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921.
922.
András Simon Erika Liktor‐Busa Gábor Tóth Zoltán Kele Judit Groska Mária Báthori 《Helvetica chimica acta》2008,91(9):1640-1645
Three new and one known ecdysteroids were identified in the MeOH extract of the roots of Serratula wolffii. The new compounds isolated were (11α)‐11‐hydroxyshidasterone ( 1 ), (2β,3α,5β,14β,22R)‐2,3,20,22,25‐pentahydroxycholest‐7‐en‐6‐one ( 2 ), and (2β,3α,5β,22R)‐2,3,20,22,25‐pentahydroxycholest‐7‐en‐6‐one ( 3 ), together with the known ponasterone A ( 4 ). This latter compound was now better characterized than earlier. The structures of compounds 1 – 4 were established by extensive spectroscopic techniques, including one‐ and two‐dimensional NMR methods. 相似文献
923.
Serra B Zhang J Morales MD Guzmán-Vázquez de Prada A Reviejo AJ Pingarrón JM 《Talanta》2008,75(4):1134-1139
The rapid detection of catalase-positive and catalase-negative bacteria in complex culture media has been accomplished by monitoring of hydrogen peroxide consumption or generation with a graphite-Teflon-peroxidase-ferrocene composite electrode. Escherichia coli and Streptococcus pneumoniae have been used as model catalase-positive and catalase-negative bacteria, respectively. Hydrogen peroxide evolution was amperometrically measured at 0.00 V. Experimental conditions, including the working solution composition, the incubation time and the hydrogen peroxide concentration, were optimized. The reusability of the biosensor was improved by placing a nylon membrane on the bioelectrode surface to prevent fouling caused by the bacterial medium. The developed methodology allowed the detection of E. coli and S. pneumoniae at concentration levels of approximately 2x10(6) and 2x10(5) cfu/mL, in assays taking 10 and 15 min, respectively, without any pre-concentration step or pre-enrichment procedure. 相似文献
924.
Soto NO Horstkotte B March JG López de Alba PL López Martínez L Cerdá Martín V 《Analytica chimica acta》2008,611(2):182-186
A multisyringe flow injection analysis system was used for the determination of hypochlorite in cleaning agents, by measurement of the native absorbance of hypochlorite at 292 nm. The methodology was based on the selective decomposition of hypochlorite by a cobalt oxide catalyst giving chloride and oxygen. The difference of the absorbance of the sample before and after its pass through a cobalt oxide column was selected as analytical signal. As no further reagent was required this work can be considered as a contribution to environmental friendly analytical chemistry. The entire analytical procedure, including in-line sample dilution in three steps was automated by first, dilution in a stirred miniature vessel, second by dispersion and third by in-line addition of water using multisyringe flow injection technique. The dynamic concentration range was 0.04-0.78 g L−1 (relative standard deviation lower than 3%), where the extension of the hypochlorite decomposition was of 90 ± 4%. The proposed method was successfully applied to the analysis of commercial cleaning products. The accuracy of the method was established by iodometric titration. 相似文献
925.
De Abreu HA Aparecida Dos S Lago I Souza GP Piló-Veloso D Duarte HA de C Alcântara AF 《Organic & biomolecular chemistry》2008,6(15):2713-2718
(+)-Bergenin (1) was isolated from Sacoglottis uchi, a species of vegetable found in the Amazon region and popularly used for the treatment of several hepatic problems. The structure of 1 was fully characterized using IR, GC-MS and NMR (1D and 2D) analyses. This phytoconstituent has been used as an oriental folk medicine for the treatment of many diseases and shows antihepatotoxic properties. Tests with beta-carotene, DPPH and a heterogeneous Fenton system were carried out, confirming the antioxidant activity of 1. Theoretical calculations were performed to investigate the formation of the radical derivatives of 1 using *H, *OH, *CH(3), and *CCl(3) as initiator radicals. DFT thermodynamic calculations showed that the methoxyl group (O-6-CH(3)) is the most favorable site for radical attack. Frontier molecular orbital analysis showed that nucleophilic radical attack is favored on the aromatic ring of 1 where the LUMO is localized, with antibonding character with respect to the O-6-CH(3) bond. The possibilities of attack at other sites on 1 were investigated in detail in order to understand the regiospecificity of this reaction. 相似文献
926.
Sánchez-Méndez A Benito JM de Jesús E de la Mata FJ Flores JC Gómez R Gómez-Sal P 《Dalton transactions (Cambridge, England : 2003)》2006,(45):5379-5389
The substituted bis(pyrazolyl)methane ligands RCH(3,5-Me2pz)2(R=SiMe3, CH2Ph, G1, G2, and G3; Gn=Fréchet-type dendritic wedges of generation n) have been prepared starting from H2C(3,5-Me2pz)2. Reaction of these didentate ligands with [NiBr2(DME)] is a straightforward procedure that allows the synthesis of the nickel(II) complexes [NiBr2{RCH(3,5-Me2pz)2}]. The molecular structure of compound (R=CH2Ph) has been determined by X-ray diffraction studies. The nickel centre coordinates two bromine and two nitrogen atoms in a tetrahedral environment, and the metallacycle Ni(NN)2C adopts a boat conformation with the benzyl group in an axial position. 1H NMR studies have been carried out to characterize these paramagnetic nickel compounds in solution. Valuable information about the disposition of the ligands and dendritic wedges in solution has been obtained thanks to the influence of the paramagnetic centre on the proton resonances. 相似文献
927.
Keszthelyi T Paszti Z Rigó T Hakkel O Telegdi J Guczi L 《The journal of physical chemistry. B》2006,110(17):8701-8714
Langmuir-Blodgett (LB) monomolecular layers of alkylhydroxamic acids and alkylphosphonic acids on copper and iron substrates have been studied by X-ray photoelectron spectroscopy (XPS) and sum-frequency vibrational spectroscopy. According to the XPS results, the structures of the hydroxamic acid and phosphonic acid Langmuir-Blodgett films are very similar: the thickness of the layer of the hydrocarbon tails is typically 1.9-2.1 nm, while the layer of headgroups is about 0.3-0.35 nm thick. The tilt angle of the carbon chains is estimated to be 20-30 degrees with respect to the sample surface normal, and the molecules are connected to the substrate via their headgroups. Analysis of the P 2p and N 1s lines indicates the presence of deprotonated headgroups. The substrate Cu 2p line includes a component which can be assigned to Cu(2+) ions in a thin Cu(OH)(2) layer. The deposition of LB layers led to significant decrease of the hydroxide-related signal, which indicates that binding of the headgroups to the surface is accompanied by the elimination of water molecules. The sum-frequency spectra also clearly indicate that well-ordered monolayers can be formed by the Langmuir-Blodgett technique. Since the non-resonant background from the metal substrates renders the analysis of the spectra more difficult, model system samples on glass were prepared. It was found that the alkyl chains of the adsorbed acids predominantly adopt the all-trans conformation and form an ordered structure. Upper limits for the mean tilt angle of the terminal methyl groups are approximately 10-20 degrees. 相似文献
928.
Colón L Crespo-Hernández CE Oyola R García C Arce R 《The journal of physical chemistry. B》2006,110(31):15589-15596
The role of base sequence and conformation on the photochemistry and photophysics of thymidylyl (3'-5')-2'-deoxyadenosine sodium salt (TpdA) and 2-deoxyadenylyl (3'-5')-thymidine ammonium salt (dApT) was studied. To this end, nanosecond transient absorption at 266 nm, steady-state irradiation at 254 nm, and quantum chemical calculations were used. The transient absorption spectra show the solvated electron broad band in the visible region for each dinucleotide. In addition, low-intensity absorption bands are observed in the UV region, which are attributed to the deprotonated and protonated neutral radicals of adenine and thymine bases. Photoionization (PI) occurs by one- and two-photon pathways; the latter accounting for approximately 70% of the net PI yield. A diffusion-limited rate constant of 2.0 x 10(10) M(-1) s(-1) was obtained for the reaction of the neutral molecule with the photoejected electron in both sequences. The photodestruction yield, measured from the chromophore loss at 260 nm, decreases in the presence of well-known electron scavengers. This suggests the participation of base radical anions as one of the photodegradation pathways, which is higher in TpdA than in dApT. The intermediacy of a radical ion pair (charge separated state) between the adjacent adenine and thymine bases is proposed in the formation of the [2 + 2] cycloadduct intermediate. The [2 + 2] cycloadduct intermediate is known to be the precursor of the thymine-adenine eight-member ring photoproduct (TA*). Conformational constrains in the radical ion pair are suggested to explain the absence of the TA* photoproduct in dApT. This hypothesis is supported by semiempirical calculations performed on all relevant reactive intermediates proposed to participate in the mechanism of formation of TA*. Altogether, the results show that sequence and conformation profoundly influence the photochemistry and the photophysics of these DNA model systems. 相似文献
929.
M. Piñeiro-Iglesias M. Miñones-Vázquez E. Vázquez-Blanco S. Muniategui-Lorenzo P. López-Mahía D. Prada-Rodríguez 《Chromatographia》2002,56(7-8):483-488
Summary The aim of this work is to establish the best conditions for concentration and purification steps in the trace analysis of
aliphatic and polycyclic aromatic hydrocarbons (PAH) from atmospheric particulate matter by gas chromatography-flame ionisation
detection (GC-FID) and high performance liquid chromatography with ultraviolet and fluorescence detection (HPLC-UV-FL). The
best results for the more volatile compound were obtained with a combination of rotary evaporation and a stream of nitrogen
(near to 100% for aliphatic hydrocarbons and from 70 to 105% for PAH). Two types of solid phase extraction (SPE)cartridges
(Supelclean
tm
LC-Silica SPE tubes and Sep-Pak? Plus silica cartridges) and glass column were examined for the purification and fractionation step. Blank chromatograms of
both types of cartridges analysed by GC-FID made this study difficult, because a PSS (programmed split-splitless) injector
was employed thereby increasing the sensitivity. This problem was not observed in the HPLC-UV-FL blank chromatograms of these
cartridges. Glass columns filled with silica and alumina were chosen because no interference was found in the GC-FID blank
chromatograms and the best recoveries in the fractionation of both aliphatic hydrocarbons and PAH were achieved. This is especially
important when aliphatic hydrocarbons concentrations are lower than 1 μg mL−1. Finally, the selected conditions were applied to the analysis of hydrocarbons in real atmospheric particulate samples. 相似文献
930.
Pau Bernadó Renato Barbieri Esteve Padrós Claudio Luchinat Miquel Pons 《Journal of the American Chemical Society》2002,124(3):374-375
Addition of Tb3+ to purple membrane (PM) suspensions changes the orientation of the menbrane normal from parallel to perpendicular with respect to the magnetic field. Residual dipolar couplings measured in protein L in the presence of PM are scaled by a factor of -1/2. NMR line broadening and cross-correlation effects induced by the addition of PM are partially reversed by Tb3+ but not by Tm3+ that has no effect on the orientation of PM. This is interpreted as the result of anisotropically restricted motion of protein L in the transiently PM-bound form. 相似文献