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101.
Ana B. Pereiro Helena I.M. Veiga José M.S.S. Esperança Ana Rodríguez 《The Journal of chemical thermodynamics》2009,41(12):1419-1423
Density, speed of sound, refractive index, and dynamic viscosity of the ionic liquids (ILs) 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, BMpyr NTf2, and trihexyl(tetradecyl) phosphonium dicyanamide, P66614 dca, were studied as a function of temperature at atmospheric pressure. Thermal expansion coefficient, αp, molecular volumes, and standard entropies of these ILs were calculated from the experimental density values. The solubility of three aromatic components (benzene, toluene, and ethylbenzene) in the selected ILs was carried out at T = 298.15 K and atmospheric pressure and compared with literature values for sulfolane. 相似文献
102.
Jana Madejová Martin Pentrák Helena Pálková Peter Komadel 《Vibrational Spectroscopy》2009,49(2):211-218
The benefit of near-infrared (NIR) spectroscopy in studies of acid-treated clay minerals is demonstrated. The effects of mineral type, composition and content of non-swelling interlayers on the dissolution rate are investigated. Detailed analysis of the NIR region is performed by comparing the first overtone (2νOH) and combination (ν + δ)OH bands with the fundamental stretching (ν) and bending (ν) vibrations. Spectra of acid-treated samples show a gradual decrease in the intensities of the structural OH overtone (near 7100 cm?1) and combination (4600–4300 cm?1) bands reflecting a fewer number of octahedral atoms. The appearance of the 2νSiOH vibration for terminal (isolated) SiOH groups near 7315 cm?1 indicates the formation of a protonated silica phase. The band near 7130 cm?1 remaining in the spectra of acid-treated samples is assigned to 2νHOSiOH of geminal silanol groups. Thus the creation of geminal silanols, previously detected by 29Si MAS-NMR spectroscopy in acid-treated hectorite, is confirmed also by NIR spectroscopy. The assignment of the 4555 cm?1 band to the (ν + δ)SiOH combination enabled calculation of the wavenumber for the SiO–H bending vibration (~810 cm?1) that is not observable in the mid-IR region due to overlapping with the Si–O band of amorphous silica (~800 cm?1). The NIR spectra confirm that trioctahedral hectorite is much more susceptible to dissolution in HCl than dioctahedral nontronite. The dissolution rate of kaolinite present in the Badin clay as an admixture is lower than that of the main mineral nontronite. The accessibility of the interlayers for protons significantly influences the stability of clay minerals in HCl. Mixed-layered mineral illite/smectite with only 30% of swelling interlayers dissolves more slowly than smectite of similar chemical composition containing mainly swelling interlayers. 相似文献
103.
José Angel Brito Helena Teruel Stéphane Massou Montserrat Gómez 《Magnetic resonance in chemistry : MRC》2009,47(7):573-577
Oxomolybdenum(VI) complexes containing diverse ligands from an electronic and topological point of view have been analysed by means of 95Mo NMR in solution with the purpose of using this technique as a tool to study their coordination chemistry and reactivity. The relationship between the electronic density on the metal tuned by the electron‐donor ability of the coordinated ligands and the 95Mo chemical shift has been proved for mono‐ and bimetallic complexes showing a hexa‐ or hepta‐coordination around the metal centre. The different origins of the signal broadening (associated either to the symmetry of the metallic polyhedron or to the presence of isomers or to the ligand de‐coordination) have been also considered to rationalise the obtained data. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
104.
Maria Helena Tirollo Taddei José Flávio Macacini Roberto Vicente Júlio Takehiro Marumo Luís Antônio Albiac Terremoto 《Journal of Radioanalytical and Nuclear Chemistry》2017,311(3):1687-1696
Nowadays, the scaling factor methodology is widely used in order to estimate the activity concentration of difficult to measure nuclides in low- and intermediate-level waste from nuclear reactors. However, very few experimental studies evaluate how operational changes in the reactors affect scaling factors. The present work examines the impact of operational changes on the scaling factors that were determined for spent ion-exchange resins and spent activated charcoal permanently withdrawn as radioactive wastes from the water cleanup system of the IEA-R1 nuclear research reactor. 相似文献
105.
CdTe quantum dots (QDs), capped with mercaptopropionic acid (MPA), were synthesized and the variation of their fluorescence properties (steady state and lifetime) with pH was assessed in solution and when immobilized in a sol-gel host. Three different sizes of CdTe QDs with excited state lifetimes ranging from 42 to 48 ns and with emission maximum at 540 nm (QD540), 580 nm (QD580) and 625 nm (QD625) were selected. The solution pH affects the maximum emission wavelength (shifts to higher wavelengths of 23, 24 and 27 nm for QD540, QD580 and QD625, respectively), the excited state lifetime and the fluorescence intensity in a reversible way. Linearization of the maximum emission wavelength variation with the pH allows the estimation of an apparent ionization constant (pKa) for each QD: 6.5 ± 0.1 (QD540), 6.1 ± 0.5 (QD580) and 5.4 ± 0.3 (QD625). The variation of the QDs fluorescence properties was further explored using confocal laser scanning microscopy allowing the implementation of a new calibration method for pH imaging in solution. QDs were successfully immobilized on the tip of an optical fiber by dip-coating using sol-gel procedure. The immobilized QDs showed a similar pH behaviour to the one observed in solution and an apparent lifetime of 80, 68 and 99 ns, respectively. The proposed QDs based methodology can be successfully used to monitor pH using wavelength encoded data in imaging and fiber optic sensing applications. 相似文献
106.
Plínio C. Sathler Charles S. Craik Toshihiko Takeuchi Russolina B. Zingali Helena C. Castro 《Applied biochemistry and biotechnology》2010,160(8):2355-2365
Ecotin is a bidentate, fold-specific inhibitor of mammalian serine-proteases produced by Escherichia coli. This molecule may be engineered to increase and/or change its affinity and specificity providing significant biotechnological
potential. Since ecotin binds tightly to serine proteases of the trypsin fold, it may help to identify the role of these enzymes
in different biological processes. In this work, we tested ecotin variants as an affinity purification reagent for identifying
enzymes in samples of tumor progression and mammary gland involution. Initially, we used a commercial source of urokinase-type
plasminogen activator (u-PA) that remained fully active after elution from an affinity column of the ecotin variant (M84R,
M85R). We then successfully identified u-PA from more complex mixtures including lysates from a prostate cancer cell line
and involuting mouse mammary glands. Interestingly, a membrane-type serine protease 1 was isolated from the Triton X-100-solubilized
PC-3 cell lysates, and surprisingly, haptoglobin, a serine-protease homolog protein, was also identified in mammary gland
lysates and in blood. Haptoglobin does not prevent ecotin inhibition of u-PA, but it may act as a carrier within blood when
ecotin is used in vivo. Finally, this affinity purification matrix was also able to identify a thrombin-like enzyme from snake venom using an ecotin
variant directed against thrombin. Overall, the ecotin variants acted as robust tools for the isolation and characterization
of proteins with a trypsin fold. Thus, they may assist in the understanding of the role of these serine proteases and homologous
proteins in different biological processes. 相似文献
107.
Bodzon-Kulakowska A Suder P Drabik A Kotlinska JH Silberring J 《Analytical and bioanalytical chemistry》2010,398(7-8):2939-2942
Glutamine synthetase is a key enzyme which has a regulatory role in the brain glutamate pool. According to previously published proteomic analysis, it was shown that the expression level of this enzyme is affected by morphine administration. In our study, we examined the activity of glutamine synthetase in various structures of rat brain (cortex, striatum, hippocampus and spinal cord) that are biochemically and functionally involved in drug addiction and antinociception caused by morphine. We were not able to observe any significant changes in the enzyme activity between morphine-treated and control samples despite previously reported changes in the expression levels of this enzyme. These findings stressed the fact that changes observed in the expression of particular proteins during proteomic studies may not be correlated with its activity. 相似文献
108.
Helena Řehulková Jana Chalupová Marek Šebela Pavel Řehulka 《Journal of mass spectrometry : JMS》2010,45(1):104-111
Peptide samples derived from enzymatic in‐gel digestion of proteins resolved by gel electrophoresis often contain high amount of salts originating from reaction and separation buffers. Different methods are used for desalting prior to matrix‐assisted laser desorption/ionization (MALDI) mass spectrometry (MS), e.g. reversed‐phase pipette tip purification, on‐target washing, adding co‐matrices, etc. As a suitable matrix for MALDI MS of peptides, α‐cyano‐4‐hydroxycinnamic acid (CHCA) is frequently used. Crystalline CHCA shows the ability to bind peptides on its surface and because it is almost insoluble in acidic water solutions, the on‐target washing of peptide samples can significantly improve MALDI MS signals. Although the common on‐target washing represents a simple, cheap and fast procedure, only a small portion of the available peptide solution is efficiently used for the subsequent MS analysis. The present approach is a combination of the on‐target washing principle carried out in a narrow‐end pipette tip (e.g. GELoader tip) and preconcentration of peptides from acidified solution by passing it through small CHCA crystals captured inside the tip on a glass microfiber frit. The results of MALDI MS analysis using CHCA‐tip peptide preconcentration are comparable with the use of homemade POROS R2 pipette tip microcolumns. Advantages and limitations of this approach are discussed. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
109.
A mixed‐polymeric electrokinetic chromatography system has been developed for the simultaneous determination of a contaminant like oversulfated condroitin sulfate (OSCS) and impurities expressed as dermatan (Der) in heparin (Hep) samples. The EKC system consisted of 0.5% w/v polymeric β‐CD, 0.4% w/v tetronic® 1107 and 400 mM tris‐phosphate buffer at pH 3.5. The optimized electrophoretic conditions included the use of an uncoated‐silica capillary of 50 cm of total length and 75 μm id, an applied voltage of ?7 kV, a temperature of 30°C and 200 nm UV‐detection. The highly sensitive method developed showed low values of LOD, 0.07% w/w (0.07 μg/mL) (OSCS) and 0.1% w/w (0.1 μg/mL) (Der), and values of LOQ 0.2% w/w (0.2 μg/mL) (OSCS) and 0.3% w/w (0.3 μg/mL) (Der) with a concentration level of Hep sample as low as 0.1 mg/mL. Additional parameters of validation such as specificity, linearity, accuracy, and robustness were evaluated according to international guidelines. Owing to its simplicity, high sensitivity, and reliability, the proposed method can be an advantageous alternative to the traditional methodologies for the analysis of Hep in raw material and specially in finished products because of the low amounts of Hep sample required. 相似文献
110.
Rosa Maria da Rocha Esperidiana A.B. Moura José Carlos Bressiani Ana Helena A. Bressiani 《Radiation Physics and Chemistry》2010,79(3):301-305
Methylsilicone resin as a polymer precursor for a SiOC ceramic material was cured and foamed by electron beam (EB) irradiation in air prior to the pyrolysis under an inert atmosphere. Methylsilicone foams were obtained without additional foaming agent when exposed to accelerated electrons with radiation doses up to 9 MGy and dose rate of 2.8 kGy/s. During irradiation the polymer was melted and simultaneously gaseous products were formed by the methyl group oxidation and by the poly-condensation crosslinking reactions. The formed gases could not escape from the molten polymer and began to aggregate into bubbles. The effect of the radiation dose on the polymer foam molecular structure, the gel fraction and the ceramic yield was analyzed. The results indicate that the maximum amount of crosslinking in methylsilicone, when EB radiation is used, occurred between 1.0 and 2.0 MGy radiation dose. Methylsilicone foams were pyrolysed in N2 atmosphere at temperatures of 1200 and 1500 °C, resulting in amorphous SiOC and partially crystalline ceramic foams, respectively. A porosity of ~84% was achieved in the pyrolyzed foams, with cell size ranging from 30 to 300 μm and density of about 0.31 g cm?3. 相似文献