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141.
Lourenço JM Ribeiro PA Botelho do Rego AM Braz Fernandes FM Moutinho AM Raposo M 《Langmuir : the ACS journal of surfaces and colloids》2004,20(19):8103-8109
The amount of counterions in layer-by-layer (LBL) films of poly(allylamine hydrochloride) (PAH) and poly(styrene sulfonate) (PSS) has been determined with X-ray photoelectron spectroscopy (XPS) for films prepared from solutions with various NaCl concentrations. Sodium and chloride counterions are present in LBL films produced from salt solutions, which are located at the surface and in the bulk of the films. The percentage of bulk counterions increases with the ionic strength of the polyelectrolyte before reaching a constant value. The bulk sodium/sulfur percentage ratios tend to 0.8 for samples washed with pure water and for samples washed with NaCl aqueous solutions, while the bulk chlorine/nitrogen percentage ratios tend to 0.5 for the same samples. The ratio between the percentages of polyelectrolyte ionic groups lies close to unity for all samples, indicating that counterions do not contribute to charge compensation in the polyelectrolyte during the adsorption process. The presence of counterions in LBL films is explained by Manning condensation near the polyelectrolyte ionic groups, leading to inter-polyelectrolyte ionic bondings via ionic networks. It is believed that condensation leads to the formation of NaCl crystallites in these LBL films, which was confirmed by X-ray diffraction measurements. 相似文献
142.
Nilo Zanatta Elizandra C. S. Lopes Leonardo Fantinel Helio G. Bonacorso Marcos A. P. Martins 《Journal of heterocyclic chemistry》2002,39(5):943-947
The synthesis of a novel series of twelve 4‐(trihalomethyl)dipyrimidin‐2‐ylamines, from the cyclo‐condensation reaction of 4‐(trichloromethyl)‐2‐guanidinopyrimidine, with β‐alkoxyvinyl trihalomethyl ketones, of general formula: X3C‐C(O)‐C(R2)=C(R1)‐OR, where: X = F, Cl; R = Me, Et, ‐(CH2)2‐, ‐(CH2)3‐; R1 = H, Me; R2 = H, Me, ‐(CH2)2‐, ‐(CH2)3‐, is reported. The reactions were carried out in acetonitrile under reflux for 16 hours, leading to the dipyrimidin‐2‐ylamines in 65‐90% yield. Depending on the substituents of the vinyl ketone, tetrahydropyrimidines or aromatic pyrimidine rings were obtained from the cyclization reaction. When X = Cl, elimination of the trichloromethyl group was observed during the cyclization step. The structure of 4‐(trihalomethyl)dipyrimidin‐2‐ylamines was studied in detail by 1H‐, 13C‐ and 2D‐nmr spectroscopy. 相似文献
143.
Luiza N.H. Arakaki Maria G. da Fonseca Edson C. da Silva Filho Ana Paula de M. Alves Kaline S. de Sousa Andr Leonardo P. Silva 《Thermochimica Acta》2006,450(1-2):12-15
The reaction of ethylene sulfide with 3-aminopropyltrimethoxysilane gave a new silylating agent, which was anchored onto a silica surface via the sol–gel procedure. This surface displayed a chelating moiety containing nitrogen and two sulfur basic centers potentially capable of extracting cations from aqueous solutions. The process of metal extraction was followed by a batch method, and fitted to a modified Langmuir equation. The maximum adsorption capacities found were: 2.06 ± 0.01, 3.72 ± 0.02, and 5.14 ± 0.02 mmol g−1 for Pb(II), Cd(II), and Hg(II), respectively. The enthalpies of bending are: −1.16 ± 0.04, −3.60 ± 0.10, and −8.94 ± 0.03 kJ mol−1 for Cd(II), Pb(II), and Hg(II), respectively. The Gibbs free energies of binding agree with the spontaneity of the proposed reactions between cations and basic centers. 相似文献
144.
Godoi AF Vilegas W Godoi RH Van Vaeck L Van Grieken R 《Journal of chromatography. A》2004,1027(1-2):127-130
Turnera diffusa Willd. var. afrodisiaca (Ward) Urb. (syn. T. aphrodisiaca) belongs to the family of Turneraceae and is an aromatic plant growing wild in the subtropical regions of America and Africa. It is widely used in the traditional medicine as e.g. anti-cough, diuretic, and aphrodisiac agent. This work presents a 3 min chromatographic analysis using low-pressure (LP) gas chromatography (GC)-ion-trap (IT) mass spectrometry (MS). The combination of a deactivated 0.6 m x 0.10 mm i.d., restrictor with a wide-bore CP-Wax 52 capillary column (10 m x 0.53 mm i.d., 1 microm) reduces the analysis time by a factor of 3-7 in comparison to the use of a conventional narrow bore column. Chromatographic conditions have been optimized to achieve the fastest separation with the highest signal/noise ratio in MS detection. These results allow fast and reliable quality control of the essential oil to be achieved. 相似文献
145.
This work was aimed at understanding the structure of SiO2–MO2 (M = Ti, Zr, Hf) and SiO2–HfO2–MO2 (M = Ti, Zr) materials, used as mixed oxide glass hosts for Er3+ ions in the fabrication of optical planar waveguides by sol-gel processing. This structural study was performed by Waveguide
Raman Spectroscopy (WRS), complemented with X-ray diffraction (XRD). The admixture of TiO2 to HfO2, SiO2–HfO2 and HfO2–ZrO2 compositions was found to cause precipitation of nanocrystals of tetragonal HfO2 or ZrO2, or the formation of hafnia-titania mixed crystals, depending on the HfO2/TiO2 molar ratio. 相似文献
146.
Iris A. Bermejo Claudio D. Navo Jorge Castro-Lpez Ana Guerreiro Ester Jimnez-Moreno Elena M. Snchez Fernndez Fayna García-Martín Hiroshi Hinou Shin-Ichiro Nishimura Jos M. García Fernndez Carmen Ortiz Mellet Alberto Avenoza Jesús H. Busto Gonalo J. L. Bernardes Ramn Hurtado-Guerrero Jesús M. Peregrina Francisco Corzana 《Chemical science》2020,11(15):3996
The Tn antigen (GalNAc-α-1-O-Thr/Ser) is a well-known tumor-associated carbohydrate determinant. The use of glycopeptides that incorporate this structure has become a significant and promising niche of research owing to their potential use as anticancer vaccines. Herein, the conformational preferences of a glycopeptide with an unnatural Tn antigen, characterized by a threonine decorated with an sp2-iminosugar-type α-GalNAc mimic, have been studied both in solution, by combining NMR spectroscopy and molecular dynamics simulations, and in the solid state bound to an anti-mucin-1 (MUC1) antibody, by X-ray crystallography. The Tn surrogate can mimic the main conformer sampled by the natural antigen in solution and exhibits high affinity towards anti-MUC1 antibodies. Encouraged by these data, a cancer vaccine candidate based on this unnatural glycopeptide and conjugated to the carrier protein Keyhole Limpet Hemocyanin (KLH) has been prepared and tested in mice. Significantly, the experiments in vivo have proved that this vaccine elicits higher levels of specific anti-MUC1 IgG antibodies than the analog that bears the natural Tn antigen and that the elicited antibodies recognize human breast cancer cells with high selectivity. Altogether, we compile evidence to confirm that the presentation of the antigen, both in solution and in the bound state, plays a critical role in the efficacy of the designed cancer vaccines. Moreover, the outcomes derived from this vaccine prove that there is room for exploring further adjustments at the carbohydrate level that could contribute to designing more efficient cancer vaccines.An anti-cancer vaccine based on an unnatural antigen with an sp2-iminosugar fragment. 相似文献
147.
A method is described for the simultaneous determination of organophosphorus and triazine pesticides in olive oil, whereby reversed-phase liquid chromatography (LC) is coupled to gas chromatography by means of an automated through-oven transfer adsorption-desorption (TOTAD) interface. The olive oil needs to be filtered only before it is loaded into the liquid chromatograph, where preseparation of the pesticide residues from the other olive oil components is carried out by using methanol-water as the eluant. The LC fraction containing the pesticides is automatically transferred to the gas chromatograph by using the TOTAD interface, which almost totally eliminates the solvent, so that water-sensitive detectors such as the nitrogen-phosphorus detector can be used. Detection limits range from 0.07 to 0.38 microg/L for organophosphorus pesticides and from 6.0 to 7.0 microg/L for triazines. The results were compared with those obtained by flame ionization detection. 相似文献
148.
We describe the first studies on the chemistry of 2-(2-oxo-3-phenylpropyl)benzaldehydes, which were converted into 3-benzylisochromen-1-ones via the corresponding 2-(2-oxo-3-phenylpropyl)benzoic acid. The 2-(2-oxo-3-phenylpropyl)benzaldehydes proved to be convenient starting materials for the synthesis of 3-phenyl-2-naphthols. Oxidation of the latter compounds resulted in a novel, efficient synthesis of 3-phenyl-1,2-naphthoquinones, which were efficiently transformed into 2-hydroxy-3-phenyl-1,4-naphthoquinones. 相似文献
149.
Lopes NP Stark CB Hong H Gates PJ Staunton J 《Rapid communications in mass spectrometry : RCM》2002,16(5):414-420
Monensin A and B were studied by electrospray ionisation tandem mass spectrometry (ESI-MS/MS) and the fragment ions were confirmed by accurate-mass measurements. Analyses were performed on both a quadrupole time-of-flight (QTOF) and a Fourier-transform ion cyclotron resonance (FTICR) mass spectrometer. The analysis revealed that fragment ions were produced by Grob-Wharton fragmentations and pericyclic rearrangements in addition to various simple neutral losses. A study of the protonated and sodiated sodium salt revealed different fragmentation pathways for these species, thus complementary structural information could be gained. A complete fragmentation pathway of monensin A and B protonated sodium salt [(M-H+Na)+H])+) and sodiated sodium salt [(M-H+Na)+Na](+) is proposed. MS(3) analysis confirmed the separate fragmentation pathways. 相似文献
150.
Bustamante JJ Garcia M Gonzalez L Garcia J Flores R Aguilar RM Trevino A Benavides L Martinez AO Haro LS 《Electrophoresis》2005,26(23):4389-4395
A method for separating proteins with a molecular mass difference of 2 kDa using SDS-PAGE under nonreducing conditions is presented. A sample mixture containing several human growth hormone (hGH) isoforms was initially separated on a weak anion-exchange column. Fractions rich in 24 kDa hGH as determined by analytical SDS-PAGE were pooled and further separated by cation-exchange chromatography. The fractions pooled from the cation-exchange chromatography contained two hGH isoforms with a 2 kDa molecular mass difference according to SDS-PAGE analysis, 22 and 24 kDa hGH. The 22 and 24 kDa hGH were separated using continuous-elution preparative double-inverted gradient PAGE (PDG-PAGE) under nonreducing conditions. The preparative electrophoresis gel was composed of three stacked tubular polyacrylamide matrices, a 4% stacking gel, a 13-18% linear gradient gel, and a 15-10% linear inverted gradient gel. Fractions containing purified 24 kDa hGH were pooled and Western blot analysis displayed immunoreactivity to antihGH antibodies. PDG-PAGE provides researchers with an electrophoretic technique to preparatively purify proteins under nonreducing conditions with molecular mass differences of 2 kDa. 相似文献