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991.
The electrodeposition of Ge, Si and, for the first time, of Si(x)Ge(1-x) from the air- and water-stable ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide ([Py(1,4)]Tf(2)N) containing GeCl(4) and/or SiCl(4) as precursors is investigated by cyclic voltammetry and high-resolution scanning electron microscopy. GeCl(2) in [Py(1,4)]Tf(2)N is electrochemically prepared in a two-compartment cell to be used as Ge precursor instead of GeCl(4) in order to avoid the chemical attack of Ge(iv) on deposited Ge. Silicon, germanium and Si(x)Ge(1-x) can be deposited reproducibly and easily in this ionic liquid. Interestingly, the Si(x)Ge(1-x) deposit showed a strong colour change (from red to blue) at room temperature during electrodeposition, which is likely to be due to a quantum size effect. The observed colours are indicative of band gaps between at least 1.5 and 3.2 eV. The potential of ionic liquids in Si(x)Ge(1-x) electrodeposition is demonstrated. 相似文献
992.
El Bialy SA 《Natural product research》2008,22(13):1176-1188
An asymmetric induction using (S)-1-arylethylamine-based chiral auxiliary and two Bu(3)SnH-mediated radical cyclisations have been developed for a total synthesis of (-)-gamma-lycorane (1). The first cyclisation proceeded in 5-endo-trig manner with moderate diastereoselectivtiy to give (3aR,7aR)-octahydroindol-2-one 6b as the major product using alpha-iodo-N-(6-oxocyclohexen-1-yl)-N-[(S)-1-phenylethyl] acetamide (5b). In the second cyclisation, the radical precursor 8 was used as substrate to construct the optically active lycorane skeleton 15 which was reduced using LiAlH4 into (-)-gamma-lycorane (1). 相似文献
993.
Guiffo-Soh G Hernandez B Coïc YM Boukhalfa-Heniche FZ Fadda G Ghomi M 《The journal of physical chemistry. B》2008,112(4):1282-1289
Circular dichroism (CD) and Raman scattering were applied to the aqueous solution of minimalist LK peptides constructed with successive KL repeats leading to the following generic primary sequence: (KL)nK. Three peptides of this family, a 3-mer (n=1), a 9-mer (n=4), and a 15-mer (n=7), are analyzed in this report. Raman spectra of the 3-mer (KLK, a random chain) and its labile-hydrogen deuterated species yield a set of interesting information for analyzing longer peptides of this series. Although the CD spectrum of the 9-mer (KLKLKLKLK) reveals a signal traditionally assigned to a random structure, the corresponding Raman spectrum allows finding a mixture of conformations in solution, adopting predominantly beta-type structures. This fact proves the utility of Raman spectroscopy to eliminate eventual ambiguity concerning conformational assignments in peptides based only on the use of CD technique. Finally, the 15-mer (KLKLKLKLKLKLKLK) gives rise to CD and Raman spectra clearly assignable to a beta-type structure. On the basis of all the observed results on the 15-mer, we can confirm that this peptide may exist as isolated beta-strands at low concentration (sub-micromolar), flat-oriented at the air/water interface, whereas at high concentrations (millimolar), non-H-bonded immersible aggregates might be formed. A hypothetical model for these beta-strand aggregates could be proposed as stabilized by an interior hydrophobic core and a hydrophilic external face, formed by leucine and lysine side chains, respectively. 相似文献
994.
Silva PL Pires PA Trassi MA El Seoud OA 《The journal of physical chemistry. B》2008,112(47):14976-14984
The solvation of six solvatochromic probes in a large number of solvents (33-68) was examined at 25 degrees C. The probes employed were the following: 2,6-diphenyl-4-(2,4,6-triphenylpyridinium-1-yl) phenolate (RB); 4-[(E)2-(1-methylpyridinium-4-yl)ethenyl] phenolate, MePM; 1-methylquinolinium-8-olate, QB; 2-bromo-4-[(E)-2-(1-methylpyridinium-4-yl)ethenyl] phenolate, MePMBr, 2,6-dichloro-4-(2,4,6-triphenyl pyridinium-1-yl) phenolate (WB); and 2,6-dibromo-4-[(E)-2-(1-methylpyridinium-4-yl)ethenyl] phenolate, MePMBr(2), respectively. Of these, MePMBr is a novel compound. They can be grouped in three pairs, each with similar pK(a) in water but with different molecular properties, for example, lipophilicity and dipole moment. These pairs are formed by RB and MePM; QB and MePMBr; WB and MePMBr(2), respectively. Theoretical calculations were carried out in order to calculate their physicochemical properties including bond lengths, dihedral angles, dipole moments, and wavelength of absorption of the intramolecular charge-transfer band in four solvents, water, methanol, acetone, and DMSO, respectively. The data calculated were in excellent agreement with available experimental data, for example, bond length and dihedral angles. This gives credence to the use of the calculated properties in explaining the solvatochromic behaviors observed. The dependence of an empirical solvent polarity scale E(T)(probe) in kcal/mol on the physicochemical properties of the solvent (acidity, basicity, and dipolarity/polarizability) and those of the probes (pK(a), and dipole moment) was analyzed by using known multiparameter solvation equations. For each pair of probes, values of E(T)(probe) (for example, E(T)(MePM) versus E(T)(RB)) were found to be linearly correlated with correlation coefficients, r, between 0.9548 and 0.9860. For the mercyanine series, the values of E(T)(probe) also correlated linearly, with (r) of 0.9772 (MePMBr versus MePM) and 0.9919 (MePMBr(2) versus MePM). The response of each pair of probes (of similar pK(a)) to solvent acidity is the same, provided that solute-solvent hydrogen-bonding is not seriously affected by steric crowding (as in case of RB). We show, for the first time, that the response to solvent dipolarity/polarizability is linearly correlated to the dipole moment of the probes. The successive introduction of bromine atoms in MePM (to give MePMBr, then MePMBr(2)) leads to the following linear decrease: pK(a) in water, length of the phenolate oxygen-carbon bond, length of the central ethylenic bond, susceptibility to solvent acidity, and susceptibility to solvent dipolarity/polarizability. Thus studying the solvation of probes whose molecular structures are varied systematically produces a wealth of information on the effect of solute structure on its solvation. The results of solvation of the present probes were employed in order to test the goodness of fit of two independent sets of solvent solvatochromic parameters. 相似文献
995.
El?bieta Hejchman Dorota Maciejewska Irena Wolska 《Monatshefte für Chemie / Chemical Monthly》2008,18(3):1337-1348
The microwave-assisted synthesis of four new 5-acetyl-4,7-dimethoxy-6-hydroxybenzofuran (khellinone) analogs is described.
The structures of the obtained derivatives in the solid state are evaluated on the basis of 13C CP/MAS NMR spectra and theoretical calculations at DFT level. A single crystal X-ray diffraction structure is presented
for 8-acetyl-7-hydroxy-4-methylcoumarin. 1,4-Bis(5-acetyl-4,7-dimethoxybenzofuran-6-yloxy)butane was evaluated for potential
anticancer activity in an in vitro screening panel of 60 human tumor cell lines. Selected leukemia, non-small cell lung cancer, CNS, melanoma, ovarian, and
breast cancer cell lines were sensitive to this compound. 相似文献
996.
Emad M. El-Telbani Mohamed F. El Shehry Galal A. M. Nawwar 《Monatshefte für Chemie / Chemical Monthly》2008,387(2):685-689
Synthesis of the title ring system is described using ethyl 4-(2,4-dichlorophenoxy)-3-oxobutanoate as starting material. The
latter was prepared through acylating Meldrum’s acid with the phenoxy acid chloride derivative. 相似文献
997.
Wael A. El-Sayed Mahmoud M. M. Ramiz Adel A.-H. Abdel-Rahman 《Monatshefte für Chemie / Chemical Monthly》2008,139(12):1499-1505
New C-furyl glycosides were synthesized in order to increase the number of compounds screened for antimicrobial activity. The antimicrobial
activity showed that the bromo as well as the nitro derivatives were the most active compounds.
Correspondence: Adel A.-H. Abdel-Rahman, Faculty of Science, Department of Chemistry, Menoufia University, Shebin El-Koam,
Egypt. 相似文献
998.
5-(4-Methylpiperidino)methyl-2-thiouracil (1) has been obtained via the Mannich reaction between 2-thiouracil, paraformaldehyde, and a cyclic secondary amine such as 4-methylpiperidine (4-MP) in ethanol. New S,N(1)-di-o-(m- and p-)bromo-(nitro-) benzyl-substituted derivatives have been synthesized successfully in the reactions of 1 with the corresponding o-(m- and p-)bromobenzyl bromides or o-(m- and p-) nitrobenzyl chlorides in DMF solution in the presence of K2CO3. The opposite method of synthesis, that is, the reaction between 2-o-(m- and p-)bromobenzylthio-1-o-(m- and p-)bromobenzyluracils and 2-o-(m- and p-)nitrobenzylthio-1-o-(m- and p-) nitrobenzyluracils (8), with paraformaldehyde and 4-methylpiperidine in ethanol failed, indicating the important role of the enol form of 2-thiouracil for the Mannich reaction to be successful. 相似文献
999.
A simple and accurate stability-indicating thin-layer chromatographic (TLC) method is developed and validated for the quantitative determination of ribavirin (RBV) in its bulk and with used for development consists of chloroform-methanol-acetic acid (60:15:15, v/v/v). The separated spots are visualized as bluish green spots after being sprayed with anisaldehyde reagent. RBV is subjected to different accelerated stress conditions. The drug is found to undergo degradation under all stress conditions, and the degradation products are well resolved from the pure drug with significantly different Rf values. The optical densities of the separated spots are found to be linear with the amount of RBV in the range of 5-40 microg/spot with a good correlation coefficient (r=0.9980). The limit of detection and limit of quantitation values are 1.40 and 4.67 microg/spot, respectively. Statistical analysis proves that the method is repeatable and accurate for the determination of RBV in the presence of its degradation products. The method meets the International Conference on Harmonisation/Food and Drug Administration regulatory requirements. The proposed TLC method is successfully applied for the determination of RBV, pure and in capsules, with good accuracy and precision; the label claim percentages are 98.8%+/-1.5%. The results obtained by the proposed TLC method are comparable with those obtained by the official method. 相似文献
1000.
Fathy Abdel‐Kader Amer Metwally Hammouda Bakr Fathy Abdel‐Wahab Abdel‐Aziz Sayed El‐Ahl 《Journal of heterocyclic chemistry》2008,45(6):1549-1569
This review presents a survey of the synthetic methods and reactions of 3‐pyrrolidinones I (R = H, alkyl, acyl, ester; R1 = H, alkyl, cyano, ester, etc). 3‐Pyrrolidinones are synthetically versatiles substrate, as they can be used for synthesis of a large variety of heterocyclic compounds, such as indoles and 5‐deazapteroic acid analogues and as a raw material for drug synthesis. The high reactivity of an active methylene group next to the carbonyl of the pyrrolidine ring is useful for various syntheses. 相似文献