General base catalysis in the decomposition of N-Cl-Valine in aqueous solution

This article analyzes the kinetics of the decomposition of N-Cl-Valine in aqueous solution, which is formed rapidly by chlorination of Valine with sodium hypochlorite. A general-base catalyzed process not yet described is reported. The experimental evidence shows two competitive decomposition paths: an unimolecular concerted fragmentation process (k = (1.8 ± 0.1) · 10^?4 s^?1 at 298 K) and the other one is an E2 elimination process whose importance increases with pH and depends on the nature and the concentration of the bases present in the medium. © 1994 John Wiley & Sons, Inc.     

Large Sample Properties of Mixture Models with Covariates for Competing Risks

We study the large-sample properties of a class of parametric mixture models with covariates for competing risks. The models allow general distributions for the survival times and incorporate the idea of long-term survivors. Asymptotic results are obtained under a commonly assumed independent censoring mechanism and some modest regularity conditions on the survival distributions. The existence, consistency, and asymptotic normality of maximum likelihood estimators for the parameters of the model are rigorously derived under general sufficient conditions. Specific conditions for particular models can be derived from the general conditions for ready check. In addition, a likelihood-ratio statistic is proposed to test various hypotheses of practical interest, and its asymptotic distribution is provided.     

An efficient lasing action from pyrromethene 556 dye-doped organically modified silicates

Organically modified solid-state silicates (ORMOSILS) doped with a new laser dye 1,3,5,7,8-pentamethylpyrromethene-2,6-disulfonate-BF₂ complex (pyrromethene 556) have been synthesized by a sol-gel method and the compositional effects on pore characteristics, fluorescence and lasing properties have been investigated. It is found that the use of dimethylsulfoxide and γ-glycidoxypropyltrimethoxysilane could greatly change the structure properties of sol-gel derived ORMOSILS cage, and thus the fluorescence and lasing properties of the materials could improve significantly. A successful laser oscillation from this dye-doped ORMOSILS sample has been achieved upon pumping with a Q-switched frequency-doubled Nd:YAG laser at 532 nm. A slope efficiency of 54% with a useful lifetime greater than 10,000 shots has been demonstrated at a pump repetition rate of 1 Hz and a pump intensity of 1 J/cm² by using the new ORMOSILS cage on our newly designed laser system. Our results have shown that it is possible to obtain a high-efficiency with a long-lifetime for a compact new laser device by low cost dye-doped solid-state ORMOSILS.     

Temperature dependence of excitonic luminescence from nanocrystalline ZnO films

The properties of the excitonic luminescence for nanocrystalline ZnO thin films are investigated by using the dependence of excitonic photoluminescence (PL) spectra on temperature. The ZnO thin films are prepared by thermal oxidation of ZnS films prepared by low-pressure metalorganic chemical vapor deposition (LP-MOCVD) technique. The X-ray diffraction (XRD) indicates that ZnO thin films have a polycrystalline hexagonal wurtzite structure with a preferred (0 0 2) orientation. A strong ultraviolet (UV) emission peak at 3.26 eV is observed, while the deep-level emission band is barely observable at room temperature. The strength of the exciton-longitudinal-optical (LO) phonon coupling is deduced from the temperature dependence of the full-width at half-maximum (FWHM) of the fundamental excitonic peak, decrease in exciton-longitudinal-optical (LO) phonon coupling strength is due to the quantum confinement effect.     

Influence of preparation method on SrMoO4 impurity content and magnetotransport properties of double perovskite Sr2FeMoO6 polycrystals

The magnetic and electric properties of the Sr₂FeMoO₆ compound produced under different preparation conditions were studied. Depending on the preparation condition, a strong variation in the nonmagnetic SrMoO₄ impurity content was found, which in turn determined the metallic or semiconducting behavior of the resistivity of the Sr₂FeMoO₆ compound. There was also evidence that SrMoO₄ played a crucial role in modifying the low magnetic field intergrain tunneling magnetoresistance in Sr₂FeMoO₆. In addition, we have established a simple method to prepare the single phase Sr₂FeMoO₆ polycrystals.     

Parity violation at neutron p-wave resonances of238U and232Th and related questions

Parity violation effects have been studied at 40 neutron p-wave resonances of the even-even nuclei²³⁸U and²³²Th. Of these 11 show parity violation effects larger than 2 standard deviations, making parity violation a rather common phenomenon. Parity mixing up to 10% has been found. The root-mean squared matrix elements for parity violation derived from these resonances are M=0.58 (+0.50/-0.25) meV for²³⁸U, respectively 1.39 (+0.35/-0.38) meV for²³²Th.     

Theory of main chain nematic polymers with spacers of varying degree of flexibility

Main chain liquid crystal polymers are modelled as either worms or jointed rods. In reality they are composed of mesogenic units (rods) linked by spacers with varying degrees of flexibility. We present a molecular model to describe non-homogeneous nematic polymers. The model takes account of molecular parameters, such as the lengths of the mesogenic group and the spacer units, and the interactions between them. The spacers are found to have an order differing from the mesogenic units. If the spacer is not very long and thus in effect is inflexible, one end of the spacer can retain to some extent the orientation of the other end, allowing orientational correlation between spacers mediated by the intermediate mesogenic unit. This is important in giving the chain a global rod-like behaviour as the nematic field becomes strong or the temperature low. The nematic order of the two components (mesogens and spacers), the nematic-isotropic transition as well as the latent entropy are examined. Furthermore, the anisotropic conformations of the polymers are investigated, which show either rod-like or random walk behaviour. Comparison of our results with experiment is found to be satisfactory.     

Difference in micellar properties of sodium dodecyl sulfonate from sodium 4-decyl naphthalene sulfonate in D2O solution studied by 1H NMR relaxation and 2D NOESY

¹H chemical shift changes of sodium 4-decyl naphthalene sulfonate (SDNS) at 313 K show that its critical micellar concentration lies between 0.82 and 0.92 mmol/dm³, which is in the same range as that of the previous study at 298 K. The spin–lattice relaxation time, spin–spin relaxation time and two-dimensional nuclear Overhauser enhancement spectroscopy experiments give information about the structure of the SDNS micelle and the dynamics of the molecules in the micelle. The size of the SDNS micelle remains almost unchanged in the temperature range from 298 to 313 K as deduced by analyzing the self-diffusion coefficient. Special arrangement of the naphthyl rings of SDNS in the micelles affects the packing of these hydrophobic chains. The methylene groups of the alkyl chain nearest the naphthalene groups penetrate into the aromatic region, which results in a more tightly packed hydrophobic micellar core than that of sodium dodecyl sulfonate.     

Partially Strictly Monotone and Nonlinear Penalty Functions for Constrained Mathematical Programs

We introduce the concept of partially strictly monotone functions and apply it to construct a class of nonlinear penalty functions for a constrained optimization problem. This class of nonlinear penalty functions includes some (nonlinear) penalty functions currently used in the literature as special cases. Assuming that the perturbation function is lower semi-continuous, we prove that the sequence of optimal values of nonlinear penalty problems converges to that of the original constrained optimization problem. First-order and second-order necessary optimality conditions of nonlinear penalty problems are derived by converting the optimality of penalty problems into that of a smooth constrained vector optimization problem. This approach allows for a concise derivation of optimality conditions of nonlinear penalty problems. Finally, we prove that each limit point of the second-order stationary points of the nonlinear penalty problems is a second-order stationary point of the original constrained optimization problem.