynamic stability and dipole moments was observed. © 1996 John Wiley & Sons, Inc. 相似文献
44.
Electrochemistry of nucleic acids was discovered about 40 years ago. During the first 15 years electrochemistry brought early evidence of DNA premelting and polymorphy of the DNA double helix. At present electrochemical methods working with stationary electrodes are able to detect DNA at attomol and in some cases, even at lower levels. A great progress in the development of electrochemical sensors for DNA hybridization and DNA damage achieved in recent years suggests that these sensors may soon become important tools in medicine and other areas of practical life of the 21st century. 相似文献
45.
Pun D Knobloch DJ Lobkovsky E Chirik PJ 《Dalton transactions (Cambridge, England : 2003)》2011,40(30):7737-7747
Metallation of a variety of α,ω-dienes has been explored with an η(9),η(5)-bis(indenyl)zirconium sandwich compound and an ansa-titanocene dinitrogen complex. The η(9),η(5)-bis(indenyl)zirconium sandwich compound, (η(9)-C(9)H(5)-1,3-Pr(2))(η(5)-C(9)H(5)-1,3-(i)Pr(2))Zr, served as an isolable source of Negishi's reagent and readily formed a kinetic mixture of cis and trans diastereomers of the corresponding zirconacyclopentanes upon diene metallation. For pure hydrocarbon substrates such as 1,6-heptadiene and 1,7-octadiene, an equimolar amount of cis and trans diastereomers were the kinetic products; isomerization to the thermodynamically favoured trans isomers was observed over time at ambient temperature or upon heating to 105 °C, respectively. By contrast, substitution of the methylene or ethylene spacer in the α, ω-diene with a fluorenyl group (e.g. 9,9-diallylfluorene) resulted in exclusive kinetic formation of the trans diastereomer. Amino-substituted dienes were also readily cyclised and one example was characterised by single-crystal X-ray diffraction. Similar studies were also conducted with the ansa-titanocene dinitrogen complex, [Me(2)Si(η(5)-C(5)Me(4))(η(5)-C(5)H(3)-3-(t)Bu)Ti](2)(μ(2),η(1),η(1)-N(2)), and both kinetic and thermodynamic selectivities evaluated. The use of a C(1) symmetric ansa-metallocene increases the number of isomeric possibilities. For diallyl tert-butyl amine, diene metallation was more selective than for the bis(indenyl)zirconium sandwich compound and isomerization was also more rapid. Preliminary functionalisation reactivity for both the zircona- and titanocycles was also explored. 相似文献
46.
Venkatramani R Davis KL Wierzbinski E Bezer S Balaeff A Keinan S Paul A Kocsis L Beratan DN Achim C Waldeck DH 《Journal of the American Chemical Society》2011,133(1):62-72
We present evidence for a near-resonant mechanism of charge transfer in short peptide nucleic acid (PNA) duplexes obtained through electrochemical, STM break junction (STM-BJ), and computational studies. A seven base pair (7-bp) PNA duplex with the sequence (TA)(3)-(XY)-(TA)(3) was studied, in which XY is a complementary nucleobase pair. The experiments showed that the heterogeneous charge transfer rate constant (k(0)) and the single-molecule conductance (σ) correlate with the oxidation potential of the purine base in the XY base pair. The electrochemical measurements showed that the enhancement of k(0) is independent, within experimental error, of which of the two PNA strands contains the purine base of the XY base pair. 7-bp PNA duplexes with one or two GC base pairs had similar measured k(0) and conductance values. While a simple superexchange model, previously used to rationalize charge transfer in single stranded PNA (Paul et al. J. Am. Chem. Soc. 2009, 131, 6498-6507), describes some of the experimental observations, the model does not explain the absence of an enhancement in the experimental k(0) and σ upon increasing the G content in the duplexes from one to two. Moreover, the superexchange model is not consistent with other studies (Paul et al. J. Phys. Chem. B 2010, 114, 14140), that showed a hopping charge transport mechanism is likely important for PNA duplexes longer than seven base pairs. A quantitative computational analysis shows that a near-resonant charge transfer regime, wherein a mix of superexchange and hopping mechanisms are expected to coexist, can rationalize all of the experimental results. 相似文献
47.
Yezek L Rowell RL Holysz L Chibowski E 《Journal of colloid and interface science》2000,225(1):227-232
The adsorption of sodium dodecyl sulfate to colloidal titanium dioxide was investigated using the electrophoretic fingerprinting approach. An electrophoretic fingerprint is a contour diagram of the observed electrophoretic mobility as a function of the bulk solution pH and plambda, the log of the bulk solution conductivity. Surfactant adsorption was observed to be strong under acidic conditions, as illustrated in the dramatic changes in the electrophoretic fingerprints. Electrokinetic data were compared with adsorption isotherm data obtained by a depletion method and good qualitative agreement was found. The observed pH changes associated with surfactant adsorption suggested ligand exchange as a possible mechanism of adsorption. Electrophoretic fingerprinting was shown to be a powerful means of examining surfactant adsorption to colloidal particles. Copyright 2000 Academic Press. 相似文献
48.
Erich Widmer Milan Soukup Reinhard Zell Emil Broger Hans Peter Wagner Marquard Imfeld 《Helvetica chimica acta》1990,73(4):861-867
Starting from the readily available, optically active (4R)-4-hydroxy-2,2,6-trimethylcyclohexanone ( 1 ), a new technical synthesis of (3R,3′R)-zeaxanthin is described. According to a 2(C9 + C6) + C10 = C40 construction scheme, the ketone 1 was first transformed with (E)-3-methylpent-2-en-4-yn-1-ol ( 5 ) into a C15-intermediate which, by a three-step sequence, could be converted into the known olefinic C15-Wittig salt 4 . Optimized conditions for the final Wittig reaction of 4 with the C10-dialdehyde 3 are discussed. Based on 1 , the overall yield of the entire technical process is ca. 40%. 相似文献
49.
Kurt Burdeska Hermann Fuhrer Guglielmo Kabas Adolf Emil Siegrist 《Helvetica chimica acta》1981,64(1):113-152
Preparation of Styryl and Stilbenyl Derivatives of Pyrimidines 2- and 4-(p-Tolyl)-substituted pyrimidines react with anils of hetero-aromatic aldehydes in the presence of dimethylformamide and potassium hydroxide or potassium t-butoxide to yield the corresponding 2- and 4-[4″-(heteroaryl)stilben-4′-yl]pyrimidines or the 2- and 4-[a-(heteroaryl)-4′-styryl]pyrimidines respectively (‘Anil synthesis’). Furthermore, the Schiff′s bases derived from p-chloroaniline and 4-(pyrimidine-2-yl and 4-yl)benzaldehydes give, with methyl- and with p-tolyl-substituted heterocycles, the corresponding heterocyclic substituted styryl and stilbenyl derivatives. Alkyl-, alkoxy- or phenyl-substituted pyrimidines undergo also the ‘Anil synthesis’. 相似文献
50.
Determination of terbinafine in pharmaceuticals and dialyzates by capillary electrophoresis 总被引:1,自引:0,他引:1
A capillary electrophoresis method has been developed for the separation and determination of terbinafine (TER) in various pharmaceutically relevant matrices. Capillary zone electrophoresis (CZE) separation and UV absorbance photometric detection were carried out in a 160 mm capillary tube with a 300 μm i.d., hydrodynamically (membrane) closed. The influences of pH, carrier cation and counterion on migration parameters of TER were studied and the following conditions were selected: a 20 mmol l−1 glycine running buffer adjusted to pH 2.7 with acetic acid, 0.2% (w/v) methylhydroxyethylcellulose (m-HEC) as an electro-osmotic flow (EOF) suppressor, a 250 μA driving current, and 20 °C. The optimized separation conditions were convenient for the determination of TER in commercial tablets and spray and in dialyzates. Here, the dialysis was used to investigate in vitro permeation of TER through the skin from the gel. The samples of dialyzates were examined with and without simple extraction procedure and the results were compared. A permeation profile of the drug present in the gel of given composition was obtained analyzing pretreated samples. The proposed electrophoretic method was successfully validated. It was suitable for the simple, sensitive, rapid and highly reproducible assay of TER. CZE analysis was completed within 5.5 min. The detection limit of TER was 1.73 μmol l−1 at a 224 nm detection wavelength. The intra- and inter-laboratory precisions over the concentration range 6.0-60.0 μmol l−1 were between 0.32-0.69% and 1.04-1.44% including R.S.D. of migration times and peak areas, respectively. The mean absolute recoveries of drugs from samples were found to be 98.34 (tablets) and 99.47% (spray). It is suggested that there are potentialities to determine TER present in unpretreated complex samples, as CZE in a hydrodynamically closed separation system may be easily on-line combinable with purification and preconcentration CE modes (e.g., isotachophoresis, ITP). 相似文献