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The kinetics of thermal reactions of the photochemically-generated species [W(CN)7OH]4− and [W(CN)6–(CNH)(H2O)]2− with 5–nitro-1,10–phenanthroline (nitrophen) in basic and acidic media, respectively, were studied in buffer solutions at pH 4.2–10.6 and ionic strength 7.5×10−2kg−1 at 20°C. The quantum yield for the formation of the photoproduct was calculated and found to depend upon pH and the ligand and [W(CN)8]4− concentrations. The rate constants and quantum yields were less compared with 1,10–phenanthroline due to the electron-withdrawing inductive effect of the nitro group in nitrophen, which makes the latter a weaker ligand. The pseudo-first-order rate constant and quantum yield values in acidic media are higher than in basic media and the mechanisms of the photochemical substitution are different in the two media. This revised version was published online in June 2006 with corrections to the Cover Date.  相似文献   
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The authors offer a mathematical model for adverse selection by individual borrowers based on preferences for offers and the default (Bad) or non-default (Good) status of booked accounts. We define the condition for borrower risk and response when there is no adverse selection (NAS). This definition provides us with a direct comparison between the prior and posterior conditional probabilities of default by an individual borrower who Takes an offer; this allows us to obtain estimates of differential response rates for individual borrowers and the Good/Bad odds for Take, Non-Take and Accept sub-populations. Performance of different response-risk segments allows us to compare price-driven risk elasticity and price-driven response elasticity in the presence of Good or Bad adverse selections; a special case applies when the borrower's capacity to repay is not an issue. We offer limited experimental results for selected price-risk segments where action-based risk and response scores are used to estimate borrower preferences. The critical role of Non-Take inference is described.  相似文献   
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ABSTRACT: BACKGROUND: The peri-adolescent period is a crucial developmental moment of transition from childhood to emergent adulthood. The present report analyses the differences in Power Spectrum (PS) of the Electroencephalogram (EEG) between late childhood (24 children between 8 and 13 years old) and young adulthood (24 young adults between 18 and 23 years old). RESULTS: The narrow band analysis of the Electroencephalogram was computed in the frequency range of 0--20 Hz. The analysis of mean and variance suggested that six frequency ranges presented a different rate of maturation at these ages, namely: low delta, delta-theta, low alpha, high alpha, low beta and high beta. For most of these bands the maturation seems to occur later in anterior sites than posterior sites. Correlational analysis showed a lower pattern of correlation between different frequencies in children than in young adults, suggesting a certain asynchrony in the maturation of different rhythms. The topographical analysis revealed similar topographies of the different rhythms in children and young adults. Principal Component Analysis (PCA) demonstrated the same internal structure for the Electroencephalogram of both age groups. Principal Component Analysis allowed to separate four subcomponents in the alpha range. All these subcomponents peaked at a lower frequency in children than in young adults. CONCLUSIONS: The present approaches complement and solve some of the incertitudes when the classical brain broad rhythm analysis is applied. Children have a higher absolute power than young adults for frequency ranges between 0-20 Hz, the correlation of Power Spectrum (PS) with age and the variance age comparison showed that there are six ranges of frequencies that can distinguish the level of EEG maturation in children and adults. The establishment of maturational order of different frequencies and its possible maturational interdependence would require a complete series including all the different ages.  相似文献   
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Photo-induced graft copolymerization of methyl methacrylate(MMA) onto sodium salt of partially carboxymethylated guar gum(Na-PCMGG, DS = 0.291) was carried out in an aqueous medium using ceric ammonium nitrate(CAN) as photoinitiator to synthesize a novel graft copolymer, Na-PCMGG-g-PMMA, which may find its potential application as a metal adsorbent. The influences of synthesis variables such as concentrations of photoinitiator(CAN), nitric acid and monomer(MMA) as well as reaction time, temperature and amount of substrate on the grafting yields were studied and the reaction conditions for optimum photo-grafting were evaluated. At optimum concentration, the maximum values of the grafting yields achieved were G = 271.61% and GE = 63.89%. The experimental results were found to be in very good agreement with the proposed kinetic scheme. The photo-graft copolymerization of MMA onto Na-PCMGG( DS = 0.291) was also carried out in the presence and absence of ultraviolet radiation for studying the efficiency of the photoinitiator. The influence of carboxymethyl groups introduced onto the guar gum molecules with regard to its behavior towards ultra-violet radiation induced grafting with MMA was also investigated. Photo-grafting process was confirmed and the products were characterized with the help of the spectroscopic(1H-NMR and FTIR) and SEM techniques.  相似文献   
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An integral equation formulation for buoyancy-driven convection problems is developed and illustrated. Buoyancy-driven convection in a bounded cylindrical geometry with a free surface is studied for a range of aspect ratios and Nusselt numbers. The critical Rayleigh number, the nature of the cellular motion, and the heat transfer enhancement are computed using linear theory. Green's functions are used to convert the linear problem into linear Fredholm integral equations. Theorems are proved which establish the properties of the eigenvalues and eigenfunctions of the linear integral operator which appears in these equations.  相似文献   
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JPC – Journal of Planar Chromatography – Modern TLC - A rapid and reliable high-performance thin-layer chromatographic method has been established for analysis of prednisolone in a...  相似文献   
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1-Methylchromeno[3,4-b]pyrrol-4(3H)-one and 1-phenylchromeno[3,4-b]pyrrol-4(3H)-one derivatives have been synthesized by cyclization of amides obtained by condensing α-halo ketones with 3-amino-chromenones, which show cytotoxic activity against lung, colon, and breast cancer cell lines.  相似文献   
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The effect of simultaneous substitution of a fluctuating cation and a divalent cation in LaMnO3 perovskite modifies the properties of the material to exhibit large valence colossal magnetoresistance (CMR) effect. A good example of these properties is (La1−2x Pr x Ca x )MnO3 (LPCMO) type CMR material. In this communication it is reported that, with the increase in x (for x=0.1, 0.15, 0.2), the T c varies between 100 and 120 K with improvisation in metal-insulator transition. Interestingly, resistance increases with x from few hundred ohms to few kilo ohms with corresponding decrease in the unit cell volume. The results of the studies using X-ray diffraction (XRD), electrical resistivity, magnetoresistance and ac susceptibility measurements on LPCMO samples for understanding the structural, transport and magnetic properties are discussed in detail.  相似文献   
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