Ionization of Acetylacetone in Me2SO—Water Mixtures. Reactivity—Selectivity Principle or Principle of Imperfect Synchronization?

Rate constants for the reversible deprotonation of acetylacetone were measured in carboxylate and amine buffers in water and in 50%, 90% and 95% Me₂SO at 20°C. The Brønsted plot for the carboxylate ions is curved in the Me₂SO—water mixtures, but straight in water. The curvature is in the direction predicted by the Reactivity—Selectivity Principle (RSP). However, the Brønsted plot for the reaction with primary amines is straight in all solvents. This suggests that the curvature observerd with the carboxylate ions is caused by loss of solvation of the base; this loss of solvation is ahead of bond formation in the transition state rather than being a manifestation of the RSP. (Note that all Brønsted plots are based on pK_a values measured in the respective solvents.) The intrinsic rate constant (k₀) for proton transfer increases with the addition of Me₂SO, and more so with the carboxylate buffers than with the amines. This increase in k₀ is attributed to delayed solvation of the developing enolate ion in the transition state; with the carboxylate buffers, an additional factor is the early loss of solvation of the base. The various solvation effects observed in this study can all be understood in the context of the Principle of Imperfect Synchronization (PIS).     

A time-domain test for some types of nonlinearity

The bispectrum and third-order moment can be viewed as equivalent tools for testing for the presence of nonlinearity in stationary time series. This is because the bispectrum is the Fourier transform of the third-order moment. An advantage of the bispectrum is that its estimator comprises terms that are asymptotically independent at distinct bifrequencies under the hypothesis of linearity. An advantage of the third-order moment is that its values in any subset of joint lags can be used in the test, whereas when using the bispectrum the entire (or truncated) third-order moment is required to construct the Fourier transform. We propose a test for nonlinearity based upon the estimated third-order moment. We use the phase scrambling bootstrap method to give a nonparametric estimate of the variance of our test statistic under the hypothesis. Using a simulation study, we demonstrate that the test obtains its target significance level, with large power, when compared to an existing standard parametric test that uses the bispectrum. Further we show how the proposed test can be used to identify the source of nonlinearity due to interactions at specific frequencies. We also investigate implications for heuristic diagnosis of nonstationarity.     

Polymerase chain reaction versus culture for detection of Ureaplasma urealyticum and Mycoplasma hominis in the urogenital tract of adults and the respiratory tract of newborns

The efficiency of the polymerase chain reaction (PCR) was compared with that of culture for detection of Ureaplasma urealyticum and Mycoplasma hominis in 726 clinical specimens comprising 189 gynecological samples, 362 urological samples, and 175 samples from newborn infants. The sensitivity of PCR versus culture was 95% for both organisms, while the sensitivity of culture versus PCR was 91% for Ureaplasma urealyticum and 84% for Mycoplasma hominis. Furthermore, PCR tests were faster than culture tests, allowing the time to diagnosis to be reduced from two to five days to 24 h.     

Standards and industrial property

This article is primarily concerned with standards seen as a means for collective appropriation of technological information. It begins with an attempt to throw light on the relationships between standards, patents and licenses. Then we develop a two-stage duopolistic model whereby each firm must decide on a programme of standardization before choosing its level of production. The risks of multiple or inefficient equilibria are strong enough to justify the intervention of standardization organizations to inform and coordinate individual firms. But the paper also explains why some organizations likeetsi try to play a new role by promoting open access to master patents when used in the definition of a standard.     

Glass fiber-filled thermoplastics. I. Wall and processing effects on rheological properties

A systematic study of wall effects on the shear viscosity of short glass fiber-filled polypropylene and polystyrene is presented. The dependence of these effects on capillary radius, shear rate, temperature, and polymer matrix is examined. The “true” viscosity curves of these materials (free from wall effects) can be obtained by an extrapolation procedure. Breakage of glass fibers in the high shear-rate processes of extrusion and injection molding lead to an appreciable reduction of the viscosity of these materials and is probably the more important effect to take into account in these processes.     

Scalarization of dyadic spectral Green's functions and networkformalism for three-dimensional full-wave analysis of planar lines andantennas

A novel and systematic method is presented for the complete determination of dyadic spectral Green's functions directly from Maxwell's equations. With the use of generalized scalarizations developed in this paper, four general and concise expressions for the spectral Green's functions for one-dimensionally inhomogeneous multilayer structures, excited by three-dimensional electric and magnetic current sources, are given in terms of modal amplitudes together with appropriate explicit singular terms at the source region. It is shown that Maxwell's equations in spectral-domain can be reduced, by using dyadic spectral eigenfunctions, to two sets of z-dependent inhomogeneous transmission-line equations for the modal amplitudes. One set of the transmission-line equations are due to the transverse current sources and the other set due to the vertical current sources. Utilizing these equations, network schematizations of the excitation, transmission and reflection processes of three-dimensional electromagnetic waves in one-dimensionally inhomogeneous multilayer structures are achieved in a full-wave manner. The determination of the spectral Green's functions becomes so simple that it is accomplished by the investigation of voltages and currents on the derived equivalent circuits. Examples of singleand multilayer structures are used to validate the general expressions and the equivalent circuits     

Compatibility equations for large deformations

Compatibility equations for large deformations are developed on the sole basis of the div and curl concepts.     

Natural isotope fractionation in the discrimination of sugar origins

More than 500 carbohydrate samples have been characterised by hydrogen, carbon and oxygen isotopic parameters measured on ethanol and water resulting from controlled fermentation. Different chemical states of the carbohydrate pool have been considered: polysaccharides from cereals, tubers and leguminosae (maize, sorghum, rice, wheat, barley, potato, bean), glucose, fructose and sucrose from fruits (pineapple, citrus, apple, soft fruits), sucrose from sugar plants (beet, cane). The overall carbon-13 content of ethanol and the deuterium and oxygen-18 contents of water before fermentation were determined by mass spectrometry of isotope ratios whereas the investigation of site-specific natural isotope fractionation by deuterium NMR has provided access to the deuterium contents in the methyl (I) and methylene (II) sites of ethanol. The results have been analysed in the multidimensional space of these isotopic variables. Hierarchical clustering, principal component and discriminant analyses have been performed. Among fruits, for example, the pineapple group exhibits a 100% discrimination with respect to the apple and citrus groups which are themselves well distinguished. A still higher discrimination is reached between the three groups, citrus, cane and beet, and the addition of 10% exogenous cane or beet sucrose to citrus juice is unambiguously detected.