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111.
Here we report the characterization of an electrochemical mercury (Hg2+) sensor constructed with a methylene blue (MB)-modified and thymine-containing linear DNA probe. Similar to the linear probe electrochemical DNA sensor, the resultant sensor behaved as a “signal-off” sensor in alternating current voltammetry and cyclic voltammetry. However, depending on the applied frequency or pulse width, the sensor can behave as either a “signal-off” or “signal-on” sensor in square wave voltammetry (SWV) and differential pulse voltammetry (DPV). In SWV, the sensor showed “signal-on” behavior at low frequencies and “signal-off” behavior at high frequencies. In DPV, the sensor showed “signal-off” behavior at short pulse widths and “signal-on” behavior at long pulse widths. Independent of the sensor interrogation technique, the limit of detection was found to be 10 nM, with a linear dynamic range between 10 nM and 500 nM. In addition, the sensor responded to Hg2+ rather rapidly; majority of the signal change occurred in <20 min. Overall, the sensor retains all the characteristics of this class of sensors; it is reagentless, reusable, sensitive, specific and selective. This study also highlights the feasibility of using a MB-modified probe for real-time sensing of Hg2+, which has not been previously reported. More importantly, the observed “switching” behavior in SWV and DPV is potentially generalizable and should be applicable to most sensors in this class of dynamics-based electrochemical biosensors. 相似文献
112.
Carlos E.D. NazarioAmanda S. Santana Cristiane Y. KawasokoCarlos A. Carollo Gabriela R. HurtadoLuiz H. Viana Sandro L. BarbosaPalimécio G. Guerrero Jr. Francisco A. MarquesVânia B. Dabdoub Miguel J. DabdoubAdriano C.M. Baroni 《Tetrahedron letters》2011,52(32):4177-4181
Sonogashira cross-coupling reactions involving (E)-iodo vinyl stannanes and terminal acetylenes were carried out in the presence of Pd(PPh3)4, CuI and several amines, affording (Z)-tributylstannyl enynes in moderate to good yields (62-91%). Utilizing the catalytic system containing Pd(PPh3)4 (5%), CuI (10%), and TBAOH (40% in aqueous media) as activator, better yields (72-91%) and lower reaction times were achieved. 相似文献
113.
Martins GV Mano JF Alves NM 《Langmuir : the ACS journal of surfaces and colloids》2011,27(13):8415-8423
In this paper, we describe the construction and characteristics of thermoresponsive, thin nanostructured films prepared by layer-by-layer sequential assembly of chitosan-graft-NIPAAm and alginate. FTIR and (1)H NMR spectra have confirmed the introduction of NIPAAm moieties onto the chitosan backbone. The LCST of the synthesized copolymer was found to be around 31-33 °C. The formation of the polyelectrolyte multilayers containing the copolymer and alginate was followed in situ by quartz crystal microbalance with dissipation monitoring technique and ex situ by UV-vis measurements. Our results revealed the linear increase of the multilayer film growth and the influence of the presence of salt. Moreover, AFM analysis has confirmed that PNIPAAm is able to reconform upon temperature swaps even when combined with other layers in a polyelectrolyte multilayer, demonstrating that the nanoassemblies are thermoresponsive. Preliminary results showed that, upon reducing culture temperature below PNIPAAm LCST, a gradual detachment of cell sheets from these PNIPAAm-based coatings has occurred. 相似文献
114.
In this work we analytically evaluate, for the first time, the exact canonical partition function for two interacting spherical particles into a spherical pore. The interaction with the spherical substrate and between particles is described by an attractive square-well and a square-shoulder potential. In addition, we obtain exact expressions for both the one particle and an averaged two particle density distribution. We develop a thermodynamic approach to few-body systems by introducing a method based on thermodynamic measures [I. Urrutia, J. Chem. Phys. 134, 104503 (2010)] for nonhard interaction potentials. This analysis enables us to obtain expressions for the pressure, the surface tension, and the equivalent magnitudes for the total and Gaussian curvatures. As a by-product, we solve systems composed of two particles outside a fixed spherical obstacle. We study the low density limit for a many-body system confined to a spherical cavity and a many-body system surrounding a spherical obstacle. From this analysis we derive the exact first order dependence of the surface tension and Tolman length. Our findings show that the Tolman length goes to zero in the case of a purely hard wall spherical substrate, but contains a zero order term in density for square-well and square-shoulder wall-fluid potentials. This suggests that any nonhard wall-fluid potential should produce a non-null zero order term in the Tolman length. 相似文献
115.
Barth AB de Oliveira GB Malesuik MD Paim CS Volpato NM 《Journal of chromatographic science》2011,49(7):512-518
A stability-indicating liquid chromatography method for the determination of the antifungal agent butenafine hydrochloride (BTF) in a cream was developed and validated using the Plackett-Burman experimental design for robustness evaluation. Also, the drug photodegradation kinetics was determined. The analytical column was operated with acetonitrile, methanol and a solution of triethylamine 0.3% adjusted to pH 4.0 (6:3:1) at a flow rate of 1 mL/min and detection at 283 nm. BTF extraction from the cream was done with n-butyl alcohol and methanol in ultrasonic bath. The performed degradation conditions were: acid and basic media with HCl 1M and NaOH 1M, respectively, oxidation with H(2)O(2) 10%, and the exposure to UV-C light. No interference in the BTF elution was verified. Linearity was assessed (r(2) = 0.9999) and ANOVA showed non-significative linearity deviation (p > 0.05). Adequate results were obtained for repeatability, intra-day precision, and accuracy. Critical factors were selected to examine the method robustness with the two-level Plackett-Burman experimental design and no significant factors were detected (p > 0.05). The BTF photodegradation kinetics was determined for the standard and for the cream, both in methanolic solution, under UV light at 254 nm. The degradation process can be described by first-order kinetics in both cases. 相似文献
116.
Gomes AG Azevedo AM Aires-Barros MR Prazeres DM 《Journal of chromatography. A》2011,1218(48):8629-8637
Plasmid DNA (pDNA) is purified directly from alkaline lysis-derived Escherichia coli (E. coli) lysates by phenyl boronate (PB) chromatography. The method explores the ability of PB ligands to bind covalently, but reversibly, to cis-diol-containing impurities like RNA and lipopolysaccharides (LPS), leaving pDNA in solution. In spite of this specificity, cis-diol free species like proteins and genomic DNA (gDNA) are also removed. This is a major advantage since the process is designed to keep the target pDNA from binding. The focus of this paper is on the study of the secondary interactions between the impurities (RNA, gDNA, proteins, LPS) in a pDNA-containing lysate and 3-amino PB controlled pore glass (CPG) matrices. Runs were designed to evaluate the role of adsorption buffer composition, feed type (pH, salt content), CPG matrix and sample pretreatment (RNase A, isopropanol precipitation). Water was chosen as the adsorption buffer over MgCl(2) solutions since it maximised pDNA yield (96.2±4.9%) and protein removal (61.3±3.0%), while providing for a substantial removal of RNA (65.5±3.5%) and gDNA (44.7±14.1%). Although the use of pH 3.5 maximised removal of impurities (~75%), the best compromise between plasmid yield (~96%) and RNA clearance (~60-70%) was obtained for a pH of 5.2. Plasmid yield was maximal (>96%) when the concentration of acetate and potassium ions in the incoming lysate feed were 1.7 M and 1.0 M, respectively. The pre-treatment of lysates with RNase A deteriorated the performance since the resulting oligoribonucleotides lack the cis-diol group at their 3' termini. Overall, the results support the idea that charge transfer interactions between the boron atom at acidic pH and electron donor groups in the aromatic bases of nucleic acids and side residues of proteins are responsible for the non-specific removal of gDNA, RNA and proteins. 相似文献
117.
Butler M Mañez PA Cabrera GM 《Journal of the American Society for Mass Spectrometry》2011,22(3):545-556
Differentiation between two isomers of hydroxypyridine N-oxide according to the metal cation adducts generated by electrospray ionization (ESI) was investigated for different metal
cations, namely Mg (II), Al (III), Ca (II), Sc (III), Fe (III), Co (II), Ni (II), Cu (II), Zn (II), Ga (III), besides the
diatomic cation VO(IV). Protonated molecules of the isomeric hydroxypyridine N-oxides as well as the singly/doubly charged adducts formed from neutral or deprotonated ligands and a doubly/triply charged
cation were produced in the gas phase using ESI, recording mass spectra with different metal ions for each isomer. While complex
formation was successful for 2-hydroxypyridine N-oxide with trivalent ions, in the case of 3-hydroxypyridine N-oxide, only peaks related to the protonated molecule were present. On the other hand, divalent cations formed specific species
for each isomer, giving characteristic spectra in every case. Hence, differentiation was possible irrespective of the metal
cation utilized. In addition, quantum chemical calculations at the B3LYP/6-31 + G(d,p) level of theory were performed in order
to gain insight into the different complexation of calcium(II) with the isomers of hydroxypyridine N-oxide. The relative stability in the gas phase of the neutral complexes of calcium made up of two ligands, as well as the
singly charged and doubly charged complexes, was investigated. The results of these calculations improved the understanding
of the differences observed in the mass spectra obtained for each isomer. 相似文献
118.
Gabriela Ciuperca 《Statistics & probability letters》2011,81(8):1267-1275
A general criterion is proposed to determine the number K of the change-points in a parametric nonlinear multi-response model. Schwarz criterion is a particular case. The change-points depend on regressor values and not on instant of measure. We prove that the proposed estimator for K is consistent. Simulation results, using Monte Carlo technique, for nonlinear models which have numerous applications, support the relevance of the theory. 相似文献
119.
Density, self-diffusion coefficient, and shear viscosity of pure liquid water are predicted for temperatures between 280 and 373 K by molecular dynamics simulation and the Green-Kubo method. Four different rigid nonpolarizable water models are assessed: SPC, SPC/E, TIP4P, and TIP4P/2005. The pressure dependence of the self-diffusion coefficient and the shear viscosity for pure liquid water is also calculated and the anomalous behavior of these properties is qualitatively well predicted. Furthermore, transport properties as well as excess volume and excess enthalpy of aqueous binary mixtures containing methanol or ethanol, based on the SPC/E and TIP4P/2005 water models, are calculated. Under the tested conditions, the TIP4P/2005 model gives the best quantitative and qualitative agreement with experiments for the regarded transport properties. The deviations from experimental data are of 5% to 15% for pure liquid water and 5% to 20% for the water + alcohol mixtures. Moreover, the center of mass power spectrum of water as well as the investigated mixtures are analyzed and the hydrogen-bonding structure is discussed for different states. 相似文献
120.