A note on optimum grouping and the relative discriminating power of qualitative to continuous normal variates

Ogawa (1951) considered the efficiency of estimation of the population mean from suitably chosen order statistics in large samples. Cox (1957) has considered the relative amount of information retained by grouping the normal curve. Cochran and Hopkins (1961) determined the discriminating power retained after partitioning normally distributed variates into qualitative ones in multivariate classification problems. And Connor (1972) discussed the asymptotic efficiencies of the test for the trend using m groups formed from a continuous variable. The same expression appears in all these investigations. This note throws some more light on the occurrence of the same expression in these seemingly unrelated problems.     

Photoinduced darkening, crystallization and reversible emission in ZnTe thin films

Laser-induced darkening and crystallization of ZnTe-based thin films is reported. ZnTe thin films of 1500-nm thickness were deposited on bare and Zn buffer layered borosilicate glass substrates. The as-deposited films were subjected to laser irradiation at 532 nm. The as-deposited films were amorphous but transformed to the crystalline state under influence of the laser treatment. The X-ray diffraction patterns revealed that the ZnTe crystallized in the zinc blende structure. In addition, presence of peaks from Te was observed, signifying the dissociation of ZnTe. The spectral transmission of the films decreased by more than 15 % under the influence of the laser irradiation and this was accompanied by a red shift in the band gap. These results clearly point to the occurrence of laser-induced darkening and crystallization of the films. To understand the mechanisms of darkening and crystallization, all the films were annealed at 500 °C for 60 min. Similar to the laser-irradiated samples, the thermally annealed films showed an amorphous–crystalline transition, presence of Te in the X-ray diffraction patterns as well as a large decrease in spectral transmission (>70 %). Photoinduced emission analysis carried out as a function of laser intensities indicated a strong red shift of about 51 meV in emission energy with increase in laser intensity due to the photodarkening. The peak position of the emission spectrum can be tuned by increasing the laser intensity and is completely reversible with decrease in laser intensity. It is proposed that laser-induced darkening occurs due to the dissociation of ZnTe into ZnTe and Te and that crystallization is a consequence of laser annealing.     

Quality control in combinatorial chemistry: determination of the quantity,purity, and quantitative purity of compounds in combinatorial libraries

The quality of combinatorial libraries determines the success of biological screening in drug discovery programs. In this paper, we evaluate and compare various methods for measuring identity, purity, and quantity (yield) of combinatorial libraries. Determination of quantitative purity reveals the true library quality and often indicates potential quality problems before full-scale library production. The relative purity can be determined for every member in a large library in a high-throughput mode, but must be cautiously interpreted. In particular, many impurities are not observable by relative purity measurements using detectors such as UV(214), UV(254), and evaporative light-scattering detection. These "invisible" impurities may constitute a significant portion of the sample weight. We found that TFA, plastic extracts, inorganic compounds, and resin washout are among these impurities. With compelling evidence, we reach a conclusion that purification is the only way to remove "invisible" impurities and improve the quantitative purity of any compound even though some compounds may have a high relative purity before purification.     

Mg-Al hydrotalcites as the first heterogeneous basic catalysts for the Kornblum oxidation of benzyl halides to benzaldehydes using DMSO

Mg-Al hydrotalcites (Mg/Al = 2, 3, 5) act as efficient heterogeneous base catalysts for the conversion of benzyl halides to the corresponding benzaldehydes using DMSO as an oxidant.     

Self-organization of rotaxane thin films into spatially correlated nanostructures: morphological and structural aspects

The self-organization of rotaxane thin films into spatially correlated nanostructures is shown to occur upon a thermal stimulus. The mechanism of formation of nanostructures and their organization has been investigated using atomic force microscopy, bright field transmission electron microscopy, selected area electron diffraction, and molecular mechanics simulations. The evolution of the nanostructures follows a complex pathway, where a rotaxane thin film first dewets from the substrate to form nanosized droplets. Droplets coalesce by ripening, generating spatially correlated motifs. In a later stage, the larger droplets change shape, nucleate, and coalesce to yield crystallites that grow into larger crystals by incorporating the surrounding droplets. The results show the following: (i) the nanostructures represent a metastable state of a crystallization process; (ii) spatial correlations emerge during ripening, but they are destroyed as stable nuclei are formed and crystallization proceeds to completion; iii) crystallization, either on graphite or amorphous carbon films, leads to a precise basal plane, viz. (010), which has minimum surface energy. The inherent degrees of freedom permitted in the rotaxane architecture favors the re-organization and nucleation of the film in the solid state. Low-energy trajectories leading to crystallites with stable surfaces and minimum energy contact plane are found to occur via concerted, small amplitude, internal motions without disruption of packing and intermolecular contacts.     

Momentum-space properties from coordinate-space electron density

Electron density and electron momentum density, while independently tractable experimentally, bear no direct connection without going through the many-electron wave function. However, invoking a variant of the constrained-search formulation of density-functional theory, we develop a general scheme (valid for arbitrary external potentials) yielding decent momentum-space properties, starting exclusively from the coordinate-space electron density. A numerical illustration of the scheme is provided for the closed-shell atomic systems He, Be, and Ne in their ground state and for 1s(1) 2s(1) singlet electronic excited state for helium by calculating the Compton profiles and the expectation values derived from given coordinate-space electron densities.     

How universal are hydrogen bond correlations? A density functional study of intramolecular hydrogen bonding in low-energy conformers of α-amino acids

Hydrogen bonding is one of the most important and ubiquitous interactions present in Nature. Several studies have attempted to characterise and understand the nature of this very basic interaction. These include both experimental and theoretical investigations of different types of chemical compounds, as well as systems subjected to high pressure. The O–H..O bond is of course the best studied hydrogen bond, and most studies have concentrated on intermolecular hydrogen bonding in solids and liquids. In this paper, we analyse and characterise normal hydrogen bonding of the general type, D–H...A, in intramolecular hydrogen bonding interactions. Using a first-principles density functional theory approach, we investigate low energy conformers of the twenty α-amino acids. Within these conformers, several different types of intramolecular hydrogen bonds are identified. The hydrogen bond within a given conformer occurs between two molecular groups, either both within the backbone itself, or one in the backbone and one in the side chain. In a few conformers, more than one (type of) hydrogen bond is seen to occur.

Interestingly, the strength of the hydrogen bonds in the amino acids spans quite a large range, from weak to strong. The signature of hydrogen bonding in these molecules, as reflected in their theoretical vibrational spectra, is analysed. With the new first-principles data from 51 hydrogen bonds, various parameters relating to the hydrogen bond, such as hydrogen bond length, hydrogen bond angle, bond length and vibrational frequencies are studied. Interestingly, the correlation between these parameters in these bonds is found to be in consonance with those obtained in earlier experimental studies of normal hydrogen bonds on vastly different systems. Our study provides some of the most detailed first-principles support, and the first involving vibrational frequencies, for the universality of hydrogen bond correlations in materials.     

Vaporization chemistry and thermodynamics in the CdGa2S4-Ga2S3 system

The chemistry and thermodynamics of vaporization of CdGa₂S₄(s), CdGa₈S₁₃(s), and Ga₂S₃(s) were studied by computer-automated, simultaneous Knudsen-effusion and torsion-effusion, vapor pressure measurements in the temperature range 967–1280 K. The vaporization was incongruent with loss of Cd(g) + 1/2 S₂(g) and production of CdGa₈S₁₃(s), a previously unknown compound, in equilibrium with CdGa₂S₄(s), until the solid became CdGa₈S₁₃ only. Then, incongruent vaporization continued with production of Ga₂S₃(s) until the solid was Ga₂S₃ only. The latter vaporized congruently. The ΔH°(298 K) of combination of one mole of CdS(s) with one mole of Ga₂S₃(s) to give CdGa₂S₄(s) was ?22.6 ± 0.9 kJ mole^?1. The 2H2(298 K) of combination of one mole of CdS(s) with four moles of Ga₂S₃(s) to give CdGa₈S₁₃(s) was ?25.5 ± 1.1 kJ mole^?1. The 2H2(298K) of CdGa₈S₁₃(s) with respect to disproportionation into CdGa₂S₄(s) and 3 Ga₂S₃(s) was ?2.8 ± 0.6 kJ mole^?1. CdGa₈S₁₃(s) was not observed at room temperature. The 2H2(298 K) of vaporization of the residual Ga₂S₃(s) was 663.4 ± 0.8 kJ mole^?1, which compared well with a value of 661.4 ± 0.3 kJ mole^?1 already available from the literature. Implications of small variations in stoichiometry of compounds in this study were observed and are discussed.     

One-pot synthesis of 2-amino-5-nitro-4,6-diarylcyclohex-1-ene-1,3,3-tricarbo-nitriles by condensation of aldehyde, malononitrile, and nitromethane in the presence of Mg-Al HT under solvent-free condition

A multicomponent one-pot reaction of aromatic aldehyde, malononitrile, and nitromethane is carried out in the presence of HTs (different Mg/Al ratios) and other solid bases, where 2-amino-5-nitro-4,6-diphenylcyclohex-1-ene-1,3,3-tricarbonitriles are obtained. HT with Mg/Al = 5 is the best catalyst for the reaction. The reaction gives best results under solvent-free condition. The catalyst can be easily separated and is recyclable. Other parameters were optimized.